Benzopyrylium Ions PDF

201
14.2 Product Class 2:

Benzopyrylium Salts
M. Ngrdi
14.2.1 Product Subclass 1:

1-Benzopyrylium Salts (Including Flavylium Salts)
Previously published information regarding this product class can be found in Houben–
Weyl, Vol. E 7a, pp 30–204. A review on 2-phenyl-1-benzopyrylium salts (flavylium salts)
was published in 1993 by Iacobucci and Sweeny.[1]
In this section, the following CAS names will be used for the structures shown in
Scheme 1: 2H-1-benzopyran-2-ones (2H-chromen-2-ones, coumarins), 4H-1-benzopyran-4-
ones (4H-chromen-4-ones, chromones), 2-aryl-4H-1-benzopyran-4-ones [2-aryl-4H-chrom-
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en-4-ones, flavones (Ar1 = Ph)], and 2-aryl-1-benzopyrylium salts [2-arylchromenium salts,
flavylium salts (Ar1 = Ph)]. The IUPAC and trivial names are given in parentheses.
Scheme 1 Trivial and Systematic Names for Some 1-Benzopyran Derivatives
O O
+
O O O O Ar1 O Ar1
2H-1-benzopyran-2-one 4H-1-benzopyran-4-one 2-aryl-4H-1-benzopyran-4-one 2-aryl-1-benzopyrylium salt

(coumarin) (chromone) (flavone, Ar1 = Ph) (flavylium salt, Ar1 = Ph)
The most important structural feature of 1-benzopyrylium salts is a positive charge dis-
tributed unevenly over the heterocyclic ring. The significant resonance structures are
shown in Scheme 2. The ring system is planar.[2–4]
Scheme 2 Resonance Structures and Numbering of 1-Benzopyrylium Salts
5 4 +
6 3
7 + 2 + +
O O O O
8 1
1-Benzopyrylium salts are strong Lewis acids. In solution they are stable only at low pH[1,5]
and as solids when combined with anions derived from strong acids of low donator poten-
tial (e.g., ClO4–, BF4–, FeCl4–). They are susceptible toward nucleophiles such as hydroxylic
solvents, e.g. water, in which they are converted into the pseudo base form. 3-Hydroxy
derivatives may take up a betaine form, while 7-hydroxy derivatives adopt a quinoidal
structure (see Scheme 3).[5]
for references see p 267

202 Science of Synthesis 14.2 Benzopyrylium Salts
Scheme 3 Hydrolysis of 1-Benzopyrylium Salts to Pseudo Bases[5]
R1 + 2 H 2O R1 + H 3O+
+
O O OH
OH O−
R1 + H2O R1 + H3O+
+ +
O O
R1 + H 2O R1 + H 3O+
+
HO O O O
Depending on substituents, pKa values for 1-benzopyrylium salts vary over a wide range,
–1.96 for the unsubstituted salt, –0.68 for the methylsulfanyl, and –3.58 for the 6-bromo
derivatives at the two extremes.[6] The range for the important 2-phenyl-1-benzopyrylium
salts is narrower (1.22–4.33).[5,7]

The positive charge of the 1-benzopyrylium ring renders hydroxy groups acidic, fore-
most at positions 2 and 4, less at positions 5 and 7. Therefore in protic solvents, in the
absence of acid, such salts are deprotonated (see Scheme 4).[8–10]
Scheme 4 Deprotonation of 2- and 4-Hydroxy-1-benzopyrylium Salts[8–10]
− H+
+
O OH O O
OH O
− H+
+
O O
Hydrolysis of 1-benzopyrylium salts gives 2-hydroxy-2H-1-benzopyrans, called pseudo

bases, while deprotonation of 2- or 4-alkyl-1-benzopyrylium salts gives the anhydro bases,
i.e. 2- or 4-alkylidene-2H-1-benzopyrans (see Scheme 5).
Scheme 5 Hydrolysis and Deprotonation of 1-Benzopyrylium Salts
H2O
X−
− HX + R1 − HX R1
1
O R O O
OH
"pseudo base" 1-benzopyrylium salt "anhydro base"
The UV spectrum of 1-benzopyrylium perchlorate has an intensive band at 349 nm (log

3.53), which is significantly modified by substitution.[11] 2-Phenyl-1-benzopyrylium salts
absorb in the range 402–587 nm, depending on substitution and solvent.[12,13] Polyhydroxy
2-aryl-1-benzopyrylium salts and their glucosides are typical coloring matters of plants,
giving a long-wavelength band in the range 388–535 nm.[14]
The effect of the positive charge is strongest at C2 and C4; the corresponding 13C sig-
nals for 2-phenyl-1-benzopyrylium perchlorate are shown in Scheme 6.[15] Signals for H2
and H4 are in the range 8.6–9.9 ppm.[11]
14.2.1 1-Benzopyrylium Salts (Including Flavylium Salts) 203
Scheme 6 Characteristic 13C NMR Signals for 2-Phenyl-1-benzopyrylium Perchlorate;

1
H NMR Signals for 3¢,4¢,7-Trihydroxy-2-phenyl-1-benzopyrylium Chloride and 1-Benzo-
pyrylium Trifluoromethanesulfonate[15–17]
159.0 9.72
8.10 8.98
127.5
118.6 7.39 8.21 8.13
−
ClO4 7.81 Cl− OTf−
+ + OH + 9.87
157.7 O 176.8 Ph HO O O
7.48
7.97
OH
7.09
The first 2-phenyl-1-benzopyrylium salts were obtained in 1881 by heating phenols in the
presence of zinc(II) chloride,[18] but they acquired importance only when it was recog-
nized by Willsttter and his school that most of the coloring matters of flowers are poly-
hydroxy 2-phenyl-1-benzopyrylium salts, mainly in the form of their 3-O-glycosides.[19,20]
Derivatives of 3-hydroxy-1-benzopyrylium salts are called anthocyanidines, the corre-
sponding glycosides anthocyanines, while those lacking a 3-hydroxy group are deoxyan-
thocyanidines.

Although they are nontoxic, and despite considerable effort, anthocyanines have so
far found no practical application as food or textile colorants. However, some 2-aryl-1-
benzopyrylium salts are patented as laser dyes.[21–24] 2-(2-Hydroxyphenyl)vinyl-1-benzo-
pyrylium salts are light sensitive and exhibit pH-dependent color changes.[22–31]
SAFETY: Many of the preparations included in this section use perchloric acid or inorganic
perchlorate salts. Finely divided mixtures of perchlorates and organic matter frequently react ex-
plosively. Organic perchlorate salts are all potentially self-contained explosives, and should thus
be handled with extreme care.
14.2.1.1 Synthesis by Ring-Closure Reactions
14.2.1.1.1 By Formation of One Heteroatom-Carbon and One C-C Bond
With one unimportant exception, the oxygen atom of the pyrylium ring is invariably
provided by a phenolic hydroxyl. The phenol partner is reacted with a compound contri-
buting three, two, one, or zero carbon atoms to the pyrylium ring, accompanied by the
formation of two new bonds or, in the last case, of one new bond. Of most significance
is the reaction of a 2-hydroxybenzaldehyde with a partner that provides two carbon at-
oms for the pyrylium ring.
For reactions of phenols with a three-carbon component, the partner in these meth-
ods has to be a 1,3-difunctional linear C3 compound with a terminal acceptor group,
which also contains a carbonyl group. The main types of three-carbon components are
shown in Scheme 7.
Scheme 7 Three-Carbon Components Suitable for Reaction with Phenols
R3 R1O
R2
R1OC CO2R2 R1OC CN R1OC COR2
OHC
3-oxocarboxylic esters 3-oxocarbonitriles alkane-1,3-diones 3-alkoxypropenals
Hal O
R2 R2 COR1
R1OC
3-halopropenones, R1 = Me prop-2-enones prop-2-ynones
3-halopropenals, R1 = H

14.2.1.1.1.1 Method 1:
Reaction of a Phenol with a 3-Oxocarboxylic Ester
The limited reactivity of 3-oxocarboxylic esters restricts the method to polyphenols, and,
as exemplified in Scheme 8, this reaction gives substituted 4-ethoxy-2-phenyl-1-benzopyr-
ylium salts 1.[32] Reaction of a 3-oxopropanonitrile with a phenol bearing a donor group
gives a 2-amino-1-benzopyrylium salt, which can be readily hydrolyzed to a 2H-1-benzopy-
ran-2-one.[33]
Scheme 8 Reaction of a 3-Oxocarboxylic Ester with Polyphenols[32]
OEt
Ph HCl(g), AcOH
R1 + EtO2C R1 Cl−
+
OH O O Ph

4-Ethoxy-5,7-dihydroxy-2-phenyl-1-benzopyrylium Chloride [1, R1 = 5,7-(OH)2];
Typical Procedure:[32]
Dry HCl(g) was passed into a soln of benzene-1,3,5-triol, (12.6 g, 0.1 mol) and ethyl 3-oxo-3-
phenylpropanoate (19.2 g, 0.1 mol) in AcOH (100 mL) for 3 h. The product was collected by
filtration and recrystallized (40% aq EtOH acidified with HCl); yield: 22.6 g (70%); mp 230–
232 8C.
14.2.1.1.1.2 Method 2:
Reaction of a Phenol with a 2-(Ethoxymethylene)-3-oxocarboxylic Ester
On reaction of ethyl 2-(ethoxymethylene)-3-oxobutanoate with a phenol, it is the enol

function that reacts, giving rise to a 3-(ethoxycarbonyl)-1-benzopyrylium salt 2 in low
yield, except in the case of resorcinol (R1 = OH) where 60% of the product is obtained
(Scheme 9).
Scheme 9 Reaction of a Phenol with Ethyl 2-(Ethoxymethylene)-3-oxobutanoate[34]
CO2Et CO2Et
HClO4
ClO4−
EtO
+
R1 = OH 60% +
R1 OH O R1 = Me 12%
R1 O
R1 = OMe 9% 2
3-(Ethoxycarbonyl)-7-hydroxy-2-methyl-l-benzopyrylium Perchlorate (2, R1 = OH);

To Ac2O (5 mL), 70% HClO4 (1 mL, 10 mmol) was added dropwise with cooling, followed by
ethyl 2-(ethoxymethylene)-3-oxobutanoate (1.86 g, 10 mmol) and 3-hydroxyphenol
(1.43 g, 13 mmol). After brief heating, the mixture was cooled and the product precipitat-
ed with Et2O; yield: 2.0 g (60%); mp 184 8C (AcOH).
14.2.1.1.1.3 Method 3:
Reaction of a Phenol with a 1,3-Dioxo Compound
1-Aryl- and 1,3-diaryl-1,3-diketones, as well as 3-aryl-3-oxoaldehydes, are widely used as

components for the synthesis of 2,4-disubstituted and 2-substituted 1-benzopyrylium
salts, e.g. 3 (Scheme 10). Generally, hydrogen chloride gas is used as the condensing agent
and a donating group in the phenol component is required.[9,35–37]
Scheme 10 Reaction of 3-Aryl-3-oxopropanals with Phenols[9,35–37]
O
OHC
HCl(g) R1 Cl−
R1 + +
O
OH R2
R2
3
R1 (in 3) = 7-OH, 5,7-(OH)2, 5,6-(OH)2, 5-OH-7-Me; R2 = H, OMe
4-Aryl-2,4-dioxobutanoic acids react with phloroglucinol-type phenols to give moderate

to good yields of pyrylium salts 4 (Scheme 11).[32,38,39]
Scheme 11 Reaction of Phenols with 4-Aryl-2,4-dioxobutanoic Acids[32,39]
O O
HO2C AcOH, HCl(g)

R1 + R2

R1 (in 4) = 5,7-(OH)2; R2 = H 57%
OH R1 (in 4) = 5,7-(OMe)2; R2 = OMe 84%
R1 (in 4) = 5,7-(OMe)2; R2 = 3,4-(OMe)2 92%
CO2H
R1 Cl−
+
O
R2
1,3-Diphenylpropane-1,3-dione reacts with resorcinol and derivatives in the presence of

perchloric acid to give 2,4-diphenyl-1-benzopyrylium perchlorates.[9,12,40–42] With unsym-
metrical analogues, the reaction gives a mixture of isomers.
A similar hydrogen chloride induced condensation of activated phenols and 1-phen-
ylbutan-1,3-dione gives 4-methyl-2-phenyl-1-benzopyrylium chlorides in moderate to low
yields.[35,43] Yields are higher (75–100%) with 2-acetylcyclohexanone derivatives.[44]
More successful is the use of the corresponding boron trifluoride complexes (giving
benzopyrylium salts 5, Scheme 12).[45] The process also works with annulated complexes,
providing benzo[e]naphtho[1,2-b]pyrylium and naphtho[2,1-b]pyrano[4,3-b]-1-benzopyryl-
ium salts in 49–83% yield.
Scheme 12 Reaction of Phenols with the Boron Trifluoride Complex of a

1-Arylalkane-1,3-dione[45,46]
O
+
1 + F2 B − HClO4
R O 2 R1 (in 5) = 7-OMe; R2 = 4-Ph 63%
R
OH R1 (in 5) = 7-OH; R2 = 4-Ph 52%
R1 ClO4−
+
O
R2

An oxonium salt may serve as an equivalent of a 1,3-diketone (Scheme 13).[42] Condensa-

tion with 2-hydroxybenzaldehyde gives the 2-substituted 1-benzopyrylium salt 6.
Scheme 13 Condensation of a 2-Hydroxybenzaldehyde with the Oxonium Equivalent of a

1,3-Diketone[42]
MeO CHO Ph
Ac2O, CHCl3
+ + ClO4−
O O
OH
O O MeO
O
ClO4− ClO4−
MeO +
Ph 41% +
O Ph
OH 6

5,7-Dihydroxy-2-phenyl-1-benzopyrylium Chloride [3, R1 = 5,7-(OH)2; R2 = H];
A soln of benzene-1,3,5-triol (5.0 g, 40 mmol) and 3-oxo-3-phenylpropanal (8.0 g, 54 mmol)
in AcOH (35 mL) was saturated with HCl(g) and kept for 12 h. The reddish brown crystals
were collected, washed with AcOH, and dried (NaOH). More of the salt was precipitated by
adding Et2O to the filtrate and this was extracted with 0.5% boiling HCl; yield: 4.2 g (38%);
mp 300 8C.
4-Carboxy-5,7-dihydroxy-2-phenyl-1-benzopyrylium Chloride [4, R1 = 5,7-(OH)2; R2 = H];

To a soln of benzene-1,3,5-triol (12.6 g, 0.1 mol) and 2,4-dioxo-4-phenylbutanoic acid
(19.2 g, 0.10 mol) in AcOH (100 mL), HCl(g) was introduced for 3 h at 70–80 8C. After cool-
ing, Et2O (100 mL) was added and the mixture stored in a refrigerator in order to complete
crystallization. The product was collected by filtration and recrystallized (EtOH); yield:
18.1 g (57%); mp 256–260 8C.
2-(Biphenyl-4-yl)-7-methoxy-4-methyl-l-benzopyrylium Perchlorate (5, R1 = 7-OMe;

R2 = 4-Ph); Typical Procedure:[46]
6-(Biphenyl-4-yl)-2,2-difluoro-4-methyl-1,3,2-oxaoxoniaboratin (2.86 g, 10 mmol) and 3-
methoxyphenol (1.24 g, 10 mmol) were dissolved in AcOH (30 mL). After adding 70%
HClO4 (3 mL), the mixture was refluxed for 1 h. The precipitate was collected by filtration
and recrystallized (AcOH); yield: 2.7 g (63%); mp 210 8C.
6-Methoxy-2-(2-oxo-2-phenylethyl)-1-benzopyrylium Perchlorate (6); Typical Procedure:[42]

To a soln of 2,2,4-trimethyl-6-phenyl-1,3-dioxanylium perchlorate (3.02 g, 10 mmol) in a
mixture of CHCl3 (20 mL) and Ac2O (1.5 mL), 2-hydroxy-5-methoxybenzaldehyde (1.5 mL,
10 mmol) was added. After refluxing for 30 min and standing overnight, the product was
collected by filtration and recrystallized (MeCN); yield: 1.55 g (41%); mp 232–234 8C.
14.2.1.1.1.4 Method 4:
Reaction of a Phenol with a 3-Chlorovinyl Aldehyde
Reaction of a 3-(dialkylamino)phenol with 3-aryl-3-chloroacrolein in the presence of per-

chloric acid gives 4-aryl-7-(dialkylamino)-1-benzopyrylium perchlorates in modest
yields,[47] except in a special case when this functionality is part of a quinolin-2(1H)-one
ring.[47,48]
14.2.1.1.1.5 Method 5:
Reaction of a Phenol with an Ethynyl Ketone
1-Arylprop-2-ynones are synthetic equivalents of 1,3-diketones and can be condensed

with activated phenols to give, without the use of an oxidant, 1-benzopyrylium salts 7 in
variable, but occasionally very high, yields (Scheme 14).[49–51]
Scheme 14 Reaction of Phenols with Ethynyl Ketones[49,50]

1. H2SO4
2. HX
R1 +
R1 (in 7) = 5,7-(OMe)2; R2 = 3,4-(MeO)2C6H3 91%
OH
O R2 R1 (in 7) = 6-OMe; R2 = Ph 48%
R1 X−
+
O R2
7
1
R (in 7) = 6-OMe, 7-OMe, 5,7-(OMe)2, 5,7-(OH)2; R2 = Ph, 3,4-(MeO)2C6H3
5,7-Dimethoxy-2-(3,4-dimethoxyphenyl)-1-benzopyrylium Chloride (Luteolinidine Tetra-

methyl Ether) [7, R1 = 5,7-(OMe)2; R2 = 3,4-(MeO)2C6H3; X = Cl]; Typical Procedure:[50]
Concd H2SO4 (19 mL) was added dropwise to a mixture of 3,5-dimethoxyphenol (11.6 g,
75 mmol) and 1-(3,4-dimethoxyphenyl)prop-2-yn-1-one (14.3 g, 75 mmol) in AcOH
(190 mL). The soln rapidly became dark red. After 3 days, the precipitated sulfate (28.4 g)
was collected by filtration and converted into the chloride by two crystallizations (6 M
HCl) to give the product as orange needles; yield: 24.8 g (91%); mp 161–162 8C (dec).
14.2.1.1.1.6 Method 6:
Reaction of a Phenol with a Vinyl Ketone
Reaction of vinyl ketones, particularly 1,3-diarylpropen-2-enones (chalcones), with phe-

nols is an important method for the preparation of 1-benzopyrylium salts because of the
ready availability of many chalcones. Since the reaction initially gives 4H-1-benzopyrans,
the use of an oxidant such as tetrachlorobenzo-1,4-quinone or triphenylcarbenium per-
chlorate is necessary in order to arrive at the 1-benzopyrylium salts 8 (Scheme 15).[52–54]

Scheme 15 Reaction of Phenols with Chalcones[52–54]
R3
HX
R1 +
OH
O
R2
R3
R3
− H2O
R1 R1
O R2 O
OH
R2

R3
oxidation
R1 X−
R1 (in 8) = 6-t-Bu; R2 = R3 = H 25% +
R1 (in 8) = 6-OH-5,7-(OMe)2; R2 = R3 = H 82%
O
R2
R1 (in 8) = 6-OMe; R2 = H; R3 = 4-OMe 26%
R1 (in 8) = 6,7- (CH CH)2; R2 = R3 = H 42%
8
An analogous procedure using monoaryl prop-2-enones yields 2-phenyl-1-benzopyrylium

salts, but very few examples are known. One such example is the reaction of phlorogluci-
nol (benzene-1,3,5-triol) with 1-phenylprop-2-enone in the presence of tetrachlorobenzo-
1,4-quinone, giving 5,7-dihydroxy-2-phenyl-1-benzopyrylium chloride (chrysidine chlo-
ride) in 87% yield.[54]
2,4-Diphenylnaphtho[2,1-b]pyrylium Tetrafluoroborate [8, R1 = 6,7-(CH=CH)2; R2 = R3 = H;

X = BF4]; Typical Procedure:[52]
2-Naphthol (16.0 g, 0.11 mol), 1,3-diphenylprop-2-en-1-one (20.0 g, 0.1 mol), and Tr+BF4–
(33.0 g, 0.105 mol) in AcOH (100 mL) were refluxed for 1 h. After cooling, the mixture
was added, with stirring, into Et2O (600 mL). The product was collected by filtration and
reprecipitated (1,2-dichloroethane/Et2O); yield: 16 g (42%); mp 240–251 8C.
14.2.1.1.1.7 Method 7:
Reaction of a 2-Hydroxybenzaldehyde (Salicylaldehyde) with
a Carbaldehyde, Ketone, or Acetal
14.2.1.1.1.7.1 Variation 1:
With an Æ-Methylene Aldehyde or Acetal
Acid-catalyzed condensation of free Æ-methylene aldehydes with 2-hydroxybenzalde-

hydes gives negligible yields of 1-benzopyrylium salts 9,[55] but use of the corresponding
acetals constitutes a viable method (Scheme 16).[56–59]
Scheme 16 Reaction of 2-Hydroxybenzaldehydes with Æ-Methylene Aldehyde Acetals[56,57]
1. Ac2O, AcOH, 0 oC
CHO R2
2. HClO4
R1 +
R1 = R2 = H 65%
OH MeO OMe R1 = H; R2 = Me 90%
R1 (in 9) = 6-Cl; R2 = Ph 100%
R1 (in 9) = 6,7-(CH CH)2; R2 = Ph 80%
R2
R1 ClO4−
+
O
3-Phenylnaphtho[1,2-b]pyrylium Perchlorate [9, R1 = 6,7-(CH=CH)2; R2 = Ph];

To a mixture of 3-hydroxy-2-naphthaldehyde (10.3 g, 60 mmol) and 1,1-dimethoxy-2-phen-
ylethane (8.3 g, 50 mmol), a mixture of Ac2O and HClO4 containing 0.7 mol of the acid was

added dropwise with cooling, followed by gentle warming for 2–3 min on a water bath.
After cooling to 20 8C, the product was precipitated with Et2O (10 mL). The salt was collect-
ed by filtration and washed with Et2O; yield: 13.6 g (80%); mp 215 8C.
14.2.1.1.1.7.2 Variation 2:
With Acetophenones
While condensation of 2-hydroxybenzaldehydes with dialkyl ketones is only successful

under special structural conditions (e.g., with tert-butyl methyl ketone[60]), its condensa-
tion with aralkyl ketones, most often with acetophenones, is a generally applicable meth-
od, giving moderate to high yields of 10 with a variety of condensing agents [perchloric
acid, iron(III) chloride, tetrafluoroboric acid, sulfuric acid, hydrogen chloride] (Scheme
17). The reactants are usually dissolved in a polar solvent, and the condensing agent is
then added.[16,58,61–70,264,302,303]
Scheme 17 Reaction of 2-Hydroxybenzaldehydes with Acetophenones[16,63–65,264,302,303]
CHO
HX
R1 + O R1 X−
R2 +
OH O
R2
10
R1 (in 10) R2 Yield (%) Ref
[64]
H 4-Ph 76
[264]
H 4-OH 79
[64]
H 4-NMe2 55
[302]
5,6-(CH=CH)2 H 44
[64]
5,6-(CH=CH)2 4-NO2 84
[303]
6-OH 4-OMe 80
[63]
7-OH 4-OMe 61
[16]
7-OH 3,4-(OH)2 75
[65]
6-NO2 H 68
[65]
6-NO2 4-NH2 83

2-(3,4-Dihydroxyphenyl)-7-hydroxy-1-benzopyrylium Chloride [10, R1 = 7-OH;

R2 = 3,4-(OH)2; X = Cl]; Typical Procedure:[16]
HCl(g) was bubbled into a soln of 3,4-dihydroxyacetophenone (12.0 g, 79 mmol) and 2,4-
dihydroxybenzaldehyde (10.9 g, 79 mmol) in EtOAc (100 mL), at 0 8C for 90 min. The mix-
ture was kept at –18 8C for 3 days and the precipitate collected by filtration. Concentra-
tion of the filtrate and addition of Et2O yielded more of the product. After washing with
EtOAc and drying under vacuum, the product was found to be pure by HPLC; yield: 17.3 g
(75%).
2-(4-Aminophenyl)-6-nitro-1-benzopyrylium Perchlorate (10, R1 = 6-NO2; R2 = 4-NH2;

X = ClO4); Typical Procedure:[65]
To 2-hydroxy-5-nitrobenzaldehyde (3.4 g, 20 mmol) and 4-aminoacetophenone (2.7 g,
20 mmol), AcOH (10 mL) was added, whereupon the yellow imine precipitated. Concd
H2SO4 (30 mL) was added in small portions to give a red soln. After standing for 15 h, the
mixture was heated on a steam bath for 3 h. To the cooled soln, HClO4 (150 mL) was added
with stirring, and the precipitate formed was collected by filtration and recrystallized
(MeOH); yield: 6.0 g (83%); mp 306 8C (dec).

14.2.1.1.1.7.3 Variation 3:
With an ø-Substituted or Cyclic Acetophenone
Reaction of 2-hydroxybenzaldehydes with ø-substituted acetophenones gives 2-aryl-3-

substituted 1-benzopyrylium salts 11. In the simplest case, propiophenones yield 2-aryl-
3-methyl-1-benzopyrylium salts,[55,71,72] while 1,2-diarylethanones give 2,3-diaryl-1-benzo-
pyrylium salts (Scheme 18).[73]
Scheme 18 Reaction of 2-Hydroxybenzaldehydes with ø-Substituted

Acetophenones[55,70–74]
R3
CHO
HX
R1 +
O R1 = R2 = H; R3 = Me 95%
OH R2
R1 = H; R2 = 2-Me; R3 = Ph 86%
R1 = H; R2 = 4-OH; R3 = Me 100%
R1 (in 11) = 8-OMe; R2 = 4-OH; R3 = Et 70%
R3
R1 X−
+
O
R2
11
The CH2CO-aryl functionality may be part of a carbocycle as well (see 12, Scheme 19);[75–81]
yields are generally high (67–98%).
Scheme 19 Reaction of 2-Hydroxybenzaldehydes with Cyclic Acetophenone

Analogues[75–81]
CHO X ClO4−
X HClO4
1 + 1
R R R2
O +
OH O
R2
12
R1 (in substrate) = H, 3,4-(CH CH)2, 4-OH, 3-OMe, 4-OMe, 3-NO2, 5-NO2; R2 = H, OMe; X = CH2, (CH2)2, CHPh, CO
Most important is the reaction of 2-hydroxybenzaldehydes with ø-hydroxy and ø-alkoxy

acetophenones, which leads to 3-oxygenated 2-phenyl-1-benzopyrylium salts 13 (Scheme
20).[73,82,83] 3-Hydroxy-2-phenyl-1-benzopyrylium salts, mainly as their 3-O-glycosides, are
the most important plant dyes. The method works also with ø-(acylamino)acetophe-
nones.[73]
The CH2CO functionality may also be incorporated into a benzo-condensed heterocy-
cle, such as a benzofuran-3(2H)-one, a 2,3-dihydro-4H-1-benzopyran-4-one, or a 2H-1-ben-
zopyran-2-one, etc., to give fused structures such as 14, (Scheme 20).[73,75,77,82–84]
Scheme 20 Reaction of 2-Hydroxybenzaldehydes with ø-Oxygenated Acetophenones and

with a 2,3-Dihydro-4H-naphtho[2,1-b]pyran-4-one[73,82,83]
R2
CHO
HX
R1 +
3 R1 = R2 = R3 = H; X = ClO4 72%
OH R O
R1 = R2 = H; R3 = Me; X = Cl 100%
R1 = OEt; R2 = 4-OMe; OR3 = NHBz; X = FeCl4 31%
O

OR3
R 1
X−
+
O
R2
13
Et2N CHO HClO4

Et2N
O AcOH O
+ ClO4−
85% +
OH O O
14
2-(4-Hydroxyphenyl)-3-methyl-1-benzopyrylium Chloride (11, R1 = H; R2 = 4-OH; R3 = Me;

X = Cl); Typical Procedure:[71]
A soln of 2-hydroxybenzaldehyde (24.4 g, 0.20 mol) and (4-hydroxyphenyl)propan-1-one
(30.0 g, 0.20 mol) in EtOAc (200 mL) and EtOH (50 mL) was saturated with HCl(g). After
15 h, the orange-red crystals were collected by filtration, washed with Et2O, and dried in
air; yield: 53 g (ca. 100%); mp 213–215 8C.
10-Phenyl-10H-benzo[b]indeno[2,1-e]pyrylium Perchlorate (12, X = CHPh; R1 = R2 = H);

A soln of 3-phenylindan-1-one (3.12 g, 15 mmol) and 2-hydroxybenzaldehyde (1.83 g,
15 mmol) in Et2O (50 mL) containing 72% HClO4 (5 mL) was saturated with HCl(g) at 0 8C
for 24 h. The salt precipitated as orange plates; yield: 4.0 g (67%); mp 237–239 8C.
3-Hydroxy-2-phenyl-1-benzopyrylium Perchlorate (13, R1 = R2 = R3 = H; X = ClO4);

Dry HCl(g) was passed into a soln of ø-hydroxyacetophenone (0.7 g, 5 mmol) and 2-hy-
droxybenzaldehyde (0.6 g, 5 mmol) in AcOH (10 mL), at 0 8C for 90 min. 70% HClO4 (5 mL)
was then added dropwise. After 10 min, the yellow crystals were collected by filtration
and recrystallized repeatedly (AcOH); yield: 1.16 g (72%); mp 227–229 8C.

3-Methoxy-2-phenyl-1-benzopyrylium Chloride (13, R1 = R2 = H; R3 = Me; X = Cl);

Dry HCl(g) was passed into a soln of ø-methoxyacetophenone (1.5 g, 10 mmol) and 2-hy-
droxybenzaldehyde (1.2 g, 10 mmol) in dry Et2O (20 mL) for 2 h at 0 8C. After standing in a
refrigerator for 6 days, some of the Et2O was removed in vacuo and the precipitate collect-
ed by filtration with the exclusion of moisture, washed several times with Et2O, and re-
crystallized (chlorobenzene or EtOAc); yield: 2.7 g (ca. 100%); mp 94–96 8C.
3-(Benzoylamino)-8-ethoxy-2-(4-methoxyphenyl)-1-benzopyrylium Tetrachloroferrate
(13, R1 = 8-OEt; R2 = 4-OMe; OR3 = NHBz; X = FeCl4); Typical Procedure:[73]
A soln of ø-(benzoylamino)-4-methoxyacetophenone (2.0 g, 7.4 mmol) and 3-ethoxy-2-hy-
droxybenzaldehyde (1.2 g, 7.4 mmol) in AcOH (10 mL) was saturated with HCl(g) for 6 h.
Addition of a sat. soln of FeCl3 in HCl precipitated a dark oil, which later crystallized. Re-
crystallization (AcOH) gave the product; yield: 1.33 g (31%); mp 201 8C.
12-(Diethylamino)-8H-naphtho[2,1-b]pyrano[4,3-b]-1-benzopyrylium Perchlorate (14);


(5-Diethylamino)-2-hydroxybenzaldehyde (1.93 g, 10 mmol) and 2,3-dihydro-4H-naph-
tho[2,1-b]pyran-4-one (1.98 g, 10 mmol) were refluxed in a mixture of AcOH (30 mL) and
70% HClO4 (3 mL) for 20 min. After cooling, the product was precipitated by the addition
of Et2O and recrystallized (AcOH/MeNO2, 10:1); yield: 4.1 g (85%); mp 360 8C.
14.2.1.1.1.7.4 Variation 4:
With a 2-Arylvinyl Methyl Ketone
2-Hydroxybenzaldehydes react with 1-arylbut-3-en-2-ones, i.e. vinylogues of acetophe-

nones, to give 2-(2-arylvinyl)-1-benzopyrylium salts 15 (Scheme 21).[85,86]
Scheme 21 Reaction of 2,4-Dihydroxybenzaldehyde with 2-Arylvinyl Methyl Ketones[86]
O
EtOAc, EtOH
CHO
HCl(g)
+ R1
HO OH
Cl−
+
HO O
R1
15
R1 = 4-OH, 4-OMe, 4-NMe2
7-Hydroxy-2-[2-(4-hydroxyphenyl)vinyl]-1-benzopyrylium Chloride (15, R1 = 4-OH);

A soln of 2,4-dihydroxybenzaldehyde (45.0 g, 0.20 mol) and 1-(4-hydroxyphenyl)-but-3-en-
2-one (45.0 g, 0.20 mol) in EtOAc (500 mL) and EtOH (100 mL) was saturated with dry
HCl(g). After 5 h, Et2O (200 mL) was added, and the colored precipitate collected by filtra-
tion and purified by suspending it in ethanolic HCl, followed by recrystallization (aq citric
acid soln containing some concd HCl); yield: 80 g (95%).
14.2.1.1.1.8 Method 8:
an Æ-Methylene Carboxylic Acid Derivative
14.2.1.1.1.8.1 Variation 1:
With an Æ-Methylene Carbonitrile
Condensation of malononitrile esters, or analogues, with 2-hydroxybenzaldehydes gives

2-amino-1-benzopyrylium salts 16, which readily hydrolyze to 2H-1-benzopyran-2-ones
(Scheme 22).[87,88]
Scheme 22 Reaction of 2-Hydroxybenzaldehydes with Æ-Methylene Carbonitriles[87]
CHO R2 R2
R1 + R1
CN
OH O NH

R2
HClO4 H2O
R1 ClO4−
R1 = H; R2 = CO2Et 73% +
R1 = H; R2 = CSNH2 68%
O NH2
R1 = H; R2 = CN 88% 16
R1 (in 16) = 8-OMe; R2 = CO2Et 82%
R1 (in 16) = 7-NMe2; R2 = CN 86%
R2
R1
O O
2-Amino-3-(ethoxycarbonyl)-1-benzopyrylium Perchlorate (16, R1 = H; R2 = EtO2C);

To a soln of 2-hydroxybenzaldehyde (2.5 g, 20 mmol) and ethyl cyanoacetate (2.3 g,
20 mmol) in MeCN (50 mL), a few drops of piperidine, followed by 70% HClO4 (2 mL) were
added. After 15 h, the product was precipitated by the addition of Et2O; yield: 3.2 g (73%);
mp 203–206 8C.
14.2.1.1.1.8.2 Variation 2:
With a 3-Oxoalkanoic Ester
The outcome of the reaction of 2-hydroxybenzaldehydes with 3-oxoalkanoic esters de-

pends on the molar ratio of the reactants.[89] With an excess of the ester, the expected 3-
(methoxycarbonyl)-2-methyl-1-benzopyrylium salt 17 is obtained (Scheme 23); however,
use of an excess of the aldehyde leads to the condensation of the reactive 2-methyl group
of the 1-benzopyrylium salt with a second molecule of the aldehyde to form a 2-(2-aryl-
vinyl) derivative 18 (Scheme 24).[90]
Scheme 23 Reaction of 2-Hydroxybenzaldehydes with 3-Oxoalkanoic Esters[75,91]
CHO CO2Me CO2Me

HClO4
R1 + R1 ClO4−
+
OH O O
17

Scheme 24 Reaction of Æ-Substituted 3-Oxoalkanoic Esters with an Excess of 2-Hydroxy-

benzaldehydes[72,89,90]
CHO EtO2C R2
HCl, HClO4
2 R1 +
R1 = H; R2 = Me 84%
OH O R1 = H; R2 = Bn 80%
R1 (in 18) = 6,7-(CH CH)2; R2 = Me 72%
R2
OH
R1 ClO4−
+
O
R1
18
When there is no substituent at the Æ-position of the 3-oxocarboxylic ester, the reaction
takes a different course; first, 3-acetyl-2H-1-benzopyran-2-one is formed, which then re-
acts with another molecule of the aldehyde, to ultimately afford a 2-(2-oxo-2H-benzopy-

ran-3-yl)-1-benzopyrylium salt.[89–91]
3-(Methoxycarbonyl)-2-methyl-l-benzopyrylium Perchlorate (17, R1 = H);

To a soln of methyl 3-oxobutanoate (6.0 g, 50 mmol) and 2-hydroxybenzaldehyde (5.0 g,
40 mmol) in dry Et2O (60 mL), a mixture of Ac2O (2 mL) and AcOH (28 mL) containing 30%
anhyd HClO4 was slowly added at a temperature below 20 8C. The yellow crystals that pre-
cipitated from the colored soln were collected by filtration and washed with a little AcOH
and Et2O; yield: 7.8 g (68%); mp 173 8C.
2-[2-(2-Hydroxyphenyl)vinyl]-3-methyl-l-benzopyrylium Perchlorate (18, R1 = H; R2 = Me);

A soln of freshly distilled ethyl 2-methyl-3-oxobutanoate (14.4 g, 10 mmol) and 2-hydroxy-
benzaldehyde (24.4 g, 20 mmol) in 70% HClO4 (21.5 g) and dry Et2O (30 mL) was saturated,
with cooling, with dry HCl(g). After 12 h, the crystals that separated from the dark red so-
lution were collected by filtration and recrystallized (HCO2H); yield: 30 g (84%); mp 243 8C.
14.2.1.1.1.9 Method 9:
Aliphatic or Alicyclic Æ,Æ¢-Bis(methylene) Ketones
The outcome of this reaction, similar to that of 3-oxocarboxylic esters, depends on the rel-
ative reactivity of the competing methylene groups and the molar ratio of the reactants.
The methylene group adjacent to the pyrylium oxygen is activated and, unless a large ex-
cess of the ketone partner is used, the 2-hydroxybenzaldehyde reacts with the initial
product, forming a 2-substituted vinyl function (vide infra).
Reaction of the symmetrical pentan-3-one with 2-hydroxybenzaldehyde gives low
yields of the expected 1-benzopyrylium salt;[92] the yield with 5-nitro-2-hydroxybenzalde-
hyde is 60%; however, the product is unstable.[93]
Reaction of 2-hydroxybenzaldehydes or naphtholaldehydes with a large excess of cy-
cloalkanone to give, for example, 19, is shown in Scheme 25.[31,94]
Scheme 25 Reaction of 2-Hydroxybenzaldehydes or Naphthaldehydes with a Cyclo-

alkanone[31]
CHO
HX
R1 + R1 X−
( )n + ( )n
OH O O
R1 (in substrate) = H, 4-OMe, 4-NEt2, 5,6- (CH CH)2; n = 1−3
CHO 1. H2SO4
2. HClO4
+ ClO4−
+
OH O O
19
Following the rules of the aldol condensation, reaction of alkyl methyl ketones, such as 1-
phenylpropan-2-one, with 2-hydroxybenzaldehyde, leads to 2-methyl-1-benzopyrylium

salts 20 (Scheme 26).[55]
Scheme 26 Reaction of 2-Hydroxybenzaldehyde with 1-Phenylpropan-2-one[55]
CHO Ph Ph
HCl(g), HClO4
+ ClO4−
+
OH O O
20
With an excess of the 2-hydroxyaldehyde component, double condensation becomes

prevalent (21, Scheme 27).[55,73,89,95,96]
Scheme 27 Reaction of an Aliphatic Æ,Æ¢-Bis(methylene) Ketone with an Excess of

2-Hydroxybenzaldehyde[55,95,96]
CHO R1 1. HCl(g), Et2O R1

OH
X−
2. HX
2 +
R1 = Me 40% +
OH O R1 = Et 93%
O
R1 = CH2CO2Me 95%
21
1,2,3,4-Tetrahydrobenzo[e]naphtho[2,1-b]pyrylium Perchlorate (19); Typical Procedure:[31]

To a soln of 3-hydroxy-2-naphthaldehyde (5.16 g, 30 mmol) in cyclohexanone (14.7 g,
0.15 mol), concd H2SO4 (50 mL) was added, with cooling to keep the temperature below
12 8C. At a maximum of 15 8C, 70% HClO4 (50 mL) was added and the mixture was poured
onto ice. After 4–5 h, the precipitate was collected by filtration, washed with EtOAc, and
recrystallized (AcOH); yield: not reported; mp 218–222 8C.
2-Methyl-3-phenyl-l-benzopyrylium Perchlorate (20); Typical Procedure:[55]

A soln of 2-hydroxybenzaldehyde (1.8 g, 15 mmol) and phenylacetone (1.95 g, 15 mmol) in
70% HClO4 (5 mL) and dry Et2O (10 mL) was saturated with HCl(g). Crystals of the reddish
blue cyclization product were collected by filtration, washed with Et2O, and recrystallized
(AcOH); yield: not reported; mp 189–191 8C.

2-[2-(2-Hydroxyphenyl)vinyl]-3-methyl-l-benzopyrylium Tetrachloroferrate
(21, R1 = Me; X = FeCl4); Typical Procedure:[95]
A soln of 2-hydroxybenzaldehyde (6.1 g, 50 mmol) and butan-2-one (3.6 g, 50 mmol) in dry
Et2O (60 mL) was saturated with dry HCl(g). After 8 h at 20 8C, the product separated as glis-
tening brown crystals; yield: 7.7 g (40%). It was transformed into the tetrachloroferrate
and purified by recrystallization (AcOH); mp 160–170 8C.
14.2.1.1.1.10 Method 10:

Reaction of 2-Acylphenols (2-Hydroxyacetophenones or
2-Hydroxybenzophenones) with Æ-Methylene Ketones
The reaction, in the presence of perchloric acid, of a 2-hydroxyacetophenone with an ace-

tophenone bearing an electron-donating substituent gives 2-aryl-4-methyl-1-benzopyryl-
ium salts 22 in low to moderate yields (Scheme 28).[97–99]
Scheme 28 Reaction of 2-Hydroxyacetophenones with Other Acetophenones[97–99]

O
O HClO4
2 R1 + R2
R1 = R2 = H 57%
OH R1 = H; R2 = 2-OH 25%
R = H; R2 = 4-OMe 53%
1
R1 (in 22) = 6-Me; R2 = H 46%

R1 (in 22) = 7-OH; R2 = 4-Ph 53%
R1 (in 22) = 5-OMe; R2 = H 10%
R1 ClO4−
+
O
R2
22
4-Methyl-2-phenyl-1-benzopyrylium salts can also be obtained in moderate yield by the re-

action of a 2-hydroxy-ø-chloroacetophenone with simple acetophenones.[100] In the ab-
sence of another reactive partner, 2-hydroxyacetophenone can undergo self-condensa-
tion to give 2-(2-hydroxyphenyl)-4-methyl-1-benzopyrylium perchlorate (23, R1 = H).[101]
The method was developed as a one-pot procedure, as illustrated in Scheme 29,[101,102]
but yields are low. Acylation of the phenol is followed by Fries rearrangement and self-
condensation.
Scheme 29 Self-Condensation of 2-Hydroxyacetophenones Prepared In Situ by Fries Rear-

rangement[101,102]
O
Ac2O
HClO4 O
2 R1 R1 R1
OH O OH
OH
R1 ClO4−
44−73% +
O
R2
23
R1 (in substrate) = 3-Me, 4-Me, 4-iPr, 3-OH
OH OH

ClO4−
+
HO O
24
With benzene-1,3,5-triol and 3-methoxyphenol, however, the primary acetylation prod-

uct reacts faster with acetic anhydride than with itself and gives rise to 4-hydroxy-2-meth-
yl-1-benzopyrylium salts (e.g., 24).[102] Condensation of acetophenones or even benzophe-
nones with cyclic Æ-methylene ketones is also possible, giving 1-benzopyrylium salts 25
(Scheme 30).[46,75] Alternatively, phosphoryl chloride can be used as condensing agent.
Scheme 30 Reaction of 2-Hydroxyacetophenones or Benzophenones with Cyclic

Æ-Methylene Ketones[46,75]
COR1
X HClO4
+
O R1 = Me; R2 = H; X = CH2 70%
R2 OH R1 = Me; R2 = H; X = (CH2)2 65%
R1 = Me; R2 = H; X = CH2O 35%
R1 = Ph; R2 = H; X = (CH2)2 80%
R1 = Ph; R2 = OMe; X = (CH2)2 85%
R1
X
ClO4−
+
R2 O
25
4-Methyl-2-phenyl-1-benzopyrylium Perchlorate (22, R1 = R2 = H); Typical Procedure:[97]

To 2-hydroxyacetophenone (13.6 g, 0.1 mol) and acetophenone (12.0 g, 0.1 mol) in AcOH
(75 mL), 75% HClO4 (14 mL) was added and the mixture was refluxed for 16 h. After cool-
ing, the precipitated salt was collected by filtration; yield: 18.2 g (57%); mp 212–213 8C.
2-(2-Hydroxy-4-methylphenyl)-4,7-dimethyl-1-benzopyrylium Perchlorate
(23, R1 = 7-Me; R2 = 4-Me); Typical Procedure:[101]
To a soln of 3-methylphenol (10.8 g, 0.1 mol) in Ac2O (30.6 g, 0.3 mol), 70% HClO4 (10 mL,
0.1 mol) was added dropwise. After heating for 30–40 min at 120–130 8C, the mixture was

cooled and diluted with 10 times its volume of Et2O. After storing for 2–3 h in a refrigera-
tor, the product was collected by filtration; yield: 10 g (55%); mp 245–247 8C.
2-Methyl-4,5,7-trihydroxy-l-benzopyrylium Perchlorate (24); General Procedure:[102]

A mixture of benzene-1,3,5-triol, Ac2O, and HClO4, in a molar ratio of 1:3:1, was heated for
40–50 min at 120–130 8C and the product was isolated; yield: 50%; mp 300 8C.
10-Methoxy-7-phenyl-5,6-dihydrobenzo[e]naphtho[1,2-b]pyrylium Perchlorate
[25, X = (CH2)2; R1 = Ph; R2 = OMe]; Typical Procedure:[46]
2-Hydroxy-4-methoxybenzophenone (2.3 g, 10 mmol) and 1-tetralone (1.5 g, 10 mmol)
were dissolved in POCl3 (30 mL) and heated for 2 h on a steam bath. After cooling, a mix-
ture of MeOH (50 mL) and 70% HClO4 (10 mL) was added dropwise. The product was sep-
arated and recrystallized (AcOH); yield: 3.7 g (85%); mp 255–265 8C.
14.2.1.1.1.11 Method 11:

Reaction of a 2-Acylphenol (2-Hydroxyacetophenone or
2-Hydroxybenzophenone) with a Compound Contributing

One Carbon Atom to the Pyrylium Ring
The partner providing the single carbon atom can be an orthoformate or an aldehyde.
This method is applicable with a wide range of electron-donating substituents and gives
4-alkoxy-1-benzopyrylium salts 26 with no other substituent on the hetero ring (Scheme
31).[103–107] With ø-substituted 2-hydroxyacetophenones, yields are generally low.[108,109]
Occasionally, the product is hydrolyzed, without isolation, to the chromone.[110]
Scheme 31 Ring Closure of 2-Hydroxyacetophenones with Orthoesters[103–107]
O OR2
HC(OR2)3
HClO4
R1 R1
OH OH
OR2
R1 ClO4−
R1 = H; R2 = Et 65% +
R1 = H; R2 = Pr 82% O
R1 = H; R2 = cyclopentyl 71%
26
R1 (in 26) = 6-Me; R2 = Et 65%
R1 (in 26) = 6-OH; R2 = Et 90%
R1 (in 26) = 7-OH; R2 = Et 65%
When an aromatic aldehyde bearing electron-donating substituents is added to the reac-

tion, e.g. with triethyl orthoformate, it reacts with the intermediate enol ether and 2-aryl-
4-ethoxy-1-benzopyrylium salts 27 are formed in 21–96% yield (Scheme 32).[111–116] This
reaction involves the abstraction of hydride ion by an unknown mechanism.
Scheme 32 Orthoester Induced Condensation of 2-Hydroxyacetophenones with Aromatic

Aldehydes[111,115,116]
O OEt
Ar1CHO, HC(OEt)3, HClO4

R1 R1 ClO4−
R1 = H; Ar1 = Ph 32% +
OH R1 = H; Ar1 = 4-HOC6H4 85%
O Ar1
R1 = H; Ar1 = 4-MeOC6H4 96% 27
R1 (in 27) = 6-OMe; Ar1 = 1-benzofuran-2-yl 74%
R1 (in 27) = 7-OH; Ar1 = 4-HOC6H4 44%
R1 (in 27) = 7-OMe; Ar1 = Ph 28%
R1 (in 27) = 7-OMe; Ar1 = 4-HOC6H4 78%
4-Ethoxy-7-hydroxy-l-benzopyrylium Perchlorate (26, R1 = 7-OH; R2 = Et);

To a soln of 2,4-dihydroxyacetophenone (1.52 g, 10 mmol) in freshly distilled HC(OEt)3
(10 mL), 70% HClO4 (1 mL) was added. After 15 min, Et2O was added, the product was col-
lected by filtration and recrystallized (AcOH); yield: 1.88 g (65%); mp 163 8C.

2-(1-Benzofuran-2-yl)-4-ethoxy-6-methoxy-l-benzopyrylium Perchlorate (27, R1 = 6-OMe;
Ar1 = 1-benzofuran-2-yl); Typical Procedure:[115]
To a soln of 2-hydroxy-5-methoxyacetophenone (1.0 g, 60 mmol) and 2-formyl-1-benzofu-
ran (2.6 g, 18 mmol) in HC(OEt)3 (8.4 mL), 70% HClO4 (0.6 mL) was added at 20 8C. After 3 h,
crystals of the product were collected by filtration and recrystallized (AcOH); yield: 1.9 g
(74%); mp 219 8C.
14.2.1.1.2 By Formation of One Heteroatom-Carbon Bond
14.2.1.1.2.1 Method 1:
Ring Closure of 3-(2-Hydroxyaryl)prop-2-en-1-ones
Since 3-(2-hydroxyaryl)prop-2-en-1-ones are readily available by condensation of 2-hy-

droxybenzaldehydes and Æ-methylene ketones, they are attractive starting materials for
the preparation of 2-substituted 1-benzopyrylium salts 28. Cyclization is performed using
perchloric acid or hydrogen chloride gas in diethyl ether (Scheme 33),[117,118] or with phos-
phoryl chloride.[111] The method is also viable for naphtho analogues.[31,60,119]
Scheme 33 Acid-Catalyzed Ring Closure of 3-(2-Hydroxyaryl)prop-2-en-1-ones[117,118]
COR1
HX
X−
R1 = Me 70% +
OH R1 = t-Bu 89%
O R1
28
When 4-(2-hydroxyphenyl)but-3-en-2-one is cyclized with hydrogen chloride gas in the

presence of an aromatic aldehyde, the primary product, having a reactive 2-methyl group,
condenses with the aldehyde, giving a 2-(2-arylvinyl)-1-benzopyrylium salt.[44,120]
1-Aryl-3-(2-hydroxyaryl)prop-2-en-1-ones (2-hydroxychalcones) are readily cyclized to
2-aryl-1-benzopyrylium salts 29 (Scheme 34).[36,121–129] Electronegative substituents on ei-
ther of the aryl rings do not inhibit cyclization.[121] A five-membered heteroaryl ring may
replace either of the two aryl groups.[130–132]

Scheme 34 Acid-Catalyzed Ring Closure of 2-Hydroxychalcones[121,122,127–129]
HClO4
R1 R2 R1 ClO4−
+
OH O
R2
29
Ring closure can also be induced by irradiation,[133,134] but from a preparative point of
view, the method is impractical.
1-Phenyl-3-(2-hydroxyphenyl)propane-1,2-diones, or their enol ethers, can be cy-
clized to 3-hydroxy-2-phenyl-1-benzopyrylium salts 30 and 3-alkoxy-2-phenyl-1-benzopyr-
ylium salts, respectively (Scheme 35).[135,136]
Scheme 35 Acid-Catalyzed Ring Closure of 1-Phenyl-3-(2-hydroxyphenyl)-

propane-1,2-dione (Enol Form)[135]

O
OH
Ph H2SO4
HSO4−
OH 62% +
OH O Ph
30
2-Methyl-l-benzopyrylium Perchlorate (28, R1 = Me); Typical Procedure:[55]

A soln of 4-(2-hydroxyphenyl)but-3-en-2-one (2.0 g, 12 mmol) and 70% HClO4 (3 mL) in Et2O
(40 mL) was saturated for 24 h at 0 8C with HCl(g). The perchlorate separated as orange
crystals; yield: 2.1 g (70%); mp 153–158 8C.
2-Phenyl-1-benzopyrylium Perchlorate (29, R1 = R2 = H); Typical Procedure:[122]

A soln of 3-(2-hydroxyphenyl)-1-phenylprop-2-en-1-one (10.0 g, 45 mmol) in a mixture of
80% HCO2H (100 mL), concd HCl (50 mL), and 70% HClO4 (30 mL) was heated to 65 8C. On
cooling, the product precipitated as yellow leaflets. After adding H2O (300 mL), the crys-
tals were collected by filtration and recrystallized (HCO2H, 90 mL) with the addition of
charcoal; yield: 12.4 g (90%); mp 174–175 8C.
3-Hydroxy-2-phenyl-1-benzopyrylium Hydrogensulfate (30); Typical Procedure:[135]

To a soln of 2-hydroxy-3-(2-hydroxyphenyl)-1-phenylprop-2-en-1-one (2.0 g, 7.3 mmol) in
AcOH (12 mL), concd H2SO4 (0.76 g) was added. After stirring for 15 h, the precipitate was
collected by filtration and washed with a little AcOH and Et2O; yield: 1.4 g (62%); mp
216 8C.
14.2.1.1.2.2 Method 2:
Ring Closure of 3-Aryl-1-(2-hydroxyaryl)prop-2-en-1-ones
(2¢-Hydroxychalcones) to Flavylium Salts
2¢-Hydroxychalcones are readily available by condensation of 2-hydroxyacetophenones

and aryl aldehydes. Ring closure in the presence of triethyl orthoformate proceeds via a
2-aryl-2,3-dihydro-4H-benzopyran-4-one. It is accompanied by dehydrogenation and leads
to 2-aryl-4-ethoxy-1-benzopyrylium salts 31 in 25–55% yield (Scheme 36),[137,138] while
borohydride reduction followed by dehydration, acid treatment, and reoxidation with
benzo-1,4-quinone gives 2-aryl-1-benzopyrylium salts unsubstituted at C4.[48,139]
Scheme 36 Acid-Catalyzed Cyclization of 3-Aryl-1-(2-hydroxyaryl)prop-2-en-1-ones

Followed by Oxidative Aromatization with an Orthoester[113,138]
O O
HX
R1 R2 R1
OH O
R2
OEt
HC(OEt)3, HClO4
R1 ClO4−
R1 = R2 = H 25% +
R1 = H; R2 = 4-OH 45%
O
R2
R1 = H; R2 = 4-OMe 55%
1 2
R (in 31) = 7-OMe; R = H 28%
31
R1 (in 31) = 7-OMe; R2 = 3,4-(OMe)2 50%
R1 (in 31) = 6-Br-7-OH; R2 = 4-OH 42%

4-Ethoxy-2-phenyl-1-benzopyrylium Perchlorate (31, R1 = R2 = H); Typical Procedure:[138]
To freshly distilled HC(OEt)3 (2 mL), 1-(2-hydroxyphenyl)-3-phenylprop-2-en-1-one (0.448 g,
2 mmol) and 70% HClO4 (0.4 mL) were added. After heating for 30 min on a steam bath, the
solution was cooled, more HC(OEt)3 (2–3 mL) was added, and heating was resumed at 70–
80 8C. The product was collected by filtration and recrystallized (AcOH); yield: 0.175 g
(25%); mp 183–184 8C.
14.2.1.1.2.3 Method 3:
Ring Closure of 1-(2-Hydroxyaryl)-3-phenylpropane-
1,3-diones (2¢-Hydroxydibenzoylmethanes)
Dibenzoylmethanes are at the same oxidation level as 1-benzopyrylium salts and can be
converted into the 4-ethoxy derivatives of the latter (e.g., 32) by treatment with triethyl
orthoformate and perchloric acid (Scheme 37).[140]
Scheme 37 Ring Closure of 1-(2-Hydroxyaryl)-3-phenylpropane-1,3-diones[140]
O O OEt
HC(OEt)3
Ph HClO4
ClO4−
80−90% +
R1 OH R1 O Ph
32
R1 = H, OBz
4-Ethoxy-2-phenyl-1-benzopyrylium Perchlorate (32, R1 = H); General Procedure:[140]

1-(2-Hydroxyaryl)-3-phenylpropane-1,3-dione was refluxed with HC(OEt)3 and 70% HClO4
in a molar ratio of 1:10:1 for 2–3 min to give the perchlorate; yield: 80–90%; mp 184 8C
(AcOH).
14.2.1.1.2.4 Method 4:
Cyclization of 1-Aryl-3-hydroxy-3-(2-hydroxyaryl)propan-1-ones
Treatment of 3-hydroxy-3-(2-hydroxyaryl)propan-1-ones, available by condensation of 2-

hydroxybenzaldehyde and ø-hydroxy- or ø-alkoxyacetophenones, with hydrochloric or
perchloric acid causes cyclization by double dehydration to give 2-aryl-1-benzopyrylium

salts 33 (Scheme 38).[82,135] The same 3-hydroxyketone is probably involved when dibenzo-
ylmethanes are reduced with borohydride, cyclized, and reoxidized to 2-aryl-1-benzopyr-
ylium salts.[141]
Scheme 38 Acid-Induced Cyclization of 3-Hydroxy-3-(2-hydroxyphenyl)propan-1-

ones[82,135]
OH O
R1
HX
X−
R1 R1 = OH; R2 = H; X = ClO4 70% +
2 O
OH R R1 = OMe; R2 = H; X = Cl 96%
R1 = R2 = OMe; X = ClO4 77%
R2
33
3-Methoxy-2-(4-methoxyphenyl)-1-benzopyrylium Perchlorate (33, R1 = R2 = OMe; X = ClO4);

HCl(g) was passed into a soln of 3-hydroxy-3-(2-hydroxyphenyl)-2-methoxy-1-(4-methoxy-

phenyl)propan-1-one (1.5 g, 5 mmol) in AcOH (10 mL), at 0 8C for 1 h; this was followed by
the addition of 70% HClO4 (5 mL) and AcOH (2 mL). After 10 min, the precipitate was col-
lected by filtration, washed with a little AcOH, and recrystallized (AcOH); yield: 1.4 g
(77%); mp 242–243 8C.
14.2.1.1.2.5 Method 5:
Oxidative Cyclization of 1-Aryl-3-(2-hydroxyaryl)propan-1-ones
In the presence of a strong acid and an oxidant, 3-(2-hydroxyaryl)propan-1-ones afford 2-

substituted (34) or 2,4-disubstituted 1-benzopyrylium salts.[142–146] Phosphoryl chloride
and tetrachlorobenzo-1,4-quinone[143] or triphenylcarbenium perchlorate may be used as
reagents (Scheme 39).[147] Oxidation may also be spontaneous[146] and yields are moderate
to low.
Scheme 39 Oxidative Cyclization of 1-Aryl-3-(2-hydroxyaryl)propan-1-ones[147]
OMe O OMe
Tr+ ClO4−
ClO4−
40% +
MeO OH OMe MeO O
OMe
34
5,7-Dimethoxy-2-(4-methoxyphenyl)-1-benzopyrylium Perchlorate (34);

To a soln of 3-(2-hydroxy-4,6-dimethoxyphenyl)-1-(4-methoxyphenyl)propan-1-one (25 mg,
0.8 mmol) in AcOH (2 mL), Tr+ClO4– (0.025 g) was added, and the mixture was heated for
15 min. After cooling, the product separated as red needles; yield: 25 mg (40%); mp 260–
261 8C.
14.2.1.1.2.6 Method 6:
Ring Closure of a 1,3-Diarylprop-2-en-1-one
This method is included as it is the only case where the oxygen atom is not derived from a
phenol. It usually gives very low yields,[62,148] except when the 1,3-diarylprop-2-en-1-one
moiety is part of a ring and there are electron-donating substituents on at least one of the
aryl rings (e.g., 35, Scheme 40).[149]
Scheme 40 Intramolecular Ring Closure of an Arylideneindanone[149]
MeO MeO
HCl, FeCl3
FeCl4−
OMe ~100% +
MeO O MeO O OMe
35
2,7,8-Trimethoxy-11H-indeno[1,2-b]-1-benzopyrylium Tetrachloroferrate (35);

To a soln of 2-(3,4-dimethoxybenzylidene)-5-methoxyindan-1-one (1.0 g, 3 mmol) in Ac2O
(25 mL), anhyd FeCl3 (5.0 g) was added; after the reaction had subsided, further FeCl3
(3.0 g) was added. After 10 min, the mixture was poured into H2O (250 mL). The product
precipitated on addition of a concentrated soln of FeCl3 in HCl and was recrystallized
(AcOH); yield: 1.5 g (ca. 100%); mp 213 8C.

14.2.1.2 Synthesis by Ring Transformation
14.2.1.2.1 Method 1:
Synthesis from 3-Acyl-2H-1-benzopyran-2-ones
3-Acyl-2H-1-benzopyran-2-ones are prepared by reacting 2-hydroxybenzaldehydes with al-

kyl 3-oxocarboxylates,[150] and can be transformed by strong mineral acids, with loss of
carbon dioxide, to give 2-substituted 1-benzopyrylium salts 36 (Scheme 41).[151,152] Similar-
ly, heating of 4-(2-acetoxyphenyl)-6-methyl-2-phenyl-[1,3]-oxazin-1-ylium perchlorate
with formic acid in water gave 4-benzoylamino-2-methyl-1-benzopyrylium perchlorate
in 61% yield (Scheme 41).[152]
Scheme 41 Acid-Induced Decarboxylation and Aromatization of 3-Acyl-2H-1-benzopyran-

2-ones[151,152]
COR2
HClO4
R1 R1 ClO4−
− CO2 +
O O R1 R2
= H; = Pr 49% O R2
1 2
R = H; R = Ph 88%
36
R1 = H; R2 = 4-MeOC6H4 95%
R1 = 5,6-(CH CH)2; R2 = 4-MeOC6H4 79%
NHCOPh
+O HCO2H, H2O
ClO4− ClO4−
61% +
N Ph O
OAc
2-Phenyl-1-benzopyrylium Perchlorate (36, R1 = H; R2 = Ph); Typical Procedure:[151]

3-Benzoyl-2H-1-benzopyran-2-one (2.0 g, 8.0 mmol) was refluxed in 33% HClO4 (90 mL) for
16 h. On cooling, the orange perchlorate crystallized; yield: 2.1 g (88%). It was washed with
Et2O and recrystallized (10% HClO4); mp 184 8C.

14.2.1.3 Aromatization
14.2.1.3.1 Method 1:
Reduction of 2H-1-Benzopyran-2-ones and
4H-1-Benzopyran-4-ones with a Metal
Reduction of 3-hydroxy-2-phenyl-4H-1-benzopyran-4-ones with magnesium in hydrochlo-

ric acid to give colored 2-phenyl-1-benzopyrylium salts 37 was originally developed as a
color test for 3-hydroxy-2-phenyl-4H-1-benzopyran-4-ones (flavon-3-ols)[153] and is of limit-
ed preparative interest (Scheme 42).
Scheme 42 Reductive Aromatization of a 7-Ammonio-3-hydroxy-2-phenyl-

4H-1-benzopyran-4-one with Magnesium and Hydrochloric Acid[65]
O
OH
Mg, aq HCl
2Cl−
+ 29% + +

H3N O Ph H 3N O Ph
37
7-Ammonio-2-phenyl-1-benzopyrylium Dichloride (37); Typical Procedure:[65]

To a soln of 7-ammonio-3-hydroxy-2-phenyl-4H-1-benzopyran-4-one (0.30 g, 12 mmol) in
EtOH (15 mL), Mg turnings (0.7 g, 30 mmol) were added, followed by, with swirling, concd
HCl (10 mL). After a few hours, the mixture was filtered and adjusted to pH 6 with NaOAc.
The hydrolyzed soln was extracted with Et2O and concentrated. Addition of 10% HCl
(2 mL) precipitated the product, which was dried in vacuo; yield: 0.10 g (29%); mp 360 8C.
14.2.1.3.2 Method 2:
Addition–Dehydroxylation of 2H-1-Benzopyran-2-ones and
4H-1-Benzopyran-4-ones Using Organometallic Compounds
Addition of organometallic compounds to 2H-1-benzopyran-2-ones or 4H-1-benzopyran-4-

ones followed by acid treatment of the intermediate alcohols (generally not isolated) is a
versatile method for the preparation of 2- and 4-substituted 1-benzopyrylium salts, re-
spectively.
14.2.1.3.2.1 Variation 1:
Aromatization of 2H-1-Benzopyran-2-ones by Addition of
a Grignard Reagent and Dehydroxylation
Addition of a Grignard reagent to a 2H-1-benzopyran-2-one and dehydration to give 1-ben-

zopyrylium salts, e.g. 38, was first reported in 1907.[154] Although the method is often
used,[155–157] yields may be very low as a result of double addition (Scheme 43).[157]
Scheme 43 Aromatization of 2H-1-Benzopyran-2-ones by Addition of a Grignard Reagent

and Dehydration[156,157]
R2 R2
R3 4
1. R MgHal R3
2. HX
R 1 R1 X−
R1 = R3 = H; R2 = Me; R4 = t-Bu 60% +
O O O R4
R1 = H; R2 = Me; R3 = Br; R4 = Ph 40%
R1 = 6-OMe; R2 = R3 = Me; R4 = Ph 80% 38
R1 = 7-OMe; R2 = Me; R3 = H; R4 = Ph 60%
R1 = H, 5,6-(CH CH)2, 6-OMe, 7-OMe; R2 = Me; R3 = H, Me, Br; R4 = t-Bu, Ph
2-tert-Butyl-4-methyl-1-benzopyrylium Perchlorate (38, R1 = R3 = H; R2 = Me; R4 = t-Bu;

X = ClO4); Typical Procedure:[157]
To a soln of 4-methyl-2H-1-benzopyran-2-one (1.0 g, 6 mmol) in dry benzene (15 mL), a soln
of a Grignard reagent prepared from t-BuCl (1.9 g, 20 mmol) and Mg (0.55 g, 22 mmol) in
Et2O (6 mL) was added. After boiling for 30 min and evaporation of most of the solvent,
20% HClO4 (50 mL) was added. The precipitated salt was collected by filtration, then

washed with H2O and Et2O; yield: 1.1 g (60%); mp 220–222 8C (AcOH).
14.2.1.3.2.2 Variation 2:
Aromatization of 4H-1-Benzopyran-4-ones by Addition of
a Grignard Reagent and Dehydroxylation
Addition of Grignard reagents to 4H-1-benzopyran-4-ones and 2-aryl-4H-1-benzopyran-4-

ones gives, after treatment with strong mineral acids, 4-substituted 1-benzopyrylium salts
39 (Scheme 44).[53,122,157–164]
Scheme 44 Addition of Grignard Reagents to 4H-1-Benzopyran-4-ones[122,157,163–165]
O R3
1. R3MgI
2. HClO4
R1 R1 ClO4−
R1 = R2 = H; R3 = Ph 14% +
O R2 O R2
R1 = R2 = Me; R3 = Ph 25%
R1 = H; R2 = t-Bu; R3 = Me 60% 39
R1 = H; R2 = Ph; R3 = Me 60%
Aryllithium compounds sometimes give higher yields, as in the reaction of 2-phenyl-4H-1-

benzopyran-4-one with 4-(dimethylamino)phenyllithium.[166] 2-Phenyl-4H-1-benzopyran-
4-ones are also amenable to the Reformatsky reaction, giving 4-(methoxycarbonylmeth-
yl)- or 4-(carboxymethyl)-substituted derivatives.[167]
2-tert-Butyl-4-methyl-1-benzopyrylium Perchlorate (39, R1 = H; R2 = t-Bu; R3 = Me);

A Grignard soln prepared from Mg (0.96 g, 40 mmol) and MeI (5.8 g, 40 mmol) in Et2O
(50 mL) was added to a soln of 2-tert-butyl-4H-1-benzopyran-4-one (4.0 g, 20 mmol) in Et2O
(100 mL). After boiling for 40 min, most of the Et2O was removed by distillation in vacuo;
then 20% HClO4 (100 mL) was added to the residue with cooling. The precipitate was col-
lected by filtration and washed with H2O and Et2O; yield: 3.6 g (60%); mp 220–222 8C.

14.2.1.3.2.3 Variation 3:
With Isolation of the Intermediate Tertiary Alcohol
Tertiary alcohols, which are intermediates in the addition of organometallic reagents to

2H-1-benzopyran-2-ones or 4H-1-benzopyran-4-ones, can either be isolated or prepared by
independent methods. On acid treatment, they are smoothly converted into 1-benzopyr-
ylium salts 40 (Scheme 45).[82,146,161,168]
Scheme 45 Aromatization of a 4-Hydroxy-4H-1-benzopyran with Perchlorate[161]
4-Tol OH 4-Tol
Ph Ph
HClO4, Ac2O
ClO4−
74% +
O Ph O Ph
40
6-Methyl-2,3-diphenyl-4-(4-tolyl)-1-benzopyrylium Perchlorate (40); Typical Procedure:[161]

To a soln of 4-hydroxy-6-methyl-2,3-diphenyl-4-(4-tolyl)-4H-1-benzopyran (16.2 g,
40 mmol) in dry Et2O, a chilled mixture of 72% HClO4 (4 g, 40 mmol) and Ac2O (6 mL) was
added dropwise. The precipitated pale yellow product was collected by filtration, washed
with dry Et2O, and recrystallized (AcOH, 50 mL); yield: 14.3 g (74%); mp 235.5–238.5 8C.
14.2.1.3.3 Method 3:
Transformations by Reaction with Activated Arenes, Arylethenes,
or Hetarenes
In the presence of phosphoryl chloride and zinc chloride, anisole and other arenes substi-
tuted with electron-donating groups condense with 2H-1-benzopyran-2-ones and 4-meth-
yl-2H-1-benzopyran-2-ones[155,169] to give 2-aryl-1-benzopyrylium salts 41 in moderate to
good yields (Scheme 46).
Reaction of 2-aryl-4H-1-benzopyran-4-ones with activated arenes is also possible in
the presence of phosphoryl chloride.[170] 2-Phenyl-4H-1-benzopyran-4-one reacts with 1,1-
diarylethenes in a mixture of phosphoryl chloride and perchloric acid to give 4-(2,2-diaryl-
vinyl)-2-phenyl-1-benzopyrylium perchlorate.[170]
Scheme 46 Lewis Acid Induced Addition of Activated Arenes to 2H-1-Benzopyran-2-ones

and 4H-1-Benzopyran-4-ones[169,170]
R2 R2
ZnCl2, POCl3
HClO4
R1 + R3 R1 ClO4−
+
O O O
R3
41
R1 = H, 7-OMe; R2 = H, Me; R3 = OMe, 1,3-(OH)2, 1,3-(OMe)2
O NMe2 R2
POCl3, NaClO4
R1 + R1 ClO4−
+
O Ph O
R3
41
R1 (in 41) = R3 = H; R2 = 4-Me2NC6H4
2-(2-Methoxyphenyl)-1-benzopyrylium Perchlorate (41, R1 = R2 = H; R3 = 2-OMe);

2H-1-Benzopyran-2-one (1.46 g, 10 mmol) was heated with fused ZnCl2 (1.5 g, 1.0 mmol)
and POCl3 (5 mL) for 35 min on a steam bath. After adding anisole (1.08 g, 10 mmol), heat-
ing was continued for another 2 h, whereupon orange crystals separated. After the addi-
tion of AcOH (15 mL), the product was collected by filtration, and washed with AcOH, and
then with Et2O. The crude product (1.9 g) was dissolved in 10% aq HClO4 (50 mL) and the
soln was filtered. On cooling, the product crystallized as orange-yellow needles; yield: not
reported; mp 196–197 8C.
4-(4-Dimethylaminophenyl)-2-phenyl-1-benzopyrylium Perchlorate (41, R1 = R3 = H;

R2 = 4-Me2NC6H4); Typical Procedure:[170]
2-Phenyl-4H-1-benzopyran-4-one (2.2 g, 10 mmol) and N,N-dimethylaniline (1.2 g,
10 mmol) were heated to boiling for 10 min with POCl3 (50 mL). After cooling, the mixture
was poured into AcOH (200 mL), and then 1% aq NaClO4 soln (2 L) was added in portions,
with stirring. The precipitate was recrystallized (AcOH); yield: not reported; mp 254 8C.

14.2.1.3.4 Method 4:
Transformations of 2H-1-Benzopyran-2-ones and 4H-1-Benzopyran-4-ones
by Reaction with C-H Acidic Pyrylium Salts
The hydrogen atoms of the 2- and 4-methyl groups in pyrylium salts are acidic and can,
therefore, react in strongly acidic media with 2H-1-benzopyran-2-ones[44,122,171] and 4H-1-
benzopyran-4-ones,[122,172] whereby the substrate becomes a 1-benzopyrylium salt and
the pyrylium salt ends up as the 2H- or 4H-pyrylidenemethylene moiety of 42 (Scheme
47). This reaction has practical importance in the preparation of cyanine dyes.
Scheme 47 Condensation of 2-Phenyl-4H-1-benzopyran-4-one with the Activated

4-Methyl Group of a 1-Pyrylium Salt[172]
O
R3
Ac2O
+ ClO4−
+ R1 = R2 = Me; R3 = H 63%
O Ph R1 O R2 R1 = R2 = Ph; R3 = H 54%
R2
R3
O
R1 ClO4−
+
O Ph
42
R1 = R2 = Me, Ph; R2,R3 = (CH CH)2; R3 = H
The method can be extended to the vinylogues of 2H-1-benzopyran-2-one, i.e. to 2-(2H-1-

benzopyran-2-ylidene)propanals, and leads to cyanine dyes 43 (Scheme 48).[173]

Scheme 48 Condensation of a Vinylogous 2H-1-Benzopyran-2-one with a Fischer Base-

Type Compound[173]
X HClO4
+
CHO 1
R = H; X = CMe2 65%
O N
R1 R1 = H; X = CH2CMe2S 60%
R1 = Me; X = CH2CMe2S 70%
X
ClO4−
+
O N
R1
43
4-[(2,6-Diphenyl-4H-pyran-4-ylidene)methyl]-2-phenyl-1-benzopyrylium Perchlorate
(42, R1 = R2 = Ph; R3 = H); Typical Procedure:[172]
A mixture of 2-phenyl-4H-1-benzopyran-4-one (3.0 g, 14.5 mmol) and 4-methyl-2,6-diphen-
ylpyrylium perchlorate (3.5 g, 10 mmol) was refluxed in Ac2O (50 mL). The product sep-

arated on cooling and was recrystallized (MeCN); yield: 4.0 g (54%); mp 294–295 8C.
2-[(1E,3E)-3-(3,3-Dimethyl-1,3-dihydro-2H-indol-2-ylidene)-1-methylprop-1-enyl]-1-benzo-
pyrylium Perchlorate (43, X = CMe2; R1 = H); General Procedure:[173]
Equimolar amounts of the aldehyde and 3,3-dimethyl-2-methylene indoline perchlorate
were dissolved in a small amount of Ac2O and heated for 15–30 min at 80–90 8C. On cool-
ing, the product precipitated. It was washed with a little Ac2O and Et2O, and recrystallized
(Ac2O or EtOH); yield: 65%; mp 234 8C.
14.2.1.3.5 Method 5:
Transformation of 4H-1-Benzopyran-4-ones by
Reaction with N,N-Dimethylacetamide
N,N-Dimethylacetamide condenses with 2-phenyl-4H-1-benzopyran-4-ones and their

naphtho analogues to give 4-[2-chloro-2-(dimethylamino)vinyl] derivatives 44 in 57–88%
yield (Scheme 49).[174]
Scheme 49 Reaction of 2-Phenyl-4H-1-benzopyran-4-one with

N,N-Dimethylacetamide[174]
Cl
O NMe2
DMA
POCl3, HClO4
ClO4−
76% +
O Ph O Ph
44
4-[2-Chloro-2-(dimethylamino)vinyl]-2-phenyl-1-benzopyrylium Perchlorate (44);

A mixture of DMA (2.18 g, 33 mmol) and 2-phenyl-4H-1-benzopyran-4-one (4.44 g,
20 mmol) in POCl3 (10 mL) was heated for 2 h on a steam bath. Excess POCl3 was removed
by distillation in vacuo and the residue was dissolved in MeOH. HClO4 (3 mL) was added
and the product, which separated on cooling, was collected by filtration and recrystal-
lized (MeCN); yield: 6.2 g (76%); mp 198–199 8C.
14.2.1.3.6 Method 6:
By Double Elimination from 2,4-Diethoxy-3,4-dihydro-2H-1-benzopyrans
2,4-Diethoxy-3,4-dihydro-2H-1-benzopyrans, accessible by tin(IV) chloride catalyzed reac-

tion of phenols with 1,1,3,3-tetraethoxypropane, on treatment with perchloric acid give
1-benzopyrylium salts 45 unsubstituted on the hetero ring (Scheme 50).[11]
Scheme 50 Acid-Induced Aromatization of 2,4-Diethoxy-3,4-dihydro-2H-1-benzopyrans[11]
OEt
HClO4
R1 R1 ClO4−
R1 = H 98% +
O OEt R1 = 8-Me 95%
O
R1 = 6-Cl 93% 45
R1 = 6-OMe 99%
R1 = 5,6-(CH CH2)2 ~100%
1-Benzopyrylium Perchlorate (45, R1 = H); Typical Procedure:[11]

To a mixture of 2,4-diethoxy-3,4-dihydro-2H-1-benzopyran (2.22 g, 10 mmol) and AcOH
(100 mL), 70% HClO4 (10 mL) was added at 0 8C and under N2. After 5 h, Et2O (200 mL) was
added and the yellow crystals were collected by filtration; yield: 2.25 g (98%); mp 195–
198 8C.
14.2.1.3.7 Method 7:
Aromatization by Dehydrogenation and Redox Reactions
Both 2H- and 4H-1-benzopyrans, as well as 3,4-dihydro-2H-1-benzopyrans oxygenated at

C4, can be dehydrogenated by several methods to give 1-benzopyrylium salts.
14.2.1.3.7.1 Variation 1:
By Acid-Induced Disproportionation
When treated with perchloric acid, trifluoroacetic acid,[175,176] or hydrochloric acid[168] at

room temperature, 2-aryl-2H-1-benzopyrans disproportionate to give 1-benzopyrylium
salts 46 and 3,4-dihydro-4H-1-benzopyrans in moderate to good yield (Scheme 51).
Scheme 51 Acid-Induced Disproportionation of 2-Aryl-2H-benzopyrans[175,176]
R2 R2 R2
HClO4
R1 R1 + R1 ClO4−
+
O Ph O Ph O Ph
46 R1 = R2 = Ph 90%
R1 = 6-OH-7-Me; R2 = H 90%
R1 = 6,7-OCH2O; R2 = H 41%
R1 = 6-OH-7-OMe; R2 = H 40%
This method can be applied to 4H-1-benzopyrans, resulting in disproportionation to give

e.g. 47 and 48 (Scheme 52).[177–180]

Scheme 52 Disproportionation of a 4H-1-Benzopyran[177]
HClO4
2
O
ClO4− +
+
O O
47 94% 48
Treatment of 4-hydroxy-2,3-dihydro-4H-1-benzopyrans, i.e. precursors of 2H-1-benzopy-

rans, with perchloric acid also results in disproportionation, but yields are generally
low.[181,182]
6-Hydroxy-7-methoxy-2-phenyl-1-benzopyrylium Perchlorate (46, R1 = 6-OH, 7-OMe;

R2 = H); Typical Procedure:[175]
6-Hydroxy-7-methoxy-2-phenyl-2H-1-benzopyran (2.0 g, 80 mmol) was heated on a steam
bath with 35% HClO4 (20 mL) for 30 min. Addition of excess Et2O precipitated the product,
which was collected by filtration; yield: 1.1 g (40%); mp 255–256 8C.
11H-Benzo[b]indeno[2,1-e]pyrylium Perchlorate (47); Typical Procedure:[177]

To a mixture of 10,11-dihydroindeno[1,2-b](4H)-benzopyran (1.0 g, 45 mmol) and AcOH
(5 mL), a 24% soln of HClO4 in AcOH (5 mL) was added dropwise at 20 8C. The soln turned
brown and the salt separated; addition of Et2O completed the precipitation. The product
was collected by filtration; yield: 0.625 g (94%). From the Et2O soln, 48 (4b,10,10a,11-tetra-
hydrobenz[b]indeno[2,1-e]pyran) (0.40 g) could be isolated.
14.2.1.3.7.2 Variation 2:
Dehydrogenation with Oxidizing Agents
Dehydrogenation of 2H- and 4H-1-benzopyrans can be performed with a variety of oxi-

dants and dehydrogenating agents such as benzoquinones[139,183,184] or triphenylcarben-
ium perchlorate.[181] For example, triphenylcarbenium perchlorate oxidizes 2-(2-phenyl-
ethynyl)-2H-1-benzopyrans and 4-(2-ethynylphenyl)-4H-1-benzopyrans (e.g., 49)[185] to the
corresponding 2-phenyl-1-benzopyrylium salts 50 (Scheme 53).
Scheme 53 Aromatization of 4H-1-Benzopyrans by Oxidation with Triphenylcarbenium

Perchlorate or Benzo-1,4-quinone[139,185]
Ph
R2 R2
Ph Li Tr+ ClO4−
ClO4−
+ R = Ph; R2 = H 63%
1
O R1 O R1 R1 = Ph; R2 = Et 61%
49 R1 = Ph; R2 = Me 64%
R1 = t-Bu; R2 = H 57%
Ph
R2
ClO4−
+
R1

O
50
OMe
O O
HClO4
OMe
MeO O
OMe
OMe
ClO4−
+ OMe
MeO O
OMe
51
Treatment of 2-aryl-2H-benzopyrans with benzo-1,4-quinone in the presence of perchloric

acid gives 2-aryl-1-benzopyrylium salts 51 in low yield.[139] Yields are satisfactory when 4H-
1-benzopyrans are oxidized with iron(III) chloride,[165] triphenylcarbenium perchlorate,[84]
or copper(II) perchlorate.[186]
4H-1-Benzopyran-4-carboxylic acids are oxidized by tetrachlorobenzo-1,4-quinone to
the corresponding 2-aryl-1-benzopyrylium salts, while with lead(IV) acetate, dehydro-
genation is accompanied by decarboxylation to give 52 (Scheme 54).[39]

Scheme 54 Oxidative Aromatization of 4H-1-Benzopyran-4-carboxylic Acids[39]
OMe CO2H
R1
MeO O
OMe
OMe
Pb(OAc)4
MeO
+
O
R1 X−
− CO2
R1 = H 79%
R1 = OMe 97% OMe
52
HX
Cl Cl OMe CO2H

O O
R1
X−
Cl Cl
+
MeO O
1
R = OMe 72%
OMe
On dehydrogenation with benzo-1,4-quinone, 4H-1-benzopyrans give better yields of the

1-benzopyrylium salts 53 than the analogous reaction of 2H-1-benzopyrans (Scheme
55).[184]
Scheme 55 Oxidative Aromatization of a 4H-1-Benzopyran with Benzo-1,4-quinone[184]
OMe O O
OMe
HClO4
OMe 84%
MeO O
OMe
OMe
OMe
ClO4−
+ OMe
MeO O
OMe
53
2,3-Dihydro-4H-1-benzopyran-4-ones (chromanones) are much more readily accessible[187]

than 2H- or 4H-1-benzopyrans and can be dehydrogenated with triphenylcarbenium per-
chlorate to 4-hydroxy-1-benzopyrylium salts 54 (Scheme 56).[188] The latter are in fact the
protonated form of 4H-1-benzopyran-4-ones 55, into which they are readily converted
when treated with a base.
Scheme 56 Oxidation of 2,3-Dihydro-4H-1-benzopyran-4-one (Chromanone) to a

1-Benzopyrylium Salt with Triphenylcarbenium Perchlorate[188]
O OH O
+ − NaHCO3, H2O
Tr ClO4
ClO4−
+ ~100%
O O O
54 55
Oxidation of 4-hydroxy-2,3-dihydro-4H-1-benzopyrans with tetrachlorobenzo-1,4-quinone

is more efficient and provides access to 1-benzopyrylium salts derived from natural flavo-
noids such as apigenin and luteolin in reasonable yields (39 and 50%, respectively).[182]
Oxygen in the presence of hydrogen chloride performs the same task, but in very low
yield.[189]
2-Aryl-3-hydroxy-2,3-dihydro-4H-1-benzopyran-4-ones can be dehydrogenated by to-
syl hydrazide and hydrochloric acid to give 4-amino-2-aryl-3-hydroxy-1-benzopyrylium
chlorides 56 in moderate to good yields (Scheme 57).[190]

Scheme 57 Dehydrogenation Coupled with Amination of a 2-Aryl-3-hydroxy-2,3-dihydro-
4H-1-benzopyran-4-one[190]
O
OH TsNHNH2
aq HCl
R1
R1 = R2 = H 67%
O
R2 R1 = 5,7-(OMe)2; R2 = 3,4-(OMe)2 92%
NH2
OH
R1 Cl−
+
O
R2
56
4-(Phenylethynyl)-2-phenyl-1-benzopyrylium Perchlorate (50, R1 = Ph; R2 = H);

Typical Procedure:[59,185]
2-Phenyl-4-(phenylethynyl)-4H-1-benzopyran (49, R1 = Ph; R2 = H)

To a suspension of phenylethynyllithium in Et2O, prepared from phenylacetylene (2.0 g,
20 mmol) with BuLi under N2, 2-phenyl-1-benzopyrylium perchlorate (3.1 g, 10 mmol) was
added with cooling. After stirring for 10–15 min, the mixture was quenched with sat. aq
NH4Cl soln. The organic phase was separated, dried, evaporated, and the residue was re-
crystallized (iPrOH) to give the product; yield: 2.6 g (84%); mp 88 8C.
4-(Phenylethynyl)-2-phenyl-1-benzopyrylium Perchlorate (50, R1 = Ph; R2 = H)

A soln of 49 (R1 = Ph; R2 = H) (0.60 g, 2 mmol) and Tr+ClO4– (0.70 g, 2 mmol) in MeNO2 (5 mL)
was heated to boiling. After cooling, the product was collected by filtration, washed with
Et2O, and recrystallized (MeCN); yield: 0.75 g (63%); mp 253 8C.
5,7-Dimethoxy-2-(3,4-dimethoxyphenyl)-1-benzopyrylium Perchlorate (Luteolinidin

Tetramethyl Ether) (51); Typical Procedure:[139]
5,7-Dimethoxy-2-(3,4-dimethoxyphenyl)-2H-1-benzopyran (1.0 g, 3 mmol) and benzo-1,4-
quinone (0.50 g, 46 mmol) were heated in AcOH (4 mL) for 10 min, and then 5% aq HClO4
(4 mL) was added. The red precipitate was collected by filtration and washed with AcOH.

The product was dissolved in EtOH/H2O/aq HCl (2:2:1), and then 33% aq FeCl3 soln was
added dropwise. The precipitated salt was collected by filtration and recrystallized
(AcOH); yield: 0.2 g (16%); mp 205–206 8C.
5,7-Dimethoxy-2-(4-methoxyphenyl)-1-benzopyrylium Chloride (52, R1 = H; X = Cl);

A mixture of 5,7-dimethoxy-2-(4-methoxyphenyl)-4H-1-benzopyran-4-carboxylic acid
(0.50 g, 1.46 mmol) and Pb(OAc)4 (0.75 g, 1.69 mmol) in AcOH containing 2% Ac2O (15 mL)
was heated at 50 8C for 2 h under N2. After evaporation of the volatile components, a soln
of H3PO4 (0.2 mL) in 20% aq MeOH (50 mL) was added, Pb3(PO4)4 was removed by filtration,
and the filtrate was passed through a Dowex 21-K (Cl–) column that had been previously
equilibrated with the same soln. The red-orange band was collected, concentrated in vac-
uo, and the residue was freeze-dried to give an orange solid; yield: 0.385 g (79%).
2-(3,4-Dimethoxyphenyl)-3,5,7-trimethoxy-1-benzopyrylium Perchlorate (53);

2-(3,4-Dimethoxyphenyl)-3,5,7-trimethoxy-4H-1-benzopyran (0.27 g, 0.75 mmol) was

warmed with benzo-1,4-quinone (0.27 g, 3.5 mmol) in 50% AcOH (3.0 mL) and then treated
with 5% aq HClO4 to give the EtOAc-insoluble perchlorate; yield: 0.29 g (84%); mp 255–
256 8C.
4-Hydroxy-1-benzopyrylium Perchlorate (54) and 4H-1-Benzopyran-4-one (55);

To a warm soln of 2,3-dihydro-4H-1-benzopyran-4-one (0.74 g, 5 mmol) in AcOH/Ac2O (8:1,
9 mL), Tr+ClO4– (1.7 g, 5 mmol) was added. The mixture was kept at 100 8C for 30 min, and
then concentrated under reduced pressure at 40 8C. The residue was triturated with Et2O.
The remaining salt [1.05 g; mp 177–178 8C (AcOH)] was hydrolyzed to 4H-1-benzopyran
with aq NaHCO3; overall yield: 0.73 g (ca. 100%).
4-Amino-3-hydroxy-2-phenyl-1-benzopyrylium Chloride (56, R1 = R2 = H);

3-Hydroxy-2-phenyl-2,3-dihydro-4H-1-benzopyran-4-one (1.0 g, 42 mmol) in EtOH (100 mL)
was refluxed with tosyl hydrazide (0.78 g, 42 mmol) and concd HCl (1 mL) for 6 h. After
cooling, hexane (50 mL) was added and the mixture was stored in a refrigerator for 12 h,
whereupon yellow crystals separated; yield: 0.76 g (67%); mp 258–260 8C.
14.2.1.3.8 Method 8:
Aromatization by O-Alkylation or Protonation
14.2.1.3.8.1 Variation 1:
By O-Alkylation
O-Alkylation of 2-aryl-4H-1-benzopyran-4-one with trimethyl orthoformate in the pres-

ence of perchloric acid gives the corresponding 2-aryl-4-methoxy-1-benzopyrylium salts
in moderate yield,[116,191] while O-alkylation of 2-aryl-2,3-dihydro-4H-1-benzopyran-4-ones
with triethyl orthoformate in the presence of perchloric acid gives, by an unknown mech-
anism, 2-aryl-4-ethoxy-1-benzopyrylium salts 57 in moderate yields (Scheme 58).[188,192]
Scheme 58 Aromatization of 2-Aryl-2,3-dihydro-4H-1-benzopyran-4-ones with Triethyl

Orthoformate[192]
HC(OEt)3, HClO4
R1
R1 = R2 = H 40%
O R1 = 6-OMe; R2 = 4-OMe 57%
R2
OEt
R1 ClO4−
+
O
R2
57
By alkylation, 2H-1-benzopyran-2-ones, 4H-1-benzopyran-4-ones,[193] 2-aryl-4H-1-benzopy-

ran-4-ones, and 4-thiono-4H-1-benzopyrans can be converted into the corresponding

2-, 4-alkoxy or 4-alkylsulfanyl derivatives. As reagent, a trialkyloxonium fluoroborate,[194]
tert-butyldimethylsilyl trifluoromethanesulfonate,[193] methyl 2-nitro- or 2,4-dinitroben-
zenesulfonate,[195] for the thiono compounds, iodomethane,[196] or, in special cases, di-
methyl sulfate[197] can be used.
Alkylation of 2H-1-benzopyran-2-ones with a trialkyloxonium tetrafluoroborate gives
2-alkoxy-1-benzopyrylium salts 58 (Scheme 59).[194,198–202]
Scheme 59 Alkylation of 2H-1-Benzopyran-2-ones with a Trialkyloxonium Tetrafluoro-

borate[194,198,199,201,202]
R2 R2
R33O+ BF4−
R1 R1 BF4−
R1 = R2 = H; R3 = Me 73% +
O O O OR3
R1 = R2 = H; R3 = Et 99%
R1 = 7-NMe2; R2 = Me; R3 = Et 90% 58
2H-1-Benzopyran-2-ones and 4H-1-benzopyran-4-ones are transformed with tert-butyldi-

methylsilyl trifluoromethanesulfonate to 2-(tert-butyldimethylsiloxy)-1-benzopyrylium
trifluoromethanesulfonates,[203] and the 4-(tert-butyldimethylsiloxy) salts, respectively,
(Scheme 60).[193,204,205] 4H-1-Benzopyran-4-ones are also alkylated with methyl 2-nitro- or
2,4-dinitrobenzenesulfonate to give 1-benzopyrylium 2-nitro- or 2,4-dinitrobenzenesulfo-
nate salts 59 (Scheme 61).[195]
Scheme 60 Alkylation of 4H-1-Benzopyran-4-ones with

tert-Butyldimethylsilyl Trifluoromethanesulfonate[193,205]
O OTBDMS
R2 R2
TBDMSOTf
OTf−
+
1 1
O R O R
R1 = H, Me; R2 = H, Me, CO2Me

Scheme 61 Alkylation of 4H-1-Benzopyran-4-ones with Methyl 2-Nitro- or 2,4-Dinitro-

benzenesulfonates[195]
R1 + MeO3S R3
R1 = H; R2 = Me; R3 = NO2 81%
O R2 R1 = R3 = H; R2 = Ph 92%
O2N R1 = 5,6-(HC CH)2; R2 = R3 = H ~100%
R1 = 7,8-(HC CH)2; R2 = R3 = H 87%
R1 = R2 = H; R3 = NO2 ~100%
OMe
R1 −O S R3
3
+
O R2
O2N
59

4-Ethoxy-2-phenyl-1-benzopyrylium Perchlorate (57, R1 = R2 = H); Typical Procedure:[192]
A mixture of 2-phenyl-2,3-dihydro-4H-1-benzopyran-4-one (0.22 g, 1 mmol), HC(OEt)3
(1.1 mL), and 70% HClO4 (0.1 mL) was heated at 60–70 8C for 3–4 min. Dilution with Et2O
deposited colorless crystals; yield: 0.14 g (40%); mp 185 8C (from AcOH).
7-(Diethylamino)-2-ethoxy-4-methyl-l-benzopyrylium Tetrafluoroborate (58, R1 = 7-NEt2;

R2 = Me; R3 = Et); Typical Procedure:[194]
7-(Diethylamino)-4-methyl-2H-1-benzopyran-2-one (1.15g, 5 mmol) and triethyloxonium
tetrafluoroborate (0.94 g, 5 mmol) were stirred in dry CH2Cl2 (15 mL), with the exclusion
of moisture, for 40 min. Et2O was added and the product was collected by filtration with
the exclusion of moisture; yield: 1.56 g (90%); mp 136 8C.
Alkylation of 4H-1-Benzopyran-4-one with tert-Butyldimethylsilyl Trifluoromethanesul-

fonate; General Procedure:[193]
To the 4H-1-benzopyran-4-one (4.27 mmol), tert-butyldimethylsilyl trifluoromethanesul-
fonate (4.27 mmol) was added dropwise under N2, and the mixture was heated for 1 h at
80 8C. The product was dissolved in CH2Cl2 and used directly for further reactions.
4-Methoxy-l-benzopyrylium 2,4-Dinitrobenzenesulfonate (59, R1 = R2 = H; R3 = NO2);

A mixture of 4H-1-benzopyran-4-one (0.73 g, 5 mmol) and methyl 2,4-dinitrobenzenesul-
fonate (1.31 g, 5 mmol) was heated for 20 min at 50 8C. The mixture soon solidified. It
was triturated with hot toluene, and the solid was collected by filtration and washed
with dry Et2O; yield: 2.04 g (ca. 100%); mp 206 8C.
14.2.1.3.8.2 Variation 2:
By Protonation of 4H-1-Benzopyran-4-ones, 2-Alkylidene-2H-1-benzopyrans,
and 4-Alkylidene-4H-1-benzopyrans
4H-1-Benzopyran-4-ones are at the same oxidation level as 4-hydroxy-1-benzopyrylium

salts 60 and can, therefore, be transformed to the latter by strong acids, e.g. perchloric
acid (Scheme 62).[188] The salts are stable, but revert to the starting materials on treatment
with base. Tosyl hydrazones of 4H-1-benzopyran-4-ones are converted into 4-amino-1-ben-
zopyrylium salts in moderate to good yields.[206] Conversion of 2H-1-benzopyran-2-ones
into 1-benzopyrylium salts by simple protonation has not been reported, but that of the
isoelectronic 2-alkylidene-2H-1-benzopyrans[93,207] and of the vinylogous 2-(1-formylethyl-

idene)-2H-1-benzopyrans[208] is known and gives the salts in quantitative yields.
Scheme 62 Aromatization of 4H-1-Benzopyran-4-one by Protonation[188]
O OH
HClO4
ClO4−
H2O +
O O
60
The vinylogues of 4H-1-benzopyran-4-ones, i.e. 4-(2-benzoylalkylidene)-4H-1-benzopyrans,

are also readily protonated by hydrogen chloride to give the 4-(2-benzoylalkyl)-1-benzo-
pyrylium salts 61 (Scheme 63).[94,144,145,180]
Scheme 63 Aromatization of a 4-Alkylidene-4H-benzopyran by Protonation[144]

R2 Bz R2 Bz
HCl
R1 R1 X−
+
O Ph O Ph
61
R1 = H, 6-OMe, 7-OMe; R2 = Ph, Bz; X = FeCl4, ClO4
Hydrolysis of 4-(dicyanomethylene)-4H-1-benzopyrans with hydriodic acid is accompa-

nied by decarboxylation, and in the case of R1 = 7-OMe also by dimethylation, leading to
4-methyl-1-benzopyrylium salts 62 in good yield (Scheme 64).[209]
Scheme 64 Hydrolysis, Decarboxylation, and Aromatization of 4-(Dicyanomethylene)-

4H-1-benzopyrans[209]
NC CN
HX X−
R1 R1
R1 = 7-OH; R2 = Et; X = I 90% +
O NR22 O NR22
R1 = 7-OH; R2 = (CH2)5; X = I 98%
R1 = 7-OMe; R1 (in 62) = OH; R2 = Me; X = ClO4 84% 62
R1 = 7-OH; R2 = Me; X = I 93%
2-(1-Aryl-alkylidene)-2H-1-benzopyrans are transformed to the corresponding 2-benzyl-1-

benzopyrylium salts in quantitative yield.[93,208]
4-Hydroxy-l-benzopyrylium Perchlorate (60, X = ClO4); Typical Procedure:[188]

To a soln of 4H-1-benzopyran-4-one (0.20 g, 1.4 mmol) in AcOH/Ac2O (1:1, 1 mL), 70% HClO4
(0.2 mL) was added. The precipitated salt was collected by filtration; yield: 0.2 g (70%); mp
177–178 8C.
4-(2-Oxo-2-phenylethyl)-2-phenyl-l-benzopyrylium Tetrachloroferrate (61, R1 = R2 = H);

Dry HCl(g) was introduced for 10 min into a soln of 4-(2-oxo-2-phenylethylidene)-2-phenyl-
4H-1-benzopyran (2.0 g, 6 mmol) in AcOH (10 mL). To the deep red soln a mixture of AcOH
(10 mL) and FeCl3 (1.0 g) was added and the oily precipitate crystallized by rubbing. The
crystals were separated, washed with Et2O, and recrystallized (AcOH); yield: not reported;
mp 156–157 8C.

2-(Dimethylamino)-7-hydroxy-4-methyl-l-benzopyrylium Iodide (62, R1 = 7-OH; R2 = Me);

A soln of 4-(dicyanomethylene)-2-(dimethylamino)-7-methoxy-4H-1-benzopyran (1.0 g,
37 mmol) in 57% HI (25 mL) was refluxed for 1 h. On cooling, the product separated. It
was collected by filtration and washed with a little H2O; yield: 1.2 g (93%); mp 258–259 8C.
14.2.1.3.9 Method 9:
Aromatization of a 2-Amino-2H-benzopyran by Protonation
Combined with Elimination of the Amino Group
2H-1-Benzopyrans substituted at C2 by a secondary amino group aromatize with loss of

the amino group when treated with acetic anhydride and perchloric acid (Scheme
65).[210,211] Similarly, protonation of 7-(diethylamino)-2-imino-2H-1-benzopyran-3-carbox-
amide by perchloric acid gives 2-amino-3-carbamoyl-7-(diethylamino)-1-benzopyrylium
perchlorate (Scheme 65).[212]
Scheme 65 Aromatization of 2-(Dialkylamino)-2H-1-benzopyrans[211,212]

R1 R1
HClO4, Ac2O
Et ClO4−
30−50% +
O O Et
N
R1 = H, 7-NEt2, 7-OMe, 5,6-(CH CH)2
O O
NH2 HClO4 NH2

+
Et2N O NH Et2N O NH2
Aromatization of 2-(Dialkylamino)-2H-1-benzopyrans; General Procedure:[211]

Aq 70% HClO4 (2 equiv) was added to a cooled, stirred soln of a 2-(dialkylamino)-2H-1-ben-
zopyran in Et2O, followed by the addition of Ac2O (2 equiv). The product, which crystal-
lized after storage in a refrigerator, was isolated and washed with Et2O and EtOAc; yield:
30–50%.
14.2.1.3.10 Method 10:

Aromatization of 2-Hydroxy-2H-benzopyrans by Protonation
Combined with Dehydration
4-Acetoxy-2-aryl-2,3-dihydro-4H-1-benzopyrans can be oxidized with dimethyldioxirane

to 2-hydroxy-2,3-dihydro-4H-1-benzopyrans, which can then be aromatized with phos-
phoryl chloride to 2-aryl-1-benzopyrylium salts.[213]
14.2.1.3.11 Method 11:

Aromatization Combined with Substitution
Some 2H-1-benzopyran-2-ones substituted at C4 by a (2-benzothiazolylidene)methylene

group can be converted into the corresponding 2-chloro-1-benzopyrylium salts by treat-
ment with phosphoryl chloride and perchloric acid.[169,214]
On treatment with thionyl chloride, 2-(methoxycarbonyl)-4H-1-benzopyran-4-one

gives rise to the 4,4-dichloro compound, which yields the 4-chloro-1-benzopyrylium salt
63 on addition of antimony(V) chloride (Scheme 66).[215]
Scheme 66 Conversion of a 4H-1-Benzopyran-4-one into a 4-Chloro-1-benzopyrylium

Salt[215]
O Cl Cl
SOCl2 SbCl5
O CO2Me O CO2Me
Cl
SbCl6−
+
O CO2Me
63

4-Chloro-2-(methoxycarbonyl)-l-benzopyrylium Hexachloroantimonate (63);
To a soln of methyl 4,4-dichloro-4H-1-benzopyran-2-carboxylate, prepared from methyl 4-
oxo-4H-1-benzopyran-2-carboxylate (2.04 g, 10 mmol) with SOCl2 in dry benzene (100 mL),
SbCl5 (2.98 g, 10 mmol) was added. The precipitate was collected by filtration and washed
with benzene and Et2O; yield: 5.2 g (94%); mp 180 8C.
14.2.1.4 Synthesis by Substituent Modification
14.2.1.4.1 Method 1:
Nucleophilic Addition of a Trialkyl Phosphite and Reoxidation
Triethyl phosphite adds to 1-benzopyrylium salts to give 4-(diethoxyphosphoryl)-4H-ben-

zopyrans, which can be reoxidized to a 4-(diethylphosphoryl)-1-benzopyrylium salt 64
(Scheme 67). If the ester is hydrolyzed before reoxidation, the corresponding 4-phospho-
no salt can be obtained.[216]
Scheme 67 Phosphorylation of a 2-Phenyl-1-benzopyrylium Salt[216]
O
P(OEt)2
P(OEt)3 Tr+ ClO4−

Br−
+ 50%
O Ph O Ph
O
P(OEt)2
ClO4−
+
O Ph
64
4-(Diethoxyphosphoryl)-2-phenyl-1-benzopyrylium Perchlorate (64);

To 2-phenyl-1-benzopyrylium bromide (1.45 g, 5 mmol), P(OEt)3 (1.3 g, 7.8 mmol) was
added at 100 8C and the EtBr evolved was distilled off directly. After heating for 30 min

at 100 8C, excess reagent was distilled off in vacuo and the residue heated for 5 min with a
mixture of Tr+ClO4– (1.7 g, 5 mmol), AcOH (7 mL), and Ac2O (1 mL). The precipitate was col-
lected by filtration; yield: 1.1 g (50%); mp 197 8C.
14.2.1.4.2 Method 2:
Addition of an Activated Arene or Alkene Followed by
Reoxidation or Disproportionation
To 1-benzopyrylium salts unsubstituted at C2 or C4, activated arenes can be added and the
intermediate 2H- or 4H-1-benzopyran can be reoxidized to 2- or 4-aryl-1-benzopyrylium
salts.[166,170,217–221] In a similar way, addition of phenylethynyllithium and reoxidation
with triphenylcarbenium perchlorate produces 2-(phenylpropynyl)-1-benzopyrylium per-
chlorate (see Section 14.2.1.3.7.2).[59]
4-Phenyl- and 4-ethoxy-1-benzopyrylium salts[217,218,221] react with N,N-dimethyl-
aniline and, in the presence of air, are spontaneously oxidized to 2-[(4-dimethylamino)-
phenyl]-1-benzopyrylium salts 65 (Scheme 68).

Scheme 68 Oxidative Arylation of a 1-Benzopyrylium Salt with an Activated Arene[217,218]
R1 R1
O2
ClO4− + ClO4−
+ R1 = Ph 61% +
O NMe2 R1 = OEt 70% O
NMe2
65
Using the same procedure, 2-aryl-1-benzopyrylium salts give 4-(dimethylamino)phenyl

derivatives, but in low yield.[166,219,220,222]
2-[4-(Dimethylamino)phenyl]-4-phenyl-l-benzopyrylium Perchlorate (65, R1 = Ph);

4-Phenyl-1-benzopyrylium perchlorate (3.1 g, 10 mmol) and N,N-dimethylaniline (0.9 g,
7.4 mmol) were heated for 15 min in dry DMF (20 mL). After cooling, Et2O (40 mL) was
added. The crystals were collected by filtration, washed with Et2O, and recrystallized
(MeNO2); yield: 2.6 g (61%); mp 255 8C.
14.2.1.4.3 Method 3:
Condensation of a 1-Benzopyrylium Salt with a Carboxylic Acid Having
an Activated Methylene Group, Combined with Disproportionation
Malonic acid and its simple or multiple vinylogues link two molecules of a 2-aryl-1-benzo-
pyrylium salt to give 66, in which one molecule ends up in the 2-aryl-1-benzopyrylium
salt form and the other becomes a 4-alkylidene-4H-1-benzopyran (Scheme 69).[180,219,220]
Scheme 69 Alkylation of 2-Aryl-1-benzopyrylium Salts with Malonic Acid and its

Vinylogues[219]
R1
O+ ClO4− HO2C CO2H NaOAc

2 +
n
R2
R1 R1
n
O+ O ClO4−
R2 R2

66
n = 0−3
R1 = H, 6-OH, 7-OH, 7-OMe, 8-OMe; R2 = H, 4-OMe, 4-OH
2-Phenyl-4-[(2-phenyl-4H-1-benzopyran-4-ylidene)methyl]-1-benzopyrylium Perchlorate
(66, n = 0; R1 = R2 = H); Typical Procedure:[219]
2-Phenyl-1-benzopyrylium perchlorate (6.2 g, 2 mmol), malonic acid (1.04 g, 10 mmol),
and NaOAc (1.5 g) were refluxed in AcOH (150 mL) for 20 min. The product separated
from the blue soln and was recrystallized (AcOH containing 1% HClO4); yield: 3.9 g (75%);
mp 254 8C.
14.2.1.4.4 Method 4:
Replacement of an Alkoxy Group by a Substituted Amino Group
In 7-(dialkylamino)-2-ethoxy-1-benzopyrylium salts, generated in situ by treatment of the

corresponding 2H-1-benzopyran-2-one with triethyloxonium tetrafluoroborate, the
ethoxy group can be replaced by a dialkylamino group to give 67 (Scheme 70).[200]
Scheme 70 Conversion of a 2H-1-Benzopyran-2-one into a 2-(Dialkylamino)-1-benzopyryl-

ium Salt[200]
R1 R1
Et3O+ BF4−
BF4−
+
Et2N O O Et2N O OEt
R1
R2R3NH
BF4−
R1 = Me; R2 = R3 = Et 67% +
R1 = R2 = H; R3 = Ph 43%
Et2N O NR2R3
R1 = H; R2,R3 = (CH2)5 71%
67
R1 = Me; R2 = H; R3 = Bn 65%
Similarly, the 4-methoxy or 4-ethoxy group of 1-benzopyrylium salts can be displaced by

secondary amines or anilines[109,218,222] or by secondary amines with heterocyclic substitu-
ents to give 68 (Scheme 71).

Scheme 71 Substitution of a 4-Ethoxy Group by a Dialkylamino Group in

1-Benzopyrylium Salts[218,222]
OEt NR4R5
3
R R3
R4R5NH
R1 ClO4− R1 ClO4−
+ +
2 2
O R O R
68
R1 = H, 7-OH, 7-OMe; R2 = H, Ph; R3 = H, OMe; R4 = Ph, 4-MeOC6H4; R5 = H; R4 = R5 = (CH2)5, (CH2)2OH
A 2- or 4-chloro substituent on a 1-benzopyrylium salt can be substituted using activated

arenes such as N,N-dimethylaniline or N-methylindole in moderate to good yields.[223]
Heterocycles with an activated methyl group, such as 4-methyl-2-phenyl-1-benzopyr-
ylium perchlorate[197,224,225] or 3-ethyl-2-methylthiazolium iodide,[188,214] can also replace a
2- or 4-alkoxy group in 1-benzopyrylium salts, giving the corresponding alkylidene-meth-
ylene derivatives.
N-Methyl-2-methylene-1,3-benzothiazoles may undergo a similar reaction; with 4-

alkoxy-1-benzopyrylium salts they give 4-(2,3-dihydro-1,3-benzothiazol-2-ylidene)-1-ben-
zopyrylium salts.[226,227]
2,7-Bis(diethylamino)-4-methyl-l-benzopyrylium Tetrafluoroborate (67, R1 = Me;

R2 = R3 = Et); Typical Procedure:[200]
To 7-(diethylamino)-4-methyl-2H-1-benzopyran-2-one (0.92 g, 4 mmol) in dry CH2Cl2
(20 mL), triethyloxonium tetrafluoroborate (0.76 g, 4 mmol) dissolved in CH2Cl2 (10 mL)
was added, with stirring, under N2. After stirring for 20–30 min at 30 8C, Et2NH (1.5 g,
20 mmol) was added, and then the mixture was refluxed for 2–3 h. After the addition of
H2O (10 mL), the organic phase was separated and concentrated to a volume of ca. 5 mL.
On the addition of Et2O (25 mL), crystals separated, which were recrystallized (hexane/ace-
tone 1:1); yield: 10 g (67%); mp 158 8C.
4-[Bis(2-hydroxyethyl)amino]-2-phenyl-1-benzopyrylium Perchlorate [68, R1 = R3 = H;

R2 = Ph; R4 = R5 = (CH2)2OH]; Typical Procedure:[222]
4-Methoxy-2-phenyl-1-benzopyrylium perchlorate (33.7 g, 0.1 mol) and bis(2-hydroxyeth-
yl)amine (11.0 g, 0.1 mol) were refluxed in MeCN (600 mL) for 30 min. The solvent was dis-
tilled off and the residue was triturated with Et2O to give pale yellow crystals; yield: 37.6 g
(92%); mp 123–125 8C.

2-Benzopyrylium Salts
A comprehensive review on the synthesis, reactions, and physical properties of this prod-
uct subclass can be found in Advances in Heterocyclic Chemistry.[228]
2-Benzopyrylium salts 69 can be characterized by the mesomeric structures shown
in Scheme 72.
Scheme 72 Mesomeric Structures of 2-Benzopyrylium Salts
5 4
4a
6 3
+
7 O O
8a 2
8 1 +
69
14.2.2 2-Benzopyrylium Salts 243
In nonprotic, nonnucleophilic solvents, 2-benzopyrylium salts are very stable but in the
solid state their perchlorates may explode and therefore must be handled with great care.
In acidic aqueous solutions (pH < 3), 2-benzopyrylium salts are stable.[229,230] Electron-do-
nating substituents extend the pH range of stability. At higher pH, hydrolysis to the cor-
responding dicarbonyl compound takes place.
2-Benzopyrylium salts are strong Lewis acids and give stable adducts with Lewis bas-
es and nucleophiles. Owing to electron attraction by the positive charge, the methyl
group of 1-methyl-2-benzopyrylium salts is activated and can be condensed with alde-
hydes.
UV spectra of 2-benzopyrylium salts show several bands, their position depending on
the substitution pattern of the salts. The yellow, orange, or even crimson color of the salts
is caused by the longest-wavelength band (up to 545 nm).[229,231,232] NMR data for 2-benzo-
pyrylium salts are scarce and lack assignments; no data for the unsubstituted compound
are available. H4 gives signals in the range 7.8–8.3.[233] Some characteristic 13C data are
shown in Scheme 73.[234]
13
Scheme 73 C NMR Data for a 2-Benzopyrylium Salt[234]

116.4
MeO 140.7
149.7
+
O
MeO 118.0 174.0
121.6
OMe
OMe
Owing to hydrolytic ring opening, no real pKa values can be determined for 2-benzopyryl-
ium salts. Pseudo pKa values are highly dependent on substitution.[234]
The nomenclature of 2-benzopyrylium salts and derivatives thereof in different oxi-
dation states is shown in Scheme 74.
Scheme 74 Nomenclature and Numbering of a 2-Benzopyrylium Salt and its Analogues
5 4
4a
6 3
+
7 O O O O
8a 2
8 1
O
2-benzopyrylium salt 1H-2-benzopyran 1H-2-benzopyran-1-one 3,4-dihydro-1H-2-benzopyran
(1H-isochromene) (isocoumarin) (isochroman)
The first 2-benzopyrylium salts were prepared in 1933.[235] In contrast to analogues such
as isocoumarins, isochromans, and 1-benzopyrylium salts, no 2-benzopyrylium salts have
been found in nature. The salts themselves have no practical applications; their synthetic
potential lies in their transformation to isoquinolines.[236,237]

14.2.2.1.1 By Formation of One Heteroatom-Carbon and One C-C Bond
14.2.2.1.1.1 Method 1:
From (2-Oxoalkyl)arenes or Their Acylated Enols with
a Carboxylic Acid Derivative (as C1 Component)
(2-Oxoalkyl)arenes containing an activated arene ring, as well as their ø-aryl derivatives,

both in the oxo or acylated enol forms, react with acyl cations generated from carboxylic
acids, their anhydrides, or acid chlorides by treatment with perchloric acid or silver per-
chlorate, respectively, and give 2-benzopyrylium salts via the corresponding acylated in-
termediate.[238–247]
14.2.2.1.1.1.1 Variation 1:
From Arylacetones with an Aliphatic Carboxylic Anhydride and
Perchloric Acid

Treatment of arylacetones bearing electron-donating groups on the aryl ring with acyl
cations generated from aliphatic anhydrides and perchloric acid gives low to fair yields
of 3-methyl-2-benzopyrylium salts 70 (Scheme 75).[247]
Scheme 75 Ring Closure of Arylacetones with an Aliphatic Carboxylic Anhydride and

Perchloric Acid[247]
R3
O
HClO4 R2
(R1CO)2O 2 R1CO+ ClO4−
R3
+ ClO4−
O
R2
R1
70 R1 = Me; R2 = OMe; R3 = H 70%
R1 = Me; R2 = R3 = OMe 68%
R1 = Me; R2,R3 = OCH2O 41%
R1 = Et; R2 = OMe; R3 = H 64%
R1 = Pr; R2 = R3 = OMe 69%
3-Methyl-2-benzopyrylium Perchlorates 70; General Procedure:[247]

To the carboxylic acid anhydride (10 mL), 70% HClO4 (1.25 mL) was added dropwise with
cooling and the acyl perchlorate formed was stirred into the arylacetone (10 mmol). Stir-
ring was continued at 20 8C, the precipitated salt was collected by filtration, washed with
ice-cold AcOH and Et2O, and dried. It was purified by recrystallization (AcOH).
14.2.2.1.1.1.2 Variation 2:
From Arylacetones with an Aromatic Acid Chloride and
Aluminum Trichloride
Friedel–Crafts-type acylation of arylacetones bearing electron-donating groups with aro-

matic acid chlorides followed by ring closure gives 1-aryl-3-methyl-2-benzopyrylium salts
71 (Scheme 76).[247] The acylium ion can also be generated with silver perchlorate in nitro-
methane, such as in the case of 3,4-methylenedioxybenzoyl chloride, but the yield is low
(16%).[247]
Scheme 76 Ring Closure of Arylacetones with an Aromatic Acid Chloride and

Aluminum Trichloride[247]
O
1. 1
Ar Cl
AlCl3, MeNO2
MeO MeO
2. HClO4
+ ClO4−
O Ar1 = Ph 65% O
MeO MeO
Ar1
71
6,7-Dimethoxy-3-methyl-l-phenyl-2-benzopyrylium Perchlorate (71, Ar1 = Ph);

To a cooled mixture of 1-(3,4-dimethoxyphenyl)acetone (1.94 g, 10 mmol), benzoyl chlo-
ride (2.3 mL, 20 mmol), and MeNO2 (4 mL), AlCl3 (3.17 g) in MeNO2 (6 mL) was added and
the mixture was stirred for 2 d. Then, it was poured onto crushed ice (50 g), concd HCl
(3 mL) was added, and the unreacted ketone, as well as MeNO2, were removed by extrac-

tion with benzene (3 30 mL). The water-soluble tetrachloroaluminate salt was trans-
formed to the perchlorate by adding 70% HClO4 (1.5 mL). The product was collected by
filtration, washed with dil aq acid, and dried; yield: 2.48 g (65%); mp 218 8C (from AcOH).
14.2.2.1.1.1.3 Variation 3:
Transformation of an Enol Lactone of a Benzyl 2-(Carboxymethyl)aryl Ketone
with an Acid Anhydride and Perchloric Acid
Benzyl 2-(carboxymethyl)aryl ketones can be readily cyclized with acetic anhydride to the
corresponding enol lactones, which can be transformed by treatment with acetic or pro-
pionic anhydride to 1-methyl- or 1-ethyl-2-benzopyrylium salts 72, respectively, in moder-
ate yields (Scheme 77).[248,249]
Scheme 77 Transformation of a Benzyl 2-(Carboxymethyl)aryl Ketone via its Enol Lactone

to a 2-Benzopyrylium Salt[248,249]
OMe OMe
OMe OMe
Ac2O, heat
MeO MeO
O O
MeO CO2H MeO
O
OMe
HO2C
HClO4, (R1CO)2O
MeO
OMe
ClO4−
+
O
MeO
R1
72 R1 = Me 40%
R1 = Et 30%
3-[2-(Carboxymethyl)-4,5-dimethoxyphenyl]-6,7-dimethoxy-1-methyl-2-benzopyrylium
Perchlorate (72, R1 = Me); Typical Procedure:[249]
To (1Z)-1-(3,4-dimethoxybenzylidene)-6,7-dimethoxy-1,4-dihydro-3H-2-benzopyran-3-one
(0.36 g, 1 mmol) in Ac2O (3 mL), 70% HClO4 (0.1 mL) was added with cooling and the mixture
was heated cautiously to 50 8C for 10 min. To the cooled mixture, Et2O was added until crys-

tallization commenced. After 24 h, the product was collected by filtration, washed with
Et2O, dried, and dissolved by heating in a minimum amount of MeNO2 containing 3 drops
of HClO4. The soln was refluxed for 2 h, cooled, and the product precipitated with Et2O to
give orange crystals; yield: 0.2 g (40%); mp 232 8C.
14.2.2.1.1.2 Method 2:
From a (Cyanomethyl)arene with Carboxylic Acid Derivatives
(as C1 Component)
Arylacetonitriles with electron-donating groups on the aryl ring can be transformed with
acylium ions (generated from an acid anhydride and perchloric acid) to 3-acylamino-2-
benzopyrylium salts 73 (Scheme 78).[250]
Scheme 78 Ring Closure of an Arylacetonitrile with an Acid Anhydride and Perchloric

Acid[250]
H
MeO MeO N
COR1

CN Ac2O, HClO4
+ (R1CO)2O
ClO4−
+
R1 = Me 94% O
MeO R1 = Et 54% MeO
R1
73
3-Acetamido-6,7-dimethoxy-1-methyl-2-benzopyrylium Perchlorate (73, R1 = Me);

To a soln of (3,4-dimethoxyphenyl)acetonitrile (1.77 g, 10 mmol) in Ac2O (10 mL), 70%
HClO4 (1.5 mL) was added dropwise at such a rate that the temperature did not rise above
50–60 8C. After 15–20 min, when all of the HClO4 had been added, copious crystallization
of the product occurred. After 24 h, the product was collected by filtration and washed
(Ac2O and Et2O); yield: 3.4 g (94%); mp 210 8C.
14.2.2.1.2 By Formation of One Heteroatom-Carbon Bond
14.2.2.1.2.1 Method 1:
Synthesis from 1,2-Dicarbofunctional Arenes
14.2.2.1.2.1.1 Variation 1:
Ring Closure of 2-Acyl-1-(2-oxoalkyl)arenes
2-Acyl-1-(2-oxoalkyl)arenes can be readily obtained by oxidation of indanes[238,251–254] or in-

denes.[236,253] With hydrogen bromide in acetic acid or hydrogen chloride gas, the corre-
sponding 2-benzopyrylium salts 74 are obtained in moderate yields (Scheme 79).[255]
Scheme 79 Ring Closure of a 2-Acyl-1-(2-oxoalkyl)arene[238,255]
R2
COR2
X−
HX, AcOH
R3 R3 +
O 45−64% O
R1 R1
74
R1 = R2 = alkyl, aryl
5,8-Dimethoxy-1,3-dimethyl-2-benzopyrylium Bromide [74, R1 = R2 = Me; R3 = 5,8-(OMe)2;

X = Br]; Typical Procedure:[255]
To a soln of 1-(2-acetyl-3,6-dimethoxyphenyl)acetone (0.714 g, 3.0 mmol) in AcOH (2 mL), a
26% soln of HBr in AcOH (3 mL) was added. After a few min, the pure product was precipi-
tated by the addition of EtOAc (50 mL); yield: 0.578 g (64%).
14.2.2.1.2.1.2 Variation 2:
Ring Closure of (2-Acylaryl)acetic Acid Derivatives
3,4-Dimethoxyphenylacetic acid can be acylated in position 6 and the product cyclized

with a mixture of acetic anhydride and perchloric acid to give 1-substituted 3-acetoxy-2-
benzopyrylium salts 75 (Scheme 80).[244]
Scheme 80 Ring Closure of (2-Acylaryl)acetic Acid Derivatives[244]
MeO MeO OAc

CO2H Ac2O, HClO4
ClO4−
+
R1 = Me 74% O

MeO COR1 MeO
R1 = 3,4-(MeO)2C6H3CH2 54%
R1
75
3-Acetoxy-1-(3,4-dimethoxybenzyl)-6,7-dimethoxy-2-benzopyrylium Perchlorate
[75, R1 = 3,4-(MeO)2C6H3CH2]; Typical Procedure:[230]
To a soln of (2-carboxymethyl-4,5-dimethoxy)phenyl 3,4-dimethoxybenzyl ketone (1.0 g,
2.7 mmol) in Ac2O (6 mL), 72% HClO4 (0.5 mL, 5 mmol) was added dropwise. On cooling,
the product precipitated; yield: 0.7 g (54%); mp 249 8C (MeNO2).
14.2.2.1.2.1.3 Variation 3:
Ring Closure of 2-Formyl-1-(2-oxoalkyl)arenes
On treatment with hydrogen chloride gas, 2-formyl-1-(2-oxoalkyl)arenes give 3-substitut-

ed 2-benzopyrylium chlorides 76 provided that the oxoalkyl group does not contain an
additional activated methylene group.[241,256] In a one-pot variation, the formyl group is in-
troduced in the same operation with triethyl orthoformate (Scheme 81).[241]
Scheme 81 Formylation of a 2-(Oxoalkyl)arene Followed by Ring Closure[241]
COR1 HC(OEt)3, HCl(g) COR1

R2 R2
CHO
R1
R2 + Cl−
O
76 R1 = Bu; R2 = 6,8-(OH)2, 7-Me 50%

R1 = alkyl, aryl; R2 = alkyl, OH, alkoxy
3-Butyl-6,8-dihydroxy-7-methyl-2-benzopyrylium Chloride
[76, R1 = Bu; R2 = 6,8-(OH)2,7-Me]; Typical Procedure:[241]
A soln of 1-(3,5-dihydroxy-4-methylphenyl)hexan-2-one (0.6 g, 2.7 mmol) in HC(OEt)3
(2 mL) was saturated with HCl(g). The pure yellow salt was precipitated by the addition
of Et2O (10 mL); yield: 0.36 g (50%); mp 160 8C (dec).

14.2.2.1.2.1.4 Variation 4:
Ring Closure of 2-Cyano-1-(2-oxoalkyl)arenes
Hydrolysis of 2-cyano-1-(2-oxoalkyl)arenes with concentrated hydrobromic acid is accom-

panied by cyclization to the 1-amino-2-benzopyrylium bromides 77 (Scheme 82).[257]
Scheme 82 Hydrolysis and Cyclization of 2-Cyano-1-(2-oxoalkyl)arenes[257]
HBr, Ac2O or Ar1

COAr1 48% aq HBr
+ Br−
Ar1 = Ph 90% O
CN
NH2
77
1-Amino-3-phenyl-2-benzopyrylium Bromide (77, Ar1 = Ph); Typical Procedure:[257]

A suspension of powdered 2-(2-oxo-2-phenylethyl)benzonitrile (3.0 g, 14 mmol) was
stirred in 48% aq HBr (90 mL) for 72 h. Addition of H2O (30 mL) precipitated the yellow

salt, which was dried in vacuo at 70 8C; yield: 3.7 g (90%); mp 292–294 8C (dec).
14.2.2.1.2.1.5 Variation 5:
By Ring Closure and Aryl Migration of [2-(Diarylmethyl)phenyl]acetic Acids
Under the action of acetic anhydride and perchloric acid, 2-(diarylmethyl)phenylacetic

acids, with one of the aryl groups bearing an electron-donating substituent, undergo rear-
rangement involving the latter and ring closure to 1,3-diaryl-2-benzopyrylium salts 78
(Scheme 83).[258]
Scheme 83 Ring Closure and Aryl Migration of 2-(Diarylmethyl)phenylacetic Acids[258]
OMe
CO2H
MeO OMe MeO
Ac2O, HClO4
ClO4−
+
R1 = OMe 66% O
MeO MeO
R1 = NO2 48%
R1 R1
78
6,7-Dimethoxy-1,3-bis(4-methoxyphenyl)-2-benzopyrylium Perchlorate (78, R1 = OMe);

To a soln of {2-[bis(4-methoxyphenyl)methyl]-4,5-dimethoxyphenyl}acetic acid (0.42 g,
1 mmol) in Ac2O (3 mL), 70% HClO4 (0.2 mL) was added dropwise. The precipitate was re-
crystallized (HCO2H) to give orange crystals; yield: 0.33 g (66%).
14.2.2.1.3 By Formation of One C-C Bond
14.2.2.1.3.1 Method 1:
Ring Closure of the O-Acylenol Form of Aryl Benzyl Ketones with
Polyphosphoric Acid
Heating of the enol acetates of aryl benzyl ketones with polyphosphoric acid (PPA) fol-
lowed by hydrolysis and the addition of perchloric acid gives 3-aryl-1-methyl-2-benzopyr-
ylium perchlorates 79 in moderate to good yields (Scheme 84). If propionic anhydride is

added to the mixture, the 1-ethyl analogue is obtained in 80% yield.[246]
Scheme 84 Ring Closure of the O-Acylenol Form of Aryl Benzyl Ketones with Polyphos-
phoric Acid[246]
OMe OMe
1. PPA, heat
MeO 2. HClO4 MeO
R1 R1
R1 = H 81% + −
OAc R1 = OMe 54% O ClO4
MeO MeO
79
3-(3,4-Dimethoxyphenyl)-6,7-dimethoxy-1-methyl-2-benzopyrylium Perchlorate
(79, R1 = OMe); Typical Procedure:[246]
A mixture of 1-acetoxy-1,2-bis(3,4-dimethoxyphenyl)ethene (0.3 g, 0.84 mmol) and PPA
(3 g) was heated at 130 8C for 40 min, then hydrolyzed with cold H2O, and acidified with

30% HClO4. The precipitate was collected by filtration and recrystallized (MeNO2/AcOH
1:1) to give orange crystals; yield: 0.2 g (54%); mp 250 8C.
14.2.2.2.1 Method 1:
By Addition of Grignard Reagents to 1H-2-Benzopyran-1-ones
(Isocoumarins)
Addition of Grignard reagents to isocoumarins followed by hydroxy group elimination

with a strong acid offers an easy route to 1-substituted 2-benzopyrylium salts 80 (Scheme
85).[232,234,259,260]
Scheme 85 Addition of Grignard Reagents to Isocoumarins Followed by Aromatiza-

tion[232,259,260]
R1 1. R2MgX, Et2O R1
2. H2O, NH4Cl HClO4, Ac2O, Et2O
O O
O R2 OH
R1
ClO4−
+
O
R2
80 R1 = H; R2 = Ph 21%
R1 = Me; R2 = Ph 30%
R1 = 4-MeOC6H4; R2 = Me 50%
R1 = R2 = Ph 45%
R1 = Ph; R2 = Me 37%
1,3-Diphenyl-2-benzopyrylium Perchlorate (80, R1 = R2 = Ph); Typical Procedure:[232]
CAUTION: On heating, this compound can explode; therefore larger quantities have to be han-
dled with care.
To a soln of 3-phenyl-1H-2-benzopyran-1-one (7.4 g, 30 mmol) in dry Et2O (75 mL) cooled to
between 0 and 5 8C, a soln of PhMgBr (16.2 g, 90 mmol) in dry Et2O (75 mL) was added.
After stirring for 5 h, the Mg salt of the tertiary alcohol was hydrolyzed with a soln of

NH4Cl (42 g) in H2O (245 mL). The organic phase was separated, washed with distilled H2O,
and dried over MgSO4. The soln was cooled to 0 8C and a mixture of 70% HClO4 (6.35 mL),
Ac2O (25 mL), and dry Et2O (20 mL) was added. The precipitated orange salt was collected
by filtration and HClO4 (0.5 mL) and Ac2O (3 mL) were added to the mother liquor to pro-
duce a second crop of the salt. The combined fractions were recrystallized (AcOH contain-
ing a few drops of HClO4); yield: 5.7 g (45%); mp 245–246 8C.
14.2.2.2.2 Method 2:
By Oxidative Fragmentation of 1H-2-Benzopyrans (Isochromans)
This method is of rather limited scope. Treatment of 6,7-dimethoxy-3-methyl-1-phenyl-

1H-2-benzopyran or bis(3-methyl-6,7-dimethoxy-1H-benzopyran) with 2,2,6,6-tetrameth-
yl-1-oxopiperidinium perchlorate in acetonitrile gives (with the loss of the substituent at
position 1) the corresponding 2-benzopyrylium perchlorate in quantitative yield (Scheme
86).[261]
Scheme 86 Dehydrogenation of 1H-2-Benzopyrans with 2,2,6,6-Tetramethyl-1-oxopiperi-
dinium Perchlorate[261]

MeO MeO
+ ClO4− + ClO4−
O + ~100% O
MeO N MeO
Ph O

Dibenzo[b,d]pyrylium Salts
Previously published information regarding this product subclass can be found in

Houben–Weyl, Vol. E 7b, pp 56–63.
Dibenzo[b,d]pyrylium salts (9-oxoniaphenanthrenes) can be represented by the fol-
lowing resonance structures involving a delocalized positive charge (Scheme 87).
Scheme 87 Numbering and Mesomerism of Dibenzo[b,d]pyrylium Salts
9 10 1 2
10a
8 3
7 6a 4a 4 X− X−
+
O O
6 5
+
H H
Nucleophiles attack dibenzo[b,d]pyrylium salts at C6 (or equivalent position in benzo de-

rivatives) without ring opening giving 6-substituted dibenzo[b,d]pyrans.[262]
Very few dibenzo[b,d]pyrylium salts have been prepared, mostly benzo derivatives,
and no natural compounds of this type are known. Practical applications are unknown,
except for a claim[263] that they can be transformed to pharmacologically active diben-
zo[b,d]pyrans by reaction with nucleophiles. A review article, which includes dibenzo[b,d]-
pyrylium salts, is also worthy of note.[228]
14.2.3 Dibenzo[b,d]pyrylium Salts 251
14.2.3.1.1 By Formation of One O-C and One C-C Bond
14.2.3.1.1.1 Method 1:
Ring Closure of an o-Acyloxybiphenyl Derivative with Polyphosphoric Acid
Treatment of o-acyloxybiphenyl derivative 82, formed in situ from the corresponding hy-
droxy derivative 81, with polyphosphoric acid followed by the addition of perchloric acid,
gives 11-alkylnaphtho[l,2-c][2]benzopyrylium perchlorate 83, by intramolecular Friedel–
Crafts acylation (Scheme 88).[262,265]
Scheme 88 Ring Closure of an o-Acyloxybiphenyl Derivative with Polyphosphoric

Acid[262,265]
OMe
MeO 1. R1CO2H, PPA, heat

OMe

2. 30% HClO4
OH
MeO
81
OMe OMe
MeO MeO
OMe OMe
+ ClO4−
OCOR1 O
MeO MeO
R1
82 83
R1 = H, Et
2,3,8,9-Tetramethoxy-11-methylnaphtho[1,2-c][2]benzopyrylium Perchlorate (83,

R1 = H):[262]
2-(3,4-Dimethoxyphenyl)-6,7-dimethoxy-3-methyl-1-naphthol (81; 0.50 g, 1.4 mmol) was
heated in 98% HCO2H (3 mL) and PPA (5 g) at 80 8C for 20 min and at 100 8C for 40 min.
The mixture was diluted with cold H2O and acidified with 30% HClO4. The orange crystal-
line product was collected by filtration and washed with AcOH and Et2O; yield: 0.50 g
(75%); mp >300 8C (MeNO2).
14.2.3.1.2 By Formation of One C-C Bond
14.2.3.1.2.1 Method 1:
Ring Closure of a 3-(2-Carboxymethylaryl)-2-benzopyrylium Salt with
Phosphorus Pentachloride
When 3-(2-carboxymethylaryl)-2-benzopyrylium salt 84 was treated with phosphorus

pentachloride,[266] intramolecular acylation at C4 followed by tautomerization of the
resulting ketone to a phenol gave 11-hydroxynaphtho[1,2-c][2]benzopyrylium salt 85
(Scheme 89).[266]

Scheme 89 Ring Closure of a 3-(2-Carboxymethylaryl)-2-benzopyrylium Salt with

Phosphorus Pentachloride[266]
OMe
HO2C
MeO PCl5, benzene
OMe 50 oC, 1 h
+ ClO4−
O 47%
MeO
84
HO OMe
MeO
OMe
+ ClO4−
O
MeO
85
2,3,8,9-Tetramethoxy 11-hydroxynaphtho[1,2-c][2]benzopyrylium Perchlorate (85):[266]

To a fine suspension of 3-[2-(carboxymethyl)-4,5-dimethoxyphenyl]-6,7-dimethoxy-2-ben-

zopyrylium perchlorate (84; 0.52 g, 1.0 mmol) in dry benzene (10 mL) was added PCl5
(0.50 g, 2 mmol). The mixture was stirred at 50 8C for 1 h, cooled, and Et3N (1.5 mL) was
added.
After 24 h, the product was collected by filtration, washed thoroughly with H2O, and
dried. The red-brown salt was refluxed in a large volume of AcOH containing several
drops of HClO4. The crystalline product was collected by filtration from the hot soln and
washed with hot AcOH and Et2O; yield: 0.22 g (47%); mp 298 8C (MeNO2).
14.2.3.2.1 Method 1:
By Autoxidation of a 9-Arylfluorene to a 9-Hydroperoxide
Followed by Acid-Catalyzed Ring Expansion
9-Arylfluorenes 86 undergo autoxidation in basic media to the corresponding 9-hydro-

peroxides 87, which rearrange on treatment with perchloric acid in acetic anhydride to
6-aryldibenzo[b,d]pyrylium perchlorates 88 (Scheme 90).[267]
Scheme 90 Autoxidation of a 9-Arylfluorene to a 9-Hydroperoxide Followed by Acid-Cata-

lyzed Ring Expansion[267,268]
Triton B, py, O2 60% HClO4, AcOH

−35 oC Ac2O, heat
Ar1 = Ph 63%
Ar1 = 4-Tol 54%
Ar1 H Ar1 OOH
86 87
ClO4−
+
O
Ar1
88
6-Phenyldibenzo[b,d]pyrylium Perchlorate (88, Ar1 = Ph):[267]

9-Phenylfluorene (2.0 g, 8.3 mmol) in dry pyridine (20 mL) was slowly added over 2 h to
Triton B (40% soln in pyridine, 4 drops) in dry pyridine (5 mL) at –35 8C while O2 was bub-
bled through the soln. A further 2 drops of Triton B was added after 40 and 80 min. Dilu-
14.2.3 Dibenzo[b,d]pyrylium Salts 253
tion of the mixture with H2O precipitated the hydroperoxide as a liquid that crystallized
when stirred. The crystals were separated, washed liberally with H2O, and dried in vacuo.
The crude 9-phenyl-9H-fluoren-9-yl hydroperoxide (87, Ar1 = Ph) was added to a mix-
ture of AcOH (20 mL) and 60% HClO4 (2 mL) to which Ac2O (6.8 mL) had been added with
cooling. The resulting suspension was brought to the boil and allowed to cool. The prod-
uct was collected by filtration, washed with 12% HClO4 (20 mL) and AcOH (3 mL). After dry-
ing in vacuo, it was recrystallized [AcOH (20 mL) and 60% HClO4 (2 mL) to which Ac2O
(6.8 mL) had been added with cooling], to give the perchlorate; yield: 1.84 g (63%); mp
244–244.5 8C (dec).
14.2.3.3.1 Method 1:
Nucleophilic Addition to the Carbonyl Group of
6H-Dibenzo[b,d]pyran-6-ones Followed by Dehydration
Addition of a Grignard reagent to a 6H-dibenzo[b,d]pyran-6-one 89 yields a tertiary alcohol

intermediate, which on dehydration by treatment with perchloric acid gives a 6-substitut-
ed dibenzo[b,d]pyrylium perchlorate 90 (Scheme 91).[269,270]
Scheme 91 Nucleophilic Addition to the Carbonyl Group of 6H-Dibenzo[b,d]pyran-6-ones

Followed by Dehydration[269]
R1 1. PhMgBr, Et2O, 30 min R1

2. HCl, Et2O, 0 oC
3. 60% HClO4
ClO4−
R1 = Cl 65%
+
O O
O Ph
89 90
R1 = H, Cl
2-Chloro-6-phenyldibenzo[b,d]pyrylium Perchlorate (90, R1 = Cl):[269]

To a stirred soln of PhMgBr in Et2O prepared from bromobenzene (1.55 g, 10 mmol) was
slowly added a soln of 2-chloro-6H-dibenzo[b,d]pyran-6-one (1.0 g, 4.3 mmol) in dry Et2O.
After 30 min, the mixture was poured onto ice and dil HCl, the organic phase separated,
washed with H2O, dried, and evaporated. The residue was dissolved in dry Et2O and satu-
rated at 0 8C with HCl(g), whereupon an orange precipitate formed at 0 8C but redissolved
at rt. Addition of 60% HClO4 precipitated the product; yield: 1.1 g (65%); mp 250 8C (dec)
(AcOH).
14.2.3.3.2 Method 2:
Dehydrogenation of a Dibenzo[b,d]pyran by
Phosphorus Pentachloride/Thionyl Chloride
The mechanism of this route is unknown and its scope unexplored.[270] Scheme 92 illus-
trates the application to the dehydrogenation of 6H-naphtho[1,2-c][1]benzopyran (91) to
give 92.

Scheme 92 Dehydrogenation of a Dibenzo[b,d]pyran by Phosphorus Pentachloride/

Thionyl Chloride[270]
1. PCl5, SOCl2, reflux, 5 min

2. 70% HClO4
+ ClO4−
O 74% O
91 92
Naphtho[1,2-c][1]benzopyrylium Perchlorate (92):[270]

6H-Naphtho[1,2-c][1]benzopyran (200 mg, 0.86 mmol) and PCl5 (186 mg, 0.57 mmol) in
SOCl2 (1.0 ml) were refluxed for 5 min. After cooling, dry Et2O (1.0 mL) and 70% HClO4 (5
drops) were added to the red-brown turbid soln to afford an orange precipitate. This was
separated, washed several times with dry Et2O, and dried in vacuo; yield: 210 mg (74%);
mp 150 8C (dec).
Product Subclass 4:

14.2.4
Dibenzo[b,e]pyrylium Salts (Xanthylium Salts)
Previously published information regarding this product subclass can be found in

Houben–Weyl, Vol. E 7b, pp 26–44. In this section, xanthones are denoted as 10H-diben-
zo[b,e]pyran-10-ones, and xanthenes as 10H-dibenzo[b,e]pyrans.
Dibenzo[b,e]pyrylium salts can be described by the resonance structures involving a
delocalized positive charge as shown in Scheme 93.
Scheme 93 Numbering and Mesomerism of Dibenzo[b,e]pyrylium Salts
9 10 1 +
8 2
7 + 3
O O
6 5 4
Dibenzo[b,e]pyrylium ions are planar. They are weak electrophiles and are stable only
when associated with anions of a strong acid, such as chloride, perchlorate, hydrosulfate,
etc.
Technically important pyrylium dyes[271–273] such as the rosamines can be represented
by the resonance structures in Scheme 94.
Scheme 94 Mesomerism of Dibenzo[b,e]pyrylium Dyes
+ +
R12N O NR12 R12N O NR12
1
H and 13C NMR data for dibenzo[b,e]pyrylium sulfate in sulfuric acid-d2[274,275] are shown
in Scheme 95.
1
Scheme 95 H and 13C NMR Data for Dibenzo[b,e]pyrylium Sulfate[274,275]
10.26 8.43 162.6 132.6

124.0
8.67 129.7
+ 8.15 + 145.8
O O 159.5
8.64 119.3
1H 13C
14.2.4 Dibenzo[b,e]pyrylium Salts (Xanthylium Salts) 255
In contrast to 10H-dibenzo[b,e]pyran-10-ones and 2H-1-benzopyrylium salts, dibenzo[b,e]-

pyrylium salts do not occur in nature. Reduction of dibenzo[b,e]pyrylium salts, typically
with sodium borohydride in water,[276] gives 10H-dibenzo[b,e]pyrans. Nucleophiles attack
at C10 (Scheme 96). In contrast to pyrylium salts, ring opening by nucleophiles is un-
known. Water hydrolyzes dibenzo[b,e]pyrylium salts to 10H-dibenzo[b,e]pyran-10-ols.[277]
Reaction with alcohols gives 10-alkoxy-10H-dibenzo[b,e]pyrans,[278] whereas reaction
with ammonia, primary, and secondary amines give the corresponding 10-amino com-
pounds.[279] Carbon nucleophiles such as methyl ketones,[180] and Grignard reagents[280]
also attack at C10.
Scheme 96 Nucleophilic Attack of Dibenzo[b,e]pyrylium Salts
R1 R1 Nu
NuM
X−
+ − MX
O O

14.2.4.1.1 By Formation of One O-C Bond and Two C-C Bonds
14.2.4.1.1.1 Method 1:
Use of a Reagent Providing C10 of the Dibenzo[b,e]pyrylium Salt
This method has several variations. Two phenol components are linked to form a diaryl
ether. The reagent providing the extra carbon atom could be a chloroacetaldehyde acetal,
an aldehyde acetal, benzaldehyde, an acid anhydride, or a benzoic acid precursor.[281–286]
14.2.4.1.1.1.1 Variation 1:
Introduction of C10 with 2-Chloro-1,1-diethoxyethane
Followed by Dehydrohalogenation
Annulated dibenzo[b,e]pyrylium salts can be prepared by this two-step procedure. For

example, treatment of 2 equivalents of 2-naphthol (93) with 2-chloro-1,1-diethoxyethane
yields the intermediate 94 which is then converted into the methylene derivative 96 via
the 1,5-diazabicyclo[4.3.0]non-5-ene adduct 95. Acid aromatization of 96 leads to the salt
97 (Scheme 97).[282]

Scheme 97 Condensation of a Phenol with 2-Chloro-1,1-diethoxyethane Followed by

Dehydrohalogenation[282]
concd HCl Cl 1. DBN, toluene

ClCH2CH(OEt)2 reflux, 4 h
reflux, 4 h 2. HClO4
2
73% 78%
OH O
93 94
+N
DMSO, reflux
ClO4−
~100%
O O
95 96

HClO4
ClO4−
+
O
97
14-Methyl-14H-dibenzo[a,j]xanthylium Perchlorate (97); Typical Procedure:[282]

A mixture of 2-naphthol (93; 14.4 g, 0.1 mol), 2-chloro-l,l-diethoxyethane (6.2 g,
0.041 mol), CHCl3 (20 mL), and concd HCl (6 mL) was refluxed for 4 h. EtOH (40 mL) was
added and refluxing was continued for 30 min. On cooling, 14-chloromethyl-14H-diben-
zo[a,j]xanthene (94) precipitated from the soln; yield: 12 g (73%); mp 177–178 8C.
14-Chloromethyl-14H-dibenzo[a,j]xanthene (94; 2.0 g, 6.0 mmol) was refluxed for 1 h
in toluene (10 mL) with DBN (2.0 mL, 16.2 mmol). On cooling, the toluene was decanted
from a viscous oil which was dissolved in EtOH and converted into the perchlorate of 14-
[(1,5-diazabicyclo[4.3.0]non-5-en-5-yl)methyl]-14H-dibenzo[a,j]xanthene (95); yield: 1.8 g
(78%); mp 186 8C (dec). This material was refluxed with DMSO (10 mL) for 30 min, diluted
with MeOH (75 mL) and cooled, giving 14-methylene-14H-dibenzo[a,j]xanthene (1.0 g, ca
100%) which can be converted into the xanthylium salt 97 by protonation (Section
14.2.4.3.1.4).
14.2.4.1.1.1.2 Variation 2:
Introduction of C10 with Trifluoroacetic Anhydride
In this variation, the acylating agent attacks at the ortho position to the phenolic hydroxy
group of an annulated phenol 98, followed by cyclization by double dehydration to yield
99 (Scheme 98).[283]
Scheme 98 Condensation of a Phenol with Trifluoroacetic Anhydride Followed by

Dehydration[283]
CF3
ClO4−
TFAA, TFA, HClO4 +
2 N OH N O N
74%
98 99
15-Trifluoromethyl-2,3,6,7,9,10,13,14-octahydro-1H,5H,8H,12H-bis-(quinolizino)[1,9a,9-
b,c;1¢,9¢a,9¢-h;i]xanthylium Perchlorate (99):[283]
2,3,6,7-Tetrahydro-1H,5H-pyrido[3,2,1-ij]quinol-8-ol (98; 1.9 g, 10 mmol) was stirred for
72 h in a mixture of TFAA (8.4 g, 40 mmol), TFA (0.5 mL), and CH2Cl2 (15 mL) at 20 8C under
dry N2. After concentration of the mixture under reduced pressure, EtOH (25 mL) contain-
ing 70% HClO4 (3 g) was added with stirring to give 99 as bronze colored needles; yield:
2.0 g (74%); mp 203–205 8C.

14.2.4.1.1.1.3 Variation 3:
Introduction of C10 with an Arylcarboxylic Acid Equivalent
Heating an activated phenol, for example 3-(dimethylamino)phenol (100), with (trichloro-

methyl)benzene[284] or benzil[285] gives by C-acylation, hydroxyalkylation, and cyclization
by dehydration, the dibenzo[b,e]pyrylium salt 101 (Scheme 99).
Scheme 99 Dibenzo[b,e]pyrylium Salts by Condensation of a Phenol with a Benzoic Acid

Equivalent[285]
PhCOCOPh, 100 oC, 4−5 h

2
− PhCO2H
Me2N OH 27%
100
Ph Ph
+ + Cl−
Me2N O NMe2 Me2N O NMe2
101
3,6-Bis(dimethylamino)-10-phenyldibenzo[b,e]pyrylium Chloride (Tetramethylrosamine,

101):[285]
An intimate mixture of benzil (22.0 g, 0.1 mol) and 3-(dimethylamino)phenol (100; 30.0 g,
0.22 mol) was heated under CO2 at 100 8C for 4–5 h. After cooling, the residue was treated
with warm Na2CO3 soln to remove benzoic acid. The dye was extracted with hot concd
HCl and H2O. The bulk of the product 101 precipitated from the acid soln after about
12 h. More product was salted out of the aqueous soln; yield: 10.0 g (27%); mp 258 8C (ace-
tone).

14.2.4.1.1.1.4 Variation 4:
Introduction of C10 with an Arylaldehyde
Two moles of phenol 102 condense with an aromatic aldehyde 103 to give a triphenyl-
methane derivative, which undergoes cyclization to 104 by dehydration coupled with
an unclear redox process (Scheme 100).[286]
Scheme 100 Condensation of a Phenol with an Aromatic Aldehyde Followed by a Redox

Reaction[286]
1. H2C(CO2H)2, AcOH
HO reflux, 48 h
2. HClO4
2 + Ar1CHO
Ar1 = Ph 65%
MeO OH Ar1 = 4-MeOC6H4 35%
102 103
Ar1

HO OH
ClO4−
+
MeO O OMe
104
2,7-Dihydroxy-3,6-dimethoxy-10-phenyldibenzo[b,e]pyrylium Perchlorate (104,

Ar1 = Ph):[286]
2-Methoxyhydroquinone (1.4 g, 10 mmol), benzaldehyde (1.06 g, 10 mmol), and malonic
acid (3.0 g, 29 mmol) were refluxed in AcOH (30 mL) for 48 h. After cooling, the mixture
was diluted with H2O (100 mL) and extracted with Et2O. Addition of concd HCl to the aque-
ous phase precipitated the chloride, which was separated and recrystallized (AcOH/HClO4
19:1) as orange needles; yield: 1.45 g (65%); mp 268–269 8C.
14.2.4.1.1.1.5 Variation 5:
Introduction of C10 with an Aldehyde Acetal
When the acetal of an aliphatic aldehyde is used as the C10 component, reaction with a
phenol 93 gives the isolable intermediate xanthene 105 (Scheme 101),[287] which has to be
dehydrogenated as described in Section 14.2.4.3.2.
Scheme 101 Condensation of a Phenol with an Aliphatic Aldehyde Acetal

To Give a Dibenzo[a,j]xanthene[287]
MeCH(OEt)2, concd HCl

EtOH, rt, 3 d
2
31%
OH O
93 105
14-Methyl-14H-dibenzo[a,j]xanthene (105):[287]
A soln of 2-naphthol (7.2 g, 5 mmol), 1,1-diethoxyethane (2.0 mL, 17 mmol), EtOH (20 mL),
and concd HCl (7 mL) was allowed to stand at rt for 3 d. The crystals of 105 that separated
were collected by filtration and dried; yield: 2.3 g (31%); mp 173 8C.
14.2.4.1.2 By Formation of One O-C and One C-C Bond
14.2.4.1.2.1 Method 1:
Reaction of an Activated Phenol with a 2-Hydroxybenzaldehyde
In the presence of acids strong enough to form stable salts with the product, activated
phenols (mainly substituted phloroglucinols 106) and 2-hydroxybenzaldehydes, such as
107, directly give the corresponding pyrylium salts 108 (Scheme 102). Using the same
method, benzoannulated xanthylium salts can be prepared by reacting 2-hydroxy-1-
naphthaldehydes with 2-naphthol.[288]
Scheme 102 Condensation of Activated Phenols and Aromatic 2-Hydroxybenzaldehydes

To Give Dibenzo[b,e]pyrylium Salts[276,287,288]
OH OH
H2SO4, AcOH
R1 OHC R1
rt, 17 h
+ HSO4−
R1 = H 60% +

HO OH HO R1 = Me 100% HO O
106 107 108
1,3-Dihydroxy-2-methyldibenzo[b,e]pyrylium Hydrogen Sulfate (108, R1 = Me):[276]

To a stirred soln of 2-methylbenzene-1,3,5-triol (106, R1 = Me; 1.3 g, 9 mmol) in a mixture
of H2SO4 (5 mL) and AcOH (11 mL), a soln of 2-hydroxybenzaldehyde (107; 1.06 mL,
10 mmol) in AcOH (2.7 mL) was added dropwise over 10 min. The mixture was stirred for
17 h, the light red precipitate was collected by filtration using a sintered glass funnel,
washed with AcOH/Et2O (1:1; 100 mL) and air dried; yield: 3.1 g (100%); mp 220 8C (dec).
Dibenzo[a,j]xanthylium Perchlorate:[287]
A suspension of 2-naphthol (7.2 g, 50 mmol) and 2-hydroxy-1-naphthaldehyde (8.6 g,
5.0 mmol) in a mixture of AcOH (50 mL) and 70% HClO4 (5 mL) was treated with HCl(g)
over 2 h. The mixture was allowed to stand for 2 d and the product was collected by filtra-
tion; yield: 7.4 g (39%); mp 330 8C.
9-(Diethylamino)benzo[a]xanthylium Tetrafluoroborate:[288]
4-(Diethylamino)-2-hydroxybenzaldehyde (3.86 g, 20 mmol) and 2-naphthol (2.92 g,
20 mmol) were dissolved in AcOH (40 mL) and refluxed in the presence of HBF4 (48–50%;
2 mL) for 30 min. The precipitate was collected by filtration and recrystallized (AcOH);
yield: 7.1 g (92%); mp 216 8C.
14.2.4.1.2.2 Method 2:
Dimerization of an o-Methylquinone
The methyl group of an o-methylquinone 109 undergoes addition to the double bond of
the same quinone followed by cyclization, dehydration, and aromatization by isomeriza-
tion to give 110 (Scheme 103).

Scheme 103 Acid-Catalyzed Dimerization of an o-Methylnaphthoquinone

to a Dibenzoxanthylium Salt[289]
O HO OH
HCl(g), acetone
rt, 6 h +
2 O O Cl−
94%
109 110
5,9-Dihydroxy-6-methyldibenzo[c,h]xanthylium Chloride (110):[289]

Into a soln of 2-methylbenzo-1,4-quinone (109; 10.0 g, 0.06 mol) in acetone (100 mL) was
introduced HCl(g) for 6 h with stirring. The precipitate was collected by filtration and
boiled repeatedly with EtOH to give 110; yield: 10.2 g (94%); mp ‡380 8C.
14.2.4.1.3 By Formation of Two C-C Bonds

14.2.4.1.3.1 Method 1:
C10 Introduced by Dichloromethyl Methyl Ether/Tin(IV) Chloride
Double Friedel–Crafts alkylation of a diaryl ether 111 with dichloromethyl methyl ether
in the presence of tin(IV) chloride is followed by aromatization via elimination of meth-
anol to yield 112. The site of substitution and cyclization is unequivocally defined by the
substitution pattern of the diaryl ether (Scheme 104).[281]
Scheme 104 Dibenzo[b,e]pyrylium Salts from the Reaction of a Diphenyl Ether with
Dichloromethyl Methyl Ether/Tin(IV) Chloride[281]
MeOCHCl2, SnCl4
CH2Cl2, −5 to 0 oC, 1 h
SnCl5−
50% +
O O
111 112
2,8-Dimethyldibenzo[b,e]pyrylium Pentachlorostannate (112); Typical Procedure:[281]

To a soln of di(4-tolyl) ether 111 (1.98 g, 0.01 mol) in CH2Cl2 (15 mL) at –5 to 0 8C, SnCl4
(5.0 g, 0.02 mol) was added. To the resulting highly colored soln was added dichlorometh-
yl methyl ether (1.15 g, 0.01 mol) and the mixture stirred at the same temperature for 1 h.
The orange product was collected by filtration and washed thoroughly with CH2Cl2; yield:
2.6 g (50%); mp 168–170 8C.
14.2.4.2.1 Method 1:
Thermolysis of a 1,3-Dibromo-7,7-diphenyl-
bicyclo[4.1.0]hept-3-ene-2,5-dione
Thermolysis of the adducts 114 of a bromoquinone 113 and diazodiphenylmethane

yields the dibenzo[b,e]pyrylium bromides 115 (Scheme 105).
Scheme 105 10-Phenyldibenzo[b,e]pyrylium Salts by Diphenylmethylenation of a Bromo-

quinone Followed by Thermolysis[290]
O O Ph
R1 R1 Ph
Ph2CN2 100 oC, 3 d
R1 = H 97%
Br Br Br Br R1 = Br 95%
O O
113 114
Ph
HO
Br−
+
R1 O
Br
115
4-Bromo-2-hydroxy-10-phenyldibenzo[b,e]pyrylium Bromide (115, R1 = H);

A soln of 1,3-dibromo-7,7-diphenylbicyclo[4.1.0]hept-3-ene-2,5-dione (114, R1 = H; 100 mg)
in benzene (0.5 mL) was heated in a sealed vial at 100 8C for 2 d to give the product as red
prisms; yield: 77 mg (97%); mp 340 8C (dec).
14.2.4.3.1 Method 1:
Aromatization of 10H-Dibenzo[b,e]pyran-10-ones
10H-Dibenzo[b,e]pyran-10-ones (9H-xanthen-9-ones) are an important group of plant nat-

ural products and several well-established methods are available for their synthesis (see
Section 14.4.10). Therefore the most straightforward access to dibenzo[b,e]pyrylium salts,
particularly those with several substituents, is the aromatization of 10H-dibenzo[b,e]py-
ran-10-ones. Nucleophiles add readily to the carbonyl of 10H-dibenzo[b,e]pyran-10-ones
to form 10-substituted 10H-dibenzo[b,e]pyran-10-ols that can be readily dehydrated by
treatment with strong acids to give 10-substituted dibenzo[b,e]pyrylium salts.
14.2.4.3.1.1 Variation 1:
Transformation of a 10H-Dibenzo[b,e]pyran-10-one by Protonation
Followed by Dehydration with Trifluoromethanesulfonic Anhydride
Treatment of a 10H-dibenzo[b,e]pyran-10-one, for example 116, with trifluoromethane-

sulfonic anhydride effects aromatization with concomitant dimerization to give 117
(Scheme 106).[291]
Scheme 106 Dehydration of 10H-Dibenzo[b,e]pyran-10-one by Trifluoromethanesulfonic

Anhydride to a Bis-pyrylium Ether[291]
(F3CSO2)2O, CH2Cl2 O
2 O
+ +
O 2F3CSO3−
78%
O
116 117

10-(Dibenzo[b,e]pyrylium-10-yloxy)dibenzo[b,e]pyrylium Bis-trifluoromethanesulfonate
(117):[291]
To a stirred soln of 10H-dibenzo[b,e]pyran-10-one (116; 0.98 g, 5.0 mmol) in CH2Cl2 (20 mL)
at rt, Tf2O (0.49 mL, 2.5 mmol) was added. The product precipitated within 1 min from the
yellow soln. After stirring the mixture for a further 15 min, the product was collected by
filtration, washed with CH2Cl2 (10 mL), and dried (0.03 Torr) to give 117 as a yellow pow-
der; yield: 1.32 g (78%); mp 144 8C (dec).
14.2.4.3.1.2 Variation 2:
Reduction and Dehydration of 10H-Dibenzo[b,e]pyran-10-ones
10H-Dibenzo[b,e]pyran-10-one 116 is readily reduced with sodium borohydride to 10H-di-

benzo[b,e]pyran-10-ol which gives, on treatment with a strong acid, dibenzo[b,e]pyrylium
salt 118 (Scheme 107).[292]
Scheme 107 A Pyrylium Salt by Reduction of Dibenzo[b,e]pyran-10-one Followed

by Dehydration with Strong Acid[292]

O
1. NaBH4, MeOH, reflux
2. 70% HClO4, Et2O, −78 oC
ClO4−
88% +
O O
116 118
Dibenzo[b,e]pyrylium Perchlorate (118):[292]

10H-Dibenzo[b,e]pyran-10-one (116; 5.89 g, 30 mmol) was reduced with NaBH4 (2.3 g,
61 mmol) in boiling abs MeOH (150 mL). After standard workup, the resulting alcohol
(mp 125–126 8C) was dissolved in dry Et2O (200 mL), cooled to –78 8C and treated with
70% HClO4 (20 mL) to yield the product, which was isolated by filtration; yield: 7.4 g
(88%); mp 237 8C.
14.2.4.3.1.3 Variation 3:
Addition of a Nucleophile to a 10H-Dibenzo[b,e]pyran-10-one
Followed by Dehydration
Organometallic compounds, such as Grignard reagents, readily add to the carbonyl group
of 10H-dibenzo[b,e]pyran-10-one 116 forming 10-substituted dibenzo[b,e]pyran-10-ols,
which are dehydrated by strong acids to dibenzo[b,e]pyrylium salts 119 (Scheme 108).[293]
If the organometallic compound has a hydrogen atom in the position Æ to the metal, the
intermediate alkylidene derivative can be isolated (Scheme 109).
Reaction of 10H-dibenzo[b,e]pyran-10-one with N-substituted indoles in the presence
of phosphoryl chloride also gives dibenzo[b,e]pyrylium salts. The hetarene functions as a
C-nucleophile and attacks at the activated carbonyl group.[294]
Scheme 108 10-Substituted Dibenzo[b,e]pyrylium Salts by Addition of a Grignard

Reagent to a 10H-Dibenzo[b,e]pyran-10-one Followed by Dehydration[293]
O Ph
1. PhMgBr, benzene, heat
2. 20% HClO4
ClO4−
42% +
O O
116 119
10-Phenyldibenzo[b,e]pyrylium Perchlorate (119); Typical Procedure:[293]

To a soln of 10H-dibenzo[b,e]pyran-10-one (116; 4.0 g, 27 mmol) in hot benzene, PhMgBr
[prepared from Mg (0.96 g, 0.08 g-atom) and bromobenzene (6.3 g, 40 mmol) in Et2O
(10 mL)] was added dropwise with stirring and the mixture heated. After addition of all
of the Grignard reagent, the mixture was stirred for a further 10 min and then slowly
added to 20% HClO4 (50 mL) cooled to –10 8C. After 5–6 min, an abundant orange precipi-
tate separated. This was collected by filtration and washed with EtOH and Et2O; yield:
3.0 g (42%); mp 277 8C (AcOH/MeNO2).
14.2.4.3.1.4 Variation 4:
Aromatization of a 10-Alkylidene-10H-dibenzo[b,e]pyran by Protonation
10-Alkylidene-10H-dibenzo[b,e]pyrans such as 120 and the congener 122, prepared by nu-

cleophilic addition to dibenzo[b,e]pyran-10-ones followed by dehydration, can be rear-
ranged to dibenzo[b,e]pyrylium salts 121 and 123 by protonation with strong acids
(Schemes 109 and 110).[293,295,296]
Dibenzo[b,e]pyrylium salts of the type 123 can be prepared directly from 10H-diben-

zo[b,e]pyran-10-one by a one-pot procedure via 10,10-dichloro-10H-dibenzo[b,e]pyran.[296]
Scheme 109 Nucleophilic Addition to a 10H-Dibenzo[b,e]pyran-10-one, Dehydration to a

10-Alkylidene-10H-dibenzo[b,e]pyran and Isomerization to a Dibenzo[b,e]pyrylium Salt by
a Strong Acid[295]
O
1. MeMgI, benzene, heat
2. sat. NH4Cl
O O
120
HClO4, AcOH
+ ClO4−
O
121
Scheme 110 Isomerization of a 10-Alkylidene-10H-dibenzo[b,e]pyran by a

Strong Acid to a 10-Substituted Dibenzo[b,e]pyrylium Salt[296]
Ar1 Ar1 Ar1
• Ar1
HClO4, AcOH, rt, 30 min

ClO4−
Ar1 = Ph 90% +
O Ar1 = 4-MeOC6H4 90% O
Ar1 = 4-EtOC6H4 90%
122 123
Ar1 = 4-iPrOC6H4 90%
7-Methyldibenzo[c,h]xanthylium Perchlorate (121);

7-Methylene-7H-dibenzo[c,h]xanthene (120):[295]
To a soln of MeMgI [prepared from MeI (7.0 g, 50 mmol) and Mg (0.90 g, 0.037 g-atom) in
Et2O (50 mL)] was added a soln of 7H-dibenzo[c,h]xanthen-7-one (1.0 g, 3.4 mmol) in dry
benzene (50 mL). H2O was removed from the reflux condenser, Et2O was distilled off,

and the mixture heated on a steam bath for 3 h. The mixture was allowed to stand over-
night at 25 8C, then it was poured slowly into sat. NH4Cl (50 mL) and extracted with Et2O.
The organic phase was dried (Na2SO4), the solvent removed under reduced pressure, and
the residue crystallized (benzene) to give 120; yield: 0.5 g (50%); mp 181 8C.
7-Methyldibenzo[c,h]xanthylium Perchlorate (121):[295]

7-Methylene-7H-dibenzo[c,h]xanthene (120; 1.0 g, 3.4 mmol) was heated in AcOH (10 mL)
with HClO4 (2 mL) on a steam bath for a few min, then left at rt for 1 h. The orange crystals
that formed were collected by filtration and recrystallized (MeNO2); yield: 1.3 g (ca. 100%),
mp 263–264 8C (dec).
10-Benzyldibenzo[b,e]pyrylium Perchlorate:[296,297]
To a cold soln of 10-benzylidene-10H-dibenzo[b,e]pyran (0.5 g, 1.85 mmol) in AcOH (4 mL)
and Ac2O (1 mL), 70% HClO4 (0.5 mL) was added. After 30 min at rt, the mixture was diluted
with Et2O, the precipitate collected by filtration and washed with Et2O; mp 226 8C.
10-(2,2-Diphenylvinyl)dibenzo[b,e]pyrylium Perchlorate (123, Ar1 = Ph):

To a stirred soln of 10-(2,2-diphenylvinylidene)-10H-dibenzo[b,e]pyran (122, Ar1 = Ph; 1.0 g,
3.8 mmol) in AcOH (25 mL) or MeOH was slowly added 70% HClO4 (2.0 mL). After a further
30 min stirring, the mixture was diluted with Et2O, cooled, and the crystalline precipitate
collected by filtration; yield: 1.57 g (90%); mp 181 8C.
14.2.4.3.2 Method 2:
Aromatization by Dehydrogenation of 10H-Dibenzo[b,e]pyrans
10H-Dibenzo[b,e]pyrans can be oxidized by several oxidants to give dibenzo[b,e]pyrylium

salts.[291,298–301] In the presence of a strong acid, 10H-dibenzo[b,e]pyran is oxidized by oxy-
gen to the pyrylium salt. On treatment with lead(IV) oxide, the 14H-dibenzo[a,j]xanthenes
124 first give the alcohols 125, which are then dehydroxylated with a strong acid to the
xanthylium salts 126 (Scheme 111).[299]
Scheme 111 Oxidation of a Dibenzo[a,j]xanthene to a Dibenzo[a,j]xanthylium Salt with

Lead(IV) Oxide[299]
Ar1 PbO2, AcOH

Ar1 OH
heat, 3 h
O O
124 125
Ar1
HClO4, Ac2O, benzene
Ar1 = Ph 78% ClO4−

Ar1 = 4-MeOC6H4 82% +
Ar1 = 4-O2NC6H4 65%
O
126
10H-Dibenzo[b,e]pyrans can be converted into dibenzo[b,e]pyrylium salts by triphenyl-

carbenium perchlorate.[300,301]
Dibenzo[b,e]pyrylium Perchlorate:[298]
To stirred Ac2O (264 g, 2.58 mol) cooled in ice was slowly added 72% HClO4 (100 mL,
1.20 mol). During this procedure, the temperature did not fall below 30 8C. The mixture
was diluted with AcOH (200 mL, 3.5 mol), placed in a vessel with a sintered glass bottom,
kept at 30 8C and oxygen was bubbled through the soln. 10H-Dibenzo[b,e]pyran (14.6 g,
0.08 mol) and FeCl3 (3.2 mg) dissolved in AcOH (500 mL) were added. During the autoxida-
tion, the temperature rose to 33 8C, crystals separated from the soln and after 45 min, the
mixture turned brown. The mixture was diluted with dry Et2O (3 L) and the product was
collected by filtration; yield: 18.2 g (82%); mp 225–226 8C.
14-Phenyldibenzo[a,j]xanthylium Perchlorate (126, Ar1 = Ph); Typical Procedures:[299]
14-Phenyl-14H-dibenzo[a,j]xanthen-14-ol (125, Ar1 = Ph):

14-Phenyl-14H-dibenzo[a,j]xanthene (124, Ar1 = Ph; 20.0 g, 56 mmol) and PbO2 (20 g,
83 mmol) were heated in AcOH (500 mL) with stirring on a water bath for 3 h. After cool-
ing, the mixture was poured onto ice, the product collected by filtration and recrystal-
lized (acetone); yield: 19.8 g (95%); mp 264–266 8C.

14-Phenyldibenzo[a,j]xanthylium Perchlorate (126, Ar1 = Ph):
To a cooled soln of 14-phenyl-14H-dibenzo[a,j]xanthen-14-ol (125, Ar1 = Ph; 20.8 g,
53.4 mmol) in a mixture of Ac2O (150 mL) and benzene (50 mL) was added 70% HClO4 (ca.
25 mL) until precipitation was complete. The product was collected by filtration, washed
with dry Et2O and recrystallized (MeNO2); yield: 19.3 g (78%); mp >300 8C.
Dibenzo[b,e]pyrylium Perchlorate:[300]
10H-Dibenzo[b,e]pyran (182 mg, 1 mmol) and triphenylcarbenium perchlorate (343 mg,
1 mmol) were heated in AcOH (10 mL) for 2 min. After cooling, the precipitate was collect-
ed by filtration and recrystallized (AcOH) to give bronze plates; yield: 190 mg (68%); mp
225–226 8C.
14.2.4.4 Synthesis by Substituent Modification
14.2.4.4.1 Method 1:
Alkylation of Xanthylium Salts in the Pyrylium Ring
Reaction of the xanthylium salt 127 with benzotriazolyl sodium gives a 1H-benzotriazol-
1-yl derivative 128, which may then be alkylated to give 129. Treatment of 129 with per-
chloric acid removes the benzotriazolo group and leads to the alkylated xanthylium salt
130 (Scheme 112).[288]

Scheme 112 Alkylation of a Xanthylium Salt via a Benzotriazol-1-ylxanthene

Intermediate[288]
N
N
THF N
N 20 min
+ N
− NaBF4
BF4− −
N
+ 91%
Et2N O + Et2N O
Na
127 128
N
1. BuLi, THF N
−78 oC N ( )11 ( )11
2. Me(CH2)11Br HClO4
ClO4−
+
Et2N O Et2N O

129 130 87% (from 36)
12-(1H-1,2,3-Benzotriazol-1-yl)-N,N-diethyl-12H-benzo[a]xanthene-9-amine (128);
To a soln of 1H-1,2,3-benzotriazole (1.19 g, 10 mmol) in dry THF (50 mL) was added NaH
(60% in mineral oil; 0.40 g, 10 mmol). The mixture was stirred at rt for 20 min before por-
tionwise addition of 9-(diethylamino)benzo[a]xanthylium tetrafluoroborate (127; 3.85 g,
10 mmol). After stirring for 20 min, the inorganic salts were removed by filtration, the sol-
vent removed under reduced pressure, and the residue recrystallized (MeOH) to give the
product; yield: 3.8 g (91%); mp 205 8C.
9-(Diethylamino)-12-dodecylbenzo[a]xanthylium Perchlorate (130); Typical Procedure:[288]

To a soln of benzotriazolylxanthene 128 (5.25 g, 1.25 mmol) in dry THF (30 mL) at –78 8C
was added 1.6 M BuLi in hexane (0.78 mL, 1.25 mmol). The soln was stirred at –78 8C for
30 min before adding 1-bromododecane (3.1 g, 1.25 mmol) in THF (10 mL). The mixture
was stirred overnight and allowed to reach rt before being quenched with sat. NH4Cl
(40 mL) and extracted with Et2O (2 30 mL). The combined organic extract was washed
with brine and H2O and dried (MgSO4). The solvent was removed under reduced pressure,
the residue dissolved in AcOH (20 mL), and 70% HClO4 (0.4 mL) was added. The product
was precipitated by the addition of H2O (50 mL), isolated by filtration, and recrystallized
(AcOH/MeNO2 10:1); yield: 6.1 g (87%); mp 171 8C.
References 267
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Benzopyrylium Ions PDF

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201

14.2 Product Class 2:

14.2.1 Product Subclass 1:

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Scheme 1 Trivial and Systematic Names for Some 1-Benzopyran Derivatives

2H-1-benzopyran-2-one 4H-1-benzopyran-4-one 2-aryl-4H-1-benzopyran-4-one 2-aryl-1-benzopyrylium salt

Scheme 2 Resonance Structures and Numbering of 1-Benzopyrylium Salts

for references see p 267

Scheme 3 Hydrolysis of 1-Benzopyrylium Salts to Pseudo Bases[5]

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Scheme 4 Deprotonation of 2- and 4-Hydroxy-1-benzopyrylium Salts[8–10]

Hydrolysis of 1-benzopyrylium salts gives 2-hydroxy-2H-1-benzopyrans, called pseudo

Scheme 5 Hydrolysis and Deprotonation of 1-Benzopyrylium Salts

The UV spectrum of 1-benzopyrylium perchlorate has an intensive band at 349 nm (log

Scheme 6 Characteristic 13C NMR Signals for 2-Phenyl-1-benzopyrylium Perchlorate;

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14.2.1.1 Synthesis by Ring-Closure Reactions

14.2.1.1.1 By Formation of One Heteroatom-Carbon and One C-C Bond

Scheme 7 Three-Carbon Components Suitable for Reaction with Phenols

3-oxocarboxylic esters 3-oxocarbonitriles alkane-1,3-diones 3-alkoxypropenals

for references see p 267

Scheme 8 Reaction of a 3-Oxocarboxylic Ester with Polyphenols[32]

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On reaction of ethyl 2-(ethoxymethylene)-3-oxobutanoate with a phenol, it is the enol

Scheme 9 Reaction of a Phenol with Ethyl 2-(Ethoxymethylene)-3-oxobutanoate[34]

3-(Ethoxycarbonyl)-7-hydroxy-2-methyl-l-benzopyrylium Perchlorate (2, R1 = OH);

1-Aryl- and 1,3-diaryl-1,3-diketones, as well as 3-aryl-3-oxoaldehydes, are widely used as

Scheme 10 Reaction of 3-Aryl-3-oxopropanals with Phenols[9,35–37]

4-Aryl-2,4-dioxobutanoic acids react with phloroglucinol-type phenols to give moderate

Scheme 11 Reaction of Phenols with 4-Aryl-2,4-dioxobutanoic Acids[32,39]

HO2C AcOH, HCl(g)

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1,3-Diphenylpropane-1,3-dione reacts with resorcinol and derivatives in the presence of

Scheme 12 Reaction of Phenols with the Boron Trifluoride Complex of a

for references see p 267

An oxonium salt may serve as an equivalent of a 1,3-diketone (Scheme 13).[42] Condensa-

Scheme 13 Condensation of a 2-Hydroxybenzaldehyde with the Oxonium Equivalent of a

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4-Carboxy-5,7-dihydroxy-2-phenyl-1-benzopyrylium Chloride [4, R1 = 5,7-(OH)2; R2 = H];

2-(Biphenyl-4-yl)-7-methoxy-4-methyl-l-benzopyrylium Perchlorate (5, R1 = 7-OMe;

6-Methoxy-2-(2-oxo-2-phenylethyl)-1-benzopyrylium Perchlorate (6); Typical Procedure:[42]

Reaction of a 3-(dialkylamino)phenol with 3-aryl-3-chloroacrolein in the presence of per-

1-Arylprop-2-ynones are synthetic equivalents of 1,3-diketones and can be condensed

Scheme 14 Reaction of Phenols with Ethynyl Ketones[49,50]

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5,7-Dimethoxy-2-(3,4-dimethoxyphenyl)-1-benzopyrylium Chloride (Luteolinidine Tetra-

Reaction of vinyl ketones, particularly 1,3-diarylpropen-2-enones (chalcones), with phe-

for references see p 267

Scheme 15 Reaction of Phenols with Chalcones[52–54]

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An analogous procedure using monoaryl prop-2-enones yields 2-phenyl-1-benzopyrylium

2,4-Diphenylnaphtho[2,1-b]pyrylium Tetrafluoroborate [8, R1 = 6,7-(CH=CH)2; R2 = R3 = H;

Acid-catalyzed condensation of free Æ-methylene aldehydes with 2-hydroxybenzalde-

Scheme 16 Reaction of 2-Hydroxybenzaldehydes with Æ-Methylene Aldehyde Acetals[56,57]

3-Phenylnaphtho[1,2-b]pyrylium Perchlorate [9, R1 = 6,7-(CH=CH)2; R2 = Ph];

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While condensation of 2-hydroxybenzaldehydes with dialkyl ketones is only successful

Scheme 17 Reaction of 2-Hydroxybenzaldehydes with Acetophenones[16,63–65,264,302,303]

for references see p 267

2-(3,4-Dihydroxyphenyl)-7-hydroxy-1-benzopyrylium Chloride [10, R1 = 7-OH;

2-(4-Aminophenyl)-6-nitro-1-benzopyrylium Perchlorate (10, R1 = 6-NO2; R2 = 4-NH2;

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Reaction of 2-hydroxybenzaldehydes with ø-substituted acetophenones gives 2-aryl-3-