QUINODIMETEIANE CHEMISTRY

TIIE GENERrlTION AND TRAPPING OF QUINODIIV~ETI-IANESFROM SUBSTITUTED

AROJItLTIC IIYDROCARBONS WITI-I HIGH-POTENTIAL QUINONES

J . W. Lo~vwAXD A. S. I<. A r ~ o o
DeQai.title?~tof' Cheiizistry, Univeisily of' Alberta, Edt7zot110~1,
illberta
Received June 17, 1'366
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9,lO-Dimeth~lanthmccne and 9,10-dimethyl-9,10-dihydroanthracene react with 2 and 3

moles, respectively, of tetrachloro-1,2-be11zoquinone to give the same 1 : l adduct of '3,lO-anthra-
quinodimethane with the quinone, the structure of nlhich IVCIS proved b y ozonolysis. A . lower
limit for the rate of adduct formation in 1,2-dichlorobenzene a t SO0 is 4.22 X 10-2 1 mole-' s-1.
7,12-Dinleth) I b c n ~ a n t h r a q ~ i i n o d i ~ n ewas
t h e generated in a similar way and the structure
of the 1:l adduct proved by ozonolysis and by Inass spectrometry. The reaction of 9,lO-a~lthra-
qui~loditiiethanewith a p-quinone gave a 1:2 adduct. '3-Methylanthracene reacts with high-
potential quillones by hydride abstraction a t the methyl group with the formation of an ether.

Quinodimethanes or ;b-xylylenes are of considerable interest both from the theoretical

and experimental standpoints. The first evidence of their existence was obtained from the
pyrolysis of p-xylene (1, 2), and subsequent investigations of the pyrolysis of related
Can. J. Chem. 1966.44:2507-2515.

coillpounds proved that analogues of ;b-xylylene can be produced by siillilar techniques

(2-5). More recently, p-xylylenes have been produced as reactive intermediates by the
reaction of nlagnesiunl wit11 4-111et11oxyi11etl~~~lbei~zyl
chloride (6) and the decoillposition
of trimet11~1-4-11~etl1ylbei1zyla~llinoniu~llhydroxide (7-10). Errede and Landrum (11)
discovered that solutions of p-xylylene are relatively stable a t low temperatures. That
9-xylylene exists in the quinodiillethane forill I rather than as a diradical I1 is s h o ~ by
~ ~its
n
spectra and its diamagnetism. I t is extremely reactive and polyillerizes readily, but con-
trolled polymerization leads to coillpounds of low molecular weight, including [2,2]-
paracyclophane.

Recently, a novel method llas been introduced by Millar and Wilson (12, 13) and Stille
and Foster (14), namely, the dehydration of the appropriate tertiary diols in high-boiling
solve~ltssuch as diethyl phthalate. In this way, quinodinlethanes derived froin the anthra-
cene and phenantllrene series have been generated and trapped by dienophiles, such as
maleic anhydride, benzoq~~inone, and dimethyl acetylene dicarboxylate.
An interest in the homogeneous dehydrogenation of hydroaroinatic coinpounds with
high-potential quinones (15) led us to investigate the dehydrogenation of aromatic hydro-
carboils as a method of generating quinodimethanes.
'The driving force for the hydrogen transfer reaction, represented schematically below,

Canadian Jour~ralof Chemistry. Volurne -14 (1966)

2507
 2505 C.-\NADIAN JOURNAL O F CHEMISTRY. VOL. 4-1, 1906

is provided by the gain in resonance energy of both reactants (15). ;\Iolecular orbital
calculations predict that the resonance energy of P-xylylenes is conlparable I\ ith that of
the beiizenoid precursor (16) (e.g. 9-xylylene itself has a resonance energy of 3S kcal/mole
compared \\it11 ca. 36 kcal/mole for ;h-xylene). Therefore, the dehydrogenation of a
dimethyl aronlatic hydrocarbon to a quinodimethane is energetically feasible. The
generating reactant also acts as a dienopllile, and therefore \\.ill trap the quinodimetl~ane.
Since the reaction is homogeneous, unlike the various methods described above, order-of-
magnitude estimates may be made of the rate of the reaction bet~veenthe quinodimethane
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and the dienophile, as sllown beloxv. By using different quinones, illlorination is obtained
on the steric requirements of the subsequent reactions.
9,10-A~ztl~raq~~i~zodimetlzane
Previous attempts to prepare anthraquinodimetliane by tlie pyrolysis of 9,lO-dimethq-l-
anthracene were unsuccessful (2). Dehydration of 9,10-dimethyl-9,10-dihq-drox~~-9,10-
dihydroanthracene in boiling diethyl phthalate in the presence of a dienophile gave
1 : l or 1:2 adducts (13, 17). We have observed that cis-9,10-dirnethyl-9,10-dihq-dro-
anthracene (18) reacts readily with 3 moles of tetracl~loro-1,2-be1~zoq~1iiione and that the
reaction is not confined to a simple dehydrogenation to 9,10-di111et11yla11t11race11e, The
product mixture Ivas complex, hut by repeated chroiiiatographg~in benzene on aluiiiina a
Can. J. Chem. 1966.44:2507-2515.

colorless crystalline compound, C221-112C1402, could be isolated in a pure form in a 16.2%

yield. The lo\\; yield reflects the difficulty of separation from other components of high
n~olecular\\-eight (estimated ca. SSO), presumably arising from rapid polymerization of
the aiithracl~~inodimethane, as has often been observed in other methods of gelleratiilg
this type of intermediate (1,2, 13, 14).
The nuclear magnetic resonance (n.m.r.) spectrum of the compoiulid exhibited singlets
which \\-ere each equivalent to t\\-o protons in the regions characteristic (10) of olefinic
protons and protons of tlie type -CI-12-0-, respectivelj-. There \\-as also a complex
band arising froiii eight aromatic protons. The infrared spectrum contained 110 bancls
attributable to carbonyl stretching, but exhibited a very strong band a t 1 4 2 2 cm-I
characteristic of a tetrachlorobenzodioxin (20). The ultraviolet spectrum was compatible
I\-ith the presence of a 1,l-diphenlllethyle~iechromophor. This evidence leads to tlie
forlnulation IV as the structure of this compound, and its formation is attributed to the
addition of 1 mole of tetrachloro-l,2-benquinonc to the carbon-carbon double bo~lcla t
the 9 position of the anthraquinodiinethane intermediate.

The structure \\-as confirmed by ozonolysis, \\-hich gave formaldehyde (isolated as the
dimedone derivative) and a yellow solid V, C21I-IloC1403, the n.m.r. spectruni of \vllicl~
rcscmbles that of IV except for the absence of the olefinic band. The infrared spectruiil of
17 shows a strong carboiiyl absorption, as expected.
9,lO-Dimethylantliracene similarly reacts \\-it11 2 llloles of tetrachloro-l,2-benzoquinone
to give IV as tlie main isolable product. The deep-red color of the quinone allo~vsmeasure-
n~eiitof the reaction rates by a simple spectrokinetic procedure, the details of ~vhiclihave
 LOWN A N D AIDOO: QUISODIIVIETI-IANE CHEMISTRY 2509

been presented else\\-here (21). I t was thus sllo\vi~that cis- and trans-9,lO-dimethyl-9,lO-
dihydroanthracene undergo rapid, triply consecutive, second-order reactions with 3 moles
of the quinone, with a relatively slow initial step. T h e reaction of 9,1O-diinetl~g~lanthracei1e
and tetracl1loro-1,2-benzoquinoi~e, n-hich n.as bimolecular, consecutive second order n it11
a fast second step (i.e. Diels-Alder reaction of the quinodimethane \\-it11 tlie quinone),
was 30-GO times faster than the reaction of the dihydrodiilietl~ylanthracenes.
On the basis of the evidence of the isolated product and the rate d a t a , the follon ing two
series of reactions can be postulated.
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Scheme 1 Scheme 2

ky a ~ k3~ >d> kl k2 and ks >> k l

III-14 represents 9,1O-dil1g;dro-9,lO-dii1ietl~g~lai1tl~racene,
RI-I? represents 9,lO-dimethg.l-
anthracene, R represents 9,10-anthraquinodiii1ethane, and IiQ represents the isolated
Can. J. Chem. 1966.44:2507-2515.

product IV. Scheme 1 implies the formation of a n interiilecliate Diels-Alder addition

compound (III-12Q)of 9,lO-dimethylantl~raceneand tetrachloro-l,2-benzoquinone, which
is then attaclied a t the CI-13groups by a further molecule of quinone with the formation of
IV. Scheme 2 represents the siillpler mechanisin, in \vllich 9,10-dimcthyla1~tl1raceiieis
dehydrogenated directly to the 9,lO-antllraquinodii~lethane (I?), which undergoes Diels-
Alder addition \\/it11 the quinonc t o yield IV. Scheme 1 is rendered unliliely by the
following observation. 9,10-Dii~ietl1yl-9,1O-dilig~dro-9,lO-etl1ai1oantliraccne-ll,l~-dicar-
boxylic anhydride (i.e. the Diels-Alder aclclitioil compound of 9,10-~1i111et11ylanthrace11e
and maleic anhydride), in \vhich tlie C H 3 groups are in an environment similar t o that in
tlie hypothetical intermediate RI-12Q, is completely inert t o the action of tetrachloro-
1,2-be1lzoquinone in 1,2-dic11lorobenzeiie a t 101° for 44 h. Since the rate d a t a obtained
are consistent only when kg is much greater than k1, scheme 1 is rejected; the results are
therefore interpreted in terms of scheme 2 involving the intermediacy of 9,lO-antlira-
quinodimethane (see Experimental). Therefore, a lower limit for the reaction rate of
9,lO-antliraquinoclimetliai~e~ v i t htetracl1loro-l,2-benzoquii1o11e in 1,2-dichlorobeuzene a t
SO0 is 4.22 X lop21 mole-' s-I.
T h e reaction of anthraquinodimetlia~~e, generated in sitll. by refluxing 9,lO-dimetliyl-
9,10-dil~ydroxy-9,lO-dihg~droai~tl~racene in ethyl phthalate, ~ v i t htetracl1loro-l,2-bcnzo-
quinone led only to tars. This result is not unexpected since the cl~loroquinoneis sensitive
to water and can undergo a variety of side reactions.
7,l%Be~zza~ztlzraq~~inodinzethane
7,12-Dimethylbenzanthracene reacted readily with tetrachloro-l,2-benzoquinoncin
benzene, and the main product was a colorless crystalline solid, C2GE11~02C1,1,the spectral
properties of which confirmed a 1:l adduct of bei~zanthracei~equinodiinetl~ai~e and tetra-
chloro-1,2-benzoquinone.Considerations of steric hindrance predict an orientation for
the quinone a t the double bond r e ~ n o t efro111 the fused benzo ring correspondi~lgto VI.
This assignment is supported by the n.1n.r. spectrum, ~vhichshows the olefinic protons to
be non-ecluivalent oving t o the different effects of the ring current froin the angular
benzene ring, in contrast to the equivalent protons shown by IV. Treatnle~ltwith ozone
 2310 CAXADI.4S JOURNAL O F CHEMISTRY. VOL. 44, 1960

folloxved by decoriiposition of the ozonide with steain gave a yello~vsolid, the i1.ni.r.
spectruili of \vhicli showed the absence of vinyl protons; the infrared spectrum shoxb-ed a
ne\v carboiipl. Mass spectronietry showed a inolecular ion pealc measuring 499.0543,
compared with 499.9540 calculated for C251-11203C14. A strong peak in the spectrum at
m/e 256 n-as expected and is due to the following fragiiientatioii.
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This iiiterpretation is based on the very recent analogy provided by the mass spectrulii
of an adduct of tetrachloro-1,2-bciizoqi1inone and abietic acid (22).

Reuctions witlz Otlze~Quinones

Can. J. Chem. 1966.44:2507-2515.

I t \\-as anticipated that the reaction of ~uiitliraquinodiiliethanewith a p-quinone would

give rise to different adducts owing to tlie different geometrical requirements of the
dienophile. 9,10-Dimctliylantliracene reacts very readily \\-it11 2,3-dicliloro-5,B-dic~.aiio-
bcnzoquinone, and a bright-yelloxv solid, C321-112N.IC110,1, nras isolated from the reaction
mixturc. Tlic infrared spectru~ilexhibited bands characteristic of C-S and cnedione
groupings. Thc n.m.r. spectrunn (Fig. 1) x v ~ scoinpatible \\-it11 structure VIII, i.e. a

4,s-benzpyrene slceleton. The structure is analogous to similar 1:2 adducts obtained by

filIillar and Wilson by the reaction of anthraquinodimethane, generated by the dehydration
of 9,lO-dimethyl-9,10-dihydroxy-9,10-dihydroanthracene, with various dienophiles (12,
13).The simplicity of the n.li1.r. spectruiil supports the proposed 4,5-benzpyrene structure,
which has a plane of symmetry, if the quinone rings are cis to one another and if both are
cis-fused a t the carbons bearing the nitrile groups (as expected) or, less likely, symmetri-
cally trans-fused. The orientation of tlie 33-dicliloro-5,6-dicyanobenzoquinone ~iloieties
 LOWN A N D AIDOO: QUINODIMETHANE CHEMISTRY 2511

is based, by analogy, on the studies of Ansell (23), in which the powerfully electron-
attracting nitrile groups so enhance the dienophilic character of the double bond to u-hich
they are attached that addition taltes place exclusively a t this bond. Attempts to prove
this point by the base-catalyzed elimination of hydrocyailic acid were unsuccessful owing
to thc general lability of the substance towards the action of strong bases.
CI
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CN CN

IX

The reactivity of the 9-methyl group in anthracene derivatives towards hydride

abstraction is not confined to 9,lO-disubstitutcd compounds. 9-Methylanthracene reacted
readily with 2,3-dichloro-5,6-dicya1~obe1~zoquinone and gave a yellow solid, C3gI-I22C12N20?,
the infrared spectru~nof which sho\\-ed bands characteristic of ether and nitrile linkages.
Can. J. Chem. 1966.44:2507-2515.

The material is assigned structure IX by analogy with a similar ether obtained by the
reaction of 2,2-dirnethylindane with the same quinone (20), and the structure was proved
by clcavage of the ether linltage with hydriodic acid and reduction of the resulting
9-iodon~ethyleneanthracenewit11 lithiunl aluillinium hydride to 9-methylanthracene.
Thc scope of the above method of generating 9- and o-quinodiinethanes in other systems,
particularly the phenanthrene and acepleiadylene series, is being investigated.

EXPERIMENTAL
Melting points were talcell on a Fisher-Johns apparatus and are uncorrected. Infrared spectra were
recorded on a Perkin-Elmer model 421 spectrophotometer. Only the principal, sharply defined peaks are
reported. Nuclear lnagnetic resonance spectra were recorded OII a Varian )\-GO analytical spectrometer
operating a t a hxed radiofrequency of GO Mc.p.s. The spectra were measured on a n approximately 15%
(w/v) solution in a n appropriate solvent, with tetramethylsilane a s a standard. Line positions are reported
in parts per million from the reference. Absorption spectra were recorded in 'spectrol-grade solvents on a
Beclanan DB recording spectrophotorneter. Mass spectra were obtained on an i\EI-MS-9 high-resolution
mass spectrometer. Microanalyses were carried out by Dr. C. DaesslC, Organic Microanalyses Ltd., Montreal,
Quebec, and by Miss D. Roberts, Microanalytical Laboratory, Chemistry Department, University of Alberta,
Edmonton, Alberta.
Renctio?~of 9,10-Di111ethylnntltracemzvitJz Tetraclzloro-1,d-brnoqziinone
:\ mixture of 4.506 g (0.022 mole) of 9,1O-dimethylanthrace11eand 10.822 g (0.044 mole) of tetrachloro-
1,2-benzoquinone in 100 ml of sodium-dried benzene was refluxed under nitrogen for 2 days, cooled, diluted
~ v i t h150 1111 of IZ-hexane, and filtered to remove hydroquinone. The filtrate was concentrated i n uaczlo t o
ca. 40 ml and passed down a colurnr~of grade I alumina to remove hydroquinone and unreacted quinone.
Elution with 1:l benzene-n-hesane and evaporation of the solvents gave a pale-yellow crystalline solid
(2.3 g) as the first fraction. Careful chromatography of this fraction on alu~ninain 1:2 benzene-n-hexane
gave, as the main component, a colorless crystalline solid (1.75 g, 18% yield), which was purified by recrystal-
lization frorn ethyl acetate, m.p. 240" fdecomp.).
;\rial. Calcd. for C??I.I13ClJO2(450.12): C, 58.6; 1-1, 2.9; C1, 31.50. 1;ound: C , 58.4; 1-1, 3.2; Cl, 31.9; ~nol.wt.
(ebullioscopic in benzene) 444.4.
Infrared spectrum: vmoX (CHC13) 1 422 cm-I (s) (characteristic (20) of a six-membered tetrachlorobenzo-
dioxan structure) ; no absorption in the region expected for 013 or C=O. Nuclear magnetic resonance spectrum
(CDCI3):5.80 (2H, singlet, vinyl protons), 3.94 (213, singlet, -CI-12-0), 7.44 (81-1, complex aromatic absorp-
tion). Absorption spectrunl (cyclohexane): A, 302 mp (log e 3.48), 253 mp (sh) (log e 4.20), 230 mp (sh)
(log c 4.69).
Subseque~ltfractions of the chromatogram consisted of mixtures of minor, higher molecular weight, colored
products which could not be separated.
 2312 C.\NADI:\?: JOURS.\I, OF CI-IISMISTRY. VOL. '14. 1966

Reaction betwecn cis-0,10-Din!etl~yl-9,10-dihydroanthrc~ce1len?zd Tetrnclrlo~o-1,R-benzocjz~ino?~e

A mixture of 1.032 g (0.004s mole) of cis-9,10-dimethyl-9,10-dihydro~i1~thrce1e (obtained by the reductio~l
of !),l0-dimethylanthracene with sodiunl and ethanol (18) and 3.786 g (0.0154 mole) of tetrachloro-l,2-
belizocl~iinonein 30 ml of d r y benzene was refluxed for 12 h, then cooled, diluted wit11 100 ml 72-hexane, and
filtered. The filtrate mas concentrated to ca. 40 ml and passed down a colu~unof grade I alumina. Elution wit11
1: 1 benzene-n-hesane and evaporation of the eluatc gave a yellow solid (0.52 g), shown by thin-layer chroma-
tography to be a mixture. Careful re-chrornatogr;lphy of this fraction on alumitla in 1:2 benzene-72-hesane
gave, a s the main component, a colorless crystalline solid, \vhich was purified by recrystallization from cth!.[
acetate (0.35 g, 16.27; yield), m.p. 240°, mixed m.p. with the pure product isolated from the previous
reaction 240". 'The spectral properties of the two sainples werc identical.
Again, subsequent fractions of both chromatograms proved to be conlplex misturcs of high niolecul;lr
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weight con~ponenis,and no attempt was made to separate them.

Ozonolysis of the Addz~ctof Antl~rngr~i?zodi~~zetlza?~e a?td Tetracl~loro-1,2-be?tzogr~iwons

A slow strcam of d r y ozone (fro111a Welsbach T-23 ozorlator) was passed successively through a solutioll
of 223 mg (0.0005 mole) of the adduct dissolved in SO ml cthyl acetate in a 250 nll Dreschel bottle and a
second bottle containing 50 1111 of water, until ozone was detected irl the efluent with moist starch - potassiun1
iodide paper. T h e two liquids were combined and subjected to steam-distillation; a yellow solid separated
in thc flask. 'I'he steam-distillate \\,as ~ n a d eneutral to phenolphthalein, and a solution o f 3 g of 5,5-dimethyl-
1,::-cyclohexanedione in 50 nil of 50% ethanol added. After 60 mi11the precipitate of formaldehyde dirnedo~le
was collected, washed \\;it11 5 mi of 20% aqueous ethanol, and dried (0.102 g, 0.7 mole).
'The yellow solid \\,as collected, dried, and purified by recrystallization from acetonitrile (0.180 g,
yield), n1.p. 270°.
Anal. Calcd. for C?lI-lloOaCl.~: C, 55.7!); I-I, 2.23; CI, 31.36. Fourtd: C , 55.81; I-I,2.45; CI, 31.05.
Infrared spectrum: u,,,;,, (KBr disk) 1 4 2 2 cm-I (s') (characteristic of a six-membered tetrachlorobenzo-
Can. J. Chem. 1966.44:2507-2515.

dioxin structure ("O)), 1 672 cm-I (CEO stretching). Nuclear magnetic resonance spectrum (CDCI,): 4.06
(21-1, singlet, -C1-120-), 7.45 (81-1, complex aromatic absorption) ; no vinyl absorption was present. Absorp-
tion spectrum (CI-13CS):A,,,.,3.05 mp (sh) (log t 3.4i?),264 m p (log eI.GS), 230 nip (sh) (log s 4.35).

Reaction of 7,12-Di1rrethylben:n?ztI~rc~cc?~e and Tetrc~clzloro- 1,2-6e?~zoq~~inone

t\ solution of 1 g (0.0032 mole) of 7,12-dinlethylbe11zt~11thracene and 2.0G g (0.0084 molc) of tetracllloro-
1,2-benzoquinone in 2U tnl! of d r y benzene xvas refluxed for 3 days, then cooled, and chromatographed on grade
I alu~niila.'The columil was developed and eluted with 1 : l benzene-71-hesane. Evaporation of thc first
fraction gave a pale-yello\v cr)~stullinesolid, which gave a single spot 011 thin-layer chromatography in a
varicty of solvents and was recr)~st;lllized from 1 : l benzene-n-hex;~ne,,n1.p. 247O (deconlp.) (0.375 g, 19%
yield). Subsequent chro~uatographic fractions gave a yellow material, which was shonr11 by thin-la).er
chromatography t o be a complex mixture of minor products which were not investigated further.
'-1nal. Calcd. for C ~ G I - I ~ ~ O ?C,
C I62.23
. I : ; I-I, 2 . S ; CI, 28.77. Fo~und:C, 62.57 ; I-I,2.70 ; C1, 28.90.
I~ifrarcdspectru~n:~,,,!,,(CI-ICla) 1 222 cm-I (s) (cl~aracteristicof a sis-~nemberedtetrachlorobe~~zodiosan
structure ('20)). Suclenr magnetic resonance spectrum (CDCI3): 4.10 (21-1, singlet, -CIH2-0), 5.93 and 6.12
(11-1, each narrow doublets, Jab < 1 c.p.s., vinyl protons), 7.30-5.00 ( l o l l , complex aromatic absorption).
Absorption spectrum (cycloherane): A,,;,, 30'3 rnp (log e 4.07), 290 111p (sh) (log e 3.I)S), 232 mp (log e 4.86).

Ozo?zolysisof tlte Addnet of Bertzantltrc~pri?zodi~~~etltc~?ze

a?td Tetrcrcl~loro-1,b-belazog~rino?ze
A solution of 47 mg (0.000095 mole) of the adduct in 70 ~ n of l ethyl acetate was subjected t o ozo~~olysis
under conditions similar to those described for the a n t h r a q u i n o d i ~ ~ ~ e t hadduct.
a ~ ~ e Deconlposition of the
ozonide ~ v i t hsteam gave a yellow crystalline solid (27 mg, 51% yield), 111.p. 253'. 'l'he mass spectrum sho\vcd
a parent peal; with a n isotopic pattern typical of four chlori~lcatoms, measured a s 499.934:; (calcd. for
C?sI-11.'03Cll:499.0540). A strong peak a t ~ ~ r 256 / e was caused by the retro-Diels--<llder fragmentation typical
of this type of adduct, asdescribed in the Discussion.
Infrared spectru~n:u,,, (ICBr disk) 1 4 2 2 cm-I (s) (characteristic of a six-membered tetrachlorobe~izo-
dioxin structure (20), 1 670 c~n-I(C=O). Nuclear magnetic resonance spectrum (CDCI3): 4.16 (21-1, singlet,
-CI-I-0-), 7.3-8.1 (101-1, complex aromatic absorption); no vinyl absorption was present. .Absorption
spectri~nl(Ck13CN): A,, 292 mp (log ~ 3 . 5 5 )258
, mp (sh) (log e 3.59), 232 mp (sh) (log t 3.99).

Reacbion of 9,10-Di?r~ethylanthrace71e
zuitl~2,S-Dicltloro-5,6-dicya~zobenzoqr~ino~~e
A solution of 2.027 g (0.0099 mole) of 9,10-dimethylanthracene in 75 ml of warm benzene was added to a
solutio~lof 6.79 g (0.03 mole) of 2,3-dichloro-S,G-dicyanobe1~zoq~1i1~0t1e in 225 ml of warm benzene, with
shaking. There was a n immediate darkening of the solution caused by charge transfer complexing; then a
copious yelloxv precipitate separated. T h e mixture was refluxed for 7 h and cooled, and the solid was collected.
Extraction of the solid with hot acetone left the insoluble brown hydroquinone, and evaporation of the extract
gave adduct VIII a s a bright-yellow crystalline solid (1.86 g, 28.2% yield), m.p. 21'7" (decomp.).
X ~ C I ~C, 5S.38; I-I, 1.85; S,S.51; Cl, 21.54. Found: C, 58.44; 1-1, 2.30;
Anal. Calcd. for C ~ ~ H I ? O ~ (65S.35):
K,5.36; Cl, 21.74; mol. nrt. (by mass spectrometry) 656 ( T I ) .
 L O W S A N D XIDOO: Q U I K O D I M E T H A 9 E CIIEMISTRY 2313
Infrared spectrum: v,,,,, (Sujol mull) 1 726 cm-I (br) (enedione C=O), 2 245 cm-1 (m) ( C e X ) . Zuclear
magnetic resonance spectrum ((CD3)2SO): 4.82 (21-1, singlet, 'angular' protons), 6.32 (21-1, singlet, vinyl
protons), 7.50-8.:30 (41-1, .-Mi2aromatic protons), -&\I3 quartet, J = 16 c.p.s., centers of gravity a i 4.17 and
4.37 (CI-I? proions). (See 1:ig. 1.) .-\bsorptio11 spectrum (CI-13CX):A,,, 375 mp (log e 3.19), 275 nip (log E
4.31), 260 mp (sh) (log e4.25), 234 m p (log e4.75).

Reactioir c$I/-il~ctlryluiillric~ce~~e
with 2,3-Diclrloro-ci,fi-dicy~~nobei~eoqrrit~o~~e
11 solution of 2.4 g (0.0106 mole) of ~,3-dichloro-;i,6-dicyar1ober1zoc~uino1ie in 45 ml of d r y benzene was
added to a solution of 1 g (0.0032 mole) of 0-~nethylanthracenein 5 ml of dry benzene. The solution clarl;ened,
;ind alter it \\,;IS refluxed for 10 min :I light-yellow precipitate separated. 'I'he mixture was relluxed for 2 h
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and cooled, and tlie solid was collected by liltration. ?'he major product was insoluble in chloroform, methanol,
acetollitrile, dimethyl sulfoxide, and benzene, and was purified by Sohslet extractio~ifrom it of impurities
with methanol, leaving a bright-yello\\r solicl (1.1 g, 34.6% yield), 111.p.215" (decomp.).
Anal. Calcd. for C3sl-I!~C12N202(609.487): C, 74.87; 14, 3.61; CI, 11.66; S , 4.61. 1;ound: C, 74.74; 1-1,
3.85; CI, 11.98; X, 4.42; mol. \vt. (by mass spectrometry) 608 (32CI).
Infrared spectrum: v,,,:,, ( I W r disk) 1 425 c~n-' (s) (C-0-C linkage GO)),2 216 cm-1 ( C s X ) .
r\dduct I S (0.227 g, 0.00U86 mole) was relluxed \\.it11 a m i x t ~ ~ ofr e 5 1111 of 57'3, hydriodic acid a11c13 ml of
water for S 11. \Vhite crystals of $1-iodomethyleneanthmce~~c (45 mg), m.p. 65-66', \\yhich had sublimed into
the condenser were removed and dried i i ~ afrczln. 'The substance, n,ithout further p~~rilication, was clissolvcd
ill I() ml of dry ether, treated with a solution of 85 mg of lithi~irna l u m i n i u r ~hydride,
~ and stirred for 4 h.
'rlie mixture was cooled, unreacted hydride decon~posedwith water, and the orgaltic layer r e ~ l ~ o v eEvapora- d.
tion of the ethcr gave yellow crystals of $1-methylantliracene, m.p. 74-75", mixed 1n.p. \\rith authentic
9-1nethylantl~racene 54-75'. The n.1n.r. spectrum in CDCI3 \x7asidentical with that of a n authentic sample of
the hydrocarbon.
Can. J. Chem. 1966.44:2507-2515.

~ ~ ) ~ ~Reactioi~
l i . ~ l of 9,10-~i~1~etb~l-9,10-dik~dro-0,10-elhoi~oo~~thiace~c-11,12-dicr~rbor~lic ilnlrydiidc witl~
Tetir~clrloro-l ,2-betr~o(plii~oi~c
A of 1.1s g (0.00:3!) mole) of !),lO-dimethyl-!),l0-diliydro-!J,l0-etl1anoanthmcene-ll,l%-dicarboxylic
anhydride and 1.65 g (0.0068 mole) of the quinone i l l 4.5 rnl of dry 1,2-dichlorobenze11e was heated in a
collstant-te~npcraturebath a t 101' for 44 h. The mixture was concentrated to a srnall volume and cooled,
and the white crystalline solid was collected arld ivnshed with benzene, yieldi~igthe unchanged a d d ~ r c t
(1 .()!) g, I)2(;b recovery), i i i . ~330°,
. mixed m.p. with a n a ~ ~ t h e ~sample
~ t i c 330' (lit. (25) rn.p. :i33-335°).

dJ(rtcrinls
I'lu-e I,?-cliclilorol~enzenewas distilled from sodium n ~ had
~ d b.p. 177-178" a t $50 Innl, t~$? 1.5518 ('74).
Co~l~mercial sarnples of tetrachloro-1,2-be11zoquinone and 2,:3-dichloro-5,6-dicyil11obe11zoqui101e\\!ere puri-
fied by sl~blimationand by recrystallizntior~froul benzene-iz-hesane, respectively, the benzene of crystalliza-
tion being removed in a vacuum desiccator.
Iieactioi~IZules
'I'he rates were dcterrni~~ed
by followi~~gspecirophoto~netricallythe disappearance of the colorcd q ~ ~ i ~ ~ o i i e .
'rhc E a values \\-ere determined by graphical extrapolatioi~.?'he experimental niethod used a r ~ ddetailed
trcattnent of the rate data have been describcd previously (21).
IGnetic Eqltutions E+rr.ployed
e ; b mole I-' = the initial conccntmtioll of hydro-
Let a mole 1-1 = the illitin1 c o n c e ~ ~ t m t i oofn c l u i ~ ~ o nlet
carbon; lei :r mole 1-1 = the amount of cluinone consumed a t time 1; let the initial extinction of the quinonc
;lt 5 600 A be E o ;let the esti~ictionof the cluinone a t 5 GOO A a t time t be E. T h e meaning of the symbols
RI-I, RI-I?,and I< used below is explained in tlie Discussion.
Uiv~olrcula~, IZeactioi~with Fast S C L U
C o i r ~ c ~ ~ ~Seco?~d-Order
tme, TL~
Step

'I'he overall ratc expression \\.hen k2 >> k is

dx/dt = k(6 - r)(a - 2%).
Il~tegmtionleads to
 2514 CANADIAN JOURNAL O F CI-IEMISTRY. VOL. 44. l9GG

Eo = Xa; E = X(a - 3 s ) ; therefore, E + En = 2X(a - s ) , where X is a proportionality constant.

When (2, - x) = a (k - 1) + ( a - x) issubstituted,
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T r i k l y Co)rsec~ltivc,
Seco~zdOrder Reactiorz with Slow Initial Step
Can. J. Chem. 1966.44:2507-2515.

T h e overall rate expression when k? and k3 >> kl is dx/dt = kl(b - x) ( a - 3s).

Integration leads to (2, > a)

En = Xn; E = X(n - XN);(2, - N) = a

(: - 1) + (a - N ) ;
- (a - x) = 2Eo + E/SX. Therefore,

S ~ ~ i i i ~ i ?ofa Rate
r y Co?csta?tts
T h e units for the following rates are liters per mole per second. The initial concentration of hydrocarboll
a n d quinone in 1,2-dichlorobenzene was 0.0100 A t .

Arrhe?~izcsRate Paraw~eters
'l'he Arrlie~liusparameters were computed by the method of least squares and their precision (standard
 LOWX AND AIDOO: QUINODI~LIETHANECI-IEMISTRY 2515
deviation) by the equations set out in in a previous paper (21). The vallies of hob,. a t SO0 mere obtained by
least-squares interpolation.
Hy+ocarbon ks00 (1 mole-' s-I) E (kcal/mole) loglo B
cis-9,lO-Dlhydro-9,lO-
dimethylan thracene 9.9SfO.lSXlO-" 14.654~0.53 7.03
trans-9,lO-Dihydro-
9,lO-dimethylanthracene 5.27&0. 16X10-3 15.00f0.40 6.97
9,lO-Dimethylnnthracene 4.22&0.10 X lo-? 12.96&0.16 6.65

ACI<NOWLEDGMEX'TS
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This research was supported by a National Research Council of Canada grant to

J. W. L. Preliminary ~vorl; in this study uras carried out while one of us (J. W. L.) was
in the Chemistry Department of Imperial College, London. The n.nl.r. and Illass spectra
were measured b ~ 7R. N. S\\rindlehurst and Dr. A. I-Iogg of this laboratory, respectively.

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 This article has been cited by:

1. . 47, 167. [Crossref]

2. Ali R. Koray, Claus Krieger, Heinz A. Staab. 1985. Bis(tricarbonyliron)-para-quinodimethanes: Preparation and Molecular
Structure. Angewandte Chemie International Edition in English 24:6, 521-522. [Crossref]
3. Ali R. Koray, Claus Krieger, Heinz A. Staab. 1985. Bis(tricarbonyleisen)-para-chinodimethane: Darstellung und Molekülstruktur.
Angewandte Chemie 97:6, 513-514. [Crossref]
4. Willy Friedrichsen, Irmgard Kallweit, Regine Schmidt. 1977. Reaktionen vono-Benzochinonen mit 1,3-Diarylbenzo[c]furanen.
Justus Liebigs Annalen der Chemie 1977:1, 116-144. [Crossref]
5. Willy Friedrichsen, Regine Epbinder. 1973. Cycloadditionen des Tetrachlor-o-benzochinons mit bicyclischen olefinen.
Tetrahedron Letters 14:23, 2059-2062. [Crossref]
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6. W. Friedrichsen. 1969. Reaktionen von o-chinonen mit dienen. Tetrahedron Letters 10:51, 4425-4428. [Crossref]
Can. J. Chem. 1966.44:2507-2515.