Open-chain nitrogen compounds. Part 11.

' Preparation, characterization,

and degradation of 1(3)-Aryl-3(1)-methyltriazenes;the effect of
substituents on the reaction of diazonium salts with methylamine2
T. PATRICK
AHERN,HANDRICK
FONG,A N D KEITHV A U G H A N ~
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Deptrrtnzent qfClzemi.ct/.y, Saint Mary's U n i ~ ~ e r s i tHalifax,

y, N . S . , Ccinada B3H3C3
Received December 10, 1976

T. PATRICK AHERK,HANDRICK F o ~ Gand

, KEITHVAUGHAN. Can. J. Chem. 55, 1701 (1977).
Treatment of the diazonium salts, X,C6H4N,+,with aqueous methylamine affords good yields
of the mono~nethyltriazenes,X.C,H,.N=N.NHMe, when the substituent is a strongly electron-
withdrawing group (X = o-, HZ-, and p-NO,; o-, m-, and p-C0,R; p-CN and p-COCH,).
Preparation of the triazene from the p-bromobenzene diazonium salt was accompanied by
formation of a pentaazadiene. Monomethyltriazenes were not obtained when dlazonium salts
containingothersubstituents(X = H,p-CH,, O-CF,,~-CI,~-F,~-NM~,,~-OH,~-OCH,,~-P~,~-
NHCOCH3) were treated with methylamine. In these cases the products were either penta-
azadiene, or 1,3-diaryltriazenes or unstable materials. The monomethyltriazenes vary con-
siderably in stability and give rise to a number of different degradation products, which were
either diaryltriazenes or 3-alkyl-1,3-diaryltriazenes
or simply arylamines. l(3)-(p-Nitropheny1)-
3(1)-methyltriazene was found to be a moderately effective methylating agent.

T. PATRICKAHERX,H A ~ D R I CFONG K et KEITHVAUGHAN. Can. J. Chem. 55, 1701 (1977)

For personal use only.

Le traitement de sels de diazonium X.C6H4Nzi avec de la methylamine en solution aqueuse

conduit avec de bolls rendenlents aux monomethyltriazenes, X.C,H,.N=N.NHMe quand le
substituant est fortement electroaffinitaire (X = o-, m-, et p-NO,; o-, 111- et p-C0,R; p-CN et
p-COCH,). La preparation du triazene a partir du sel dep-bromobenzene diazonium est accom-
pagnee par la formation d'un pentaazadiene. On n'obtient pas de n~ononiCthyltriazenesquand
on traite les sels de diazonium contenant d'autres substituants (X = H, p-CH,, o-CF,, p-Cl,
p-F, p-NMe,, p-OH, p-OCH,, p-Ph, p-NHCOCH,) par de la methylamine. Dans ces cas, les
produits sont soit un pentaazadiene ou des diaryl-1,3 triazenes ou des composCs instables. La
stabilite des monomethyltriazenes varie considirablement; leur degradation conduit a un cer-
tain nombre de differents produits q ~ sont~ i soit des diaryltriazenes ou des alkyl-3 diaryl-1,3
triazenes ou simplenient des arylamines. On a trouve que le p-nitrophenyl-l(3) methyl-3(1)
triazene est un agent methylant lnoderement actif.
[Traduit par le journal]

lntroduetion Chemically, methylation by monomethyltri-

I-Aryl-3-alkyltriazenes can be obtained by the
reaction of aryl azides with aliphatic Grignard
reagents (3,4), or, in some instances, by reaction
of diazonium salts with alkylamines (1, 5).
Monomethyltriazenes have significant carcino-
genic activity (6, 7), and have been implicated
(8) as metabolites in the carcinogenesis of 1-
aryl-3,3-dimethy!triazenes, which have shown
considerable potential as antitumour agents (9).
The activity of monomethyltriazenes is believed
to derive from the facility with which they
methylate biological substrates, such as the
heterocyclic base units of nucleic acids (10).
'For part I, see ref. 1.
'Preliminary communication, see ref. 2.
,Author to ~ h o mall correspondence should be sent.
(Present address. until Aunust 1977: D e ~ a r t m e n t of
Pharmacy, University of ton, ~ i r m i n g h a m ,England
B4 7ET.)
azenes is also known, as for example in the
esterification of carboxylic acids ( I I). Clearly,
an understanding of the formation and proper-
ties of ~nonomethyltriazenesis important from
both chemical and pharmacologicaI viewpoints.
In part I (I), the reaction of diazotized an-
thranilate esters with primary aliphatic amines
was shown to give excellent yields of semi-stable
I-aryl-3-alkyltriazenes. which were formed with-
out contamination by pentaazadiene. This result
was surprising because it has been stated (12, 13)
that the reaction of diazonium salts with primary
alkylamines is complicated by the formation of
pentaazadienes due to further coupling of the
diazonium ion with the triazene. In a subsequent
communication (2), it was shown that, in general,
diazonium salts with strongly electron-with-
drawing substituents in the aryl group give rise
to pentaazadiene-free triazenes when treated
 1702 C 4 N . J . CHEM.

with methylamine. This report gives a full 1 j 3 ) - jp - . \ / I ~ ~ t h o x j ~ m i . b o t ~ ~ l p-3

account of the reactions of a number of diazon-
ium salts with methylarni~lcand describes the
characterization and degradation of the mono-
methyltriazenes forlned in these reactions.
Can. J. Chem. Downloaded from www.nrcresearchpress.com by Depository Services Program on 11/12/14
/ ~fe1)
t i-~?~ethj,ltrirrzene
yl)
(24')-(0.98 g, 84%), m p 94-96'C (from benzene) (lit. (5)
m p 97.5-C); v,,,, 3180, 3160, 1705, and 1600 c m - ' ; 6
(CDCI,) 3.40 (br s, 3H, N-Me), 3.88 (s, 3H, 0 - M e ) , 7.31
(br d, J = 8 Hz, 2H, aromatic), 8.0 (d, J = 8 Hz, 2H,
aromatic); M + 193(53%) (CIIH,,N3O2), rnie 190(0.7%)
(:M - H,), 165(92) ( M - N2), 151(652) ( M - CHzNz),

Experimental 133(13%), 134(17%) (:M - COZCH,), 120(100?<)

(C7H,N0), 106(3.5%), 103(5%); 92(27%).
Melting poil!ts mere recorded on a hot-stage apparatus 1 / 3 1 - 1p - Erl~osycorbonylp/~et~j~I) - 311) - rncthyltriazene
(Reichert) and are corrected. Infrared spectra were /2e)-(yield 64%) rnp 83-85 C (benzene - petroleum
recorded ~ v i t h Nujol suspensions o n a Perkin-Elmer ether): v,,,,, 3200, 3180, 1710, and 1610 c m - ' ; 6 (CDCI,)
model 467 grating spectrophotorneter; n m r spectra were 1.35 (t, J = 7 Hz, 3H, C-Me), 3.35 (br s, 3H, N-Me), 4.33
measured o n a Varian A-60A spectrometer using tetra- (q. J = 7 Hz, ZH, 0-CH,), 7.30 (br d, J = 8 Hz, 2H,
methylsilane as internal standard. Mass spectra were aromatic), and 8.0 (d, J = 8 Hz, 2H, aromatic).
recorded with a DupontiC.E.C. Model 21-491 spectrorn- I(3)-ir~1-!VitrophetlyIj-3f I j-rnethj./triozene (2f)-(0.65
eter using direct insertion. g, 60%), Inp 94-96-C (from ether - petroleum ether);
v,,,, 3380, 1580(W), 1535, and 1345 cni-': 6 (CDCI3)
1 j 3j -A?!,/-3(1) -methyltrinzetres (20-h) 3.32 (s, 3H, N-Me), 7.3-8.3 (m, 4H, aromatic), and 8.5
C e n e r ~Proced~rrr
l ((71' S, I H , N H ) ; M - 180(41%) (C7H8N4O2); til'e
A solution of the aromatic amine (0.006 mol) in 2 IM 165(0.3%) (114 - CH,), 164(0.6%) (M - O), 150(77%)
hydrochloric acid (9.0 ml), diluted mith \%ater (20 ml), (.\I - C H 3 N H ) , 138(36:) (Atll - - H a N , ) , 122(10076)
was diazotized at 0 - C with sodium nitrite (0.45 g) in mater (C6H4N02), 108(4.6%), 106(12%), 92(684,).
and the resulting solution stirred for 1 h, o r until clear. l ( 3 ) - /t~~-:\lethox~~~n~~bonylp!~c~t~yl) -3 (1) -t~ietl~j~/triozet~c~
The diazoniuni salt solution was treated with 40% aque- (2~)-(1.19 g, 90x1, m p 107-1 10-C (froni benzene);
ous methylamine (2.8 n ~ l ) ,whereupoll a precipitate of \,,, 3240 and 1720 c m - I : b (CDCI,) 3.26 (br s, 3H,
For personal use only.

the triazene usually appeared immediately. Sometinies N-Me), 3.86 (s, 3H, 0 - M e ) , 7.3-8.3 (m, 4H, aromatic),
the precipitate u a s gurnlny in texture and required and 9.1 (br s, l H , N H ) .
careful purification to obtain crystalline material without l-Metk,yl-3-(o-t1itrophet~~~l) trinzrr~e/2/1)-(0.8 I g, 75x1,
decomposition. I n one case (2g), the triazene u a s formed m p 38-40-C; v,,,, 3330, 1615, 1520, and 1340 c m - ' ;
initially as a viscous, oily precipitate which \\as isolated 6 (CDCI,) 3.65 (s, 3H, I\;-Me), 6.8-8.3 (ni, 4 H , aro-
by extraction into chloroform. matic), and 11.5 (br s, I H , N H ) . The o-nitrophenyltri-
This procedure afforded the following tria7enes. azene decomposed completely within h o ~ ~ of r s prepar-
113)-(~1-Nitropl1etryl)-311)-t11c~tlryltriazet1~~ (2a)-(0.62- ation, even u h e n stored in a vacuum desiccator. Some
0.95 g, 57-889.',), n ~ p11 1-1 13-C (benzene) (lit. (5) m p samples were found to contain o-nitroaniline after de-
114 C); v,,, 3180, 3140, 1605, 1600, 1515, 1340 c m - ' : 6 con~position.
(CDCI,) 3.5 (br s, 3H, N-Me), 7.4 (br d, 2H, aromatic), Attempted pr~7~1orariorzof l-(o-Cyanopl1enylj-3-1~1ethyl-
8.13 (d, J = 9 Hz, 2H, aromatic), and 9.2 ppm (br s, IH,
N H ) ; M + 180(417) (C7H8N4O2),ni,e 165(l%) (!W
CH,), 150(77:)
- rrii~zer~e
Anthra~lilonitrile (0.75 g) u a s dissolved in hot 2.5 :M
('M - C H , N H ) , 138(97%) (.M - hydrochloric acid (10 ml) diluted with water (20 n ~ l ) and ,
CH,N,), 122(100z) (C,H,NO,), 108(20$;), 106(12%), diazotized at 0 C with sodium nitrite (0.45 g). Aqueous
and 92(74%). methylamine (2.8 nil of 404,) \bas added t o the clear
l ( 3 ) -ip-Cj.~lnopherryI)-3(1) -1iiethyItric1zet1e(2b)-(0.8 1 solution and a yellow colouration developed, folloued
g, 83%) m p 135.5-136 C (dec.), (yellow prisms J'rom by the formation of a bro\vn, oily precipitate. The
benzene - petroleum ether); ,,v, 3185, 3155, 2220, and mixture was extracted lvith chloroforn?: the residue in the
1605 c m - ' ; 6 (CDCI,, t 5 5 C ) 3.40 (br s, 3H, N-Me), chloroform (yield 0.96 g) displayed triazene character-
7.3-7.8 (ni, 4 H , aromatic), and 8.6 (br s, l H , NH): 6 istics in the ir spectrum, v,,,, 3400 (NH), 2210 (C-N),
(CDCI,, -30 C) 3.22 (d, J = 2 Hz, NHMe), 3.62 (s, and 1480 (N=N) c n i - ' , but decon~posedimmediately.
=N-Me), 7.15-7.85 ( n ~ aromatic),
, 8.4 (br s, N H ) , and
9.7 (br S, N H ) ; M + 160(31%) (C8H8N,+),til/e 132(16%) Reactiorz of p-Brotl~obenzene Diaroniutn Chloride ~ , i t h
(IW - N,), 130(34%) (IM - CH,NH), 120(1%) (CiH6- ~etl1yLmine
NO), 118(78Vl,) ( A 1 - CH,X2), 102(100z) (NC.C,H,), 11-Bromoaniline (1.03 e ) was dissolved in 2 ,M hydro-
and 92(17%). chioric acid (9 ml), diiuted with water (20 ml); and
113) -(p-Acrtylpl~etl~~lj -3-r~iethyltrinzene (2c)-(0.77 g, diazotized at O'C with sodium nitrite (0.45 g). The clear
7 3 > 9 as a yellow gummy solid uhich recrystallized from diazonium salt solution was treated lvith 40% aqueous
benzene- petroleum ether ~ i t rnp h 90-92 C ; v,,,,, 3180, niethylamine (2.8 ml) in one portion. A yellow precipitate
3160, 1660, and 1600 cn1-'; 6 (CDCI,) 2.56 (s, 3H, acetyl separated immediately, which was filtered to yield a
Me), 3.43 (br s, 3H, N-Me), 7.33 (br d, J = 8 Hz, 2H, solid mixture of 1(3)-(p-bron1ophenyl)-3(1)-methyltri-
aromatic), 7.96 (d, J = 8 Hz, 2H, aromatic), and 8.8 azene (21) and 1,5-bis-(p-bromopheny1)-3-methylpenta-
(br s, l H , N H ) ; M + 177(50%) (C,H,,N,O), mle 162 azadiene (7b) (approximate proportion 9 : 1) (1.02 g), m p
(0.4%) (iM - CH,), 149(16%) (114 - N2), 147(409.',) 68-70'C; v,,,, 3190, 3160, 1590, and 1540 cm-': 6
(M - CH,NH), 135(987) (:M - C H l N , ) , 134(53%) (CDCI,) 3.25 (s, triazene N-Me), 3.76 (s, pentaazadiene
(M - C H 3 C 0 ) , 120(10OW3 (C7H6NO), 106(27%), 92 N-Me), and 7.1-7.6 (m, aromatic). Recrystallization of
( 5 7 3 , and 77(37%). the solid mixture from ethanol - dimethyl sulfoxide

resulted in decomposition and formation of a different
high melting solid, m p 180-183'C; v,,, 1570 (W) cm-',
which could not be identified.
1,3-Bis- (o-tripuorolnethylphenj~l)triazet~e/4d)
o-Aminobenzotrifluoride (0.97 g) in 2 M hydrochloric
acid (9.0 ml) was diazotized at O'C with sodium nitrite
(0.45 g). The diazoniuni salt precipitate was dissolved by
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dilution and 40% aqueous methylamine (2.8 ml) was
added in one portion. The yellow solution was stirred
for 0.5 h and filtered to afford an off-white solid. Re-
crystallization froni ethanol gave 1,3-bis-(o-trifluoro-
methylphenyljtriazene (51 mg) mp 177-179'C (lit. (19)
m p 170-171.5'C); v,,,,, 3355, 1610, and 1590cni-': 6
(CDCI,) 7.1-7.9 (ni, 8H, aromatic), 9.7 (br s, IM, N H ) ;
M I 333(1%) (CI4HON3F6),n , ' e 314(1%) ( M - F),
305(16%) ( M - Nz), 216(17,), 173(487,',)(CF,C,H,N,),
160(4%) (NH.C,H,CF,), 145(100%) (C,H,CF,), 131(4%)
( C ~ H S N ~115(4%),
), 104(4%).
13a)
~,3-Bis-fy-r~itrophrrr~~l)-3-~~irthylfriazene
The y-nitrophenyltriazene 20 recrystallizes unchanged
from benzene xhen the crystallization is done quickly.
Prolonged heating in benzene solution or in alcohol,
resulted in deconiposition. The product of the decom-
position was identified as 1,3-bis-(p-nitropheny1)-3-
methyltriazene (yield 31%) m p 228-230'C (froni ethanol)
For personal use only.
(lit. (14) m p 219'C); v,,,, 1600, 1590, 1500, and 1330
cnl-'; 6 (DMSO-d,) 3.35 (s, N-Me), 7.43 (d, J = 9 Hz,
aromatic), and 7.91 (d, J = 9 Hz, aromatic); M +
301(2%) (C13H11N504);r11;e 273(4%) (M- N,), 180(2%)
(144- C,H3NO2), 166(1%) (M - C6H3NzO2), 150(76%)
( N z C 6 H 4 N 0 2 or CHzN,C6H,N02), 122(100%) (C6H4-
NO,), 105(14%), 92(26%).
1,3-Bis-(o-nirrophet~yI)-3-methyltricizene (36)
I-Methyl-3-(0-nitropheny1)triazene was dissolved in
9 5 2 ethanol at room temperature. After standing, a
yellow solid separated, which mas identified as I ,3-bis-
(0-nitropheny1)-3-methyltriazene (yield 3%) m p 107-
llOCC (from ethanol), v,,,, 1600, 1520, and 1355 cm-' ;
M + 301(2.4%) ( C I 3 H 1I N S 0 4 ) rn/e 273(2%) (dbf - N2),
255(0.4%) ( M - NOz), 180(2%) (IM - C,H,NO,),
167(0.6%) (1M - C s H 2 N z 0 2 ) , 150(1007,) iNzC6H4NOz
or CHzNC,H,N02), 123(30%) (C,HsN02), 105(4.4%),
92(22%',).
I ,3- Bis- ( p - n ~ e r h o s j ~ c n r b o n y / p / ~rrinzene
~ ~ n j ~ I ) i4c)
The 11-methoxycarhonylphenyltriazene 2d recrystallizes
unchanged from benzene when the crystallization is done
quickly. However, recrystallization in ethanol, and also
o n occasion in benzene, when heating is prolonged,
results in decomposition. The product of decomposition
was identified as the bis-(y-methoxycarbonylpheny1)tri-
azene 4c (yield 10%) mp 205-210'C (from benzene) (lit.
(15) mp 218-219'C); v,,, 3230, 1720, 1710, 1690, and
1610cm-' ; 6 (CDCI,) 3.93 (s, 6H, 0-Me), 7.46 (d, J =
8 Hz, 4H, aromatic), and 8.06 (d, J = 8 Hz, 4H, aro-
matic): M 313(0.6%) (Cl,H1sN30,), nz/e 285(7%)
+
( M - N,), 254(8%) ( M - C H 3 C 0 2 ) , 194i0.67,) (C,-
HJN~C~H~ 161(37%)
), (CH302CCsH4N2), 135(100%)
(C6H4C0,CH3), 120(25%) (C7H6NO), 103(25%,),92(7%).
Reactiotz of o-Airro~enzeneclinzoni~rrlz
Salt wit11 Att7fnotiia
o-Nitroaniline (0.83 g) mas dissolved in 2,W hydro-
chloric acid (9.0 nil), diluted uith water (100 ml), and
ET AL. 1703
diazotized at OcC with sodium nitrite (0.45 g) over a
period of 1 h. The clear solution was treated with con-
centrated ammonia (2.18 ml) in one portion and, after
stirring for 5 min, the precipitate was collected to yield an
unidentified reddish-brown solid (77 nig), which rapidly
decomposed. O n standing, further precipitation in the
mother liquor produced o-nitroaniline (19 mg) identical
with a comn~ercialsample.
Reaction of Benzenrdiazot~iumChloride with .Vfethylntnine
(cr) 1,5-Diphetiyl-3-methylpentorrzadiene (70)
Aniline (0.635 g) was dissolved in 2 !M hydrochloric
acid (9.0 ml), diluted with water (20 ml), and diazotized
at OcC with sodium nitrite (0.45 g). After stirring for
0.75 h, the diazonium salt solution was treated quickly
with 40% aqueous methylamine (2.8 ml). The yellow
precipitate was filtered to afford the pentaazadiene
(0.56 g), m p 109-110 C (lit. (16) mp 112-113'C) (yellow
needles from benzene or ethanol); v,,,,, 1580 (W) c m - ' ;
6 (CDCI,) 3.81 (s, 3H, N-Me) and 7.3-7.8 (m, 10H,
aromatic).
ib) 1,3-Dip/renj~lrriuzet~c~
140j
The procedure in (a) was repeated uith a smaller
volume (1.Oml) of 40% methylamine, added in three
successive portions (0.5, 0.3, and 0.2 nil) immediately
after the addition of sodium nitrite. A precipitate
appeared froni the yellow solution after 5 min, and the
mixture was filtered to yield 1,3-diphenyltriazene (0.22 g,
27%), identical with a sample prepared below.
Reactions of Ber~zerrediazot~i~i~~
Cliloridc
(a) With Acetatrride
A solution of acetamide (1.5 g) in mater was added to
a solution of benzene diazonium chloride (0.006 mol) in
one portion at OcC and the solution remained clear.
Sodium acetate (6 g) was added, uhereupon the solution
turned yellow and a precipitate slowly appeared. After
stirring for 1 h, the solid was filtered and recrystallized
from petroleum ether to give 1,3-diphenyltriazene (0.28
g, 4779, mp 95-97-C (lit. (17) nip 98-99*C), v,,,, 3150
and 1590 cnl-', identical with a sample prepared by
diazotization of aniline alone.
i b j With Urea
Likewise, a solution of benzene diazonium chloride
(0.006 mol) was treated with a solution of urea (1.36 g),
followed by addition of sodium acetate, whereupon 1,3-
diphenyltriazcne (78 nig) precipitated.
(c) With Sodiun? Acrfate
Treatment of a solution of benzene diazonium chloride
(0.006 mol) with an excesc of sodium acetate produced a
yellow solution which, after standing for 1 h, afforded a
yellow precipitate of 1,3-diphenyltriazene (0.11 g).
1,3-Bis-(p-tolyl) trinzene 146)
p-Toluidine (0.64 g) was dissolved in 2 1M hydrochloric
acid (9 ml), diluted with water (100 nil), and diazotized
at 0°C with sodium nitrite (0.45 g). Aqueous methylamine
(2.8 ml of 40%) was added in one portion, whereupon
the solution went cloudy. After 5 min, the tan-coloured
precipitate was filtered and triturated with methanol.
The methanol solution was filtered and the filtrate diluted
with water to afford, 1,3-bis-(p-tolyl)triazene,mp 116°C
(lit. (18) m p 116.5'C), v,,,, 3170 and 1605 cm-', identical

with a sample prepared by diazotization of p-toluidine
alone.
3-Merl7yl-l,2,3-brrzzorrinzin-4-one
Anthranilic acid (0.86 g), dissolved in 2 M hydrochloric
acid (9.5 ml) and diluted with water (20 ml), was diazo-
tized at O'C with sodium nitrite (0.45 g) and treated with
40% aqueous methylamine (2.8 ml). The solution turned
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yellow, but no immediate precipitate was observed. After
standing overnight a white precipitate had formed, which
was filtered to yield 3-methyl-1,2,3-benzotriazin-4-one
(0.175 g) mp 121-122'C, identical in all respects with an
authentic sample (1).
Chlorofor~nextraction of the mother liquor afforded a
second batch of the triazinone (0.135 g), nlp 116-120'C.
Methylatiot~of 3,5-Dinirrobenzoic Acid
The p-nitrophenyltriazene 2a (0.63 g, 3.5 n ~ n ~ o was
l)
suspended in ether (10 ml) and stirred at room tempera-
ture while a solution of 3,5-dinitrobenzoic acid (0.75 g)
in ether (20ml) was added dropwise. The mixture was
left for 17 h at room temperature, filtered, and partially
evaporated. The crystalline precipitate was separated to
give methyl 3,5-dinitrobenzoate (0.14 g). Evaporation of
the ether filtrate gave a red, oily residue which solidified
o n standing. The solid was scrubbed with 2 Nhydrochloric
acid, filtered, washed with water, scrubbed with 5%
For personal use only.
aqueous sodium carbonate, filtered, washed with water,
and dried to give a second batch of methyl 3,5-dinitro-
benzoate (combined yield 0.72 g), which was identical
with a sample obtained from reaction of 3,5-dinitro-
benzoyl chloride with methanol.
Discussion
Treatment of the para-substituted benzene
diazonium chlorides la-e with methylamine in
aqueous solution gave good yields of the mono-
methyltriazenes 2a-e. The meta-substituted tri-
azenes 2f and g were also obtained readily from
the corresponding diazonium salts If and g.
However the o-nitrophenyltriazene 2h was ob-
tained only with considerable difficulty; treat-
ment of o-nitrobenzene diazonium salt with
methylamine frequently resulted in decomposi-
tion. The meta- and uara-substituted triazenes
20-g are moderately stable yellow solids, but
usually deconlpose on standing, with the ex-
ception of the p-cyanophenyltriazene 26, which
appears to be completely stable. By contrast,
the o-nitrophenyltriazene 2h decomposes very
quickly in the solid state and in solution. As
previously described (1, 20), the o-alkoxy-
carbonyl- and o-acetylphenyltriazenes 2i and 2 j
are also unstable and readily cyclize to benzo-
triazinones and methylenebenzotriazines, re-
spectively. In the present work, the triazene
obtained by coupling ~nethylaminewith diazo-
tized anthranilic acid cyclized spontaneously to
afford 3-methyl-1,2,3-benzotriazin-4-one. The
VOL. 5 5 , 1977
product of the reaction of methylamine with o-
cyanobenzene diazonium salt displayed ir charac-
teristics of the o-cyanophenyltriazene 2 (X =
o-CN), but decomposed very quickly preventing
full characterization.
-
As described more fully elsewhere (2!), the
spectral properties of the para-substituted
phenyltriazenes 2a-e show that these triazenes
exist as a mixture of tautorners in equilibrium
(ArN=NNHMe % ArNHN=NMe). The N-
methyl proton resonances in the nmr spectra of
2a-e are considerably broadened by the tauto-
meric equilibrium; the presence of both tauto-
rners was confirmed in the case of the p-cyano-
derivative 26 by low temperature nmr measure-
ment. The infrared spectra of these triazenes also
give evidence for two tautomers. Two bands
appear in the regions 1415-1430 and 1480-1485
c m - ' , assigned to the azo-group (N=N)
stretching vibration in the 1-aryl- and 3-aryl-
tautomers, respectively. Furthermore, the para-
substituted triazenes 20-e show two N H
absorption bands in the ir a t 3140-3160 and
3 180-3185 cm- l , whereas the ortho-substituted
triazenes 2h and 2i display only one N H band
a t 3300-3330 cnl-'. The low temperature nmr
study showed conclusively that the o-ethoxy-
carbonylphenyltriazene 2i (R = Et) (and by
analogy the o-nitrophenyltriazene 212) exists
solely as the 3-aryl tautomer.
The structures of the monomethyltriazenes
were confirmed, whenever possible, by mass
spectral analysis: the observed fragmentation
pathways are shown in Scheme 1. The 191- and
p-nitrophenyltriazenes have strikingly similar
mass spectra showing fragments arising from
pathways (a) N-methyl fragmentation, (b)
fragmentation a t N,-N,, (c) loss of the frag-
ment diazomethane, CH,N,, and (d) N-aryl
Can. J. Chem. Downloaded from www.nrcresearchpress.com by Depository Services Program on 11/12/14

S C H ~ MI. EMas\ spectral fragmentation of 1(3)-AryI-3(1)bmeth) ltriazenes

For personal use only.

fragmentation. Surprisingly, the nitro-derivatives tween N-2 and N-3, and path c. N-aryl frag-
did not show fragmentation by direct loss of N, mentation (Scheme 2).
(path f ) , although this pathway was clearly
evident in the fragmentation of other yuru-
substituted triazelies 2b, c, and d. The p-acetyl
derivative 2c and the ester 2d fragmented by
loss of the substituent, X, unlike the nitro- and
cyanophenyltriazenes. These results are signifi-
cantly different f r o ~ nthe mass spectra reported
(22a) for the unsubstituted 3-alkyl-I-phenyl-
triazenes (c.g.. 2 X = H), which fragment by the
analogous pathways b. c, and d, but did not show
fragmentation by loss of N, (path f ) or by
breakage of the N-alkyl linkage (path a).
Several types of decomposition product have
been obtained from the unstable triazenes 2,
but the course of the decomposition does not
appear to be determined by the reaction medium.
The y-nitrophenyltriazene 2a could be purified
by rapid crystallization from benzene, but de-
composed when boiled in ethanol to afford the
alkyldiaryltriazene 3u. The structure of 3u was
apparent from the ir spectrum. which did not
show a n N H band, from the nmr spectrum, The alkyldiaryltriazene 3b was similarly ob-
which displayed N-methyl resonance and the tained when the o-nitrophenyltriazene 2h was
expected aromatic pattern, and from the mass treated with ethanol. 3b has a mass spectrum
spectrum. which showed the molecular ion a t alnlost identical (in both fragment mass nu~nbers
M + 301. The principal fragments in the mass and relative intensities) to that of the purci-
spectrum of 3u showed that fragmentation occurs isomer 3u. The formation of the alkyldiaryltri-
by path a loss of N,, path b fragmentation be- azenes 3a and b in protic media must involve
 1706 C A N . J . C H E M . VOL, 5.'.
Can. J. Chem. Downloaded from www.nrcresearchpress.com by Depository Services Program on 11/12/14
S C H E ~2.I EMass 5pcctraI fragmentation of 1.3-his-(p-nitrophenyl-3-methyltriazene
two courses of cleavage (Scheme 3). Thermal loss
of nitrogen gives the secoildary ainine 5 (reaction
ii), whereas proto~latioii at N-3, follo~ved by
retrocoupling (reaction i), liberates free aryl
diazoniuin ion. which may then couple with the
secondary amine to g i ~ e the trisubstituted
For personal use only.
triaze~le.
Attempted purification of the o-nitrophenyl-
triazene 212 in benzene gave only o-nitroaniline,
which was also the product of solid state de-
composition of 211. The facility with which this
triazene reverts to the arylamine is possibly a
coilsequence of the preference of 2h to exist as
the 3-aryl-tautomer, Ar.NH--N=N-R. This
preference has been attributed to intramolecular
hydrogen bonding (21). o-Nitroaniline was also
recovered in low yield directly from the reac6on
of o-nitrobenzene diazoniuin salt with am-
monia; in this case the diazo~liumsalt probably
couples with NH, to gile a inonoaryltriazene,
1977
mle 273
Ar,N=N.NH,, which would rapidly lose N, to
give the amine, as has been observed previously
when the diazoniu~n salt from o-aininoaceto-
phenone was treated with ammonia (20).
A slightly different deco~npositioncourse was
experienced in the case of the p-niethoxy-
carbonylphenyltriazene 2 4 which reacted in hot
ethanol to give the diaryltriazene 4c. Analogous
decomposition probably occurred when o-
aminobenzotrifluoride was diazotized and treated
with methylainine, in which case the diaryl-
triazene 4d was obtained in low yield, pre-
sumably by decomposition of a n unstable mono-
methyltriazene 2 (X = o-CF,). The formation of
these diaryltriazenes from inono~nethyltriazenes
must involve protolysis and fragmentation by
pathways i and iii (Scheme 3), giving A r N 2 -
and ArNH,, respectively, followed by coupling
of the two fragments. Similar formation of
diaryltriazenes and alkyldiaryltriazenes has been

observed in the reaction of p-nitrobenzene
diazoniu~nsalt with butylamine (22b).
The decomposition mechanism outlined in
Scllelne 3 has much similarity to the reported
reactions of alkyltriaze~ieswith Lewis acids. For
example, Kreher and G o t h (23) obtained the
Can. J. Chem. Downloaded from www.nrcresearchpress.com by Depository Services Program on 11/12/14
secondary amine 5 as the major product of
reaction of 1-aryl-3-alkyltriaze~~eswith alumin-
ium trihalides, analogous to pathway ii (Scheme
3). However when silica gel is used as the
catalyst (24). the secondary amine is the minor
product, the major product being the primary
amine 6, presumably formed in a manner
analogous to pathway iii. The carboniurn ion-
pair mechanism (reaction 1) is fakoured to
account for the formation of 5 ; significantly the
tautomer involved here is the 3-aryl-1-methyl-
triazene.
Acidic alumina was found to favour decomposi-
tion of the o-alkoxycarbonylphenyltriazenes2i
For personal use only.
by pathway ii (I).
The preparation of 1-(p-toly1)-3-methyltri-
azene ( 2 k ) is now described in "Organic Syn-
thesis" (25), but success in this preparation
depends upon tho addition of the diazonium
salt l k solution to the methylamine solution at
- 10°C. These reaction conditions are signifi-
cantly different from those used here to prepare
the triazenes 2~-11,and \vhe~ip-toluidine was
diazotized and treated with methylamine a t OcC;
n o monomethyltriazene was formed. The only
product obtained in this case was the diaryl-
triazene 46. which could arise by decomposition
of the monomethvltriazene 2k as in Scheme 3
The corresponding reaction of benzene-
diazonium chloride with methylamine proved to
be very difficult to reproduce. When a large
excess of methylamine was added in one portion
to a solutioii of benzene diazonium chloride, the
product was the pentaazadiene 70, n o mono-
methyltriazene being ekident: slow addition of
inethylanline gave no identifiable materials a t
all. For n o o b ~ i o u sreason, the diphenyltriazene
40 was obtained when niethvlamine was added
in successive portions to the diazonium salt
solution. Diphenyltriazene (40) was the only
~ r o d u c t obtained when benzene diazonium
chloride solution was treated with (a) acetamide
f o l l o ~ e dby sodium acetate, or ( b ) urea followed
by sodium acetate. or (c) sodium acetate alone.
The un\villingness of benzenediazoniurn chlor-
E T AL. 1707
ide to couple with amides in aqueous solution
does not parallel the beliaviour in organic
solvents. For example, reaction of p-chloro- or
p-bromobenzeiie diazonium chlorides with for-
mamide in ethereal suspension affords the re-
markably stable 1-aryl-3-formyltriazenes 8 (26).
reaction 2. The lack of formation of acyl
A r h=N NH CHO + hdCl - H,O 4 COZ
triazenes in the present work is not consistent
with a report (27) that acetamide couples with
benzenediazoniurn chloride in the presence of
sodium hydroxide to give the :V-acetyltriazene
CH,CO,NH,N=NC,H ,. However, no reaction
was observed betueen acetainide and the
diazoniu~nsalt frorn sulfanilic acid (28).
The formation of diphe~lyltriazeiiefrom com-
pletely diazotized aniline in the absence of amino
co~npoundscan be rationalized in terms of the
equilibria involved in the diazotization process
(reaction 3) 129). It is generally accepted that the
equilibrium 9 = 10 % 11 is present in diazonium
solutions, and addition of base (e.g.. sodium
acetate) would shift the equilibriu~nto the left
giving a build up of P h N H , N x O . Condensation
of two nlolecules of this nitrosamine. or a reac-
tion with P h N 2 - , could give the triazene 4.
Although the nature of the con\ersion 9 -t 4 is
not fully understood. it clearly does take place
in specific cases. Primary nitrosaniines have been
isolated from diazotization of heterocyclic
a ~ n i n e sand can be converted into triazenes by
sinlply warming in methanol (30).
The preparation of the p-bromophenyltriazene
21, when p-bromobenzene diazoniuni chloride
was coupled with methylamine, was accompanied
by fornlation of the pentaazadiene 76. The
presence of the pentaazadiene was confirmed by
the observation in the nmr spectrum of IV-
methyl resonance at 3.76 ppm, analogous to the
N-methyl resonance of the pentaazadiene '7a.
 1708 C A N . J. CHEM. VOL. 55. 1977

Attempted ~urificationof the mixture of triazene

A
towards the 3-aryl-tautomer 12 reported pre-
and pentaazadiene resulted in decomposition. viously (21) [5]. A further correlation exists
Similarly attempts to prepare the p-chloro- and
p-fluorophenyl-3-methyltriazenes under these
conditions gave unstable materials, which could
not be characterized.
Can. J. Chem. Downloaded from www.nrcresearchpress.com by Depository Services Program on 11/12/14

Attempts to prepare mono~nethyltriazenes between these results and the protolysis experi-
with electron-donating substituents in the aryl ments of Matrka and co-workers (31); the
group, by this method, were a total failure. basicity of the triazene is affected similarly by
Treatment of the diazonium salts 1 (X = changes in electron density at N-3 [6].
Me,N-. HO-, MeO-. and Ph-) with
methylamine at OcC invariably produced a black
oil or tar. Diazotization of p-aminoacetanilide
and coupling with methylamine afforded a
promising solid, which ]nay have been triazene,
but it decomposed imnlediately after filtration.
Monomethyltriazenes are useful chemically as Acknowledgements
methylating agents. and for example, readily The financial assistance of the National
esterify aromatic carboxylic acids ( I 1 , 25). The Research Council of Canada (in part) is grate-
p-nitrophenylmethyltriazene 20 was found to fully acknowledged. The authors wish to express
esterifv 3.5-dlnitrobenzoic acid. but the reaction their thanks to D r . Malcolm F. 6 . Stevens for
was considerably slower than expected. The
For personal use only.

helpful discussions.
rapid evolution of nitrogen that is described for
the reaction of the p-tolyltriazene 2k (25) with 1. R. J . L E BLAKCand K . V ~ U G H ACan. N . J . Chem. 50.
the dinitrobenzoic acid was certainly not 2544 ( 1972).
evident in the reaction of the p-nitrophenyl- 2. T. P. A H E Rand~ K . V A U C H A NChem.
. Commun. 701
triazene. which does not appear to offer any (1973).
particular adbantage as a ~nethylatingagent 3. 0. DIMROTH. Ber. 36. 909 (1903): 38. 670 (1905): 40.
2390 (1907).
4. V. Z V E R I N A
and M . MATRKA.Chem. Listy. 63, 51
Conclusion (1969).
These ~ e s u l t s show that the formation of 5. M . MATRKA. Cezk. Farm. 21,442 (1972).
mono~nethyltr~azenesby a d d ~ t l o n of methyl- 6. T. M . O N Gand F. J . DE SERRES.Mutat. Res. (Amster-
dam), 13,276 (1971); 20, 17 (1973).
amlne to a d ~ a z o n l u m salt solutlon can be 7. F. A . S C H M I Dand D. J . HUTCHINSON. PI-OC.An].
ach~evedcleanly oiily v~lienelectron-wlthdrawlng Assoc. Cancer Res. l 4 , 7 5 (1973).
subst~tuentsare p ~ e s e n tIn the a1 yl group of the 8. R. PREUSSMAK, A . VOR. HODENBURG, and H. HENGY.
dlazonlum salt The non-formation of penta- Biochem. Pharm. 18. l(1969): T . A . C O ~ N O RP. S ,M.
azad~enes In these reactions suggests that the GODDARD,K . MERAL.W . C. J. ROSS,and D. E. V.
W I L M A NBiochem.
. Pharm. 25,241 (1976).
effect of the subst~tuent IS to decrease the 9. T . A . CONNORS. FEBS Lett. 57. 226 (1975).
nucleophll~c reactl~lty of the triazene by a 10. R. PRELSSMAK and A . V O N HODENBURG. Biochem.
resonance phenomenon [4] Delocal~zat~on of Pharm. 19, 1505 (1970).
11. E. H . WHITE.H . MASKILL. D. J . WOODCOCK. and M .
A. SCHKOEDER. Tetrahedron Lett. 1713 (1969).
12. H . ZOLLINGER. Diazo and azo chemistry. Intersci-
ence. New York, N Y . 1961. p . 179.
13. P. A . S. SMITH.Open-chain nitrogen compounds.
Vol. 11. Beqjamin, New York, NY. 1966. p. 285.
14. R. MELD O L A and F . W . STREATFIELD. J . Chem. Soc.
electron density a t the alkyl-bearing nitrogen 53.666 (1888).
reduces the nucleophilic strength of the triazene 15. L. FISERA,J . KOVAC,E. KOMAKOVA, and J . LESKO.
Tetrahedron. 30, 4126 (1974).
moiety, thus rendering it less reactive in the 16. H. GOLDSCHMIDT and V. BADL.Ber. 22,934(1889).
coupling reaction. A similar electron movement, 17. C. S U L I N G . Methoden der organisch Chemie
induced by the electron-attracting group, ac- (Houben-Weyl). 20/3,711, (1965).
counts for the shift in the tautomeric equilibrium 18. 0. PIT. WITT.Ber. 10,. 1309 (1877).
 A H E R N ET AL. 1709

19. M. R . PETTITTand J. C. TATLOW.J. Chem. Soc. 1071 25. E. H. WHITE,A . A . B A U M ,and D. E. EITEL.Org.
(1954). Synth. Coll. Vol. V. 797 (1973).
20. H. FOKGand K . VAUGHAN. Can. J . Chem. 53, 3714 26. T . IGNASIAK. J . SUSZKO,and B. IGNASI&K. J . Chem.
(1975). Soc. Perkin Trans. I. 2126 (1975).
21. K . VAUGHAN.J . Chem. Soc. Perkin Trans. 11, 17 27. G . ODDOand A . ALGERINO. Ber, 69,279 (1936).
( 1977). 28. H . EAGLEand P. VICKERS. J . Biol. Chem. 114. 193
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and medicine. Edited hy A. Frigerio and N. Castag- 29. R . N. BLTLER.Chem. Rev. 75,241 (1975).
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( t ~ )H . OELSCHLAGER and H. BLC'ME. Arzneim: (1970).
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For personal use only.