Reactions of 2-amino-4,5,6,7-tetrahydro[1]benzothiophene-3-carbonitrile and 6-amino-1,4-dihydro-3-methyl-1,4-diphenylpyrano[2,3-c]pyrazole-5-carbonitrile with substituted benzylidenemalononitriles, α,β-acetylenic esters and ketones

Article abstract of DOI:10.3184/030823409X435874

Reactions of 2-amino-4,5,6,7-tetrahydro[1]benzothiophene-3-carbonitrile (1a) with substituted benzylidenemalononitriles gave 4-amino-2-(1-cyano-2- arylvinyl)benzothieno[2,3-d]pyrimidine derivatives (3) as (E,Z)-mixtures and in one case (2c) as separated (

Full text of DOI:10.3184/030823409X435874

214 RESEARCH PAPER
APRILꢃꢀꢄꢅꢆ±ꢄꢅꢇ
JOURNAL OF CHEMICAL RESEARCH 2009
Reactions of 2-amino-4,5,6,7-tetrahydro[1]benzothiophene-3-carbonitrile
and 6-amino-1,4-dihydro-3-methyl-1,4-diphenylpyrano[2,3-c]pyrazole-
5-carbonitrile with substituted benzylidenemalononitriles, Į,ȕ-acetylenic
esters and ketones
Ahmed Said Ahmed Youssef
Chemistry Department, Faculty of Science, Ain Shams University, Abbassia, P.O. 11566, Cairo, Egypt
Reactions of 2-amino-4,5,6,7-tetrahydro[1]benzothiophene-3-carbonitrile (1a) with substituted benzylidenemalono-
nitriles gave 4-amino-2-(1-cyano-2-arylvinyl)benzothieno[2,3-d]pyrimidine derivatives (3) as (E,Z)-mixtures and in
one case (2c) as separated (Z)- and (E)-isomers. Similar treatment of 6-amino-1,4-dihydro-3-methyl-1,4-diphenyl-
pyrano[2,3-c]pyrazole-5-carbonitrile (4) yielded similarly-formed pyrazolopyranopyrimidine derivatives (5a,b) as (Z)-
and (E)-stereoisomers. Attempted acetylation of the aminobenzothienopyrimidines resulted in degradation of the
pyrimidine ring and the formation of N-(3-cyano-4,5,6,7-tetrahydro[1]benzothien-2-yl)acetamide (1b). Treatment of
4 with acetylenic esters and ketones (6a–d) afforded the (Z)-substituted enaminopyrano[2,3-c]pyrazole derivatives.
Reacting 1a with aroyl phenyl acetylenes gave by Michael addition the enamino-ketones (8a–c).
Keywords: fused [1]benzothiophenes, pyrazoles, pyrans, pyrimidines, o-aminonitriles, malononitriles, Michael additions,
acetylenic esters and ketones
Itisreported1 thatthereactionof2-amino-4,5,6,7-tetrahydro[1]
benzothiophene-3-carbonitrile with methyl E-methoxyacrylate
gives a benzothienopyridine derivative. In continuation
of our own studies2 on this aminonitrile and on 6-amino-
1,4-dihydro-3-methyl-1,4-diphenylpyrano[2,3-c]pyrazole-
3-carbonitrile, the present work deals with their reactions with
substituted benzylidenemalononitriles and with D,E-acetylenic
esters and ketones. The reported biological activities3-6 of
the thienopyrimidines and pyranopyrimidines prompted the
DXWKRUꢀ WRꢀ VWXG\ꢀ WKHVHꢀ UHDFWLRQVꢀ RQꢀ WKHꢀ KRSHꢀ RIꢀ ¿QGLQJꢀ QHZꢀ
biologically active compounds.
derivatives 2a–cꢀ LQꢀ UHÀX[LQJꢀ QꢁEXWDQROꢀ DIIRUGHGꢀ WKHꢀ
benzothieno[2,3-d]pyrimidine derivatives 3a±c as (E,Z)
mixtures: (E/Z)-3c isomers in the case of 2c. Similar treatment
of 6-amino-1,4-dihydro-3-methyl-1,4-diphenylpyrano[2,3-c]
pyrazole-5-carbonitrile (4) with 2b and 2d gave the
pyrazolopyranopyrimidine derivatives 5a,b in (Z)-and (E)-
forms as the minor and major stereoisomers, respectively.
The structures of compounds 3 and 5 are substantiated
by their microanalytical and spectral data. Their IR spectra
VKRZꢀ DEVRUSWLRQVꢀ FKDUDFWHULVWLFꢀ RIꢀ 1+ꢀ DQGꢀ &Ł1ꢀ JURXSVꢂꢀ
1
Analysis of the H NMR spectra allowed the inference that
each compound of (E/Z)-3a-c exists as a mixture of (E)
and (Z)-stereoisomers in ratio of 2:3. The presence of the
two stereoisomers was evidenced by the observation of two
VLJQDOVꢀFRQVLVWHQWꢀZLWKꢀWKHꢀROH¿QLFꢀSURWRQꢀIRUꢀFRPSRXQGVꢀ3a
Results and discussion
Treatment of 2-amino-4,5,6,7-tetrahydro[1]benzothiophene-3-
carbonitrile(1a) with the substituted benzylidenemalononitrile
NH2
CN
CN
CN
Ar
R
C
C
R
N
NHR
S
2
S
N
Ar
1
a, R = H, Ar = 4-Me2NC6H4
b, R = Me, Ar = 2,5-(MeO)2C6H3
c, R = H, Ar = 4-ClC6H4
(E/Z)-3
a, R = H, Ar = 4-Me2NC6H4
CN
a, R = H
b, R = Ac
d, R = Me, Ar = 4-BrC6H4
b, R = Me, Ar = 2,5-(MeO)2C6H3
c, R = H, Ar = 4-ClC6H4
Cl
NH2
NH2
N
H
N
S
N
S
N
H
CN
CN
Cl
NH2
(E)-3c
(Z)-3c
Ph
Ph
O
Ph
O
NH2
Me
CN
Me
Me
N
Me
N
Ar
N
N
N
N
O
NH2
N
N
Ar
N
N
Me
Ph
4
Ph
CN
Ph
CN
(Z)-5a,b
(E)-5a,b
a, Ar = 2,5-(MeO)2C6H3
b, Ar = 4-BrC6H4
* Correspondent. E-mail: ahmedy84@hotmail.com

JOURNAL OF CHEMICAL RESEARCH 2009 215
Ph
and 3c, and the methyl protons for compound 3b. The higher
ratio of (Z)-isomers as compared with the (E) counterparts can
be attributed to the existence of the aryl moiety on the less
KLQGHUHGꢀ VLGHꢂꢀ &RQ¿JXUDWLRQDOꢀ DVVLJQPHQWVꢀ WRꢀ ꢈZ)-3, (E)-3,
(Z)-5 and (E)-5ꢀDUHꢀEDVHGꢀRQꢀWKHꢀDVVXPSWLRQꢀWKDWꢀWKHꢀROH¿QLFꢀ
or methyl protons of the (E)-isomers are more deshielded by
the aryl group as well as the hetero ring, compared with the
(Z)-counterparts. The EI MS spectra of compounds 3 and 5
did not show the molecular ion peaks, probably due to their
ready decomposition in the ionisation chamber, but they
showed some abundant peaks (see Experimental).
R1
Me
CN
C
C
COR2
R1
O
6a-e
N
a, R1= CO2Et, R2= OEt
b, R1= Ph, R2= OMe
N
O
N
H
Ph
(Z)-7a-d
c, R1= Ph, R2= C6H4Cl-4
R2
d, R1= Ph, R2= C6H4OMe-4
e, R1= R2= Ph
CN
Ph
CN
Ph
The formation of compounds 3 and 5 can be explained
as shown in Scheme 1. Nucleophilic attack by the amino
group of compound 1a or 4 at one of the cyano groups7 of
compounds 2 gives intermediate A, and cyclisation to the ring
cyano group follows to give 3 and 5.
H
H
N
H
S
N
H
S
8a-c
O
Ar
O
Ar
a, Ar = C6H4Cl-4
b, Ar = C6H4OMe-4
c, Ar = Ph
Treatment of compounds 3a±cꢀ ZLWKꢀ UHÀX[LQJꢀ DFHWLFꢀ
anhydride in the hope of obtaining their N-acetyl derivatives
was unsuccessful: 2-acetylamino[1]benzothiophene-3-carbo-
nitrile (1b) was the only isolated product in each case. The
structure of 1b was substantiated by the infrared and 1H NMR
spectra, the latter of which were devoid of any absorption
DWWULEXWDEOHꢀ WRꢀ DU\Oꢀ JURXSVꢂꢀ7KHꢀ VWUXFWXUHꢀ ZDVꢀ FRQ¿UPHGꢀ E\ꢀ
comparison with an authentic sample8ꢀSUHSDUHGꢀE\ꢀUHÀX[LQJꢀ
1a with acetic anhydride.
A rationalisation for the conversion of compounds 3a±c into
1b is presented in Scheme 2. Protonation at N1 ring nitrogen by
a trace of acetic acid present in acetic anhydride, followed by
ring cleavage, gives the substituted benzylidenemalononitrile
derivatives 2a±c, and 1a. Acetylation of 1a with acetic
anhydride gives 1b. The detection by TLC of the substituted
benzylidenemalononitriles 2a±c in the reaction mixtures lends
support to this proposal.
Reactions of 6-amino-1,4-dihydro-3-methyl-1,4-diphenyl
pyrano[2,3-c]pyrazole-5-carbonitrile (4) with the acetylenic
esters and ketones 6a-dꢀLQꢀUHÀX[LQJꢀHWKDQROꢀLQꢀWKHꢀSUHVHQFHꢀ
of a catalytic amount of triethylamine gave the ethenylamino-
pyrano[2,3-c]pyrazole derivatives (Z)-7a±d. However, the
WUHDWPHQWꢀ RIꢀ ꢄ±DPLQRꢁꢆꢃꢉꢃꢊꢃꢇꢁWHWUDK\GUR>ꢅ@EHQ]RWKLRSKHQHꢁ
3-carbonitrile (1a) with acetylenic ketones 6c±eꢀLQꢀUHÀX[LQJꢀ
n-butanol in presence of piperidine yielded the enaminoketones
(Z)-8a±c as amino-imino tautomeric mixtures in 3:2 ratios.
The infrared spectra of compounds 7 and 8 show NH, CN and
C=O group absorptions. The (ZꢋꢁFRQ¿JXUDWLRQꢀLVꢀDVVLJQHGꢀWRꢀ7
and 8 is based on the higher GꢀYDOXHꢀREVHUYHGꢀIRUꢀWKHꢀROH¿QLFꢀ
proton, as it is more deshielded by the oxo group in case of 7a
as well as the aryl groups in case of compounds 7b±d and 8, as
compared with the (E)-counterpart. The low frequency of the
absorption of the CO groups is evidence for the existence of 7
and 8 in their chelated forms shown. In chloroform solution,
the 1H NMR spectra of compounds 8 show two broad singlet
signals for NH and OH protons. This is consistent with their
existence as an amino-imino dynamic equilibrium in ratios of
ꢌꢀꢍꢀꢄꢂꢀ7KHꢀGRZQꢀ¿HOGꢀVKLIWVꢀRIꢀWKHꢀ1+ꢀDQGꢀ2+ꢀSURWRQVꢀDUHꢀLQꢀ
harmony with their existence as chelated forms as shown. The
higher proportion of the amino tautomers compared with the
imines is due to their relative thermodynamic stabilities.
Further support for the assigned structures of compounds
7 and 8 is found in their mass spectra. Compounds 7a, c and
8a±c reveal the molecular ions, and other abundant peaks.
However, the molecular ion peaks are missing in the cases of
compounds 7b, d but they show some important peaks.
Conclusion
It is concluded that reactions of the aminobenzothiophene
and aminopyranopyrazole carbonitrile derivatives with
substituted benzylidenemalononitriles proceed by attack of
NH
C
N
CN
C
R
R
R
NH2
NH
3 or 5
C
C(CN)2
NH2
Ar
Ar
Ar
N
N
CN
CN
2
1a or 4
A
Scheme 1
H
NH2
N
NH2
+ H+
N
- H+
N
N
X
X
X
S
N
H
S
N
H
S
N
3
R
X =
H+
Ac2O
Ar
NC
X
1b
1a
CN
2
Scheme 2

216 JOURNAL OF CHEMICAL RESEARCH 2009
ꢌꢄꢏꢇꢀꢈ1+ꢋꢃꢀꢌꢏꢌꢌꢀꢈDU\Oꢁ+ꢋꢃꢀꢄꢒꢌꢆꢃꢀꢄꢒꢅꢅꢃꢀꢄꢐꢌꢇꢀꢈDON\Oꢁ+ꢋꢃꢀꢄꢅꢒꢊꢀꢈ&Ł1ꢋꢃꢀ
1621 (C=N), 1558, 1521 (C=C), 826 cm-1 (G2-H). NMR (CDCl3):
GH 1.79 (m, 4, 2 CH2), 2.49 (m, 4, 2 CH2), 4.62 (br.s, NH2
exchangeable), 7.52 (dd, 2, ArH, Jo = 8.64 Hz, Jm = 1.96 Hz), 7.74
(s, 1, CH= ), 7.86 (dd, 2, ArH, Jo = 8.6 Hz, Jm = 1.9 Hz). EI MS:
m/z (%) 190 (M+. + 2 of 2c, 28), 188 (M+. of 2c, 76), 180 (M+. + 2 of
1a, 2), 178 (M+. of 1a, 38) 177 (14), 163 (11), 161 (32) 154 (12), 152
(base), 151 (11), 150 (97), 137 (25), 126 (21), 100 (12), 99 (14), 76
(23), 75 (24), 74 (13), 63 (18), 62 (16), 51 (24), 50 (32). Anal. Calcd
for C19H15ClN4S: C, 62.20; H, 4.12; N, 15.27. Found: C, 61.88; H,
3.92; N, 15.48%.
(E)-2-(4-Amino-5,6,7,8-tetrahydro[1]benzothieno[2,3-
d]pyrimidin-2-yl)-3-(4-chlorophenyl)-propenonitrile (E-3c): Yellow
needles; 16% yield, PꢂSꢂꢀꢅꢆꢏ±ꢅꢆꢄ°C (dilute ethanol). IR: Qmax 3439,
3342, 3215 (NH), 3093 (aryl-H), 2939, 2921, 2863 (alkyl-H), 2220
ꢈ&Ł1ꢋꢃꢀ ꢅꢊꢆꢅꢀ ꢈ& 1ꢋꢃꢀ ꢅꢉꢒꢉꢃꢀ ꢅꢉꢊꢏꢀ ꢈ& &ꢋꢃꢀ ꢐꢅꢒꢀ FP-1 (G2-H). NMR
(CDCl3): GH 1.87 (m, 4, 2 CH2), 2.69 (m, 4, 2 CH2), 4.75 (br.s, NH2
exchangeable), 7.44 (dd, 2, ArH, Jo = 8.6 Hz, Jm = 1.85 Hz), 7.88 (dd,
2, ArH, Jo = 8.6 Hz, Jm = 1.92 Hz), 8.38 (s, 1, CH= ). EI MS: m/z (%)
302 (31), 301 (24), 300 (base), 299 (21), 274 (25), 273 (16), 272 (78),
271 (11), 178 (M+. of 1a, 2.8), 89 (38), 77 (15), 76 (10), 75 (13), 63
(25), 58 (11), 51 (15). Anal. Calcd for C19H15ClN4S: C, 62.20; H,
4.12; N, 15.27. Found: C, 62.48; H, 4.31; N, 15.42%.
the amino group at one of the two cyano groups and not at
the E-carbon of the unsaturated system.7,13 On the other hand,
in their reactions with acetylenic esters and ketones, attack of
the amino group at the E-carbon of the acetylenic system14-16
takes place, rather than at the carbonyl function.
Experimental
Melting points were measured on an electrothermal melting point
apparatus. Elemental analyses were carried out at the Microanalytical
Unit of Cairo University. IRspectra were measured on a Unicam
SP1200 spectrometer using the KBr wafer technique. 1H NMR
spectra were measured on a Varian Gemini 200 MHz instrument
with chemical shifts (Gꢋꢀ H[SUHVVHGꢀ LQꢀ SSPꢀ GRZQ¿HOGꢀ IURPꢀ 0H4Si.
Mass spectra were recorded on a Shimadzu GC-MS QP 1000 EX
instrument operating at 70 eV. Column chromatography and TLC
were run on silica Gel Voeim, activity III/30 mm according to
Brockmann & Schodder, and TLC aluminium sheets silica gel 60
F254ꢀꢈ0HUFNꢋꢂꢀµ/LJKWꢀSHWUROHXPꢎꢀUHIHUVꢀWRꢀWKHꢀIUDFWLRQꢀEꢂSꢂꢀꢊꢏ±ꢐꢏ°C,
XQOHVVꢀRWKHUZLVHꢀVSHFL¿HGꢂ
2-Amino-4,5,6,7-tetrahydro[1]benzothiophene-3-carbonitrile(1a),8
6-amino-1,4-dihydro-3-methyl-1,4-diphenylpyrano[2,3-c]pyrazole-
5-carbonitrile (4),9 substituted benzylidenemalononitriles (2),10 and
acetylenic esters11 and ketones12 (6) were prepared according to
literature methods.
Reaction of aminonitrile 4 with substituted benzylidenemalononitriles
2b,d
A mixture of 4 (3 mmol) and a substituted benzylidene malononitrile
(2b,dꢋꢀ ꢈꢌꢀ PPROꢋꢀ LQꢀ QꢁEXWDQROꢀ ꢈꢄꢏꢀ P/ꢋꢀ ZDVꢀ UHÀX[HGꢀ IRUꢀ ꢄꢏꢀ Kꢂꢀ
The reaction mixture was concentrated and chromatographed over
silica gel. In the case of the reaction 4 with 2b, successive elution with
light petroleum/ether (4:1 v/v) gave (E)-5a, then with light petroleum/
ether (2:3 v/v) afforded (Z)-5a. However, in the case of the reaction
with 2d; elution with petroleum ether/ether (9:1 v/v) yielded (E)-5b,
then with petroleum ether/ether (1:1 v/v) gave (Z)-5b.
Reactionofaminonitrile1awithsubstitutedbenzylidenemalononitriles
2a–c
A mixture of 1a (3 mmol) and a substituted benzylidenemalononitrile
(2a±cꢋꢀ ꢈꢌꢀ PPROꢋꢀ LQꢀ QꢁEXWDQROꢀ ꢈꢄꢏꢀ P/ꢋꢀ ZDVꢀ KHDWHGꢀ WRꢀ UHÀX[ꢀ IRUꢀ
20 h. The reaction mixture was then concentrated and left to stand
at room temperature overnight to give a solid. Crystallisation from
the indicated solvent gave the fused aminopyrimidinecarbonitrile
(E/Z)-(3a±c). The n-butanol mother liquor in the case of the reaction
of 1a with 2c was evaporated and chromatographed over silica gel.
Successive elution with light petroleum/diethyl ether (9:1 v/v)
afforded (E)-3c, and then with light petroleum/diethyl ether) (1:1 v/v)
gave (Z)-3c.
(E)-2-(5-Amino-1,4-dihydro-3-methyl-1,4-diphenylpyrazolo[4',3':5,
6]pyrano[2,3-d]pyrimidin-7-yl)-3-(2,5-dimethoxyphenyl)-but-2-
enonitrile (E-5aꢋꢍꢀ<HOORZꢀFU\VWDOVꢓꢀꢌꢊꢑꢀ\LHOGꢃꢀPꢂSꢂꢀꢅꢄꢉ±ꢅꢄꢊ°C (light
SHWUROHXPꢀ EꢂSꢂꢀ ꢆꢏ±ꢊꢏ°C). IR: Qmax 3422, 3326, 3234 (NH), 3062
ꢈDU\Oꢁ+ꢋꢃꢀ ꢄꢒꢄꢉꢃꢀ ꢄꢐꢆꢇꢀ ꢈDON\Oꢁ+ꢋꢃꢀ ꢄꢄꢅꢄꢀ ꢈ&Ł1ꢋꢃꢀ ꢅꢊꢊꢅꢀ ꢈ& 1ꢋꢃꢀ ꢅꢊꢏꢅꢃꢀ
1593 (C=C), 756, 693 cm-1 (G5H). NMR (CDCl3): GH 1.82 (s, 3, CH3
pyrazole), 2.29 (s, 3, CH3), 3.78, 3.82 (two singlets, 6, 2 OCH3), 4.85
(s, 1, CH), 5.82 (br.s, NH2ꢀH[FKDQJHDEOHꢋꢃꢀꢊꢂꢒꢇ±ꢇꢂꢊꢒꢀꢈPꢃꢀꢅꢌꢃꢀ$U+ꢋꢂꢀ
EI MS: m/z (%) 382 (11), 351 (12), 266 (14), 263 (18), 262 (70), 261
(36), 186 (16), 185 (87), 174 (32), 129 (17), 128 (36), 127 (12), 105
(18), 91 (61), 78 (10), 77 (base), 65 (12), 64 (18), 63 (15), 51 (58),
50 (14). Anal. Calcd for C33H28N6O3: C, 71.21; H, 5.07; N, 15.09.
Found: C, 70.98; H, 5.26; N, 14.88%.
(Z)-2-(5-Amino-1,4-dihydro-3-methyl-1,4-diphenylpyrazolo
[4',3':5,6]pyrano[2,3-d]pyrimidin-7-yl)-3-(2,5-dimethoxyphenyl)-
but-2-enonitrile (Z-5aꢋꢍꢀ<HOORZꢀFU\VWDOVꢓꢀꢌꢏꢑꢀ\LHOGꢃꢀPꢂSꢂꢀꢅꢌꢇ±ꢅꢌꢒ°C
(ethanol). IR: Qmax 3404, 3330, 3208 (NH), 3045 (aryl-H), 2931,
ꢄꢐꢌꢒꢀ ꢈDON\Oꢁ+ꢋꢃꢀ ꢄꢄꢅꢊꢀ ꢈ&Ł1ꢋꢃꢀ ꢅꢊꢆꢄꢀ ꢈ& 1ꢋꢃꢀ ꢅꢉꢆꢏꢀ ꢈ& &ꢋꢃꢀ ꢇꢆꢆꢃꢀ ꢊꢇꢌꢀ
cm-1 (G5H). NMR (CDCl3): GH 1.61 (s, 3, CH3 pyrazole), 2.17 (s, 3,
CH3), 3.77, 3.82 (two singlets, 6, 2 OCH3), 4.77 (s, 1, CH), 5.85 (br.
s, NH2ꢀH[FKDQJHDEOHꢋꢃꢀꢊꢂꢆꢆ±ꢇꢂꢌꢇꢀꢈPꢃꢀꢅꢌꢃꢀ$U+ꢋꢂꢀ(,ꢀ06ꢍꢀm/z (%) 448
(M+.-[Ph + OCH3], 78), 418 (29), 417 (40), 351 (44), 333 (57), 332
(93), 167 (14), 166 (21), 165 (41), 154 (23), 139 (45), 124 (33), 104
(24), 92 (31), 91 (100), 77 (52), 76 (14), 67 (20), 66 (26), 65 (31), 64
(17), 63 (13), 55 (49), 51 (71), 50 (18). Anal. Calcd for C33H28N6O3:
C, 71.21; H, 5.07; N, 15.09. Found: C, 71.35; H, 4.98; N, 15.29%.
(E)-2-(5-Amino-1,4-dihydro-3-methyl-1,4-diphenylpyrazolo
[4',3':5,6]pyrano[2,3-d]pyrimidin-7-yl)-3-(4-bromophenyl)-but-
2-enonitrile (E-5bꢋꢍꢀ <HOORZꢀ FU\VWDOVꢓꢀ ꢌꢐꢑꢀ \LHOGꢃꢀ PꢂSꢂꢀ ꢄꢅꢐ±ꢄꢄꢏ°C
ꢈSHWUROHXPꢀHWKHUꢀEꢂSꢂꢀꢐꢏ±ꢅꢏꢏ°C). IR: Qmax 3494, 3389 (NH), 3050
ꢈDU\Oꢁ+ꢋꢃꢀ ꢄꢒꢄꢏꢃꢀ ꢄꢐꢉꢄꢀ ꢈDON\Oꢁ+ꢋꢃꢀ ꢄꢄꢏꢇꢀ ꢈ&Ł1ꢋꢃꢀ ꢅꢊꢏꢐꢀ ꢈ& 1ꢋꢃꢀ ꢅꢉꢇꢐꢃꢀ
1547 (C=C), 827 (G2H) 762, 693 cm-1 (G5H). NMR (CDCl3): GH 1.79
(s, 3, CH3 pyrazolo), 2.30 (s, 3, CH3), 4.79 (s, 1, CH), 5.75 (br.s,
NH2ꢀH[FKDQJHDEOHꢋꢃꢀꢊꢂꢉꢒ±ꢇꢂꢊꢒꢀꢈPꢃꢀꢅꢆꢃꢀ$U+ꢋꢂꢀ(,ꢀ06ꢍꢀm/z (%) 354
(M+-NCC=C(CH3)C6H4Br-p, 1), 352 (21), 351 (91), 350 (41), 349
(100), 348 (25), 168 (18), 140 (21), 77 (14), 76 (13), 75 (15), 51 (20).
Anal. Calcd for C31H23BrN6O: C, 64.70; H, 4.03; N, 14.60. Found:
C, 64.85; H, 4.19; N, 14.49%.
(E/Z)-2-(4-Amino-5,6,7,8-tetrahydro[1]benzothieno[2,3-d]
pyrimidin-2-y1)-3-(4-N,N-dimethylaminophenyl)propenonitrile (3a):
ꢐꢏꢑꢀ <LHOGꢃꢀ PꢂSꢂꢀ ꢅꢄꢏ±ꢅꢄꢄ°&ꢀ ꢈOLJKWꢀ SHWUROHXPꢀ EꢂSꢂꢀ ꢆꢏ±ꢊꢏ°C). IR:
Qmax 3447, 3329, 3207 (NH), 3060 (aryl-H), 2933, 2911, 2838 (alkyl-
+ꢋꢃꢀ ꢄꢅꢒꢊꢀ ꢈ&Ł1ꢋꢃꢀ ꢅꢊꢄꢏꢈ& 1ꢋꢃꢀ ꢅꢉꢐꢐꢃꢀ ꢅꢉꢄꢄꢀ ꢈ& &ꢋꢃꢀ ꢐꢉꢆꢃꢀ ꢇꢊꢉꢀ FP-1.
NMR (CDCl3): GH 1.77 (m, 4, 2CH2), 2.49 (m, 4, 2CH2),3.08 (s, 6,
NMe2 for E-isomer), 3.14 (s, 6, NMe2 for Z-isomer), 4.59 (br.s, NH2
exchangeable), 6.77 (dd, 2, ArH, Jo = 7.88 Hz, Jm = 2.54 Hz), 7.48
(s, 1, CH= for Z-isomer), 7.81 (dd, 2, ArH, Jo = 7.26 Hz, Jm = 2.64
Hz),8.26 (s, 1, CH= for E-isomer). EI MS: m/z (%) 197 (M+ of 2a, 3),
180 (M+ + 2 of 1a, 3), 178 (M+ of 1a, 41), 177 (15), 150 (100). Anal.
Calcd for C21H21N5S: C, 67.17; H, 5.64; N, 18.65. Found: C, 66.95;
H, 5.89; N, 18.86%.
(E/Z)-2-(4-Amino-5,6,7,8-tetrahydro[1]benzothieno[2,3-d]
pyrimidin-2-yl)-3-(2,5-dimethoxyphenyl)-but-2-enonitrile (3b): 83%
<LHOGꢃꢀ PꢂSꢂꢀ ꢅꢉꢐ±ꢅꢊꢏ°&ꢀ ꢈOLJKWꢀ SHWUROHXPꢀ EꢂSꢂꢀ ꢐꢏ±ꢅꢏꢏ°C). IR: Qmax
3446, 3329, 3207 (NH), 3030 (aryl-H), 2933, 2911, 2837 (alkyl-
+ꢋꢃꢀꢄꢅꢒꢊꢀꢈ&Ł1ꢋꢃꢀꢅꢊꢄꢏꢀꢈ& 1ꢋꢃꢀꢅꢉꢄꢅꢀFP-1 (C=C). NMR (CDCl3): GH
1.74 (m, 4, 2 CH2), 2.42 (m, 4, 2 CH2), 2.56 (s, 3, CH3, for Z-
isomer), 2.58 (s, 3, CH3, for E- isomer), 3.77, 3.82 (two singlets, 6,
2 OCH3), 4.65 (br.s, NH2ꢀ H[FKDJHDEOHꢋꢃꢀ ꢊꢂꢇꢌ±ꢇꢂꢇꢄꢀ ꢈPꢃꢀ ꢌꢃꢀ $U+ꢋꢂꢀ
Anal. Calcd for C22H22N4O2S: C, 65.00; H, 5.46; N, 13.78. Found:
C, 64.79; H, 5.53; N, 13.85%.
(E/Z)-2-(4-Amino-5,6,7,8-tetrahydro[1]benzothieno[2,3-d]
pyrimidin-2-yl)-3-(4-chlorophenyl)propenonitrile
(3c):
Yellow
FU\VWDOVꢓꢀꢉꢏꢑꢀ\LHOGꢃꢀPꢂSꢂꢀꢅꢄꢌ±ꢅꢄꢉ°C (dilute ethanol). IR: Qmax 3440,
ꢌꢌꢌꢄꢃꢀꢌꢄꢏꢐꢀꢈ1+ꢋꢃꢀꢌꢏꢌꢉꢀꢈDU\Oꢁ+ꢋꢃꢀꢄꢒꢄꢒꢃꢀꢄꢐꢊꢌꢀꢈDON\Oꢁ+ꢋꢃꢀꢄꢄꢄꢏꢀꢈ&Ł1ꢋꢃꢀ
1656 (C=N), 1595, 1560 (C=C), 824 cm-1 (G2H). NMR (CDCl3):
GH 1.87(m,4,2CH2),2.71(m,4,2CH2),4.73(br.s,NH2 exchangeable).
For Z-isomer: GH 7.44 (dd, 2, ArH, Jo = 8.6 Hz, Jm = 1.6 Hz), 7.73 (s,
1, CH= ), 7.86 (dd, 2, ArH, Jo = 8.6 Hz, Jm = 1.86 Hz). For E-isomer:
GH 7.52 (dd, 2, ArH, Jo = 8.6 Hz, Jm = 1.8 Hz), 7.88 (dd, 2, ArH,
Jo =8.4Hz, Jm =1.9Hz), 8.38(s, 1, CH=). EIMS:m/z(%)302(28), 300
(100), 272 (77), 190 (M+ + 2 of 2c, 25), 188 (M+ of 2c, 75), 153 (M + .
of 2c -Cl, 100), 134 (15), 126 (25), 102 (12), 101 (10), 100 (17), 89
(40), 80 (30), 77 (13), 63 (26), 62 (27), 51 (24), 50 (55). Anal. Calcd
for C19H15ClN4S: C, 62.20; H, 4.12; N, 15.27. Found: C, 62,32; H,
4.27; N, 14.99%.
(Z)-2-(5-Amino-1,4-dihydro-3-methyl-1,4-diphenylpyrazolo
[4',3':5,6]pyrano[2,3-d]pyrimidin-7-yl)-3-(4-bromophenyl)-but-
2-enonitrile (Z-5bꢋꢍꢀ <HOORZꢀ FU\VWDOVꢓꢀ ꢄꢌꢑꢀ \LHOGꢃꢀ PꢂSꢂꢀ ꢄꢏꢉ±ꢄꢏꢇ°C
(ethanol). IR: Qmax 3395, 3307, 3207 (NH), 3076 (aryl-H), 2954,
ꢄꢐꢇꢐꢃꢀꢄꢐꢅꢐꢀꢈDON\Oꢁ+ꢋꢃꢀꢄꢄꢅꢉꢀꢈ&Ł1ꢋꢃꢀꢅꢊꢉꢏꢃꢀꢅꢊꢆꢅꢀꢈ& 1ꢋꢃꢀꢅꢊꢏꢊꢃꢀꢅꢉꢆꢄꢀ
(C=C), 832 cm-1 (G 5-H). NMR (CDCl3): GH 1.74 (s, 3, CH3 pyrazole),
2.17 (s, 3, CH3), 4.72 (s, 1, CH), 5.81 (br.s, NH2 exchangeable),
(Z)-2-(4-Amino-5,6,7,8-tetrahydro[1]benzothieno[2,3-d]
pyrimidin-2-yl)-3-(4-chlorophenyl)-propenonitrile (Z-3c): 23% Yield,
PꢂSꢂꢀꢅꢏꢐ±ꢅꢅꢏ°&ꢀꢈOLJKWꢀSHWUROHXPꢀEꢂSꢂꢀꢆꢏ±ꢊꢏ°C). IR: Qmax 3446, 3329,

JOURNAL OF CHEMICAL RESEARCH 2009 217
ꢊꢂꢄꢆ±ꢇꢂꢇꢏꢀꢈPꢃꢀꢅꢆꢃꢀ$U+ꢋꢂꢀ(,ꢀ06ꢍꢀm/z (%) 497 (M+-Ph, 1.4), 479 (M+.
-[Ph + 18], 2.7), 400 (M+-[Ph + 18 + Br], 7.2), 374 (M+-[Ph + 18 +
Br + CN], 2), 291 (1.5), 289 (1.5), 287 (15), 286 (100), 285 (19), 284
(96), 116 (13), 102 (11), 91 (18), 77 (22), 76 (13), 75 (12), 51 (26),
50 (12). Anal. Calcd for C31H23BrN6O: C, 64.70; H, 4.03; N, 14.60.
Found: C, 64.52; H, 3.98; N, 14.75%.
Reaction of 2-amino-4,5,6,7-tetrahydro[1]benzothiophene-3-carbo-
nitrile (1a) with acetylenic ketones 6c±e
A mixture of 1a (3 mmol), each of 6c±e (3 mmol) and a few drops of
SLSHULGLQHꢀZDVꢀUHÀX[HGꢀLQꢀQꢁEXWDQROꢀꢈꢅꢉꢀP/ꢋꢀIRUꢀꢄꢏꢀKꢂꢀ7KHꢀUHDFWLRQꢀ
mixture is concentrated and allowed to stand at room temperature
overnight to give a semisolid material. Trituration with methanol
JDYHꢀ Dꢀ VROLGꢂꢀ 5HFU\VWDOOLVDWLRQꢀ IURPꢀ HWKDQROꢀ DIIRUGHGꢀ ꢏꢂꢅ±ꢏꢂꢄꢀ Jꢀ
recovered 1a. Leaving the mother liquor at room temperature
overnight afforded a solid product (8a±c) which was recrystallised
from the indicated solvent.
Reaction of acetic anhydride with the aminonitriles 3a–c
The benzothienopyrimidine derivatives 3a±c (0.4 g) were each
UHÀX[HGꢀLQꢀDFHWLFꢀDQK\GULGHꢀꢈꢅꢉꢀP/ꢋꢀIRUꢀꢆꢀKꢂꢀ7KHꢀUHDFWLRQꢀPL[WXUHꢀ
was cooled and poured into ice-cold water to give the same product,
2-acetylamino-4,5,6,7-tetrahydro[1]benzothiophene-3-carbonitrile
(1bꢋꢃꢀ PꢂSꢂꢀ ꢄꢏꢐ±ꢄꢅꢏ°C (light petroleum/benzene) (lit.8ꢀ PꢂSꢂꢀ ꢄꢅꢉ±
216°&ꢋꢀLQꢀꢊꢉ±ꢐꢇꢑꢀ\LHOGVꢂꢀ,5ꢍꢀQmax 3266, 3219 (NH), 2992, 2926,
ꢄꢐꢆꢏꢀꢈDON\Oꢁ+ꢋꢃꢀꢄꢄꢏꢒꢀꢈ&Ł1ꢋꢃꢀꢅꢊꢐꢐꢀꢈ& 2ꢋꢃꢀꢅꢊꢌꢇꢃꢀꢅꢉꢉꢅꢀꢈ& &ꢋꢂꢀ105ꢀ
(DMSO-d6): GH 1.76 (m, 4, 2CH2), 2.18 (s, 3, CH3), 2.58 (m, 4,
2CH2), 11.52 (br.s, NH exchangeable). This substance was identical
in all respects (m.p., mixed m.p. and TLC) with an authentic sample
prepared from the reaction of 1a with acetic anhydride.
2-[[2-(4-Chlorobenzoyl)-1-phenylethenyl]amino]-4,5,6,7-tetra-
hydro[1]benzothiophene-3-carbonitrile (8a) (as amino-imino
tautomer)ꢍꢀ%URZQꢀFU\VWDOVꢓꢀꢌꢄꢑꢀ\LHOGꢃꢀPꢂSꢂꢀꢅꢐꢅ±ꢅꢐꢌ°C (petroleum
HWKHUꢀEꢂSꢂꢀꢐꢏ±ꢅꢏꢏ°C). IR: Qmax 3445 br. NH, 3059 (aryl-H), 2940,
ꢄꢐꢌꢇꢀꢈDON\Oꢁ+ꢋꢃꢀꢄꢄꢏꢉꢀꢈ&Ł1ꢋꢃꢀꢅꢊꢆꢉꢀꢈ& 2ꢋꢃꢀꢅꢉꢐꢆꢃꢀꢅꢉꢅꢒꢀꢈ& 1ꢀDQGꢔRUꢀ
C=C), 845 (G2H), 779, 695 cm-1 (G5H). NMR (CDCl3): GH 1.75 (m, 4,
2 CH2), 2.48 (m, 4, 2 CH2), 4.76 (br.s, NH exchangeable for amino-
WDXWRPHUꢋꢃꢀꢊꢂꢅꢅꢀꢈVꢃꢀꢅꢃꢀ&+ ꢀꢋꢃꢀꢇꢂꢌꢊ±ꢇꢂꢒꢆꢀꢈPꢃꢀꢒꢃꢀ$U+ꢋꢃꢀꢅꢌꢂꢊꢇꢀꢈEUꢂVꢃꢀ2+ꢀ
exchangeable for imino-tautomer). EI MS: m/z (%) 420 (M+ + 2, 10),
418 (M+, 22), 279 (M+-COC6H4Cl, 17), 141 (27), 139 (COC6H4Cl,
100), 138 (15), 111 (28), 77 (11). Anal. Calcd for C24H19ClN2OS: C,
68.81; H, 4.57; N, 6.69. Found: C, 68.65; H, 4.71; N, 6.52%.
4,5,6,7-Tetrahydro-2-[[2-(4-methoxybenzoyl)-1-phenylethenyl]
amino][1]benzothiophene-3-carbonitrile (8b) (as amino-imino
tautomer)ꢍꢀ%URZQꢀFU\VWDOVꢓꢀꢄꢆꢑꢀ\LHOGꢃꢀPꢂSꢂꢀꢅꢐꢐ±ꢅꢒꢏ°C (methanol/
benzene). IR: Qmax 3432, 3335, 3218 NH, 2937, 2903, 2837 (alkyl-
+ꢋꢃꢀꢄꢅꢒꢊꢀꢈ&Ł1ꢋꢃꢀꢅꢊꢄꢏꢀꢈ& 2ꢋꢃꢀꢅꢉꢒꢏꢃꢀꢅꢉꢅꢒꢀFP-1 (C=N and/or C=C).
NMR (CDCl3): GH 1.57 (br.s, 4, 2CH2), 2.28 (br.s, 4, 2CH2), 3.66 (s,
3, OCH3), 4.49 (br.s, NH exchangeable for amino-tautomer), 5.93 (s,
ꢅꢃꢀ&+ ꢀꢋꢃꢀꢊꢂꢇꢏ±ꢇꢂꢇꢐꢀꢈPꢃꢀꢒꢃꢀ$U+ꢋꢃꢀꢅꢌꢂꢆꢉꢀꢈEUꢂVꢃꢀ2+ꢀH[FKDQJHDEOHꢀIRUꢀ
imino-tautomer). EI MS: m/z (%) 416 (M+ + 2, 8), 414 (M+., 30), 415
(20), 135 (COC6H4OMe, 100), 77 (15). Anal. Calcd for C25H22N2O2S:
C, 72.44; H, 5.35; N, 6.76. Found: C, 72.61; H, 5.12; N, 6.92%.
2-[(2-Benzoyl-1-phenylethenyl)amino]-4,5,6,7-tetrahydro[1]
benzothiophene-3-carbonitrile (8c) (as amino-imino tautomer):
<HOORZꢀQHHGOHVꢓꢀꢆꢌꢑꢀ<LHOGꢃꢀPꢂSꢂꢀꢄꢏꢅ±ꢄꢏꢌ°C (methanol/benzene). IR:
QmaxꢀꢌꢆꢆꢐꢀEUꢂꢀ1+ꢃꢀꢌꢏꢊꢄꢀꢈDU\Oꢁ+ꢋꢃꢀꢄꢒꢄꢄꢃꢀꢄꢐꢆꢏꢀꢈDON\Oꢁ+ꢋꢃꢀꢄꢄꢏꢌꢀꢈ&Ł1ꢋꢃꢀ
1654 (C=O), 1611, 1591, 1569 (C=N and/or C=C), 769, 694 cm-1
(G5H). NMR (CDCl3): GH 1.61 (m, 4, 2CH2), 2.27 (m, 4, 2CH2), 4.58
ꢈEUꢂVꢃꢀ1+ꢀH[FKDQJHDEOHꢀIRUꢀDPLQRꢁWDXWRPHUꢋꢃꢀꢉꢂꢒꢇꢀꢈVꢃꢀꢅꢃꢀ&+ ꢀꢋꢃꢀꢇꢂꢏꢉ±
7.79 (m, 10, ArH), 13.46 (br.s, OH exchangeable for imino-tautomer).
EI MS m/z (%) 386 (M+ + 2, 4), 385 (52), 384 (M+, 25), 383 (11), 356
(10), 282 (14), 281 (10), 280 (14), 279 (17), 105 (COC6H5, 100), 77
(41). Anal. Calcd for C24H20N2OS: C, 74.97; H, 5.24; N, 7.29. found:
C, 74.62; H, 4.99; N, 7.46%.
Reactions of the aminonitrile 4 with acetylenic esters and ketones
6a±d
An acetylenic ester (6a,b) or ketone (6c,d) (2 mmol) was added to a
solution of 4 (2 mmol) in ethanol (20 mL) containing triethylamine
ꢈWKUHHꢀ GURSVꢋꢀ DQGꢀ WKHꢀ PL[WXUHꢀ ZDVꢀ UHÀX[HGꢀ IRUꢀ ꢄꢏꢀ Kꢂꢀ7KHꢀ UHDFWLRQꢀ
mixture was then concentrated and left to stand at room temperature
overnight to provide a solid. Recrystallisation from the indicated
solvent gave the relevant adduct (7a±d).
(Z)-1,4-Dihydro-3-methyl-1,4-diphenyl-6-[(1,2-diethoxycarbonyl-
ethenyl)amino]pyrano[2,3-c]pyrazole-5-carbonitrile (Z-7a): 40%
<LHOGꢃꢀPꢂSꢂꢀꢅꢏꢏ±ꢅꢏꢄ°C (light petroleum/benzene). IR: Qmax 3434 br.
ꢈ1+ꢋꢃꢀꢄꢒꢐꢏꢃꢀꢄꢒꢄꢆꢃꢀꢄꢐꢇꢅꢀꢈDON\Oꢁ+ꢋꢃꢀꢄꢄꢅꢆꢀꢈ&Ł1ꢋꢃꢀꢅꢇꢄꢇꢀꢈ& 2ꢋꢃꢀꢅꢊꢌꢅꢀ
(C=N), 1600, 1542 (C=C), 753, 692 (G5H). NMR (DMSO-d6): GH
1.20 (m, 6, 2CH2CH3), 2.08 (S, 3, CH3), 4.22 (m, 4, 2CH2CH3), 5.20
ꢈVꢃꢀꢅꢃꢀ&+ꢋꢃꢀꢊꢂꢉꢇꢀꢈVꢃꢀꢅꢃꢀ&+ ꢀꢋꢃꢀꢇꢂꢄꢊ±ꢇꢂꢆꢌꢀꢈPꢃꢀꢅꢏꢃꢀ$U+ꢋꢃꢀꢐꢂꢊꢏꢀꢈEUꢂVꢃꢀ1+ꢀ
exchangeable). EI MS: m/z (%) 498 (M+., 1), 453 (M+-OEt, 8), 425
(M+.-CO2Et,12) 408 (M+.-2OEt, 15), 352 (M+.-2CO2Et, 20), 328 (30),
262 (91), 185 (77), 174 (43), 128 (40), 119 (32), 93 (100), 91 (36),
77 (35). Anal. Calcd for C28H26N4O5: C, 67.46; H, 5.26; N, 11.24.
Found: C, 67.29; H, 5.32; N, 11.35%.
(Z)-Methyl 3-[(5-cyano-1,4-dihydro-1,4-diphenyl-3-methylpyrano
[2,3-c]pyrazol-6-yl)amino]-3-phenylprop-2-enoate (Z-7b): Yellow
FU\VWDOVꢓꢀ ꢌꢒꢑꢀ \LHOGꢃꢀ PꢂSꢂꢀ ꢅꢆꢉ±ꢅꢆꢐ°&ꢀ ꢈOLJKWꢀ SHWUROHXPꢀ EꢂSꢂꢀ ꢐꢏ±
100°C). IR: Qmax 3340, 3280, 3180 (NH), 3050 (aryl-H), 2960, 2900,
ꢄꢐꢆꢏꢀꢈDON\Oꢁ+ꢋꢃꢀꢄꢅꢊꢏꢀꢈ&Ł1ꢋꢃꢀꢅꢇꢄꢏꢀꢈ& 2ꢋꢃꢀꢅꢊꢉꢏꢀꢈ& 1ꢋꢃꢀꢅꢉꢒꢏꢃꢀꢅꢉꢉꢏꢀ
(C=C), 760, 690 cm-1 (G5H). NMR (DMSO-d6): GH 1.91 (s, 3, CH3),
3.93 (s, 3, OCH3), 4.59 (br.s, NH, exchangeable), 5.10 (s, 1, CH),
ꢊꢂꢆꢐꢀꢈVꢃꢀꢅꢀ&+ ꢀꢋꢃꢀꢇꢂꢏꢉ±ꢇꢂꢐꢅꢀꢈPꢃꢀꢅꢉꢃꢀ$U+ꢋꢂꢀ(,ꢀ06ꢍꢀm/z (%) 460 (25),
459 (22), 458 (52), 457 (M+-OCH3, 85), 265 (18), 264 (56), 263 (78),
261 (15), 197 (16), 195 (34), 185 (20), 138 (13), 137 (12), 136 (20),
131 (20), 129 (26), 128 (32), 127 (10), 116 (30), 115 (36), 105 (16),
103 (16), 102 (12), 101 (14), 89 (12), 77 (54), 75 (16), 64 (12), 59
(100), 51 (26). Anal. Calcd for C30H24N4O3: C, 73.76; H, 4.95; N,
11.47. Found: C, 73.51; H, 5.08; N, 11.69%.
(Z)-6-[[2-(4-Chlorobenzoyl)-1-phenylethenyl]amino]-1,4-dihydro-
3-methyl-1,4-diphenylpyrano[2,3-c]pyrazole-5-carbonitrile (Z-7c):
ꢆꢌꢑꢀ<LHOGꢃꢀ PꢂSꢂꢀ ꢅꢆꢄ±ꢅꢆꢉ°&ꢀ ꢈOLJKWꢀ SHWUROHXPꢀ EꢂSꢂꢀ ꢐꢏ±ꢅꢏꢏ°C). IR:
Qmax 3433 br. (NH), 3059 (aryl-H), 2971, 2921, 2857 (alkyl H), 2205
ꢈ&Ł1ꢋꢃꢀꢅꢊꢉꢐꢀꢈ& 2ꢋꢃꢀꢅꢉꢐꢐꢀꢈ& 1ꢀDQGꢔRUꢀ& &ꢋꢃꢀꢐꢌꢏꢀFP-1 (G2H) NMR
(CDCl3): GH 2.10 (s, 3, CH3), 5.05 (br.s, NH exchangeable), 5.45 (s,
ꢅꢃꢀ&+ꢋꢃꢀꢊꢂꢆꢉꢀꢈVꢃꢀꢅꢃꢀ&+ ꢀꢋꢃꢀꢇꢂꢅꢒ±ꢇꢂꢐꢉꢀꢈPꢃꢀꢅꢒꢃꢀ$U+ꢋꢂꢀ(,ꢀ06ꢍꢀm/z (%)
570 (M+. + 2, 0.2), 568 (M+., 0.5), 459 (M+. + 2-C6H4Cl, 0.9), 457
(M+-C6H4Cl, 1.5), 263 (22), 246 (13), 219 (52), 139 (COC6H4Cl, 32),
119 (19), 91 (100), 77 (30). Anal. Calcd for C35H25ClN4O2: C, 73.87;
H, 4.43; N, 9.84. Found: C, 73.95; H, 4.64; N, 9.72%.
(Z)-1,4-Dihydro-6-[[2-(4-methoxybenzoyl)-1-phenylethenyl]
amino]-3-methyl-1,4-diphenylpyrano[2,3-c]pyrazole-5-carbonitrile
(Z-7dꢋꢍꢀꢄꢊꢑꢀ<LHOGꢃꢀPꢂSꢂꢀꢅꢉꢐ±ꢅꢊꢏ°C (light petroleum/benzene). IR:
Qmax 3446, 3358, 3246 (NH), 3060 (aryl-H), 2934, 2839 (alkyl-H),
ꢄꢄꢅꢆꢀ ꢈ&Ł1ꢋꢃꢀ ꢅꢊꢆꢉꢀ ꢈ& 2ꢋꢃꢀ ꢅꢊꢅꢏꢀ ꢈ& 1ꢋꢃꢀ ꢅꢉꢇꢆꢃꢀ ꢅꢉꢅꢉꢀ ꢈ& &ꢋꢃꢀ ꢐꢌꢄꢀ
(G2H), 764, 696 cm-1 (G5H). NMR (CDCl3): GH 1.56 (s, 3, CH3), 3.87
(s, 3, OCH3), 4.76 (br.s, NH exchangeable), 5.37 (s, 1, CH), 6.87 (s,
1, CH= ), 7.02 (dd, 2, ArH, Jo = 8.8 Hz, Jmꢀ ꢀꢄꢂꢏꢀ+]ꢋꢃꢀꢇꢂꢌꢊ±ꢇꢂꢊꢅꢀꢈPꢃꢀ
15, ArH), 7.55 (dd, 2, ArH, Jo = 8.8 Hz, Jm = 2.4 Hz). EI MS m/z (%)
327 (M+-C6H5C=CHCOC6H4OMe, 3), 326 (21), 325 (100), 324 (14),
310 (12), 255 (19). Anal. Calcd for C36H28N4O3: C, 76.58; H, 4.99;
N, 9.92. Found: C, 76.70; H, 4.66; N, 10.15%.
Received 1 October 2008 ; accepted 11 February 2009
Paper 08/0201 doi: 10.3184/030823409X435874
Published online: 29 April 2009
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