Diarylimidoylcyanides, an attractive class of intermediate: Novel synthesis of α-anilino-β-nitroenamines, N, N′- Disubstituted amidines and substituted phenyl glyoxate

Article abstract of DOI:10.1080/00397910500446902

The first report of the use of diarylimidoyl cyanides for the synthesis of α-anilino-β-nitrostyrenes, benzamides, and glyoxalic esters is presented, and the advantage of this class of intermediate over diarylimidoyl chlorides is discussed. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/00397910500446902

Synthetic Communicationsw, 36: 715–727, 2006
Copyright # Taylor & Francis Group, LLC
ISSN 0039-7911 print/1532-2432 online
DOI: 10.1080/00397910500446902
Diarylimidoylcyanides, an Attractive
Class of Intermediate: Novel Synthesis
of a-Anilino-b-Nitroenamines,
N, N0- Disubstituted Amidines and
Substituted Phenyl Glyoxate
Abhijit Roychowdhury, Versha V. Kumar, and A. P. Bhaduri
Medicinal Chemistry Division, Central Drug Research Institute,
Lucknow, India
Abstract: The first report of the use of diarylimidoyl cyanides for the synthesis of
a-anilino-b-nitrostyrenes, benzamides, and glyoxalic esters is presented, and the
advantage of this class of intermediate over diarylimidoyl chlorides is discussed.
Keywords: Diarylimidoyl cyanides, b-nitroenamines, amidines, phenyl glyoxate
INTRODUCTION
Diarylimidoyl chlorides (1)[1,2] represent a class of intermediates that have
been exploited to synthesize a number of new chemical entities,[3,4] many
of them exhibiting biological properties to warrant filing of patents.[5,6]
However, these reactive chloro compounds are unstable, hydrolyze in air to
benzanilides or amides, and even in an atmosphere of argon have a short
shelf life.[1b,7] To overcome these problems, the exploration of the synthetic
utility of diarylimidoyl cyanides (2), which were found stable at room
temperature for months, was envisaged.
Received in the USA September 15, 2005
Dedicated to the late Dr. S. Sharma.
C.D.R.I. Communication No. 6311.
Address correspondence to Abhijit Roychowdhury, Southern Research Institute,
2000 Ninth Ave. S., Birmingham, AL 35205, USA. E-mail: roychowdhury@sri.org
715

716
A. Roychowdhury et al.
Figure 1. Diarylimidoyl chloride and diarylimidoyl cyanide.
Diarylimidoyl cyanides did receive attention of earlier workers
(Iminonitriles as “masked form of a-amino acids”).[8,9] but careful evaluation
of them as intermediates was not systematically carried out. In principle, dia-
rylimidoyl cyanides can mimic a large number of reactions of diarylimidoyl
chlorides and have built-in structural features that can be exploited to
deliver products not accessible from the reactive imidoyl chlorides (Figure 1).
The various observations made to illustrate these points are recorded in
this communication.
RESULTS AND DISCUSSION
The geometry across the C55N in diarylimidoyl chloride has been well studied
and reviewed, but little has been done for diarylimidoyl cyanides.[10] This
prompted us to resolve the stereochemistry across C55N in this class of
compounds on the basis of PMR studies before exploring their synthetic
utility. To achieve this objective, nOe difference studies of a model
compound 3 were carried out. Of the two possible geometric orientations
(3a and 3b), one (3b) only could explain the observed nOe on the ortho-
aromatic protons in ring A, because of the methyl protons present on ring
B, which suggested the depicted geometry for compound 3. These data and
the UV absorption band at 260 nm supported the E stereochemistry of diary-
limidoyl cyanides (Figure 2).
The base-catalyzed reaction of a reactive methylene compound, such as in
a nitroalkane, with diarylimidoyl cyanide gave b-nitroenamines, which have
Figure 2. nOe experiment.

Diarylimidoylcyanides
717
Scheme 1.
been used as building blocks for preparing a wide range of chemical entities
and precursors. (For synthetic applications of b-nitrostyrenes, see)[11]
The synthesis of b-nitroenamines has been well established and
documented,[12] but its synthesis from diarylimidoyl cyanides has never
been reported. Thus, under mild reaction conditions, in presence of
DBU, nitromethane reacted with a-anilino diarylimidoyl cyanides to yield
b-nitroenamines (8–11) in 38–44% yeild (Scheme 1).
The possible path for the synthesis is hypothesized as the attack of
the nitronate anion across the carbon nitrogen double bond followed by the
elimination of the cyano as HCN.
The stereochemistry of the resulting product was ascertained on the basis
of nOe difference studies on the model compound 11. PMR studies on the
compound indicated a positive nOe experienced by vinylinic and methyl
protons, which was only possible in isomer 11a. This established the
E-geometry (11a) of the b-nitroenamines (Figure 3).[10]
Like diarylimidoyl chloride, reactions of diarylimidoyl cyanides with
secondary amines in the presence of triethylamine yielded the respective
substituted benzamidines (13–17) (Scheme 2).
Although the chemistry of nucleophillic substitution across the carbon
nitrogen double bond has been well established,[13] it was interesting to
note that no earlier study established the geometry of the substituted
amidines. The nOe studies carried out with compound 15 established the
E-stereochemistry of the reaction products, as a positive nOe was observed
on irradiating the methyl protons on the aromatic ring B with the ortho-
aromatic protons of the phenyl ring A (Figure 4).
Figure 3. nOe experiment.

718
A. Roychowdhury et al.
Scheme 2.
A few examples exhibiting the synthetic utility of diarylimidoyl cyanides
are furnished. For example, acid hydrolysis smoothly yielded the esters of
substituted phenyl glyoxalic acids (20–24) (Scheme 3).
The synthesis of such esters has been reported either by oxidation of
hydoxy-carboxylic acids or their esters,[14] by alcohols,[15] by palladium-
catalyzed carbonylation of arylhalides,[16] or by other routes[17] but never
from diarylimidoyl cyanides.
However, base hydrolysis under basic conditions gave unstable inter-
mediates (26–29) (isolated and characterized), which further hydrolyzed to
the respective benzamides (30–33) (Scheme 4).
CONCLUSION
These examples do indicate that in the well-studied reactions of diarylimidoyl
chlorides, diarylimidoyl cyanides can be excellent alternative substrates. In
conclusion, our studies do justify better synthetic utility of diarylimidoyl
cyanides.
Figure 4. nOe experiment.

Diarylimidoylcyanides
719
Scheme 3.
EXPERIMENTAL
General
Melting points were determined in a hot-stage apparatus and are uncorrected.
IR spectra (cm21) were recorded on Beckmann Aculab-10, Perkin Elmer 881,
and Shimadzu FTIR-8210PC spectrophotometers, either on KBr discs or neat.
UV spectra (in nm) were measured on a Hitachi 34 spectrometer in 95%
1
MeOH unless otherwise stated. H NMR and 13C NMR experiments were
carried out on a Bruker 400 FT NMR, Bruker Avance DRX 300, and
Bruker Avance DPX 200 spectrometers, and unless otherwise stated, all
spectra were obtained using CDCl3 (CHCl3 d: 7.26 ppm). The irradiated
protons and the corresponding protons have been underlined for the nOe.
Electron impact (EI) mass spectra were recorded on a JOEL, JMS-D-300
spectrometer with the ionization potential of 70eV and are reported in the
form m/e (intensity relative to base ¼ 100) along with its intensity.
Elemental analysis was carried out on a Carlo-Erba EA 1108 elemental
analyzer, and the compounds were dried in Abderhalden. Reactions were
monitored by TLC on a silica gel 60 (E. Merck) of 0.25-mm thickness
either using iodine or Dragendorff spray for detection. Column
Scheme 4.

720
A. Roychowdhury et al.
chromatography, unless otherwise stated, carried on Merck silica gel (70–230
mesh). Room temperature was in the range of 25–288C. Combined organic
extracts were dried over anhydrous Na2SO4 and evaporated under reduced
pressure with a rotatory evaporation. Solvents and reagents were purchased
from E. Merck, Ranbaxy, Qualigens, S.D. Fine Chemicals, Sigma-Aldrich,
Janssen, and Fluka Chemicals. All the compounds reported earlier have
been referenced respectively; others are being reported first time.
Synthesis of a-N-(2-methylphenyl)iminophenylacetonitrile (3): Solution of
a-N-(2-methylphenylamino)phenylacetonitrile (0.25 mmol) in DMF (5.0 mL,
anhydrous) was stirred at 1108C for 14 h; thereafter the solvent was distilled
off in vacuo. The residue was washed with brine (20 mL) and extracted
with EtOAc (3 ꢀ 25 mL). Usual workup gave a semisolid residue, which
was purified by column chromatography using hexane–EtOAc (9.9:0.1,
v/v) as eluent to yield (43.0%, 0.3 g) the product as light yellow solid.
1
;;
Mp 1258C; IR (KBr): 2283(C N); H NMR (300 MHz): d 2.45(s, 3H,
CH3); 7.10–7.13(m, 1H, ArH); 7.24–7.30 (m, 5H, ArH); 7.59–7.61
(m, 1H, ArH); 7.91 (d, 1H, J ¼ 8.0, ArH); 8.18 (d, 1H, J ¼ 8.0, ArH); MS:
221 (Mþ, 5.8); anal. calcd. for C15H12N2 (220.27): C, 81.79; H, 5.48; N,
12.71. Found: C, 81.83; H, 5.71; N, 12.64.
nOe: 1H NMR (300 MHz): d 2.45 (s, 3H, CH3); 7.24–7.30 (m, 5H, ArH).
General Procedure for the Synthesis of b-Nitro Enamines (8–11)
CH3NO2 (1.0 mmol) was added to a solution of desired diarylimidoyl cyanide
(4–7) (1.0 mmol) in CH3CN (5.0 mL) in the presence of DBU (0.5 mL). The
mixture was stirred for 16–22 h at room temperature. Thereafter the solvent
was distilled off in vacuo; residue was washed with water (20 mL) and
extracted with EtOAc (3 ꢀ 20 mL). Usual workup furnished an oily residue,
which was purified by column chromatography using hexane–CHCl3 (7:3,
v/v) as eluent to yield the products. These were recrystallized from EtOH.
E-(2-Nitro-1-phenyl-vinyl)-phenyl amine (8)[18]: Yield 44.0% (0.105 g); mp
1
1258C. IR (KBr): 1596 (C55C); H NMR (300 MHz): d 7.50–7.55 (m, 5H,
ArH & CH); 7.67–7.87 (m, 6H, ArH); MS: 241 (Mþ, 3.3); 13C NMR
(300 MHz): d 101.6 (CH), 115.1 (Ar), 126.8, 127.6, 128.0, 129.3, 135.0,
146.7 (all Ar), 151.3 (C55N).
E-[1-(4-chlorophenyl)-2-nitro-vinyl]-phenyl amine (9): Yield 41.0%
1
(0.112 g); mp 1618C. IR (KBr): 1593 (C55C); H NMR (300MHz): d 7.52–
7.58 (m, 4H, ArH & CH); 7.70 (t, 2H, J ¼ 9.0, ArH); 7.87–7.90 (m, 4H,
ArH); MS: 275 (Mþ, 6.4); 13CNMR (300MHz): d 102.1 (CH), 115.2, 126.5,
127.6, 128.1, 129.3, 133.0 (all Ar), 151.3(C55N). Anal. calcd. for C14H9ClN2
(240.05): C, 69.86; H, 3.76; N, 11.63. Found: C, 70.01; H, 3.68; N, 11.59.

Diarylimidoylcyanides
721
E-[1-(4-methylphenyl)-2-nitro-vinyl]-phenyl amine (10): Yield 43.0%
1
(0.109 g); mp 1588C. IR (KBr): 1591 (C55C); H NMR (300 MHz): d 2.46
(s, 3H, CH3), 7.51–7.59(m, 4H, ArH & CH); 7.78 (t, 2H, J ¼ 9.0, ArH);
7.89–7.92 (m, 4H, ArH); MS: 255 (Mþ, 6.8). 13CNMR (300 MHz): d 20.5
(CH3), 102.1 (CH), 115.2, 126.5, 127.6, 128.1, 129.3, 133.0 (all Ar), 151.3
(C55N).
E-(2-Nitro-1-phenyl-vinyl)-o-methyl-phenyl amine (11)[19]: Yield 38.0%
1
(0.096 g); mp 1608C. IR (KBr): 1595 (C55C); H NMR (300 MHz): d 2.40
(s, 3H, CH3), 6.52 (d, 1H, J ¼ 9.0, ArH), 6.83–6.90 (m, 2H, ArH & CH);
7.02 (t, 2H, J ¼ 7.0, ArH); 7.21–7.33 (m, 6H, ArH), 13CNMR (300 MHz):
d 12.50 (CH3), 102.1 (CH), 115.0, 118.8, 124.5, 126.5, 127.6, 128.1, 129.3,
1
134.0, 147.5 (all Ar), 151.3 (C55N); MS: 255 (Mþ, 6.8). nOe: H NMR
(300 MHz): d2.40 (s, 3H, CH3), 6.83–6.90 (m, 2H, ArH & CH).
General Procedure for the Synthesis of Substituted
Amidines (13–17):
The respective primary/secondary(s) (0.5 mmol) were added to a solution of
diarylimidoyl cyanide (4, 6, 7, & 12) (0.5 mmol) in toluene (10.0 ml) in the
presence TEA (0.1 mL, 1.0 mmol) and stirred at 95–1058C for 8–12 h.
Thereafter the solvent was distilled off in vacuo; the residue obtained was
washed with brine (20 mL) and extracted with EtOAc (4 ꢀ 25 mL). Usual
workup gave an oily residue, which was purified by column chromatography
using hexane–EtOAc (9.7:0.3, v/v) as eluent to yield the respective amidines.
Recrystallization in EtOH yielded white crystalline solid.
E-[(4-Methyl-piperidine-1-yl)-N-phenyl-methylene]-phenylamine (13):
Yield 41.0% (0.056 g); mp 1288C. IR (KBr): 1583 (C55N); 1H NMR
(300 MHz): d 1.54–1.67 (m, 4H, N–CH2), 1.78–2.00 (m, 1H, CH), 2.18
(s, 3H, CH3), 3.35 (s, 4H, NCH2), 6.72–6.78 (m, 2H, ArH) 7.12–7.24
(m, 5H, ArH), 7.31–7.42 (m, 3H, ArH); 13CNMR (300 MHz): d 19.50
(CH3), 27.8 (CH), 32.4 (CH2), 44.20 (CH2), 122.5, 125.8, 126.8, 127.4,
128.1, 129.3, 134.0, 154.0 (all Ar), 164.3 (C55N); MS: 279 (Mþ, 4.8); anal.
calcd. for C19H22N2 (278.39): C, 81.97; H, 7.96; N, 10.06. Found: C, 82.48;
H, 8.01; N, 10.53.
E-[(4-Methyl-phenyl)-(piperidine-1-yl)-methylene]-phenylamine
(14):
Yield 40.0% (0.055 g); mp 818C. IR (KBr): 1583 (C55N); 1H NMR
(300 MHz): d 160–1.67 (m, 6H, N-CH2), 2.26 (s, 3H, CH3), 3.37 (s, 4H,
NCH2), 6.54 (d, 2H, J ¼ 6, ArH), 6.72 (t, 1H, J ¼ 9, ArH), 6.97–7.01
(m, 6H, ArH); MS: 279 (Mþ, 42.2); 13CNMR (300 MHz): d 21.0 (CH3),
26.2 (CH2), 25.8 (CH2), 46.45 (CH2), 122.5, 125.8, 126.8, 127.4, 128.1,

722
A. Roychowdhury et al.
129.7, 130.0, 140.4, 154.5 (all Ar), 164.3 (C55N); anal. calcd. for C19H22N2
(278.39): C, 81.97; H, 7.96; N, 10.06. Found: C, 81.64; H, 7.73; N, 10.40.
E-[(4-Phenyl-piperazine-1-yl)-N-phenyl-methylene]-o-methyl-phenylamine
1
(15): Yield 20.0% (0.035 g); mp 1188C. IR (KBr): 1581 (C55N); H NMR
(300 MHz): d 1.80–1.86 (m, 6H, N–CH2), 2.20 (s, 3H, CH3), 2.78–2.96
(m, 4H, NCH2), 4.11 (bs, 1H, CH), 6.31 (d, 2H, J ¼ 7, ArH), 6.34–6.95
(m, 4H, ArH), 7.10–7.33 (m, 8H, ArH); 13C NMR (300 MHz): d 12.5
(CH3), 48.58 (CH2), 58.25 (CH2), 118.5, 113.45, 121.5, 125.8, 126.8, 127.4,
128.1, 129.7, 130.0, 132.3 140.4, 144.5, 154.5 (all Ar), 164.3 (C55N); MS:
1
355 (Mþ, 15.5). nOe: H NMR (300 MHz): d2.20 (s, 3H, CH3), 6.34–6.95
(m, 4H, ArH).
E-p-Bromo-[(N-phenyl)-(piperidine-1-yl)-methylene]-phenylamine (16) [20]
:
Yield 41.5% (0.071 g); mp 1268C. IR (KBr): 1576 (C55N); 1H NMR
(300 MHz): d 1.71 (m, 6H, N–CH2), 3.55 (bs, 4H, N–CH2), 6.41 (d, 2H,
J ¼ 7, ArH), 7.10–7.15 (m, 3H, ArH), 7.32–7.45 (m, 4H, ArH); 13C NMR
(300 MHz): d 25.9 (CH2), 30.0 (CH2), 46.45 (CH2), 121.5, 124.2, 125.8,
126.8, 127.4, 128.1, 129.7, 130.0, 134.5, 140.4, 154.5 (all Ar), 164.3
(C55N); MS: 344 (Mþ, 56.9). Anal. calcd. for C18H19BrN2 (343.26): C,
62.98; H, 5.57; N, 8.15. Found: C, 62.72; H, 6.00; N, 8.78.
E-p-Bromo[(4-methylpiperidine-1-yl)-(N-phenyl)-methylene]-phenylamine
1
(17): Yield 38.5% (0.087 g); mp 1308C. IR (KBr): 1577 (C55N); H NMR
(300 MHz): d 1.84 (d, 4H, J ¼ 25.8, N–CH2), 2.18 (s, 3H, CH3), 2.70–
3.01 m, 1H, CH), 3.36–3.41 (m, 4H, NCH2), 6.50 (d, 2H, J ¼ 7, ArH), 6.88
(d, 4H, J ¼ 9, ArH), 7.03–7.34 (m, 8H, ArH); 13C NMR (300 MHz): d 18.9
(CH3), 27.5 (CH), 25.9 (CH2), 32.5 (CH2), 43.45 (CH2), 121.5, 124.2,
125.8, 126.8, 127.4, 128.5, 129.7, 133.0, 134.5, 152.5 (all Ar), 164.3
(C55N); MS: 420 (Mþ, 7.7). Anal. calcd. for C24H23BrN2 (419.35): C,
68.73; H, 5.52; N, 6.67. Found: C, 68.77; H, 5.62; N, 6.97.
General Procedure for the Synthesis of Compounds (20–24)
1 N HCl (1–2 mL) was added to a solution of desired diarylimidoyl cyanide
(4–6, 18, & 19) (1.0 mmol) in MeOH (10 mL) and the mixture was stirred
at room temperature for 6–8 h. Thereafter the solvent was distilled off in
vacuo and extracted with EtOAc (3 ꢀ 25 mL). Usual workup yielded an
oily residue, which was purified by column chromatography using hexane–
CHCl3 (7.5:2.5, v/v) as eluent to yield the compounds.
Carbomethoxycarbonylbenzene (20)[14e,21]: yield 64.0% (0.104 g); Oil. IR
1
(neat): 1718 (C55O); H NMR (200 MHz): d 3.92 (s, 3H, OCH3), 7.41–
7.64 (m, 3H, ArH), 8.03–8.10 (m, 2H, ArH); 13C NMR (300 MHz): d 43.5

Diarylimidoylcyanides
723
(OCH3), 129.5, 130.4, 134.5, 136.7 (all Ar), 168.3 (C55O), 182.5 (C55O); MS:
165 (Mþ, 1.3).
4-(Carbomethoxycarbonyl) chlorobenzene (21)[22,23]
:
Yield 60.0%
1
(0.111 g); mp 558C. IR (neat): 1728 (C55O); H NMR (300 MHz): d 3.90
(s, 3H, OCH3), 7.39–7.43 (m, 2H, ArH), 7.95–8.00 (m, 2H, ArH);
13C NMR (300 MHz): d 43.5 (OCH3), 129.5, 130.4, 134.5, 136.7, 139.8 (all
Ar), 168.3 (C55O), 182.5 (C55O); MS: 198 (Mþ, 2.6).
4-(Carbomethoxycarbonyl) methylbenzene (22)[23]: Yield 52.0%(0.092 g);
1
oil. IR (Neat): 1729 (C55O); H NMR (300 MHz): d 2.40 (s, 3H, CH3),
3.90 (s, 3H, OCH3), 7.25 (t, 2H, J ¼ 8, ArH), 7.92 (d, 2H, J ¼ 8, ArH);
13C NMR (300 MHz): d 20.5 (CH3), 43.5 (OCH3), 129.5, 130.4, 134.5,
136.7, 143.7 (all Ar), 168.3 (C55O), 181.8 (C55O); MS: 179 (Mþ, 1.0), 148
(25.4).
3-(Carbomethoxycarbonyl) nitrobenzene (23): Yield 55.0% (0.124 g); mp
1
828C. IR (KBr): 1722 (C55O); H NMR (300 MHz): d 3.99 (s, 3H, OCH3),
7.26–7.73 (m, 1H, ArH), 8.36–8.47 (m, 2H, ArH), 8.87 (s, 1H, ArH);
13C NMR (300 MHz): d 43.5 (OCH3), 124.6, 130.4, 132.0, 134.5, 149.7 (all
Ar), 168.3 (C55O), 182.5 (C55O); MS: 210 (Mþ, 4.3).
2-(Carbomethoxycarbonyl) thiophene (24)[24]: Yield 55.0% (0.093 g); oil.
1
IR (Neat): 1708 (C55O); H NMR (400 MHz): d 3.90 (s, 3H, OCH3), 7.10–
7.17 (m, 1H, ArH & thiophene), 7.20–7.29 (m, 1H, ArH & thiophene),
7.54–7.56 (m, 1H, ArH & thiophene); 13C NMR (300 MHz): d 43.5
(OCH3), 124.5, 127.4, 137.5, 142.7 (all Ar), 168.3 (C55O), 178.6 (C55O);
MS: 171 (Mþ, 2.7). Anal. calcd. for C7H6O3S (170.17): C, 49.40; H, 3.55.
Found: C, 49.61; H, 3.72.
General Procedure for the Synthesis of Compounds (26–29)
NaOH (0.04 g, 1.0 mmol), was added to a solution of diarylimidoyl cyanides
(4, 5, 12 & 25) (1.0 mmol) in MeOH (10 mL) and the mixture was stirred for
6–8 h, at room temperature. Thereafter the solvent was distilled off in vacuo,
neutralized with NaHCO3 (aq.) to pH 7, and then extracted by EtOAc
(3 ꢀ 20 mL). Usual workup yielded an oily residue, which was purified by
column chromatography using hexane–CHCl3 (5:5, v/v) as eluent to yield
the product.
[2-Methoxy-1-phenyl-methylene]-phenylamine (26)[25]
:
Yield 62.0%
1
(0.132 g); oil; IR (neat): 1661 (C55O); H NMR (300 MHz): d 4.02 (s, 3H,
OCH3), 7.28–7.56 (m.6H, ArH), 7.66–7.69 (m, 2H, ArH), 7.89 (d, 2H,
J ¼ 8, ArH); 13C NMR (300 MHz): d 47.5 (OCH3), 122.6, 127.5, 128.0,

724
A. Roychowdhury et al.
130.1, 131.5, 153.6 (all Ar), 164.3 (C55OCH3); MS: 212 (Mþ, 21.2); anal.
calcd. for C14H13NO (211.250): C,79.59; H,6.20; N,6.63. Found: C, 79.51;
H, 6.46; N, 6.89.
[1-(4-Chloro-phenyl)-2-methoxy-methylene]-phenylamine (27): Yield
55.0% (0.134 g); oil; IR (neat): 1660 (C55O), 1595 (C55N); 1H NMR
(300 MHz): d 3.96 (s, 3H, OCH3), 6.72 (d, 2H, J ¼ 8.75, ArH), 6.73–7.01
(m, 1H, ArH), 7.17–7.26 (m, 7H, ArH); MS: 246 (Mþ, 5.9), 216 (25.5);
13C NMR (300 MHz): d 33.5 (C55OCH3), 122.6, 127.5, 128.0, 130.1, 131.5,
136.4, 153.6 (all Ar), 164.3(C55O); anal. calcd. for C14H12ClNO (245.69);
C, 68.43; H, 4.92; N, 5.70. Found: C, 68.44; H, 5.14; N, 6.08.
p-Bromo-phenyl-[2-methoxy-1-phenyl-methylene]-amine (28): Yield
1
44.0% (0.127 g); oil; IR (neat): 1685 (C55O), H NMR (300 MHz): d 3.96
(s, 3H, OCH3), 6.54 (d, 2H, J ¼ 9, ArH), 7.22–7.35 (m, 7H, ArH); MS:
291 (Mþ, 18.6), 259 (13.1); 13C NMR (300 MHz): d 33.5 (OCH3), 121.5,
122.6, 124.5, 127.5, 128.0, 130.1, 131.5, 133.3, 136.4, 152.4 (all Ar), 164.3
(C55OCH3); anal. calcd. for C14H12BrNO (290.14): C, 57.95; H, 4.16; N,
4.82. Found: C, 57.61, H, 4.08; N, 4.63.
[2-Methoxy-1-thiophene-methylene]-phenylamine (29): Yield 67.0%
1
(0.145 g); oil; IR (neat): 1656 (C55O), 1595 (C55N); H NMR (400 MHz):
d 3.98 (s, 3H, OCH3), 6.85–6.94 (m, 3H, ArH & thiophene); 13C NMR
(300 MHz): d 33.5 (OCH3), 120.0, 121.5, 122.6, 124.5, 127.5, 128.0, 149.6
(all Ar), 164.3 (C55OCH3); MS: 291 (Mþ, 4.3), 186 (12.4); anal. calcd. for
C14H11NOS (217.29): C, 66.33; H, 5.10; N, 6.44. Found: C, 66.48; H, 5.49; N, 6.51.
General Procedure for the Synthesis of Substituted
Benzanilides (30–33)
SiO2 (catalytic amount) was added to a stirred solution of compounds (26–29)
in MeOH (10 mL) and was allowed to stir at room temperature for 3–4 h. It
was then filtered and concentrated to yield a semisolid residue, which was
then recrystallized in EtOH.
N-(Benzoyl) aniline (30)[26]: Yield 55.0% (0.108 g); mp 1608C. IR (KBr):
1625 (C55O), 3344 (NH); H NMR (300 MHz): d 7.26–7.54 (m, 6H, ArH);
1
7.64–7.68 (m, 2H, ArH); 7.86 (d, 2H, J ¼ 8, ArH); 9.8 (bs, 1H, NH);
13C NMR (300 MHz): d 122.6, 127.5, 128.0, 130.1, 131.5, 133.6, 153.6 (all
Ar), 165.3(C55O); MS: 198 (Mþ, 7.0); anal. calcd. for C13H11NO (197.23);
C, 79.16; H, 5.62; N, 7.10. Found: C, 79.58; H, 5.36; N, 7.36.
N-(4-Chlorobenzoyl) aniline (31)[26]: Yield 47.0% (0.108 g); mp 1938C. IR
(KBr): 1652 (C55O), 3301 (NH); 1H NMR (300 MHz): d 6.78 (d, 2H,

Diarylimidoylcyanides
725
J ¼ 7.5, ArH); 7.10–7.39 (m, 7H, ArH); 8.62 (bs, 1H, NH); 13C NMR
(300 MHz): d 122.6, 127.5, 128.0, 130.1, 131.5, 137.2, 153.6 (all Ar), 165.3
(C55O); MS: 232 (Mþ, 30.4).
N-(Benzoyl)-4-bromoaniline (32)[27]: Yield 40.0% (0.110 g); mp 2038C. IR
(KBr): 1639 (C55O), 3334 (NH); 1H NMR (300 MHz): d 6.52 (d, 2H,
J ¼ 7.5, ArH); 7.07–7.43 (m, 7H, ArH); 12.80 (bs, 1H, NH); 13C NMR
(300 MHz): d 122.6, 127.5, 128.0, 130.1, 131.5, 133.6, 153.6 (all Ar), 165.3
(C55O); MS: 198 (Mþ, 7.0).
N-(Thiopheno-2-carbonyl)-aniline (33)[11c,28]: Yield 54.0% (0.110 g); mp
1
1158C. IR (KBr): 1631 (C55O), 3305 (NH); H NMR (300 MHz): d 7.14–
7.20 (m, 2H, ArH & thiophene); 7.39 (t, 1H, J ¼ 8, ArH); 7.56–7.65
(m, 5H, ArH), 11.81 (bs, 1H, NH); 13C NMR (300 MHz): d 124.6, 127.5,
128.0, 130.1, 137.5, 138.6, (all Ar), 165.2 (C55O); MS: 204 (Mþ, 2.3);
anal. calcd. for C11H9NOS (203.26); C, 65.0; H, 4.46; N, 6.89. Found: C,
65.46; H, 4.50; N, 6.91.
ACKNOWLEDGMENTS
A.R.C. and V.V.K. thank Council of Scientific and Industrial Research (CSIR)
for their Senior Research Fellowship (SRF) and Research Assiociateship
(RA). Spectral analysis from the personnel of RSIC, CDRI, is highly acknowl-
edged. We greatly appreciate all the help and fruitful discussions with S.
Batra, CDRI, Lucknow, India.
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