Synthesis of aryl(orbenzyl)-(Z)-N-[2-amino-1,2-dicyanovinyl]formamidines

Article abstract of DOI:10.1081/SCC-100107009

Starting from readily available ethyl(Z)-N-(2-amino-1,2-dicyanovinyl)formimidate (1), the N-aryl (or benzyl)-N′-(2-amino-1,2-dicyanovinyl)formamidines (2) can be prepared in good yields by reaction with aromatic amines at room temperature in the presence of a catalytic amount of anilinium hydrochloride.

Full text of DOI:10.1081/SCC-100107009

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SYNTHESIS OF ARYL(OR BENZYL)-(Z)-N-[2-AMINO-1,2-
DICYANOVINYL]FORMAMIDINES
Asieh Yahya-Zadeh a & Brian L. Booth b
a Department of Chemistry , University of Guilan , P.O. Box 1914, Rasht, Iran
b Department of Chemistry , University of Manchester Institute of Science and
Technology , Manchester, M60 1QD, UK
Published online: 16 Aug 2006.
To cite this article: Asieh Yahya-Zadeh & Brian L. Booth (2001) SYNTHESIS OF ARYL(OR BENZYL)-(Z)-N-[2-AMINO-1,2-
DICYANOVINYL]FORMAMIDINES, Synthetic Communications: An International Journal for Rapid Communication of Synthetic
Organic Chemistry, 31:23, 3617-3622, DOI: 10.1081/SCC-100107009
To link to this article: http://dx.doi.org/10.1081/SCC-100107009
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SYNTHETIC COMMUNICATIONS, 31(23), 3617–3622 (2001)
SYNTHESIS OF ARYL(OR
BENZYL)-(Z)-N-[2-AMINO-1,2-
DICYANOVINYL]FORMAMIDINES
Asieh Yahya-Zadeh1, and Brian L. Booth2
*
1Department of Chemistry, University of Guilan,
P.O. Box 1914, Rasht, Iran
2Department of Chemistry, University of
Manchester Institute of Science and Technology,
Manchester M60 1QD, UK
ABSTRACT
Starting from readily available ethyl(Z )-N-(2-amino-1,2-
dicyanovinyl)formimidate (1), the N-aryl (or benzyl)-N 0-(2-
amino-1,2-dicyanovinyl)formamidines (2) can be prepared
in good yields by reaction with aromatic amines at room
temperature in the presence of a catalytic amount of anilinium
hydrochloride.
Amidines are an important class of compounds which have proved to
be intermediates in a number of biological processes.1–3 The chemistry and
preparation of amidines have been reviewed by Shriner and Neumann.4
Several alkyl, aryl amidine and also the amidrazone have been reported
* Corresponding author.
3617
Copyright & 2001 by Marcel Dekker, Inc.
www.dekker.com

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YAHYA-ZADEH AND BOOTH
by our group.5–7 We decided that we could prepare various aryl and benzyl
amidines of type (2a–2d) by reaction of imidate (1) with aromatic amines.
In order to synthesis the required amidines (2a–2d), the following
method, which involves treatment of imidate (1) with the appropriate
aryl or benzyl amine, was used (Scheme 1). Ethyl(Z )-N-(2-amino-1,2-dicya-
novinyl)formimidate (1) was prepared according to a previously reported
procedure by treatment of equimolar quantities of triethylorthoformate and
diaminomaleonitrile in refluxing dioxane.6,8
Scheme 1.
Having obtained the imidate (1) in good yield (94%) it was then
treated with aryl or benzylamine in a 1 : 1 molar ratio in ethanol in the
presence of a catalytic amount of anilinium hydrochloride. The reaction
mixture was stirred under an inert atmosphere at room temperature
with the exclusion of light. A homogeneous solution was obtained and
within 10 min a white solid precipitated out. The product was filtered off

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ARYL AND BENZYL AMIDINES
3619
after 3–4 h. It was washed with diethyl either and was found be pure by
1
TLC, H and 13C NMR spectroscopy.
The elemental analysis results of amidine (2) were satisfactory. The
mass spectrum showed a peak at m/z 260, 286, 272 and 242 for 2a, 2b, 2c
and 2d, respectively. Initial fragmentation, involve loss of the amidine seg-
ment (M-C5H4N5)þ. The 1H NMR spectra of compound 2a and 2b in
[2H6]dimethyl sulfoxide ([2H6]DMSO) had some interesting features. The
two benzylic protons (H6) appeared as a doublet at d 4.58 and d 4.68 ppm
respectively, caused by a coupling to the NH proton which appeared as a
broad doublet at d 8.08–8.16 ppm. The HC¼N proton was also a doublet
(JH,NH 6.0–6.5 Hz), at d 7.62–7.78 ppm and showed a small additional coup-
ling (<1 Hz) to the benzylic protons. The fact that the HC¼N and the
benzylic protons are coupled to NH was also confirmed by D2O exchange,
after which the two doublets (HC¼N and CH2) appeared as sharp singlets.
The 13C NMR spectrum show two peaks of relatively low intensity at
d 118.8120.1 and d 119.9–121.4 ppm due to the two cyano groups and a
peak due to HC¼N at d 149.0–154.5 ppm in the amidine molecule. The
infrared spectrum of amidine (2a–2d) showed two strong absorption in
the region 2195–2230 cmꢀ1 characteristic of CN stretching vibrations,
together with an NH and a C¼N stretching vibration at 3480–3120 and
1655–1640 cmꢀ1 respectively.
EXPERIMENTAL
1
The H NMR spectra were recorded on Hitachi–Perkin–Elmer R24B
(60 MHz) or Bruker XL 300 (300 MHz) instruments (with J-values given
in Hz), 13C NMR spectra (with DEPT 135) either on a Bruker WP80 or

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YAHYA-ZADEH AND BOOTH
XL300 instrument, and IR spectra on a Shimadzu IR-435 spectrophot-
ometer. Mass spectra were recorded on a Kratos Concept instrument. The
melting points were measured on an Electrothermal digital melting point
apparatus and are uncorrected.
General Procedure for the Preparation of the
N-Aryl-N 0-[2-amino-1,2-dicyanovinyl]formamidines (2a–2d)
The aromatic amine (1.01 g, 6.07 mmol) was added to a suspension of
1 (1.00 g, 6.09 mmol) in dry ethanol or ethyl acetate, which contained ani-
linum hydrochloride (0.02). The mixture was stirred at room temperature
until TLC (9 : 1 chloroform/ethanol eluant) showed that all the formimidate
had disappeared (usually 3 to 4 h) and the amidine was isolated by filtration.
The most cases the product was pale green to white. The precipitate was
washed with dry diethyl ether and was dried under vacuum to give the
analytically pure products (2a–2d).
(2-Chlorobenzyl)-(Z)-N-[2-amino-1,2-dicyanovinyl]formamidine (2a): m.p.
108–110ꢁC (decomp.). Yield 92%. [Found. C, 55.5; H, 3.7; N, 27.3; Cl,
13.6. Calc. for C12H10N5Cl requires C, 55.6; H, 3.8; N, 27.0, Cl, 13.5%];
m/z (FAB) 260 (M þ 1)þ 65.5%, 259 (M)þ 78%, 224 (M-Cl)þ 18.2%, 165
[(M-1)-C4H3N3]þ 100%, 164 (M-C4H4N3]þ 90.8%, 142 (12.12%), 125
(81.8%), 119 (30.3%), 109 (9.0%); dH (300 MHz, d6-DMSO, TMS Int.
Ref.) 4.58 (d, 2H, 3J6,NH 6.5 Hz, H6), 6.80 (s, 2H, NH2), 7.40–7.44 (complex
m, 2H, H11 and H12), 7.45–7.56 (complex m, 2H, H9 and H10), 7.78 (d, 1H,
3
3J5,NH 6.5 Hz, H5), 8.16 (br.d, 1H, JNH,5 6.5 Hz, NH) ppm; dC (75 MHz,
d6-DMSO) 45.9 (C6), 110.0 (C1), 119.1 (C2), 120.1 (C3), 121.4 (C4), 131.2
(C11), 132.9 (C12), 133.0 (C10), 133.5 (C9), 136.6 (C8), 139.7 (C7), 154.5
(C5) ppm; nmax (Nujol mull) 3420s, 3380s, 3320s, 3180m (NH str.), 3000m,
2980m, 2950m, 2220s (CN str.), 2200s (CN str.), 1655s (C¼N str.), 1580m,
(NH bend), 1470m, 1460s, 1450s, 1430m, 1380s, 1360s, 1260s, 1235w,
1220w, 1170m, 1060s, 1040s, 1015s, 980w, 950s, 815s, 790m, 760s cmꢀ1
.
(3,4-Dimethoxybenzyl)-(Z)-N-[2-amino-1,2-dicyanovinyl]formamidine (2b):
m.p. 124–126ꢁC (decomp.). Yield 94%. [Found. C, 59.2; H, 5.5; N, 24.3.
Calc. for C14H15N5O2 C, 58.9; H, 5.3; N, 24.6%]; m/z (EI) 286 (M þ 1)þ
3.2%, 245 [(M þ 1)-CH2N2]þ 1.8%, 168 [(M þ 1)-C5H2N4]þ 9.8%, 151
(M-C5H4N5)þ 100%; dH (300 MHz, d6-DMSO) 3.95 (s, 3H, OCH3),
3
3.97 (s, 3H, OCH3), 4.68 (d, 2H, J6,NH 6 Hz, CH2), 6.40 (s, 2H, NH2),
3
6.78–7.02 (m, 3H, H8, H9 and H12), 7.62 (d, IH, J5,NH 6 Hz, H5), 8.08
3
(br, d, 1H, J5,NH 6 Hz, NH) ppm; dC (75 MHz, d6-DMSO) 43.9 (C6,
by DEPT 135), 55.5 and 55.7 (C13 and C14), 110.4 (C1), 115.8 and 116.1
(C9, C12), 119.3 and 120.4 (C3 and C4), 121.1 (C2), 124.1 (C8), 135.2 (C7),

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3621
152.0 and 152.7 (C10 and C11), 154.4 (C5) ppm; nmax (Nujol mull) 3480s,
3380s (NH str.), 2225s (CN str.), 2205s (CN str.), 1645s (C¼N str.), 1600m
(NH bend), 1520m, 1275s, 1250m, 1230w, 1170s, 1155w, 1040s, 980m, 965w,
880s, 850s, 815s, 780s cmꢀ1
.
(3,4-Dimethoxyphenyl)-(Z)-N-[2-amino-1,2-dicyanovinyl]formamidine (2c):
m.p. 138–140ꢁC (decomp.). Yield 96%. [Found. C, 57.9; H, 4.8; N, 25.4.
Calc. for C13H13N5O2 C, 57.6; H, 4.8; N, 25.8%]; m/z (EI) 272 (M þ 1)þ
8.9%, 271 (M)þ 47.8%, 270 (M-1)þ 11.0%, 244 [(M-1)-CN]þ 32.9%, 164
[(M-1)-C4H2N4]þ 37.6%; dH (300 MHz, d6-DMSO) 3.60 (s, 6H, 2 ꢂ OCH3),
3
6.25 (br.s, 2H, NH2), 6.76 (d, 1H, J8,7 8.5 Hz, H8), 7.45–7.70 (br. complex
m, 3H, H7, H11 and H5), 9.70 (br.s, 1H, NH) ppm; dC (75 MHz, d6-DMSO)
59.4 and 59.7 (C12 and C13), 110.0 (C1), 116.0 (C7), 116.3 (C8), 116.6
(C11), 119.0 and 120.0 (C3 and C4), 122.5 (C2), 137.1 (C6), 149.0 (C5),
153.0 and 153.3 (C9 and C10) ppm; nmax (Nujol mull) 3470s, 3340s, 3235s
(NH str.), 2230s (CN str.), 2195s (CN str.), 1640m (C¼N str.), 1600m (NH
bend), 1580s, 1510s, 1300s, 1255s, 1230s, 1165s, 1145s, 1130s, 1025s, 965w,
935s, 830s, 795s, 765s cmꢀ1
.
(4-Methoxyphenyl)-(Z)-N-[2-amino-1,2-dicyanovinyl]formamidine (2d):
m.p. 123–124ꢁC (decomp.). Yield 93%. [Found. C, 59.7; H, 4.5; N, 28.7.
Calc. for C12H11N5O C, 59.8; H, 4.6; N, 29.0%]; m/z (EI) 242 (M þ 1)þ
100%, 241 (M)þ 2.8%, 215 (M-CN)þ 40.9%, 136 [(M þ 1)-C4H2N4]þ 4.9%,
124 [(M þ 1)-C5H2N4]þ 44.9%, 108 [(M þ 1)-C5H4N5]þ 4.3%; dH (300 MHz,
d6-DMSO) 3.78 (s, 3H, OCH3), 6.40 (br.s, 2H, NH2), 6.92 (d, 2H, 3J8,7 8 Hz,
H8 and H10), 7.42–7.90 (br. complex m, 3H, H7, H11 and H5), 9.90 (br.s,
1H, NH) ppm; dC (75 MHz, d6-DMSO) 59.1 (C12), 109.0 (C1), 118.1 (C8
and C10), 118.8 and 119.9 (C3 and C4), 122.3 (C2), 124.5 (C7 and C11),
136.6 (C6), 150.9 (C5), 159.1 (C9) ppm; nmax (Nujol mull) 3470w, 3450s,
3345s, 3300m, 3250s, 3120m, (NH str.), 2215s (CN str.), 2195s (CN str.),
1650m (C¼N str.), 1600m (NH bend), 1575w, 1515m, 1310s, 1290m,
1245s, 1220s, 1175m, 1030s, 960w, 820s, 785s cmꢀ1
.
REFERENCES
1. Booth, B.L.; Alves, M.J.; Proenca, M.F.J.R.P. J. Chem. Soc., Perkin
Trans. 1 1990, 1705.
2. Voet, A.B.; Schwartz, A.W. Bioorg. Chem. 1983, 12, 8.
3. Neilson, D.G. in, The Chemistry of Amidines and Imidates, Wiley,
London, 1975, p. 1.
4. Shriner, R.L.; Neumann, F.W. Chem. Rev. 1944, 35, 351.
5. Booth, B.L.; Alves, M.J.; Proenca, M.F.J.R.P. J. Chem. Soc., Perkin
Trans. 1 1992, 913.

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6. Alves, M.J.; Booth, B.L.; Al-Duaij, O. Kh.; Eastwood, P.R.; Nezhat, L.;
Proenca, M.F.J.R.P.; Ramos, A.S. J. Chem. Research (S) 1993, 402; J.
Chem. Research (M) 1993, 2701.
7. Booth, B.L.; Alves, M.J.; Carvalho, A.; Eastwood, P.R.; Nezhat, L. J.
Chem. Soc., Perkin Trans. 2 1994, 1949.
8. Woodward, D.W. U.S. Patent 2 534 331/1950.
Received in the UK November 6, 2000

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