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DOI: 10.1055/s-2002-34223
A New Reaction of N-substituted Formamides with Trichloroethylene under Conditions of Phase-Transfer Catalysis (PTC)
Publication History
Publication Date:
23 September 2002 (online)
Abstract
Reaction of N-aryl formamides 1 with trichloroethylene (TRI) carried out in the presence of 50% aq sodium hydroxide and a catalyst, tetra-butylammonium hydrogen sulfate (TBAHS), affords substituted enamidines 2, and pyrrole-2,5-diylidenediamines 3, in good yields. Formation of these products is rationalized.
Key words
phase-transfer catalysis - formamides - trichloroethylene
- 1
Hopf H.Witulski B. Modern Acetylene ChemistryStang PJ.Diederich F. VCH; Weinheim: 1995. p.48 -
2a
Dehmlow EV.Dehmlow SS. Phase Transfer Catalysis 3rd ed.: Verlag Chemie; Weinheim: 1993. -
2b
Starks CM.Liotta CL.Halpern M. Phase-transfer Catalysis Chapman and Hall; New York London: 1994. -
2c
Mkosza M.FedoryÒski M. In Handbook of Phase Transfer CatalysisSasson Y.Neumann R. Blackie Academic and Professional; London: 1997. p.135 -
3a
JoÒ A.czyk Gierczak AH. Synthesis 1998, 962 -
3b
JoÒ A.czyk Gierczak AH. Tetrahedron 2000, 56: 6083 - 4
Pielichowski J.Bogda D. Polish J. Chem. 1988, 40: 483 -
5a
Pielichowski J.Bogda D. Liebigs Ann. Chem. 1988, 595 -
5b
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Martynov AV.Mirskova AN.Kalikhman ID.Voronkov MG. Zh. Org. Khim. 1988, 24: 509 ; Chem. Abstr. 1989, 110, 153824 - 8
Pielichowski J.Popielarz R. Tetrahedron 1984, 40: 2671 -
12a
Fukuda M.Okamoto Y.Sakurai H. Bull. Chem. Soc. Jpn. 1977, 50: 1895 -
12b
Prajznar B. Rocz. Chem. 1962, 36: 1449 ; Chem. Abstr. 1963, 59, 5139. -
13a
Von Braun J.Jostes F.Heymons A. Chem. Ber. 1927, 60: 92 -
13b
Yamagida S.Fujita T.Ohoka M.Katagiri I.Miyabe M.Komori S. Bull. Chem. Soc. Jpn. 1973, 46: 303 -
13c
Meth-Cohn O.Westwood KT. J. Chem. Soc., Perkin Trans. 1 1983, 2089 - 14 Only a few structures, related to
azacyclic products 3, are described:
Anwar M.Abdel-Hay FI.Fahmy M. Rev. Roum. Chim. 1978, 23: 1085 ; Chem. Abstr. 1979, 90, 54899b - 15
Speziale AJ.Smith LR. J. Am. Chem. Soc. 1962, 84: 1868 - 16 Aniline reacted with TRI at ca 120 °C
affording mixture of products:
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References
JoÒczyk, A.; Michalski, K., manuscript in preparation.
9
Experimental Procedure:
Amide 1a (0.73 g, 6 mmol), diethyl ether
(15 mL), cyclohexane (5 mL), TRI (1.58 g, ca 1.1 mL, 12 mmol) and
TBAHS (0.02 g, 0.06 mmol) were vigorously stirred while 50% aq
NaOH (4.8 g, 3.2 mL, 60 mmol) was added dropwise at 20-25 °C.
After addition, the reaction was carried out for 15 min, the mixture
was poured into the ice with water, the phases were separated, the
water phase was extracted with CH2Cl2 (5 × 20
mL), the combined organic extracts were dried (MgSO4)
and concentrated. The products 2a and 3a were isolated by column chromatography [Merck
silica gel 60 (230-400 mesh), eluent CH2Cl2]. 2a:
1H NMR (400 MHz,
CDCl3): δ = 3.98
(2 H, s),
6.36 (1 H, s), 6.91-7.49 (10 H, m); 13C
NMR (100 MHz, CDCl3): δ = 33.7, 115.2,
120.9, 123.5, 127.6, 128.0, 129.0, 129.4, 133.3, 139.4, 148.2, 152.2.
Anal. Calcd for C16H13Cl3N2:
C, 56.58; H, 3.86; N, 8.25; Cl 31.31. Found: 56.63; H, 3.79; 8.26;
31.23. 3a: 1H NMR (400
MHz, CDCl3): δ = 6.81 (2 H, s), 6.91-7.62
(15 H, m); 13C NMR (100 MHz, CDCl3): δ = 122.1,
124.0, 125.4, 127.3, 128.4, 128.8, 134.5, 149.0, 157.2. Anal. Calcd
for C22H17N3: C, 81.71; H, 5.36;
N, 12.99. Found: C, 81.58; H, 5.36; N, 13.06.
Spectral
data for 2 and 3. 2b:
1H NMR (400 MHz,
CDCl3): δ = 2.33 (3 H, s), 2.40 (3
H, s), 3.98 (2 H, s), 6.33 (1 H, s), 6.73-7.40 (8 H, m); 13C
NMR (100 MHz, CDCl3): δ = 21.4, 33.8,
114.9, 117.9, 121.6, 124.3, 124.7, 128.1, 128.7, 128.8, 129.1, 133.4,
138.8, 139.3, 139.4, 148.3, 152.1. Anal. Calcd for C18H17Cl3N2:
C, 58.80; H, 4.66; N, 7.62; Cl 28.93. Found: C, 58.72; H, 4.58;
N, 7.73; Cl, 28.86. 3b: 1H
NMR (400 MHz, CDCl3): δ = 2.37 (6 H,
s), 2.45 (3 H, s), 5.29 (2 H, s), 6.79-7.41 (12 H, m); 13C
NMR (100 MHz, CDCl3):
δ = 21.3,
21.5, 119.0, 122.8, 124.6, 125.3, 125.6, 128.3, 128.5, 129.1, 134.4,
138.5, 149.1, 157.2. Anal. Calcd for C25H23N3:
C, 82.16; H, 6.34; N, 11.50. Found: C, 82.10; H, 6.39; N, 11.45. 2c:
1H NMR (400 MHz,
CDCl3): δ = 2.32 (3 H, s), 2.39 (3
H, s), 3.95 (2 H, s), 6.34 (1 H, s), 6.83-7.35 (8 H, m); 13C
NMR (100 MHz, CDCl3): δ = 20.8, 21.2,
33.6, 114.7, 120.8, 127.6, 129.4, 130.0, 132.8, 133.4, 136.7, 138.0,
145.8, 152.3. Anal. Calcd for C18H17Cl3N2:
C, 58.80; H, 4.66; N, 7.62; Cl 28.93. Found: C, 58.54; H, 4.70;
N, 7.68; Cl, 29.00. 3c: 1H
NMR (400 MHz, CDCl3): δ = 2.34 (6 H,
s), 2.39 (3 H, s), 5.29 (2 H, s), 6.82-7.47 (12 H, m); 13C NMR
(100 MHz, CDCl3): δ = 20.8, 21.2, 121.7,
122.0, 125.1, 128.2, 129.3, 129.5, 126.6, 131.9, 133.3, 137.1, 146.7,
157.3. Anal. Calcd for C25H23N3:
C, 82.16; H, 6.34; N, 11.50. Found: C, 82.14; H, 6.38; N, 11.60. 2d:
1H NMR (400 MHz,
CDCl3): δ = 3.95 (2 H, s), 6.38 (1
H, s), 6.82-7.43 (8 H, m); 13C
NMR (100 MHz, CDCl3): δ = 33.5, 115.9, 122.2,
128.8, 129.1, 129.7, 132.7, 133.9, 137.7, 146.5, 152.5. Anal. Calcd
for C16H11Cl5N2: C,
47.04; H, 2.71; N, 6.86; Cl 43.39. Found: C, 47.08; H, 2.80; N,
6.92; Cl, 43.34. 3d: 1H
NMR (400 MHz, CDCl3): δ = 5.30 (2 H,
s), 6.82-7.48 (12 H, m); 13C
NMR (100 MHz, CDCl3): δ = 122.5, 122.7, 125.2,
126.3, 128.3, 128.8, 138.0, 146.4, 153.5. Anal. Calcd for C22H14Cl3N3:
C, 61.92; H, 3.31; N, 9.85; Cl, 24.92. Found: C, 61.83; H, 3.28;
N, 9.74; Cl, 24.80. 2e:
1H
NMR (400 MHz, CDCl3): δ = 3.77 (3 H,
s), 3.80 (3 H, s), 3.92 (2 H, s), 6.87 (1 H, s), 6.93-7.42
(8 H, m); 13C NMR (100 MHz, CDCl3): δ = 33.3,
55.2, 55.3, 114.0, 114.4, 121.9, 129.3, 131.6, 133.4, 141.5, 152.5,
155.8, 159.1. Anal. Calcd for C18H17Cl3N2O2:
C, 54.09; H, 4.29; N, 7.01; Cl 26.61. Found: C, 53.97; H, 4.20;
N, 7.10; Cl, 26.53. 3e: 1H
NMR (400 MHz, CDCl3): δ = 3.78 (9 H,
s), 3.81 (2 H, s), 6.83-7.48 (12 H, m); 13C
NMR (100 MHz, CDCl3): δ = 55.2, 55.3,
65.7, 113.9, 114.1, 123.1, 124.9, 127.3, 129.6, 142.5, 156.4, 157.4,
158.4. Anal. Calcd for C25H23N3O3:
C, 72.62; H, 5.61; N, 10.16. Found: C, 72.74; H, 5.50; N, 10.24.
Crystallographic data for the structures 2a and 3a have been deposited with the Cambridge Crystallographic Data Center and allocated the deposition numbers CCDC 188398 and CCDC 188399, respectively. Copies of the data can be obtained, free of charge, on application to CCDC, 12 Union Road, Cambridge CB2 1EZ, (UK) [fax:+44(1223)336033 or e-mail: deposit@ccdc.cam.ac.uk].
11Structurally related amidines have already been synthesized via reaction of N-substituted amides with POCl3 [12] or PCl5. [12b] [13]