Isocyanates and methylene active compounds
Russ.Chem.Bull., Int.Ed., Vol. 55, No. 5, May, 2006
877
for 3 days and concentrated by evaporation, Et2O and a
5% solution of HCl were added to the residue, and the resultꢀ
ing mixture was stirred until a precipitate completely disapꢀ
peared. The organic layer was separated, and a precipitate that
formed was recrystallized from an ether—acetone (1 : 1) mixꢀ
ture. The yield was 0.30 g (40%), m.p. 155—156 °С. Found (%):
C, 57.95; H, 3.34; N, 9.19. С22H15Cl2N3O4. Calculated (%):
C, 57.89; H, 3.29; N, 9.21. IR, ν/cm–1: 1674 (C(O)N),
1733, 1782 (C(O) of cycle). 1H NMR, δ: 2.32, 2.45 (both s,
3 H each, Me); 3.25 (br.s, 0.5 H, СН); 7.35—7.38 (m, 1 H,
oꢀH arom.); 7.44—7.54 (m, 5 H, Ph); 7.58 (d, 1 H, mꢀH arom.,
3JH,H = 8.0 Hz); 7.64 (s, 1 H, CH=CCl arom.); 12.86 (br.s,
0.5 H, OH).
(СН arom.); 129.89 (CCl arom.); 133.48 (CAr—N); 134.23
(CCl arom.); 165.78 (C=CN); 177.80 (C—C=C); 187.86
(COOMe); 201.75 (CH2CO).
3ꢀMethylꢀ5ꢀoxoꢀ1ꢀphenylꢀ4,5ꢀdihydroꢀ1Hꢀpyrazoleꢀ4ꢀcarbꢀ
oxanilide (16). Triethylamine (0.40 mL, 2.87 mmol) was added
to a mixture of 3ꢀmethylꢀ1ꢀphenylꢀ2ꢀpyrazolinꢀ5ꢀone (14) (0.5 g,
2.87 mmol) and phenyl isocyanate (0.34 g, 2.87 mmol). The
reaction mixture turned dark rapidly. The mixture was stored for
3 days. The dark oil was separated, washed with petroleum ether,
and dried in vacuo. A solution of 5% hydrochloric acid was
poured to a solution of the oil in acetone to an acidic pH value,
and a precipitate that formed was filtered off and recrystallized
from acetone. The yield was 0.34 g (40%), m.p. 96—98 °С.
Found (%): C, 65.39; H, 5.10; N, 13.30. С17H15N3O2•H2O.
Triethylammonium 4ꢀ(3,5ꢀdimethylꢀ1ꢀphenylꢀ1Hꢀpyrazoleꢀ4ꢀ
ylcarbonyl)ꢀ1ꢀdiphenylthiophosphinoylꢀ2,3,5ꢀtrioxopyrrolidinꢀ
4ꢀide (9). Triethylamine (0.35 mL, 2.43 mmol) was poured to a
solution of methyl 4ꢀ(3,5ꢀdimethylꢀ1ꢀphenylpyrazolyl) 2,4ꢀdiꢀ
oxobutanoate (6) (0.5 g, 1.67 mmol) in benzene (15 mL). The
reaction solution instantly gained the yellowꢀgreen color. The
reaction mixture was stored for 10 min, and a solution of dipheꢀ
nyl thiophosphoryl isocyanate (0.43 g, 1.67 mmol) in benzene
(5 mL) and ether (15 mL) were added. A formed precipitate of
unreacted compound 6 was separated, and the filtrate was conꢀ
centrated by evaporation. The residue was multiply recrystalꢀ
lized from an ether—acetone (1 : 2) mixture. The yield was
0.05 g (5%), m.p. 111—113 °С. Found (%): C, 65.01; H, 6.01;
N, 8.64. С28H21N3O4PS•С6H16N. Calculated (%): C, 64.97;
Calculated (%): C, 65.59; H, 4.82; N, 13.50. IR, ν/cm–1
:
1674 (C(O)N), 3361 (CONH). 1H NMR, δ: 2.26 (s, 3 H,
Me); 6.65—7.32 (m, 10 H, Ph); 10.31 (s, 1 H, NH); 12.30
(br.s, 1 H, OH).
Triethylammonium 1,3ꢀdiphenyl 2ꢀthiobarbiturate (18). Triꢀ
ethylamine (0.23 mL, 1.68 mmol) in ether was added dropwise
to a solution of 1,3ꢀdiphenylꢀ2ꢀthiobarbituric acid (17) (0.5 g,
1.68 mmol) in acetone. A rapidly formed precipitate was filtered
off in 3 h, washed with Et2O, and dried. The yield was 0.44 g
(66%), m.p. 138—140 °С. Found (%): C, 65.58; H, 6.82;
N, 10.31. С6H11N2O2S•0.5H2O•C6H16N. Calculated (%):
C, 65.02; H, 6.65; N, 10.34. 1H NMR, δ: 1.09 (t, 9 H,
3
CH3CH2N, JH,H = 7.2 Hz); 2.77 (q, 6 H, CH3CH2N, 3JH,H
=
H, 5.89; N, 8.92. 1H NMR, δ: 1.20 (t, 9 H, CH3CH2N, 3JH,H
=
7.2 Hz); 4.96 (br.s, 1 Н, С–H); 7.25 (dd, 4 H, oꢀH arom.,
4
7.2 Hz); 2.22, 2.27 (both s, 3 H each, Me); 3.12 (q, 6 H,
3JH,H = 7.7 Hz, JH,H = 1.2 Hz); 7.32 (dt, 2 H, pꢀH arom.,
3
4
CH3CH2N, JН,Н = 7.2 Hz); 7.29—7.49 (m, 11 H, Ph); 7.95
3JH,H = 7.7 Hz, JH,H = 1.2 Hz); 7.41 (t, 4 H, mꢀH arom.,
3
4
(dd, 4 H, oꢀН arom., JH,H = 7.2 Hz, JH,H = 1.2 Hz); 10.17
3JH,H = 7.7 Hz); 11.09 (br.s, 1 H, N+H).
(br.s, 1 H, N+H). 31P NMR, δ: 50.07.
Triethylammonium 1,3ꢀdiphenylꢀ5ꢀphenylcarbamoylꢀ2ꢀthioꢀ
barbiturate (19). Triethylamine (0.23 mL, 1.68 mmol) was added
dropwise to a solution of 1,3ꢀdiphenylꢀ2ꢀthiobarbituric acid (17)
(0.5 g, 1.68 mmol) and phenyl isocyanate (0.2 g, 1.68 mmol) in
an acetone—ether (1 : 1) mixture (50 mL). A precipitate that
formed dissolved upon the addition of acetone. The solvent was
distilled off, and the residue was washed with ether and dried.
The yield was 0.80 g (92%), m.p. 230 °С. Found (%): C, 67.42;
H, 6.10; N, 10.78. С23H16N3O3S•C6H16N. Calculated (%):
Triethylammonium 3,4ꢀdichlorophenylcarbamoyl(methoxyꢀ
carbonyl)chloroacetylmethide (11). Triethylamine (0.45 mL,
3.3 mmol) was added dropwise to a solution of methyl 4ꢀchloroꢀ
3ꢀoxobutanoate (10) (0.5 g, 3.3 mmol) and 3,4ꢀdichlorophenyl
isocyanate (0.62 g, 3.3 mmol). A white precipitate appeared
upon vigorous stirring and was filtered off and dried. The yield
was 1.35 g (93%), m.p. 226—227 °С. Found (%): C, 49.16;
H, 5.58; Cl, 24.24; N, 6.41. С12H9Cl3NO4•С6H16N. Calcuꢀ
lated (%): C, 49.15; H, 5.69; Cl, 24.23; N, 6.37. IR, ν/cm–1
1591 (C(O)N), 1624 (C(O)), 1663 (COOMe), 2576 (NH+),
:
C, 67.44; H, 6.20; N, 10.85. 1H NMR, δ: 1.15 (t, 9 H,
3
CH3CH2N, JH,H = 7.2 Hz); 2.95 (q, 6 H, CH3СH2N, 3JH,H
=
1
3
3
3256 (CONH). H NMR, δ: 1.39 (t, 9 H, CH3CH2N, JH,H
=
7.2 Hz); 6.98 (t, 1 Н, pꢀH arom., JH,H = 7.3 Hz); 7.22 (t,
2 H, pꢀH arom., JH,H = 7.8 Hz); 7.28 (d, 4 H, oꢀH arom.,
3JH,H = 7.8 Hz); 7.37 (t, 2 H, mꢀH arom., JH,H = 7.3 Hz);
3
7.2 Hz); 3.07—3.09 (m, 6 H, CH3CH2N); 3.88 (s, 3 H, OMe);
4.72 (s, 2 H, CH2Cl); 7.19 (dd, 1 H, oꢀН arom., 3JH,H = 8.0 Hz,
4JH,H = 2.4 Hz); 7.44 (d, 1 H, mꢀН arom., 3JH,H = 8.0 Hz); 7.55
(d, 1 H, oꢀН arom., 3JH,H = 2.4 Hz); 10.27 (s, 1 H, NH); 12.01
(s, 1 H, Et3NH).
3
3
7.46 (t, 4 H, mꢀH arom., JH,H = 7.8 Hz); 7.54 (d, 2 H,
3
oꢀH arom., JH,H = 7.3 Hz); 10.79 (br.s, 1 Н, N+H); 11.78 (s,
1 Н, CONH).
Methyl 2ꢀ(3,4ꢀdichloroanilino)ꢀ4ꢀoxoꢀ4,5ꢀdihydrofuranꢀ3ꢀ
carboxylate (13). A solution of 5% hydrochloric acid was poured
with stirring to a suspension of salt 11 (0.5 g, 1.13 mmol) in
acetone to an acidic pH value. A suspension was filtered off and
washed with acetone, the solvent was distilled off, and the resiꢀ
due was dried. A white powder (360 mg) was obtained. The yield
was 97%, m.p. 225—226 °С. Found (%): C, 47.68; H, 2.98;
Cl, 23.51; N, 4.64. С12H9Cl2NO4. Calculated (%): C, 47.69;
H, 2.98; Cl, 23.59; N, 4.65. 1H NMR, δ: 3.89 (s, 3 H, ОMe);
1,3ꢀBis(3,4ꢀdichlorophenyl)ꢀ5ꢀ(2ꢀphenylcarboranꢀ1ꢀ
yl)barbituric acid (23). Sodium hydride (0.046 g, 1.9 mmol) was
added to a solution of methyl 2ꢀphenylcarboranylꢀ1 acetate (20)
(0.44 g, 1.5 mmol) in THF (20 mL). The reaction solution
instantly turned yellow (with gas evolution). The mixture was
stirred for 20 min, and 3,4ꢀdichlorophenyl isocyanate (0.31 g,
1.65 mmol) was added. The reaction mixture was stored for
12 h, the solvent was distilled off, and ether was poured to the
residue. A white precipitate that formed was filtered off, disꢀ
solved in benzene, treated with TFA to a weakly acidic pH value,
and filtered. The filtrate was concentrated by evaporation, and
the residue was recrystallized from a hexane—acetone (1 : 1)
mixture (50 mL). The yield was 0.3 g (31%), m.p. >260 °С.
3
4.73 (s, 2 H, CH2); 7.20 (dd, 1 H, oꢀН arom., JH,H = 8.0,
4JH,H = 2.4 Hz); 7.45 (d, 1 H, mꢀН arom., 3JH,H = 8.0 Hz); 7.56
3
(d, 1 H, oꢀН arom., JH,H = 2.4 Hz); 10.28 (s, 1 H, NH).
13C NMR, δ: 51.91 (Me); 75.60 (СН2); 120.49, 123.03