Nꢀ(2,2,2ꢀTrichloroꢀ1ꢀhydroxyethyl)aminals
Russ.Chem.Bull., Int.Ed., Vol. 64, No. 1, January, 2015
81
5
mmol), Et N (0.7 mL, 5 mmol), and TMSCl (0.85 mL, 7 mmol)
(CH=N); 151.2 (Cquat). IR (KBr), /cm–1: 900, 1018, 1126,
1155, 1180 (SiO, SiC); 1481; 1579; 1649 (C=N).
3
in anhydrous CH Cl (10 mL) in the yield of 1.52 g (92%). Light
2
2
brown crystals, m.p. 61—63 C. Found (%): C, 36.48; H, 4.31;
Nꢀ(4ꢀBromoꢀ2ꢀthienylmethylidene)ꢀ2,2,2ꢀtrichloroꢀ1ꢀ(triꢀ
methylsilyloxy)ethanamine (4i) was obtained from imine 1i (1.34 g,
N, 4.10. C H Cl NOSSi. Calculated (%): C, 36.32; H, 4.27;
1
0
14
3
1
N, 4.24. H NMR (CDCl ), : 0.29 (s, 9 H, Me Si); 5.58 (s, 1 H,
4 mmol), Et N (0.6 mL, 4.3 mmol), and TMSCl (0.56 mL,
3
3
3
CHCCl ); 7.12—7.14 (m, 1 H, CH ); 7.49—7.53 (m, 2 H,
4.4 mmol) in anhydrous CH Cl (13 mL) in the yield of 1.40 g
3
Ar
2
2
1
3
CHAr); 8.64 (s, 1 H, CH=N). C NMR (CDCl ), : 0.32
(86%). Light yellow oil. Found (%): C, 29.28; H, 3.16; N, 3.41;
S, 7.96. C H BrCl NOSSi. Calculated (%): C, 29.32; H, 3.20;
3
(
1
Me Si); 94.5 (CHCCl ); 101.5 (C , CCl ); 127.7; 131.1;
32.8; 141.6 (Cquat); 155.5 (CH=N). IR (Nujol), /cm : 1140
3 3 quat 3
10 13
3
–
1
1
N, 3.42; S, 7.83. H NMR (CDCl ), : 0.28 (s, 9 H, Me Si); 5.61
3
3
(
OSi); 1280; 1670 (C=N).
,2,2ꢀTrichloroꢀNꢀ[(3,5ꢀdimethylꢀ1ꢀphenylꢀ1Hꢀpyrazolꢀ4ꢀ
(s, 1 H, CHCCl ); 7.40, 7.41 (both s, 1 H each, CH ); 8.55 (s, 1 H,
3 Ar
13
2
CH=N). C NMR (CDCl ), : 0.29 (Me Si); 93.9 (CHCCl );
3 3 3
yl)methylidene]ꢀ1ꢀ(trimethylsilyloxy)ethanamine (4e) was obꢀ
101.2 (Cquat, CCl ); 128.1; 134.5; 142.3 (Cquat); 154.0 (CH=N).
3
IR (KBr), /cm– : 845, 901, 1070, 1161 (SiO, SiC); 1419; 1466;
1
tained from imine 1e (1.33 g, 3.8 mmol), Et N (0.54 mL,
3
3
.9 mmol), and TMSCl (0.62 mL, 4.9 mmol) in anhydrous CH Cl2
1520; 1633; 1664 (CH=N).
2
(
10 mL) within 23 h in the yield of 1.44 g (89%). Orange oil.
2,2,2ꢀTrichloroꢀNꢀ(4,5ꢀdimethylꢀ2ꢀthienylmethylidene)ꢀ1ꢀ
(trimethylsilyloxy)ethanamine (4j) was obtained from imine 1j
Found (%): C, 48.51; H, 5.25; N, 9.94. C H Cl N OSi. Calꢀ
culated (%): C, 48.75; H, 5.29; N, 10.03. H NMR (CDCl ),
1
7
22
3
3
1
(1.13 g, 3.94 mmol), Et N (0.6 mL, 4.3 mmol), and TMSCl
3
3
: 0.29 (s, 9 H, Me Si); 2.49, 2.51 (both s, 3 H each, Me); 5.58
(0.56 mL, 4.4 mmol) in anhydrous CH Cl (10 mL) in the yield
3
2
2
(
d, 1 H, CHCCl , J = 1.6 Hz); 7.12—7.14 (d, 2 H, CHPh,
of 1.15 g (81%). Orange oil. Found (%): C, 40.21; H, 5.03;
N, 3.87; S, 9.01. C H Cl NOSSi. Calculated (%): C, 40.17;
3
J = 7.5 Hz); 7.49—7.53 (m, 3 H, CHPh); 8.55 (d, 1 H, CH=N,
J = 1.6 Hz). C NMR (CDCl ), : 0.42 (Me Si); 11.8 (Me); 12.8
12
18
3
1
13
H, 5.06; N, 3.90; S, 8.94. H NMR (CDCl ), : 0.27 (s, 9 H,
3
3
3
(
1
(
Me); 95.3 (CHCCl ); 102.2 (C , CCl ); 115.5 (Cquat); 125.3;
Me Si); 2.16, 2.39 (both s, 3 H each, Me); 5.51 (s, 1 H, CHCCl );
7.20 (s, 1 H, CH ); 8.47 (s, 1 H, CH=N). C NMR (CDCl ),
Ar 3
3
quat
3
3
3
13
28.2; 129.2; 134.9 (Cquat); 141.8 (Cquat); 150.6 (Cquat); 156.0
CH=N). IR (neat), /cm–1: 1140 (OSi); 1280; 1670 (C=N).
,2,2ꢀTrichloroꢀNꢀ(4ꢀchlorobenzylidene)ꢀ1ꢀ(trimethylsilylꢀ
: 0.36 (Me Si); 13.5 (Me); 13.8 (Me); 94.8 (CHCCl ); 101.8
3
3
2
(Cquat, CCl ); 134.3 (Cquat, CArMe); 136.0; 136.5 (Cquat); 140.3
3
(Cquat); 155.3 (CH=N). IR (KBr), /cm 1: 845, 901, 1072,
1124 with shoulder, 1171 (SiO, SiC); 1419; 1468; 1633; 1666
(CH=N); 1686.
–
oxy)ethanamine (4f) was obtained from imine 1f (1.37 g, 4.8 mmol),
Et N (0.7 mL, 5 mmol), and TMSCl (0.85 mL, 7 mmol) in
anhydrous CH Cl (9 mL) within 17.5 h in the yield of 1.42 g
3
2
2
(
83%). Colorless oil. Found (%): C, 40.16; H, 4.18; N, 3.84.
2,2,2ꢀTrichloroꢀNꢀ[(E)ꢀ3ꢀphenylpropꢀ2ꢀenꢀ1ꢀylidene]ꢀ1ꢀ
(trimethylsilyloxy)ethanamine (4k) was obtained from imine 1k
C H Cl NOSi. Calculated (%): C, 40.13; H, 4.21; N, 3.90.
1
12
15
4
H NMR (CDCl ), : 0.29 (s, 9 H, Me Si); 5.60 (d, 1 H,
(1.36 g, 4.9 mmol), Et N (0.7 mL, 5 mmol), and TMSCl (0.85 mL,
3
3
3
CHCCl , J = 1.6 Hz); 7.44, 7.81 (both d, 2 H each, CH ,
7 mmol) in anhydrous CH Cl (8 mL) within 15.5 h in the yield
of 1.47 g (86%). Orangeꢀyellow solid, m.p. 35—36 C. Found (%):
3
Ar
2
2
13
J = 8.5 Hz); 8.50 (d, 1 H, CH=N, J = 1.6 Hz). C NMR (CDCl ),
3
: 0.34 (Me Si); 95.0 (CHCCl ); 101.4 (C , CCl ); 129.1;
C, 48.05; H, 5.32; N, 4.00. C H Cl NOSi. Calculated (%):
3
3
quat
3
14 18
3
1
1
30.4; 133.6 (Cquat); 137.9 (Cquat); 161.2 (CH=N).
,2,2ꢀTrichloroꢀNꢀ(2ꢀhydroxybenzylidene)ꢀ1ꢀ(trimethylsilylꢀ
oxy)ethanamine (4g) was obtained from imine 1g (675 mg,
C, 47.94; H, 5.17; N, 3.99. H NMR (CDCl ), : 0.28 (s, 9 H,
3
2
Me Si); 5.47 (d, 1 H, CHCCl , J = 1.4 Hz); 7.08 (dd, 1 H,
3
3
PhCH=CH, J = 16.0 Hz, J = 8.6 Hz); 7.16 (d, 1 H, PhCH=CH,
J = 16.0 Hz); 7.37—7.43 (m, 3 H, HPh); 7.54 (dd, 2 H, HPh
J = 8.0 Hz, J = 1.3 Hz); 8.30 (dd, 1 H, CH=N, J = 8.6 Hz,
2
3
.5 mmol), Et N (0.35 mL, 2.5 mmol), and TMSCl (0.41 mL,
,
3
.2 mmol) in anhydrous CH Cl (6 mL) in the yield of 840 mg
2
2
13
(
C
1
98%). Orangeꢀyellow oil. Found (%): C, 42.52; H, 4.72; N, 4.11.
12H16Cl NO Si. Found (%): C, 42.30; H, 4.73; N, 4.11.
H NMR (CDCl ), : 0.31 (s, 9 H, Me Si); 5.63 (d, 1 H, CHCCl ,
J = 1.4 Hz). C NMR (CDCl ), : 0.30 (Me Si); 95.5 (CHCCl );
3 3 3
101.5 (Cquat, CCl ); 127.3; 127.7; 128.9; 129.9 (PhCH=CH);
3
2
3
135.3 (Cquat); 145.4 (PhCH=CH); 164.4 (CH=N). IR (neat),
3
3
3
–
1
J = 1.6 Hz); 6.95 (td, 1 H, CH , J = 7.4 Hz, J = 0.8 Hz); 7.01
/cm : 1140 (OSi); 1280; 1670 (C=N).
Ar
(
(
(
1
d, 1 H, CH , J = 8.3 Hz); 7.37—7.42 (m, 2 H, CH ); 8.61
2,2,2ꢀTrichloroꢀNꢀ(4ꢀnitrobenzylidene)ꢀ1ꢀ(trimethylsilylꢀ
oxy)ethanamine (4m) was obtained from imine 1m (1.48 g,
Ar
Ar
3
1
d, 1 H, N=CH, J = 1.6 Hz); 12.66 (s, 1 H, ArOH). C NMR
CDCl ), : 0.25 (Me Si); 93.0 (CHCCl ); 101.1 (C , CCl );
5 mmol), Et N (0.7 mL, 5 mmol), and TMSCl (0.85 mL, 7 mmol)
3
3
3
quat
3
3
17.4; 118.2 (Cquat); 119.1; 132.8; 133.7; 161.1 (Cquat); 165.2
CH=N). IR (KBr), /cm–1: 1010, 1041, 1078 (OSi, CSi); 1255,
in anhydrous CH Cl2 (10 mL) in the yield of 1.63 g (89%).
2
(
Yellow crystals, m.p. 90—91 C. Found (%): C, 38.89; N, 7.58;
1
2
281 (CO, phenol); 1342; 1392; 1460; 1493; 1579; 1632 (C=N);
300—3446 (Hꢀbonded).
H, 4.09. C H Cl N O Si. Calculated (%): C, 38.98; N, 7.56;
12
15
3
2
3
1
H, 4.08. H NMR (CDCl ), : 0.31 (s, 9 H, Me Si); 5.71 (d, 1 H,
3
3
2
,2,2ꢀTrichloroꢀNꢀ(2ꢀfurylmethylidene)ꢀ1ꢀ(trimethylsilylꢀ
CHCCl , J = 1.9 Hz); 8.03, 8.31 (both d, 2 H each, CH ,
3 Ar
13
oxy)ethanamine (4h) was obtained from imine 1h (1.21 g, 5 mmol)
J = 8.7 Hz); 8.61 (d, 1 H, CH=N, J = 1.9 Hz). CNMR (CDCl ),
3
Et N (0.7 mL, 5 mmol), and TMSCl (0.83 mL, 6.5 mmol) in
: 0.28 (Me Si); 94.4 (CHCCl ); 101.0 (C , CCl ); 124.0;
3
3
3
quat
3
anhydrous CH Cl (8 mL) in the yield of 1.48 g (94%). Colorless
solid, m.p. 31.5 C. Found (%): C, 38.08; H, 4.69; N, 4.27.
129.9; 140.4 (Cquat); 149.8 (Cquat); 159.7 (CH=N). IR (Nujol),
/cm : 1160 (OSi); 1370; 1490; 1670 (C=N).
2
2
–
1
C H Cl NO Si. Calculated (%): C, 38.17; H, 4.48; N, 4.45.
2,2,2ꢀTrichloroꢀNꢀ(2,6ꢀdichlorobenzylidene)ꢀ1ꢀ(trimethylꢀ
silyloxy)ethanamine (4n) was obtained from imine 1n (809 mg,
10
14
3
2
1
H NMR (CDCl ), : 0.27 (s, 9 H, Me Si); 5.65 (d, 1 H, CHCCl ,
3
3
3
J = 1.6 Hz); 6.54 (dd, 1 H, CH , J = 1.8 Hz, J = 1.6 Hz); 6.97
2.5 mmol), Et N (0.35 mL, 2.5 mmol), and TMSCl (0.41 mL,
Ar
3
(
d, 1 H, CH , J = 3.6 Hz); 7.61 (s, 1 H, CHAr); 8.35 (d, 1 H,
3.2 mmol) in anhydrous CH Cl (5 mL) in the yield of 853 g
(86%). Colorless crystals, m.p. 34—35 C. Found (%): C, 36.92;
Ar
2
2
13
CH=N, J = 1.6 Hz). C NMR (CDCl ), : 0.21 (Me Si); 94.1
3
3
(
CHCCl ); 101.3 (C , CCl ); 112.1; 117.0; 146.1; 150.3
H, 3.75; N, 3.44; C H C NOSi. Calculated (%): C, 36.62;
3
quat
3
12 14 l5