Novel 1,5,3ꢀdithiazepanes
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 11, November, 2012 2147
162 [NCH(CH3)SCH2CH2S CH(CH3)]+ (13); 120
[CH(CH3)SCH2CH2S]+ (35); 105 [CHSCH2CH2S]+ (100); 92
[SCH2CH2S]+ (30); 69 [CH3CHNNCH]+ (52); 59 [NCHS]+
(57); 57 [N2CH2CH2]+ (12); 45 [CHS]+ (40); 42 [CH3NCH]+
(72). Found (%): C, 46.92; H, 7.56; N, 13.69; S, 31.24. C8H16N2S2.
Calculated (%): C, 47.02; H, 7.89; N, 13.71; S, 31.38.
flask equipped with a stirrer, a reflux condenser, and a dropping
funnel was maintained at a given temperature and charged with
formaldehyde, acetaldehyde, propanal, butanal, and pentanal
(0.1 mol). Ethaneꢀ1,2ꢀdithiol (0.05 mol) was added dropwise
with stirring for 3 h to a desired RCHO : 3 ratio of 2 : 1. Then
phenylhydrazine or benzylhydrazine (0.05 mol) was added dropꢀ
wise and the reaction mixture was stirred at a specific temperaꢀ
ture (0, 20, 40, or 70 C) for 3.5 h (see Scheme 4, pathway i). An
alternative pathway involved BuONa—BuOH (20 : BuONa =
= 1 : 2) (see Scheme 4, pathway ii). After completion of
the reaction, the mixture was neutralized with HCl (pathꢀ
way ii). The products were extracted with chloroform, the
extracts were dried with CaCl2 and concentrated on a rotary
2,4ꢀDiethylꢀ3ꢀpropylideneaminoꢀ1,5,3ꢀdithiazepanes (15a—c)
(5 : 1 : 1). Light yellow oil, yield 69% (pathway i). 1H NMR
(20 C), : 0.94 (t, 6 H, Me, 3J = 7.5 Hz); 1.03 (t, 3 H, Me,
3J = 7.5 Hz); 1.66 (sextet, 2 H each, CH2a, J = 7.2 Hz (15b,c));
1.72 (sextet, 2 H, CH2a, J = 7.5 Hz (15a)); 1.81 (sextet, 2 H each,
CH2b, J = 7.2 Hz (15b,c)); 2.01 (sextet, 2 H, CH2b, J = 7.5 Hz
(15a)); 2.24 (m, 2 H, CH2); 2.82—2.97 (m, 4 H, CH2); 4.76 (t, 4 H,
CH2(2), CH2(4), J = 6.2 Hz); 6.90 (t, H, CHAr
13C NMR, : 11.48; 11.58; 26.64; 28.54; 34.78; 68.32 (15b);
74.26 (15a); 72.12 (15c); 143.18 (15b); 147.00 (15a,c). IK
,
3J = 5.0 Hz).
evaporator, and the residues were separated by column chromaꢀ
tography on SiO2 (C6H6—AcOEt—CHCl3 = 5 : 1 : 1 (comꢀ
pounds 29—31)).
=
= 1776 (15a). 15a. MS, m/z (Irel (%)): 246 [M]+ (5); 190
[NCH(C2H5)SCH2CH2SCH(C2H5)]+ (7); 134 [CH(C2H5)ꢀ
SCH2CH2S]+ (23); 112 [CH3CH2CHNNCH(C2H5)]+ (25); 105
[CHSCH2CH2S]+ (100); 83 [CH3CH2CH2NNCH]+ (60); 56
[CH3CH2CHN]+ (30); 45 [CHS]+ (22); 41 [CH2CH2CH]+ (41).
3ꢀButylideneaminoꢀ2,4ꢀdipropylꢀ1,5,3ꢀdithiazepane (16a).
Light yellow oil, yield 74% (pathway i). 1H NMR (20 C),
: 0.81—0.90 (m, 9 H, Me); 1.28—1.62 (m, 6 H, CH2); 2.63—2.65
(m, 4 H, CH2); 2.65—2.79 (m, 2 H, CH2); 3.50—3.70 (m, 4 H,
CH2); 4.70—4.80 (m, 4 H, CH2); 6.85 (m, H, CHAr). 13C NMR,
: 13.63; 13.77; 20.06; 20.56; 28.66; 34.62; 37.57; 66.23; 141.77.
IK = 1996. MS, m/z (Irel (%)): 288 [M]+ (3); 148 [CH(C3H7)Sꢀ
CH2CH2S)]+ (20); 105 [CHSCH2CH2S]+ (100); 97 [CH3CH2ꢀ
CH2CHNNCH]+ (50); 70 [CH3CH2 CH2CHN]+ (18); 55
[CH3CH2 CH2C]+ (45); 43 [CH2CH2CH2]+ (30). Found (%):
C, 58.07; H, 9.63; N, 9.59; S, 22.11. C14H28N2S2. Calculatꢀ
ed (%): C, 58.28; H, 9.78; N, 9.71; S, 22.23.
2,4ꢀDibutylꢀ3ꢀpentylideneaminoꢀ1,5,3ꢀdithiazepanes (17a—c)
(Faa). Light yellow oil, yield 76% (pathway i). 1H NMR (20 C),
: 1.61—1.67 (m, 9 H, Me); 2.42—2.61 (m, 18 H, CH2); 4.72
(t, 2 H, CH2, J = 6.2 Hz (17b)); 4.79—4.82 (t, 2 H each, CH2
(17a,c)); 6.41—6.42 (m, H, CHAr). 13C NMR, : 18.62; 20.26;
24.48; 25.26; 28.57; 31.32; 33.80; 34.82; 67.95 (17b); 74.08 (17a);
73.32 (17c); 131.85 (17b); 131.91 (17a); 131.81 (17c). IK = 2258
(17a). 17a. MS, m/z (Irel (%)): 330 [M]+ (3); 162 [CH(C4H9)Sꢀ
CH2CH2S)]+ (20); 111 [CH3CH2CH2CH2CHNNCH]+ (35);
105 [CHSCH2CH2S]+ (100); 84 [CH3CH2CH2CH2CHN]+
(26); 69 [CH3CH2CH2CH2C]+ (30); 56 [CH3CH2CH2CH2]+
(19); 43 [CH2CH2CH2]+ (28).
3ꢀ(2,4ꢀDimethylꢀ1,3ꢀoxazetanꢀ3ꢀyl)ꢀ2,4ꢀdimethylꢀ1,5,3ꢀ
dithiazepane (18) (pathway i). MS, m/z (Irel (%)): 248 [M]+ (40);
162 [NCH(CH3)SCH2CH2SCH(CH3)]+ (15); 120 [CH(CH3)Sꢀ
CH2CH2S]+ (37); 105 [CHSCH2CH2S]+ (100); 92 [SCH2CH2S]+
(32); 86 [NCH(CH3)OCH(CH3)]+ (32); 69 [CH3CHNNCH]+
(54); 59 [NCHS]+ (57); 57 [N2CH2CH2]+ (12); 45 [CHS]+ (40);
42 [CH3NCH]+ (72).
3ꢀ(2,4ꢀDiethylꢀ1,3ꢀoxazetanꢀ3ꢀyl)ꢀ2,4ꢀdiethylꢀ1,5,3ꢀdithiazeꢀ
pane (19) (pathway i). MS, m/z (Irel (%)): 304 [M]+ (5); 190
[NCH(C2H5)SCH2CH2SCH(C2H5)]+ (5); 134 [CH(C2H5)ꢀ
SCH2CH2S]+ (21); 115 [NCH(C2H5)OCH(C2H5)]+ (31); 112
[CH3CH2CHNNCH(C2H5)]+ (23); 105 [CHSCH2CH2S]+ (100);
83 [CH3CH2CH2NNCH]+ (58); 56 [CH3CH2CHN]+ (28);
45 [CHS]+ (20); 41 [CH2CH2CH]+ (39).
3ꢀAnilinoꢀ1,5,3ꢀdithiazepane (22). Light yellow oil, yield 87
(pathway i) and 66% (pathway ii). 1H NMR (20 C), : 3.08 (s, 4 H,
CH2); 4.31 (s, 4 H, CH2); 6.18 (s, H, NH); 6.96 (d, 4 H, CH2,
J = 8 Hz); 6.88 (t, 2 H, CH2, J1 = 7.6 Hz, J2 = 7.2 Hz); 7.26
(t, 4 H, CH2, J1 = 7.6 Hz, J2 = 8 Hz). 13C NMR, : 35.46; 61.19;
114.51; 120.15; 129.35; 146.02. IK = 2118. MS, m/z (Irel (%)):
226 [M]+ (60); 147 [NNCH2SCH2CH2SCH]+ (50); 120
[NCH2SCH2CH2S]+ (100); 106 [C6H5NHN]+ (15); 91
[C6H5N]+ (35); 77 [C6H5]+ (23); 75 [NHNCH2S]+ (25); 60
[NCH2S]+ (25); 46 [CH2S]+ (10). Found (%): C, 52.94; H, 6.16;
N, 12.24; S, 28.18. C10H14N2S2. Calculated (%): C, 53.06;
H, 6.23; N, 12.38; S, 28.33.
3ꢀAnilinoꢀ2,4ꢀdimethylꢀ1,5,3ꢀdithiazepanes (23a—c). Orange
oil, yield 75 (pathway i) and 73% (pathway ii). 1H NMR (20 C),
: 1.45 (d, 6 H, Me, J = 6.8 Hz); 3.02—3.18 (m, 4 H, CH2); 4.51
(q, 2 H, CH, 2J = 6.8 Hz (23b)); 4.90 (br.s, 2 H, CH2 (23a));
4.15 (br.s, 2 H, CH2 (23c)); 6.03 (s, H, NH (23b)); 5.76 (s, H,
NH (23a,c)); 6.91—6.94 (m, 3 H, CHAr (23b)); 6.75—6.89
(m, 3 H each, CHAr (23a,c)); 7.19—7.29 (m, 2 H, CHAr).
13C NMR, : 21.59; 34.47; 72.26 (23b); 67.10 (23a); 68.10 (23c);
112.33; 118.22; 129.13 (23b); 129.25 (23a,c); 150.44 (23b); 148.32
(23a,c). IK = 2144 (23a). MS, m/z (Irel (%)): 254 [M]+ (8); 161
[NCH(CH3)SCH2CH2SCHCH2]+ (25); 134 [NCH(CH3)Sꢀ
CH2CH2S]+ (100); 106 [C6H5NN]+ (25); 78 [C6H6]+ (5); 60
[NCH2S]+ (10).
3ꢀBenzylaminoꢀ1,5,3ꢀdithiazepane (24). Light yellow oil,
yield 77 (pathway i) and 69% (pathway ii). 1H NMR (20 C),
: 2.51 (s, 4 H, CH2); 3.52 (s, 2 H, CH2); 4.71 (s, 4 H, CH2); 6.15
(br.s, 1 H, NH); 7.09—7.24 (m, 5 H, CHAr). 13C NMR, : 37.35;
53.80; 59.15; 122.24; 125.41; 127.97; 141.65. Found (%): C, 54.33;
H, 6.13; N, 11.09; S, 26.57. C11H16N2S2. Calculated (%):
C, 54.96; H, 6.71; N, 11.65; S, 26.68.
3ꢀBenzylaminoꢀ2,4ꢀdimethylꢀ1,5,3ꢀdithiazepane (25). Light
yellow oil, yield 69 (pathway i) and 63% (pathway ii). 1H NMR
(20 C), : 1.43 (br.s, 6 H, Me); 2.67 (s, 4 H, CH2); 3.99 (s, 2 H,
CH2); 4.23 (m, 4 H, CH2); 6.35 (br.s, 1 H, NH); 7.11—7.33
(m, 5 H, CHAr). 13C NMR, : 22.55; 34.76; 53.82; 61.15; 121.77;
124.39; 126.37; 142.24. Found (%): C, 58.01; H, 7.35; N, 10.22;
S, 23.61. C13H20N2S2. Calculated (%): C, 58.16; H, 7.51;
N, 10.44; S, 23.89.
2ꢀEthylꢀ1,3ꢀdithiolane (26). Yield 35% (pathway i). The
product obtained is identical with 2ꢀethylꢀ1,3ꢀdithiolane deꢀ
scribed earlier.16 MS, m/z (Irel (%)): 134 [M]+ (70); 105 [CHSꢀ
CH2CH2S]+ (100); 74 [CH3CH2CHS]+ (10); 59 [CHSCH2]+
(20); 45 [CHS]+ (65).
Heterocyclization of phenylꢀ and benzylhydrazines with aldeꢀ
hydes and ethaneꢀ1,2ꢀdithiol (general procedure). A threeꢀnecked