respectively. Examples of strong interactions of this type
have been discussed in a review by Hassel and Rømming15 and
are considered to involve a lone pair on the carbonyl and the
133.52 (2 × sp2 tertiary C), 44.58 (CH2, from DEPT), 14.77
(CH3, from DEPT); νmax/cmϪ1 2981, 2931, 2875, 1634 (C᎐O),
᎐
1535, 1252, 1122, 1047, 612; m/z 349 (Mϩ ϩ 4, 6%),
347(Mϩ ϩ 2, 22), 345 (Mϩ, 25), 309 (M Ϫ HCl, 9), 274
(M Ϫ HCl2, 8), 218 (M Ϫ C3H5Cl2O, 11), 210 (M Ϫ C4H4ClOS,
10), 79 (ClCSϩ, 94). Crystal data for 2b: C8H5Cl2NO2S4,
d-orbitals of the halogen. We think it likely that the C᎐O ؒ ؒ ؒ Cl
᎐
contacts in the structure of 2b are probably examples of weak
interactions of this type.
¯
M = 346.3, triclinic, P1 (no. 2), a = 7.814(2), b = 8.211(1),
c = 10.115(2) Å, α = 86.50(1), β = 88.77(2), γ = 85.46(1)Њ,
V = 645.6(2) Å3, Z = 2, Dc = 1.781 g cmϪ3, µ(Cu-Kα) = 104.9
cmϪ1, F(000) = 348, T = 293 K; yellow rhombs, 0.43 × 0.27 ×
0.21 mm, Siemens P4/PC diffractometer, ω-scans, 2088 inde-
pendent reflections. The structure was solved by direct methods
and the non-hydrogen atoms refined anisotropically using full
matrix least-squares based on F 2 to give R1 = 0.047, wR2 = 0.128
for 1784 independent observed absorption corrected reflections
[|Fo| > 4σ(|Fo|), 2θ ≤ 126Њ] and 155 parameters.†.
Experimental
Melting points were determined on a Kofler hot-stage appar-
atus and are uncorrected. IR spectra were recorded on a Bruker
Vector 200 A instrument in KBr pellets. 1H NMR and 13C
NMR spectra were recorded on a Bruker DRX 400 in CDCl3 or
d5-pyridine solution. CH groups were distinguished by DEPT
experiments. J values are given in Hz. Mass spectra were
recorded on VG7070E and VG-AutoSpec instruments using
electron impact ionisation. Light petroleum refers to the frac-
tion bp 40–60 ЊC.
N,N-Bis(5-chloro-3-oxo-1,2-dithiol-4-yl)benzylamine
2c.
Orange solid (from light petroleum–CH2Cl2), mp 164–165 ЊC
(Found Mϩ, 406.8743. C13H7Cl2NO2S4 requires M, 406.8737)
(Found: C, 38.4; H, 1.8; N, 3.5. C13H7Cl2NO2S4 requires C,
38.2; H, 1.7; N, 3.4%); δH (d5-pyridine) 7.76 (d, J 7.3, 2H, ArH),
7.31 (t, J 7.7, 2H, ArH), 7.21 (t, J 7.4, 1H, ArH), 5.05 (s, 2H,
General procedure for the preparation of N,N-bis(5-chloro-3-
oxo-1,2-dithiol-4-yl)alkylamines 2a–g
Disulfur dichloride was added dropwise to a stirred solution of
N-alkyldiisopropylamine 1a–g and DABCO dissolved in 1,2-
dichloroethane (150 ml) at Ϫ40 ЊC. The mixture was stirred for
15 min at Ϫ40 ЊC, then for 3 days at room temperature. Formic
acid was then added dropwise at 5 ЊC and the mixture was
refluxed for 45 min to 1.5 h. The reaction mixture was filtered
through Celite and the solvent was removed in a rotary evapor-
ator. Medium pressure liquid chromatography (MPLC) (silica
gel Merck 60, light petroleum to CH2Cl2) of the residue
afforded products 2a–g, in addition to the previously reported
products 7b–g. The reaction conditions and yields of products
are given in Table 1.
CH ); δ (d -pyridine) 187.26 (C᎐O), 148.07, 137.35 and 134.40
᎐
2
C
5
(3 × sp2 tertiary C), 129.36, 128.74 and 128.28 (3 × ArH, from
DEPT), 53.06 (CH2, from DEPT); νmax/cmϪ1 3053, 2934, 1658
(C᎐O), 1541, 1453, 1381, 1069, 955, 694, 560; m/z 411 (Mϩ ϩ 4,
᎐
1%), 409 (Mϩ ϩ 2, 6), 407 (Mϩ, 6), 371 (M Ϫ HCl, 2), 91
(C7H7ϩ, 100).
N,N-Bis(5-chloro-3-oxo-1,2-dithiol-4-yl)(2-chloroethyl)amine
2d. Yellow crystals (from light petroleum–CH2Cl2), mp 97–
98 ЊC (Found Mϩ, 378.8180. C8H4Cl3NO2S4 requires M,
378.8190) (Found: C, 25.5; H, 1.15; N, 3.5. C8H4Cl3NO2S4
requires C, 25.2; H, 1.1; N, 3.7%); δH (CDCl3) 3.93 (t, J 6.8, 2H,
N,N-Bis(5-chloro-3-oxo-1,2-dithiol-4-yl)isopropylamine 2a.
Orange solid (from light petroleum–CH2Cl2), mp 138–140 ЊC
(Found Mϩ, 358.8734. C9H7Cl2NO2S4 requires M, 358.8737)
(Found: C, 30.25; H, 2.0; N, 3.8. C9H7Cl2NO2S4 requires C,
30.0; H, 2.0; N, 3.9%); δH (CDCl3) 4.34 (heptet, 1H, J 7.0, CH),
CH ), 3.75 (t, J 6.8, 3H, CH ); δ (CDCl ) 186.16 (C᎐O), 147.57
᎐
2
2
C
3
and 133.35 (2 × sp2 tertiary C), 50.63 and 42.97 (2 × CH2, from
DEPT); νmax/cmϪ1 2964, 1627 (C᎐O), 1547, 1533, 1078, 1007,
᎐
821; m/z 383 (Mϩ ϩ 4, 7%), 381 (Mϩ ϩ 2, 15), 379 (Mϩ, 14), 347
(Mϩ ϩ 4 Ϫ HCl, 16), 345 (Mϩ ϩ 2 Ϫ HCl, 16), 343 (Mϩ Ϫ HCl,
62), 308 (Mϩ Ϫ HCl2, 14), 160 (C5H3ClNOSϩ, 45), 79 (ClCSϩ,
100).
1.21 (d, 6H, J 7.0, 2 × CH ); δ (CDCl ) 187.02 (C᎐O), 150.52
᎐
3
C
3
and 133.86 (2 × sp2 tertiary C), 51.40 (CH), 21.45 (CH3); νmax
/
cmϪ1 2978, 2929, 1646 (C᎐O), 1524, 1382, 1260, 1123, 805, 714,
᎐
620; m/z 363 (Mϩ ϩ 4, 16%), 361 (Mϩ ϩ 2, 58), 359 (Mϩ, 68),
344 (M Ϫ CH3, 32), 323 (M Ϫ HCl, 74), 317 (M Ϫ C3H6, 29),
256 (M Ϫ C3H7SCO, 77), 225 (C5HCl2NOS2, 37), 79 (ClCSϩ,
94), 43 (C3H7ϩ, 100).
N,N-Bis(5-chloro-3-oxo-1,2-dithiol-4-yl)(2-phenylthioethyl)-
amine 2e. Yellow solid (from light petroleum–CH2Cl2), mp 81–
83 ЊC (Found Mϩ, 452.8631. C14H9Cl2NO2S5 requires M,
452.8614) (Found: C, 37.2; H, 2.1; N, 3.0. C14H9Cl2NO2S5
requires C, 37.0; H, 2.0; N, 3.1%); δH (CDCl3) 7.35 (dt, Jab 8.0,
Jac/ad 1.5, 2H, Phortho), 7.27 (td, Jba 8.0, Jbe 2.3, 2H, Phmeta), 7.18
(tt, Jcb 7.3, Jca 1.9, 1H Phpara), 3.81 (t, J 7.9, 2H, CH2), 3.17 (t,
N,N-Bis(5-chloro-3-oxo-1,2-dithiol-4-yl)amine 3. Orange
solid (from light petroleum–CH2Cl2), mp 144–145 ЊC (Found
Mϩ, 316.8201. C6HCl2NO2S4 requires M, 316.8267) (Found: C,
22.8; H, 0.35; N, 4.35. C6HCl2NO2S4 requires C, 22.65; H, 0.3;
N, 4.4%); δH (CDCl3) 5.54 (br s, 1H, NH); δC (CDCl3) 185.52
J 7.9, 2H, CH ); δ (CDCl ) 185.99 (C᎐O), 147.12, 135.20 and
᎐
2
C
3
133.31 (3 × sp2 tertiary C), 129.47, 128.97 and 126.34 (3 ×
CHaromat, from DEPT), 49.19 and 32.98 (2 × CH2, from DEPT);
νmax/cmϪ1 3042, 3008, 2977, 2935, 1655 (C᎐O), 1582, 1542, 1478,
(C᎐O), 139.65 and 129.36 (2 × sp2 tertiary C); νmax/cmϪ1 3302
᎐
᎐
1441, 1069, 802, 740, 690; m/z 453 (Mϩ, 1%), 346 (Mϩ ϩ
2 Ϫ C6H5S, 26), 344 (Mϩ Ϫ C6H5S, 34), 79 (ClCSϩ, 95), 77
(C6H5ϩ, 100).
(N–H), 1614 (C᎐O), 1575, 1550, 1453, 1283, 1094, 563; m/z 321
᎐
(Mϩ ϩ 4, 24%), 319 (Mϩ ϩ 2, 84), 317 (Mϩ, 100), 256
(M Ϫ HSCO, 35) (Found Mϩ, 255.8517. C5Cl2NO2S3 requires
M, 255.8519), 225 (M Ϫ COS2, 16) (Found Mϩ, 224.8854.
C5HCl2NO2S2 requires M, 224.8877), 218 (M Ϫ CHCl2O, 17)
(Found Mϩ, 217.8866. C5NOS4 requires M, 217.8863), 210
(M- C2ClOS, 20) (Found Mϩ, 209.8909. C4HClNOS3 requires
M, 209.8909), 79 (ClCSϩ, 47) (Found Mϩ, 78.9407. CClS
requires M, 209.8909).
N,N-Bis(5-chloro-3-oxo-1,2-dithiol-4-yl)(2-phthalimidoethyl)-
amine 2f. Orange solid (from light petroleum–CH2Cl2), mp
162–163 ЊC (Found Mϩ, 489.8747. C16H8Cl2N2O4S4 requires M,
489.8744) (Found: C, 39.3; H, 1.7; N, 5.6. C16H8Cl2N2O4S4
requires C, 39.1; H, 1.6; N, 5.7%); δH (CDCl3) 7.83 (dd, Jab
5.4, Jac 3.1, 2H, PhthHortho), 7.70 (dd, Jba 5.4, Jbd 3.1, 2H,
PhthHmeta), 4.14 (t, J 5.9, 2H, CH2), 3.91 (t, J 5.9, 2H, CH2);
N,N-Bis(5-chloro-3-oxo-1,2-dithiol-4-yl)ethylamine 2b. Yel-
low solid (from light petroleum–CH2Cl2), mp 132-133 ЊC
(Found Mϩ, 344.8579. C8H5Cl2NO2S4 requires M, 344.8502)
(Found: C, 27.9; H, 1.5; N, 4.0. C8H5Cl2NO2S4 requires C,
27.75; H, 1.5; N, 4.0%); δH (CDCl3) 3.70 (q, 2H, J 7.1, CH2),
δ (CDCl ) 187.01 (C᎐O), 168.42 (N–C᎐O), 155.19, 146.56 and
᎐
᎐
C
3
145.31 (3 × sp2 tertiary C), 134.36 and 123.72 (2 × CHaromat),
p1/1999/2237 for crystallographic files in .cif format.
1.18 (t, 3H, J 7.1, CH ); δ (CDCl ) 185.99 (C᎐O), 146.54 and
᎐
3
C
3
2240
J. Chem. Soc., Perkin Trans. 1, 1999, 2237–2241