Y. Shvo, R. Green / Journal of Organometallic Chemistry 675 (2003) 77Á
/83
83
3
2
.6. Ethyl dichloro(2-chlorocyclooctyl)ethanoate (Table
, 9)
3.11. 2-Trichloromethyl-6-chlorobicyclo[3.3.0]octane
(Table 3, 3)
1
1
B.p.ꢀ
6H), 4.2Á
6.5, 48.8, 61.9(d), 63.8, 91.6, 166.0. IR (neat): nꢀ
/
118 8C/0.3 mmHg. H-NMR: dꢀ
/
1.3Á
/
2.6 (m,
B.p.ꢀ
/
70 8C/0.1 mmHg. H-NMR: dꢀ
/
1.7Á2.3 (m,
/
1
3
13
1
3
1
3
1
/
4.4 (m, 1Hꢁ
/
2H). C-NMR: dꢀ
/
13.9, 22.3Á
/
8H), 2.8 (m, 3H), 4.2 (m, 1H). C-NMR (J MOD): dꢀ
31.1(d, o), 32.1(o), 34.9(o), 45.5(e), 55.9(e), 65.3(e),
69.0(e), 103.5(o). IR (neat): nꢀ1450, 1303, 1237, 1064,
1031, 845, 812, 779, 719. MS: m/z (%)ꢀ262(1), 224(6),
198(17), 189(42), 153(46), 143(87), 117(24), 107(100),
/
/
1760,
ꢃ1
468, 1446, 1235(br), 1029 cm . MS: m/z (%)ꢀ
01(19), 281(11), 265(90), 229(100), 201(16), 193(88),
56(32), 119(23), 109(25), 91(7), 79(9).
/
/
/
91(31), 79(81), 67(33), 59(22), 51(17), 39(34).
3.7. 1,1,1,3-Tetrachloro-7-heptene (Table 3, 1, 1:1
addition product)
3.12. Ethyl dichloro(2-bicyclo[3.3.0]-6-
chlorooctyl)ethanoate (Table 3, 4)
1
b.p.ꢀ
.3 (m, 2H), 3.2 (ddd, 2H), 4.2 (m, 1H), 5.1 (m, 2H), 5.8
m, 1H). MS: m/z (%)ꢀ199(11), 163(27), 149(13),
/
39 8C/0.1 mmHg. H-NMR: dꢀ
/
1.9 (m, 2H),
1
B.p.ꢀ
/
90 8C/0.05 mmHg. H-NMR: dꢀ
/1.4 (t, 3H),
2
(
1
2
6
1
.6Á2.2 (m, 8H), 2.6Á
/
/
2.8 (m, 3H), 4.1 (m, 1H), 4.3 (q,
31.1(t), 35.2(d), 49.9, 56.0, 59.4,
0.3, 62.4, 65.4, 88.1, 170.5. IR (neat): nꢀ1756, 1451,
/
1
3
H). C-NMR: dꢀ
/
1
27(60), 109(37), 91(45), 67(89), 55(85), 41(100).
/
ꢃ1
369, 1296, 1242(br), 1023, 847,830, 693 cm . MS: m/z
3.8. 1,1,1,3,6,8,8,8-Hexachlorooctane (Table 3, 1, 2:1
addition product)
(
1
5
%)ꢀ
/
300(1), 263(14), 227(11), 189(58), 156(100),
28(24), 117(44), 107(39), 91(35), 79(49), 67(25),
3(14), 41(23).
1
B.p.ꢀ
/
114Á
/
120 8C/0.3 mmHg. H-NMR: dꢀ
/
1.6Á2.4
/
(
m, 4H), 3.2 (dddd, 4H), 4.3 (m, 2H). MS: m/z (%)ꢀ
/
3
1
4
17(50), 281(33), 245(50), 221(30), 183(28), 159(31),
43(55), 123(44), 109(100), 87(33), 75(58), 61(23),
3(58).
References
[1] (a) M. Ascher, D.Vofsi, J. Chem. Soc. 1963, 1887 and 3921.;
(
b) S. Murai, N. Sonoda, S. Tsutsumi, J. Org. Chem. 29 (1964)
104;
c) Y. Mori, J. Tsuji, Tetrahedron 29 (1973) 827.
[2] (a) H. Matsumoto, T. Nikaido, M. Nagai, J. Org. Chem. 41
1976) 396;
(b) W.J. Bland, R. Davis, J.L.A. Durrant, J. Organomet. Chem.
80 (1985) 397;
c) R. Grigg, J. Devlin, A. Ramasubbo, R.M. Scott, P. Stevenson,
2
3.9. Ethyl 2,2,4-trichloro-7-octenoate (Table 3, 2, 1:1
addition product)
(
(
1
B.p.ꢀ
/
69 8C/0.2 mmHg. H-NMR: dꢀ
/1.4 (t, 3H),
2
1
.9 (q, 2H), 2.2 (m, 2H), 3.1 (ddd, 2H), 4.3 (m, 3H), 5.0
(
1
3
(
m, 2H), 5.8 (m, 1H). C-NMR: dꢀ
/
13.7, 30.1, 37.6,
2.8, 57.3, 64.0, 82.7, 116.1, 136.4, 165.4. IR (neat): nꢀ
768, 1725(sh), 1446, 1255(br), 1202, 1097, 1027, 918,
J. Chem. Soc. Perkin Trans. I (1987) 1515.
[3] T. Susuki, J. Tsuji, J. Org. Chem. 35 (1970) 2982.
[4] R. Davis, J.L.A. Durrant, M.S. Khazal, T.E. Bitterwolf, J.
Organomet. Chem. 386 (1990) 229.
5
1
6
1
/
ꢃ1
97 cm . MS: m/z (%)ꢀ237(45), 201(23), 156(54),
/
[
[
[
5] R. Davis, M.S. Khazal, J. Organomet. Chem. 397 (1990) 51.
6] J. Tsuji, K. Sato, H. Nagashima, Tetrahedron 41 (1985) 393.
7] (a) M.S. Kharasch, W.H. Urry, E.V. Jensen, J. Am. Chem. Soc.
27(30), 109(19), 91(37), 81(56), 67(61), 55(33), 41(100).
6
7 (1945) 1626;
b) M.S. Kharasch, O. Reinmuth, W.H. Urry, J. Am. Chem. Soc.
9 (1947) 1105.
8] R. Davis, I.F. Groves, J. Chem. Soc. Dalton Trans. (1982) 2281.
3
(
.10. Ethyl ethyl 2,2,4,7,9,9-hexachlorodecanedioate
Table 3, 2, 2:1 addition product)
(
6
[
1
B.p.ꢀ
/
124 8C/0.1 mmHg. H-NMR: dꢀ
/
1.4 (t, 6H),
[9] I. Somech, Y. Shvo, J. Organomet. Chem. 601 (2000) 153.
10] (a) O. Gandolfi, M. Cais, J. Organomet. Chem. 125 (1977) 141;
1
3
[
2
.1 (m, 4H), 2.7 (dddd, 4H), 4.3 (m, 6H). C-NMR:
13.7, 30.5, 33.8Á35.3, 49.8, 52.5(d), 56.9, 57.3, 64.1,
2.3, 165.2. IR (neat): nꢀ(1797)*, 1756, 1748(sh), 1445,
396, 1255, 1201, 1097, 1024, 963. *GCÁMS: m/z (%)ꢀ
92(6), 355(6), 321(29), 283(25), 245(29), 209(31),
83(29), 156(49), 122(45), 91(66), 75(100), 51(60).
(
b) W.J. Bland, R. Davis, J.L.A. Durrant, J. Organomet. Chem.
60 (1984) C75;
c) W.J. Bland, R. Davis, J.L.A. Durrant, J. Organomet. Chem.
80 (1985) 95.
dꢀ
/
/
1
8
1
3
1
/
(
/
/
2
[11] A.N. Nesmeyanov, R.Kh. Freidlina, E.C. Chukovskaya, R.G.
Petrova, A.B. Belyavski, Tetrahedron 17 (1962) 61.
[
12] (a) D.P. Tate, W.R. Knipple, J.M. Augl, Inorg. Chem. 1 (1962)
4
*
The 2:1 addition product was partially decomposed
33;
b) M.A. Schroeder, M.S. Wrighton, J. Org. Chem. 74 (1974) C29;
c) R.B. King, J. Organomet. Chem. 8 (1967) 139.
during its work-up, to give (assumably) the lactone.
Thus, distillation of the reaction mixture afforded a
mixture of these two products.
(
(
[13] R. Davis, K. Stephens, M. Hajek, J. Mol. Cat. 92 (1994) 269.