2204
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 10, October, 2004
Nikishin et al.
+
+
+
+
13
and 93 [C H Cl] , 69 [C H ] , 55 [C H ] , 43 [C H ] ,
4 H, CH Cl, J = 5.9 Hz). C NMR (CDCl ), δ: 21.02, 30.11
4
+
8
5
9
4
7
3
7
2
3
4
1 [C H ] .
1
(CH ); 44.57 (CH Cl).
3
5
2
2
1
1b
ꢀChlorononane (2b), b.p. 200—201 °C (cf. lit. data : b.p.
02—204 °C). MS, m/z: 162 and 164 [M] , 91 and 93 [C H Cl] ,
6ꢀChlorohexanoic acid (6c), b.p. 150—152 °C (10 Torr) (cf.
lit. data12: b.p. 153 °C (12 Torr)). H NMR (CDCl ), δ:
1.73—1.79 (m, 6 H, CH ); 2.38 (t, 2 H, CH COOH, J = 6.5 Hz);
3.48 (t, 2 H, CH Cl, J = 5.7 Hz). C NMR (CDCl ), δ: 20.22,
2 3
+
+
1
2
6
4 8
3
+
+
+
+
9 [C H ] , 55 [C H ] , 43 [C H ] , 41 [C H ] .
5
9
4
7
3
7
3
1
5
2
2
13
3
ꢀChloroheptane (2c), b.p. 153—154 °C. H NMR (CDCl ),
3
δ: 0.85—1.10 (m, 6 H, Me); 1.31—1.53 and 1.70—1.87 (both m,
21.81, 32.82, 33.70 (CH ); 44.44 (CH Cl); 179.45 (C=O). IR,
2 2
13
–1
+
4
H each, CH ); 3.43—3.52 (m, 1 H, CH). C NMR (CDCl ),
ν/cm : 1707 (C=O). MS, m/z: 151 and 153 [M + H] .
1,6ꢀDichlorohexane (4d), b.p. 83—85 °C (10 Torr) (cf. lit.
2
3
δ: 10.86, 13.90 (Me); 22.22, 28.65, 31.42, 37.76 (CH );
2
data11b: b.p. 218—220 °C). H NMR (CDCl ), δ: 1.43—1.51
1
6
5.77 (CH).
3
Benzyl chloride (2d), b.p. 75—77 °C (20 Torr) (cf. lit. data11c:
and 1.73—1.82 (both m, 4 H each, CH ); 3.54 (t, 4 H, CH Cl,
2
2
1
13
b.p. 79—80 °C (21 Torr)). H NMR (CDCl ), δ: 4.65 (c, 2 H,
CH Cl); 7.38—7.52 (m, 5 H, Ph). C NMR (CDCl ), δ: 46.20
J = 6.3 Hz). C NMR (CDCl ), δ: 21.01, 32.32 (CH ); 44.85
3 2
3
13
(CH Cl).
2
2
3
(
1
CH ); 128.32, 128.51, 128.65 (C(2), C(3), C(4), C(5), C(6));
7ꢀChloroheptanoic acid (6d), b.p. 168—169 °C (10 Torr) (cf.
2
+
+
lit. data12: b.p. 171 °C (12 Torr)). H NMR (CDCl ), δ:
1
37.40 (C(1)). MS, m/z: 126 and 128 [M] , 91 [C H ] .
7 7
3
2
ꢀPhenylethyl chloride (2e), b.p. 88—90 °C (20 Torr) (cf. lit.
1.81—1.91 (m, 8 H, CH ); 2.42 (t, 2 H, CH COOH, J = 6.6 Hz);
3.60 (t, 2 H, CH Cl, J = 5.8 Hz). C NMR (CDCl ), δ: 20.12,
2 3
2
2
1
1d
1
13
data : b.p. 82—84 °C (16 Torr)). H NMR (CDCl ), δ: 3.10 (t,
3
2
7
H, CH , J = 3.7 Hz); 3.75 (t, 2 H, CH Cl, J = 3.8 Hz);
20.65, 21.81, 31.72, 33.43 (CH ); 44.31 (CH Cl); 179.21 (C=O).
2 2
IR, ν/cm : 1707 (C=O). MS, m/z: 165 and 167 [M + H] .
2
2
+
–1
+
.23—7.32 (m, 5 H, Ph). MS, m/z: 140 and 142 [M] , 105
+
+
[
M – Cl] , 91 [M – CH Cl] .
2
1
0ꢀChlorodecenꢀ1ꢀene (2f). Found (%): C, 68.69; H, 11.10;
This study was financially supported by the Russian
Foundation for Basic Research (Project No. 02ꢀ03ꢀ
32810a) and the State Foundation for Support of Leading
Scientific Schools (Grant No. 2121.2003.3).
Cl, 19.65. C10H19Cl. Calculated (%): C, 68.96; H, 10.92;
Cl, 20.11. H NMR (CDCl ), δ: 1.33—1.48 (m, 10 H, CH );
.71—1.82 and 2.03—2.12 (both m, 2 H each, CH ); 3.52 (t,
H, CH Cl, J = 5.6 Hz); 4.95 (t, 2 H, CH =CH, J = 8.0 Hz);
.72—5.89 (m, 1 H, CH=CH ).
Methyl 5ꢀchlorovalerate (2g), b.p. 100—103 °C (30 Torr)
cf. lit. data1 : b.p. 106—107 °C (38 Torr)). Found (%): C, 48.29;
1
3
2
1
2
5
2
2
2
2
References
1e
(
1
2
. G. I. Nikishin, L. L. Sokova, V. D. Makhaev, and N. I.
Kapustina, Mendeleev Commun., 2003, 264.
. R. A. Sheldon and J. K. Kochi, in Organic Reactions, J. Wiley
and Sons, Inc., New York—London—Sydney—Toronto,
H, 7.25; Cl, 23.08. C H ClO . Calculated (%): C, 48.00;
H, 7.33; Cl, 23.33. H NMR (CDCl ), δ: 1.71—1.85 (m, 4 H,
6
11
2
1
3
CH ); 2.38 (t, 2 H, CH COO, J = 5.4 Hz); 3.52 (t, 2 H, CH Cl,
2
2
2
13
J = 5.9 Hz); 3.68 (s, 3 H, Me). C NMR (CDCl ), δ: 22.19
Me); 31.79, 33.11, 44.38 (CH ); 51.52 (Me); 173.54 (C=O).
3
1
972, 19, p. 279.
(
2
3
. G. I. Nikishin, L. L. Sokova, V. D. Makhaev, L. A. Petrova,
A. V. Ignatenko, and N. I. Kapustina, Izv. Akad. Nauk, Ser.
Khim., 1998, 1391 [Russ. Chem. Bull., 1998, 47, 1353 (Engl.
Transl.)].
,3ꢀDichloropropane (4a), b.p. 123 °C (cf. lit. data 1f: b.p.
1
1
1
1
3
(
20—122 °C). H NMR (CDCl ), δ: 2.15—2.36 (m, 2 H, CH );
.72 (t, 4 H, CH Cl, J = 6.0 Hz). C NMR (CDCl ), δ: 34.81
3
2
13
2
3
CH ); 41.43 (CH Cl).
2 2
4
5
6
. B. A. Lorsbach and M. J. Kurth, Chem. Rev., 1999, 99, 1549.
. K. Tanaka and F. Toda, Chem. Rev., 2000, 100, 1025.
. N. I. Kapustina, L. L. Sokova, V. D. Makhaev, A. R. Borisov,
and G. I. Nikishin, Izv. Akad. Nauk, Ser. Khim., 2000, 1870
γꢀButyrolactone (5a), b.p. 202—203 °C (cf. lit. data11g: b.p.
1
2
2
04—205 °C). H NMR (CDCl ), δ: 2.13—2.28 (m, 2 H, CH );
.43 (t, 2 H, J = 7.9 Hz); 4.30 (t, 2 H, CH , J = 7.0 Hz).
C NMR (CDCl ), δ: 21.91, 27.54, 68.37 (CH ); 177.68 (C=O).
IR, ν/cm : 1772 (C=O).
3
2
2
13
3
2
[
Russ. Chem. Bull., Int. Ed., 2000, 49, 1842].
–
1
7
8
. J. K. Kochi, J. Org. Chem., 1965, 30, 3265.
. D. H. R. Barton and E. P. Serebryakov, Proc. Chem. Soc.,
1
,4ꢀDichlorobutane (4b), b.p. 161—162 °C (cf. lit. data11h:
1
b.p. 46—48 °C (15 Torr)). H NMR (CDCl ), δ: 1.91—1.98 (m,
H, CH ); 3.59 (t, 4 H, CH Cl, J = 6.0 Hz). C NMR (CDCl ),
3
1
1
962, 309.
3
4
2
2
3
9
. G. I. Nikishin, E. K. Starostin, B. A. Golovin, A. V.
Kessenikh, and A. V. Ignatenko, Izv. Akad. Nauk SSSR, Ser.
Khim., 1971, 1842 [Bull. Acad. Sci. USSR, Div. Chem. Sci.,
δ: 29.61 (CH ); 44.11 (CH Cl).
2
2
δꢀValerolactone (5b), b.p. 220—221 °C (cf. lit. data11i: b.p.
5
4
8—60 °C (0.5 Torr)). 1H NMR (CDCl ), δ: 1.79—1.83 (m,
3
1
971, 20, 1742 (Engl. Transl.)].
H, CH ); 2.56 (t, 2 H, CH , J = 6.4 Hz); 4.36 (t, 2 H, CH ,
J = 5.4 Hz). C NMR (CDCl ), δ: 19.00, 22.23, 29.80, 69.56
2
2
2
1
1
0. L. Fieser and M. Fieser, Reagents for Organic Synthesis,
J. Wiley, New York—London—Sydney, 1968.
1. Beilstein Handbuch der organischen Chemie, 1928, (a) 1, 154;
13
3
–
1
(
CH ); 171.87 (C=O). IR, ν/cm : 1712 (C=O).
2
5
1
2
ꢀChlorovaleric acid (6b), m.p. 16—17 °C (cf. lit. data :
(
2
b) 1, 128; (c) 5, 292; (d) 5, 354; (e) 2, 679; (f) 1, 105; (g) 17,
34; (h) 1, 119; (i) 17, 235; (j) 1, 131; (k) 1, 144.
1
m.p. 16—18 °C). H NMR (CDCl ), δ: 1.79—1.82 (m, 4 H,
3
CH ); 2.40 (t, 2 H, CH COOH, J = 6.5 Hz); 3.55 (t, 2 H,
2
2
1
2. G. I. Nikishin, A. V. Aleksandrov, A. V. Ignatenko, and
13
CH Cl, J = 5.7 Hz). C NMR (CDCl ), δ: 21.79, 31.55, 33.08
2
3
E. K. Starostin, Izv. Akad. Nauk SSSR, Ser. Khim., 1984,
–
1
(
CH ); 44.28 (CH Cl); 179.03 (C=O). IR, ν/cm : 1704 (C=O).
2 2
2
628 [Bull. Acad. Sci. USSR, Div. Chem. Sci., 1984, 33, 2407
+
MS, m/z:: 139 and 137 [M+H] .
,5ꢀDichloropentane (4c), b.p. 68—70 °C (15 Torr) (cf. lit.
(
Engl. Transl.)].
1
data1 : b.p. 63—66 °C (10 Torr)). 1H NMR (CDCl ), δ:
1g
Received December 24, 2003;
in revised form April 15, 2004
3
1
.39—1.44 (m, 2 H, CH ); 1.79—1.85 (m, 4 H, CH ); 3.55 (t,
2 2