Heterogeneous polymerization
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 8, August, 2009
1679
washed with hexane cooled to –50 °C. Compound 6c was obꢀ
tion mixture was stirred for 16 h with cooling by cold water.
The mixture was then poured into 10% HCl (100 mL) and vigorꢀ
ously shaken. The organic layer was concentrated. The resiꢀ
due was mixed with a 10% solution of HCl in methanol, refluxed
for 10 min, then cooled, and filtered and the obtained white
powder was dried in vacuo at 80 °C. In all cases, the yield
was virtually quantitative (94—98%). After weighing, the polyꢀ
mer was refluxed in toluene (100 mL) for 1 h. The solution
obtained after cooling and filtering through a glass filter was
concentrated to a constant weight, the residue was dissolved in
a calculated amount of cyclohexane. The solution was analyzed
tained as a white crystalline friable powder in a yield of 27.30 g
1
(
20%), [α]25
–101.50° (c 1, CHCl ). Н NMR (СDСl , δ):
5
89
3
3
0
.76 (d, 6 Н, 2 СН , J = 6.9 Hz); 0.92 (m, 18 H, 6 CH ); 1.06
3 3
(
d, 6 H, 2 CH , J = 6.9 Hz); 0.95—1.10 (m, 4 H, 2 CH ); 1.42
3 2
(
m, 2 H, 2 CH); 1.48 (m, 2 H, 2 CH); 1.69 (m, 4 H, 2 CH ); 2.02
2
(
4
1
m, 4 H, 2 CH ); 2.56 (dd, 2 CHCO, J = 1.8 Hz, J = 4.8 Hz);
.68 (td, 2 H, 2 OCH, J = 4.4 Hz, J = 10.9 Hz). С NMR (δ):
2
13
5.67, 19.45, 20.86, 21.31, 22.08 (СН ); 22.90 (CH ); 25.77
3
2
(
CH); 27.14 (CH(СН ) ); 31.43 (CH); 34.30 (CH ); 40.66
3 2 2
(
CH ); 46.73 (CH); 51.73 (CHC(O)OCH); 74.42 (OCH); 173.08
2
13
(
C(O)OCH). Found (%): С, 75.37; H, 11.30. С Н О . Calcuꢀ
by polarimetry. The С NMR spectrum of PMCP was recorded
3
0
54
4
lated (%): С, 75.26; H, 11.37; О, 13.37.
in CDCl at 50 °С.
3
(
–)ꢀ2,3ꢀDiisopropylsuccinic acid (7). A darkꢀbrown homoꢀ
geneous solution obtained after addition of compound 6с (42.30 g,
8 mmol) to 96% H SO (400 mL) was stirred for 20—25 min
References
8
2
4
at 40 °C and then poured into ice water (1.5 L). After coolꢀ
ing, the obtained emulsion was extracted with diethyl ether
1. P. Pino, G. Guastalla, B. Rotzinger, R. Mulhaupt, in Tranꢀ
sitionꢀMetalꢀCatalyzed Polymerizations — Alkenes and Dienes,
Ed. R. P. Quirk, Harwood, New York, 1983, p. 435.
2. J. C. Chadwick, G. Morini, G. Balbontin, I. Camurati, J. J.
R. Heere, I. Mingozzi, F. Testoni, Macromol. Chem. Phys.,
2001, 202, 1995.
3. H. Mori, M. Sawada, T. Higuchi, K. Hasebe, N. Otsuka,
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4. P. Corradini, V. Barone, R. Fusco, G. Guerra, Gazz. Chim.
Ital., 1983, 113, 601.
(
5×200 mL). The combined organic phase was evaporated,
the residue was mixed with 20% КОН (300 mL) and stirred
for 30 min. The emulsion was then washed with hexane
(
2×100 mL). The virtually colorless aqueous phase formed was
acidified with 37% HCl to pH = 0 and extracted with diꢀ
ethyl ether (3×200 mL). The combined organic phases were
dried with anhydrous Na SO and concentrated. A white solꢀ
2
4
id residue of the acid was then used without additional puriꢀ
2
5
fication. The yield was 95%, m.p. 166—167 °C, [α]
–39.10
5
89
(
c 1, EtOH). 1Н NMR (DMSOꢀd , δ): 0.79, 0.98 (both d,
5. L. Brambilla, G. Zerbi, F. Piemontesi, S. Nascetti, G. Moriꢀ
ni, J. Mol. Catal. A: Chem., 2007, 263, 163.
6. M. Boero, M. Parrinello, H. Weiss, S. Huffer, J. Phys.
Chem. A, 2001, 105, 5096.
6
6
2
1
Н each, 4 СН , J = 6.8 Hz); 1.92 (m, 2 H, 2 CH(CH ) );
3 3 2
.45 (s, 2 H, 2 CHCO); 12.05 (br.s, 2 H, 2 OH). С NMR (δ):
13
7.71, 21.86 (CH ); 25.84 (CH(CH ) ); 50.08 (CHCO); 174.51
3
3 2
(
COOH).
Monoethyl (–)ꢀ2,3ꢀdiisopropylsuccinate (8) was prepared
analogously to 2, [α]25 –28.50 (c 1, CHCl ).
7. M. Seth, P. M. Margl, T. Ziegler, Macromolecules, 2002,
35, 7815.
8. M. Toto, G. Morini, G. Guerra, P. Corradini, L. Cavallo,
Macromolecules, 2000, 33, 1134.
9. L. Cavallo, S. Del Piero, J.ꢀM. Ducere, R. Fedele, A. Melꢀ
chior, G. Morini, F. Piemontesi, M. Tolazzi, J. Phys. Chem.
C, 2007, 111, 4412.
5
89
3
Diethyl (–)ꢀ2,3ꢀdiisopropylsuccinate (9) was prepared analꢀ
ogously to 3, [α]25 –36.00 (c 1, CHCl ).
5
89
3
(
+)ꢀ2,3ꢀDiisopropylꢀ1,4ꢀbutanediol (13) was prepared analꢀ
2
5
ogously to 12, [α]
+4.40 (c 1, CHCl ).
5
89
3
(
+)ꢀ2,3ꢀDiisopropylꢀ1,4ꢀdimethoxybutane (11) was prepared
10. V. Busico, R. Cipullo, G. Monaco, G. Talarico, M. Vacatelꢀ
lo, J. C. Chadwick, A. L. Segre, O. Sundmeijer, Macromoleꢀ
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13. P. Pino, G. Fochi, O. Piccolo, U. Giannini, J. Am. Chem.
Soc., 1982, 104, 7381.
2
5
analogously to 10, [α]
+18.20 (c 1, CHCl ).
5
89
3
Preparation of a heterogeneous catalyst (general procedure).
All procedures were performed under dry argon. Magnesium
ethoxide (10.0 g, 87 mmol) was carefully added with stirring to
a 1 : 1 (v/v) TiCl —toluene mixture (100 mL). The suspension
formed was heated to 90 °C and the internal donor (3.0 mL,
4—16 mmol) was added (in the last experiment (see Table 1),
without addition of a donor), the mixture was stirred for 2 h at
20 °C. The reaction mixture obtained after cooling to 60 °C was
4
1
14. J. Vizzini, F. Ciardelli, J. C. W. Chien, Macromolecules, 1992,
25, 108.
1
filtered, the precipitate was washed with hot hexane (4×50 mL)
15. G. B. Butler, G. Allen, J. C. Bevington, Comprehensive Polyꢀ
mer Science, Pergamon Press, Oxford, 1989, 4, 423.
16. G. W. Coates, R. M. Waymouth, J. Am. Chem. Soc., 1993,
115, 91.
and again refluxed for 2 h in an analogous TiCl —toluene mixꢀ
4
ture (100 mL). The brown mixture formed was again filtered, the
precipitate was washed with hot heptane (2×50 mL), hot hexane
(
4×50 mL) and then extensively dried in vacuo. The weight of
17. L. Resconi, R. M. Waymouth, J. Am. Chem. Soc., 1990,
112, 4953.
the obtained catalyst was 8—10 g.
Polymerization reaction of hexaꢀ1,5ꢀdiene (general proceꢀ
dure). All procedures were performed under dry argon. A preꢀ
conditioned (for 5 min) suspension of catalyst (190 mg) in an
18. G. W. Coates, R. M. Waymouth, J. Am. Chem. Soc., 1991,
113, 6270.
19. Pat. WO 0063261; Chem. Abstrs, 2000, 133, 322299.
20. (a) V. K. Gupta, S. Satish, S. Bhardway, Eur. Polym. J.,
1995, 31, 145; (b) H. Mori, M. Endo, M. Terano, J. Mol.
Catal. A: Chem., 1999, 145, 211.
0
.5 М solution of Et Al (4 mL, 2 mmol) in hexane was added
3
at once to a solution of 1.0 М Et Al (3 mL, 3 mmol), an exterꢀ
3
nal donor (0.05 g, 0.25 mmol) (or without it), and hexaꢀ1,5ꢀdiene
(
3.50 g, 42 mmol) in heptane (50 mL). The reacꢀ
21. US Pat. 2003181743; Chem. Abstrs, 2004, 139, 261651.