Preparation of functionalized polymers utilizing a soluble highl

Details Preparation of functionalized polymers utilizing a soluble highl Preparation of functionalized polymers utilizing a soluble highl

1991-08-01

1993-05-18

Prescott, Arthur C.

Chemistry of carbon compounds

Miscellaneous organic carbon compounds

C-metal

556110, 521 25, C07F 304

Patent

active

052118860

ABSTRACT:
Calcium-substituted polymeric reagents are provided. These reagents can be prepared via the oxidative addition of a soluble highly reactive calcium species to organic and inorganic polymers containing alkyl, aryl, or alkylaryl pendent groups substituted with halide atoms, cyanide molecules, 1,3-dienes, or any conjugated polyunsaturated system. Preferably, the polymer is a cross-linked p-bromopolystyrene, p-chloropolystyrene, p-fluoropolystyrene, or chloromethylated polystyrene. Preferably, the soluble highly reactive calcium species is prepared from the reduction of Ca(II) salts with an alkali metal arene, such as lithium biphenylide. These calcium-substituted polymeric reagents react with a variety of electrophiles to yield functionalized polymers. Reaction with Cu(I) salts yields calcium-substituted polymeric cuprate reagents, which can react, for example, with acid chlorides to form ketones, alkyl halides containing functionality, and undergo 1,4-conjugate addition with .alpha.,.beta.-unsaturated ketones, aldehydes, esters, and amides. Bifunctionalization of the polymer can be achieved by the addition of highly reactive calcium to a functionalized polymer containing a halogen. Polymers can be cross-coupled with dyes, UV stabilizers, biologically active substrates, molecules that impart specifically desired characteristics, among other desirable functional groups.

REFERENCES:
patent: 3501332 (1970-03-01), Buckman
patent: 4830903 (1989-05-01), Levy
patent: 4892733 (1990-01-01), Bichon et al.
patent: 4963264 (1990-10-01), Davis
patent: 4966784 (1990-10-01), Tanaka et al.
Osborn, "Synthetic Ion-Exchangers", MacMillan Co., pp. 32 and 33, (1956).
A. Akelah et al., Chem. Rev., 81, 557 (1981).
L. C. Anand et al., Macromol. Syn., 4, 9 (1972).
S. C. Berk et al., J. Org. Chem., 53, 5789 (1988).
B. Bogdanovic, Acc. Chem. Res., 21, 261 (1988).
D. Braun, Makromol. Chem., 30, 85 (1959).
B. Brix et al., J. Org. Chem., 53, 3365 (1988).
T. P. Burns et al., J. Org. Chem., 52, 3674 (1987).
F. Camps et al., Tetrahedron Lett., 20, 1713 (1971).
A. J. Chalk, Polmer Lett., 6, 649 (1968).
J. P. Collman et al., Principles and Applications of Organotransition Metal Chemistry; University Science Books: Mill Valley, Calif.; pp. 682-738 (1987).
G. Corfield et al., Org. Coat. Appl. Poly. Sci. Proc., 46, 445 (1981).
G. D. Darling et al., J. Org. Chem., 51, 2270 (1986).
G. W. Ebert et al., J. Org. Chem., 49, 5280 (1984).
G. W. Ebert et al., J. Org. Chem., 53, 4482 (1988).
A. T. Ellis et al., Anal. Proc., 17, 48 (1980).
D. C. Evans et al., J. Polm. Sci., Polm. Chem. Ed., 12, 247 (1974).
M. J. Farrall et al., J. Org. Chem., 41, 3877 (1976).
M. J. Farrall et al., Nouv. J. Chim., 7, 449 (1983).
J. M. J. Frechet et al., Proc. ACS Symp., 1976, S. S. Labana, ed., Academic Press, p. 59 (1977).
J. M. J. Frechet, Tetrahedron, 37, 663 (1981).
P. K. Freeman et al., J. Org. Chem., 48, 879 (1983).
T. M. Fyles et al., Can. J. Chem., 54, 935 (1976).
B. G. Gowenlock et al., J. Organomet. Chem. Library, Organomet. Chem. Rev., 3, 1 (1977).
R. H. Grubbs et al., Chemtech, 512 (Aug. 1977).
T. P. Hanusa, Polyhedron, 9, 1345 (1990).
S. Harvey et al., J. C. S., Chem. Commun., 652 (1988).
S. Harvey et al., J. Org. Chem., 53, 3134 (1988).
P. Hodge, Polymer-Supported Reactions in Organic Synthesis, P. Hodge and D. C. Sherrington, eds., John Wiley and Sons, New York, pp. 146-150 (1980).
P. Hodge, Synthesis and Separations Using Functional Polymers, D. C. Sherrington and P. Hodge, eds., John Wiley and Sons, Ltd., New York, pp. 43-122 (1988).
S. Itsuno et al., J. Org. Chem., 52, 4644 (1987).
S. Itsuno et al., J. Polm. Mater. Sci. Eng., 57, pp. 570-574 (1987).
B. Jepson et al., Separation Sci. and Tech., 25, 1893 (1990).
P. Knochel et al., J. Org. Chem., 53, 2390 (1988).
P. Lecavalier et al., React. Polm., 3, 315 (1985).
R. L. Letsinger et al., J. Am. Chem. Soc., 86, 5163 (1964).
C. C. Leznoff, Chem. Soc. Rev., 3, 65 (1974).
J. Lieto et al., Chemtech, 46 (Jan. 1983).
W. E. Lindsell, Comprehensive Organometallic Chemistry, Ch. 4.1 and 4.2; Wilkinson, Stone & Abel, ed.; Pergamon Press, Oxford (1982).
B. H. Lipshutz, Tetrahedron, 40, 5005 (1984).
B. H. Lipshutz, Tetrahedron, 42, 2873 (1986).
B. H. Lipshutz, Synthesis, 325 (1987).
P. Markov et al., J. Organomet. Chem., 81, 1 (1974).
M. J. McCormick et al., J.C.S. Chem. Commun., 778 (1990).
L. R. Melby et al., J. Am. Chem. Soc., 89, 450 (1967).
R. B. Merrifield, J. Am. Chem. Soc., 85, 2149 (1963).
M. Metelko et al., Synth. Commun., 18, 1821 (1988).
Z. M. Michalska et al., Chemtech, 117 (Feb. 1975).
D. C. Neckers, J. Chem. Ed., 52, 695 (1975).
J. F. Normant, Synthesis, 63 (Feb. 1972).
J. F. Normant, Pure and Appl. Chem., 50, 709 (1978).
R. A. O'Brien et al., J. Org. Chem., 55, 788 (1990).
A. Patchornik et al., J. Am. Chem. Soc., 92, 7587 (1970).
C. U. Pittman, Jr. et al., Chemtech, 560 (Sep. 1973).
G. H. Posner, Org. Reactions (N.Y.), 19, 1 (1972).
G. H. Posner, Org. Reactions (N.Y.), 22, 253 (1975).
C. L. Raston et al., J. C. S., Chem. Commun., 1702 (1984).
R. D. Rieke et al., J. Am. Chem. Soc., 94, 7178 (1972).
R. D. Rieke et al., J. Am. Chem. Soc., 96, 1775 (1974).
R. D. Rieke et al., ACS Symposium Series, 333, 223 (1987).
R. D. Rieke et al., Synth. Commun., 19, 1833 (1989).
R. D. Rieke, Science, 246, 1260 (1989).
R. D. Rieke et al., J. Org. Chem., 56, 3109 (1991).
K. Soai et al., J. Org. Chem., 55, 4832 (1990).
D. E. Stack et al., J. Am. Chem. Soc., 113, 4672 (1991).
R. M. Wehmeyer et al., Tetrahedron Lett., 29, 4513 (1988).
T.- C. Wu et al., Tetrahedron Lett., 29, 6753 (1988).
T.- C. Wu et al., J. Org. Chem., 53, 2381 (1988).
T.- C. Wu et al., J. Org. Chem., 55, 5045 (1990).
H. Xiong et al., J. Org. Chem., 54, 3247 (1989).
S. H. Yu et al., J. Org. Chem., 36, 2123 (1971).
L. Zhu et al., J. Org. Chem., 56, 1445 (1991).
S. Itsuno et al., J. Polm. Mater. Sci. Eng., 57, 570 (1987).

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