CYCLODIMERIZATION OF ETHYLENE AND 1,3-BUTADIENE TO VINYLCYCLOBUTANE - HOMOGENEOUS TITANIUM CATALYSTS
CYCLODIMERIZATION OF ETHYLENE AND 1,3-BUTADIENE TO VINYLCYCLOBUTANE - HOMOGENEOUS TITANIUM CATALYSTS
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DOI：
10.1021/ja00774a056
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发表时间：
1972-01-01
影响因子：
15
通讯作者：
CANNELL, LG
中科院分区：
文献类型：
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作者：
CANNELL, LG
四苯基钛4和7r-C5H5Ti (CH2Ph) 35是单组分钛催化剂的例子，而双组分Ziegler型催化剂可以由许多碳氢可溶性钛化合物和各种还原剂原位制备。后者的例子是（it-C4H90） 4Ti与Et2Al， LiAlH4或n-C4H9Li作为还原剂，以及C5H6TiCl3，（acac） 2TiO或（C8H8） 2Ti与Et3Al结合。虽然乙烯基环丁烷的产率变化很大，但这似乎是具有开放配位的还原性有机钛的一个相当普遍的催化性质。与乙烯基环丁烷形成竞争的产品包括；顺式1,4 -己二烯，1-丁烯从乙烯，聚丁二烯，4-乙烯基-1-环己烯（部分热），开链辛三烯，环己烯（热二聚体在170），和C= C异构化产物，如乙基环丁烷和2,4 -己二烯。已知钛酸四丁酯- et3al在单独存在任何一种反应物时（反应温度为30-60℃）可将乙烯转化为1-丁烯，将丁二烯转化为1,2 -聚丁二烯；然而，当丁二烯一起存在时，它抑制乙烯二聚化，而二聚化可以在更高的温度下进行，135-155。各种竞争反应的重要性取决于特定的催化剂体系，幸运的是，可以通过添加给体(2)(a)来修饰。化学。Soc。， 92, 6785 (1970)；(b) RG Miller， T. J. Kealy, AL Barney，同上，89,3756 (1967)；(c) T. Alderson， EL Jenner和R. V. Lindsey, Jr.，同上，87,5638 (1965)；(d) G. Hata，同上，86,3903 (1964)；(e) R. Cramer，会计化学。Res. 1,186 (1968)；(f) M. Iwamoto和S. Yuguchi, Chem。Commun。， 28 (1968)；公牛。化学。Soc。日本。， 41,150 (1968)；2001年（1966年）39；(g) g . Hata和A. Miyake，同上，41,2443 (1968)；(h)田岛和国冈，化学。Commun。， 603 (1968)；(i) G. Henrici-Ólivé和S. oliv<e:1>，有机金属公司。化学。， 35,381（1972）。(3)李建军，李建军，李建军。化学。Soc。， 90,6071 (1968)；RK里昂,/。Org。化学。， 34, 3202（1969）。(4) U. Giannini和U. Zucchini，化学Commun。940 (1968)；(b) U. Zucchini， E. Albizzati和U. Giannini,/。有机金属。化学。， 26,357（1971）。
Tetrabenzyltitanium4 and 7r-C5H5Ti (CH2Ph) 35 serve as examples of single component titanium catalysts while two-component catalysts of the Ziegler type can be prepared in situ from a number of hydrocarbonsoluble titanium compounds and various reducing agents. Examples of the latter are (it-C4H90) 4Ti together with Et2Al, LiAlH4 or n-C4H9Li as reducing agents and also C5H6TiCl3,(acac) 2TiO, or (C8H8) 2Ti in combination with Et3Al. Although yields of vinyl-cyclobutane vary greatly, it appears that this is a quite general catalytic property of reduced organotitanium species possessingopen coordination sites. Products formed in competition with vinylcyclobutane include; cis-1, 4-hexadiene, 1-butene from ethy-lene, poly butadiene, 4-vinyl-1-cyclohexene (partially thermal), open-chain octatrienes, cyclohexene (thermal dimer at 170), and C= C isomerization products such as ethylidenecyclobutane and 2, 4-hexadiene. Tetra-butyl titanate-Et3Al is known to convert ethylene to 1-butene and butadiene to 1, 2-polybutadiene when either reactant is present alone (reaction temperature of 30-60); 6however, when present together, butadiene suppresses ethylene dimerization, and codimerization can then take place at a higher temperature, 135-155. The importance of the various competing reactions depended upon the particular catalyst system which, fortunately, could be modified by addition of donor (2)(a) C. A. Tolman, Amer. Chem. Soc., 92, 6785 (1970);(b) RG Miller, T. J. Kealy, and AL Barney, ibid., 89, 3756 (1967);(c) T. Alderson, EL Jenner, and R. V. Lindsey, Jr., ibid., 87, 5638 (1965);(d) G. Hata, ibid., 86, 3903 (1964);(e) R. Cramer, Accounts Chem. Res., 1, 186 (1968);(f) M. Iwamoto and S. Yuguchi, Chem. Commun., 28 (1968); Bull. Chem. Soc. Jap., 41, 150 (1968); 39, 2001 (1966);(g) G. Hata and A. Miyake, ibid., 41, 2443 (1968);(h) Y. Tajima and E. Kunioka, Chem. Commun., 603 (1968);(i) G. Henrici-Ólivé and S. Olivé, Organometal. Chem., 35,381 (1972).(3) P. D. Bartlett and K. W. Schueller, J. Amer. Chem. Soc., 90, 6071 (1968); RK Lyon,/. Org. Chem., 34, 3202 (1969).(4) U. Giannini and U. Zucchini, Chem. Commun., 940 (1968);(b) U. Zucchini, E. Albizzati, and U. Giannini,/. Organometal. Chem., 26,357 (1971).