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    • 1. 发明授权
    • Chelating tertiary amino metal amides
    • 螯合叔氨基金属酰胺
    • US4268455A
    • 1981-05-19
    • US713902
    • 1976-08-12
    • Arthur W. Langer, Jr.Thomas A. Whitney
    • Arthur W. Langer, Jr.Thomas A. Whitney
    • C07C29/42C07F5/06
    • C07C29/42
    • Chelating tertiary amino metal amides selected from compounds having the formulae: Mg.sup. ++ [Chel N].sub.2.sup..crclbar. wherein [Chel N].sup..crclbar. is not ##STR1## [Chel N].sup..crclbar. M.sup..sym., [Chel N].sup..crclbar. M.sup..sym. M'H.sub.m R.sub.n X.sub.p, Z Mg.sup..sym. [Chel N--M'H.sub.m R.sub.n X.sub.p ].sup..crclbar., Mg.sup. ++ --[Chel N--M'H.sub.m R.sub.n X.sub.p ].sup..crclbar. [M'H.sub.m R.sub.n X.sub.p Z].sup..crclbar., Chel N-Mg.sym.[N--Mg.sup..sym. H.sub.m R.sub.n X.sub.p Z].sup..crclbar. and Mg.sup. ++ [Chel N--M'H.sub.m R.sub.n X.sub.p ].sub.2 .sup..crclbar., wherein M is a Group IA metal, M' is a metal selected from the group consisting of Li, Na, Mg, Be, Zn, Cd, B, Al, Ga, In, Zr, Ti, Sn and Cu and m and n=0 to 4, p=0 to 3 and (m+n+ p)=the valence of M' and (m+n)= at least 1 and X is a nonreactive group selected from the group consisting of chlorine, bromine, iodine, C.sub.1 to C.sub.20 alkoxide, C.sub.1 to C.sub.20 thioalkoxide, C.sub.2 to C.sub.40 hydrocarbyl secondary amide and C.sub.2 to C.sub.40 hydrocarbyl secondary phosphide, R is hydrocarbyl group and Z is selected from the group consisting of R, X and H.In an alternative embodiment, the instant invention relates to chiral optically active chelating tertiary amino metal amides selected from compounds having the formulae: [Chel*N].sup..crclbar. M.sup..sym. ; [Chel*N].sup..crclbar. M.sup..sym. M'H.sub.m R.sub.n X.sub.p, Z Mg.sup..sym. [Chel*N--M'H.sub.m R.sub.n X.sub.p ].sup..crclbar., Mg.sup. ++ [Chel*N--M'H.sub.m R.sub.n X.sub.p ].sup..crclbar. [M'H.sub.m R.sub.n X.sub.p Z].sup..crclbar., Chel*N--Mg.sup..sym. [M'H.sub.m R.sub.n X.sub.p ].sup..crclbar., Mg.sup. ++ [Chel*N--M'H.sub.m R.sub.n X.sub.p ].sub.2.sup..crclbar. and Mg.sup. ++ [Chel*N].sub.2 .sup..crclbar. wherein M, M', R, X, m, n, p and Z are as defined previously and where * denotes optical activity.The compounds of the instant invention are useful in metalations, synthesis, asymmetric synthesis and other reactions,. When chiral optically active chelating tertiary amino metal amides are used, the reactions which can be performed include all of the above, plus other reactions which produce chiral or stereoregular products.
    • 选择具有下式的化合物的螯合叔氨基金属酰胺:Mg ++ [Chel N] 2( - )其中[Chel N]( - )不是[Chel N]( - )M(+),[Chel ( - )M(+)M'HmRnXp,Z Mg(+)[Chel N-M'HmRnXp]( - ),Mg ++ - [Chel N-M'HmRnXp]( - )[M'HmRnXpZ] ( - ),Chel N-Mg(+)[N-Mg(+)HmRnXpZ]( - )和Mg ++ [Chel N-M'HmRnXp] 2( - ),其中M是IA族金属,M' 是选自Li,Na,Mg,Be,Zn,Cd,B,Al,Ga,In,Zr,Ti,Sn和Cu中的金属,m和n = 0〜4,p = 0〜3 和(m + n + p)= M'的价数,(m + n)=至少1,X是选自氯,溴,碘,C1至C20烷氧基,C1至C20硫代烷氧化物的非反应性基团 ,C 2至C 40烃基仲酰胺和C 2至C 40烃基二次膦,R为烃基,Z选自R,X和H.在替代实施方案中,本发明涉及手性光学活性螯合叔氨基 金属酰胺选自具有t的化合物 他公式:[Chel * N]( - )M(+); ( - )M(+)M'HmRnXp,Z Mg(+)[Chel * N-M'HmRnXp]( - ),Mg ++ [Chel * N-M'HmRnXp]( - )[ (+)[M'HmRnXp]( - ),Mg ++ [Chel * N-M'HmRnXp] 2( - )和Mg ++ [Chel * N] 2( - )其中M,M',R,X,m,n,p和Z如前所定义,其中*表示光学活性。 本发明的化合物可用于金属化,合成,不对称合成和其它反应。 当使用手性光学活性螯合叔氨基金属酰胺时,可以进行的反应包括以上所有的反应,加上产生手性或立构规整产物的其它反应。