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公开(公告)号:US5986139A
公开(公告)日:1999-11-16
申请号:US172
申请日:1998-01-26
IPC分类号: B01J31/18 , C07B61/00 , C07C209/52 , C07C213/08 , C07C215/16 , C07D333/36 , C07C209/00
CPC分类号: C07C209/52 , C07D333/36
摘要: A process for the preparation of primary or secondary amines by hydrogenation of imines with hydrogen at elevated pressure and in the presence of a dinuclear Ir(III) complex having ditertiary diphosphine ligands, halide bridges, halide and hydride ligands, or an Ir(III) halide complex salt containing ditertiary diphosphine ligands, as catalyst, wherein the catalyst corresponds to formula I or Ia or to mixtures of at least two compounds of formula I, at least two compounds of formulae I and Ia, or at least two compounds of formula Ia[(DIP)IrX.sub.q Y.sub.r ].sub.2 (I),[(DIP)X.sub.4 ].sup..crclbar. Me.sup..sym. (Ia),whereinDIP is the ditertiary diphosphine ligand of a ferrocenyldiphosphine the phosphine groups of which are either bonded directly or via a bridge group --CR.sub.v R.sub.w -- to the ortho positions of a cyclopentadienyl ring or are each bonded to a cyclopentadienyl ring of a ferrocenyl, so that a 5-, 6- or 7-membered ring is formed together with the Ir atom;R.sub.v and R.sub.w are each independently of the other hydrogen, C.sub.1 -C.sub.8 alkyl, C.sub.1 -C.sub.4 fluoroalkyl, phenyl or benzyl, or are phenyl or benzyl each having from 1 to 3 C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.4 -alkoxy substituents;X is Cl, Br or I;Y is H;q is a number 2 or 3 and r is 0 or 1, the sum of q+r being equal to 3; andMe.sup..sym. is an alkali metal cation or quaternary ammonium.
摘要翻译: PCT No.PCT / EP96 / 03147 371日期1998年1月26日 102(e)1998年1月26日PCT PCT 1996年7月17日PCT公布。 公开号WO97 / 05094 日期1997年2月13日一种通过在升高的压力下在氢气下氢化亚胺和在具有二重二膦配体,卤化物桥,卤化物和氢化物配体的双核Ir(III)络合物存在下制备伯胺或仲胺的方法,或 含有二重二膦配体的Ir(III)卤化物配盐作为催化剂,其中催化剂对应于式I或Ia或至少两种式I化合物,至少两种式I和Ia化合物或至少 两种式Ia [(DIP)IrXqYr 2(I),[(DIP)X 4]( - )Me(+)(Ia)的化合物,其中DIP是二茂铁基二膦的二元二膦配体,其膦基为 直接或通过桥基-CRvRw-键合到环戊二烯基环的邻位,或者各自键合到二茂铁基的环戊二烯基环,使得与Ir原子一起形成5-,6-或7-元环 ; Rv和Rv各自独立地为另一个氢,C 1 -C 8烷基,C 1 -C 4氟烷基,苯基或苄基,或各自具有1至3个C 1 -C 4烷基或C 1 -C 4 - 烷氧基取代基的苯基或苄基; X是Cl,Br或I; Y是H; q是数字2或3,r是0或1,q + r的和等于3; 和Me(+)是碱金属阳离子或季铵。
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2.
公开(公告)号:US06008393A
公开(公告)日:1999-12-28
申请号:US000071
申请日:1998-01-22
IPC分类号: C07D209/08 , B01J31/22 , B01J31/24 , C07B61/00 , C07C209/52 , C07C211/45 , C07C219/02 , C07F15/00 , C07F17/02 , C07F19/00
CPC分类号: B01J31/1845 , B01J31/1875 , B01J31/188 , B01J31/2295 , B01J31/24 , B01J31/2409 , B01J31/2414 , B01J31/2433 , B01J31/2452 , B01J31/2457 , B01J31/2476 , B01J31/248 , B01J31/2495 , C07C209/52 , C07C219/02 , C07F15/004 , C07F17/02 , B01J2231/643 , B01J2531/02 , B01J2531/0266 , B01J2531/821 , B01J2531/827 , B01J2531/842 , B01J31/04 , B01J31/26
摘要: Compounds of formulae I: (DIP)IrX.sub.q Y.sub.r (Z), Ia: (DIP)IrX.sub.s Y.sub.t (Z).sub.2 and Ib: (DIP)Ir(Z).sub.3 or mixtures of at least two of those compounds, wherein DIP is a ditertiary diphosphine, the two phosphine groups of which are bonded to a C.sub.2 -, C.sub.3 - or C.sub.4 -carbon chain, with the result that the diphosphine forms a 5- to 7-membered ring together with the Ir atom, X is Cl, Br or I, Y is a hydrogen atom, q and r are 0, 1 or 2 and the sum of q+r is 2, s and t are 0 or 1 and the sum of s+t is 1, and Z is the anion of an organic oxy acid that contains a group C(.dbd.O), S(.dbd.O)O or P(.dbd.O)O in the anion. The compounds are excellent catalysts for the hydrogenation of imines, especially for the enantioselective hydrogenation of prochiral imines.
摘要翻译: PCT No.PCT / EP96 / 03146 Sec。 371日期:1998年1月22日 102(e)1998年1月22日PCT PCT 1996年7月17日PCT公布。 公开号WO97 / 05150 日期:1997年2月13日化学式I:(DIP)IrXqYr(Z),Ia:(DIP)IrXsYt(Z)2和Ib:(DIP)Ir(Z)3的化合物或这些化合物中的至少两种的混合物,其中 DIP是二价二膦,其两个膦基与C2-,C3-或C4-碳键连接,结果是二膦与Ir原子一起形成5-至7-元环,X是 Cl,Br或I,Y是氢原子,q和r是0,1或2,q + r的和为2,s和t分别为0或1,s + t的和为1,Z 是在阴离子中含有基团C(= O),S(= O)O或P(= O)O)的有机氧酸的阴离子。 该化合物是用于亚胺加氢的优异催化剂,特别是用于前手性亚胺的对映选择性氢化。
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