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    • 8. 发明授权
    • Chiral pyridylphosphines and their application in asymmetric catalytic
hydrogenation of 2-arylpropenoic acids
    • 手性吡啶基膦及其在2-芳基丙烯酸的不对称催化氢化中的应用
    • US5886182A
    • 1999-03-23
    • US988376
    • 1997-12-10
    • Albert Sun-Chi ChanCheng-Chao Pai
    • Albert Sun-Chi ChanCheng-Chao Pai
    • C07F9/58C07F9/6568C07F9/50
    • C07F9/65683C07F9/587
    • Novel, optically active phosphorous compounds of the formula, ##STR1## wherein R.sup.1 represents hydrogen atoms, straight or branched-chain alkyl groups having from 1 to 6 carbon atoms, R.sup.2 represents hydrogen atoms, halogen atoms, lower alkyl groups (1 to 6 carbon atoms), lower alkoxy groups (1 to 6 carbon atoms), hydroxy group, chiral hydroxyalkyl groups, and amino groups (1.degree., 2.degree., 3.degree.) vinyl groups or allyl groups and R.sup.3 represents phenyl groups, aryl groups, cyclohexyl groups, substituted and unsubstituted cycloalkyl groups, heteroaromatic rings, are described. The compounds of the formula serve as highly useful ligands in the preparation of ruthenium complexes which are effective catalysts for the asymmetric hydrogenation of 2-arylpropenoic acids leading to high valued 2-arylpropionic acids.
    • 新型的具有下式的光学活性的磷化合物,其中R1代表氢原子,具有1-6个碳原子的直链或支链烷基,R2代表氢原子,卤素原子,低级烷基(1-6个碳原子) 原子),低级烷氧基(1至6个碳原子),羟基,手性羟基烷基和氨基(1,2,3)乙烯基或烯丙基,R 3表示苯基,芳基,环己基 ,取代和未取代的环烷基,杂芳环。 该配方的化合物在钌配合物的制备中起着非常有用的配体作用,这是用于2-芳基丙烯酸的不对称氢化的有效催化剂,导致高价值的2-芳基丙酸。
    • 10. 发明授权
    • Chiral aminophosphines
    • 手性氨基膦
    • US5952527A
    • 1999-09-14
    • US241091
    • 1999-02-01
    • Albert Sun-Chi ChanFu-Yao Zhang
    • Albert Sun-Chi ChanFu-Yao Zhang
    • C07C211/60C07C231/18C07C233/47C07C233/87C07D209/26C07D307/52C07D307/54C07F9/46C07F15/00C07F9/02
    • C07F9/46C07C211/60C07C231/18C07D209/26C07D307/52C07D307/54C07F15/008C07B2200/07C07C2102/10
    • This invention relates to (R)- and (S)-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthyl-2,2'-diamine (R-1 and S-1) and (R)- and (S)-2,2'-bis(diarylphospinoamino)-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthyl (R-2 and S-2) and (R)- and (S)-2,2'-bis(diaklphospinoamino)-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthyl (R-3 and S-3); to a process for the preparation of R-1 and S-1 in which (R) or (S)-1,1'-binaphthyl-2,2'-diamine is partially hydrogenated in the presence of Adam's catalyst (5-20 wt/o of starting material) at 20-100.degree. C. for 20-100 hours in glacial acetic acid (solvent); to a process for the preparation of R-2, S-2, R-3 and S-3 in which R-1 or S-1 is reacted with chlorodiarylphosphine or chlorodialkylphosphine in the presence of n-butyllithium; and to the rhodium complexes containing 2 or 3 as effective catalysts for the asymmetric hydrogenation of prochiral substrates such as olefins to produce higher valued chiral products; and to the asymmetric catalytic hydrogenation of enamides under mild conditions using the Rh-(2) or Rh-(3) as catalyst with chemical yields as high as 100% and enantiomeric excess (e.e.) as high as 99%.
    • 本发明涉及(R) - 和(S)-5,5',6,6',7,7',8,8'-八氢-1,1'-联萘-2,2'-二胺(R -1和S-1)和(R) - 和(S)-2,2'-双(二芳基磷酰氨基)-5,5',6,6',7,7',8,8'-八氢-1 ,1'-联萘(R-2和S-2)和(R) - 和(S)-2,2'-双(二烷基氨基)-5,5',6,6',7,7',8 ,8'-八氢-1,1'-联萘(R-3和S-3); 涉及制备R-1和S-1的方法,其中(R)或(S)-1,1'-联萘-2,2'-二胺在Adam催化剂存在下部分氢化(5-20 wt / o的原料)在20-100℃下在冰乙酸(溶剂)中反应20-100小时; 涉及制备R-2,S-2,R-3和S-3的方法,其中R-1或S-1与氯二芳基膦或氯二烷基膦在正丁基锂存在下反应; 以及含有2或3的铑络合物作为用于前置手性底物如烯烃的不对称氢化的有效催化剂,以产生更高价值的手性产物; 和使用Rh-(2)或Rh-(3)作为催化剂的温和条件下的酰胺的不对称催化氢化,化学产率高达100%,对映体过量(e.e。)高达99%。