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    • 1. 发明授权
    • Method for producing epoxides through olefin oxidation with air or oxygen
    • 用空气或氧气通过烯烃氧化制备环氧化物的方法
    • US06326502B1
    • 2001-12-04
    • US09462523
    • 2000-01-07
    • Rolf Peter SchulzUwe DingerdissenWolfgang Anton HerrmannGerhard Lobmaier
    • Rolf Peter SchulzUwe DingerdissenWolfgang Anton HerrmannGerhard Lobmaier
    • C07D30106
    • C07D301/06C07D303/04
    • The present invention provides a process for the epoxidation of alkenes of the formula (1) where R1, R2, R3 and R4 are, independently of one another, hydrogen, C1-C20-alkyl, C1-C12-alkoxy, C6-C10-aryl, —CHOH—CH3, —CH—NH2—CH3 or carboxy, using air or oxygen over a catalyst comprising compounds of the formula (2) MoxOy(L)z  (2) where x is 1, 2 or 3, y is an integer from 0 to 2x+1, z is an integer from 1 to 2x, where the ligand L is a compound of the formula (3) or (4) where X is a nitrogen, oxygen or sulfur atom, Y is hydrogen, C1-C8-alkyl, C1-C8-alkoxy, F, Cl, Br, I, COOCH3, C6-C14-aryl or C3-C8-cycloalkyl, R7 and R8 form a ring containing from 4 to 8 carbon atoms onto which one or two aromatic rings may be fused, R5 and R6 are hydrogen, branched or straight-chain C1-C12-alkyl or branched or straight-chain C1-C12-haloalkyl which are substituents on the ring formed by R7 and R8 and/or the rings fused onto this ring, or the ligand L is a compound of the formula (5), (6) or (7) where R is hydrogen, C1-C8-alkyl, C1-C8-haloalkyl, C1-C8-alkoxy, COOCH3, C6-C14-aryl or C3-C8-cycloalkyl and n is 1 or 2 and m is from 1 to 6, wherein the reaction is carried out in a pressure vessel which is completely lined with an inert material.
    • 本发明提供了式(1)的烯烃的环氧化方法,其中R 1,R 2,R 3和R 4彼此独立地为氢,C 1 -C 20 - 烷基,C 1 -C 12 - 烷氧基,C 6 -C 10 - 芳基,-CHOH-CH 3,-CH-NH 2 -CH 3或羧基,使用空气或氧气在包含式(2)化合物的催化剂上,其中x为1,2或3,y为0至2×+ 1的整数, z是1至2的整数,其中配体L是式(3)或(4)的化合物,其中X是氮,氧或硫原子,Y是氢,C1-C8-烷基,C1-C8-烷基, 烷氧基,F,Cl,Br,I,COOCH 3,C 6 -C 14 - 芳基或C 3 -C 8 - 环烷基,R 7和R 8形成含有4至8个碳原子的环,一个或两个芳环可以被稠合,R5和 R6是在由R7和R8形成的环和/或稠合在该环上的环上的取代基的氢,支链或直链C 1 -C 12烷基或支链或直链C 1 -C 12 - 卤代烷基,或配体L 是式(5),(6)或(7)的化合物,其中R是氢,C1-C8-烷基,C1-C8 卤代烷基,C 1 -C 8 - 烷氧基,COOCH 3,C 6 -C 14 - 芳基或C 3 -C 8 - 环烷基,n为1或2,m为1至6,其中反应在完全衬里的压力容器中进行 用惰性材料。
    • 6. 发明授权
    • Manganiferous polyoxometallates, synthesis and use thereof
    • 含锰多金属氧酸盐,其合成和用途
    • US6022986A
    • 2000-02-08
    • US11986
    • 1998-04-23
    • Bernd ScharbertRolf Peter SchulzBernt KrebsRainer BohnerChristian Thulig
    • Bernd ScharbertRolf Peter SchulzBernt KrebsRainer BohnerChristian Thulig
    • B01J23/34B01J27/02B01J27/187C01B19/00C01G45/00C11D3/02C11D3/39C11D3/395D21C9/10C07F15/00
    • C11D3/3932B01J23/34B01J27/02C01B19/002C01G45/006D21C9/1036C01P2002/77C01P2002/82C01P2002/86C01P2006/60C01P2006/80
    • The invention is directed to manganese-containing polyoxometallates of the formula (1)(Q).sub.q (Mn.sub.p A.sub.a X.sub.x Y.sub.y M.sub.m O.sub.d Z.sub.z (H.sub.2 O).sub.b)cH.sub.2 O (1)where Q is one or more cations selected from the group consisting of H, Li, K, Na, Rb, Cs, Ca, Mg, Sr, Ba, Al, PR.sup.1 R.sup.2 R.sup.3 R.sup.4 and NR.sup.1 R.sup.2 R.sup.3 R.sup.4 where R.sup.1, R.sup.2, R.sup.3 and R.sup.4 =H or C.sub.1 -C.sub.20 -alkyl, C.sub.5 -C.sub.8 -cycloalkyl or aryl;Mn is manganese;A is a heterometal and is one or more transition metals from transition groups II to VIII apart from Zn, in particular Ru, V, Ti, Zr, Cr, Fe, Co, Cu, Sn, Ni, Re or Os;X is one or more elements selected from the group consisting of Ga, B, P, Si, Ge, As, F, Cl, Br and I;Y is Sb, S, Te, Se and Bi;M is one or more transition metals selected from the group consisting of Mo, W, Nb, Ta and V;Z is one or more anions selected from the group consisting of OH.sup.-, F.sup.-, Cl.sup.-, Br.sup.-, I.sup.-, N.sub.3.sup.-, NO.sub.3.sup.-, ClO.sub.4.sup.-, NCS--, SCN--, PF.sub.6.sup.-, RSO.sub.3.sup.-, RSO.sub.4.sup.-, CF.sub.3 SO.sub.3.sup.-, BR.sub.4.sup.-, BF.sub.4.sup.-, OAc.sup.-, where R=H, C.sub.1 -C.sub.20 -alkyl, C.sub.5 -C.sub.8 -cycloalkyl or aryl. The indexes q, p, a, x, y, m, d, z and the numbers b and c are defined in the specification. The oxidation catalyst according to the invention is particularly effective in activating peroxidic compounds and oxygen.
    • PCT No.PCT / EP96 / 03669 371日期:1998年4月23日 102(e)1998年4月23日PCT PCT 1996年8月20日PCT公布。 公开号WO97 / 07886 日期1997年3月6日本发明涉及式(1)(Q)q(MnpAaXxYyMmOdZz(H2O)b)cH2O(1)的含锰多金属氧酸盐,其中Q是一种或多种选自H, Li,K,Na,Rb,Cs,Ca,Mg,Sr,Ba,Al,PR1R2R3R4和NR1R2R3R4,其中R1,R2,R3和R4 = H或C1-C20-烷基,C5-C8-环烷基或芳基; 锰是锰; A是异金属,并且是从Zn,特别是Ru,V,Ti,Zr,Cr,Fe,Co,Cu,Sn,Ni,Re或Os中的过渡族II至VIII的一种或多种过渡金属; X是选自Ga,B,P,Si,Ge,As,F,Cl,Br和I中的一种或多种元素; Y是Sb,S,Te,Se和Bi; M是选自Mo,W,Nb,Ta和V的一种或多种过渡金属; Z是选自OH-,F-,Cl-,Br-,I-,N3-,NO3-,ClO4-,NCS-,SCN-,PF6-,RSO3-,RSO4-的一种或多种阴离子, ,CF 3 SO 3 - ,BR 4 - ,BF 4 - ,OAc-,其中R = H,C 1 -C 20 - 烷基,C 5 -C 8 - 环烷基或芳基。 指标q,p,a,x,y,m,d,z和数字b和c在说明书中定义。 根据本发明的氧化催化剂在活化过氧化合物和氧中是特别有效的。
    • 7. 发明授权
    • Catalysts for olefin selective epoxidation with atmospheric oxygen
    • 用于烯烃选择性环氧化与大气氧的催化剂
    • US06248913B1
    • 2001-06-19
    • US09462451
    • 2000-01-07
    • Gerhard LobmaierWolfgang Anton HerrmannRolf Peter Schulz
    • Gerhard LobmaierWolfgang Anton HerrmannRolf Peter Schulz
    • C07F1100
    • C07D301/08B01J31/1616B01J31/2243B01J2231/72B01J2531/64C07D301/06
    • A catalyst for the selective oxidation of olefins in the presence of air or oxygen, comprising a compound of the formula (1) MoxOy(L)z  (1) where x is 1, 2 or 3, y is an integer from 0 to 2x+1, z is an integer from 1 to 2x, wherein the ligand L is a compound of the formula (2) or (3)  where n is 0 or 1, X is a nitrogen, oxygen or sulfur atom, Y is hydrogen, C1-C8-alkyl, C1-C8-alkoxy, F, Cl, Br, I, COOCH3, C6-C14-aryl or C3-C8-cycloalkyl, R3 and R4 form a ring containing from 4 to 8 carbon atoms onto which one or two aromatic rings may be fused, R1 and R2 are hydrogen, branched or straight-chain C1-C12-alkyl or branched or straight-chain C1-C12-haloalkyl which substitute the ring formed by R3 and R4 and/or the rings fused onto this ring, or the ligand L is a compound of the formula (4) or (5) where R is hydrogen, C1-C8-alkyl, C1-C8-alkoxy, COOCH3, carbonyl oxygen, C6-C14-aryl or C3-C8-cycloalkyl and n is 1 or 2 and m is from 1 to 6.
    • 在空气或氧气存在下选择性氧化烯烃的催化剂,其包含式(1)的化合物,其中x为1,2或3,y为0至2×+ 1的整数,z为1的整数 至2,其中配体L为式(2)或(3)的化合物,其中n为0或1,X为氮,氧或硫原子,Y为氢,C1-C8-烷基,C1-C8-烷基, 烷氧基,F,Cl,Br,I,COOCH 3,C 6 -C 14 - 芳基或C 3 -C 8 - 环烷基,R 3和R 4形成含有4至8个碳原子的环,一个或两个芳环可以被稠合,R1和 R2是取代由R3和R4形成的环和/或稠合到该环上的环的氢,支链或直链C 1 -C 12烷基或支链或直链C 1 -C 12 - 卤代烷基,或配体L是 式(4)或(5)的化合物,其中R是氢,C 1 -C 8 - 烷基,C 1 -C 8 - 烷氧基,COOCH 3,羰基氧,C 6 -C 14 - 芳基或C 3 -C 8 - 环烷基,n是1或2 m为1〜6。