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    • 1. 发明授权
    • Method for producing mono-aminofunctionalized dialkylphosphinic acids and esters and salts thereof by means of acrylnitriles and use thereof
    • 通过丙烯腈生产单氨基官能化二烷基次膦酸及其酯和盐的方法及其用途
    • US09035088B2
    • 2015-05-19
    • US13127072
    • 2009-10-06
    • Michael HillWerner KrauseMartin Sicken
    • Michael HillWerner KrauseMartin Sicken
    • C07F9/22C07F9/32C07F9/30C07F9/48C08K5/5313C09K21/12
    • C07F9/3211C07F9/301C07F9/3264C07F9/4816C07F9/4866C08K5/5313C09K21/12
    • The invention relates to a method for producing mono-aminofunctionalized dialkylphosphinic acids and esters and salts thereof by means of acrylnitriles, characterized in that a) a phosphinic acid source (I) is reacted with olefins (IV) to yield an alkylphosphonic acid, salt or ester (II) thereof in the presence of a catalyst A, b) the thus obtained alkylphosphonic acid, salt or ester (II) thereof is reacted with an acrylnitrile of formula (V) to yield a mono-functionalized dialkylphosphinic acid derivative (VI) in the presence of a catalyst B, and c) the thus obtained mono-functionalized dialkylphosphinic acid derivative (VI) is reacted to yield a mono-aminofunctionalized dialkylphosphinic acid derivative (III) in the presence of a catalyst C or a reduction agent, wherein R1, R2, R3, R4, R5, R6, R7 are the same or different and stand independently of each other, among other things, for H, C1-C18 alkyl, C6-C18 aryl, C6-C18 aralkyl, C6-C18 alkylaryl and X stands for H, C1-C18 alkyl, C6-C18 aryl, C6-C18 aralkyl, C6-C18 alkylaryl, Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Cu, Ni, Li, Na, K and/or a protonized nitrogen base, and Y stands for a mineral acid, a carboxylic acid, a Lewis acid or an organic acid, n=an integer or fractional number of 0 to 4 and the catalysts A and C are formed by transition metals, transition metal compounds and/or catalyst systems composed of a transition metal and/or a transition metal compound and at least one ligand, and catalyst B is formed by compounds forming peroxides, peroxo compounds, azo compounds, alkali metals, alkaline earth metals, alkali hydrides, alkaline earth hydrides and/or alkali alcoholates and alkaline earth alcoholates.
    • 本发明涉及一种通过丙烯腈生产单氨基官能化二烷基次膦酸及其酯及其盐的方法,其特征在于a)将次膦酸源(I)与烯烃(Ⅳ)反应,得到烷基膦酸盐或盐 酯(II),b)将由此得到的烷基膦酸,其盐或酯(II)与式(V)的丙烯腈反应,得到单官能化二烷基次膦酸衍生物(Ⅵ) 在催化剂B存在下,和c)将由此得到的单官能化二烷基次膦酸衍生物(Ⅵ)反应,得到单氨基官能化二烷基次膦酸衍生物(Ⅲ),其中催化剂C或还原剂存在下,其中 对于H,C 1 -C 18烷基,C 6 -C 18芳基,C 6 -C 18芳烷基,C 6 -C 18烷基,R 1,R 2,R 3,R 4,R 5,R 6,R 7相同或不同,彼此独立 烷基芳基,X代表H,C1-C18烷基,C6-C 18芳基,C 6 -C 18芳烷基,C 6 -C 18烷基芳基,Mg,Ca,Al,Sb,Sn,Ge,Ti,Fe,Zr,Zn,Ce,Bi,Sr,Mn,Cu,Ni,Li,Na,K 和/或质子化的氮碱,Y表示无机酸,羧酸,路易斯酸或有机酸,n = 0至4的整数或分数,催化剂A和C由过渡金属形成 由过渡金属和/或过渡金属化合物和至少一种配体组成的过渡金属化合物和/或催化剂体系和催化剂B通过形成过氧化物,过氧化合物,偶氮化合物,碱金属,碱土金属, 碱金属氢化物,碱土金属氢化物和/或碱金属醇盐和碱土金属盐。
    • 2. 发明申请
    • Method for Producing Dialkylphosphinic Acids and Esters and Salts Thereof by Means of Vinyl Compounds and Use Thereof
    • 通过乙烯基化合物生产二烷基次膦酸及其酯及其盐的方法及用途
    • US20110237720A1
    • 2011-09-29
    • US13125361
    • 2009-10-06
    • Michael HillWerner KrauseMartin Sicken
    • Michael HillWerner KrauseMartin Sicken
    • C08K5/5313C07F9/32C07F9/30C07F5/06C07F7/28
    • C07F9/301C07F9/302C07F9/306C07F9/3211C07F9/3217C07F9/3241C07F9/3264C07F9/4816C07F9/4866C08K5/5313C08L21/00C09K21/12
    • The invention relates to a method for producing mono-carboxyfunctionalized dialkylphosphinic acids and esters and salts thereof by means of vinyl compounds, characterized in that a) a phosphinic acid source (I) is reacted with olefins (IV) to yield an alkylphosphonic acid, salt or ester (II) thereof in the presence of a catalyst A, b) the thus obtained alkylphosphonic acid, salt or ester (II) thereof is reacted with acetylenic compounds of formula (V) to yield a mono-functionalized dialkylphosphinic acid derivative (VI) in the presence of a catalyst B, and c) the thus obtained mono-functionalized dialkylphosphinic acid derivative (VI) is reacted with carbon monoxide to yield a mono-carboxyfunctionalized dialkylphosphinic acid derivative (III) in the presence of a catalyst C, wherein R1, R2, R3, R4, R5, R6 are the same or different and stand independently of each other, among other things, for H, C1-C18 alkyl, C6-C18 aryl, C6-C18 aralkyl, C6-C18 alkylaryl, and X and Y are the same or different and stand independently of each other for H, C1-C18 alkyl, C6-C18 aryl, C8-C18 aralkyl, C6-C18 alkylaryl, Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Cu, Ni, Li, Na, K and/or a protonized nitrogen base, and the catalysts A, B, C and D are formed by transition metals and/or transition metal compounds and/or catalyst systems composed of a transition metal and/or a transition metal compound and at least one ligand.
    • 本发明涉及通过乙烯基化合物制备单羧基官能化的二烷基次膦酸及其酯和盐的方法,其特征在于a)将次膦酸源(I)与烯烃(IV)反应,得到烷基膦酸盐 或其酯(II),b)将如此得到的烷基膦酸,其盐或酯(II)与式(V)的炔属化合物反应,得到单官能化二烷基次膦酸衍生物(VI ),c)将如此得到的单官能化二烷基次膦酸衍生物(Ⅵ)与一氧化碳反应,得到单羧基官能化二烷基次膦酸衍生物(Ⅲ),其中催化剂C存在下,其中 对于H,C 1 -C 18烷基,C 6 -C 18芳基,C 6 -C 18芳烷基,C 6 -C 18烷基芳基,C 6 -C 18烷基,C 6 -C 18芳基, X和Y相同或相同 对于H,C 1 -C 18烷基,C 6 -C 18芳基,C 8 -C 18芳烷基,C 6 -C 18烷基芳基,Mg,Ca,Al,Sb,Sn,Ge,Ti,Fe,Zr,Zn, Ce,Bi,Sr,Mn,Cu,Ni,Li,Na,K和/或质子化的氮碱,催化剂A,B,C和D由过渡金属和/或过渡金属化合物和/或催化剂 由过渡金属和/或过渡金属化合物和至少一种配体组成的体系。
    • 7. 发明申请
    • Method for the Production of Mixed-Substituted Dialkylphosphinic Acids, Esters, and Salts, and Use Thereof
    • 混合取代的二烷基次膦酸,酯和盐的制备方法及其用途
    • US20110245386A1
    • 2011-10-06
    • US13140236
    • 2009-10-06
    • Michael HillWerner KrauseMartin Sicken
    • Michael HillWerner KrauseMartin Sicken
    • C08K5/5313C07F9/30C07F9/32C08L67/02C08L77/06
    • C09K21/12C07F9/301C07F9/306C07F9/3211C07F9/4816C07F9/4866C08K5/5313
    • The invention relates to a method for producing mixed-substituted dialkyiphosphinic acids, esters, and salts, characterized in that a) a phosphinic acid source (I) is reacted with olefins (IV) in the presence of a catalyst A to obtain an alkylphosphonous acid, the salt or ester (II) thereof, b) the obtained alkylphosphonous acid, the salt or ester (II) thereof is reacted with an olefin (IV) in the presence of a catalyst B to obtain the mixed-substituted dialkylphosphinic acid derivative (III), wherein R1, R2, R3, R4, R11, R12, R13, R14 are identical or different from each other and independently represent, inter alia, H, C1-C18-alkyl, C6-C18-aryl, C6-C18-aralkyl, C6-C18-alkylaryl, X represents H, C1-C18-alkyl, C8-C18-aryl, C6-C18-aralkyl, C8-C18-alkylaryl, Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Cu, Ni, Li, Na, K and/or a protonated nitrogenous base, catalyst A represents transition metals and/or transition metal compounds and/or catalyst systems composed of a transition metal and/or a transition metal compound and at least one ligand, and catalyst B represents compounds forming peroxides, and/or peroxo compounds, and/or azo compounds.
    • 本发明涉及一种制备混合取代二亚磷酸,酯和盐的方法,其特征在于a)在催化剂A存在下,使次膦酸源(I)与烯烃(Ⅳ)反应得到烷基亚磷酸 ,其盐或酯(II),b)在催化剂B存在下,将得到的烷基亚膦酸,其盐或酯(II)与烯烃(IV)反应,得到混合取代的二烷基次膦酸衍生物 III),其中R 1,R 2,R 3,R 4,R 11,R 12,R 13,R 14彼此相同或不同,并且独立地表示H,C 1 -C 18烷基,C 6 -C 18 - 芳基,C 6 -C 18 - 烷基,C 6 -C 18烷基芳基,X代表H,C 1 -C 18烷基,C 8 -C 18 - 芳基,C 6 -C 18 - 芳烷基,C 8 -C 18烷基芳基,Mg,Ca,Al,Sb,Sn,Ge,Ti ,Fe,Zr,Zn,Ce,Bi,Sr,Mn,Cu,Ni,Li,Na,K和/或质子化的含氮碱,催化剂A表示过渡金属和/或过渡金属化合物和/ 一个过境 n金属和/或过渡金属化合物和至少一种配体,催化剂B表示形成过氧化物的化合物,和/或过氧化合物和/或偶氮化合物。
    • 9. 发明申请
    • Method for Producing Dialkylphosphinic Acids and Esters and Salts Thereof by Means of Acrylnitriles and Use Thereof
    • 通过丙烯腈生产二烷基次膦酸及其酯及其盐的方法及用途
    • US20110213060A1
    • 2011-09-01
    • US13127069
    • 2009-10-06
    • Michael HillWerner KrauseMartin Sicken
    • Michael HillWerner KrauseMartin Sicken
    • C08K5/5313C07F9/32C07F9/30
    • C08K5/5313C07F9/301C07F9/3211C07F9/4816C07F9/4866C09K21/12
    • The invention relates to a method for producing mono-carboxyfunctionalized dialkylphosphinic acids and esters and salts thereof, characterized in that a) a phosphinic acid source (I) is reacted with olefins (IV) to yield an alkylphosphonic acid, salt or ester (H) thereof in the presence of a catalyst A, b) the thus obtained alkylphosphonic acid, salt or ester (II) thereof is reacted with compounds of formula (V) to yield mono-functionalized dialkylphosphinic acid derivatives (VI) in the presence of a catalyst B, and c) the thus obtained mono-functionalized dialkylphosphinic acid derivatives (VI) are reacted to yield a mono-carboxyfunctionalized diakylphosphinic acid derivative (III) in the presence of a catalyst C, wherein R1, R2, R3, R4, R5, R6, R7 are the same or different and stand independently of each other, among other things, for H, C1-C18 alkyl, C6-C18 aryl, C6-C18 aralkyl, C6-C18 alkylaryl and X and Y are the same or different and stand independently of each for H, C1-C18 alkyl, C6-C18 aryl, C6-C18 aralkyl, C6-C18 alkylaryl, Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Cu, Ni, Li, Na, K and/or a protonized nitrogen base, and the catalyst A is formed by transition metals and/or transition metal compounds and/or catalyst systems composed of a transition metal and/or a transition metal compound and at least one ligand, and catalyst B is formed by compounds forming peroxides and/or peroxo compounds and/or azo compounds and/or alkali metals and/or alkaline earth metals, alkali hydrides, alkaline earth hydrides and/or alkali alcoholates and alkaline earth alcoholates, and catalyst C is an acid or a base.
    • 本发明涉及一种用于制备单羧基官能化二烷基次膦酸及其酯和盐的方法,其特征在于:a)将次膦酸源(I)与烯烃(Ⅳ)反应,得到烷基膦酸,盐或酯(H) 在催化剂A存在下,将由此得到的烷基膦酸,其盐或酯(II)与式(Ⅴ)化合物反应得到单官能化二烷基次膦酸衍生物(Ⅵ),在催化剂存在下 B和c)由此得到的单官能化二烷基次膦酸衍生物(Ⅵ)在催化剂C存在下反应得到单羧基官能化二烷基次膦酸衍生物(Ⅲ),其中R1,R2,R3,R4,R5, 对于H,C 1 -C 18烷基,C 6 -C 18芳基,C 6 -C 18芳烷基,C 6 -C 18烷基芳基,X和Y相同或不同,R 6,R 7相同或不同,彼此独立地相互独立地表示 并独立于H,C1-C18烷基 1,C 6 -C 18芳基,C 6 -C 18芳烷基,C 6 -C 18烷基芳基,Mg,Ca,Al,Sb,Sn,Ge,Ti,Fe,Zr,Zn,Ce,Bi,Sr,Mn,Cu,Ni,Li ,Na,K和/或质子化的氮碱,并且催化剂A由过渡金属和/或过渡金属化合物和/或由过渡金属和/或过渡金属化合物和至少一种配体组成的催化剂体系形成, 催化剂B由形成过氧化物和/或过氧化合物和/或偶氮化合物和/或碱金属和/或碱土金属,碱金属氢化物,碱土金属氢化物和/或碱金属醇盐和碱土金属醇盐的化合物和催化剂C形成 是酸或碱。
    • 10. 发明申请
    • Method for Producing Mono-Carboxyfunctionalized Dialkylphosphinic Acids and Esters and Salts Thereof by means of Vinylenes-Nitriles and Use Thereof
    • 通过乙烯基腈制备单羧基官能化二烷基次膦酸及其酯及其盐的方法及用途
    • US20110213059A1
    • 2011-09-01
    • US13125363
    • 2009-10-06
    • Michael HillWerner KrauseMartin Sicken
    • Michael HillWerner KrauseMartin Sicken
    • C08K5/5313C07F9/30C07F9/32
    • C07F9/3217C07F9/301C07F9/302C07F9/306C07F9/3211C07F9/3241C07F9/3264C07F9/4816C07F9/4866C08K5/5313C09K21/12
    • The invention relates to a method for producing mono-carboxyfunctional zed dialkylphosphinic acids and esters and salts thereof by means of vinylenes/nitriles, characterized in that a) a phosphinic acid source (I) is reacted with olefins (IV) to yield an alkylphosphonic acid, salt or ester (II) thereof in the presence of a catalyst A, b) the thus obtained alkylphosphonic acid, salt or ester (II) thereof is reacted with acetylenic compounds of formula (V) to yield a mono-functionalized dialkylphosphinic acid derivative (VI) in the presence of a catalyst B, and c) the thus obtained mono-functionalized dialkylphosphinic acid derivative (VI) is reacted with a hydrogen cyanide source to yield a mono-functionalized dialkylphosphinic acid derivative (VII) in the presence of a catalyst C, and d) the thus obtained monofunctionalized dialkylphosphinic acid derivative (VII); is reacted to yield a monocarboxyfunctionalized dialkylphosphinic acid derivative (III) in the presence of a catalyst D, wherein R1, R2, R3, R4, R5, R6 are the same or different and stand independently of each other, among other things, for H, C1-C18 alkyl, C6-C18 aryl, C6-C18 aralkyl, C6-C18 alkylaryl, and X and Y are the same or different and stand independently of each other for H, C1-C18 alkyl, C6-C18 aryl, C6-C18 aralkyl, C6-C18 alkylaryl, Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Cu, Ni, Li, Na, K and/or a protonized nitrogen base, and the catalysts A, B and C are formed by transition metals and/or transition metal compounds and/or catalyst systems composed of a transition metal and/or a transition metal compound and at least one ligand, and the catalyst D is an acid or a base.
    • 本发明涉及通过乙烯/腈制备单羧基官能化的二烷基次膦酸及其酯和盐的方法,其特征在于a)将次膦酸源(I)与烯烃(Ⅳ)反应,得到烷基膦酸 ,其盐或酯(II),b)将如此得到的烷基膦酸,其盐或酯(II)与式(V)的炔属化合物反应,得到单官能化二烷基次膦酸衍生物 (Ⅵ)在催化剂B存在下反应,和c)将由此得到的单官能化二烷基次膦酸衍生物(Ⅵ)与氰化氢源反应,得到单官能化二烷基次膦酸衍生物(Ⅶ) 催化剂C,和d)由此获得的单官能二烷基次膦酸衍生物(VII); 在催化剂D的存在下反应得到单羧基官能化的二烷基次膦酸衍生物(III),其中R1,R2,R3,R4,R5,R6相同或不同,彼此独立地表示H ,C 1 -C 18烷基,C 6 -C 18芳基,C 6 -C 18芳烷基,C 6 -C 18烷基芳基,X和Y相同或不同,H,C 1 -C 18烷基,C 6 -C 18芳基,C 6 -C 18芳烷基,C 6 -C 18烷基芳基,Mg,Ca,Al,Sb,Sn,Ge,Ti,Fe,Zr,Zn,Ce,Bi,Sr,Mn,Cu,Ni,Li,Na,K和/ 质子化的氮碱,并且催化剂A,B和C由过渡金属和/或过渡金属化合物和/或由过渡金属和/或过渡金属化合物和至少一种配体组成的催化剂体系形成,催化剂D 是酸或碱。