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    • 3. 发明授权
    • Method for the production of monofunctionalized dialkylphosphinic acids, esters and salts, and use thereof
    • 用于制备单官能二烷基次膦酸,酯和盐的方法及其用途
    • US09279085B2
    • 2016-03-08
    • US13140555
    • 2009-10-06
    • Michael HillHarald BauerWerner KrauseMartin Sicken
    • Michael HillHarald BauerWerner KrauseMartin Sicken
    • C07F9/02C07F9/22C07F9/28C08K5/53C09K21/12C07F9/30C07F9/32C08K5/5313
    • C09K21/12C07F9/301C07F9/3211C08K5/5313
    • The invention relates to a method for producing monofunctionalized dialkylphosphinic acids, esters, and salts, characterized in that 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 thereof, whereupon said alkylphosphonous acid, the salt or ester (II) thereof is reacted with compounds containing C═C, C═O, or C═N double bonds to obtain compounds of type (III), wherein R1, R2, R3, R4, R5, R6 are identical or different from each other and independently represent, inter alia, H, C1-C18-alkyl, C6-C18-aryl, C6-C18-aralkyl, X represents, inter alia, H, C1-C18-alkyl, C6-C18-aryl, and/or Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Cu, Ni, Li, Na, K, H, and wherein A represents OH, NH2, NHR, NR2, or O—CO—R8, and W represents a mineral acid, carboxylic acid, Lewis acid, or organic acid, wherein n is a whole or a fractional number from 0 to 4, and 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. The use of said dialkylphosphonic acids, esters, and salts is also disclosed.
    • 本发明涉及一种制备单官能化二烷基次膦酸,酯和盐的方法,其特征在于,在催化剂A存在下,次膦酸源(I)与烯烃(Ⅳ)反应得到烷基亚磷酸,其盐或 酯,因此所述烷基亚膦酸,其盐或酯(II)与含有C = C,C = O或C = N双键的化合物反应,得到式(III)化合物,其中R1,R2,R3 ,R 4,R 5,R 6彼此相同或不同,并且独立地代表H,C 1 -C 18 - 烷基,C 6 -C 18 - 芳基,C 6 -C 18 - 芳烷基,X尤其表示H, C18烷基,C6-C18-芳基和/或Mg,Ca,Al,Sb,Sn,Ge,Ti,Fe,Zr,Zn,Ce,Bi,Sr,Mn,Cu,Ni,Li,Na,K ,H,其中A表示OH,NH2,NHR,NR2或O-CO-R8,W表示无机酸,羧酸,路易斯酸或有机酸,其中n为0或分数 至4,催化剂A代表转化我 tals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。 还公开了所述二烷基膦酸,酯和盐的用途。
    • 5. 发明授权
    • Process for preparing mono-allyl-functionalized dialkylphosphinic acids, salts and esters thereof with allylic compounds, and the use thereof
    • 用烯丙基化合物制备单烯丙基官能化二烷基次膦酸,其盐和酯的方法及其用途
    • US08772519B2
    • 2014-07-08
    • US13127110
    • 2009-10-06
    • Michael HillWerner KrauseMartin Sicken
    • Michael HillWerner KrauseMartin Sicken
    • C07F9/30C07F9/32C07F5/06
    • C09K21/12C07F9/302C07F9/3217C08K5/5313
    • The invention relates to a process for preparing mono-allyl-functionalized dialkylphosphinic acids, esters and salts with allylic compounds, characterized in that a) a phosphinic acid source (I) is reacted with olefins (IV) in the presence of a catalyst A to give an alkylphosphonous acid, or salt or ester thereof (II), b) the alkylphosphonous acid, or salt or ester thereof (II) thus formed is reacted with allylic compounds of the formula (V) in the presence of a catalyst B and of a base to give a mono-allyl-functionalized dialkylphosphinic acid derivative (III), where R1, R2, R3, R4, R5, R6, R7, R8, R9 are the same or different and are each independently, inter alia, H, C1-C18-alkyl, C6-C18-aryl, C6-C18-aralkyl, C6-C18-alkylaryl, and X is 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 protonated nitrogen base, and the catalysts A and B are transition metals and/or transition metal compounds and/or catalyst systems which are composed of a transition metal and/or a transition metal compound and at least one ligand.
    • 本发明涉及用烯丙基化合物制备单烯丙基官能化二烷基次膦酸,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, 得到烷基亚磷酸或其盐或酯(II),b)将如此形成的烷基亚膦酸或其盐或酯(II)与式(Ⅴ)的烯丙基化合物在催化剂B的存在下反应,和 得到单烯丙基官能化的二烷基次膦酸衍生物(III)的碱,其中R 1,R 2,R 3,R 4,R 5,R 6,R 7,R 8,R 9相同或不同,并且各自独立地为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是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/或质子化氮碱, 催化剂A和B是过渡金属和/或过渡金属 nds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。
    • 6. 发明授权
    • Method for producing mono-carboxy-functionalized dialkylphosphinic acids, esters and salts using a vinyl ester of a carboxylic acid and the use thereof
    • 使用羧酸的乙烯基酯制备单羧基官能化的二烷基次膦酸,酯和盐的方法及其用途
    • US08735476B2
    • 2014-05-27
    • US13132153
    • 2009-10-06
    • Michael HillMathias DietzWerner KrauseMartin Sicken
    • Michael HillMathias DietzWerner KrauseMartin Sicken
    • C08K5/5313
    • C09K21/12C07F9/301C07F9/4816C07F9/4866C08K5/5313
    • The invention relates to a method for producing mono-carboxy-functionalized dialkylphosphinic acids, esters and salts using a vinyl ester of a carboxylic acid. The method is characterized by the following steps: a) reacting a phosphinic acid source (I) with olefins (IV) in the presence of a catalyst A to give an alkylphosphinic acid, the salt or the ester (II) thereof, b) reacting the alkylphosphinic acid so obtained, the salt or the ester (II) thereof with a vinyl ester of a carboxylic acid of formula (V) in the presence of a catalyst B to give a mono-functionalized dialkylphosphinic acid derivative (VI) and c) reacting the mono-functionalized dialkylphosphinic acid derivative (VI) so obtained in the presence of a catalyst C to give a mono-functionalized dialkylphosphinic acid derivative (VII) and d) reacting the mono-functionalized dialkylphosphinic acid derivative (VII); with an oxidant or in the presence of a catalyst D to give a mono-carboxy-functionalized dialkylphosphinic acid derivative (III).
    • 本发明涉及使用羧酸的乙烯基酯制备单羧基官能化的二烷基次膦酸,酯和盐的方法。 该方法的特征在于以下步骤:a)在催化剂A存在下使次膦酸源(I)与烯烃(IV)反应,得到烷基次膦酸,其盐或其酯(II),b)使 如此获得的烷基次膦酸,其盐或其酯(II)与式(V)的羧酸的乙烯基酯在催化剂B的存在下反应,得到单官能化的二烷基次膦酸衍生物(Ⅵ)和c) 使在催化剂C存在下得到的单官能化二烷基次膦酸衍生物(Ⅵ)反应,得到单官能化二烷基次膦酸衍生物(Ⅶ),和d)使单官能化二烷基次膦酸衍生物(Ⅶ)反应; 与氧化剂或在催化剂D存在下反应,得到单羧基官能化的二烷基次膦酸衍生物(III)。
    • 9. 发明申请
    • 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膦酸及其酯及其盐的方法及用途
    • US20110213078A1
    • 2011-09-01
    • US13127072
    • 2009-10-06
    • Michael HillWerner KrauseMartin Sicken
    • Michael HillWerner KrauseMartin Sicken
    • C08L67/02C07F9/30C07F9/32C07F5/06C07F7/28C08G63/183C08L77/06C08G69/26
    • 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。
    • 10. 发明申请
    • Method for Producing Mono-Aminofunctionalized Dialkylphosphinic Acids and Esters and Salts Thereof and Use Thereof
    • 单氨基官能化二烷基膦酸及其酯及其盐的制备方法及用途
    • US20110213061A1
    • 2011-09-01
    • US13125359
    • 2009-10-06
    • Michael HillWerner KrauseMartin Sicken
    • Michael HillWerner KrauseMartin Sicken
    • C08K5/5313C07F9/30C08L67/02C08L77/06
    • C09K21/12C07F9/301C07F9/3211C08K5/5313
    • The invention relates to a method for producing mono-aminofunctionalized 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 (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 mono-functionalized dialkylphosphinic acid derivative (VII); is reacted to yield a mono-aminofunctionalized dialkylphosphinic acid derivative (III) in the presence of a catalyst D or a reduction agent, 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 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=0 to 4 and the catalysts A, B, C and D 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.
    • 本发明涉及一种用于制备单氨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(Ⅱ) 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)的炔属化合物反应,得到单官能化二烷基次膦酸衍生物(Ⅵ) 催化剂B和c)由此获得的单官能化二烷基次膦酸衍生物(VI)与氰化氢源反应,在催化剂C存在下得到单官能化二烷基次膦酸衍生物(Ⅶ),和d) 得到单官能化二烷基次膦酸衍生物(VII); 在催化剂D或还原剂的存在下反应得到单氨基官能化二烷基次膦酸衍生物(III),其中R1,R2,R3,R4,R5,R6相同或不同并且彼此独立, 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代表H,C 1 -C 18烷基,C 6 -C 18芳基,C 6 -C 18芳烷基, C18烷基芳基,Mg,Ca,Al,Sb,Sn,Ge,Ti,Fe,Zr,Zn,Ce,Bi,Sr,Mn,Cu,Ni,Li,Na,K和/或质子化氮碱,Y 代表无机酸,羧酸,路易斯酸或有机酸,n = 0〜4,催化剂A,B,C和D由过渡金属,过渡金属化合物和/或催化剂体系 过渡金属和/或过渡金属化合物和至少一种配体。