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    • 7. 发明申请
    • PROCESS FOR PREPARING ACYLPHOSPHANES AND THEIR OXIDES AND SULPHIDES
    • 制备亚磷酸及其氧化物和硫化物的方法
    • WO2006074983A1
    • 2006-07-20
    • PCT/EP2006/050081
    • 2006-01-09
    • CIBA SPECIALTY CHEMICALS HOLDING INC.SOMMERLADE, Reinhard H.FRITZSCHE, KatharinaFISCHER, Walter
    • SOMMERLADE, Reinhard H.FRITZSCHE, KatharinaFISCHER, Walter
    • C07F9/50
    • C07F9/5068C07F9/5036C07F9/5337
    • A process for the preparation of bis-acylphosphanes of formula R 1 P(COR 2 ) 2 wherein R 1 is unsubstituted phenyl or phenyl substituted by one to five halogen, C 1 -C 8 -alkyl, C 1 -C 8 -alkylthio and/or C 1 -C 8 -alkoxy; R 2 is C 1 -C 18 -alkyl or C 2 -C 18 -alkenyl ; C 1 C 18 -alkyl or C 2 -C 18 -alkenyl substituted once or more than once by halogen -OR 10 , -OCO-R 10 , -OCO-Hal, -COO-R 10 , -N(R 11 )-CO-R 10 , -N(R 11 )-CO-Hal, -CO-NR 11 R 10 , -CH=CH-CO-OR 10 or -CH=CH-phenyl; -C(C 1 -C 4 alkyl)=C(C 1 -C 4 alkyl)-CO-OR 10 or -C(C 1 -C 4 alkyl)=C(C 1 -C 4 alkyl)-phenyl; C 5 -C 12 cycloalkyl, C 2 -C 18 alkenyl, phenyl-C 1 -C 4 alkyl, phenyl, naphthyl, biphenyl or a 5- or 6-membered -0-, S- or N-containing heterocyclic ring, the radicals phenyl, naphthyl, biphenyl or the 5- or 6-membered -0-, S- or N-containing heterocyclic ring being unsubstituted or substituted by one to five halogen, C 1 -C 8 alkyl, C 1 -C 8 alkoxy and/or C 1 -C 8 alkylthio; the process comprises the steps in a) selective reduction of dichlorophenylphosphanes of the formula R 1 P(CI) 2 by means of hydrogen at a temperature in the range from 20 to 200°C and under hydrogen pressure of atmospheric pressure to 20bar in the presence of a hydrogenation catalyst, a tert. aliphatic amine or an aromatic amine and in the presence of a non protic solvent which is unreactive under the hydrogenation conditions to obtain cyclic phenylphosphanes (R 1 P) n (n = 4 to 6); or b) selective reduction of R 1 P(CI) 2 by means of hydrogen at a temperature in the range from 80 to 25O°C and under hydrogen pressure of 25 to 250bar in the presence of a hydrogenation catalyst, a tert. aliphatic amine or an aromatic amine and in the presence of a non protic solvent which is unreactive under the hydrogenation conditions to obtain R 1 PH 2 ; c) subsequent reaction with an acid halide of formula in the presence of an apropriate base R 2 COHal wherein R 2 is as defined above.
    • 制备式R 1 P(COR 2 2)2的双酰基磷烷的方法,其中R 1,R 2, 被未取代的苯基或被1至5个卤素取代的苯基,C 1 -C 8 - 烷基,C 1 -C 8 - / - 烷硫基和/或C 1 -C 8 - 烷氧基; R 2是C 1 -C 18 - 烷基或C 2 -C 18亚烷基或C 2 -C 18 - 烯基; C 1 -C 18 - 烷基或被卤素取代一次或多于一次的C 1 -C 12 - C 18 - -OR 10,-OCO-R 10,-OCO-Hal,-COO-R 10,-N(R 11) CO-R 10,-N(R 11)-CO-Hal,-CO-NR 11, -CH = CH-CO-OR 10或-CH = CH-苯基; -C(C 1 -C 4 烷基)= C(C 1 -C 4 烷基)-CO 或-C(C 1 -C 4烷基)= C(C 1 -C 3 - 烷基) SUB> 4 烷基) - 苯基; C 5 -C 12亚烷基,C 2 -C 18链烯基,苯基-C 1 -C 12烷基, 苯基,萘基,联苯基或5-或6-元-O-,S-或N-杂环,基团苯基,萘基,联苯基或 5-或6-元-O-,S-或N-杂环是未取代的或被一至五个卤素取代,C 1 -C 8烷基,C C 1 -C 8烷氧基和/或C 1 -C 8烷硫基;或者C 1 -C 8烷氧基和/或C 1 -C 8烷硫基; 该方法包括以下步骤:a)通过氢在20至200℃的温度下选择性还原式R 1 P(Cl)2 H 2的二氯苯基膦 在氢气催化剂存在下,在大气压至20bar的氢气压力下, 脂肪族胺或芳族胺,并且在非氢化溶剂的存在下,在氢化条件下不反应以获得环状苯基膦(R 1 P)N n(n = 4) 至6); 或b)通过氢气在80至250℃的温度和25℃的氢气压力下通过氢气选择性还原R 1 P(Cl)2 H 2至 250bar在氢化催化剂存在下, 脂族胺或芳族胺,并且在非氢化溶剂的存在下,在氢化条件下不反应以获得R 1 H 2 H 2; c)随后在其中R 2 2如上定义的适当碱基R 2 CO 2的存在下与式的酰卤反应。