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有机膦化合物

不对称膦化合物的研究及其应用极大地丰富了有机磷化学领域。含磷的抗氧剂、稳定剂,以及作为稀有元素的萃取剂和络合剂,在化工行业中得到广泛应用。生物体内的有机膦化合物不仅是重要的能源来源,也是合成DNA和RNA主链的重要组成部分。

在各个领域中,有机膦化合物的应用非常广泛。它们被用于核酸、辅酶、有机磷神经毒气、杀虫剂、杀菌剂、除草剂、化学治疗剂、增塑剂、抗氧化剂、表面活性剂、络合剂、萃取剂、浮选剂和阻燃剂等。

从化学结构上看,有机膦化合物大致可以分为以下几类:

  1. 膦酸酯:磷酸是一种三元酸,在有机基团替换其三个氢原子后形成。敌敌畏就是一个典型的混酯例子。
  2. 硫代、二硫代和三硫代膦酸酯:当磷酸分子中的氧原子被硫原子置换时,就形成了硫代膦酸酯,如对硫磷、乐果、稻瘟净等。
  3. 磷酰胺和硫代磷酰胺:如果将磷酸分子中的羟基替换为氨基,则形成磷酰胺;而剩余的氧原子被硫原子替换则形成硫代磷酰胺,甲胺磷和育畜磷就属于这一类结构。
  4. 焦膦酸酯、硫代焦膦酸酯和焦磷酰胺:通过脱去两个磷酸分子中的水形成焦磷酸,随后有机基、硫原子或氨基取代其氢、氧或羟基,治螟磷即为此类型化合物的实例。
  5. 膦酸酯和硫代膦酸酯:如果将磷酸分子中的一分子羟基替换为有机基团,则生成P-C键称为膦酸。部分已有的膦酸及其硫代替物作为农药推广使用,如苯硫磷。
  6. 亚磷酸衍生物:一些农药是亚磷酸的衍生物,在这些化合物中,磷原子处于三价状态,脱叶亚磷即为一例。
  7. :当磷化氢分子中的氢被有机基团置换时,则称为膦。这类化合物与氮的化合物氨、胺和铵盐结构相似。
  8. 磷酸或膦酸分子中羟基被卤素置换:在这一类化合物中,磷酸或膦酸分子中的羟基被卤素替换。
中文名称 英文名称 CAS号 化学式 结构式图片
—— 4-bromophenyl diphenylphosphane sulfide 1474-09-5 C18H14BrPS
4-bromophenyl diphenylphosphane sulfide
—— (2-trifluoromethylphenyl)diphenylphosphine 25688-44-2 C19H14F3P
(2-trifluoromethylphenyl)diphenylphosphine
—— Phosphine, tri-7-octenyl- 816420-00-5 C24H45P
Phosphine, tri-7-octenyl-
—— 2,2'-bis(diphenylphosphino)propane 57585-26-9 C27H26P2
2,2'-bis(diphenylphosphino)propane
—— (2-cyclohexylphenyl)dicyclohexylphosphine 625856-27-1 C24H37P
(2-cyclohexylphenyl)dicyclohexylphosphine
—— 1-(diphenylphosphanyl)-2-isopropylbenzene 60998-16-5 C21H21P
1-(diphenylphosphanyl)-2-isopropylbenzene
—— (4-fluorophenyl)diphenylphosphine 18437-72-4 C18H14FP
(4-fluorophenyl)diphenylphosphine
—— m-Tolyl-diphenylphosphin 7579-70-6 C19H17P
m-Tolyl-diphenylphosphin
—— α,α'-bis(diphenylphosphino)-p-xylene 71403-19-5 C32H28P2
α,α'-bis(diphenylphosphino)-p-xylene
—— diphenyl (4‐aminophenyl) phosphine 33834-35-4 C18H16NP
diphenyl (4‐aminophenyl) phosphine
—— ethyl 4-(diphenylphosphino)benzoate 223510-97-2 C21H19O2P
ethyl 4-(diphenylphosphino)benzoate
—— 1,3-bis(diphenylphosphanyl)benzene 1179-05-1 C30H24P2
1,3-bis(diphenylphosphanyl)benzene
—— Phenyl-dioctylphosphin 14086-46-5 C22H39P
Phenyl-dioctylphosphin
—— bis(4-methylphenyl)phenylphosphine sulfide 16822-31-4 C20H19PS
bis(4-methylphenyl)phenylphosphine sulfide
—— ethyldimethylphospine sulfide 4319-08-8 C4H11PS
ethyldimethylphospine sulfide
—— di(t-butyl)(o-methoxyphenyl)phosphine 53098-11-6 C15H25OP
di(t-butyl)(o-methoxyphenyl)phosphine
—— 1,2-Ethanediylbis<di-o-methoxyphenylphosphine> 85599-21-9 C30H32O4P2
1,2-Ethanediylbis<di-o-methoxyphenylphosphine>
—— o-bromo-benzyl-di(tert-butyl)phosphine 73424-08-5 C15H24BrP
o-bromo-benzyl-di(tert-butyl)phosphine
—— (3-aminopropyl)dimethylphosphine 29518-98-7 C5H14NP
(3-aminopropyl)dimethylphosphine
—— (4-chloroquinolin-8-yl)-4-methylbenzenesulfonate 1022094-18-3 C16H12ClNO3S
(4-chloroquinolin-8-yl)-4-methylbenzenesulfonate
—— tris(2-diphenylphosphinophenyl)phosphine 53218-00-1 C54H42P4
tris(2-diphenylphosphinophenyl)phosphine
—— N-[2-(Diphenylphosphino)benzylidene]hydroxylamine 153358-05-5 C19H16NOP
N-[2-(Diphenylphosphino)benzylidene]hydroxylamine
—— Sodium phenylphosphinate 4297-95-4 C6H5NaO2P+
Sodium phenylphosphinate
—— 22560-50-5 CH4Cl2NaO6P2
—— Hexapotassium dihydrogen [hexane-1,6-diylbis[nitrilobis(methylene)]]tetrakisphosphonate 53473-28-2 C7H12K6N2O12P4
Hexapotassium dihydrogen [hexane-1,6-diylbis[nitrilobis(methylene)]]tetrakisphosphonate
—— Naphthalen-1-yl phosphate 81012-89-7 C10H7O4P-2
Naphthalen-1-yl phosphate
—— Sodium 3,3',3''-phosphinetriyltribenzenesulfonate 63995-70-0 C18H12Na3O9PS3
Sodium 3,3',3''-phosphinetriyltribenzenesulfonate
—— dichloro(4-ethoxyphenyl)phosphine 53534-62-6 C8H9Cl2OP
dichloro(4-ethoxyphenyl)phosphine
—— (p-tolyl)2P(CH2)3P(p-tolyl)2 115583-11-4 C31H34P2
(p-tolyl)2P(CH2)3P(p-tolyl)2
—— diethyl(diphenylphosphinomethyl)amine 2071-27-4 C17H22NP
diethyl(diphenylphosphinomethyl)amine
—— 4-chlorophenyldichlorophosphine 1005-33-0 C6H4Cl3P
4-chlorophenyldichlorophosphine
—— (1-methoxy-1-oxopropan-2-yl)triphenylphosphonium bromide 2689-62-5 Br*C22H22O2P
(1-methoxy-1-oxopropan-2-yl)triphenylphosphonium bromide
—— [Ph2Si(CH2PPh2)] 577785-19-4 C38H34P2Si
[Ph2Si(CH2PPh2)]
—— dimethyl(pentafluorophenyl)phosphine 5075-61-6 C8H6F5P
dimethyl(pentafluorophenyl)phosphine
—— ethylenebis(triphenylphosphonium) dibromide 1519-45-5 2Br*C38H34P2
ethylenebis(triphenylphosphonium) dibromide
—— (2-methylbenzyl)diphenylphosphine oxide 158871-10-4 C20H19OP
(2-methylbenzyl)diphenylphosphine oxide
—— dimethyl(p-tolyl)phosphine sulfide 54844-87-0 C9H13PS
dimethyl(p-tolyl)phosphine sulfide
—— dichloropropylphosphine 15573-31-6 C3H7Cl2P
dichloropropylphosphine
—— (7-carboxyheptyl)triphenylphosphonium bromide 52956-93-1 Br*C26H30O2P
(7-carboxyheptyl)triphenylphosphonium bromide
—— Bis(trimethylsilyl) phosphite 3663-52-3 C6H18O3PSi2-
Bis(trimethylsilyl) phosphite
—— phenethyldiphenylphosphine oxide 3582-84-1 C20H19OP
phenethyldiphenylphosphine oxide
—— Pd(dippf)Cl<sub>2</sub> 215788-65-1 C22H36Cl2FeP2Pd
Pd(dippf)Cl<sub>2</sub>
—— (N,N-diethylamino)methyldibutylphosphine oxide 25409-81-8 C13H30NOP
(N,N-diethylamino)methyldibutylphosphine oxide
—— [p-phenylenebis(methylene)]bis[triphenylphosphonium] dichloride 1519-47-7 C44H38P2*2Cl
[p-phenylenebis(methylene)]bis[triphenylphosphonium] dichloride
—— 1,5-bis(diisopropylphosphino)pentane 188642-92-4 C17H38P2
1,5-bis(diisopropylphosphino)pentane
—— Bis[(4-methoxyphenyl)methyl](phenyl)phosphane 88104-25-0 C22H23O2P
Bis[(4-methoxyphenyl)methyl](phenyl)phosphane
—— bis(3,5-dimethylphenyl)phosphine oxide 187344-92-9 C16H19OP
bis(3,5-dimethylphenyl)phosphine oxide
—— dicyclohexylmethylphosphine 50420-46-7 C13H25P
dicyclohexylmethylphosphine
—— (di-tert-butylphosphino)(dicyclohexylphosphino)methane 185537-55-7 C21H42P2
(di-tert-butylphosphino)(dicyclohexylphosphino)methane
—— n-butylthiophosphoryl dichloride 6588-22-3 C4H9Cl2PS
n-butylthiophosphoryl dichloride