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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
(2,4-二氯苄基)三苯基氯化膦 <(2,4-dichlorophenyl)-methyl>triphenylphosphonium chloride 2492-23-1 C25H20Cl2P*Cl
(2,4-二氯苄基)三苯基氯化膦
(1R,2R)-(+)-1,2-二氨基环己烷-N,N′-双(2-苯基膦-1-萘酰基) (1R,2R)-(+)-1,2-diaminocyclohexane-N,N’-bis(2-diphenylphosphino-1-naphthoyl) 174810-09-4 C52H44N2O2P2
(1R,2R)-(+)-1,2-二氨基环己烷-N,N′-双(2-苯基膦-1-萘酰基)
(1-氨基戊基)磷酸 1-amino-pentylphosphonic acid 13138-37-9 C5H14NO3P
(1-氨基戊基)磷酸
(1-十六烷基)三苯基溴化磷鎓 (1-hexadecyl)triphenylphosphonium bromide 14866-43-4 Br*C34H48P
(1-十六烷基)三苯基溴化磷鎓
((2,4,6-三异丙基)苯基)二-环己基膦 X-phos 303111-96-8 C27H45P
((2,4,6-三异丙基)苯基)二-环己基膦
—— 121268-17-5 C4H15NNaO8P2
—— Bis(3,5,3',5'-dimethoxydibenzylideneacetone) palladium(0) 811862-77-8 C42H44O10Pd
Bis(3,5,3',5'-dimethoxydibenzylideneacetone) palladium(0)
—— Potassium hydrogen (1-hydroxy-1-phosphonoethyl)phosphonate 13502-12-0 C2H7KO7P2
Potassium hydrogen (1-hydroxy-1-phosphonoethyl)phosphonate
—— Decasodium diethylenetriaminepentamethylenephosphonate 93841-76-0 C9H18N3Na10O15P5
Decasodium diethylenetriaminepentamethylenephosphonate
—— Propanenitrile, 3,3'-phosphinylidenebis- 5964-09-0 C6H8N2OP+
Propanenitrile, 3,3'-phosphinylidenebis-
—— Disodium 2-naphthyl phosphate 31681-98-8 C10H8Na2O4P+
Disodium 2-naphthyl phosphate
—— Dihexylenetriaminepentakismethylenephosphonic acid, sodium salt 35657-77-3 C17H44N3NaO15P5+
Dihexylenetriaminepentakismethylenephosphonic acid, sodium salt
—— Dioctylisopentylphosphine oxide 53521-41-8 C21H45OP
Dioctylisopentylphosphine oxide
—— Fructose 1-(barium phosphate) 53823-70-4 C6H11BaO9P
Fructose 1-(barium phosphate)
—— Bromotris(triphenylphosphine)rhodium 14973-89-8 C54H45BrP3Rh-
Bromotris(triphenylphosphine)rhodium
—— Tetrabutylphosphonium 3115-68-2 C16H36P+
Tetrabutylphosphonium
—— trimesitylphosphoniumyl 23897-15-6 C27H33P
trimesitylphosphoniumyl
—— 3-(4-methoxyphenyl)-1H-isochromene-1-thione 92964-70-0 C16H12O2S
3-(4-methoxyphenyl)-1H-isochromene-1-thione
—— PPh<sub>3</sub>AuNTf<sub>2</sub> 866395-16-6 C20H16AuF6NO4PS2
PPh<sub>3</sub>AuNTf<sub>2</sub>
—— 9-phenyl-9,10-dihydro-9-phosphaanthracene 59273-35-7 C19H15P
9-phenyl-9,10-dihydro-9-phosphaanthracene
—— 2-chlorobenzyl-TPP 18583-55-6 C25H21ClP
2-chlorobenzyl-TPP
—— Triphenyl(3-((triphenylphosphoranyl)methyl)benzyl)phosphorane 10273-74-2 C44H38P2+2
Triphenyl(3-((triphenylphosphoranyl)methyl)benzyl)phosphorane
—— Dimethyl(trifluormethyl)phosphinoxid 26348-91-4 C3H6F3OP
Dimethyl(trifluormethyl)phosphinoxid
—— Pentafluorphenyl-dimethyl-phosphinoxid 5525-96-2 C8H6F5OP
Pentafluorphenyl-dimethyl-phosphinoxid
—— D-3-Bromocamphor-10-sulfonic acid monohydrate 206860-46-0 C10H17BrO5S
D-3-Bromocamphor-10-sulfonic acid monohydrate
—— 1-diethylphosphino-3-diphenylphosphinopropane 82195-32-2 C19H26P2
1-diethylphosphino-3-diphenylphosphinopropane
—— 2-(dimethylphosphinoyl)ethanamine 933745-16-5 C4H12NOP
2-(dimethylphosphinoyl)ethanamine
—— di(1-adamantyl)-tert-butylphosphine 321921-71-5 C24H39P
di(1-adamantyl)-tert-butylphosphine
—— AdBippyPhos 1239478-87-5 C44H47N4P
AdBippyPhos
—— Ethylenebis(triphenylphosphonium) dibromide 1519-45-5 C38H34I2P2
Ethylenebis(triphenylphosphonium) dibromide
—— Bis(triphenylphosphine)copper tetrahydroborate 16903-61-0 C36H34BCuP2-
Bis(triphenylphosphine)copper tetrahydroborate
—— di-t-butyl(isobutyl)phosphine 87522-71-2 C12H27P
di-t-butyl(isobutyl)phosphine
—— α,α'-bis(diethylphosphino)xylene 695150-63-1 C16H28P2
α,α'-bis(diethylphosphino)xylene
—— Bis(2-ethylhexyl) phosphite 3658-48-8 C16H34O3P+
Bis(2-ethylhexyl) phosphite
—— dimethyl(oxo)phosphonium 7211-39-4 C2H6OP
dimethyl(oxo)phosphonium
—— Ethyl phenylphosphinate 2511-09-3 C8H10O2P+
Ethyl phenylphosphinate
—— Ethenephosphonic acid 1746-03-8 C2H4O3P+
Ethenephosphonic acid
—— 1,3,2-Dioxaphosphorinane, 5,5-dimethyl-, 2-oxide 4090-60-2 C5H10O3P+
1,3,2-Dioxaphosphorinane, 5,5-dimethyl-, 2-oxide
—— 1-Hydroxyethanediphosphonic acid, sodium salt 3794-83-0 C2H8NaO7P2
1-Hydroxyethanediphosphonic acid, sodium salt
—— Oxo(diphenyl)[2-(triethylsilyl)ethyl]-lambda~5~-phosphane 922737-68-6 C20H29OPSi
Oxo(diphenyl)[2-(triethylsilyl)ethyl]-lambda~5~-phosphane
—— 3-fluorophenyl-diphenylphosphine 21388-29-4 C18H14FP
3-fluorophenyl-diphenylphosphine
—— isopropylbis(o-methylphenyl)phosphane 625856-26-0 C17H21P
isopropylbis(o-methylphenyl)phosphane
—— <sup>n</sup>Bu<sup>i</sup>Pr<sub>2</sub>P 63059-00-7 C10H23P
<sup>n</sup>Bu<sup>i</sup>Pr<sub>2</sub>P
—— bis(2-hydroxyphenyl)phenylphosphine oxide 112122-94-8 C18H15O3P
bis(2-hydroxyphenyl)phenylphosphine oxide
—— Hexyl-dioxido-oxo-lambda5-phosphane 4721-24-8 C6H13O3P-2
Hexyl-dioxido-oxo-lambda5-phosphane
—— {3-[(Di-tert-butylphosphanyl)methyl]phenyl}methanol 646069-76-3 C16H27OP
{3-[(Di-tert-butylphosphanyl)methyl]phenyl}methanol
—— Risedronic acid sodium 115436-72-1 C7H11NNaO7P2+
Risedronic acid sodium
—— (2,2-Dimethylpropane-1,3-diyl)bis(dimethylphosphane) 89129-51-1 C9H22P2
(2,2-Dimethylpropane-1,3-diyl)bis(dimethylphosphane)
—— Phosphonic acid, propyl- 4672-38-2 C3H8O3P+
Phosphonic acid, propyl-
—— 1,3-bis(di-n-butylphosphino)-propane 131285-34-2 C19H42P2
1,3-bis(di-n-butylphosphino)-propane