在常温常压下稳定,避免氧化物接触。
二苯基磷酸是重要的医药、农药中间体。目前,常见的制备方法为:先用苯和三氯化磷(溶剂为苯),以三氯化铝为催化剂生成苯基二氯化磷;再利用三氯化铝作为催化剂进行歧化反应生成二苯基氯化磷;接着,在低温条件下通入氧气将二苯基氯化磷氧化成二苯基磷酰氯,最后水解得到二苯基磷酸。然而,现有的合成工艺存在污染大、对设备性能要求高以及总收率低(仅30%)和成本高的问题。
制备一种新型的二苯基磷酸制备方法具体包括以下步骤:
将208克甲苯与184克三氯氧磷(量为1.2摩尔)投入1000毫升四口瓶中,用冰水降温至15℃。在15~25℃之间滴加208克甲苯和219克二乙胺(量为3摩尔)的混合液,并保温反应3小时。
反应后,抽滤回收产物二乙胺盐酸盐,可将其处理成二乙胺重复使用。然后,常压蒸馏回收溶剂甲苯,继续减压蒸馏得到132~136℃、-0.096MPa下的馏分二氯磷酰二乙胺(质量为205克,量为1.08摩尔),反应收率为90%。
在干燥的1000毫升反应瓶中加入27克镁条,搅拌加热至50℃后停止加热,并利用余热升温至60~70℃。随后,滴加步骤3制得的引发料,观察反应现象,如温度迅速上升并产生白色烟雾,则说明反应已引发。
在100~110℃之间(最高不超过120℃,最低不低于90℃)缓慢滴加步骤4中的混合液,并在90~110℃下保温反应2小时。完成反应后,将温度降至55℃。
将205克二氯磷酰二乙胺与65克甲苯混合制成混合液,在步骤6反应完成后温度降至55℃时滴加该混合液,控制滴加温度为55~65℃。保温反应3小时后收取产物。
在2000毫升四口瓶中加入100克盐酸和230克水(量为12.8摩尔),搅拌并控制四口瓶内温度在30~40℃之间。向四口瓶中滴加步骤7中的反应产物,滴完后升温至70~80℃回流反应4小时。
冷却过滤,烘干固体物得到产品二苯基磷酸178克(量为0.92摩尔)。步骤5~8的格氏反应和水解反应收率为85%,以三氯氧磷计的总收率则为76.6%。
中文名称 | 英文名称 | CAS号 | 化学式 | 分子量 |
---|---|---|---|---|
[甲氧基(苯基)磷酰基]苯 | methyl diphenylphosphinate | 1706-90-7 | C13H13O2P | 232.219 |
二苯基磷酸乙酯 | ethyl diphenylphosphinate | 1733-55-7 | C14H15O2P | 246.246 |
二苯基膦酸丙酯 | diphenylphosphonic acid propyl ester | 10122-97-1 | C15H17O2P | 260.273 |
—— | isopropyl diphenylphosphinate | 1706-91-8 | C15H17O2P | 260.273 |
—— | (Diphenylphosphinyloxy)trimethylsilan | 18789-78-1 | C15H19O2PSi | 290.374 |
—— | butyl diphenylphosphinate | 20610-34-8 | C16H19O2P | 274.299 |
—— | dioxybis(diphenylphosphine oxide) | 4250-08-2 | C24H20O4P2 | 434.368 |
—— | Diphenylphosphine oxide | 4559-70-0 | C12H11OP | 202.193 |
—— | hexyl diphenylphosphinate | 19259-66-6 | C18H23O2P | 302.353 |
—— | diphenylphosphine oxide | 24630-80-6 | C12H11OP | 202.193 |
二苯基次磷酸苯基酯 | phenyl diphenylphosphinate | 1706-96-3 | C18H15O2P | 294.29 |
[环戊基甲氧基(苯基)磷酰基]苯 | (cyclopentylmethoxy)diphenylphosphine oxide | 91237-89-7 | C18H21O2P | 300.337 |
—— | Diphenylphosphoryl methyl carbonate | 170303-71-6 | C14H13O4P | 276.229 |
二苯基次磷酸苄酯 | benzyl diphenylphosphinate | 5573-42-2 | C19H17O2P | 308.317 |
三苯基氧化膦 | Triphenylphosphine oxide | 791-28-6 | C18H15OP | 278.29 |
—— | 4-chlorophenyl diphenylphosphinate | 21713-55-3 | C18H14ClO2P | 328.735 |
—— | p-tolyl diphenylphosphinate | 21713-53-1 | C19H17O2P | 308.317 |
中文名称 | 英文名称 | CAS号 | 化学式 | 分子量 |
---|---|---|---|---|
[甲氧基(苯基)磷酰基]苯 | methyl diphenylphosphinate | 1706-90-7 | C13H13O2P | 232.219 |
—— | phenyl-p-tolyl-phosphinic acid | 13118-96-2 | C13H13O2P | 232.219 |
二苯基磷酸乙酯 | ethyl diphenylphosphinate | 1733-55-7 | C14H15O2P | 246.246 |
—— | bis(3-aminophenyl)phosphinic acid | 25806-71-7 | C12H13N2O2P | 248.221 |
—— | C12H10F2O2P2 | 85450-58-4 | C12H10F2O2P2 | 286.155 |
二苯基膦酸丙酯 | diphenylphosphonic acid propyl ester | 10122-97-1 | C15H17O2P | 260.273 |
[2-氯乙氧基(苯基)磷酰基]苯 | 2-chloroethyl diphenylphosphinate | 92982-05-3 | C14H14ClO2P | 280.691 |
—— | isopropyl diphenylphosphinate | 1706-91-8 | C15H17O2P | 260.273 |
—— | allyl diphenylphosphinate | 1706-95-2 | C15H15O2P | 258.257 |
—— | (Diphenylphosphinyloxy)trimethylsilan | 18789-78-1 | C15H19O2PSi | 290.374 |
—— | ethylene bis(diphenylphosphinate) | —— | C26H24O4P2 | 462.422 |
—— | butyl diphenylphosphinate | 20610-34-8 | C16H19O2P | 274.299 |
—— | isobutyl diphenylphosphinate | 10122-98-2 | C16H19O2P | 274.299 |
—— | Diphenylphosphinsaeure-tert.-butylester | 1706-92-9 | C16H19O2P | 274.299 |
—— | 1,3-propyl bis(diphenylphosphinate) | —— | C27H26O4P2 | 476.449 |
—— | isopentyl diphenylphosphinate | 41044-86-4 | C17H21O2P | 288.326 |
—— | 2,2,2-trifluoroethyl diphenylphosphinate | —— | C14H12F3O2P | 300.217 |
—— | Diphenylphosphine oxide | 4559-70-0 | C12H11OP | 202.193 |
—— | hexyl diphenylphosphinate | 19259-66-6 | C18H23O2P | 302.353 |
—— | diphenyl-phosphinic acid-(2-dimethylamino-ethyl ester) | 114537-02-9 | C16H20NO2P | 289.314 |
—— | 3-methylbut-2-enyl phenyl(phenyl)phosphinate | —— | C17H19O2P | 286.31 |
二苯基膦酸酐 | diphenylphosphinic anhydride | 5849-36-5 | C24H20O3P2 | 418.369 |
—— | octyl diphenylphosphinate | 3389-73-9 | C20H27O2P | 330.407 |
—— | Essigsaeure-diphenylphosphinsaeure-anhydrid | 7594-78-7 | C14H13O3P | 260.229 |
—— | [(Diethylboryl)oxy](diphenyl)phosphine oxide | 92810-16-7 | C16H20BO2P | 286.118 |
(2-溴苯基)-苯基次膦酸 | (2-bromo-phenyl)-phenyl-phosphinic acid | 109817-40-5 | C12H10BrO2P | 297.088 |
—— | (2-methylphenyl)phenylphosphinic acid | 18593-18-5 | C13H13O2P | 232.219 |
—— | (2-iodo-phenyl)-phenyl-phosphinic acid | 5435-79-0 | C12H10IO2P | 344.088 |
二苯基次磷酸苯基酯 | phenyl diphenylphosphinate | 1706-96-3 | C18H15O2P | 294.29 |
—— | oxiran-2-ylmethyl diphenylphosphinate | 195726-46-6 | C15H15O3P | 274.256 |
二苯基次磷酸苄酯 | benzyl diphenylphosphinate | 5573-42-2 | C19H17O2P | 308.317 |
—— | phenethyl diphenylphosphinate | 3389-75-1 | C20H19O2P | 322.343 |
—— | cyclohexyl diphenylphosphinate | 1706-93-0 | C18H21O2P | 300.337 |
—— | 4-methylbenzyl diphenylphosphinate | 87671-55-4 | C20H19O2P | 322.343 |
—— | 3,3-dimethyl-2-oxobutyl diphenylphosphinate | —— | C18H21O3P | 316.337 |
二苯基甲氧基膦 | diphenylphosphinous acid methyl ester | 4020-99-9 | C13H13OP | 216.219 |
—— | 4-chlorophenyl diphenylphosphinate | 21713-55-3 | C18H14ClO2P | 328.735 |
—— | 4-bromophenyl diphenylphosphinate | 21713-54-2 | C18H14BrO2P | 373.186 |
—— | p-tolyl diphenylphosphinate | 21713-53-1 | C19H17O2P | 308.317 |
—— | 4-methoxyphenyl diphenylphosphinate | 34253-15-1 | C19H17O3P | 324.316 |
—— | 4-fluorophenyl diphenylphosphinate | 72358-74-8 | C18H14FO2P | 312.28 |
—— | 4-iodobenzyl diphenylphosphinate | —— | C19H16IO2P | 434.213 |
—— | Diphenyl(trifluoracetoxy)phosphanoxid | 78811-86-6 | C14H10F3O3P | 314.201 |
1-辛烯-2-基二苯基膦酸酯 | 1-octen-2-yl diphenylphosphinate | 81238-73-5 | C20H25O2P | 328.391 |