CN1056498A - 膦酰化方法 - Google Patents
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- CN1056498A CN1056498A CN91102854A CN91102854A CN1056498A CN 1056498 A CN1056498 A CN 1056498A CN 91102854 A CN91102854 A CN 91102854A CN 91102854 A CN91102854 A CN 91102854A CN 1056498 A CN1056498 A CN 1056498A
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- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000005954 phosphonylation reaction Methods 0.000 title description 3
- -1 carboxylic acyl acyl chlorides Chemical class 0.000 claims abstract description 26
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 23
- GJMMXPXHXFHBPK-UHFFFAOYSA-N [P].[Cl] Chemical compound [P].[Cl] GJMMXPXHXFHBPK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 11
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 8
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 3
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical group ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- SWRNIYAQKATHDJ-UHFFFAOYSA-N dichloro(dichlorophosphanyl)phosphane Chemical compound ClP(Cl)P(Cl)Cl SWRNIYAQKATHDJ-UHFFFAOYSA-N 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 230000007062 hydrolysis Effects 0.000 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- 150000008064 anhydrides Chemical class 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 claims description 3
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- 239000011260 aqueous acid Substances 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 125000001246 bromo group Chemical group Br* 0.000 claims description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical group CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 125000005265 dialkylamine group Chemical group 0.000 claims description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- ARJOQCYCJMAIFR-UHFFFAOYSA-N prop-2-enoyl prop-2-enoate Chemical compound C=CC(=O)OC(=O)C=C ARJOQCYCJMAIFR-UHFFFAOYSA-N 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 159000000000 sodium salts Chemical group 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 125000004104 aryloxy group Chemical group 0.000 claims 2
- 229910052783 alkali metal Inorganic materials 0.000 claims 1
- 239000012670 alkaline solution Substances 0.000 claims 1
- 239000000047 product Substances 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 150000003009 phosphonic acids Chemical class 0.000 description 6
- NLBSQHGCGGFVJW-UHFFFAOYSA-N 2-carboxyethylphosphonic acid Chemical compound OC(=O)CCP(O)(O)=O NLBSQHGCGGFVJW-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 239000012362 glacial acetic acid Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- WTKZGYCDNMZULF-UHFFFAOYSA-N OP(=O)OCl Chemical compound OP(=O)OCl WTKZGYCDNMZULF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- PVCINRPAXRJLEP-UHFFFAOYSA-N dichloro(ethoxy)phosphane Chemical compound CCOP(Cl)Cl PVCINRPAXRJLEP-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002483 hydrogen compounds Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N pentanoic acid group Chemical group C(CCCC)(=O)O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- ZJAOAACCNHFJAH-UHFFFAOYSA-N phosphonoformic acid Chemical compound OC(=O)P(O)(O)=O ZJAOAACCNHFJAH-UHFFFAOYSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
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- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
- C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
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- Chemical & Material Sciences (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Saccharide Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
一种生产有机膦酰基羧酸的方法,该方法包括在
反应步骤中,使不饱和羧酸(或所述酸的盐或酐)与氯
磷反应产物一起加热以产生有机磷酰基羧酸酰氯的
混合物,在水解步骤中,用含水介质处理该混合物以
产生所述的有机膦酰基羧酸。本方法提供比较简单
的高产率生产酸的方法。
Description
本发明有关用于生产有机膦酰基羧酸,特别是羧乙基膦酸的膦酰化方法。
已描述羧乙基膦酸,也称3-膦酰基丙酸,可用作聚酯的阻燃剂和缓蚀剂。它可以多步工序通过二乙基亚磷酸酯和丙烯酸乙酯反应而制得。丙烯酸、亚磷酸和三氯化磷反应可得到所要的产物。但其产率很低,而且混有大量有机羟基三膦酸。
现在我们已发现一种高产率的有机膦酰基羧酸的简便生产方法。
因此,本发明提供一种有机膦酰基羧酸的生产方法,该方法包括:在反应步骤中,将不饱和羧酸(或所述酸的盐或酐)与氯磷反应产物一起加热以产生含有有机磷酰基羧酸酰氯的混合物;在水解步骤中,用含水介质处理该混合物以产生所述的有机膦酰基羧酸。
不饱和羧酸的通式为R2CH=CR1CO2H,其中R1为氢或C1-C6烷基(例如,甲基或乙基),R2为氢、C1-C6烷基或C6-C18芳基(如甲基、乙基或苯基)或羧基。不饱和羧酸可为如马来酸、巴豆酸或甲基丙烯酸,但最好为丙烯酸。可用碱金属盐(如,钠盐)或季铵盐(如,一种液体盐如四丁基铵盐)代替游离的羧酸。
不饱和羧酸可以其酐的形式使用,酐可为如,一种混合酐、对称酐(如丙烯酸酐)或环酐(如马来酸酐)。
氯磷反应产物可通过三氯化磷与含活泼氢的化合物如羟基化合物、一种硫醇、一种氨基化合物反应,或通过三氯化磷与三烷基或三芳基亚磷酸酯的反应来制备。
羟基化合物的通式为R3OH,其中R3为C1-C8烷基(如,甲基、乙基、丁基、己基或2-乙基己基)、C6-C18芳基(如,苯基)或C7-C19芳烷基(如苄基或2-苯乙基)。最好羟基化合物为乙醇或苯酚。
另一种方法是,含活泼氢的化合物为一种硫醇,其通式为R3SH,其中R3为C1-C8烷基、C6-C18芳基或C7-C19芳烷基,例如甲硫醇、乙硫醇或苯硫酚。
在另一个替换实施例中,含活泼氢的化合物为一种硫醇,其通式为R3R4NH,其中R3为C1-C8烷基、C6-C18芳基或C7-C19芳烷基,R4为氢、C1-C8烷基、C6-C18芳基或C7-C19芳烷基。这种氨基化合物的例子包括二烷基胺,例如二甲胺、二乙胺或二苯胺。
最好氯磷化合物是由三氯化磷和三烷基或三芳基亚磷酸酯制成的,亚磷酸酯最好是三甲基亚磷酸酯。反应最好在有催化剂存在下进行。最好的催化剂是鏻化合物,如氯代三丁甲基鏻或溴代四丁基鏻。
氯磷反应产物可为三氯化磷。另一方面,氯磷反应产物可为单烷氧基或单芳氧基二氯化磷。可用氯磷反应产物与不饱和酸(或其盐或酐)反应,但先得进行分离或纯化。在-100°-50℃(合适的温度为-100--50℃)时,将含活泼氢的化合物加到三氯化磷中,同时除去付产物氯化氢可制得氯磷反应产物,或在催化剂存在下,使三氯化磷与三烷基或三芳基亚磷酸酯反应而制得。该氯磷反应产物可在制备后立即使用,或经纯化后使用。
本发明方法的反应步骤可在50-150℃(如80-120℃)的加热条件下进行,反应时间为0.5-10小时(如0.5-5小时)。本方法在无水和惰性气氛条件下进行,惰性气体如氮气。最好将羧酸缓慢加到氯磷反应产物(或三氯化磷)中,在添加结束时,再进一步加热反应混合物。
反应过程中,所产生的任何付产挥发物都要从反应中排出。反应结束时,反应产物含有有机羧基膦酸的酰基氯,该酸的通式为H2OC-CR1H-CR2H-PO3H2。当活泼氢化合物是羟基化合物或一种硫醇时,酰基氯是一种酯酰基氯,当用胺时,则酰基氯是酰胺酰基氯。当存在不纯反应产物时,最好在提纯后,将酰基氯加到含水介质如水或含水酸或碱中使其水解以生成相应的酸或盐,然后通过蒸发和/或结晶使其分离。另一种方法是,加入碱以沉淀不溶性盐。
所有工序可分批进行,特别是在单个反应器内,先添加氯磷反应产物,然后加羧酸(或盐或酐),最后将混合物加到水中以进行水解步骤。本方法也可连续进行。
通过下列实施例可说明本发明:
实例1:
在-78℃,将乙醇(1摩尔)在1小时内加到三氯化磷(1摩尔)中,随后加热至室温,同时蒸出氯化氢和乙基氯,以留下粗的氯磷反应产物。将反应产物真空蒸馏,可得到纯的乙基偶磷二氯糖醇(ethyl phosphoro dichloridite)(约含5%未反应三氯化磷)。
在105℃的氮气氛中,在经纯化的乙氧基二氯化磷(1当量)中于1小时内加入丙烯酸(1.4当量)。使得到的反应混合物迴流2小时以得到油质反应产物,认为该产物含有羧乙基膦酸的氯代酯。
将反应产物冷至0℃,并加入过量的水,边搅拌边外部冷却至合适的温升。水可引起水解,使得到的水溶液迴流1小时可完成水解。经真空蒸发留下纯度为86%的粗羧乙基膦酸,按乙氧基二氯化磷计收率为95%。该粗产物含有少量1,1,3-三膦酰基-n-丙-1-醇和亚磷酸和磷酸付产物。该粗产物可这样使用,经冰醋酸重结晶留下收率为68%的具有结构H和Pnmr光谱的羧乙基膦酸(mp165-6℃)
实例2
用粗的氯磷反应产物代替已纯化的乙基偶磷二氯糖醇重复例1的方法。得到粗羧乙基膦酸产物,其产率为97%,纯度为73%。
实例3
用苯酚代替乙醇重复例1的方法,苯氧基二氯化磷与丙烯酸的反应及随后的杂质与例1相类似,然而有机含氧二氯化磷是用不同方法制得的。
将苯酚(1当量)加到经纯化的三氯化磷(6当量)中,在室温下搅拌得到的混合物12小时,然后迴流2小时。加热反应产物以蒸出未反应的三氯化磷直到剩余反应物温度为135℃;苯氧基二氯化磷剩余物纯度为95%。
在本方法中将这种二氯化物与丙烯酸一起使用,产物经水解得到纯度为79%的粗羧乙基膦酸,其收率为87%。
例4
用1当量三氯化磷代替乙氧基二氯化磷,并把丙烯酸量增加至2.3当量,使用例1的方法。得到纯度为70%的粗羧乙基膦酸,按三氯化磷计产率为88%。
例5
将三氯化磷(550g,4摩尔)和氯代三丁甲基鏻(7.6g,0.03摩尔)置于氮气氛下的搅拌烧瓶内。
将得到的溶液冷至10℃,在45分钟内加完三甲基亚磷酸酯(248g,2摩尔),自始至终保持该溶液温度低于20℃。在室温下使产物静置24小时。
按31P nmr测得该步混合物组分为:三氯化磷为6.6(摩尔%);甲基偶磷二氯糖醇92.3(摩尔%);2甲基偶磷氯糖醇1.1(摩尔%)。
将得到的混合物加热至90℃,在1.5小时内加完丙烯酸(475g,6.6摩尔)。然后将反应物加热至115℃,加热1小时,接着使其冷却。将产物倒在3kg的冰/水上经进行水解。当加料终止时温度达到50℃。加热得到的水溶液并使其回流,蒸出水5小时,最后在真空中干燥。
定量回收得到的产物为灰白色的固体结晶,其组成如下(以重量计):92.6%3-膦酰基丙酸;3.3%的1,1,3-三膦酰基-n-丙-1-醇;30%亚磷酸和1.1%磷酸。
由两倍重量当量的冰醋酸重结晶可得到按甲氧基二氯化磷计产率为70%的纯3-膦酰基丙酸。
实例6
将三氯化磷(45.8g,333毫摩尔)和氯代三丁甲基鏻(0.32g,1.25毫摩尔)置于充氮的烧瓶中,该烧瓶装有氮管道、搅拌器和迴流冷凝器,然后在30分钟内加入三乙基亚磷酸酯(27.7g,167毫摩尔),冷却烧瓶以使反应温度保持在30℃以下。静置72小时后,将所得到的乙基偶磷二氯糖醇加热至100℃,在30分钟内加完丙烯酸(39.6g,555毫摩尔),然后再加热至110℃,加热时间为1小时。使得到的油冷却,然后将其加到250g冰/水中以进行水解。将所得到的水溶液蒸发至干,可得到76.6g粗产物,分析表明其组成如下(以重量计):92.6%3-膦酰基丙酸;3.1%1,1,3-三膦酰基-n-丙-1-醇;3.8%亚磷酸和0.5%磷酸。
用200g冰醋酸使该产物重结晶可得到3-膦酰基丙酸,按原料Pcl3和三乙基亚磷酸酯计,其产率为72%,纯度为99.2%。
Claims (17)
1、一种生产有机膦酰基羧酸的方法,其特征为:在反应步骤中,将不饱和羧酸(或所述酸的盐或酐)与氯磷反应产物一起加热以产生有机磷酰基羧酸酰氯的混合物,在水解步骤中,用含水介质处理该混合物以产生所述的有机膦酰基羧酸。
2、按照权利要求1的方法,其特征为:不饱和羧酸具有通式R2CH=CR1CO2H,其中R1为H或C1-C6的烷基,R2为H、C1-C6烷基、C6-C18芳基或羧基。
3、按照权利要求1或2的方法,其特征为:不饱和羧酸是马来酸、巴豆酸、甲基丙烯酸或丙烯酸。
4、按照权利要求1的方法,其特征为:所用的不饱和羧酸是该酸的碱金属盐(如钠盐)形式。
5、按照权利要求1的方法,其特征为:所用的不饱和羧酸是该酸的季铵盐(如,四丁基铵盐)形式。
6、按照权利要求1的方法,其特征为:所用的不饱和羧酸是该酸的酐形式,如混合酐、对称酐(如丙烯酸酐)或环酐(如马来酸酐)。
7、按照权利要求1-6的任一项方法,其特征为:氯磷反应产物是三氯化磷。
8、按权利要求1-6的任一项方法,其特征为:氯磷反应产物是单烷氧基或单芳氧基的二氯化磷。
9、按权利要求1-6的任一项方法,其特征为:该氯磷反应产物首先由三氯化磷与含活泼氢的化合物如羟基化合物、一种硫醇或一种氨基化合物反应而制得。
10、按权利要求9的方法,其特征为该化合物是羟基化合物,其通式为R3OH,式中R3是C1-C8烷基、C6-C18芳基或C7-C19芳烷基(如,甲基、乙基、丁基、己基、2-乙基己基、苯基、苄基或2-苯乙基)。
11、按权利要求9的方法,其特征为:该化合物是一种硫醇,其通式为R3SH,其中R3是C1-C8烷基、C6-C18芳基或C7-C19芳烷基(如甲硫醇、乙硫醇或苯硫酚)
12、按权利要求9的方法,其特征为:该化合物是一种氨基化合物,其通式为R3R4NH,式中R3是C1-C8烷基、C6-C18芳基或C7-C19芳烷基,R4是氢、C1-C8烷基、C6-C18芳基或C7-C19芳烷基(如二烷基胺)。
13、按权利要求1-6之任一项的方法,其特征为:氯磷反应产物首先由三氯化磷与三烷基或三芳基亚磷酸酯(如三甲基亚磷酸酯)反应而制得。
14、按权利要求13的方法,其特征为:氯磷反应产物是在催化剂(如氯代三丁甲基鏻或溴代四丁基鏻)存在下制得的。
15、按前述任一项权利要求的方法,其特征为:反应步骤是在50-150℃(如80-120℃)的温度下进行的。
16、按前述任一项权利要求的方法,其特征为:反应时间为0.5-10小时,如0.5-5小时。
17、按前述任一项权利要求的方法,其特征为:引起水解的含水介质是水、含水酸或含水碱或含水的碱溶液。
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GB909008405A GB9008405D0 (en) | 1990-04-12 | 1990-04-12 | Phosphonylation process |
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JP (1) | JPH04305588A (zh) |
KR (1) | KR910018392A (zh) |
CN (1) | CN1056498A (zh) |
AT (1) | ATE125259T1 (zh) |
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ES2077096T3 (es) | 1995-11-16 |
EP0451596B1 (en) | 1995-07-19 |
GB2242902B (en) | 1993-10-06 |
GB9008405D0 (en) | 1990-06-13 |
GB2242902A (en) | 1991-10-16 |
EP0451596A1 (en) | 1991-10-16 |
DE69111282T2 (de) | 1996-01-11 |
GB9106267D0 (en) | 1991-05-08 |
KR910018392A (ko) | 1991-11-30 |
ATE125259T1 (de) | 1995-08-15 |
JPH04305588A (ja) | 1992-10-28 |
DE69111282D1 (de) | 1995-08-24 |
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