CN1028996C - 氨基甲烷膦酸和氨基甲基-次膦酸的制法 - Google Patents
氨基甲烷膦酸和氨基甲基-次膦酸的制法 Download PDFInfo
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- MGRVRXRGTBOSHW-UHFFFAOYSA-N (aminomethyl)phosphonic acid Chemical compound NCP(O)(O)=O MGRVRXRGTBOSHW-UHFFFAOYSA-N 0.000 title abstract description 3
- 238000004519 manufacturing process Methods 0.000 title abstract description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 title description 4
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 title description 2
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims abstract description 3
- 229910052736 halogen Chemical group 0.000 claims abstract description 3
- 150000002367 halogens Chemical group 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 23
- 239000002253 acid Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 125000004442 acylamino group Chemical group 0.000 claims description 9
- -1 methylidene, ethyl Chemical group 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims 1
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 abstract 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 abstract 1
- OHWRASKXEUIFFB-UHFFFAOYSA-N NCP(O)=O Chemical class NCP(O)=O OHWRASKXEUIFFB-UHFFFAOYSA-N 0.000 abstract 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 abstract 1
- 239000000543 intermediate Substances 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 16
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- FDNUAHPLMXZWLS-UHFFFAOYSA-N (acetamidomethyl)phosphonic acid Chemical compound CC(=O)NCP(O)(O)=O FDNUAHPLMXZWLS-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 108010077895 Sarcosine Proteins 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 238000012822 chemical development Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000008029 eradication Effects 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
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- 238000012423 maintenance Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
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- 238000010992 reflux Methods 0.000 description 1
- FSYKKLYZXJSNPZ-UHFFFAOYSA-N sarcosine Chemical compound C[NH2+]CC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-N 0.000 description 1
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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
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/301—Acyclic saturated acids which can have further substituents on alkyl
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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)]
- 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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Abstract
氨基甲烷膦酸和氨基甲基——次膦酸作为生物活性化合物或者作为制备生物活性化合物的中间产物是令人感兴趣的。按照发明，具有式I的其R1代表OH、C1-C4-烷基或苯基这样的化合物，可以用技术上简单的方法制备，就是使式II的化合物与水在80至300℃反应，式中R2代表H、C1-C6-烷基、苯甲基，苯基和必要时被C1-C4-烷基、——烷氧基和/或卤素取代的苯基，R1有如上的定义。
Description
已知氨基甲烷膦酸具有灭草和植物生长调节作用;氨基甲基-一次膦酸同样是在技术方面很有价值的生物活性化合物，或者是可用于制备生物活性化合物的中间产物（见L.Maier的文章“氨基次膦酸化学的发展”，载于杂志“phosphorus and suefur”1983.Vol.14，p295-322，特别是317-323及在此处引用的文献）。此外，氨基甲烷膦酸是很有价值的制备N-膦酸基甲基甘氨酸的中间产物（见EP-A-214578）。
氨基甲烷膦酸可由酰基氨基甲烷膦酸通过用盐酸水解制备（US-A-2304156;US-A-2328358;M.Soroka，Synthesis 1989，547）。此方法的缺点是，如果没有专门措施，则氨基甲烷膦酸在分离时得不到较高产率。这样M.Soroka描写了借助吡啶或环氧丙烷进行分离的方法，吡啶或环氧丙烷导至氯化氢与氨基甲烷膦酸分开。另一个缺点是，如果不对酰基氨基甲烷膦酸进行费钱地高度净化，则由其制备方法所决定，它会含有痕迹量甲醛。当用盐酸进行水解处理时，会产生所不希望的副产物双氯甲基醚。已经证明双氯甲基醚是致癌物质。因此，非常需要找到工业规模的不产生双氯甲基醚副产物的可行的水解方法。
本发明的对象是制备式Ⅰ化合物的方法，
式中R1代表羟基、C1-C4-烷基、优先C1-C2-烷基，特别是甲基，或者苯基，特点是使具有通式Ⅱ的酰基氨基甲烷膦酸或者酰基氨基甲基次膦酸和水于80至300℃，优先150至250℃反应。
式中R2代表氢，含有1至6个C-原子，优先1至3个C-原子的烷基，苯甲基或者代表未取代的或由C1-C4-烷基组，C1-C4-烃氧基组和卤素中的一个或多个基取代的苯基。R1具有上述的意义。
具有通式Ⅱ的原料可用部分已知的方法或部分近似已知的方法得到。例如具有式Ⅱ的酰基氨基甲烷膦酸可由N-（羟甲基）-酰胺和PCl3制备（见US-A2328358;US-A2304156或M.Soroka，Synthesis 1989，547和此处引用的文献）。
具有式Ⅱ的酰基氨基甲烷膦酸和酰基氨基甲基--次膦酸此外还可按照德国专利申请p40 26 026.7的方法制备。优先的具有式Ⅱ的原料例如是甲酰基氨基甲烷膦酸，乙酰基氨基甲烷膦酸、苯甲酰基氨基甲烷膦酸、（乙酰基氨基甲基）-（甲基）--次膦酸和（苯甲酰基氨基）-（苯基）--次膦酸。
将具有式Ⅱ的原料与水，必要时可与过量的水混合，并升到反应温度，在此，取决于温度必要时需在压力下工作。
水过量多少对此反应不是特别关键的，例如为了便于操作使水过量2至30摩尔，优先10至25摩尔是适宜的。反应温度是80至300℃，优先150至250℃。反应时间取决于基质、反应温度和压力，在一般情况下为5到40小时，优先10至35小时。
反应结束后，可以用简单方法例如可通过将羧酸作为固体（例如苯甲酸）分开，或通过蒸馏（例如醋酸）实现分离。所产生的氨基甲烷膦酸或氨基甲基次膦酸在一般情况下已具有高纯度。如果需要则可按照一般方法，优先通过重结晶而得到高纯产品。
例1
将20克（0.093摩尔）苯甲酰基氨基甲烷膦酸和20克水加到耐压封管（Bombenrohr）中，并于200℃维持20小时。冷却后用100毫升水浸渍反应产物。紧接着将苯甲酸吸滤。将滤出液在真空中蒸馏浓缩至内温达75℃。残留下10.3克（理论值的100%）氨基甲烷膦酸，此氨基甲烷膦酸通过31P-核磁共振光谱分析表明其纯度为95%。
例2
将20克（0.093摩尔）苯甲酰基氨基甲烷膦酸和20克水加到耐压封管中，于150℃维持20小时，然后经冷却后、用甲醇浸渍反应产物并进行吸滤，可得到8.2克（理论值的80%）氨基甲烷膦酸，其分解温度是310℃。
例3
20克（0.093摩尔）苯甲酰基氨基甲烷膦酸和20克水在回流下维持30小时。冷却后反应产物用100毫升甲醇浸渍并进行吸滤。可得到分解温度为275℃的氨基甲烷膦酸5.3克（理论值的52%）。可以从滤出液中分离出未反应的苯甲酰基氨基甲烷膦酸。
例4
将21.3克（0.1摩尔）苯甲酰基氨基甲基-甲基-次膦
酸和42克水加到耐压密封管中，并于200℃保持20小时，冷却后用水浸渍并抽滤掉苯甲酸。滤出液在真空下浓缩至干燥。结晶残渣用甲醇浸渍并吸滤、可得到8克（理论值的73%）氨基甲基-甲基-次膦酸，其分解温度为255-261℃。
例5
将20克（0.073摩尔）苯甲酰基氨基甲基-苯基-次膦酸和40毫升水加到耐压封管中，并于225℃保持23小时。然后将苯甲酸进行抽滤并用水冲洗。将滤出液在真空中浓缩至干燥，留下12.5克（理论值的100%）粗氨基甲基-苯基-次膦酸。在用甲醇浸渍后，得熔点为276-278℃的氨基甲基-苯基-次膦酸。
例6
将14.4克（0.094摩尔）乙酰基氨基甲烷膦酸和28克水装入耐压密封管中，于200℃保持20小时，然后进行冷却，并将得到的反应溶液在真空中除去水和醋酸。将残留物用30毫升甲醇和1毫升水的混合物进行浸渍，得到9.6克（理论值的92%）氨基甲烷膦酸，其分解温度为270-278℃。
Claims (16)
1、式Ⅰ化合物的制备方法，式中R1代表羟基、C1-C4
-烷基或苯基，其特点是，使通式Ⅱ的酰基氨基甲烷膦酸或酰基氨基甲基--次膦酸与水在80至300℃反应，式中R2代表氢、
含1至6个C-原子的烷基，苯甲基或苯基，苯基是未取代的或者是由C1-C4-烷基组、C1-C4烷氧基组和卤素的一个或多个基取代的，并且R1具有上述的意义。
2、按照权利要求1的方法，其特点是，R′代表羟基。
3、按照权利要求1的方法，其特点是，R1代表甲基、乙基或苯基。
4、按照权利要求1、2或3的方法，其特点是，R2代表H、C1-C3-烷基或苯甲基。
5、按照权利要求1、2或3的方法，其特点是，R2代表苯基。
6、按照权利要求1、2或3的方法，其特点是，反应温度是150至250℃。
7、按照权利要求1、2或3的方法，其特点是，以1摩尔式Ⅱ化合物为基准，使加入的水过量2至30摩尔。
8、按照权利要求1、2或3的方法，其特点是，反应时间范围是5至40小时。
9、按照权利要求4的方法，其中反应温度是150至250℃。
10、按照权利要求5的方法，其中反应温度是150至250℃。
11、按照权利要求7的方法，其中反应温度是150至250℃。
12、按照权利要求8的方法，其中反应温度是150至250℃。
13、按照权利要求7的方法，其中R2是苯基。
14、按照权利要求7的方法，其中R2是H，C1-C3烷基或苯甲基。
15、按照权利要求13的方法，其中反应温度是150到250℃。
16、按照权利要求14的方法，其中反应温度是150至250℃。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4026027.5 | 1990-08-17 | ||
| DE4026027A DE4026027A1 (de) | 1990-08-17 | 1990-08-17 | Verfahren zur herstellung von aminomethanphosphonsaeure und aminomethyl-phosphinsaeuren |
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| Publication Number | Publication Date |
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| CN1059148A CN1059148A (zh) | 1992-03-04 |
| CN1028996C true CN1028996C (zh) | 1995-06-21 |
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| CN91105718A Expired - Fee Related CN1028996C (zh) | 1990-08-17 | 1991-08-16 | 氨基甲烷膦酸和氨基甲基-次膦酸的制法 |
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| Country | Link |
|---|---|
| EP (1) | EP0543845B1 (zh) |
| JP (1) | JP3111076B2 (zh) |
| KR (1) | KR100214903B1 (zh) |
| CN (1) | CN1028996C (zh) |
| AT (1) | ATE118008T1 (zh) |
| AU (1) | AU653954B2 (zh) |
| BR (1) | BR9106767A (zh) |
| CA (1) | CA2089650C (zh) |
| DE (2) | DE4026027A1 (zh) |
| DK (1) | DK0543845T3 (zh) |
| ES (1) | ES2069901T3 (zh) |
| GR (1) | GR3015357T3 (zh) |
| HU (1) | HU213457B (zh) |
| IE (1) | IE912920A1 (zh) |
| IL (1) | IL99203A (zh) |
| PT (1) | PT98700B (zh) |
| WO (1) | WO1992003449A1 (zh) |
| ZA (1) | ZA916502B (zh) |
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| RU2613837C1 (ru) * | 2015-12-03 | 2017-03-21 | Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский технологический университет" "МИСиС" | Способ получения ионно-плазменного вакуумно-дугового керамикометаллического покрытия TiN-Ni для твердосплавного режущего инструмента расширенной области применения |
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| FR2683222B1 (fr) * | 1991-10-31 | 1995-05-19 | Rhone Poulenc Agrochimie | Procede de production d'acides, de sels et/ou esters aminoalcanephosphoniques. |
| CN104744507B (zh) * | 2015-04-09 | 2016-11-09 | 泰索新材料科技（杭州）有限公司 | 一种氨甲基苯基次膦酸及其制备方法 |
| CN104746168B (zh) * | 2015-04-09 | 2016-10-12 | 泰索新材料科技（杭州）有限公司 | 一种阻燃尼龙66纤维及其制备方法 |
| CN104762689B (zh) * | 2015-04-09 | 2017-01-04 | 泰索新材料科技（杭州）有限公司 | 一种阻燃尼龙6纤维及其制备方法 |
| CN104762688B (zh) * | 2015-04-09 | 2017-01-04 | 泰索新材料科技（杭州）有限公司 | 一种阻燃尼龙66及其制备方法 |
| CN108927292B (zh) * | 2017-05-24 | 2021-10-22 | 中蓝连海设计研究院有限公司 | 一种氨基膦酸类化合物及其制备方法和用途 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3824961A1 (de) * | 1988-07-22 | 1990-01-25 | Basf Ag | Verfahren zur herstellung von bis(aminomethyl)-phosphinsaeure oder deren sauren oder basischen salzen |
| HU203360B (en) * | 1988-11-25 | 1991-07-29 | Monsanto Co | Process for producing n-acylamino methylphosphonates |
-
1990
- 1990-08-17 DE DE4026027A patent/DE4026027A1/de not_active Withdrawn
-
1991
- 1991-08-07 DK DK91914121.8T patent/DK0543845T3/da active
- 1991-08-07 HU HU9300423A patent/HU213457B/hu unknown
- 1991-08-07 DE DE59104516T patent/DE59104516D1/de not_active Expired - Fee Related
- 1991-08-07 AT AT91914121T patent/ATE118008T1/de not_active IP Right Cessation
- 1991-08-07 BR BR919106767A patent/BR9106767A/pt not_active Application Discontinuation
- 1991-08-07 AU AU83095/91A patent/AU653954B2/en not_active Ceased
- 1991-08-07 WO PCT/EP1991/001494 patent/WO1992003449A1/de active IP Right Grant
- 1991-08-07 JP JP03513167A patent/JP3111076B2/ja not_active Expired - Fee Related
- 1991-08-07 EP EP91914121A patent/EP0543845B1/de not_active Expired - Lifetime
- 1991-08-07 CA CA002089650A patent/CA2089650C/en not_active Expired - Fee Related
- 1991-08-07 ES ES91914121T patent/ES2069901T3/es not_active Expired - Lifetime
- 1991-08-15 IL IL9920391A patent/IL99203A/en not_active IP Right Cessation
- 1991-08-16 ZA ZA916502A patent/ZA916502B/xx unknown
- 1991-08-16 IE IE292091A patent/IE912920A1/en unknown
- 1991-08-16 CN CN91105718A patent/CN1028996C/zh not_active Expired - Fee Related
- 1991-08-16 PT PT98700A patent/PT98700B/pt not_active IP Right Cessation
-
1993
- 1993-02-16 KR KR1019930700446A patent/KR100214903B1/ko not_active IP Right Cessation
-
1995
- 1995-03-10 GR GR950400515T patent/GR3015357T3/el unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2613837C1 (ru) * | 2015-12-03 | 2017-03-21 | Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский технологический университет" "МИСиС" | Способ получения ионно-плазменного вакуумно-дугового керамикометаллического покрытия TiN-Ni для твердосплавного режущего инструмента расширенной области применения |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1059148A (zh) | 1992-03-04 |
| DK0543845T3 (da) | 1995-06-19 |
| EP0543845A1 (de) | 1993-06-02 |
| ATE118008T1 (de) | 1995-02-15 |
| AU8309591A (en) | 1992-03-17 |
| BR9106767A (pt) | 1993-08-24 |
| HUT64355A (en) | 1993-12-28 |
| AU653954B2 (en) | 1994-10-20 |
| DE59104516D1 (de) | 1995-03-16 |
| DE4026027A1 (de) | 1992-02-20 |
| CA2089650A1 (en) | 1992-02-18 |
| HU9300423D0 (en) | 1993-05-28 |
| ES2069901T3 (es) | 1995-05-16 |
| KR100214903B1 (en) | 1999-08-02 |
| IE912920A1 (en) | 1992-02-26 |
| JP3111076B2 (ja) | 2000-11-20 |
| CA2089650C (en) | 2001-10-23 |
| HU213457B (en) | 1997-06-30 |
| PT98700A (pt) | 1992-07-31 |
| GR3015357T3 (en) | 1995-06-30 |
| ZA916502B (en) | 1992-04-29 |
| EP0543845B1 (de) | 1995-02-01 |
| WO1992003449A1 (de) | 1992-03-05 |
| IL99203A (en) | 1995-08-31 |
| JPH06500310A (ja) | 1994-01-13 |
| IL99203A0 (en) | 1992-07-15 |
| PT98700B (pt) | 1999-01-29 |
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