CN1035294A - 制备n-膦酰基甲基亚氨基双乙酸和酰氯的方法 - Google Patents
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- AZIHIQIVLANVKD-UHFFFAOYSA-N N-(phosphonomethyl)iminodiacetic acid Chemical compound OC(=O)CN(CC(O)=O)CP(O)(O)=O AZIHIQIVLANVKD-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims description 22
- 150000001263 acyl chlorides Chemical class 0.000 title claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 41
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 33
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 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 claims abstract description 26
- -1 carboxyl acyl chloride Chemical class 0.000 claims abstract description 20
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011541 reaction mixture Substances 0.000 claims abstract description 11
- 238000002425 crystallisation Methods 0.000 claims abstract description 5
- 230000008025 crystallization Effects 0.000 claims abstract description 5
- 238000001704 evaporation Methods 0.000 claims abstract description 4
- 230000008020 evaporation Effects 0.000 claims abstract description 3
- 150000007522 mineralic acids Chemical class 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 3
- 239000002253 acid Substances 0.000 abstract description 3
- 235000011167 hydrochloric acid Nutrition 0.000 description 18
- 238000009835 boiling Methods 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 6
- 239000012346 acetyl chloride Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000018199 S phase Effects 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- KKHJQZVEUKJURX-UHFFFAOYSA-N 2-(carboxymethylamino)acetic acid;hydrochloride Chemical compound Cl.OC(=O)CNCC(O)=O KKHJQZVEUKJURX-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- HAXVIVNBOQIMTE-UHFFFAOYSA-L disodium;2-(carboxylatomethylamino)acetate Chemical compound [Na+].[Na+].[O-]C(=O)CNCC([O-])=O HAXVIVNBOQIMTE-UHFFFAOYSA-L 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YBPUBXQZBUQACE-UHFFFAOYSA-N 2-aminoacetic acid;phosphoric acid Chemical compound NCC(O)=O.OP(O)(O)=O YBPUBXQZBUQACE-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 150000003840 hydrochlorides Chemical class 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/58—Preparation of carboxylic acid halides
- C07C51/60—Preparation of carboxylic acid halides by conversion of carboxylic acids or their anhydrides or esters, lactones, salts into halides with the same carboxylic acid part
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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 System
- 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, i.e. RP(=X)(XH)2 (X = S, Se)
- C07F9/3804—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se) not used, see subgroups
- C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
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Abstract
本发明涉及同时制备N-膦酰基甲基亚氨基双乙酸和羧酰氯。按照本发明,三氯化磷和C1-4羧酸最好在0-20℃,以摩尔比为1∶3进行反应,自羧酰氯中分离所形成的亚磷酸相,再分离出羧酰氯,在还含有羧酸和羧酰氯的亚磷酸相用水稀释后,于60-120℃,以亚氨基双乙酸、亚磷酸和甲醛为约1∶1-1.1∶1-1.2的摩尔比,在有外加无机强酸,最好是盐酸的存在下,使其与亚氨基双乙酸和甲醛水溶液反应,随后蒸发反应混合物至析出结晶。
Description
本发明涉及同时制备N-膦酰基甲基亚氨基双乙酸和低级羧酰氯的新方法。
N-膦酰基甲基亚氨基双乙酸是一种制备具广谱活性的甘氨酸磷酸盐除草剂的重要中间体。同样地,羧酰氯也是常用于有机化学分析中的重要试剂,但是在文献中还没有介绍过同时制备两种产物的实用方法。
GB-PS 2,154,509介绍了制备N-膦酰基甲基亚氨基双乙酸的方法。按照该方法,首先用盐酸处理亚氨基双乙酸钠盐水溶液,然后再用三氯化磷和甲醛的水溶液进行处理。按照该反应是先将盐酸加入亚氨基双乙酸钠盐水溶液中,同时蒸除部分水,随后于110-112℃加入三氯化磷。所得到的反应混合物中含有亚氨基双乙酸盐酸盐、氯化钠、水和亚磷酸。接着于约108-110℃将甲醛水溶液加入反应混合物中,在该温度使其反应至少1.5小时。反应结束时,将氢氧化钠加入该反应混合物中,过滤,滤饼用水洗涤多次后干燥之,收率约为87.9%。该方法的缺点是,除了形成亚磷酸外,存在的水会与加入的三氯化磷反应形成盐酸,而除去盐酸需花高费用且又严重污染环境。同时形成的氯化钠既不能被利用,且会污染终产物,唯有经多次洗涤后才能从终产物中除去。
在GB PS 2,021,589中,制备N-膦酰基甲基亚氨基双乙酸是先在40℃下,使三氯化磷和水反应,接着在沸腾下将亚氨基双乙酸加到溶液中,随后加入甲醛水溶液,再蒸除2/3水。加入乙醇后,N-膦酰基甲基亚氨基双乙酸从溶液中沉淀出来,用乙醇和水洗涤沉淀的结晶。与其它方法比较,该方法的缺点是,按摩尔数计,用于分解三氯化磷形成的3摩尔盐酸中的大部分,在该方法中未被得到利用,因为进行膦酰基甲基化程序只需用去所形成盐酸的三分之一就已足够了。盐酸的破坏不但严重地影响该方法的经济效益,而且会造成环境污染。
基于相似原理和具共同特点的其它公知方法中,三氯化磷的氯原子被用于形成盐酸或被转化为氯化钠,要除去盐酸和氯化钠便会严重地影响经济效益和产物的品质。
本发明的主题是使所用的三氯化磷中的氯原子能全部地被利用来制备N-膦酰基甲基亚氨基双乙酸,另一个主题是排除环境污染,分解诸如盐酸和氯化钠之类的有害副产物以及避免其形成。
采用亚氨基双乙酸和三氯化磷同时制备N-膦酰基甲基亚氨基双乙酸和低级羧酰氯的本发明方法,其特征在于使三氯化磷和C1-4羧酸以约1∶3的摩尔比进行反应,通过使所形成的亚磷酸和羧酰氯彼此分离,从而分离出羧酰氯。在还含有羧酸和羧酰氯的亚磷酸相用水稀释后,在60-120℃,在有外加无机酸存在下,最好是在有盐酸存在下,使其与亚氨基双乙酸和甲醛水溶液反应,而后进行蒸发直至析出结晶产物。亚氨基双乙酸与亚磷酸和甲醛的摩尔比为约1∶1-1.1∶1-1.2。
于0-20℃使三氯化磷和羧酸(最好是乙酸)反应。由三氯化磷和羧酸反应而形成的亚磷酸相中,含有羧酸和羧酰氯、后来还含有盐酸,也可通过蒸馏来减少。将反应混合物蒸发至其原体积的三分之二,即可促进所得N-膦酰基甲基亚氨基双乙酸在合成终止时沉淀出来。
为实现本发明的优点,从三氯化磷和羧酸反应后所得的反应混合物中欲除去各非反应组分并无重要的要求,除去各非反应组分的沉淀或未反应原料也并不重要。而亚磷酸和羧酰氯及羧酸的分离可通过简单的相沉淀法、蒸馏法或亚磷酸相萃取法进行。
羧酸和三氯化磷可以给定的摩尔比,在-10-+100℃,最好在0-20℃,按下列化学方程式进行反应:
PCl3+3RCOOH-H3PO3+RCOCl
该反应除冷却和搅拌外,最好将三氯化磷加入羧酸中,但本步骤亦可按相反次序加入这些物质。反应后形成的酰氯和亚磷酸呈两相,并彼此分离。分离上层的酰氯相供进一步使用,下层的亚磷酸相通常含有80-98%亚磷酸,2-0%羧酸和1-5%羧酰氯。从反应混合物分离得到的下层相,在给定的温度下可直接与甲醛水溶液反应。实际实施本方法时,是在该混合物的沸点温度下将甲醛水溶液加入含有亚磷酸、亚氨基双乙酸和盐酸的混合物中。蒸发后,沉淀出晶状最终产物,可过滤分离之。
本方法的优点可概括如下:
1.当三氯化磷和羧酸以适宜摩尔比反应时,可同时形成适于制备N-膦酰基甲基亚氨基双乙酸的亚磷酸,和可分离出有用的羧酰氯。
2.三氯化磷的氯原子可全部被利用且无需除去过量的有害的盐酸。
3.可节省部分环境投资且中和后的副产物(NaCl)不会污染环境。
4.主要反应混合物中不含氯化钠,因而可消除终产物中夹带的氯化钠杂质。
5.用一般的化学仪器即可实施本方法。
下列非限制性实施例将用于详细说明本发明。
实施例1
量180g(3mole)乙酸至一可冷却、可加热并装配有一搅拌器、温度计和回流冷凝器的四颈烧瓶中。在40℃以下,沿漏斗加入137.3g(1.0mole)三氯化磷。然后将反应混合物加热至40-50℃,于该温度下搅拌30分钟。
使所得到的混合物静置,同时进行各相的分离。分离的含有乙酰氯的上层相,备用于技术目的。总计96g含有亚磷酸,另外还含有6%(重量)盐酸,2%(重量)乙酰氯和10%(重量)乙酸的下层相与30cm3水混合后置入附设漏斗。
将119.7g(0.9mole)亚氨基双乙酸、130cm3水和48克37%(重量)盐酸导入上述烧瓶中后,在搅拌下,自附设漏斗加入上述步骤中得到的,含有亚磷酸的下层相。将如此得到的混合物加热至沸点,同时加入97g(1.1mole)34%甲醛水溶液。煮沸该反应混合物,再回流1小时后,蒸除其三分之二体积,然后将其冷却至10℃,过滤所得到的结晶,冷水洗涤并干燥之,得到沸点为208-209℃的N-膦酰基甲基亚氨基双乙酸173g。
按亚氨基双乙酸计算,收率为84.6%。
实施例2
按照实施例1的方法,所不同的是,蒸馏由三氯化磷和乙酸反应而得到的,存在于下层相的三氯化磷、一定量的盐酸、乙酸和乙酰氯。将用于反应的37%盐酸的量增至74.7g。将如此得到的含有2%盐酸、1%乙酰氯和4%乙酸的亚磷酸相进一步按实施例1步骤进行反应,结果得到沸点为209℃的N-膦酰基甲基亚氨基双乙酸173.1g。其得量为理论收率的84.7%。
实施例3
按实施例1所述的方法,所不同的是通过重复加入三氯化磷及其后的沉淀步骤,使三氯化磷和乙酸反应所得到的亚磷酸相中含有乙酸和乙酰氯的量减少。将如此得到的,含有7%乙酸、1.5%乙酰氯和4%盐酸的亚磷酸相加入152.5g(0.9mole)亚氨基双乙酸盐酸和150ml水的混合物中。将如此得到的混合物加热至沸点,并在1小时内加入97g(1.1mole)34%甲醛水溶液。接着煮沸再回流2小时,随后蒸发至原体积的三分之二,结晶出N-膦酰基甲基亚氨基双乙酸。得到其沸点为209-210℃的产物176g,其得量为理论收率的86.2%。
Claims (3)
1、一种用亚氨基双乙酸和三氯化磷同时制备N-膦酰基甲基亚氨基双乙酸和低级酰氯的方法,其中包括在0-20℃,使摩尔比为约1∶3的三氯化磷和C羧酸反应,自羧酰氯中分离所形成的亚磷酸相,再分离出羧酰氯,在上述亚磷酸相用水稀释后,于60-120℃,以亚氨基双乙酸、亚磷酸和甲醛为约1∶1-1.1∶1-1.2的摩尔比,在有外加无机强酸,最好是盐酸的存在下,使还含有羧酸和羧酰氯的亚磷酸相与亚氨基双乙酸和甲醛水溶液反应,随后蒸发反应混合物至析出结晶。
2、一种按照权利要求1的方法,其中包括用乙酸作为羧酸。
3、一种按照权利要求1的方法,其中包括在三氯化磷和羧酸反应期间,在与甲醛反应前,通过蒸馏或用三氯化磷处理,分别降低所得到的、存在于亚磷酸相中的羧酸和羧酰氯及盐酸的含量。
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US5312973A (en) * | 1993-03-25 | 1994-05-17 | Finchimica S.P.A. | Process for producing n-phosphono-methyl-imino-diacetic acid |
DE19909200C1 (de) * | 1999-03-03 | 2000-03-09 | Sueddeutsche Kalkstickstoff | Verfahren zur Herstellung von N-Phosphonomethyliminodiessigsäure |
DE19914375A1 (de) * | 1999-03-30 | 2000-10-05 | Sueddeutsche Kalkstickstoff | Verfahren zur Herstellung von N-Phosphonomethyliminodiessigsäure |
BR112015000995B1 (pt) | 2012-07-17 | 2020-04-28 | Monsanto Technology Llc | método para a síntese de n-(fosfonometil)glicina ou um de seus derivados selecionados a partir do grupo que consiste em seus sais, seus ésteres de fosfonato e seus sais de éster de fosfonato |
US10364262B2 (en) | 2012-07-17 | 2019-07-30 | Monsanto Technology Llc | Method for the synthesis of N-phosphonomethyliminodiacetic acid |
BR112015000990B1 (pt) | 2012-07-17 | 2020-04-28 | Monsanto Technology Llc | Método para a síntese de um ácido aminoalquilenofosfônico ouseus ésteres fosfatos |
RU2674022C9 (ru) | 2012-07-17 | 2019-01-24 | МОНСАНТО ТЕКНОЛОДЖИ ЭлЭлСи | Способ синтеза альфа-аминоалкиленфосфоновой кислоты |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE251806C (zh) * | 1900-01-01 | |||
HU177486B (en) * | 1978-04-11 | 1981-10-28 | Nitrokemia Ipartelepek | Process for preparing phosphonic acid derivatives |
US4724103A (en) * | 1984-02-27 | 1988-02-09 | Monsanto Company | Process for preparing N,N-diacetic acid aminomethylenephosphonic acid |
-
1988
- 1988-02-08 HU HU88561A patent/HU205944B/hu not_active IP Right Cessation
-
1989
- 1989-01-24 NZ NZ227702A patent/NZ227702A/xx unknown
- 1989-01-27 DK DK039689A patent/DK39689A/da not_active Application Discontinuation
- 1989-01-27 AU AU28860/89A patent/AU2886089A/en not_active Abandoned
- 1989-01-27 GB GB8901807A patent/GB2215721B/en not_active Expired - Fee Related
- 1989-01-31 PT PT89577A patent/PT89577B/pt active IP Right Grant
- 1989-02-01 FR FR898901267A patent/FR2626884B1/fr not_active Expired - Fee Related
- 1989-02-03 BE BE8900120A patent/BE1002135A5/fr not_active IP Right Cessation
- 1989-02-03 BR BR898900622A patent/BR8900622A/pt unknown
- 1989-02-03 CN CN89100721.0A patent/CN1035294A/zh active Pending
- 1989-02-06 GR GR890100071A patent/GR890100071A/el unknown
- 1989-02-06 NL NL8900279A patent/NL8900279A/nl not_active Application Discontinuation
- 1989-02-07 JP JP1028530A patent/JPH01228995A/ja active Pending
- 1989-02-07 IT IT8919339A patent/IT1228299B/it active
- 1989-02-07 PL PL27761189A patent/PL277611A1/xx unknown
- 1989-02-07 ES ES8900422A patent/ES2010126A6/es not_active Expired
- 1989-02-08 CS CS89842A patent/CS272248B2/cs unknown
- 1989-02-08 DE DE3903716A patent/DE3903716A1/de not_active Withdrawn
Also Published As
Publication number | Publication date |
---|---|
FR2626884B1 (fr) | 1991-11-08 |
ES2010126A6 (es) | 1989-10-16 |
NL8900279A (nl) | 1989-09-01 |
IT1228299B (it) | 1991-06-07 |
GR890100071A (el) | 1994-03-31 |
FR2626884A1 (fr) | 1989-08-11 |
PT89577B (pt) | 1994-01-31 |
DE3903716A1 (de) | 1989-08-17 |
DK39689A (da) | 1989-08-09 |
NZ227702A (en) | 1990-10-26 |
PT89577A (pt) | 1989-10-04 |
CS272248B2 (en) | 1991-01-15 |
GB8901807D0 (en) | 1989-03-15 |
DK39689D0 (da) | 1989-01-27 |
CS84289A2 (en) | 1990-03-14 |
BR8900622A (pt) | 1989-10-10 |
IT8919339A0 (it) | 1989-02-07 |
HUT49359A (en) | 1989-09-28 |
PL277611A1 (en) | 1989-09-18 |
GB2215721B (en) | 1991-06-26 |
AU2886089A (en) | 1989-08-10 |
JPH01228995A (ja) | 1989-09-12 |
HU205944B (en) | 1992-07-28 |
BE1002135A5 (fr) | 1990-07-24 |
GB2215721A (en) | 1989-09-27 |
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