CN1037516A - 制备n-膦酰基甲基甘氨酸的方法 - Google Patents
制备n-膦酰基甲基甘氨酸的方法 Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 11
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 10
- 125000001188 haloalkyl group Chemical group 0.000 claims abstract description 4
- -1 oxoethanoic acid alkyl ester hemiacetal Chemical class 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 239000011541 reaction mixture Substances 0.000 claims description 4
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 3
- 229920002866 paraformaldehyde Polymers 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 2
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
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- 238000002360 preparation method Methods 0.000 description 7
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 5
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- MGRVRXRGTBOSHW-UHFFFAOYSA-N (aminomethyl)phosphonic acid Chemical compound NCP(O)(O)=O MGRVRXRGTBOSHW-UHFFFAOYSA-N 0.000 description 4
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
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- 235000011054 acetic acid Nutrition 0.000 description 2
- 150000001243 acetic acids Chemical class 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000004705 aldimines Chemical class 0.000 description 2
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
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- 125000004185 ester group Chemical group 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
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- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
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- 238000004519 manufacturing process Methods 0.000 description 2
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- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BSCCSDNZEIHXOK-UHFFFAOYSA-N phenyl carbamate Chemical compound NC(=O)OC1=CC=CC=C1 BSCCSDNZEIHXOK-UHFFFAOYSA-N 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
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- 150000003839 salts Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 235000013311 vegetables Nutrition 0.000 description 2
- 239000001605 (5-methyl-2-propan-2-ylcyclohexyl) acetate Substances 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- GFMYEVPBEJFZHH-UHFFFAOYSA-N CP(O)(O)O Chemical compound CP(O)(O)O GFMYEVPBEJFZHH-UHFFFAOYSA-N 0.000 description 1
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- XHXUANMFYXWVNG-ADEWGFFLSA-N Menthyl acetate Natural products CC(C)[C@@H]1CC[C@@H](C)C[C@H]1OC(C)=O XHXUANMFYXWVNG-ADEWGFFLSA-N 0.000 description 1
- XYUPSBLFPTWJLC-GSVOUGTGSA-N N-(carboxymethyl)-D-alanine Chemical compound OC(=O)[C@@H](C)NCC(O)=O XYUPSBLFPTWJLC-GSVOUGTGSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 125000004442 acylamino group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000001371 alpha-amino acids Chemical class 0.000 description 1
- 235000008206 alpha-amino acids Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000004965 chloroalkyl group Chemical group 0.000 description 1
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 description 1
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- 238000001816 cooling Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- NTNZTEQNFHNYBC-UHFFFAOYSA-N ethyl 2-aminoacetate Chemical compound CCOC(=O)CN NTNZTEQNFHNYBC-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002333 glycines Chemical class 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002373 hemiacetals Chemical class 0.000 description 1
- 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 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000004715 keto acids Chemical class 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- UFEJKYYYVXYMMS-UHFFFAOYSA-N methylcarbamic acid Chemical compound CNC(O)=O UFEJKYYYVXYMMS-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 150000003142 primary aromatic amines Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 108700022952 strombine Proteins 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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)]
- C07F9/44—Amides thereof
-
- 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
- C07F9/3813—N-Phosphonomethylglycine; Salts or complexes thereof
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Abstract
制备N-膦酰基甲基甘氨酸的方法,包括在反应
条件下,将乙醛酸或其衍生物与如下式之N-酰基氨
基甲基膦酸反应,
式中R选自具1-6个碳原子的烷基,具有1-6
个碳原子的卤代烷基,苯甲基和苯基。
Description
本发明涉及制备N-膦酰基甲基甘氨酸的方法,更具体地说是涉及N-膦酰基甲基甘氨酸的改进的制备方法,其中将N-酰基氨基甲基膦酸与乙醛酸或其衍生物反应,而无需分离N-酰基甲基膦酸或相关的中间产物。
N-膦酰基甲基甘氨酸是一种高效的,市售的重要的植物毒剂,它应用于控制萌发种子,出芽种子,成熟和成长树木,草木植物和水生植物等的生长。N-膦酰基甲基甘氨酸的盐类可方便地制成水剂,而用作广谱植物的芽后植物毒剂或除草剂。
加拿大专利1,039,739号(Gaertner)中描述了一种制备N-膦酰基甲基甘氨酸的方法,其中将氨基甲基膦酸或其酯类与乙醛酸衍生物反应,以生成羰基醛亚胺甲基磷酸酯。然后,将羰基醛亚胺甲基磷酸酯经催化氢化生成N-膦酰基甲基甘氨酸或其酯类。酯基团可以经过水解而生成N-膦酰基甲基甘氨酸。
美国专利3,799,758(Franz)中,描述了N-膦酰基甲基甘氨酸的一种制备方法,其中将甘氨酸乙酯、甲醛和亚磷酸二乙酯反应,然后进行水解。在Franz描述的另一种制法中,包括在氢氧化钠存在下,用氯代甲基次膦酸将甘氨酸进行膦甲基化,并且将N-膦基甲基甘氨酸用氯化汞氧化。
美国专利4,369,142(Moser)中,叙述了一种制备N-膦酰基甲基甘氨酸的方法,其中在二氧化硫催化剂存在下,使氨基甲基膦酸在一含水介质中与乙二醛反应。
在H.Yanagawa等人所著“Noval Formation of α-Amino Acidsand Their Derivatives form Oxo Acids and Ammomia in an Aqueous Medium”[J.Biochem,91,2087-2090(1982)]中,披露了应用乙醛酸与氨、甲胺和硫酸铵反应以制取甘氨酸和/或其衍生物。其中2088页表Ⅰ中,说明了在27℃和105℃,pH为4和8时,各种氨基酸的合成。另外在2088页左下栏底至右上栏上部,叙述了在酸性pH和低温条件比碱性pH和高温条件,对甘氨酸的生成更为有利。
在J.Kihlberg所著“Synthesis of strombine.A New Method for Monocarboxymethylation of Primary Amines”,[Acta Chemica Scandinavica B 37,911-916(1983)]中,描述了二个当量的乙醛酸和脂族和芳香族伯胺的反应,该反应先经相应的亚胺衍生物的形成。在914页表Ⅰ中,描述了在25-70℃温度下,各种胺起始原料与2个当量的乙醛酸的反应,生成相应的N-甲酰基-N-羧基-甲基胺,并易于使之水解成N-羧基甲基胺。
美国专利4,670,191(Kleiner)中,公开了一种制备N-膦酰基甲基甘氨酸的方法,其中在10-100℃温度下,使氨基甲基膦酸与2个摩尔当量的乙醛酸反应。
由以上所述各已知技术,不论是单独或结合起来应用,虽然可制得产率令人满意的N-膦酰基甲基甘氨酸,但各种已知方法或多或少都有其缺点。现在可以提供一种直接生产N-膦酰基甲基甘氨酸或其衍生物的方法,它可应用便宜的原料,以低成本和简便生产过程生产出高产率产品,并且无需分离中间产物。
上述的或其他的各种优点可通过下述N-膦酰基甲甘氨酸的制备方法来实现,即在反应条件下,使乙醛酸和如下式所示的N-酰基氨基甲基膦酸反应,
式中R选自具1-6个碳原子的烷基,具1-6个碳原子的卤代烷基,苯甲基和苯基。
所述的烷基是指直链或带支链的基团,如甲基,乙基,异丙基,环丙基,环己基,叔丁基,异丁基,正丁基和各种形式的苯基,己基等。各种具6个以上碳原子的烷基可应用于本发明方法,但似乎并无特别优点,优选用甲基。
所述卤代烷基包括所有上述各种烷基且已被一个或多个卤原子取代的基团,所述卤素例如氯、溴和碘。优选用氯代烷基。
所述苯甲基和苯基之含义为本专业技术人员所熟知,且该苯甲基和苯基可以是被取代的或未被取代的。典型的取代基包括硝基,甲基或卤素如氯,但使用较廉价的未取代的苯基可取得满意的效果。
所述乙醛酸也可包括水合的,半缩醛或其乙缩醛衍生物,或是乙醛酸的酯类,其中适宜的酯基团可以如上述具1-6个碳原子的烷基。其应用效果皆良好。
本方法适用的N-酰基氨基甲基膦酸是已知的。与“Synthesis”(1978年6月,479和480页)的报导有所不同的是,已经发现简单的烷基和芳基胺可以和三氯化磷和甲醛反应,使其进行膦酰甲基化且可取得高产率,在本发明方法第一步骤中,优选使用上述过程。
乙醛酸和N-酰基氨基甲基膦酸的摩尔比可影响N-膦酰基甲基甘氨酸的产率。为取得定量产率,优选用1摩尔的N-酰基氨基甲基膦酸和2摩尔(或更多)的乙醛酸。可用少于1∶2的摩尔比,但N-膦酰基甲基甘氨酸产率则降低。
本发明方法包括,在水中或含水介质中将N-酰基氨基甲基膦酸与乙醛酸加热,在同一反应器进行水解/还原烷基化并生成N-膦酰基甲基甘氨酸。可选用经纯化的N-酰基氨基甲基膦酸;或粗制的、由膦酰甲基化反应中经除油的N-酰基氨基甲基膦酸,皆可得到良好效果。应用粗制的,未经分离的N-酰基氨基甲基膦酸可避免昂贵的分离步骤,提高整个过程产率,减少废料,而这些正是我们所希望达到的效果。
反应温度可在较大范围内变化。虽然可在室温下反应,但反应缓慢。优选温度至少是50℃,最好是至少70℃。在同一反应器内进行水解/还原烷基化过程时,最高限温度仅取决于N-酰基氨基甲基膦酸的水解稳定性。因而,反应可在回流温度(约110℃)或在加压下在150℃温度下进行。当应用N-苯甲酰基氨基甲基膦酸,乙醛酸和含水盐酸时,从制备观点考虑,优选温度为135-140℃。
下列各实施例可进一步说明本发明方法,但非限定本发明方法。
实施例1
由乙酰胺制备N-膦酰基甲基甘氨酸。
在50毫升烧瓶中加入乙酰胺(1.48克,0.025摩尔),多聚甲醛(0.79克,0.0265摩尔)和7毫升冰乙酸。加热混合物使成溶液(约100℃),然后冷至室温。一次加入三氯化磷(4.11克,0.03摩尔),温度升至40℃。将溶液加热至107℃经3小时,然后在55℃下蒸干成油状物。
生成的油状物在25毫升水中用5.10克(0.55摩尔)的一水合乙醛酸处理。溶液回流过夜,溶液经高效液相色谱分析,可知含N-膦酰基甲基甘氨酸(产率69.9%),和N-甲酰基-N-膦酰基甲基甘氨酸(产率7.72%)。
实施例2
用乙醛酸甲基酯甲基半缩醛作为还原剂,由乙酰胺制备N-膦酰基甲基甘氨酸。
按实施例1所述方法将乙酰胺(2.96克,0.05摩尔)进行膦酰甲基化。加热至107℃经3小时后,加入2-羟基-2-甲氧基乙酸甲酯和5毫升水,反应溶液蒸干至成粘稠油状物,该油状物用50毫升浓盐酸处理,并加热回流过夜。
反应混合物经离子交换纯化,可得6.2克N-膦酰基甲基甘氨酸,按乙酰胺用量计,产率为73.4%。
实施例3
由苯甲酰胺制备N-膦酰基甲基甘氨酸
在100毫升烧瓶中加入苯甲酰胺(3.02克,0.025摩尔),多聚甲醛(0.79克,0.0265摩尔)和20毫升冰乙酸。加热混合物至成溶液(约100℃),在冰浴中冷却至10℃。保持温度低于30℃,滴加三氯化磷(3.6克,0.0265摩尔)。经1小时将溶液加热至120℃,并在120℃保持2小时。加热后,在降压下将溶液蒸干,以除去乙酸,以得到N-苯甲酰基氨基甲基膦酸(呈油状物)。
用乙醛酸单水合物(4.85克,0.053摩尔)和25毫升盐酸处理该油状物,回流加热8小时。经高效液相色谱分析生成溶液,结果可知含82.4%N-膦酰基甲基甘氨酸(按苯甲酰用量计)。
实施例4
应用高温度/压力还原烷基化,由苯甲酰胺制备
按实施例3所示方法,将苯甲酰胺(6.1克,0.05摩尔)进行膦酰甲基化。将乙酸蒸出后,将油状物转移到250毫升配置压力计和释压阀的Fisher-Porter瓶中。在30毫升浓盐酸(含水)中,油状物用乙醛酸单水合物(10.4克,0.11摩尔)来处理。将混合物用氮气加压至2.07×105牛顿/米2(30磅/英寸2),并在油浴中使油温升至130-138℃进行加热。定时释压使器内压力保持于2.90×105至3.58×105牛顿/米(42-52磅/英寸2)。3.5小时后,停止放气,并使反应冷却。
反应混合物经高效液相色谱分析,可知含N-膦酰基甲基甘氨酸(产率82.5%)和N-甲酰基-N-膦酰基甲基甘氨酸(产率4.5%)(以苯甲酰用量计)。
实施例5
由氨基甲酸苯酯制备N-膦酰基甲基甘氨酸
在50毫升烧瓶中加入氨基甲酸苯酯(3.53克),甲醛(0.79克)和乙酸(20毫升)。混合物加热至85℃,然后在冰浴中冷却至15℃。一次加入三氯化磷(4.11克),经1小时将溶液加热至107℃。在107℃加热2.5小时并在室温下搅拌过夜后,将溶液洗脱至油中。
将油状物在25毫升水中与乙醛酸单水合物一起加热回流12小时。反应温合物经高效液相色谱分析,可知含N-膦酰基甲基甘氨酸(产率21.6%),N,N-亚氨基甲基膦酸(产率15.9%),亚氨基二乙酸(产率25.9%)。
实施例6
由N-氯代乙酰基氨基甲基膦酸制备N-膦酰基甲基甘氨酸
在500毫升烧瓶中加入N-氯代乙酰基氨基甲基膦酸(0.2克,0.001摩尔),乙醛酸(0.22克,0.002摩尔)和2毫升水。反应混合物回流加热12小时。经高效液相色谱分析制得溶液中可知含N-膦酰基甲基甘氨酸(产率76.8%),N-甲酰基-N-膦酰基甲基甘氨酸(产率5.6%)和氨基甲基膦酸(产率3.5%)。
虽然经详述各特别实施例来说明本发明方法,但应指出它们仅用于说明。对本专业技术人员来说,经参照本说明书则另外的实施例和操作技术应是显而易见的。例如当盐酸存在时,N-酰基氨基甲基膦酸与乙醛酸作用时,酰基取代基转化成相应的羧酸,可将之回收,而用于制备本发明方法中的酰胺原料。另一个例子是,乙醛酸的其它衍生物如除了烷基酯类之外,也可应用于本发明方法。因此,在不脱离本发明所述实质范围内,可进行各种修正。
Claims (16)
1、制备N-膦酰基甲基甘氨酸的方法,其中包括在反应条件下,使乙醛酸或其衍生物和如下式之N-酰基氨基甲基膦酸反应,
式中R选自具1-6个碳原子的烷基,具有1-6个碳原子的卤代烷基,苯甲基和苯基。
2、按权利要求1的方法,其中乙醛酸与N-酰基氨基甲基膦酸之摩尔比至少是2∶1。
3、按权利要求1的方法,其中使N-酰基氨基甲基膦酸鸵胰┧峄蚱溲苌锓从Γ⒓尤戎廖露任?0-180℃。
4、按权利要求3的方法,其中温度在70-150℃之间。
5、按权利要求1的方法,其中R是烷基。
6、按权利要求5的方法,其中R是甲基。
7、按权利要求1的方法,其中R是苯基。
9、按权利要求8的方法,其中无机酸是盐酸或硫酸。
10、按权利要求8的方法,其中R是苯基。
11、按权利要求10的方法,其中无机酸是盐酸。
12、按权利要求8的方法,其中R是甲基。
13、按权利要求12的方法,其中用不含无机酸的水。
14、按权利要求8的方法,其中乙醛酸衍生物是乙醛酸烷基酯,而其中烷基含1-6个碳原子。
15、按权利要求8的方法,其中乙醛酸衍生物是乙醛酸烷基酯半缩醛,而其中烷基具1-6个碳原子。
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US07/188,930 US4851159A (en) | 1988-05-02 | 1988-05-02 | Process for the preparation of N- phosphonomethylglycine |
US188,930 | 1988-05-02 |
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CN1037516A true CN1037516A (zh) | 1989-11-29 |
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EP (1) | EP0341233B1 (zh) |
JP (1) | JPH068304B2 (zh) |
KR (1) | KR910009821B1 (zh) |
CN (1) | CN1022247C (zh) |
AR (1) | AR248029A1 (zh) |
AT (1) | ATE120199T1 (zh) |
AU (1) | AU606516B2 (zh) |
BR (1) | BR8902030A (zh) |
CA (1) | CA1339749C (zh) |
DE (1) | DE68921787T2 (zh) |
ES (1) | ES2013216T3 (zh) |
HK (1) | HK1007149A1 (zh) |
HU (1) | HUT50189A (zh) |
IE (1) | IE67349B1 (zh) |
IL (1) | IL90099A0 (zh) |
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US5041627A (en) * | 1988-11-25 | 1991-08-20 | Monsanto Company | Preparation of N-acyl-aminomethylphosphonates |
HU203360B (en) * | 1988-11-25 | 1991-07-29 | Monsanto Co | Process for producing n-acylamino methylphosphonates |
IE883838L (en) * | 1988-12-22 | 1990-06-22 | Barclay Intellectual Propertie | N-phosphonomethylglycine |
TW263511B (zh) * | 1990-10-10 | 1995-11-21 | Hoechst Ag | |
US5262314A (en) * | 1991-09-06 | 1993-11-16 | E. I. Du Pont De Nemours And Company | Enzymatic oxidation of glycolic acid in the presence of non-enzymatic catalyst for decomposing hydrogen peroxide |
US5180846A (en) * | 1991-11-06 | 1993-01-19 | E. I. Du Pont De Nemours & Company | Hydrogenation of enzymatically-produced glycolic acid/aminomethylphosphonic acid mixtures |
US5834262A (en) * | 1992-01-06 | 1998-11-10 | E. I. Du Pont De Nemours And Company | Oxidation of glycolic acid to glyoxylic acid using a microbial cell transformant as catalyst |
US5233080A (en) * | 1992-09-25 | 1993-08-03 | E. I. Du Pont De Nemours And Company | Preparation of N-acylaminomethylphosphonic acids and aminomethylphosphonic acids |
US5429674A (en) * | 1994-09-12 | 1995-07-04 | Ppg Industries, Inc. | N-acyl aminomethylene phosphonates and their use in waterborne coating compositions |
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US3779758A (en) * | 1969-03-25 | 1973-12-18 | Photocircuits Corp | Photosensitive process for producing printed circuits employing electroless deposition |
IL48619A (en) * | 1974-12-11 | 1978-04-30 | Monsanto Co | Process for the production of n-(phosphonomethyl)-glycine compounds |
US4369142A (en) * | 1981-12-03 | 1983-01-18 | Ciba-Geigy Corporation | Process for producing N-phosphonomethylglycine |
US4568432A (en) * | 1984-12-28 | 1986-02-04 | Monsanto Company | Process for preparing glyphosate and glyphosate derivatives |
DE3532344A1 (de) * | 1985-09-11 | 1987-03-19 | Hoechst Ag | Verfahren zur herstellung von n-phosphonomethylglycin |
US4684483A (en) * | 1985-09-23 | 1987-08-04 | Monsanto Company | Preparation of N-substituted amino acids |
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1988
- 1988-05-02 US US07/188,930 patent/US4851159A/en not_active Expired - Lifetime
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EP0341233A2 (en) | 1989-11-08 |
IL90099A0 (en) | 1989-12-15 |
ES2013216A4 (es) | 1990-05-01 |
US4851159A (en) | 1989-07-25 |
ZA893203B (en) | 1990-07-25 |
KR910009821B1 (ko) | 1991-11-30 |
NZ228929A (en) | 1990-10-26 |
EP0341233B1 (en) | 1995-03-22 |
HK1007149A1 (en) | 1999-04-01 |
MX165448B (es) | 1992-11-11 |
AU3377989A (en) | 1989-11-02 |
AU606516B2 (en) | 1991-02-07 |
KR890017264A (ko) | 1989-12-15 |
ATE120199T1 (de) | 1995-04-15 |
AR248029A1 (es) | 1995-05-31 |
CA1339749C (en) | 1998-03-17 |
MY104009A (en) | 1993-10-30 |
DE68921787D1 (de) | 1995-04-27 |
CN1022247C (zh) | 1993-09-29 |
JPH068304B2 (ja) | 1994-02-02 |
DE68921787T2 (de) | 1995-09-21 |
ES2013216T3 (es) | 1995-05-16 |
BR8902030A (pt) | 1989-12-05 |
EP0341233A3 (en) | 1990-06-20 |
JPH01313487A (ja) | 1989-12-18 |
HUT50189A (en) | 1989-12-28 |
IE67349B1 (en) | 1996-03-20 |
IE891397L (en) | 1989-11-02 |
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