CN1040362A - N-磺甲基甘氨酸酯、其制备方法和在制备草甘膦型除草剂中的用途 - Google Patents
N-磺甲基甘氨酸酯、其制备方法和在制备草甘膦型除草剂中的用途 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
- C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C309/13—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton
- C07C309/14—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton containing amino groups bound to the carbon skeleton
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- 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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Abstract
本发明涉及下式的N—磺甲基甘氨酸酯:
HO3S—CH2—NH—CH2—COOR1(I)其中COOR1为可水解的羧酸酯基团。它也涉及式(I)化合物的制备方法,包括使二氧化硫、甲醛和有R1OH醇存在时与甘氨酸或与甘氨酯酯进行接触。它也涉及式(I)化合物在草甘膦型除草剂制备中的用途,它通过将式(I)化合物与式(R2O)2P(O)H的亚磷酸酯或膦酸酯反应,其中(R2O)2P为可水解的膦酸酯基团,然后再进行后续的水解反应来实现该用途。
Description
本发明涉及N-磺甲基甘氨酸酯化合物,这些化合物的制备方法以及这些化合物在草甘膦型除草剂的制备中的用途。
草甘膦(N-膦酰基甲基甘氨酸)及其盐类是广谱的除草剂,这在该技术领域中是公知的。例如,在下列专利:美国专利US3,779,758;US3,835,000;US3,868,407;US3,950,402;US4,083,893;US4,147,719和欧洲专利EP-A-0,019,384中,都阐述了这些除草剂及其制备方法。另外,从美国专利4,069,048中可了解到化合物N-磺甲基甘氨酸。
本发明的目的在于提供一种方法来得到草甘膦型除草剂,它具有许多优点:经济实惠、有限的工序数、优良的得率和易于发展成工业生产规模。
首先本发明涉及一种下式的N-磺甲基甘氨酸酯:
在式中:
COOR1为可水解的羧酸酯基团。
可水解的基团在该技术领域中是公知的。在本发明的范围里,可水解的COOR1基团意指在水存在下,任意地在酸介质或碱介质中,可被分解给出相应的-COOH酸和R1OH醇的所有基团。
可水解的COOR1基意指一个R1基特别是从下列基团中选择出来的基团:
C1-C18(较好地为C1-C12)的直链或支链烷基,
C2-C18(较好地为C2-C12)的直链或支链烯基,
C2-C18(较好地为C2-C12)的直链或支链炔基,
C3-C18(较好地为C3-C12)的直链或支链环烷基,
C6-C14(较好地为C6-C10)的直链或支链芳基,
C7-C15(较好地为C7-C11)的直链或支链芳烷基,
这些基团可任意地被一个或多个的卤(素)原子或者C1-C6烷氧基或硫代烷基所取代,另外,芳基或芳烷基能包含1至4个选自氧原子、硫原子和氮原子的杂原子(例如,呋喃基、苯硫基或者吡啶基)。
更为优先地,R1选自C1-C6烷基或C6-C10芳基或C7-C11芳烷基,所说的基团可任意地被一个或多个卤(素)原子或者C1-C6烷氧基所取代。
在本说明书中,化合物的化学式用非离子形式表示。不过对于熟悉该技术领域的人仍然是清楚的,即相对于氨基酸,例如式(Ⅰ)的化合物,这些可呈两性离子形式存在。
制备方法
一种制备方法包括使甲醛、二氧化硫和式为H2N-CH2-COOR1的甘氨酸酯进行接触。
较好地用下列摩尔配比进行此反应:
甘氨酸酯 1摩尔
二氧化硫 0.95摩尔至饱和
甲醛 0.95摩尔至3摩尔
但较好地要超过甘氨酸酯的摩尔配比(1.5至2.5摩尔)
通常在0和100℃之间,较好地在10℃和90℃之间,通过简单的混合来进行此反应。
所采用的甲醛呈一种或另一种易得到的形式。根据最通常的形式,可采用在1%和饱和之间(较好为30%至40%)浓度的水溶液。
反应可在惰性溶剂存在下进行;有时因为反应介质通常含水,特别是使用了甲醛水溶液后,这类溶剂就无用了。
在甲醛采用非水形式场合下,可用大量的单一溶剂或混合溶剂。
在非质子传递溶剂中,可提及诸如正戊烷、异戊烷、2-甲基己烷和2,2,5-三甲基己烷等饱和脂族烃类;诸如苯、甲苯、二甲苯和乙基苯等芳族烃类;诸如四氢呋喃和异戊醚等饱和脂族醚类;诸如苄基乙基醚的芳族醚类;诸如甲乙酮、甲基异丁基酮和苯乙酮等饱和脂族酮类或芳族酮类;诸如氟代苯、1-氯代-2-甲基丙烷和异丁基氯等饱和脂族卤代烃类或芳族卤代烃类;以及诸如异丁酸异丁酯、乙酸乙酯和苯甲酸甲酯等饱和脂族酯类或芳族酯类。所有这些溶剂可单独存在或以混合形式存在。
在质子传递溶剂中,可提及诸如甲醇、乙醇、异丙醇和苯酚等饱和脂族醇类或芳族醇类,以及诸如乙酸和苯甲酸等饱和脂族酸类或芳族酸类。
另一个具有明显有利性和出乎意料的制备方法包括将甲醛、二氧化硫、式R1OH的醇和式H2N-CH2-COOH的甘氨酸进行反应。
较好地用下列摩尔配比进行此反应:
甘氯酸 1摩尔
二氧化硫 0.95摩尔至饱和
甲醛 0.95至3摩尔
但较好地要超过甘氨酸酯的配比(1.5至2.5摩尔)
R1OH 大于0.95摩尔
但较好地要超过甘氨酸的配比(大于1.2摩尔),较理想地为大于1.5摩尔,而大于1.8摩尔非常有利。
根据本发明的有利形式,R1OH醇可用作溶剂,上述的其它质子传递溶剂可随意地用作助溶剂。较好地,可选乙醇作溶剂。
此外,采用上述相同的条件进行此反应。
既然后者的方法导致N-磺甲基甘氨酸酯具有实际上定量的得率,所以它尤为优选,而且完全出乎意料。
本发明的目的也为提供在已知的草甘膦型除草剂的制备中式(Ⅰ)化合物的用途,其用途包括使式(Ⅰ)化合物与下式的亚磷酸酯进行接触:
对于熟悉该技术领域的人员,这些可水解基团是公知的。可水解的(R2O)2P(O)基团意指在水作用下,随意地在酸介质或碱介质中,被分解成醇R2OH和酸(O)P(OH)2的基团。
可水解的(R2O)2P(O)基团意指一个基团其中的R2基团特别是从下列基团中选择出来:
C1-C18(较好地为C1-C12)的直链或支链烷基,
C2-C18(较好地为C2-C12)的直链或支链烯基,
C2-C18(较好地为C2-C12)的直链或支链炔基,
C3-C18(较好地为C3-C12)的直链或支链环烷基,
C6-C14(较好地为C6-C10)的直链或支链芳基,
C7-C15(较好地为C7-C11)的直链或支链芳烷基,
这些基团可随意地被一个或多个卤(素)原子或者C1-C6烷氧基或者硫代烷基基团所取代,另外,芳基或芳烷基能包含1-4个选自氧原子、硫原子和氮原子的杂原子(例如呋喃基、吡啶基和苯硫基)
更为优选地,R2为选自C1-C6烷基或C6-C10芳基或C7-C11芳烷基,所说的基团能任意地被一个或多个卤(素)原子或者C1-C6烷氧基所取代。
在体相或惰性溶剂中进行此反应。
在非质子传递溶剂中,可提及诸如正戊烷、异戊烷、2-甲基己烷和2,2,5-三甲基己烷等饱和脂族烃类;诸如苯、甲苯、二甲苯和乙苯等芳族烃类;诸如四氢呋喃和异戊醚等饱和脂族醚类;诸如苄基乙基醚的芳族醚类;诸如甲乙酮、甲基异丁基酮和苯乙酮等饱和脂族酮类和芳族酮类;诸如氟代苯、1-氯代-2-甲基丙烷和异丁基氯等饱和脂族卤代烃类或芳族卤代烃类,以及诸如异丁酸异丁酯、乙酸乙酯和苯甲酸甲酯等饱和脂族酯类或芳族酯类。所有这些溶剂可单独存在或以其混合物形式存在。
在质子传递溶剂中,可提及诸如甲醇、异丙醇和苯酸等饱和脂族醇类或芳族醇类,以及诸如乙酸和苯甲酸的饱和脂族酸类或芳族酸类。
反应温度在50℃和250℃或者溶剂的沸点之间,较好地为100℃至200℃。
虽然一种反应物相对于另一种反应物可以大为过量(3/1至1/3的摩尔比率),但在实践中一种反应物超过20%更为有利,且并不与化学计量学相背离。
下列实施例具体阐述了本发明:
将甘氨酸(7.5克,100毫摩尔),95%乙醇(120立方厘米)和31.5%甲醛水溶液(19克,200毫摩尔)相继地引入一只带有酒精温度计的双颈烧瓶中。所得的悬浮物用SO2饱和直到完全溶解为止(将温度升高至45℃)。在室温下搅拌1小时30分钟后,开始出现沉淀物。继续搅拌3小时。将沉淀物过滤并用乙醇(30立方厘米)洗涤,然后用醚(30立方厘米)洗涤。干燥后得到纯度大于95%(用NMR在360兆赫处测定)的磺甲基甘氨酸乙酯(18.8克)对于起始的甘氨酸来说,其得率为95.5%。
熔点(Koffer)=154℃
将磺甲基甘氨酸乙酯(2.46克,12.5毫摩尔)、二甲苯(20立方厘米)以及亚磷酸二异丙酯(2.07克;12.5毫摩尔)相继引入带有温度计和冷凝器的双颈烧瓶中。在105℃下将悬浮液加热1小时,在由水喷射泵提供的真空蒸去溶剂,可回收得一种橙色油(3.81克),经滴定显示含有40%的被护草甘膦。
Claims (12)
1、一种N-磺甲基甘氨酸酯化合物,其特征在于它具有下式
其中COOR1为可水解的羧酸酯基团。
2、根据权利要求1所述的N-磺甲基甘氨酸酯,其特征在于其中COOR1基团是这样的,即R1是选自下列基团:
C1-C18(较好为C1-C12)的直链或支链烷基,
C2-C18(较好为C2-C12)的直链或支链烯基,
C2-C18(较好为C2-C12)的直链或支链炔基,
C3-C18(较好为C3-C12)的直链或支链环烷基,
C6-C14(较好为C6-C10)的直链或支链芳基,
C7-C15(较好为C7-C11)的直链或支链芳烷基,
这些基因可任意地被一个或多个卤(素)原子或C1-C6烷氧基或硫代烷基所取代,另外,芳基或芳烷基能含有1至4个选自氧原子,硫原子和氮原子的杂原子。
3、根据权利要求2所述的N-磺甲基甘氨酸酯,其特征在于其中COOR1基团是这样的,即R1是选自C1-C6烷基或C6-C10苯基或C7-C11芳烷基,所说的基团可任意地被一个或多个卤(素)原子或者C1-C6烷氧基或C1-C6硫代烷基所取代。
4、根据权利要求1、2或3所述的N-磺甲基甘氨酸酯的制备方法,其特征在于使甲醛、二氧化硫和下式的甘氨酸酯进行接触,
其中COOR1的含义如同权利要求1所述。
5、根据权利要求4所述的N-磺甲基甘氨酸酯的制备方法,其特征在于其中化合物是以下列摩尔配比进行接触:
甘氨酸酯 1摩尔
二氧化硫 0.95摩尔至饱和
甲醛 0.95摩尔至3摩尔
6、权利要求1、2或3所述的N-磺甲基甘氨酸酯的制备方法,其特征在于将使甲醛、二氧化硫、式R1OH的醇和甘氨酸进行接触。
7、根据权利要求6所述的N-磺甲基甘氨酸酯的制备方法,其特征在于其中化合物是以下列摩尔配比进行接触:
甘氨酸 1摩尔
二氧化硫 0.95摩尔至饱和
甲醛 0.95摩尔至3摩尔
R1OH 大于0.95摩尔
8、根据权利要求7所述的N-磺甲基甘氨酸酯的制备方法,其特征在于其中R1OH的摩尔配比大于1.2摩尔,R1OH被用作为溶剂是优选的。
9、根据权利要求4或6所述的N-磺甲基甘氨酸酯的制备方法,其特征在于其中反应是在0℃和100℃之间,在任意的惰性溶剂(或助溶剂)中进行。
10、根据权利要求1、2或3所述的式(Ⅰ)N-磺甲基甘氨酸酯在草甘膦型除草剂制备中的用途,其特征在于使式(Ⅰ)的N-磺甲基甘氨酸酯与下式的膦酸酯或亚磷酸酯进行接触,以便得到式(Ⅲ)的化合物
(R2O)2P为可水解的膦酸酯基团,
然后该化合物能任意地用已知方法进行水解。
11、根据权利要求10所述的用途,其特征在于其中R2选自下列基团:
C1-C18(较好为C1-C12)的直链或支链烷基,
C2-C18(较好为C2-C12)的直链或支链烯基,
C2-C18(较好为C2-C12)的直链或支链炔基,
C3-C18(较好为C3-C12)的直链或支链环烷基,
C6-C14(较好为C6-C10)的直链或支链芳基,
C7-C15(较好为C7-C11)的直链或支链芳烷基,
这些基团可任意地被一个或多个卤(素)原子或者C1-C6烷氧基或硫代烷基所取代,另外,芳基或芳烷基能包含1至4个选自氧原子、硫原子和氮原子的杂原子。
12、根据权利要求10所述的用途,其特征在于其中(Ⅰ)∶(Ⅱ)的摩尔配比在1/3和3之间,而有利地是采用0.8和1.2之间。
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CN92102843A Pending CN1064868A (zh) | 1988-08-18 | 1992-04-17 | N-磺甲基甘氨酸酯在制备草甘膦型除草剂的用途 |
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