；1 A7314523 87 經濟部中央標準局頁工消費合作社印製 五、發明説明（/) 本發明是有關製造膦酸基甲基甘胺腈或其鹽類及類 之製法。. N -膦酸基甲基甘胺猜為一已知之化合物，可充作除草萷 。其也可K水解作用轉化成商業上重要的除草萷N -膦酸基 甲基甘胺酸。 N-膦酸基甲基甘胺腈述於如US 4,221,583中。經由N-膦 酸基甲基甘胺腈中間物形成的另一種N -膦酸基甲基甘胺酸 之製法述於U S 3 , 9 2 3 , 8 7 7中，而咸信也經由N -膦酸基甲基 甘胺腈為中間物的另一相關製法述於U S 4，4 1 5 , 5 0 3 : ~ 吾等目前發現，在酸及惰性溶劏存在'下，三烷基亞膦酸 醋膦酸化劑在亞甲基胺基乙睛三-聚體上之作用•可提供一 個改進之製法，此適合商業規模之製造，且可提供N -膦酸 基甲基甘胺腈及其烷基詣鹽型式之良好產率，並僅含極少 的雜質。 依據本發明在此提出N -膦酸基甲基甘胺腈烷基酯酸式鹽 之製法，此方法包括在無水條件下及無水酸及惰性溶劑存 在下，將亞甲基胺基乙腈三聚體與三烷基亞膦酸酯反應， 其中亞甲基胺基乙腈三聚體起始物至少部份可溶，而N -膦 酸基甲基甘胺睛烷基酯酸式Μ之產物實質上不溶，且之後 -回收Ν -膦酸基甲基甘胺腈烷基|旨沈_澱之酸式鹽。 此中所用的亞甲基胺基乙腈三聚體係指流程1所示之式 (I )化合物，此流程1說明本發明之.製法。於流程1中， 於三烷基亞膦酸酯U )中之R基表C、- γ垸基，且較好是 Ci-5烷基，且三烷基亞膦酸詣因此較好是三（Ci-7烷基） ---------批衣------iT------^ (請先Μ讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ 297公釐） sl45〇s^ld'Ql 五、發明説明（> ) 玷膦酸酯或三烷基）亞膦酸醅。 三烷基亞膦酸酯較好是三甲基亞膦酸酯、三乙基亞膝酸 _或三丁基亞膦酸酯。三甲基亞膦酸酯是可買得到的膦酸 化劑，因此其是N -膦酸基甲基甘胺睛商品化製造時將別有 效率之原料。就產品之商業化產製而言，較高碳烷基亞膦 睃酯，如三丁基亞膦酸酯及三戊基亞膦酸酯可提供一些益 處，K下中將詳述。 適用於本發明製法中之無水酸類，及其可形成N -膦酸基 甲基甘胺腈烷基酯不溶性鹽，為精藝者明白的。鹵化^尤 其適用於本製法中。特別是氯化氫為有·效且易得的無水酸 〇 經濟部中央標牟局員工消費合作社印製 (請先閎請背面之注意事項再填寫本頁) 溶劑應該是惰性的，基於其在反應條件下不會顯著地作 用，且特別是溶劑應可穩定地拮抗三垸基亞膦酸酯之作用 。其中亞甲基胺基乙腈三聚體起始物至少部份可溶且N -膦 酸基甲基甘胺腈烷基酯酸式鹽產物霣質上不溶之適合的惰 性溶劑是精藝者熟知的。也要了解，亞甲基胺基乙腈三聚 體起始物應至少部份可溶於惰性溶劑中°此意味亞甲基胺 基乙腈三聚體起始物應充份可溶，即使所有的起始物在膦 酸化反應之初並未溶解，在溶液中應有足量可開始鱗酸化 反應。之後當反應進行時有更多的起始物會溶解，且溶液 中之起始物耗盡直到賁質上所有的起始物於膦酸化反應完 成時已溶解。適合的惰性溶萷實例包括腈類’如乙睛、酯 類如乙酸乙藷、鹵烷類如二氯化乙.輝及二氯甲烷，詷類如 甲基異丁基詷，醚類如二乙醚，或四氫呋喃，及鹵化之芳 本纸張尺度適用中國國家標準（CNS ) A4規格（2丨〇'〆297公董） 〇7 A7 〇7 A7 經濟部中央標準局員工消費合作社印製 '---_B7 一__ 五、發明説明（孑） 埃徑如簞氯苯。乙腈為尤其有效之溶劑，其中亞甲基胺基 &腾三聚體在本發明製法中所用的濃度下通常是可完全可 溶的。 基本上N -膦酸基甲基甘胺腈烷棊酯酸式鹽產物是完全不 '溶於溶劑的；在反應條件下至少部份的H -膦酸基甲基甘胺 睛院基酯酸式鹽產物會沈澱此即已足夠，且因此可回收之 °然而一般而言，N -膦酸基甲基甘胺腈烷基酯酸性鹽在大 ^份有機溶劑中為極低溶解度，且此代表本發明製法特別 有益處。 . . 〜 反應合宜地在環境溫度下進行，然而若必要時可使用較 胃或較低溫度，如由-5〇υ至20 (λ °C之溫度範圍。熱會在反 應過程中產生，因此若必要時可冷卻反懕以維持溫度實質 上在較佳值下，如在環境溫度或略高溫度下。 當W氯化氫氣體為酸時，其可直接通過反應混合物或於 無水溶劑中呈溶液型式加至反應混合物中。 在無水汽及在非氧化條件下，如於乾且非氧化之大氣下 ’進行反應較適合。當氯化氫氣體直接通過反應混合物， 氣體本身可提供必要的乾燥及非氧化大氣。若氯化氫以於 無水溶劑之溶液型式加至反應混合物中，則希望可使用適 — 合的憤性氣體，如無水氮氣來提供乾且非氧化大氣。 較好在此使用實質上化學計量比率之三烷基亞膦酸酯。 酸之比率依所使用之特殊酸而定。.若.使用氫氯酸，較好每 莫耳亞甲基胺基乙腈三聚體可使用3至12莫耳氬氯酸。 本發明製法的持別好處在於，產物Μ實質上純的型式沈 -5 - 本紙張又度適用中國國家標準（CNS ) Α4規格（2〖〇Χ297公釐） -----------装------訂------% (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 或點產不用者藉酸別 甘 酯優解相且再可膦分。基 酸其水解，。氯N-身中甲 膦有之水環應基至本環基 亞中酯性循反戊加其循酸 基法基水再磷或並中再膦 丁製戊與醇化基，其於N-三合或是烷氯丁去-括造 如混1|醇將三之移段包製 ,一基综並與成地一階可出 酯此丁之來如形宜·«.解將提一 酸之腈碳出，中合水，即 膦劑胺高分酯程中之醇面 亞化甘較地酸過^)藷戊方： 基酸基此易膦1)^基或步括 烷膦甲。容亞Ιιίί)*戊醇 一包 三為基醇可基1S劑或丁進法 之，酸戊相垸(r溶基的明方 碳醏膦或機三應應丁步發此 高酸N-醇有的反反腈 I 本， 較膦，丁且多明自胺進據法 用亞地是，更發用甘成根製 使基別別的成本作基形此之 在戊特分混形於餾甲解因酸 三。物相於-蒸基水 胺; 1 A7314523 87 Printed by the Page Consumption Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (/) The present invention relates to a method for manufacturing phosphonic acid methylglycinnitrile or its salts and the like. . N-phosphonomethylglycine is a known compound that can be used as a herbicide. It can also be converted into commercially important herbicide N-phosphonomethylglycine by hydrolysis of K. N-phosphonomethylglycinil is described in, for example, US 4,221,583. Another method for preparing N-phosphonomethylglycine through intermediates of N-phosphonomethylglycinil is described in US 3, 9 2 3, 8 7 7, and Xianxin also uses N-phosphine Another related method of making acid methylglycinil as an intermediate is described in US 4, 4 1 5, 5 0 3: ~ We have found that in the presence of acids and inert solvents, trialkylphosphinic acid The role of acetic acid phosphonate acidifier on the methyleneamino acetonitrile tri-mer • Provide an improved manufacturing method, which is suitable for commercial-scale manufacturing, and can provide N-phosphonomethyl glycinnitrile and its alkyl The good yield of the base salt type, and contains only very few impurities. According to the present invention, a method for preparing an acid salt of an alkyl ester of N-phosphonomethylglycinnitrile is proposed. The method includes trimerizing methyleneaminoacetonitrile under anhydrous conditions and in the presence of anhydrous acid and an inert solvent. Reaction with trialkylphosphinate, where the starting material of the methyleneaminoacetonitrile trimer is at least partially soluble, and the product of the N-phosphonomethylglycinyl alkyl ester acid formula M is essentially On the insoluble, and then-recover the acid salt of N-phosphonomethylglycinil alkyl | The methyleneamino acetonitrile trimerization system used herein refers to the compound of formula (I) shown in Scheme 1. This Scheme 1 illustrates the preparation method of the present invention. In Scheme 1, the R group in trialkylphosphinate U) represents C, -γ alkyl, and is preferably Ci-5 alkyl, and the trialkylphosphinate is therefore preferably tri (Ci-7 alkyl) --------- approved clothing ------ iT ------ ^ (Please read the precautions on the back before filling this page) This paper size is applicable China National Standard (CNS) Α4 specification (210Χ 297 mm) sl45〇s ^ ld'Ql 5. Description of the invention (>) phosphinate or trialkyl) phosphonite. The trialkylphosphinate is preferably trimethylphosphinate, triethylphosphinic acid or tributylphosphinate. Trimethylphosphinate is a commercially available phosphonating agent, so it is an efficient raw material for the commercial production of N-phosphonomethylglycine eye. As far as the commercial production of products is concerned, higher-carbon alkylphosphinates, such as tributylphosphinate and tripentylphosphinate, can provide some benefits, which will be detailed in K below. The anhydrous acids suitable for use in the production method of the present invention, and the insoluble salts thereof which can form N-phosphonomethyl methylglycinil alkyl esters, are understood by the skilled artisan. Halogenation is especially suitable for this method. In particular, hydrogen chloride is an effective and easily available anhydrous acid. Printed by the Employee Consumer Cooperative of the Central Standard Bureau of the Ministry of Economic Affairs (please pay attention to the back side before filling out this page) The solvent should be inert, based on its reaction conditions The effect will not be significant, and especially the solvent should stably antagonize the effect of trialkylphosphinate. Suitable inert solvents in which the starting material of the methyleneamino acetonitrile trimer is at least partially soluble and the acid salt product of N-phosphonomethylglycine nitrile alkyl ester are insoluble in nature are well known to skilled artisans of. It should also be understood that the methyleneamino acetonitrile trimer starting material should be at least partially soluble in an inert solvent. This means that the methyleneamino acetonitrile trimer starting material should be sufficiently soluble, even if all The starting material did not dissolve at the beginning of the phosphonization reaction, and there should be sufficient amount in the solution to start the scale acidification reaction. Later, when the reaction proceeds, more starting materials will dissolve, and the starting materials in the solution will be exhausted until all the starting materials on the cardinal material have been dissolved when the phosphonization reaction is completed. Examples of suitable inert solvents include nitriles such as acetonitrile, esters such as ethyl acetate, haloalkanes such as ethyl dichloride. Dichloromethane and dichloromethane, quines such as methyl isobutyl quinone, ethers such as di Ether, or tetrahydrofuran, and halogenated aromatic papers are compliant with the Chinese National Standard (CNS) A4 specifications (2 丨 〇'〆297 directors) 〇7 A7 〇7 A7 Printed by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs'- -_B7 One__ V. Description of the invention (宑) Ai Jingruru chlorobenzene. Acetonitrile is a particularly effective solvent, in which the methyleneamino & trimer is usually completely soluble at the concentration used in the process of the present invention. Basically, the acid salt product of N-phosphonomethylglycinnitrile alkyl ester is completely insoluble in the solvent; at least part of the H-phosphonomethylglycinol ester acid under reaction conditions It is enough that the product of the formula salt will precipitate, and therefore it can be recovered. However, in general, the acid salt of N-phosphonomethylmethylglycinnitrile alkyl ester has a very low solubility in a large amount of organic solvent, and this It is particularly beneficial to represent the manufacturing method of the present invention. .. ~ The reaction is conveniently carried out at ambient temperature, however, if necessary, a lower stomach or lower temperature can be used, such as a temperature range from -5〇υ to 20 (λ ° C. Heat will be generated during the reaction, so If necessary, it can be cooled to maintain the temperature substantially at a preferred value, such as at ambient temperature or slightly higher temperature. When the hydrogen chloride gas is an acid, it can directly pass through the reaction mixture or be in a solution type in an anhydrous solvent Add to the reaction mixture. It is more suitable to carry out the reaction in the absence of water vapor and under non-oxidizing conditions, such as dry and non-oxidizing atmosphere. When hydrogen chloride gas passes directly through the reaction mixture, the gas itself can provide the necessary dry and non-oxidizing atmosphere If hydrogen chloride is added to the reaction mixture as a solution in an anhydrous solvent, it is desirable to use a suitable inert gas, such as anhydrous nitrogen, to provide a dry and non-oxidizing atmosphere. It is preferred to use a substantially stoichiometric ratio here Trialkylphosphinate. The acid ratio depends on the particular acid used. If hydrochloric acid is used, it is preferred to use 3 to 3 moles per mole of methylene methyleneaminoacetonitrile trimer. 12molar hydrochloric acid. The special advantage of the method of the present invention is that the product M is substantially pure type Shen-5-this paper is again applicable to the Chinese National Standard (CNS) Α4 specification (2 〖〇Χ297mm)- --------- installed ------ ordered ------% (please read the notes on the back before filling in this page) Printed or ordered by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs No need to borrow the alloglycol acid phase and the phosphine can be separated. The base acid is hydrolyzed. The water ring of the methylphosphine in the chloro N-body should be based on this ring group. The base method is to re-phosphorize or re-phosphorate butyl to make pentyl and alcoholic groups, which can be mixed with N-trihydric or chlorochlorobutane-containing alcohols. It can be estered with the first stage of the process. This is a good solution. «. The solution will give out the nitrile carbon of the first acid, and neutralize the water, that is, the alcohol surface in the esterification process of the phosphine amine is higher than the acid. ) Potato pentagon: the base acid group is easy to be phosphine 1) ^ group or step including alkane phosphine. Rongya Ιιίί) * A package of three amyl alcohols is an alcohol-based 1S agent or Dingjin method. The acidic pentane (r-soluble carbamide phosphinate or machine three should be reacted with this high-acid N-alcohol. Anti-nitrile I, compared with phosphine, butyl butodamine, is based on the amine method, and is more often used as a root system to make other types of costs as the basis. This is in the form of a mixture of pentanol and dimethoate. 3. Phase-to-distilled water amine
Sl45ftQ1 五、發明説明（仏） 澱因而可容易地分離。 N -膦酸基甲基甘胺腈之垸基酯至H -膦酸基甲基甘胺酸或 其鹽之水解作用是一個熟知之過程，且述於如U S 3 , 923，8 7 7 中》 本發明之製法可呈批次、連續或半連續反應方式操作， 且特別適用於高效率之商業化搡作，及持別適用於聯合後 續反應，K製成N -膦酸基甲基甘胺酸或其鹽。 '於典型之製程中，N -膦酸基甲基甘胺腈烷基醋之不溶栓 酸式鹽Μ過濾回收自反應，同時反摩溶劑可再循環，$所 需加上純化階段。再水解Ν -膦酸基甲基.甘胺腈烷基g|之酸 式鹽，如以氫氯酸水溶液處理，且形成了 N-膦酸基甲基甘 胺酸。 本紙伕尺度適用中國國家標隼（CNS ) A4規格（210X297公瘦^ 装------訂------t (請先聞讀背面之注意事項再填寫本頁) A7 B7 so. 〇?；- 五、發明説明（女） i )在無水條件及無水酸及憒性溶劑存在下，將亞甲基 瞭基乙腈三聚體與三丁基亞膦酸酯或三戊基亞膦酸酯反應 ，其中亞甲基胺基乙臏三聚體起始物至少部份可溶，且 N -膦酸基甲基甘胺腈烷基酯酸式鹽之產物實質上不溶，且 之後： ii )過滹（i )階段之反應混合物，以至含有溶劑，及丁 基氯或戊基氯之濾液中回收沈澱的N_膦酸基甲基甘胺腈烷 基酯之酸式鹽； iii )在酸性條件下水解N -膦酸基甲基甘胺睛烷基詣之酸 式鹽，Μ形成膦酸基甲基甘胺酸及丁醇或戊醇； iv )蒸餾得自（ii )階段之滹液.，並再循環溶劑至（丨）階 段，丁基氯或戊基氯至（iii)階段，其中其進行水解以分別 形成丁醇或戊醇； v )以相分離回收（出）階段之丁醇或戊醇，將之與三氯 化磷反應以分別形成三丁基亞膦酸酯及三戊基亞麟酸g| , 並將三丁基亞膦酸酯或三戊基亞膦酸酯再循環至（丨）階段 ;及 vi)回收（iii)階段之H -膦酸基甲基甘胺酸多睛產物ύ (iii)階段的Ν -膦酸基甲基甘胺酸產物可以结晶作用合宜 - 地回收。 本發明將Μ下列實例加以說明，其中所有部份及百分率 除非另有所示均以重量計。 置例1 亞甲基胺基乙腈三聚體（1.7克，O.OOS3克萁耳）及三甲 本紙張尺度適用中國國家標隼（CNS ) Α4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁) •訂 泉 經濟部中央標準局員工消費合作社印製 ^^4523 經濟部中央標準局負工消費合作社印製 五、發明説明（卜） 基亞膦酸酯（3 . 1克* 0 . 0 2 5克莫耳）懸浮於3 0毫升乙酸乙酯 中。混合物搜拌並維持在約室溫溫度下，同時緩慢加入無 水H C 1 。於加入過程中形成白色的沈澱。G C分析顯示，反 應經過在室溫溫度下置一夜後其中所有的三聚體已耗盡。 固體再Μ過濾分離，並Κ溶劑洗滌。可得3 . 6克產物，相 當於6 7 %產率。固體M G C及N M R分析，且發現是膦酸基甲 基甘胺腈二甲g旨之鹽酸鹽。KGC或NMR鑑定知產物基本上 是純的無顯著摻雜物。 茸例2 〜 除了以乙睛為溶劑外，重覆實例1之步驟。可得3 . 1克 纯的膦酸基甲基甘胺睛二甲酯相當於5 6 %產率。 啻例3 除了於加入反應槽前，1 . 8 2 5克（0 . 0 5克莫耳）無水H C 1係 溶於3 0毫升乙腈中Κ外，重覆寅例2之步驟。可得到3 . 4 克基本上純的膦酸甲基甘胺腈二甲酯，相當於63¾產率。 官例4 亞甲基肢基乙腈三聚體1.7克及三甲基亞膦酸酯3.2克 懸浮於40毫升二氯甲烷中。混合物搜拌且溫度維持在35 t - K下，同時於2小時之期間内加入無水H C〖。於加入之過 程中形成白色沈澱。經冷卻至後，過濾產物，M20毫 升冷的二氯甲烷洗滌再乾燥K得2 .9 -克膦酸基甲基甘胺腈 之二甲酯（54.1¾產率）。質子NMR顯示產物基本上是纯的 I I I - - I n I I - n - - - T n n In (I I n4¾ ，T彳 (請先閱讀背面之注意事項再填寫本頁) 本纸張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） A7 B7 五、發明説明（夕） 啻例5 亞甲基胺基乙腈三聚體3.4克及三丁基亞膦酸酯（14克 ，9 0 $濃度）溶於4 0毫升乙腈中。混合物攢拌並將溫度維 持在3 5 Ό以下*同時於3小時之期間内，以3 0毫升/分之 速率加入無水H C 1 。於加入過程中彤成白色沈澱。經冷卻 至0 t之後，過濾產物，Μ冰冷的乙腈洗滌，再乾燥生成 13.2克膦酸基甲基甘胺腈之二丁酯（88¾產率）。質子NMR 顯示產生基本上是純的。 窗例 重覆賁例5步驟，除了使用乙酸乙g旨取代乙腈之外。亞 甲基胺基乙腈僅部份可溶於乙酸乙酯中，且懸浮於反應混 合物中。可得11 . 9克基本上純的膦酸基甲基甘胺腈二丁醒 (79 . 7¾ 產率）。 化學式（說明闬） (請先閱讀背面之注意事項再填寫本頁 士衣· ·-» 經濟部中央標準局員工消費合作社印製 -9 - 本纸張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 五、發明説明（ 流程1 CNCH,Sl45ftQ1 V. Description of the invention (仏) It can therefore be easily separated. The hydrolysis of the N-phosphonomethylglycine nitrile alkyl ester to H-phosphonomethylglycine or a salt thereof is a well-known process and is described in, for example, US 3, 923, 8 7 7 》 The preparation method of the present invention can be operated in batch, continuous or semi-continuous reaction mode, and is particularly suitable for high-efficiency commercial operation, and is especially suitable for joint follow-up reaction, K is made into N-phosphonomethyl methylglycol Amino acid or its salt. 'In a typical process, the insoluble thrombogenic acid salt of N-phosphonomethylglycine nitrile alkyl vinegar is recovered from the reaction by filtration, and the anti-friction solvent can be recycled. The purification stage is required. Then hydrolyze the acid salt of N-phosphonomethyl.glycinnitrile alkyl g |, such as treatment with aqueous hydrochloric acid, and form N-phosphonomethylglycine. The size of this paper is applicable to the Chinese National Standard Falcon (CNS) A4 specification (210X297 male thin ^ pack ------ order ------ t (please read the precautions on the back before filling this page) A7 B7 so . 〇 ?;-V. Description of the invention (female) i) In the absence of anhydrous conditions and the presence of anhydrous acid and a volatile solvent, the methylene-based acetonitrile trimer with tributylphosphonite or tripentylidene Phosphonate reaction, in which the starting material of the methyleneaminoethylethylene trimer is at least partially soluble, and the product of the acid salt of N-phosphonomethylglycinnitrile alkyl ester is substantially insoluble, and then : Ii) The acid salt of the N-phosphonomethylglycinnitrile alkyl ester recovered from the reaction mixture after the phase (i) stage, or the filtrate containing solvent and butyl chloride or pentyl chloride; iii ) Hydrolysis of the acid salt of N-phosphonomethylglycinol alkyls under acidic conditions, M forms phosphonicomethylglycine and butanol or pentanol; iv) Distillation is obtained from stage (ii) The liquid., And recycle the solvent to (丨) stage, butyl chloride or pentyl chloride to (iii) stage, where it is hydrolyzed to form butanol or amyl alcohol, respectively; v) recovered by phase separation Out) stage of butanol or pentanol, which is reacted with phosphorus trichloride to form tributylphosphonite and tripentyl linalic acid g |, respectively, and tributylphosphonite or tripentane The phosphonite ester is recycled to the (丨) stage; and vi) The H-phosphonomethylglycine acid multi-eye product in the recovery (iii) stage (iii) N-phosphonomethylglycine at the stage (iii) The acid product can be conveniently recovered by crystallization. The present invention illustrates the following examples, in which all parts and percentages are by weight unless otherwise indicated. Example 1 Methyleneamino acetonitrile trimer (1.7 g, O.OOS3 g of ear) and the top three paper size are applicable to China National Standard Falcon (CNS) Α4 specifications (210X297 mm) (please read the notes on the back first Please fill out this page again.) • Printed by the Quanquan Bureau of Economy, Central Standards Bureau, Employee Consumer Cooperative ^^ 4523 Printed by the Ministry of Economy, Central Standards Bureau, Negative Consumer Cooperative. V. Description of the invention (Bu) Phosphonite (3.1 g * 0.025 mol) suspended in 30 ml of ethyl acetate. The mixture was stirred and maintained at about room temperature, while anhydrous H C 1 was slowly added. A white precipitate formed during the addition. G C analysis showed that after the reaction was left overnight at room temperature, all the trimers had been exhausted. The solid was separated by M filtration and washed with K solvent. 3.6 g of product was obtained, equivalent to 67% yield. The solid M G C and N M R were analyzed and found to be the hydrochloride salt of phosphonic acid methylglycinil dimethyl g. KGC or NMR identified that the product was essentially pure without significant dopants. Example 2 ~ The steps of Example 1 were repeated except that acetonitrile was used as the solvent. Available 3.1 grams of pure phosphonic acid methyl glycinol dimethyl equivalent to 56% yield. Example 3 The procedure of Example 2 was repeated except that 1.825 g (0.05 gmol) of anhydrous H C 1 was dissolved in 30 ml of acetonitrile before being added to the reaction tank. 3.4 g of substantially pure methylphosphonomethylglycine nitrate is obtained, which corresponds to a yield of 63¾. Official Example 4 1.7 g of methylene limbyl acetonitrile trimer and 3.2 g of trimethylphosphinate were suspended in 40 ml of methylene chloride. The mixture was mixed and the temperature was maintained at 35 t-K, while anhydrous H C〗 was added over a period of 2 hours. A white precipitate formed during the addition. After cooling to, the product was filtered, washed with 20 mL of cold dichloromethane and then dried to give 2.9-grams of dimethylphosphonomethylglycinil dimethyl ester (54.14% yield). Proton NMR shows that the product is basically pure III--I n II-n---T nn In (II n4¾, T 彳 (please read the precautions on the back before filling in this page) This paper size is applicable to Chinese national standards (CNS) A4 specification (210X 297mm) A7 B7 5. Description of the invention (Xi) Example 5 Methyleneamino acetonitrile trimer 3.4g and tributylphosphonite (14g, 90 $ concentration) ) Dissolved in 40 ml of acetonitrile. The mixture was stirred and maintained at a temperature below 3 5 Ό * while adding anhydrous HC 1 at a rate of 30 ml / min over a period of 3 hours. It became white during the addition Precipitation. After cooling to 0 t, the product was filtered, washed with M ice-cold acetonitrile, and dried to produce 13.2 g of dibutyl phosphonomethylglycinnitrile (88¾ yield). Proton NMR showed that the production was essentially pure The window example repeats the steps of Example 5 except that ethyl acetate is used instead of acetonitrile. Methyleneamino acetonitrile is only partially soluble in ethyl acetate and is suspended in the reaction mixture. Available 11.9 Grams of substantially pure phosphonic acid methylglycine nitrile dibutylbenzene (79. 7¾ yield). Chemical formula ( Ming Lu) (Please read the precautions on the back before filling in this page. ··-»Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs-9-This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 5) Description of invention (Process 1 CNCH,
2 .CH2CN 、ir CH. 、N， (I) ch2cn A7 B7 3P(〇R)3 + 3HC1 (II) ch2cn 3 HNv2. CH2CN, ir CH., N, (I) ch2cn A7 B7 3P (〇R) 3 + 3HC1 (II) ch2cn 3 HNv
)R :h2——p—II . 0 +3RC1 (HI) I u tn tn - f — - In I I n I I n - T n - n - n n >% (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標隼局員工消費合作社印製 -10 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）) R: h2——p—II. 0 + 3RC1 (HI) I u tn tn-f —-In II n II n-T n-n-nn &%; (Please read the notes on the back before filling in this Page) Printed by the Employee Consumer Cooperative of the Central Standard Falcon Bureau of the Ministry of Economic Affairs -10 This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm)