CN1062855C - 羟甲基-亚氨基二乙酸的碱金属盐的制备方法 - Google Patents
羟甲基-亚氨基二乙酸的碱金属盐的制备方法 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
- C07C227/18—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters
-
- 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
本发明提供了一种制备羟甲基-亚氨基二乙酸的碱金属盐的制备方法，包括亚氨基二乙酸碱金属盐与甲醛源反应。
Description
N-磷酰甲基甘氨酸(草甘膦)是一种重要的广谱除草剂。
草甘膦的一种常规的前体是具有下述结构的N-磷酰甲基亚氨二乙酸获得式(I)化合物的常规途径，一般包括将亚氨二乙酸(IDA)磷酰甲基化，后者的获得是通过用无机酸酸化粗制亚氨基二乙腈的水解产物(IDAN)，使IDA结晶出，过滤并干燥IDA，以回收(IDA)。上述方法在从IDA分离碱金属盐溶液时，由于过滤步骤含有未回收的IDA而造成损耗。实际上，为使碱金属盐沉淀需分级结晶，然后通过离心从IDA溶液中分离该沉淀。在U.S.专利3，808，269中，公开了从硫酸钠和氨基酸水溶液中回收IDA的方法，该方法中通过调节溶液的pH为1.5-3，使氨基酸形成IDA沉淀和第一母液，分离并回收其中的IDA沉淀。通过浓缩液体可从第一母液中使硫酸钠沉淀出来并调节温度避免IDA一起沉淀出。此后可重复此方法。可是，尽管在溶液中存在附加产物，在一些程度上连续分级结晶步骤是不经济的。U.S.专利3，852，344号公开了一种类似的方法。其中用盐酸代替硫酸。氯化钠作为副产物被回收而不是硫酸钠。
U.S.专利5，011，988号公开了另一种方法，该方法可在，269号专利方法生成的废流中进行。因此，调节上述废流的温度，使得在同一母液中沉淀出IDA和硫酸钠+水合物。然后从母液中分离混合结晶，并循环至IDA生产工艺的早期步骤中。
如U.S.专利3，288，846中Irani公开的，在盐酸存在下，可从IDA酸，甲醛和磷酸制备磷酰甲基亚氨二乙酸结晶。≥1CH2O加入过程≥0.5hrs＠＞70℃
如在U.S.专利4，724，103号中公开的，为了简化前述方法，可用碱金属碱水解亚氨二乙腈以形成亚氨二乙酸的碱金属盐，再将其转化成IDA的强酸盐并磷酰甲基化来制备化合物(I)。具体说来，将IDA的碱金属盐进行一系列反应，首先与强无机酸形成IDA的强酸盐和强酸的碱金属盐，然后使IDA的强酸盐与磷酸和甲醛反应进行磷酰甲基化以提供化合物(I)和碱金属盐。加入足够溶解碱金属盐的水，式(I)化合物作为沉淀分离出。类似的，U.S.专利4，775，498号公开了一种制备N，N-二乙酸氨基亚甲基磷酸的方法，该方法通过于第一份IDA碱金属盐的水溶液加入三氯化磷并形成磷酸和亚氨二乙酸盐酸盐和碱金属氯化物的混合物，在混合物中加入甲醛的同时加入第二份IDA的碱金属盐，加入足量的水以溶解其碱金属盐，调节所得混合物的pH值至N，N-二乙酸氨基亚甲基膦酸的等电点，并分离沉淀的酸：
可是，IDA的碱金属盐溶液，如IDANa2，由于在室温下其溶解度仅为大约22％，且在60℃数量级下为大约40％，它的商业规模的贮藏和运输都是不实用的。甚至即使40％的溶解是可接受的，但保持上述溶解度所需要的高温耗费大且不方便。
因此期望从容易商业规模贮藏和/或在室温下运输的中间体生成磷酰甲基亚氨二乙酸(PMIDA)。
根据本发明，在此提供了制备N-磷酰甲基亚氨二乙基(I)的另一种方法，该方法中IDA碱金属盐的溶液与甲醛反应以形成羟甲基亚氨基二乙酸(HMIDA)的碱金属盐。随后HMIDA可与如磷酸这样的磷源反应，以良好收率生成PMIDA。本发明者发现羟甲基-IDA容易与磷酸反应形成PMIDA，特别是根据现有技术的观点，必须以IDA酸/酸盐作为反应物来说这一发现是令人惊异的。
尽管在本发明方法中IDA的其它碱金属盐，如MxH(2-x)IDA(其中M是碱金属，且x是1或2)，包括(但不限于)K2IDA也可使用，但优选使用它的碱金属盐Na2IDA。在本方法中使用的IDA碱金属盐的浓度为以IDA酸重量计的大约20-40％，优选以IDA酸重量计大约31％。碱金属IDA一般包括1％游离碱金属氢氧化物，作为从IDA(较适宜从IDAN)形成的盐的结果存在。
优选以化学计算量的甲醛加入到碱金属IDA中，虽然IDA与甲醛的摩尔比为大约0.5至大约2均宜。为了方便，同福尔马林(含有大约1％未反应甲酵的，以重量计44％的甲醛溶液)较优越，但其它甲醛源，如三噁烷或多聚甲醛也可采用。为了限制碱金属N-甲基-IDA副产物的形成，碱金属IDA与甲醛源的反应可在低于大约70℃，优选低于大约40℃，最优选在大约30至40℃之间的温度下进行。可用两小时的时间加入甲醛，优选用一小时或较少的时间加入，加入速率仅受除去反应热速率的限制。
在室温下至少高至46.3％浓度(等于39.6％DSIDA)即试验最高浓度，所得的羟甲基亚氨二乙酸碱金属盐溶液是稳定的(当然较高的浓度是可能的)。因此，上述溶液可很容易地以商业规模储藏和/或运输。
此后该溶液与磷酸源，和pKa值低于磷酸PKa的强酸充分反应。强酸例如是硫酸、氢碘酸、氢溴酸、羟甲基磺酸，优选盐酸，以生成磷酰甲基-IDA。此外，可以PCl3的形式提供磷酸和盐酸。反应方案示于如下：该反应可在大约100℃下进行。较低的温度会使产率降低。如果该方法在减压(例如，20-30psi)下进行，甚至可获得较高的产率。
下述实施例详述本发明的方法。通过使133.1g的IDAH2与168.9g的50％NaOH和130g的H2O反应可制备所用的亚氨基二乙酸二钠盐，该盐形成41％的溶液并含有1％游离NaOH。
实施例1
制备一摩尔的48.5％的IDA二钠盐(DSIDA)并冷却到40℃。将1.2M44％的甲醛加入到用冰浴冷却到35℃的浆状DSIDA·6H2O结晶中。在22℃搅拌过夜，大部分结晶溶解并反应形成羟甲基-IDANa2。热至45℃15分钟后，剩下的少量结晶也溶解了。所得的46.3％的HMIDANa2溶液在室温下一个月仍无结晶。
实施例2
将1.0mole41％DSIDA溶液冷却到40℃，在该浆液中加入多聚甲醛(1.0mole，91％)并使温度保持在40℃。约一小时后，所有反应物都溶解，冷却到室温后，44.5％HMIDANa2溶液仍无结晶。
实施例3
将一摩尔41％IDA二钠盐装入到反应容器中并在58℃保温。于20分钟内，将87.7克(1.3mole)的44.45％甲醛加入到容器中，使温度升至61℃。
在另一个1升反应器中，将337.3g(3.42mol)的37％HCl，96.4g(1.16mole)99％H3PO3和50gH2O加热至沸腾，加入另外92g的H2O，沸点升至100℃之上。温度一旦到达100℃，用二个小时的时间，加入IDA二钠盐和甲醛反应产物，羟甲基-IDA二钠盐。在这段时间内，将反应温度保持在107°至110℃之间。将混合物保持此状态另外二小时，用一小时冷却到17℃，过滤并用100ml冰水洗涤，获得100％纯度的PMIDA，产率70％。
实施例4
在1升园底烧瓶中，伴随搅拌，将含有1.9％游离NaOH的41％DSIDA溶液432g(1.00M)冷却，用90分钟的时间将68.2g(1.0mole)44％甲醛加入到DSIDA浆液中，使温度保持在30℃，如果需要，用压缩气流冷却烧瓶。将羟甲基-IDA二钠盐(HMIDANa2)溶液冷却到室温，并移入1升锥形烧瓶中。
然后在1升园底烧瓶中装入35.5g 37％HCl(0.36M)和128.9g 70％ H3PO3(1.10M)。将烧瓶加热至沸腾，并用90分钟时间分别将322.4g 37％HCl(3.27M)和500.2g HMIDANa2溶液(1.00M)泵入反应混合物中。在这段时间中，从反应烧瓶中蒸馏出275g水。
加入所有HMIDA和HCl后，停止蒸馏出水，使试剂回流，同时用10分钟时间加入另外的30.7g(0.45M)44％的甲醛。
再回流反应物2小时，此时将275g馏出物加回到反应物中，接着冷却至室温。
过滤PMIDA浆液，滤块用50ml水洗涤，然后干燥获得190.4g纯度＞99％的PMIDA，这相当于回收83％的PMIDA，用LC分析该液，显示另有25.7g PMIDA，总的转化率为94.7％。
实施例5
在1升园底烧瓶中，伴随搅拌，使含有1.9％游离NaOH的41％DSIDA溶液432g(1.00M)冷却。在30℃，用90分钟时间，将51.0g(0.75M)44％甲醛加入到DSIDA浆液中。如果需要，用10psi压缩空气流冷却烧瓶，保持温度在30℃。将所得的羟甲基-IDA二钠盐(HMIDANa2)溶液冷却到室温，并转移到1升的锥形烧瓶中。
然后在1升园底烧瓶中装入70g 37％ HCl(0.71M)和140g 70％H3PO3(1.2M)将混合物溶液加热至沸腾，用三小时，分别于反应混合物中泵入275g 37％HCl(2.79M)和HMIDANa2溶液(1.0M)。在此加料时间，蒸馏出265g水。
HMIDA和HCl全部加入后，使试剂回流，同时用约30分钟的时间，将另外的37g 44％的甲醛(0.54M)供给反应。
将反应物保持回流状态另外四小时，在此回流期结束时，将265g蒸馏物回归到反应物中，接着冷却至室温。过滤PMIDA浆液，用50ml冷水洗涤滤块，然后干燥。得到纯度＞99％的200.6g的PMIDA。这相当于回收了88.4％的PMIDA。用HPLC分析该液相，发现含有1.3％的PMIDA，这相当于产率4.1％。总转化率为92.5％。
实施例6
在1升园底烧瓶中，伴随搅拌，使含有1.9％游离NaOH的41％DSIDA溶液432(1.00M)冷却。在30℃，用90分钟时间，将68.0g(1.0M)44％甲醛加入到DSIDA浆液中。如果需要，用10psi压缩空气流冷却烧瓶，保持温度在30℃，将所得的羟甲基-IDA二钠盐(HMIDANa2)溶液冷却到室温并转移到1升锥形烧瓶中。
在第二个加料瓶即500ml锥形烧瓶中，装入151.3g PCl3(1.10M)。然后将1升的园底烧瓶装入42.4g H2O。然后以1.26g/min(相当于加料大约120分钟)向反应烧瓶中加入PCl3。
反应在室温下开始。以1.26g/min供给PCl3五分钟后，以3.7mls/min速度(相当于大约120分钟内加完HMIDANa2)开始加入HMIDANa2溶液(1.0M)。在使用外来热源之前，反应放热至85℃，最后在115℃下回流。
完成PCl3和HMIDANa2加料后，借助HMIDA供料泵于反应物中加入18.7g 37％HCl。此后，反应保持在此状态十分钟，然后，用30分钟时间(随便的，非长链的时间)，在反应物表面之下加入另外的0.3 M44.0％甲醛(20.5g)。再回流反应二小时。
回流完后，将反应物冷却至25℃。过滤PMIDA浆液，用50ml水洗涤滤块，然后干燥，获得202.0g PMIDA，纯度为99.8％。这相当于回收89.5％的PMIDA。
Claims (7)
1．羟甲基-亚氨基二乙酸的碱金属盐的制备方法，该方法包括在低于70℃的温度下，将亚氨基二乙酸碱金属盐与选自甲醛、多聚甲醛、福尔马林和三噁烷的甲醛源反应，其中按亚氨基二乙酸重量计，所用亚氨基二乙酸碱金属盐的浓度为20-40％并且亚氨基二乙酸碱金属盐与甲醛源的摩尔比为0.5-2。
2．根据权利要求1的方法，所述反应在30至40℃的温度下进行。
3．根据权利要求1的方法，其中所述的亚氨基二乙酸的碱金属盐是二钠盐。
4．根据权利要求1的方法，其中所述的亚氨基二乙酸的碱金属盐是二钾盐。
5．根据权利要求1的方法，其中所述的亚氨基二乙酸的碱金属盐是单钠盐。
6．根据权利要求1的方法，其中所述的亚氨基二乙酸的碱金属盐是单钾盐。
7．根据权利要求1的方法，其中所述亚氨基二乙酸碱金属盐与甲醛源的摩尔比为化学计算量。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/969,705 US5312972A (en) | 1992-10-29 | 1992-10-29 | Conversion of hydroxymethyl-iminodiacetic acid to phosphonomethyl-iminodiacetic acid |
| US969,705 | 1992-10-29 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99106382.1A Division CN1235974A (zh) | 1992-10-29 | 1999-05-05 | 膦酰甲基－亚氨基二乙酸的制备方法 |
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| Publication Number | Publication Date |
|---|---|
| CN1096290A CN1096290A (zh) | 1994-12-14 |
| CN1062855C true CN1062855C (zh) | 2001-03-07 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93120707A Expired - Fee Related CN1062855C (zh) | 1992-10-29 | 1993-10-28 | 羟甲基-亚氨基二乙酸的碱金属盐的制备方法 |
| CN99106382.1A Pending CN1235974A (zh) | 1992-10-29 | 1999-05-05 | 膦酰甲基－亚氨基二乙酸的制备方法 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN99106382.1A Pending CN1235974A (zh) | 1992-10-29 | 1999-05-05 | 膦酰甲基－亚氨基二乙酸的制备方法 |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US5312972A (zh) |
| EP (1) | EP0595598B1 (zh) |
| JP (1) | JPH06192189A (zh) |
| CN (2) | CN1062855C (zh) |
| AT (1) | ATE154604T1 (zh) |
| AU (1) | AU659348B2 (zh) |
| BR (1) | BR9304379A (zh) |
| CA (1) | CA2109269A1 (zh) |
| DE (1) | DE69311675T2 (zh) |
| ES (1) | ES2105128T3 (zh) |
| MY (1) | MY109423A (zh) |
| NZ (1) | NZ250045A (zh) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5986128A (en) * | 1996-11-01 | 1999-11-16 | Monsanto Company | Use of monosodium iminodiacetic acid solutions in the preparation of N-phosphonomethyliminodiacetic acid |
| US6054608A (en) * | 1997-05-05 | 2000-04-25 | Monsanto Company | Method for preparing formylphosphonic acid |
| CA2434154A1 (en) * | 2001-01-12 | 2002-07-18 | Basf Aktiengesellschaft | Method for producing n-phosphonomethyl iminodiacetic acid |
| BRPI0610412A2 (pt) | 2005-04-25 | 2010-06-22 | Monsanto Technology Llc | alteração da distribuição de tamanho do cristal de ácido n-(fosfonometil)iminodiacético para filtração melhorada e qualidade do produto |
| CN100400543C (zh) * | 2006-09-08 | 2008-07-09 | 四川贝尔实业有限责任公司 | 亚氨基二乙腈水解制备双甘膦的方法 |
| BRPI1012917A2 (pt) | 2009-05-28 | 2017-06-27 | Straitmark Holding Ag | método para a afabricação de ácidos fosfonalquil iminodiacéticos |
| MX2012004901A (es) * | 2009-10-27 | 2012-06-19 | David Lemin | Metodo para la elaboracion de acido fosfonoalquil iminodiacetico. |
| ES2609488T3 (es) | 2012-07-17 | 2017-04-20 | Straitmark Holding Ag | Método para la síntesis de N-(fosfonometil)glicina |
| BR112015000993B1 (pt) | 2012-07-17 | 2020-04-28 | Monsanto Technology Llc | método para a síntese de um ácido alfaaminoalquileno fosfônico ou de um éster do mesmo |
| RU2694047C2 (ru) | 2012-07-17 | 2019-07-09 | МОНСАНТО ТЕКНОЛОДЖИ ЭлЭлСи | Способ синтеза аминоалкиленфосфоновой кислоты |
| IN2015DN01082A (zh) * | 2012-07-17 | 2015-06-26 | Straitmark Holding Ag | |
| CN104402924A (zh) * | 2014-11-26 | 2015-03-11 | 杭州上拓环境科技有限公司 | 一种双甘膦无钠生产新工艺 |
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| US4439373A (en) * | 1982-12-27 | 1984-03-27 | Stauffer Chemical Company | Process for preparing phosphonomethylated amino acids |
| EP0121492A1 (fr) * | 1983-02-07 | 1984-10-10 | Heinz Emmenegger | Bain galvanique pour le dépôt electrolytique d'alliage or-cuivre-cadmium, procédé d'utilisation de ce bain, article résultant de ce procédé |
| EP0155926A1 (en) * | 1984-02-27 | 1985-09-25 | Monsanto Company | Improved process for preparing N,N-diacetic acid aminomethylenephosphonic acid |
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|---|---|---|---|---|
| US2331677A (en) * | 1942-10-27 | 1943-10-12 | American Cyanamid Co | Methylol beta, beta'-iminodipropionic acid |
| GB781212A (en) * | 1954-05-06 | 1957-08-14 | Hamol S A | Improvements in the preparation of new formaldehyde derivatives |
| GB1142294A (en) * | 1966-02-08 | 1969-02-05 | Albright & Wilson Mfg Ltd | Improvements in production of amino alkylene phosphonic acids |
| HU184601B (en) * | 1979-07-09 | 1984-09-28 | Alkaloida Vegyeszeti Gyar | Process for producing n-/phosphono-methyl/-glycine |
| US4921991A (en) * | 1985-02-22 | 1990-05-01 | Guy Lacroix | Preparation of esters of the N-phosphonomethylglycine and the N-phosphonomethyl glycines |
| HU200780B (en) * | 1988-02-08 | 1990-08-28 | Nitrokemia Ipartelepek | Process for producing n-phosphonomethyl iminodiacetic acid from double salt of iminodiacetic acid |
| DE69012218T3 (de) * | 1989-06-15 | 2001-03-29 | Finchimica Srl | Verfahren zur Herstellung von N-Phosphonomethylglycin. |
-
1992
- 1992-10-29 US US07/969,705 patent/US5312972A/en not_active Expired - Fee Related
-
1993
- 1993-10-26 ES ES93308517T patent/ES2105128T3/es not_active Expired - Lifetime
- 1993-10-26 AT AT93308517T patent/ATE154604T1/de not_active IP Right Cessation
- 1993-10-26 DE DE69311675T patent/DE69311675T2/de not_active Revoked
- 1993-10-26 CA CA002109269A patent/CA2109269A1/en not_active Abandoned
- 1993-10-26 EP EP93308517A patent/EP0595598B1/en not_active Revoked
- 1993-10-26 NZ NZ250045A patent/NZ250045A/en unknown
- 1993-10-27 MY MYPI93002253A patent/MY109423A/en unknown
- 1993-10-27 BR BR9304379A patent/BR9304379A/pt not_active IP Right Cessation
- 1993-10-28 AU AU50314/93A patent/AU659348B2/en not_active Ceased
- 1993-10-28 CN CN93120707A patent/CN1062855C/zh not_active Expired - Fee Related
- 1993-10-28 JP JP5270537A patent/JPH06192189A/ja active Pending
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1999
- 1999-05-05 CN CN99106382.1A patent/CN1235974A/zh active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4439373A (en) * | 1982-12-27 | 1984-03-27 | Stauffer Chemical Company | Process for preparing phosphonomethylated amino acids |
| EP0121492A1 (fr) * | 1983-02-07 | 1984-10-10 | Heinz Emmenegger | Bain galvanique pour le dépôt electrolytique d'alliage or-cuivre-cadmium, procédé d'utilisation de ce bain, article résultant de ce procédé |
| EP0155926A1 (en) * | 1984-02-27 | 1985-09-25 | Monsanto Company | Improved process for preparing N,N-diacetic acid aminomethylenephosphonic acid |
Also Published As
| Publication number | Publication date |
|---|---|
| AU659348B2 (en) | 1995-05-11 |
| AU5031493A (en) | 1994-05-12 |
| EP0595598B1 (en) | 1997-06-18 |
| NZ250045A (en) | 1995-11-27 |
| CN1096290A (zh) | 1994-12-14 |
| BR9304379A (pt) | 1994-07-05 |
| CA2109269A1 (en) | 1994-04-30 |
| ATE154604T1 (de) | 1997-07-15 |
| DE69311675T2 (de) | 1997-12-18 |
| US5312972A (en) | 1994-05-17 |
| CN1235974A (zh) | 1999-11-24 |
| MY109423A (en) | 1997-01-31 |
| ES2105128T3 (es) | 1997-10-16 |
| JPH06192189A (ja) | 1994-07-12 |
| EP0595598A1 (en) | 1994-05-04 |
| DE69311675D1 (de) | 1997-07-24 |
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