CN1022631C - N-膦酰基甲基甘氨酸的生产方法 - Google Patents
N-膦酰基甲基甘氨酸的生产方法 Download PDFInfo
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
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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 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)]
-
- 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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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B5/00—Recording by magnetisation or demagnetisation of a record carrier; Reproducing by magnetic means; Record carriers therefor
- G11B5/62—Record carriers characterised by the selection of the material
- G11B5/73—Base layers, i.e. all non-magnetic layers lying under a lowermost magnetic recording layer, e.g. including any non-magnetic layer in between a first magnetic recording layer and either an underlying substrate or a soft magnetic underlayer
- G11B5/735—Base layers, i.e. all non-magnetic layers lying under a lowermost magnetic recording layer, e.g. including any non-magnetic layer in between a first magnetic recording layer and either an underlying substrate or a soft magnetic underlayer characterised by the back layer
- G11B5/7356—Base layers, i.e. all non-magnetic layers lying under a lowermost magnetic recording layer, e.g. including any non-magnetic layer in between a first magnetic recording layer and either an underlying substrate or a soft magnetic underlayer characterised by the back layer comprising non-magnetic particles in the back layer, e.g. particles of TiO2, ZnO or SiO2
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明涉及N-膦酰基甲基甘氨酸的生产方法。该方法是在有效量的选自锰和钴的盐和其盐的络合物和有效量的溴离子的存在下,将N-膦酰基甲基亚氨基二乙酸与含分子氧的气体接触。
Description
本发明涉及使用均相催化体系由N-膦酰基甲基亚氨基二乙酸的氧化制备N-膦酰甲基甘氨酸的方法,特别涉及在溴离子存在下以钴盐或锰盐作催化剂,由N-膦酰基甲基亚氨基二乙酸(NPID)的氧化生产N-膦酰基甲基甘氨酸的方法。
N-膦酰基甲基甘氨酸在农药化学中称为草甘膦,是一种高效的并具有商业重要性的植物毒性剂,用于控制种子萌芽、秧苗、生长和建成的木本和草本植被以及水生植物。N-膦酰基甲基甘氨酸和其盐类易于制成水基配方作为控制许多植物品种的芽后植物素性剂。N-膦酰基甲基甘氨酸和其盐类的特征在于其广谱活性,即对范围比较宽的植物种类的生长控制。
在先有技术中,由N-膦酰基甲基亚氨基二乙酸氧化成N-膦酰基甲基甘氨酸的已知方法很多。例如,Hershman的美国专利3,696,398公开的是在主要由活性炭组成的催化剂存在下,用含分子氧的气体作为氧化剂,将N-膦酰基甲基亚氨基二乙酸进行氧化以生产N-膦酰基甲基甘氨酸的方法;美国专利3,950,402公开了一种在水介质中,用游离含氧气体和贵金属催化剂(如载体上的钯、铂、铑),将N-膦酰基甲基亚氨基二乙酸氧化成N-膦酰基甲基甘氨酸的方法,美国专利3,954,848公开了一种用过氧化氢和一种酸,如硫酸或乙酸,氧化N-膦酰基亚氨基二乙酸的方法,匈牙利专利申请No.011706公开了一种在金属或金属化合物存在下,用过氧化物氧化N-膦酰基甲基亚氨基二乙酸的方法。
文献中也有许多在各种催化剂存在下,将烷基芳烃氧化成芳香酸的方法。例如,Sheldon和Kochi的《Metal Catalyzed Oxidations of Organic Compounds》(Academic Press,New York(1981)pp.126-129)叙述了溴化物(如溴化氢、溴化钠或有机溴化物)对钴和锰催化的烷基芳烃的自动氧化,具有显著的协同效应。
在上述先有技术中,使用非均相催化剂(如活性炭或沉积在活性炭上的铂)或酸,如硫酸,催化的反应,将N-膦酰基甲基亚氨基二乙酸氧化成N-膦酰基甲基甘氨酸的方法,已经能得满意的结果,但是仍然有必要将这些方法进行改进,以制备高产率的N-膦酰基甲基甘氨酸,并最大限度减少副产物(如磷酸酯)的形成。
在选自锰盐、钴盐、锰盐络合物和钴盐络合物的有效量催化剂和有效量溴离子存在下,将N-膦酰基甲基亚氨基二乙酸与含分子氧的气体接触以生产膦酰基甲基甘氨酸,可具有各种优点。
本发明的方法包括在溴离子存在下,以混合物或溶液形式,将N-膦酰基甲基亚氨基二乙酸与钴和/或锰盐或盐络合物相接触。此混合物或溶液与含分子氧的气体相接触,同时将整个反应加热至足够高的温度,以引发和进行N-膦酰基甲基亚氨基二乙酸的氧化反应,生产N-膦酰基甲基甘氨酸。
本发明的催化剂可为任何一种或多种本领域技术熟练者所悉知的锰盐,例如乙酸锰、硫酸锰和例如乙酰基丙酮酸锰(二或三价)那样的络合物,或钴盐,例如硫酸钴、乙酰基丙酮酸钴(二或三价)、氯化钴、溴化钴、硝酸钴和乙酸钴。
加入N-膦酰基甲基亚氨二乙酸的催化剂,可以是盐的形式或由加入能溶于反应混合物中的钴或锰的金属离子源(如二氧化锰)即时产生的盐。但是必须注意,在实例所述的条件下氯代酞菁锰离子是无催化性的。
本发明的钴或锰催化剂的浓度可在较大的限度内变化。催化剂浓度可在1摩尔至0.0001摩尔(每升)总金属离子浓度之间变化。对于钴和锰而言,反应对催化剂浓度有一级依赖关系,即催化剂浓度增加时,反应速率呈线性增加。优先选择的催化剂金属离子的浓度是在约0.1摩尔至约0.001摩尔的范围内。此浓度对反应能产生适合的快速率,反应易于控制并有利于N-膦酰基甲基甘氨酸的选择性。
任何溴离子源都可用于本发明的方法,例如元素溴或溴化铵、碱土金属溴化物之类的溴盐或包括溴化钠、溴化钾等的碱金属溴化物。
本发明方法的溴离子浓度可在较广限度内变化。溴离子浓度最好是与N-膦酰基甲基亚氨基二乙酸浓度***,溴离子/N-膦酰基甲基亚氨基二乙酸的摩尔比为0.05/1或更小时,看不出有什么优点。所使用的溴离子/N-膦酰基甲基亚氨基二乙酸的摩尔比最好是在约0.05/1至0.4/1之间,更优先选择的是约0.25至约0.35/1之间的摩尔比。溴离子/N-膦酰基甲基亚氨基二乙酸的摩尔比大于约0.4/1时,仅应速率降低。特别有利的溴离子/N-膦酰基甲基亚氨基二乙酸摩尔比为约0.25/1至0.35/1之间。
反应温度在约50℃至150℃的范围内足以引发和进行氧化反应,一般说来,反应温度上升,则反应速率增加。为达到易于控制反应速率和使反应的选择性有利于N-膦酰基甲基甘氨酸的形成,优先选择的温度范围为约70℃至约120℃之间,如使用较高的温度,如方便起见,必须使压力维持在能使反应体系保持液相并阻止沸腾的压力。
为了本发明的实施,必须将N-膦酰基甲基亚氨基二乙酸与有效量的锰或钴盐催化剂和有效量溴离子一起与含分子氧的气体相接触。“含分子氧气体”意即分子氧或任何含分子氧与一种或多种在反应条件下与氧或反应物或反应产物不发生反应的稀释剂相混合的气体,这种稀释剂气体有空气、氦、氩、氮或其他惰性气体或氧烃混合物。优先选择的分子氧源是未稀释的氧。
氧浓度(即氧分压)影响反应速率和有利于N-膦酰基甲基甘氨酸的选择性。氧分压增加时,反应速率和N-膦酰基甲基甘氨酸的选择性则增加。增加总反应压力或增加含氧气体中的分子氧浓度可提高氧的分压。氧分压的变化范围最好是从约2.06×105N/m2(30psig)至2.06×107N/m2(3000psig),特别是约3.1×106N/m2(450psig)至1.38×107N/m2(2000psig)。
鉴定本发明所公开的内容,对于本领域的技术熟练者来说,N-膦酰基甲基亚氨基二乙酸的溶液或混合物在钴或锰盐和溴离子存在下,与含分子氧的气体相接触的方式是可以十分不相同的。例如,N-膦酰基甲基亚氨基二乙酸可用搅动的方式(如鼓泡、搅拌、振摇等),与含氧气体相接触。本发明的方法仅要求含分子氧气体与含钴或锰盐催化剂和溴离子的N-膦酰基甲基亚氨基二乙酸水溶液或混合物很好地接触。
反应的初始pH,影响反应速率和N-膦酰基甲基甘氨酸的选择性。例如,用锰盐作催化剂时,初始pH增加,则反应速率增加,但N-膦酰基甲基甘氨酸的选择性有所降低。反应的初始pH可在约0.1至约7之间变化;优先选择的范围为约0.1至约3之间;最优先选择的pH范围为未调节的N-膦酰基甲基亚氨基二乙酸水溶液的pH,它随着N-膦酰基甲基亚氨基二乙酸的浓度和反应温度而变化。
氧化反应可在溶液或淤浆中发生。例如,在溶液中发生时,反应混合物中N-膦酰基甲基亚氨基二乙酸的初始浓度为在所要求的反应温度和溶液的初始pH下N-膦酰基甲基亚氨基二乙酸的溶解度
的函数。溶剂温度和初始pH发生改变,N-膦酰基甲基亚氨基二乙酸的溶解度也会改变。用钴盐作催化剂时,优先选择的N-膦酰基甲基亚氨基二乙酸的初始浓度为反应条件下含溶剂体系的饱和淤浆,这种浓度可得到最大产率的N-膦酰基甲基甘氨酸。但在以锰盐作催化剂时,N-膦酰基甲基亚氨基二乙酸的初始浓度应小于6wt%左右,以防止锰从溶液中沉淀出来并中断反应。
反应一般是在水溶液中进行,即含有至少约50wt%的水。优先选择的溶剂是蒸馏的去离子水。
现以下述各实例对本发明进一步说明,但本发明并非局限于此。下述各实例的反应均在Engineer autoclave 300ml高压釜中进行,釜顶装有搅拌器,有用作样品进口、气体进口和冲洗气体出口的三个阀口。搅拌器保持足够的搅动,以使气-液澈底混合。将所给量的催化剂和溴化物溶于或悬浮于含所给量N-膦酰基甲基亚氨基二乙酸的蒸馏无离子水溶液中。将反应釜密封,加热至给定的温度,再用氧加压至给定的压力。在加热前开始搅拌。
N-膦酰基甲基甘氨酸的选择性的百分率测定是用所得到的N-膦酰基甲基甘氨酸和N-甲酰基-N-膦酰基甲基甘氨酸的摩尔数除以所消耗的N-膦酰基甲基亚氨基二乙酸总摩尔数,再乘以100。百分转化率的测定是用所消耗的N-膦酰基甲基亚氨基二乙酸摩尔数除以初始N-膦酰基甲基亚氨基二乙酸的总摩尔数,再乘以100。
实例1
本例说明使用乙酸锰催化剂而无溴离子存在时,N-膦酰基甲基甘氨酸的形成。
将N-膦酰基甲基亚氨基二乙酸(9.08g0.04mol)和水(100ml)加入一钛高压釜(Autoclave Engineers制造),然后再加入乙酸锰(1.088g,0.006mol),内容物在氮气氛中加热至80℃,然后在约300cc/min。流率的吹扫氧气产生的3.1×106N/m2(450psig)的压力下加热2小时。于15、30、60、90、120和150分钟时取样测定。2.5小时后用高压液相色谱法测定,其转化率大于95%,选择性低于10%。
实例2
本例说明使用溴化锰催化剂而无附加溴离子所得到的反应结果。
将N-膦酰基甲基亚氨基二乙酸(13.62g,0.6mol)和四水合二溴化锰(1.29g,0.0045mol)与水(120ml)一起,加入实例1中所述的相同高压釜中,在实例1中所述压力下加热至80℃。90分钟后用高压液相色谱法分析反应混合物,结果表明转化率为67.18%,选择性为10.24%。
实例3
本例说明在本发明的方法中与溴化锰催化剂一起加入元素溴所产生的效果。
在实例1的钛高压釜中加入N-膦酰基甲基亚氨基二乙酸(27.24g,0.12mol)、水(120ml)、四水合二溴化锰(2.577g,0.0089mol)和元素溴(0.48g,0.03mol)。将反应混合物加热加压(如实例1)4小时又15分钟。用高压液相色谱法分析反应介质,其转化率为99.85%,选择性为35.07%。
实例4
使用与实例3相同的高压釜、温度和压力,在高压釜中加入N-膦酰基甲基亚氨基二乙酸(13.62g,0.06mol)、水(120ml)、二溴化锰四水合物(1.29g,0.0045mol)和溴化钠(2.4g,0.023mol)。1小时后用高压液相色谱法分析反应混合物,发现99.46%的N-膦酰基甲基亚氨基二乙酸已经转化,N-膦酰基甲基甘氨酸的选择性为50.45%。
实例1-4清楚地说明,对于在所述反应条件下,N-膦酰基甲基亚氨基二乙酸向N-膦酰基甲基甘氨酸的转化,溴离子起着确定的作用。
实例5-18
用七水合硫酸钴催化剂(1.34g,0.005mol)的和1800psig(1.24×107N/m2)的吹扫氧气(流率300cc/min.)在100克水中进行了一系列实验。可变因素是溴化物浓度、N-膦酰基甲基亚氨基二乙酸(NPID)浓度和温度。表Ⅰ所示为95%(或更高)转化后的结果。(见表1)
上表结果显示,溴离子的存在增加了N-膦酰基甲基甘氨酸的选择性,并降低了反应中的磷酸酯副产物。
实例19
本例是使用不同反应条件的本发明的方法。
在实例1的高压釜中加入NPID(10.87g,0.048mol)、水(125ml)、六水合二溴化钴
(1.6g,0.005mol)和溴化钠(0.5g,0.005mol)。将混合物加热至87.5℃,并用吹扫氧气加压至12.4×106N/m2(1800psi)3小时。混合物冷却至室温后,用高压液相色谱法进行分析。分析结果显示,有96%的NPID已经转化,N-膦酰基甲基甘氨酸的选择性为90.8%。
虽然本发明列举了特定的具体实施方案,并进行了比较详尽的叙述,但这仅是为了说明本发明而已。鉴于公开的本发明,其他的具体实施方案和操作技术对于本领域的技术熟练者来说是显而易见知,因而可以做不离开本发明所述精神的改变。
表1
实例 NaBr NPID 温度 操作时间 选择性 PO4
克 克 (℃) (Hrs.) %
5 1.23 20.44 90 3 1/4 86.11 5.65
6 1.23 30.00 85 6 85.60 5.30
7 2.46 20.44 95 2 1/2 85.20 5.99
8 1.23 20.44 90 3 1/4 86.70 5.79
9 1.23 10.87 95 2 84.79 4.91
10 2.46 10.87 90 3 1/4 87.53 5.00
11 1.23 30.00 95 2 1/4 82.87 7.46
12 2.46 20.44 85 6 87.13 5.06
13 2.46 30.00 90 4 1/2 85.11 5.96
14 0 30.00 90 2 3/4 73.36 14.45
15 0 20.44 95 1 3/4 78.46 10.41
16 0 10.87 90 2 1/2 84.85 6.52
17 0 20.44 85 4 1/4 84.01 7.80
18 1.23 10.87 85 4 1/4 89.33 3.72
Claims (13)
1、生产N-膦酰基甲基甘氨酸的方法,该方法包括在水溶液中,在选自锰和钴的盐和盐的络合物的催化剂和有效量溴离子存在下,将N-膦酰基甲基亚氨基二乙酸(NPID)与含分子氧的气体相接触,其中催化剂的浓度为每升水溶液含1摩尔至0.0001摩尔的总金属离子,溴离子/N-膦酰基甲基亚氨基二乙酸的摩尔比为0.05-0.4。
2、权利要求1的方法,其中催化剂的浓度为每升水溶液含0.1摩尔至0.001摩尔的总金属离子。
3、权利要求1的方法,其中溴离子/N-膦酰基甲基亚氨基二乙酸的摩尔比在0.25和0.35之间。
4、权利要求1的方法,其中的催化剂是锰盐。
5、权利要求4的方法,其中的催化剂浓度为每升水溶液含0.1摩尔至0.001摩尔的总金属离子,溴离子/N-膦酰基甲基亚氨基二乙酸的摩尔比在0.05和0.4之间。
6、权利要求5的方法,其中含氧气体的氧分压在2.06×105N/m2和2.06×107N/m2之间。
7、权利要求6的方法,其中的氧分压在3.1×106/m2和1.38×107N/m2之间。
8、权利要求5的方法,其中N-膦酰基甲基亚氨基二乙酸是处于初始pH在0.1和3之间的水介质中。
9、权利要求1的方法,其中的催化剂是钴盐。
10、权利要求9的方法,其中的含氧气体的氧分压在2.06×105N/m2和2.06×107N/m2之间。
11、权利要求10的方法,其中的氧分压在3.1×106N/m2和1.38×107N/m2之间。
12、权利要求9的方法,其中的NPID是处于初始pH为pH0.1和pH3之间的水介质中。
13、权利要求1的方法,其中的NPID是处于淤浆之中。
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US6365772B1 (en) | 1995-05-30 | 2002-04-02 | Hampshire Chemical Corp. | Facile synthesis of phosphonomethylglycine from phosphonomethyliminodiacetic acid |
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