WO1994022881A1 - Process for preparing n-phosphonomethylglycinonitrile or derivatives thereof - Google Patents

Process for preparing n-phosphonomethylglycinonitrile or derivatives thereof Download PDF

Info

Publication number
WO1994022881A1
WO1994022881A1 PCT/GB1994/000501 GB9400501W WO9422881A1 WO 1994022881 A1 WO1994022881 A1 WO 1994022881A1 GB 9400501 W GB9400501 W GB 9400501W WO 9422881 A1 WO9422881 A1 WO 9422881A1
Authority
WO
WIPO (PCT)
Prior art keywords
phosphonomethylglycinonitrile
alkyl ester
acid salt
stage
acid
Prior art date
Application number
PCT/GB1994/000501
Other languages
French (fr)
Inventor
Ian Hodgkinson
Original Assignee
Zeneca Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zeneca Limited filed Critical Zeneca Limited
Priority to US08/532,832 priority Critical patent/US5606093A/en
Priority to AU62137/94A priority patent/AU685432B2/en
Priority to BR9406353A priority patent/BR9406353A/en
Priority to JP6521780A priority patent/JPH08508285A/en
Priority to HU9502820A priority patent/HU218171B/en
Priority to DE69401501T priority patent/DE69401501T2/en
Priority to EP94909207A priority patent/EP0693075B1/en
Publication of WO1994022881A1 publication Critical patent/WO1994022881A1/en
Priority to GR960403579T priority patent/GR3022293T3/en

Links

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)]
    • C07F9/40—Esters thereof
    • C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl
    • 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

Definitions

  • the present invention relates to a process for the manufacture of N-phosphonomethylglycinonitrile or salts and esters thereof.
  • N-phosphonomethylglycinonitrile is a known compound, useful as a herbicide. It may also be converted by hydrolysis into the commercially important herbicide N-phosphonomethylglycine.
  • N-phosphonomethylglycinonitrile is described for example in
  • a process for the manufacture of an acid salt of an alkyl ester of N-phosphonomethyl- glycinonitrile which comprises reacting methyleneaminoacetonitrile trimer with a trialkylphosphite under anhydrous conditions and in the presence of an anhydrous acid and an inert solvent in which the methyleneaminoacetonitrile trimer starting material is at least partially soluble and the acid salt of the alkyl ester of N-phosphonomethylglycinonitrile product is substantially insoluble and thereafter recovering the precipitated acid salt of the alkyl ester of N-phosphonomethylglycinonitrile.
  • methyleneaminoacetonitrile trimer as used herein refers to the compound of formula (I) as shown in Scheme 1 which
  • the groups R in the trialkylphosphite (II) represent C 1-7 alkyl groups and preferably C 1-5 alkyl groups and the trialkylphosphite is thus preferably a tri(C 1-7 alkyl)phosphite or a tri (C 1-5 alkyl)phosphite.
  • the trialkylphosphite is preferably trimethylphosphite, triethylphosphite or tributylphosphite.
  • Trimethylphosphite is a readily available phosphonating agent which is thus a particularly effective feedstock for the commercial manufacture of
  • N-phosphonomethylglycinonitrile N-phosphonomethylglycinonitrile.
  • Higher alkyl phosphites such as
  • tributylphosphite and tripentylphosphite may provide advantages in terms of commercial production of product as indicated in more detail below.
  • Suitable anhydrous acids which can be used in the process of the present invention and which will form an insoluble salt of the alkyl ester of N-phosphonomethylglycinonitrile product will occur to those skilled in the art.
  • Hydrogen halides are especially suitable for use in the process of the present invention.
  • Hydrogen chloride in particular is an effective and readily available anhydrous acid.
  • the solvent should be inert in the sense that it is not significantly attacked under the reaction conditions, and in particular the solvent should be stable against attack by the trialkylphosphite.
  • Suitable inert solvents in which the methyleneaminoacetonitrile trimer starting material is at least partially soluble and the acid salt of the alkyl ester of N-phosphonomethylglycinonitrile product is substantially insoluble will occur to those skilled in the art. It is to be understood that the methyleneaminoacetonitrile trimer starting material should be at least partially soluble in the inert solvent.
  • the methyleneaminoacetonitrile trimer starting material should be sufficiently soluble that, even though all the starting material may not be dissolved at the commencement of the phosphonation reaction, sufficient will be in solution for the phosphonation reaction to start. Thereafter more starting material will dissolve as the reaction progresses and the starting material in solution is depleted until substantially all the starting material has dissolved by the time the phosphonation reaction is completed.
  • Suitable inert solvents include nitriles such as acetonitrile, esters such as ethyl acetate, haloalkanes such as ethylene dichloride and dichloromethane, ketones such as metylisobutyl ketone, ethers such as diethyl ether or tetrahydrofuran and halogenated aromatic hydrocarbons such as monochlorobenzene.
  • Acetonitrile is an especially effective solvent in which the methyleneaminoacetonitrile trimer is generally completely soluble at the concentrations used in the process of the present invention. It is not essential that the acid salt of the alkyl ester of
  • N-phosphonomethylglycinonitrile product is completely insoluble in the solvent; it is sufficient that at least a proportion of the acid salt of the alkyl ester of N-phosphonomethylglycinonitrile product precipitates under the reaction conditions and is recovered accordingly.
  • the acid salt of the alkyl ester of N-phosphonomethylglycinonitrile has a very low solubility in the majority of organic solvents and this represents a particular advantage of the process of the present invention.
  • the reaction conveniently takes place substantially at ambient temperature although higher or lower temperatures, for example temperatures in the range from -50°C to 200°C, for example from -10°C to 50°C may be used if desired.
  • Heat may be generated during the course of the reaction and the reaction may if desired be cooled to maintain the temperature substantially at the preferred value, for example at ambient or slightly above.
  • gaseous hydrogen chloride When gaseous hydrogen chloride is used as the acid, it may either be passed directly into the reaction mixture or may be added to the reaction mixture as a solution in the dry solvent.
  • the reaction suitably takes place under in the absence of moisture and under non-oxidising conditions, for example under a dry and non-oxidising atmosphere.
  • gaseous hydrogen chloride is passed directly into the reaction mixture, the gas itself provides the necessary dry and non- oxidising atmosphere.
  • a suitable inert gas such as dry nitrogen to provide the dry and non- oxidising atmosphere.
  • a substantially stoichiometric proportion of trialkylphosphite Preferably there is used a substantially stoichiometric proportion of trialkylphosphite.
  • the proportion of the acid will depend on the
  • hydrochloric acid there is preferably employed from 3 to 12 moles of hydrochloric acid per mole of
  • a higher trialkylphosphite such as tributylphosphite or tripentylphosphite as phosphonating agent.
  • the product of the hydrolysis of the butyl or pentyl ester of N-phosphonomethylglycinonitrile is butanol or pentanol respectively.
  • the higher alkanols are immiscible with the aqueous hydrolysis phase and the organic phase can be readily separated and the alkanol re-cycled and used for the formation of more trialkyl phosphite, for example by reaction with phosphorous trichloride.
  • butyl or pentyl chloride formed in the course of the reaction of the present invention may conveniently be removed from the reaction solvent (filtrate) by distillation and added to the hydrolysis stage of the butyl or pentyl ester of N-phosphonomethylglycinonitrile where it is itself hydrolysed to form further butanol or pentanol respectively which becomes included in the re-cycle.
  • N-phosphonomethylglycinonitrile product is substantially insoluble and thereafter; ii) filtering the reaction mixture from stage (i) to recover the precipitated acid salt of the alkyl ester of
  • N-phosphonomethylglycinonitrile from the filtrate containing solvent and butyl chloride or pentyl chloride;
  • N-phosphonomethylglycinonitrile under acidic conditions to form N-phosphonomethylglycine and butanol or pentanol;
  • Example 2 The procedure of Example 1 was repeated except that acetonitrile was used as solvent. 3.1g of essentially pure dimethyl ester of phosphonomethylglycinonitrile was obtained, corresponding to a yield of 56%.
  • Example 2 The procedure of Example 2 was repeated except that 1.825g (0.05 g mol) of anhydrous HCl was dissolved in 30ml of acetonitrile prior to addition to the reaction vessel. 3.4g of essentially pure dimethyl ester of phosphonomethylglycinonitrile was obtained, corresponding to a yield of 63%.
  • Methyleneaminoacetonitrile trimer 1.7g and trimethylphosphite 3.2g were suspened in 40ml of dichloromethane. The mixture was stirred and maintained at a temperature below 35 C whilst anhydrous HCl was introduced over a period of 2 hours. During the addition, a white precipitate was formed. After cooling to 0°C, the product was filtered, washed with 20ml chilled dichloromethane and dried to give 2.9g of the dimethyl ester of phophonomethylglycinonitrile (54.1% yield). Proton nmr indicated that the product was essentially pure.
  • Example 5 The procedure of Example 5 was repeated except that ethyl acetate was used in place of acetonitrile. The methyleneaminoacetonitrile was only partially soluble in the ethyl acetate and was suspended in the reactin mixture. 11.9g of essentially pure dibutyl ester of phosphonomethylglycinonitrile (79.7% yield) were obtained. CHEMICAL FORMULAE

Landscapes

  • 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)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Glass Compositions (AREA)
  • Iron Core Of Rotating Electric Machines (AREA)

Abstract

A process for the manufacture of an acid salt of an alkyl ester of N-phosphonomethylglycinonitrile comprises reacting methyleneaminoacetonitrile trimer with a trialkylphosphite under anhydrous conditions and in the presence of an anhydrous acid and an inert solvent in which the methyleneaminoacetonitrile trimer starting material is at least partially soluble and the acid salt of the alkyl ester of N-phosphonomethylglycinonitrile product is substantially insoluble and thereafter recovering the precipitated acid salt of the alkyl ester of N-phosphonomethylglycinonitrile.

Description

PROCESS FOR PREPARING N-PHOSHONOMETHYLGLYCINONITRILE OR
DERIVATIVES THEREOF.
The present invention relates to a process for the manufacture of N-phosphonomethylglycinonitrile or salts and esters thereof.
N-phosphonomethylglycinonitrile is a known compound, useful as a herbicide. It may also be converted by hydrolysis into the commercially important herbicide N-phosphonomethylglycine.
N-phosphonomethylglycinonitrile is described for example in
US 4,221,583. An alternative process for the manufacture of
N-phosphonomethylglycine via the intermediate formation of
N-phosphonomethylglycinonitrile is described in US 3,923,877 whilst a related process which is also believed to proceed via
N-phosphonomethylglycinonitrile as an intermediate is described in
US 4,415,503.
We have now found that the action of a trialkylphosphite phosphonating agent on methyleneaminoacetonitrile trimer in the presence of an acid and an inert solvent provides an improved process which is well adapted to manufacture on a commercial scale and which provides excellent yields of N-phosphonomethylglycinonitrile in the form of a salt of its alkyl ester containing an exceptionally low level of impurities.
According to the present invention there is provided a process for the manufacture of an acid salt of an alkyl ester of N-phosphonomethyl- glycinonitrile which comprises reacting methyleneaminoacetonitrile trimer with a trialkylphosphite under anhydrous conditions and in the presence of an anhydrous acid and an inert solvent in which the methyleneaminoacetonitrile trimer starting material is at least partially soluble and the acid salt of the alkyl ester of N-phosphonomethylglycinonitrile product is substantially insoluble and thereafter recovering the precipitated acid salt of the alkyl ester of N-phosphonomethylglycinonitrile.
The description methyleneaminoacetonitrile trimer as used herein refers to the compound of formula (I) as shown in Scheme 1 which
illustrates the process of the present invention. In Scheme 1, the groups R in the trialkylphosphite (II) represent C1-7alkyl groups and preferably C1-5 alkyl groups and the trialkylphosphite is thus preferably a tri(C1-7 alkyl)phosphite or a tri (C1-5 alkyl)phosphite. The trialkylphosphite is preferably trimethylphosphite, triethylphosphite or tributylphosphite. Trimethylphosphite is a readily available phosphonating agent which is thus a particularly effective feedstock for the commercial manufacture of
N-phosphonomethylglycinonitrile. Higher alkyl phosphites such as
tributylphosphite and tripentylphosphite may provide advantages in terms of commercial production of product as indicated in more detail below.
Suitable anhydrous acids which can be used in the process of the present invention and which will form an insoluble salt of the alkyl ester of N-phosphonomethylglycinonitrile product will occur to those skilled in the art. Hydrogen halides are especially suitable for use in the process of the present invention. Hydrogen chloride in particular is an effective and readily available anhydrous acid.
The solvent should be inert in the sense that it is not significantly attacked under the reaction conditions, and in particular the solvent should be stable against attack by the trialkylphosphite. Suitable inert solvents in which the methyleneaminoacetonitrile trimer starting material is at least partially soluble and the acid salt of the alkyl ester of N-phosphonomethylglycinonitrile product is substantially insoluble will occur to those skilled in the art. It is to be understood that the methyleneaminoacetonitrile trimer starting material should be at least partially soluble in the inert solvent. By this is meant that the methyleneaminoacetonitrile trimer starting material should be sufficiently soluble that, even though all the starting material may not be dissolved at the commencement of the phosphonation reaction, sufficient will be in solution for the phosphonation reaction to start. Thereafter more starting material will dissolve as the reaction progresses and the starting material in solution is depleted until substantially all the starting material has dissolved by the time the phosphonation reaction is completed. Examples of suitable inert solvents include nitriles such as acetonitrile, esters such as ethyl acetate, haloalkanes such as ethylene dichloride and dichloromethane, ketones such as metylisobutyl ketone, ethers such as diethyl ether or tetrahydrofuran and halogenated aromatic hydrocarbons such as monochlorobenzene. Acetonitrile is an especially effective solvent in which the methyleneaminoacetonitrile trimer is generally completely soluble at the concentrations used in the process of the present invention. It is not essential that the acid salt of the alkyl ester of
N-phosphonomethylglycinonitrile product is completely insoluble in the solvent; it is sufficient that at least a proportion of the acid salt of the alkyl ester of N-phosphonomethylglycinonitrile product precipitates under the reaction conditions and is recovered accordingly. In general, however the acid salt of the alkyl ester of N-phosphonomethylglycinonitrile has a very low solubility in the majority of organic solvents and this represents a particular advantage of the process of the present invention.
The reaction conveniently takes place substantially at ambient temperature although higher or lower temperatures, for example temperatures in the range from -50°C to 200°C, for example from -10°C to 50°C may be used if desired. Heat may be generated during the course of the reaction and the reaction may if desired be cooled to maintain the temperature substantially at the preferred value, for example at ambient or slightly above.
When gaseous hydrogen chloride is used as the acid, it may either be passed directly into the reaction mixture or may be added to the reaction mixture as a solution in the dry solvent.
The reaction suitably takes place under in the absence of moisture and under non-oxidising conditions, for example under a dry and non-oxidising atmosphere. When gaseous hydrogen chloride is passed directly into the reaction mixture, the gas itself provides the necessary dry and non- oxidising atmosphere. If the hydrogen chloride is added to the reaction mixture as a solution in the dry solvent, it may be desirable to use a suitable inert gas such as dry nitrogen to provide the dry and non- oxidising atmosphere.
Preferably there is used a substantially stoichiometric proportion of trialkylphosphite. The proportion of the acid will depend on the
particular acid used. If hydrochloric acid is used, there is preferably employed from 3 to 12 moles of hydrochloric acid per mole of
methyleneaminoacetonitrilee trimer.
It is a particular advantage of the process of the present invention that the product precipitates in a substantially pure form allowing ready isolation.
Hydrolysis of the alkyl ester of N-phosphonomethyl-glycinonitrile to N-phosphonomethylglycine or a salt thereof is a well-known process and is
Figure imgf000006_0001
acid, and N-phosphonomethyIglycine is formed.
There are advantages for such a combined process in using a higher trialkylphosphite such as tributylphosphite or tripentylphosphite as phosphonating agent. In particular, the product of the hydrolysis of the butyl or pentyl ester of N-phosphonomethylglycinonitrile is butanol or pentanol respectively. The higher alkanols are immiscible with the aqueous hydrolysis phase and the organic phase can be readily separated and the alkanol re-cycled and used for the formation of more trialkyl phosphite, for example by reaction with phosphorous trichloride. Furthermore, the butyl or pentyl chloride formed in the course of the reaction of the present invention (scheme 1) may conveniently be removed from the reaction solvent (filtrate) by distillation and added to the hydrolysis stage of the butyl or pentyl ester of N-phosphonomethylglycinonitrile where it is itself hydrolysed to form further butanol or pentanol respectively which becomes included in the re-cycle.
Thus according to a further aspect of the present invention there is provided a process for the manufacture of N-phosphonomethylglycine which comprises
i) reacting methyleneaminoacetonitrile trimer with tributylphosphite or tripentylphosphite under anhydrous conditions and in the presence of an anhydrous acid and an inert solvent in which the methyleneaminoacetonitrile trimer starting material is at least partially soluble and the acid salt of the alkyl ester of
N-phosphonomethylglycinonitrile product is substantially insoluble and thereafter; ii) filtering the reaction mixture from stage (i) to recover the precipitated acid salt of the alkyl ester of
N-phosphonomethylglycinonitrile from the filtrate containing solvent and butyl chloride or pentyl chloride;
iii) hydrolysing the acid salt of the alkyl ester of
N-phosphonomethylglycinonitrile under acidic conditions to form N-phosphonomethylglycine and butanol or pentanol;
iv) distilling the filtrate from stage (ii) and re-cycling the
solvent to stage (i) and the butyl chloride or pentyl chloride to stage (iii) where it undergoes hydrolysis to form butanol or pentanol respectively;
v) recovering the butanol or pentanol from stage (iii) by phase
separation, reacting it with phosphorous trichloride to form tributylphosphite and tripentylphosphite respectively and recycling the tributylphosphite or tripentylphoshite to stage (i); and
vi) recovering the N-phosphonomethylglycine product from stage (iii). The N-phosphonomethylglycine product from stage (iii) is conveniently recovered by crystallisation.
The present invention is illustrated by the following Examples in which all parts and percentages are by weight unless otherwise stated.
EXAMPLE 1
Methyleneaminoacetonitrile trimer 1.7g (0.0083g mol) and
trimethylphosphite 3.1g (0.025g mol) were suspended in 30ml of ethyl acetate. The mixture was stirred and maintained at about room temperature whilst anhydrous HCl was introduced slowly. During the addition, a white precipitate was formed. GC analysis showed that all the trimer had been consumed after the reaction had been allowed to stand overnight at ambient temperature. The solid was then isolated by filtration and washed with solvent. 3.6g of product were obtained, corresponding to a 67% yield. The solid was analysed by GC and NMR and was found to be the hydrochloride salt of the dimethyl ester of phosphonomethylglycinonitrile. The product was essentially pure with no significant contaminants identified by GC or NMR.
EXAMPLE 2
The procedure of Example 1 was repeated except that acetonitrile was used as solvent. 3.1g of essentially pure dimethyl ester of phosphonomethylglycinonitrile was obtained, corresponding to a yield of 56%.
EXAMPLE 3
The procedure of Example 2 was repeated except that 1.825g (0.05 g mol) of anhydrous HCl was dissolved in 30ml of acetonitrile prior to addition to the reaction vessel. 3.4g of essentially pure dimethyl ester of phosphonomethylglycinonitrile was obtained, corresponding to a yield of 63%.
EXAMPLE 4
Methyleneaminoacetonitrile trimer 1.7g and trimethylphosphite 3.2g were suspened in 40ml of dichloromethane. The mixture was stirred and maintained at a temperature below 35 C whilst anhydrous HCl was introduced over a period of 2 hours. During the addition, a white precipitate was formed. After cooling to 0°C, the product was filtered, washed with 20ml chilled dichloromethane and dried to give 2.9g of the dimethyl ester of phophonomethylglycinonitrile (54.1% yield). Proton nmr indicated that the product was essentially pure.
EXAMPLE 5
Methyleneaminoacetonitrile trimer 3.4g and tributylphosphite (14g of 90%strength) were dissolved in 40ml of acetonitrile. The mixture was stirred and maintained at a temperature below 35°C whilst anhydrous HCl was introduced over a period of 3 hours at a rate of 30ml/min. During the addition, a white precipitate was formed. After cooling to 0°C, the product was filtered, washed with chilled acetonitrile and dried to give 13.2g of the dibutyl ester of phophonomethylglycinonitrile (88% yield). Proton nmr indicated that the product was essentially pure.
EXAMPLE 6
The procedure of Example 5 was repeated except that ethyl acetate was used in place of acetonitrile. The methyleneaminoacetonitrile was only partially soluble in the ethyl acetate and was suspended in the reactin mixture. 11.9g of essentially pure dibutyl ester of phosphonomethylglycinonitrile (79.7% yield) were obtained. CHEMICAL FORMULAE
(IN DESCRIPTION)
Scheme 1
V
Figure imgf000009_0001

Claims

1. A process for the manufacture of an acid salt of an alkyl ester of N-phosphonomethylglycinonitrile which comprises reacting
methyleneaminoacetonitrile trimer with a trialkylphosphite under anhydrous conditions and in the presence of an anhydrous acid and an inert solvent in which the methyleneaminoacetonitrile trimer starting material is at least partially soluble and the acid salt of the alkyl ester of N-phosphonomethylglycinonitrile product is substantially insoluble and thereafter recovering the precipitated acid salt of the alkyl ester of N-phosphonomethylglycinonitrile.
2. A process according to claim 1 wherein the trialkylphosphite is a tri(C1-7 alkyl)phosphite.
3. A process according to claim 2 wherein the trialkylphosphite is a tri(C1-5 alkyl)phosphite.
4. A process according to any of the preceding claims wherein the
anhydrous acid is hydrogen chloride.
5. A process according to claim 4 wherein there is used a substantially stoichiometric proportion of trialkylphosphite and from 3 to 12 moles of hydrochloric acid per mole of methyleneaminoacetonitrile trimer.
6. A process according to any of the preceding claims wherein the inert solvent is a nitrile, an ester, a haloalkane, a ketone, an ether or a halogenated aromatic hydrocarbon.
7. A process according to claim 5 wherein the inert solvent is
acetonitrile, ethyl acetate, methyl isobutyl ketone, diethyl ether, tetrahydrofuran, ethylene dichloride, dichloromethane or
monoch1 orobenzene.
8. A process according to any of the preceding claims wherein the
reaction takes place at a temperature of from -10ºC to 50ºC.
9. A process for the manufacture of N-phosphonomethylglycine which comprises
i) reacting methyleneaminoacetonitrile trimer with a
trialkylphosphite under anhydrous conditions and in the presence of an anhydrous acid and an inert solvent in which the methyleneaminoacetonitrile trimer starting material is at least partially soluble and the acid salt of the alkyl ester of
N-phosphonomethylglycinonitrile product is substantially insoluble and thereafter
ii) recovering the precipitated acid salt of the alkyl ester of
N-phosphonomethylglycinonitrile and
iii) hydrolysing the acid salt of the alkyl ester of
N-phosphonomethylglycinonitrile to form N-phosphonomethylglycine.
10. A process for the manufacture of N-phosphonomethylglycine which
comprises
i) reacting methyleneaminoacetonitrile trimer with tributylphosphite or tripentylphosphite under anhydrous conditions and in the presence of an anhydrous acid and an inert solvent in which the methyleneaminoacetonitrile trimer starting material is at least partially soluble and the acid salt of the alkyl ester of N-phosphonomethylglycinonitrile product is substantially insoluble and thereafter;
ii) filtering the reaction mixture from stage (i) to recover the
precipitated acid salt of the alkyl ester of
N-phosphonomethylglycinonitrile from the filtrate containing solvent and butyl chloride or pentyl chloride;
iii) hydrolysing the acid salt of the alkyl ester of
N-phosphonomethylglycinonitrile under acidic conditions to form N-phosphonomethylglycine and butanol or pentanol;
iv) distilling the filtrate from stage (ii) and re-cycling the
solvent to stage (i) and the butyl chloride or pentyl chloride to stage (iii) where it undergoes hydrolysis to form butanol or pentanol respectively; v) recovering the butanol or pentanol from stage (iii) by phase separation, reacting it with phosphorous trichloride to form tributylphosphite and tripentylphosphite respectively and recycling the tributylphosphite or tripentylphoshite to stage (i); and
vi) recovering the N-phosphonomethylglycine product from stage (iii)
PCT/GB1994/000501 1993-04-07 1994-03-15 Process for preparing n-phosphonomethylglycinonitrile or derivatives thereof WO1994022881A1 (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
US08/532,832 US5606093A (en) 1993-04-07 1994-03-15 Process for preparing N-phosphonomethylglycinonitrile or derivatives thereof
AU62137/94A AU685432B2 (en) 1993-04-07 1994-03-15 Process for preparing N-phosphonomethylglycinonitrile or derivatives thereof
BR9406353A BR9406353A (en) 1993-04-07 1994-03-15 Process for the manufacture of an acid salt of an alkyl ester of N-phosphono-methyl-glycine-nitrile and N-phosphono-methyl-glycine
JP6521780A JPH08508285A (en) 1993-04-07 1994-03-15 Method
HU9502820A HU218171B (en) 1993-04-07 1994-03-15 Process for preparing n-phosphonomethylglycinonitrile or derivatives thereof
DE69401501T DE69401501T2 (en) 1993-04-07 1994-03-15 METHOD FOR PRODUCING N-PHOSPHONOMETHYLGLYCINONITRILES OR DERIVATIVES THEREOF
EP94909207A EP0693075B1 (en) 1993-04-07 1994-03-15 Process for preparing n-phosphonomethylglycinonitrile or derivatives thereof
GR960403579T GR3022293T3 (en) 1993-04-07 1997-01-16 Process for preparing n-phosphonomethylglycinonitrile or derivatives thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9307234.6 1993-04-07
GB939307234A GB9307234D0 (en) 1993-04-07 1993-04-07 Process

Publications (1)

Publication Number Publication Date
WO1994022881A1 true WO1994022881A1 (en) 1994-10-13

Family

ID=10733470

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1994/000501 WO1994022881A1 (en) 1993-04-07 1994-03-15 Process for preparing n-phosphonomethylglycinonitrile or derivatives thereof

Country Status (16)

Country Link
US (1) US5606093A (en)
EP (1) EP0693075B1 (en)
JP (1) JPH08508285A (en)
CN (1) CN1042337C (en)
AT (1) ATE147745T1 (en)
AU (1) AU685432B2 (en)
BR (1) BR9406353A (en)
CA (1) CA2158472A1 (en)
DE (1) DE69401501T2 (en)
DK (1) DK0693075T3 (en)
ES (1) ES2096459T3 (en)
GB (1) GB9307234D0 (en)
GR (1) GR3022293T3 (en)
HU (1) HU218171B (en)
MY (1) MY131567A (en)
WO (1) WO1994022881A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996015135A1 (en) * 1994-11-16 1996-05-23 Zeneca Limited Process for the manufacture of n-phosphonomethylglycine
WO1998029106A2 (en) * 1996-12-30 1998-07-09 Monsanto Company Method for preparing cyanophosphonate derivatives from phosphoric anhydride and cyanide

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AR027024A1 (en) * 1999-12-23 2003-03-12 Basf Ag PROCEDURE FOR THE PREPARATION OF N-PHOSPHONOMETILGLYCIN

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3923877A (en) * 1972-11-08 1975-12-02 Ici Ltd Preparation of N-phosphonomethyl glycine
US4083898A (en) * 1976-12-13 1978-04-11 Monsanto Company Process for preparing O-aryl, N-phosphonomethylglycinonitriles
EP0068732A1 (en) * 1981-06-19 1983-01-05 Monsanto Company Herbicidally active monoesters and diesters of n-alkyl substituted amino methyl phosphonic acid and process for preparing same
US4415503A (en) * 1982-09-28 1983-11-15 Stauffer Chemical Company Method for preparation of N-phosphonomethylglycine

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3923877A (en) * 1972-11-08 1975-12-02 Ici Ltd Preparation of N-phosphonomethyl glycine
US4083898A (en) * 1976-12-13 1978-04-11 Monsanto Company Process for preparing O-aryl, N-phosphonomethylglycinonitriles
EP0068732A1 (en) * 1981-06-19 1983-01-05 Monsanto Company Herbicidally active monoesters and diesters of n-alkyl substituted amino methyl phosphonic acid and process for preparing same
US4415503A (en) * 1982-09-28 1983-11-15 Stauffer Chemical Company Method for preparation of N-phosphonomethylglycine

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996015135A1 (en) * 1994-11-16 1996-05-23 Zeneca Limited Process for the manufacture of n-phosphonomethylglycine
US5679843A (en) * 1994-11-16 1997-10-21 Zeneca Limited Process for the production of N-phosphonomethylalycine and salts thereof
CN1061982C (en) * 1994-11-16 2001-02-14 曾尼卡有限公司 Process for manufacture of N-phosphonomethylglycine
WO1998029106A2 (en) * 1996-12-30 1998-07-09 Monsanto Company Method for preparing cyanophosphonate derivatives from phosphoric anhydride and cyanide
WO1998029106A3 (en) * 1996-12-30 1999-02-11 Monsanto Co Method for preparing cyanophosphonate derivatives from phosphoric anhydride and cyanide

Also Published As

Publication number Publication date
GR3022293T3 (en) 1997-04-30
BR9406353A (en) 1996-02-06
HU218171B (en) 2000-06-28
GB9307234D0 (en) 1993-06-02
JPH08508285A (en) 1996-09-03
EP0693075A1 (en) 1996-01-24
DE69401501D1 (en) 1997-02-27
US5606093A (en) 1997-02-25
CN1120842A (en) 1996-04-17
CA2158472A1 (en) 1994-10-13
DK0693075T3 (en) 1997-07-14
ATE147745T1 (en) 1997-02-15
HUT72039A (en) 1996-03-28
DE69401501T2 (en) 1997-04-30
HU9502820D0 (en) 1995-11-28
ES2096459T3 (en) 1997-03-01
MY131567A (en) 2007-08-30
EP0693075B1 (en) 1997-01-15
AU6213794A (en) 1994-10-24
CN1042337C (en) 1999-03-03
AU685432B2 (en) 1998-01-22

Similar Documents

Publication Publication Date Title
US7084298B2 (en) Method for producing n-phosphonomethyl iminodiacetic acid
US4427599A (en) Method for preparation of N-phosphonomethylglycine
EP0693075B1 (en) Process for preparing n-phosphonomethylglycinonitrile or derivatives thereof
RU2260010C2 (en) Method for preparing n-phosphonomethylglycine and intermediate substance for its preparing
EP0104775B1 (en) Production of n-phosphonomethylglycine
EP0693074B1 (en) Process for the manufacture of aminomethanephosphonic acid
US4487724A (en) Method for preparation of N-phosphonomethylglycine
KR100776105B1 (en) Process for Preparing Methylene Bisphosphonic Acid Salts
US20040236144A1 (en) Method for producing $g(a)-aminophosphonic acids
US4429124A (en) Method for preparation of N-phosphonomethylglycine
US4476063A (en) N-Acylaminomethyl-N-cyanomethyl phosphonates
KR100878928B1 (en) Method for Producing N-Phosphonomethylglycine
US4534902A (en) Method for preparation of N-phosphonomethylglycine
US4569802A (en) Method for preparation of N-phosphonomethylglycine
US4535181A (en) N-carboalkoxymethyl-N-halomethyl amides
US4454063A (en) O,O-dialkyl-N-phosphonomethyl-N-halomethyl acetamide
CA1222524A (en) Method for preparation of n-phosphonomethylglycine
US4425283A (en) Method for preparation of N-phosphonomethylglycine
JPH0469391A (en) Production of dialkyl phosphite
NO833829L (en) PROCEDURE FOR THE PREPARATION OF N-PHOSPHONOMETHYLGYLINE
HU194897B (en) Process for preparing n-(phosphonomethyl)-glycine
JPH0374236B2 (en)

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 94191710.X

Country of ref document: CN

AK Designated states

Kind code of ref document: A1

Designated state(s): AU BB BG BR BY CA CN CZ FI GE HU JP KG KP KR KZ LK LV MD MG MN MW NO NZ PL RO RU SD SK TJ UA US UZ VN

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
WWE Wipo information: entry into national phase

Ref document number: 1994909207

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2158472

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 08532832

Country of ref document: US

WWP Wipo information: published in national office

Ref document number: 1994909207

Country of ref document: EP

WWG Wipo information: grant in national office

Ref document number: 1994909207

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 1997 838467

Country of ref document: US

Date of ref document: 19970407

Kind code of ref document: A