CA1039739A - Process for the production of n-(phosphonomethyl) glycine - Google Patents
Process for the production of n-(phosphonomethyl) glycineInfo
- Publication number
- CA1039739A CA1039739A CA241,438A CA241438A CA1039739A CA 1039739 A CA1039739 A CA 1039739A CA 241438 A CA241438 A CA 241438A CA 1039739 A CA1039739 A CA 1039739A
- Authority
- CA
- Canada
- Prior art keywords
- glycine
- phosphonomethyl
- hydrogen
- acid compound
- reaction
- Prior art date
- Legal status (The legal status 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 status listed.)
- Expired
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)]
- C07F9/3804—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
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)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Abstract of the Disclosure N-(phosphonomethyl)glycine is produced by the re-duction of a carbonylaldiminomethanephosphonate. The carbonyl-aldiminomethanephosphonate is produced by the reaction of glyoxal or glyoxylic acid or its esters with aminomethyl-phosphonic acid esters. The N-(phosphonomethyl)glycine produced is useful as a post-emergent herbicide.
Description
~39739 PROCESS FOR THE PRODUCTION OF
N-(PHOSPHONOMETHYL)GLYCINE
:
This invention relates to a process for pr~ducing N-(phosphonomethyl)glycine by the reduction of carbonylaldimino-methanephosphonate. The carbonylaldiminomethanephosphonates are produced by the reaction of glyoxylic acid esters or ;
glyoxal with aminomethanephosphonic acid esters.
It is known that N-(phosphonomethyl)glycine can be produced by the oxidation of N-(phosphonomethyl)iminodiacetic acid either electrolytically or by chemical oxidation.
It has now been discovered that N-(phosphonomethyl)-glyclne cAn be produced by the catalytic reduction of carbonyl-,~ .. ...
aldlminomethanephosphonic acld ester~ and subsequent hydrolysis of the esters.
In accordance with the process of thi~ invention, _-(phosphonometh~l)glycine is produced by reacting an ~mino-methylphosphoniC acid compound o~ the formula O OX
: (I) H2N - CH2 P ~
Y
whereln X and Y are each lndiridually hydrogen or lower alkyl group~ With an aldehyde of the ~ormula O O
(II) Z - C - C - H
;;20:~ wh-reln Z i8 hydrogen~ hydroxyl or lower alkoxyl to ~orm a carbonylaldim1nomethanephosphonate of the formula Z~ C - C = N - CH2P <
herelD~x~y~end Z are a~ above~defined and then hydrogenating said~arbonylaldimi~omethanephosphonate to yield a compound of AG-1009 ~
~ C~39739 the ~ormula e H I / OX
Z - C - CH2 - N - CH2 - P \
OY " .
; wherein XJ Y and Z have the above de~ined meanings.
- When Z represents hydrogen, the compound is treated with an oxidizing agent either be~ore the hydrogenation step or after said step to convert the aldehyde to a carboxylic acid.
When ~lkoxyl groups are presentJ they are hydrolyzed to the hydroxyl groups employing an acid such as a hydrohalic acidJ
sulfuric acid or the like.
More particularlyJ the process of this invention is conducted by forming an admixture of the aminomethanephosphonate and glyoxal or glyoxylic acid or ester in a solventJ heating said admixture to a temperature su~ficiently elevated to ; initiate the condensation reaction and remove the water o~ re-actlon to form the carbonylaldiminomethanephosphonate.
- m e carbonylaldimlnomethanephosphonate ls then oxldlzed i~ Z ls hydrogen to yleld a carboxyaldiminomethane-phosphonate. The c~rbonyl or carboxy-aldiminomethanephosphonate is then hydrogenated, émploying hydrogen With a hydrogenation ca,talyst such a~ a noble metal catalyst, to yield E-(phosphono-`msthyl)glyclne or it~ esters. Ester groups are then ~ hydrolyz-d to yield N-(phosphonomethyl)glyclne.
;~ In conducting the inltial condensation step o~ the ;~ prooosB Or this i~vention, it iæ pre~erable to employ a æolvent ln~whlch the re&ctants and reaction product are soluble. Sol~
vents`which~can be~employed are the aromatlc hydrocarbons such as~ben&ene~, toluone, xylene and the 11ke.
By~the~terms~ lower alky1" and "lower alkoxyl"J as employed~here1n, 18 meant alkyl~and~alkoxyl groups containing 30~ ~ m~ t~5;oarbon~atoms. The alkyl and alkoxyl groups are, 1~3~739 :
for example, methyl, ethyl, propyl, butyl, pentyl and the like and their isomers and methoxyl, ethoxyl and pentoxyl and the isomers of such alkoxyl groups. In conducting the condensation step in the process o~ this invention, it is preferred to employ the molar ratios o~ the glyoxal or glyoxylic acid or ester to aminomethylphosphonate o~ at least 1 to 1. It is even more preferre,d to employ molar ratios of from 1.5 to 2 to 1.
In conducting the condensation step of the process of this invention, the temperature of reaction can range from 0- to 140-C. or even higher. It is preferred for ease of reaction and to obtain the best rate to conduct the process of this invention at from about 50- to about 115-C. and preferably at the reflux temperature of the particular solvent being em-ployed.
In hydrogenating the intermediate aldiminomethylene-phosphonates in accordance with the process of this invention, one can employ gaseous hydrogen and a hydrogenation catalyst, either supported on an inert carrier or as a finely divided metal catalyst such as Raney nickelJ Raney Cobalt, palladium, platinum, rhodium, iridium and the like.
! The amount of metal catalyst can vary over a w~de r~nge depending upon the rate of hydrogenQtlon deslred. Thus, the metal catalyst 18 employed in amounts of from 0.001 to ~0 or more parts by weight per 100 parts by weight of the carbonyl-iminomethanephosphonate. For ease of reactlon and convenience, .:
lt i8 preferred to employ from .01 to .1 parts by welght of the ~ catalyst per 100 parts by weight of the carbonyllminomethane-I ~ phosphonate.
In conductin~ the hydrogenation Etep of the process of ~ -this invention, the temperature can vary widely, i.e., from O~C.or below up to 150-C. or higher and the hydrogen pressure can be from 1 to 100 atmospheres or even higher. For convenience, it is ~: :
~ ........... .. .. . . . .
1~3~739 pre~erred to employ temperatures in the range of from O-C. to about 75-Co and hydrogen pressures o~ from 1 to 100 atmospheres or higher. It is pre~erred to employ hydrogen pressures of from 1 to 10 atmospheres.
The time of reaction in either step of the process of this invention is not critical and can vary from as low as 1 minute to as high as 40 minutes or higher. It is, of course, obvious to those skilled in the art that the yield of product will vary with the reaction time and the temperature of the reaction.
The N-(phosphonomethyl)glyclne product produced in accordance with this invention, is useful as a poæt-emergent herbiclde.
The ~ollowing examples serve to further illustrate the invention. All parts are parts by weight unless otherwise expressly set ~orth.
To a ~olution of 13.0 e. (o. lo mole) of n-butyl glyoxylate in 100 ml. Or toluene was added with stirring di-; 20 ethyl aminomethylphosphonate (8.3 g., 0.05 moles) and the mix-ture heated to remove water of conden~ation by azeotropic d1stillation. The reaction was complete in less than 15 minutes.
The toluene was removed under vacuum in a rotary evapo-rator leaving an amber oll as a residue. The amber oll was di~tilled in a wiped-wall molecular still at 150-C. to 171-C.
;~ (wall tomperature) and 5-23 microns pressure. A yellow oil dist1llate (6.9 g.) was recovered. The yellow oil was re-dlst1lled in a Hiokman molecular still (magnetlcally stirred) to~yleld a fraction b.p. 134-137-C. at 12-13 microns nD 1.4514, which was analyzed. ~ ;~
Calcld. for CllH22NO~P: P = 11.09 1~39739 : ~ ~
- Found: P = 11.22 ' This material was identified as diethyl carbo-n-butoxyaldimino- ''' methanephosphonate.
'~ In a second run employing only a 25~ excess o~ n-butyl glyoxylate, a 45% yield of a less pure product was obtained.
. ~ .-EXAMPLE 2 ~;, To a solution of diethyl aminomethanephosphonate (8.3 g. ,' or O.OS0 mole) ln 100 ml. o~ toluene was added 40~ aqueous - ,' glyoxa' (3.6 g. or 0.025 mole). A mild exotherm was observed after which the mixture was heated to reflux and water removed ~,~ by azeotropic distillation.
, . . .
Removal o~ toluene, ~ollowed by molecular distillation in a wlped-wall stlll at 150-152-C. (wall temperature) and 5-29 micron6 pressure ylelded 2.0 grams o~ a light yellow oil nD 1.4575, ~ ' identlfled as diethyl formylmethyleneiminomethanephosphonate.
Calc'd. for C7Hl~NO~P: P = 14.95% ,;' ~ Found: P - 15.24% ~ ' ; ~
The aldimlno ester ~rom Example 1 is dissolved ~n 5 ' tlmes its volume o~ ethanol and 1 percent by welght of a 10%
palladlum on charcoal catalyst is added to the solution in a stainless steel pres~ure ve~sel. The pressure vessel 18 evacuated until ethanol beglns to distlll, then hydrogen iB
passed in slowly until the pressUre reaches 100 psi (292.6 ~ '~
;~ kilograms per square centlmeter). The rocker ls started and , ~,' ,~ the presSUre ~alls to a stable value. The reactor is heat,ed to 50-C. and repressurlzed to 100 psl (292.6 kilograms per ,, sgUare~oentimeter) untll the pr0ssure remalns stable. ,~
e reactor ls cooled and vented and the solutlon is 30 ~ r11tered to remove the catalyst and concentrated. The residual oll contalning n-butyl N-(diethoxyphosph1nylmethyl)glycinate i~
AG-lO09 1~3~739 su~ficiently pure for hydrolysis. The n-butyl N-(diethoxy-phosphinylmethyl)glycinate is hydrolyzed by heating to boiling with excess concentrated hydrobromic acid, concentrating and separating the product by crystallization. The product is N-(phosphonomethyl)glycine.
EXAMP~E 4 A solution of 34 grams (0.20 mole) of silver nitrate in lO0 ml. of water is treated with a solution of sodium hydroxide (16 grams) in 15 ml. of water. To this suspension of brown silver oxide is added, with cooling in small portions at 15 to 20-C., diethyl ~ormylmethyleneiminomethanephosphonate (20.7 grams). After stirring brie~ly, the solution is flltered to remove the precipitated metallic silver and the filtrate is carefully acidified with dilute hydrochloric acid to a pH of 3.
Concentration o~ the solution and drying by azeotropic distillation with ethanol, followed by filtration to remove sodium nitrate, gives the crude unsaturated acid, '1 . .
dlethyl carboxyaldlminomethanephosphonate.
To the above solutlon, is added 1 gram of 10%
palladium on carbon catalyst ln a stainless steel pressure ve8sel. The pre8sure ve58el is sealed and evacuated until the ethanol begins to vaporlze. Hydrogen is passed into the pressure vessel to a gauge reading o~ 100 psi (292.6 kilograms per square centimeter), the rocker is started and the reaction allowed to proceed until the pressure stabilizes. Repressurizing and heat-ing to 50-C. completes the reaction.
The pressure vessel is vented and the mixture ~iltered to remove the catalyst. The filtrate i8 concentrated and filtered again and flnally taken to dryness, leaving the crude ;~
saturated carboxylic acid which contalns some ester but which is ~ -satisfactory for hydrolysls. The above acid (ester) ls heated ', .
- -~ ~7~
AG-loog ~t39739 ::
to boiling with excess 48% hydrobromic acid until hydrolysis is :
completed. The solution is then concentrated and crystallized to yield N-(phosphonomethyl)glycine.
' i , : ; :
N-(PHOSPHONOMETHYL)GLYCINE
:
This invention relates to a process for pr~ducing N-(phosphonomethyl)glycine by the reduction of carbonylaldimino-methanephosphonate. The carbonylaldiminomethanephosphonates are produced by the reaction of glyoxylic acid esters or ;
glyoxal with aminomethanephosphonic acid esters.
It is known that N-(phosphonomethyl)glycine can be produced by the oxidation of N-(phosphonomethyl)iminodiacetic acid either electrolytically or by chemical oxidation.
It has now been discovered that N-(phosphonomethyl)-glyclne cAn be produced by the catalytic reduction of carbonyl-,~ .. ...
aldlminomethanephosphonic acld ester~ and subsequent hydrolysis of the esters.
In accordance with the process of thi~ invention, _-(phosphonometh~l)glycine is produced by reacting an ~mino-methylphosphoniC acid compound o~ the formula O OX
: (I) H2N - CH2 P ~
Y
whereln X and Y are each lndiridually hydrogen or lower alkyl group~ With an aldehyde of the ~ormula O O
(II) Z - C - C - H
;;20:~ wh-reln Z i8 hydrogen~ hydroxyl or lower alkoxyl to ~orm a carbonylaldim1nomethanephosphonate of the formula Z~ C - C = N - CH2P <
herelD~x~y~end Z are a~ above~defined and then hydrogenating said~arbonylaldimi~omethanephosphonate to yield a compound of AG-1009 ~
~ C~39739 the ~ormula e H I / OX
Z - C - CH2 - N - CH2 - P \
OY " .
; wherein XJ Y and Z have the above de~ined meanings.
- When Z represents hydrogen, the compound is treated with an oxidizing agent either be~ore the hydrogenation step or after said step to convert the aldehyde to a carboxylic acid.
When ~lkoxyl groups are presentJ they are hydrolyzed to the hydroxyl groups employing an acid such as a hydrohalic acidJ
sulfuric acid or the like.
More particularlyJ the process of this invention is conducted by forming an admixture of the aminomethanephosphonate and glyoxal or glyoxylic acid or ester in a solventJ heating said admixture to a temperature su~ficiently elevated to ; initiate the condensation reaction and remove the water o~ re-actlon to form the carbonylaldiminomethanephosphonate.
- m e carbonylaldimlnomethanephosphonate ls then oxldlzed i~ Z ls hydrogen to yleld a carboxyaldiminomethane-phosphonate. The c~rbonyl or carboxy-aldiminomethanephosphonate is then hydrogenated, émploying hydrogen With a hydrogenation ca,talyst such a~ a noble metal catalyst, to yield E-(phosphono-`msthyl)glyclne or it~ esters. Ester groups are then ~ hydrolyz-d to yield N-(phosphonomethyl)glyclne.
;~ In conducting the inltial condensation step o~ the ;~ prooosB Or this i~vention, it iæ pre~erable to employ a æolvent ln~whlch the re&ctants and reaction product are soluble. Sol~
vents`which~can be~employed are the aromatlc hydrocarbons such as~ben&ene~, toluone, xylene and the 11ke.
By~the~terms~ lower alky1" and "lower alkoxyl"J as employed~here1n, 18 meant alkyl~and~alkoxyl groups containing 30~ ~ m~ t~5;oarbon~atoms. The alkyl and alkoxyl groups are, 1~3~739 :
for example, methyl, ethyl, propyl, butyl, pentyl and the like and their isomers and methoxyl, ethoxyl and pentoxyl and the isomers of such alkoxyl groups. In conducting the condensation step in the process o~ this invention, it is preferred to employ the molar ratios o~ the glyoxal or glyoxylic acid or ester to aminomethylphosphonate o~ at least 1 to 1. It is even more preferre,d to employ molar ratios of from 1.5 to 2 to 1.
In conducting the condensation step of the process of this invention, the temperature of reaction can range from 0- to 140-C. or even higher. It is preferred for ease of reaction and to obtain the best rate to conduct the process of this invention at from about 50- to about 115-C. and preferably at the reflux temperature of the particular solvent being em-ployed.
In hydrogenating the intermediate aldiminomethylene-phosphonates in accordance with the process of this invention, one can employ gaseous hydrogen and a hydrogenation catalyst, either supported on an inert carrier or as a finely divided metal catalyst such as Raney nickelJ Raney Cobalt, palladium, platinum, rhodium, iridium and the like.
! The amount of metal catalyst can vary over a w~de r~nge depending upon the rate of hydrogenQtlon deslred. Thus, the metal catalyst 18 employed in amounts of from 0.001 to ~0 or more parts by weight per 100 parts by weight of the carbonyl-iminomethanephosphonate. For ease of reactlon and convenience, .:
lt i8 preferred to employ from .01 to .1 parts by welght of the ~ catalyst per 100 parts by weight of the carbonyllminomethane-I ~ phosphonate.
In conductin~ the hydrogenation Etep of the process of ~ -this invention, the temperature can vary widely, i.e., from O~C.or below up to 150-C. or higher and the hydrogen pressure can be from 1 to 100 atmospheres or even higher. For convenience, it is ~: :
~ ........... .. .. . . . .
1~3~739 pre~erred to employ temperatures in the range of from O-C. to about 75-Co and hydrogen pressures o~ from 1 to 100 atmospheres or higher. It is pre~erred to employ hydrogen pressures of from 1 to 10 atmospheres.
The time of reaction in either step of the process of this invention is not critical and can vary from as low as 1 minute to as high as 40 minutes or higher. It is, of course, obvious to those skilled in the art that the yield of product will vary with the reaction time and the temperature of the reaction.
The N-(phosphonomethyl)glyclne product produced in accordance with this invention, is useful as a poæt-emergent herbiclde.
The ~ollowing examples serve to further illustrate the invention. All parts are parts by weight unless otherwise expressly set ~orth.
To a ~olution of 13.0 e. (o. lo mole) of n-butyl glyoxylate in 100 ml. Or toluene was added with stirring di-; 20 ethyl aminomethylphosphonate (8.3 g., 0.05 moles) and the mix-ture heated to remove water of conden~ation by azeotropic d1stillation. The reaction was complete in less than 15 minutes.
The toluene was removed under vacuum in a rotary evapo-rator leaving an amber oll as a residue. The amber oll was di~tilled in a wiped-wall molecular still at 150-C. to 171-C.
;~ (wall tomperature) and 5-23 microns pressure. A yellow oil dist1llate (6.9 g.) was recovered. The yellow oil was re-dlst1lled in a Hiokman molecular still (magnetlcally stirred) to~yleld a fraction b.p. 134-137-C. at 12-13 microns nD 1.4514, which was analyzed. ~ ;~
Calcld. for CllH22NO~P: P = 11.09 1~39739 : ~ ~
- Found: P = 11.22 ' This material was identified as diethyl carbo-n-butoxyaldimino- ''' methanephosphonate.
'~ In a second run employing only a 25~ excess o~ n-butyl glyoxylate, a 45% yield of a less pure product was obtained.
. ~ .-EXAMPLE 2 ~;, To a solution of diethyl aminomethanephosphonate (8.3 g. ,' or O.OS0 mole) ln 100 ml. o~ toluene was added 40~ aqueous - ,' glyoxa' (3.6 g. or 0.025 mole). A mild exotherm was observed after which the mixture was heated to reflux and water removed ~,~ by azeotropic distillation.
, . . .
Removal o~ toluene, ~ollowed by molecular distillation in a wlped-wall stlll at 150-152-C. (wall temperature) and 5-29 micron6 pressure ylelded 2.0 grams o~ a light yellow oil nD 1.4575, ~ ' identlfled as diethyl formylmethyleneiminomethanephosphonate.
Calc'd. for C7Hl~NO~P: P = 14.95% ,;' ~ Found: P - 15.24% ~ ' ; ~
The aldimlno ester ~rom Example 1 is dissolved ~n 5 ' tlmes its volume o~ ethanol and 1 percent by welght of a 10%
palladlum on charcoal catalyst is added to the solution in a stainless steel pres~ure ve~sel. The pressure vessel 18 evacuated until ethanol beglns to distlll, then hydrogen iB
passed in slowly until the pressUre reaches 100 psi (292.6 ~ '~
;~ kilograms per square centlmeter). The rocker ls started and , ~,' ,~ the presSUre ~alls to a stable value. The reactor is heat,ed to 50-C. and repressurlzed to 100 psl (292.6 kilograms per ,, sgUare~oentimeter) untll the pr0ssure remalns stable. ,~
e reactor ls cooled and vented and the solutlon is 30 ~ r11tered to remove the catalyst and concentrated. The residual oll contalning n-butyl N-(diethoxyphosph1nylmethyl)glycinate i~
AG-lO09 1~3~739 su~ficiently pure for hydrolysis. The n-butyl N-(diethoxy-phosphinylmethyl)glycinate is hydrolyzed by heating to boiling with excess concentrated hydrobromic acid, concentrating and separating the product by crystallization. The product is N-(phosphonomethyl)glycine.
EXAMP~E 4 A solution of 34 grams (0.20 mole) of silver nitrate in lO0 ml. of water is treated with a solution of sodium hydroxide (16 grams) in 15 ml. of water. To this suspension of brown silver oxide is added, with cooling in small portions at 15 to 20-C., diethyl ~ormylmethyleneiminomethanephosphonate (20.7 grams). After stirring brie~ly, the solution is flltered to remove the precipitated metallic silver and the filtrate is carefully acidified with dilute hydrochloric acid to a pH of 3.
Concentration o~ the solution and drying by azeotropic distillation with ethanol, followed by filtration to remove sodium nitrate, gives the crude unsaturated acid, '1 . .
dlethyl carboxyaldlminomethanephosphonate.
To the above solutlon, is added 1 gram of 10%
palladium on carbon catalyst ln a stainless steel pressure ve8sel. The pre8sure ve58el is sealed and evacuated until the ethanol begins to vaporlze. Hydrogen is passed into the pressure vessel to a gauge reading o~ 100 psi (292.6 kilograms per square centimeter), the rocker is started and the reaction allowed to proceed until the pressure stabilizes. Repressurizing and heat-ing to 50-C. completes the reaction.
The pressure vessel is vented and the mixture ~iltered to remove the catalyst. The filtrate i8 concentrated and filtered again and flnally taken to dryness, leaving the crude ;~
saturated carboxylic acid which contalns some ester but which is ~ -satisfactory for hydrolysls. The above acid (ester) ls heated ', .
- -~ ~7~
AG-loog ~t39739 ::
to boiling with excess 48% hydrobromic acid until hydrolysis is :
completed. The solution is then concentrated and crystallized to yield N-(phosphonomethyl)glycine.
' i , : ; :
Claims (9)
1. A process for the production of N-(phosphono-methyl)glycine compounds of the formula wherein X and Y are independently hydrogen or lower alkyl and Z is hydrogen or lower alkoxyl which comprises contacting a carbonylaldiminomethanephosphonic acid compound of the formula wherein X, Y and Z are as above defined with hydrogen in the presence of a hydrogenation catalyst whereby said carbonyl-iminomethanephosphonic acid compound is reduced to said N-(phosphonomethyl)glycine compound.
2. A process as claimed in Claim 1 wherein the reaction is conducted under pressure.
3. A process as claimed in Claim 2 wherein the hydrogen pressure is from 1 to 100 atmospheres.
4. A process as claimed in Claim 3 wherein the hydrogen pressure is from 1 to 10 atmospheres.
5. A process as claimed in Claim 1 wherein the hydrogenation catalyst is Raney nickel, Raney cobalt, platinum, palladium, rhodium or iridium.
6. A process as claimed in Claim 5 wherein the hydrogenation catalyst is palladium.
7. A process as claimed in Claim 6 wherein the carbonylaldiminomethanephosphonic acid compound is a lower alkoxyl ester.
8. A process as claimed in Claim 7 wherein the hydrogenation product is hydrolyzed to N-(phosphonomethyl)glycine.
9. A process as claimed in Claim 7 wherein the carbonylaldiminomethanephosphonic acid compound is diethylcarbo-n-butoxyaldiminomethanephosphonate.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US53158574A | 1974-12-11 | 1974-12-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1039739A true CA1039739A (en) | 1978-10-03 |
Family
ID=24118246
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA241,438A Expired CA1039739A (en) | 1974-12-11 | 1975-12-10 | Process for the production of n-(phosphonomethyl) glycine |
Country Status (18)
| Country | Link |
|---|---|
| JP (1) | JPS5182228A (en) |
| AU (1) | AU501435B2 (en) |
| BE (1) | BE836475A (en) |
| BG (1) | BG28263A3 (en) |
| BR (1) | BR7508189A (en) |
| CA (1) | CA1039739A (en) |
| CS (1) | CS191288B2 (en) |
| DE (1) | DE2555573A1 (en) |
| ES (1) | ES443320A1 (en) |
| FR (1) | FR2294181A1 (en) |
| GB (1) | GB1482342A (en) |
| IL (1) | IL48619A (en) |
| IT (1) | IT1050328B (en) |
| NL (1) | NL7514313A (en) |
| RO (1) | RO69249A (en) |
| SU (1) | SU683628A3 (en) |
| YU (1) | YU312675A (en) |
| ZA (1) | ZA757746B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4851159A (en) * | 1988-05-02 | 1989-07-25 | Monsanto Company | Process for the preparation of N- phosphonomethylglycine |
| US5180846A (en) * | 1991-11-06 | 1993-01-19 | E. I. Du Pont De Nemours & Company | Hydrogenation of enzymatically-produced glycolic acid/aminomethylphosphonic acid mixtures |
| US5578190A (en) * | 1984-12-28 | 1996-11-26 | Monsanto Company | Process for the preparation of glyphosate and glyphosate derivatives |
| USRE35389E (en) * | 1985-09-11 | 1996-12-03 | Hoechst Aktiengesellschaft | Process for the preparation of N-phosphonomethylglycine |
| WO2014012991A1 (en) | 2012-07-17 | 2014-01-23 | Straitmark Holding Ag | Method for the synthesis of n-(phosphonomethyl)glycine |
| WO2014012988A1 (en) | 2012-07-17 | 2014-01-23 | Straitmark Holding Ag | Method for the synthesis of n-(phosphonomethyl)glycine |
| US10280189B2 (en) | 2012-07-17 | 2019-05-07 | Monsanto Technology Llc | Method for the synthesis of aminoalkylenephosphonic acid |
| US10364262B2 (en) | 2012-07-17 | 2019-07-30 | Monsanto Technology Llc | Method for the synthesis of N-phosphonomethyliminodiacetic acid |
| US10464958B2 (en) | 2012-07-17 | 2019-11-05 | Monsanto Technology Llc | Method for the synthesis of alpha-aminoalkylenephosphonic acid |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0081459B1 (en) * | 1981-12-03 | 1985-06-19 | Ciba-Geigy Ag | Process for preparing n-phosphonomethyl glycine |
| US4444580A (en) * | 1982-11-01 | 1984-04-24 | Monsanto Company | N-Substituted N-(phosphonomethyl)aminoethanal derivatives as herbicides |
| HUT41415A (en) * | 1984-12-28 | 1987-04-28 | Monsanto Co | Process for preparing n-phosphono-methyl-glycine derivatives |
| US4568432A (en) * | 1984-12-28 | 1986-02-04 | Monsanto Company | Process for preparing glyphosate and glyphosate derivatives |
| EP0541333A1 (en) * | 1991-11-06 | 1993-05-12 | E.I. Du Pont De Nemours And Company | Hydrogenation of enzymatically-produced glyoxylic acid/aminomethylphosphonic acid mixtures |
-
1975
- 1975-12-08 IL IL48619A patent/IL48619A/en unknown
- 1975-12-09 NL NL7514313A patent/NL7514313A/en unknown
- 1975-12-09 ES ES443320A patent/ES443320A1/en not_active Expired
- 1975-12-10 GB GB50567/75A patent/GB1482342A/en not_active Expired
- 1975-12-10 BR BR7508189*A patent/BR7508189A/en unknown
- 1975-12-10 ZA ZA757746A patent/ZA757746B/en unknown
- 1975-12-10 JP JP50146491A patent/JPS5182228A/en active Granted
- 1975-12-10 BE BE162605A patent/BE836475A/en not_active IP Right Cessation
- 1975-12-10 CA CA241,438A patent/CA1039739A/en not_active Expired
- 1975-12-10 IT IT30160/75A patent/IT1050328B/en active
- 1975-12-10 CS CS758400A patent/CS191288B2/en unknown
- 1975-12-10 YU YU03126/75A patent/YU312675A/en unknown
- 1975-12-10 DE DE19752555573 patent/DE2555573A1/en not_active Ceased
- 1975-12-10 SU SU752197009A patent/SU683628A3/en active
- 1975-12-10 AU AU87396/75A patent/AU501435B2/en not_active Expired
- 1975-12-10 BG BG031738A patent/BG28263A3/en unknown
- 1975-12-10 RO RO7584153A patent/RO69249A/en unknown
- 1975-12-10 FR FR7537834A patent/FR2294181A1/en active Granted
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5578190A (en) * | 1984-12-28 | 1996-11-26 | Monsanto Company | Process for the preparation of glyphosate and glyphosate derivatives |
| US5874612A (en) * | 1984-12-28 | 1999-02-23 | Baysdon; Sherrol L. | Process for the preparation of glyphosate and glyphosate derivatives |
| USRE35389E (en) * | 1985-09-11 | 1996-12-03 | Hoechst Aktiengesellschaft | Process for the preparation of N-phosphonomethylglycine |
| US4851159A (en) * | 1988-05-02 | 1989-07-25 | Monsanto Company | Process for the preparation of N- phosphonomethylglycine |
| US5180846A (en) * | 1991-11-06 | 1993-01-19 | E. I. Du Pont De Nemours & Company | Hydrogenation of enzymatically-produced glycolic acid/aminomethylphosphonic acid mixtures |
| WO2014012991A1 (en) | 2012-07-17 | 2014-01-23 | Straitmark Holding Ag | Method for the synthesis of n-(phosphonomethyl)glycine |
| WO2014012988A1 (en) | 2012-07-17 | 2014-01-23 | Straitmark Holding Ag | Method for the synthesis of n-(phosphonomethyl)glycine |
| US9676799B2 (en) | 2012-07-17 | 2017-06-13 | Straitmark Holding Ag | Method for the synthesis of N-(phosphonomethyl)glycine |
| US10280189B2 (en) | 2012-07-17 | 2019-05-07 | Monsanto Technology Llc | Method for the synthesis of aminoalkylenephosphonic acid |
| US10364262B2 (en) | 2012-07-17 | 2019-07-30 | Monsanto Technology Llc | Method for the synthesis of N-phosphonomethyliminodiacetic acid |
| US10464958B2 (en) | 2012-07-17 | 2019-11-05 | Monsanto Technology Llc | Method for the synthesis of alpha-aminoalkylenephosphonic acid |
Also Published As
| Publication number | Publication date |
|---|---|
| BE836475A (en) | 1976-06-10 |
| IL48619A (en) | 1978-04-30 |
| DE2555573A1 (en) | 1976-06-16 |
| FR2294181B1 (en) | 1979-04-06 |
| JPS5182228A (en) | 1976-07-19 |
| BG28263A3 (en) | 1980-03-25 |
| ES443320A1 (en) | 1977-04-16 |
| IT1050328B (en) | 1981-03-10 |
| SU683628A3 (en) | 1979-08-30 |
| ZA757746B (en) | 1976-11-24 |
| RO69249A (en) | 1982-04-12 |
| BR7508189A (en) | 1976-08-24 |
| CS191288B2 (en) | 1979-06-29 |
| YU312675A (en) | 1983-01-21 |
| JPS5438087B2 (en) | 1979-11-19 |
| AU501435B2 (en) | 1979-06-21 |
| GB1482342A (en) | 1977-08-10 |
| NL7514313A (en) | 1976-06-15 |
| IL48619A0 (en) | 1976-02-29 |
| FR2294181A1 (en) | 1976-07-09 |
| AU8739675A (en) | 1977-06-16 |
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