CA1231103A - Process for the preparation of phosphinothricin - Google Patents
Process for the preparation of phosphinothricinInfo
- Publication number
- CA1231103A CA1231103A CA000450957A CA450957A CA1231103A CA 1231103 A CA1231103 A CA 1231103A CA 000450957 A CA000450957 A CA 000450957A CA 450957 A CA450957 A CA 450957A CA 1231103 A CA1231103 A CA 1231103A
- Authority
- CA
- Canada
- Prior art keywords
- acid
- salts
- preparation
- formula
- ammonia
- 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 System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids R2P(=O)(OH); Thiophosphinic acids, i.e. R2P(=X)(XH) (X = S, Se)
- C07F9/301—Acyclic saturated acids which can have further substituents on alkyl
Abstract
Abstract of the Disclosure:
Preparation of 4-(hydroxymethylphosphinyl)-2-aminobutyric acid of the formula (I) by treatment of 4-(hydroxymethylphosphinyl)-2-oxobutyric acid of the formula
Preparation of 4-(hydroxymethylphosphinyl)-2-aminobutyric acid of the formula (I) by treatment of 4-(hydroxymethylphosphinyl)-2-oxobutyric acid of the formula
Description
;~3~3 ~3221-4115 The invention relates to a novel process for the preparation of 4-(hydroxymethylphosphinyl)~2~aminobutYric acid t- phosphinothri~;n) of the formula I
o NH2 3 P C~l2-cH2-cH-cooH (I) OH
and its salts in particular the ammon;um salts.
The compound I us known end is described as 3 bactericide or herbicide in, for example, Help. Chum.
Act 55~ 224 ~1972~ and Herman Offenlegungsschrift
o NH2 3 P C~l2-cH2-cH-cooH (I) OH
and its salts in particular the ammon;um salts.
The compound I us known end is described as 3 bactericide or herbicide in, for example, Help. Chum.
Act 55~ 224 ~1972~ and Herman Offenlegungsschrift
2,717~440~ Numerous methods for the preparation of I
have already been described in the literature Shelve. Chimp Act 55f 229 (1972); Japan. Cook Shea (27.11.
1973); Rock. Chum. 49~ 2 127 ~1975); J. Pratt. Chemise 318, 157 (1976); ETA 9~022 (12.07.1979); Pot. J. Chew. 53, ~37, (1979); ETA 18 145 (13.12.1979~; AYE Shea 595;
KIWI. 94, 84 295 b (15.05.1980) and ETA 11 245], but, with few exceptions, these do not give satisfactory yields.
According to the process described in ETA 11,245, I is formed by the following reaction I.) NH3 OH --P-CH OH --CHICANO
have already been described in the literature Shelve. Chimp Act 55f 229 (1972); Japan. Cook Shea (27.11.
1973); Rock. Chum. 49~ 2 127 ~1975); J. Pratt. Chemise 318, 157 (1976); ETA 9~022 (12.07.1979); Pot. J. Chew. 53, ~37, (1979); ETA 18 145 (13.12.1979~; AYE Shea 595;
KIWI. 94, 84 295 b (15.05.1980) and ETA 11 245], but, with few exceptions, these do not give satisfactory yields.
According to the process described in ETA 11,245, I is formed by the following reaction I.) NH3 OH --P-CH OH --CHICANO
3 2 2 2 . ) OH
Oboe OAT 3. ) H2SO4 in a yield of about 85%.
The disadvantage of thus process is the quite sub staunchly amount of salt obtained and the expensive swooper-lion of I from the reaction mixture, since the Amman ' acid formed has volubility properties like those of inorganic salts. Impurities which are formed in the preparation of the starting compound by addition of the methanephosphonous acid ester onto acrolein-cyanohydrin acetate likewise have an adverse effect on the course of the last stage and significantly reduce the yield. An additional disadvantage is that it is not possible to synthesize optically active I by this process.
It has now been found that the disadvantages described are avoided, without the yield being reduced, by treating 4-(hydroxymethylphosphinyl)-2-oxobutyric acid of the formula II
O O
If 11 H3C-P-CH -OH -C-COOH (II) OH
or its salts, with ammonia or a primary amine in which the C-N
bond is split hydrogenolytically by means of hydrogenation catalysts, in the presence of a hydrogenation catalyst at temperatures of -10 to +150C in a hydrogen atmosphere.
The reductive lamination of ~-oxycarboxylic acids to the corresponding ~-aminocarboxylic acids is known per so. Never the-less, the result of the process according to the invention is in many respects to be regarded as surprising.
On the one hand, it had to be assumed that the phosphinic acid part of the ~-oxobutyric acid II would also be reduced under the hydrogenation conditions [Help. Chimp Act 49, 842 (1966); J. Am. Chum. Sock 90, 3 4~9 (1968); J. Organometallic Chum. 97, C 31 (1975); and Chum. Ben. 113, 1 356 (1980)}. On the other hand, it was
Oboe OAT 3. ) H2SO4 in a yield of about 85%.
The disadvantage of thus process is the quite sub staunchly amount of salt obtained and the expensive swooper-lion of I from the reaction mixture, since the Amman ' acid formed has volubility properties like those of inorganic salts. Impurities which are formed in the preparation of the starting compound by addition of the methanephosphonous acid ester onto acrolein-cyanohydrin acetate likewise have an adverse effect on the course of the last stage and significantly reduce the yield. An additional disadvantage is that it is not possible to synthesize optically active I by this process.
It has now been found that the disadvantages described are avoided, without the yield being reduced, by treating 4-(hydroxymethylphosphinyl)-2-oxobutyric acid of the formula II
O O
If 11 H3C-P-CH -OH -C-COOH (II) OH
or its salts, with ammonia or a primary amine in which the C-N
bond is split hydrogenolytically by means of hydrogenation catalysts, in the presence of a hydrogenation catalyst at temperatures of -10 to +150C in a hydrogen atmosphere.
The reductive lamination of ~-oxycarboxylic acids to the corresponding ~-aminocarboxylic acids is known per so. Never the-less, the result of the process according to the invention is in many respects to be regarded as surprising.
On the one hand, it had to be assumed that the phosphinic acid part of the ~-oxobutyric acid II would also be reduced under the hydrogenation conditions [Help. Chimp Act 49, 842 (1966); J. Am. Chum. Sock 90, 3 4~9 (1968); J. Organometallic Chum. 97, C 31 (1975); and Chum. Ben. 113, 1 356 (1980)}. On the other hand, it was
- 4 - 2322l-4ll5 to be expected that the undesired 4 thydroxymethylphosph;-Noel hydroxybutyric acid of the formula III
I
H3c-p-cH2-cH2 - Schick ( I I I ) 0~1 or its salts, would be formed Doreen the reaction. For example, it is known from pull. Chum. Sock Japan 36, 763 (1~63) that, besides the desired aminoglutaric acid a substantial amount of cC-hYdroxYglutaric acid is formed on reductive am;nat;on of ~-ketoglutaric acid (the car-boxy analog of II).
In view of these facts, the high chemical yield and the purity of the process product on application of the process according to the invention were not to be ox-pealed.
The extent to which such a process was unexpected us made particularly clear by the fact that, although many professes for the preparation of I have been described, not a single one has considered thus possibility, even though a large number of Amman acid syntheses are based on reductive lamination of ~-oxocarboxylic acids.
The compound II required as the starting compound for the process according to the invention and its salts can be prepared from commercially available 3-(alkoxyme-thylphosphinyl)-propion;c acid esters of the general for-mule IV O
if H C-PCCH -OH -COO (IV) OR
I I
in itch R and R1 can be identical or different and each denote a (c1-c4)-alkyl radical accordir10 to ETA 30"424~
Possible salts are the Mooney and bis-sal-ts of II, on par-titular the sodium, potassium and ammonium salts.
Solvents or delineates which are preferably suitable for the process according Jo the invention are lower Alcoa hots, such as methanol, ethanol and isopropanol, and water, and also mixtures of these solvents and d;luents.
The WriteNow temperatures are in general ~10 to 150C, preferably 20-100C.
Hydrogenation catalysts which can preferably be used are heterogeneous catalysts, such as for example, platinum, palladium, nickel, cobalt and rhodium catalysts in their most diverse use forms. It is also possible lo use homogeneous catalysts, such as, or example, potassium pentacyano-cobaltate or metal hydrides (for example Lyle or Nub).
Possible amine for the process according to the invention are, besides ammonia, also those primary amine in which the C N bond us split hydrogenolytically by the hydrogenation catalysts mentioned. These amine aver in particular, benzylamine, benzhydrylamine, tr;~ylaMine,D~L-1-phenyle~hylarnine, (I phenylethylamine and (I
phenylethylamine.
An equilnolar amount or up to a 10-fold excess of the ammonia or primary amine is employed The process according to the inventiol1 is carried out in a hydrogeli atmosphere, in general under pressures of between 1 and 20n bar, preferably between 1 and 50 barn :~3~3 .
depending on the nature of the catalyst used The reaction can be regarded as having ended when no further hydrogen us consumed under the given reaction conditions constant pressure).
In the process according to the invention the apparatus for isolation of the process product is very simple especially when heterogeneous catalysts which can easily be separated off by filtration and/or centric fugat;on are used since the process product us already it obtained on a sufficient chemical purity after evapora tying off the solvent or delineate under reduced pressure The yields are about 85-95%.
The crude process product can additionally be subsequently luncher purified either by recrystallization or by chromatography.
The process according to the invention is thus-treated on more detail with the aid of the following prop ration examples to 1 Ammonium salt of 4-(hydroxyme hylphosph-iry l? -2-aminobutyric acid 9~0 9 (0.05 mole of 4-(hydroxymethylphosphinyl~
2-oxobutyric acid were dissolved in 50 ml of methanol Shea had been saturated with ammonia at 10C. After addition of 1 g of Haney nucleoli hydrogenation was car fled out under 100 bar and at 50C on a shaken autoclave join the uptake of hydrogen held ended the autoclave was let down the catalyst was f;lteled of-F and the excess amlnonia and the solvent were distilled off under reduced pressure. 9.8 g of colorless product which hack solidified to a glass-like solid and could be powdered in a mortar were obta1rled as the distillation residue. Melting range:
205-215C (decompos;t;on). The product consisted o-f the desired ammonium salt of phosph;nothricin to the en tent of 90% (HPLC analysis).
Example 2 9.0 9 (O.G5 mole of 4--(hydroxymethylphc)sph;nyl)-2-oxobutyric acid were hydrogenated in the presence of 1 g of s% strength palladium-on-active charcoal under 5 bar and at 5nc analogously to Example 1.
After drying in vacua, 9.8 9 of powdered, color-less product which melted at 208-215C,. with decolnpos;-lion, and consisted of the ammon;um salt of , to the ox-tent of 93% tHPLC analysis), Syria obtained.
En e 3 Roy g (0~1 mole) of hydroxymethylphosph;nyl)-Z-oxobutyr;c acid Lowry hydrogenated, after addition of 1 9 of 10% strel1gth of platinum-on-act;ve charcoal, under
I
H3c-p-cH2-cH2 - Schick ( I I I ) 0~1 or its salts, would be formed Doreen the reaction. For example, it is known from pull. Chum. Sock Japan 36, 763 (1~63) that, besides the desired aminoglutaric acid a substantial amount of cC-hYdroxYglutaric acid is formed on reductive am;nat;on of ~-ketoglutaric acid (the car-boxy analog of II).
In view of these facts, the high chemical yield and the purity of the process product on application of the process according to the invention were not to be ox-pealed.
The extent to which such a process was unexpected us made particularly clear by the fact that, although many professes for the preparation of I have been described, not a single one has considered thus possibility, even though a large number of Amman acid syntheses are based on reductive lamination of ~-oxocarboxylic acids.
The compound II required as the starting compound for the process according to the invention and its salts can be prepared from commercially available 3-(alkoxyme-thylphosphinyl)-propion;c acid esters of the general for-mule IV O
if H C-PCCH -OH -COO (IV) OR
I I
in itch R and R1 can be identical or different and each denote a (c1-c4)-alkyl radical accordir10 to ETA 30"424~
Possible salts are the Mooney and bis-sal-ts of II, on par-titular the sodium, potassium and ammonium salts.
Solvents or delineates which are preferably suitable for the process according Jo the invention are lower Alcoa hots, such as methanol, ethanol and isopropanol, and water, and also mixtures of these solvents and d;luents.
The WriteNow temperatures are in general ~10 to 150C, preferably 20-100C.
Hydrogenation catalysts which can preferably be used are heterogeneous catalysts, such as for example, platinum, palladium, nickel, cobalt and rhodium catalysts in their most diverse use forms. It is also possible lo use homogeneous catalysts, such as, or example, potassium pentacyano-cobaltate or metal hydrides (for example Lyle or Nub).
Possible amine for the process according to the invention are, besides ammonia, also those primary amine in which the C N bond us split hydrogenolytically by the hydrogenation catalysts mentioned. These amine aver in particular, benzylamine, benzhydrylamine, tr;~ylaMine,D~L-1-phenyle~hylarnine, (I phenylethylamine and (I
phenylethylamine.
An equilnolar amount or up to a 10-fold excess of the ammonia or primary amine is employed The process according to the inventiol1 is carried out in a hydrogeli atmosphere, in general under pressures of between 1 and 20n bar, preferably between 1 and 50 barn :~3~3 .
depending on the nature of the catalyst used The reaction can be regarded as having ended when no further hydrogen us consumed under the given reaction conditions constant pressure).
In the process according to the invention the apparatus for isolation of the process product is very simple especially when heterogeneous catalysts which can easily be separated off by filtration and/or centric fugat;on are used since the process product us already it obtained on a sufficient chemical purity after evapora tying off the solvent or delineate under reduced pressure The yields are about 85-95%.
The crude process product can additionally be subsequently luncher purified either by recrystallization or by chromatography.
The process according to the invention is thus-treated on more detail with the aid of the following prop ration examples to 1 Ammonium salt of 4-(hydroxyme hylphosph-iry l? -2-aminobutyric acid 9~0 9 (0.05 mole of 4-(hydroxymethylphosphinyl~
2-oxobutyric acid were dissolved in 50 ml of methanol Shea had been saturated with ammonia at 10C. After addition of 1 g of Haney nucleoli hydrogenation was car fled out under 100 bar and at 50C on a shaken autoclave join the uptake of hydrogen held ended the autoclave was let down the catalyst was f;lteled of-F and the excess amlnonia and the solvent were distilled off under reduced pressure. 9.8 g of colorless product which hack solidified to a glass-like solid and could be powdered in a mortar were obta1rled as the distillation residue. Melting range:
205-215C (decompos;t;on). The product consisted o-f the desired ammonium salt of phosph;nothricin to the en tent of 90% (HPLC analysis).
Example 2 9.0 9 (O.G5 mole of 4--(hydroxymethylphc)sph;nyl)-2-oxobutyric acid were hydrogenated in the presence of 1 g of s% strength palladium-on-active charcoal under 5 bar and at 5nc analogously to Example 1.
After drying in vacua, 9.8 9 of powdered, color-less product which melted at 208-215C,. with decolnpos;-lion, and consisted of the ammon;um salt of , to the ox-tent of 93% tHPLC analysis), Syria obtained.
En e 3 Roy g (0~1 mole) of hydroxymethylphosph;nyl)-Z-oxobutyr;c acid Lowry hydrogenated, after addition of 1 9 of 10% strel1gth of platinum-on-act;ve charcoal, under
5 bar and at 50C analogously to Example 1.
After dry;nt~ on vacua, 19.5 9 of a colorless pow-don weaken had a melting range of 205-210C (decornposit;on) and consisted of the ammon;um salt of I to the extent of 87% (HPLC analysis, were obtained.
9~0 9 (0.05 mole) of 4 thydroxymethylphosphinyl)~
2-oxobutyr;c acid were dissolved on 50 ml of methanol and the saltier juicy added drops at 20 25C under a ho drocJen pressure of about 1~0 to 1.2 bar Al the course of 1 hour, to a vigorously stirred suspension of 1 9 of 5%
strength palladiurn-on-active charcoal in 50 ml of Matthew not saturated with ammonia. An apparatus built in-house and correspontling to Hillel Lyle, Volume IV/1c, page 34 et seq. was used When the uptake of hydrogen had ended, the mixture was worked up analogously to Example 1.
9.8 9 of a colorless powder which melted between 208 and 213C, with decomposition and consisted of the ammonium salt of phosphinothricin to the extent of 95%
10 (HPLC analysis), were obtained. It was possible to oboe lain 8 of pure I (ammonium salt) of melting point 210C
(decomposition) from the crude product by crystallization from methanol water Exampif~ 5 2. 0 g (OWE mole) of 4-(hydroxymethylphc)s~
ph;nyl)-2-oxobutyr;c acid were dissolved in 50 ml of water, into which about 0.5~0~6 (mole) of ammonia had been passed at 1ûC, and, after addition of Do g of 5%
strength pi l ladium-on-active charcoal, hydrogenation was carried out under 2 bar and at 25C in a shaken auto-slave. When the uptake of hydrogen had ended, the mix-lure was worked up as in Example I After drying in vacua, 2.1 g of a colorless powder which consisted of the ammonium salt of I to the extent of 89% (HPLC analysis) were obtained.
example 6 11.Z (aye mole) o-f the bus sodium salt of 4-~hydroxylnethylphosphinyl)~2 oxobutyr;c acid anal 5~4 to (OOZE m()lej of ben~ylarnir~e were dissolved on 50 fill of ;.L~3~3 _ 9 _ r,lethanol and after addition of 2 g of 5% strength pall-d;um-on-act;ve charcoal, hydrogenation was carried out under 5 bar and a'; 50C in a shaken autoclave I~Jhen the uptake of hydrogen had ended, the catalyst was filtered off and the filtrate was distilled under reduced pros-sure During this procedure, most of the methanol passed over together with Tulane and traces of unrequited Ben ~ylamine. After drying the oily roused on vacua, 11 g of a colorless powder which consisted of the bus sodium salt of 4-(hydroxymethylphosphinyl)-2-aminobutyric acid to the extent of 90% (HPLC analysis) were obtained.
After dry;nt~ on vacua, 19.5 9 of a colorless pow-don weaken had a melting range of 205-210C (decornposit;on) and consisted of the ammon;um salt of I to the extent of 87% (HPLC analysis, were obtained.
9~0 9 (0.05 mole) of 4 thydroxymethylphosphinyl)~
2-oxobutyr;c acid were dissolved on 50 ml of methanol and the saltier juicy added drops at 20 25C under a ho drocJen pressure of about 1~0 to 1.2 bar Al the course of 1 hour, to a vigorously stirred suspension of 1 9 of 5%
strength palladiurn-on-active charcoal in 50 ml of Matthew not saturated with ammonia. An apparatus built in-house and correspontling to Hillel Lyle, Volume IV/1c, page 34 et seq. was used When the uptake of hydrogen had ended, the mixture was worked up analogously to Example 1.
9.8 9 of a colorless powder which melted between 208 and 213C, with decomposition and consisted of the ammonium salt of phosphinothricin to the extent of 95%
10 (HPLC analysis), were obtained. It was possible to oboe lain 8 of pure I (ammonium salt) of melting point 210C
(decomposition) from the crude product by crystallization from methanol water Exampif~ 5 2. 0 g (OWE mole) of 4-(hydroxymethylphc)s~
ph;nyl)-2-oxobutyr;c acid were dissolved in 50 ml of water, into which about 0.5~0~6 (mole) of ammonia had been passed at 1ûC, and, after addition of Do g of 5%
strength pi l ladium-on-active charcoal, hydrogenation was carried out under 2 bar and at 25C in a shaken auto-slave. When the uptake of hydrogen had ended, the mix-lure was worked up as in Example I After drying in vacua, 2.1 g of a colorless powder which consisted of the ammonium salt of I to the extent of 89% (HPLC analysis) were obtained.
example 6 11.Z (aye mole) o-f the bus sodium salt of 4-~hydroxylnethylphosphinyl)~2 oxobutyr;c acid anal 5~4 to (OOZE m()lej of ben~ylarnir~e were dissolved on 50 fill of ;.L~3~3 _ 9 _ r,lethanol and after addition of 2 g of 5% strength pall-d;um-on-act;ve charcoal, hydrogenation was carried out under 5 bar and a'; 50C in a shaken autoclave I~Jhen the uptake of hydrogen had ended, the catalyst was filtered off and the filtrate was distilled under reduced pros-sure During this procedure, most of the methanol passed over together with Tulane and traces of unrequited Ben ~ylamine. After drying the oily roused on vacua, 11 g of a colorless powder which consisted of the bus sodium salt of 4-(hydroxymethylphosphinyl)-2-aminobutyric acid to the extent of 90% (HPLC analysis) were obtained.
Claims
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the preparation of 4-(hydroxymethyl-phosphinyl)-2-aminobutyric acid of the formula I
and its salts, which comprises treating 4-(hydroxymethyl-phosphinyl)-2-oxobutyric acid of the formula II
or its salts, with ammonia or a primary amine in which the C-N
bond is split hydrogenolytically by means of hydrogenation catalyst, in the presence of a hydrogenation catalyst at -10 to +150°C in a hydrogen atmosphere.
and its salts, which comprises treating 4-(hydroxymethyl-phosphinyl)-2-oxobutyric acid of the formula II
or its salts, with ammonia or a primary amine in which the C-N
bond is split hydrogenolytically by means of hydrogenation catalyst, in the presence of a hydrogenation catalyst at -10 to +150°C in a hydrogen atmosphere.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3312165.6 | 1983-04-02 | ||
| DE19833312165 DE3312165A1 (en) | 1983-04-02 | 1983-04-02 | METHOD FOR PRODUCING PHOSPHINOTHRICIN |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1231103A true CA1231103A (en) | 1988-01-05 |
Family
ID=6195457
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000450957A Expired CA1231103A (en) | 1983-04-02 | 1984-03-30 | Process for the preparation of phosphinothricin |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0121226B1 (en) |
| JP (1) | JPS59184196A (en) |
| AT (1) | ATE23342T1 (en) |
| CA (1) | CA1231103A (en) |
| DD (1) | DD215554A5 (en) |
| DE (2) | DE3312165A1 (en) |
| HU (1) | HU196816B (en) |
| IL (1) | IL71424A (en) |
| ZA (1) | ZA842388B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5281747A (en) * | 1989-05-13 | 1994-01-25 | Ciba-Geigy Corporation | Substituted aminoalkylphosphinic acids |
| CN103665032A (en) * | 2013-12-09 | 2014-03-26 | 江苏七洲绿色化工股份有限公司 | Preparation method of glufosinate |
| CN105218579A (en) * | 2015-09-28 | 2016-01-06 | 江苏七洲绿色化工股份有限公司 | A kind of synthetic method of L-type grass ammonium phosphine ammonium salt |
| CN106565776A (en) * | 2016-11-10 | 2017-04-19 | 安徽国星生物化学有限公司 | Separating and purifying method for 4-(methyl hydroxyl phosphoryl)-2-carbonyl butyric acid |
| WO2019015909A1 (en) | 2017-07-21 | 2019-01-24 | Basf Se | Production of glufosinate by reaction of 3-[n-butoxy(methyl)phosphoryl]-1-cyanopropyl acetate to afford a mixture of n-butyl (3-amino-3-cyanopropyl)methylphosphinate and (3-amino-3-cyanopropyl)methylphosphinic acid ammonium salt |
| WO2019121362A1 (en) | 2017-12-19 | 2019-06-27 | Basf Se | METHOD FOR PRODUCING PHOSPHORUS-CONTAINING α-AMINONITRILES |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3544376A1 (en) * | 1985-12-14 | 1987-06-19 | Hoechst Ag | DIPEPTIDES WITH C-TERMINAL PHOSPHINOTHRICIN, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE FOR CONTROLLING UNWANTED PLANT GROWTH |
| GB8911017D0 (en) * | 1989-05-13 | 1989-06-28 | Ciba Geigy Ag | Substituted aminoalkylphosphinic acids |
| IL101539A (en) | 1991-04-16 | 1998-09-24 | Monsanto Europe Sa | Non-hygroscopic mono-ammonium salts of n-phosphonomethyl glycine derivatives their preparation and pesticidal compositons containing them |
| HU212802B (en) | 1991-07-19 | 1996-11-28 | Monsanto Europe Sa | Phytoactive sack-like composition containing glyphosate-izopropylamine salt |
| CN104761583A (en) | 2007-03-23 | 2015-07-08 | 明治制果药业株式会社 | Method for producing phosphorus-containing alpha-keto acid |
| BRPI0702341B1 (en) * | 2007-05-16 | 2016-06-14 | Ricardo Amaral Remer | soluble solid glufosinate for pesticide, process for obtaining it and process for controlling agricultural pests |
| CN103539815B (en) * | 2013-10-14 | 2016-03-23 | 苏州联合伟业科技有限公司 | The production technique of 4-(hydroxyl-(methyl) phosphinyl)-2-Oxobutyric acid |
| CN107552071A (en) * | 2017-09-26 | 2018-01-09 | 安徽国星生物化学有限公司 | A kind of preparation method for the Raney's nickel that cobalt salt is modified and the method for synthesizing glufosinate-ammonium |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2849003A1 (en) * | 1978-11-11 | 1980-08-21 | Hoechst Ag | CYANHYDRINE DERIVATIVES CONTAINING PHOSPHORUS AND METHOD FOR THE PRODUCTION THEREOF |
-
1983
- 1983-04-02 DE DE19833312165 patent/DE3312165A1/en not_active Withdrawn
-
1984
- 1984-03-27 HU HU841214A patent/HU196816B/en unknown
- 1984-03-28 DE DE8484103398T patent/DE3461190D1/en not_active Expired
- 1984-03-28 AT AT84103398T patent/ATE23342T1/en not_active IP Right Cessation
- 1984-03-28 EP EP84103398A patent/EP0121226B1/en not_active Expired
- 1984-03-29 DD DD84261393A patent/DD215554A5/en not_active IP Right Cessation
- 1984-03-30 CA CA000450957A patent/CA1231103A/en not_active Expired
- 1984-03-30 ZA ZA842388A patent/ZA842388B/en unknown
- 1984-03-31 JP JP59062239A patent/JPS59184196A/en active Granted
- 1984-04-02 IL IL71424A patent/IL71424A/en not_active IP Right Cessation
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5281747A (en) * | 1989-05-13 | 1994-01-25 | Ciba-Geigy Corporation | Substituted aminoalkylphosphinic acids |
| CN103665032A (en) * | 2013-12-09 | 2014-03-26 | 江苏七洲绿色化工股份有限公司 | Preparation method of glufosinate |
| CN105218579A (en) * | 2015-09-28 | 2016-01-06 | 江苏七洲绿色化工股份有限公司 | A kind of synthetic method of L-type grass ammonium phosphine ammonium salt |
| CN105218579B (en) * | 2015-09-28 | 2017-11-07 | 江苏七洲绿色化工股份有限公司 | A kind of synthetic method of L types glufosinate-ammonium ammonium salt |
| CN106565776A (en) * | 2016-11-10 | 2017-04-19 | 安徽国星生物化学有限公司 | Separating and purifying method for 4-(methyl hydroxyl phosphoryl)-2-carbonyl butyric acid |
| WO2019015909A1 (en) | 2017-07-21 | 2019-01-24 | Basf Se | Production of glufosinate by reaction of 3-[n-butoxy(methyl)phosphoryl]-1-cyanopropyl acetate to afford a mixture of n-butyl (3-amino-3-cyanopropyl)methylphosphinate and (3-amino-3-cyanopropyl)methylphosphinic acid ammonium salt |
| US10822358B2 (en) | 2017-07-21 | 2020-11-03 | Basf Se | Process for preparing phosphorus-containing alpha-aminonitriles |
| WO2019121362A1 (en) | 2017-12-19 | 2019-06-27 | Basf Se | METHOD FOR PRODUCING PHOSPHORUS-CONTAINING α-AMINONITRILES |
| US11220520B2 (en) | 2017-12-19 | 2022-01-11 | Basf Se | Method for preparing phosphorus-containing α-aminonitriles |
Also Published As
| Publication number | Publication date |
|---|---|
| IL71424A (en) | 1987-10-20 |
| ATE23342T1 (en) | 1986-11-15 |
| HU196816B (en) | 1989-01-30 |
| ZA842388B (en) | 1984-11-28 |
| DE3461190D1 (en) | 1986-12-11 |
| IL71424A0 (en) | 1984-07-31 |
| EP0121226A1 (en) | 1984-10-10 |
| DE3312165A1 (en) | 1984-10-04 |
| JPS59184196A (en) | 1984-10-19 |
| HUT34757A (en) | 1985-04-28 |
| DD215554A5 (en) | 1984-11-14 |
| JPH047753B2 (en) | 1992-02-12 |
| EP0121226B1 (en) | 1986-11-05 |
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