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
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 238000000034 method Methods 0.000 title claims description 20
- IAJOBQBIJHVGMQ-UHFFFAOYSA-N Phosphinothricin Natural products CP(O)(=O)CCC(N)C(O)=O IAJOBQBIJHVGMQ-UHFFFAOYSA-N 0.000 title description 2
- IAJOBQBIJHVGMQ-BYPYZUCNSA-N glufosinate-P Chemical compound CP(O)(=O)CC[C@H](N)C(O)=O IAJOBQBIJHVGMQ-BYPYZUCNSA-N 0.000 title description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 150000003141 primary amines Chemical class 0.000 claims abstract description 5
- YJTNHDYMQPHXFO-UHFFFAOYSA-N 4-(hydroxymethylphosphinyl)-2-oxobutyric acid Chemical compound CP(O)(=O)CCC(=O)C(O)=O YJTNHDYMQPHXFO-UHFFFAOYSA-N 0.000 claims abstract description 3
- FNJQGUKETYGBGL-UHFFFAOYSA-N OC(=O)C(N)CCP(=O)CO Chemical compound OC(=O)C(N)CCP(=O)CO FNJQGUKETYGBGL-UHFFFAOYSA-N 0.000 claims abstract description 3
- 150000003839 salts Chemical class 0.000 claims description 12
- 238000005984 hydrogenation reaction Methods 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000002253 acid Substances 0.000 description 11
- 230000002829 reductive effect Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 150000003863 ammonium salts Chemical class 0.000 description 6
- 239000003610 charcoal Substances 0.000 description 5
- 238000004128 high performance liquid chromatography Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- -1 methanephosphonous acid ester Chemical class 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- BHHGXPLMPWCGHP-UHFFFAOYSA-N Phenethylamine Chemical compound NCCC1=CC=CC=C1 BHHGXPLMPWCGHP-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZNEMGFATAVGQSF-UHFFFAOYSA-N 1-(2-amino-6,7-dihydro-4H-[1,3]thiazolo[4,5-c]pyridin-5-yl)-2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]ethanone Chemical compound NC=1SC2=C(CN(CC2)C(CC=2OC(=NN=2)C=2C=NC(=NC=2)NC2CC3=CC=CC=C3C2)=O)N=1 ZNEMGFATAVGQSF-UHFFFAOYSA-N 0.000 description 1
- MEHLEOUIWVWVBF-UHFFFAOYSA-N 1-cyanoprop-2-enyl acetate Chemical compound CC(=O)OC(C=C)C#N MEHLEOUIWVWVBF-UHFFFAOYSA-N 0.000 description 1
- TYEYBOSBBBHJIV-UHFFFAOYSA-N 2-oxobutanoic acid Chemical compound CCC(=O)C(O)=O TYEYBOSBBBHJIV-UHFFFAOYSA-N 0.000 description 1
- SJZRECIVHVDYJC-UHFFFAOYSA-N 4-hydroxybutyric acid Chemical compound OCCCC(O)=O SJZRECIVHVDYJC-UHFFFAOYSA-N 0.000 description 1
- DRSHXJFUUPIBHX-UHFFFAOYSA-N COc1ccc(cc1)N1N=CC2C=NC(Nc3cc(OC)c(OC)c(OCCCN4CCN(C)CC4)c3)=NC12 Chemical compound COc1ccc(cc1)N1N=CC2C=NC(Nc3cc(OC)c(OC)c(OCCCN4CCN(C)CC4)c3)=NC12 DRSHXJFUUPIBHX-UHFFFAOYSA-N 0.000 description 1
- 241001441571 Hiodontidae Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- 208000003251 Pruritus Diseases 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 235000018936 Vitellaria paradoxa Nutrition 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229940124277 aminobutyric acid Drugs 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- MGHPNCMVUAKAIE-UHFFFAOYSA-N diphenylmethanamine Chemical compound C=1C=CC=CC=1C(N)C1=CC=CC=C1 MGHPNCMVUAKAIE-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- BTCSSZJGUNDROE-UHFFFAOYSA-N gamma-aminobutyric acid Chemical compound NCCCC(O)=O BTCSSZJGUNDROE-UHFFFAOYSA-N 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical group O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/301—Acyclic saturated acids which can have further substituents on alkyl
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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Steroid Compounds (AREA)
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 |
---|---|---|---|
DE19833312165 DE3312165A1 (en) | 1983-04-02 | 1983-04-02 | METHOD FOR PRODUCING PHOSPHINOTHRICIN |
DEP3312165.6 | 1983-04-02 |
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 |
HU212802B (en) | 1991-07-19 | 1996-11-28 | Monsanto Europe Sa | Phytoactive sack-like composition containing glyphosate-izopropylamine salt |
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 |
JP5368971B2 (en) | 2007-03-23 | 2013-12-18 | Meiji Seikaファルマ株式会社 | Method for producing phosphorus-containing α-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 AT AT84103398T patent/ATE23342T1/en not_active IP Right Cessation
- 1984-03-28 DE DE8484103398T patent/DE3461190D1/en not_active Expired
- 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 ZA ZA842388A patent/ZA842388B/en unknown
- 1984-03-30 CA CA000450957A patent/CA1231103A/en not_active Expired
- 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 |
JPS59184196A (en) | 1984-10-19 |
HUT34757A (en) | 1985-04-28 |
DE3461190D1 (en) | 1986-12-11 |
IL71424A0 (en) | 1984-07-31 |
JPH047753B2 (en) | 1992-02-12 |
EP0121226B1 (en) | 1986-11-05 |
HU196816B (en) | 1989-01-30 |
ATE23342T1 (en) | 1986-11-15 |
DE3312165A1 (en) | 1984-10-04 |
EP0121226A1 (en) | 1984-10-10 |
DD215554A5 (en) | 1984-11-14 |
ZA842388B (en) | 1984-11-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA1231103A (en) | Process for the preparation of phosphinothricin | |
BG64562B1 (en) | Method for the preparation and purification of n-alkylated asparginic derivative | |
DE69934712T2 (en) | METHOD OF PREPARING N-NEOHEXYL- (A) -ASPARTYL-L-PHENYL ALANINE METHYL ESTERS FROM INTERMEDIATE COMPOUNDS CONTAINING IMIDAZOLIDIN-4-ON | |
US5099067A (en) | Use of ammonium formate as a hydrogen transfer reagent for reduction of chiral nitro compounds with retention of configuration | |
US4048224A (en) | Process for resolving alanine, 3-fluoro and 2-deutero-3-fluoro-DL-alanine | |
EP0260588B1 (en) | Process for the preparation of alpha-N-[(hypoxanthin-9-yl)-pentyloxycarbonyl]-arginine | |
EP0190667B1 (en) | Process for the preparation of methyl n-methylanthranilate | |
JPS5811867B2 (en) | Method for producing 5,5-dimethyl-4-phenyloxazolidin-2-one derivative | |
EP0052819B1 (en) | Process for preparing amidinecarboxylic acids | |
CA1119614A (en) | Process for the production of 4-aminobutyric acid or its derivatives | |
EP1599446B1 (en) | An improved process for the preparation of gabalactam | |
WO2002074727B1 (en) | A process for the preparation of cyclic amino acids | |
US4469876A (en) | Process for the production of L-proline | |
GB2219294A (en) | Preparation of methyl 3-aminocrotonate | |
EP0718273A1 (en) | Ethyl 6-formyl-4-hexenoate | |
EP0056343B1 (en) | Process for the preparation of 4-aminobutyramide | |
EP0781270B1 (en) | Ring-opening amidation process | |
US6905666B2 (en) | Process for the selective decomposition of hydrazine in a hydrazine/substituted hydrazine/water mixture | |
EP0322236A2 (en) | Catalytic process for preparing optically active threonine | |
JPH0521916B2 (en) | ||
JPH0332538B2 (en) | ||
KR790001684B1 (en) | Process for the preparation of 5-benzyl picolinic acids | |
HU192998B (en) | Process for producing 5-vinyl-7-pyrrolydinone with decomposing n-oxide of their 5-dimethyl-aminoetyl-derivatives | |
US5227509A (en) | Process for manufacture of organic esters of strong acids | |
JPH06256269A (en) | Production of n,n-diisopropyl-2-ethylhezylamine |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
MKEX | Expiry |