CA1256447A - Esters of the family of n-phosphonomethylglycine and their use in the preparation of known herbicides - Google Patents
Esters of the family of n-phosphonomethylglycine and their use in the preparation of known herbicidesInfo
- Publication number
- CA1256447A CA1256447A CA000473047A CA473047A CA1256447A CA 1256447 A CA1256447 A CA 1256447A CA 000473047 A CA000473047 A CA 000473047A CA 473047 A CA473047 A CA 473047A CA 1256447 A CA1256447 A CA 1256447A
- Authority
- CA
- Canada
- Prior art keywords
- formula
- group
- process according
- compound
- phenyl
- 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 8
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 title abstract description 9
- 239000004009 herbicide Substances 0.000 title abstract description 7
- 150000002148 esters Chemical class 0.000 title 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- -1 phosphonic acid diesters Chemical class 0.000 claims abstract description 6
- 150000003008 phosphonic acid esters Chemical class 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 239000000376 reactant Substances 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 238000007327 hydrogenolysis reaction Methods 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000004923 naphthylmethyl group Chemical group C1(=CC=CC2=CC=CC=C12)C* 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims 1
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims 1
- SLRMQYXOBQWXCR-UHFFFAOYSA-N 2154-56-5 Chemical compound [CH2]C1=CC=CC=C1 SLRMQYXOBQWXCR-UHFFFAOYSA-N 0.000 claims 1
- 239000012736 aqueous medium Substances 0.000 claims 1
- 229910052736 halogen Inorganic materials 0.000 claims 1
- 125000003710 aryl alkyl group Chemical group 0.000 abstract description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000005755 formation reaction Methods 0.000 description 5
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 4
- 108010049175 N-substituted Glycines Proteins 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- KGSVNOLLROCJQM-UHFFFAOYSA-N 2-(benzylamino)acetic acid Chemical compound OC(=O)CNCC1=CC=CC=C1 KGSVNOLLROCJQM-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000006264 debenzylation reaction Methods 0.000 description 3
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 3
- 150000002332 glycine derivatives Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004471 Glycine Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- ULOLIZHBYWAICY-UHFFFAOYSA-N ethyl 2-(benzylamino)acetate Chemical compound CCOC(=O)CNCC1=CC=CC=C1 ULOLIZHBYWAICY-UHFFFAOYSA-N 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 230000002363 herbicidal effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- MGRVRXRGTBOSHW-UHFFFAOYSA-N (aminomethyl)phosphonic acid Chemical compound NCP(O)(O)=O MGRVRXRGTBOSHW-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- KUMNEOGIHFCNQW-UHFFFAOYSA-N diphenyl phosphite Chemical compound C=1C=CC=CC=1OP([O-])OC1=CC=CC=C1 KUMNEOGIHFCNQW-UHFFFAOYSA-N 0.000 description 1
- 125000005982 diphenylmethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- NTNZTEQNFHNYBC-UHFFFAOYSA-N ethyl 2-aminoacetate Chemical compound CCOC(=O)CN NTNZTEQNFHNYBC-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- OXHDYFKENBXUEM-UHFFFAOYSA-N glyphosine Chemical compound OC(=O)CN(CP(O)(O)=O)CP(O)(O)=O OXHDYFKENBXUEM-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- NXJCBFBQEVOTOW-UHFFFAOYSA-L palladium(2+);dihydroxide Chemical compound O[Pd]O NXJCBFBQEVOTOW-UHFFFAOYSA-L 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 150000005691 triesters Chemical class 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
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/44—Amides thereof
-
- 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
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
- A01N57/20—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing acyclic or cycloaliphatic radicals
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
- A01N57/22—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing aromatic radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Biochemistry (AREA)
- Environmental Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Dentistry (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
ABSTRACT
"ESTERS OF THE FAMILY OF N-PHOSPHONOMETHYLGLYCINE
AND THEIR USE IN THE PREPARATION OF KNOWN HERBICIDES"
A process for the preparation of phosphonic acid diesters having the formula:
"ESTERS OF THE FAMILY OF N-PHOSPHONOMETHYLGLYCINE
AND THEIR USE IN THE PREPARATION OF KNOWN HERBICIDES"
A process for the preparation of phosphonic acid diesters having the formula:
Description
X~J~
The present inven-tion relates to a process for the preparation of N-substituted phosphonic acid - esters of the N-phosphonomethylglycine family which may be used for the synthesis of herbicides.
Numerous herbicides belonging to the N-phosphonomethylglycine family are known (US Patents 3,455,675, 4,388,103 and 4,397,676, French Patent
The present inven-tion relates to a process for the preparation of N-substituted phosphonic acid - esters of the N-phosphonomethylglycine family which may be used for the synthesis of herbicides.
Numerous herbicides belonging to the N-phosphonomethylglycine family are known (US Patents 3,455,675, 4,388,103 and 4,397,676, French Patent
2,129,327 European Patents 53,871, 54,382 and 73,574 PCT Patent No. W083/03,608, British Patent 2,090,596 and Begian Patents 894,244, 894,245, 894,590, 894,591 894,592, 894,593, 894,594 and 894,595).
One object of the invention is to provide a very simple and improved process for preparing herbicides, which employs relatively simple reactants, particularly glycine and its simple derivatives.
Other objects and advantages of the invention will become apparent in the course of the description which follows.
Mention has already been made (French Patent 2,129,327) of the formation of triesters of N-phosphone-methylglycine by the reaction of ethyl glycinate with formaldehyde and with diethyl phosphite.
This process is unsatisfactory, since it is considered to be excessively directed towards the formation of N,N-bis-(phosphonomethyl)glycine. For this reason it has been proposed (French Patent 2,193,830) to prepare N-phosphono-methylglycine by reacting an N-arylalkylglycine with formaldehyde and phosphorous jrc:~
~l25~
acid, with subsequent elimination of the N-arylalXyl group by the action of hydrobromic or hydroiodic acid.
However, this process is not considered to be satisfactory either, because of the low yields obtained and because of the formation of lachrymatory benzyl bromide. It has therefore been proposed to prepare N-phosphonomethylglycine by the reaction of N-substituted glycine with formaldehyde and with phosphorous acid, followed by a hydrogenolysis of the (N,N-disubstituted) N-phosphonomethylglycine which is obtained. This process has the disadvantage of being carried out in a very dilute medium and of being very lengthy. Also, more recently (European Patent 81,459) there has been a move towards reactants other than glycine and formaldehyde, and aminomethylphosphonic acid has been reacted with glyoxal in the presence of SO2 .
It has now been found, and this is the subject of the p~esent invention, that herbicides of the N-phosphonomethylglycine family can be obtained by virtue of new intermediate products, which are themselves accessible from N-substituted glycine derivatives and formaldehyde.
The present invention relates to a process for the preparation of phosphonic acid diesters of the formula:
jrc:~
olRl R
0 = P - CH2 - N - CH - CO - OH (I) OR
in which R represents a hydrogenolysable group, preferably an aralkyl group and R represents a hydrolysable group.
The radical R may, in particular, be a radical of the formula:
I (II) Ar - C -R
in which Ar is an aromatic group, preferably aryl and more particularly phenyl; this radical Ar may, if desired, carry one or more substituents which do not interfere with the reactions involved in the process (alkyl, alkoxy, nitro and others, the number of carbon atoms being pref0rably equal to 6 at most), although it does not appear particularly advantageous to employ such substituents, and R and R each represent a hydrogen atom or a radical Ar or an alkyl group, preferably having at most 6 carbon atoms.
Radicals R which may be mentioned are the benzyl, l-phenylethyl, l-phenylpropyl, naphthylmethyl, .~
jrc:~
~5~ 7 D~ --l-naphthylethyl, l-naphthylpropyl, diphenylmethyl and trityl (i.e. triphenylmethyl) radicals. Ben~yl is preferred.
R is a hydrolysable radical; examples of hydrolysable radicals which may be mentloned are optionally substituted hydrocarbyl radicals, particularly alkyl or phenyl radicals which are optionally substituted by halogen atoms or by phenyl, cyano, alkoxy or alkoxycarbonyl groups. R
generally contains at most 12 carbon atoms and is advantageously an alkyl radical containing from 1 to 6 carbon atoms or a phenyl radical.
The process for the preparation of the compounds of formula (I) is carried out by the reaction of a phosphite (or phosphonic acid ester) of the formula:
o _ Rl O = P - ~ (III) when R is as hereinbefore defined, with formaldehyde and an N-substituted glycine derivative, the substituent on the nitrogen atom being a hydrogenolysable substituent; this N-substituted glycine derivative is in practice a compound of the formula R-NH-CH2-CO-OH.
t~
jrc~
The reaction is generally carried out at between 0 and 100C, preferably be~cween 10 and 90C, by simply mixing the reactants. Although a large excess (3/1 to l/3 in molar ratios) of one of the reactants relative to the other is possible, it is in practice more advantageous to operate as close to stoichiometry as possible and not to depart by more than 20 mole ~ from this stoichiometry. It is indeed one of the major advantages of the invention that it does not require an excess of one of the reactants relative to the others.
Another advantage of the invention lies in the good yields obtained in the preparation of the compounds according to the invention.
Formaldehyde is employed in any of the conveniently accessible forms. According to the most commonly used method it is employed in the form of an aqueous solution of a concentration between 1~ and saturation, preferably of 30~ to 40~.
The reaction may be carried out in the presence of an inert solvent; sometimes such a solvent serves no purpose but the reaction mixture usually contains water, especially because of the use of formaldehyde in an aqueous solution.
The reaction product is isolated by any means known per se.
The products of the formula (~) may be converted into known herbicidal products of the `~
jrc~
~L2~ 7 formula:
OIRl 0 = P - CH2 - NH - CH~ - CO-OH
ORl (IV) wherein R is as hereinbefore defined, by simple hydrogenolysis of the group R. In most cases this is a debenzylation. It is carried out advantageously in an aqueous or alcoholic medium at ambient or elevated temperature, and at atmospheric pressure or above. The usual catalysts of hydrogenolysis of the radicals R in question may be employed as a catalyst. Suitable catalysts which may be mentioned are palladium, platinum, and Raney nickel.
This cakalyst may be employed with or without an inert support. It is also possible to employ the abovementioned metals, particularly palladium and platinum, in the form of salts, hydroxides, or oxides, which are converted to the corresponding metal under the action of hydrogen. Palladium-based catalysts, such as palladium on charcoal or palladium on barium sulphate, or palladium hydroxide on charcoal, are employed as a preferred debenzylation catalyst. At the end of the reaction, the catalyst may be separated by filtration and the filtrate evaporated; this yields the product of the formula (IV) in a practically pure irc:~
S~ 7 state. A major advantage of the invention lies in the fact that the reaction time for this debenzylation is relatively short, which makes it possible to use reduced quantities of catalyst.
Then it is desired to prepare known non-esterified forms of herbicides, such as for example N-phosphonomethylglycine itself, the product of the formula (IV) may be hydrolysed completely or partically in a known manner, e.g. by heating with an aqueous solution of an acid or alkaline agent, particularly a hy-droxide or carbonate of an alkali metal or alkaline-earth metal, or hydrochloric, sulphuric, phosphoric, perchloric or arylsulphonic acids. This hydrolysis may also be accompanied by a salt formation or a conversion to other herbicidal derivatives. Thus the hydrogenolysis according to the invention can be followed by a hydrolysis and/or a salt formation reaction.
The examples which follow and which are given without implying a limitation illustrate the invention and show how it can be put into practice.
Example 1 N-Benzylglycine (39 g), water (80 ml) and an aqueous solution (20.3 ml) of formaldehyde (0.248 mole) are mixed.
Diphenylphosphite (C6H50)2PH(0) (58g = 0.248 mole) is added dropwise at ambient temperature. After 30 minutes, the temperature is allowed to rise to 30 and stirring is continued for one hour. The product is filtered off, ~ .
.~.0 jrc:,~
- 8 ~
washed with water and dried. Af-ter recrystal~Lsation from a mixture of isopropyl ether and isopropanol in the ratio of 10/1 by volume, a white powder (57.4 g) is obtained (yield 59.1~), which melts at 91C and consists of the product of the formula:
0 = P - CH -N - CH - COOH (V) Example 2:
N-Benzylglycine (16.5 g), water (28 ml) and diethylphosphite (C2H50)2PH(0) (13.8 g) are mixed-An aqueous 37% strength formaldehyde solution (9 ml = 0.11 mole) is added at 20C. Non exothermic effect is observed. The mixture is heated for five hours at 50 and then cooled, and CH2C12 (40 ml) is added. The organic phase is seyarated off and water (40 ml) followed by N aqueous NaOH solution (100 ml) are added. The aqueous phase is decanted, extracted with CH2C12 and acidified. The organic phase is dried and evaporated. A product (23.5 g = 74% yield) is obtained of the formula:
C2H5f TH2-C6H5 0 = P - CE -N - CH - COOH (VI) Example 3:
Ethyl N-benzylglycinate is saponified in situ. An aqueous 30% strength NaOH solution (0.5 1 = 5 moles) and water (1 1) are mixed into this ~' jrc:~
solution, ethyl N-benzylglycinate (965 g ) is poured -gradually over one hour. The temperature rises to 45 C. The ethanol is distilled off, the residue is cooled and a 6 N aqueous hydrochloric acid solution tO.82 1) is added. The N-benzylglycine precipitates.
Diethylphosphite (690 g) and 37% strength aqueous formaldehyde (0.45 1 = 5 moles) are added. The mixture is heated for 5 hours 30 minutes at 50C. Thereafter, the procedure of Example 2 is followed. The product of formula (VI) (1116 g = 71% yield) is obtained.
~i .
jrc:~'~
One object of the invention is to provide a very simple and improved process for preparing herbicides, which employs relatively simple reactants, particularly glycine and its simple derivatives.
Other objects and advantages of the invention will become apparent in the course of the description which follows.
Mention has already been made (French Patent 2,129,327) of the formation of triesters of N-phosphone-methylglycine by the reaction of ethyl glycinate with formaldehyde and with diethyl phosphite.
This process is unsatisfactory, since it is considered to be excessively directed towards the formation of N,N-bis-(phosphonomethyl)glycine. For this reason it has been proposed (French Patent 2,193,830) to prepare N-phosphono-methylglycine by reacting an N-arylalkylglycine with formaldehyde and phosphorous jrc:~
~l25~
acid, with subsequent elimination of the N-arylalXyl group by the action of hydrobromic or hydroiodic acid.
However, this process is not considered to be satisfactory either, because of the low yields obtained and because of the formation of lachrymatory benzyl bromide. It has therefore been proposed to prepare N-phosphonomethylglycine by the reaction of N-substituted glycine with formaldehyde and with phosphorous acid, followed by a hydrogenolysis of the (N,N-disubstituted) N-phosphonomethylglycine which is obtained. This process has the disadvantage of being carried out in a very dilute medium and of being very lengthy. Also, more recently (European Patent 81,459) there has been a move towards reactants other than glycine and formaldehyde, and aminomethylphosphonic acid has been reacted with glyoxal in the presence of SO2 .
It has now been found, and this is the subject of the p~esent invention, that herbicides of the N-phosphonomethylglycine family can be obtained by virtue of new intermediate products, which are themselves accessible from N-substituted glycine derivatives and formaldehyde.
The present invention relates to a process for the preparation of phosphonic acid diesters of the formula:
jrc:~
olRl R
0 = P - CH2 - N - CH - CO - OH (I) OR
in which R represents a hydrogenolysable group, preferably an aralkyl group and R represents a hydrolysable group.
The radical R may, in particular, be a radical of the formula:
I (II) Ar - C -R
in which Ar is an aromatic group, preferably aryl and more particularly phenyl; this radical Ar may, if desired, carry one or more substituents which do not interfere with the reactions involved in the process (alkyl, alkoxy, nitro and others, the number of carbon atoms being pref0rably equal to 6 at most), although it does not appear particularly advantageous to employ such substituents, and R and R each represent a hydrogen atom or a radical Ar or an alkyl group, preferably having at most 6 carbon atoms.
Radicals R which may be mentioned are the benzyl, l-phenylethyl, l-phenylpropyl, naphthylmethyl, .~
jrc:~
~5~ 7 D~ --l-naphthylethyl, l-naphthylpropyl, diphenylmethyl and trityl (i.e. triphenylmethyl) radicals. Ben~yl is preferred.
R is a hydrolysable radical; examples of hydrolysable radicals which may be mentloned are optionally substituted hydrocarbyl radicals, particularly alkyl or phenyl radicals which are optionally substituted by halogen atoms or by phenyl, cyano, alkoxy or alkoxycarbonyl groups. R
generally contains at most 12 carbon atoms and is advantageously an alkyl radical containing from 1 to 6 carbon atoms or a phenyl radical.
The process for the preparation of the compounds of formula (I) is carried out by the reaction of a phosphite (or phosphonic acid ester) of the formula:
o _ Rl O = P - ~ (III) when R is as hereinbefore defined, with formaldehyde and an N-substituted glycine derivative, the substituent on the nitrogen atom being a hydrogenolysable substituent; this N-substituted glycine derivative is in practice a compound of the formula R-NH-CH2-CO-OH.
t~
jrc~
The reaction is generally carried out at between 0 and 100C, preferably be~cween 10 and 90C, by simply mixing the reactants. Although a large excess (3/1 to l/3 in molar ratios) of one of the reactants relative to the other is possible, it is in practice more advantageous to operate as close to stoichiometry as possible and not to depart by more than 20 mole ~ from this stoichiometry. It is indeed one of the major advantages of the invention that it does not require an excess of one of the reactants relative to the others.
Another advantage of the invention lies in the good yields obtained in the preparation of the compounds according to the invention.
Formaldehyde is employed in any of the conveniently accessible forms. According to the most commonly used method it is employed in the form of an aqueous solution of a concentration between 1~ and saturation, preferably of 30~ to 40~.
The reaction may be carried out in the presence of an inert solvent; sometimes such a solvent serves no purpose but the reaction mixture usually contains water, especially because of the use of formaldehyde in an aqueous solution.
The reaction product is isolated by any means known per se.
The products of the formula (~) may be converted into known herbicidal products of the `~
jrc~
~L2~ 7 formula:
OIRl 0 = P - CH2 - NH - CH~ - CO-OH
ORl (IV) wherein R is as hereinbefore defined, by simple hydrogenolysis of the group R. In most cases this is a debenzylation. It is carried out advantageously in an aqueous or alcoholic medium at ambient or elevated temperature, and at atmospheric pressure or above. The usual catalysts of hydrogenolysis of the radicals R in question may be employed as a catalyst. Suitable catalysts which may be mentioned are palladium, platinum, and Raney nickel.
This cakalyst may be employed with or without an inert support. It is also possible to employ the abovementioned metals, particularly palladium and platinum, in the form of salts, hydroxides, or oxides, which are converted to the corresponding metal under the action of hydrogen. Palladium-based catalysts, such as palladium on charcoal or palladium on barium sulphate, or palladium hydroxide on charcoal, are employed as a preferred debenzylation catalyst. At the end of the reaction, the catalyst may be separated by filtration and the filtrate evaporated; this yields the product of the formula (IV) in a practically pure irc:~
S~ 7 state. A major advantage of the invention lies in the fact that the reaction time for this debenzylation is relatively short, which makes it possible to use reduced quantities of catalyst.
Then it is desired to prepare known non-esterified forms of herbicides, such as for example N-phosphonomethylglycine itself, the product of the formula (IV) may be hydrolysed completely or partically in a known manner, e.g. by heating with an aqueous solution of an acid or alkaline agent, particularly a hy-droxide or carbonate of an alkali metal or alkaline-earth metal, or hydrochloric, sulphuric, phosphoric, perchloric or arylsulphonic acids. This hydrolysis may also be accompanied by a salt formation or a conversion to other herbicidal derivatives. Thus the hydrogenolysis according to the invention can be followed by a hydrolysis and/or a salt formation reaction.
The examples which follow and which are given without implying a limitation illustrate the invention and show how it can be put into practice.
Example 1 N-Benzylglycine (39 g), water (80 ml) and an aqueous solution (20.3 ml) of formaldehyde (0.248 mole) are mixed.
Diphenylphosphite (C6H50)2PH(0) (58g = 0.248 mole) is added dropwise at ambient temperature. After 30 minutes, the temperature is allowed to rise to 30 and stirring is continued for one hour. The product is filtered off, ~ .
.~.0 jrc:,~
- 8 ~
washed with water and dried. Af-ter recrystal~Lsation from a mixture of isopropyl ether and isopropanol in the ratio of 10/1 by volume, a white powder (57.4 g) is obtained (yield 59.1~), which melts at 91C and consists of the product of the formula:
0 = P - CH -N - CH - COOH (V) Example 2:
N-Benzylglycine (16.5 g), water (28 ml) and diethylphosphite (C2H50)2PH(0) (13.8 g) are mixed-An aqueous 37% strength formaldehyde solution (9 ml = 0.11 mole) is added at 20C. Non exothermic effect is observed. The mixture is heated for five hours at 50 and then cooled, and CH2C12 (40 ml) is added. The organic phase is seyarated off and water (40 ml) followed by N aqueous NaOH solution (100 ml) are added. The aqueous phase is decanted, extracted with CH2C12 and acidified. The organic phase is dried and evaporated. A product (23.5 g = 74% yield) is obtained of the formula:
C2H5f TH2-C6H5 0 = P - CE -N - CH - COOH (VI) Example 3:
Ethyl N-benzylglycinate is saponified in situ. An aqueous 30% strength NaOH solution (0.5 1 = 5 moles) and water (1 1) are mixed into this ~' jrc:~
solution, ethyl N-benzylglycinate (965 g ) is poured -gradually over one hour. The temperature rises to 45 C. The ethanol is distilled off, the residue is cooled and a 6 N aqueous hydrochloric acid solution tO.82 1) is added. The N-benzylglycine precipitates.
Diethylphosphite (690 g) and 37% strength aqueous formaldehyde (0.45 1 = 5 moles) are added. The mixture is heated for 5 hours 30 minutes at 50C. Thereafter, the procedure of Example 2 is followed. The product of formula (VI) (1116 g = 71% yield) is obtained.
~i .
jrc:~'~
Claims (9)
1. A process for the preparation of phosphonic acid diesters having the formula:
(I) in which R represents a hydrogenolysable group of the formula:
(II) in which Ar is a phenyl group, which is optionally substituted by alkyl or alkoxy having at most 6 carbon atoms, or nitro and R3 and R4 each represent a hydrogen atom or a phenyl radical or an alkyl group having at most 6 carbon atoms, or R represents a hydrogenolysable group which is naphthylmethyl, 1-naphthylethyl or 1-naphthylpropyl, and R1 represents a hydrolysable group which is a C1-12 alkyl or phenyl radical which is optionally substituted by halogen, phenyl, cyano, C1-6 alkoxy or C2-6 alkoxycarbonyl, wherein a phosphonic acid ester of the formula (R1C)2P(O)H is reacted with formaldehyde and a compound of the formula R-NH-CH2-COOH, R and R1 having the meanings given above.
(I) in which R represents a hydrogenolysable group of the formula:
(II) in which Ar is a phenyl group, which is optionally substituted by alkyl or alkoxy having at most 6 carbon atoms, or nitro and R3 and R4 each represent a hydrogen atom or a phenyl radical or an alkyl group having at most 6 carbon atoms, or R represents a hydrogenolysable group which is naphthylmethyl, 1-naphthylethyl or 1-naphthylpropyl, and R1 represents a hydrolysable group which is a C1-12 alkyl or phenyl radical which is optionally substituted by halogen, phenyl, cyano, C1-6 alkoxy or C2-6 alkoxycarbonyl, wherein a phosphonic acid ester of the formula (R1C)2P(O)H is reacted with formaldehyde and a compound of the formula R-NH-CH2-COOH, R and R1 having the meanings given above.
2. A process according to claim 1, in which R is the benzyl radical.
3. Process according to claim 1, in which R1 is an alkyl radical having from 1 to 6 carbon atoms or is the phenyl radical.
4. Process according to claim 1, wherein the reaction is carried out between 0 and 100°C, each reactant being present in a proportion which does not differ by more than 20% from stoichiometry.
5. Process according to claim 1, wherein the reaction is carried out in an aqueous medium.
6. Process according to claim 1 followed by the hydrogenolysis of the compound of formula (I) obtained to prepare a compound of the formula:
(IV) wherein R1 is as defined in claim 1.
(IV) wherein R1 is as defined in claim 1.
7. Process according to claim 6, wherein the said process is followed by a hydrolysis and/or a salt-forming reaction.
8. A compound of formula (I) wherein R and R1 are as defined in claim 1.
9. The compound of formula (I) wherein each of the symbols R1 represents phenyl and R represents benzyl.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8402988A FR2560198B1 (en) | 1984-02-23 | 1984-02-23 | ESTERS OF THE N-PHOSPHONOMETHYLGLYCIN FAMILY AND THEIR USE FOR THE PREPARATION OF KNOWN HERBICIDES |
| FR8402988 | 1984-02-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1256447A true CA1256447A (en) | 1989-06-27 |
Family
ID=9301450
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000473047A Expired CA1256447A (en) | 1984-02-23 | 1985-01-29 | Esters of the family of n-phosphonomethylglycine and their use in the preparation of known herbicides |
Country Status (22)
| Country | Link |
|---|---|
| EP (1) | EP0153261B1 (en) |
| JP (1) | JPS60193995A (en) |
| KR (1) | KR850007065A (en) |
| AT (1) | ATE40376T1 (en) |
| AU (1) | AU584600B2 (en) |
| BR (1) | BR8500765A (en) |
| CA (1) | CA1256447A (en) |
| DD (1) | DD232050A5 (en) |
| DE (1) | DE3567874D1 (en) |
| DK (1) | DK84185A (en) |
| ES (1) | ES8607975A1 (en) |
| FI (1) | FI75831C (en) |
| FR (1) | FR2560198B1 (en) |
| GB (1) | GB2155476B (en) |
| HU (1) | HU197022B (en) |
| IE (1) | IE850203L (en) |
| IL (1) | IL74169A (en) |
| PL (1) | PL147957B1 (en) |
| PT (1) | PT79998B (en) |
| RO (1) | RO90931B (en) |
| YU (1) | YU45234B (en) |
| ZA (1) | ZA85726B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2560198B1 (en) * | 1984-02-23 | 1987-05-07 | Rhone Poulenc Agrochimie | ESTERS OF THE N-PHOSPHONOMETHYLGLYCIN FAMILY AND THEIR USE FOR THE PREPARATION OF KNOWN HERBICIDES |
| FR2579210B1 (en) * | 1985-03-21 | 1987-09-11 | Rhone Poulenc Agrochimie | PREPARATION OF PHOSPHONATE GROUP HERBICIDES AND INTERMEDIATES FROM BENZOXAZINES |
| DE4326887A1 (en) * | 1993-08-11 | 1995-02-16 | Hoechst Ag | Process for the preparation of N-substituted aminoalkylenephosphonic esters |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1436843A (en) * | 1972-07-21 | 1976-05-26 | Ici Ltd | Preparation of n-phosphonomethyl-glycine |
| RO67869A (en) * | 1972-12-11 | 1981-06-22 | Mensanto Co,Us | PROCESS FOR THE PREPARATION OF N-PHOSPHONOMETHYL GLUCIUM N-OXIDES DERIVATIVES |
| US3835000A (en) * | 1972-12-21 | 1974-09-10 | Monsanto Co | Electrolytic process for producing n-phosphonomethyl glycine |
| HU173170B (en) * | 1974-06-27 | 1979-03-28 | Chinoin Gyogyszer Es Vegyeszet | Process for producing n-phosphonomethyl-glycine |
| EP0000767B1 (en) * | 1977-08-11 | 1980-11-26 | Ciba-Geigy Ag | Glycylmethyl-phosphinic acid derivatives, their preparation and their use |
| EP0055695A1 (en) * | 1980-12-30 | 1982-07-07 | Ciba-Geigy Ag | Process for preparing N-phosphonomethyl glycine |
| US4422982A (en) * | 1982-06-30 | 1983-12-27 | Stauffer Chemical Company | Method for preparation of N-phosphonomethylglycine |
| FR2560198B1 (en) * | 1984-02-23 | 1987-05-07 | Rhone Poulenc Agrochimie | ESTERS OF THE N-PHOSPHONOMETHYLGLYCIN FAMILY AND THEIR USE FOR THE PREPARATION OF KNOWN HERBICIDES |
-
1984
- 1984-02-23 FR FR8402988A patent/FR2560198B1/en not_active Expired
-
1985
- 1985-01-25 IL IL74169A patent/IL74169A/en unknown
- 1985-01-29 GB GB08502164A patent/GB2155476B/en not_active Expired
- 1985-01-29 IE IE850203A patent/IE850203L/en unknown
- 1985-01-29 CA CA000473047A patent/CA1256447A/en not_active Expired
- 1985-01-30 AU AU38163/85A patent/AU584600B2/en not_active Ceased
- 1985-01-30 ZA ZA85726A patent/ZA85726B/en unknown
- 1985-02-21 AT AT85420029T patent/ATE40376T1/en active
- 1985-02-21 PL PL1985252061A patent/PL147957B1/en unknown
- 1985-02-21 PT PT79998A patent/PT79998B/en not_active IP Right Cessation
- 1985-02-21 KR KR1019850001078A patent/KR850007065A/en not_active Application Discontinuation
- 1985-02-21 BR BR8500765A patent/BR8500765A/en unknown
- 1985-02-21 JP JP60033630A patent/JPS60193995A/en active Pending
- 1985-02-21 EP EP85420029A patent/EP0153261B1/en not_active Expired
- 1985-02-21 DE DE8585420029T patent/DE3567874D1/en not_active Expired
- 1985-02-22 HU HU85673A patent/HU197022B/en not_active IP Right Cessation
- 1985-02-22 ES ES540626A patent/ES8607975A1/en not_active Expired
- 1985-02-22 FI FI850733A patent/FI75831C/en not_active IP Right Cessation
- 1985-02-22 DD DD85273479A patent/DD232050A5/en unknown
- 1985-02-22 DK DK84185A patent/DK84185A/en not_active Application Discontinuation
- 1985-02-22 YU YU273/85A patent/YU45234B/en unknown
- 1985-02-23 RO RO117743A patent/RO90931B/en unknown
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