AU599729B2 - Preparation of phosphorus-containing intermediates for herbicides - Google Patents
Preparation of phosphorus-containing intermediates for herbicides Download PDFInfo
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- AU599729B2 AU599729B2 AU82618/87A AU8261887A AU599729B2 AU 599729 B2 AU599729 B2 AU 599729B2 AU 82618/87 A AU82618/87 A AU 82618/87A AU 8261887 A AU8261887 A AU 8261887A AU 599729 B2 AU599729 B2 AU 599729B2
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- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000000543 intermediate Substances 0.000 title abstract description 5
- 239000004009 herbicide Substances 0.000 title abstract description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title 1
- 229910052698 phosphorus Inorganic materials 0.000 title 1
- 239000011574 phosphorus Substances 0.000 title 1
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 125000005843 halogen group Chemical group 0.000 claims abstract description 7
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 33
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
- 238000004064 recycling Methods 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 239000012074 organic phase Substances 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000005599 alkyl carboxylate group Chemical group 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 239000012736 aqueous medium Substances 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 150000008282 halocarbons Chemical class 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 150000002825 nitriles Chemical group 0.000 claims description 2
- 239000002798 polar solvent Substances 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 45
- 239000012071 phase Substances 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 5
- 239000008346 aqueous phase Substances 0.000 description 5
- 238000004587 chromatography analysis Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- OJTRKMSUJCHVMW-UHFFFAOYSA-N 2-chloro-n-methyl-n-methylsulfonylacetamide Chemical group CS(=O)(=O)N(C)C(=O)CCl OJTRKMSUJCHVMW-UHFFFAOYSA-N 0.000 description 4
- SAEILGZODTXRSQ-UHFFFAOYSA-N N-[di(propan-2-yloxy)phosphorylmethyl]-1-phenylmethanamine Chemical compound C(C1=CC=CC=C1)NCP(OC(C)C)(=O)OC(C)C SAEILGZODTXRSQ-UHFFFAOYSA-N 0.000 description 4
- -1 hydrocarbon radical Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- YTSVWPKOWYIUDR-UHFFFAOYSA-N (benzylamino)methylphosphonic acid Chemical compound OP(O)(=O)CNCC1=CC=CC=C1 YTSVWPKOWYIUDR-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- BWGGHAYKVNTLCJ-UHFFFAOYSA-N Cl.C(C1=CC=CC=C1)NCP(OC(C)C)(=O)OC(C)C Chemical compound Cl.C(C1=CC=CC=C1)NCP(OC(C)C)(=O)OC(C)C BWGGHAYKVNTLCJ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical compound CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes 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)]
- C07F9/40—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
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- 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)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Fertilizers (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Cephalosporin Compounds (AREA)
Abstract
Preparation of intermediates for herbicides of formula: <IMAGE> by reaction of products of formula: <IMAGE> with products of formula: <IMAGE> in which R, R<1>, R<2>, R<3> and R<4> are organic radicals or H in some cases and X is halogen. The molar ratio II/III is greater than 1.5.
Description
lie 599729 PH 4286 COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952-1973 COMPLETE SPECIFICATION
(ORIGINAL)
FOR OFFICE USE: ,9 'e d> O0 Class Application Number: Lodged: Complete Specification Lodged: Accepted: Published: Priority.
Related Art: Its f rrs t-I .j i" i. o i i Int Class 9 0 Name of Applicant: Address of Applicant: Actual Inventor(s) Address for Service: RHONE-POULENC AGROCHIMIE 14-20 Rue 'Pierre Baizet, Lyon 69009, France.
Jean.,-Pierre CORBET and Michel MULHAUSER Davies Collison, Patent Attorneys, 1 Little Collins Street, Melbourne, Victoria 3000, Australia Complete Specification for the .nvention entitled: "PREPARATION OF PL2JSPHORUS-CONTAINING INTERMEDIATES FOR HERBICID ES" The following statement is a full description of this invention, including the best method of performing it known to us:- I 'I -2- This invention relates to a process for the preparation of compounds which are useful as intermediates for herbicides.
The present invention relates to a process for the preparation of a compound of formula: 2 4 OR R I I (1) 0 F CH2 N CH 2 CO N S0 2
R
0 0 o oo0 10 wherein o0,
R
1 represents an optionally substituted o -D oo hydrocarbon radical, preferably alkyl, aryl or cycloalkyl, o 00 each of which may be substituted; suitable substituents 0o include halogen atoms and phenyl, cyano, alkyl, alkoxy and o0oo 15 alkylcarboxylate groups in which the alkyl groups preferably 0 00 contain from 1 to 4 carbon atoms; R' generally contains from 00 0 0 0 6 0 o0 1 to 18 carbon atoms, preferably from 1 to 7 carbon atoms, 0 o 0 and more particularly from 3 to 7 carbon atoms when R is a cycloalkyl group; preferably R 1 represents an alkyl group 0 o 00 20 containing from 1 to 4 carbon atoms, optionally substituted by halogen, especially chlorine or fluorine, e.g. CF 3 R represents a hydrogen atom or has one of the meanings given for R and is preferably an alkyl group containing from 1 to 4 carbon atoms,
R
2 and R 3 are such that OR 2 and OR 3 in which R 2 and R' may together form a single optionally substituted 1, 1 -3divalent radical, are hydrolysable groups; R 2 and R 3 preferably represent an optionally substituted alkyl, aryl or arylalkyl radical (suitable substituents are those mentioned for R 1 or R and R 3 may together form a single optionally substituted divalent radical preferably containing from 2 to 6 carbon atoms, e.g. an optionally o subsituted alkylene radical an ethylene or propylene 0 o. 2 3 a radical); R and R generally each contain from 1 to 12 o o 0 .o carbon atoms and preferably from 1 to 8 carbon atoms; and 00 0 S10 R represents a radical of formula Ar(R 5
(R
6
)C-
0 0 0 0 0 So in which Ar is an optionally substituted aromatic group, preferably phenyl, a an and R 6 each represent a hydrogen 0 0 a at atom or an (aromatic) radical Ar or an alkyl group o0° preferably containiing not more than 6 carbon atoms 0; 0 4 15 (preferably R represents benzyl), a e ooa by reacting a compound of formula: OR 2
OR
wherein R2, R3 and R4 are as hereinbefore defined with a compound of formula: ni t 0 z(II) 0 P Cl 2
I
OR
3 wherein R R and R are as hereinbefore defined with a compound of formula: X" C2 Co a SO 2 h i
(III)
wherein -4- X represents a halogen atom, e.g. chlorine, bromine or iodine, preferably chlorine, and R and RIare as hereinbef-ore defined.
Suitable substituents for the group Ar include alkyl and alkoxy groups, preferably containing from I to 4 o 0S carbon atoms, nitro radicals and halogen atoms.
Such a reaction is known from European Patent Application No. 0,189,725. The compou~nds of formula are intermediates for herbicides.
The present invention seeks to' provide an improved process for the preparation of the compounds of formula for a more satisfactory implementation on an industrial scale. The present invention also seeks to provide a simplified preparation process.
is It has been fuund that the molar ratio of the compound. of formula II to the compound of formula III is important in the reaction: in particular the use of a molar ratio greater than 1.5 4llows the presence of add~itional acceptor for acid to be avoide,:. This leads to two important advantages: firstly, it enables any stage for the removal of the said acceptor for acid to be omitted and secondly, it enables the yield to be increased.
Another important consequence of this total or near total absence of additional acceptor for acid is that it enables a recycling process to be carried out, further improving sigrificantly the ,-,ield and the implementation or) an industrial scale.
I r The present invention accordingly provides a process for the preparation of a compound of formula (I) wherein the various symbols are as hereinbefore defined by the reaction of a compound of formula (II) wherein the various symbols are as hereinbefore defined with a compound of formula (III) as hereinbefore defined, the molar ratio of c the compound of formula (II) to the compound of formula (III) being greater than The reaction according to the invention may be carried out in the absence, or more preferably in the presence, of a solvent. In fact, the presence of the solvent enables the temperature to be controlled more satisfactorily. The reaction is preferably carried out in an inert organic solvent at an elevated temperature.
Suitable solvents include nitriles (especially acetonitrile), ketones (especially acetone, cyclohexanone, methyl ethyl ketone and methyl isobutyl ketone), halogenated or non-halogenated hydrocarbons (especially benzene, toluene, xylenes and chlorobenzene), esters such as alkyl alkanoates (especially ethyl acetate), and aprotic polar solvents such as dimethylformamide and N-methylpyrrolidone.
The reaction temperature is generally from 30 to 150°C and preferably from 40 to 120 0
C.
The reaction product of formula may be isolated by any means known per se.
Some compounds of formula (II) are known 7 iinilir ill.^ l ^l j ^l^ -6- (Tetrahedron Letters no. 46, p. 4645, 1973). They can be prepared conveniently by reacting tris(aralkyl)hexahydrotriazines with diorganophosphites.
The compounds of formula (III) are also known.
The molar ratio of compound (II) to compound S' (III) is preferably greater than 1.8 and advantageously from S1.9 to 4.
According to a preferred feature, the process of the invention is carried out in the total or near total absence of additional acid acceptor. Near total absence means that the reaction medium may contain traces of acceptor for various reasons.
According to a further feature of the process according to the invention, the process is carried out continuously by recycling the compound of formula (II).
S.
C This recycling is accomplished at the end of the S' reaction, by extraction of unreacted compound of formula (II) into an acidic aqueous medium and then, after neutralization, transferring the compound of formula (II) into an organic phase for reaction with further compounid of formula (III).
The process is more particularly suitable for compounds in which R and R 1 are alkyl groups containing from 1 to 4 carbon atoms, preferably methyl, and/or in which R 2 and R 3 are alkyl, phenyl or benzyl groups.
The following Examples illustrate the invention.
F a u ra~ -7- Example 1 A mixture of diisopropyl N-benzylaminomethanephosphonate 285; 11.43 g; 4 x 10 2 moles) and "2 N-methyl-N-methysulphonylchloroacetamide (3.71 g; 2 x 10 2 moles) is heated for 2 h at 80°C. The reaction mixture is diluted to 50 cc with toluene and treated with water and oo°0a with hydrochloric acid. The aqueous phase and the toluene o 0:0 phase are separated. The toluene phase is concentrated and 0,C0 it is observed, by chromatography, that 8.025 g of the product is obtained, which corresponds to a yield of 92.4% relative to the N-methyl-N-methylsulphonylchloroacetamide employed.
The aqueous phase containing diisopropyl N-benzyl-aminomethanephosphonate hydrochloride is poured S 15 into toluene (20 rc), the mixture is neutralized with a stoichiometric quantity of aqut.uus 2 N sodium hydroxide.
e The aqueous phase and the toluene phase are separated. The S* toluene phase contains diisopropyl N-benzylamino- -2 methanephosphonate (1.82 x 10 2 moles) in the form of the base which can be recycled, after the distillation of toluene if j required.
SExample 2 The same trial carried out at 70 0 C leads to a yield, as determined by chromatography, of 72.5% relative to the N-methyl-N-meth, vsulphonylchloroacetamide employed.
Example 3 The same trial carried out at 90°C leads to a -8yield, as determined by, chromatography, of 86.7% relative to the N-me thyl-N-me thyl sulphor' Ichloroace tami le employed.
Comartive Example Diisopropyl N-benzylaminomethanephosphonate (5.71 2 x 10 -2 mole) and N-methyl-N-methylsulphonylchloroacetamide (3.71 g; 2 x 10 2 mole) are heated for 2 h at 0:0::80 0 C. A solution of triethyl:imine (2.8 cc; 2 x 102 molle) in toluene (15 cc) is poured gradually.. in the course of h, into the reaction mixture which is maintained at 80 0
C.
It The mixture is th'en cooled to 20 0 C, poured into water cc) at ambient temperature and the aqueous phase and the toluene phase are a;eparated. The toluene phase is conc:,,entrated under vacuum. It is observed, by chromatography, that 6.6 9 of the expected product was 1obtained, which corresponds to a yield of 75.8% relative to V. a the 2 reagents charged.
*~1Example4 l,3,5-trilbenzylhexahydrotriazine (59.5 0.166 mole) diisopropyl plbosphite (83 g; 0.5 mole) and toluene (100 g) are heated for 41 h 30 min at 120 0 C. The mixture is cooled to 20 0 C. An analysis by chromatography shows that the reaction yield of diisopropyl N-benzylaminomethanephosphoria Ie is quantitative. N-methyl-N-methylsuolphony'1chloroacetamide (37.1 g; 0.2 mole) is added. The reaction mixture is heated to 80 0Cfor 2 hours and then cooled to ambirnt temperature. It is then poured into water I i ~il -9- (150 g) and aqueous 37% HC1 (12 cc) is added in order to adjust the pH to 1. The phases are decanted and separated.
The organic phase has a weight of 173 g. The aqueous phase (265 g) is neutralized to pH 6 with aqueous 30% sodium hydroxide (30 cc) after adding toluene (100 The phases are decanted and separated. The second organic phase has a o oo weight of 195 g.
S The first organic phase (173 g) contains f 0 44.6% of the product expected, which amounts to 0.18 mole.
10 The second organic phase (195 g) contains 42% of diisopropyl St N-benzylaminomethanephosphonate which amounts to 0.287 mole.
S1st recycling T> e 2nd organic phase (195 g) is azeotropically dried (67 g of toluene and water are removed) and a solution (120 g) containing diisopropyl N-benzylaminomeqthanephosphonate (0.25 mole) and N-methyl-N-methylsulphonylchloroacetamide (37.1 g; 0.2 mole) in toluene is added and the mixture is heated for 2 h at 80 C. The reaction mass is treated exactly as before.
2nd recycling A 2nd recycling of diisopropyl N-benzylaminomethanephosphonate was carrried out exactly as above.
All the results are given in the table below: A diisopropyl N-benzylaminomethanephosphonate B N-methyl-N-methylsulphonylchloroacetamide ar t L m C condensation product expected R-ai materials jA recycled Yield of em ployed A 0.5 mole 89% B 0. 2 mole 1st recycling A 0. 25 mole 0.28 mole 100% B 0. 2 mole 2nd recycling A 0.25 mole 0.18 mole 100% B 0.2 mole O 0 0 a 00
C
6 9 t C
CO
00 0 000 0 40 0 C 'C 00 0 0 00 O 0 400000 C 0
CC
CC
Claims (9)
1. A process for the preparation of a c mpound of the formula: OR 2 a I (I) o P C N Cu 2 co so 2 1 O I 0 wherein 0 1 R represents an optionally substituted *081@ O t €oo°hydrocarbon rarcical; @o'I o a R represents a hydrogen atom 6r an optionally substituted hydrocarbon radical; n *e R 2 and R) are such that OR 2 and OR, in which R2 and R 3 may together form a single optionally substituted divalent radical, are hydrolysable groups; and 4 5 R represents a radical of formula Ar(R )C- in which Ar is an optionally substituted aromatic group, and R 5 and R 6 are a hydrogen atom or a radical Ar or an alkyl group,, which process comprises the reaction of A compound of the formula: OR 2 0 ;e .CH^ 2 -H R 1R QR 3 I 0 and R" may together form a single optionally substituted divatent radical, are hydrolysable groups; and /2 4 wi whe.ein R 2 R' and R 4 are as hereinbefore defined th a compound of formula: X C CO 02 a (XI) 0 9
9. 0 9 0 o a. 4 0 *400 *9 0 .4 *9 9. 4 9 09 wherein X represents a halogen atom and R and R2 are as hereinbefore defined, the molar ratio of compound (II) to compound (11) being greater than 1.5; and wherein said reaction temperature is from 30 0 C to 150 0 C. 2. A process according to claim 1 in which R' represents a hydrocarbon radical optionally substituted by halogen, phenyl, cyano, alkyl,, alkoxy or alkylcarboxylate. 3. A process according to claim 2 in which the hydrocarbon ralical represented by R' is alkyl, aryl or cycloalkyl. A process according to claim 1, 2 or 3 in which the hydrocarbon radical represented by R 1 contains from 1 to 7 carbon atoms or from-. 3 to 7 carbon atoms when R' repres.ents a cycloalkyl group, A pxaaess according to any one of the preceding claims in which R' represents an alkyl group containing from 1 to 4 carbon atoms optionally substituted by halogen. 6. A process according to any one of the preceding claims in which R represents an alkyl group containing from 1 to 4 carbon atoms. 7. A process according to any one of the preceding claims in which R 2 and R 3 represent an alkyl, aryl or 9 9 9 9 o o~ 9 CO -13- arylalkyl radical optionally substitute by halogen, phenyl, cyano, alkyl, alkoxy or alkylcarboxylate, or R 2 and R 3 together represent a single optionally substituted divalent radical containing from 2 to 6 carbon atoms. 8. A process according to any one of the preceding claims wherein R and R 1 each represent an alkyl group containing from I to 4 carbon atoms. 9. A process according to any one of the preceding claims wherein R and R 1 each represent methyl. A process according to any one of the preceding claims wherein R 2 and R 3 each represent an alkyl, phenyl or benzyl group.
11. A process according to any one of the preceding claims wherein R 4 represents benzyl. I 12. A process according to any one of the preceding claims wherein X represents chlorine.
13. A process according to any one of the preceding claims, wherein the molar ratio of compound (II) to compound (III) is greater than 1.8. 4. A process according to any one of claims I to 12 wherein the molar ratio of compound (II) to compound (III) is from 1.9 to 4. A process according to any one of the preceding claimus wherein the reaction is carried out in the total or near total absence of additional acid acceptor. -14-
16. A process according to any one of the preceding claims wherein the reaction is carried out from 30° to 150 C.
17. A process according to any one of claims 1 to wherein the reaction is carried out from 40° to 120 0 C.
18. A process according to any one of the preceding 0"oo" claims wherein the reaction is carried out in the presence aovent of a solvent. 9 co 0 0 t o0 0 19. A process according to claim 18, wherein the 0 t solvent is a nitrile, a ketone, an ester, a halogenated or non-halogenated hydrocarbon, or an aprotic polar solvent. o 20. A process according to any one of the preceding claims, wherein unreacted compound of formula (II) is recycled. S21. A process according to claim 20, wherein the recycling is accomplished, at the end of the reaction, by extractiQn of unreacted compound of formula (II) into an acidic aqueous medium, separation and then, after neutralization, transferring the compound of formula (II) into an organic phase for reaction with further compound of formula (III).
22. A process according to claim 1 substantially as hereinbefore described in any one of Examples 1 to 4.
23. A compound of formula as defined in claim 1 when prepared by a process claimed in any one of claims 1 to 22. to or indicated~ in the specification and-/-(i5r- claims of this application, individual]L~y-oif"collectively, and any and all Dated this 16th day of December 1987 t, RHONE-POULENC AGROCHIMIE By its Patent Attorneys DAVIES COLLISON
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8618308A FR2608609B1 (en) | 1986-12-18 | 1986-12-18 | PREPARATION OF PHOSPHORUS INTERMEDIATES FOR HERBICIDE USE |
| FR8618308 | 1986-12-18 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU8261887A AU8261887A (en) | 1988-06-23 |
| AU599729B2 true AU599729B2 (en) | 1990-07-26 |
Family
ID=9342391
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU82618/87A Ceased AU599729B2 (en) | 1986-12-18 | 1987-12-16 | Preparation of phosphorus-containing intermediates for herbicides |
Country Status (18)
| Country | Link |
|---|---|
| EP (1) | EP0275804B1 (en) |
| JP (1) | JPS63165391A (en) |
| KR (1) | KR880007408A (en) |
| CN (1) | CN87105951A (en) |
| AT (1) | ATE67998T1 (en) |
| AU (1) | AU599729B2 (en) |
| BR (1) | BR8706887A (en) |
| CA (1) | CA1297493C (en) |
| DD (1) | DD264921A5 (en) |
| DE (1) | DE3773482D1 (en) |
| DK (1) | DK665087A (en) |
| ES (1) | ES2025201B3 (en) |
| FR (1) | FR2608609B1 (en) |
| GR (1) | GR3003011T3 (en) |
| HU (1) | HU202881B (en) |
| IL (1) | IL84482A (en) |
| PT (1) | PT86395B (en) |
| ZA (1) | ZA879478B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU6723887A (en) * | 1985-12-04 | 1987-06-30 | Rhone-Poulenc Agrochimie | Process for the preparation of n-sulfonyl n-(phosphonomethylglycyl) amines usable as weed-killers |
| AU573410B2 (en) * | 1984-12-26 | 1988-06-09 | Rhone-Poulenc Agrochimie | N-sulphonyl-(n-(phoponomethyl)glycyl)amine derivatives |
| AU577916B2 (en) * | 1985-01-14 | 1988-10-06 | Rhone-Poulenc Agrochimie | N-(phosphonomethylglycyl) sulphonylamine type herbicides |
-
1986
- 1986-12-18 FR FR8618308A patent/FR2608609B1/en not_active Expired
-
1987
- 1987-11-16 IL IL84482A patent/IL84482A/en unknown
- 1987-12-12 KR KR870014226A patent/KR880007408A/en not_active Application Discontinuation
- 1987-12-16 CA CA000554483A patent/CA1297493C/en not_active Expired - Lifetime
- 1987-12-16 AU AU82618/87A patent/AU599729B2/en not_active Ceased
- 1987-12-17 PT PT86395A patent/PT86395B/en not_active IP Right Cessation
- 1987-12-17 EP EP87420345A patent/EP0275804B1/en not_active Expired - Lifetime
- 1987-12-17 HU HU875755A patent/HU202881B/en not_active IP Right Cessation
- 1987-12-17 CN CN198787105951A patent/CN87105951A/en active Pending
- 1987-12-17 DD DD87310642A patent/DD264921A5/en not_active IP Right Cessation
- 1987-12-17 DK DK665087A patent/DK665087A/en not_active Application Discontinuation
- 1987-12-17 ZA ZA879478A patent/ZA879478B/en unknown
- 1987-12-17 DE DE8787420345T patent/DE3773482D1/en not_active Expired - Fee Related
- 1987-12-17 AT AT87420345T patent/ATE67998T1/en not_active IP Right Cessation
- 1987-12-17 BR BR8706887A patent/BR8706887A/en unknown
- 1987-12-17 ES ES87420345T patent/ES2025201B3/en not_active Expired - Lifetime
- 1987-12-17 JP JP62320034A patent/JPS63165391A/en active Pending
-
1991
- 1991-10-03 GR GR90401219T patent/GR3003011T3/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU573410B2 (en) * | 1984-12-26 | 1988-06-09 | Rhone-Poulenc Agrochimie | N-sulphonyl-(n-(phoponomethyl)glycyl)amine derivatives |
| AU577916B2 (en) * | 1985-01-14 | 1988-10-06 | Rhone-Poulenc Agrochimie | N-(phosphonomethylglycyl) sulphonylamine type herbicides |
| AU6723887A (en) * | 1985-12-04 | 1987-06-30 | Rhone-Poulenc Agrochimie | Process for the preparation of n-sulfonyl n-(phosphonomethylglycyl) amines usable as weed-killers |
Also Published As
| Publication number | Publication date |
|---|---|
| HU202881B (en) | 1991-04-29 |
| EP0275804B1 (en) | 1991-10-02 |
| CA1297493C (en) | 1992-03-17 |
| PT86395A (en) | 1988-01-01 |
| JPS63165391A (en) | 1988-07-08 |
| ATE67998T1 (en) | 1991-10-15 |
| EP0275804A1 (en) | 1988-07-27 |
| PT86395B (en) | 1990-11-20 |
| IL84482A (en) | 1992-11-15 |
| ES2025201B3 (en) | 1992-03-16 |
| BR8706887A (en) | 1988-07-26 |
| KR880007408A (en) | 1988-08-27 |
| DE3773482D1 (en) | 1991-11-07 |
| IL84482A0 (en) | 1988-04-29 |
| AU8261887A (en) | 1988-06-23 |
| DD264921A5 (en) | 1989-02-15 |
| FR2608609A1 (en) | 1988-06-24 |
| DK665087D0 (en) | 1987-12-17 |
| GR3003011T3 (en) | 1993-02-17 |
| DK665087A (en) | 1988-06-19 |
| FR2608609B1 (en) | 1989-06-02 |
| CN87105951A (en) | 1988-06-29 |
| ZA879478B (en) | 1988-06-14 |
| HUT48634A (en) | 1989-06-28 |
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