CA1297493C - Preparation of phosphorus-containing intermediates for herbicides - Google Patents
Preparation of phosphorus-containing intermediates for herbicidesInfo
- Publication number
- CA1297493C CA1297493C CA000554483A CA554483A CA1297493C CA 1297493 C CA1297493 C CA 1297493C CA 000554483 A CA000554483 A CA 000554483A CA 554483 A CA554483 A CA 554483A CA 1297493 C CA1297493 C CA 1297493C
- Authority
- CA
- Canada
- Prior art keywords
- process according
- compound
- formula
- optionally substituted
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000004009 herbicide Substances 0.000 title abstract description 5
- 239000000543 intermediate 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
- 150000001875 compounds Chemical class 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 8
- 125000005843 halogen group Chemical group 0.000 claims abstract description 8
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 8
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 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
- 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
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 125000005599 alkyl carboxylate group Chemical group 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 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
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 150000008282 halocarbons 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
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- 239000002798 polar solvent Substances 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 42
- 239000012071 phase Substances 0.000 description 11
- 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 5
- 238000004587 chromatography analysis Methods 0.000 description 5
- -1 hydrocarbon radical Chemical class 0.000 description 5
- 239000000203 mixture Substances 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
- 239000000047 product Substances 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-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
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000008346 aqueous phase Substances 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-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
- 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
- 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
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- NFORZJQPTUSMRL-UHFFFAOYSA-N dipropan-2-yl hydrogen phosphite Chemical compound CC(C)OP(O)OC(C)C NFORZJQPTUSMRL-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-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
- 239000002994 raw material Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 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
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)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Fertilizers (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Cephalosporin Compounds (AREA)
Abstract
ABSTRACT
PREPARATION OF PHOSPHORUS-CONTAINING
INTERMEDIATES FOR HERBICIDES
A process for the preparation of intermediates for herbicides, of formula:
(I) by reacting a compound of formula:
(II) with a compound of formula:
X - CH2 - CO - ? - SO2 - R1 (III) in which R is hydrogen or a hydrocarbon radical, R1 is a hydrocarbon radical, OR2 and OR3 are hydrolysable groups and X is halogen, the molar ratio (II): (III) being greater than 1.5.
PREPARATION OF PHOSPHORUS-CONTAINING
INTERMEDIATES FOR HERBICIDES
A process for the preparation of intermediates for herbicides, of formula:
(I) by reacting a compound of formula:
(II) with a compound of formula:
X - CH2 - CO - ? - SO2 - R1 (III) in which R is hydrogen or a hydrocarbon radical, R1 is a hydrocarbon radical, OR2 and OR3 are hydrolysable groups and X is halogen, the molar ratio (II): (III) being greater than 1.5.
Description
~z97~9~1 This invention relates to a process for the preparation o~ compounds which are uGe~ul ~s intermediate6 for herbicides.
The present invention rela~tes to a process for the preparation of a compound of forDnula:
.: OR2 a4 ( I ) 9 ' P ~ CH2 ~ N ~ CH2 ~ ~0 - N - S02 -oR3 R
10 wherein R represents an optionally substituted hydrocarbon radical, pre$erably alkyl, aryl or cycloalkyl, each of which may be substituted; suitable substituents ; include halogen atoms and phenyl, cyano, alkyl, alkoxy and alkylcarboxylate groups in which the alkyl groups preferably contain from 1 to 4 carbon atoms; Rl generally contains from 1 to 18 carbon atoms, preferably from 1 to 7 carbon àtoms, and more particularly from 3 to 7 carbon atoms when R~ is a cycloalkyl group; preferably Rl represents an alkyl group containing from 1 to 4 carbon atoms, optionally ~ubstituted by halogen, especially chlorine or fluorine, e.g. CF3;
R represents a hydrogen atom or has one of the meanings given for Rl, and is preferably ~n alkyl group containing from 1 to 4 carbon ato~s, ~5 R2 and R3 are such that oR2 and oR3, in which R2 and R3 may together ~orm a single optionally ~ubstituted - ~2~49;~
divalent radical~ are hydrolysable groups; R~ and R3 preferably represent an optionally substituted alkyl~ aryl or arylalkyl radical (suitable substituen~s are those mentioned for Rl) or R2 and R3 may together form a single optionally substituted divalent radical preferably containing from 2 to 6 carbon atoms, e.g. an optionally subsituted alkylene radical (e.g. an ethylene or propylene radical); R2 and R3 generally each contain from 1 to 12 carbon atoms and preferably from 1 to 8 carbon atoms; and R4 represents a radical of formula Ar(R5)(R6)C-in which Ar is an optionally substituted aromatic group, preferably phenyl, and R5 and R~ each represent a hydrogen atom or an (aromatic) radical Ar or an alkyl group preferably containing not more than 6 carbon atoms 15 (preferably R4 represents benzyl), by reacting a compound of formula:
oa2 (Il) I
OR
wherein R2, R3 and R4 are as hereinbefore defined with a ~o~pound of formula:
The present invention rela~tes to a process for the preparation of a compound of forDnula:
.: OR2 a4 ( I ) 9 ' P ~ CH2 ~ N ~ CH2 ~ ~0 - N - S02 -oR3 R
10 wherein R represents an optionally substituted hydrocarbon radical, pre$erably alkyl, aryl or cycloalkyl, each of which may be substituted; suitable substituents ; include halogen atoms and phenyl, cyano, alkyl, alkoxy and alkylcarboxylate groups in which the alkyl groups preferably contain from 1 to 4 carbon atoms; Rl generally contains from 1 to 18 carbon atoms, preferably from 1 to 7 carbon àtoms, and more particularly from 3 to 7 carbon atoms when R~ is a cycloalkyl group; preferably Rl represents an alkyl group containing from 1 to 4 carbon atoms, optionally ~ubstituted by halogen, especially chlorine or fluorine, e.g. CF3;
R represents a hydrogen atom or has one of the meanings given for Rl, and is preferably ~n alkyl group containing from 1 to 4 carbon ato~s, ~5 R2 and R3 are such that oR2 and oR3, in which R2 and R3 may together ~orm a single optionally ~ubstituted - ~2~49;~
divalent radical~ are hydrolysable groups; R~ and R3 preferably represent an optionally substituted alkyl~ aryl or arylalkyl radical (suitable substituen~s are those mentioned for Rl) or R2 and R3 may together form a single optionally substituted divalent radical preferably containing from 2 to 6 carbon atoms, e.g. an optionally subsituted alkylene radical (e.g. an ethylene or propylene radical); R2 and R3 generally each contain from 1 to 12 carbon atoms and preferably from 1 to 8 carbon atoms; and R4 represents a radical of formula Ar(R5)(R6)C-in which Ar is an optionally substituted aromatic group, preferably phenyl, and R5 and R~ each represent a hydrogen atom or an (aromatic) radical Ar or an alkyl group preferably containing not more than 6 carbon atoms 15 (preferably R4 represents benzyl), by reacting a compound of formula:
oa2 (Il) I
OR
wherein R2, R3 and R4 are as hereinbefore defined with a ~o~pound of formula:
2 - CN~ - CO ~ ~ - sn2 - Rl (III) R
wherein 1~97493 X represents a halogen atom, e.g. chlorine, bromine or iodine, preferably chlorine, ana R and Rl are as hereinbefore defined.
Suitable substituents for the group Ar include 5 alkyl and alkoxy groups, preferably containing from 1 to 4 carbon atoms, nitro radicals and halogen atoms.
Such a reaction is known from European Patent Application No. 0,189,725. The compounds of formula (I) are intermediates for herbicides.
The present invention seeks to provide an improved process for the preparation of the compounds of formula ~I) for a more satisfactory implementation on an industrial scale. The present invention also seeks to provide a simplified preparation process.
It has been found that the molar ratio of the compound~of formula II to the compound of formula I~I is important in the reaction: in particular the use of a molar ratio greater than 1.5 allows the presence of addi~ional acceptor for acid to be avoided. This leads to two 20 important advantages: firstly, it enables any stage for the removal of the said acceptor for acid to be omitted and ~econdly, it enables the yield to be increased.
Another important consequence of this total or near total absence of additional accep~or Xor acid is that it enables a recycling process to be carried out, further improving significantly the yield and ~he implementation on an industrial ~cale.
.
~2g~7~3 The present invention accordingly provides a process for the preparation of a compound o formula (I) wherein the various 6ymbols are as hereinbefore deined by the reaction of a compound of formula ~ wherein the 5 various symbols are as hereinbefore defined with a compound of formula (III) as hereinbefore defined, the molar ratio of the compound of formula (II) to the compound of formula (~II) being greater than l~5.
The reaction according to the invention may be 10 carried out in the absence, or more preferably in the presence, of a solvent. In fact, the presence of the ~olvent 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 20 alkanoates (especially ethyl acetate), and aprotic polar ~olven~s ~uch as dimethylformamide and N-methylpyrrolidone.
The reaction temperature is generally from 30 to 150C and preferably from 40 to l20C.
The reaction product of formula (I) may be 25 isolated by any means known per ~e.
Some compounds of formula (II) are known .. . . . . .
~7493 ., ~Tetrahedron Letters no. 46, p. 4645~ 1973)o They can be prepared conveniently by reacting tris(aralkyl)hexahydro-triazines with diorganophosphites.
The compounds of formula (III) are also known~
The molar ratio of compound (II~ ~o compound (III) i~ pre~erably greater than 1.8 and advantageously from 1.9 to 4.
According to a preferred feature, the process of the invention is carried out in the total or near total 10 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 15 continuously by recycling the compound of formula (II).
This recycling is accomplished at the end of the reaction, by extraction of unreacted compound of formu}a (II) into an acidic aqueous medium and then, after neutralization, transferring the compound of formula ~II) into an organic phase for reaction with further compound of formula (III).
The process is more particularly suitable for compounds in which R and Rl are alkyl groups containing from 1 to 4 carbon atoms, preferably methyl, and/or in which R2 and R3 are alkyl, phenyl or ~enzyl groups.
The following Examples illustrate the invention.
~2974~
Example 1 A mixture of diisopropyl N-benzylaminomethane-pho~phonate ~M.W. 285; 11043 9; 4 x 10 2 moles) and N-methyl-~-methylsulphonylchloroacetamide ~3~71 9; 2 x 10 2 5 moles~ is hea~ed for 2 h at 80C. The reaction mixture is dilu~ed to 50 cc with toluene and treated with water and with hydrochloric acid. The agueous phase and the ~oluene phase are separated. The toluene phase is concentrated and it is observed, by chromatography, that 8.025 9 of the 10 product is obtained, which corresponds to a yield of 92.44 relative to the N-methyl N-methylsulphonylchloroacetamide employed.
The agueous phase containing diisopropyl N-benzyl-aminomethanephosphonate hydrochloride is poured 15 into toluene (20 cc), the mixture is neutralized wi~h a stoichiometric quantity of aqueous 2 N sodium hydroxide.
The aqueous phase and the toluene phase are separated. The toluene phase contains diisopropyl N-benzylamino-methanephosphonate (1.82 x 10 2 moles) in the ~orm of the ba~e 20 which oan be recycled,after the distillation of toluene if required.
Example 2 The same trial carried out at 70C leads to a yield, as determined by chromatography, of 72.5~ relative to 25 the N-methyl-N-methylsulphonylchloroacetamide employed.
Example 3 The same trial carried ou~ at 90C leads to a IZ9749:3 ~ 8--yield, as determined by chromatography, of 86.7~ relative to - the N-methyl-N-methylsulphonylchloroacetamide employed.
Comparative Example Diisopropyl N-benzylaminomethanephosphonate (5.71 g; 2 x 10 2 mole) and N-methyl-N-methy]Lsulphonylchloro-acetamide (3.71 g; 2 x 10 2 mole) are heated for 2 h at 80C. A solution of triethylamine (2.8 cc; 2 x 10 2 mole) in toluene (15 cc) is poured gradually, in the course of 5 h, into the reaction mixture which is maintained at 80C.
10 The mixture is then cooled to 20C, poured into water (15 cc) at ambient temperature and the a~ueous phase ancl the toluene phase are separated. The toluene phase is concentrated under vacuum. It is observed, by chromatography, that 6.6 9 of the expec~ed product was 15 obtained, which corresponds to a yield of 75.8% relative ~o the 2 reagents charged.
Example 4 1,3,5-tribenzylhexa~ydrotriazine (59.5 9; 0.166 mole), diisopropyl phosphite (83 9; 0.5 mole) and toluene 2~ (100 g) are heated for 4 h 30 min at 120C. The mixture is cooled to 20C. An analysis by chromatography shows that the reaction yield of diisopropyl N-benzylaminome-thanephosphonate is guantitative. N-methyl-N-methyl-6ulphonylchloroacetamide (37.1 9; 0.2 mole) i5 added. The 25 reaction mixture is heated to 80C for 2 hours and then cooled to ambient ~emperature. It is then poured into water , , ~, , ~ ' ' .' ! , ` ' ' ' :1 ,,, : ,, ,\ ~` . .`. ` ' "' `
1297~3 (150 9) and aqueous 374 ~Cl (12 cc) is added in order to adjust the pH to 1. The phases are decanted and separated.
The organic phase has a weigh~ of 173 9. The aqueous phase (265 g) is neutralized to pB = 6 with aqueous 30~ sodium 5 hydroxide (30 cc) after adding toluene (100 9). The phases are decanted and separated. The second organic phase has a weight of 195 y.
The first organic phase (173 9) contains 44.6% of the product expected, which amounts to 0.18 mole.
10 The ~econd organic phase (195 g) contains 42% o diisoprOpyl N-benzylaminomethanephosphonate, which amounts to 0.287 mole.
1st recycling The 2nd organic phase (195 9) is azeotropically 15 dried (67 g of toluene and water are removed) and a solution (120 g) containing diisopropyl N-benzylaminomethane-phosph~nate ~0.25 mole) and ~-methyl-N-methylsulphonyl-chloroacetamide (37.1 g; 0.2 mole) in toluene is added and the mixture is heated for 2 h at 80C. The reaction mass is 20 treated exactly as before.
2nd recycling A ~nd recycling of diisopropyl N-benzylaminO-methanephosphonate was carried out exactly as above 7 All the results are given in the table below:
25 A = diisopropyl N-benzylaminomethanephosphonate B = N-methyl-N-methylsulphonylchloroacetamide ~;297493 C - condensat~on product expected _ Raw materials A - recycled Yield of empl oyed C/B
_ _ _ _ A - 0.5 mole ~9~6 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 _ _
wherein 1~97493 X represents a halogen atom, e.g. chlorine, bromine or iodine, preferably chlorine, ana R and Rl are as hereinbefore defined.
Suitable substituents for the group Ar include 5 alkyl and alkoxy groups, preferably containing from 1 to 4 carbon atoms, nitro radicals and halogen atoms.
Such a reaction is known from European Patent Application No. 0,189,725. The compounds of formula (I) are intermediates for herbicides.
The present invention seeks to provide an improved process for the preparation of the compounds of formula ~I) for a more satisfactory implementation on an industrial scale. The present invention also seeks to provide a simplified preparation process.
It has been found that the molar ratio of the compound~of formula II to the compound of formula I~I is important in the reaction: in particular the use of a molar ratio greater than 1.5 allows the presence of addi~ional acceptor for acid to be avoided. This leads to two 20 important advantages: firstly, it enables any stage for the removal of the said acceptor for acid to be omitted and ~econdly, it enables the yield to be increased.
Another important consequence of this total or near total absence of additional accep~or Xor acid is that it enables a recycling process to be carried out, further improving significantly the yield and ~he implementation on an industrial ~cale.
.
~2g~7~3 The present invention accordingly provides a process for the preparation of a compound o formula (I) wherein the various 6ymbols are as hereinbefore deined by the reaction of a compound of formula ~ wherein the 5 various symbols are as hereinbefore defined with a compound of formula (III) as hereinbefore defined, the molar ratio of the compound of formula (II) to the compound of formula (~II) being greater than l~5.
The reaction according to the invention may be 10 carried out in the absence, or more preferably in the presence, of a solvent. In fact, the presence of the ~olvent 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 20 alkanoates (especially ethyl acetate), and aprotic polar ~olven~s ~uch as dimethylformamide and N-methylpyrrolidone.
The reaction temperature is generally from 30 to 150C and preferably from 40 to l20C.
The reaction product of formula (I) may be 25 isolated by any means known per ~e.
Some compounds of formula (II) are known .. . . . . .
~7493 ., ~Tetrahedron Letters no. 46, p. 4645~ 1973)o They can be prepared conveniently by reacting tris(aralkyl)hexahydro-triazines with diorganophosphites.
The compounds of formula (III) are also known~
The molar ratio of compound (II~ ~o compound (III) i~ pre~erably greater than 1.8 and advantageously from 1.9 to 4.
According to a preferred feature, the process of the invention is carried out in the total or near total 10 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 15 continuously by recycling the compound of formula (II).
This recycling is accomplished at the end of the reaction, by extraction of unreacted compound of formu}a (II) into an acidic aqueous medium and then, after neutralization, transferring the compound of formula ~II) into an organic phase for reaction with further compound of formula (III).
The process is more particularly suitable for compounds in which R and Rl are alkyl groups containing from 1 to 4 carbon atoms, preferably methyl, and/or in which R2 and R3 are alkyl, phenyl or ~enzyl groups.
The following Examples illustrate the invention.
~2974~
Example 1 A mixture of diisopropyl N-benzylaminomethane-pho~phonate ~M.W. 285; 11043 9; 4 x 10 2 moles) and N-methyl-~-methylsulphonylchloroacetamide ~3~71 9; 2 x 10 2 5 moles~ is hea~ed for 2 h at 80C. The reaction mixture is dilu~ed to 50 cc with toluene and treated with water and with hydrochloric acid. The agueous phase and the ~oluene phase are separated. The toluene phase is concentrated and it is observed, by chromatography, that 8.025 9 of the 10 product is obtained, which corresponds to a yield of 92.44 relative to the N-methyl N-methylsulphonylchloroacetamide employed.
The agueous phase containing diisopropyl N-benzyl-aminomethanephosphonate hydrochloride is poured 15 into toluene (20 cc), the mixture is neutralized wi~h a stoichiometric quantity of aqueous 2 N sodium hydroxide.
The aqueous phase and the toluene phase are separated. The toluene phase contains diisopropyl N-benzylamino-methanephosphonate (1.82 x 10 2 moles) in the ~orm of the ba~e 20 which oan be recycled,after the distillation of toluene if required.
Example 2 The same trial carried out at 70C leads to a yield, as determined by chromatography, of 72.5~ relative to 25 the N-methyl-N-methylsulphonylchloroacetamide employed.
Example 3 The same trial carried ou~ at 90C leads to a IZ9749:3 ~ 8--yield, as determined by chromatography, of 86.7~ relative to - the N-methyl-N-methylsulphonylchloroacetamide employed.
Comparative Example Diisopropyl N-benzylaminomethanephosphonate (5.71 g; 2 x 10 2 mole) and N-methyl-N-methy]Lsulphonylchloro-acetamide (3.71 g; 2 x 10 2 mole) are heated for 2 h at 80C. A solution of triethylamine (2.8 cc; 2 x 10 2 mole) in toluene (15 cc) is poured gradually, in the course of 5 h, into the reaction mixture which is maintained at 80C.
10 The mixture is then cooled to 20C, poured into water (15 cc) at ambient temperature and the a~ueous phase ancl the toluene phase are separated. The toluene phase is concentrated under vacuum. It is observed, by chromatography, that 6.6 9 of the expec~ed product was 15 obtained, which corresponds to a yield of 75.8% relative ~o the 2 reagents charged.
Example 4 1,3,5-tribenzylhexa~ydrotriazine (59.5 9; 0.166 mole), diisopropyl phosphite (83 9; 0.5 mole) and toluene 2~ (100 g) are heated for 4 h 30 min at 120C. The mixture is cooled to 20C. An analysis by chromatography shows that the reaction yield of diisopropyl N-benzylaminome-thanephosphonate is guantitative. N-methyl-N-methyl-6ulphonylchloroacetamide (37.1 9; 0.2 mole) i5 added. The 25 reaction mixture is heated to 80C for 2 hours and then cooled to ambient ~emperature. It is then poured into water , , ~, , ~ ' ' .' ! , ` ' ' ' :1 ,,, : ,, ,\ ~` . .`. ` ' "' `
1297~3 (150 9) and aqueous 374 ~Cl (12 cc) is added in order to adjust the pH to 1. The phases are decanted and separated.
The organic phase has a weigh~ of 173 9. The aqueous phase (265 g) is neutralized to pB = 6 with aqueous 30~ sodium 5 hydroxide (30 cc) after adding toluene (100 9). The phases are decanted and separated. The second organic phase has a weight of 195 y.
The first organic phase (173 9) contains 44.6% of the product expected, which amounts to 0.18 mole.
10 The ~econd organic phase (195 g) contains 42% o diisoprOpyl N-benzylaminomethanephosphonate, which amounts to 0.287 mole.
1st recycling The 2nd organic phase (195 9) is azeotropically 15 dried (67 g of toluene and water are removed) and a solution (120 g) containing diisopropyl N-benzylaminomethane-phosph~nate ~0.25 mole) and ~-methyl-N-methylsulphonyl-chloroacetamide (37.1 g; 0.2 mole) in toluene is added and the mixture is heated for 2 h at 80C. The reaction mass is 20 treated exactly as before.
2nd recycling A ~nd recycling of diisopropyl N-benzylaminO-methanephosphonate was carried out exactly as above 7 All the results are given in the table below:
25 A = diisopropyl N-benzylaminomethanephosphonate B = N-methyl-N-methylsulphonylchloroacetamide ~;297493 C - condensat~on product expected _ Raw materials A - recycled Yield of empl oyed C/B
_ _ _ _ A - 0.5 mole ~9~6 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 _ _
Claims (19)
1. A process for the preparation of a compound of the formula:
(I) wherein R1 represents an optionally substituted hydrocarbon radical;
R represents a hydrogen atom or an optionally substituted hydrocarbon radical;
R2 and R3 are such that OR2 and OR3, in which R2 and R3 may together form a single optionally substituted divalent radical, are hydrolysable groups; and R4 represents a radical of formula Ar(R5)(R6)C-in which Ar is an optionally substituted aromatic group, and R5 and R6 are a hydrogen atom or a radical Ar or an alkyl group, which process comprises the reaction of a compound of the formula:
(III) wherein R2, R3 and R4 are as defined above with a compound of formula:
(III) wherein X represents a halogen atom and R and R1 are as defined above, the molar ratio of compound (II) to compound (III) being greater than 1.5; and wherein the reaction is carried out at a temperature from 30 to 150°C, and in the total or near total absence of additional acid acceptor.
(I) wherein R1 represents an optionally substituted hydrocarbon radical;
R represents a hydrogen atom or an optionally substituted hydrocarbon radical;
R2 and R3 are such that OR2 and OR3, in which R2 and R3 may together form a single optionally substituted divalent radical, are hydrolysable groups; and R4 represents a radical of formula Ar(R5)(R6)C-in which Ar is an optionally substituted aromatic group, and R5 and R6 are a hydrogen atom or a radical Ar or an alkyl group, which process comprises the reaction of a compound of the formula:
(III) wherein R2, R3 and R4 are as defined above with a compound of formula:
(III) wherein X represents a halogen atom and R and R1 are as defined above, the molar ratio of compound (II) to compound (III) being greater than 1.5; and wherein the reaction is carried out at a temperature from 30 to 150°C, and in the total or near total absence of additional acid acceptor.
2. A process according to claim 1 in which R1 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 radical represented by R1 is alkyl, aryl or cycloalkyl.
4. A process according to claim 3 in which the hydrocarbon radical represented by R1 contains from 1 to 7 carbon atoms or from 3 to 7 carbon atoms when R1 represents a cycloalkyl group.
5. A process according to claim 4 in which R1 represents an alkyl group containing from 1 to 4 carbon atoms optionally substituted by halogen.
6. A process according to claim 1, 2, 3, 4 or 5 in which R represents an alkyl group containing from 1 to 4 carbon atoms.
7. A process according to claim 1, 2, 3, 4 or 5 in which R2 and R3 represent an alkyl, aryl or arylalkyl radical optionally substituted by halogen, phenyl, cyano, alkyl, alkoxy or alkylcarboxylate, or R2 and R3 together represent a single optionally substituted divalent radical containing from 2 to 6 carbon atoms.
8. A process according to claim 1 wherein R and R1 each represent an alkyl group containing from 1 to 4 carbon atoms.
9. A process according to claim 8 wherein R and R1 each represent methyl.
10. A process according to claim 1, 2, 3, 4, 5, 8 or 9 wherein R2 and R3 each represent an alkyl, phenyl or benzyl group.
11. A process according to claim 1, 2, 3, 4, 5, 8 or 9 wherein R4 represents benzyl.
12. A process according to claim 1, 2, 3, 4, 5, 8 or 9 wherein X represents chlorine.
13. A process according to claim 1, 2, 3, 4, 5, 8 or 9 wherein the molar ratio of compound (II) to compound (III) is greater than 1.8.
14. A process according to claim 1, 2, 3, 4, 5, 8 or 9 wherein the molar ratio of compound (II) to compound (III) is from 1.9 to 4.
15. A process according to claim 1, 2, 3, 4, 5, 8 or 9 wherein the reaction is carried out from 40° to 120°C.
16. A process according to claim 1 wherein the reaction is carried out in the presence of a solvent.
17. A process according to claim 16, wherein the solvent is a nitrile, a ketone, an ester, a halogenated or non-halogenated hydrocarbon, or an aprotic polar solvent.
18. A process according to clalm 1 wherein unreacted compound of formula (II) is recycled.
19. A process according to claim 18, wherein the recycling is accomplished, at the end of the reaction, by extraction 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).
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 (1)
| Publication Number | Publication Date |
|---|---|
| CA1297493C true CA1297493C (en) | 1992-03-17 |
Family
ID=9342391
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000554483A Expired - Lifetime CA1297493C (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) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2575161B1 (en) * | 1984-12-26 | 1989-03-31 | Rhone Poulenc Agrochimie | PREPARATION OF PHOSPHORUS INTERMEDIATES FOR HERBICIDE USES |
| FR2576024B1 (en) * | 1985-01-14 | 1988-01-08 | Rhone Poulenc Agrochimie | TYPE N HERBICIDES - (PHOSPHONOMETHYLGLYCYL) SULFONYLAMINES |
| FR2590901B1 (en) * | 1985-12-04 | 1988-07-29 | Rhone Poulenc Agrochimie | PROCESS FOR THE PREPARATION OF N-SULFONYL N- (PHOSPHONOMETHYL-GLYCYL) AMINES FOR USE AS 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 AU AU82618/87A patent/AU599729B2/en not_active Ceased
- 1987-12-16 CA CA000554483A patent/CA1297493C/en not_active Expired - Lifetime
- 1987-12-17 EP EP87420345A patent/EP0275804B1/en not_active Expired - Lifetime
- 1987-12-17 ZA ZA879478A patent/ZA879478B/en unknown
- 1987-12-17 DD DD87310642A patent/DD264921A5/en not_active IP Right Cessation
- 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 BR BR8706887A patent/BR8706887A/en unknown
- 1987-12-17 JP JP62320034A patent/JPS63165391A/en active Pending
- 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 ES ES87420345T patent/ES2025201B3/en not_active Expired - Lifetime
- 1987-12-17 PT PT86395A patent/PT86395B/en not_active IP Right Cessation
- 1987-12-17 DK DK665087A patent/DK665087A/en not_active Application Discontinuation
-
1991
- 1991-10-03 GR GR90401219T patent/GR3003011T3/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| FR2608609A1 (en) | 1988-06-24 |
| PT86395A (en) | 1988-01-01 |
| DK665087D0 (en) | 1987-12-17 |
| DD264921A5 (en) | 1989-02-15 |
| IL84482A (en) | 1992-11-15 |
| JPS63165391A (en) | 1988-07-08 |
| HUT48634A (en) | 1989-06-28 |
| EP0275804A1 (en) | 1988-07-27 |
| GR3003011T3 (en) | 1993-02-17 |
| ZA879478B (en) | 1988-06-14 |
| EP0275804B1 (en) | 1991-10-02 |
| AU599729B2 (en) | 1990-07-26 |
| HU202881B (en) | 1991-04-29 |
| PT86395B (en) | 1990-11-20 |
| FR2608609B1 (en) | 1989-06-02 |
| ES2025201B3 (en) | 1992-03-16 |
| AU8261887A (en) | 1988-06-23 |
| DE3773482D1 (en) | 1991-11-07 |
| KR880007408A (en) | 1988-08-27 |
| BR8706887A (en) | 1988-07-26 |
| IL84482A0 (en) | 1988-04-29 |
| CN87105951A (en) | 1988-06-29 |
| DK665087A (en) | 1988-06-19 |
| ATE67998T1 (en) | 1991-10-15 |
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