GB1565252A - Process for the production of o,o-dialkylphorsphorodithiates - Google Patents
Process for the production of o,o-dialkylphorsphorodithiates Download PDFInfo
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- GB1565252A GB1565252A GB49703/76A GB4970376A GB1565252A GB 1565252 A GB1565252 A GB 1565252A GB 49703/76 A GB49703/76 A GB 49703/76A GB 4970376 A GB4970376 A GB 4970376A GB 1565252 A GB1565252 A GB 1565252A
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- 238000000034 method Methods 0.000 title claims description 44
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 22
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 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 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 11
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- -1 aromatic halogenated hydrocarbon Chemical class 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 7
- 150000003053 piperidines Chemical class 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- NNWUEBIEOFQMSS-UHFFFAOYSA-N 2-Methylpiperidine Chemical compound CC1CCCCN1 NNWUEBIEOFQMSS-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 2
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 2
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims description 2
- 239000012071 phase Substances 0.000 description 8
- NQRYJNQNLNOLGT-UHFFFAOYSA-N tetrahydropyridine hydrochloride Natural products C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 7
- 239000002904 solvent Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- NSWLMOHUXYULKL-UHFFFAOYSA-N 2-chloro-1-piperidin-1-ylethanone Chemical compound ClCC(=O)N1CCCCC1 NSWLMOHUXYULKL-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 125000003386 piperidinyl group Chemical group 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003254 radicals Chemical group 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- ZXPCCXXSNUIVNK-UHFFFAOYSA-N 1,1,1,2,3-pentachloropropane Chemical compound ClCC(Cl)C(Cl)(Cl)Cl ZXPCCXXSNUIVNK-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229940106681 chloroacetic acid Drugs 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003839 salts 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
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
- C07F9/165—Esters of thiophosphoric acids
- C07F9/1651—Esters of thiophosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
-
- 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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
- C07F9/576—Six-membered rings
- C07F9/59—Hydrogenated pyridine rings
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)
- Hydrogenated Pyridines (AREA)
Description
(54) PROCESS FOR THE PRODUCTION OF
O,O-DIALKYLPHOSPHORODITHIOATES
(71) We, CIBA-GEIGY AG., a body corporate organised according to the laws of
Switzerland, of Basle, Switzerland, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: The present invention relates to a process for the production of 0,0 - diaLkylphosphoro dithioates of the formula
wherein R represents methyl or ethyl, and Rl and R2 are identical or different, and each represent an alkyl, alkenyl or alkoxyalkyl group having in each case at most 5 carbon atoms.
The 0,0 - dialkylphosphorodithioates of the formula I are selective herbicides which are suitable, in particular, for the control of weeds in rice crops. These compounds and their use are described in the U.S. Patent
Specification No. 3,833,600. One compound of the formula I, namely 0,0 - di - n - propyl S - (2 - (2' - methyl - I - piperidinyl) - 2oxoethyl) - phosphorodithioate, is also described in the Pesticide Manual, 4th Edition, British
Crop Protection Council, November, 1974.
According to U.S. Patent Specification No.
3,833,600, the compounds of the formula I are produced by reacting in an inert solvent a salt, for example the sodium or potassium salt of a 0,0 - dialkyldithiophosphate of the formula
wherein Rl and R2 have the meaning defined above, with a chloroacetylpiperidine of the formula
wherein R has the meaning given above. The chloroacetyl - piperidines required as starting material are for their part obtained by reaction of chloroacetyl chloride with a corresponding piperidine substituted by the radical
R according to the above definition.
According to an alternative likewise mentioned in the U.S. Patent Specification No.
3,833,600, the 0,0 - dialkylphosphorodithio ates of the formula I can be produced also by reacting an ester of a 0,0 - dialkyldithiophosphorylacetic acid, e.g. the phenyl ester, benzyl ester or ethylene glycol ester, with the piperidine substituted by the radical R. In this process, the ester of a 0,0 - dialkylthiophosphorylacetic acid, used as starting material, has to be produced in a preliminary step by reaction of the sodium or potassium salt of a 0,0 - dialkylthiophosphoric acid with a corresponding chloroacetic acid ester. A disadvantage of this process is that two separate reaction steps have to be performed before the desired final products of the formula I are obtained. The object of the present invention is therefore to simplify the known production processes and, simultaneously, to increase the attainable yield of the desired final product of the formula I.
The process according to the invention for the production of 0,0 - dialkylphosphorodithioates of the formula I comprises reacting an essentially equimolar mixture of a piperidine derivative of the formula II
wherein R has the meaning given under formula I, and a free 0,0 - dialkyldithiophosphoric acid of the formula III
wherein R1 and R2 have the meaning defined above, or a sodium, potassium or ammonium salt thereof, in the presence of an acid-binding agent, with chloroacetyl chloride.
The reaction can be performed in the absence of a solvent. Preferably, however, the reaction is carried out in a two-phase system consisting of water and an organic solvent immiscible with water. Preferred solvents are aliphatic and aromatic hydrocarbons such as hexane, cyclohexane, benzene and, in particular, toluene, as well as aliphatic or aromatic halogenated hydrocarbons, e.g. chlorobenzene, dichloroethane, trichloroethylene, methylene chloride, and carbon tetrachloride.
The process of the invention can be performed in the temperature range of between 0 and 20"C; preferably it is performed at between 5 and 15 C The reaction occurs practically immediately after addition of the halogenoacetyl halide. The duration of the reaction is therefore governed virtually by the extent to which the evolved heat of reaction can be conducted away to maintain the aforementioned temperatures. The reaction can normally be performed within 10 minutes to 4 hours.
There are used for the reaction substantially equimolar amounts of the reactants, with slightly more or slightly less than the equivalent amount of the one or of the other reactant being possible.
Suitable acid-binding agents are alkali metal hydroxides or alkalinesarth metal hydroxides.
The acid-binding agent preferably used is sodium hydroxide or potassium hydroxide.
The amount of acid-binding agent is prefer
ably 2 moles per mole of piperidine of the formula II to be reacted. If the 0,0 - di allyldithiophosphoric acid of the formula m is used in the form of the sodium or potassium salt, then 1 mole of acid-binding agent per mole of reacted piperadine of the formula is sufficient
A preferred embodiment of the process of the invention comprises adding one equivalent of chloroacetyl chloride at a temperature of between 5 and 15"C, with vigorous stirring, to a two-phase system consisting of a solution of a piperidine of the formula II in toluene and an aqueous solution of one equivalent of a sodium or potassium salt of a O,O - dialkyldithiophosphoric acid of the formula III and one equivalent of sodium or potassium hydroxide.
The process of the invention has the advantage not only that the production of 0,0 - dialkylphosphorodithioates of the formula I is simplified but also that the desired final products are obtained in better yield than they are in the known two-stage process. This has to be regarded as surprising since with each of its two reactive chlorine atoms chloroacetyl chloride can react essentially either with the piperidine derivative of the formula II or with the 0,0 - dialkyldithiophosphoric acid of the formula III. Surprisingly, however, the reaction occurs uniformly and the 0,0 - dialkylphosphorodithioates of the formula I are formed in yields in excess of 90% of theory.
A further advantage of the process of the invention is that the ecological difficulties are reduced compared with those arising with the conventional two-stage process.
The process of the invention is further illustrated by the following Examples.
Example 1
Into a two-phase system consisting of 50 ml of toluene and 30 ml of water there are placed 9.9 g (0.1 mole) of 2 - methylpiperidine, 26.0 g (0.125 mole) of the potassium salt of 0,0di - n - propyldithiophosphoric acid and 5.0 g (0.125 mole) of sodium hydroxide. To this mixture there is then added dropwise at 5 to 15"C, with stirring, 11.8 g 'v0.14 mole) of chloroacetyl chloride. After completion of the addition, the reaction mixture is heated, with further stirring, to room temperature. The organic phase is afterwards separated and washed with water until neutral, and the solvent is distilled off at 80"C and 20 Torr.
There is obtained as residue 34.9 g of a yellow oil consisting to the extent of 94% of 0,0di - n - propyl - S - [2 - (2' - methyl - 1piperidinyl) - 2 - oxoethyli - dithio - phosphate, which corresponds to a net yield of 93% of theory relative to 2 - methylpiperidine.
Example 2
110 g (0.515 mole) of 0,0 - di - n - propyldithiophosphoric acid and 50 g (0.503 mole) of 2 - methylpiperidine are introduced, with stirring, into a two-phase mixture, cooled to 15"C, consisting of 250 g of toluene and 150 g of 30% aqueous sodium hydroxide solution (1.12 moles of NaOH). To the mixture obtained there is subsequently added drop wise, at 8 to 12"C, 60 g (0.506 mole) o chloroacetyl chloride. After completion of the addition, the reaction mixture is briefly heated to 25"C and 60 ml of water is added. The aqueous phase is separated from the mixture and is neutralised by addition of about 5 g of 80% sulphuric acid, and the organic phase is extracted with 120 ml of water, whereupon the aqueous phase is neutralised afresh by the addition of about 1 ml of 80% sulphuric acid.
The aqueous phase is afterwards separated and the organic phase is freed from the solvent in vacuo. There is obtained 175 g of a yellow oil consisting to the extent of 93% of O,O- di - n - propsl - S - [2 - (2' - methyl - 1piperidinyl) - 2 - oxoethyll - dithiophosphate, an amount corresponding to a yield of 93% of theory relative to the amount of 2 - methylpyridine used.
WHAT WE CLAIM IS:- 1. Process for the production of 0,0 - dialkylphosphorodithioates of the formula I
wherein R represents methyl or ethyl, and R, and R2 are identical or different, and each represent an alkyl, alkenyl or alkoxylalkyl group having in each case at most 5 carbon atoms, which process comprises reacting a substantially equimolar mixture of a piperidine derivative of the formula II
wherein R has the meaning given under formula I, and a 0,0 - dialkyldithiophosphoric free acid of the formula m
wherein R1 and R2 have the meaning defined above, or a sodium, potassium or ammonium salt thereof, in the presence of an acid-binding agent, with chloroacetyl chloride.
2. Process according to Claim 1, wherein the reaction is performed in a two-phase system consisting of water and an organic solvent immiscible with water.
3. Process according to Claim 2, wherein the reaction is performed in a two-phase system consisting of water and an aliphatic or aromatic hydrocarbon or an aliphatic or aromatic halogenated hydrocarbon.
4. Process according to Claim 3, wherein the reaction is performed in a two-phase system consisting of water and toluene.
5. Process according to any of Claims 1 to 4, wherein the reaction is performed in the temperature range of between 0 and 20"C.
6. Process according to Claim 5, wherein the reaction is performed in the temperature range of between 5 and 15"C.
7. Process according to any of Claims 1 to 6, wherein the acid-binding agent used is an alkali metal hydroxide or alkaline-earth metal hydroxide.
8. Process according to Claim 7, wherein the acid-binding agent used is sodium hydroxide or potassium hydroxide.
9. Process according to Claim 1, which process comprises adding one equivalent of chloroacetyl chloride at a temperature of between 5 and 15"C, with vigorous stirring, to a two-phase system consisting of a solution of a piperidine derivative of the formula II in toluene and an aqueous solution of one equivalent of a sodium or potassium salt of a 0,0dialkyldithiophosphoric acid of the formula
III and one equivalent of sodium or potassium hydroxide.
10. Process according to Claim 1 substantially as described in Example 1 or 2.
11. An 0,0 - dialkylphosphoro - dithioate as defined in Claim 1 when prepared by the process claimed in any of Claims 1 to 10.
12. Process according to any of Claims 1 to 9 wherein the compound of formula II is 2 - methyl - piperidine and the compound of formula m is 0,0 - di - n - propyldithiophosphoric acid.
13. 0,0 - Di - n - propyl - S - [2 methyl - 1 - piperidinyl) - 2 - oxo - ethyl] dithiophosphate when produced by the process of Claim 10 or 12.
**WARNING** end of DESC field may overlap start of CLMS **.
Claims (13)
1. Process for the production of 0,0 - dialkylphosphorodithioates of the formula I
wherein R represents methyl or ethyl, and R, and R2 are identical or different, and each represent an alkyl, alkenyl or alkoxylalkyl group having in each case at most 5 carbon atoms, which process comprises reacting a substantially equimolar mixture of a piperidine derivative of the formula II
wherein R has the meaning given under formula I, and a 0,0 - dialkyldithiophosphoric free acid of the formula m
wherein R1 and R2 have the meaning defined above, or a sodium, potassium or ammonium salt thereof, in the presence of an acid-binding agent, with chloroacetyl chloride.
2. Process according to Claim 1, wherein the reaction is performed in a two-phase system consisting of water and an organic solvent immiscible with water.
3. Process according to Claim 2, wherein the reaction is performed in a two-phase system consisting of water and an aliphatic or aromatic hydrocarbon or an aliphatic or aromatic halogenated hydrocarbon.
4. Process according to Claim 3, wherein the reaction is performed in a two-phase system consisting of water and toluene.
5. Process according to any of Claims 1 to 4, wherein the reaction is performed in the temperature range of between 0 and 20"C.
6. Process according to Claim 5, wherein the reaction is performed in the temperature range of between 5 and 15"C.
7. Process according to any of Claims 1 to 6, wherein the acid-binding agent used is an alkali metal hydroxide or alkaline-earth metal hydroxide.
8. Process according to Claim 7, wherein the acid-binding agent used is sodium hydroxide or potassium hydroxide.
9. Process according to Claim 1, which process comprises adding one equivalent of chloroacetyl chloride at a temperature of between 5 and 15"C, with vigorous stirring, to a two-phase system consisting of a solution of a piperidine derivative of the formula II in toluene and an aqueous solution of one equivalent of a sodium or potassium salt of a 0,0dialkyldithiophosphoric acid of the formula
III and one equivalent of sodium or potassium hydroxide.
10. Process according to Claim 1 substantially as described in Example 1 or 2.
11. An 0,0 - dialkylphosphoro - dithioate as defined in Claim 1 when prepared by the process claimed in any of Claims 1 to 10.
12. Process according to any of Claims 1 to 9 wherein the compound of formula II is 2 - methyl - piperidine and the compound of formula m is 0,0 - di - n - propyldithiophosphoric acid.
13. 0,0 - Di - n - propyl - S - [2 methyl - 1 - piperidinyl) - 2 - oxo - ethyl] dithiophosphate when produced by the process of Claim 10 or 12.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US63678075A | 1975-12-01 | 1975-12-01 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB1565252A true GB1565252A (en) | 1980-04-16 |
Family
ID=24553290
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB49703/76A Expired GB1565252A (en) | 1975-12-01 | 1976-11-29 | Process for the production of o,o-dialkylphorsphorodithiates |
Country Status (2)
| Country | Link |
|---|---|
| CH (1) | CH602774A5 (en) |
| GB (1) | GB1565252A (en) |
-
1976
- 1976-11-29 CH CH1500276A patent/CH602774A5/xx not_active IP Right Cessation
- 1976-11-29 GB GB49703/76A patent/GB1565252A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CH602774A5 (en) | 1978-07-31 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PS | Patent sealed | ||
| 704A | Declaration that licence is not available as of right for an excepted use (par. 4a/1977) | ||
| PE20 | Patent expired after termination of 20 years |
Effective date: 19961128 |