MXPA99008291A - An improved procedure for the synthesis of o-dimet, fosforoamidotioato - Google Patents
An improved procedure for the synthesis of o-dimet, fosforoamidotioatoInfo
- Publication number
- MXPA99008291A MXPA99008291A MXPA/A/1999/008291A MX9908291A MXPA99008291A MX PA99008291 A MXPA99008291 A MX PA99008291A MX 9908291 A MX9908291 A MX 9908291A MX PA99008291 A MXPA99008291 A MX PA99008291A
- Authority
- MX
- Mexico
- Prior art keywords
- dimethyl
- solvent
- sodium hydroxide
- molar ratio
- ammonia
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 20
- 230000002194 synthesizing Effects 0.000 title description 3
- 230000015572 biosynthetic process Effects 0.000 title description 2
- 238000003786 synthesis reaction Methods 0.000 title description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 69
- 239000002904 solvent Substances 0.000 claims abstract description 23
- 239000012074 organic phase Substances 0.000 claims abstract description 21
- 239000011541 reaction mixture Substances 0.000 claims abstract description 16
- 239000008346 aqueous phase Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-M azane;hydroxide Chemical compound N.[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-M 0.000 claims abstract description 7
- 238000007792 addition Methods 0.000 claims abstract description 6
- XFBJRFNXPUCPKU-UHFFFAOYSA-N chloro-dimethoxy-sulfanylidene-$l^{5}-phosphane Chemical compound COP(Cl)(=S)OC XFBJRFNXPUCPKU-UHFFFAOYSA-N 0.000 claims abstract description 5
- NKYPKIVMIGIWOB-UHFFFAOYSA-N [amino(methoxy)phosphinothioyl]oxymethane Chemical compound COP(N)(=S)OC NKYPKIVMIGIWOB-UHFFFAOYSA-N 0.000 claims abstract 3
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 9
- NNKVPIKMPCQWCG-UHFFFAOYSA-N Methamidophos Chemical compound COP(N)(=O)SC NNKVPIKMPCQWCG-UHFFFAOYSA-N 0.000 claims description 4
- 239000000010 aprotic solvent Substances 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000003944 tolyl group Chemical group 0.000 claims description 3
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N o-xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 238000010924 continuous production Methods 0.000 abstract description 4
- 238000003379 elimination reaction Methods 0.000 abstract 1
- CMXPERZAMAQXSF-UHFFFAOYSA-M sodium;1,4-bis(2-ethylhexoxy)-1,4-dioxobutane-2-sulfonate;1,8-dihydroxyanthracene-9,10-dione Chemical compound [Na+].O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=CC=C2O.CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC CMXPERZAMAQXSF-UHFFFAOYSA-M 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 5
- 239000003513 alkali Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 239000003849 aromatic solvent Substances 0.000 description 2
- RJBIAAZJODIFHR-UHFFFAOYSA-L dioxidothiophosphorylamine Chemical class NP([O-])([O-])=S RJBIAAZJODIFHR-UHFFFAOYSA-L 0.000 description 2
- 230000000749 insecticidal Effects 0.000 description 2
- 239000002917 insecticide Substances 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000002572 peristaltic Effects 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Abstract
The present invention relates to a continuous process for preparing O, O-dimethyl phosphoramidothioate. According to this process, O, O-dimethyl phosphorochlorothioate is reacted with ammonia and sodium hydroxide, the addition of sodium hydroxide controls the pH of the reaction mixture. The reaction mixture formed contains an aqueous phase and an organic phase. The organic phase of the reaction mixture is separated from the aqueous phase, a second organic phase is extracted from the aqueous phase with solvent, and the O, O-dimethyl phosphoramidothioate is isolated from the combined organic phases by elimination of the solvent in vacuo. In one embodiment of the present invention, the reaction of O, O-dimethyl phosphorochloridothioate with ammonia and sodium hydroxide is carried out in the presence of a solven
Description
AN IMPROVED PROCEDURE FOR THE SYNTHESIS OF
0.0-DIMETILO PHOSPHOROAMIDOTIOATO
TECHNICAL FIELD OF THE INVENTION The field of this invention is that of insecticides phosphorus idotioate. More specifically, the present invention relates to a continuous process improved to synthesize 0.0-dimethyl phosphoramidothioate by controlling the pH of the reaction mixture with the addition of sodium hydroxide. BACKGROUND OF THE INVENTION O, O-dialkyl phosphoramidothioates are intermediates used in the preparation of phosphorone-midothioate insecticides. Specifically, 0.0-dimethyl phosphoramidothioate is a necessary intermediate in the production of O, S-dimethyl phosphoramidothioate. The 0.0-dimethyl phosphaaroamidothioate is generally produced by the reaction of 0.0-dimethylphosphorochloridothioate with two equivalents of aqueous ammonia with or without solvent. The US patent No. 3,309,256 discloses that O, O-dimethyl chlorophosphorothiaate reacts with ammonia or a primary alkylamine to produce 0, 0-dimethyl phosphoroamidethioate. In a manner similar to the method described in US Pat. No. 3,309,266, US Pat. No. 3,639,547 discloses that the 0.0-dimethyl phosphoramidothioate can be prepared by ammoniating an O, O-dimethyl allophosphorothioate. With the above methods, the yield of the formed 0.0-dimethyl phosphoramidothioate is low and the purification process, which requires ammonia recovery, is expensive. Therefore, there remains a need in the art for an efficient method for preparing 0.0-10-dimethyl phosphoramidothioate with a higher net yield and, preferably, without the need for an ammonia recovery process.
BRIEF DESCRIPTION OF THE INVENTION f The present invention provides a method for increasing the net yield of phosphoroamidothioate 4 of 0.0-r dimethyl. According to the continuous process of the invention, 0.0-dimethyl phosphorochloridothioate is reacted with ammonia and sodium hydroxide, the addition of sodium hydroxide controls the pH of the reaction mixture, the reaction mixture formed contains a phase aqueous phase and an organic phase, the organic phase of the reaction mixture is separated from the aqueous phase, a second organic phase of the aqueous phase is then extracted with solvent, and the phospho-roamidothioate 0.0-d isisolated? methyl, resulting from the organic phases In one embodiment of the present invention, the 0.0-dimethyl phosphorocyclopropothioate reacts with ammonia and sodium hydroxide in the presence of a solvent The solvent of the invention is toluene. an object of this invention is to provide an improved process for synthesizing 0.0-di-ethyl phosphoramidothioate It is another object of this invention to control the pH of the reaction mixture by the addition of sodium hydroxide for to yield optimum net yields of O-O-dimethyl phospho-roat idotioate.
DETAILED DESCRIPTION OF THE INVENTION
The present invention provides a method for increasing the net yield of 0.0-dimethyl phosphoramidoidioate. The method of the present invention is a continuous "split alkali" process. The 0, 0-d? Methyl phosphorocloridothioate reacts with ammonia and sodium hydroxide. The addition of sodium hydroxide is used to control the pH of the reaction mixture. The molar ratio of ammonia to 0.0-dimethyl phosphorochloridothioate is from about 1.3: 1 to about 1: 6: 1, and preferably from about 1.40: 1 to about 1.45: 1, and more preferably approximately 1.41: 1. The molar ratio of sodium hydroxide to phosphoroc oridothioate of 0.0-dimethyl is from about 0.90: 1 to about 1: 1 and, preferably, from about 0.93: 1 to about 0.96: 1 and, more preferably, approximately 0.93: 1. The pH of the reaction is from about 9.2 to about 10.2 and, preferably, from about 9.2 to about 9.3. The temperature of the reaction is from about 35 ° C to about 45 ° C and, preferably, 40 ° C. The residence time of the reaction is from about 2 hours to about 4 hours and, preferably, about 3 hours. In one embodiment of the present invention, the reaction of 0.0-dimethyl phosphorochloridothioate with ammonia and sodium hydroxide is carried out in the presence of a solvent. An aprotic aromatic solvent is preferred. Such solvents are well known in the art and include toluene, xylene and mesitylene. Toluene is a preferred aromatic aprotic solvent. The molar ratio of toluene to 0.0-dimethyl phosphoroclophodothioate is from about 0.5: 1 to about 2: 1 and, preferably, from about 0.75: 1 to about 1: 1. The resulting reaction mixture contains an aqueous phase and an organic phase. The organic phase is separated from the aqueous phase in a batch separator. A second organic phase is then extracted from the aqueous phase of the reaction mixture. The solvent is removed in vacuo over the combined organic phases to produce the resulting 0.0-dimethyl phospho-roamidothioate. In a preferred embodiment of the present invention, a solvent is used to extract the second organic phase from the aqueous phase. The solvent may include any aprotic aromatic solvents known in the art. These solvents are the same as those solvents previously identified for use in the final reaction stage. A preferred solvent is toluene. The Examples given below illustrate preferred embodiments of the present invention and are not limiting of the specification or the claims in any way.
EXAMPLES Example 1 - Preparation of 0.0-dimethyl phosphoramidothioate using a continuous "net alkali" (solventless) continuous process. 0.0-Dimethyl phosphororochloridothioate was charged to the reactor. Simultaneously, 25% sodium hydroxide was charged at a rate that maintained 0.93 molar equivalents with respect to the 0, 0-dimethylol phosphorochloride, and 18% ammonium hydroxide was charged at a rate that maintained 1.41 molar equivalents with with respect to the 0, 0-dimethyl phosphoroclopdothioate. The reagents were added using variable speed peristaltic pumps. The flow rates were checked at regular intervals weighing and the pump speeds were adjusted to maintain proper flow rates throughout the experiments. The residence time of the reaction was 3 hours. The reaction temperature was maintained at 40 ° C with stirring. The reaction mixture was continuously removed to maintain the desired volume. The organic and aqueous phases were separated and the aqueous phase was extracted with solvent to recover 0, 0-d? Methyl phosphoramidothioate. A net yield of about 98.5% of 0, 0-dimethyl phosphoramidothioate was achieved. Table 1 shows the% net yield of 0.0-dimethyl phospho-roamidothioate produced by varying the pH of the reaction mixture. The pH was controlled by varying the molar ratio of sodium hydroxide to phosphororochloridothioate of O-dimethyl. The molar ratio of ammonia to 0.0-dimethyl phosphorochloride thioate was maintained at 1.41 and the temperature was maintained at 40 ° C. Optimum yields (98% -99%) were obtained at a pH of 9.2-9.3, using a molar ratio of 0.93 mole of sodium hydroxide to 1 mole of 0, 0-dimethyl phosphorochlorido-t-olate. Using a molar ratio of sodium hydroxide to 0.0-dimethyl phosphorochloridothioate of 0.90 mol, a pH drop below 7 was achieved; unreacted 0.0-dimethyl phosphorochloridothioate appeared in the organic phase and the net yield was reduced to 94.2%. TABLE 1 Moles NaOH per% Rendi- pH% FCTDM *% FCTDM * mol of JMFCT * net phase Org. Phase ac. 0, 93, 98, 5, 9.2-9.3, zero, 0.6, 96, 97, 5, 9, 9, 9, 9, 9, 0, 0, 90, 2, < 7 to 3% 2.2 0, 95 98.1 9.3-9.5 zero 1.1 1, 05 93.5 9.7-11.0 zero 4.8 1.00 93.8 9.8 -10.2 zero 5.1
* FCTDM = unreacted O, O-dimethyl phosphorochloridothioate. Table 2 shows the net% yield of O, O-dimethyl phospho-roamidothioate produced using the net "alkali" (ie solvent-free) procedure at varying temperatures, using 1.41 moles of ammonia, 0 , 93 mole of sodium hydroxide and 1.0 mole of O, O-dimethyl phosphorochloridothioate: Optimum yield (98.5%) was obtained at a temperature of 40 ° C. Yields at 35 ° C and 45 ° C were lower (94.2% and 95.9%, respectively).
TABLE 2 Temp. % RendipH% FCTDM *% FCTDM * ° C net phase Org. Phase ac. 40 98.5 9.2-9.3 zero 0, 6 45 95, 9 8, 8-8, 9 zero 4.4 * FCTDM = = phosphorocloridothioate of 'do.
The procedure of the test described above was repeated, except that a solvent was used. Thus, the reaction was carried out in toluene. The toluene was present in an amount such that the ratio of toluene to O-O-dimethyl fos-forumamidothioate was about 1: 1. The results of this second test were similar to the results shown in Tables 1 and 2 above. Although the invention has been described in detail in the foregoing with an illustrative, it should be understood that said detail has only that purpose and that those skilled in the art can make variations therein without departing from the spirit and scope of the invention, except in what may be limited by the claims.
Claims (19)
1. A process for producing 0.0-d? Methyl phosphoramidothioate consisting of: a. reacting 0.0-dimethyl phosphorochloridothioate with ammonia and sodium hydroxide; b. forming a reaction mixture containing an aqueous phase and an organic phase, wherein the pH of the reaction mixture is controlled by the addition of sodium hydroxide; c. separating the organic phase from the reaction mixture from the aqueous phase; d. extracting with a solvent a second organic phase from the aqueous phase, and e. isolate O, O-dimethyl phosphoramidothioate from the organic phases.
2. The process of Claim 1, wherein the molar ratio of ammonia to 0.0-dimethyl phosphorochloridothioate is from about 1.3: 1 to about 1.6: 1.
3. The process of Claim 1, wherein the molar ratio of ammonia to phosphororochloridothioate 0.0-d methyl is from about 1.4: 1 to about 1.45: 1.
4. The process of Claim 1, wherein the molar ratio of ammonia to phosphoroclopdothioate 0.0-dimethyl is about 1.41: 1.
5. The process of Claim 1, wherein the molar ratio of sodium hydroxide to 0.0-d-methyl phosphorochloridothioate is from about 0.90: 1 to about 1: 1.
6. The process of Claim 1, wherein the molar ratio of sodium hydroxide to O, O-dimethyl phosphorochloridothioate is from about 0.93: 1 to about 0.96: 1.
7. The process of Claim 1, wherein the molar ratio of sodium hydroxide to O, O-dimethyl phosphorchlorochlorothioate is about 0.93: 1.
8. The method of Claim 1, wherein the pH is from about 9.2 to about 10.2.
9. The method of Claim 1, wherein the pH is from about 9.2 to about 9.3.
10. The method of Claim 1, wherein the temperature is from about 35 ° C to about 45 ° C.
11. The method of Claim 1, wherein the temperature is 40 ° C.
12. The method of Claim 1, wherein the reaction in step a. it is carried out in the presence of an aromatic aprotic solvent.
13. The process of Claim 12, wherein the solvent is one selected from the group consisting of toluene, xylene and mesitylene. _
14. The process of Claim 12, wherein the solvent is toluene.
15. The process of Claim 12 wherein the molar ratio of the solvent to the 0.0-dimethyl phosphorochloridothioate is from about 0.5: 1 to about 2: 1.
16. The process of Claim 12, wherein the molar ratio of the solvent to the 0.0-dimethyl phosphorochloridothioate is from about 0.75: 1 to about 1: 1
17. The method of Claim 1, wherein the second organic phase in step d. It is extracted using an aromatic aprotic solvent.
18. The process of Claim 17, wherein the solvent is toluene.
19. The process of Claim 1, wherein the 0.0-d? Methyl phosphoramidothioate is isolated from the organic phase by removal of the solvent in vacuo.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09153913 | 1998-09-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| MXPA99008291A true MXPA99008291A (en) | 2000-07-01 |
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