CN100590128C - Method for preparing methamidophos in high content - Google Patents
Method for preparing methamidophos in high content Download PDFInfo
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- CN100590128C CN100590128C CN200410071778A CN200410071778A CN100590128C CN 100590128 C CN100590128 C CN 100590128C CN 200410071778 A CN200410071778 A CN 200410071778A CN 200410071778 A CN200410071778 A CN 200410071778A CN 100590128 C CN100590128 C CN 100590128C
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- spermine
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- NNKVPIKMPCQWCG-UHFFFAOYSA-N methamidophos Chemical compound COP(N)(=O)SC NNKVPIKMPCQWCG-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims description 19
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims description 20
- 238000002360 preparation method Methods 0.000 claims description 3
- MCWXGJITAZMZEV-UHFFFAOYSA-N dimethoate Chemical compound CNC(=O)CSP(=S)(OC)OC MCWXGJITAZMZEV-UHFFFAOYSA-N 0.000 abstract description 4
- -1 dichlorothio phosphamide Chemical compound 0.000 abstract description 3
- QYPPJABKJHAVHS-UHFFFAOYSA-N Agmatine Natural products NCCCCNC(N)=N QYPPJABKJHAVHS-UHFFFAOYSA-N 0.000 abstract 2
- QYPPJABKJHAVHS-UHFFFAOYSA-P agmatinium(2+) Chemical compound NC(=[NH2+])NCCCC[NH3+] QYPPJABKJHAVHS-UHFFFAOYSA-P 0.000 abstract 2
- 238000006243 chemical reaction Methods 0.000 description 55
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 49
- PFNFFQXMRSDOHW-UHFFFAOYSA-N spermine Chemical compound NCCCNCCCCNCCCN PFNFFQXMRSDOHW-UHFFFAOYSA-N 0.000 description 46
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 39
- 229940063675 spermine Drugs 0.000 description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000000543 intermediate Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 12
- 238000009413 insulation Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 238000004454 trace mineral analysis Methods 0.000 description 11
- 239000010410 layer Substances 0.000 description 10
- WQYSXVGEZYESBR-UHFFFAOYSA-N thiophosphoryl chloride Chemical compound ClP(Cl)(Cl)=S WQYSXVGEZYESBR-UHFFFAOYSA-N 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 8
- 239000012295 chemical reaction liquid Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 6
- 150000004985 diamines Chemical class 0.000 description 6
- 238000005576 amination reaction Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- SUABMOWIQWUPPE-UHFFFAOYSA-N dihydrogen phosphate;methylazanium Chemical compound NC.OP(O)(O)=O SUABMOWIQWUPPE-UHFFFAOYSA-N 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- 239000012044 organic layer Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 235000011121 sodium hydroxide Nutrition 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 230000017105 transposition Effects 0.000 description 5
- 238000004587 chromatography analysis Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- FJCSSYLOOPRWEW-UHFFFAOYSA-N S(Cl)Cl.[P].C1=CC=CC=C1 Chemical compound S(Cl)Cl.[P].C1=CC=CC=C1 FJCSSYLOOPRWEW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 239000002917 insecticide Substances 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 150000003573 thiols Chemical class 0.000 description 2
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- KEDSOMNVJMZAJP-UHFFFAOYSA-N O=P(SC)(N)OC.[Cl] Chemical compound O=P(SC)(N)OC.[Cl] KEDSOMNVJMZAJP-UHFFFAOYSA-N 0.000 description 1
- KCPJLBUDMSTBRT-UHFFFAOYSA-N [P].ClSCl Chemical compound [P].ClSCl KCPJLBUDMSTBRT-UHFFFAOYSA-N 0.000 description 1
- YASYVMFAVPKPKE-UHFFFAOYSA-N acephate Chemical compound COP(=O)(SC)NC(C)=O YASYVMFAVPKPKE-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- KVILUFYYUJUTDJ-UHFFFAOYSA-N benzene;n,n-diethylethanamine Chemical compound C1=CC=CC=C1.CCN(CC)CC KVILUFYYUJUTDJ-UHFFFAOYSA-N 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- OMFXVFTZEKFJBZ-HJTSIMOOSA-N corticosterone Chemical compound O=C1CC[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@H](CC4)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 OMFXVFTZEKFJBZ-HJTSIMOOSA-N 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- JCEGDDHHSZJJHV-UHFFFAOYSA-N methanamine;phosphane Chemical compound P.NC JCEGDDHHSZJJHV-UHFFFAOYSA-N 0.000 description 1
- 238000000199 molecular distillation Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000003822 preparative gas chromatography Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229960001196 thiotepa Drugs 0.000 description 1
- 239000003053 toxin Substances 0.000 description 1
- 230000005945 translocation Effects 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A process for preparing the high-content methamidophos features that dichlorothio phosphamide, 0-methyl-monochlorothio phosphamide and S-methyl-monochlorothio phosphamide are used as raw materials orintermediate to prepare agmatine and methamidophos not containing trimethylester [PS(CH3o)3]. The content of agmatine is increased by 7%. The content of methamidophos is increased by 12%.
Description
The present invention relates to a kind of preparation method of methamidophos in high content, the invention particularly relates to a kind of by changing old intermediate in the former methylamine phosphine production method, and synthetic new midbody compound by way of the method for preparing methamidophos in high content.
Acephatemet is a kind of broad spectrum insecticide, used nearly 30 years in China, for a long time, it is the insecticide variety of domestic maximum tonnage always, it also is the main pesticide species that Chinese exports is earned foreign exchange, after 2007, because its high poison, as pesticide species, in China's use that will be under an embargo, but acephatemet is as the intermediate or the raw material of low-toxin farm chemicals products such as acephate and chlorine methamidophos, and still as the important export kind, it still has lastingly, wide prospect of production, acephatemet more requires high quality as the application of export varieties and intermediate from now on, high-content.
So far, in state-owned more than 50 tame acephatemet manufacturers, the production technique of using is similar basically, acephatemet according to the present explained hereafter of using of these enterprises, its content is generally about 73%, wherein main impurity is trimethyl, spermine and methyl-sulfate, the total content of these three kinds of impurity in the acephatemet product occupies more than 23%, if adopt these impurity of physical method for separation, such as adopting known acephatemet crystallization process etc., though also can improve methylamine phosphate content to 80%～90%, but production cost must improve 50%～100%, Here it is in decades, the acephatemet commodity that numerous domestic acephatemet manufacturing enterprise produces, and content still can not surpass 75% basic reason so far.Trimethyl is the by product that certainly leads to in the old explained hereafter acephatemet process, occupy content in the product more than 7%, spermine is a main raw material of producing acephatemet, in the product of existing explained hereafter, occupy content more than 8%, the two not only reduces content, and the reduction yield, increase production cost.
The purpose of this invention is to provide a kind of method, when improving methylamine phosphate content, improve yield, more reduce cost by preparing new intermediate, using new way production acephatemet instead.
Result of study of the present invention shows, the old and new's technology is raw material equally with the phosphorus thiochloride, but novel process is carried out amination earlier to phosphorus thiochloride, the building-up reactions of carrying out subsequent step with methyl alcohol etc. is produced acephatemet again, in the whole process, not only do not produce the trimethyl by product fully, and thus can the spermine primitive reaction is complete, thereby the yield that calculates with the main raw material phosphorus thiochloride improved.
The acephatemet production craft step that existing reality is being used:
Step 1:
The phosphorus thiochloride monochloride
Step 2:
Spermine
Step 3:
Acephatemet
The process of above-mentioned steps one certainly leads to the trimethyl [(CH more than 7%
3O)
3PS], trimethyl is a colourless transparent liquid, the boiling point height mixes with monochloride, and is water insoluble, because monochloride poor heat stability, should not distill, thus be difficult to remove after the trimethyl generation, so trimethyl is present in the spermine of step 2, have a strong impact on the reaction (step 3) that spermine changes into acephatemet, cause spermine not react completely.Trimethyl is the passivator of this catalyzer of methyl-sulfate, because it can also be become other by products such as thiol trimethyl by the methyl-sulfate transposition, and identical dense crossing down, the transposition ability slightly is better than spermine, cause in the process of above-mentioned steps three, when chemical reaction reaches balance, always have spermine not react completely a little more than trimethyl content, not only consume raw material so pay the trimethyl that produces, and reduce methylamine phosphate content and transposition yield.
For addressing the above problem, the present invention adopts acephatemet new process of production step:
Step 1:
Phosphorus thiochloride A diamines
A (new intermediate)---dichloro thio-phosphamide, outward appearance is colourless transparent liquid, and is water insoluble, is dissolved in most of organic solvents, boiling point: 126 ℃/16mm Hg,
Diamines, the main by product that this step generates, content 3～4%, outward appearance is a white solid, and 62 ℃ of fusing points are water-soluble, are insoluble to organic solvent, and easy and HCl salify easily decomposes in alkaline aqueous solution.
Step 2:
A B
B (new intermediate)-O-methyl-chlorothio phosphamide, the appearance colorless transparent liquid, water insoluble, be dissolved in most of machine solvents, 112～114 ℃/10mm of boiling range Hg,,
Step 3:
a、
b、
C
C (new intermediate)-S-methyl-chlorine thiol phosphamide, outward appearance is a white solid, 46 ℃ of fusing points, solubleness: water 30%, toluene 8%, ethylene dichloride 35%,
Circuitous alkali easily decomposes.
In the above-mentioned processing step of the present invention, adopted A, B, three new intermediates of C, owing to be in the first amination of step 1, technology of the present invention can not produce the sort of trimethyl that old technology will inevitably produce, though produced another kind of by product---diamines in step 1, diamines is water-soluble, is insoluble to organic solvent, utilize this characteristic, be easy to remove diamines through washing, and, routinely, use the reaction of complete same materials, first step produces by product and produces by product than back step, and raw materials cost more reduces, and the newer second child plants technology, the content of monochloride≤91% in the old technology, the content of spermine≤92%, the content of acephatemet≤73%, the content of novel process spermine≤98%, methylamine phosphate content 〉=85%, the novel process cost reduces more than 7% than old technology.
It is raw material that the present invention has also selected with dichloride (a kind of intermediate of old explained hereafter acephatemet), and first amination generates B, is prepared the method for acephatemet again by the continuous back of B, can reach identical effect, and concrete processing step is as follows:
Step I:
Dichloride B diamines
Step II is identical with above-mentioned steps 3.
Example 1:
Molecule proportioning: phosphorus thiochloride: NH
4OH: methyl alcohol: NaOH=1: 2.15: 4: 1.2
Prepare 5～7% NH earlier
4The OH aqueous solution and 65% phosphorus thiochloride benzole soln are standby.
In the disposable input 500ml reaction flask of 100g65% phosphorus thiochloride benzene oil, start and stir, be cooled to-8 ℃, beginning Dropwise 5 %NH
4Below the OH aqueous solution, controlled temperature-5 ℃, drip 280g altogether, after dripping off, in 0 ℃ of insulation reaction, use the gas-chromatography trace analysis, phosphorus thiochloride content≤0.5% o'clock is the amination terminal point in the test reaction liquid; Divide the water layer that desalts, organic layer is the A compound.Controlled temperature is about 20 ℃ then, under agitation begin to drip anhydrous methanol (98%) 53g, insulation reaction is 2 hours under this temperature, begin to drip 30%NaOH aqueous solution 65g again, 25～30 ℃ of insulation reaction of controlled temperature, use the gas-chromatography trace analysis, the content of A and B two compounds is all reduced to below 0.5% simultaneously in test reaction liquid, be reaction end, standing demix divides the water layer that desalts, organic layer is distilled under high vacuum, boil off benzene and methyl alcohol as far as possible, reclaim the benzene and the methyl alcohol mixed liquor that steam, apply mechanically to get ready to criticize, distill the organic solution in the retention reaction flask that finishes, be the high-content spermine that does not contain trimethyl, content 98% must weigh 48g, yield is calculated as 83% with phosphorus thiochloride.
With this 98% spermine,, also can obtain 85% methamidophos in high content even carry out translocation reaction according to old technology.
Example 2:
Molecule proportioning: dichloride: NH
4OH=1: 2.15, first compound concentration is that 15～17% ammoniacal liquor is standby.
Disposable input dichloride (97%) (O-methyl thio-phosphoryl dichloride) 146g goes in the 500ml four-hole reaction flask, and disposable input 70g benzene starts and stirs simultaneously, and temperature in the reaction flask is reduced to-8 ℃, and beginning slowly drips NH
4OH, control reaction solution PH6～6.5, control reaction temperature is no more than-6 ℃, drips 16%NH altogether
4OH 196g dropwises, and controlled temperature continued stirring reaction 0.5 hour at 0 ℃, added a little NH
4OH transfers PH to 7, and reaction solution is placed the 1000ml separating funnel, standing demix 0.5 hour, divide and go upper aqueous layer, add the 70g icy salt solution again, the thorough washing reaction solution, standing demix again, divide and go upper aqueous layer, take off layer organic solution and be purpose compd B (O-methyl-chlorothio phosphamide), get heavy 118+70 (B+ benzene) g of B, content 97% (to remove the benzene solvent of adding), yield 92%.
Example 3:
Disposable input 146g dichloride (97%) is gone in the 500ml four-hole reaction flask, and disposable input 70g benzene starts and stirs simultaneously, and feed temperature in the reaction flask is reduced to-5 ℃, slowly feeds ammonia, and the ammonia water that overflows from reaction flask absorbs.Control reaction temperature is no more than 0 ℃, controls reaction end with gas chromatographic analysis, dichloride content≤0.5% o'clock in the test reaction liquid, i.e. and reaction finishes, then the NH that produces of elimination reaction
4Cl salt washs filtering mother liquor about-5 ℃ with icy salt solution, behind flush away diamines and other water-soluble impurity, branch vibration layer is got organic layer, promptly gets B compound 119+70 (B+ benzene) g, content 98% (to remove the benzene solvent of adding), yield 94% basically.
Example 4:
Molecule proportioning: B: methyl alcohol: liquid caustic soda=1: 4: 1.15
Disposable input 200gB compound benzene oil (61.7%) is gone in the 500ml four-hole reaction flask, start and stir, slowly drop into simultaneously 111g anhydrous methanol (98%), feed temperature in the reaction flask is reduced to 0 ℃, slowly drip NaOH (30%), control reaction temperature is no more than 5 ℃, drips 30%NaOH 130g altogether, dropwise, 5 ℃ of following insulation reaction 1 hour, use the gas-chromatography trace analysis, the content of B compound≤0.5% in reaction solution, be reaction end, then, standing demix, branch vibration layer, the organic layer solution of leaving and taking is boiled off benzene and methyl alcohol with high vacuum as far as possible, get the spermine 113g that does not contain trimethyl.Content 98%, yield 93%.
Example 5:
Molecule proportioning: B: sodium methylate=1: 1.1
Disposable input 200gB compound benzene oil (61.7%) is gone in the four-hole reaction flask, start and stir, slowly add simultaneously the 52.5g sodium methylate, slowly be warming up to 30 ℃, insulation reaction 1 hour is warming up to 65 ℃ again, back flow reaction 2 hours, use the gas-chromatography trace analysis, the content of B compound≤0.5% is reaction end in reaction solution, be cooled to room temperature, filter, remove the NaCl salt in the reaction solution, the filtrated stock molecular distillation, boil off solvent benzol as far as possible, get the spermine 117.5g that does not contain trimethyl, content 98%, yield 96%.
Example 6:
Feed intake: do not contain spermine (100%) 152g of trimethyl,
Methyl-sulfate (98%) 9g.
Earlier spermine (98%) is mixed with 62% benzene oil 250g, in the disposable input 500ml four-hole reaction flask, starts and stir, be warming up to 50 ℃, begin to drip methyl-sulfate, controlled temperature is below 50 ℃, after dropwising, make temperature of reaction be stabilized in 50～60 ℃, continue insulation 1.5～2 hours, use the liquid phase chromatography trace analysis, spermine content≤0.5% in the test reaction liquid, be terminal point, cool the temperature to 0 ℃ then.At 0 ℃ of left and right sides standing demix, the upper strata is the benzene oil reservoir, recyclable applying mechanically, and lower floor is methamidophos from crude oil, must measure 166g, content 87%, yield 95%.
Example 7:
Elder generation is mixed with spermine (92%) 40% benzene oil 250g, in the disposable input 500ml four-hole reaction flask, start to stir and be warming up to 17 ℃, begin to drip methyl-sulfate, drip 18g altogether, be controlled at about 17 ℃, insulation reaction 5 hours, use the liquid phase chromatography trace analysis, spermine content≤0.5% o'clock in reaction solution is reaction end, feeds HCl gas then in reaction solution, the acephatemet hydrochloride that generates crystalline deposit gradually comes out, use the liquid phase chromatography trace analysis, the content of acephatemet≤0.5% o'clock in the test soln, logical HCl gas finishes, the acephatemet hydrochloride that again mass crystallization is gone out filters, oven dry is collected the filtrated stock recovery set and is used.With the acephatemet hydrochloride dry product (120.8g) that filters out, another drops in the four-hole reaction flask, slowly adds 36.5% triethylamine benzole soln in the reaction flask, start and stir, keep about 25 ℃ of temperature, stirring reaction is after 5 hours, the acephatemet hydrochloride changes into triethylamine hydrochloride, filter and collect triethylamine hydrochloride recovery triethylamine, filtrated stock is divided into two layers, and the upper strata is the benzene layer, lower floor is methamidophos in high content, content 95% must be measured 99g, yield 94%.
Example 8:
Weight ratio: B: (CH
3O)
2SO
2: sodium methylate=1: 0.06: 0.45
In the disposable input four-hole of 98%B compound 100g reaction flask, start and stir, temperature rises to 50 ℃, beginning slowly drips methyl-sulfate (98%), 50～60 ℃ of controlled temperature, and, use the liquid chromatography trace analysis in this temperature insulation reaction 3～5 hours, B compounds content≤0.5% o'clock is terminal point in test reaction liquid.Then, slowly drop into 200g methyl alcohol (98%), slowly drop into 45g sodium methylate (98%) again, 50～60 ℃ of controlled temperature, insulation reaction 3～5 hours is used the liquid chromatography trace analysis, C compounds content≤0.5% o'clock is reaction end in test reaction liquid, filters, and removes NaCl salt, filtrated stock is distilled under high vacuum, boil off solvent methanol as far as possible, promptly get methamidophos in high content crude oil, must measure 109g, content 83%, yield 95%.
Example 9:
Molecule proportioning: phosphorus thiochloride: NH
4OH: methyl alcohol=1: 2.15: 6
In the disposable input 500ml four-hole reaction flask of 100g65% phosphorus thiochloride benzene oil, start and stir, be cooled to-8 ℃, begin to drip 7%NH
4The OH aqueous solution, below the controlled temperature-5 ℃, drip 280g altogether, drip off the back in 0 ℃ of insulation reaction, use the vapor-phase chromatography trace analysis, phosphorus thiochloride content≤0.5% o'clock is the amination terminal point in the test reaction liquid, divides and removes the amine salt water layer, organic layer is the A intermediate, controlled temperature under agitation begins to drip anhydrous methanol (98%) 80g at reflux state then, and insulation reaction is 4～6 hours under reflux temperature, the HCl gas water that overflows absorbs, use the gas-chromatography trace analysis, the content of A and B two intermediates is all reduced to below 0.5% simultaneously in the test reaction liquid, is reaction end, under high vacuum, boil off benzene and methyl alcohol as far as possible, be the high-content spermine that does not contain trimethyl, content 98%, must measure 49g, yield counts 88% with phosphorus thiochloride.
The present invention has utilized above-mentioned A, B, C, three new compounds as the intermediate for preparing spermine or acephatemet dexterously, overcome old technology and must pay the defective of producing trimethyl and influencing acephatemet transposition yield and content thus, improving yield, under the prerequisite that reduces cost, produce high-load spermine and acephatemet, transposition yield improves more than 7%, and methylamine phosphate content improves more than 10%.
The present invention is also ingenious to have utilized the acephatemet hydrochloride intermediate acephatemet of further purifying, and the content of acephatemet is reached more than 95%, reduces more than 50% than the cost of crystallization process purification acephatemet, be belong to can industrializing implementation a kind of good method of purification.
Claims (3)
1, utilize in A compound, B compound, three compounds of C compound any one not contain PS (CH as raw material or intermediate preparation
3O)
3O, the method for O-dimethyl thiophosphoryl amide or acephatemet,
A, B, three molecular structure of compounds formulas of C:
2, with PSCl
3Method for A, B, C compound in the feedstock production claim 1.
3, with CH
3OCl
2PS is the method for B in the feedstock production claim 1, C compound.
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| US10669295B2 (en) * | 2018-07-19 | 2020-06-02 | Arysta Lifescience Inc. | Process for preparation of O,O-dimethyl phosphoramidothioate and N-(methoxy-methylsulfanylphosphoryl) acetamide |
| CN111718370A (en) * | 2020-07-28 | 2020-09-29 | 杭州润盛科技有限公司 | Preparation method of O, O' -dimethyl thiophosphoryl amide |
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| 甲胺磷合成工艺改进及其进展. 诸锡云.农药，第30卷第6期. 1991 |
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|---|---|
| CN1727352A (en) | 2006-02-01 |
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