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CN103044479B - The synthetic method of bactericide of silthiopham - Google Patents

The synthetic method of bactericide of silthiopham Download PDF

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CN103044479B
CN103044479B CN201210534346.0A CN201210534346A CN103044479B CN 103044479 B CN103044479 B CN 103044479B CN 201210534346 A CN201210534346 A CN 201210534346A CN 103044479 B CN103044479 B CN 103044479B
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silicon based
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methyl
trimethyl silicon
washing
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CN103044479A (en
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程绎南
李洪连
谢桂英
靳文波
孙淑君
游秀峰
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Henan Agricultural University
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Abstract

The present invention relates to a kind of synthetic method of bactericide of silthiopham, the method is: by 4,5-dimethyl-2-(trimethyl silicon based) thiophene-3-methyl-formiate and allylamine back flow reaction 5-15h in solvent one, room temperature is down to after reaction terminates, washing, organic phase drying, concentrated, recrystallization and get final product; Or reaction terminates rear first negative pressure and steams solvent one, then be down to room temperature, washing, dichloromethane extraction, organic phase drying, concentrated, recrystallization and get final product; The molar ratio of described 4,5-dimethyl-2-(trimethyl silicon based) thiophene-3-methyl-formiates and allylamine is 1:1-2.The method has that cheaper starting materials is easy to get, reaction conditions is gentle, reaction yield high, is applicable to large-scale production.

Description

The synthetic method of bactericide of silthiopham
Technical field
The invention belongs to technical field of organic synthesis, be specifically related to a kind of synthetic method of sterilant N-allyl group-4,5-dimethyl-2-(trimethyl silicon based) thiophene-3-methane amide (Silthiopham).
Background technology
Silthiopham is the sterilant for preventing and treating take-all developed by About Monsanto Chemicals, has unusual effect to the control of take-all.But limit it apply because its current synthesis technique exists the problem such as raw material supply and severe reaction conditions.
US Patent No. 005486621A reports its synthetic method, and the method is with 2-butanone, sulphur, cyanoacrylate etc. for starting raw material, and synthesis obtains object product, but total recovery is only less than 10%.And this synthetic method step is long, each intermediate separation difficulty etc.US Patent No. 006140511A reports the synthetic method of improvement, but the synthesis of important intermediate 3-(trimethyl silicon based) propine acid amides involved by the method, run into very large challenge.Although this patent provides its multiple synthetic method, involved synthetic method or raw material obtain difficult, or need use the highly basic to water and air sensitivity such as butyllithium or amido lithium, are difficult to apply; In addition, because this intermediate has higher boiling point, its separation and purification also encounters difficulty.Document Organic Process Research & Development 6 (2002), 357-366 reports new synthetic route, this synthetic method has synthesized object product with sulfydryl butanone, methoxy-methyl acrylate for starting raw material, although this process recovery ratio increases, but severe reaction conditions, still need to use the hazardous materials to air-sensitive such as butyllithium or amido lithium (LDA), be difficult to scale production.
Summary of the invention
The object of the invention is to overcome prior art deficiency; a kind of sterilant N-allyl group-4 is provided; the synthetic method of 5-dimethyl-2-(trimethyl silicon based) thiophene-3-methane amide (Silthiopham); the method has that cheaper starting materials is easy to get, reaction conditions is gentle, reaction yield high, is applicable to large-scale production.
For achieving the above object, the present invention adopts following technical scheme:
A kind of synthetic method of bactericide of silthiopham, the method is: by 4,5-dimethyl-2-(trimethyl silicon based) thiophene-3-methyl-formiate and allylamine be back flow reaction (generation amine exchange reaction) 5-15h in solvent one, room temperature is down to after reaction terminates, washing, organic phase drying, concentrated, recrystallization and get final product; Or reaction terminates rear first negative pressure and steams solvent one, then be down to room temperature, washing, dichloromethane extraction, organic phase drying, concentrated, recrystallization and get final product; The molar ratio of described 4,5-dimethyl-2-(trimethyl silicon based) thiophene-3-methyl-formiates and allylamine is 1:1-2, and synthetic route is as follows:
Concrete, described solvent one is one or more the mixture in halohydrocarbon, alcohols, aromatic hydrocarbon and polar aprotic solvent; The addition of solvent one is generally the 5-10 of reactant quality doubly.In described solvent one, halohydrocarbon is as methylene dichloride, chloroform, tetracol phenixin etc.; Alcohols is as methyl alcohol, ethanol, Virahol etc.; Aromatic hydrocarbon is as toluene, dimethylbenzene, chlorobenzene etc.; Polar aprotic solvent is as DMF, methyl-sulphoxide, tetrahydrofuran (THF) etc.
Described 4,5-dimethyl-2-(trimethyl silicon based) thiophene-3-methyl-formiate preferably obtains through following method: by 3-sulfydryl butanone and 3-(trimethyl silicon based) Methyl propiolate under rare gas element (as nitrogen etc.) protection and alkaline catalysts effect in solvent two back flow reaction 5-20h, room temperature is down to after reaction terminates, washing, organic phase is through washing, dry, concentrated, column chromatography for separation and get final product; Or reaction terminates rear first negative pressure and steams solvent two, then be down to room temperature, washing, dichloromethane extraction, organic phase is through washing, dry, concentrated, column chromatography for separation and get final product; The molar ratio of described 3-sulfydryl butanone and 3-(trimethyl silicon based) Methyl propiolate is 1:0.5-1; Synthetic route is as follows:
Described alkaline catalysts is preferably one or more the mixture in alkaline carbonate, alkalimetal hydride and alkali metal alcoholates; Described solvent two is preferably one or more the mixture in halohydrocarbon, alcohols, aromatic hydrocarbon and polar aprotic solvent; The consumption of described catalyzer is generally the 0.2-2 of 3-(trimethyl silicon based) Methyl propiolate quality doubly; Described solvent two addition is generally the 5-10 of reactant quality doubly.Alkaline carbonate is as sodium carbonate, sodium bicarbonate, salt of wormwood, saleratus etc.; Alkalimetal hydride is as sodium hydride, potassium hydride KH etc.; Alkali metal alcoholates is as sodium methylate, sodium ethylate, potassium methylate, potassium ethylate etc.In described solvent two, halohydrocarbon is as methylene dichloride, chloroform, tetracol phenixin etc.; Alcohols is as methyl alcohol, ethanol, Virahol etc.; Aromatic hydrocarbon is as toluene, dimethylbenzene, chlorobenzene etc.; Polar aprotic solvent is as DMF, methyl-sulphoxide, tetrahydrofuran (THF) etc.
Described 3-(trimethyl silicon based) Methyl propiolate preferably obtains through following method: by Methyl propiolate and trimethylchlorosilane under rare gas element (as nitrogen etc.) protection and organic alkali catalyst effect in solvent three back flow reaction (generation condensation reaction) 3-12h, room temperature is down to after reaction terminates, washing, organic phase drying, concentrated, column chromatography for separation and get final product; Or reaction terminates rear first negative pressure and steams solvent three, then be down to room temperature, washing, dichloromethane extraction, organic phase drying, concentrated, column chromatography for separation and get final product; The molar ratio of described Methyl propiolate and trimethylchlorosilane is 1:1-2; Synthetic route is as follows
Described organic alkali catalyst is preferably organic amine; Described solvent three is preferably one or more the mixture in halohydrocarbon, aromatic hydrocarbon and polar aprotic solvent.The consumption of described catalyzer is generally the 0.2-2 of Methyl propiolate quality doubly; Described solvent three addition is generally the 5-10 of reactant quality doubly.Described organic amine, as triethylamine, horse quinoline, piperazine etc.; In described solvent three, halohydrocarbon is as methylene dichloride, chloroform, tetracol phenixin etc.; Aromatic hydrocarbon is as toluene, dimethylbenzene, chlorobenzene etc.; Polar aprotic solvent is as DMF, methyl-sulphoxide etc.
Accompanying drawing explanation
Fig. 1 is employing the inventive method gained 4,5-dimethyl-2-(trimethyl silicon based) thiophene-3-methyl-formiate 1h-NMR collection of illustrative plates, 1h NMR (400MHz, CDCl 3) δ: 3.84 (s, 3H); 2.35 (s, 3H); 2.30 (s, 3H); 0.31 (s, 9H);
Fig. 2 is employing the inventive method gained 4,5-dimethyl-2-(trimethyl silicon based) thiophene-3-methyl-formiate 13c-NMR collection of illustrative plates, 13c NMR (100MHz, CDCl 3) δ: 165.1; 144.5; 138.6; 138.0; 136.6; 51.0; 13.7; 13.4; 0.0.GC-MS:m/z 242.0(M +,2%);227(100);197(34);179(29);
Fig. 3 is employing the inventive method gained N-allyl group-4,5-dimethyl-2-(trimethyl silicon based) thiophene-3-methane amide 1h-NMR collection of illustrative plates, Mp:85 ~ 87 DEG C; 1h NMR (300MHz, CDCl 3) δ: 5.97-5.86 (m, 1H); 5.67 (br s, 1H); 5.26 (apparent dq, j=17.1,1.4 Hz, 1H); 5.19 (apparent dq, j=10.2,1.2,1H); 4.04 (t, j=5.8,2H), 2.34 (s, 3H); 2.16 (s, 3H); 0.30 (s, 9H).GC-MS: m/z267 (M+, 2%);252 (100);211 (10), 194 (7)。Anal. Calcd for C 13H 21NOSSi: C, 58.38; H, 7.91; N, 5.24; S, 11.99. Found: C, 58.20; H, 8.05; N, 5.30; S,12.05。
Embodiment
The present invention is further illustrated by the following examples, but protection scope of the present invention is not limited thereto.
embodiment 1
A synthetic method for bactericide of silthiopham, the method comprises the following steps:
1) 3-(trimethyl silicon based) Methyl propiolate is prepared
By 0.84g(10mmol) Methyl propiolate and 1.41g(13mmol) trimethylchlorosilane puts into and fills in three mouthfuls of reaction flasks of 5mL methylene dichloride; slow dropping contains 1.0g(10mmol) the 5mL methylene dichloride mixing solutions of triethylamine; finish, reaction system is reflux 3 hours under nitrogen atmosphere protection.Room temperature is down to after reaction terminates, then 5mL water stirring and evenly mixing is added, stratification, after separating aqueous phase, organic phase anhydrous sodium sulfate drying, filtration, filtrate concentrates with Rotary Evaporators, and concentrated raffinate is separated with the moving phase silica gel column chromatography that ethyl acetate and sherwood oil volume ratio are 1:20-50, obtain 1.4g weak yellow liquid 3-(trimethyl silicon based) Methyl propiolate, yield 89%.
) prepare 4,5-dimethyl-2-(trimethyl silicon based) thiophene-3-methyl-formiate
By 1.56g(15mmol) 3-sulfydryl butanone and 1.56g(10mmol) 3-(trimethyl silicon based) Methyl propiolate puts into and fills in three mouthfuls of reaction flasks of 20mL toluene; add 0.5g (9mmol) sodium methylate again; finish, reaction system is heating reflux reaction 10 hours under nitrogen atmosphere protection.Reaction terminate after be down to room temperature, add 10mL water stir after stratification, after separating aqueous phase; Organic phase more respectively with 8mL saturated aqueous common salt wash twice, anhydrous sodium sulfate drying, filtration, filtrate concentrates with Rotary Evaporators, concentrated raffinate silica gel column chromatography is separated and obtains 2g weak yellow liquid 4,5-dimethyl-2-(trimethyl silicon based) thiophene-3-methyl-formiate, yield 83%, profiling results is shown in Fig. 1,2.
) prepare N-allyl group-4,5-dimethyl-2-(trimethyl silicon based) thiophene-3-methane amide
By 2.4g(10mmol) 4,5-dimethyl-2-(trimethyl silicon based) thiophene-3-methyl-formiate adds and is equipped with in three mouthfuls of reaction flasks of 10mL chloroform, then at room temperature drip 5mL with dropping funnel and be dissolved with 0.7g(12mmol) chloroformic solution of allylamine, drip and finish, reaction system reflux 15h.Be down to room temperature after reaction terminates, then add 8mL water stirring and evenly mixing, stratification, filter after organic phase anhydrous sodium sulfate drying, after filtrate is concentrated, obtain crude product.This crude product normal hexane recrystallization obtains 2.3g white needle-like crystals N-allyl group-4,5-dimethyl-2-(trimethyl silicon based) thiophene-3-methane amide, and yield 86%, profiling results is shown in Fig. 3.
embodiment 2
A synthetic method for bactericide of silthiopham, the method comprises the following steps:
1) 3-(trimethyl silicon based) Methyl propiolate is prepared
By 0.84g(10mmol) Methyl propiolate and 2.16g(20mmol) trimethylchlorosilane puts into and fills in three mouthfuls of reaction flasks of 10mL toluene; slow dropping contains the 5mL toluene mixed solution of 0.9g (10mmol) morpholine; finish, reaction system is reflux 8 hours under nitrogen atmosphere protection.Room temperature is down to after reaction terminates, then 10mL water stirring and evenly mixing is added, stratification, after separating aqueous phase, organic phase anhydrous sodium sulfate drying, filtration, filtrate concentrates with Rotary Evaporators, and concentrated raffinate is separated with the moving phase silica gel column chromatography that ethyl acetate and sherwood oil volume ratio are 1:20-50, obtain 1.2g weak yellow liquid 3-(trimethyl silicon based) Methyl propiolate, yield 77%.
) prepare 4,5-dimethyl-2-(trimethyl silicon based) thiophene-3-methyl-formiate
By 1.04g(10mmol) 3-sulfydryl butanone and 1.56g(10mmol) 3-(trimethyl silicon based) Methyl propiolate puts into and fills 30mL N; in three mouthfuls of reaction flasks of dinethylformamide; add 1.4g (10mmol) salt of wormwood again; finish, reaction system is heating reflux reaction 20 hours under nitrogen atmosphere protection.Reaction terminates negative pressure and steams solvent N, after dinethylformamide, be down to room temperature, through the washing of 10mL water, 30mL dichloromethane extraction, organic phase more respectively with 8mL saturated aqueous common salt wash twice, anhydrous sodium sulfate drying, filtration, filtrate concentrates with Rotary Evaporators, and concentrated raffinate silica gel column chromatography is separated and obtains 1.5g weak yellow liquid 4,5-dimethyl-2-(trimethyl silicon based) thiophene-3-methyl-formiate, yield 62%%, profiling results is shown in Fig. 1,2.
) prepare N-allyl group-4,5-dimethyl-2-(trimethyl silicon based) thiophene-3-methane amide
By 2.4g(10mmol) 4,5-dimethyl-2-(trimethyl silicon based) thiophene-3-methyl-formiate adds and is equipped with in three mouthfuls of reaction flasks of 15mL toluene, then at room temperature drip 5mL with dropping funnel and be dissolved with 1.14g(20mmol) toluene solution of allylamine, drip and finish, reaction system reflux 5h.Be down to room temperature after reaction terminates, then add 8mL water stirring and evenly mixing, stratification, filter after organic phase anhydrous sodium sulfate drying, after filtrate is concentrated, obtain crude product.This crude product normal hexane recrystallization obtains 2.4g white needle-like crystals N-allyl group-4,5-dimethyl-2-(trimethyl silicon based) thiophene-3-methane amide, and yield 90%, profiling results is shown in Fig. 3.
embodiment 3
A synthetic method for bactericide of silthiopham, the method comprises the following steps:
1) 3-(trimethyl silicon based) Methyl propiolate is prepared
By 0.84g(10mmol) Methyl propiolate and 1.08g(10mmol) trimethylchlorosilane puts into and fills 5mL N; in three mouthfuls of reaction flasks of dinethylformamide; slow dropping contains the 5mL N of 2.0g (20mmol) triethylamine; dinethylformamide mixing solutions; finish, reaction system is reflux 12 hours under nitrogen atmosphere protection.Reaction terminates rear negative pressure and steams solvent N, dinethylformamide, then room temperature is down to, through 10mL water washing, 30mL dichloromethane extraction, organic phase anhydrous sodium sulfate drying, filtration, filtrate concentrates with Rotary Evaporators, and concentrated raffinate is separated with the moving phase silica gel column chromatography that ethyl acetate and sherwood oil volume ratio are 1:20-50, obtain 1.1g weak yellow liquid 3-(trimethyl silicon based) Methyl propiolate, yield 71%.
) prepare 4,5-dimethyl-2-(trimethyl silicon based) thiophene-3-methyl-formiate
By 2.08g(20mmol) 3-sulfydryl butanone and 1.56g(10mmol) 3-(trimethyl silicon based) Methyl propiolate puts into and fills in three mouthfuls of reaction flasks of 20mL chloroform; add 0.4g (17mmol) sodium hydride again; finish, reaction system is heating reflux reaction 5 hours under nitrogen atmosphere protection.Room temperature is down to after reaction terminates, add the mixing of 10mL water, stratification, separate aqueous phase, organic phase more respectively with 8mL saturated aqueous common salt wash twice, anhydrous sodium sulfate drying, filtration, filtrate with Rotary Evaporators concentrate, concentrated raffinate silica gel column chromatography is separated and obtains 1.8g weak yellow liquid 4,5-dimethyl-2-(trimethyl silicon based) thiophene-3-methyl-formiate, yield 74%, profiling results is shown in Fig. 1,2.
) prepare N-allyl group-4,5-dimethyl-2-(trimethyl silicon based) thiophene-3-methane amide
By 2.4g(10mmol) 4,5-dimethyl-2-(trimethyl silicon based) thiophene-3-methyl-formiate adds and is equipped with in three mouthfuls of reaction flasks of 20mL ethanol, then at room temperature drip 10mL with dropping funnel and be dissolved with 0.7g(12mmol) ethanolic soln of allylamine, drip and finish, reaction system reflux 10h.Reaction terminates rear negative pressure and steams etoh solvent, and residue is down to room temperature, with 8mL water washing, 20mL dichloromethane extraction, filters after organic phase anhydrous sodium sulfate drying, obtains crude product after filtrate is concentrated.This crude product normal hexane recrystallization obtains 2.2g white needle-like crystals N-allyl group-4,5-dimethyl-2-(trimethyl silicon based) thiophene-3-methane amide, and yield 82%, profiling results is shown in Fig. 3.
embodiment 4
A synthetic method for bactericide of silthiopham, the method comprises the following steps:
1) 3-(trimethyl silicon based) Methyl propiolate is prepared
By 0.84g(10mmol) Methyl propiolate and 1.41g(13mmol) trimethylchlorosilane puts into and fills in three mouthfuls of reaction flasks of 15mL toluene; slow dropping contains the 5mL toluene mixed solution of 0.8g (9.5mmol) piperazine; finish, reaction system is reflux 8 hours under nitrogen atmosphere protection.Room temperature is down to after reaction terminates, then the mixing of 10mL water is added, stratification, organic phase anhydrous sodium sulfate drying, filtration, filtrate concentrates with Rotary Evaporators, concentrated raffinate is separated with the moving phase silica gel column chromatography that ethyl acetate and sherwood oil volume ratio are 1:20-50, obtains 1.3g weak yellow liquid 3-(trimethyl silicon based) Methyl propiolate, yield 83%.
) prepare 4,5-dimethyl-2-(trimethyl silicon based) thiophene-3-methyl-formiate
By 1.56g(15mmol) 3-sulfydryl butanone and 1.56g(10mmol) 3-(trimethyl silicon based) Methyl propiolate puts into and fills in three mouthfuls of reaction flasks of 20mL ethanol; add 0.14g (2mmol) sodium ethylate again; finish, reaction system is heating reflux reaction 10 hours under nitrogen atmosphere protection.Reaction terminates rear negative pressure and steams etoh solvent, and residue is down to room temperature, with 8mL water washing, 20mL dichloromethane extraction, after separating aqueous phase; Organic phase more respectively with 8mL saturated aqueous common salt wash twice, anhydrous sodium sulfate drying, filtration, filtrate concentrates with Rotary Evaporators, concentrated raffinate silica gel column chromatography is separated and obtains 1.6g weak yellow liquid 4,5-dimethyl-2-(trimethyl silicon based) thiophene-3-methyl-formiate, yield 66%, profiling results is shown in Fig. 1,2.
) prepare N-allyl group-4,5-dimethyl-2-(trimethyl silicon based) thiophene-3-methane amide
By 2.4g(10mmol) 4,5-dimethyl-2-(trimethyl silicon based) thiophene-3-methyl-formiate adds and is equipped with in three mouthfuls of reaction flasks of 20mL tetrahydrofuran (THF), then at room temperature drip 10mL with dropping funnel and be dissolved with 0.7g(12mmol) tetrahydrofuran solution of allylamine, drip and finish, reaction system reflux 8h.Reaction terminates rear negative pressure and steams solvents tetrahydrofurane, and residue is down to room temperature, with 8mL water washing, 20mL dichloromethane extraction, separates aqueous phase, filters after organic phase anhydrous sodium sulfate drying, obtains crude product after filtrate is concentrated.This crude product normal hexane recrystallization obtains 2.0g white needle-like crystals N-allyl group-4,5-dimethyl-2-(trimethyl silicon based) thiophene-3-methane amide, and yield 75%, profiling results is shown in Fig. 3.

Claims (4)

1. a synthetic method for bactericide of silthiopham, is characterized in that:
By 3-sulfydryl butanone and 3-(trimethyl silicon based) Methyl propiolate under protection of inert gas and alkaline catalysts effect in solvent two back flow reaction 5-20h, room temperature is down to after reaction terminates, washing, namely organic phase obtains 4,5-dimethyl-2-(trimethyl silicon based) thiophene-3-methyl-formiate through washing, dry, concentrated, column chromatography for separation; Or reaction terminates rear first negative pressure and steams solvent two, then be down to room temperature, washing, dichloromethane extraction, namely organic phase obtains 4,5-dimethyl-2-(trimethyl silicon based) thiophene-3-methyl-formiate through washing, dry, concentrated, column chromatography for separation; The molar ratio of described 3-sulfydryl butanone and 3-(trimethyl silicon based) Methyl propiolate is 1:0.5-1;
The back flow reaction 5-15h in solvent one by 4,5-dimethyl-2-(trimethyl silicon based) thiophene-3-methyl-formiate and allylamine, is down to room temperature after reaction terminates, washing, and namely organic phase drying, concentrated, recrystallization obtain Silthiopham; Or reaction terminates rear first negative pressure and steams solvent one, then be down to room temperature, washing, dichloromethane extraction, namely organic phase drying, concentrated, recrystallization obtain Silthiopham; The molar ratio of described 4,5-dimethyl-2-(trimethyl silicon based) thiophene-3-methyl-formiates and allylamine is 1:1-2, and described solvent one is one or more the mixture in halohydrocarbon, alcohols, aromatic hydrocarbon and polar aprotic solvent.
2. the synthetic method of bactericide of silthiopham as claimed in claim 1, it is characterized in that, described alkaline catalysts is one or more the mixture in alkaline carbonate, alkalimetal hydride and alkali metal alcoholates; Described solvent two is one or more the mixture in halohydrocarbon, alcohols, aromatic hydrocarbon and polar aprotic solvent.
3. the synthetic method of bactericide of silthiopham as claimed in claim 1, it is characterized in that, described 3-(trimethyl silicon based) Methyl propiolate is prepared through following method: by Methyl propiolate and trimethylchlorosilane under protection of inert gas and organic alkali catalyst effect in solvent three back flow reaction 3-12h, room temperature is down to after reaction terminates, washing, organic phase drying, concentrated, column chromatography for separation and get final product; Or reaction terminates rear first negative pressure and steams solvent three, then be down to room temperature, washing, dichloromethane extraction, organic phase drying, concentrated, column chromatography for separation and get final product; The molar ratio of described Methyl propiolate and trimethylchlorosilane is 1:1-2.
4. the synthetic method of bactericide of silthiopham as claimed in claim 3, it is characterized in that, described organic alkali catalyst is organic amine; Described solvent three is one or more the mixture in halohydrocarbon, aromatic hydrocarbon and polar aprotic solvent.
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CN105111229B (en) * 2015-06-08 2019-03-08 杭州师范大学 A kind of synthetic method of Silthiopham
CN105717210A (en) * 2016-01-30 2016-06-29 郭庆龙 Determination method for residual quantity of silthiopham in vegetables and fruits
CN105445400A (en) * 2016-01-30 2016-03-30 郭庆龙 GC-EI-MS measuring method for residual quantity of silthiopham
CN105548443A (en) * 2016-01-30 2016-05-04 郭庆龙 GC-MS/MS (gas chromatography-tandem mass spectrometry) fast measurement method for silthiopham residual quantity
CN105699522A (en) * 2016-01-30 2016-06-22 郭庆龙 GC-EI-MS (gas chromatography-electron impact ionization-mass spectrometry) quick measurement method for silthiopham residue
CN105628846A (en) * 2016-01-30 2016-06-01 郭庆龙 Method for determining silthiofam residues in fruits and vegetables by GC-EI-MS (gas chromatography-mass spectrometry with electron impact ionization)
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