CN103044479A - Synthetic method for bactericide of silthiopham - Google Patents
Synthetic method for bactericide of silthiopham Download PDFInfo
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Abstract
The invention relates to a synthetic method for bactericide of silthiopham, and the synthetic method comprises the following steps of: enabling 4,5-dimethyl-2-(trimethyl silica based) thiophene-3-methyl formate and allyl amine to flow back in a solvent I for reaction for 5-15 hours, cooling to room temperature after reaction, washing, and obtaining an organic phase through drying, concentration and recrystalization; or firstly evaporating the solvent I under negative pressure after reaction, then cooling to room temperature, washing, extracting dichloromethane, and obtaining the organic phase through drying, concentration and recrystalization, wherein the feeding molar ratio of 4,5-dimethyl-2-(trimethyl silica based) thiophene-3-methyl formate and allyl amine is 1:(1-2). The method has the characteristics that the raw material is cheap and easily available, the reaction temperature is mild, the reaction yield is high and the like, thus being applicable to large-scale production.
Description
Technical field
The invention belongs to technical field of organic synthesis, be specifically related to a kind of sterilant N-allyl group-4, the synthetic method of 5-dimethyl-2-(trimethyl silicon based) thiophene-3-methane amide (Silthiopham).
Background technology
Silthiopham be by About Monsanto Chemicals exploitation be used for preventing and treating the sterilant of take-all, the control of take-all is had unusual effect.Yet because its present synthesis technique exists the problems such as raw material supply and severe reaction conditions limiting it and applies.
US Patent No. 005486621A has reported its synthetic method, and the method is take 2-butanone, sulphur, cyanoacrylate etc. as starting raw material, has syntheticly obtained the purpose 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 has reported improved synthetic method, yet related important intermediate 3-(trimethyl silicon based) the propine acid amides of the method is synthetic, runs into very large challenge.Although this patent provides its multiple synthetic method, related synthetic method or raw material obtain difficulty, or need use butyllithium or amido lithium etc. to the highly basic of water and air sensitivity, are difficult to apply; In addition, because this intermediate has higher boiling point, its separation and purification has also run into difficulty.Document Organic Process Research ﹠amp; Development 6 (2002), 357-366 has reported new synthetic route, this synthetic method has been synthesized the purpose product take sulfydryl butanone, methoxy-methyl acrylate as starting raw material, although this process recovery ratio increases, but severe reaction conditions, still need use butyllithium or amido lithium (LDA) etc. to the dangerous raw material of air-sensitive, be difficult to scale production.
Summary of the invention
The object of the invention is to overcome the 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 raw material is cheap and easy to get, reaction conditions is gentle, the reaction yield high, is fit to large-scale production.
For achieving the above object, the present invention adopts following technical scheme:
A kind of synthetic method of sterilant Silthiopham, the method is: with 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, reaction is down to room temperature after finishing, washing, organic phase drying, concentrated, recrystallization and get final product; Or reaction finish after first negative pressure steam solvent one, be down to again room temperature, washing, dichloromethane extraction, organic phase drying, concentrated, recrystallization and get final product; Described 4, the molar ratio of 5-dimethyl-2-(trimethyl silicon based) thiophene-3-methyl-formiate 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 the polar aprotic solvent; The addition of solvent one is generally 5-10 times of reactant quality.In the described solvent one, halohydrocarbon such as methylene dichloride, chloroform, tetracol phenixin etc.; Alcohols such as methyl alcohol, ethanol, Virahol etc.; Aromatic hydrocarbon such as toluene, dimethylbenzene, chlorobenzene etc.; Polar aprotic solvent such as DMF, methyl-sulphoxide, tetrahydrofuran (THF) etc.
Described 4,5-dimethyl-2-(trimethyl silicon based) thiophene-3-methyl-formiate preferably makes through following method: with 3-sulfydryl butanone and 3-(trimethyl silicon based) Methyl propiolate under rare gas element (such as nitrogen etc.) protection and alkaline catalysts effect in solvent two back flow reaction 5-20h, reaction is down to room temperature after finishing, washing, organic phase is through washing, dry, concentrated, column chromatography for separation and get final product; Or reaction finish after first negative pressure steam solvent two, be down to again 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 the alkali metal alcoholates; Described solvent two is preferably one or more the mixture in halohydrocarbon, alcohols, aromatic hydrocarbon and the polar aprotic solvent; The consumption of described catalyzer is generally 0.2-2 times of 3-(trimethyl silicon based) Methyl propiolate quality; Described solvent two additions are generally 5-10 times of reactant quality.Alkaline carbonate such as yellow soda ash, sodium bicarbonate, salt of wormwood, saleratus etc.; Alkalimetal hydride such as sodium hydride, potassium hydride KH etc.; Alkali metal alcoholates such as sodium methylate, sodium ethylate, potassium methylate, potassium ethylate etc.In the described solvent two, halohydrocarbon such as methylene dichloride, chloroform, tetracol phenixin etc.; Alcohols such as methyl alcohol, ethanol, Virahol etc.; Aromatic hydrocarbon such as toluene, dimethylbenzene, chlorobenzene etc.; Polar aprotic solvent such as DMF, methyl-sulphoxide, tetrahydrofuran (THF) etc.
Described 3-(trimethyl silicon based) Methyl propiolate preferably makes through following method: with Methyl propiolate and trimethylchlorosilane under rare gas element (such as nitrogen etc.) protection and organic alkali catalyst effect in solvent three back flow reaction (generation condensation reaction) 3-12h, reaction is down to room temperature after finishing, washing, organic phase drying, concentrated, column chromatography for separation and get final product; Or reaction finish after first negative pressure steam solvent three, be down to again 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 the polar aprotic solvent.The consumption of described catalyzer is generally 0.2-2 times of Methyl propiolate quality; Described solvent three additions are generally 5-10 times of reactant quality.Described organic amine is such as triethylamine, horse quinoline, piperazine etc.; In the described solvent three, halohydrocarbon such as methylene dichloride, chloroform, tetracol phenixin etc.; Aromatic hydrocarbon such as toluene, dimethylbenzene, chlorobenzene etc.; Polar aprotic solvent such as DMF, methyl-sulphoxide etc.
Embodiment
Fig. 1 is for adopting the inventive method gained 4,5-dimethyl-2-(trimethyl silicon based) thiophene-3-methyl-formiate
1The H-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 for adopting the inventive method gained 4,5-dimethyl-2-(trimethyl silicon based) thiophene-3-methyl-formiate
13The C-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 for adopting the inventive method gained N-allyl group-4,5-dimethyl-2-(trimethyl silicon based) thiophene-3-methane amide
1The H-NMR collection of illustrative plates, Mp:85～87 ℃;
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/z?267?(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 to this.
Embodiment 1
A kind of synthetic method of sterilant Silthiopham, the method may further comprise the steps:
1) preparation 3-(trimethyl silicon based) Methyl propiolate
With 0.84g(10mmol) Methyl propiolate and 1.41g(13mmol) trimethylchlorosilane puts in three mouthfuls of reaction flasks that fill the 5mL methylene dichloride; slowly drip and contain 1.0g(10mmol) the 5mL methylene dichloride mixing solutions of triethylamine; finish reaction system reflux 3 hours under nitrogen atmosphere protection.Reaction is down to room temperature after finishing, then add 5mL water stirring and evenly mixing, standing demix, after telling water, organic phase is with anhydrous sodium sulfate drying, filtration, and filtrate is concentrated with Rotary Evaporators, and concentrated raffinate separates with silica gel column chromatography take ethyl acetate and sherwood oil volume ratio as the moving phase of 1:20-50, get 1.4g weak yellow liquid 3-(trimethyl silicon based) Methyl propiolate, yield 89%.
) preparation 4,5-dimethyl-2-(trimethyl silicon based) thiophene-3-methyl-formiate
With 1.56g(15mmol) 3-sulfydryl butanone and 1.56g(10mmol) 3-(trimethyl silicon based) Methyl propiolate puts in three mouthfuls of reaction flasks that fill 20mL toluene; add again 0.5g (9mmol) sodium methylate; finish reaction system heating reflux reaction 10 hours under nitrogen atmosphere protection.Be down to room temperature after reaction finishes, add the 10mL water rear standing demix that stirs, tell water after; Organic phase is used respectively 8mL saturated aqueous common salt washed twice, anhydrous sodium sulfate drying, filtration again, filtrate is concentrated with Rotary Evaporators, concentrated raffinate obtains 2g weak yellow liquid 4 with the silica gel column chromatography separation, 5-dimethyl-2-(trimethyl silicon based) thiophene-3-methyl-formiate, yield 83%, collection of illustrative plates the results are shown in Figure 1,2.
) preparation N-allyl group-4,5-dimethyl-2-(trimethyl silicon based) thiophene-3-methane amide
With 2.4g(10mmol) 4,5-dimethyl-2-(trimethyl silicon based) thiophene-3-methyl-formiate adding 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 finishes, then add 8mL water stirring and evenly mixing, standing demix, organic phase is filtered after with anhydrous sodium sulfate drying, obtains crude product after filtrate is concentrated.This crude product gets 2.3g white needle-like crystals N-allyl group-4 with the normal hexane recrystallization, 5-dimethyl-2-(trimethyl silicon based) thiophene-3-methane amide, and yield 86%, collection of illustrative plates the results are shown in Figure 3.
Embodiment 2
A kind of synthetic method of sterilant Silthiopham, the method may further comprise the steps:
1) preparation 3-(trimethyl silicon based) Methyl propiolate
With 0.84g(10mmol) Methyl propiolate and 2.16g(20mmol) trimethylchlorosilane puts in three mouthfuls of reaction flasks that fill 10mL toluene; slowly drip the 5mL toluene mixing solutions that contains 0.9g (10mmol) morpholine; finish reaction system reflux 8 hours under nitrogen atmosphere protection.Reaction is down to room temperature after finishing, then add 10mL water stirring and evenly mixing, standing demix, after telling water, organic phase is with anhydrous sodium sulfate drying, filtration, and filtrate is concentrated with Rotary Evaporators, and concentrated raffinate separates with silica gel column chromatography take ethyl acetate and sherwood oil volume ratio as the moving phase of 1:20-50, get 1.2g weak yellow liquid 3-(trimethyl silicon based) Methyl propiolate, yield 77%.
) preparation 4,5-dimethyl-2-(trimethyl silicon based) thiophene-3-methyl-formiate
With 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 again 1.4g (10mmol) salt of wormwood; finish reaction system heating reflux reaction 20 hours under nitrogen atmosphere protection.Reaction finishes negative pressure and steams solvent N, behind the dinethylformamide, be down to room temperature, through the washing of 10mL water, 30mL dichloromethane extraction, organic phase is used respectively 8mL saturated aqueous common salt washed twice, anhydrous sodium sulfate drying, filtration again, filtrate is concentrated with Rotary Evaporators, and concentrated raffinate obtains 1.5g weak yellow liquid 4,5-dimethyl-2-(trimethyl silicon based) thiophene-3-methyl-formiate with the silica gel column chromatography separation, yield 62%%, collection of illustrative plates the results are shown in Figure 1,2.
) preparation N-allyl group-4,5-dimethyl-2-(trimethyl silicon based) thiophene-3-methane amide
With 2.4g(10mmol) 4,5-dimethyl-2-(trimethyl silicon based) thiophene-3-methyl-formiate adding 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 finishes, then add 8mL water stirring and evenly mixing, standing demix, organic phase is filtered after with anhydrous sodium sulfate drying, obtains crude product after filtrate is concentrated.This crude product gets 2.4g white needle-like crystals N-allyl group-4 with the normal hexane recrystallization, 5-dimethyl-2-(trimethyl silicon based) thiophene-3-methane amide, and yield 90%, collection of illustrative plates the results are shown in Figure 3.
Embodiment 3
A kind of synthetic method of sterilant Silthiopham, the method may further comprise the steps:
1) preparation 3-(trimethyl silicon based) Methyl propiolate
With 0.84g(10mmol) Methyl propiolate and 1.08g(10mmol) trimethylchlorosilane puts into and fills 5mL N; in three mouthfuls of reaction flasks of dinethylformamide; slowly drip the 5mL N that contains 2.0g (20mmol) triethylamine; the dinethylformamide mixing solutions; finish reaction system reflux 12 hours under nitrogen atmosphere protection.Negative pressure steamed solvent N after reaction finished, dinethylformamide, then be down to room temperature, through 10mL water washing, 30mL dichloromethane extraction, organic phase is with anhydrous sodium sulfate drying, filtration, and filtrate is concentrated with Rotary Evaporators, and concentrated raffinate separates with silica gel column chromatography take ethyl acetate and sherwood oil volume ratio as the moving phase of 1:20-50, get 1.1g weak yellow liquid 3-(trimethyl silicon based) Methyl propiolate, yield 71%.
) preparation 4,5-dimethyl-2-(trimethyl silicon based) thiophene-3-methyl-formiate
With 2.08g(20mmol) 3-sulfydryl butanone and 1.56g(10mmol) 3-(trimethyl silicon based) Methyl propiolate puts in three mouthfuls of reaction flasks that fill the 20mL chloroform; add again 0.4g (17mmol) sodium hydride; finish reaction system heating reflux reaction 5 hours under nitrogen atmosphere protection.Reaction is down to room temperature after finishing, add 10mL water mixing, standing demix, tell water, organic phase is used respectively 8mL saturated aqueous common salt washed twice, anhydrous sodium sulfate drying, filtration again, and filtrate is concentrated with Rotary Evaporators, concentrated raffinate obtains 1.8g weak yellow liquid 4 with the silica gel column chromatography separation, 5-dimethyl-2-(trimethyl silicon based) thiophene-3-methyl-formiate, yield 74%, collection of illustrative plates the results are shown in Figure 1,2.
) preparation N-allyl group-4,5-dimethyl-2-(trimethyl silicon based) thiophene-3-methane amide
With 2.4g(10mmol) 4,5-dimethyl-2-(trimethyl silicon based) thiophene-3-methyl-formiate adding 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.Negative pressure steamed etoh solvent after reaction finished, and residue is down to room temperature, and with 8mL water washing, 20mL dichloromethane extraction, organic phase is filtered after with anhydrous sodium sulfate drying, obtains crude product after filtrate is concentrated.This crude product gets 2.2g white needle-like crystals N-allyl group-4 with the normal hexane recrystallization, 5-dimethyl-2-(trimethyl silicon based) thiophene-3-methane amide, and yield 82%, collection of illustrative plates the results are shown in Figure 3.
A kind of synthetic method of sterilant Silthiopham, the method may further comprise the steps:
1) preparation 3-(trimethyl silicon based) Methyl propiolate
With 0.84g(10mmol) Methyl propiolate and 1.41g(13mmol) trimethylchlorosilane puts in three mouthfuls of reaction flasks that fill 15mL toluene; slowly drip the 5mL toluene mixing solutions that contains 0.8g (9.5mmol) piperazine; finish reaction system reflux 8 hours under nitrogen atmosphere protection.Reaction is down to room temperature after finishing, then add 10mL water mixing, standing demix, organic phase anhydrous sodium sulfate drying, filtration, filtrate is concentrated with Rotary Evaporators, concentrated raffinate separates with silica gel column chromatography as the moving phase of 1:20-50 with the sherwood oil volume ratio take ethyl acetate, gets 1.3g weak yellow liquid 3-(trimethyl silicon based) Methyl propiolate, yield 83%.
) preparation 4,5-dimethyl-2-(trimethyl silicon based) thiophene-3-methyl-formiate
With 1.56g(15mmol) 3-sulfydryl butanone and 1.56g(10mmol) 3-(trimethyl silicon based) Methyl propiolate puts in three mouthfuls of reaction flasks that fill 20mL ethanol; add again 0.14g (2mmol) sodium ethylate; finish reaction system heating reflux reaction 10 hours under nitrogen atmosphere protection.Negative pressure steamed etoh solvent after reaction finished, and residue is down to room temperature, with 8mL water washing, 20mL dichloromethane extraction, tell water after; Organic phase is used respectively 8mL saturated aqueous common salt washed twice, anhydrous sodium sulfate drying, filtration again, filtrate is concentrated with Rotary Evaporators, concentrated raffinate obtains 1.6g weak yellow liquid 4 with the silica gel column chromatography separation, 5-dimethyl-2-(trimethyl silicon based) thiophene-3-methyl-formiate, yield 66%, collection of illustrative plates the results are shown in Figure 1,2.
) preparation N-allyl group-4,5-dimethyl-2-(trimethyl silicon based) thiophene-3-methane amide
With 2.4g(10mmol) 4,5-dimethyl-2-(trimethyl silicon based) thiophene-3-methyl-formiate adding 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.Negative pressure steamed solvents tetrahydrofurane after reaction finished, and residue is down to room temperature, with 8mL water washing, 20mL dichloromethane extraction, told water, and organic phase is filtered after with anhydrous sodium sulfate drying, obtains crude product after filtrate is concentrated.This crude product gets 2.0g white needle-like crystals N-allyl group-4 with the normal hexane recrystallization, 5-dimethyl-2-(trimethyl silicon based) thiophene-3-methane amide, and yield 75%, collection of illustrative plates the results are shown in Figure 3.
Claims (6)
1. the synthetic method of a sterilant Silthiopham is characterized in that, with 4,5-dimethyl-2-(trimethyl silicon based) thiophene-3-methyl-formiate and allylamine back flow reaction 5-15h in solvent one, after finishing, reaction is down to room temperature, washing, organic phase drying, concentrated, recrystallization and get final product; Or reaction finish after first negative pressure steam solvent one, be down to again room temperature, washing, dichloromethane extraction, organic phase drying, concentrated, recrystallization and get final product; Described 4, the molar ratio of 5-dimethyl-2-(trimethyl silicon based) thiophene-3-methyl-formiate and allylamine is 1:1-2.
2. the synthetic method of sterilant Silthiopham as claimed in claim 1 is characterized in that, described solvent one is one or more the mixture in halohydrocarbon, alcohols, aromatic hydrocarbon and the polar aprotic solvent.
3. the synthetic method of sterilant Silthiopham as claimed in claim 1, it is characterized in that, described 4,5-dimethyl-2-(trimethyl silicon based) thiophene-3-methyl-formiate makes through following method: with 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, reaction is down to room temperature after finishing, washing, organic phase is through washing, dry, concentrated, column chromatography for separation and get final product; Or reaction finish after first negative pressure steam solvent two, be down to again 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.
4. the synthetic method of sterilant Silthiopham as claimed in claim 3 is characterized in that, described alkaline catalysts is one or more the mixture in alkaline carbonate, alkalimetal hydride and the alkali metal alcoholates; Described solvent two is one or more the mixture in halohydrocarbon, alcohols, aromatic hydrocarbon and the polar aprotic solvent.
5. the synthetic method of sterilant Silthiopham as claimed in claim 3, it is characterized in that, described 3-(trimethyl silicon based) Methyl propiolate makes through following method: with Methyl propiolate and trimethylchlorosilane under protection of inert gas and organic alkali catalyst effect in solvent three back flow reaction 3-12h, reaction is down to room temperature after finishing, washing, organic phase drying, concentrated, column chromatography for separation and get final product; Or reaction finish after first negative pressure steam solvent three, be down to again 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.
6. the synthetic method of sterilant Silthiopham as claimed in claim 5 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 the polar aprotic solvent.
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| CN105111229A (en) * | 2015-06-08 | 2015-12-02 | 杭州师范大学 | Synthetic method for silthiopham |
| 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 |
| 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) |
| 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 |
| CN105717210A (en) * | 2016-01-30 | 2016-06-29 | 郭庆龙 | Determination method for residual quantity of silthiopham in vegetables and fruits |
| CN105717218A (en) * | 2016-01-30 | 2016-06-29 | 郭庆龙 | GC-MS/MS determining method for residual silthiopham quantity |
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| 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 |
| 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) |
| 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 |
| CN105717210A (en) * | 2016-01-30 | 2016-06-29 | 郭庆龙 | Determination method for residual quantity of silthiopham in vegetables and fruits |
| CN105717218A (en) * | 2016-01-30 | 2016-06-29 | 郭庆龙 | GC-MS/MS determining method for residual silthiopham quantity |
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