CN104710332B - A kind of preparation method of thiazolinyl sulfide - Google Patents
A kind of preparation method of thiazolinyl sulfide Download PDFInfo
- Publication number
- CN104710332B CN104710332B CN201510085261.2A CN201510085261A CN104710332B CN 104710332 B CN104710332 B CN 104710332B CN 201510085261 A CN201510085261 A CN 201510085261A CN 104710332 B CN104710332 B CN 104710332B
- Authority
- CN
- China
- Prior art keywords
- methyl
- milligrams
- formula
- formulas
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 0 CC(C)SC1=CC=*CC1 Chemical compound CC(C)SC1=CC=*CC1 0.000 description 1
Landscapes
- Catalysts (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses the preparation method of a kind of thiazolinyl sulfide: the styrenic derivatives shown in Formulas I adds the disulfide compound shown in Formula II, with dimethyl sulfoxide as reaction dissolvent, and under the effect of elemental iodine catalyst and copper catalyst, under air atmosphere reacting by heating, after reaction terminates, gained reactant liquor post processing prepares the thiazolinyl sulfide shown in formula III.The inventive method is raw materials used cheap, low cost, and productivity is high, and flow process is simple.
Description
Technical field
The present invention relates to the preparation method of a kind of sulfide, a kind of stereoselective trans thiazolinyl sulfide
Preparation method.
Background technology
Thiazolinyl sulfide is important synthetic intermediate, is widely present in many natural products, is also that many has biology
The construction unit generally existed in the compound of activity.
Document Lee, C.-F. (Org.Lett.2011,13,5204) disclose the C-S by copper catalyzed ethylene halogen Yu mercaptan
Coupling efficiently synthesizes thiazolinyl sulfide, and its method includes preparation process and purifies deduction process.
One, preparation process is as follows:
With 4-iodine methylene-1-t-butylcyclohexane as substrate (0.6mmol), addition cyclohexanethiol (0.5mmol),
Cu2O (0.5mol%), KOH (1mmol), with dioxane (0.25mL) as solvent, then react 12h at 110 DEG C, obtain trans
[cyclohexyl] [(4 '-tert-butyl group) cyclohexyl alkene methyl] thick product of thioether.
Two, purification process is as follows:
Thick product is cooled down, vacuum filtration, remove solid with ethyl acetate eluting and obtain thick liquid, concentrate, make with petroleum ether
For flowing phase, obtain pure trans [cyclohexyl] [(4 '-tert-butyl group) cyclohexyl alkene methyl] thioether by post layer chromatography.
Above-mentioned synthetic method has the advantage that combined coefficient is high, but the method needs relatively costly mercaptan or thiophenol；
Additionally, the substrate vinyl halide that the method is selected is costly, therefore use above-mentioned synthetic method relatively costly, be unfavorable for industrialization
Universal.
Summary of the invention
Purpose: in order to overcome the deficiencies in the prior art, the invention provides the trans thiazolinyl sulfide of a kind of low cost
Preparation method.
To achieve these goals, the technical solution used in the present invention is:
The preparation method of a kind of thiazolinyl sulfide, described method is: add Formula II in the styrenic derivatives shown in Formulas I
Shown disulfide compound, with dimethyl sulfoxide as reaction dissolvent, and in elemental iodine catalyst and the effect of copper catalyst
Under, reacting by heating under air atmosphere, after reaction terminates, gained reactant liquor post processing prepares the thiazolinyl sulfide shown in formula III；
The chemical equation of the present invention is as follows:
In Formulas I or formula III, R1For methyl, the tert-butyl group, fluorine, chlorine or hydrogen；
In Formula II or formula III, R2For methyl, fluorine, chlorine or hydrogen.
R in Formula II, on different phenyl ring2Represent identical group.
Preferably R1For hydrogen, 2-methyl, 3-methyl, 4-methyl, 4-chlorine or the 4-tert-butyl group.
Preferably R2For hydrogen, 2-methyl, 3-methyl, 4-methyl, 4-chlorine, 2-fluorine or 4-fluorine.
Styrenic derivatives shown in described Formulas I with the ratio of the amount of the material of the disulfide compound shown in Formula II is
1∶0.5。
Described copper catalyst is copper trifluoromethanesulfcomposite Cu (OTf)2, Schweinfurt green Cu (OAc)2, acetylacetone copper Cu (acac)2、
Hydro-Giene (Water Science). CuI, Cu-lyt. CuCl or copper oxide CuO, preferably Cu (OTf)2。
Styrenic derivatives shown in described Formulas I, the ratio of amount of material of copper catalyst are 1: 0.1～0.3, preferably 1:
0.1。
Styrenic derivatives shown in described Formulas I, the ratio of amount of material of elemental iodine catalyst are 1: 1～1.5, preferably
1∶1。
The reaction temperature of the present invention is generally 120～150 DEG C, preferably 120 DEG C, and the response time is generally 5～10h, excellent
Elect 6h as.
The volumetric usage of described dimethyl sulfoxide is typically calculated as 3 with the amount of the material of the styrenic derivatives shown in Formulas I
～10mL/mmol.
Described reactant liquor post-processing approach is: after reaction terminates, reacting liquid filtering, and unnecessary iodine and molten is removed in filtrate water eccysis
Agent, distills after merging organic facies, and gained residue uses silica gel column chromatography, and eluant is petroleum ether, and TLC detects eluent, receives
Collection merges the eluent containing product, and distillation and concentration removes solvent, vacuum drying, prepares the thiazolinyl sulfide shown in formula III.
The substrate that the present invention uses is styrene or derivatives thereof, disulfide analog derivative, and copper catalyst used
Cu(OTf)2, elemental iodine etc. be usual products, price benzenethiol more of the prior art or thiophenol, vinyl halide are just
Preferably, the preparation method of thiazolinyl sulfide of the present invention has the advantage that technological process is simple, low cost, productivity are high, additionally, the present invention
Preparation process pollute few, atom economy utilization rate is high, and synthetic system is cheap.
Detailed description of the invention
With specific embodiment, technical scheme is described further below, but protection scope of the present invention is not
It is limited to this.
Embodiment one:
By 52 milligrams of (0.5mmol) styrene, 54.5 milligrams of (0.25mmol) diphenyl disulfides, 18.1 milligrams
(0.05mmol)Cu(OTf)2, 127 milligrams of (0.5mmol) elemental iodines add in reaction tubes, add 2mL DMSO, 120 DEG C
Heating 6 hours, reaction cools down after terminating, and filters, and unnecessary iodine and solvent are removed in filtrate water eccysis, merges organic facies and distills, institute
Obtaining residue silica gel column chromatography, petroleum ether drip washing, TLC detects, and merges the effluent containing product, and Rotary Evaporators distillation removes
Solvent, vacuum drying is gone to obtain yellow liquid 78.4 milligrams trans-2-thiophenyl styrene, productivity 74%.
Embodiment two:
By 59 milligrams of (0.5mmol) 2-methyl styrenes, 54.5 milligrams of (0.25mmol) diphenyl disulfides, 18.1 milligrams
(0.05mmol)Cu(OTf)2, 127 milligrams of (0.5mmol) elemental iodines add in reaction tubes, add 2mL DMSO, 120 DEG C
Heating 6 hours, reaction cools down after terminating, and filters, and unnecessary iodine and solvent are removed in filtrate water eccysis, merges organic facies and distills, institute
Obtaining residue silica gel column chromatography, petroleum ether drip washing, TLC detects, and merges the effluent containing product, and Rotary Evaporators distillation removes
Remove solvent, vacuum drying obtain yellow liquid 85.8 milligrams trans-(2 '-methyl)-2-thiophenyl styrene, productivity 76%.1H
NMR (500MHz, CDCl3) δ 7.42-7.40 (m, 3H), 7.34-7.31 (m, 2H), 7.25-7.23 (m, 1H), 7.16-7.14
(m, 3H), 6.97 (d, J=15.0Hz, 1H), 6.78 (d, J=15.0Hz, 1H), 2.33 (s, 3H)；13C NMR (125MHz,
CDCl3) δ 135.6,135.5,135.1,130.4,130.0,129.6,129.1,127.6,126.8,126.2,125.4,
124.3,19.8；LRMS (EI, 70eV) m/z (%): 226 (M+, 100), 211 (43), 178 (34).
Embodiment three:
By 59 milligrams of (0.5mmol) 3-methyl styrenes, 54.5 milligrams of (0.25mmol) diphenyl disulfides, 18.1 milligrams
(0.05mmol)Cu(OTf)2, 127 milligrams of (0.5mmol) elemental iodines add in reaction tubes, add 2mL DMSO, 120 DEG C
Heating 6 hours, reaction cools down after terminating, and filters, and unnecessary iodine and solvent are removed in filtrate water eccysis, merges organic facies and distills, institute
Obtaining residue silica gel column chromatography, petroleum ether drip washing, TLC detects, and merges the effluent containing product, and Rotary Evaporators distillation removes
Remove solvent, vacuum drying obtain yellow liquid 71.2 milligrams trans-(3 '-methyl)-2-thiophenyl styrene, productivity 63%.1H
NMR (500MHz, CDCl3) δ 7.42-7.40 (m, 2H), 7.35-7.32 (m, 2H), 7.26-7.24 (m, 2H), 7.20-7.19
(m, 1H), 7.16-7.14 (m, 2H), 7.06-7.04 (M, 1H) 6.86 (d, J=15.5Hz, 1H), 6.71 (d, J=15.5Hz,
1H), 2.33 (s, 3H)；13C NMR (125MHz, CDCl3) δ 138.3,136.5,135.4,132.1,129.8,129.1,
128.6,126.9,126.7,123.2,123.1；LRMS (EI, 70eV) m/z (%): 226 (M+, 100), 211 (30), 178
(30)。
Embodiment four:
By 59 milligrams of (0.5mmol) 4-methyl styrenes, 54.5 milligrams of (0.25mmol) diphenyl disulfides, 18.1 milligrams
(0.05mmol)Cu(OTf)2, 127 milligrams of (0.5mmol) elemental iodines add in reaction tubes, add 2mL DMSO, 120 DEG C
Heating 6 hours, reaction cools down after terminating, and filters, and unnecessary iodine and solvent are removed in filtrate water eccysis, merges organic facies and distills, institute
Obtaining residue silica gel column chromatography, petroleum ether drip washing, TLC detects, and merges the effluent containing product, and Rotary Evaporators distillation removes
Remove solvent, vacuum drying obtain yellow liquid 91.5 milligrams trans-(4 '-methyl)-2-thiophenyl styrene, productivity 81%.1H
NMR (500MHz, CDCl3) δ 7.40-7.37 (m, 2H), 7.33-7.30 (m, 2H), 7.24-7.21 (m, 3H), 7.12-7.09
(m, 2H), 6.81 (d, J=15.5Hz, 1H), 6.738 (d, J=15.5Hz, 1H), 2.32 (s, 3H)；13C NMR (125MHz,
CDCl3) δ 137.5,135.6,133.8,132.4,129.6,129.4,129.1,126.7,126.0,121.9,21.2；LRMS
(EI, 70eV) m/z (%): 226 (M+, 100), 211 (64), 178 (40).
Embodiment five:
By 80 milligrams of (0.5mmol) 4-t-butyl styrene, 54.5 milligrams of (0.25mmol) diphenyl disulfides, 18.1 milligrams
(0.05mmol)Cu(OTf)2, 127 milligrams of (0.5mmol) elemental iodines add in reaction tubes, add 2mL DMSO, 120 DEG C
Heating 6 hours, reaction cools down after terminating, and filters, and unnecessary iodine and solvent are removed in filtrate water eccysis, merges organic facies and distills, institute
Obtaining residue silica gel column chromatography, petroleum ether drip washing, TLC detects, and merges the effluent containing product, and Rotary Evaporators distillation removes
Remove solvent, vacuum drying obtain yellow liquid 92.4 milligrams trans-(4 '-tert-butyl group)-2-thiophenyl styrene, productivity 69%.1H NMR (500MHz, CDCl3) δ 7.40-7.38 (m, 2H), 7.35-7.29 (m, 6H), 7.25-7.21 (m, 1H), 6.83 (d, J
=15.5Hz, 1H), 6.75 (d, J=15.5Hz, 1H), 1.31 (s, 9H)；13C NMR (125MHz, CDCl3) δ 150.9,
135.7,133.8,132.4,129.5,129.1,126.7,125.8,125.6,122.1,34.6,31.2；LRMS (EI, 70eV)
M/z (%): 268 (M+, 80), 253 (100).
Embodiment six:
By 69.5 milligrams of (0.5mmol) 4-chlorostyrenes, 54.5 milligrams of (0.25mmol) diphenyl disulfides, 18.1 milligrams
(0.05mmol)Cu(OTf)2, 127 milligrams of (0.5mmol) elemental iodines add in reaction tubes, add 2mL DMSO, 120 DEG C
Heating 6 hours, reaction cools down after terminating, and filters, and unnecessary iodine and solvent are removed in filtrate water eccysis, merges organic facies and distills, institute
Obtaining residue silica gel column chromatography, petroleum ether drip washing, TLC detects, and merges the effluent containing product, and Rotary Evaporators distillation removes
Removing solvent, vacuum drying obtains yellow solid, and mp 48-49 DEG C 82.4 milligrams is trans-(2 '-chlorine)-2-thiophenyl styrene, produces
Rate 67%.
Embodiment seven:
By 52 milligrams of (0.5mmol) styrene, 61.5 milligrams of (0.25mmol) 4,4 '-dimethyl diphenyl disulfide, 18.1
Milligram (0.05mmol) Cu (OTf)2, 127 milligrams of (0.5mmol) elemental iodines add in reaction tube, add 2mL DMSO,
120 DEG C are heated 6 hours, and reaction cools down after terminating, and filters, and unnecessary iodine and solvent are removed in filtrate water eccysis, merges organic facies and steams
Evaporating, gained residue silica gel column chromatography, petroleum ether drip washing, TLC detects, and merges the effluent containing product, Rotary Evaporators
Solvent is distilled off, and vacuum drying obtains 71.2 milligrams of trans-2-(4 '-methyl)-thiophenyl styrene of yellow liquid, productivity
63%.
Embodiment eight:
By 52 milligrams of (0.5mmol) styrene, 61.5 milligrams of (0.25mmol) 3,3 '-dimethyl diphenyl disulfide, 18.1
Milligram (0.05mmol) Cu (OTf)2, 127 milligrams of (0.5mmol) elemental iodines add in reaction tube, add 2mL DMSO,
120 DEG C are heated 6 hours, and reaction cools down after terminating, and filters, and unnecessary iodine and solvent are removed in filtrate water eccysis, merges organic facies and steams
Evaporating, gained residue silica gel column chromatography, petroleum ether drip washing, TLC detects, and merges the effluent containing product, Rotary Evaporators
Solvent is distilled off, and vacuum drying obtains 65.5 milligrams of trans-2-(3 '-methyl)-thiophenyl styrene of yellow liquid, productivity
58%.
Embodiment nine:
By 52 milligrams of (0.5mmol) styrene, 61.5 milligrams of (0.25mmol) 2,2 '-dimethyl diphenyl disulfide, 18.1
Milligram (0.05mmol) Cu (OTf)2, 127 milligrams of (0.5mmol) elemental iodines add in reaction tube, add 2mL DMSO,
120 DEG C are heated 6 hours, and reaction cools down after terminating, and filters, and unnecessary iodine and solvent are removed in filtrate water eccysis, merges organic facies and steams
Evaporating, gained residue silica gel column chromatography, petroleum ether drip washing, TLC detects, and merges the effluent containing product, Rotary Evaporators
Solvent is distilled off, and vacuum drying obtains 58.7 milligrams of trans-2-(2 '-methyl)-thiophenyl styrene of yellow liquid, productivity
52%.
Embodiment ten:
By 52 milligrams of (0.5mmol) styrene, 63.5 milligrams of (0.25mmol) 4,4 '-difluorodiphenyl disulfide, 18.1 millis
Gram (0.05mmol) Cu (OTf)2, 127 milligrams of (0.5mmol) elemental iodines add in reaction tubes, add 2mL DMSO, and 120
DEG C heating 6 hours, reaction cools down after terminating, and filters, and unnecessary iodine and solvent are removed in filtrate water eccysis, merges organic facies and also distills,
Gained residue silica gel column chromatography, petroleum ether drip washing, TLC detects, and merges the effluent containing product, and Rotary Evaporators distills
Removing solvent, vacuum drying obtains 70.1 milligrams of trans-2-(4 '-fluorine)-thiophenyl styrene of yellow liquid, productivity 61%.
Embodiment 11:
By 52 milligrams of (0.5mmol) styrene, 63.5 milligrams of (0.25mmol) 2,2 '-difluorodiphenyl disulfide, 18.1 millis
Gram (0.05mmol) Cu (OTf)2, 127 milligrams of (0.5mmol) elemental iodines add in reaction tubes, add 2mL DMSO, and 120
DEG C heating 6 hours, reaction cools down after terminating, and filters, and unnecessary iodine and solvent are removed in filtrate water eccysis, merges organic facies and also distills,
Gained residue silica gel column chromatography, petroleum ether drip washing, TLC detects, and merges the effluent containing product, and Rotary Evaporators distills
Removing solvent, vacuum drying obtains 87.4 milligrams of trans-2-(2 '-fluorine)-thiophenyl styrene of yellow liquid, productivity 76%.
Embodiment 12:
By 52 milligrams of (0.5mmol) styrene, 71.7 milligrams of (0.25mmol) 4,4 '-dichloro disulfide, 18.1 millis
Gram (0.05mmol) Cu (OTf)2, 127 milligrams of (0.5mmol) elemental iodines add in reaction tubes, add 2mL DMSO, and 120
DEG C heating 6 hours, reaction cools down after terminating, and filters, and unnecessary iodine and solvent are removed in filtrate water eccysis, merges organic facies and also distills,
Gained residue silica gel column chromatography, petroleum ether drip washing, TLC detects, and merges the effluent containing product, and Rotary Evaporators distills
Removing solvent, vacuum drying obtains 86.1 milligrams of trans-2-(4 '-chlorine)-thiophenyl styrene of yellow liquid, productivity 70%.
Claims (8)
1. the preparation method of a thiazolinyl sulfide, it is characterised in that described method is: in the styrenic derivatives shown in Formulas I
Add the disulfide compound shown in Formula II, with dimethyl sulfoxide as reaction dissolvent, and be catalyzed at elemental iodine catalyst and copper
Reacting by heating under the effect of agent, under air atmosphere, after reaction terminates, gained reactant liquor post processing prepares the thiazolinyl shown in formula III
Sulfide；Described copper catalyst is copper trifluoromethanesulfcomposite；
In Formulas I or formula III, R1For methyl, the tert-butyl group, fluorine, chlorine or hydrogen；
In Formula II or formula III, R2For methyl, fluorine, chlorine or hydrogen；
R in Formula II, on different phenyl ring2Represent identical group.
2. the method for claim 1, it is characterised in that described R1For hydrogen, 2-methyl, 3-methyl, 4-methyl, 4-chlorine or 4-
The tert-butyl group.
3. the method for claim 1, it is characterised in that described R2For hydrogen, 2-methyl, 3-methyl, 4-methyl, 4-chlorine, 2-
Fluorine or 4-fluorine.
4. the method for claim 1, it is characterised in that shown in the styrenic derivatives shown in described Formulas I and Formula II
The ratio of the amount of the material of disulfide compound is 1:0.5.
5. the method for claim 1, it is characterised in that styrenic derivatives shown in described Formulas I, copper catalyst
The ratio of the amount of material is 1:0.1～0.3.
6. the method for claim 1, it is characterised in that the styrenic derivatives shown in described Formulas I, elemental iodine are catalyzed
The ratio of the amount of the material of agent is 1:1～1.5.
7. the method for claim 1, it is characterised in that described reaction temperature is 120～150 DEG C, the response time be 5～
10h。
8. the method for claim 1, it is characterised in that described reactant liquor post-processing approach is: after reaction terminates, reaction
Liquid filters, and unnecessary iodine and solvent are removed in filtrate water eccysis, distills after merging organic facies, and gained residue uses silica gel column chromatography,
Eluant is petroleum ether, and TLC detects eluent, collects and merges the eluent containing product, and distillation and concentration removes solvent, and vacuum is done
Dry, prepare the thiazolinyl sulfide shown in formula III.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510085261.2A CN104710332B (en) | 2015-02-17 | 2015-02-17 | A kind of preparation method of thiazolinyl sulfide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510085261.2A CN104710332B (en) | 2015-02-17 | 2015-02-17 | A kind of preparation method of thiazolinyl sulfide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104710332A CN104710332A (en) | 2015-06-17 |
| CN104710332B true CN104710332B (en) | 2017-01-04 |
Family
ID=53410123
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510085261.2A Expired - Fee Related CN104710332B (en) | 2015-02-17 | 2015-02-17 | A kind of preparation method of thiazolinyl sulfide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104710332B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111620798A (en) * | 2020-06-04 | 2020-09-04 | 沅江华龙催化科技有限公司 | (Z) -beta-iodine-beta-methylthio olefin and synthesis method thereof |
| CN111559971A (en) * | 2020-06-04 | 2020-08-21 | 沅江华龙催化科技有限公司 | Method for constructing iodoalkenyl thioether from olefin, iodine and dimethyl sulfoxide |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3291779A (en) * | 1963-03-27 | 1966-12-13 | Dow Chemical Co | Cuprous p-halothiophenoxide |
| CN1443156A (en) * | 2000-07-17 | 2003-09-17 | 巴斯福股份公司 | Preparation of 4-thioalkylbromobenzene derivatives |
| JP2010265242A (en) * | 2009-05-18 | 2010-11-25 | Sumitomo Seika Chem Co Ltd | Manufacturing method for aromatic thiol compound and aromatic sulfide compound |
| CN102249962A (en) * | 2011-06-08 | 2011-11-23 | 同济大学 | Preparation method of 1,1-disulfur-1-olefin |
| CN102351622A (en) * | 2011-08-19 | 2012-02-15 | 浙江大学 | Method for preparing (Z)-1,2-disulfide-1-olefin by catalysis of metal copper salt |
| JP2012214400A (en) * | 2011-03-31 | 2012-11-08 | Sumitomo Seika Chem Co Ltd | Method for manufacturing aromatic sulfide compound |
-
2015
- 2015-02-17 CN CN201510085261.2A patent/CN104710332B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3291779A (en) * | 1963-03-27 | 1966-12-13 | Dow Chemical Co | Cuprous p-halothiophenoxide |
| CN1443156A (en) * | 2000-07-17 | 2003-09-17 | 巴斯福股份公司 | Preparation of 4-thioalkylbromobenzene derivatives |
| JP2010265242A (en) * | 2009-05-18 | 2010-11-25 | Sumitomo Seika Chem Co Ltd | Manufacturing method for aromatic thiol compound and aromatic sulfide compound |
| JP2012214400A (en) * | 2011-03-31 | 2012-11-08 | Sumitomo Seika Chem Co Ltd | Method for manufacturing aromatic sulfide compound |
| CN102249962A (en) * | 2011-06-08 | 2011-11-23 | 同济大学 | Preparation method of 1,1-disulfur-1-olefin |
| CN102351622A (en) * | 2011-08-19 | 2012-02-15 | 浙江大学 | Method for preparing (Z)-1,2-disulfide-1-olefin by catalysis of metal copper salt |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104710332A (en) | 2015-06-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| AU2008318091B2 (en) | A process for continuously producing 3-isothiazolone derivatives and their intermediate products thereof | |
| CN104710332B (en) | A kind of preparation method of thiazolinyl sulfide | |
| CN105801575A (en) | Synthetic method of imidazo[1,2-a]pyridine | |
| CN105801530A (en) | Synthetic method of 4-substituted chiral gamma-butyrolactone | |
| CN105175328A (en) | Method for synthesizing quinoline derivative by utilizing arylamine, aromatic aldehyde and ketone | |
| CN105503822B (en) | The preparation method of trifluoromethyl benzothiophene derivative | |
| CN105949147B (en) | A kind of method of green syt 2-mercaptobenzothiazole analog derivative | |
| CN105218540A (en) | The preparation method of a kind of C-3 position thiocarbamoyl imidazole also [1,2-a] pyridine compounds and their | |
| CN105949161B (en) | A kind of preparation method of 3- aromatic thiohydroxies chromocor compound | |
| CN112500339A (en) | Synthesis method of 8-acylquinoline derivative | |
| CN103724319B (en) | The preparation method of a kind of benzothiophenes and purification method thereof | |
| CN104860857B (en) | Methylthiosemicarbazone synthesis technique | |
| CN101327450B (en) | Aminoacid ion liquid carried Salen metallic catalyst and preparation method | |
| CN105481738B (en) | A kind of method of the copper catalysis synthesis trifluoroethyl thioether of aromatic hydrocarbons 2,2,2 | |
| CN112094220B (en) | Green synthesis method of 3-sulfone methyl-1H-indole compound | |
| CN107915694A (en) | 1 [2 (2,4 3,5-dimethylphenyl sulfydryl) phenyl] piperazine hydrochloride and preparation method thereof | |
| CN103073520B (en) | Method for synthesizing 2-phenyl benzothiazole and derivative thereof | |
| CN106187943B (en) | A kind of preparation method of 1,4- benzothiazines | |
| CN102344419A (en) | Preparation method of broad-spectrum antifungal drug fluconazole | |
| CN109896944B (en) | Method for synthesizing 1, 4-naphthoquinone cyclopropane compound | |
| CN109574948A (en) | A kind of preparation method of bis- (tertbutyloxycarbonyl) amine | |
| CN114213298B (en) | Method for preparing thiosulfonate compound by directly oxidizing thiophenol | |
| CN105524002A (en) | Preparation method of quinoxalin-2-one derivative and product purification method | |
| CN113149926B (en) | Preparation method of 3, 5-disubstituted isoxazole derivative | |
| CN112694432B (en) | Preparation method of arbidol key intermediate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 325000 Zhejiang, Ouhai, South East Road, No. 38, Wenzhou National University Science Park Incubator Applicant after: Wenzhou University Address before: 325035 Zhejiang province Chashan Wenzhou Higher Education Park of Wenzhou University Applicant before: Wenzhou University |
|
| COR | Change of bibliographic data | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170104 Termination date: 20190217 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |