CN1680337A - Microwave radiation synthesis of 1,3-substituted imidazole-2-thioketone - Google Patents
Microwave radiation synthesis of 1,3-substituted imidazole-2-thioketone Download PDFInfo
- Publication number
- CN1680337A CN1680337A CN 200510049201 CN200510049201A CN1680337A CN 1680337 A CN1680337 A CN 1680337A CN 200510049201 CN200510049201 CN 200510049201 CN 200510049201 A CN200510049201 A CN 200510049201A CN 1680337 A CN1680337 A CN 1680337A
- Authority
- CN
- China
- Prior art keywords
- thioketones
- microwave radiation
- imidazole
- synthetic
- methylimidazole
- 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.)
- Granted
Links
Landscapes
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
Synthesis of 1,3-dibasic imidazole-2-thio-ketone by micro-wave radiation is carried out by taking 1,3-dibasic imidazole onium salt and potassium thiacetic with amount ratio 1:1-3, synthesizing 1,3-dibasic imidazole-2-thio-ketone with power 50-300W and reacting time 2-20mins, extracting, filtering, washing and concentrating. R1=alkyl(C1-4), benzyl, R2=alkyl(C1-4), benzyl, allyl, ethoxyl, and acetoxy ethyl. Its advantages include fast reacting speed, simple operation and after treatment, and no pollution.
Description
Technical field
The present invention relates to a kind of microwave radiation and synthesize 1, the method for 3-disubstituted imidazole-2-thioketones.
Background technology
Imidazoles-2-thioketones is a class important compound that is widely used in medicine and chemical field, as 1-Methylimidazole-2-thioketones (Methimazole
) can be used for treating the Tiroidina parasecretion; Some imidazoles-2-thioketones class medicine also can be used for treatment of arthritis.In addition, imidazole thione has anti-oxidant and anti-flaming function, can be used as rubber antioxidants as the benzoglyoxaline thioketones; 1,3-dialkylimidazolium-2-thioketones can be used as the catalyzer of synthetic epoxy resin and can significantly improve the performance of resin.Arduengo has applied for synthetic 1 in 1992, patent (the USP5 of 3-dialkylimidazolium-2-thioketones, 104,993), this synthetic method is in the presence of salt of wormwood, with 1,3-alkyl imidazole salt and sulphur are raw material synthetic 1,3-dialkylimidazolium-2-thioketones, long reaction time (24～48 hours) also requires anhydrously, and methyl alcohol has bigger murder by poisoning again.
Summary of the invention
The purpose of this invention is to provide a kind of microwave radiation and synthesized 1, the method for 3-disubstituted imidazole-2-thioketones
Equivalence ratio be 1: 1～3 1,3-disubstituted imidazole salt and thioacetic acid potassium, synthetic 1 under the microwave radiation condition, 3-disubstituted imidazole-2-thioketones, the power of microwave radiation are 50～300W, the microwave radiation reaction times is 2～20 minutes, reaction formula is:
R wherein
1=alkyl (C
1～4), benzyl, R
2=alkyl (C
1～4), benzyl, allyl group, hydroxyethyl, acetyl oxygen ethyl, X=Cl, Br, BF
4, PF
6
The present invention compares with existent method, has the following advantages:
1. improve speed of response greatly with microwave radiation, the reaction times is 2～20 minutes usually;
2. operation is easy, need not to dewater;
3. post-reaction treatment is simple, only needs dissolving extraction, filtration, washing, concentrates, and the purity of crude product is greater than 80%;
4. reaction need not organic solvent, and is pollution-free.
Embodiment
Following examples will help to understand the present invention, but be not limited to content of the present invention:
Embodiment 11,3 methylimidazoles-2-thioketones synthetic
In 20 milliliters of single port bottles with 10 mmole chlorinations 1,3-methylimidazole and 11 mmole thioacetic acid potassiums mix, load onto reflux condensing tube, reaction is 5 minutes under 150W power microwave radiation, naturally cool to room temperature, after reaction mixture dissolves with 50 milliliters of ethyl acetate-water (volume ratio 1: 1), insert in the separating funnel, tell organic phase, after dry 2 hours, concentrate with anhydrous potassium sulfate, (eluent is a normal hexane: ethyl acetate=2: 1) with silica gel column chromatography, 1,998 milligrams of 3-methylimidazoles-2-thioketones, yield is 75%.
1HNMR(500MHz，CDCl
3)：δ＝3.60(s，6H)，6.71(s，2H)；
13CNMR(500MHz，CDCl
3)：δ＝34.56，117.55，162.12；
IR(cm
-1)2957，1445，1230，1045；
MS([M+H]
+)：128.8；
Embodiment 21,3-methylimidazole-2-thioketones synthetic
Reactions steps is with embodiment 1, and different is with bromination 1, and the 3-methylimidazole is a raw material, obtains product, and yield is 78%.
Embodiment 31,3-methylimidazole-2-thioketones synthetic
Reactions steps is with embodiment 1, and different is with 1, and 3-methylimidazole a tetrafluoro borate is a raw material, obtains product, and yield is 79%.
Embodiment 41,3-methylimidazole-2-thioketones synthetic
Reactions steps is with embodiment 1, and different is to react 8 minutes under 100W power microwave radiation, obtains product, and yield is 82%.
Synthesizing of embodiment 5 1-butyl-3-Methylimidazole-2-thioketones
Reactions steps is with embodiment 1, and different is with bromination 1-butyl-3-Methylimidazole is raw material, obtains product, and yield is 78%.
1HNMR(500MHz，CDCl
3)：δ＝0.96(t，3H)，1.38(m，2H)，1.75(m，2H)，3.61(s，3H)，4.03(t，2H)，6.71(dd，2H)；
13CNMR(500MHz，CDCl
3)：13.74，19.82，31.02，35.10，47.83，116.63，117.74，161.72
IR(cm
-1)2958，2933，1568，1462，1414；
MS([M+H]
+)：170.8；
Synthesizing of embodiment 6 1-butyl-3-Methylimidazole-2-thioketones
Reactions steps is with embodiment 5, and different is with 1-butyl-3-Methylimidazole hexafluorophosphate is raw material, and reaction is 6 minutes under 120W power microwave radiation, obtains product, and yield is 82%.
Synthesizing of embodiment 7 1-butyl-3-Methylimidazole-2-thioketones
Reactions steps is with embodiment 6, and different is to use 15 mmole thioacetic acid potassiums, and reaction is 6 minutes under 120W power microwave radiation, obtains product, and yield is 85%.
Synthesizing of embodiment 8 1-allyl group-3-Methylimidazole-2-thioketones
Reactions steps is with embodiment 1, and different is with bromination 1-allyl group-3-Methylimidazole is raw material, obtains product, and yield is 72%.
1HNMR(500MHz，CDCl
3)：δ＝3.62(s，3H)，4.68(d，2H)，5.25(m，2H)，5.93(m，1H)，6.70(dd，2H)；
13CNMR(500MHz，CDCl
3)：35.30，50.36，116.39，117.99，119.23，132.06，162.62；
IR(cm
-1)：2925，1568，1459，1398；
MS([M+H]
+)：154.7；
Synthesizing of embodiment 9 1-benzyl-3-Methylimidazole-2-thioketones
Reactions steps is with embodiment 1, and different is with bromination 1-benzyl-3-Methylimidazole is raw material, obtains product, and yield is 82%.
1HNMR(500MHz，CDCl
3)：δ＝3.63(s，3H)，5.24(s，2H)，6.60(dd，2H)；
13CNMR(500MHz，CDCl
3)：35.39，51.50，116.49，118.14，128.28，128.44，129.00，136.02，162.50；
IR(cm
-1)：3137，1455，1409，1393；
MS([M+H]
+)：204.8；
Synthesizing of embodiment 10 1-acetyl oxygen ethyl-3-Methylimidazole-2-thioketones
Reactions steps is with embodiment 1, and different is that ethyl-the 3-Methylimidazole is a raw material, obtains product with bromination 1-acetyl oxygen, and yield is 81%.
1HNMR(500MHz，CDCl
3)：δ＝1.30(t，3H)，3.62(s，3H)，4.25(m，2H)，4.87(s，2H)，6.74(dd，2H)；
13CNMR(500MHz，CDCl
3)：14.22，35.42，48.78，61.97，117.43，118.08，163.83，167.57；
IR(cm
-1)：2987，1732，1570，1425，1403，1389；
MS([M+H]
+)：200.8
Claims (4)
1. one kind synthetic 1, the method of 3-disubstituted imidazole-2-thioketones, it is characterized in that equivalence ratio be 1: 1～3 1,3-disubstituted imidazole salt and thioacetic acid potassium, synthesize 1 under the microwave radiation condition, 3-disubstituted imidazole-2-thioketones, the power of microwave radiation are 50～300W, the microwave radiation reaction times is 2～20 minutes, and reaction formula is:
R wherein
1=alkyl (C
1～4), benzyl, R
2=alkyl (C
1～4), benzyl, allyl group, hydroxyethyl, acetyl oxygen ethyl, X=Cl, Br, BF
4, PF
6
2. according to claim 1 a kind of synthetic 1, the novel method of 3-disubstituted imidazole-2-thioketones, the power that it is characterized in that said microwave radiation is 50～200W.
3. according to claim 1 a kind of synthetic 1, the novel method of 3-disubstituted imidazole-2-thioketones is characterized in that the said microwave radiation reaction times is 2～10 minutes.
4. according to claim 1 a kind of synthetic 1, the novel method of 3-disubstituted imidazole-2-thioketones is characterized in that with 1, and the equivalence ratio of 3-disubstituted imidazole salt and thioacetic acid potassium is 1: 1～2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100492011A CN1300117C (en) | 2005-01-24 | 2005-01-24 | Microwave radiation synthesis of 1,3-substituted imidazole-2-thioketone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100492011A CN1300117C (en) | 2005-01-24 | 2005-01-24 | Microwave radiation synthesis of 1,3-substituted imidazole-2-thioketone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1680337A true CN1680337A (en) | 2005-10-12 |
| CN1300117C CN1300117C (en) | 2007-02-14 |
Family
ID=35067170
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100492011A Expired - Fee Related CN1300117C (en) | 2005-01-24 | 2005-01-24 | Microwave radiation synthesis of 1,3-substituted imidazole-2-thioketone |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1300117C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107964590A (en) * | 2017-11-29 | 2018-04-27 | 山东省医学科学院药物研究所 | A kind of technique of solvent extraction efficiently concentrating recycling noble silver |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5104993A (en) * | 1989-08-04 | 1992-04-14 | E. I. Du Pont De Nemours And Company | 1,3-dialkylimidazole-2-thione catalysts and method of making same |
| DE69016124T2 (en) * | 1989-08-04 | 1995-08-10 | Du Pont | Coating mixtures containing 1,3-dialkylimidazole-2-thione catalysts. |
-
2005
- 2005-01-24 CN CNB2005100492011A patent/CN1300117C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107964590A (en) * | 2017-11-29 | 2018-04-27 | 山东省医学科学院药物研究所 | A kind of technique of solvent extraction efficiently concentrating recycling noble silver |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1300117C (en) | 2007-02-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1300117C (en) | Microwave radiation synthesis of 1,3-substituted imidazole-2-thioketone | |
| CN1294122C (en) | Process for microwave synthesis of 1,3-disubstituted imidazole-2-thioketone | |
| CN113968894B (en) | Method for preparing cycloastragenol by degrading astragaloside IV | |
| CN1903830A (en) | Preparation method of 2-bromo-2-nitro-1,3-propylene glycol | |
| CN1045086C (en) | Preparation method of thiocarbamate compound | |
| CN1176055C (en) | Process for producing 4-methoxyl methyl-2,3,5.6-tetrachlorophenmethylol | |
| CN1702063A (en) | Process for synthesizing benzidine derivatives | |
| CN1834093A (en) | Synthetic process of chiral 2-amido-1-(6-fluorine-3,4-dihydrobenzopyranyl) alCohol | |
| CN1876644A (en) | (4R-cis)-6-formyl-2,2-dimethyl-1,3- dioxane -4- tertiary butyl acetate synthesis method | |
| CN109761845B (en) | Synthesis method of N-nitroso-4-aminobutyric acid ester compound | |
| CN110317170B (en) | Green synthesis method of 3-phenanthridinyl propyl formate compound | |
| CN1121409C (en) | Process for preparing medicine | |
| CN1266155C (en) | 6-chloro-4-hydroxy-2-methyl-2H-thieno-(2,3-e)-1,2-thiazine-1,1-dioxide-3 | |
| CN106475136B (en) | A kind of azochlorosulfonate acid ion catalyst, preparation method and its application | |
| CN1706825A (en) | New synthesis process of sultopride hydrochloride | |
| CN1251363A (en) | Novel process for synthesizing high-purity N-alkyl pyridine salt | |
| CN1101381C (en) | Method for extracting huperzine A as acetylcholinesterase depressant | |
| CN1850835A (en) | Method for preparing z-deoxy-D-glucose | |
| CN112574232B (en) | Method for recovering cefuroxime acid from cefuroxime acid waste residue liquid | |
| CN101063153A (en) | Method for improving single batch conversion bubatrate concentration in alloisomerism preparation of styrene glycol | |
| CN1663950A (en) | Method for synthesizing dibenzyl diselenide | |
| CN1072181A (en) | Zuyeyidal-2-dimethylamino compound hydrochloride dihydrate crystallization and preparation method thereof | |
| CN117551060B (en) | Method for purifying epichlorohydrin containing ether impurities | |
| CN1473762A (en) | Process for producing aluminium hydroxide using biological fermenting waste gas CO2 | |
| CN1158252C (en) | Process for preparing biurea |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20070214 Termination date: 20100224 |