CN1300117C - Microwave radiation synthesis of 1,3-substituted imidazole-2-thioketone - Google Patents
Microwave radiation synthesis of 1,3-substituted imidazole-2-thioketone Download PDFInfo
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- CN1300117C CN1300117C CNB2005100492011A CN200510049201A CN1300117C CN 1300117 C CN1300117 C CN 1300117C CN B2005100492011 A CNB2005100492011 A CN B2005100492011A CN 200510049201 A CN200510049201 A CN 200510049201A CN 1300117 C CN1300117 C CN 1300117C
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- microwave radiation
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- thioketones
- disubstituted imidazole
- benzyl
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Abstract
本发明公开了一种微波辐射合成1，3-二取代咪唑-2-硫酮的方法。当量比为1∶1～3的1，3-二取代咪唑鎓盐和硫代乙酸钾，在微波辐射条件下合成1，3-二取代咪唑-2-硫酮，微波辐射的功率为50～300W，微波辐射反应时间为2～20分钟，反应式为：其中R1＝烷基(C1～4)、苄基，R2＝烷基(C1～4)、苄基、烯丙基、羟乙基、乙酰氧乙基，X＝Cl，Br，BF4，PF6。本发明与已有的方法相比，具有以下优点：1.用微波辐射大大提高反应速度，通常反应时间为2～20分钟；2.反应操作简便，无需除水；3.反应后处理简单，只需溶解提取、过滤、洗涤、浓缩，粗产物的纯度大于80%；4.反应无需有机溶剂，无污染。
The invention discloses a method for synthesizing 1,3-disubstituted imidazole-2-thione by microwave radiation. 1,3-disubstituted imidazolium salt and potassium thioacetate with an equivalent ratio of 1:1～3, synthesize 1,3-disubstituted imidazole-2-thione under microwave radiation conditions, and the power of microwave radiation is 50～ 300W, microwave radiation reaction time is 2-20 minutes, the reaction formula is: where R 1 = alkyl (C 1-4 ), benzyl, R 2 = alkyl (C 1-4 ), benzyl, allyl , hydroxyethyl, acetoxyethyl, X=Cl, Br, BF 4 , PF 6 . Compared with the existing method, the present invention has the following advantages: 1. The reaction speed is greatly improved by microwave radiation, and the reaction time is usually 2 to 20 minutes; 2. The reaction operation is simple and convenient, without removing water; 3. The post-reaction treatment is simple, Only need to dissolve and extract, filter, wash and concentrate, and the purity of the crude product is greater than 80%; 4. The reaction does not require organic solvents and is pollution-free.
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=C
1-4Alkyl, benzyl, R
2=C
1～4Alkyl, benzyl, allyl group, 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=C
1～4Alkyl, benzyl, R
2=C
1～4Alkyl, benzyl, allyl group, acetyl oxygen ethyl, X=Cl, Br, BF
4, PF
6
2. according to claim 1 a kind of synthetic 1, the method for 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 method for 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 method for 3-disubstituted imidazole-2-thioketones is characterized in that 1, and the equivalence ratio of 3-disubstituted imidazole salt and thioacetic acid potassium is 1: 1～2.
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|---|---|---|---|
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| CNB2005100492011A CN1300117C (en) | 2005-01-24 | 2005-01-24 | Microwave radiation synthesis of 1,3-substituted imidazole-2-thioketone |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0411927A1 (en) * | 1989-08-04 | 1991-02-06 | E.I. Du Pont De Nemours And Company | Coating compositions containing 1,3-dialkylimidazole-2-thione catalysts |
| 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 |
-
2005
- 2005-01-24 CN CNB2005100492011A patent/CN1300117C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0411927A1 (en) * | 1989-08-04 | 1991-02-06 | E.I. Du Pont De Nemours And Company | Coating compositions containing 1,3-dialkylimidazole-2-thione catalysts |
| 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 |
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