CN1785975A - Synthesis method of beta indolone - Google Patents
Synthesis method of beta indolone Download PDFInfo
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- CN1785975A CN1785975A CN 200510129305 CN200510129305A CN1785975A CN 1785975 A CN1785975 A CN 1785975A CN 200510129305 CN200510129305 CN 200510129305 CN 200510129305 A CN200510129305 A CN 200510129305A CN 1785975 A CN1785975 A CN 1785975A
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- beta
- indolone
- acidic ion
- monovalent
- ion liquid
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Abstract
The present invention discloses a method for synthesizing beta-indolone. Said method includes the following steps: using an equivalent alpha, beta unsaturated oxo-compound and slightly-excess indole as raw material, in the catalysis system of acidic ion liquid [hmin]+HSO4-/ethyl alcohol heating and refluxing for 2-10hr, distilling to remove ethyl alcohol, using ethyl ether to extract mixture, combining extracts, evaporating to remove ethyl ether so as to obtain the required crude product of beta-indolone.
Description
Technical field
The present invention relates to a kind of pentatomic ring that contains, condense with other ring, heteroatoms is the preparation of the heterogeneous ring compound of nitrogen-atoms, be specifically related to the synthetic method of the beta indolone that a kind of indoles and beta-unsaturated carbonyl compounds addition obtain.
Background technology
Indoles, this structure fragment appears in the various compounds with pharmacology physiologically active widely.Wherein beta indolone is a kind of material with physiologically active, also is many natural product synthetic intermediates simultaneously.Therefore, explore the synthetic method of this series compound, caused people's extensive interest.Up to the present, this compounds synthetic mainly is that reversal of the Michael addition by indoles and α, β beta-unsaturated carbonyl compounds realizes.Simultaneously, reversal of the Michael addition itself is a kind of reaction of Atom economy, can realize " zero release ", reduces industrial pollution.
Based on above reason, to the method for synthetic beta indolone, carried out research extensively and profoundly both at home and abroad.Many research papers have all been reported by the Louis acid catalysis synthesising target compound.Simultaneously, the application of acidic resins, acidic silica gel also all has report.But all there are some shortcomings in these above reactions: 1, the stronger acidic conditions of needs; 2, expensive, hypertoxic catalyzer; 3, than the long reaction times; 4, lower productive rate; 5, Fu Za aftertreatment; 6, the effect that recycles of catalyst system is undesirable.(Wang, S.-Y.; Ji, S.-J.; Loh, T.-P.; Synlett., 2003,15,2377) this just needs people to go to seek a kind of reaction system that more meets the Green Chemistry developing direction, for later suitability for industrialized production is laid a solid foundation.
In recent years, ionic liquid has caused that as a kind of green solvent people pay close attention to widely.Since functional ionic liquid can single-minded ground catalysis the reaction of certain or a certain class, so its synthetic and application is the focus that current chemists study.In recent years, according to bibliographical information, the ionic liquid that contains acidic functionality had obtained using widely in synthetic, the esterification of heavily group, the beta-amido carbonyl compound of oxime and acetalation.
Summary of the invention
The object of the invention provides a kind of employing and is easy to realize that the catalyst system of recycle prepares the method for a series of beta indolone, to improve productive rate, shortens the reaction times.
For achieving the above object, the present invention is with acidic ion liquid [hmim]
+HSO
4 -/ ethanol is as catalyst system, and the technical scheme of employing is: a kind of synthetic method of beta indolone, with the α of monovalent, β beta-unsaturated carbonyl compounds and excessive slightly indoles at acidic ion liquid [hmim]
+HSO
4 -In/alcoholic acid the catalyst system, reflux 2-10 hour, described acidic ion liquid is not more than 20% of α, β beta-unsaturated carbonyl compounds in molar equivalent, described ethanol is solvent, ethanol is removed in distillation then, the mixture ether extraction, united extraction liquid steams and removes the crude product that ether promptly obtains required beta indolone.
In the technique scheme, described acidic ion liquid [hmim]
+HSO
4 -The preparation method be, the bromo normal hexane of the Methylimidazole of monovalent and monovalent shone under microwave condition 10～15 minutes, then with methylene dichloride dissolving, added the vitriol oil of monovalent, reflux is more than 2 days, reaction finishes the back and concentrates.
Optimized technical scheme is reflux 3 days.
Further technical scheme, the amount of described acidic ion liquid is counted 8～10% of α, β beta-unsaturated carbonyl compounds with molar equivalent.
In the technique scheme, the crude product that reaction obtains can obtain purified target compound by suitable purification.And residual material is exactly the acidic ion liquid that adds after the ether extraction, only need remove remaining ether by distillation, just can recycle.
Because the technique scheme utilization, the present invention compared with prior art has following advantage:
The inventive method productive rate height, the time is short, and is simple to operate, and catalyst system can recycle several times easily, and activity can not reduce.
Embodiment
Below in conjunction with embodiment the present invention is further described:
Embodiment one: acidic ion liquid [hmim]
+HSO
4 -Preparation
Get the Methylimidazole of 10mmol and the bromo normal hexane of 10mmol and under microwave condition, shone 10-15 minute,, add the vitriol oil of 10mmol, reflux 3 days then with the dissolving of 50mL methylene dichloride.After reaction finishes, concentrate and just obtain [hmim]
+HSO
4 -
Its reaction formula is:
Embodiment two: 1,3-phenylbenzene-3-(3-indyl) ketone synthetic
Get 0.5mmol 1,3-phenylbenzene α, the indoles of beta unsaturated ketone and 0.6mmol is at 10mol%[hmim]
+HSO
4 -In the catalyst system of/4mL EtOH, reflux 3h.Ethanol, mixture ether extraction are removed in distillation then.United extraction liquid, steaming removes ether and obtains crude product.By suitable purification, can obtain purified 1,3-phenylbenzene-3-(3-indyl) ketone.
Its reaction formula is:
Embodiment three: 1-phenyl-3-(2-thiophene phenyl)-3-(3-indyl) ketone synthetic
Get 0.5mmol 1-phenyl-3-(2-thiophene phenyl) α, the indoles of beta unsaturated ketone and 0.6mmol is at 10mol%[hmim]
+HSO
4 -In the catalyst system of/4mL EtOH, reflux 3h.Ethanol, mixture ether extraction are removed in distillation then.United extraction liquid, steaming removes ether and obtains crude product.By suitable purification, can obtain purified 1-phenyl-3-(2-thiophene phenyl)-3-(3-indyl) ketone.
Its reaction formula is:
Embodiment four: 1,3-phenylbenzene-3-(3-(2-methyl) indyl) ketone synthetic
Get 0.5mmol 1,3-phenylbenzene α, the indoles of beta unsaturated ketone and 0.6mmol is at 10mol%[hmim]
+HSO
4 -In the catalyst system of/4mL EtOH, reflux 2.5h.Ethanol, mixture ether extraction are removed in distillation then.United extraction liquid, steaming removes ether and obtains crude product.By suitable purification, can obtain purified 1,3-phenylbenzene-3-(3-(2-methyl) indyl) ketone.
Its reaction formula is:
Claims (3)
1. the synthetic method of a beta indolone is characterized in that: with the α of monovalent, β beta-unsaturated carbonyl compounds and excessive slightly indoles at acidic ion liquid [hmim]
+HSO
4 -In/alcoholic acid the catalyst system, reflux 2-10 hour, described acidic ion liquid is not more than 20% of α, β beta-unsaturated carbonyl compounds in molar equivalent, described ethanol is solvent, ethanol is removed in distillation then, the mixture ether extraction, united extraction liquid steams and removes the crude product that ether promptly obtains required beta indolone.
2. the synthetic method of beta indolone according to claim 1 is characterized in that: described acidic ion liquid [hmim]
+HSO
4 -The preparation method be, the bromo normal hexane of the Methylimidazole of monovalent and monovalent shone under microwave condition 10～15 minutes, then with methylene dichloride dissolving, added the vitriol oil of monovalent, reflux is more than 2 days, reaction finishes the back and concentrates.
3. the synthetic method of beta indolone according to claim 1, it is characterized in that: the amount of described acidic ion liquid is counted 8～10% of α, β beta-unsaturated carbonyl compounds with molar equivalent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510129305 CN1785975A (en) | 2005-06-29 | 2005-11-28 | Synthesis method of beta indolone |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200510040883.X | 2005-06-29 | ||
| CN200510040883 | 2005-06-29 | ||
| CN 200510129305 CN1785975A (en) | 2005-06-29 | 2005-11-28 | Synthesis method of beta indolone |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1785975A true CN1785975A (en) | 2006-06-14 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200510129305 Pending CN1785975A (en) | 2005-06-29 | 2005-11-28 | Synthesis method of beta indolone |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103172553A (en) * | 2013-04-18 | 2013-06-26 | 安徽工业大学 | Method for catalytic synthesis of beta-indolone by using ionic liquid |
-
2005
- 2005-11-28 CN CN 200510129305 patent/CN1785975A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103172553A (en) * | 2013-04-18 | 2013-06-26 | 安徽工业大学 | Method for catalytic synthesis of beta-indolone by using ionic liquid |
| CN103172553B (en) * | 2013-04-18 | 2015-05-20 | 安徽工业大学 | Method for catalytic synthesis of beta-indolone by using ionic liquid |
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