CN1683297A - Synthetic method for 4-(1,5-dimethyl-1-vinyl-4-hexenyl) phenol - Google Patents
Synthetic method for 4-(1,5-dimethyl-1-vinyl-4-hexenyl) phenol Download PDFInfo
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- CN1683297A CN1683297A CN 200510033408 CN200510033408A CN1683297A CN 1683297 A CN1683297 A CN 1683297A CN 200510033408 CN200510033408 CN 200510033408 CN 200510033408 A CN200510033408 A CN 200510033408A CN 1683297 A CN1683297 A CN 1683297A
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- hexenyl
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Abstract
The present invention relates to synthesis process of 4-(1, 5-dimethyl-1-vinyl-4-hexenyl) phenol, normally named as antifeedant, and the synthesis process is superior to available ones. The synthesis process has geraniol as main material and includes the reaction with vinyl ethyl ether, Claisen rearrangement reaction to obtain 3-vinyl-rhodinal, reaction with hexahydropyridine, enamiation, conjugate addition with methyl vinyl ketone and cyclization and condensation to 4-(1, 5-dimethyl-1-vinyl-4-hexenyl)-2-cyclohexene ketone, and dehydrogenation to obtain the product 4-(1, 5-dimethyl-1-vinyl-4-hexenyl) phenol. The present invention uses natural product as main material, and has simple reaction process, high selectivity and high yield.
Description
Technical field
The present invention relates to the synthetic method of 4-(1,5-dimethyl-1-vinyl-4-hexenyl) phenol.
Background technology
4-(1,5-dimethyl-1-vinyl-4-hexenyl) phenol also claims antifeedant (+)-Sporochnol, being people such as Shen separated and identifies a monoterpenes phenol from Caribbean Sea marine alga in 1993, and experiment shows that this natural product has significant antifeedant activity to the herbivorous fishing gear.Report to some extent about the synthetic of this material at present, and document (Enantiomer 1997,2, and 297; Tetrahedron:Asymmetry 1999,10, and 1153; J.Chem.Res.2000,530; TetrahedronLetters 2002,43,4641) to 4-(1,5-dimethyl-1-vinyl-4-hexenyl) more detailed report has been done in the chemosynthesis of phenol, but the synthetic method that is provided in these documents, and synthesis step is many, mostly between 5～15 steps, the reaction conditions complexity, the agents useful for same costliness, productive rate is also lower.
Summary of the invention
At the deficiencies in the prior art and shortcoming, the invention provides a kind of is the method for synthetic 4-(1, the 5-dimethyl-1-vinyl-4-hexenyl) phenol of raw material with the crude substance.
The present invention is to be raw material with the Geraniol, obtain 3-vinyl geranial with the ethyl vinyl ether reaction through the Claisen rearrangement, then with hexahydropyridine reaction enamine after and methylene acetone is gripped addition altogether and cyclocondensation gets 4-(1,5-dimethyl-1-vinyl-4-hexenyl)-and the 2-cyclonene, obtain product through dehydrogenation again.
Synthetic method provided by the invention specifically comprises following step;
(1): Geraniol and ethyl vinyl ether reacted 12～40 hours down at-5～5 ℃ under catalyst action, after the purification crude product were heated 20～40 minutes down at 170～190 ℃, and purifying obtains 3-vinyl geranial then;
(2): descending reaction after 1～5 hour at 20～25 ℃ under the effect of siccative in prepared aldehyde of step (1) and hexahydropyridine, reacted 15～40 hours down at 20～25 ℃ with methylene acetone again, adding the acid back then refluxed 2～6 hours, make 4-(1,5-dimethyl-1-vinyl-4-hexenyl)-2-cyclonene behind the purifying;
(3): the ketenes that makes in the step (2) under the effect of catalyzer and siccative, was refluxed in alcoholic solution 8～20 hours, make final product 4-(1,5-dimethyl-1-vinyl-4-hexenyl) phenol behind the purifying.
Wherein the ethyl vinyl ether described in the step (1) is new distillatory ethyl vinyl ether; Described catalyzer is a mercury salt, is preferably mercuric acetate; Preferred 178～182 ℃ of the Heating temperature of purification back crude product; Described purification process is to carry out chromatography with silicagel column (sherwood oil/trichloromethane=1/1～4); Entire reaction course all needs to carry out under the protection of nitrogen or rare gas element;
Siccative described in the step (2) is an Anhydrous potassium carbonate; Described methylene acetone is new distillatory methylene acetone; The preferred Glacial acetic acid of described acid; Described purification process carries out chromatography with silicagel column (petroleum ether/ethyl ether=50～10/1) after being meant extraction, drying; Entire reaction course needs to carry out under the protection of nitrogen or rare gas element;
The preferred PdCl of catalyzer described in the step (3)
2The preferred anhydrous sodium carbonate of described siccative; Described pure preferred tertiary butanols; Described purification process is meant filtration, carry out chromatography with silicagel column (ethyl acetate/normal hexane=1/5～10) after boiling off solvent; Entire reaction course needs to carry out under nitrogen or protection of inert gas.
The method of synthetic 4-provided by the present invention (1,5-dimethyl-1-vinyl-4-hexenyl) phenol is a raw material with the crude substance Geraniol, effectively utilized the Geraniol resource of China's abundant, and reactions steps is few, simple to operate, agents useful for same is also more cheap, and productive rate is higher.
Embodiment
1, the preparation of 3-vinyl geranial
Put into 15.4g (0.1mol) Geraniol and 9.5g (0.03mol) mercuric acetate in the 250ml round-bottomed flask, add then and newly distilled 72g (1mol) ethyl vinyl ether, logical nitrogen is cooled to 0 ℃ of reaction 24 hours then.Follow Na with 10%
2CO
3Behind the reactant aqueous solution 0.5 hour, use the extracted with diethyl ether organic phase, behind the anhydrous sodium sulfate drying, solvent evaporated, residuum is heated to 180 ℃ in oil bath, and keeps 0.5 hour.Product gets 9.38g aldehyde (2), productive rate 52.1% through silicagel column (sherwood oil/trichloromethane=1/2) chromatography.
IR(film)：1722，1452，1378，1004，917cm
-1；
1H?NMR(CDCl
3)：δ1.15(s，3H)，1.40(t，2H)，1.59(s，3H)，1.66(s，3H)，1.90(m，2H)，2.36(d，2H)，5.08(t，1H)，5.86-4.96(m，3H)，9.70(t，1H)；
13C?NMR(CDCl
3)：202.5，144.7，131.1，123.8，112.7，52.6，41.0，38.6，25.3，22.3，17.2ppm；MS(m/e)：180(M
+).
2, the preparation of 4-(1,5-dimethyl-1-vinyl-4-hexenyl)-2-cyclonene
At room temperature, 7.5g (0.1mol) hexahydropyridine, 9g (0.05mol) aldehyde (2) and 4g Anhydrous potassium carbonate are put into the 100ml round-bottomed flask, react after 2 hours, filter, and under reduced pressure steam excessive hexahydropyridine.Fresh distillatory 7g (0.1mol) methylene acetone joins in the above-mentioned residuum under nitrogen, at room temperature reacted 24 hours, adding the 4ml Glacial acetic acid then returns and heats up in a steamer 4 hours, thin up afterwards, use extracted with diethyl ether again, anhydrous sodium sulfate drying boils off ether, crude product gets 7.79g ketenes (3), productive rate 67.2% through silicagel column (petroleum ether/ethyl ether=20/1) chromatography.
IR(film)：1687，1620，1450，1380，1141，1002，916，835?cm
-1；
1H?NMR(CDCl
3)：δ0.96(d，3H)，1.33(t，2H)，1.51(s，3H)，1.60(s，3H)，1.80(m，2H)，2.06(m，2H)，2.26(m，2H)，2.43(m，1H)，5.67-4.90(m，3H)，5.14(t，1H)，5.94(dd，1H)，6.88(tt，1H)；
13C?NMR(CDCl
3)：199.8，153.1，144.6，131.5，129.9，124.2，114.2，44.2，44.8，38.7，37.7，25.5，23.8ppm；MS(m/e)：232(M
+).
3, the preparation of 4-(1,5-dimethyl-1-vinyl-4-hexenyl) phenol
0.464g (0.002mol) ketenes (3), 0.354g (0.002mol) PdCl
2And 1.06g (0.01mol) anhydrous sodium carbonate joins under nitrogen in the 50ml trimethyl carbinol and to reflux 10 hours, reaction mixture filters then, steam solvent, crude product gets 0.302g (+)-Sporochnol, productive rate 65.7% through silicagel column (ethyl acetate/normal hexane=1/8) chromatography.
IR(film)：3372，1612，1511，1459，1375，914，829cm
-1；
1H?NMR(CDCl
3)：δ1.33(s，3H)，1.50(s，3H)，1.66(s，3H)，1.77-1.64(m，4H)，4.65(s，1H)，5.08-4.98(m，3H)，6.02(dd，1H)，6.76(d，2H)，7.17(d，2H)；
13C?NMR(CDCl
3)：153.5，147.2，139.6，131.3，127.8，124.7，114.8，111.4，43.6，41.2，25.6，25.0，23.3，17.5ppm；MS(m/e)：230(M
+).
Claims (4)
1, a kind of 4-(1,5-dimethyl-1-vinyl-4-hexenyl) synthetic method of phenol, this method is raw material with the Geraniol, react through obtaining 3-vinyl geranial with ethyl vinyl ether, then with hexahydropyridine reaction enamine after and methylene acetone is gripped addition altogether and cyclocondensation gets 4-(1,5-dimethyl-1-vinyl-4-hexenyl)-and the 2-cyclonene, obtain product through dehydrogenation again, it is characterized in that comprising following reactions steps:
(1) Geraniol and ethyl vinyl ether reacted 12～40 hours down at-5～5 ℃ under the mercury salt catalyst action, after the purification crude product were heated 20～40 minutes down at 170～190 ℃, and purifying obtains 3-vinyl geranial then;
(2) descending reaction after 1～5 hour at 20～25 ℃ under the effect of siccative in prepared aldehyde of step (1) and hexahydropyridine, reacted 15～40 hours down at 20～25 ℃ with methylene acetone again, adding the acid back then refluxed 2～6 hours, make 4-(1,5-dimethyl-1-vinyl-4-hexenyl)-2-cyclonene behind the purifying;
(3) with the ketenes that makes in the step (2) at PdCl
2Under the effect of catalyzer and siccative, in t-butanol solution, refluxed 8～20 hours, make final product 4-(1,5-dimethyl-1-vinyl-4-hexenyl) phenol behind the purifying.
2, the synthetic method of 4-according to claim 1 (1,5-dimethyl-1-vinyl-4-hexenyl) phenol is characterized in that the ethyl vinyl ether described in the step (1) is new distillatory ethyl vinyl ether; Described catalyzer is a mercuric acetate; The Heating temperature of back crude product of purifying is 178～182 ℃, and described purification process is to be that chromatography is carried out in sherwood oil/trichloromethane=1/1～4 with silicagel column; Entire reaction course is all carried out under protection of nitrogen gas.
3, the synthetic method of 4-according to claim 1 (1,5-dimethyl-1-vinyl-4-hexenyl) phenol is characterized in that the siccative described in the step (2) is an Anhydrous potassium carbonate; Described methylene acetone is new distillatory methylene acetone; Described acid is Glacial acetic acid, and described purification process is meant that extraction, dry back are that chromatography is carried out in petroleum ether/ethyl ether=50～10/1 with silicagel column; Entire reaction course is carried out under protection of nitrogen gas.
4, the synthetic method of 4-according to claim 1 (1,5-dimethyl-1-vinyl-4-hexenyl) phenol is characterized in that the siccative described in the step (3) is an anhydrous sodium carbonate; Described purification process is meant filtration, to boil off behind the solvent with silicagel column be that chromatography is carried out in ethyl acetate/normal hexane=1/5～10; Entire reaction course is carried out under nitrogen protection.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100358857C (en) * | 2006-04-12 | 2008-01-02 | 浙江大学 | 2-cyclohexenones and process for preparing same |
| CN110590523A (en) * | 2019-11-04 | 2019-12-20 | 天津市安凯特科技发展有限公司 | Synthesis method of cryptone |
-
2005
- 2005-03-07 CN CN 200510033408 patent/CN1254461C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100358857C (en) * | 2006-04-12 | 2008-01-02 | 浙江大学 | 2-cyclohexenones and process for preparing same |
| CN110590523A (en) * | 2019-11-04 | 2019-12-20 | 天津市安凯特科技发展有限公司 | Synthesis method of cryptone |
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| CN1254461C (en) | 2006-05-03 |
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