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Silicon hetero-beta-dynascone and preparation method thereof

A technology of dynasty ketone and silylated ketone is applied in the field of silylated-β-dynastic ketone compound and its general synthesis, and achieves the effects of wide application range, readily available raw materials, simple and easy experimental equipment and operation.

Active Publication Date: 2014-02-26
ZHENGZHOU TOBACCO RES INST OF CNTC
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The gem-dimethylcyclohexene skeleton exists in a large number of synthetic and natural fragrance compounds. However, there is no new fragrance raw material developed to synthesize silicon analogs containing the gem-dimethylcyclohexene skeleton through Si / C substitution.

Method used

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  • Silicon hetero-beta-dynascone and preparation method thereof
  • Silicon hetero-beta-dynascone and preparation method thereof
  • Silicon hetero-beta-dynascone and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0027] Add 1 mol of 1,1-dimethylsilacyclobutane II, 1 mol of 6-hepten-1-yn-3-one, 1% equivalent of Pd(PPh 3 ) 4 and 5 L of benzene solvent, heated to 80°C, and reacted for 4 hours with magnetic stirring. Concentrate after the reaction, decolorize and separate on a silica gel column, and use a mixed solvent of petroleum ether: ether=10:1 as an eluent to obtain the pure product sila-β-dynasone I (purity > 98%, colorless liquid). The rate is 57%. The NMR and high resolution mass spectrometry data of this compound are as follows: 1 H NMR (CDCl 3 ) δ = 6.78 (s, H), 5.89-5.79 (m, H), 5.06-4.96 (m, 2H), 2.82-2.78 (t, J = 5.5 Hz, 2H), 2.37-2.32 (m, 4H), 1.82-1.76 (m, 2H), 0.70-0.67 (m, 2H), 0.135 (s, 6H). 13 C NMR (CDCl 3 ) δ = 201.47, 156.24, 137.58, 136.69, 114.92, 36.22, 28.53, 27.99, 20.96, 11.17, -2.31. HRMS: m / z : calcd for C 12 h 20 OSi [M+H] + : 209.1356, found 209.1352.

[0028] The reaction formula is as follows:

[0029]

[0030] Two-step Reaction Synthesi...

Embodiment 2

[0032] Into a 10 L round bottom flask, add 1 mol of 1,1-dimethylsilacyclobutane II, 1 mol of methyl propiolate, 10% equivalent of Pd(OAc) 2 +2PPh 3 and 5 L of tetrahydrofuran solvent, heated to boiling, and reacted with magnetic stirring for 5 hours. Concentrate after the reaction, decolorize and separate on a silica gel column, use a mixed solvent of petroleum ether: ethyl ether = 5:1 as an eluent to obtain pure product 1,1-dimethyl-3-methoxycarbonyl-silacyclohexene, and analyze The data can be found in the literature ( Bull. Chem. Soc. Jpn. , 1991, 64, 1461).

[0033] Add 10 mmol of 1,1-dimethyl-3-methoxycarbonyl-silacyclohexene and 150 mL of THF to a 250 mL round bottom flask, then cool to 0 °C with an ice bath, and 10 mmol of homoallyl bromide and 50 mg of magnesium chips were slowly added dropwise for 1 hour. The reaction was quenched with 1 M dilute hydrochloric acid solution, the resulting solution was extracted three times with diethyl ether, the solvent was remov...

Embodiment 3

[0037] Into a 5 L round bottom flask, add 1.5 mol of 1,1-dimethylsilacyclobutane II, 1 mol of ethyl propiolate, 10% equivalent of Pd(PPh 3 ) 4 and 2 L of toluene solvent, heated to 90°C, and stirred mechanically for 2 hours. Concentrate after the reaction, decolorize and separate on a silica gel column, use petroleum ether: ether=10:1 mixed solvent as eluent, obtain pure product 1,1-dimethyl-3-ethoxycarbonyl-silacyclohexene (purity > 95%, colorless liquid), isolated yield 64%. The NMR and high resolution mass spectrometry data of this compound are as follows: 1 H NMR (CDCl 3 ): δ = 6.98 (s, 1H), 4.22-4.15 (m, 2 H), 2.41-2.37 (t, 2H), 1.86-1.78 (m, 2H), 1.33-1.28 (t, 4H), 0.70-0.66 (m, 2H), 0.12 (s, 6H); 13 C NMR (CDCl3 ): d = 167.17, 148.26, 1137.75, 60.60, 29.18, 21.16, 14.22, 11.07, -2.37; HRMS: m / z : calcd for C 10 h 18 o 2 Si [M+H] + : 199.1149, found 199.1145.

[0038] Add 10 mmol of 1,1-dimethyl-3-ethoxycarbonyl-silacyclohexene and 150 mL of THF to a 250 mL r...

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Abstract

The invention provides silicon hetero-beta-dynascone represented by the formula I, namely, 1-(3-silicon hetero-3,3-dimethylcyclohex-1-enyl)pent-4-ene-1-one. The compound is a fragrance material compound with a strong pineapple fragrance. Under the catalytic action of palladium and with an inserting ring-expansion reaction of terminated alkyne on silicon heterocyclic butane, the silicon hetero-beta-dynascone is prepared with high yield. The method has the advantages of easily obtained raw materials, wide applicable range, high separation yield, simple and easily practicable experimental equipment and operation, and convenient industrialization.

Description

technical field [0001] The invention belongs to the field of fragrance chemistry, and in particular relates to a sila-beta-dynastyne compound and a general synthesis method thereof. Background technique [0002] The development of the flavor and fragrance industry depends on the continuous discovery of new high-quality fragrance raw materials. Compared with natural fragrance raw materials, synthetic fragrance raw materials not only have definite ingredients, stable supply and moderate price, but also have no seasonal dependence. β-Dynastone (Dynascone, IV) is a fruity, pineapple-like aroma ingredient, which is a patented product of Firmenich (US4264467 A). In recent years, replacing a quaternary carbon atom in the structure of natural fragrance raw materials with a silicon atom to design and synthesize fragrance compounds has become a new method for developing fragrance raw materials, that is, the Si / C substitution method. In 2010, Givaudan disclosed a patent (US 008182781...

Claims

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Application Information

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IPC IPC(8): C07F7/08
Inventor 刘俊辉孙世豪向兰康屈展李鹏张启东卢斌斌刘珊宗永立张建勋
Owner ZHENGZHOU TOBACCO RES INST OF CNTC
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