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Silica hybrid dehydroherbac and preparing method thereof

A technology of dehydroherbone and sila, which is applied in the compound field of sila dehydroherbone, and achieves the effects of wide application range, simple and easy operation of experimental equipment and operation, and easy availability of raw materials

Active Publication Date: 2014-01-22
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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  • Silica hybrid dehydroherbac and preparing method thereof
  • Silica hybrid dehydroherbac and preparing method thereof
  • Silica hybrid dehydroherbac and preparing method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0027] Add 1 mol of 1,1-dimethylsilacyclobutane II, 1 mol of 3-butyn-2-one III, 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, use petroleum ether: ether=10:1 mixed solvent as eluent, obtain pure product sila dehydroherbone I (purity > 98%, colorless liquid), and the isolated yield 50%. The NMR and high resolution mass spectrometry data of this compound are as follows: 1 H NMR (CDCl 3 ) δ = 6.80 (s, 1H), 2.34-2.31 (m, 5H), 1.81-1.76 (m, 2H), 0.69-0.66 (m, 2H), 0.13 (s, 6H); 13 C NMR (CDCl 3 ) δ = 200.35, 156.47, 138.19, 27.75, 25.32, 20.95, 11.14, -2.30. HRMS: m / z : calcd for C 9 h 16 OSi [M+H] + : 169.1443, found 169.1449.

Embodiment 2

[0029] Add 2 mol of 1,1-dimethylsilacyclobutane II, 1 mol of 3-butyn-2-one III, 5% equivalent of (PPh 3 ) 2 PdCl 2 and 2 L of benzene solvent, heated to boiling, and reacted with magnetic stirring for 2 hours. Concentrate after the reaction, decolorize and separate on a silica gel column, and use a mixed solvent of petroleum ether: ether = 10:1 as the eluent to obtain the pure product sila dehydroherbalone I with an isolated yield of 65%. See Example 1 for NMR and high-resolution mass spectrometry data.

[0030] The reaction formula of embodiment 1 and embodiment 2 is as follows:

[0031]

[0032] Synthesis of siladehydroherbone I by two-step reaction

Embodiment 3

[0034] 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).

[0035] 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 , slowly dropwise added 10 mmol of MeMgBr 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 removed by rotary evaporation, decolorized and s...

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Abstract

The invention provides silica hybrid dehydroherbac, namely, 1-(3-silica hybrid-3, 3-dimethyl cyclohexyl-1-alkenyl) butanone. The silica hybrid dehydroherbac is shown in the formula I. The compound is a perfume compound with strong herb fragrance and oriental arborvitae fragrance and is also an important precursor of an organosilicon perfume compound corresponding to the perfume compounds including herbac, Roman musk, helvetolide and the like. Under the action of palladium catalysis, an inserting ring expansion reaction is conducted on silacyclobutane by end group alkyne, and the silica hybrid dehydroherbac is prepared with high yield. According to a method for preparing the silica hybrid dehydroherbac, raw materials are easy to obtain, the application range is wide, the separation production rate is high, experiment devices are simple, operation is easy to conduct, and industrialization is facilitated.

Description

technical field [0001] The invention belongs to the field of fragrance chemistry, and in particular relates to a compound of sila dehydroherbone 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. Dehydroherbac / Artemone (Dehydroherbac / Artemone, IV) is a kind of fragrance raw material with the fragrance of field herbs and the aroma of thujone, which is a patented product of Givaudan (US 20060046955A1); at the same time, dehydroherbac / Artemone It is also a synthetic intermediate of important fragrance raw materials (US 20040234568A1) such as herbal ketone, Roman musk, and Heifer musk. In recent years, replacing a quaternary carbon atom in t...

Claims

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Application Information

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IPC IPC(8): C07F7/08
Inventor 刘俊辉张启东柴国壁孙世豪李鹏刘珊卢斌斌屈展宗永立张建勋
Owner ZHENGZHOU TOBACCO RES INST OF CNTC
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