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Silica hybrid dehydroherbac and preparing method thereof

A technology of herbal ketones and silicon impurities, applied in the field of compounds and their general synthesis, to achieve the effects of easy-to-obtain raw materials, high separation yield, simple experimental equipment and operation

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

[0028] Add 1 mol of 1,1-dimethylsilacyclobutane II, 1 mol of 3-butyn-2-one III, 10% equivalent of (PPh 3 ) 2 PdCl 2 and 5 L of benzene solvent, heated to 80°C, and reacted with magnetic stirring for 4 hours. Cool the reactant to room temperature, add 10% equivalent Ru / C, maintain H 2 Pressure and normal pressure, after 2 hours after the reaction, concentrated to remove the solvent, decolorized and separated on a silica gel column, and used a mixed solvent of petroleum ether: ether=10:1 as an eluent to obtain the pure product Sizadone I (purity > 98%, Colorless liquid), isolated yield 60%. The NMR and high resolution mass spectrometry data of this compound are as follows: 1 H NMR (CDCl 3 ) δ = 2.45-2.38 (m, 1H), 2.12 (s, 3H), 2.06-2.02 (m, 1H), l.85-1.82 (m, 1H), 1.46-1.40 (m, 1H), 1.19- 1.11 (m, 1H), 0.89-0.86 (m, 1H), 0.74-0.71 (m, 1H), 0.60-0.54 (m, 1H), 0.47-0.41 (m, 1H), 0.07 (m, 3H), 0.03 (m, 3H). 13 C NMR (CDCl 3 ) δ 212.92, 49.79, 31.24, 26.91, 23.12, 16.88, 13...

Embodiment 2

[0030] Into a 5 L round bottom flask, add 1.5 mol of 1,1-dimethylsilacyclobutane II, 1 mol of 3-butyn-2-one III, 5% equivalent of Pd(PPh 3 ) 4 and 2 L of toluene solvent, heated to 100°C, and reacted with magnetic stirring for 2 hours. Cool the reactant to room temperature, add 10% equivalent of Pd / C, maintain H 2 Pressure and normal pressure, after 1 hour after the reaction, concentrate to remove the solvent, decolorize and separate on a silica gel column, use a mixed solvent of petroleum ether: ethyl ether = 10:1 as the eluent, and obtain the pure product Sizadone I, with an isolation yield of 56% . See Example 1 for NMR and high-resolution mass spectrometry data.

[0031] The reaction formula of embodiment 1 and embodiment 2 is as follows:

[0032]

[0033] Synthesis of Sizaherdone I by Two-step Reaction

Embodiment 3

[0035] 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).

[0036] Add 10 mmol of 1,1-dimethyl-3-methoxycarbonyl-silacyclohexene and 150 mL of THF to a 250 mL round bottom flask, add 10% equivalent Ni / C, and maintain H 2 Normal pressure, 1 hour after reaction. Then it was cooled to 0° C. with an ice bath, and 10 mmol of MeMgBr was slowly added dropwise under magnetic stirring for 1 hour. The reaction was quenched with 1 M dilute hydrochloric acid solution, the resulting ...

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PUM

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Abstract

The invention provides silica hybrid dehydroherbac, namely, 1-(3-silica hybrid-3, 3-dimethyl cyclohexyl) butanone. The silica hybrid dehydroherbac is shown in the formula I. The compound is a perfume compound with strong herb fragrance. Under the action of palladium catalysis, an inserting ring expansion reaction is conducted on silacyclobutane by end group alkyne, and after the ring expansion reaction is accomplished, hydrogenation is conducted directly, so that 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 spice chemistry, and in particular relates to a compound of silica herbone 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. Herbacone (herbac, IV) is a kind of fragrance raw material with strong herbal fragrance and high permeability. It is a product of International Flavor and Fragrance Company (IFF). 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 201...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F7/08
Inventor 刘俊辉孙世豪张启东李鹏毛健屈展刘珊卢斌斌宗永立张建勋
Owner ZHENGZHOU TOBACCO RES INST OF CNTC
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