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A kind of silica herbal ketone and preparation method thereof

A technology of herbal ketone and silicon impurity, which is applied in the field of compound and its general synthesis, to achieve the effect of easy-to-obtain raw materials, simple and easy-to-operate experimental equipment and operation, and high separation yield

Active Publication Date: 2016-01-20
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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  • A kind of silica herbal ketone and preparation method thereof
  • A kind of silica herbal ketone and preparation method thereof
  • A kind of silica herbal ketone and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0027] Add 1mol of 1,1-dimethylsilacyclobutane II, 1mol of 3-butyn-2-one III, 10% equivalent of (PPh 3 ) 2 PdCl 2 and 5L 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, 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: ethyl ether = 10:1 as the 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 HNMR (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 CNMR (CDCl 3 )δ212.92, 49.79, 31.24, 26.91, 23.12, 16.88, 13.38, -1.77, -4.20.HRMS: m / z :calcdforC ...

Embodiment 2

[0029] 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 2L 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 of reaction, concentrate to remove the solvent, decolorize and separate on a silica gel column, use a mixed solvent of petroleum ether: 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.

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

[0031]

[0032] Synthesis of Sizaherdone 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 5L 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: ether = 5:1 as an eluent to obtain the 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, 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 1M dilute hydrochloric acid solution, the resulting solution w...

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Abstract

The present invention provides sila herbone represented by formula I, that is, 1-(3-sila-3,3-dimethylcyclohexyl)ethanone. This compound is a fragrance compound with a strong herbal aroma. The invention adopts the intercalation and ring expansion reaction of terminal alkynes to silacyclobutane under the catalysis of palladium, and directly hydrogenates the silacyclobutane after completion of the ring expansion reaction to prepare the silacyclobutane with high yield. The method has easy-to-obtain raw materials, wide application range, high separation yield, simple experimental equipment and operation, and is convenient for industrialization.

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 Patents(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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