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A kind of sila dehydro herbal ketone and preparation method thereof

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

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 sila dehydro herbal ketone and preparation method thereof
  • A kind of sila dehydro herbal ketone and preparation method thereof
  • A kind of sila dehydro herbal ketone and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0026] Add 1 mol of 1,1-dimethylsilacyclobutane II, 1 mol of 3-butyn-2-one III, 1% equivalent of Pd(PPh 3 ) 4 and 5L of benzene solvent, heated to 80°C, and reacted with magnetic stirring for 4 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 (purity>98%, colorless liquid), and the isolated yield is 50%. The NMR and high resolution mass spectrometry data of this compound are as follows: 1 HNMR (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 CNMR (CDCl 3 )δ=200.35,156.47,138.19,27.75,25.32,20.95,11.14,-2.30.HRMS: m / z :calcdforC 9 h 16 OSi[M+H] + :169.1443, found 169.1449.

Embodiment 2

[0028] Add 2mol of 1,1-dimethylsilacyclobutane II, 1mol of 3-butyn-2-one III, 5% equivalent of (PPh 3 ) 2 PdCl 2 and 2L of benzene solvent, heated to boiling, and reacted with magnetic stirring for 2 hours. After the reaction, it was concentrated, decolorized and separated on a silica gel column, and a mixed solvent of petroleum ether: ether = 10:1 was used as the eluent to obtain the pure product sila dehydroherbone I with an isolated yield of 65%. See Example 1 for NMR and high-resolution mass spectrometry data.

[0029] The reaction formula of embodiment 1 and embodiment 2 is as follows:

[0030]

[0031] Synthesis of siladehydroherbone I by two-step reaction

Embodiment 3

[0033] 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).

[0034] Add 10mmol of 1,1-dimethyl-3-methoxycarbonyl-silacyclohexene and 150mL of THF to a 250mL round bottom flask, then cool to 0°C with an ice bath, and slowly drop Add 10 mmol of MeMgBr, dropwise for 1 hour. The reaction was quenched with 1M dilute hydrochloric acid solution, the resulting solution was extracted three times with ether, the solvent was removed by rotary evaporation, decolorized and separated on a silica...

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Abstract

The present invention provides sila dehydroherbalone represented by formula I, that is, 1-(3-sila-3,3-dimethylcyclohex-1-enyl)ethanone. The compound is a fragrance compound with a strong herbal fragrance and arborvitae fragrance, and is also an important precursor of organosilicon fragrance compounds corresponding to fragrance compounds such as herbal ketone, roman musk, and hevre musk. The invention adopts the ring-expansion reaction of terminal alkyne to silacyclobutane under the catalysis of palladium to prepare the sila dehydroherbalone 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 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 same aroma as thujone. It is a patented product of Givaudan (US20060046955A1); Synthetic intermediates of important fragrance raw materials (US20040234568A1) such as herbal ketone, Roman musk, and Heifer musk. In recent years, replacing a quaternary carbon atom in the structure of natural fragrance raw materials with ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07F7/08
Inventor 刘俊辉张启东柴国璧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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