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A kind of sila-beta-dynasty ketone and its preparation method

A kind of technology of dynasty ketone and silylated ketone, which is applied in the field of silylated-β-dynastic ketone compound and its general synthesis, and achieves the effects of simple and easy experimental equipment and operation, wide application range and high separation yield.

Active Publication Date: 2016-03-16
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-beta-dynasty ketone and its preparation method
  • A kind of sila-beta-dynasty ketone and its preparation method
  • A kind of sila-beta-dynasty ketone and its preparation method

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0026] 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 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, use a mixed solvent of petroleum ether: ether = 10:1 as an eluent, and obtain the pure product sila-β-dynasone I (purity>98%, colorless liquid), and isolate the product The rate is 57%. The NMR and high resolution mass spectrometry data of this compound are as follows: 1 HNMR (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 =5.5Hz,2H),2.37-2.32(m,4H),1.82-1.76(m,2H),0.70-0.67(m,2H),0.135(s,6H). 13 CNMR (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 :calcdforC 12 h 20 OSi[M+H] + :209.1356, found 209.1352.

[0027] The reaction formula is as follows:

[0028]

[0029] Two-step Reaction Synthesis of Sila-β-Dynastone I

Embodiment 2

[0031] 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).

[0032] 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 10mmol homoallyl bromide and 50mg magnesium chips, and add 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 evaporatio...

Embodiment 3

[0036] Add 1.5 mol of 1,1-dimethylsilacyclobutane II, 1 mol of ethyl propiolate, 10% equivalent of Pd(PPh 3 ) 4 and 2L of toluene solvent, heated to 90°C, and reacted with mechanical 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 an eluent to obtain the 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 HNMR (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 CNMR (CDCl 3 ):d=167.17,148.26,1137.75,60.60,29.18,21.16,14.22,11.07,-2.37;HRMS: m / z :calcdforC 10 h 18 o 2 Si[M+H] +:199.1149,found199.1145.

[0037] Add 10mmol of 1,1-dimethyl-3-ethoxycarbonyl-silacyclohexene and 150mL of THF to a 250mL round bottom flask, then cool to 0°C with an ice ...

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Abstract

The present invention provides sila-β-dynasty ketone represented by formula I, that is, 1-(3-sila-3,3-dimethylcyclohex-1-enyl)pent-4-en-1- ketone. This compound is a fragrance compound with a strong pineapple aroma. The invention adopts the intercalation and ring expansion reaction of terminal alkyne to silacyclobutane under the catalysis of palladium to prepare the sila-beta-dynasone 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 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 fragrance material, which is a patented product of Firmenich (US4264467A). 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 (US008182781...

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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