CN1817842A - Synthesis of ketone-substituted alpha-ionone, ketone-substituted beta-ionone, ether and ester derivative by one-step method - Google Patents
Synthesis of ketone-substituted alpha-ionone, ketone-substituted beta-ionone, ether and ester derivative by one-step method Download PDFInfo
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- CN1817842A CN1817842A CN 200510003347 CN200510003347A CN1817842A CN 1817842 A CN1817842 A CN 1817842A CN 200510003347 CN200510003347 CN 200510003347 CN 200510003347 A CN200510003347 A CN 200510003347A CN 1817842 A CN1817842 A CN 1817842A
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Abstract
Synthesis of ketone-substituted alpha-ionone, ketone-substituted beta-ionone and its ester and ether derivative by one-step method is carried out by taking raw materials and copper halide or active copper powder and tert-butyl alcohol peroxide in solvent with proportion of 1mol:0.01-1mol:2-20mol:2-10ml and reacting at 40-80 degrees C for 45mins-8hrs.The tert-butyl alcohol peroxide is added by three times, adding time intermittence is that t1=0, t2=15mins-2hrs and t3=15mins-3hrs, copper halide is added before reacting or adding tert-butyl alcohol peroxide. It has higher recovery rate, non-toxic and environmental pollution and is safe. It can be used for essences and additives of fruits, tobaccos and flowers.
Description
Technical field
The present invention relates to copper halide or active copper powder and tertbutanol peroxide, catalyzed oxidation α-Zi Luolantong, the allylic of alpha, beta-lonone and ether thereof, ester derivative, the method for one-step synthesis ketenes.
Background technology
α-Zi Luolantong, alpha, beta-lonone and ether thereof, ester derivative is a natural aromatic plant as sweet osmanthus, violet, Herba Passiflorae Caeruleae, tealeaves, the important aroma constituent of tobacco etc., be widely used in fine chemistry industry, in pharmacy and the perfume industry, the allylic oxidation of its tetrahydrobenzene structure (and No. 3 positions, No. 4 position oxidations), not only can obtain other compounds so that further derive by this active group of carbonylate, and this compounds of what is more important is through allylic oxidation (and No. 3 positions, No. 4 position oxidations) after, the fragrance rare uniqueness that becomes, thereby be used for fruit, tobacco, in fresh flower essence or the additive, the flavouring flavoring has higher using value.
α-Zi Luolantong, though the method for the allylic oxidation one-step synthesis ketone of the tetrahydrobenzene structure of alpha, beta-lonone and ester derivative has caused scientist's concern very early, as: Oppenauer andOberrauch has prepared 4-oxidation-alpha, beta-lonone with chromic acid tert-butyl and chromium trioxide oxidation alpha, beta-lonone, Prelog and Osgan makes 3-oxidation-α-Zi Luolantong with chromic acid tert-butyl reflux oxidation α-Zi Luolantong in benzene, productive rate is 21%, it is 14% that usefulness Manganse Dioxide such as Hiroyuki and pentane acetic oxide α-violet ester make 3-acetic oxide-α-violet ester productive rate, Aasen, A.J. and Enzell, C.R. waiting and making 3-acetic oxide-α-violet ester productive rate with chromium trioxide acetic oxide α-violet ester in acetate is 17%, this shows that all there is the lower shortcoming of productive rate in these methods.
α-Zi Luolantong, the traditional method of the allylic oxidation one-step synthesis ketone of alpha, beta-lonone and ester derivative has been used stoichiometry chromium reagent (oxide compound of chromium or chromic salt or chromic acid tert-butyl), the productive rate of these methods not high (about 20%) can produce the more toxic chromium waste material that contains after the reaction.And there are shortcomings such as the title complex used precious metal, complicated reagent or reaction times is long in the method that is used for other substrates of report recently.
In addition, ether, butyl ether, benzyl oxide or phenyl ethyl ether with α-ionol and β-ionol, ether, butyl ether, benzyl oxide or the phenyl ethyl ether of one step allylic oxidation synthesis of ketone-substituted alpha-ionol, ketone yet there are no bibliographical information for ether, butyl ether, benzyl oxide or the phenyl ethyl ether of β-ionol.
Summary of the invention
A kind of raw material that the objective of the invention is to overcome above-mentioned shortcoming and provide is inexpensive, and the productive rate height can not produce toxic waste, the single stage method synthesis of ketone-substituted α-Zi Luolantong of safety and environmental protection, and ketone is for alpha, beta-lonone and ether thereof, ester derivative.
Single stage method synthesis of ketone-substituted α-Zi Luolantong of the present invention, ketone is for alpha, beta-lonone and ether thereof, ester derivative, be at organic solvent (acetonitrile with raw material and copper halide (halo mantoquita) or active copper powder and tertbutanol peroxide (tertbutyl peroxide), acetone, methylene dichloride, benzene or hexanaphthene) in 40～80 ℃ the reaction 45min～8h, wherein, raw material: copper halide (halo mantoquita) or active copper powder: tertbutanol peroxide: organic solvent is 1mol: 0.01～1mol: 2～20mol: 2～10ml, tertbutanol peroxide divides three addings, and the time of adding intermittently is t
1=0, t
2=15min～2h, t
3=15min～3h, copper halide (halo mantoquita) before reaction, once add or add tertbutanol peroxide at every turn before add (dividing three addings).
Above-mentioned one-step synthesis ketone-substituted alpha-jononeionone, ketone is for alpha, beta-lonone and ether thereof, the method of ester derivative, weighing according to the above ratio, in the reactor that agitator and prolong are housed, add raw material, organic solvent, copper halide (halo mantoquita) or active copper powder, stir the tertbutanol peroxide of dropping 1/3 down, 40～80 ℃ drip 1/3 tertbutanol peroxide behind reaction 15min～2h down again, after reacting 15min～3h again, drip remaining 1/3 tertbutanol peroxide again, continue reaction 15min～3h, steam solvent and butanols and tertbutanol peroxide under the decompression, add 10% sodium sulfite solution 20ml when leaving 5-10ml solution approximately, use 90ml extracted with diethyl ether three times, merge organic phase, evaporation is desolvated, and separates through silica gel column chromatography and (uses sherwood oil: ethyl acetate 4: 1), get product.
Above-mentioned single stage method synthesis of ketone-substituted α-Zi Luolantong, ketone is for alpha, beta-lonone and ether thereof, ester derivative, weighing according to the above ratio, in the reactor that agitator and prolong are housed, add raw material, organic solvent, copper halide (halo mantoquita) or active copper powder, stir the tertbutanol peroxide of dropping 1/3 down, reaction drips 1/3 tertbutanol peroxide after 1.5 hours again under 55 ℃, after reacting 1.5 hours again, drip remaining 1/3 tertbutanol peroxide again, continue reaction 2 hours, steam solvent and butanols and tertbutanol peroxide under the decompression, add 10% sodium sulfite solution 20ml when leaving 5-10ml solution approximately, use 90ml extracted with diethyl ether three times, merge organic phase, evaporation is desolvated, and separates through silica gel column chromatography and (uses sherwood oil: ethyl acetate 4: 1), get product.
Above-mentioned one-step synthesis ketone-substituted alpha-jononeionone, ketone is for alpha, beta-lonone and ether thereof, the method of ester derivative, in the reactor that agitator and prolong are housed, add raw material, organic solvent, 1/3 copper halide or active copper powder, stir the tertbutanol peroxide of dropping 1/3 down, 40～80 ℃ add down 1/3 copper halide or active copper powder behind reaction 15min～2h, drip 1/3 tertbutanol peroxide again, after reacting 15min～3h again, add 1/3 copper halide or active copper powder again, drip remaining 1/3 tertbutanol peroxide, continue reaction 15min～3h h, steam solvent and butanols and tertbutanol peroxide under the decompression, the sodium sulfite solution 20ml of adding 10% when leaving 5-10ml solution approximately, with 90ml extracted with diethyl ether three times, merge organic phase, evaporation is desolvated, (use sherwood oil: ethyl acetate 4: 1), get product through the silica gel column chromatography separation.
Above-mentioned one-step synthesis ketone-substituted alpha-jononeionone, ketone is for alpha, beta-lonone and ether thereof, the method of ester derivative, in the reactor that agitator and prolong are housed, add raw material, organic solvent, 1/3 copper halide or active copper powder, stir the tertbutanol peroxide of dropping 1/3 down, 55 ℃ add down 1/3 copper halide or active copper powder behind the reaction 1.5h, drip 1/3 tertbutanol peroxide again, after reacting 1.5h again, add 1/3 copper halide or active copper powder again, drip remaining 1/3 tertbutanol peroxide, continue reaction 2h, steam solvent and butanols and tertbutanol peroxide under the decompression, the sodium sulfite solution 20ml of adding 10% when leaving 5-10ml solution approximately, with 90ml extracted with diethyl ether three times, merge organic phase, evaporation is desolvated, (use sherwood oil: ethyl acetate 4: 1), get product through the silica gel column chromatography separation.
Above-mentioned single stage method synthesis of ketone-substituted α-Zi Luolantong, ketone is for alpha, beta-lonone and ether thereof, ester derivative, and wherein organic solvent is acetonitrile, acetone, methylene dichloride, benzene or hexanaphthene.
Above-mentioned single stage method synthesis of ketone-substituted α-Zi Luolantong, ketone is for alpha, beta-lonone and ether thereof, ester derivative, product is respectively ketone-substituted alpha-jononeionone 2a, ketone for alpha, beta-lonone 2b, ketone-substituted alpha-ionol carboxylicesters 2c, ketone ether (or the butyl ether for β-ionol carboxylicesters 2e, ketone-substituted alpha-ionol, benzyl oxide, phenyl ethyl ether) 2d, ketone are for ether (or the butyl ether of β-ionol, benzyl oxide, phenyl ethyl ether) 2f.
The present invention compared with prior art, with copper halide (halo mantoquita) or active copper powder and tertbutanol peroxide (tertbutyl peroxide) at organic solvent (acetonitrile, acetone, methylene dichloride, benzene or hexanaphthene) in 40～80 ℃ the reaction 0.5～8h, the catalyzed oxidation α-Zi Luolantong, alpha, beta-lonone and ether thereof, ester derivative, ketone-substituted alpha-jononeionone and ester thereof and ether have been prepared, ketone has been obtained 40～80% higher yields for alpha, beta-lonone and ester thereof and ether, can not produce the more toxic chromium waste material that contains after the reaction, safety and environmental protection, and its raw material is inexpensive, production cost is low, thereby has market popularization value.
Embodiment
Embodiment 1: the method for synthetic 3-oxidation α-Zi Luolantong 2a
At the bottom of being housed, the 100ml garden of stirrer and prolong adds α-Zi Luolantong 1a 0.96g (5mmol) in the flask, 40ml acetonitrile and 0.15g (1.5mmol) protochloride ketone, stir and drip tertbutanol peroxide 17mmol down, reaction drips tertbutanol peroxide 17mmol after 2 hours again under 55 ℃, after reacting 2 hours again, drip tertbutanol peroxide 16mmol again, continue reaction 2 hours, steam solvent acetonitrile and butanols and tertbutanol peroxide under the decompression, the sodium sulfite solution 20ml of adding 10% when leaving 5-10ml solution approximately, with 90ml extracted with diethyl ether three times, merge organic phase, evaporation is desolvated, (use sherwood oil: ethyl acetate 4: 1), get 3-oxidation α-Zi Luolantong 2a 0.82g, yield is 80% through the silica gel column chromatography separation.
Embodiment 2: the method for synthetic 4-oxidation alpha, beta-lonone 2b
At the bottom of being housed, the 100ml garden of stirrer and prolong adds alpha, beta-lonone 1b 0.96g (5mmol) in the flask, 30ml methylene dichloride and 0.15g (1.5mmol) protochloride ketone, stir and drip tertbutanol peroxide 17mmol down, reaction drips tertbutanol peroxide 17mmol after 2 hours again under 55 ℃, after reacting 2 hours again, drip tertbutanol peroxide 16mmol again, continue reaction 4h hour. steam methylene dichloride and butanols and tertbutanol peroxide under the decompression, the sodium sulfite solution 20ml of adding 10% when leaving 5-10ml solution approximately, with 90ml extracted with diethyl ether three times, merge organic phase, evaporation is desolvated, separate through silica gel column chromatography and (to use sherwood oil: ethyl acetate 4: 1), get 4-oxidation alpha, beta-lonone 2b 0.78g, yield is 76%.
Embodiment 3: the method for synthetic 3-acetic oxide α-violet ester 2c
At the bottom of being housed, the 100ml garden of stirrer and prolong adds α-ionol acetic ester 1c 1.18g (5mmol) in the flask, 40ml acetonitrile and 0.15g (1.5mmol) protochloride ketone, stir and drip tertbutanol peroxide 17mmol down, 55 ℃ are reacted after 2 hours down, drip tertbutanol peroxide 17mmol again, after reacting 2 hours again, drip tertbutanol peroxide 16mmol again, continue reaction 2-4 hour, steam solvent acetonitrile and butanols and tertbutanol peroxide under the decompression, the sodium sulfite solution 20ml of adding 10% when leaving 5-10ml solution approximately, with 90ml extracted with diethyl ether three times, merge organic phase, evaporation is desolvated, and separates through silica gel column chromatography and (uses sherwood oil: ethyl acetate 4: 1), get 3-acetic oxide α-violet ester 2c0.9g, yield is 72%
Embodiment 4: the method for synthetic 3-oxidation α-ionol ether 2d
At the bottom of being housed, the 100ml garden of stirrer and prolong adds α-ionol ether 1d1.18g (5mmol) in the flask, 40ml acetonitrile and 0.05g (0.5mmol) protochloride ketone, temperature remains on 55 ℃, stir and drip tertbutanol peroxide 4mol down, drip tertbutanol peroxide 3mol behind the reaction 20min, drip tertbutanol peroxide 3mol again after reacting 20min again, continue reaction 20min, steam solvent acetonitrile and butanols and tertbutanol peroxide under the decompression, the sodium sulfite solution 20ml of adding 10% when leaving 5-10ml solution approximately, with 90ml extracted with diethyl ether three times, merge organic phase, evaporation is desolvated, (use sherwood oil: ethyl acetate 4: 1), get 3-oxidation α-ionol ether 2d0.66g, yield is 56% through the silica gel column chromatography separation.
Embodiment 5: the method for synthetic 4-oxidation of beta-ionol ether 2f
At the bottom of being housed, the 100ml garden of stirrer and prolong adds β-ionol ether 1f 1.18g (5mmol) in the flask, 40ml acetonitrile and 0.025g (0.25mmol) protochloride ketone, temperature remains on 55 ℃, stir and drip tertbutanol peroxide 4mmol down, drip tertbutanol peroxide 3mol again behind the reaction 15min, drip tertbutanol peroxide 3mol again after reacting 15min again, continue reaction 15min, steam solvent acetonitrile and butanols and tertbutanol peroxide under the decompression, the sodium sulfite solution 20ml of adding 10% when leaving 5-10ml solution approximately, with 90ml extracted with diethyl ether three times, merge organic phase, evaporation is desolvated, (use sherwood oil: ethyl acetate 4: 1), get 4-oxidation of beta-ionol ether 2f0.61g, yield is 52% through the silica gel column chromatography separation.
Embodiment 6: the method for synthetic 4-acetic oxide β-violet ester 2e
At the bottom of being housed, 100 milliliters of gardens of stirrer and prolong add α-ionol acetic ester 1e1.18g (5mmol) in the flask, 30ml acetonitrile and 0.5g (0.5mmol) protochloride ketone, stir and drip tertbutyl peroxide 5mmol down, 55 ℃ add 0.25g (0.25mmol) protochloride ketone again and drip tertbutyl peroxide 5mmol behind the reaction 20min down, after reacting 20min again, add 0.25g (0.25mmol) protochloride ketone again, drip tertbutyl peroxide 5mmol, continue reaction 20min, steam solvent acetonitrile and butanols and tertbutyl peroxide under the decompression, the sodium sulfite solution 20ml of adding 10% when leaving 5-10ml solution approximately, with 90ml extracted with diethyl ether three times, merge organic phase, evaporation is desolvated, separate through silica gel column chromatography and (to use sherwood oil: ethyl acetate 4: 1), get 3-acetic oxide α-violet ester 2e0.78g, yield is 62%.
Embodiment 7: the method for synthetic 3-acetic oxide α-violet ester 2c
At the bottom of being housed, 100 milliliters of gardens of stirrer and prolong add α-ionol acetic ester 1c1.18g (5mmol) in the flask, 30ml acetone and 0.5g (0.5mmol) protochloride ketone, stir and drip tertbutyl peroxide 17mmol down, reaction added 0.25g (0.25mmol) protochloride ketone again and drips tertbutyl peroxide 17mmol after 2 hours under 55 ℃, after reacting 2 hours again, go into 0.25g (0.25mmol) protochloride ketone again, drip tertbutyl peroxide 16mmol, continue reaction 2 hours, steam solvent acetone and butanols and tertbutyl peroxide under the decompression, the sodium sulfite solution 20ml of adding 10% when leaving 5-10ml solution approximately, with 90ml extracted with diethyl ether three times, merge organic phase, evaporation is desolvated, separate through silica gel column chromatography and (to use sherwood oil: ethyl acetate 4: 1), get 3-acetic oxide α-violet ester 2c 0.81g, yield is 65%.
Embodiment 8-25:
| Embodiment | Obtain product | Raw material | Method | Organic solution | Yield |
| 8 | 3-oxidation α-ionol ether | α-ionol ether | With embodiment 4 | Acetonitrile, acetone, methylene dichloride, benzene or hexanaphthene | 54％ |
| 9 | 3-oxidation α-ionol butyl ether | α-ionol butyl ether | With embodiment 4 | Acetonitrile, acetone, methylene dichloride, benzene or hexanaphthene | 51％ |
| 10 | 3-oxidation α-ionol benzyl oxide | α-ionol benzyl oxide | With embodiment 4 | Acetonitrile, acetone, methylene dichloride, benzene or hexanaphthene | 50％ |
| 11 | The stupid ether of 3-oxidation α-ionol | The stupid ether of α-ionol | With embodiment 4 | Acetonitrile, acetone, methylene dichloride, benzene or hexanaphthene | 55％ |
| 12 | 4-oxidation of beta-ionol ether | β-ionol ether | With embodiment 4 | Acetonitrile, acetone, methylene dichloride, benzene or hexanaphthene | 42％ |
| 13 | 4-oxidation of beta-ionol butyl ether | β-ionol butyl ether | With embodiment 4 | Acetonitrile, methylene dichloride, benzene or hexanaphthene | 40％ |
| 14 | 4-oxidation α-ionol benzyl oxide | β-ionol benzyl oxide | With embodiment 4 | Acetonitrile, acetone, methylene dichloride, benzene or hexanaphthene | 54％ |
| 15 | The stupid ether of 4-oxidation of beta-ionol | The stupid ether of β-ionol | With embodiment 4 | Acetonitrile, acetone, methylene dichloride, benzene or hexanaphthene | 52％ |
| 16 | 3-oxidation butyric acid α-violet ester | Butyric acid α-violet ester | With embodiment 3 | Acetonitrile, acetone, methylene dichloride, benzene or | 64％ |
| Hexanaphthene | |||||
| 17 | 3-oxidation valeric acid α-violet ester | Valeric acid α-violet ester | With embodiment 3 | Acetonitrile, methylene dichloride, benzene or hexanaphthene | 62％ |
| 18 | 3-Oxybenzene acetate α-violet ester | Toluylic acid α-violet ester | With embodiment 3 | Acetonitrile, acetone, methylene dichloride, benzene or hexanaphthene | 65％ |
| 19 | 3-Oxybenzene formic acid α-violet ester | Phenylformic acid α-violet ester | With embodiment 3 | Acetonitrile, acetone, methylene dichloride, benzene or hexanaphthene | 60％ |
| 20 | 3-oxidation cinnamic acid α-violet ester | Cinnamic acid α-violet ester | With embodiment 3 | Acetonitrile, acetone, methylene dichloride, benzene or hexanaphthene | 66％ |
| 21 | 4-oxidation butyric acid β-violet ester | Butyric acid β-violet ester | With embodiment 3 | Acetonitrile, acetone, methylene dichloride, benzene or hexanaphthene | 54％ |
| 22 | 4-oxidation valeric acid β-violet ester | Valeric acid β-violet ester | With embodiment 5 | Acetonitrile, acetone, methylene dichloride, benzene or hexanaphthene | 53％ |
| 23 | 4-Oxybenzene acetate β-violet ester | Toluylic acid β-violet ester | With embodiment 5 | Acetonitrile, acetone, methylene dichloride, benzene or hexanaphthene | 55％ |
| 24 | 4-Oxybenzene formic acid β-violet ester | Phenylformic acid β-violet ester | With embodiment 5 | Acetonitrile, acetone, methylene dichloride, benzene or hexanaphthene | 50％ |
| 25 | 4-oxidation cinnamic acid β-violet ester | Cinnamic acid β-violet ester | With embodiment 5 | Acetonitrile, acetone, methylene dichloride, benzene or hexanaphthene | 50％ |
Claims (7)
1, a kind of single stage method synthesis of ketone-substituted α-Zi Luolantong, ketone is for alpha, beta-lonone and ether thereof, ester derivative, this method is with raw material and copper halide or active copper powder and tertbutanol peroxide 40～80 ℃ of reaction 45min～8h in organic solvent, wherein, raw material: copper halide or active copper powder: tertbutanol peroxide: organic solvent is 1mol: 0.01～1mol: 2～20mol: 2～10ml, tertbutanol peroxide divides three addings, and the time of adding intermittently is t
1=0, t
2=15min～2h, t
3=15min～3h, copper halide before reaction, once add or add tertbutanol peroxide at every turn before add.
2, one-step synthesis ketone-substituted alpha-jononeionone as claimed in claim 1, ketone is for alpha, beta-lonone and ether thereof, the method of ester derivative, in the reactor that agitator and prolong are housed, add raw material, organic solvent, copper halide or active copper powder, temperature remains between 40～80 ℃, stir the tertbutanol peroxide of dropping 1/3 down, drip 1/3 tertbutanol peroxide again behind reaction 15min～2h, after reacting 15min～3h again, drip remaining 1/3 tertbutanol peroxide again, continue reaction 15min～3h, steam solvent and butanols and tertbutanol peroxide under the decompression, add 10% sodium sulfite solution 20ml when leaving 5-10ml solution approximately, use 90ml extracted with diethyl ether three times, merge organic phase, evaporation is desolvated, and through using sherwood oil: ethyl acetate is that 4: 1 silica gel column chromatography separates, and gets product.
3, one-step synthesis ketone-substituted alpha-jononeionone as claimed in claim 2, ketone is for alpha, beta-lonone and ether thereof, the method of ester derivative, in the reactor that agitator and prolong are housed, add raw material, organic solvent, copper halide or active copper powder, temperature remains on 55 ℃, stir the tertbutanol peroxide of dropping 1/3 down, drip 1/3 tertbutanol peroxide again behind the reaction 1.5h, after reacting 1.5h again, drip remaining 1/3 tertbutanol peroxide again, continue reaction 2h, steam solvent and butanols and tertbutanol peroxide under the decompression, add 10% sodium sulfite solution 20ml when leaving 5-10ml solution approximately, use 90ml extracted with diethyl ether three times, merge organic phase, evaporation is desolvated, and through using sherwood oil: ethyl acetate is that 4: 1 silica gel column chromatography separates, and gets product.
4, one-step synthesis ketone-substituted alpha-jononeionone as claimed in claim 1, ketone is for alpha, beta-lonone and ether thereof, the method of ester derivative, in the reactor that agitator and prolong are housed, add raw material, organic solvent, 1/3 copper halide or active copper powder, temperature remains between 40～80 ℃, stir the tertbutanol peroxide of dropping 1/3 down, the copper halide or the active copper powder of adding 1/3 behind reaction 15min～2h, drip 1/3 tertbutanol peroxide again, after reacting 15min～3h again, add 1/3 copper halide or active copper powder again, drip remaining 1/3 tertbutanol peroxide, continue reaction 15min～3h, steam solvent and butanols and tertbutanol peroxide under the decompression, add 10% sodium sulfite solution 20ml when leaving 5-10ml solution approximately, use 90ml extracted with diethyl ether three times, merge organic phase, evaporation is desolvated, and through using sherwood oil: ethyl acetate is that 4: 1 silica gel column chromatography separates, and gets product.
5, one-step synthesis ketone-substituted alpha-jononeionone as claimed in claim 4, ketone is for alpha, beta-lonone and ether thereof, the method of ester derivative, in the reactor that agitator and prolong are housed, add raw material, organic solvent, 1/3 copper halide or active copper powder, temperature remains on the tertbutanol peroxide of dropping 1/3 under 55 ℃ of stirrings, the copper halide or the active copper powder of adding 1/3 behind the reaction 1.5h, drip 1/3 tertbutanol peroxide again, after reacting 1.5h again, add 1/3 copper halide or active copper powder again, drip remaining 1/3 tertbutanol peroxide, continue reaction 1.5h, steam solvent and butanols and tertbutanol peroxide under the decompression, the sodium sulfite solution 20ml of adding 10% when leaving 5-10ml solution approximately, with 90ml extracted with diethyl ether three times, merge organic phase, evaporation is desolvated, through using sherwood oil: ethyl acetate is that 4: 1 silica gel column chromatography separates, and gets product.
6, as the described one-step synthesis ketone-substituted alpha-jononeionone of one of claim 1-5, ketone is for the method for alpha, beta-lonone and ether thereof, ester derivative, and wherein organic solvent is acetonitrile, acetone, methylene dichloride, benzene or hexanaphthene.
7, one-step synthesis ketone-substituted alpha-jononeionone as claimed in claim 6, ketone is for alpha, beta-lonone and ether thereof, the method of ester derivative, wherein product is respectively ketone-substituted alpha-jononeionone 2a, ketone is for alpha, beta-lonone 2b, ketone-substituted alpha-ionol carboxylicesters 2c, ketone is for β-ionol carboxylicesters 2e, the ether 2d of ketone-substituted alpha-ionol, the butyl ether 2d of ketone-substituted alpha-ionol, the benzyl oxide 2d of ketone-substituted alpha-ionol, the phenyl ethyl ether 2d of ketone-substituted alpha-ionol, ketone is for the ether 2f of β-ionol, ketone is for the butyl ether 2f of β-ionol, ketone is for the benzyl oxide 2f of β-ionol, ketone is for the phenyl ethyl ether 2f of β-ionol.
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| CN102260153A (en) * | 2011-05-31 | 2011-11-30 | 湖南中烟工业有限责任公司 | Method for synthesizing 4-oxo-beta-damascone |
| JP2014532745A (en) * | 2011-11-09 | 2014-12-08 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Process for producing oxovinylionol and its O-protected derivative |
| EP2776447B1 (en) | 2011-11-09 | 2018-05-30 | Basf Se | Method for producing oxo-vinyl-ionol and o-protected derivatives thereof |
| EP2776447B2 (en) † | 2011-11-09 | 2022-01-05 | Basf Se | Method for producing oxo-vinyl-ionol and o-protected derivatives thereof |
| CN106478418A (en) * | 2016-10-09 | 2017-03-08 | 湖北中烟工业有限责任公司 | The cigarette preparation method and applications of latent perfume 3 cinnamic acid esters of monomer |
| CN106631781A (en) * | 2016-10-09 | 2017-05-10 | 湖北中烟工业有限责任公司 | Preparation method of cigarette precursor-aroma phenylpropionic ester and application thereof |
| CN106478418B (en) * | 2016-10-09 | 2018-10-02 | 湖北中烟工业有限责任公司 | The preparation method and applications of the latent fragrant monomer 3- cinnamic acid esters of cigarette |
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| CN100361948C (en) | 2008-01-16 |
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