CN101698636B - Method for synthesizing beta-damascenone - Google Patents
Method for synthesizing beta-damascenone Download PDFInfo
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- CN101698636B CN101698636B CN 200910197780 CN200910197780A CN101698636B CN 101698636 B CN101698636 B CN 101698636B CN 200910197780 CN200910197780 CN 200910197780 CN 200910197780 A CN200910197780 A CN 200910197780A CN 101698636 B CN101698636 B CN 101698636B
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Abstract
The invention discloses a method for synthesizing beta-damascenone, comprising three steps as follows: performing Grignard reaction on cyclized ethyl geranate and allylmagnesium chloride to obtain 2,6,6-trimethyl-1-(4-hydroxy-heptose-1,6-diene-4-base)-hexamethylene-1-alkene; decomposing 2,6,6-trimethyl-1-(4-hydroxy-heptose-1,6-diene-4-base)-hexamethylene-1-alkene to obtain 2,6,6-trimethyl-1-(butyl-3-acyl)-hexamethylene-1-alkene and 2,6,6-trimethyl-1(butyl-3-acyl)-hexamethylene-1-alkene; and performing isomerisation to obtain the beta-damascenone. The method for synthesizing beta-damascenone in the invention makes an improvement on decomposition reaction in a traditional method, uses easily obtained raw materials, has mild reaction conditions, safer and friendly process and high product yield. The product has intensive and pleasant rose fragrance, is an important raw material in daily health essence and is a very useful edible flavor.
Description
Technical field
The present invention relates to a kind of synthetic method of β-damascone.
Background technology
Alicyclic ring ketone such as damascone and Tujue's ketenes, especially α and β-damascone and β-Tujue's ketenes, the popularity of using in daily essence and food flavour industry constantly increases.β-damascone has strong and happy rose fragrance, and is elegant in smell, and still daily use chemicals and are not very useful flavouring agents with the important source material of essence.
Its chemical name of β-damascone is: 2,6,6-trimethylammonium-1-(but-2-ene acyl)-hexamethylene-1-alkene.The synthetic method of at present common β-damascone, take beta-cyclized ethyl geranate as raw material and allylmgcl carry out grignard reaction and generate 2,6,6-trimethylammonium-1-(4-hydroxyl-heptan-1,6-diene-4-yl)-hexamethylene-1-alkene, 2,6,6-trimethylammonium-1-(4-hydroxyl-heptan-1,6-diene-4-yl)-hexamethylene-1-alkene carries out decomposition reaction and generates 2,6,6-trimethylammonium-1-(fourth-3-alkene acyl)-hexamethylene-1-alkene uses acid catalysis, at last to 2,6,6-trimethylammonium-1-(fourth-3-alkene acyl)-hexamethylene-1-alkene carries out isomerization reaction and makes β-damascone.2,6,6-trimethylammonium-1-(4-hydroxyl-heptan-1,6-diene-4-yl)-hexamethylene-when 1-alkene carries out decomposition reaction, use metal hydride [Tetrahedron Letters, Vol.23, No.3, pp335-338,1982], and the metal hydride moisture-sensitive easily fires, and therefore is unfavorable for safety in production.
Summary of the invention
The object of the invention provides a kind of mild condition, easy handling, environmentally safe close friend, reacts the synthetic method of the high β-damascone of yield.
The reaction mechanism of synthetic method of the present invention is as follows:
The first step, take ether as solvent, chlorallylene and magnesium are made the allylmgcl Grignard reagent, and beta-cyclized ethyl geranate and allylmgcl are carried out grignard reaction and are made 2,6,6-trimethylammonium-1-(4-hydroxyl-heptan-1,6-diene-4-yl)-hexamethylene-1-alkene;
Second step is aided with phase-transfer catalyst with caustic alkali, to upper step reaction make 2,6,6-trimethylammonium-1-(4-hydroxyl-heptan-1,6-diene-4-yl)-hexamethylene-1-alkene carries out decomposition reaction and generates 2,6,6-trimethylammonium-1-(fourth-3-alkene acyl)-hexamethylene-1-alkene;
The 3rd step, use acid catalysis, to 2,6 of decomposition reaction generation of upper step, 6-trimethylammonium-1-(fourth-3-alkene acyl)-hexamethylene-1-alkene carries out isomerization reaction, makes β-damascone.
The reaction formula of β of the present invention-damascone synthetic method is as follows:
A: the first step reaction, the preparation of 2,6,6-trimethylammonium-1-(4-hydroxyl-heptan-1,6-diene-4-yl)-hexamethylene-1-alkene
B: second step reaction, the preparation of 2,6,6-trimethylammonium-1-(fourth-3-alkene acyl)-hexamethylene-1-alkene
C: three-step reaction, the preparation of β-damascone
Technical scheme of the present invention
β of the present invention-damascone synthetic method comprises the steps:
The first step: the preparation of 2,6,6-trimethylammonium-1-(4-hydroxyl-heptan-1,6-diene-4-yl)-hexamethylene-1-alkene
1., chlorallylene Grignard reagent
In reaction vessel, with the quality of magnesium and solvent 1 in magnesium: solvent is that 1: 2.4～2.6 ratio joins wherein, the control mixing speed is 120r/min, the mass ratio that begins to drip chlorallylene and solvent 2 is by chlorallylene: solvent is 1.1～1.2: 1 mixed solution, the control drop rate is 5g/min, dropwise, insulation reaction 1h namely gets the chlorallylene Grignard reagent;
Above-mentioned said solvent 1 and solvent 2 are anhydrous diethyl ether or isopropyl ether;
The amount of the chlorallylene that wherein drips is chlorallylene by itself and magnesium in mass ratio: magnesium is 84.2g: 28.8g;
2., 2,6, the preparation of the thick oil of 6-trimethylammonium-1-(4-hydroxyl-heptan-1,6-diene-4-yl)-hexamethylene-1-alkene
1. in the chlorallylene Grignard reagent of gained, the control mixing speed is 120r/min in step, and during beta-cyclized ethyl geranate was added dropwise to, the beta-cyclized ethyl geranate amount of dropping is beta-cyclized ethyl geranate by the mass ratio of itself and magnesium: magnesium was 3.47: 1;
The drop rate of gate ring ethyl geranate is 6g/min, dropwises, and insulation reaction 2～3h gets reaction solution A;
3., the separating, washing of reaction solution
With step 2. the reaction solution A of gained be cooled to 20～25 ℃, pour in the saturated aqueous ammonium chloride, standing demix is told the upper strata organic layer, lower aqueous layer, the upper strata organic layer is extremely neutral with the tap water washing, and standing demix discards lower aqueous layer again, namely get 2,6,6-trimethylammonium-1-(4-hydroxyl-heptan-1,6-diene-4-yl)-hexamethylene-1-alkene is oil slightly;
Wherein the amount of saturated aqueous ammonium chloride by itself and step 2. the mass ratio of the reaction solution A of gained be saturated aqueous ammonium chloride: the step 2. reaction solution A of gained is 2.8: 1;
4., underpressure distillation
With step 3. gained 2,6,6-trimethylammonium-1-(4-hydroxyl-heptan-1,6-diene-4-yl)-hexamethylene-1-alkene is slightly oily, underpressure distillation behind the normal pressure recovery solvent, first paragraph is the chieftain of 70～120 ℃/4mmHg, second segment is the finished product 2 of 120～122 ℃/4mmHg, 6,6-trimethylammonium-1-(4-hydroxyl-heptan-1,6-diene-4-yl)-hexamethylene-1-alkene, finished product 2,6,6-trimethylammonium-1-(4-hydroxyl-heptan-1,6-diene-4-yl)-hexamethylene-1-alkene is more than 90% through gas chromatographic analysis content.
Second step: the preparation of 2,6,6-trimethylammonium-1-(fourth-3-alkene acyl)-hexamethylene-1-alkene
1., the hybrid reaction of raw material
In reaction vessel, sodium hydroxide with 40% or 40% potassium hydroxide by its with the first step in step 4. finally 2 of gained, 6,6-trimethylammonium-1-(4-hydroxyl-heptan-1,6-diene-4-yl)-and the mass ratio of hexamethylene-1-alkene i.e. 40% sodium hydroxide or 40% potassium hydroxide: 2,6,6-trimethylammonium-1-(4-hydroxyl-heptan-1,6-diene-4-yl)-and hexamethylene-1-alkene is 1: 1.65～1.67 ratio, the sodium hydroxide with 40% or 40% potassium hydroxide join in the container;
With phase-transfer catalyst by its with the first step in step 4. finally 2 of gained, 6,6-trimethylammonium-1-(4-hydroxyl-heptan-1,6-diene-4-yl)-and the mass ratio of hexamethylene-1-alkene is phase-transfer catalyst: 2,6,6-trimethylammonium-1-(4-hydroxyl-heptan-1,6-diene-4-yl)-hexamethylene-1-alkene is that 1: 13.4～21.8 ratio also joins in the container;
The control mixing speed is 120r/min, temperature is 20～30 ℃, begin to drip step in the first step 4. final gained 2,6,6-trimethylammonium-1-(4-hydroxyl-heptan-1,6-diene-4-yl)-hexamethylene-1-alkene, the control drop rate is 6g/min, dropwises, and reaction solution is warming up to 80 ℃ gradually, continue to stir 2～3h, get reaction solution B;
Above-mentioned said phase-transfer catalyst is tetra-n-butyl ammonium bromide or triethyl benzyl ammonia chloride (TEBA) or cetyl trimethylammonium bromide;
2., the separating and extracting of reaction solution
With above-mentioned steps 1. the reaction solution B of gained be cooled to 20～25 ℃, add tap water, standing demix is told organic layer, is slightly oil of 2,6,6-trimethylammonium-1-(fourth-3-alkene acyl)-hexamethylene-1-alkene;
Wherein the amount of tap water by itself and above-mentioned steps 1. the mass ratio of the reaction solution B of gained be tap water: the above-mentioned steps 1. reaction solution B of gained is 1: 1.8;
3., underpressure distillation
With above-mentioned steps 2. gained 2,6,6-trimethylammonium-1-(fourth-3-alkene acyl)-hexamethylene-thick oil of 1-alkene carries out underpressure distillation, first paragraph is the chieftain of 60～104 ℃/4mmHg, and second segment is the finished product 2,6 of 104～106 ℃/4mmHg, 6-trimethylammonium-1-(fourth-3-alkene acyl)-hexamethylene-1-alkene, finished product 2,6, (fourth-3-alkene acyl)-hexamethylene-1-alkene is more than 90% through gas chromatographic analysis content to 6-trimethylammonium-1-;
The 3rd step: the preparation of β-damascone
1., the hybrid reaction of raw material
In reaction vessel, with step in the second step 3. gained 2,6, the mass ratio of 6-trimethylammonium-1-(fourth-3-alkene acyl)-hexamethylene-1-alkene and solvent 3 is by 2,6,6-trimethylammonium-1-(fourth-3-alkene acyl)-hexamethylene-1-alkene: solvent 3 be 1: 7.4～7.6 with solvent 3 join the step that contains in the second step 3. gained 2,6, in the container of 6-trimethylammonium-1-(fourth-3-alkene acyl)-hexamethylene-1-alkene;
With tosic acid by the step in itself and the second step 3. gained 2,6, the mass ratio of 6-trimethylammonium-1-(fourth-3-alkene acyl)-hexamethylene-1-alkene is tosic acid: 2,6,6-trimethylammonium-1-(fourth-3-alkene acyl)-hexamethylene-1-alkene is that 1: 20.1～21.8 ratio also joins it in container, and the control mixing speed is 120r/min, and temperature of reaction is controlled at 60 ℃, reaction 2～3h gets reaction liquid C;
Above-mentioned said solvent 3 is tetrahydrofuran (THF), toluene or dimethylbenzene;
2., the separating and extracting of reaction solution
With above-mentioned steps 1. the reaction liquid C of gained be cooled to 20～25 ℃, add 10% yellow soda ash neutralization, standing demix is told organic layer, is slightly oil of 2,6,6-trimethylammonium-1-(but-2-ene acyl)-hexamethylene-1-alkene;
Wherein the amount of 10% yellow soda ash is by 1. i.e. 10% yellow soda ash of mass ratio of the reaction liquid C of gained of itself and above-mentioned steps: the above-mentioned steps 1. reaction liquid C of gained is 1: 3.3～3.7;
3., vacuum fractionation
With above-mentioned steps 2. gained 2,6,6-trimethylammonium-1-(but-2-ene acyl)-hexamethylene-1-alkene is oil slightly, after normal pressure reclaims solvent, carry out vacuum fractionation, first paragraph is the chieftain of 70～98 ℃/5～6mmHg, and second segment is finished product β-damascone of 98～100 ℃/5～6mmHg, and finished product β-damascone is through gas chromatographic analysis cis, trans-isomer(ide) total content 〉=98%.
Beneficial effect of the present invention
The present invention has overcome in the prior art, and 2,6,6-trimethylammonium-1-(4-hydroxyl-heptan-1,6-diene-4-yl)-hexamethylene-when 1-alkene carries out decomposition reaction, use moisture-sensitive easily fires, and is unfavorable for the metal hydride of keeping the safety in production.The present invention uses sodium hydroxide or potassium hydroxide to be aided with the phase-transfer catalyst of quaternary ammonium salt when carrying out decomposition reaction, so that decomposition reaction mild condition, easy handling, environmentally safe close friend, reaction yield are high, and the content of finished product β-damascone 〉=98%.
Description of drawings
Fig. 1, the reaction formula of β-damascone synthetic method
Embodiment
Below by embodiment the present invention is further set forth, but do not limit the present invention.
Embodiment 1
(1), 2,6, the preparation of 6-trimethylammonium-1-(4-hydroxyl-heptan-1,6-diene-4-yl)-hexamethylene-1-alkene
In 500 milliliters of there-necked flasks of agitator, thermometer, dropping funnel and spherical condensation tube are housed, add 28.8 gram (1.2mol) magnesium, iodine and anhydrous diethyl ether (add-on is 100 milliliters), the control mixing speed is 120r/min, begin to drip 84.2 gram (1.1mol) chlorallylene and anhydrous diethyl ether (add-on is 100 milliliters) mixed solutions, the control drop rate is 5g/min, dropwise insulation reaction 1h.Then, begin to drip 100 gram content and be 98% beta-cyclized ethyl geranate (0.5mol), control drop rate is 6g/min, dropwises, and continues stirring 2h.Reaction solution is poured into 1000 milliliters of saturated aqueous ammonium chlorides, tell organic layer, once extremely neutral with the washing of 500 ml waters.Underpressure distillation behind the normal pressure recovery solvent, first paragraph is chieftain's 17 grams of 70～120 ℃/4mmHg, second segment is the finished product 2 of 120～122 ℃/4mmHg, 6,6-trimethylammonium-1-(4-hydroxyl-heptan-1,6-diene-4-yl)-and hexamethylene-1-alkene, weight is 108.5 grams (gas-chromatography content is 92.34%), the reaction yield is 85.6% (in beta-cyclized ethyl geranate).
(2), 2,6, the preparation of 6-trimethylammonium-1-(fourth-3-alkene acyl)-hexamethylene-1-alkene
Agitator is being housed, thermometer, in 250 milliliters of there-necked flasks of dropping funnel and spherical condensation tube, add 65 gram weight concentration and be 40% sodium hydroxide (0.65mol) and 7.1 gram (0.022mol) phase-transfer catalyst tetra-n-butyl ammonium bromides, in 20～30 ℃, the control mixing speed is 120r/min, the content that step reaction makes in the dropping be 92.34% 2,6,6-trimethylammonium-1-(4-hydroxyl-heptan-1,6-diene-4-yl)-hexamethylene-1-alkene 108.5 grams (0.43mol), the control drop rate is 6g/min, dropwise, reaction solution is warming up to 80 ℃ gradually, continue to stir 2～3h.Gas chromatographic analysis raw material 2,6,6-trimethylammonium-1-(4-hydroxyl-heptan-1,6-diene-4-yl)-and hexamethylene-1-alkene content is below 0.5%, reaction finishes, and is cooled to 20～25 ℃, add 100 ml waters, tell organic layer, carry out underpressure distillation, first paragraph is chieftain's 6 grams of 60～104 ℃/4mmHg, second segment is the finished product 2 of 104～106 ℃/4mmHg, 6,6-trimethylammonium-1-(fourth-3-alkene acyl)-hexamethylene-1-alkene, weight is 84.5 grams (gas-chromatography content is 94.05%), the reaction yield is 96.3% (with 2,6,6-trimethylammonium-1-(4-hydroxyl-heptan-1,6-diene-4-yl)-hexamethylene-1-alkene meter).
(3), the preparation of β-damascone
In 1000 milliliters of there-necked flasks of agitator, thermometer, dropping funnel and spherical condensation tube are housed, add 84.5 grams 2,6,6-trimethylammonium-1-(fourth-3-alkene acyl)-hexamethylene-1-alkene (gas-chromatography content is 94.05%) and solvent (adopt tetrahydrofuran (THF), 732 milliliters of add-ons) and 4.2 the gram tosic acid (add-on is 2,6,6-trimethylammonium-1-(fourth-3-alkene acyl)-hexamethylene-1-alkene weight 5%), the control mixing speed is 120r/min, temperature of reaction is controlled at 60 ℃, reaction 2～3h.Gas chromatographic analysis raw material 2,6,6-trimethylammonium-1-(fourth-3-alkene acyl)-hexamethylene-1-alkene content is below 0.5%, and reaction finishes, and is cooled to 20～25 ℃, add the neutralization of 10% yellow soda ash, standing demix is told organic layer, is 2,6,6-trimethylammonium-1-(but-2-ene acyl)-hexamethylene-1-alkene is oil slightly.Vacuum fractionation behind the normal pressure recovery solvent, first paragraph is chieftain's 4 grams of 70～98 ℃/5～6mmHg, second segment is finished product β-damascone of 98～100 ℃/5～6mmHg, weight is 77.5 grams ((gas chromatographic analysis) cis, trans-isomer(ide) total content are 99.25%), the reaction yield is 96.8% (with 2,6,6-trimethylammonium-1-(fourth-3-alkene acyl)-hexamethylene-1-alkene meter).
Embodiment 2
(1), 2,6, the preparation of 6-trimethylammonium-1-(4-hydroxyl-heptan-1,6-diene-4-yl)-hexamethylene-1-alkene
In 500 milliliters of there-necked flasks of agitator, thermometer, dropping funnel and spherical condensation tube are housed, add 28.8 gram (1.2mol) magnesium, iodine and isopropyl ether (add-on is 100 milliliters), the control mixing speed is 120r/min, begin to drip 84.2 gram (1.1mol) chlorallylene and isopropyl ether (add-on is 100 milliliters) mixed solutions, the control drop rate is 5g/min, dropwise insulation reaction 1h.Then, begin to drip 100 gram content and be 98% beta-cyclized ethyl geranate (0.5mol), control drop rate is 6g/min, dropwises, and continues stirring 3h.Reaction solution is poured into 1000 milliliters of saturated aqueous ammonium chlorides, tell organic layer, once extremely neutral with the washing of 500 ml waters.Underpressure distillation behind the normal pressure recovery solvent, first paragraph is chieftain's 12 grams of 70～120 ℃/4mmHg, second segment is the finished product 2 of 120～122 ℃/4mmHg, 6,6-trimethylammonium-1-(4-hydroxyl-heptan-1,6-diene-4-yl)-and hexamethylene-1-alkene, weight is 109 grams (gas-chromatography content is 93.5%), the reaction yield is 87.1% (in beta-cyclized ethyl geranate).
(2), 2,6, the preparation of 6-trimethylammonium-1-(fourth-3-alkene acyl)-hexamethylene-1-alkene
Agitator is being housed, thermometer, in 250 milliliters of there-necked flasks of dropping funnel and spherical condensation tube, add 66 gram weight concentration and be 40% sodium hydroxide (0.66mol) and 5 gram (0.022mol) phase-transfer catalyst TEBA triethyl benzyl ammonia chlorides, the control mixing speed is 120r/min, in 20～30 ℃, the gas-chromatography content that step reaction makes in the dropping be 93.5% 2,6,6-trimethylammonium-1-(4-hydroxyl-heptan-1,6-diene-4-yl)-hexamethylene-1-alkene 109 grams (0.44mol), the control drop rate is 6g/min, dropwise, reaction solution is warming up to 80 ℃ gradually, continue to stir 2～3h.Gas chromatographic analysis raw material 2,6,6-trimethylammonium-1-(4-hydroxyl-heptan-1,6-diene-4-yl)-and hexamethylene-1-alkene content is below 0.5%, reaction finishes, and is cooled to 20～25 ℃, add 100 ml waters, tell organic layer, carry out underpressure distillation, first paragraph is chieftain's 4.5 grams of 60～104 ℃/4mmHg, second segment is the finished product 2 of 104～106 ℃/4mmHg, 6,6-trimethylammonium-1-(fourth-3-alkene acyl)-hexamethylene-1-alkene, weight is 81.5 grams (gas-chromatography content is 94.55%), the reaction yield is 91.2% (with 2,6,6-trimethylammonium-1-(4-hydroxyl-heptan-1,6-diene-4-yl)-hexamethylene-1-alkene meter).
(3), the preparation of β-damascone
In 1000 milliliters of there-necked flasks of agitator, thermometer, dropping funnel and spherical condensation tube are housed, add 81.5 grams 2,6,6-trimethylammonium-1-(fourth-3-alkene acyl)-hexamethylene-1-alkene (gas-chromatography content is 94.55%) and solvent (adopt toluene, 706 milliliters of add-ons) and 4.1 the gram tosic acid (add-on is 2,6,6-trimethylammonium-1-(fourth-3-alkene acyl)-hexamethylene-1-alkene weight 5%), the control mixing speed is 120r/min, temperature of reaction is controlled at 60 ℃, reaction 2～3h.Gas chromatographic analysis raw material 2,6,6-trimethylammonium-1-(fourth-3-alkene acyl)-hexamethylene-1-alkene content is below 0.5%, and reaction finishes, and is cooled to 20～25 ℃, add the neutralization of 10% yellow soda ash, standing demix is told organic layer, is 2,6,6-trimethylammonium-1-(but-2-ene acyl)-hexamethylene-1-alkene is oil slightly.Vacuum fractionation behind the normal pressure recovery solvent, first paragraph is chieftain's 3.5 grams of 70～98 ℃/5～6mmHg, second segment is finished product β-damascone of 98～100 ℃/5～6mmHg, weight is 74.5 grams ((gas chromatographic analysis) cis, trans-isomer(ide) total content are 98.75%), the reaction yield is 95.6% (with 2,6,6-trimethylammonium-1-(fourth-3-alkene acyl)-hexamethylene-1-alkene meter).
Embodiment 3
(1), 2,6, the preparation of 6-trimethylammonium-1-(4-hydroxyl-heptan-1,6-diene-4-yl)-hexamethylene-1-alkene
In 500 milliliters of there-necked flasks of agitator, thermometer, dropping funnel and spherical condensation tube are housed, add 28.8 gram (1.2mol) magnesium, iodine and anhydrous diethyl ether (add-on is 100 milliliters), the control mixing speed is 120r/min, begin to drip 84.2 gram (1.1mol) chlorallylene and anhydrous diethyl ether (add-on is 100 milliliters) mixed solutions, the control drop rate is 5g/min, dropwise insulation reaction 1h.Then, begin to drip 100 gram content and be 98% beta-cyclized ethyl geranate (0.5mol), control drop rate is 6g/min, dropwises, and continues stirring 3h.Reaction solution is poured into 1000 milliliters of saturated aqueous ammonium chlorides, tell organic layer, once extremely neutral with the washing of 500 ml waters.Underpressure distillation behind the normal pressure recovery solvent, first paragraph is chieftain's 13 grams of 70～120 ℃/4mmHg, second segment is the finished product 2 of 120～122 ℃/4mmHg, 6,6-trimethylammonium-1-(4-hydroxyl-heptan-1,6-diene-4-yl)-and hexamethylene-1-alkene, weight is 107.5 grams (gas-chromatography content is 93.64%), the reaction yield is 86.0% (in beta-cyclized ethyl geranate).
(2), 2,6, the preparation of 6-trimethylammonium-1-(fourth-3-alkene acyl)-hexamethylene-1-alkene
Agitator is being housed, thermometer, in 250 milliliters of there-necked flasks of dropping funnel and spherical condensation tube, add 64.5 gram weight concentration and be 40% sodium hydroxide (0.645mol) and 8.0 gram (0.022mol) phase-transfer catalyst cetyl trimethylammonium bromides, the control mixing speed is 120r/min, in 20～30 ℃, the gas-chromatography content that step reaction makes in the dropping be 93.64% 2,6,6-trimethylammonium-1-(4-hydroxyl-heptan-1,6-diene-4-yl)-hexamethylene-1-alkene 107.5 grams (0.43mol), the control drop rate is 6g/min, dropwise, reaction solution is warming up to 80 ℃ gradually, continue to stir 2～3h.Gas chromatographic analysis raw material 2,6,6-trimethylammonium-1-(4-hydroxyl-heptan-1,6-diene-4-yl)-and hexamethylene-1-alkene content is below 0.5%, reaction finishes, and is cooled to 20～25 ℃, add 100 ml waters, tell organic layer, carry out underpressure distillation, first paragraph is chieftain's 5.5 grams of 60～104 ℃/4mmHg, second segment is the finished product 2 of 104～106 ℃/4mmHg, 6,6-trimethylammonium-1-(fourth-3-alkene acyl)-hexamethylene-1-alkene, weight is 76.5 grams (gas-chromatography content is 94.55%), the reaction yield is 87.6% (with 2,6,6-trimethylammonium-1-(4-hydroxyl-heptan-1,6-diene-4-yl)-hexamethylene-1-alkene meter).
(3), the preparation of β-damascone
In 1000 milliliters of there-necked flasks of agitator, thermometer, dropping funnel and spherical condensation tube are housed, add 76.5 grams 2,6,6-trimethylammonium-1-(fourth-3-alkene acyl)-hexamethylene-1-alkene (gas-chromatography content is 94.55%) and solvent (adopt dimethylbenzene, 663 milliliters of add-ons) and 3.8 the gram tosic acid (add-on is 2,6,6-trimethylammonium-1-(fourth-3-alkene acyl)-hexamethylene-1-alkene weight 5%), the control mixing speed is 120r/min, temperature of reaction is controlled at 60 ℃, reaction 2～3h.Gas chromatographic analysis raw material 2,6,6-trimethylammonium-1-(fourth-3-alkene acyl)-hexamethylene-1-alkene content is below 0.5%, and reaction finishes, and is cooled to 20～25 ℃, add the neutralization of 10% yellow soda ash, standing demix is told organic layer, is 2,6,6-trimethylammonium-1-(but-2-ene acyl)-hexamethylene-1-alkene is oil slightly.Vacuum fractionation behind the normal pressure recovery solvent, first paragraph is chieftain's 2.5 grams of 70～98 ℃/5～6mmHg, second segment is finished product β-damascone of 98～100 ℃/5～6mmHg, weight is 70 grams ((gas chromatographic analysis) cis, trans-isomer(ide) total content are 99.0%), the reaction yield is 95.8% (with 2,6,6-trimethylammonium-1-(fourth-3-alkene acyl)-hexamethylene-1-alkene meter).
Claims (1)
1. the synthetic method of a β-damascone is characterized in that comprising following synthesis step:
The first step: the preparation of 2,6,6-trimethylammonium-1-(4-hydroxyl-heptan-1,6-diene-4-yl)-hexamethylene-1-alkene
1., chlorallylene Grignard reagent
In reaction vessel, with the quality of magnesium and solvent 1 in magnesium: solvent is that 1: 2.4～2.6 ratio joins wherein, the control mixing speed is 120r/min, the mass ratio that begins to drip chlorallylene and solvent 2 is by chlorallylene: solvent is 1.1～1.2: 1 mixed solution, the control drop rate is 5g/min, dropwise, insulation reaction 1h namely gets the chlorallylene Grignard reagent;
Above-mentioned said solvent 1 and solvent 2 are anhydrous diethyl ether or isopropyl ether;
The amount of the chlorallylene that wherein drips is chlorallylene by itself and magnesium in mass ratio: magnesium is 84.2g: 28.8g;
2., 2,6, the preparation of the thick oil of 6-trimethylammonium-1-(4-hydroxyl-heptan-1,6-diene-4-yl)-hexamethylene-1-alkene
1. in the chlorallylene Grignard reagent of gained, the control mixing speed is 120r/min in step, and during beta-cyclized ethyl geranate was added dropwise to, the beta-cyclized ethyl geranate amount of dropping is beta-cyclized ethyl geranate by the mass ratio of itself and magnesium: magnesium was 3.47: 1;
The drop rate of gate ring ethyl geranate is 6g/min, dropwises, and insulation reaction 2～3h gets reaction solution A;
3., the separating, washing of reaction solution
With step 2. the reaction solution A of gained be cooled to 20～25 ℃, pour in the saturated aqueous ammonium chloride, standing demix is told the upper strata organic layer, lower aqueous layer, the upper strata organic layer is extremely neutral with the tap water washing, and standing demix discards lower aqueous layer again, namely get 2,6,6-trimethylammonium-1-(4-hydroxyl-heptan-1,6-diene-4-yl)-hexamethylene-1-alkene is oil slightly;
Wherein the amount of saturated aqueous ammonium chloride by itself and step 2. the mass ratio of the reaction solution A of gained be saturated aqueous ammonium chloride: the step 2. reaction solution A of gained is 2.8: 1;
4., underpressure distillation
With step 3. gained 2,6,6-trimethylammonium-1-(4-hydroxyl-heptan-1,6-diene-4-yl)-and hexamethylene-1-alkene is slightly oily, underpressure distillation behind the normal pressure recovery solvent, and first paragraph is the chieftain of 70～120 ℃/4mmHg, second segment is the finished product 2 of 120～122 ℃/4mmHg, 6,6-trimethylammonium-1-(4-hydroxyl-heptan-1,6-diene-4-yl)-hexamethylene-1-alkene;
Second step: the preparation of 2,6,6-trimethylammonium-1-(fourth-3-alkene acyl)-hexamethylene-1-alkene
1., the hybrid reaction of raw material
In reaction vessel, sodium hydroxide with 40% or 40% potassium hydroxide by its with the first step in step 4. finally 2 of gained, 6,6-trimethylammonium-1-(4-hydroxyl-heptan-1,6-diene-4-yl)-and the mass ratio of hexamethylene-1-alkene i.e. 40% sodium hydroxide or 40% potassium hydroxide: 2,6,6-trimethylammonium-1-(4-hydroxyl-heptan-1,6-diene-4-yl)-and hexamethylene-1-alkene is 1: 1.65～1.67 ratio, the sodium hydroxide with 40% or 40% potassium hydroxide join in the container;
With phase-transfer catalyst by its with the first step in step 4. finally 2 of gained, 6,6-trimethylammonium-1-(4-hydroxyl-heptan-1,6-diene-4-yl)-and the mass ratio of hexamethylene-1-alkene is phase-transfer catalyst: 2,6,6-trimethylammonium-1-(4-hydroxyl-heptan-1,6-diene-4-yl)-hexamethylene-1-alkene is that 1: 13.4～21.8 ratio also joins in the container;
The control mixing speed is 120r/min, temperature is 20～30 ℃, begin to drip step in the first step 4. final gained 2,6,6-trimethylammonium-1-(4-hydroxyl-heptan-1,6-diene-4-yl)-hexamethylene-1-alkene, the control drop rate is 6g/min, dropwises, and reaction solution is warming up to 80 ℃ gradually, continue to stir 2～3h, get reaction solution B;
Above-mentioned said phase-transfer catalyst is tetra-n-butyl ammonium bromide or triethyl benzyl ammonia chloride (TEBA) or cetyl trimethylammonium bromide;
2., the separating and extracting of reaction solution
With above-mentioned steps 1. the reaction solution B of gained be cooled to 20～25 ℃, add tap water, standing demix is told organic layer, is slightly oil of 2,6,6-trimethylammonium-1-(fourth-3-alkene acyl)-hexamethylene-1-alkene;
Wherein the amount of tap water by itself and above-mentioned steps 1. the mass ratio of the reaction solution B of gained be tap water: the above-mentioned steps 1. reaction solution B of gained is 1: 1.8;
3., underpressure distillation
With above-mentioned steps 2. gained 2,6,6-trimethylammonium-1-(fourth-3-alkene acyl)-hexamethylene-thick oil of 1-alkene carries out underpressure distillation, first paragraph is the chieftain of 60～104 ℃/4mmHg, second segment is the finished product 2 of 104～106 ℃/4mmHg, 6,6-trimethylammonium-1-(fourth-3-alkene acyl)-hexamethylene-1-alkene;
The 3rd step: the preparation of β-damascone
1., the hybrid reaction of raw material
In reaction vessel, with step in the second step 3. gained 2,6, the mass ratio of 6-trimethylammonium-1-(fourth-3-alkene acyl)-hexamethylene-1-alkene and solvent 3 is by 2,6,6-trimethylammonium-1-(fourth-3-alkene acyl)-hexamethylene-1-alkene: solvent 3 be 1: 7.4～7.6 with solvent 3 join the step that contains in the second step 3. gained 2,6, in the container of 6-trimethylammonium-1-(fourth-3-alkene acyl)-hexamethylene-1-alkene;
With tosic acid by the step in itself and the second step 3. gained 2,6, the mass ratio of 6-trimethylammonium-1-(fourth-3-alkene acyl)-hexamethylene-1-alkene is tosic acid: 2,6,6-trimethylammonium-1-(fourth-3-alkene acyl)-hexamethylene-1-alkene is that 1: 20.1～21.8 ratio also joins it in container, and the control mixing speed is 120r/min, and temperature of reaction is controlled at 60 ℃, reaction 2～3h gets reaction liquid C;
Above-mentioned said solvent 3 is tetrahydrofuran (THF), toluene or dimethylbenzene;
2., the separating and extracting of reaction solution
With above-mentioned steps 1. the reaction liquid C of gained be cooled to 20～25 ℃, add 10% yellow soda ash neutralization, standing demix is told organic layer, is slightly oil of 2,6,6-trimethylammonium-1-(but-2-ene acyl)-hexamethylene-1-alkene;
Wherein the amount of 10% yellow soda ash is by 1. i.e. 10% yellow soda ash of mass ratio of the reaction liquid C of gained of itself and above-mentioned steps: the above-mentioned steps 1. reaction liquid C of gained is 1: 3.3～3.7;
3., vacuum fractionation
With above-mentioned steps 2. gained 2,6,6-trimethylammonium-1-(but-2-ene acyl)-hexamethylene-1-alkene slightly oil, after normal pressure reclaims solvent, carry out vacuum fractionation, first paragraph is the chieftain of 70～98 ℃/5～6mmHg, and second segment is finished product β-damascone of 98～100 ℃/5～6mmHg.
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