CN102531865B - Preparation method of 1-(2,6,6-trimethylcyclohex-3-enyl) butyl-2-en-1-one - Google Patents
Preparation method of 1-(2,6,6-trimethylcyclohex-3-enyl) butyl-2-en-1-one Download PDFInfo
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Abstract
The invention provides a preparation method of 1-(2,6,6-trimethylcyclohex-3-enyl)butyl-2-en-1-one. The method comprises the following steps that: 4-acetyl-3,5,5-trimethylcyclohexene and chlorodimethylsilane are reacted in an organic solvent in the presence of an acid-binding agent to obtain an intermediate; and the intermediate and acetaldehyde are subjected to a condensation reaction under the catalytic action of a metal salt catalyst, and the finished product is obtained through dehydration. The intermediate with low steric hindrance is prepared, then the intermediate and acetaldehyde are subjected to the condensation reaction under the action of the common metal salt catalyst and 1-(2,6,6-trimethylcyclohex-3-enyl)but-2-en-1-one is obtained after dehydration, thus the method has a simple operation process and higher yield. In addition, the reaction is performed under milder conditions, thus the danger of the reaction process is lowered and the large-scale production can be realized easily.
Description
Technical field
The invention belongs to chemical synthesis technical field, relate in particular to the preparation method of a kind of 1-(2,6,6-3-methyl cyclohexanol-3-thiazolinyl) but-2-ene-1-ketone.
Background technology
1-(2,6,6-3-methyl cyclohexanol-3-thiazolinyl) but-2-ene-1-ketone, have formula (I) structure, English name is 1-(2,6,6-trimethylcyclohex-3-enyl) but-2-en-1-one, CAS is numbered 0057378-68-4, and FEMA is encoded to 3622.
1-(2,6,6-3-methyl cyclohexanol-3-thiazolinyl) but-2-ene-1-ketone is a kind of famous and precious rose ketone series spices, there is stronger fragrance of a flower fragrance, good diffusive force and lower threshold value, it has satisfactory stability in multiple product, add on a small quantity the rose fragrance that gets final product remarkable improving product, be therefore widely used in daily chemical essence and food spice.
1-(2,6,6-3-methyl cyclohexanol-3-thiazolinyl) but-2-ene-1-ketone not yet finds at nature, and it is generally by 4-ethanoyl-3,5,5-trimethyl cyclohexene and acetaldehyde under alkaline condition after condensation Dehydration obtain, reaction process is shown below:
Due to 4-ethanoyl-3, 5, 5-trimethyl cyclohexene sterically hindered larger, when adopting aforesaid method to be prepared, need to adopt special catalyst to carry out catalysis and can obtain smoothly 1-(2, 6, 6-3-methyl cyclohexanol-3-thiazolinyl) but-2-ene-1-ketone, as first US Patent No. 4334098 is reacted methylphenylamine to prepare methylphenylamine base magnesium bromide or methylphenylamine base magnesium chloride with Grignard reagents such as alkyl magnesium bromide or alkylmagnesium chloride, adopt again methylphenylamine base magnesium bromide or methylphenylamine base magnesium chloride to 4-ethanoyl-3, 5, 5-trimethyl cyclohexene is processed and is obtained carrying out aldol condensation with acetaldehyde again after active intermediate and prepare 1-(2, 6, 6-3-methyl cyclohexanol-3-thiazolinyl) but-2-ene-1-ketone, the method is complex steps not only, and reaction product yield is lower, the highlyest only can reach 53%.Application number is the preparation method that 200710071158.8 Chinese patent literature discloses a kind of 1-(2,6,6-3-methyl cyclohexanol-3-thiazolinyl) but-2-ene-1-ketone; it is first by 4-ethanoyl-3; 5,5-trimethyl cyclohexene adds in Grignard reagent, drips subsequently excessive acetaldehyde; reaction finishes with dilute acid soln termination reaction dehydration; organic phase is washed till neutrality with alkaline solution, purifies and obtains target product, although the method is easy to operate; but its productive rate is still lower, only can reach 50% left and right.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of 1-(2,6,6-3-methyl cyclohexanol-3-thiazolinyl) preparation method of but-2-ene-1-ketone, and method provided by the invention is simple to operate, reaction safety, and yield is high.
The preparation method who the invention provides a kind of 1-(2,6,6-3-methyl cyclohexanol-3-thiazolinyl) but-2-ene-1-ketone, comprises the following steps:
A) 4-ethanoyl-3,5,5-trimethyl cyclohexene and chlorodimethyl silane react under the existence of acid binding agent in organic solvent, obtain 3,5,5-trimethylammonium-4-(1-dimethylsilyl bis vinyl) hexamethylene-1-alkene;
B) under the katalysis of metal salt catalyst, described step a) obtain 3,5,5-trimethylammonium-4-(1-dimethylsilyl bis vinyl) hexamethylene-1-alkene and acetaldehyde generation condensation reaction, after dehydration, obtain 1-(2,6,6-3-methyl cyclohexanol-3-thiazolinyl) but-2-ene-1-ketone.
Preferably, described step a) specifically comprises:
4-ethanoyl-3,5,5-trimethyl cyclohexene and chlorodimethyl silane react under the existence of acid binding agent and catalyzer in organic solvent.
Preferably, described catalyzer is potassiumiodide.
Preferably, described step a) in, described acid binding agent is triethylamine, pyridine, imidazoles, quadrol or DMAP.
Preferably, described step a) in, described temperature of reaction is that room temperature is to the boiling reflux temperature of organic solvent; The described reaction times is 1h～18h.
Preferably, described step a) in, described 4-ethanoyl-3, the mol ratio of 5,5-trimethyl cyclohexene, chlorodimethyl silane and acid binding agent is 1: (0.8～3): (0.8～3).
Preferably, described step b) in, described metal salt catalyst is chlorate, Bromide, iodized salt, carbonate or vitriol.
Preferably, described metal salt catalyst is lithium chloride, sodium-chlor, aluminum chloride, calcium chloride, magnesium chloride, Calcium Bromide, magnesium bromide, sodium iodide, calcium iodide, sodium carbonate, Quilonum Retard or Lithium Sulphate.
Preferably, described step b) in, the temperature of described condensation reaction is-10 ℃～20 ℃, the time of described condensation reaction is 1h～10h.
Preferably, described step b), in, described 3,5, the mol ratio of 5-trimethylammonium-4-(1-dimethylsilyl bis vinyl) hexamethylene-1-alkene, acetaldehyde and metal salt catalyst is 1: (0.3～3.0): (0.01～1.2).
Compared with prior art, the present invention is with 4-ethanoyl-3,5,5-trimethyl cyclohexene is raw material, first itself and chlorodimethyl silane are reacted under the existence of acid binding agent in organic solvent, obtain sterically hindered less intermediate 3,5,5-trimethylammonium-4-(1-dimethylsilyl bis vinyl) hexamethylene-1-alkene; This intermediate under the katalysis of metal salt catalyst can with acetaldehyde generation condensation reaction, after dehydration, obtain 1-(2,6,6-3-methyl cyclohexanol-3-thiazolinyl) but-2-ene-1-ketone.First the present invention prepares sterically hindered less intermediate, then under the effect of plain metal salt catalyst, makes this intermediate and acetaldehyde generation condensation reaction, obtains 1-(2 after dehydration, 6,6-3-methyl cyclohexanol-3-thiazolinyl) but-2-ene-1-ketone, not only simple to operate, and yield is higher.In addition, the present invention is without the grignard reagent that adopts preparation condition harshness, usings common metal salt as catalyzer, react under comparatively gentle condition, reduced the danger of reaction process, is easy to realize scale operation.Experiment shows, while adopting method provided by the invention to prepare 1-(2,6,6-3-methyl cyclohexanol-3-thiazolinyl) but-2-ene-1-ketone, its yield can reach more than 62%, and purity is more than 95%.
Embodiment
The preparation method who the invention provides a kind of 1-(2,6,6-3-methyl cyclohexanol-3-thiazolinyl) but-2-ene-1-ketone, comprises the following steps:
A) 4-ethanoyl-3,5,5-trimethyl cyclohexene and chlorodimethyl silane react under the existence of acid binding agent in organic solvent, obtain 3,5,5-trimethylammonium-4-(1-dimethylsilyl bis vinyl) hexamethylene-1-alkene;
B) under the katalysis of metal salt catalyst, described step a) obtain 3,5,5-trimethylammonium-4-(1-dimethylsilyl bis vinyl) hexamethylene-1-alkene and acetaldehyde generation condensation reaction, after dehydration, obtain 1-(2,6,6-3-methyl cyclohexanol-3-thiazolinyl) but-2-ene-1-ketone.
First the present invention prepares sterically hindered less intermediate, then under the effect of plain metal salt catalyst, makes this intermediate and acetaldehyde generation condensation reaction, obtains 1-(2 after dehydration, 6,6-3-methyl cyclohexanol-3-thiazolinyl) but-2-ene-1-ketone, not only simple to operate, and yield is higher.In addition, the present invention is without the grignard reagent that adopts preparation condition harshness, usings common metal salt as catalyzer, react under comparatively gentle condition, reduced the danger of reaction process, is easy to realize scale operation.
Under the condition that first the present invention exists at acid binding agent, make 4-ethanoyl-3,5,5-trimethyl cyclohexene and chlorodimethyl silane react in organic solvent; obtain 3; 5,5-trimethylammonium-4-(1-dimethylsilyl bis vinyl) hexamethylene-1-alkene, reaction formula is as follows:
The present invention is by acid binding agent, 4-ethanoyl-3; 5; 5-trimethyl cyclohexene and chlorodimethyl silane mix in organic solvent; 4-ethanoyl-3; 5,5-trimethyl cyclohexene and chlorodimethyl silane react, and obtain intermediate: 3; 5,5-trimethylammonium-4-(1-dimethylsilyl bis vinyl) hexamethylene-1-alkene.For reaction is carried out smoothly, first the present invention is preferably dissolved in acid binding agent and chlorodimethyl silane in organic solvent, then under agitation condition, slowly adds 4-ethanoyl-3, and 5,5-trimethyl cyclohexene reacts; Or first acid binding agent is dissolved in organic solvent, slowly adds chlorodimethyl silane, then under agitation condition, slowly add 4-ethanoyl-3,5,5-trimethyl cyclohexene reacts.
In the present invention, described acid binding agent is organic bases, includes but not limited to triethylamine, pyridine, imidazoles, quadrol or DMAP etc., is preferably triethylamine or pyridine.Described organic solvent is aprotic polar solvent, includes but not limited to DMF (DMF), N, and N-diethylformamide, methyl-sulphoxide or acetonitrile etc., be preferably DMF.
Described 4-ethanoyl-3, the temperature that 5,5-trimethyl cyclohexene and chlorodimethyl silane react is preferably room temperature to the boiling reflux temperature of organic solvent, more preferably the boiling reflux temperature of organic solvent; Time is preferably 1h～18h, more preferably 2h～6h.In the present invention, described boiling reflux temperature refers to the temperature that organic solvent seethes with excitement under reflux state, and those skilled in the art can or determine according to actually operating according to the organic solvent of selecting.The present invention preferably reacts under the reaction of stirring, refluxing.In the present invention, described 4-ethanoyl-3, the mol ratio of 5,5-trimethyl cyclohexene, chlorodimethyl silane and acid binding agent is preferably 1: (0.8～3): (0.8～3), more preferably 1: (1.0～1.5): (1～2).
In order to improve speed of reaction, the present invention preferably makes 4-ethanoyl-3 under the condition of catalyst, and 5,5-trimethyl cyclohexene and chlorodimethyl silane react.Described catalyzer is preferably potassiumiodide, described potassiumiodide and described 4-ethanoyl-3, and the mol ratio of 5,5-trimethyl cyclohexene is preferably (0.2～0.6): 1, more preferably (0.2～1.0): 1.
After completion of the reaction, after the reaction mixture obtaining is purified, obtain intermediate, described intermediate is for obtaining 3,5,5-trimethylammonium-4-(1-dimethylsilyl bis vinyl) hexamethylene-1-alkene.In the present invention, described purification is specially pours described reaction mixture in frozen water into, add sherwood oil to extract, by saturated sodium bicarbonate aqueous solution washing for the organic phase after extraction, with obtaining intermediate after anhydrous magnesium sulfate drying, normal pressure recovery sherwood oil, underpressure distillation.
Obtain after intermediate, it is carried out to infrared analysis and nuclear magnetic resonance spectroscopy, result shows, it has the characteristic feature peak of 3,5,5-trimethylammonium-4-(1-dimethylsilyl bis vinyl) hexamethylene-1-alkene, be 3,5,5-trimethylammonium-4-(1-dimethylsilyl bis vinyl) hexamethylene-1-alkene.
Obtain after intermediate, under the katalysis of metal salt catalyst, described intermediate and acetaldehyde generation condensation reaction, obtain 1-(2,6,6-3-methyl cyclohexanol-3-thiazolinyl) but-2-ene-1-ketone after dehydration, and reaction formula is as follows:
The present invention reacts after intermediate, metal salt catalyst and acetaldehyde are mixed in organic solvent.In the present invention, described metal salt catalyst includes but not limited to chlorate, Bromide, iodized salt, carbonate or vitriol etc., be preferably lithium chloride, sodium-chlor, aluminum chloride, calcium chloride, magnesium chloride, Calcium Bromide, magnesium bromide, sodium iodide, calcium iodide, sodium carbonate, Quilonum Retard or Lithium Sulphate, more preferably lithium chloride, sodium-chlor, aluminum chloride, calcium chloride or magnesium chloride, most preferably be sodium-chlor, calcium chloride or magnesium chloride.Described organic solvent includes but not limited to dimethyl sulfoxide (DMSO) (DMSO), DMF, tetrahydrofuran (THF), methylene dichloride, methyl alcohol, second alcohol and water etc., is preferably DMF, ethanol, water or dimethyl sulfoxide (DMSO).
In the present invention, the temperature of described intermediate and described acetaldehyde generation condensation reaction is preferably-10 ℃～20 ℃, more preferably 0～10 ℃; The time of described condensation reaction is preferably 1h～10h, more preferably 3h～8h.The mol ratio of described intermediate, acetaldehyde and metal salt catalyst is preferably 1: (0.3～3.0): (0.01～1.2), more preferably 1: (1.2～2.0): (0.05～1.0).
For reaction is carried out smoothly, the present invention is preferably dissolved in metal catalyst and acetaldehyde in organic solvent, slowly adds described intermediate to carry out condensation reaction.Metal catalyst and acetaldehyde are dissolved in after organic solvent, the reaction mixture obtaining are remained on to the temperature of carrying out condensation reaction, can react after slowly adding described intermediate.
Described intermediate and acetaldehyde after completion of the reaction, dewater to it.The present invention preferably dewaters under acidic conditions, and described acidic conditions is provided by acidic cpd, preferably by sulfuric acid, phosphoric acid or tosic acid etc., is provided.
After dehydration, after being purified, the reaction mixture obtaining obtains 1-(2,6,6-3-methyl cyclohexanol-3-thiazolinyl) but-2-ene-1-ketone.In the present invention, described purification is preferably described reaction mixture separated, with alkaline aqueous solution, the organic phase washing obtaining is extremely neutral, except desolventizing, obtains final product after rectification under vacuum.In the present invention, described alkaline aqueous solution is preferably aqueous sodium hydroxide solution.
Obtain after final product, it is carried out to mass spectroscopy, infrared analysis and nuclear magnetic resonance spectroscopy, result shows, it has the characteristic peak of 1-(2,6,6-3-methyl cyclohexanol-3-thiazolinyl) but-2-ene-1-ketone, it is 1-(2,6,6-3-methyl cyclohexanol-3-thiazolinyl) but-2-ene-1-ketone.
First the present invention prepares sterically hindered less intermediate, then under the effect of plain metal salt catalyst, makes this intermediate and acetaldehyde generation condensation reaction, obtains 1-(2 after dehydration, 6,6-3-methyl cyclohexanol-3-thiazolinyl) but-2-ene-1-ketone, not only simple to operate, and yield is higher.In addition, the present invention is without the grignard reagent that adopts preparation condition harshness, usings common metal salt as catalyzer, react under comparatively gentle condition, reduced the danger of reaction process, is easy to realize scale operation.Experiment shows, while adopting method provided by the invention to prepare 1-(2,6,6-3-methyl cyclohexanol-3-thiazolinyl) but-2-ene-1-ketone, its yield can reach more than 62%, and purity is more than 95%.
In order to further illustrate the present invention, below in conjunction with embodiment, the preparation method of 1-provided by the invention (2,6,6-3-methyl cyclohexanol-3-thiazolinyl) but-2-ene-1-ketone is described in detail.
Embodiment 1
In reaction flask, add 400mL N, dinethylformamide (DMF), 95g (110mL, 1.0mol) chlorodimethyl silane and 121g (1.2mol) triethylamine, under agitation condition, drip 166g (1.0mol) 4-ethanoyl-3,5,5-trimethyl cyclohexene, dropwised in 0.5 hour; Continue reflux and stir, react 6 hours; The reaction mixture obtaining is cooling, pour in 300mL frozen water, add petroleum ether extraction 3 times, each 200mL; Merge organic phase, with saturated sodium bicarbonate solution washing, anhydrous magnesium sulfate drying, normal pressure reclaims sherwood oil, after underpressure distillation, obtains 191g intermediate.
Described intermediate is carried out to infrared analysis and nuclear magnetic resonance spectroscopy, and result is as follows:
IR(film)：3040(sp
2C-H)，1662(＞SiOC＝C)，1610(C＝C)cm-1；
1h NMR (CDCl3): δ 0.28 (d, J=2.8Hz, 6H, SiMe
2), 0.82～1.15 (9H, 3-and 5-Me), 1.52～2.00 (2H, m, 6-H
2), 2.30～2.50 (2H, m, 4-and 3-H), 4.10 (m, 2H ,=CH
2), 5.50～5.65 (2H, m, 1-and 2-H) ppm;
From above-mentioned data, described intermediate is 3,5,5-trimethylammonium-4-(1-dimethylsilyl bis vinyl) hexamethylene-1-alkene, and content (GC) is 98.5%, with respect to 4-ethanoyl-3, and the productive rate 85% of 5,5-trimethyl cyclohexene.
Embodiment 2
In reaction flask, add potassiumiodide and 101g (1mol) triethylamine that 400mL DMF, 17g (0.1mol) are dry, continue slowly to add 95g (110mL, 1.0mol) chlorodimethyl silane, then under the condition stirring, drip 166g (1.0mol) 4-ethanoyl-3,5,5-trimethyl cyclohexene; Continue reflux and stir, react 8 hours; To obtain reaction mixture and be cooled to room temperature, pour in 300mL frozen water, add petroleum ether extraction 3 times, each 200mL; Merge organic phase; with saturated sodium bicarbonate solution washing, with anhydrous magnesium sulfate drying, normal pressure reclaims sherwood oil; after underpressure distillation; obtain 210g intermediate 3,5,5-trimethylammonium-4-(1-dimethylsilyl bis vinyl) hexamethylene-1-alkene; the content of described intermediate (GC) is 98.3%; with respect to 4-ethanoyl-3, the productive rate 92% of 5,5-trimethyl cyclohexene.
Embodiment 3
In there-necked flask, add 100mL water, 200mL N, the NaCl of dinethylformamide, 17.5g (0.3mol) and 66.1g (1.5mol) acetaldehyde, be cooled to 0 ℃, under agitation condition, slowly drip 3 of 227g (1.0mol) embodiment 2 preparations, 5,5-trimethylammonium-4-(1-dimethylsilyl bis vinyl) hexamethylene-1-alkene, it is 0 ℃～5 ℃ that reacting liquid temperature is controlled, about 1h dropwises, and then continues to react 6h at 0 ℃～5 ℃;
Reaction finishes rear the sulphuric acid soln termination reaction the dehydration that by 400mL mass concentration, are 20%, and the aqueous sodium hydroxide washes that organic phase is 15% by 50mL mass concentration, to neutral, continues, except rectification under vacuum after desolventizing, to obtain 132g final product; Described final product is carried out respectively to mass spectroscopy, infrared analysis and nuclear magnetic resonance spectroscopy, and result is as follows:
MS(m/z)：192(M
+，45)，177(15)，137(8)，123(14)，109(16)，107(22)，91(18)，93(19)，81(39)，69(100)，55(13)；
IR:3045,1670,1640,1620 and 975cm
-1;
1h NMR (90MHz; CDCl
3): δ 0.84 (d, J=7Hz); 0.90 and 0.94 (2s); 1.90 (dxd; J=8 and 2Hz); 2.48 (m); 5.5 (m); 6.18 and 6.82 (2m) ppm
From above-mentioned data, described final product is 1-(2,6,6-3-methyl cyclohexanol-3-thiazolinyl) but-2-ene-1-ketone, content is (GC) 95%, with respect to intermediate 3, the yield of 5,5-trimethylammonium-4-(1-dimethylsilyl bis vinyl) hexamethylene-1-alkene is 65%.
Embodiment 4
To the CaCl that adds 300mL ethanol, 11.1g (0.1mol) in there-necked flask
2and 88.1g (2mol) acetaldehyde, be cooled to 0 ℃, under agitation condition, slowly drip 3 of 227g (1.0mol) embodiment 2 preparations, 5,5-trimethylammonium-4-(1-dimethylsilyl bis vinyl) hexamethylene-1-alkene, it is 0 ℃～5 ℃ that reacting liquid temperature is controlled, and about 1h drips, and then continues reaction 3h;
The phosphoric acid solution termination reaction that it is 20% by 400mL mass concentration that reaction finishes dehydration, the aqueous sodium hydroxide washes that organic phase is 15% by 50mL mass concentration is to neutral, except rectification under vacuum after desolventizing, obtain 146g 1-(2,6,6-3-methyl cyclohexanol-3-thiazolinyl) but-2-ene-1-ketone, content (GC) is 95%, with respect to intermediate 3,5, the yield of 5-trimethylammonium-4-(1-dimethylsilyl bis vinyl) hexamethylene-1-alkene is 72%.
The mass-spectrometric data of described 1-(2,6,6-3-methyl cyclohexanol-3-thiazolinyl) but-2-ene-1-ketone is as follows:
MS(m/z)：192(M
+)，177，137，123，109，107，91，93，81，69，55。
Embodiment 5
To the CaCl that adds 300mL DMF, 11.1g (0.1mol) in there-necked flask
2and 66.1g (1.5mol) acetaldehyde, be cooled to 0 ℃, under agitation condition, slowly drip 3 of 227g (1.0mol) embodiment 2 preparations, 5,5-trimethylammonium-4-(1-dimethylsilyl bis vinyl) hexamethylene-1-alkene, it is 0 ℃～5 ℃ that reacting liquid temperature is controlled, and about 1h drips, and continues reaction 3h;
The sulphuric acid soln termination reaction that it is 20% by 400mL mass concentration that reaction finishes dehydration, the aqueous sodium hydroxide washes that organic phase is 15% by 50mL mass concentration is to neutral, except rectification under vacuum after desolventizing, obtain 164g 1-(2,6,6-3-methyl cyclohexanol-3-thiazolinyl) but-2-ene-1-ketone, content (GC) is 95%, with respect to intermediate 3,5, the yield of 5-trimethylammonium-4-(1-dimethylsilyl bis vinyl) hexamethylene-1-alkene is 81%.
The mass-spectrometric data of described 1-(2,6,6-3-methyl cyclohexanol-3-thiazolinyl) but-2-ene-1-ketone is as follows:
MS(m/z)：192(M
+)，177，137，123，109，107，91，93，81，69，55。
Embodiment 6
In there-necked flask, add 300mL dimethyl sulfoxide (DMSO) (DMSO), 9.5g (0.1mol) MgCl
2and 44.1g (1mol) acetaldehyde, be cooled to 0 ℃, under agitation condition, slowly drip 3 of 227g (1.0mol) embodiment 2 preparations, 5,5-trimethylammonium-4-(1-dimethylsilyl bis vinyl) hexamethylene-1-alkene, reacting liquid temperature is controlled 0 ℃～5 ℃, about 1h drips, and continues reaction 5h;
The tosic acid solution that it is 40% by 500mL mass concentration that reaction finishes, termination reaction dehydration, the aqueous sodium hydroxide washes that organic phase is 15% by 50mL mass concentration, to neutral, except rectification under vacuum after desolventizing, obtains 126g 1-(2,6,6-3-methyl cyclohexanol-3-thiazolinyl) but-2-ene-1-ketone, content (GC) is 95%, with respect to intermediate 3, the yield of 5,5-trimethylammonium-4-(1-dimethylsilyl bis vinyl) hexamethylene-1-alkene is 62%.
The mass-spectrometric data of described 1-(2,6,6-3-methyl cyclohexanol-3-thiazolinyl) but-2-ene-1-ketone is as follows:
MS(m/z)：192(M
+)，177，137，123，109，107，91，93，81，69，55。
From above-described embodiment, while adopting method provided by the invention to prepare 1-(2,6,6-3-methyl cyclohexanol-3-thiazolinyl) but-2-ene-1-ketone, its yield is more than 62%, to reach as high as 81%.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (9)
1. the preparation method of a 1-(2,6,6-3-methyl cyclohexanol-3-thiazolinyl) but-2-ene-1-ketone, comprises the following steps:
A) 4-ethanoyl-3,5,5-trimethyl cyclohexene and chlorodimethyl silane react under the existence of acid binding agent in organic solvent, obtain 3,5,5-trimethylammonium-4-(1-dimethylsilyl bis vinyl) hexamethylene-1-alkene;
B) under the katalysis of metal salt catalyst, described step a) obtain 3,5, in organic solvent, there is condensation reaction in 5-trimethylammonium-4-(1-dimethylsilyl bis vinyl) hexamethylene-1-alkene and acetaldehyde, after dehydration, obtain 1-(2,6,6-3-methyl cyclohexanol-3-thiazolinyl) but-2-ene-1-ketone; Described metal salt catalyst is chlorate, Bromide, iodized salt, carbonate or vitriol.
2. preparation method according to claim 1, is characterized in that, described step a) specifically comprises:
4-ethanoyl-3,5,5-trimethyl cyclohexene and chlorodimethyl silane react under the existence of acid binding agent and catalyzer in organic solvent.
3. preparation method according to claim 2, is characterized in that, described catalyzer is potassiumiodide.
4. according to the preparation method described in claim 1～3 any one, it is characterized in that, in described step a), described acid binding agent is triethylamine, pyridine, imidazoles, quadrol or DMAP.
5. according to the preparation method described in claim 1～3 any one, it is characterized in that, in described step a), described temperature of reaction is that room temperature is to the boiling reflux temperature of organic solvent; The described reaction times is 1h～18h.
6. according to the preparation method described in claim 1～3 any one, it is characterized in that, in described step a), described 4-ethanoyl-3, the mol ratio of 5,5-trimethyl cyclohexene, chlorodimethyl silane and acid binding agent is 1:(0.8～3): (0.8～3).
7. preparation method according to claim 1, is characterized in that, described metal salt catalyst is lithium chloride, sodium-chlor, aluminum chloride, calcium chloride, magnesium chloride, Calcium Bromide, magnesium bromide, sodium iodide, calcium iodide, sodium carbonate, Quilonum Retard or Lithium Sulphate.
8. according to the preparation method described in claim 1～3 any one, it is characterized in that, in described step b), the temperature of described condensation reaction is-10 ℃～20 ℃, and the time of described condensation reaction is 1h～10h.
9. according to the preparation method described in claim 1～3 any one, it is characterized in that, in described step b), described 3, the mol ratio of 5,5-trimethylammonium-4-(1-dimethylsilyl bis vinyl) hexamethylene-1-alkene, acetaldehyde and metal salt catalyst is 1:(0.3～3.0): (0.01～1.2).
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| CN113387784B (en) * | 2021-07-12 | 2022-10-11 | 山东新和成药业有限公司 | Acid-base catalyst and application thereof in delta-damascenone synthesis |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4250332A (en) * | 1979-10-26 | 1981-02-10 | International Flavors & Fragrances Inc. | Process for preparing acyl trimethyl cyclohexene derivatives and use of intermediates therefor in augmenting or enhancing the aroma or taste of a consumable material |
| US4334098A (en) * | 1978-07-27 | 1982-06-08 | International Flavors & Fragrances Inc. | Trans,trans-Δ-damascone, mixtures containing major proportions of same, processes for preparing same and organoleptic uses thereof |
| CN101125805A (en) * | 2007-09-14 | 2008-02-20 | 杭州格林香料化学有限公司 | Method for preparing 1-(2,6,6-trimethylcyclohex-3-enyl)but-2-en-1-one |
-
2011
- 2011-12-27 CN CN201110445395.2A patent/CN102531865B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4334098A (en) * | 1978-07-27 | 1982-06-08 | International Flavors & Fragrances Inc. | Trans,trans-Δ-damascone, mixtures containing major proportions of same, processes for preparing same and organoleptic uses thereof |
| US4250332A (en) * | 1979-10-26 | 1981-02-10 | International Flavors & Fragrances Inc. | Process for preparing acyl trimethyl cyclohexene derivatives and use of intermediates therefor in augmenting or enhancing the aroma or taste of a consumable material |
| CN101125805A (en) * | 2007-09-14 | 2008-02-20 | 杭州格林香料化学有限公司 | Method for preparing 1-(2,6,6-trimethylcyclohex-3-enyl)but-2-en-1-one |
Non-Patent Citations (2)
| Title |
|---|
| 3-羟基-1-(2,6,6-三甲基-3-环己烯基)-1-丁酮的合成及其向卷烟烟气释放δ-突厥酮的研究;邓昌健等;《合成化学》;20040430;第12卷(第02期);157－160 * |
| 邓昌健等.3-羟基-1-(2,6,6-三甲基-3-环己烯基)-1-丁酮的合成及其向卷烟烟气释放δ-突厥酮的研究.《合成化学》.2004,第12卷(第02期), |
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