CN86100869A - The chemosynthesis of the main essence of oak moss - Google Patents
The chemosynthesis of the main essence of oak moss Download PDFInfo
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- CN86100869A CN86100869A CN86100869.3A CN86100869A CN86100869A CN 86100869 A CN86100869 A CN 86100869A CN 86100869 A CN86100869 A CN 86100869A CN 86100869 A CN86100869 A CN 86100869A
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Abstract
The carbocyclic ring that the invention belongs in the organic chemistry is synthetic, with the diethyl malonate is raw material, in the methanol solution of sodium methylate with 2-ketene-4-cyclic condensation, transesterification reaction takes place simultaneously, generate 3,6-dimethyl-dihydro-β-ray lock methyl acid (1), (I) in the acetic anhydride and the vitriol oil, carry out aromatization reaction after, directly add salt solution and separate out solid, obtain 2,4-diacetoxy-3,6-dimethyl-methyl benzoate (II), (II) in the methanol solution of sodium methylate, make the main essence of oak moss 3,6-dimethyl-β-ray lock methyl acid through hydrolysis and transesterify.
Description
The carbocyclic ring that the invention belongs in the what organic chemistry is synthetic
Oak moss is a kind of parasitic lichens that is grown on the Oak Tree, produces in Mediterranean Sea coastwise contries.Because requirement increases day by day, natural resource can not satisfy the demands, so people have carried out the chemosynthesis work of oak moss main note composition, in West Germany's publication 2,359, reported with dimethyl malonate 233(1974) and done raw material, condensation obtains 3 in the methanol solution of sodium methylate, and 6-dimethyl-dihydro-β-resorcylic acid methyl esters makes its aromatize with reagent such as N-bromo caprolactone amine again, obtain oak moss main note composition-3,6-dimethyl-β-resorcylic acid methyl esters.By expensive raw material price such as what dimethyl malonate and N-bromo caprolactone amine, with N-bromo hexanolactam aromatize, the time of reaction is long, so can't reduce cost.West Germany's publication 2,653 177(1978) has been used acetic anhydride, and cheap reagent such as the vitriol oil makes 3,6-dimethyl-dihydro-β-resorcylic acid methyl esters aromatize, but working method and treating processes are very cumbersome, have consumed a large amount of solvents and reagent.With aromatize product 2,4-diacetoxy-3,6-dimethyl-methyl benzoate (compound ii) distillation purifying, productive rate is very low.Make the compound ii hydrolysis with tosic acid again, the reaction times reaches 54 hours, obtains brown product, needs to use decolorizing with activated carbon, and not only difficult removing abandoned coloring matter, and productive rate is low, has only about 60 percent.So product cost is still very high, operation is also inconvenient.
In order to seek a raw material cheapness, easy and simple to handle, the synthetic route of the oak moss main note composition of Production Flow Chart economical rationality, it is raw material that the present invention adopts diethyl malonate, obtains chemical structure with 2-hexenone-4 condensation and cyclization and transesterification reaction to be in the methanol solution of sodium methylate:
3,6-dimethyl-dihydro-β-resorcylic acid methyl esters (chemical compounds I).
In above-mentioned condensation reaction system, all ester compounds are carrying out transesterification reaction simultaneously: diethyl malonate generates dimethyl malonate through transesterify, and then condensation obtains chemical compounds I; And diethyl malonate is direct and 2-hexenone-4 is condensed into 3,6-dimethyl-dihydro-β-resorcylic acid ethyl ester, be methyl compound (I) also through transesterify, so methyl compound (I) becomes primary product, account for product more than 95%, the ethyl ester product below 5% will be converted to methyl esters (I) in the reaction afterwards.
Compound (I) carries out aromatization reaction in acetic anhydride and concentrated sulfuric acid solution, directly add cool brine and separate out solid after reaction finishes, and obtains 2,4-diacetoxy-3, and 6-dimethyl-methyl benzoate (II), chemical structural formula is:
Compound (II).In the methanol solution of sodium methylate, through transesterify and hydrolysis reaction, use hcl acidifying again, obtain chemical structural formula and be:
Product 3,6-dimethyl-β-resorcylic acid methyl esters (III).The ethyl ester below 5% that the first step condensation reaction stays generates product (III) through transesterify this moment.
The condensation and cyclization among the present invention and the concrete steps of transesterification reaction are, diethyl malonate is added in the methanol solution of sodium methylate, adds 2-hexenone-4 again, and the mole ratio of diethyl malonate and 2-hexenone-4 is 1: 0.8-1, reflux 8-10 hour, remove and abandon solvent, add water, use the dilute hydrochloric acid acidifying, solid is separated out, filter, be washed to neutrality, drying obtains compound (I).
Aromatization reaction among the present invention is to make compound (I) in the presence of excessive acetic anhydride, stirs in nitrogen gas stream, adds the vitriol oil, compound (I) is 1 with the mole ratio of the vitriol oil: 1-2, and then 110 ℃ of reactions 1-1.5 hour, stir in ice-water bath cold back, by adding cold water or cool brine, unreacted aceticanhydride hydrolysis this moment has a large amount of solids to separate out simultaneously, filters, washing is clean, drying obtains 2,4-diacetoxy-3,6-dimethyl-methyl benzoate (II).More help reaction if in aromatization reaction, add Glacial acetic acid again as solvent.
Compound (II) is placed the methanol solution of an amount of sodium methylate, and reflux was hydrolyzed and transesterify in 1 to 2 hour.Boil off methyl alcohol, be dissolved in water, the dilute hydrochloric acid acidifying is filtered, washing, and drying obtains product (III).
H
1NMR, IR, the MS spectrum confirms that all product is 3,6-dimethyl-β-resorcylic acid methyl esters comments fragrant result to think that fragrance is pure.
Equally, can make diethyl malonate and 2-hexenone-4 condensation and transesterify in the propanol solution of sodium propylate, synthesize 3,6-dimethyl-dihydro-β-resorcylic acid propyl ester with aforesaid method of the present invention.The cold treatment process of saltouing behind the above-mentioned aromatization reaction also can be used for Synthetic 2,4-diacetoxy-3,6-dimethyl-ethyl benzoate and propyl ester.And then in the correspondent alcohol solution of corresponding sodium alkoxide, carry out transesterify and hydrolysis reaction, synthesize 3,6-dimethyl-β-resorcylic acid ethyl ester or propyl ester.
Adopt the present invention, have following advantage: (one) does raw material with cheap diethyl malonate, replace unit price than synthetic this spices of ethyl ester high ten dimethyl malonate doubly, also transesterification reaction and condensation reaction are incorporated in the same system and carry out, simplified production technique, the cost of product is reduced greatly.
(2) make 3, during 6-dimethyl-dihydro-β-resorcylic acid methyl esters aromatize, adopt freezing salting-out process,, and saved solvent and reagent simple and effectively with the product separation and purification.
(3) adopt gentle reaction conditions, make 2,4-diacetoxy-3,6-dimethyl-methyl benzoate (II) refluxes in the methanol solution of sodium methylate, the product colour that obtains is shallow, productive rate height, recrystallization obtain white crystals (the product color that other existing methods obtain is dark, is difficult to remove with discoloring agents such as activated carbon and abandons colored substance).And the reaction times is short, and reaction in 1 to 2 hour just can finish.
(4) first and three-step reaction make solvent with methyl alcohol, product is also used recrystallizing methanol, solvent is simple, just what reclaims and reuses.
Example 1:3,6-dimethyl-dihydro-β-resorcylic acid methyl esters (I)
On 1000 milliliters of three-necked bottles, load onto whipping appts, dropping funnel, prolong and calcium chloride tube.
In reaction flask, add 400 milliliters of absolute methanol solutions of 50 gram sodium methylates, stir, add 122 gram (0.76 mol) diethyl malonates, after adding, add 69 gram (0.7 mol) 2-hexenones-4 again, reflux 10 hours, methyl alcohol is abandoned in steaming, adds 200 ml waters, stirs, use the dilute hydrochloric acid acidifying, solid is separated out, and filters, washing is neutral, dry 121 gram products, fusing point: 151-152 ℃, the productive rate 88% of getting.
Example 2:3,6-dimethyl-dihydro-β-resorcylic acid methyl esters
In 1000 milliliters of three-necked bottles, add 450 milliliters of absolute methanol solutions of 54 gram (1 mol) sodium methylates, stir, add 160 gram (1 mol) diethyl malonates, add 93 gram (0.95 mol) 2-hexenones-4 again, reflux 10 hours.Methyl alcohol is abandoned in steaming, adds 250 gram ml waters, uses the dilute hydrochloric acid acidifying, and solid is separated out, and filters, and washing is neutral, dry 159 gram products, the productive rate 84% of getting.Fusing point: 151-152 ℃.
Example 3:2,4-diacetoxy-3,6-dimethyl-methyl benzoate (II)
On 1000 milliliters of three-necked bottles, adorn whipping appts, thermometer, dress dropping funnel and prolong and ventage on fork type pipe.
In reaction flask, put 59.4 gram (0.3 mol) 3,6-dimethyl-dihydro-β-resorcylic acid methyl esters (I), add 210 milliliters of acetic anhydride and 120 milliliters of acetic acid, under nitrogen environment, stir, from dropping funnel, drip the vitriol oil 48 grams (0.48 mol) of content 95-98%, drip off the back and heat up half an hour, 110 ℃ were refluxed 15 hours, and stir in ice-water bath cold back, by adding 300 milliliters of cool brines, separate out solid, suction filtration, washing is clean, drying obtains 63.7 grams 2,4-diacetoxy-3,6-dimethyl-methyl benzoate, 84 ℃ of fusing points.
Example 4:2,4-diacetoxy-3,6-dimethyl-methyl benzoate (II)
The device of fit on 1000 milliliters of four-necked bottles " example 3 " is put into 59.4 gram (0.3 mol) compounds (I) in the bottle, add 200 milliliters of acetic anhydride, stir under nitrogen gas stream, drip the vitriol oil 48 grams (0.048 mol) of 95-98%, 90 ℃ kept one hour, be warmed up to 110 ℃ again, stirred one hour, cooling, the frozen water cooling drips 200 ml waters down, high degree of agitation, and crystallization is separated out, filter, washing clear white solid, dry 58 gram products (II), productive rate 69%.
Example 5:3,6-dimethyl-β-resorcylic acid methyl esters (III)
On 1000 milliliters of reaction flasks, reinstall stream prolong and CaCl2 drying tube.The 500 ml methanol solution that add 22 gram (0.40 mol) sodium methylates in the bottle add 112 gram (0.4 mol) 2,4-diacetoxy-3 again, 6-dimethyl-methyl benzoate refluxes one and half, steams and removes methyl alcohol, add 300 ml waters, the ice-water bath cooling uses dilute hydrochloric acid acidifying, solid to separate out down, filter dry powdery solid, 144 ℃ of the fusing points of getting, first alcohol and water recrystallization gets white crystals 75 grams, compound (III), fusing point 144.5 grams, productive rate 96%.
Example 6:3,6-dimethyl-β-resorcylic acid methyl esters
The 800 ml methanol solution that add 54 gram (1 mol) sodium methylates in 2000 milliliters of reaction flasks add 140 gram (0.50 mol) compounds (II) again, reflux one hour, boil off methyl alcohol, add 400 ml waters, the dilute hydrochloric acid acidifying is used in cooling down in the ice-water bath, filter, washing, drying obtains product, 143 ℃ of fusing points, first alcohol and water recrystallization, obtain white crystals 92 grams, 144.4 ℃ of fusing points
Productive rate 94%.
Example 7.3,6-dimethyl-β-resorcylic acid ethyl ester
The device of dress " example 3 " on 1000 milliliters of four-necked bottles, put into 106 gram (0.5 mol) 3 in the bottle, 6-dimethyl-dihydro-β-resorcylic acid ethyl ester, 330 milliliters of aceticanhydrides, 200 milliliters of acetic acid stir in nitrogen gas stream, drip 80 gram (0.8 mol) vitriol oils, add 90 ℃ of reactions of back intensification one hour, be raised to 110 ℃ of reactions one hour again, cold after, under frozen water cooling, add 330 milliliters of cold food salt solution, separate out solid, filter, washing is clean, dry 108 gram (0.37 mol) 2,4-diacetoxy-3,6-dimethyl-ethyl benzoate.Productive rate 74%, put it in 1000 milliliters of reaction flasks, add 500 milliliters of ethanolic solns of 25 gram (0.37 mol) sodium ethylates, refluxed 1.5 hours, boil off ethanol, add 300 ml waters, in ice-water bath, use the dilute hydrochloric acid acidifying, filter, washing, the dry solid powder that gets gets white crystals body 74 grams, fusing point 127-128 ℃ productive rate 95% with ethyl alcohol recrystallization
Claims (4)
1, a kind of oak moss main note composition 3, the chemical synthesis process of 6-dimethyl-β-resorcylic acid methyl esters is characterized in that doing raw material with diethyl malonate, and with 2-hexenone-4 cyclic condensation, the generation chemical structural formula is in the methanol solution of sodium methylate:
3,6-dimethyl-dihydro-β-resorcylic acid methyl esters (I).
Compound (I) carries out aromatization reaction in the acetic anhydride and the vitriol oil after, directly add cold water or cool brine is separated out solid, obtain 2,4-diacetoxy-3,6-dimethyl-methyl benzoate (II), its chemical structural formula is:
Compound (II) refluxes in the methanol solution of sodium methylate, obtains product through the dilute hydrochloric acid acidifying, and its chemical structural formula is:
3,6-dimethyl-β-resorcylic acid methyl esters (III).
2,, it is characterized in that the mole ratio of diethyl malonate and 2-hexenone-4 is 1 in the condensation reaction: 0.8-1 by in the claim 1 described chemical synthesis process.
3, it is characterized in that by claim 1 described chemical synthesis process compound (II) is hydrolyzed and transesterification reaction in the methanol solution of sodium methylate, synthetic compound (III).
4, described by claim 3, its feature is 1 in the mole ratio of what compound (II) and sodium methylate: 1-2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN86100869.3A CN1005192B (en) | 1986-01-10 | 1986-01-10 | Chemical synthesis of the main essence of oak moss |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN86100869.3A CN1005192B (en) | 1986-01-10 | 1986-01-10 | Chemical synthesis of the main essence of oak moss |
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| Publication Number | Publication Date |
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| CN86100869A true CN86100869A (en) | 1987-07-22 |
| CN1005192B CN1005192B (en) | 1989-09-20 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN86100869.3A Expired CN1005192B (en) | 1986-01-10 | 1986-01-10 | Chemical synthesis of the main essence of oak moss |
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| CN (1) | CN1005192B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102351706A (en) * | 2011-08-04 | 2012-02-15 | 江苏中烟工业有限责任公司 | Method for synthesizing ethyldivaricatinate and application of ethyldivaricatinate |
| CN106631794A (en) * | 2016-09-28 | 2017-05-10 | 国际香料和香精公司 | Process for preparing perfume 2,5-dimethylmethyl resorcylate |
| CN109096113A (en) * | 2018-09-13 | 2018-12-28 | 天津市安凯特科技发展有限公司 | A method of synthesis oak moss aromatisation |
| CN112778126A (en) * | 2020-12-31 | 2021-05-11 | 濮阳天源生物科技有限公司 | Method for synthesizing oak moss by catalysis of supported solid alkali |
-
1986
- 1986-01-10 CN CN86100869.3A patent/CN1005192B/en not_active Expired
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102351706A (en) * | 2011-08-04 | 2012-02-15 | 江苏中烟工业有限责任公司 | Method for synthesizing ethyldivaricatinate and application of ethyldivaricatinate |
| CN102351706B (en) * | 2011-08-04 | 2013-08-07 | 江苏中烟工业有限责任公司 | Method for synthesizing ethyldivaricatinate and application of ethyldivaricatinate |
| CN106631794A (en) * | 2016-09-28 | 2017-05-10 | 国际香料和香精公司 | Process for preparing perfume 2,5-dimethylmethyl resorcylate |
| CN109096113A (en) * | 2018-09-13 | 2018-12-28 | 天津市安凯特科技发展有限公司 | A method of synthesis oak moss aromatisation |
| CN109096113B (en) * | 2018-09-13 | 2021-05-25 | 天津市安凯特科技发展有限公司 | Method for aromatizing synthetic oak moss |
| CN112778126A (en) * | 2020-12-31 | 2021-05-11 | 濮阳天源生物科技有限公司 | Method for synthesizing oak moss by catalysis of supported solid alkali |
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| Publication number | Publication date |
|---|---|
| CN1005192B (en) | 1989-09-20 |
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