CN109516905A - The preparation method of inexpensive dihydro jasmone - Google Patents
The preparation method of inexpensive dihydro jasmone Download PDFInfo
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- CN109516905A CN109516905A CN201811435763.3A CN201811435763A CN109516905A CN 109516905 A CN109516905 A CN 109516905A CN 201811435763 A CN201811435763 A CN 201811435763A CN 109516905 A CN109516905 A CN 109516905A
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- dihydro jasmone
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/65—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/307—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of halogen; by substitution of halogen atoms by other halogen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/317—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
- C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
- C07C2601/10—Systems containing only non-condensed rings with a five-membered ring the ring being unsaturated
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- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses the preparation methods of inexpensive dihydro jasmone, comprising the following steps: one, chlorination reaction；Two, dechlorination reaction；Three, decarboxylic reaction.The preparation method of low cost dihydro jasmone of the present invention is compared with traditional technology, it is cheap and easily-available with raw material used, auxiliary reagent is all industrial foundation raw material, reaction condition is simple, without complex reaction condition, and the higher feature of yield, therefore have the advantages that it is cheap, be relatively easy to realize industrial production.
Description
Technical field
The present invention relates to a kind of compound producing method, the preparation method of specially inexpensive dihydro jasmone, is a kind of
The method of fragrance industry industrial production propionic acid.
Background technique
Dihydro jasmone is a kind of fragrance, and dihydro jasmone has strong and lasting jasmine fragrance and dense and warm fruity
Fragrance belongs to modulation jasmine, bergamot, lily, yulan, tuberose, fingered citron type essence, is used for cosmetics, perfumed soap；Modulation is fragrant
The flavor essences such as any of several broadleaf plants, apricot, peach, pears are used for food.
Mainly it is prepared with following three kinds of methods: (1) using cyclopentene diketone as raw material, in sulfuric acid medium, with amyl format
Reagent is reacted and is obtained；(2) with bis- (carboxylic acid, ethyl ester base) pentamethylene of 1,2- dioxy -3,5- for raw material, in acetonitrile solution, with iodine first
Alkane reaction methylation, generates bis- (carboxylic acid, ethyl ester base) pentamethylene of 3- methyl-1-methoxyl group-2- oxygen-3,5-, adds in alkene aqueous slkali
Heat generates 2- methyl -5- methoxyl group -4- carboxyl -4- cyclopentenone, further heats up heating, and generation 3- methyl -5- ring penta washes -
1,2- diketone, then in 40% sulfuric acid, react and obtain with amyl grignard reagent；(3) it using undecenoic acid as raw material, is deposited in phosphoric acid
Under, it is cyclized and is obtained at (0.007~0.011MPa) and 80 DEG C under reduced pressure.The raw material system being related to due to the above method
It is standby relatively difficult, it is at high price, therefore cause the production cost of dihydro jasmone high.There is presently no a kind of production works
The preparation method of easy, high income the inexpensive dihydro jasmone of skill.
Summary of the invention, by chlorination, then under alkaline condition, dehydrochlorination obtains 2- amyl -2- cyclopentenone -3-
Methyl acetate, then
The present invention is precisely in order to solving the above problems and providing a kind of using cheap dihydrojasmonate as raw material
The preparation method of inexpensive dihydro jasmone.
The present invention through the following technical solutions to achieve the above objectives:
The preparation method of inexpensive dihydro jasmone, comprising the following steps: one, chlorination reaction, using acetic acid as solvent, borontrifluoride
In the presence of borate ether, dihydrojasmonate is generated into 2- amyl -2- chlorine ring penta through chlorination reaction under chlorinating agent effect
Ketone -3- methyl acetate；Two, the chlorination reaction product of step 1 is transferred in alcohol solvent by dechlorination reaction, makes 2- amyl -2- chlorine
Cyclopentanone -3- methyl acetate carries out dechlorination reaction under alkalinity, further obtains 2- amyl -2- cyclopentenone -3- methyl acetate；
Three, the dechlorination reaction product of step 2 is transferred in aprotic solvent by decarboxylic reaction, through under catalyst, 2- amyl -2- ring
Decarboxylation generates dihydro jasmone under reflux conditions for pentenone -3- methyl acetate and a small amount of water.Chlorinating agent in step 1 is
One of sym-closene, N- chlorosuccinamide, sulfonic acid chloride.The dosage of chlorinating agent is in step 1 with dihydro jasmone
The amount of the substance of sour methyl esters calculates, and the dosage of sym-closene is 40~60%, further preferably 40~50%.N- neoprene two
Acid imide, sulfonic acid chloride dosage be 100~200%, further preferably 110~120%.The alkali of step 2 neutral and alkali conditioned response
For one of pyridine, triethylamine, piperidines.Aprotic solvent in step 3 is N, N- dimethylformamide, dimethyl sulfoxide, N-
One of methyl pyrrolidone.Catalyst in step 3 is chlorate.The dosage of catalyst in step 3 is with 2- amyl-
The amount of the substance of 2- cyclopentenone -3- methyl acetate calculates, and the dosage of chlorate is 10~100%, preferably 10~20%.Step 3
One of the preferred lithium chloride of middle chlorate, sodium chloride.
The preparation method of low cost dihydro jasmone of the present invention is cheap with raw material used compared with traditional technology
It being easy to get, auxiliary reagent is all industrial foundation raw material, and reaction condition is simple, no complex reaction condition, and the higher feature of yield, because
This have the advantages that it is cheap, be relatively easy to realize industrial production.
Specific embodiment
The technical solution in the present invention is clearly and completely described combined with specific embodiments below, it is clear that described
Embodiment be only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, ability
Domain those of ordinary skill every other embodiment obtained without making creative work, belongs to guarantor of the present invention
The range of shield.
Embodiment 1:
Dihydrojasmonate 226g, i.e. 1mol are added in the 1000ml three-necked flask equipped with mechanical stirring and thermometer,
Boron trifluoride ether 57g, i.e. 0.4mol, acetic acid 800g are warming up to 60 DEG C, are slowly added to sym-closene 93g in batches, i.e.,
0.4mol adds, 80 DEG C is warming up to after adding for about 1 hour, continues to be stirred to react to raw material disappearance, and GC can be assisted to analyze and be
Standard is cooled to room temperature, and filters out sym-closene, and filter cake is washed with 200g acetic acid, merging filtrate, is depressurized at 80 DEG C with water pump
Acetic acid is recycled, stops recycling when no liquid steams, obtains 2- amyl -2- chlorine cyclopentanone -3- methyl acetate crude product, be through weighing
248g, by 2- amyl -2- chlorine cyclopentanone -3- methyl acetate crude product be added equipped with mechanical stirring, condenser pipe, thermometer 1000ml
In three-necked flask, ethyl alcohol 500g, triethylamine 150g, about 1.5mol are added, carry out dechlorination reaction to raw material and completely disappear, it can be with
It assists then recycling 90% or more ethyl alcohol subject to GC analysis, 80g water washing is added, oil reservoir is depressurized thick steam and obtains 2- amyl -2-
Cyclopentenone -3- methyl acetate crude product is weighed as 185g, and it is 85% that GC, which analyzes content, then by 2- amyl -2- cyclopentenone -
3- methyl acetate crude product is transferred in the 1000ml three-necked flask of the thermometer equipped with magnetic agitation, is separately added into sodium chloride 5g, two
Methyl sulfoxide 600g, water 18g, take distilling apparatus, and slowly heating steams low-boiling fraction, while carbon dioxide gas is discharged, directly
Until the temperature in reaction flask reaches the boiling point of dimethyl sulfoxide and releases simultaneously without gas, then depressurized back by water pump
Dimethyl sulfoxide is received, after recycling, 50g washing is added and removes inorganic salts and a small amount of solvent, oil reservoir obtains dihydro through rectification under vacuum
Jasmone 112g is measured purity and reaches 98.6%, and three-step reaction total recovery is about 69.3%.
Embodiment 2:
Dihydrojasmonate 226g, i.e. 1mol are added in the 1000ml three-necked flask equipped with mechanical stirring and thermometer,
Boron trifluoride ether 57g, i.e. 0.4mol, acetic acid 800g, room temperature are added dropwise sulfonic acid chloride 150g, i.e. 1.1mol, about 2 hour and add, add
It is warming up to 50 DEG C after complete, continues to be stirred to react to raw material disappearance, can assist then being subtracted at 80 DEG C with water pump subject to GC analysis
Receipts acetic acid is pushed back, stops recycling when no liquid steams, 2- amyl -2- chlorine cyclopentanone -3- methyl acetate crude product is obtained, through weighing
For 235g, 2- amyl -2- chlorine cyclopentanone -3- methyl acetate crude product is added equipped with mechanical stirring, condenser pipe, thermometer
In 1000ml three-necked flask, ethyl alcohol 500g, pyridine 120g, about 1.5mol are added, dechlorination reaction to raw material is carried out and completely disappears,
It can assist then recycling 90% or more ethyl alcohol subject to GC analysis, 80g water washing is added, oil reservoir is depressurized thick steaming and obtains 2- penta
Base -2- cyclopentenone -3- methyl acetate crude product is weighed as 201g, and it is 85% that GC, which analyzes content, then by 2- amyl -2- ring penta
Ketenes -3- methyl acetate crude product is transferred in the 1000ml three-necked flask of the thermometer equipped with magnetic agitation, is separately added into lithium chloride
6.8g, N, N- dimethylformamide 600g, water 18g, take distilling apparatus, and slowly heating steams low-boiling fraction, while dioxy is discharged
Change carbon gas, until the temperature in reaction flask reaches N, the boiling point of N- dimethylformamide and until being released simultaneously without gas, so
N is recovered under reduced pressure by water pump afterwards, N- dimethylformamide after recycling, is added 50g washing and removes inorganic salts and a small amount of solvent, oil
Layer obtains dihydro jasmone 115g through rectification under vacuum, is measured purity and reaches 98.5%, three-step reaction total recovery is about 67.5%.
It is obvious to a person skilled in the art that invention is not limited to the details of the above exemplary embodiments, Er Qie
In the case where without departing substantially from spirit or essential attributes of the invention, the present invention can be realized in other specific forms.Therefore, no matter
From the point of view of which point, the present embodiments are to be considered as illustrative and not restrictive, and the scope of the present invention is by appended power
Benefit requires rather than above description limits, it is intended that all by what is fallen within the meaning and scope of the equivalent elements of the claims
Variation is included within the present invention.
In addition, it should be understood that although this specification is described in terms of embodiments, but not each embodiment is only wrapped
Containing an independent technical solution, this description of the specification is merely for the sake of clarity, and those skilled in the art should
It considers the specification as a whole, the technical solutions in the various embodiments may also be suitably combined, forms those skilled in the art
The other embodiments being understood that.
Claims (9)
1. the preparation method of inexpensive dihydro jasmone, comprising the following steps: one, chlorination reaction, using acetic acid as solvent, in trifluoro
In the presence of changing borate ether, dihydrojasmonate is generated into 2- amyl -2- chlorine ring through chlorination reaction under chlorinating agent effect
Pentanone -3- methyl acetate；Two, the chlorination reaction product of step 1 is transferred in alcohol solvent by dechlorination reaction, makes 2- amyl -2-
Chlorine cyclopentanone -3- methyl acetate carries out dechlorination reaction under alkalinity, further obtains 2- amyl -2- cyclopentenone -3- acetic acid first
Ester；Three, the dechlorination reaction product of step 2 is transferred in aprotic solvent by decarboxylic reaction, through under catalyst, 2- amyl-
Decarboxylation generates dihydro jasmone under reflux conditions for 2- cyclopentenone -3- methyl acetate and a small amount of water.
2. the preparation method of low cost dihydro jasmone according to claim 1, it is characterised in that in the step 1
Chlorinating agent is one of sym-closene, N- chlorosuccinamide, sulfonic acid chloride.
3. the preparation method of low cost dihydro jasmone according to claim 2, it is characterised in that chlorine in the step 1
It is calculated for the dosage of reagent with the amount of the substance of dihydrojasmonate, the dosage of sym-closene is 40~60%, into one
Step preferably 40~50%.
4. the preparation method of low cost dihydro jasmone according to claim 2, it is characterised in that chlorine in the step 1
Calculated for the dosage of reagent with the amount of the substance of dihydrojasmonate, N- chlorosuccinamide, sulfonic acid chloride dosage be 100
~200%, further preferably 110~120%.
5. the preparation method of low cost dihydro jasmone according to claim 1, it is characterised in that alkali in the step 2
Property conditioned response alkali be one of pyridine, triethylamine, piperidines.
6. the preparation method of low cost dihydro jasmone according to claim 1, it is characterised in that in the step 3
Aprotic solvent is one of N, N- dimethylformamide, dimethyl sulfoxide, N-Methyl pyrrolidone.
7. the preparation method of low cost dihydro jasmone according to claim 1, it is characterised in that in the step 3
Catalyst is chlorate.
8. the preparation method of low cost dihydro jasmone according to claim 7, it is characterised in that in the step 3
The dosage of catalyst is calculated with the amount of the substance of 2- amyl -2- cyclopentenone -3- methyl acetate, and the dosage of chlorate is 10~
100%, preferably 10~20%.
9. the preparation method of low cost dihydro jasmone according to claim 7, it is characterised in that chlorine in the step 3
One of the preferred lithium chloride of salt dissolving, sodium chloride.
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| CN201811435763.3A CN109516905A (en) | 2018-11-28 | 2018-11-28 | The preparation method of inexpensive dihydro jasmone |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111848373A (en) * | 2020-08-03 | 2020-10-30 | 万香科技股份有限公司 | Method for synthesizing dihydrojasmone under alkaline condition |
| CN111892493A (en) * | 2020-08-03 | 2020-11-06 | 万香科技股份有限公司 | Method for synthesizing dihydrojasmone |
| CN111943825A (en) * | 2020-08-03 | 2020-11-17 | 万香科技股份有限公司 | Method for synthesizing dihydrojasmone under acidic condition |
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| CN101429122A (en) * | 2008-12-11 | 2009-05-13 | 淮安万邦香料工业有限公司 | Decarboxylation method used in synthesis of methyl dihydrojasmonate |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111848373A (en) * | 2020-08-03 | 2020-10-30 | 万香科技股份有限公司 | Method for synthesizing dihydrojasmone under alkaline condition |
| CN111892493A (en) * | 2020-08-03 | 2020-11-06 | 万香科技股份有限公司 | Method for synthesizing dihydrojasmone |
| CN111943825A (en) * | 2020-08-03 | 2020-11-17 | 万香科技股份有限公司 | Method for synthesizing dihydrojasmone under acidic condition |
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