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CN102826977A - Synthesis method and application of 7-methoxy-3,7-dimethyloctyl aldehyde - Google Patents

Synthesis method and application of 7-methoxy-3,7-dimethyloctyl aldehyde Download PDF

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Publication number
CN102826977A
CN102826977A CN2012103601665A CN201210360166A CN102826977A CN 102826977 A CN102826977 A CN 102826977A CN 2012103601665 A CN2012103601665 A CN 2012103601665A CN 201210360166 A CN201210360166 A CN 201210360166A CN 102826977 A CN102826977 A CN 102826977A
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dimethyl
octanal
methoxyl group
deionized water
enamine
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吴义龙
张树林
周春飞
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TIANNING FLAVOR (JIANGSU) CO Ltd
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TIANNING FLAVOR (JIANGSU) CO Ltd
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Abstract

The invention discloses a synthesis method and application of 7-methoxy-3,7-dimethyloctyl aldehyde. The synthesis method comprises the following steps: synthesis of intermediate enamine I: reacting a dimethyl amine deionized water solution with a certain concentration, a 4A molecular sieve and 3,7-dimethyl-6-octenal, carrying out vacuum filtration, and stratifying; and synthesis of 7-methoxy-3,7-dimethyloctyl aldehyde: reacting methanol, strong-acid solid composite catalyst, I, cyclohexane, potassium hydroxide and sodium carbonate, washing and stratifying. The low-price 3,7-dimethyl-6-octenal is used as the raw material, amines are utilized to implement carbonyl protection to convert the 3,7-dimethyl-6-octenal into enamine compounds, and the strong-acid solid composite catalyst is utilized to catalyze the etherification between the C=C bond and the methanol and implement neutralization and amine removal, thereby obtaining the target product. The invention has the advantages of simple production technique, mild operating conditions, low requirements for production equipment, cheap and accessible raw materials and high yield. The 7-methoxy-3,7-dimethyloctyl aldehyde has fresh subtle fragrance as well as fragrance of leaves, Convallaria majalis flowers and the like, and can be used in cosmetic essence.

Description

A kind of 7-methoxyl group-3,7-dimethyl-octanal compound method and obtain the application of product
 
Technical field
The invention belongs to the foodstuff additive field, relate to a kind of synthetic perfume, specifically a kind of 7-methoxyl group-3, the compound method of 7-dimethyl-octanal and obtain the application of product.
Background technology
Along with development and national economy, people's lives progressively have and simply having adequate food and clothingly turn to fairly well-offly, and for the development of perfume industry product provides a wide big market, especially natural perfume enjoys favor.But, on kind quantity and quality product, receive certain influence because natural animal-plant spices often receives factors such as restriction and the processing of natural condition.The innovation of essence and the raising of quality also more and more rely on new synthetic perfume kind.Because synthetic perfume does not receive the restriction of natural condition, steady quality, the big I of industrial scale is arranged by people oneself, and the price of product is also than natural sources considerably cheaper.Therefore, development and the new synthetic perfume of developing development also seem more and more important.Particularly along with modern science research and analysis state of the art improves constantly separable and main fragrant composition and the structure thereof of analysis in the natural perfume, thereby develop through chemical synthesis process.Both the natural perfume deficiency can be solved, Financial cost can be reduced again.
7-methoxyl group-3,7-dimethyl-octanal are to have fresh delicate fragrance, and fragrance such as Ye Xiang and flores convallariae can be used in the makeup.In addition, it not only is widely used in the daily use chemicals processing industry, also is simultaneously one of important intermediate of synthetic neotonin agricultural chemicals alkene worm propyl ester.
Summary of the invention
The purpose of this invention is to provide a kind of 7-methoxyl group-3; The compound method of 7-dimethyl-octanal and obtain the application of product; The present invention has adopted low price, obtain easily 3,7-dimethyl--6-octenal is a raw material; Implement carbonyl-protection with amine and make it to become olefinic amine compound, strong acid solid composite catalyst carbon carbon two strong and methyl alcohol carry out etherificate and neutralization and take off amine and obtain title product.This synthetic route production technique is simple, and operational condition is gentle, and production unit requires low, and raw materials cost is lower and be easy to get, and yield is higher.
The objective of the invention is to realize through following technical scheme:
A kind of 7-methoxyl group-3,7-dimethyl-octanal compound method, it is characterized in that: this compound method comprises the midbody enamine ISynthetic and 7-methoxyl group-3,7-dimethyl-octanal synthetic, specific as follows:
1) midbody enamine ISynthetic,
In bottle, dropping into concentration is the n n dimetylaniline deionized water solution of 25%-40%, and adding quality is the dewatering agent four A molecular sieves of n n dimetylaniline deionized water solution 0.1%-1%, and temperature of reaction is-15 ~-5 ℃; In 1-5 hour, being added drop-wise to concentration under the violent stirring is 3 of 75%-95%, and 7-dimethyl--6-octenal drips and finishes in the n n dimetylaniline deionized water solution; After 10-25 ℃ of continuation reaction finished reaction in 1-10 hour; Carry out suction filtration, filtrating is poured in the separating funnel standing demix into; Tell lower aqueous layer, oil reservoir is told lower aqueous layer once more with the washing of saturated common salt deionized water thorough mixing; Adding quality in the oil reservoir is the four A molecular sieve dehydrations of the 1%-10% of oil reservoir, and the oil phase of sloughing moisture gets enamine solution through filtering I, content is 90%-95%, yield is 85%-95%; N n dimetylaniline and 3,7-dimethyl--6-octenal mol ratio is 1:5-5:1.
2) 7-methoxyl group-3,7-dimethyl-octanal is synthetic
In bottle, add concentration and be 99.5% methyl alcohol, stir down with cryosel bathe be cooled to-5 ~-15 ℃ for use; Get the strong acid type solid composite catalyst, it is slowly added in the methyl alcohol, controlled temperature is not more than-2 ℃; Finish, under agitation add enamine I,0.5-1 hour dropping time, and control reaction temperature is not higher than-2 ℃; Drip and finish, remove ice bath, make temperature rise to 15-20 ℃, stirring reaction 1-5 hour; Above-mentioned solution is added normal hexane dilution 105-50% hexane solution; During degree of cooling to-2 ~-8 ℃ of left and right sides, dropping concentration is that the Pottasium Hydroxide deionized water solution of 20%-40% takes off amine, and holding temperature is no more than 15 ℃; When solution pH value during, use the saturated sodium bicarbonate deionized water solution instead and regulate PH to 5-7 to 3-5; With in the solution of becoming reconciled carry out suction filtration, filter cake washs with normal hexane, incorporates filtrating into, the filtrating standing demix; Water layer merges to organic layer and adds the four A molecular sieve standing and drying that quality is the 1%-10% of feed liquid with n-hexane extraction 3-5 time, boils off the solvent normal hexane behind the elimination sal epsom; Raffinate rectification under vacuum under nitrogen protection, vacuum tightness under the 400-800Pa condition, interior temperature 100-150 ℃; Temperature is 100-106 ℃ and collects colourless cut, obtains 7-methoxyl group-3,7-dimethyl-octanal; Yield is 85%-95%, and content is 90%-95%; Wherein the mol ratio of methyl alcohol and strong acid type solid composite catalyst is 1:3-3:1, and the mol ratio of strong acid solid composite catalyst and enamine is 1:5-5:1.
Among the present invention, the strong acid solid composite catalyst is a SiO2/ZrO2 strong acid solid composite catalyst.
The 7-methoxyl group-3 that a kind of above-mentioned compound method obtains, the application of 7-dimethyl-octanal in daily chemical essence and the production of sweet taste essence.Be used for the fragrant and fragrant daily use chemicals of leaf of the lily of the valley.With the 7-methoxyl group-3 of gained, 7-dimethyl-octanal is applied to rose as raw material, and lemon is in the lily daily use chemicals.
The present invention mainly contains two-step reaction and forms, and the first step is the midbody enamine ISynthetic, second step was a 7-methoxyl group-3,7-dimethyl-octanal synthetic.The 7-methoxyl group-3 that obtains, 7-dimethyl-octanal is applied to rose as raw material, and lemon is in daily use chemicals such as lily and the sweet taste essence.
Synthetic route of the present invention is following:
Figure 2012103601665100002DEST_PATH_IMAGE004
The present invention has adopted low price; Obtain easily 3; 7-dimethyl--6-octenal is a raw material, makes it to become olefinic amine compound with amine enforcement carbonyl-protection, and two being good for methyl alcohol of strong acid solid composite catalyst catalyzed carbon carbon carries out etherificate and neutralize taking off the operational path that amine obtains title product.It is simple that this synthetic route has production technique, and operational condition is gentle, and production unit requires low, and raw materials cost is lower and be easy to get, and yield is than advantages such as height.
Embodiment
Embodiment 1
A kind of 7-methoxyl group-3,7-dimethyl-octanal compound method, reaction in two steps, the first step is the midbody enamine ISynthetic, second step was a 7-methoxyl group-3,7-dimethyl-octanal synthetic.
It at first is the first step: the midbody enamine ISynthetic, in bottle, drop into concentration and be 30% n n dimetylaniline deionized water solution, add dewatering agent four A molecular sieves (its amount is 1% of n n dimetylaniline deionized water solution amount); Temperature of reaction is-5 ℃, in 3 hours, drip concentration under the violent stirring and be 80% 3,7-dimethyl--6-octenal is in the n n dimetylaniline deionized water solution; Drip and finish, after 20 ℃ of continuation reactions finished reaction in 8 hours, carry out suction filtration; Filtrating is poured in the separatory leak standing demix into.Tell lower aqueous layer, oil reservoir is told lower aqueous layer once more with the washing of saturated common salt deionized water thorough mixing.Add four an amount of A molecular sieve dehydrations (its amount is 5% of oil reservoir) in the oil reservoir, the oil phase of sloughing moisture is through filtering, weigh the limpid enamine solution of little Huang I, content is 93%, yield is 90%.N n dimetylaniline and 3,7-dimethyl--6-octenal mol ratio is 1:3.
Second step was: 7-methoxyl group-3,7-dimethyl-octanal is synthetic, in bottle, adds concentration and be 99.5% methyl alcohol, stir down with cryosel bathe be cooled to-10 ℃ for use.Take by weighing the strong acid solid composite catalyst, it is slowly added in the methyl alcohol, controlled temperature is not more than-2 ℃.Finish, under agitation add enamine I,1 hour dropping time, and control reaction temperature is not higher than-2 ℃.Drip and finish, remove ice bath, make temperature rise to 20 ℃, stirring reaction 3 hours.Above-mentioned solution is added an amount of normal hexane dilution.Degree of cooling drips concentration and is 30% Pottasium Hydroxide deionized water solution and take off amine when-5 ℃ of left and right sides, and holding temperature is no more than 15 ℃.When solution pH value to 3, this is regulated about PH to 6 with the saturated sodium bicarbonate deionized water solution.With in the solution of becoming reconciled carry out suction filtration, filter cake washs with normal hexane, incorporates filtrating into; Filtrating standing demix, water layer be with n-hexane extraction 3-5 time, merges to organic layer and add 4a molecular sieve standing and drying (be feed liquid 8%); Boil off the solvent normal hexane behind the elimination sal epsom, colourless cut is collected in raffinate rectification under vacuum under nitrogen protection under 100-106 ℃/400-800Pa condition; Obtain 7-methoxyl group-3,7-dimethyl-octanal.The yield of weighing is 90%, and content is 93%.Methyl alcohol wherein, the mol ratio of strong acid solid composite catalyst is 1:2, the mol ratio of strong acid solid composite catalyst and enamine is 1:3.The strong acid solid composite catalyst is a SiO2/ZrO2 strong acid solid composite catalyst.
Embodiment 2
A kind of 7-methoxyl group-3,7-dimethyl-octanal compound method, concrete steps are following:
It at first is the first step: the midbody enamine ISynthetic, in bottle, drop into concentration and be 35% n n dimetylaniline deionized water solution, adds an amount of dewatering agent four A molecular sieves (its amount be n n dimetylaniline deionized water solution 1%); Temperature of reaction is-10 ℃, in 4 hours, drip concentration under the violent stirring and be 90% 3,7-dimethyl--6-octenal is in the n n dimetylaniline deionized water solution; Drip and finish, after 25 ℃ of continuation reactions finished reaction in 2 hours, carry out suction filtration; Filtrating is poured in the separatory leak standing demix into.Tell lower aqueous layer, oil reservoir is told lower aqueous layer once more with the washing of saturated common salt deionized water thorough mixing.Add four an amount of A molecular sieve dehydrations (its amount is 6% of oil reservoir) in the oil reservoir, the oil phase of sloughing moisture is through filtering, weigh the limpid enamine solution of little Huang I, content is 90%, yield is 90%.N n dimetylaniline and 3,7-dimethyl--6-octenal mol ratio is 1:1.
Second step was: 7-methoxyl group-3,7-dimethyl-octanal is synthetic, in bottle, adds concentration and be 99.5% methyl alcohol, stir down with cryosel bathe be cooled to-15 ℃ for use.Take by weighing the strong acid solid composite catalyst, it slowly is added dropwise in the methyl alcohol, controlled temperature is not more than-2 ℃.Finish, under agitation add enamine I,1 hour dropping time, and control reaction temperature is not higher than-2 ℃.Drip and finish, remove ice bath, make temperature rise to 20 ℃, stirring reaction 1 hour.Above-mentioned solution is added an amount of normal hexane dilution.Degree of cooling drips concentration and is 20% Pottasium Hydroxide deionized water solution and take off amine when-4 ℃ of left and right sides, and holding temperature is no more than 15 ℃.When solution pH value to 4, this is regulated about PH to 7 with the saturated sodium bicarbonate deionized water solution.With in the solution of becoming reconciled carry out suction filtration, filter cake washs with normal hexane, incorporates filtrating into; Filtrating standing demix, water layer be with n-hexane extraction 3-5 time, merges to organic layer and add 4a molecular sieve standing and drying (be feed liquid 5%); Boil off the solvent normal hexane behind the elimination sal epsom, colourless cut is collected in raffinate rectification under vacuum under nitrogen protection under 100-106 ℃/400-800Pa condition; Obtain 7-methoxyl group-3,7-dimethyl-octanal.The yield of weighing is 95%, and content is 90%.Methyl alcohol wherein, the mol ratio of strong acid solid composite catalyst is 1:1, the mol ratio of strong acid solid composite catalyst and enamine is 1:1.The strong acid solid composite catalyst is a SiO2/ZrO2 strong acid solid composite catalyst.
The 7-methoxyl group-3 that above-mentioned two steps obtain, 7-dimethyl-octanal has fresh delicate fragrance, and fragrance such as Ye Xiang and flores convallariae can be used for being applied to rose as raw material in the cosmetic essence, and lemon is in the daily use chemicals such as lily.

Claims (5)

1. 7-methoxyl group-3,7-dimethyl-octanal compound method, it is characterized in that: this compound method comprises the midbody enamine ISynthetic and 7-methoxyl group-3,7-dimethyl-octanal synthetic, specific as follows:
1) midbody enamine ISynthetic,
In bottle, dropping into concentration is the n n dimetylaniline deionized water solution of 25%-40%, and adding quality is the dewatering agent four A molecular sieves of n n dimetylaniline deionized water solution 0.1%-1%, and temperature of reaction is-15 ~-5 ℃; In 1-5 hour, being added drop-wise to concentration under the violent stirring is 3 of 75%-95%, and 7-dimethyl--6-octenal drips and finishes in the n n dimetylaniline deionized water solution; After 10-25 ℃ of continuation reaction finished reaction in 1-10 hour; Carry out suction filtration, filtrating is poured in the separating funnel standing demix into; Tell lower aqueous layer, oil reservoir is told lower aqueous layer once more with the washing of saturated common salt deionized water thorough mixing; Adding quality in the oil reservoir is the four A molecular sieve dehydrations of the 1%-10% of oil reservoir, and the oil phase of sloughing moisture gets enamine solution through filtering I, content is 90%-95%, yield is 85%-95%; N n dimetylaniline and 3,7-dimethyl--6-octenal mol ratio is 1:5-5:1;
2) 7-methoxyl group-3,7-dimethyl-octanal is synthetic
In bottle, add concentration and be 99.5% methyl alcohol, stir down with cryosel bathe be cooled to-5 ~-15 ℃ for use; Get the strong acid type solid composite catalyst, it is slowly added in the methyl alcohol, controlled temperature is not more than-2 ℃; Finish, under agitation add enamine I,0.5-1 hour dropping time, and control reaction temperature is not higher than-2 ℃; Drip and finish, remove ice bath, make temperature rise to 15-20 ℃, stirring reaction 1-5 hour; Above-mentioned solution is added normal hexane be diluted to the 10%-50% hexane solution; During degree of cooling to-2 ~-8 ℃ of left and right sides, dropping concentration is that the Pottasium Hydroxide deionized water solution of 20%-40% takes off amine, and holding temperature is no more than 15 ℃; When solution pH value during, use the saturated sodium bicarbonate deionized water solution instead and regulate PH to 5-7 to 3-5; With in the solution of becoming reconciled carry out suction filtration, filter cake washs with normal hexane, incorporates filtrating into, the filtrating standing demix; Water layer merges to organic layer and adds the four A molecular sieve standing and drying that quality is the 1%-10% of feed liquid with n-hexane extraction 3-5 time, boils off the solvent normal hexane behind the elimination sal epsom; Raffinate rectification under vacuum under nitrogen protection, vacuum tightness under the 400-800Pa condition, interior temperature 100-150 ℃; Temperature is 100-106 ℃ and collects colourless cut, obtains 7-methoxyl group-3,7-dimethyl-octanal; Yield is 85%-95%, and content is 90%-95%; Wherein the mol ratio of methyl alcohol and strong acid type solid composite catalyst is 1:3-3:1, and the mol ratio of strong acid solid composite catalyst and enamine is 1:5-5:1.
2. 7-methoxyl group-3 according to claim 1,7-dimethyl-octanal compound method is characterized in that: step 2) in, the strong acid solid composite catalyst is a SiO2/ZrO2 strong acid solid composite catalyst.
3. 7-methoxyl group-3 that the described compound method of claim 1 obtains, the application of 7-dimethyl-octanal in daily chemical essence and sweet taste essence are produced.
4. 7-methoxyl group-3 according to claim 4, the application of 7-dimethyl-octanal in daily chemical essence and the production of sweet taste essence is characterized in that: be used for the fragrant and fragrant daily use chemicals of leaf of the lily of the valley.
5. 7-methoxyl group-3 according to claim 4, the application of 7-dimethyl-octanal in daily chemical essence and the production of sweet taste essence, it is characterized in that: with the 7-methoxyl group-3 of gained, 7-dimethyl-octanal is applied to rose as raw material, and lemon is in the lily daily use chemicals.
CN2012103601665A 2012-09-25 2012-09-25 Synthesis method and application of 7-methoxy-3,7-dimethyloctyl aldehyde Pending CN102826977A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107032971A (en) * 2017-04-27 2017-08-11 上海应用技术大学 A kind of preparation method of the octenal of 3,7 dimethyl, 6 carbonyl 2
CN107536004A (en) * 2016-06-28 2018-01-05 长谷川香料株式会社 Low-fat food flavor improving agent

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3978135A (en) * 1971-12-21 1976-08-31 Rhone-Poulenc S.A. Preparation of ethers from citronellal or homologues thereof

Patent Citations (1)

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Publication number Priority date Publication date Assignee Title
US3978135A (en) * 1971-12-21 1976-08-31 Rhone-Poulenc S.A. Preparation of ethers from citronellal or homologues thereof

Non-Patent Citations (1)

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Title
孙揭阳: "甲氧基香茅醛合成工艺研究", 《化学世界》, no. 3, 25 March 2009 (2009-03-25), pages 167 - 170 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107536004A (en) * 2016-06-28 2018-01-05 长谷川香料株式会社 Low-fat food flavor improving agent
CN107032971A (en) * 2017-04-27 2017-08-11 上海应用技术大学 A kind of preparation method of the octenal of 3,7 dimethyl, 6 carbonyl 2
CN107032971B (en) * 2017-04-27 2020-05-12 上海应用技术大学 A kind of preparation method of 3,7-dimethyl-6-carbonyl-2-octenal

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Application publication date: 20121219