CN100594205C - Method for synthesizing 2,7-dimethyl-octa-2,4,6-trienedial - Google Patents
Method for synthesizing 2,7-dimethyl-octa-2,4,6-trienedial Download PDFInfo
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- CN100594205C CN100594205C CN200810061140A CN200810061140A CN100594205C CN 100594205 C CN100594205 C CN 100594205C CN 200810061140 A CN200810061140 A CN 200810061140A CN 200810061140 A CN200810061140 A CN 200810061140A CN 100594205 C CN100594205 C CN 100594205C
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Abstract
The invention discloses a new method for synthesis of 2, 7-dimethyl-2, 4, 6-octatrien-1, 8-dialdehyde. The method synthesizes 2, 7-dimethyl-2, 4, 6-octatrien-1, 8-dialdehyde using trans-1, 4-dichloro-2-butylene as the raw material, which undergoes Grignard reaction, condensation reaction and acidic hydrolysis reaction. The method has the advantages that, firstly, trans-1, 4-dichloro-2-butylene isadopted as the raw material for synthesizing 2, 7-dimethyl-2, 4, 6-octatrien-1, 8-dialdehyde after three procedural reactions, so the total yield is high; secondly, synthesis of 2, 7-dimethyl-2, 4, 6-octatrien-1, 8-dialdehyde has good reaction selectivity and little by-products; and thirdly, the process is simple with convenient operation.
Description
Technical field
The present invention relates to a kind of 2,7-dimethyl-2,4,6-sarohornene-1, the synthetic method of 8-dialdehyde.
Background technology
2,7-dimethyl-2,4,6-sarohornene-1, the 8-dialdehyde, 157～159 ℃ of fusing points, normal temperature are stable down, are soluble in ethanol, sherwood oil, be slightly soluble in water, be the key intermediate of synthetic carotenoid, in synthesizing important application arranged at β-Hu Luobusu, canthaxanthin, astaxanthin, it synthesizes the domestic bibliographical information of not seeing.Carotenoid can be used as medicine, pigment, foodstuff additive and fodder additives, is used for medicine, food, makeup and aquaculture.Along with the application of China's carotenoid increases day by day, 2,7-dimethyl-2,4,6-sarohornene-1,8-dialdehyde study on the synthesis is significant.Bibliographical information 2,7-dimethyl-2,4,6-sarohornene-1, the synthetic method of 8-dialdehyde mainly contains following several:
1.1959 year, the Isler of Roche Holding Ag is a raw material with 1-oxyethyl group-1-propylene, through eight steps reaction such as ethoxylation, ethinylation, hydrogenation Synthetic 2, and 7-dimethyl-2,4,6-sarohornene-1, the 8-dialdehyde, reaction formula is as follows:
This operational path severe reaction conditions, total recovery has only 21%.
BASF AG in nineteen sixty diethoxy acetone be raw material, synthesized 2 through Wittig-Horner reaction, deprotection base, 7-dimethyl-2,4,6-sarohornene-1, the 8-dialdehyde, reaction formula is as follows:
Though reactions steps is short, weak point is that reaction yield is low, and triethyl phosphinate relative cost is higher, has special smell.
3.Hagen is linking agent in 1994 with the benzene sulfinic acid sodium salt, 2-(3-chloro-1-methyl isophthalic acid-propenyl)-5,5-dimethyl-1,3-two uh alkane be the raw material Synthetic 2,7-dimethyl-2,4,6-sarohornene-1, the 8-dialdehyde, reaction formula is as follows:
From reaction formula as can be seen, 2,7-dimethyl-2,4,6-sarohornene-1,8-dialdehyde preparation technology long flow path has seven step reactions, the various auxiliary materials of using are also more, complex process.
Summary of the invention
The objective of the invention is the problem that exists in the above-mentioned route, provide a kind of 2,7-dimethyl-2,4,6-sarohornene-1, the preparation method of 8-dialdehyde.
It comprises the steps:
1) with tetrahydrofuran (THF) 300ml, magnesium powder 12.0g, gas phase content is 99.0% anti-form-1,4-two chloro-2-butylene 2.1～4.2ml, iodine 0.1g adds in the reactor, heating, control reaction temperature is 30～35 ℃, dropping gas phase content is 99.0% anti-form-1,4-two chloro-2-butylene 11.3～22.6ml, drip to finish heat temperature raising to 40～60 ℃, insulation reaction 2～5 hours, dropping contains 100～400ml tetrahydrofuran solution of 29.5～295g dimethoxy acetone, drip and finish, insulation reaction 6～12 hours is cooled to 20～40 ℃ and obtains reaction solution;
2) reaction solution being added drop-wise to 150～600ml weight percent concentration is hydrolysis in 10～20% diluted acids, and hydrolysis temperature is 0～20 ℃, continues to stir 0.5～2 hour, heat temperature raising to 30～50 ℃, tetrahydrofuran (THF) is removed in decompression, adds 100～600ml water, filter, the flushing of filter cake water, vacuum-drying obtains 2,7-dimethyl-2,4,6-sarohornene-1,8-dialdehyde.
Described diluted acid is dilute sulphuric acid, dilute hydrochloric acid or dilute acetic acid.Diluted acid is preferably dilute sulphuric acid.
Advantage of the present invention is: 1) adopt anti-form-1,4-two chloro-2-butylene are starting raw material, through the three-step reaction Synthetic 2, and 7-dimethyl-2,4,6-sarohornene-1,8-dialdehyde, total recovery height.2) 2,7-dimethyl-2,4,6-sarohornene-1, in 8-dialdehyde synthetic, good reaction selectivity, by product is few.3) this method technology is simpler, easy to operate.
Embodiment
2,7-dimethyl-2,4,6-sarohornene-1, the reaction formula of the synthetic method of 8-dialdehyde is:
Below in conjunction with embodiment the present invention is described in detail.
Embodiment 1
With tetrahydrofuran (THF) 300ml, magnesium powder 12.0g, gas phase content is 99.0% anti-form-1, and 4-two chloro-2-butylene 2.1ml, iodine 0.1g add in the reactor, heating, control reaction temperature is 30 ℃, dropping gas phase content is 99.0% anti-form-1,4-two chloro-2-butylene 11.3ml, drip to finish heat temperature raising to 40 ℃, insulation reaction 2 hours, dropping contains the 100ml tetrahydrofuran solution of 29.5g dimethoxy acetone, drip and finish, insulation reaction 6 hours is cooled to 20 ℃ and obtains reaction solution; It is hydrolysis in 10% dilute sulphuric acid that reaction solution is added drop-wise to the 150ml weight percent concentration, and hydrolysis temperature is 0 ℃, continues to stir 0.5 hour, heat temperature raising to 30 ℃, tetrahydrofuran (THF) is removed in decompression, adds 100ml water, filter, the flushing of filter cake water, vacuum-drying obtains 2,7-dimethyl-2,4,6-sarohornene-1,8-dialdehyde.
Embodiment 2
With tetrahydrofuran (THF) 300ml, magnesium powder 12.0g, gas phase content is 99.0% anti-form-1, and 4-two chloro-2-butylene 4.2ml, iodine 0.1g add in the reactor, heating, control reaction temperature is 35 ℃, dropping gas phase content is 99.0% anti-form-1,4-two chloro-2-butylene 22.6ml, drip to finish heat temperature raising to 60 ℃, insulation reaction 5 hours, dropping contains the 400ml tetrahydrofuran solution of 295g dimethoxy acetone, drip and finish, insulation reaction 12 hours is cooled to 40 ℃ and obtains reaction solution; It is hydrolysis in 20% dilute hydrochloric acid that reaction solution is added drop-wise to the 600ml weight percent concentration, and hydrolysis temperature is 20 ℃, continues to stir 2 hours, heat temperature raising to 50 ℃, tetrahydrofuran (THF) is removed in decompression, adds 600ml water, filter, the flushing of filter cake water, vacuum-drying obtains 2,7-dimethyl-2,4,6-sarohornene-1,8-dialdehyde.
Embodiment 3
In the 1000ml flask, add tetrahydrofuran (THF) (THF) 300ml, Mg powder 12.0g, anti-form-1,4-two chloro-2-butylene 5g (content: 99.0%), iodine 0.1g, heating makes it to cause, and control reaction temperature is 30～35 ℃ then, drips remaining 26.6g anti-form-1,4-two chloro-2-butylene, drip and finish, be warming up to 50 ℃, insulation reaction is until the completely dissolve of Mg powder; Drip the 200mlTHF solution that contains 118g dimethoxy acetone then in above-mentioned reaction solution, drip and finish, insulation reaction 8 hours is cooled to 20 ℃; To be added drop-wise to hydrolysis in 300ml 10% dilute sulphuric acid in the reaction solution, hydrolysis temperature is controlled below 20 ℃, dropwises the back and continues to stir 30 minutes, has a large amount of product precipitations to separate out; Temperature is controlled at below 50 ℃, and THF is removed in decompression, to wherein adding 300ml water, filters again, filter cake washes with less water, and wet product vacuum-drying below 50 ℃ gets 2,7-dimethyl-2,4,6-sarohornene-1,8-dialdehyde finished product 21.9g, yield 52.5% (content: 98.3%).
Embodiment 4
In the 1000ml flask, add THF300ml, Mg powder 12.0g, anti-form-1,4-two chloro-2-butylene 5g (content: 99.0%), iodine 0.1g, heating makes it to cause, and control reaction temperature is 30～35 ℃ then, drips remaining 26.6g anti-form-1,4-two chloro-2-butylene, drip and finish, be warming up to 50 ℃, insulation reaction is until the completely dissolve of Mg powder; Drip the 200ml THF solution that contains 59g dimethoxy acetone then in above-mentioned reaction solution, drip and finish, insulation reaction 8 hours is cooled to 20 ℃; To contain and be added drop-wise to hydrolysis in 300ml 10% dilute sulphuric acid in the reaction solution, hydrolysis temperature is controlled below 20 ℃, dropwises the back and continues to stir 30 minutes, has a large amount of products precipitations to separate out; Temperature is controlled at below 50 ℃, and THF is removed in decompression, to wherein adding 300ml water, filters again, filter cake washes with less water, and wet product vacuum-drying below 50 ℃ gets 2,7-dimethyl-2,4,6-sarohornene-1,8-dialdehyde finished product 12.7g, yield 30.3% (content: 97.7%).
Embodiment 5
In the 1000ml flask, add THF300ml, Mg powder 12.0g, anti-form-1,4-two chloro-2-butylene 5g (content: 99.0%), iodine 0.1g, heating makes it to cause, and control reaction temperature is 30～35 ℃ then, drips remaining 26.6g anti-form-1,4-two chloro-2-butylene, drip and finish, be warming up to 50 ℃, insulation reaction is until the completely dissolve of Mg powder; Drip the 200ml THF solution that contains 118g dimethoxy acetone then in above-mentioned reaction solution, drip and finish, insulation reaction 8 hours is cooled to 20 ℃; To be added drop-wise to hydrolysis in 300ml 10% dilute hydrochloric acid in the reaction solution, hydrolysis temperature is controlled below 20 ℃, dropwises the back and continues to stir 30 minutes, has a large amount of product precipitations to separate out; Temperature is controlled at below 50 ℃, and THF is removed in decompression, to wherein adding 300ml water, filters again, filter cake washes with less water, and wet product vacuum-drying below 50 ℃ gets 2,7-dimethyl-2,4,6-sarohornene-1,8-dialdehyde finished product 21.4g, yield 51.2% (content: 98.1%).
Claims (3)
1, a kind of 2,7-dimethyl-2,4,6-sarohornene-1, the preparation method of 8-dialdehyde is characterized in that comprising the steps:
1) with tetrahydrofuran (THF) 300ml, magnesium powder 12.0g, gas phase content is 99.0% anti-form-1,4-two chloro-2-butylene 2.1～4.2ml, iodine 0.1g adds in the reactor, heating, control reaction temperature is 30～35 ℃, dropping gas phase content is 99.0% anti-form-1,4-two chloro-2-butylene 11.3～22.6ml, drip to finish heat temperature raising to 40～60 ℃, insulation reaction 2～5 hours, dropping contains 100～400ml tetrahydrofuran solution of 29.5～295g dimethoxy acetone, drip and finish, insulation reaction 6～12 hours is cooled to 20～40 ℃ and obtains reaction solution;
2) reaction solution being added drop-wise to 150～600ml weight percent concentration is hydrolysis in 10～20% diluted acids, and hydrolysis temperature is 0～20 ℃, continues to stir 0.5～2 hour, heat temperature raising to 30～50 ℃, tetrahydrofuran (THF) is removed in decompression, adds 100～600ml water, filter, the flushing of filter cake water, vacuum-drying obtains 2,7-dimethyl-2,4,6-sarohornene-1,8-dialdehyde.
2, according to claim 1 a kind of 2,7-dimethyl-2,4,6-sarohornene-1, the preparation method of 8-dialdehyde is characterized in that described diluted acid is dilute sulphuric acid, dilute hydrochloric acid or dilute acetic acid.
3, according to claim 1 and 2 a kind of 2,7-dimethyl-2,4,6-sarohornene-1, the preparation method of 8-dialdehyde is characterized in that described diluted acid is a dilute sulphuric acid.
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| CN103172504B (en) * | 2011-12-26 | 2014-10-08 | 南京工业大学 | Synthetic method of 2,7-dimethyl-2,4,6-octytriene-1,8-dialdehyde |
| CN105254479A (en) * | 2015-10-16 | 2016-01-20 | 上虞新和成生物化工有限公司 | Synthetic method for vitamin A intermediate C14 aldehyde |
| CN113292402A (en) * | 2021-05-06 | 2021-08-24 | 暨南大学 | Method for synthesizing 3, 8-dimethyl-3, 5, 7-octatriene-1, 10-dialdehyde |
| CN113461850B (en) * | 2021-08-13 | 2022-03-29 | 中国科学院长春应用化学研究所 | Trans-1, 4-poly (4, 8-2-methyl-1, 3, 7-nonane triene) and preparation method thereof |
| CN113773185B (en) * | 2021-09-10 | 2022-08-05 | 万华化学集团股份有限公司 | Preparation method of 3, 6-dimethoxy-2, 7-dimethyl-4-octenedialdehyde |
| CN114940644B (en) * | 2022-06-20 | 2024-04-09 | 万华化学集团股份有限公司 | Crystallization method of 2, 7-dimethyl-2, 4, 6-octatriene-1, 8-dialdehyde |
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