CN109053404A - A kind of synthetic method of 2- hexenoic aldehyde - Google Patents
A kind of synthetic method of 2- hexenoic aldehyde Download PDFInfo
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- CN109053404A CN109053404A CN201811046994.5A CN201811046994A CN109053404A CN 109053404 A CN109053404 A CN 109053404A CN 201811046994 A CN201811046994 A CN 201811046994A CN 109053404 A CN109053404 A CN 109053404A
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- hexenoic aldehyde
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- C—CHEMISTRY; METALLURGY
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/42—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by hydrolysis
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/48—Preparation of compounds having groups
- C07C41/50—Preparation of compounds having groups by reactions producing groups
- C07C41/56—Preparation of compounds having groups by reactions producing groups by condensation of aldehydes, paraformaldehyde, or ketones
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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
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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Abstract
The invention discloses a kind of synthetic methods of 2- hexenoic aldehyde.Raw material n-butanal reacts under catalyst Catalyzed by p-Toluenesulfonic Acid with alkylol, under boron trifluoride and the catalysis of 3 mixed solution of B (C6F5) addition reaction occurs for obtained acetal and vinyl alkyl ethers, obtained addition product heats up under dilute acid solution catalytic action boils hydrolysis distillation, obtains 2- hexenoic aldehyde crude product by continuous rectification under vacuum and obtains high-purity 2- hexenoic aldehyde.Route of the present invention is cut down the consumption of raw materials, and yield is considerable, and product has competitive advantage.
Description
Technical field
This explanation is related to a kind of synthetic method of 2- hexenoic aldehyde, belongs to technical field of organic synthesis.
Background technique
2- hexenoic aldehyde, weak yellow liquid, 150~152 DEG C of boiling point, be in strong fresh fruit, greenery faint scent.Have it is cis- and
Trans- two kinds of isomers (note: 2- hexenoic aldehyde described in the invention is transisomer).Natural product are present in tealeaves, mulberry leaf, radish
In the oil such as leaf and in cucumber, apple, peach, orange peel, strawberry, passion fruit, pawpaw etc..
The high temperature of many potential four or five ten degrees Celsius of tolerances of plant, but under normal temperature state, endure the mechanism of high temperature
In the state of shutting down, only the mechanism just be will start under high temperature environment.If temperature steeply rises, plant copes with the tune of high temperature
Section mechanism just has little time to react, and causes plant strain growth slow.2015, professor Shan Nei Jing Xiong research group of Kobe University
The blade of many plants can largely generate a kind of volatile matter of entitled 2- hexenoic aldehyde after fracture, and in an experiment, research group uses
Preparation containing 2- hexenoic aldehyde sprays crucifer-arabidopsis, then puts it into 45 degrees Celsius of room temperature of room two
Hour.As a result, the former survival rate is higher by 60% compared with the arabidopsis of no sprinkling 2- hexenoic aldehyde.In other similar experiment
In, the harvest of the cucumber, strawberry, tomato plant of 2- hexenoic aldehyde has been sprayed, the vegetable and fruit for not spraying said preparation is above.
2- hexenoic aldehyde is widely used in daily chemical essence formula at present, is mainly used for preparing raspberry, mango, egg
The types essence such as fruit, apple, strawberry, the product have fresh greenery fragrance, can be used for the blending of artificial flower, essential oil, all kinds of fragrance of a flower
Fragrance.
Art methods, mainly using hexanal after bromo with glycol reaction, then obtain through hydrolysis.This method reaction
Step is more, and technique is cumbersome, and yield is relatively low after multistep reaction, is not suitable for industrialized production.
Summary of the invention
For overcome the deficiencies in the prior art, the present invention provides by n-butanal first with alkylol generate acetal object again with second
Alkenyl alkyl ethers, which react to be made after addition product hydrolyzes again, obtains high-purity 2- hexenoic aldehyde scheme by continuous rectification under vacuum.
To achieve the goals above, the present invention adopts the following technical scheme: the first step, n-butanal and alkylol are in catalyst
Reaction obtains acetal under Catalyzed by p-Toluenesulfonic Acid；Second step, acetal and vinyl alkyl ethers are mixed in boron trifluoride and B (C6F5) 3
It closes under solution catalyzing, addition reaction occurs and obtains addition product；Third step, addition product heat up under dilute acid solution catalysis and hydrolyze
To 2- hexenoic aldehyde crude product.The air-distillation of crude product elder generation obtains high-purity 2- hexenoic aldehyde using continuous rectification under vacuum, obtains after dilution
2- hexenoic aldehyde low concentration solution becomes daily essence, fragrance.
Further, in the above-mentioned technical solutions, first step acetal product reacts to obtain from n-butanal with alkylol, alkyl
Selected from alkylols such as methyl, ethyl, propyl, normal-butyl, isobutyl groups.
Further, in the above-mentioned technical solutions, first step aldolisation is dry using the anhydrous calcium chloride of 5%-20% equivalent
Dry, reaction temperature is at 20 DEG C to 60 DEG C.
Further, in the above-mentioned technical solutions, first step aldolisation n-butanal and alkylol molar ratio are 1:2-3.
Further, in the above-mentioned technical solutions, second step addition product is reacted from acetal object with vinyl alkyl ethers
It arrives, alkyl is selected from the vinyl alkyl ethers such as methyl, ethyl, propyl, normal-butyl, isobutyl group.
Further, in the above-mentioned technical solutions, second step addition reaction carries out under the conditions of dried over anhydrous, reaction temperature
At -10 DEG C -60 DEG C.
Further, in the above-mentioned technical solutions, second step addition reaction vinyl alkyl ethers are with acetal object molar ratio
1:1-4。
Further, in the above-mentioned technical solutions, second step addition reaction boron trifluoride catalyst is selected from boron trifluoride second
Ether, boron trifluoride tetrahydrofuran or boron trifluoride acetonitrile.Boron trifluoride and B (C6F5) 3 mass ratio are 2-5:1.
Further, in the above-mentioned technical solutions, excessive acetal object may be reused after second step addition reaction.
Further, in the above-mentioned technical solutions, third step hydrolysis dilute acid concentration is 1-50%.
Further, in the above-mentioned technical solutions, third step hydrolysis acid includes the nothings such as phosphoric acid, sulfuric acid, hydrochloric acid, oxalic acid
Machine acid and organic acid.
Further, in the above-mentioned technical solutions, third step hydrolysis diluted acid may be reused.
Further, in the above-mentioned technical solutions, purifying products elder generation air-distillation goes out the low-boiling point materials such as alkylol, water,
Rectification under vacuum obtains 2- hexenoic aldehyde again.
Further, in the above-mentioned technical solutions, 2- hexenoic aldehyde qualification index are as follows: purity > 99%, trans/cis > 100-
150:1, weak yellow liquid are in strong fresh fruit, greenery faint scent.
Advantageous effect of the invention
The present invention avoid at present more generally by hexanal after bromo with glycol reaction, then be made through hydrolyzing, but pass through original
Material n-butanal and alkylol obtain acetal, are then catalyzed under 3 mixed solution of boron trifluoride and B (C6F5) with vinyl alkyl ethers
Addition product is obtained, then heating hydrolysis obtains 2- hexenoic aldehyde crude product under dilute acid solution catalytic action, is then passed through and continuously subtracts
Pressure rectifying obtains high-purity 2- hexenoic aldehyde.The present invention uses 3 mixed catalyst of boron trifluoride and B (C6F5), and reaction process is along anti-
Selectivity is high, and catalyst amount is low.Variation route reduces consumption of raw materials, and yield is considerable, and product has competitive advantage.
Specific embodiment
Example one: aldolisation needs n-butanal 144g, methanol 128g, p-methyl benzenesulfonic acid 0.14g, anhydrous calcium chloride 7.2g,
Addition reaction needs methoxy ethylene 58g, 48% boron trifluoride ether solution 0.29g and 0.10 g B (C6F5) 3, n-butanal with
Methanol Molar ratio is 1:2,40-60 DEG C of dropwise addition.Acetal and methoxy ethylene molar ratio are 1:1, and -10-0 DEG C of reactions, hydrolysis is instead
It should need 10% dilute sulfuric acid 204g.
Synthetic method is as follows:
(1) ethyl alcohol, anhydrous calcium chloride and p-methyl benzenesulfonic acid (2) is added to 500mL reaction flask and n-butanal is added dropwise, temperature control is in 40-60
Stratification (4) rectifying obtains 188.8g acetal object, yield 80%(5 after DEG C (3) are stirred 1 hour after being added dropwise) take rectifying to go out
The acetal object 118g come reacts under boron trifluoride ether and the catalysis of 3 mixed solution of B (C6F5) with methoxy ethylene, temperature control -10-
0 DEG C of reaction 1h, sample detection obtain addition product 123g, yield 70%(7 along inverse proportion for 1:119(6) rectifying) sulfuric acid solution is added
Enter and boiled in 500mL reaction flask, then dropwise reaction liquid, distilled when being added dropwise, obtain trans- 2- hexenoic aldehyde hydrolyzate 138g(8) first
Atmospheric distillation alkenyl methyl ether is in low-boiling-point substance out, and in decompressing and continuous rectifying, when pressure is -0.09MPa, tower top temperature is 78-80 DEG C
When collect 2- hexenoic aldehyde sterling 66g, cis-isomer is not detected in yield 67.3%, GC:99.5%.
Example two: aldolisation needs n-butanal 216g, methanol 288g, p-methyl benzenesulfonic acid 2.1g, anhydrous calcium chloride 21.6g,
Addition reaction needs methoxy ethylene 58g, 48% boron trifluoride ether solution 0.58g and 0.25g B (C6F5) 3, n-butanal and first
Alcohol molar ratio is 1:3,20-40 DEG C of dropwise addition.Acetal and methoxy ethylene molar ratio are 2:1,10-20 DEG C of reaction.Hydrolysis
Need 10% phosphoric acid,diluted 204g.
Synthetic method is as follows:
(1) ethyl alcohol, anhydrous calcium chloride and p-methyl benzenesulfonic acid (2) is added to 500mL reaction flask and n-butanal is added dropwise, temperature control is in 20-40
Stratification (4) rectifying obtains 300g acetal object, yield 85%(5 after DEG C (3) are stirred 1 hour after being added dropwise) take rectifying to come out
Acetal object 236g and methoxy ethylene reacted under boron trifluoride ether and the catalysis of 3 mixed solution of B (C6F5), temperature control 10-20
DEG C reaction 1h, sample detection is 1:144(6 along inverse proportion) rectifying obtains addition product 148g, yield 84%(7) add phosphoric acid solution
Enter and boiled in 500mL reaction flask, then dropwise reaction liquid, distilled when being added dropwise, obtain trans- 2- hexenoic aldehyde hydrolyzate 164g(8) first
Atmospheric distillation alkenyl methyl ether is in low-boiling-point substance out, and in decompressing and continuous rectifying, when pressure is -0.09MPa, tower top temperature is 78-80 DEG C
When collect 2- hexenoic aldehyde sterling 77.3g, yield 78.9%, cis-isomer is not detected in G/C content 99.3%.
Example three: aldolisation needs n-butanal 144g, methanol 140.8g, p-methyl benzenesulfonic acid 0.28g, anhydrous calcium chloride
14.4g, addition reaction need methoxy ethylene 58g, 48% boron trifluoride ether solution 1.16g and 0.30g B (C6F5) 3, positive fourth
Aldehyde and Methanol Molar ratio are 1:2.2,20-40 DEG C of dropwise addition.Acetal and methoxy ethylene molar ratio are 1:1,20-30 DEG C of reaction.
Hydrolysis needs 10% dilute sulfuric acid 408g.
Synthetic method is as follows:
(1) ethyl alcohol, anhydrous calcium chloride and p-methyl benzenesulfonic acid (2) is added to 500mL reaction flask and n-butanal is added dropwise, temperature control is in 20-40
Stratification (4) rectifying obtains 207g acetal object, yield 87.7%(5 after DEG C (3) are stirred 1 hour after being added dropwise) take rectifying to go out
The acetal object 118g come reacts under boron trifluoride ether and the catalysis of 3 mixed solution of B (C6F5) with methoxy ethylene, temperature control 20-
30 DEG C of reaction 1h, sample detection are 1:122(6 along inverse proportion) rectifying obtains addition product 128g, yield 72%(7) by sulfuric acid solution
It is added in 1000mL reaction flask and boils, then dropwise reaction liquid, distilled when being added dropwise, obtain trans- 2- hexenoic aldehyde hydrolyzate 148g
(8) first atmospheric distillation alkenyl methyl ether is in low-boiling-point substance out, in decompressing and continuous rectifying, when pressure is -0.09MPa, tower top temperature 78-
2- hexenoic aldehyde sterling 66.6g is collected at 80 DEG C, cis-isomer is not detected in yield 68%, GC:99.7%.
Example four: aldolisation needs n-butanal 288g, methanol 281.6g, p-methyl benzenesulfonic acid 0.28g, anhydrous calcium chloride
14.4g, addition reaction need methoxy ethylene 58g, 48% boron trifluoride ether solution 0.29g and 0.10g B (C6F5) 3, positive fourth
Aldehyde and Methanol Molar ratio are 1:2.2,20-40 DEG C of dropwise addition.Acetal and methoxy ethylene molar ratio are 3:1,0-10 DEG C of reaction.Water
Solution reaction needs 10% phosphoric acid,diluted 204g.
Synthetic method is as follows:
(1) ethyl alcohol, anhydrous calcium chloride and p-methyl benzenesulfonic acid (2) is added to 1000mL reaction flask and n-butanal is added dropwise, temperature control is in 20-40
Stratification (4) rectifying obtains 400g acetal object, yield 84.7%(5 after DEG C (3) are stirred 1 hour after being added dropwise) take rectifying to go out
The acetal object 354g come reacts under boron trifluoride ether and the catalysis of 3 mixed solution of B (C6F5) with methoxy ethylene, temperature control 0-10
DEG C reaction 1h, sample detection is 1:136(6 along inverse proportion) rectifying obtains addition product 151g, yield 86%(7) add phosphoric acid solution
Enter and boiled in 500mL reaction flask, then dropwise reaction liquid, distilled when being added dropwise, obtain trans- 2- hexenoic aldehyde hydrolyzate 170g(8) first
Atmospheric distillation alkenyl methyl ether is in low-boiling-point substance out, and in decompressing and continuous rectifying, when pressure is -0.09MPa, tower top temperature is 78-80 DEG C
When collect 2- hexenoic aldehyde sterling 79.4g, cis-isomer is not detected in yield 81%, GC:99.7%.
The above is only the preferable specific embodiments of the present invention, but scope of protection of the present invention is not limited thereto, any
Those familiar with the art within the technical scope of the present disclosure, according to the technique and scheme of the present invention and its invents
Design is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (9)
1. a kind of synthetic method of 2- hexenoic aldehyde, which comprises the steps of: the first step, n-butanal and alkylol exist
Under Catalyzed by p-Toluenesulfonic Acid, condensation reaction occurs and obtains acetal；Second step, acetal and vinyl alkyl ethers are in boron trifluoride and B
(C6F5) under the catalysis of 3 mixed solutions, addition reaction occurs and obtains addition product；Third step addition product rises under dilute acid solution catalysis
Warm water solution obtains 2- hexenoic aldehyde.
2. a kind of synthetic method of 2- hexenoic aldehyde according to claim 1, it is characterised in that: the first step alkylol
In, alkyl is selected from methyl, ethyl, propyl, normal-butyl or isobutyl group.
3. a kind of synthetic method of 2- hexenoic aldehyde according to claim 1, it is characterised in that: the first step reaction, just
Butyraldehyde and alkylol molar ratio are 1:2-3；Dry using 5%-20% equivalent anhydrous calcium chloride, reaction temperature is at 20 DEG C to 60 DEG C.
4. a kind of synthetic method of 2- hexenoic aldehyde according to claim 1, it is characterised in that: the second step vinyl alkane
In base ether, alkyl is selected from methyl, ethyl, propyl, normal-butyl or isobutyl group.
5. a kind of synthetic method of 2- hexenoic aldehyde according to claim 1, it is characterised in that: in second step addition reaction,
Vinyl alkyl ethers and acetal object molar ratio are 1:1-4；Reaction system carries out under the conditions of dried over anhydrous, and reaction temperature is -10
DEG C to 60 DEG C.
6. a kind of synthetic method of 2- hexenoic aldehyde according to claim 1, it is characterised in that: in second step addition reaction,
Boron trifluoride and B (C6F5) 3 mass ratio are 2-5:1；Boron trifluoride catalyst is selected from boron trifluoride ether, boron trifluoride tetrahydro furan
It mutters or boron trifluoride acetonitrile.
7. a kind of synthetic method of 2- hexenoic aldehyde according to claim 1, it is characterised in that: in third step hydrolysis,
Dilute suplhuric acid is selected from phosphoric acid, sulfuric acid, hydrochloric acid or oxalic acid, concentration range 1-50%.
8. a kind of synthetic method of 2- hexenoic aldehyde according to claim 1, it is characterised in that: the air-distillation of 2- hexenoic aldehyde elder generation
Except low-boiling point materials such as alkylol, water out obtain high-purity 2- hexenoic aldehyde using continuous rectification under vacuum, obtained after dilution 2- oneself
Olefine aldehydr low concentration solution becomes daily essence, fragrance.
9. a kind of synthetic method of 2- hexenoic aldehyde according to claim 1, it is characterised in that: 2- hexenoic aldehyde qualification index
Are as follows: purity > 99%, trans/cis > 100-150:1, weak yellow liquid are in strong fresh fruit, greenery faint scent.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113461498A (en) * | 2021-07-19 | 2021-10-01 | 老河口光联科技有限公司 | Environment-friendly preparation method of acetal |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2628257A (en) * | 1950-11-09 | 1953-02-10 | Union Carbide & Carbon Corp | Production of unsaturated aldehydes |
| CN106380383A (en) * | 2016-08-27 | 2017-02-08 | 湖北荆洪生物科技股份有限公司 | Synthesis method of 2-hexenal |
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2018
- 2018-09-08 CN CN201811046994.5A patent/CN109053404A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2628257A (en) * | 1950-11-09 | 1953-02-10 | Union Carbide & Carbon Corp | Production of unsaturated aldehydes |
| CN106380383A (en) * | 2016-08-27 | 2017-02-08 | 湖北荆洪生物科技股份有限公司 | Synthesis method of 2-hexenal |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113461498A (en) * | 2021-07-19 | 2021-10-01 | 老河口光联科技有限公司 | Environment-friendly preparation method of acetal |
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