CN104649861A - Method for improving yield of allyl alcohol maleinoid form product - Google Patents
Method for improving yield of allyl alcohol maleinoid form product Download PDFInfo
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- CN104649861A CN104649861A CN201410815850.7A CN201410815850A CN104649861A CN 104649861 A CN104649861 A CN 104649861A CN 201410815850 A CN201410815850 A CN 201410815850A CN 104649861 A CN104649861 A CN 104649861A
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- 238000000034 method Methods 0.000 title claims abstract description 28
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000012071 phase Substances 0.000 claims abstract description 26
- 238000007075 allylic rearrangement reaction Methods 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 125000003118 aryl group Chemical group 0.000 claims abstract description 8
- 239000003377 acid catalyst Substances 0.000 claims abstract description 4
- 125000002877 alkyl aryl group Chemical group 0.000 claims abstract description 4
- 239000008346 aqueous phase Substances 0.000 claims abstract description 4
- 150000002170 ethers Chemical class 0.000 claims abstract description 4
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 4
- 150000002576 ketones Chemical class 0.000 claims abstract description 4
- 235000021466 carotenoid Nutrition 0.000 claims description 11
- 150000001747 carotenoids Chemical class 0.000 claims description 11
- 229920006395 saturated elastomer Polymers 0.000 claims description 11
- 235000019155 vitamin A Nutrition 0.000 claims description 11
- 239000011719 vitamin A Substances 0.000 claims description 11
- FPIPGXGPPPQFEQ-UHFFFAOYSA-N 13-cis retinol Natural products OCC=C(C)C=CC=C(C)C=CC1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-UHFFFAOYSA-N 0.000 claims description 8
- FPIPGXGPPPQFEQ-BOOMUCAASA-N Vitamin A Natural products OC/C=C(/C)\C=C\C=C(\C)/C=C/C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-BOOMUCAASA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- FPIPGXGPPPQFEQ-OVSJKPMPSA-N all-trans-retinol Chemical compound OC\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-OVSJKPMPSA-N 0.000 claims description 8
- 229940045997 vitamin a Drugs 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 150000003505 terpenes Chemical class 0.000 claims description 3
- 150000003722 vitamin derivatives Chemical class 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- 239000007792 gaseous phase Substances 0.000 abstract 1
- 235000021003 saturated fats Nutrition 0.000 abstract 1
- 239000000463 material Substances 0.000 description 54
- 239000000047 product Substances 0.000 description 29
- 238000010438 heat treatment Methods 0.000 description 16
- 239000000126 substance Substances 0.000 description 14
- BFAKENXZKHGIGE-UHFFFAOYSA-N bis(2,3,5,6-tetrafluoro-4-iodophenyl)diazene Chemical compound FC1=C(C(=C(C(=C1F)I)F)F)N=NC1=C(C(=C(C(=C1F)F)I)F)F BFAKENXZKHGIGE-UHFFFAOYSA-N 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 10
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 9
- 238000009413 insulation Methods 0.000 description 8
- 239000003550 marker Substances 0.000 description 8
- 238000006386 neutralization reaction Methods 0.000 description 8
- 238000011084 recovery Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 7
- 238000005755 formation reaction Methods 0.000 description 7
- 238000000926 separation method Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 235000011149 sulphuric acid Nutrition 0.000 description 4
- 239000001117 sulphuric acid Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 235000013350 formula milk Nutrition 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000017105 transposition Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/56—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by isomerisation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for improving the yield of an allyl alcohol maleinoid form product, the formula (1) are isomerized into a mixture of the formula (2) and the formula (3), the formula (1), the formula (2) and the formula (3) are selected from alkyl, aryl and alkaryl, R2 is selected from H, alkyl and aryl, in a solvent and with the existence of a heterogeeous acid catalyst, the formula (1) is subjected to reaction, the solvent is water or a multiphase solvent system which comprises an aqueous phase and an organic solvent phase, and the organic solvent phase comprises an organic solvent which is selected from ethers, ketone or saturated fat hydrocarbon or a mixture of the same and is unmixed with water, the formula (1) is subjected to allylic rearrangement reaction, and a certain proportion of formula (3) is added into the allylic rearrangement reaction system of the formula (1); the gaseous phase interior label content of the formula (3) is greater than 95%. According to the invention, the forming of the product maleinoid form (2) is facilitated, the proportion of the maleinoid form (2) to the transform (3) is enhanced, and the yield of the maleinoid form (2) can be improved by about 13% compared with an original system.
Description
Technical field
The present invention relates to a kind of method improving vinyl carbinol cis-product productive rate, is a kind of method that ratio by changing cis-product and trans product improves cis-product productive rate.
Background technology
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、
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As implied above, formula 1 is the important starting material of vitamin A and carotenoid, formula 1 allylic rearrangement product has cis 2 and trans 3 two kinds of cis-trans-isomers, report according to Patents, cis 2 can be used for the synthesis material of vitamin A and carotenoid, and the raw material that trans 3 are not suitable as synthesise vitamins A and carotenoid.According to the 2-in-1 one-tenth Patents report of cis, the cis 2 of formation and the ratio of trans 3 do not participate in the synthesis of vitamin A or carotenoid at trans 3 of 85 ︰ about 15,15%, cause the waste of raw materials for production and the raising of production cost.
About changing the research contents of cis 2 and trans 3 ratios, Patents reports two kinds of directions, one is in building-up reactions, and change reaction conditions and change along inverse ratio, changeable reaction conditions comprises temperature, acidity, sour kind and other external additive etc.; Two is directly set up cis 2 and trans 3 reaction conditionss changed, and due to trans 3, comparatively cis 2 is stable, and need the external world to provide energy to open the chemical bond of trans 3, then active intermediate starts to form cis-trans equilibrium system, obtains a certain proportion of cis 2.First method, Patents refer to and adopts interpolation chemical catalyst to form certain specific complex intermediate, changes cis-trans and forms equilibrium relationship, to a certain degree can change the ratio of cis 2 and trans 3; But this technology exists more problem, as higher in catalyzer cost, usage quantity is larger; Catalyzer has certain destructiveness to material, affects the yield of product; Catalyst residue affects follow-up separating-purifying in material, increases the cost of separating-purifying.Second method, RELATED APPLICATIONS mentions the photochemical catalysis trans 3 adopting specific wavelength, certain energy is provided to trans 3, this energy size and the activation energy opened needed for trans 3 chemical bonds have certain relation, open trans 3 formation of chemical bonds and have certain active intermediate, this active intermediate can form a certain proportion of cis 2 by certain equilibrium relationship; Also there are problems in this technology, the equipment investment cost as produced special wavelength light is comparatively large, special wavelength light acts on the mode of material, the design etc. of structure of reactor simultaneously.
Patent report is by the reaction mechanism of reactant formula 1 formation reaction product cis 2 and trans 3 and processing parameter, concrete reaction mechanism is that reactant formula 1 is reacted through allylic rearrangement in acid condition, there occurs a group (hydroxyl) in allyl group system move and cause double bond to be subjected to displacement, obtain reaction product cis 2 and trans 3 two kinds of cis-trans-isomers, take R1 as methyl, R2 is the material of-H is example, concrete reaction process is as follows, reactant (3-methyl-4-amylene-1-alkynes-3-alcohol) can obtain cis and six trans carbon alcohol (Z-3-methyl-2-amylene-4-alkynes-1-alcohol and E-3-methyl-2-amylene-4-alkynes-1-alcohol) through the transposition of perhydroxyl radical allylic under acid catalysis.
。
Summary of the invention
For the above-mentioned technical problem of prior art, the object of this invention is to provide a kind of method improving vinyl carbinol cis-product productive rate, a certain proportion of trans product is joined in the reaction system of synthesizing cis product, have and do not need to introduce foreign matter, do not need to change the advantage that existing separation system can improve cis-product productive rate, the method is without investing and remarkable in economical benefits.
For achieving the above object, the present invention is achieved by the following technical solutions:
A kind of method improving vinyl carbinol cis-product productive rate, penta-1-alkene-3-alcohol the isomery according to formula (1) turns to steric isomer Z-penta-2-alkene-1-alcohol (2) of formula (2) and (3) and the mixture of E-penta-2-alkene-1-alcohol (3)
In various,
R
1be selected from alkyl, aryl and alkaryl,
R
2be selected from H, alkyl and aryl,
Described method comprises: in a solvent and under the existence of heterogeneous acid catalyst, formula (1) is reacted, wherein, described solvent is water or multiphase solvent system, described multiphase solvent system comprises aqueous phase and organic solvent phase, and described organic solvent comprises the organic solvent immiscible with water being selected from ethers, ketone or saturated fatty hydro carbons and composition thereof mutually, described formula (1) carries out allylic rearrangement reaction, carries out adding a certain proportion of formula (3) in allylic rearrangement system in reactant formula (1); In the gas phase of described formula (3), mark content is more than 95%.
The interpolation molar weight of described formula (3) is the 10%-30% of formula (1) molar weight.
The condition of the allylic rearrangement of described formula (1) is heterogeneous liquid liquid system or acid ion resin.
The condition of the allylic rearrangement of described formula (1) is carried out in multi-solvents.
Described formula (2) is for the manufacture of isoprenoid.
The intermediate that described formula (2) is vitamin A and derivative or carotenoid.
The present invention adds a certain proportion of reaction product formula (3) in reaction system, formula (3) changes the balanced proportions relation of cis 2 and trans 3 in allylic rearrangement, to a certain degree suppress the formation of product trans (3), be conducive to the formation improving product cis (2), improve the ratio of cis (2) and trans (3), the comparable substance system of cis (2) yield improves about 13%.After allylic rearrangement, the product cis (2) formed and product trans (3), need rectifying separation to operate, obtain the product cis (2) of high-content and the product trans (3) of high-content, product cis (2) is for the synthesis of vitamin A and the important intermediate of carotenoid.And product trans (3) can realize utilizing, by suppression trans (3) reaction ratio, the ratio of cis (2) can be improved, the Financial cost reducing synthesise vitamins A and carotenoid is of great importance.In the material gas phase of trans (3) that add in the present invention, mark content wants high by 95%, and the too low impact on allylic rearrangement reaction of content is not obvious; The molar weight that simultaneously trans (3) add should not be too high, higher than formula (1) molar weight 30% time, easily cause the separation difficulty of follow-up cis (2) and trans (3), increase the cost of separation.
Embodiment
Below in conjunction with specific embodiment, the present invention is further illustrated, but protection scope of the present invention is not limited to this.
The present invention improves the method for vinyl carbinol cis-product productive rate, penta-1-alkene-3-alcohol the isomery according to formula (1) turns to steric isomer Z-penta-2-alkene-1-alcohol (2) of formula (2) and (3) and the mixture of E-penta-2-alkene-1-alcohol (3)
In various, R1 is selected from alkyl, aryl and alkaryl, and R2 is selected from H, alkyl and aryl,
The method comprises: in a solvent and under the existence of heterogeneous acid catalyst, formula (1) is reacted, wherein, described solvent is water or multiphase solvent system, described multiphase solvent system comprises aqueous phase and organic solvent phase, and described organic solvent comprises the organic solvent immiscible with water being selected from ethers, ketone or saturated fatty hydro carbons and composition thereof mutually, described formula (1) carries out allylic rearrangement reaction, carries out adding a certain proportion of formula (3) in allylic rearrangement system in reactant formula (1); In the gas phase of described formula (3), mark content is more than 95%.The interpolation molar weight of formula (3) is the 10%-30% of formula (1) molar weight.The condition of the allylic rearrangement of formula (1) is heterogeneous liquid liquid system or acid ion resin.The condition of the allylic rearrangement of formula (1) is carried out in multi-solvents.
Formula of the present invention (2) for the manufacture of isoprenoid, such as formula the intermediate that (2) are vitamin A and derivative or carotenoid.
embodiment 1
In 1000 ml there-necked flasks, add R
1for methyl, R
2for formula (1) the material 100.0g of-H, isopropyl ether 500.0g, add the material formula (3) of mark content 96% in 10.0g gas phase, dilute sulphuric acid is appropriate, pH value is between 2.0-3.0, and rear heating in water bath to 34 ~ 36 DEG C, stir insulation 60min, obtain organic oil reservoir solution 590.2g with the layering of 1000ml separating funnel, gas phase marker method surveys cis formula (2) component concentration 12.7%.
The saturated NaHCO of organic oil reservoir 2 × 150.0ml that upper step is obtained
3solution neutralization twice, with water-ring pump pulling vacuum and heating recovery isopropyl ether, obtains concentrated solution.Concentrated solution oil pump will be obtained and carry out rectification under vacuum operation, namely cut is cis formula (2), quality is 75.0g, mark 98% in cis formula (2) gas phase, cis formula (2) is to the yield 73.5% of material formula (1), still raffinate is the mixture quality of the polymkeric substance such as trans formula (3) is 34.0g, to the pin material rate 30.9% of material formula (1) and material formula (3) sum.
embodiment 2
In 1000ml there-necked flask, add R
1for methyl, R
2for formula (1) the material 100.0g of-H, isopropyl ether 500.0g, add the material formula (3) of 20.0 g content 96%, dilute sulphuric acid is appropriate, pH value is between 2.0-3.0, and rear heating in water bath to 34 ~ 36 DEG C, stir insulation 60 min, obtain organic oil reservoir solution 610.3g with the layering of 1000ml separating funnel, gas phase marker method surveys cis formula (2) component concentration 13.5%.
The saturated NaHCO of organic oil reservoir 2 × 150.0ml that upper step is obtained
3solution neutralization twice, with water-ring pump pulling vacuum and heating recovery isopropyl ether, obtains concentrated solution.Concentrated solution oil pump will be obtained and carry out rectification under vacuum operation, namely cut is cis formula (2), quality is 81.1g, mark 98.5% in cis formula (2) gas phase, cis formula (2) is to the yield 79.8% of material formula (1), still raffinate is the mixture quality of the polymkeric substance such as trans formula (3) is 36.4g, to the pin material rate 30.3% of material formula (1) and material formula (3) sum.
embodiment 3
In 1000ml there-necked flask, add R
1for methyl, R
2for formula (1) the material 100.0g of-H, isopropyl ether 500.0g, add the material formula (3) of 10.0g content 96%, adding acid ion resin quality is 20.0g, rear heating in water bath to 44 ~ 46 DEG C, stir insulation 40min, filter obtain organic oil reservoir solution 603.3g with Bush's funnel.Gas phase marker method surveys cis formula (2) component concentration 13.3%.
The saturated NaHCO of organic oil reservoir 2 × 150.0ml that upper step is obtained
3solution neutralization twice, with water-ring pump pulling vacuum and heating recovery isopropyl ether, obtains concentrated solution.Concentrated solution oil pump will be obtained and carry out rectification under vacuum operation, namely cut is cis formula (2), quality is 82.1g, mark 97% in cis formula (2) gas phase, cis formula (2) is to the yield 79.6% of material formula (1), still raffinate is the mixture quality of the polymkeric substance such as trans formula (3) is 26.3g, to the pin material rate 23.9% of material formula (1) and material formula (3) sum.
embodiment 4
In 1000ml there-necked flask, add R
1for methyl, R
2for formula (1) the material 100.0g of-H, isopropyl ether 500.0g, add the material formula (3) of 20.0g content 96%, adding acid ion resin quality is 20.0g, rear heating in water bath to 44 ~ 46 DEG C, stir insulation 40min, filter obtain organic oil reservoir solution 614.8g with Bush's funnel.Gas phase marker method surveys cis formula (2) component concentration 13.9%.
The saturated NaHCO of organic oil reservoir 2 × 150.0ml that upper step is obtained
3solution neutralization twice, with water-ring pump pulling vacuum and heating recovery isopropyl ether, obtains concentrated solution.Concentrated solution oil pump will be obtained and carry out rectification under vacuum operation, namely cut is cis formula (2), quality is 84.7g, mark 97.4% in cis formula (2) gas phase, cis formula (2) is to the yield 82.5% of material formula (1), still raffinate is the mixture quality of the polymkeric substance such as trans formula (3) is 34.4g, to the pin material rate 28.7% of material formula (1) and material formula (3) sum.
embodiment 5
In 1000ml there-necked flask, add R
1for methyl, R
2for formula (1) the material 100.0g of-H, hexanaphthene 500.0g, add the material formula (3) of 10.0 g content 96%, dilute sulphuric acid is appropriate, pH value is between 2.0-3.0, rear heating in water bath to 54 ~ 56 DEG C, stir insulation 40min, obtain organic oil reservoir solution 602.4g with 1000ml separating funnel separatory.Gas phase marker method surveys cis formula (2) component concentration 12.9%.
The saturated NaHCO of organic oil reservoir 2 × 150.0ml that upper step is obtained
3solution neutralization twice, with water-ring pump pulling vacuum and heating recovery hexanaphthene, obtains concentrated solution.Concentrated solution oil pump will be obtained and carry out rectification under vacuum operation, namely cut is cis formula (2), quality is 77.2g, mark 97.7% in cis formula (2) gas phase, cis formula (2) is to the yield 75.4% of material formula (1), still raffinate is the mixture quality of the polymkeric substance such as trans formula (3) is 31.8g, to the pin material rate 28.9% of material formula (1) and material formula (3) sum.
embodiment 6
In 1000ml there-necked flask, add R
1for methyl, R
2for formula (1) the material 100.0g of-H, hexanaphthene 500.0g, add the material formula (3) of 20.0g content 96%, dilute sulphuric acid is appropriate, pH value between 2.0-3.0, rear heating in water bath to 55 ~ 65 DEG C, stir insulation 40min, obtain organic oil reservoir solution 615.1g with 1000ml separating funnel separatory.Gas phase marker method surveys cis formula (2) component concentration 14.2%.
The saturated NaHCO of organic oil reservoir 2 × 150.0ml that upper step is obtained
3solution neutralization twice, with water-ring pump pulling vacuum and heating recovery hexanaphthene, obtains concentrated solution.Concentrated solution oil pump will be obtained and carry out underpressure distillation operation, namely cut is cis formula (2), quality is 85.2g, mark 97.7% in cis formula (2) gas phase, cis formula (2) is to the yield 83.2% of material formula (1), still raffinate is the mixture quality of the polymkeric substance such as trans formula (3) is 33.8g, to the pin material rate 28.2% of material formula (1) and material formula (3) sum.
embodiment 7
In 1000ml there-necked flask, add R
1for methyl, R
2for the formula 1 material 100.0g of-H, hexanaphthene 500.0g, add the material formula (3) of 10.0g content 96%, adding acid ion resin quality is 20.0g, rear heating in water bath to 54 ~ 56 DEG C, stir insulation 60min, filter obtain organic oil reservoir solution 605.2g with Bush's funnel.Gas phase marker method surveys cis formula (2) component concentration 13.7%.
The saturated NaHCO of organic oil reservoir 2 × 150.0ml that upper step is obtained
3solution neutralization twice, with water-ring pump pulling vacuum and heating recovery hexanaphthene, obtains concentrated solution.Concentrated solution oil pump will be obtained and carry out rectification under vacuum operation, namely cut is cis formula (2), quality is 82.7g, mark 97.8% in cis formula (2) gas phase, cis formula (2) is to the yield 80.9% of material formula (1), still raffinate is the mixture quality of the polymkeric substance such as trans formula (3) is 25.9g, to the pin material rate 23.5% of material formula (1) and material formula (3) sum.
embodiment 8
In 1000ml there-necked flask, add R
1for methyl, R
2for the formula 1 material 100.00g of-H, hexanaphthene 500.00g, add the material formula (3) of 20g content 96%, adding acid ion resin quality is 20g, rear heating in water bath to 54 ~ 56 DEG C, stir insulation 60min, filter obtain organic oil reservoir solution 616.7g with Bush's funnel.Gas phase marker method surveys cis formula (2) component concentration 14.2%.
The saturated NaHCO of organic oil reservoir 2 × 150ml that upper step is obtained
3solution neutralization twice, with water-ring pump pulling vacuum and heating recovery isopropyl ether, obtains concentrated solution.Concentrated solution oil pump will be obtained and carry out rectification under vacuum operation, namely cut is cis formula (2), quality is 85.7g, mark 97.1% in cis formula (2) gas phase, cis formula (2) is to the yield 83.2% of material formula (1), still raffinate is the mixture quality of the polymkeric substance such as trans formula (3) is 33.2g, to the pin material rate 27.7% of material formula (1) and material formula (3) sum.
The present invention adds a certain proportion of reaction product formula (3) in reaction system, formula (3) changes the balanced proportions relation of cis 2 and trans 3 in allylic rearrangement, to a certain degree suppress the formation of product trans (3), be conducive to the formation improving product cis (2), improve the ratio of cis (2) and trans (3), the comparable substance system of cis (2) yield improves about 13%.After allylic rearrangement, the product cis (2) formed and product trans (3), need rectifying separation to operate, obtain the product cis (2) of high-content and the product trans (3) of high-content, product cis (2) is for the synthesis of vitamin A and the important intermediate of carotenoid.And product trans (3) can realize utilizing, by suppression trans (3) reaction ratio, the ratio of cis (2) can be improved, the Financial cost reducing synthesise vitamins A and carotenoid is of great importance.
Above-described embodiment only illustrates inventive concept of the present invention for explaining, but not the restriction to rights protection of the present invention, all changes utilizing this design the present invention to be carried out to unsubstantiality, all should fall into protection scope of the present invention.
Claims (6)
1. one kind is improved the method for vinyl carbinol cis-product productive rate, penta-1-alkene-3-alcohol the isomery according to formula (1) turns to steric isomer Z-penta-2-alkene-1-alcohol (2) of formula (2) and (3) and the mixture of E-penta-2-alkene-1-alcohol (3)
In various,
R1 is selected from alkyl, aryl and alkaryl,
R2 is selected from H, alkyl and aryl,
Described method comprises: in a solvent and under the existence of heterogeneous acid catalyst, formula (1) is reacted, wherein, described solvent is water or multiphase solvent system, described multiphase solvent system comprises aqueous phase and organic solvent phase, and described organic solvent comprises the organic solvent immiscible with water being selected from ethers, ketone or saturated fatty hydro carbons and composition thereof mutually, it is characterized in that: described formula (1) carries out allylic rearrangement reaction, carry out in allylic rearrangement system, adding a certain proportion of formula (3) in reactant formula (1); In the gas phase of described formula (3), mark content is more than 95%.
2. improve the method for vinyl carbinol cis-product productive rate as claimed in claim 1, it is characterized in that: the molar weight of described adding type (3) is the 10%-30% of formula (1) molar weight.
3. improve the method for vinyl carbinol cis-product productive rate as claimed in claim 1, it is characterized in that: the condition of the allylic rearrangement of described formula (1) is heterogeneous liquid liquid system or acid ion resin.
4. improve the method for vinyl carbinol cis-product productive rate as claimed in claim 1, it is characterized in that: the condition of the allylic rearrangement of described formula (1) is carried out in multi-solvents.
5. improve the method for vinyl carbinol cis-product productive rate as claimed in claim 1, it is characterized in that: described formula (2) is for the manufacture of isoprenoid.
6. improve the method for vinyl carbinol cis-product productive rate as claimed in claim 1, it is characterized in that: the intermediate that described formula (2) is vitamin A and derivative or carotenoid.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410815850.7A CN104649861B (en) | 2014-12-25 | 2014-12-25 | A kind of method improving 1-propenol-3 cis-product productivity |
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| CN201410815850.7A CN104649861B (en) | 2014-12-25 | 2014-12-25 | A kind of method improving 1-propenol-3 cis-product productivity |
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| CN104649861A true CN104649861A (en) | 2015-05-27 |
| CN104649861B CN104649861B (en) | 2016-06-29 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113943210A (en) * | 2021-11-02 | 2022-01-18 | 厦门金达威维生素有限公司 | Method for transposition of non-transposed six-carbon alcohol |
Citations (5)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113943210A (en) * | 2021-11-02 | 2022-01-18 | 厦门金达威维生素有限公司 | Method for transposition of non-transposed six-carbon alcohol |
| CN113943210B (en) * | 2021-11-02 | 2024-05-03 | 厦门金达威维生素有限公司 | Non-translocated six-carbon alcohol translocation method |
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|---|---|
| CN104649861B (en) | 2016-06-29 |
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Application publication date: 20150527 Assignee: ZHEJIANG NHU PHARMACEUTICAL Co.,Ltd. Assignor: SHANGYU NHU BIO-CHEM Co.,Ltd. Contract record no.: X2023980043734 Denomination of invention: A method for improving the yield of cis product of allyl alcohol Granted publication date: 20160629 License type: Common License Record date: 20231019 |