CN109942423A - A kind of method synthesizing 9,10- dihydroxy, 18 carbon methyl stearate - Google Patents
A kind of method synthesizing 9,10- dihydroxy, 18 carbon methyl stearate Download PDFInfo
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- CN109942423A CN109942423A CN201910301621.6A CN201910301621A CN109942423A CN 109942423 A CN109942423 A CN 109942423A CN 201910301621 A CN201910301621 A CN 201910301621A CN 109942423 A CN109942423 A CN 109942423A
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Abstract
The invention discloses a kind of methods for synthesizing 9,10- dihydroxy, 18 carbon methyl stearate, using epoxy aliphatic acid methyl ester as raw material, under the action of catalyst sulfuric acid, and one-step synthesis 9,18 carbon methyl stearate of 10- dihydroxy；Specifically first epoxy aliphatic acid methyl ester is added in four-hole boiling flask, co-catalyst acetonitrile is then added, sulfuric acid is first added it in water as catalyst, is added in four-hole boiling flask by way of dropwise addition；The bis- 18 carbon methyl stearates of hydroxyl of 9,10- are obtained after reaction；After the reaction was completed, water phase is separated, then reaction product is dissolved in organic solvent, pure products are obtained after repeated recrystallize, organic solvent is reused after being evaporated under reduced pressure.No matter 9,10- dihydroxy, the 18 carbon methyl stearate of the method for the present invention synthesis has had reached higher level on yield or purity, and reaction raw materials have higher conversion ratio, realize making full use of for raw material.
Description
Technical field
The present invention relates to a kind of methods for synthesizing 9,10- dihydroxy, 18 carbon methyl stearate, belong to organic synthesis field.
Background technique
As lack of energy is got worse and people are to the pay attention to day by day of environmental problem, exploitation green is novel renewable
Resource be increasingly valued by people.9,10- dihydroxy, 18 carbon methyl stearate is among the critically important chemical industry of one kind
Body.The structure of 9,10- dihydroxy, 18 carbon methyl stearate is more special, more on molecule compared with common fatty acid methyl ester
The branch of two secondary hydroxyls is conducive to just containing there are two secondary hydroxyl and an ester group three active function groups in such molecule
It is further modified.Its derivative can be used for medicine, the synthesis of polyurethane and the synthesis of novel surfactant.Its structure
Formula is as follows:
(Benessere V, Cucciolito M E, Santis A D, the et al. such as Vincenzo Benessere
Sustainable Process for Production of Azelaic Acid Through Oxidative Cleavage
of Oleic Acid[J]. Journal of the American Oil Chemists Society, 2015, 92(11-
12) two-step method synthesis azelaic acid: 1701-1707.) is had studied, oleic acid is first oxidized to 9 under 60 wt% Hydrogen Peroxides,
18 carbon stearic acid of 10- dihydroxy, is then cracked with hypochlorite oxidation, but it does not do triangular web to epoxy addition and grinds
Study carefully.
Xinjiang physics and chemistry institute, Chinese Academy of Sciences A Yixia wood etc. (Speciality Petrochemicals, 2007, (5) 29-31) selects Hydrophobic Ionic
Liquid B MIMPF6For solvent, it is hard that 9,10- dihydroxy, 18 carbon is obtained in the case where wolframic acid does catalysts conditions with 50 wt% hydrogen peroxide
Resin acid, yield reach as high as 85%.But it does not study synthesis 18 carbon methyl stearate of 9,10- dihydroxy.
My Man Jiangai power etc. (Chinese invention patent CN 101177392A) methyl oleate and formic acid are in 30 wt% peroxides
Change and synthesize 9,10- dihydroxy, 18 carbon methyl stearate under hydrogen condition, but does not do the research of triangular web to epoxy addition.
Summary of the invention
The present invention is intended to provide a kind of method for synthesizing 9,10- dihydroxy, 18 carbon methyl stearate.
Present invention aims at synthesize a kind of change with three active function groups of band there are two secondary hydroxyl and an ester group
18 carbon methyl stearate of intermediate -9,10- dihydroxy is learned, is conducive to further be derived and be modified.
The present invention provides a kind of methods for synthesizing 9,10- dihydroxy, 18 carbon methyl stearate, with epoxyfatty acid first
Ester is raw material, under the action of catalyst sulfuric acid and co-catalyst acetonitrile, one-step synthesis 9, and 18 carbon stearic acid first of 10- dihydroxy
Ester.
The above method, comprising the following steps:
First epoxy aliphatic acid methyl ester is added in four-hole boiling flask, co-catalyst acetonitrile is then added, sulfuric acid is as catalyst elder generation
It adds it in water, under the conditions of (200r/min-1000r/min) stirring rate and 30 DEG C -60 DEG C, by way of dropwise addition
It is added in four-hole boiling flask；Then at a temperature of 50 DEG C -90 DEG C, when reacting 0.5-4h, it is stearic to obtain 9,10- dihydroxy, 18 carbon
Sour methyl esters；After the reaction was completed, water phase is separated, then reaction product is dissolved in organic solvent, is obtained after repeated recrystallize pure
Product, organic solvent are reused after being evaporated under reduced pressure.
The molecular structural formula of above-mentioned raw materials epoxy aliphatic acid methyl ester is as follows:
。
It is as follows that the present invention reacts synthetic route:
。
Acetonitrile in above-mentioned reaction is co-catalyst.
The molar ratio of epoxy aliphatic acid methyl ester and water (water needed for ring-opening reaction) in above-mentioned reaction is 1:1-1:10.
The molar ratio of epoxy aliphatic acid methyl ester and acetonitrile in above-mentioned reaction is 1:0-1:2.
The mass ratio of epoxy aliphatic acid methyl ester and sulfuric acid in above-mentioned reaction is 0.5%-2%.Sulfuric acid is first molten into water, sulfuric acid
With the mass ratio 0.83%-33% of water, the drop rate of aqueous sulfuric acid is 1mL/min.
Organic solvent used in above-mentioned reaction is one of ethyl acetate, acetone, chloroform or petroleum ether, and dosage is
5mL/g-100mL/g(is on the basis of raw material epoxy aliphatic acid methyl ester).
In the above method, the conversion ratio of raw material can reach 99.99%, 9,10- dihydroxy, the 18 carbon methyl stearate of synthesis
Yield can reach 94%, purity can reach 96%.
In the above method, after the reaction was completed, water phase is separated, then reaction product is dissolved in organic solvent, through 3-5 weight
Pure products are obtained after crystallization, organic solvent is reused after being evaporated under reduced pressure.The 3-5 product purity being recrystallized to give is from existing
Highest purity 85% be increased to 96%.Organic solvent can achieve 100% recycling after recycling by vacuum distillation.
Beneficial effects of the present invention:
1. having synthesized 18 carbon methyl stearate of new chemical intermediate -9,10- dihydroxy, there are multiple active function groups (two
Secondary hydroxyl and an ester group), be conducive to modification and the derivative reaction in later period.
2. no matter the 18 carbon methyl stearate of 9,10- dihydroxy of the method synthesis has reached on yield or purity
Higher level has been arrived, has been promoted from known existing maximum output 85% to 94%.
3. all common industrial goods being easy to get of raw material used in this product, there is very high conversion ratio in reaction
(99.99%)) making full use of for raw material, is realized.
Detailed description of the invention
Fig. 1 is the infrared spectrum after 18 carbon methyl stearate of the 9,10- dihydroxy purification that the embodiment of the present invention 1 synthesizes.
Specific embodiment
The present invention is further illustrated below by embodiment, but is not limited to following embodiment.
Embodiment 1:
By 100.00g epoxy aliphatic acid methyl ester, (average molecular weight 312, epoxide number 0.3298mol/100g, hydroxyl value are
It 0KOHmg/g) is placed in 500mL four-hole boiling flask, 13.60g acetonitrile is being added, after mixing evenly, by 2.0gH2SO4It is added to
It in 60g ionized water, then is added dropwise in four-hole boiling flask, reacts 4h at a reflux temperature.After reaction, it is washed with deionized water
Remove sulfuric acid and acetonitrile.Then remaining product is dissolved in the ethyl acetate of heat, the acetic acid second of heat is re-dissolved in after precipitation to be cooled
It in ester, is so repeated 3 times, obtains 9,10- dihydroxy, the 18 carbon methyl stearate of purity 95%, yield 90%.Product is main
Index is as follows: (1) epoxide number: 0.0016mol/100g(2) hydroxyl value: 333.03KOHmg/g.
In Fig. 1, epoxy aliphatic acid methyl ester (EMO) is in 840cm-1The disappearance of upper epoxy group vibration absorption peak, Yi Ji
3464cm-1The appearance of hydroxyl peak illustrates to have synthesized 9,10- dihydroxy, 18 carbon methyl stearate (DHOME).
Embodiment 2:
By 100.00g epoxy aliphatic acid methyl ester, (average molecular weight 312, epoxide number 0.3298mol/100g, hydroxyl value are
It 0KOHmg/g) is placed in 500mL four-hole boiling flask, 27.20g acetonitrile is being added, after mixing evenly, by 1.50gH2SO4It is added to
It in 42g ionized water, then is added dropwise in four-hole boiling flask, reacts 2h under 80 °C.After reaction, desulfuration is washed with deionized water
Acid and acetonitrile.Then remaining product is dissolved in the chloroform of heat, be re-dissolved in after precipitation to be cooled in the chloroform of heat, is so repeated
3 times, obtain 9,10- dihydroxy, the 18 carbon methyl stearate of purity 96%, yield 94%.Product main indicator is as follows: (1) ring
Oxygen value: 0.0001mol/100g(2) hydroxyl value: 347.83KOHmg/g.
Embodiment 3:
By 100.00g epoxy aliphatic acid methyl ester (average molecular weight 312, epoxide number 0.3298mol/100g, hydroxyl value 0
KOHmg/g it) is placed in 500mL four-hole boiling flask, 6.8g acetonitrile is being added, after mixing evenly, by 0.5gH2SO4Be added to 6g from
It in sub- water, then is added dropwise in four-hole boiling flask, reacts 0.5h under 50 °C.After reaction, sulfuric acid is washed with deionized water
And acetonitrile.Then remaining product is dissolved in the acetone of heat, be re-dissolved in after precipitation to be cooled in the acetone of heat, so repeatedly 3
It is secondary, obtain 9,10- dihydroxy, the 18 carbon methyl stearate of purity 94%, yield 60%.Product main indicator is as follows: (1) ring
Oxygen value: 0.0030mol/100g(2) hydroxyl value: 222.02KOHmg/g.
Embodiment 4:
By 100.00g epoxy aliphatic acid methyl ester (average molecular weight 312, epoxide number 0.3298mol/100g, hydroxyl value 0
KOHmg/g it) is placed in 500mL four-hole boiling flask, 0g acetonitrile is being added, after mixing evenly, by 1gH2SO4It is added to 18g ionized water
In, then be added dropwise in four-hole boiling flask, 1h is reacted under 60 °C.After reaction, sulfuric acid is washed with deionized water.Then will
Remaining product is dissolved in the ethyl acetate of heat, is re-dissolved in the ethyl acetate of heat after precipitation to be cooled, is so repeated 3 times, obtains
9,10- dihydroxy, the 18 carbon methyl stearate of purity 95%, yield 78%.Product main indicator is as follows: (1) epoxide number:
0.0001mol/100g(2) hydroxyl value: 288.65KOHmg/g.
Embodiment 5:
By 100.00g epoxy aliphatic acid methyl ester (average molecular weight 312, epoxide number 0.3298mol/100g, hydroxyl value 0
KOHmg/g it) is placed in 500mL four-hole boiling flask, 13.60g acetonitrile is being added, after mixing evenly, by 1.50gH2SO4It is added to
It in 30g ionized water, then is added dropwise in four-hole boiling flask, reacts 2h under 70 °C.After reaction, desulfuration is washed with deionized water
Acid and acetonitrile.Then remaining product is dissolved in the petroleum ether of heat, be re-dissolved in after precipitation to be cooled in the petroleum ether of heat, so
It is repeated 3 times, obtains 9,10- dihydroxy, the 18 carbon methyl stearate of purity 95%, yield 92%.Product main indicator is as follows:
(1) epoxide number: 0.0002mol/100g(2) hydroxyl value: 340.43KOHmg/g.
Claims (8)
1. a kind of method for synthesizing 9,10- dihydroxy, 18 carbon methyl stearate, it is characterised in that: be with epoxy aliphatic acid methyl ester
Raw material, under the action of catalyst sulfuric acid and co-catalyst acetonitrile, one-step synthesis 9,18 carbon methyl stearate of 10- dihydroxy.
2. the method for synthesis 9,10- dihydroxy, 18 carbon methyl stearate according to claim 1, it is characterised in that: former
Expect that the molecular structural formula of epoxy aliphatic acid methyl ester is as follows:
。
3. the method for synthesis 9,10- dihydroxy, 18 carbon methyl stearate according to claim 1 or 2, it is characterised in that:
The following steps are included:
First epoxy aliphatic acid methyl ester is added in four-hole boiling flask, co-catalyst acetonitrile is then added, sulfuric acid is as catalyst elder generation
It adds it in water, in stirring rate are as follows: 200r/min-1000r/min, temperature are as follows: under conditions of 30 DEG C -60 DEG C, pass through
The mode of dropwise addition is added in four-hole boiling flask；Then at a temperature of 50 DEG C -90 DEG C, when reacting 0.5-4h, 9,10- dihydroxy is obtained
18 carbon methyl stearates；After the reaction was completed, water phase is separated, then reaction product is dissolved in organic solvent, through repeatedly tying again
Pure products are obtained after crystalline substance.
4. the method for synthesis 9,10- dihydroxy, 18 carbon methyl stearate according to claim 3, it is characterised in that: ring
The molar ratio of oxygen fatty acid methyl ester and acetonitrile is 1:0-1:2.
5. the method for synthesis 9,10- dihydroxy, 18 carbon methyl stearate according to claim 3, it is characterised in that: sulphur
Sour first molten into water, the mass ratio of epoxy aliphatic acid methyl ester and sulfuric acid is 0.5%-2%, and the mass ratio of sulfuric acid and water is 0.83%-
33%, the drop rate of aqueous sulfuric acid is 1mL/min.
6. the method for synthesis 9,10- dihydroxy, 18 carbon methyl stearate according to claim 3, it is characterised in that: institute
It is one of ethyl acetate, acetone, chloroform or petroleum ether with organic solvent, dosage is 5mL/g-100mL/g epoxidised fatty
Sour methyl esters.
7. the method for synthesis 9,10- dihydroxy, 18 carbon methyl stearate according to claim 3, it is characterised in that: former
The conversion ratio of material can reach 99.99%, and the yield of 9,10- dihydroxy, the 18 carbon methyl stearate of synthesis can reach 94%, purity
96% can be reached.
8. the method for synthesis 9,10- dihydroxy, 18 carbon methyl stearate according to claim 3, it is characterised in that: anti-
After the completion of answering, water phase is separated, then reaction product is dissolved in organic solvent, obtains pure products after 3-5 recrystallization, it is organic
Solvent is reused after being evaporated under reduced pressure；3-5 times the product purity being recrystallized to give can reach 96%；Organic solvent passes through decompression
It can achieve 100% recycling after distillation recovery.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1946661A (en) * | 2004-04-20 | 2007-04-11 | 香港大学 | Supported ruthenium nanoparticle catalyst for cis -dihydroxylation and oxidative cleavage of alkenes |
| CN101397250A (en) * | 2007-09-28 | 2009-04-01 | 上海爱默金山药业有限公司 | Preparation method of aliphatic ester polyol |
| JP2012024654A (en) * | 2010-07-20 | 2012-02-09 | Nippon Kayaku Co Ltd | Method for producing polyacid-supporting catalyst |
| CN109438236A (en) * | 2018-11-19 | 2019-03-08 | 张家港市飞航科技有限公司 | A kind of vegetable oil polyol and its preparation method and application |
-
2019
- 2019-04-16 CN CN201910301621.6A patent/CN109942423A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1946661A (en) * | 2004-04-20 | 2007-04-11 | 香港大学 | Supported ruthenium nanoparticle catalyst for cis -dihydroxylation and oxidative cleavage of alkenes |
| CN101397250A (en) * | 2007-09-28 | 2009-04-01 | 上海爱默金山药业有限公司 | Preparation method of aliphatic ester polyol |
| JP2012024654A (en) * | 2010-07-20 | 2012-02-09 | Nippon Kayaku Co Ltd | Method for producing polyacid-supporting catalyst |
| CN109438236A (en) * | 2018-11-19 | 2019-03-08 | 张家港市飞航科技有限公司 | A kind of vegetable oil polyol and its preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| BEHR, ARNO ET AL.: "Efficient ruthenium-catalysed oxidative cleavage of methyl oleate with hydrogen peroxide as oxidant", 《RSC ADVANCES》 * |
| SUN, YONGQIANG ET AL.: "Synthesis and properties of dihydroxyoleic acid methyl ester ethoxylates", 《JOURNAL OF DISPERSION SCIENCE AND TECHNOLOGY》 * |
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Application publication date: 20190628 |