CN104774152B - A kind of synthetic method of the fluorine methyl propionates of R 2 - Google Patents
A kind of synthetic method of the fluorine methyl propionates of R 2 Download PDFInfo
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- CN104774152B CN104774152B CN201510194887.7A CN201510194887A CN104774152B CN 104774152 B CN104774152 B CN 104774152B CN 201510194887 A CN201510194887 A CN 201510194887A CN 104774152 B CN104774152 B CN 104774152B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/307—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of halogen; by substitution of halogen atoms by other halogen atoms
Abstract
The invention discloses a kind of synthetic method of the fluorine methyl propionates of R 2.Methods described includes step：(1) in the presence of organic base, make the perfluorinated reagent fluorination of S methyl lactates, obtain the fluorine methyl propionate crude products of R 2, rectifying crude product obtains the fluorine methyl propionates of R 2 and kettle is residual；(2) by kettle it is residual mixed with the solution containing inorganic base, liquid separation obtains aqueous phase and organic phase, and from organic phase reclaim organic base；(3) (1) step is repeated with the organic base of recovery, obtains the fluorine methyl propionates of R 2.
Description
Technical field
The present invention relates to the method for producing high optical activity R-2- fluorine methyl propionates, and in particular to one kind reduces environment
Pollution, yield and ee values are all higher, and are applied to industrial synthetic route.
Background technology
At present, the synthesis of R-2- fluorine methyl propionate mainly has three kinds of methods：
First, using S- methyl lactates as raw material, thionyl chloride processing is first passed through, then is handled through perfluoro-compound, obtains product
Second, using S- methyl lactates as raw material, methane sulfonyl chloride processing is first passed through, then is handled through perfluoro-compound, obtains product
(DE-A4131242；EP 1 671 939)；
Third, using S- methyl lactates as raw material, handled through sulfuryl fluoride, then product (WO2008/ is obtained after refined
090755)；
By the available R-2- fluorine methyl propionate of three of the above synthetic method, but due to current post-processing technology
Limitation, preparing R-2- fluorine methyl propionate using prior art can produce largely that the waste water containing fluorine ion, discharge beyond standards contain
The waste water of fluorine ion, environment can be caused largely to pollute, drink the exceeded water of fluorinated volume, can caused in the different degrees of fluorine of human body
Poison.For high-concentration fluorine-contained industrial wastewater, typically handled using calcium salt precipitation method, i.e., the feeding lime into waste water, make fluorine ion
Precipitate and remove with calcium ion generation CaF2.Although this method is simple, processing is convenient, expense is low, water outlet after treatment is deposited very
The shortcomings of difficult up to standard, body refuse sedimentation is slowly and dehydration is difficult.Therefore, how from source reduce fluorine ion waste water emission problem into
The key issue of synthesis R-2- fluorine methyl propionates.
And at present in main flow synthetic technology, how do not mentioned in above synthetic method especially in synthesis R-2- fluorine propionic acid
When methyl esters, the processing method to distilling out product and the waste water after recovery organic base.
In summary, this area lacks a kind of preparation method for the R-2- fluorine methyl propionates how to reduce environmental pollution；Cause
This, there is an urgent need to develop preparation side that is a kind of reducing environmental pollution and being adapted to industrialized R-2- fluorine methyl propionate for this area
Method.
The content of the invention
Present invention aims to obtain a kind of ee values high in high yield, and environmental pollution is small, is adapted to industrialized R-2- fluorine third
The preparation method of sour methyl esters.
The invention provides a kind of synthetic method of R-2- fluorine methyl propionate, methods described includes step：
(1) in the presence of organic base, make the perfluorinated reagent fluorination of S- methyl lactates, it is thick to obtain R-2- fluorine methyl propionates
Product, rectifying crude product obtains R-2- fluorine methyl propionate and kettle is residual；
(2) by kettle it is residual mixed with the solution containing inorganic base, liquid separation obtains aqueous phase and organic phase, and from organic phase recovery have
Machine alkali；
(3) (1) step is repeated with the organic base of recovery, obtains R-2- fluorine methyl propionates.
In another preference, the fluorination reagent is selected from the mixing of sulfuryl fluoride or hydrogen fluoride and sulfuryl fluoride.
In another preference, the organic base is selected from DMA, positive tri-n-butylamine or its combination.
In another preference, the inorganic base is selected from sodium hydroxide, potassium hydroxide, calcium hydroxide or its combination.
In another preference, the mol ratio of the organic base and S- methyl lactates is 0.5-3:1.
In another preference, the mol ratio of the sulfuryl fluoride and S- methyl lactates is 0.3-1.1:1；
In another preference, the mol ratio of the hydrogen fluoride and S- methyl lactates is 0-5:1；More preferably, the fluorination
The mol ratio of hydrogen and S- methyl lactates is 1.5-5:1；Most preferably, it is 2.0-4:1.
In another preference, in the presence of positive tri-n-butylamine, the perfluorinated reagent fluorine of S- methyl lactates is made at subzero 10-0 DEG C
Change.
In another preference, in the presence of DMA, the perfluorinated examination of S- methyl lactates is made at 60-150 DEG C
Agent is fluorinated.
In another preference, organic phase described in step (2) reclaims organic base through short-path distillation.
In another preference, the aqueous phase obtained in step (2) is mixed with inorganic base, filtered, remove fluoride.
Accordingly, the invention provides the preparation of a kind of reducing environmental pollution and suitable industrialized R-2- fluorine methyl propionate
Method.
Embodiment
The purpose of the present invention is to propose to a kind of industry manufacture with optically active important agricultural chemicals and medicine intermediate
Method, and emphasis is improved organic base species and dosage, feed way, is desirably to obtain higher yield and ee values, drop
Low cost.
In the present invention, term " containing " or " comprising " represent that various composition can be applied to the mixture or group of the present invention together
In compound.Therefore, term " mainly by ... form " and " consist of " are included in term " containing " or " comprising ".
The present invention relates to a kind of synthetic method of R-2- fluorine methyl propionate.This method is in organic base by S- methyl lactates
In the presence of, selection is passed through or is not passed through hydrogen fluoride gas, is fluorinated through sulfuryl fluoride, and then short steaming, rectifying obtains R-2- fluorine propionic acid first
Ester, the residual recyclable organic base of kettle, and it is recycling without reducing reactivity.This method high income, ee values are high, only produce seldom
" three wastes ", and raw material is cheap and easy to get.
Compound R -2- fluorine the methyl propionate of the present invention is using S- methyl lactates as raw material, thus it is speculated that is obtained by following mechanism：
A preferred embodiment of the present invention is,
Bottoms add inorganic base, reclaim DMA, and recycling without reducing reactivity.
Specifically, the synthetic method of R-2- fluorine methyl propionate provided by the invention includes step：
The first step, obtain R-2- fluorine methyl propionate crude products and its refine；
Second step, the recovery of the organic base used in the first step；
3rd step, the processing of waste water caused by organic base is reclaimed in second step；With
4th step, the organic base reclaimed in second step are applied mechanically.
In the above-mentioned first step, in the presence of organic base, making the perfluorinated reagent fluorination of S- methyl lactates, reaction terminates,
Decompression steams R-2- fluorine methyl propionate crude products, and rectifying crude product obtains R-2- fluorine methyl propionate and kettle is residual；Yield more than 90%, is obtained
R-2- fluorine methyl propionates optical purity more than 99.5%.
In one embodiment of the invention, S- methyl lactates and tri-n-butylamine are mixed, is cooled to subzero 10 DEG C,
Fluorization agent is passed through in the range of subzero 10 DEG C to 0 DEG C, it is complete to the reaction of S- methyl lactates.
In another embodiment of the invention, the addition S- methyl lactates in DMA, 60-150 DEG C
Under be passed through fluorization agent to react complete, hour in reaction time 0.5-10.
In above two embodiment, the mol ratio of organic base and S- methyl lactates is 0.5-3:1, preferably 1-3:1,
More preferably 1.2-2.5:1.
In above two embodiment, the fluorination reagent is selected from the mixing of sulfuryl fluoride or hydrogen fluoride and sulfuryl fluoride；Sulphur
The mol ratio of acyl fluorides and S- methyl lactates is 0.3-1.1:1, more preferably 0.35-1:1；The mol ratio of hydrogen fluoride and S- methyl lactates
For 0-5:1, preferably 2-4:1.
In above-mentioned second step, the solution containing inorganic base, insulation point will be added dropwise after the residual heating of the kettle obtained in the first step
Liquid obtains aqueous phase and organic phase；Organic phase can apply mechanically through being distilled to recover organic base in the 4th step.The inorganic base is selected from hydrogen-oxygen
Change sodium, potassium hydroxide, calcium hydroxide or its combination
In one embodiment of the invention, organic phase reclaims organic base using short-path distillation mode.
In above-mentioned 3rd step, it will mix, be filtrated to get solid with inorganic base insulation after the heated aqueous obtained in second step
Body；Fluoride ion concentration has very big difference to aqueous phase before and after the processing.The inorganic base is selected from sodium hydroxide, potassium hydroxide, hydrogen
Calcium oxide or its combination.
In the preferred embodiment of the present invention, the heated aqueous that will be obtained in second step, is added portionwise inorganic base,
Filtered after insulated and stirred.
In above-mentioned 4th step, the operation of the first step is typically repeated, except that the organic base wherein used is
Recovery obtains in two steps.
Above-mentioned 3rd step and the 4th step might not be carried out in this order, such as, but not limited to, are recycled in second step
Organic base after directly carry out the 4th step.
Main advantages of the present invention：
1st, using specific organic base so that the dosage of fluorination reagent needed for reaction is greatly reduced；
2nd, combination fluorination reagent is chosen so that the fluorination reaction time lowers significantly, and overall yield of reaction is high, optical purity
Good, the yield of final products is more than 90%, optical purity more than 99.5%.
3rd, organic base needed for reaction uses recovery system, improves the utilization rate of organic base, reduces the discharge of waste material,
And recovery system will not reduce reactivity and the optical activity of product.
4th, waste water caused by reaction passes through recovery system, greatly reduces fluorinion in waste water concentration, reduces to ring
The influence in border.
Unless specific instructions, various raw materials of the invention can be by being commercially available；Or the routine side according to this area
Method is prepared.Unless otherwise defined or described herein, all specialties used herein are ripe with art technology with scientific words
It is identical to practice meaning known to personnel.In addition any method similar or impartial to described content and material all can be applied to this
In inventive method.
Above-mentioned synthetic method is the synthetic route of part of compounds of the present invention, according to above-mentioned example, people in the art
Member can synthesize other compounds of the present invention by adjusting different methods, or, those skilled in the art are according to existing
Known technology can synthesize the compound of the present invention.The compound of synthesis can further pass through column chromatography, high-efficient liquid phase color
The mode such as spectrometry or crystallization is further purified.
Other aspects of the present invention are apparent to those skilled in the art due to this disclosure
's.
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than limitation the scope of the present invention.The experimental method of unreceipted actual conditions in the following example, generally marked according to country
Quasi- measure.If without corresponding national standard, built according to general international standard, normal condition or according to manufacturer
The condition of view is carried out.Unless otherwise indicated, otherwise all number is parts by weight, and all percentage is weight percentage, institute
The polymer molecular weight stated is number-average molecular weight.
Unless otherwise defined or described herein, all specialties used herein and scientific words and the skilled people of art technology
Meaning known to member is identical.In addition any method similar or impartial to described content and material all can be applied to the present invention
In method.
Embodiment 1
Following examples will be helpful to further understand the present invention, but not limit present disclosure.
Step 1 R-2- fluorine methyl propionate reacts and refined
In 5L reaction bulbs, S- methyl lactate 1249.2g are added, tri-n-butylamine 2669g, -10 DEG C is cooled to, is incubated in -10-
0 DEG C is passed through sulphonyl fluorine gas 1286g, complete to the reaction of S- methyl lactates.Crude product is steamed, rectifying, obtains R-2- fluorine propionic acid first
Ester 1056.5g, yield 83%, pass through gas Chromatographic Determination content 99.8%, ee values 97.24%.The residual 3945g of kettle.
The recovery one of the positive tri-n-butylamine of step 2
The residual 3945g of kettle obtained in step 1, is heated to 60 DEG C, and 15% sodium hydroxide solution 4160g is added dropwise.Drip
Finish, liquid separation after insulation, obtain aqueous phase 5445g, organic phase short-path distillation, obtain tri-n-butylamine 2461g, yield 92.2%, content
99.13%, moisture content 400ppm.
The processing one of step 3 waste water
The waste water 5445g obtained in step 2, is heated to 60 DEG C, and sodium hydroxide 616g is added portionwise, and insulated and stirred is certain
After time, filtering, solid 1855g is obtained.Fluoride ion concentration is respectively 594ppm and 103ppm to aqueous phase before and after the processing.
The positive tri-n-butylamine of step 4 applies mechanically two
In 5L reaction bulbs, S- methyl lactate 1145g, tri-n-butylamine 2447g (recovery of the step 2 of embodiment one), cooling are added
To -10 DEG C, it is incubated that sulphonyl fluorine gas is passed through at -10-0 DEG C is complete to the reaction of S- methyl lactates.Crude product is steamed, rectifying, is obtained
R-2- fluorine methyl propionate 971.5g, yield 83.2%, pass through gas Chromatographic Determination content 99.9%, ee values 98.06%.Kettle is residual
3620g。
Embodiment 2-7
The dosage of organic base and S- methyl lactates is changed, with embodiment 1, it the results are shown in Table 1 for other
Table 1:
| Embodiment | Organic base:The mol ratio of S- methyl lactates | Content (%) | Yield (%) |
| 2 | 0.5:1 | 98.5 | 42 |
| 3 | 1:1 | 99.1 | 70 |
| 4 | 1.5:1 | 99.2 | 80 |
| 5 | 2:1 | 99.5 | 84 |
| 6 | 2.5:1 | 99.5 | 85 |
| 7 | 3:1 | 99.4 | 81 |
Embodiment 8
Step 1 R-2- fluorine methyl propionate reacts and refined
In 5L reaction bulbs, S- methyl lactate 1249.2g, DMA 1600g are added, is warming up to 100 DEG C, insulation
Hydrogen fluoride gas 480g, sulphonyl fluorine gas 455g are passed through at 95-105 DEG C, it is complete to the reaction of S- methyl lactates.Steam crude product,
Rectifying, R-2- fluorine methyl propionate 1205g are obtained, yield 94.6%, pass through gas Chromatographic Determination content 99.6%, ee values
99.54%.The residual 2359g of kettle.
Step 2 N, the recovery one of accelerine
The residual 2359g of kettle obtained in step 1, is heated to 60 DEG C, and 15% potassium hydroxide solution 4610 is added dropwise.Drip
Finish, liquid separation after insulation, obtain aqueous phase 5023g, organic phase short-path distillation, obtain DMA 1485g, yield
92.8%, content 99.19%, moisture content 410ppm.
The processing one of step 3 waste water
The waste water 5023g obtained in step 2, is heated to 60 DEG C, and sodium hydroxide 1578g is added portionwise, and insulated and stirred is certain
After time, filtering, solid 3654g is obtained.Fluoride ion concentration is respectively 1024ppm and 156ppm to aqueous phase before and after the processing.
Step 4 N, accelerine apply mechanically two
In 5L reaction bulbs, adding S- methyl lactate 1145g, DMA 1466g, (step 2 of embodiment two is returned
Receive), 100 DEG C are warming up to, is incubated and hydrogen fluoride gas 440g is passed through at 95-105 DEG C, sulphonyl fluorine gas 417g, to S- methyl lactates
Reaction is complete.Crude product is steamed, rectifying, R-2- fluorine methyl propionate 1110g is obtained, yield 95.1%, passes through gas Chromatographic Determination
Content 99.8%, ee values 99.48%.The residual 2158g of kettle.
Embodiment 9-14
The dosage of sulfuryl fluoride and S- methyl lactates is changed, with embodiment 8, it the results are shown in Table 2 for other
Table 2:
| Embodiment | Sulfuryl fluoride:The mol ratio of S- methyl lactates | Content (%) | Yield (%) |
| 9 | 0.3:1 | 99.0 | 85 |
| 10 | 0.35:1 | 99.2 | 94 |
| 11 | 0.4:1 | 99.3 | 95 |
| 12 | 0.5:1 | 99.6 | 94 |
| 13 | 1.0:1 | 99.5 | 95 |
| 14 | 1.1:1 | 99.5 | 94 |
Embodiment 15-20
The dosage of hydrogen fluoride and S- methyl lactates is changed, with embodiment 8, it the results are shown in Table 3 for other
Table 3:
| Embodiment | Hydrogen fluoride:The mol ratio of S- methyl lactates | Content (%) | Yield (%) |
| 15 | 1:1 | 98.9 | 80 |
| 16 | 1.5:1 | 98.6 | 86 |
| 17 | 2.5:1 | 99.2 | 93 |
| 18 | 3:1 | 99.6 | 92 |
| 19 | 4:1 | 99.4 | 95 |
| 20 | 5:1 | 99.0 | 92 |
Embodiment 21
Step 1 R-2- fluorine methyl propionate reacts and refined
In 5L reaction bulbs, S- methyl lactate 1249.2g, DMA 1600g are added, is warming up to 100 DEG C, insulation
Sulphonyl fluorine gas 643g is passed through at 95-105 DEG C, it is complete to the reaction of S- methyl lactates.Crude product is steamed, rectifying, obtains R-2- fluorine
Methyl propionate 1158.6g, yield 91.0%, pass through gas Chromatographic Determination content 99.7%, ee values 99.14%.The residual 2213g of kettle.
Step 2 N, the recovery one of accelerine
The residual 2213g of kettle obtained in step 1, is heated to 60 DEG C, and 15% potassium hydroxide solution 4390g is added dropwise.Drip
Finish, liquid separation after insulation, obtain aqueous phase 4780g, organic phase short-path distillation, obtain DMA 1472g, yield
92.0%, content 99.28%, moisture content 380ppm.
The processing one of step 3 waste water
The waste water 4780g obtained in step 2, is heated to 60 DEG C, and sodium hydroxide 486g is added portionwise, and insulated and stirred is certain
After time, filtering, solid 1055g is obtained.Fluoride ion concentration is respectively 386ppm and 58ppm to aqueous phase before and after the processing.
Step 4 N, accelerine apply mechanically two
In 5L reaction bulbs, adding S- methyl lactate 1145g, DMA 1466g, (step 2 of embodiment two is returned
Receive), 100 DEG C are warming up to, is incubated and sulphonyl fluorine gas 589g is passed through at 95-105 DEG C, it is complete to the reaction of S- methyl lactates.Steam thick
Product, rectifying, R-2- fluorine methyl propionate 1063g are obtained, yield 91.1%, pass through gas Chromatographic Determination content 99.9%, ee values
99.24%.The residual 2037g of kettle.
Embodiment 22-27
The dosage of organic base and S- methyl lactates is changed, with embodiment 8 or embodiment 21, it the results are shown in Table for other
4
Table 4:
| Embodiment | Organic base:The mol ratio of S- methyl lactates | Content (%) | Yield (%) |
| 22 | 0.5:1 | 98.5 | 46 |
| 23 | 1:1 | 99.5 | 88 |
| 24 | 1.5:1 | 99.6 | 92 |
| 25 | 2:1 | 99.5 | 93 |
| 26 | 2.5:1 | 99.7 | 92 |
| 27 | 3:1 | 99.4 | 91 |
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not limited to the substantial technological content model of the present invention
Enclose, substantial technological content of the invention is broadly to be defined in the right of application, any technology that other people complete
Entity or method, if with the right of application defined in it is identical, also or a kind of equivalent change, will
It is considered as being covered by among the right.
All it is incorporated as referring in this application in all documents that the present invention refers to, it is independent just as each document
It is incorporated as with reference to such.In addition, it is to be understood that after the above of the present invention has been read, those skilled in the art can be right
The present invention makes various changes or modifications, and these equivalent form of values equally fall within the application appended claims limited range.
Claims (3)
1. a kind of synthetic method of R-2- fluorine methyl propionate, it is characterised in that methods described includes step：
(1) in the presence of DMA, the perfluorinated reagent fluorination of S- methyl lactates is made at 60-150 DEG C, obtains R-2-
Fluorine methyl propionate crude product, rectifying crude product obtains R-2- fluorine methyl propionate and kettle is residual；The N, accelerine and S- lactic acid first
The mol ratio of ester is 1-3:1；
(2) by kettle it is residual mixed with the solution containing inorganic base, liquid separation obtains aqueous phase and organic phase, and from organic phase reclaim N, N- bis-
Methylaniline；Obtained aqueous phase is mixed with inorganic base, filtered, and removes fluoride；
(3) (1) step is repeated with the organic base of recovery, obtains R-2- fluorine methyl propionates；
The fluorination reagent is selected from the mixing of sulfuryl fluoride or hydrogen fluoride and sulfuryl fluoride；
The inorganic base is selected from sodium hydroxide, potassium hydroxide, calcium hydroxide or its combination.
2. synthetic method as claimed in claim 1, it is characterised in that the mol ratio of the sulfuryl fluoride and S- methyl lactates is
0.3-1.1:1；The mol ratio of the hydrogen fluoride and S- methyl lactates is 0-5:1.
3. synthetic method as claimed in claim 1, it is characterised in that organic phase reclaims through short-path distillation described in step (2)
N, accelerine.
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Address after: 324004 No. 20 Chuncheng Road, Quzhou High-tech Industrial Park, Quzhou City, Zhejiang Province Co-patentee after: Shanghai Kangpeng Science and Technology Co., Ltd. Patentee after: Zhejiang Zhong Xiaokang roc Chemical Co., Ltd. Address before: 324004 No. 20 Chuncheng Road, Quzhou High-tech Industrial Park, Quzhou City, Zhejiang Province Co-patentee before: Shanghai Kangpeng Chemical Co., Ltd. Patentee before: Zhejiang Zhong Xiaokang roc Chemical Co., Ltd. |
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