CN103910628A - Method For Manufacturing Alpha-fluoroacrylates - Google Patents

Method For Manufacturing Alpha-fluoroacrylates Download PDF

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Publication number
CN103910628A
CN103910628A CN201310740700.XA CN201310740700A CN103910628A CN 103910628 A CN103910628 A CN 103910628A CN 201310740700 A CN201310740700 A CN 201310740700A CN 103910628 A CN103910628 A CN 103910628A
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formula
manufacture method
compound shown
substituent
organic solvent
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Inventor
神原将
日高麻衣
大塚达也
石原寿美
黑木克亲
山本明典
岸川洋介
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Daikin Industries Ltd
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Daikin Industries Ltd
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Priority to CN201711083010.6A priority Critical patent/CN107721854A/en
Priority to CN201810497015.1A priority patent/CN108546231A/en
Publication of CN103910628A publication Critical patent/CN103910628A/en
Pending legal-status Critical Current

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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
    • C07C67/317—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
    • C07C67/327—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups by elimination of functional groups containing oxygen only in singly bound form
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/62—Halogen-containing esters
    • C07C69/65—Halogen-containing esters of unsaturated acids
    • C07C69/653—Acrylic acid esters; Methacrylic acid esters; Haloacrylic acid esters; Halomethacrylic acid esters

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The present invention provides a method for manufacturing alpha-fluoroacrylates at a low manufacture cost without using a raw material compound having strong toxicity. The method is to manufacture the compound represented by the formula (1), and comprises the step of contacting a compound represented by formula (2) with an alkali halide to obtain the compound represented by formula (1). In the formula, R1 represents an alkyl group, and R2 represents hydrogen and can have the alkyl group, an aryl group or a miscellaneous aryl possessing a substituent group, R3 represents the alkyl group, and the definitions of other symbols are ditto.

Description

The manufacture method of alpha-fluoro acrylic ester
Technical field
The present invention relates to the manufacture method of alpha-fluoro acrylic ester.
Background technology
Alpha-fluoro acrylic ester as the synthetic intermediate of medicine (such as microbiotic), synthetic intermediate that fibre-optic sheath material is used, coating with synthetic intermediate, the synthetic intermediate of semi-conductor anticorrosive additive material and the monomer of functional high-polymer etc. of material of great use.
All the time, as the manufacture method of alpha-fluoro acrylic ester, for example known: under the existence of highly basic, make fluoro acetic ester and formaldehyde reaction and obtain the method for alpha-fluoro acrylic ester, mix with fluoro acetic ester by oxalic acid two (rudimentary) ester, make the method (patent documentation 1) of this mixture and formaldehyde reaction.
On the other hand, the manufacture method of this alpha-fluoro acrylic ester replacing as β, known: to use the dried Potassium monofluoride of spraying, by one kettle way, manufactured the method (non-patent literature 1) of the alpha-acrylic ester of β replacement by the aldehyde outside chloromalonic acid and formaldehyde.
Patent documentation
Patent documentation 1: No. 3262968 specification sheets of United States Patent (USP)
Non-patent literature
Non-patent literature 1:Chemistry Letters, 1981, p.1259-1260
There is the problems such as the toxicity height of starting compound in the method for recording in patent documentation 1.
On the other hand, according to the method for recording in non-patent literature 1, if can be used as the formalin of formalin to replace formaldehyde aldehyde in addition, can be in the case of not obtaining alpha-fluoro acrylic ester the intermediate via record in patent documentation 1.But, in fact, once there is water in this reaction, just substantially cannot obtain alpha-fluoro acrylic ester, therefore, according to the method for recording in non-patent literature 1, cannot use formalin to manufacture alpha-fluoro acrylic ester.Therefore, the present inventor attempts using formaldehyde gas and polyoxymethylene, manufactures alpha-fluoro acrylic ester according to the method for recording in non-patent literature 1.But, under any circumstance all substantially cannot obtain alpha-fluoro acrylic ester.
Summary of the invention
Therefore, the object of the invention is to, a kind of manufacture method that does not use starting compound that toxicity is high, manufactures alpha-fluoro acrylic ester with low manufacturing cost is provided.
The present invention includes following mode.
The manufacture method of the compound shown in 1. 1 kinds of following formulas of item (1), comprises the operation A that the compound shown in following formula (2) is contacted and obtain the compound shown in formula (1) with alkali metal halide.
[in formula, R 1represent alkyl, R 2represent hydrogen, can there is substituent alkyl, can there is substituent aryl and maybe can there is substituent heteroaryl.]
[in formula, R 3represent alkyl, the implication of other symbol is the same.]
The manufacture method of item 2. as described in item 1, described alkali metal halide is potassium halide.
The manufacture method of item 3. as described in item 1, described alkali metal halide is Potassium monofluoride.
The manufacture method of item 4. as described in any one in item 1～3, operation A implements in organic solvent.
The manufacture method of item 5. as described in item 4, described organic solvent is polar organic solvent.
The manufacture method of item 6. as described in item 4, described organic solvent is the organic solvent with 100 DEG C of above boiling points.
The manufacture method of item 7. as described in any one in item 4～6, described organic solvent is tetramethylene sulfone, dimethyl sulfoxide (DMSO), glyme, diglyme, methyl-2-pyrrolidone, propylene carbonate or NSC 11801.
8. manufacture method as described in any one in item 1～7, operation A does not substantially exist under the condition of water and implements.
9. 1 kinds of compositions, contain the compound shown in the compound shown in following formula (1) and following formula (3), and the mass ratio of the compound shown in the quality of the compound shown in formula (3) and formula (1) is at 0.01～10%(w/w) scope in.
[in formula, R 1represent alkyl, R 2represent hydrogen, can there is substituent alkyl, can there is substituent aryl and maybe can there is substituent heteroaryl.]
[in formula, R 4and R 5identical or different, represent hydrogen, can there is substituent alkyl, can there is substituent aryl and maybe can there is substituent heteroaryl, the implication of other symbol is the same.]
Invention effect
According to the present invention, can not use starting compound that toxicity is high, manufacture alpha-fluoro acrylic ester with low manufacturing cost.
Embodiment
In this manual, as " alkyl " (comprising " alkyl " in substituting groups such as " list-alkylaminos "), for example, can enumerate C1～6 alkyl such as methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, neo-pentyl, hexyl.
In this manual, as " C1～3 alkyl ", for example, can enumerate methyl, ethyl, propyl group, sec.-propyl etc.
In this manual, as " alkoxyl group ", for example, can enumerate C1～6 alkoxyl groups such as methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert.-butoxy, pentyloxy, neopentyl oxygen, hexyloxy.
In this manual, as " halogen ", for example, can enumerate fluorine, chlorine, bromine, iodine.
In this manual, as " aryl ", can enumerate C6～18 aryl such as phenyl, xenyl, naphthyl, anthryl, phenanthryl, acenaphthenyl (Acenaphthylenyl).
In this manual, as " heteroaryl ", for example, can enumerate: as the atom that forms ring, except carbon atom, contain 1～4 heteroatomic 5～14 yuan (monocycle, dicyclo or three-ring type) heterocyclic radicals that are selected from nitrogen-atoms, sulphur atom and Sauerstoffatom.
In this manual, as " heteroaryl ", concrete example is as enumerated:
(1) the monocyclic aromatic heterocycle such as furyl, thienyl, pyridyl, pyrimidyl, pyridazinyl, pyrazinyl, pyrryl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, oxadiazolyl, thiadiazolyl group, triazolyl, tetrazyl, triazinyl; And
(2) polycycle (for example two ring types) aromatic heterocycle such as quinolyl, isoquinolyl, quinazolyl, quinoxalinyl, benzofuryl, benzothienyl, benzoxazolyl, benzoisoxazole base, benzothiazolyl, benzimidazolyl-, benzotriazole base, indyl, indazolyl, Pyrrolopyrazine base, imidazopyridyl, Imidazopyrazines base, Imidazothiazole base, Pyrazolopyridine base, pyrazolo thienyl, method for preparation of pyrazolotriazine base.
Manufacture method of the present invention is the manufacture method of the compound shown in following formula (1), and this manufacture method comprises the operation A that the compound shown in following formula (2) is contacted and obtain the compound shown in above-mentioned formula (1) with alkali metal halide.
[in formula, R 1represent alkyl, R 2represent hydrogen, can there is substituent alkyl, can there is substituent aryl and maybe can there is substituent heteroaryl.]
[in formula, R 3represent alkyl, other implication meeting is the same.]
R 1be preferably methyl or ethyl, more preferably methyl.
R 2the alkyl that shown " can have substituent alkyl " for example for example, replaced for being selected from the substituting group of above (1～3) in halogen, alkyl (preferably C1～6 alkyl), alkoxyl group (preferably C1～6 alkoxyl group), amino, list-alkylamino (preferably list-C1～6 alkylamino) and two-alkylamino (preferably two-C1～6 alkylamino).
R 2the aryl that shown " can have substituent aryl " for example for example, replaced for being selected from the substituting group of above (1～3) in halogen, alkyl (preferably C1～6 alkyl), alkoxyl group (preferably C1～6 alkoxyl group), amino, list-alkylamino (preferably list-C1～6 alkylamino) and two-alkylamino (preferably two-C1～6 alkylamino).
R 2the heteroaryl that shown " can have substituent heteroaryl " for example for example, replaced for being selected from the substituting group of above (1～3) in halogen, alkyl (preferably C1～6 alkyl), alkoxyl group (preferably C1～6 alkoxyl group), amino, list-alkylamino (preferably list-C1～6 alkylamino) and two-alkylamino (preferably two-C1～6 alkylamino).
R 2be preferably hydrogen or alkyl, be particularly preferably hydrogen.
Compound shown in above-mentioned formula (1) is preferably methyl-2-fluoro acrylic ester or ethyl-2-fluoro acrylic ester, is particularly preferably methyl-2-fluoro acrylic ester.
R 3be preferably C1～3 alkyl, more preferably methyl or ethyl, be particularly preferably methyl.
Particularly preferably R of compound shown in above-mentioned formula (2) 1and R 3be methyl, R 2for the compound of hydrogen.
Compound shown in above-mentioned formula (2) is known compound, can, by known methods such as the methods recorded in Japanese kokai publication hei 6-184234 communique, particularly make the method for alpha-fluoromalonic acid dimethyl ester and formaldehyde reaction or manufacture according to its method.
As the alkali metal halide using in operation A, for example, can enumerate lithium halide (such as lithium fluoride, lithium chloride, lithiumbromide, lithium iodide etc.), sodium halide (such as Sodium Fluoride, sodium-chlor, Sodium Bromide, sodium iodide etc.), potassium halide (such as Potassium monofluoride, Repone K, Potassium Bromide, potassiumiodide etc.), caesium halide (such as cesium fluoride, cesium chloride, cesium bromide, cesium iodide etc.) etc.
Wherein, be preferably for example sodium halide, potassium halide, more preferably for example sodium-chlor, Sodium Bromide, Potassium monofluoride, Repone K, Potassium Bromide.
The amount of this alkali metal halide, with respect to 1 mole of the compound shown in above-mentioned formula (2), conventionally in the scope of 0.001～5 mole, preferably in the scope of 0.01～1 mole.
Operation A preferably in organic solvent, implement or under solvent-free (pure, neat) implement.
The in the situation that operation A implementing in organic solvent, the compound shown in above-mentioned formula (2) contacts with above-mentioned alkali metal halide, for example can be by they being dropped in above-mentioned organic solvent and mixing as required to implement.
The organic solvent using in operation A can be polar organic solvent or non-polar organic solvent.The organic solvent using in operation A is preferably polar organic solvent.
As the organic solvent using in operation A, for example, can enumerate dimethyl sulfoxide (DMSO), dimethyl formamide, N,N-DIMETHYLACETAMIDE, ethylene glycol, polyoxyethylene glycol, polypropylene glycol, glycol derivative (such as glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, TRIGLYME, tetraethyleneglycol dimethyl ether), quinoline, tetrahydroquinoline, methyl-2-pyrrolidone, dimethyl-imidazolinone, hexamethylphosphoramide, NSC 11801, propylene carbonate base, dimethylbenzene, sym-trimethylbenzene, alkanes (such as decane, dodecane) etc.
Wherein, preference is as tetramethylene sulfone, dimethyl sulfoxide (DMSO), dimethyl formamide, N,N-DIMETHYLACETAMIDE, glycol dimethyl ether, diethylene glycol dimethyl ether, propylene carbonate, more preferably for example tetramethylene sulfone, dimethyl sulfoxide (DMSO), glyme, diglyme, methyl-2-pyrrolidone, propylene carbonate or NSC 11801.
This organic solvent can use separately one, also can be used in combination two or more.
This organic solvent is preferably to have 100 DEG C of above boiling points, more preferably have 120 DEG C of above boiling points, further preferably have the organic solvent of 150 DEG C of above boiling points.The upper limit of this boiling point does not limit, and is generally 300 DEG C.
Because this organic solvent has high boiling point as above, can be by the compound underpressure distillation of formula lower boiling point (1), thus obtain with high yield.
As this organic solvent, particularly preferably for example tetramethylene sulfone.
The amount of this organic solvent, with respect to the compound 1g shown in above-mentioned formula (2), conventionally in the scope of 0～100mL, preferably in the scope of 0.01～10mL, more preferably in the scope of 0.1～1mL.
Under the preferred condition that does not substantially have water of operation A, implement.
At this, " not having in fact water " refers to that the water-content of the reaction mixture of operation A is 1.0%(w/w in the time that reaction starts) below.
In the reaction system of operation A, exist water, the yield of the compound shown in formula (1) reduces.
In the reaction of operation A, can be according to expecting to use stopper.As the example of stopper, for example, can enumerate butylated hydroxytoluene (BHT), 4-methoxyphenol, Resorcinol, thiodiphenylamine, benzoquinones, thiodiphenylamine etc.
The amount of this stopper, with respect to compound 1 weight part shown in above-mentioned formula (2), conventionally in the scope of 0.0003～0.25 weight part, preferably in the scope of 0.0005～0.05 weight part, more preferably in the scope of 0.001～0.01 weight part.
The temperature of reaction of the reaction of operation A is conventionally in the scope of 60～160 DEG C, preferably in the scope of 70～150 DEG C, more preferably in the scope of 80～140 DEG C.
By adopting higher temperature of reaction, further Reaction time shorten.
The reaction times of the reaction of operation A is set as for example yield and reaches the maximum time, particularly, and conventionally in the scope of 1～24 hour, more preferably in the scope of 1～12 hour, further preferably in the scope of 2～12 hours.
In manufacture method of the present invention, the compound shown in the formula of generation (1) can react while take out from reaction system by methods such as underpressure distillation.
The yield of the raw material in manufacture method of the present invention is preferably more than 40%, more preferably more than 50%, more preferably more than 60%.
In manufacture method of the present invention, obtain the compound shown in formula (3) together with the compound shown in formula (1).
[in formula, R 4and R 5identical or different, represent hydrogen, can there is substituent alkyl, can there is substituent aryl and maybe can there is substituent heteroaryl, the implication of other symbol is the same.]
At this, R 4and R 5identical or different, from above-mentioned R 1, R 2or R 3, and can be identical with any in them.
As this compound, for example, can enumerate Methylal(dimethoxymethane).
Composition of the present invention contains the compound shown in the compound shown in above-mentioned formula (1) and above-mentioned formula (3), and the mass ratio of the compound shown in the quality of the compound shown in above-mentioned formula (3) and above-mentioned formula (1) is at 0.01～10%(w/w) scope in.
This mass ratio can utilize gas-chromatography to obtain under following condition.
[condition of gas-chromatography]
Post: DB-5MS60m, 0.25mm, 0.25 μ m
Carrier gas: He
Vaporizer temperature: 300 DEG C
Column oven: heat up 8 DEG C/min 200 DEG C 40 DEG C (10 minutes)
Detector temperature: 320 DEG C
Detector FID
For composition of the present invention, the mass ratio of the compound shown in the quality of the compound shown in above-mentioned formula (3) and above-mentioned formula (1) is at 0.01～10%(w/w) scope in, preferably at 0.01～5%(w/w) scope in, more preferably at 0.01～3%(w/w) scope in, further preferably at 0.01～1%(w/w) scope in, further preferably at 0.01～0.5%(w/w) scope in, can be suitable as thus for example synthetic intermediate of medicine (for example microbiotic), the synthetic intermediate that fibre-optic sheath material is used, the synthetic intermediate of material for coating, the synthetic intermediate composition of the synthetic intermediate of semi-conductor anticorrosive additive material and the monomer of functional high-polymer etc., and favourable aspect the manufacturing cost of said composition, thus, also favourable aspect the manufacturing cost of the finished product.
Compound shown in the formula (1) obtaining by manufacture method of the present invention can according to expect by solvent extraction, dry, filter, distillation, concentrated and their the known process for purification such as combination refine.
Embodiment
Embodiment 1
In 100mL eggplant type flask, drop into Potassium monofluoride 2.91g(50mmol), butylated hydroxytoluene (BHT) 55.1mg(0.250mmol), the fluoro-2-hydroxymethyl of dimethyl-2-malonic ester 45.0g(250mmo1) and tetramethylene sulfone 11.5mL(14.5g) and mix.Under normal pressure, with 90 DEG C of heating 15 minutes, then, under reduced pressure with 105 DEG C of heating 1 hour, in reaction, distill, to obtain methyl-2-fluoro acrylic ester with the form of the mixture of methyl alcohol.
Output be 18.2g(as with the mixture of methyl alcohol be 26.8g), yield is 70%.
This mixture contains Methylal(dimethoxymethane).Under following condition, utilizing the quality of Methylal(dimethoxymethane) and the mass ratio of methyl-2-fluoro acrylic ester that gas-chromatography calculates is 0.16%(w/w).
[condition of gas-chromatography]
Post: DB-5MS60m, 0.25mm, 0.25 μ m
Carrier gas: He
Vaporizer temperature: 300 DEG C
Column oven: heat up 8 DEG C/min 200 DEG C 40 DEG C (10 minutes)
320 DEG C of detector temperatures
Detector FID
According to the present invention, can be not via the intermediate that is difficult to separate, with low manufacturing cost and with high yield manufacture alpha-fluoro acrylic ester.

Claims (9)

1. a manufacture method for the compound shown in following formula (1), is characterized in that:
Comprise the operation A that the compound shown in following formula (2) is contacted and obtain the compound shown in described formula (1) with alkali metal halide,
In formula, R 1represent alkyl, R 2represent hydrogen, can there is substituent alkyl, can there is substituent aryl and maybe can there is substituent heteroaryl,
In formula, R 3represent alkyl, the implication of other symbol is the same.
2. manufacture method as claimed in claim 1, is characterized in that:
Described alkali metal halide is potassium halide.
3. manufacture method as claimed in claim 1, is characterized in that:
Described alkali metal halide is Potassium monofluoride.
4. the manufacture method as described in any one in claim 1～3, is characterized in that:
Operation A implements in organic solvent.
5. manufacture method as claimed in claim 4, is characterized in that:
Described organic solvent is polar organic solvent.
6. manufacture method as claimed in claim 4, is characterized in that:
Described organic solvent is the organic solvent with 100 DEG C of above boiling points.
7. the manufacture method as described in any one in claim 4～6, is characterized in that:
Described organic solvent is tetramethylene sulfone, dimethyl sulfoxide (DMSO), glyme, diglyme, methyl-2-pyrrolidone, propylene carbonate or NSC 11801.
8. the manufacture method as described in any one in claim 1～7, is characterized in that:
Operation A does not substantially exist under the condition of water and implements.
9. a composition that contains the compound shown in the compound shown in following formula (1) and following formula (3), is characterized in that:
In formula, R 1represent alkyl, R 2represent hydrogen, can there is substituent alkyl, can there is substituent aryl and maybe can there is substituent heteroaryl,
In formula, R 4and R 5identical or different, represent hydrogen, can there is substituent alkyl, can there is substituent aryl and maybe can there is substituent heteroaryl, the implication of other symbol is the same,
The mass ratio of the compound shown in the quality of the compound shown in described formula (3) and described formula (1) is at 0.01～10%(w/w) scope in.
CN201310740700.XA 2012-12-28 2013-12-27 Method For Manufacturing Alpha-fluoroacrylates Pending CN103910628A (en)

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