CN101544623A - Preparing method of beta-hydroxy-gamma-butyrolactone - Google Patents
Preparing method of beta-hydroxy-gamma-butyrolactone Download PDFInfo
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- CN101544623A CN101544623A CN200910127443A CN200910127443A CN101544623A CN 101544623 A CN101544623 A CN 101544623A CN 200910127443 A CN200910127443 A CN 200910127443A CN 200910127443 A CN200910127443 A CN 200910127443A CN 101544623 A CN101544623 A CN 101544623A
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- hydroxy
- hydroxyl
- gamma
- butyrolactone
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/32—Oxygen atoms
- C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Furan Compounds (AREA)
Abstract
The present invention relates to a method for preparing beta-hydroxy-gamma-butyrolactone (4-hydroxy-dihydrofuran-2-one) through reducing tetronic acid. Preferably the hydrogen is used as the reducing agent, and more preferably the reaction is executed in the presence of reducing catalysts of solid catalyst, etc. According to the method, the lactone which is useful as the raw material of intermediate of functional material, medicine or pesticide, etc. can be prepared conveniently, efficiently and economically. Furthermore the carbon atom connected with the oxygen atom of cyclic lactone in the lactone ring is not substituted.
Description
Technical field
The present invention relates to the preparation method of beta-hydroxy-gamma-butyrolactone, described beta-hydroxy-gamma-butyrolactone is useful as the raw material of intermediate of functional material, medicine or agricultural chemicals etc.
Background technology
As the method for preparing hydroxy-lactone (4-hydroxyl dihydrofuran-2-ketone etc.), known have various methods.For example, in the United States Patent (USP) No. 4968817 (patent documentations 1) following method is disclosed: in the presence of noble metal catalyst, by making Racemic glycidol and reaction of carbon monoxide, preparation 4-hydroxyl dihydrofuran-2-ketone.But in the method, must react with the poisonous gas carbon monoxide down, be unfavorable for industrial production in high pressure (more than about 3MPa).
In addition, in (the international version of applied chemistry, English (Angew.Chem.Int.Ed., Eng.), the 5th volume, disclose the coexistence system of utilizing hydrogen peroxide and formic acid in the 994th page of (1966) (non-patent literature 1) and handled the 3-butenoic acid,, prepared the method for 4-hydroxyl dihydrofuran-2-ketone further by the effect of hydrochloric acid; In WO98/04543 communique (patent documentation 2), disclose under alkaline condition, handled carbohydrate such as lactose with aqueous hydrogen peroxide solution,, prepared the method for 4-hydroxyl dihydrofuran-2-ketone then by acid treatment; And make through 3 of above-mentioned acid treatment gained with acetone, 4-dihydroxyl butyric acid reverts to acetonide, and (ア セ ト ニ De Acetonide), by with the salt acid treatment of this ketone acetal, prepares the method for 4-hydroxyl dihydrofuran-2-ketone.
Disclose in the EP761663 communique (patent documentation 3) the salt acid treatment of 4-chloro-ethyl 3-hydroxybutanoate,, prepared the method for 4-hydroxyl dihydrofuran-2-ketone by neutralizing with sodium hydroxide; Disclose in the WO99/33817 communique (patent documentation 4) and made Racemic glycidol generation cyano groupization,, prepared the method for 4-hydroxyl dihydrofuran-2-ketone again by lactonizing after the hydrolysis.
But because these methods all make water as solvent, dephlegmate then needs the plenty of time, heat energy, so be unfavorable for industrial production.In addition, used acid or alkali must in and salify.Further, though also can consider with organic solvent extraction 4-hydroxyl dihydrofuran-2-ketone, because the water-soluble height of 4-hydroxyl dihydrofuran-2-ketone, so extraction efficiency is low.Therefore, in the method for above-mentioned non-patent literature 1 and patent documentation 1～3, can not prepare target compound efficiently.And, in the method for above-mentioned non-patent literature 1 and patent documentation 1, use superoxide, in the method for patent documentation 3, use cyano compound, must take more care during operation.
Synlett (シ Application レ Star ト) has put down in writing by carnitine is heat-treated in the 71st page of (1997) (non-patent literature 2), prepares the method for 4-hydroxyl dihydrofuran-2-ketone.But in the method, must use the high boiling solvent of dimethyl sulfoxide (DMSO) and so on, be difficult to separated product.
Open in the 2001-302653 communique (patent documentation 4) the spy, put down in writing the method for preparing 4-hydroxyl dihydrofuran-2-ketone by epoxy carboxylic acid or derivatives thereof.Utilize this method, though can synthesize lactone efficiently as target, but as starting raw material 3, the industrial production of 4-epoxy butyric ester is not established as yet, more wishes to establish a kind of method of using the industrial feedstock production 4-hydroxyl dihydrofuran-2-ketone that is easier to obtain.
Tetrahedron Letters (テ ト ラ ヘ De ロ Application レ -ズ), the 30th volume has been put down in writing in the 2513rd page of (1989) (non-patent literature 3) by using salt acid treatment 4,4-dimethyl-3,4-epoxy valerate prepares the method for 4-hydroxyl-5-ethyl dihydrofuran-2-ketone.But in the method, use 4 do not have to replace 3,4-epoxy valerate generates 3-hydroxyl-4-chloro pentane acid ester during as raw material, can't obtain lactone.
In addition, Tetrahedron, the 47th volume has been put down in writing in the 7171st page of (1991) (non-patent literature 4) by with 3% aqueous sulfuric acid processing 4-ethyl-3, and 4-epoxy valerate prepares the method for 4-hydroxyl-5-ethyl dihydrofuran-2-ketone.But in the method, because the epoxy group(ing) of raw material epoxy valerate replaced by ethyl, so can not obtain not having on 5 substituent 4-acyloxy dihydrofuran-2-ketone.In addition,, must extract target compound, but because the water-soluble height of target compound is difficult to extraction by water layer because of using 3% aqueous sulfuric acid.
No. 4968817, [patent documentation 1] United States Patent (USP)
[patent documentation 2] WO98/04543 communique
[patent documentation 3] EP761663 communique
[patent documentation 4] WO99/33817 communique
The international version of [non-patent literature 1] applied chemistry, English (Angew.Chem.Int.Ed., Eng.), the 5th volume, 994 pages (1966)
[non-patent literature 2] Synlett, 71 pages (1997)
[non-patent literature 3] Tetrahedron Letters, the 30th volume, 2513 pages (1989)
[non-patent literature 4] Tetrahedron, the 47th volume, 7171 pages (1991)
Summary of the invention
The problem that invention will solve
The object of the present invention is to provide the preparation method of lactone, described lactone is: in the beta-hydroxy-gamma-butyrolactone class, and the unsubstituted lactone of the carbon atom that is connected with the Sauerstoffatom of cyclic lactone base (for example, carbon atom of 5 of dihydrofuran-2-ketone etc.).
Other purpose of the present invention is to provide the method that can be prepared lactone by 4-hydroxyl etheric acid lactone (tetronic acid) efficiently.
Another object of the present invention is to provide the preparation method of lactone, this method is used can be efficiently from the isolating reductive agent of product.
Another purpose of the present invention is to provide the preparation method of lactone, even this method is used catalyzer, also catalyzer can be separated efficiently.
The method of dealing with problems
In order to address the above problem, present inventors are through found that of concentrating on studies, and the reduction by 4-hydroxyl etheric acid lactone can prepare beta-hydroxy-gamma-butyrolactone (4-hydroxyl dihydrofuran-2-ketone), so finished the present invention.
That is to say, the invention provides the preparation method of beta-hydroxy-gamma-butyrolactone (4-hydroxyl dihydrofuran-2-ketone), this method can obtain the beta-hydroxy-gamma-butyrolactone shown in the following formula (2) (4-hydroxyl dihydrofuran-2-ketone) for by the 4-hydroxyl etheric acid lactone shown in the following formula of reduction (1).
[changing 1]
[changing 2]
As reductive agent, can preferably use hydrogen.
Preferred reduction is carried out in the presence of catalyzer, as catalyzer, can preferably use solid catalyst.
The effect of invention
According to the present invention, can with industrial preparation sell and the 4-hydroxyl etheric acid lactone that is easy to obtain as raw material, prepare the high beta-hydroxy-gamma-butyrolactone of utility value (4-hydroxyl dihydrofuran-2-ketone) at an easy rate, this beta-hydroxy-gamma-butyrolactone (4-hydroxyl dihydrofuran-2-ketone) is the unsubstituted lactone of carbon atom that is connected with the Sauerstoffatom of the cyclic lactone base of lactonic ring.In addition, when using hydrogen, beta-hydroxy-gamma-butyrolactone (4-hydroxyl dihydrofuran-2-ketone) can be separated at an easy rate as reductive agent.When especially reacting in the presence of solid catalyst, removing easily of catalyzer can separate beta-hydroxy-gamma-butyrolactone (4-hydroxyl dihydrofuran-2-ketone) efficiently.
Embodiment
[4-hydroxyl etheric acid lactone]
According to the present invention,, can prepare beta-hydroxy-gamma-butyrolactone (4-hydroxyl-dihydrofuran-2-ketone) by reduction 4-hydroxyl etheric acid lactone.Herein, 4-hydroxyl etheric acid lactone is usually shown in following formula (1-1), though can exist with the form of the tautomer of ketone type (1a) and enol form (1b), but in this manual, 4-hydroxyl etheric acid lactone can be any in the enol form shown in the ketone type shown in (1a), (1b) or both mixtures.
[changing 3]
[reductive agent]
Can use used known reductive agent usually during reduction arbitrarily, be not particularly limited.For example, can enumerate hydrogen (H
2), sodium borohydride (NaBH
4) etc.Wherein, can most preferably use hydrogen.By using hydrogen as reductive agent, after reaction finishes, can be easily will excessive reductive agent and reductive agent oxide compound, the separation of target product beta-hydroxy-gamma-butyrolactone.
The usage quantity of reductive agent can be selected from normally used scope, is not particularly limited.When using hydrogen, can under nitrogen atmosphere, react, perhaps can hydrogen and for example helium, nitrogen etc. are the mixed-gas atmosphere of inactive gas to reaction under, react as reductive agent.
[catalyzer]
By in the presence of catalyzer, carrying out the reduction of 4-hydroxyl etheric acid lactone, can further prepare beta-hydroxy-gamma-butyrolactone efficiently.
As catalyzer, can use arbitrarily to promote the various catalyzer of 4-hydroxyl etheric acid lactone reductive, be not particularly limited.For example, can enumerate precious metal such as Pd, Pt, Rh, Ru or contain the precious metal catalyzer such as compound of these precious metal elements; Metals such as Ni, Fe, Cu or contain the base metal class catalyzer of these metallic compounds.These catalyzer can use separately or use mixing more than two kinds.Wherein, preferred Rh, Pd, Ni or contain the catalyzer of these metals.In addition, above-mentioned metallic compound comprises oxide compound, various coordination compoundes etc.
Reduction can be carried out in homogeneous system, also can use solid catalyst to carry out in nonhomogeneous system.Above-mentioned solid catalyst comprises precious metal solid catalyst, base metal class solid catalyst, described precious metal solid catalyst, be with the precious metal catalyst loading in, for example, silica gel, aluminum oxide, gac etc. suitably form on the carrier; Described base metal class solid catalyst for example, is improved sponge nickel etc. and the base metal such as goods, Ni that improved reducing activity supports on suitable carrier and forms to shape of base metal catalysts etc.
Can in order to improve operation efficiency, preferably use solid catalyst by catalyzer is removed in catalyzer filtration etc. easily from reaction solution after reaction.
The usage quantity of catalyzer is about 0.000001～100 weight part with respect to 1 weight part 4-hydroxyl etheric acid lactone, is preferably about 0.0001～10 weight part, more preferably 0.005～0.5 weight part (especially about 0.001～0.5 weight part).In addition, when using supported catalyst as catalyzer, the usage quantity of above-mentioned catalyzer is the weight that deducts from the weight of supported catalyst after the vehicle weight.
Temperature of reaction can suitably be selected according to the stability of the formation speed of lactone, raw material 4-hydroxyl etheric acid lactone, product (beta-hydroxy-gamma-butyrolactone) etc.For example can preferably from-10～100 ℃ of scopes, especially preferably select from-30～150 ℃ of scopes from 15～40 ℃ of scopes.
Reaction is mostly under normal pressure or add and depress (for example, about 0.1～50MPa, about preferred 0.1～10MPa) and carry out.In addition, owing to operational reason, also can under reduced pressure react.
Reaction can be carried out existing under the solvent or do not exist under the solvent, carries out existing under the solvent usually.As solvent, for example, can use ether, isopropyl ether, butyl ether, tetrahydrofuran (THF), diox, 1, ether solvents such as 2-glycol dimethyl ether; Nitrile such as acetonitrile, benzonitrile; Sulfoxide kind solvents such as dimethyl sulfoxide (DMSO); Tetramethylene sulfone classes such as tetramethylene sulfone; Esters solvents such as methyl acetate, ethyl acetate, butylacetate; Lactone such as gamma-butyrolactone; Amide solvents such as dimethyl formamide; Alcoholic solvents such as methyl alcohol, ethanol, propyl alcohol, Virahol, propyl carbinol, sec-butyl alcohol, the trimethyl carbinol; Saturated or unsaturated hydrocarbons kind solvents such as pentane, hexane, heptane, octane, sherwood oil; Methylene dichloride, chloroform, 1, halogenated hydrocarbon solvents such as 2-ethylene dichloride, chlorobenzene, bromobenzene; High boiling solvent such as polyoxyethylene glycol, silicone oil.Wherein, can especially preferably use esters solvents such as acetic ester.Solvent can use separately also and can use mixing more than 2 kinds.
The usage quantity of solvent is so long as solubilized or disperse reacted constituent, and the amount that does not influence degree such as economy gets final product, and is not particularly limited.For example, supply to 4-hydroxyl etheric acid lactone in the reaction system with respect to 100 weight parts, can be from the scope about 1～100000 weight part, preferably the scope from about 1～10000 weight part is selected.
Reaction can be carried out with any means in intermittent type, semibatch and the continous way.The beta-hydroxy-gamma-butyrolactone that generates can be carried out purifying with separation purification method commonly used (with the separation of neutralization, extraction, distillation, rectifying, molecular distillation, partial crystallization, recrystallization, column chromatography etc.) as required.
The preparation intermediate that the beta-hydroxy-gamma-butyrolactone that obtains like this can be used as functional material or medicine or agricultural chemicals etc. uses.Particularly, because in the beta-hydroxy-gamma-butyrolactone class, the carbon atom that is connected with the Sauerstoffatom of cyclic lactone base (5 carbon atom of dihydrofuran-2-ketone etc.) is not substituted, and the raw material of pretending to high functionality material (linear macromolecule of unprotected side chain etc.) is of great use.
Embodiment
Below, by embodiment the present invention is described in more detail, but the present invention is not subjected to any restriction of these embodiment.
In addition, the NMR spectrogram of embodiment gained compound, be to use 500MHz,
1H-NMR spectrogram determinator (Brooker (Bruker) corporate system " AVANCE500 "), and measure for interior mark with tetramethylsilane (TMS).
(embodiment 1) (adopting rhodium-aluminium oxide catalyst to prepare beta-hydroxy-gamma-butyrolactone)
In two mouthfuls of flasks of capacity 50ml, add rhodium-aluminium oxide catalyst (NE-CHEMCAT (エ ヌ イ-ケ system キ ヤ Star ト) system; Trade(brand)name " 5%Rh aluminum oxide ") 0.05g, ethyl acetate (with the pure medicine system of light) 9.06g, 4-hydroxyl etheric acid lactone (the Tokyo system of changing into) 1g behind the nitrogen replacement, install hydrogen balloon, make system become nitrogen atmosphere.After stirring 7.5 hours under the room temperature, stopped reaction, filtering reaction mixed solution.With the gained filtrate decompression, and under 40 ℃, concentrate, obtain thick 4-hydroxyl dihydrofuran-2-ketone (compound shown in the formula (2)) 0.83g with liquid form.
Carry out above-mentioned thick 4-hydroxyl dihydrofuran-2-ketone
1When H-NMR analyzes, obtain result shown below.
The yield of 4-hydroxyl dihydrofuran-2-ketone is 72 moles of %, and main by product is dihydrofuran-2-ketone (12 moles of % of yield).
4-hydroxyl dihydrofuran-2-ketone
1H-NMR spectrogram (CDCl
3): δ 2.53 (td, J=1.0,17.9Hz, 1H), 2.76 (dd, J=17.9,6.1Hz, 1H), 4.30 (d, J=10.3Hz, 1H), 4.42 (dd, J=10.3,4.5Hz, 1H), 4.6-4.7 (m, 1H).
(embodiment 2) (adopting palladium carbon catalyst to prepare beta-hydroxy-gamma-butyrolactone)
Except using 10% palladium carbon catalyst (NE-CHEMCAT system): trade(brand)name " PE, 50% moisture product ") 0.105g replaces rhodium-aluminium oxide catalyst, all, obtain the mixture of thick 4-hydroxyl dihydrofuran-2-ketone (compound shown in the formula (2)) and 4-hydroxyl etheric acid lactone according to carrying out with embodiment 1 identical operations.
The yield of 4-hydroxyl dihydrofuran-2-ketone is 2.1 moles of %.
(embodiment 3) (adopting nickel catalyzator to prepare beta-hydroxy-gamma-butyrolactone)
((the Kawaken Fine ChemicalsCo. of fine chemistry company is ground in the river except using sponge nickel catalyst,) system: trade(brand)name " NDHT90-M ") 0.12g replaces outside rhodium-aluminium oxide catalyst, all, obtain the mixture of thick 4-hydroxyl dihydrofuran-2-ketone (compound shown in the formula (2)) and 4-hydroxyl etheric acid lactone according to carrying out with embodiment 1 identical operations.
The yield of 4-hydroxyl dihydrofuran-2-ketone is 0.40 mole of %.
(embodiment 4) (adopting nickel catalyzator to prepare beta-hydroxy-gamma-butyrolactone)
In being the Erlenmeyer flask of 100ml, capacity adds entry 20ml, sodium hydroxide 4.5g, ((the Kawaken Fine Chemicals Co. of fine chemistry company is ground in the river to wherein adding the Ni/Al alloy then,) system: the 1.00g ND type), launched 45 minutes in 100 ℃ of hot water baths.Wash with water then 5 times, with tetrahydrofuran (THF) (THF) washing 1 time.
In the nickel catalyzator that makes like this, add THF, make the slurry that total amount is 1.2g, further add 4-hydroxyl etheric acid lactone 100mg, THF2.0ml, under the hydrogen of 5MPa, in 80 ℃ of reactions 5 hours.Subsequently, make system turn back to room temperature, normal pressure, filter again, concentrate, obtain thick 4-hydroxyl dihydrofuran-2-ketone (compound shown in the formula (2)).The transformation efficiency of 4-hydroxyl etheric acid lactone is 90%, and the selection rate of reaction is 90%.
(embodiment 5) (adopting palladium carbon catalyst to prepare beta-hydroxy-gamma-butyrolactone)
Under 5MPa hydrogen, make 4-hydroxyl etheric acid lactone 50mg, palladium carbon catalyst (NE-CHEMCAT system) 50mg, tetrahydrofuran (THF) (THF) 2.0ml in 50 ℃ of reactions 5 hours.Subsequently, make system turn back to room temperature, normal pressure, filter again, concentrate, obtain thick 4-hydroxyl dihydrofuran-2-ketone (compound shown in the formula (2)).The transformation efficiency of 4-hydroxyl etheric acid lactone is 50%, and the selection rate of reaction is 90%.
Claims (4)
1. the preparation method of a beta-hydroxy-gamma-butyrolactone, this method comprises, by reducing the 4-hydroxyl etheric acid lactone shown in the following formula (1), obtains the beta-hydroxy-gamma-butyrolactone shown in the following formula (2),
[changing 1]
[changing 2]
2. the preparation method of the described beta-hydroxy-gamma-butyrolactone of claim 1 wherein, uses hydrogen as reductive agent.
3. the preparation method of claim 1 or 2 described beta-hydroxy-gamma-butyrolactones wherein, reduces in the presence of catalyzer.
4. the preparation method of the described beta-hydroxy-gamma-butyrolactone of claim 3, wherein, catalyzer is a solid catalyst.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008085485 | 2008-03-28 | ||
| JP085485/08 | 2008-03-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101544623A true CN101544623A (en) | 2009-09-30 |
Family
ID=41051664
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910127443A Pending CN101544623A (en) | 2008-03-28 | 2009-03-11 | Preparing method of beta-hydroxy-gamma-butyrolactone |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP2009256316A (en) |
| CN (1) | CN101544623A (en) |
| DE (1) | DE102009012954A1 (en) |
| TW (1) | TW200948794A (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4968817A (en) | 1984-07-27 | 1990-11-06 | National Distillers And Chemical Corporation | Manufacture of gamma-crotonolactone by carbonylation of glycidol |
| JP3855033B2 (en) | 1995-09-08 | 2006-12-06 | 高砂香料工業株式会社 | Process for producing optically active 3-hydroxy-γ-butyrolactone |
| ES2176756T3 (en) | 1996-07-29 | 2002-12-01 | Warner Lambert Co | PERFECTED PROCESS FOR SYNTHESIS OF THE PROTECTED ESTERS OF THE ACID (S) -3,4-DIHYDROXIBUTIRIC. |
| TW411336B (en) | 1997-12-25 | 2000-11-11 | Mitsubishi Rayon Co | Process for preparing <beta>-hydroxy-<gamma>-butyrolactones and <beta>-(meth)acryloyloxy-<gamma>-butyrolactones |
| JP4598917B2 (en) | 2000-04-28 | 2010-12-15 | ダイセル化学工業株式会社 | Method for producing lactone |
-
2009
- 2009-01-27 JP JP2009015925A patent/JP2009256316A/en active Pending
- 2009-03-11 CN CN200910127443A patent/CN101544623A/en active Pending
- 2009-03-12 DE DE200910012954 patent/DE102009012954A1/en not_active Withdrawn
- 2009-03-26 TW TW98109830A patent/TW200948794A/en unknown
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| Publication number | Publication date |
|---|---|
| JP2009256316A (en) | 2009-11-05 |
| TW200948794A (en) | 2009-12-01 |
| DE102009012954A1 (en) | 2009-10-08 |
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Application publication date: 20090930 |