CN101258139B - Method for preparing 3-hydroxyl phthalic anhydride - Google Patents
Method for preparing 3-hydroxyl phthalic anhydride Download PDFInfo
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- CN101258139B CN101258139B CN2005800515346A CN200580051534A CN101258139B CN 101258139 B CN101258139 B CN 101258139B CN 2005800515346 A CN2005800515346 A CN 2005800515346A CN 200580051534 A CN200580051534 A CN 200580051534A CN 101258139 B CN101258139 B CN 101258139B
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- phthalic anhydride
- hydroxyl phthalic
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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
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
- C07D307/89—Benzo [c] furans; Hydrogenated benzo [c] furans with two oxygen atoms directly attached in positions 1 and 3
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- Furan Compounds (AREA)
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Abstract
A process for producing anhydrous 3-hydroxyphthalic acid of the formula: (2) characterized in that an anhydrous 3-halophthalic acid is reacted with an alkali metal bicarbonate in the presence of a phase-transfer catalyst in an inert solvent. This process is useful as an industrial-scale synthetic process for anhydrous 3-hydroxyphthalic acid.
Description
Technical field
The present invention relates to can be used as heat stable resin raw material such as Resins, epoxy, polyester, polyimide or as the preparation method of the 3-hydroxyl phthalic anhydride of physiologically active substance raw materials such as medicine, agricultural chemicals.
Background technology
The present known example of the preparation method of 3-hydroxyl phthalic, 3-hydroxyl phthalic anhydride seldom, known to following two examples are only arranged.
(1) in the presence of copper catalyst,, generates the method (referring to for example patent documentation 1) of 3-and 4-hydroxyl phthalic with 3-and 4-bromophthalic acid and caustic alkali heat treated.
(2) in the presence of triethylamine; with 2-oxo-2; 5-dihydrofuran and pivalyl chloride reaction generate 2-valeryl oxo furans; affixture with 2-valeryl oxo furans and maleic anhydride uses vitriolization then, thereby generates the method (referring to for example non-patent literature 1) of 3-hydroxyl phthalic anhydride.
Patent documentation 1: No. the 112nd, 706, Israel's patent
Non-patent literature 1:Synthesis, 788 (8) 1985
Summary of the invention
The technical problem that invention will solve
Disclosed method will at high temperature be reacted with strong alkali aqueous solution in the aforementioned background art (1), so do not have in the material of the reactive tank that uses in the technical scale to be suitable for.Therefore, use is unsatisfactory in industrial production.And resulting 3-hydroxyl phthalic is the mixture with isomer 4-hydroxyl phthalic, and the worry of the carboxyl decarboxylation of the raw material bromophthalic acid in the system that responds in addition is also undesirable from this respect.
The method reaction process of record is long in the above-mentioned background technology (2), the industrial advantageous method of can not saying so.Also have the raw material that uses special simultaneously, the cost height is difficult to acquisition and can satisfies shortcomings such as industrial amount.
The means of dealing with problems
For addressing the above problem, the inventor has carried out various researchs, found that the preparation method of 3-hydroxyl phthalic anhydride, it is characterized in that, in inert solvent, in the presence of phase-transfer catalyst, with 3-halophthalic acid acid anhydride and the weak base reaction that is called alkali metal hydrocarbonate.
The invention effect
3-hydroxyl phthalic anhydride of the present invention can be used as heat stable resin raw material such as Resins, epoxy, polyester, polyimide or as physiologically active substance raw materials such as medicine, agricultural chemicals.Preparation method of the present invention is in the presence of a small amount of phase-transfer catalyst, the use cost weak base that is called alkali metal hydrocarbonate cheap, that obtain and can use safely easily, obtaining the 3-hydroxyl phthalic anhydride from 3-halophthalic acid acid anhydride, is very useful.
Embodiment
That is to say, the present invention relates in inert solvent, in the presence of phase-transfer catalyst, the 3-halophthalic acid acid anhydride and the MHCO of through type (1)
3Shown alkali metal hydrocarbonate reaction, wherein M is Na or K, the method for the 3-hydroxyl phthalic anhydride of preparation formula (2),
In the formula, X is the halogen that is selected from F, Cl, Br or I,
Among the preparation method of the present invention, the halogen of the 3-halophthalic acid acid anhydride shown in the general formula (1) can both be with high reactivity hydroxylation no matter be what kind, the 3-hydroxyl phthalic anhydride shown in the acquisition formula (2).Therefore, X be selected from the halogen of F, Cl, Br or I any can, but industrial preferred use cost is cheap, the 3-monochloro phthalic anhydride of easy acquisition.
The form of the alkali metal hydrocarbonate that uses among the present invention both can be that powder also can be granular, but the preferred usually alkali metal hydrocarbonate that uses granularity for the about 300 μ m of about 1-.Specifically, preferred 10～250 μ m of the median size of employed alkali metal hydrocarbonate more preferably below the 150 μ m, are more preferably below the 100 μ m.With respect to 1 moles of halogenated Tetra hydro Phthalic anhydride, the usage quantity of alkali metal hydrocarbonate is 0.8～1.5 mole, preferred 1.0～1.3 moles.
As phase-transfer catalyst of the present invention, so long as the temperature of reaction (170～250 ℃) that sets in the inventive method stable existence down, the compound with phase-transfer catalyst function gets final product, and can use known phase-transfer catalyst, for example, ammonium salt,
Salt, sulfonium salt, crown ether-like etc.The example of spendable ammonium salt has, for example, and tetramethyl ammonium chloride, TPAOH, TBAH, Tetrabutyl amonium bromide, benzyl trimethyl ammonium chloride etc.;
The example of salt has, for example, and tetraphenylphosphonibromide bromide
, tetraphenylphosphonichloride chloride
, tetrabutyl chlorination
Deng; The example of sulfonium salt has sulfonium iodide, triphenyl bromination sulfonium etc.; And the example of crown ether-like has 18-hat-6, dibenzo-18-hat-6 etc.Other examples for compounds with phase-transfer catalyst function also have triphenylphosphine etc., but are not restricted to the compound of being lifted.Among the preparation method of the present invention, preferably use tetraphenylphosphonibromide bromide
, tetraphenylphosphonichloride chloride
Or tetrabutyl chlorination
Deng
Salt, perhaps sulfonium salt such as sulfonium iodide or triphenyl bromination sulfonium.With respect to the halophthalic acid acid anhydride shown in the general formula (1), the consumption of phase-transfer catalyst is 0.1～10 weight %, preferred 0.3～5 weight %.
Use solvent in the reaction.A kind of solvent is usually used in reaction of the present invention, according to circumstances also can use mutual dissolved more than 2 kinds solvent carry out.Use phase-transfer catalyst among the present invention, do not indicate to use two kinds of immiscible each other solvents.The solvent that uses has near the temperature of reaction (170～250 ℃) or surpasses the boiling point of temperature of reaction, should suitably select according to the temperature of reaction of setting.And, employed solvent should not participate in the reaction, that is to say for halophthalic acid acid anhydride, alkali metal hydrocarbonate and phase-transfer catalyst must be do not have active.Such solvent can use the halocarbon solvent, for example, 1,2-dichlorobenzene, 1,2, phenyl polychloride such as 4-trichlorobenzene, 2, many chlorotoluenes such as 3-toluene dichloride.Also can use the polar solvent of the non-proton property of dehydration, for example tetramethylene sulfone, N-N-methyl-2-2-pyrrolidone N-.The polar solvent of these non-proton property both can use separately, also can use the preferred mode of using of mixing with the halocarbon solvent of front.With respect to the 3-halophthalic acid acid anhydride shown in the general formula (1), the usage quantity of solvent is 10～800 weight %, preferred 30～400 weight %.
Reaction of the present invention is undertaken by following process usually: in the solution of the above-mentioned solvent of 3-halophthalic acid acid anhydride, add alkali metal hydrocarbonate and phase-transfer catalyst continuously, the suspension liquid that obtains is stirred the time of setting under the temperature of reaction of setting, finish up to reaction.Specifically, under 170～250 ℃, preferred 200～240 ℃ of temperature, stir and reacted in 1～24 hour, preferred 2～12 hours usually.
After reaction finishes, reaction solution is carried out conventional aftertreatment, separable thus purifying is as the 3-hydroxyl phthalic anhydride of target compound.For example, after reaction finishes, the reaction solution placement is cooled to room temperature, then reaction solution is poured out, solvent is evaporated, can obtain the crude product of 3-hydroxyl phthalic anhydride thus.Crude product both can be directly used in subsequent handling, also can use known means of purification such as extraction, heat filtering, recrystallization to carry out purifying as required.
Embodiment
Below set forth the present invention with specific embodiment, but the present invention is not subjected to the restriction of embodiment content.In addition, the condition determination of the high performance liquid chromatography among the embodiment is as follows.
Instrument kind: the high performance liquid chromatograph SPD-10A that Shimadzu Seisakusho Ltd. makes
Post: ODS-80T (3
* 150mm) 40 ℃
Elutriant: acetonitrile/0.01M disodium-hydrogen 3/7 (volume ratio), pH=2.5
Detect wavelength: 254nm
In addition, said reactivity in this specification sheets, be meant from above-mentioned high performance liquid chromatography measurement result obtained, total peak area (comprises the peak of following reaction product, unreacting material and by product etc., but the peak that does not comprise solvent) account for the ratio of the peak area of the hydroxyl phthalic anhydride shown in the formula (2) as reaction product, represent with percentage.
(embodiment 1)
In four 200ml flasks that agitator, thermometer, distillation prolong, nitrogen input tube are housed, the 3-monochloro phthalic anhydride 54.77g (0.30 mole), 1,2 that packs into, 4-trichlorobenzene 40g is heated to 210 ℃ when stirring under nitrogen gas stream.Then, with Powdered carbonic acid hydrogen sodium 27.72g (0.33 mole) and tetraphenylphosphonibromide bromide by the median size=74 μ m of the size-grade distribution calculating of sieving vibrating machine
1.64g (0.0039 mole) added in the clock time at 40 minutes under nitrogen gas stream in batches.After the adding, suspension liquid is remained on 210 ℃, under agitation reacted 7 hours simultaneously.Extract reaction solution sample, use high-performance liquid chromatogram determination, the result shows that the reactivity of the 3-hydroxyl phthalic anhydride shown in the formula (2) is 84.6%.
(embodiment 2)
Use 3-fluoro Tetra hydro Phthalic anhydride 49.83g (0.30 mole) to replace the 3-monochloro phthalic anhydride, under the reaction conditions identical, operate with example 1.Extract reaction solution sample, use high-performance liquid chromatogram determination, the result shows that the reactivity of the 3-hydroxyl phthalic anhydride shown in the formula (2) is 86.0%.
(embodiment 3)
Use 1,2,4-trichlorobenzene 20g and N-Methyl pyrrolidone 20g be as solvent, operates under the reaction conditions identical with example 1.Extract reaction solution sample, use high-performance liquid chromatogram determination, the result shows that the reactivity of the 3-hydroxyl phthalic anhydride shown in the formula (2) is 83.0%.
(embodiment 4)
Use granular sodium bicarbonate (median size=225 μ m that calculate by the size-grade distribution of sieve vibrating machine) to replace Powdered carbonic acid hydrogen sodium, under the reaction conditions identical, operate with example 1.Supernatant samples is answered in negate, uses high-performance liquid chromatogram determination, and the result shows that the reactivity of the 3-hydroxyl phthalic anhydride shown in the formula (2) is 40.0%.
(Comparative Examples 1)
Except not using tetraphenylphosphonibromide bromide
Under the reaction conditions identical, operate with example 1 outward.Extract reaction solution sample, use high-performance liquid chromatogram determination, the result shows that the reactivity of the 3-hydroxyl phthalic anhydride shown in the formula (2) is 0.3%.
Industrial applicibility
The 3-hydroxyl phthalic anhydride that is obtained by preparation method of the present invention can be used as the heat stable resin raw material such as epoxy resin, polyester, polyimides or as physiological activator raw materials such as medicine, agricultural chemicals. For example, hydroxyl is derived to generate acid anhydrides or its dicarboxylic anhydride for ester group or ether. Particularly, the unsymmetric structure compound separation that preparation method of the present invention will be difficult to synthesize is single product, is very useful from this point.
Claims (5)
1. the method for the 3-hydroxyl phthalic anhydride shown in the preparation formula (2) is characterized in that, in inert solvent, and in the presence of phase-transfer catalyst, 3-halophthalic acid acid anhydride and the MHCO shown in the formula (1)
3Shown alkali metal hydrocarbonate reaction, wherein, M is Na or K,
Wherein X is the halogen that is selected from F, Cl, Br or I.
2. the described method of claim 1, wherein phase-transfer catalyst is
Salt or sulfonium salt.
3. claim 1 or 2 described methods, wherein the median size of supercarbonate is below 100 μ m.
4. claim 1 or 2 described methods, wherein temperature of reaction is 170～250 ℃.
5. the described method of claim 3, wherein temperature of reaction is 170～250 ℃.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2005/017596 WO2007034558A1 (en) | 2005-09-26 | 2005-09-26 | Process for producing anhydrous 3-hydroxyphthalic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101258139A CN101258139A (en) | 2008-09-03 |
| CN101258139B true CN101258139B (en) | 2010-12-22 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2005800515346A Active CN101258139B (en) | 2005-09-26 | 2005-09-26 | Method for preparing 3-hydroxyl phthalic anhydride |
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|---|---|
| JP (1) | JP4871287B2 (en) |
| CN (1) | CN101258139B (en) |
| WO (1) | WO2007034558A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AR103071A1 (en) * | 2014-12-30 | 2017-04-12 | Dow Global Technologies Llc | PROCESS TO PRODUCE 4-AZIDOSULPHONYLPHALL ANHYDRIDE |
| CN105330634A (en) * | 2015-12-07 | 2016-02-17 | 济南轩鸿生物医药有限公司 | One-pot method for preparing 3-hydroxyphtalic anhydride |
| US20220025119A1 (en) | 2020-07-26 | 2022-01-27 | Shenshen Li | Waste mitigation methods and materials |
| CN112390761A (en) * | 2020-11-16 | 2021-02-23 | 常州大学 | Synthetic method of paddy field herbicide pyriminobac-methyl |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IL112706A (en) * | 1995-02-20 | 1998-04-05 | Bromine Compounds Ltd | Process for the preparation of hydroxyphthalic acids by low-temperature hydrolysis of bromophthalic acids |
| CN1246107A (en) * | 1997-12-02 | 2000-03-01 | 玛奈克股有限公司 | Method for preparing oxy-diphthalic anhydrides |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61140578A (en) * | 1984-12-11 | 1986-06-27 | Kawasaki Kasei Chem Ltd | Production of 4-hydroxyphthalic acid anhydride |
| JP3056539B2 (en) * | 1990-06-08 | 2000-06-26 | オクシデンタル ケミカル コーポレイション | Process for preparing oxydiphthalic anhydride and acyloxyphthalic anhydride |
| US6028203A (en) * | 1998-12-14 | 2000-02-22 | General Electric Company | Phase transfer catalyzed method for prepared oxybisphthalic compounds |
| US6727370B1 (en) * | 2003-02-24 | 2004-04-27 | General Electric Company | Method for preparing oxydiphthalic anhydrides using bicarbonate as catalyst |
-
2005
- 2005-09-26 JP JP2007536376A patent/JP4871287B2/en not_active Expired - Fee Related
- 2005-09-26 WO PCT/JP2005/017596 patent/WO2007034558A1/en active Application Filing
- 2005-09-26 CN CN2005800515346A patent/CN101258139B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IL112706A (en) * | 1995-02-20 | 1998-04-05 | Bromine Compounds Ltd | Process for the preparation of hydroxyphthalic acids by low-temperature hydrolysis of bromophthalic acids |
| CN1246107A (en) * | 1997-12-02 | 2000-03-01 | 玛奈克股有限公司 | Method for preparing oxy-diphthalic anhydrides |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4871287B2 (en) | 2012-02-08 |
| WO2007034558A1 (en) | 2007-03-29 |
| JPWO2007034558A1 (en) | 2009-03-19 |
| CN101258139A (en) | 2008-09-03 |
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