WO2010013620A1 - Process for producing phthalic anhydride derivative - Google Patents
Process for producing phthalic anhydride derivative Download PDFInfo
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- WO2010013620A1 WO2010013620A1 PCT/JP2009/063080 JP2009063080W WO2010013620A1 WO 2010013620 A1 WO2010013620 A1 WO 2010013620A1 JP 2009063080 W JP2009063080 W JP 2009063080W WO 2010013620 A1 WO2010013620 A1 WO 2010013620A1
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- phthalic anhydride
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- general formula
- acid
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- 0 CC1CC(C*)CC1 Chemical compound CC1CC(C*)CC1 0.000 description 2
- RBIDPZJTXCPESJ-UHFFFAOYSA-N Cc(cc1)ccc1-c1cc(C)ccc1 Chemical compound Cc(cc1)ccc1-c1cc(C)ccc1 RBIDPZJTXCPESJ-UHFFFAOYSA-N 0.000 description 1
- RZTDESRVPFKCBH-UHFFFAOYSA-N Cc(cc1)ccc1-c1ccc(C)cc1 Chemical compound Cc(cc1)ccc1-c1ccc(C)cc1 RZTDESRVPFKCBH-UHFFFAOYSA-N 0.000 description 1
- YWYHGNUFMPSTTR-UHFFFAOYSA-N Cc(cc1)ccc1Oc1ccc(C)cc1 Chemical compound Cc(cc1)ccc1Oc1ccc(C)cc1 YWYHGNUFMPSTTR-UHFFFAOYSA-N 0.000 description 1
- ABMKWMASVFVTMD-UHFFFAOYSA-N Cc1ccccc1-c1ccccc1C Chemical compound Cc1ccccc1-c1ccccc1C ABMKWMASVFVTMD-UHFFFAOYSA-N 0.000 description 1
- CYXMOAZSOPXQOD-UHFFFAOYSA-N Cc1ccccc1Oc1ccccc1C Chemical compound Cc1ccccc1Oc1ccccc1C CYXMOAZSOPXQOD-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
Definitions
- the present invention is a phthalic anhydride derivative useful as a raw material of a heat-resistant resin such as a polyesterimide resin or polyimide, a curing agent such as an epoxy resin, or a resin modifier, particularly an ester group-containing phthalic anhydride derivative or an ethynyl group
- a heat-resistant resin such as a polyesterimide resin or polyimide
- a curing agent such as an epoxy resin
- a resin modifier particularly an ester group-containing phthalic anhydride derivative or an ethynyl group
- the present invention relates to a method for producing a phthalic anhydride derivative.
- the present invention also relates to a method for purifying a phthalic anhydride derivative.
- An ester group-containing phthalic anhydride derivative is useful as a raw material for heat-resistant resins such as a polyesterimide resin, a curing agent such as an epoxy resin, or a resin modifier.
- a method for producing it for example, (1) benzene, Method by reaction of trimellitic anhydride chloride with phenols or diols in an organic solvent such as toluene (see, for example, Patent Document 1), (2) Heating trimellitic anhydride and phenols at 250 to 300 ° C (3) transesterification of trimellitic anhydride with a lower alkanoic acid ester of a phenol in the presence of an inorganic compound such as a silica / alumina compound as a catalyst. (For example, see Patent Document 2) or a method performed in the presence of a specific solvent (for example, see Patent Document 3) Such as are known.
- the ethynyl group-containing phthalic anhydride derivative is extremely useful as a raw material for providing a material having adhesiveness, heat resistance and mechanical strength required in the polyimide field.
- a method for producing an ethynyl group-containing phthalic anhydride derivative for example, phenylethynyl phthalic anhydride, a method is known in which ethynylbenzene and bromophthalic anhydride are reacted in the presence of a large excess of a basic organic substance. (For example, refer nonpatent literature 2). JP 2005-298623 A JP-A-7-41472 Japanese Patent Laid-Open No. 10-147582 J. Polym. Sci., Vol 4, 1531-41, Part A, (1966) Highperform. Polym. Vol. 6, 423 (1994)
- Patent Document 1 In the method disclosed in Patent Document 1 cited in the background art, after the reaction of trimellitic anhydride chloride and phenols in the presence of a basic substance, the hydrohalide salt of the basic substance produced as a by-product is treated with water. Is removed. At this time, since a part of the phthalic anhydride skeleton of the reaction product undergoes hydrolysis and ring-opening, reclosing with acetic anhydride is necessary.
- the method disclosed in Patent Document 2 using an inorganic catalyst has a problem that it is difficult to remove the inorganic catalyst to be used, and the resulting ester group-containing phthalic anhydride derivative is likely to be an impurity.
- Non-Patent Document 2 is a method in which ethynylbenzene and bromophthalic anhydride are reacted in the presence of a large excess of a basic organic substance, and then by-produced hydrobromic acid. The salt is removed and the resulting reaction product is crystallized in water. At this time, as described above, a part of the phthalic anhydride skeleton undergoes hydrolysis to open a ring, and thus re-ring closure by heat is necessary.
- the present invention provides a method for efficiently producing a phthalic anhydride derivative without opening the phthalic anhydride skeleton. Similarly, a method for efficiently purifying a phthalic anhydride derivative without opening the phthalic anhydride skeleton is also provided.
- the present inventor has conducted various studies to solve the above problems, and in the presence of a basic substance, an organic halide containing a phthalic anhydride skeleton and an organic proton donor are reacted to produce phthalic anhydride.
- an organic halide containing a phthalic anhydride skeleton and an organic proton donor are reacted to produce phthalic anhydride.
- a hydrohalic acid salt of a basic substance as a by-product with an organic acid
- phthalic anhydride is obtained without ring-opening the phthalic anhydride skeleton of the obtained product. It has been found that derivatives can be produced efficiently.
- the present inventor is a method for purifying a phthalic anhydride derivative obtained by reacting an organic halide containing a phthalic anhydride skeleton with an organic proton donor in the presence of a basic substance, comprising: It was found that the phthalic anhydride derivative can be efficiently purified without dissolving the phthalic anhydride skeleton of the product by dissolving and removing the resulting hydrohalic acid salt of the basic substance with an organic acid.
- the phthalic anhydride derivatives of the present invention are raw materials for heat-resistant resins such as polyesterimide resins, curing agents such as epoxy resins, or resin modifiers.
- used as The method for producing a phthalic anhydride derivative according to the present invention does not have the problem of requiring ring opening by hydrolysis of the phthalic anhydride skeleton and the need for a re-ring closing step as in the prior art, and requires a special solvent or catalyst. It is useful because it can be efficiently produced by a simple method.
- the present invention is a method for producing a phthalic anhydride derivative by reacting an organic halide containing a phthalic anhydride skeleton with an organic proton donor in the presence of a basic substance, wherein
- the present invention relates to a method comprising dissolving and removing a hydrohalide salt of a substance with an organic acid.
- a typical first aspect of the present invention is an organic proton donor represented by the general formula (1):
- Ar 1 represents the following formula (2):
- a divalent aromatic group selected from the group consisting of R 1 and R 2 are the same or different and are hydrogen or an alkyl group having 1 to 4 carbon atoms)
- trimellitic anhydride represented by general formula (4) in the presence of a basic substance:
- a typical second embodiment of the present invention is an organic proton donor, represented by the general formula (5):
- Ar 2 represents the following formula (6):
- General formula (7) which is an organic halide containing a phthalic anhydride skeleton:
- the ethynyl group-containing phthalic anhydride derivative represented by the formula (1) is a method comprising the step of dissolving and removing a by-product basic hydrohalide salt with an organic acid.
- the organic acid is preferably selected from the group consisting of formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, and mixtures thereof.
- the basic substance is a trialkylamine and / or a pyridine derivative.
- the present invention is also a method for purifying a phthalic anhydride derivative obtained by reacting an organic halide containing a phthalic anhydride skeleton with an organic proton donor in the presence of a basic substance, which comprises a by-product base.
- the present invention relates to a method comprising the step of dissolving and removing a hydrohalic acid salt of an organic substance with an organic acid.
- the method of the present invention is a method for producing a phthalic anhydride derivative.
- a basic hydrohalide salt is by-produced and a derivative containing a phthalic anhydride skeleton (ie, a phthalic anhydride derivative) is obtained as a final product.
- a derivative containing a phthalic anhydride skeleton ie, a phthalic anhydride derivative
- the organic halide containing a phthalic anhydride skeleton represented by the general formula (II) includes a halogenated phthalic anhydride in which Y 1 is a direct bond; or Y 1 is — And trimellitic anhydride halide which is O-.
- the trimellitic anhydride halide represented by the general formula (3) or the halogenated phthalic anhydride represented by the general formula (7) is preferable.
- trimellitic anhydride halide represented by the general formula (3) examples include trimellitic anhydride chloride, trimellitic anhydride bromide, trimellitic anhydride iodide and the like, but trimellitic anhydride chloride is preferable.
- halogenated phthalic anhydride represented by the general formula (7) examples include chlorophthalic anhydride, bromophthalic anhydride, and iodophthalic anhydride, and bromophthalic anhydride is preferable.
- the organic proton donor represented by the general formula (III) is an aromatic hydroxy compound in which n is 1 and Y 2 is —O—;
- An aromatic alkenylene or alkynylene compound wherein Y 2 is an alkenylene or alkynylene having 2 to 4 carbon atoms eg ethenylene, propenylene or 1- or 2-butenylene, or ethynylene, propynylene or 1- or 2-butynylene
- Y 1 is —C (O) —
- Y 2 is —O—.
- the organic proton donor represented by the general formula (III) is an aromatic hydroxy compound or aromatic Means a group diol compound.
- the organic proton donor represented by the general formula (III) is preferably an aromatic diol compound represented by the general formula (1) or an aromatic ethynyl compound represented by the general formula (5).
- R 1 and R 2 are hydrogen or a linear or branched alkyl group having 1 to 4 carbon atoms such as methyl , Ethyl, propyl, isopropyl, butyl, t-butyl.
- Preferred aromatic diol compounds include hydroquinone, resorcinol, pyrocatechol, 4,4′-biphenyldiol, 2,2′-biphenyldiol, 3,4′-biphenyldiol, R 1 and R 2 are hydrogen, , 4′-dihydroxydiphenyl ether, 2,2′-dihydroxydiphenyl ether, and the like.
- R 1 and R 2 are hydrogen or a linear or branched alkyl group having 1 to 4 carbon atoms such as methyl, Those which are ethyl, propyl, isopropyl, butyl, t-butyl.
- ethynyl benzene, ethynyl biphenyl, ethynyl biphenyl ether, ethynyl phthalic anhydride, etc., in which R 1 and R 2 are hydrogen are exemplified.
- the production of the phthalic anhydride derivative of the present invention is carried out by reacting an organic halide containing a phthalic anhydride skeleton with an organic proton donor in the presence of a basic substance.
- the reaction conditions may be appropriately set according to the ordinary knowledge of those skilled in the art depending on the starting materials and basic materials used.
- the reaction conditions in representative embodiments of the present invention are outlined below, but the present invention is not limited to these.
- the ester group-containing phthalic anhydride derivative represented by the general formula (4) is produced in the presence of a basic substance with respect to 2 moles of trimellitic anhydride.
- the reaction is carried out by reacting an aromatic diol compound in an amount of 0.95 to 1.50 mol.
- Such a reaction is preferably carried out in a solvent, particularly in a non-aqueous solvent.
- Solvents that can be used are not particularly limited, but acetonitrile, tetrahydrofuran, 1,4-dioxane, picoline, pyridine, chloroform, toluene, xylene, dichloromethane, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N , N-dimethylacetamide, N, N-diethylacetamide, dimethyl sulfoxide, ⁇ -butyrolactone, and the like. These solvents may be used alone or in combination of two or more.
- Such a reaction is usually performed at ⁇ 10 to 50 ° C., preferably 0 to 30 ° C.
- the reaction temperature is higher than 50 ° C., a side reaction occurs partially, which causes a decrease in yield, which is not preferable.
- the basic substance used in such a reaction is not particularly limited, but tri (C 1-6 -alkyl) amine such as trimethylamine, triethylamine, diisopropylmethylamine, or pyridine, methylpyridine, N, N-dimethylamino- Examples include pyridine derivatives such as 4-pyridine.
- the basic substances may be used alone or in combination of two or more.
- the amount used is equimolar or more, preferably 1.1 to 3.0 times the molar amount of trimellitic anhydride, so that the ester group-containing phthalic anhydride derivative represented by the general formula (4) can be obtained. Obtained with high purity.
- the organic acid that dissolves and removes the basic hydrohalide salt as a by-product is a linear or branched alkanoic acid having 1 to 4 carbon atoms, preferably formic acid, acetic acid, Although propionic acid, butyric acid or isobutyric acid can be mentioned, it is preferable to use acetic acid for economic reasons.
- the amount used is equimolar or more, preferably 1.0 to 2.0 times the molar amount of the basic substance.
- the method for dissolving and removing may be selected by those skilled in the art depending on the properties of the starting material, reaction product, and by-product basic material such as hydrohalide.
- by-product basic material such as hydrohalide.
- the organic acid is added directly to the reaction system, or the precipitate is filtered off, By washing this with an organic acid, only the basic substance can be dissolved and removed, and the target product can be isolated.
- “by-product basic hydrohalide is dissolved and removed with an organic acid” means about 90 of the theoretical amount (weight) of by-product basic hydrohalide.
- phthalic anhydride derivatives particularly ester group-containing phthalic anhydride derivatives represented by the general formula (4) of the present invention are hardly soluble or substantially insoluble in organic acids. Therefore, this allows the ester group-containing phthalic anhydride derivative represented by the general formula (4) of the present invention to be about 90% or more, preferably 95% or more, more preferably 99% without opening the phthalic anhydride skeleton. % Or higher purity.
- an ethynyl group-containing phthalic anhydride derivative represented by the general formula (8) of the present invention is generally performed with an aromatic ethynyl compound represented by the general formula (5).
- the halogenated phthalic anhydride represented by the formula (7) is preferably reacted in the presence of a basic substance at 50 to 130 ° C., preferably around 60 to 100 ° C.
- the basic substance used in such a reaction is not particularly limited, but tri (C 1-6 -alkyl) amine such as trimethylamine, triethylamine, diisopropylmethylamine, or pyridine, methylpyridine, N, N-dimethylamino- Examples include pyridine derivatives such as 4-pyridine.
- the basic substances may be used alone or in combination of two or more.
- the amount used is equimolar or more, preferably 1.1 to 3.0 times the molar amount of the halogenated phthalic anhydride.
- Such a reaction is preferably carried out in a solvent, particularly in a non-aqueous solvent.
- Solvents that can be used are not particularly limited, but acetonitrile, tetrahydrofuran, 1,4-dioxane, picoline, pyridine, chloroform, toluene, xylene, dichloromethane, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N , N-dimethylacetamide, N, N-diethylacetamide, dimethyl sulfoxide, ⁇ -butyrolactone, and the like. These solvents may be used alone or in combination of two or more.
- Such a reaction is preferably carried out in the presence of a catalyst.
- the catalyst used is, for example, a divalent or zero-valent palladium complex, and a suitable one is represented by general formula (9) or general formula (10).
- Y includes, for example, chlorine, bromine or iodine atom, or R 3 COO—.
- R 3 is a linear or branched alkyl group having 1 to 4 carbon atoms.
- L include a ligand containing each atom of P, As, and Sb. Specific examples include (R 4 ) 3 P.
- R 4 is aryl optionally substituted with an alkyl group having 1 to 8 carbon atoms. Examples include bis (triphenylphosphine) dichloropalladium (II), tetrakis (triphenylphosphine) palladium (0), and the like.
- the compound which substituted P atom by As atom and Sb atom can also be mentioned.
- the palladium complex represented by the general formula (9) a mixture of the compound represented by PdY 2 and the ligand L may be used.
- copper halide can also be used as a co-catalyst. When used, the reaction can proceed smoothly. However, when these are used with an ethynyl compound, it may react with copper to form an explosive unstable compound, copper acetylide. Care must be taken when using copper chloride. Examples of the copper halide include copper chloride, copper bromide, and copper iodide, with copper iodide being preferred.
- the by-product basic hydrohalide salt is dissolved and removed using an organic acid in the same manner as in the production of the ester group-containing phthalic anhydride derivative represented by the general formula (4).
- the organic acid include linear or branched alkanoic acids having 1 to 4 carbon atoms, preferably formic acid, acetic acid, propionic acid, butyric acid or isobutyric acid.
- acetic acid is used. It is preferred to use.
- the amount used is equimolar or more, preferably 1.0 to 2.0 times the molar amount of the basic substance.
- the method for dissolving and removing may be selected by those skilled in the art depending on the properties of the starting material, reaction product, and by-product basic substance hydrohalide.
- the organic acid is added directly to the reaction system, or the precipitate is filtered off, By washing this with an organic acid, only the basic substance can be dissolved and removed, and the target product can be isolated.
- “by-product basic hydrohalide is dissolved and removed with an organic acid” means about 90 of the theoretical amount (weight) of by-product basic hydrohalide. % Or more, preferably 95% or more, more preferably 99% or more is dissolved in an organic acid by the method as described above and removed.
- phthalic anhydride derivatives particularly ethynyl group-containing phthalic anhydride derivatives represented by the general formula (8) of the present invention are hardly soluble or substantially insoluble in organic acids. Therefore, this allows the ethynyl group-containing phthalic anhydride derivative represented by the general formula (8) of the present invention to be about 90% or more, preferably 95% or more, more preferably 99% without opening the phthalic anhydride skeleton. % Or higher purity.
- the present invention is a method of purifying a phthalic anhydride derivative obtained by reacting an organic halide containing a phthalic anhydride skeleton with an organic proton donor in the presence of a basic substance, It can be said that the method includes a step of dissolving and removing the hydrohalic acid salt of the basic substance by-produced with an organic acid.
- Examples of such “basic substances”, “organic halides containing a phthalic anhydride skeleton”, “organic proton donors”, and “phthalic anhydride derivatives” in this method, and preferred implementation conditions are as described above. .
- Example 1 In a 500 mL four-necked flask equipped with a stirrer, thermometer, upward reflux tube, and nitrogen gas introduction tube, hydroquinone 22.0 g (0.20 mol), pyridine 47.5 g (0.60 mol), N, N -100 g of dimethylformamide was charged and dissolved in a nitrogen atmosphere with stirring. After cooling to 0 ° C., a solution prepared by dissolving 84.2 g (0.40 mol) of trimellitic anhydride chloride in 200 g of N, N-dimethylformamide was reacted while dropping dropwise at 0 to 10 ° C. in a nitrogen atmosphere. .
- Example 2 Using 37.2 g (0.20 mol) of 4,4′-biphenol in place of hydroquinone, the same operation as in Example 1 was carried out, and it was confirmed that no pyridine derived from pyridine hydrochloride was contained in the product. This was confirmed by liquid chromatography measurement. The purity of the target product, 4,4′-bis (trimellitic acid ester anhydride) biphenyl, was 96.2%.
- Example 3 In a 500 mL four-necked flask equipped with a stirrer, thermometer, upward reflux tube and nitrogen gas introduction tube, 68.1 g (0.30 mol) of 4-bromophthalic anhydride, 100 g of toluene, 36.4 g of triethylamine (0 .36 mol) and 0.31 g (0.45 ⁇ 10 ⁇ 3 mol) of bistriphenylphosphine dichloropalladium were charged and heated to 80 ° C. Next, 30.6 g (0.30 mol) of phenylacetylene was reacted while being dropped. After dropping, the mixture was aged for 15 hours.
- the precipitated phenylethynylphthalic anhydride and triethylamine hydrochloride were solid-liquid separated and washed with 40 g of propionic acid to dissolve and remove the triethylamine hydrochloride. It was confirmed by NMR measurement that the product did not contain triethylamine derived from triethylamine hydrochloride. The purity of the target phenylethynyl phthalic anhydride was 97.8%.
- the phthalic anhydride derivative obtained by the production method of the present invention in particular, an ester group-containing phthalic anhydride derivative, an ethynyl group-containing phthalic anhydride derivative, can be used as a curing agent, a modifier, such as a polyesterimide resin raw material, an epoxy resin, It is particularly useful as a low water absorption polyesterimide raw material and heat resistant material.
- a modifier such as a polyesterimide resin raw material, an epoxy resin
- the present invention provides a very useful production method that can efficiently remove by-products without ring-opening the phthalic anhydride skeleton. It is to provide.
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Abstract
Description
で表される無水フタル酸骨格を含む有機ハロゲン化物と、下記一般式(III):
nが1である場合、
Arは、下記式:
nが2である場合、
Arは、下記式:
ただし、Y1が-C(O)-である場合、Y2は、-O-である〕
で表される有機プロトン供与体とを反応させて、下記一般式(I):
で表される無水フタル酸誘導体を製造する方法であって、副生する塩基性物質のハロゲン化水素酸塩:B・HXを有機酸で溶解除去する工程を含むことを特徴とする方法に関する。 In a more specific embodiment of the present invention, in the presence of the basic substance B, the following general formula (II):
An organic halide containing a phthalic anhydride skeleton represented by the following general formula (III):
When n is 1,
Ar is represented by the following formula:
If n is 2,
Ar is represented by the following formula:
However, when Y 1 is —C (O) —, Y 2 is —O—.]
Is reacted with an organic proton donor represented by the following general formula (I):
The method further comprises a step of dissolving and removing a hydrohalic acid salt B: HX as a by-product basic substance with an organic acid.
で表される芳香族ジオール化合物と、無水フタル酸骨格を含む有機ハロゲン化物である一般式(3):
And an organic halide containing a phthalic anhydride skeleton represented by the general formula (3):
で表される無水トリメリット酸ハライドとを塩基性物質の存在下に反応させて、一般式(4):
Is reacted with trimellitic anhydride represented by general formula (4) in the presence of a basic substance:
で示されるエステル基含有無水フタル酸誘導体を製造する方法であって、副生する塩基性物質のハロゲン化水素酸塩を有機酸で溶解除去する工程を含む方法に関する。
It is related with the method of manufacturing the ester group containing phthalic anhydride derivative shown by these, Comprising: Dissolving and removing the hydrohalic acid salt of the basic substance byproduced with an organic acid.
で表されるハロゲン化無水フタル酸とを塩基性物質の存在下に反応させて、一般式(8):
Is reacted with a halogenated phthalic anhydride represented by the general formula (8):
で示されるエチニル基含有無水フタル酸誘導体を製造する方法であって、副生する塩基性物質のハロゲン化水素酸塩を有機酸で溶解除去する工程を含む方法に関する。
The ethynyl group-containing phthalic anhydride derivative represented by the formula (1) is a method comprising the step of dissolving and removing a by-product basic hydrohalide salt with an organic acid.
塩基性物質のハロゲン化水素酸塩由来の残存塩基性物質は、高速液体クロマトグラフィー及びNMR測定により確認した。
高速液体クロマトグラフィー測定
機種:島津製作所製高速液体クロマトグラフィー SPD-10A
カラム:ODS-80T (3φ×150mm) 40℃
溶離液:アセトニトリル:水:燐酸=400:600:0.5(容量比)
検出波長:254nm
NMR測定
機種:日本電子データム製 JEOL FT-NMR400 Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the contents of the examples. In addition, the purity in an Example was measured by the high performance liquid chromatography.
The remaining basic substance derived from the basic hydrohalide was confirmed by high performance liquid chromatography and NMR measurement.
High-performance liquid chromatography measurement Model: High-performance liquid chromatography SPD-10A manufactured by Shimadzu Corporation
Column: ODS-80T (3φ × 150mm) 40 ° C
Eluent: acetonitrile: water: phosphoric acid = 400: 600: 0.5 (volume ratio)
Detection wavelength: 254 nm
NMR measurement Model: JEOL FT-NMR400 manufactured by JEOL Datum
撹拌機、温度計、上向き還流管、窒素ガス導入管を付けた500mLの四つ口フラスコに、ハイドロキノン22.0g(0.20モル)、ピリジン47.5g(0.60モル)、N,N-ジメチルホルムアミド100gを仕込み、攪拌しながら窒素雰囲気下で溶解させた。0℃に冷却後、N,N-ジメチルホルムアミド200g中に無水トリメリット酸クロリド84.2g(0.40モル)を溶解させた溶液を、窒素雰囲気下0~10℃で滴下しながら反応させた。反応後、析出した1,4-ビス(トリメリト酸エステル酸無水物)ベンゼン及びピリジン塩酸塩を固液分離し、酢酸54gで洗浄して、ピリジン塩酸塩を溶解除去した。生成物中にピリジン塩酸塩由来のピリジンが含まれないことを、高速液体クロマトグラフィー測定で確認した。目的物である1,4-ビス(トリメリト酸エステル酸無水物)ベンゼンの純度は、95.3%であった。 (Example 1)
In a 500 mL four-necked flask equipped with a stirrer, thermometer, upward reflux tube, and nitrogen gas introduction tube, hydroquinone 22.0 g (0.20 mol), pyridine 47.5 g (0.60 mol), N, N -100 g of dimethylformamide was charged and dissolved in a nitrogen atmosphere with stirring. After cooling to 0 ° C., a solution prepared by dissolving 84.2 g (0.40 mol) of trimellitic anhydride chloride in 200 g of N, N-dimethylformamide was reacted while dropping dropwise at 0 to 10 ° C. in a nitrogen atmosphere. . After the reaction, precipitated 1,4-bis (trimellitic acid ester anhydride) benzene and pyridine hydrochloride were separated into solid and liquid and washed with 54 g of acetic acid to dissolve and remove pyridine hydrochloride. It was confirmed by high performance liquid chromatography measurement that pyridine derived from pyridine hydrochloride was not contained in the product. The purity of 1,4-bis (trimellitic acid ester anhydride) benzene, which is the target product, was 95.3%.
ハイドロキノンの代わりに4,4’-ビフェノール37.2g(0.20モル)を使用し、例1と同様の操作を行い、生成物中にピリジン塩酸塩由来のピリジンが含まれないことを、高速液体クロマトグラフィー測定で確認した。目的物である4,4’-ビス(トリメリト酸エステル酸無水物)ビフェニルの純度は、96.2%であった。 (Example 2)
Using 37.2 g (0.20 mol) of 4,4′-biphenol in place of hydroquinone, the same operation as in Example 1 was carried out, and it was confirmed that no pyridine derived from pyridine hydrochloride was contained in the product. This was confirmed by liquid chromatography measurement. The purity of the target product, 4,4′-bis (trimellitic acid ester anhydride) biphenyl, was 96.2%.
撹拌機、温度計、上向き還流管、窒素ガス導入管を付けた500mLの四つ口フラスコに、4-ブロモ無水フタル酸68.1g(0.30モル)、トルエン100g、トリエチルアミン36.4g(0.36モル)、ビストリフェニルホスフィンジクロロパラジウム0.31g(0.45×10-3モル)を仕込み、80℃に加熱した。次に、フェニルアセチレン30.6g(0.30モル)を滴下しながら反応させた。滴下後、15時間熟成させた。析出するフェニルエチニルフタル酸無水物及びトリエチルアミン塩酸塩を固液分離し、プロピオン酸40gで洗浄して、トリエチルアミン塩酸塩を溶解除去した。生成物中にトリエチルアミン塩酸塩由来のトリエチルアミンが含まれないことを、NMR測定で確認した。目的物であるフェニルエチニルフタル酸無水物の純度は、97.8%であった。 (Example 3)
In a 500 mL four-necked flask equipped with a stirrer, thermometer, upward reflux tube and nitrogen gas introduction tube, 68.1 g (0.30 mol) of 4-bromophthalic anhydride, 100 g of toluene, 36.4 g of triethylamine (0 .36 mol) and 0.31 g (0.45 × 10 −3 mol) of bistriphenylphosphine dichloropalladium were charged and heated to 80 ° C. Next, 30.6 g (0.30 mol) of phenylacetylene was reacted while being dropped. After dropping, the mixture was aged for 15 hours. The precipitated phenylethynylphthalic anhydride and triethylamine hydrochloride were solid-liquid separated and washed with 40 g of propionic acid to dissolve and remove the triethylamine hydrochloride. It was confirmed by NMR measurement that the product did not contain triethylamine derived from triethylamine hydrochloride. The purity of the target phenylethynyl phthalic anhydride was 97.8%.
Claims (7)
- 塩基性物質の存在下、無水フタル酸骨格を含む有機ハロゲン化物と有機プロトン供与体とを反応させて、無水フタル酸誘導体を製造する方法において、副生する塩基性物質のハロゲン化水素酸塩を有機酸で溶解除去する工程を含むことを特徴とする、方法。 In a method for producing a phthalic anhydride derivative by reacting an organic halide containing a phthalic anhydride skeleton with an organic proton donor in the presence of a basic substance, A method comprising dissolving and removing with an organic acid.
- 塩基性物質Bの存在下、下記一般式(II):
で表される無水フタル酸骨格を含む有機ハロゲン化物と、下記一般式(III):
nが1である場合、
Arは、下記式:
nが2である場合、
Arは、下記式:
ただし、Y1が-C(O)-である場合、Y2は、-O-である〕
で表される有機プロトン供与体とを反応させて、下記一般式(I):
で表される無水フタル酸誘導体を製造する方法において、副生する塩基性物質のハロゲン化水素酸塩:B・HXを有機酸で溶解除去する工程を含むことを特徴とする、方法。 In the presence of the basic substance B, the following general formula (II):
An organic halide containing a phthalic anhydride skeleton represented by the following general formula (III):
When n is 1,
Ar is represented by the following formula:
If n is 2,
Ar is represented by the following formula:
However, when Y 1 is —C (O) —, Y 2 is —O—.]
Is reacted with an organic proton donor represented by the following general formula (I):
A method for producing a phthalic anhydride derivative represented by formula (1), comprising a step of dissolving and removing a hydrohalide salt of B: HX as a by-product with an organic acid. - 有機プロトン供与体が、一般式(1):
で表される芳香族ジオール化合物であり、無水フタル酸骨格を含む有機ハロゲン化物が、一般式(3):
で表される無水トリメリット酸ハライドであり、そして得られる無水フタル酸誘導体が、一般式(4):
で表されるエステル基含有無水フタル酸誘導体である、請求項1または2に記載の方法。 The organic proton donor is represented by the general formula (1):
An organic halide having a phthalic anhydride skeleton represented by the general formula (3):
And the resulting phthalic anhydride derivative is represented by the general formula (4):
The method of Claim 1 or 2 which is an ester group containing phthalic anhydride derivative represented by these. - 有機プロトン供与体が、一般式(5):
で表される芳香族エチニル化合物であり、無水フタル酸骨格を含む有機ハロゲン化物が、一般式(7):
で表されるハロゲン化無水フタル酸であり、そして得られる無水フタル酸誘導体が、一般式(8):
で表されるエチニル基含有無水フタル酸誘導体である、請求項1または2に記載の方法。 The organic proton donor is represented by the general formula (5):
And an organic halide containing a phthalic anhydride skeleton is represented by the general formula (7):
And the resulting phthalic anhydride derivative is represented by the general formula (8):
The method of Claim 1 or 2 which is an ethynyl group containing phthalic anhydride derivative represented by these. - 有機酸が、ギ酸、酢酸、プロピオン酸、酪酸、イソ酪酸およびこれらの混合物よりなる群から選ばれる、請求項1~4のいずれか1項に記載の方法。 The method according to any one of claims 1 to 4, wherein the organic acid is selected from the group consisting of formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, and a mixture thereof.
- 塩基性物質が、トリアルキルアミンおよび/またはピリジン誘導体である、請求項1~5のいずれか1項に記載の方法。 The method according to any one of claims 1 to 5, wherein the basic substance is a trialkylamine and / or a pyridine derivative.
- 塩基性物質の存在下、無水フタル酸骨格を含む有機ハロゲン化物と有機プロトン供与体とを反応させることにより得られる無水フタル酸誘導体とを精製する方法であって、副生する塩基性物質のハロゲン化水素酸塩を有機酸で溶解除去する工程を含むことを特徴とする、方法。 A method for purifying a phthalic anhydride derivative obtained by reacting an organic halide containing a phthalic anhydride skeleton with an organic proton donor in the presence of a basic substance, wherein A method comprising dissolving and removing a hydride salt with an organic acid.
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2011057621A (en) * | 2009-09-10 | 2011-03-24 | Air Water Inc | Method for producing diester of trimellitic anhydride |
JP2013528573A (en) * | 2010-04-16 | 2013-07-11 | ネクサム ケミカル エイビー | New crosslinker |
KR20150015466A (en) * | 2012-04-20 | 2015-02-10 | 넥삼 케미컬 에이비 | PROCESS FOR PRODUCING (ETHYNE-l,2-DIYL)BIS(ISOBENZOFURAN-l,3-DIONE) |
WO2015125734A1 (en) * | 2014-02-24 | 2015-08-27 | マナック株式会社 | Halohexahydrophthalic acid derivative |
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CN115301287B (en) * | 2022-08-22 | 2023-11-10 | 天津众泰材料科技有限公司 | Preparation method of high-purity p-phenylene-bis (trimellitate) dianhydride |
CN115583928A (en) * | 2022-09-27 | 2023-01-10 | 南京大学 | Preparation method of phthalic anhydride derivative |
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JPH04208279A (en) * | 1990-11-30 | 1992-07-29 | Honsyu Kagaku Kogyo Kk | Production of bistrimellitic anhydride bisphenol ester |
JPH0853436A (en) * | 1994-08-11 | 1996-02-27 | Honshu Chem Ind Co Ltd | Production of trimellitate anhydrides |
JP2003073372A (en) * | 2001-08-30 | 2003-03-12 | Manac Inc | Method for producing phenylethynyl phthalic anhydride derivative |
JP2008063247A (en) * | 2006-09-05 | 2008-03-21 | Manac Inc | Ester group-containing tetracarboxylic acid derivative and method for producing the same |
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CN1257898C (en) * | 2003-11-27 | 2006-05-31 | 中国科学院长春应用化学研究所 | 4-phenylacetylene benzoic anhydride preparation method |
JP4574403B2 (en) * | 2004-03-25 | 2010-11-04 | 富士フイルム株式会社 | Arylethynylphthalic acid derivative and method for producing the same |
CN1312145C (en) * | 2004-08-03 | 2007-04-25 | 上海市合成树脂研究所 | Process for preparation of 4-phenylacetylene phthalic anhydride |
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JPH04208279A (en) * | 1990-11-30 | 1992-07-29 | Honsyu Kagaku Kogyo Kk | Production of bistrimellitic anhydride bisphenol ester |
JPH0853436A (en) * | 1994-08-11 | 1996-02-27 | Honshu Chem Ind Co Ltd | Production of trimellitate anhydrides |
JP2003073372A (en) * | 2001-08-30 | 2003-03-12 | Manac Inc | Method for producing phenylethynyl phthalic anhydride derivative |
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Cited By (6)
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JP2011057621A (en) * | 2009-09-10 | 2011-03-24 | Air Water Inc | Method for producing diester of trimellitic anhydride |
JP2013528573A (en) * | 2010-04-16 | 2013-07-11 | ネクサム ケミカル エイビー | New crosslinker |
KR20150015466A (en) * | 2012-04-20 | 2015-02-10 | 넥삼 케미컬 에이비 | PROCESS FOR PRODUCING (ETHYNE-l,2-DIYL)BIS(ISOBENZOFURAN-l,3-DIONE) |
JP2015514730A (en) * | 2012-04-20 | 2015-05-21 | ネクサム ケミカル エイビー | Method for producing (ethyne-1,2-diyl) bis (isobenzofuran-1,3-dione) |
KR102081717B1 (en) * | 2012-04-20 | 2020-02-26 | 넥삼 케미컬 에이비 | PROCESS FOR PRODUCING (ETHYNE-l,2-DIYL)BIS(ISOBENZOFURAN-l,3-DIONE) |
WO2015125734A1 (en) * | 2014-02-24 | 2015-08-27 | マナック株式会社 | Halohexahydrophthalic acid derivative |
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