JPH0637493B2 - Purification method of carboxylic anhydride - Google Patents
Purification method of carboxylic anhydrideInfo
- Publication number
- JPH0637493B2 JPH0637493B2 JP15235988A JP15235988A JPH0637493B2 JP H0637493 B2 JPH0637493 B2 JP H0637493B2 JP 15235988 A JP15235988 A JP 15235988A JP 15235988 A JP15235988 A JP 15235988A JP H0637493 B2 JPH0637493 B2 JP H0637493B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- acid
- represented
- group
- purity
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title claims description 3
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 title 1
- 238000000746 purification Methods 0.000 title 1
- 239000002253 acid Substances 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 150000008065 acid anhydrides Chemical class 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 claims description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 2
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- -1 imide compound Chemical class 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- MIJDSYMOBYNHOT-UHFFFAOYSA-N 2-(ethylamino)ethanol Chemical compound CCNCCO MIJDSYMOBYNHOT-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- LAWOZCWGWDVVSG-UHFFFAOYSA-N dioctylamine Chemical compound CCCCCCCCNCCCCCCCC LAWOZCWGWDVVSG-UHFFFAOYSA-N 0.000 description 1
- 239000000986 disperse dye Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- VGEMYWDUTPQWBN-UHFFFAOYSA-N n-ethyl-2-methoxyethanamine Chemical compound CCNCCOC VGEMYWDUTPQWBN-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
Landscapes
- Plural Heterocyclic Compounds (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、色素の中間体であるジカルボン酸無水物の精
製法に関する。TECHNICAL FIELD The present invention relates to a method for purifying a dicarboxylic acid anhydride which is an intermediate of a dye.
下記一般式（Ｉ） （式（Ｉ）中、Ｘはアルキル基、ハロゲン原子、または
水素原子を表す。） で示される化合物は、液晶用染料又は分散染料の中間体
として重要な化合物である。The following general formula (I) (In the formula (I), X represents an alkyl group, a halogen atom, or a hydrogen atom.) The compound represented by is an important compound as an intermediate for a dye for liquid crystal or a disperse dye.
しかしながら、式（Ｉ）の化合物は、溶剤溶解性が皆無
に近く、精製することが出来なかった。However, the compound of formula (I) had almost no solubility in solvents and could not be purified.
そのため、これらの純度の低い中間体より誘導される染
料は、不純物を多く含み、品質が不安定であった。Therefore, the dyes derived from these low-purity intermediates contained many impurities and were unstable in quality.
本発明者らは、一般式（Ｉ９） （式（Ｉ）中、Ｘはアルキル基、ハロゲン原子、または
水素原子を表す。） で示される粗酸無水物を溶媒中、下記一般式（II） （式（II）中、Ｒ１及びＲ２は各々独立に炭素数１〜10
のアルキル基、アルコキシアルキル基、又はヒドロキシ
アルキル基を表す。） で示される２級アミンにてアミック酸として溶媒可溶化
し、副生成物を濾別し、濾液より高純度アミック酸を分
離した後、酸処理をすることにより高純度の酸無水物
（Ｉ）が得られることを見出した。The present inventors have made general formula (I9) (In the formula (I), X represents an alkyl group, a halogen atom, or a hydrogen atom.) In a solvent, a crude acid anhydride represented by the following general formula (II) is used. (In the formula (II), R 1 and R 2 each independently have 1 to 10 carbon atoms.
Represents an alkyl group, an alkoxyalkyl group or a hydroxyalkyl group. ) Is solubilized as amic acid with a secondary amine represented by the following formula, the by-product is separated by filtration, the high-purity amic acid is separated from the filtrate, and then acid treatment is carried out to obtain a high-purity acid anhydride (I ) Was obtained.
式（Ｉ）で示される化合物の置換基Ｘで示されるアルキ
ル基としては、メチル基、エチル基、プロピル基、ブチ
ル基、ベンチル基など炭素数１〜10の炭化水素及びその
ハロゲン、アシルアルコキシ又はヒドロキシ置換体を意
味し、ハロゲン原子としてはフッ素、塩素、臭素、沃素
を意味する。Examples of the alkyl group represented by the substituent X of the compound represented by the formula (I) include a hydrocarbon having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group and a benzyl group, and a halogen, an acylalkoxy or It means a hydroxy-substituted compound, and the halogen atom means fluorine, chlorine, bromine or iodine.
式（II）で示される２級アミンの例としては、ジメチル
アミン、ジエチルアミン、ジブチルアミン、ジオクチル
アミン、ジシクロヘキシルアミン、ジエタノールアミ
ン、Ｎ−ヒドロキシエチル−Ｎ−エチルアミン、Ｎ−メ
トキシエチル−Ｎ−エチルアミンなどが挙げられる。Examples of the secondary amine represented by the formula (II) include dimethylamine, diethylamine, dibutylamine, dioctylamine, dicyclohexylamine, diethanolamine, N-hydroxyethyl-N-ethylamine and N-methoxyethyl-N-ethylamine. Can be mentioned.
又、溶媒としては、反応系中で生成するアミック酸を溶
解し、イミド体を溶解しない溶媒ならば何でもよいが、
好ましくはメタノール、エタノール、プロパノール、ブ
タノールなどのアルコール類、メチルセロソルブ、エチ
ルセロソルブ、ブチルセロソルブなどのセロソルブ類が
特に好ましい。The solvent may be any solvent that dissolves the amic acid generated in the reaction system and does not dissolve the imide compound.
Particularly preferred are alcohols such as methanol, ethanol, propanol, butanol, and cellosolves such as methyl cellosolve, ethyl cellosolve, and butyl cellosolve.
酸処理に用いる酸としては、無機系の酸ならばいずれで
もよいが、好ましくは塩酸、臭化水素酸、硫酸、硝酸、
リン酸などである。The acid used for the acid treatment may be any inorganic acid, preferably hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid,
For example, phosphoric acid.
式（Ｉ）と式（II）で示される化合物を処理する温度と
しては、10〜300℃であるが、好ましくは室温から200℃
である。処理時間は0.5〜30時間、好ましくは１時間〜2
0時間である。The temperature for treating the compounds represented by formula (I) and formula (II) is 10 to 300 ° C, preferably room temperature to 200 ° C.
Is. Treatment time is 0.5 to 30 hours, preferably 1 to 2 hours
It's 0 hours.
以下、実施例により、本発明を詳しく説明する。 Hereinafter, the present invention will be described in detail with reference to examples.
実施例１ で表される化合物の粗製物（純度60％；薄層クロマトグ
ラムよる。以下同様）100ｇ及びｎ−ジブチルアミン72g
をエチルセロソルブ１中120℃で14時間反応した。室
温まで冷却した後、反応液を濾過し濾液を減圧濃縮し、
下記式で表される化合物の混合体を100g得た。Example 1 100 g of crude compound (purity: 60%; according to thin-layer chromatogram; the same shall apply hereinafter) and 72 g of n-dibutylamine
Was reacted in ethyl cellosolve 1 at 120 ° C. for 14 hours. After cooling to room temperature, the reaction solution was filtered and the filtrate was concentrated under reduced pressure.
100 g of a mixture of compounds represented by the following formula was obtained.
次に上式で示されるアミック酸100gを10％塩酸水溶液２
中で90℃に昇温し、30時間加水分解した後、反応液を
濾過し、結晶を水洗した後乾燥し、精キノフタロン
（ａ）60gを得た。 Next, add 100 g of the amic acid represented by the above formula to a 10% aqueous hydrochloric acid solution 2
The temperature was raised to 90 ° C. and hydrolysis was carried out for 30 hours. Then, the reaction solution was filtered, and the crystals were washed with water and dried to obtain 60 g of purified quinophthalone (a).
純度は95％であった。The purity was 95%.
実施例２ で表される化合物の粗製物（純度55％）100g及びジ−
（メトキシエチル）アミン90gをアミルアルコール１
中150℃で15時間反応した。室温まで冷却後、反応液を
濾過し濾液を減圧濃縮し、下記式で示される化合物の混
合体を100g得た。Example 2 100 g of a crude product of compound represented by (purity 55%) and di-
90 g of (methoxyethyl) amine and amyl alcohol 1
The reaction was carried out at 150 ° C for 15 hours. After cooling to room temperature, the reaction solution was filtered and the filtrate was concentrated under reduced pressure to obtain 100 g of a mixture of compounds represented by the following formula.
次に上記式で示されるアミック酸100gを10％臭化水素酸
水溶液２中で90℃に昇温し、20時間加水分解した後、
反応液を濾過し、結晶を水洗した後乾燥し、精キノフタ
ロン（ｂ）55gを得た。 Next, 100 g of the amic acid represented by the above formula was heated to 90 ° C. in a 10% aqueous solution of hydrobromic acid 2 and hydrolyzed for 20 hours.
The reaction solution was filtered, the crystals were washed with water and then dried to obtain 55 g of purified quinophthalone (b).
純度は94％であった。The purity was 94%.
実施例３ で表される化合物の粗製物（純度65％）100g、ジエタノ
ールアミン80gをエチレングリコール１中180℃で15時
間反応した。反応液を濾過し濾液を水５に排出し、下
記式で示される化合物の混合体110gを得た。Example 3 100 g of a crude product of the compound represented by (purity 65%) and 80 g of diethanolamine were reacted in ethylene glycol 1 at 180 ° C. for 15 hours. The reaction liquid was filtered and the filtrate was discharged into water 5 to obtain 110 g of a mixture of compounds represented by the following formula.
次に上記式で示されるアミック酸100gを５％塩酸水溶液
５中で90℃に昇温し、20時間反応した。反応液を濾過
し、結晶を水洗した後乾燥し、精キノフタロン（ｃ）60
gを得た。 Next, 100 g of the amic acid represented by the above formula was heated to 90 ° C. in 5% hydrochloric acid aqueous solution 5 and reacted for 20 hours. The reaction solution was filtered, and the crystals were washed with water and then dried to obtain purified quinophthalone (c) 60.
got g.
純度は98％であった。The purity was 98%.
Claims (1)
水素原子を表す。） で示される酸無水物を溶媒中、下記一般式（II） （式（II）中、Ｒ１及びＲ２は各々独立に炭素数１〜10
のアルキル基、アルコキシアルキル基、又はヒドロキシ
アルキル基を表す。） で示される２級アミンと反応させてアミック酸として溶
媒可溶化し、副生成物を濾別し、濾液よりアミック酸を
分離した後、酸で加水分解することを特徴とする式
（Ｉ）で示される酸無水物の精製法。1. A general formula (I) (In the formula (I), X represents an alkyl group, a halogen atom, or a hydrogen atom.) An acid anhydride represented by the following formula (II) (In the formula (II), R 1 and R 2 each independently have 1 to 10 carbon atoms.
Represents an alkyl group, an alkoxyalkyl group or a hydroxyalkyl group. ) The solvent is solubilized as an amic acid by reacting with a secondary amine represented by the formula (1), the by-product is filtered off, the amic acid is separated from the filtrate, and then hydrolyzed with an acid (I). A method for purifying an acid anhydride represented by.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15235988A JPH0637493B2 (en) | 1988-06-22 | 1988-06-22 | Purification method of carboxylic anhydride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15235988A JPH0637493B2 (en) | 1988-06-22 | 1988-06-22 | Purification method of carboxylic anhydride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01319480A JPH01319480A (en) | 1989-12-25 |
| JPH0637493B2 true JPH0637493B2 (en) | 1994-05-18 |
Family
ID=15538819
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15235988A Expired - Lifetime JPH0637493B2 (en) | 1988-06-22 | 1988-06-22 | Purification method of carboxylic anhydride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0637493B2 (en) |
-
1988
- 1988-06-22 JP JP15235988A patent/JPH0637493B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01319480A (en) | 1989-12-25 |
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