JPS62169747A - Manufacture of by-product-free and isomerically pure naphthalenedicarboxylic acid or naphthalenedicarboxylic acidester - Google Patents
Manufacture of by-product-free and isomerically pure naphthalenedicarboxylic acid or naphthalenedicarboxylic acidesterInfo
- Publication number
- JPS62169747A JPS62169747A JP423487A JP423487A JPS62169747A JP S62169747 A JPS62169747 A JP S62169747A JP 423487 A JP423487 A JP 423487A JP 423487 A JP423487 A JP 423487A JP S62169747 A JPS62169747 A JP S62169747A
- Authority
- JP
- Japan
- Prior art keywords
- naphthalene dicarboxylic
- dicarboxylic acid
- acid
- product
- free
- 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.)
- Pending
Links
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 title claims description 16
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 239000002253 acid Substances 0.000 claims description 17
- 238000002425 crystallisation Methods 0.000 claims description 11
- 230000008025 crystallization Effects 0.000 claims description 11
- 150000002148 esters Chemical class 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- WPUMVKJOWWJPRK-UHFFFAOYSA-N naphthalene-2,7-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=CC2=CC(C(=O)O)=CC=C21 WPUMVKJOWWJPRK-UHFFFAOYSA-N 0.000 claims description 6
- 150000001805 chlorine compounds Chemical class 0.000 claims description 5
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 4
- -1 naphthalene dicarboxylic acid ester Chemical class 0.000 claims description 4
- 230000008022 sublimation Effects 0.000 claims description 3
- 238000000859 sublimation Methods 0.000 claims description 2
- DFFZOPXDTCDZDP-UHFFFAOYSA-N naphthalene-1,5-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1C(O)=O DFFZOPXDTCDZDP-UHFFFAOYSA-N 0.000 claims 1
- KHARCSTZAGNHOT-UHFFFAOYSA-N naphthalene-2,3-dicarboxylic acid Chemical compound C1=CC=C2C=C(C(O)=O)C(C(=O)O)=CC2=C1 KHARCSTZAGNHOT-UHFFFAOYSA-N 0.000 claims 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 6
- QNLZIZAQLLYXTC-UHFFFAOYSA-N 1,2-dimethylnaphthalene Chemical compound C1=CC=CC2=C(C)C(C)=CC=C21 QNLZIZAQLLYXTC-UHFFFAOYSA-N 0.000 description 4
- YGYNBBAUIYTWBF-UHFFFAOYSA-N 2,6-dimethylnaphthalene Chemical compound C1=C(C)C=CC2=CC(C)=CC=C21 YGYNBBAUIYTWBF-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 238000005292 vacuum distillation Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- WUQGUKHJXFDUQF-UHFFFAOYSA-N naphthalene-1,2-dicarbonyl chloride Chemical compound C1=CC=CC2=C(C(Cl)=O)C(C(=O)Cl)=CC=C21 WUQGUKHJXFDUQF-UHFFFAOYSA-N 0.000 description 2
- NZZGQZMNFCTNAM-UHFFFAOYSA-N naphthalene-2,6-dicarbonyl chloride Chemical compound C1=C(C(Cl)=O)C=CC2=CC(C(=O)Cl)=CC=C21 NZZGQZMNFCTNAM-UHFFFAOYSA-N 0.000 description 2
- VBDXXRIRGGMSFW-UHFFFAOYSA-N naphthalene-2,7-dicarbonyl chloride Chemical compound C1=CC(C(Cl)=O)=CC2=CC(C(=O)Cl)=CC=C21 VBDXXRIRGGMSFW-UHFFFAOYSA-N 0.000 description 2
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000002061 vacuum sublimation Methods 0.000 description 2
- LRQYSMQNJLZKPS-UHFFFAOYSA-N 2,7-dimethylnaphthalene Chemical compound C1=CC(C)=CC2=CC(C)=CC=C21 LRQYSMQNJLZKPS-UHFFFAOYSA-N 0.000 description 1
- WYQFWTCGSQMPMT-UHFFFAOYSA-N 6-formylnaphthalene-2-carbonyl chloride Chemical class C(=O)C1=CC2=CC=C(C=C2C=C1)C(=O)Cl WYQFWTCGSQMPMT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000012320 chlorinating reagent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 238000000260 fractional sublimation Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/04—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid halides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/58—Preparation of carboxylic acid halides
- C07C51/64—Separation; Purification; Stabilisation; Use of additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、副産物を含まずかつ異性体純粋なナフタリン
ジカルボン酸またはナフタリンジカルボン酸エステル、
特に異性体純粋な１．５−。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to by-product-free and isomerically pure naphthalene dicarboxylic acid or naphthalene dicarboxylic acid ester,
Particularly isomerically pure 1.5-.
２．３−．２．６−および２，７ナフタリンゾカルボン
酸ないしはそれらのエステルの新規製造法に関する。2.3-. The present invention relates to a new method for producing 2,6- and 2,7 naphthalenezocarboxylic acids or esters thereof.
従来の技術
ジアルキル−、アシル−アルキル−またはジアシルナフ
タリンの酸化の場合、置換モノカルボン酸のほかに、ジ
カルボン酸が、出発物質の組成によって異なる、それぞ
れの異性体の割合を有する異性体混合物として生じる。PRIOR ART In the oxidation of dialkyl-, acyl-alkyl- or diacylnaphthalenes, in addition to substituted monocarboxylic acids, dicarboxylic acids are obtained as isomer mixtures with proportions of the respective isomers that vary depending on the composition of the starting materials. .
この反応生成物は分離が極めて困難である。This reaction product is extremely difficult to separate.
しかし、幾多の使用領域、たとえば多価ポリエステルへ
の処理のためには、高い純度および異性体純度が要求さ
れ、該純度は異性体純粋な出発物質の使用によっては経
済的に達成することができない。However, for many areas of use, for example processing into polyhydric polyesters, high purity and isomer purity are required, which cannot be economically achieved by using isomer-pure starting materials. .
発明が解決するための手段
本発明の課題は、簡単で容易に制御できる方法で副産物
を有せずかつ異性体の純粋なナフタリンジカルボン酸ま
たはナフタリンジカルボン酸エステルを主としてアルキ
ル−またはアシルナフタリン異性体混合物の酸化の際に
得られるナフタリンジカルボン酸混合物から製造するこ
とである。SUMMARY OF THE INVENTION It is an object of the present invention to process in a simple and easily controllable manner without by-products and isomerically pure naphthalene dicarboxylic acid or naphthalene dicarboxylic acid esters, mainly alkyl- or acylnaphthalene isomer mixtures. from the naphthalene dicarboxylic acid mixture obtained during the oxidation of
問題点を解決するだめの手段
この課題の解決は、特許請求の範囲第１項〜第４項によ
る方法によって行なわれる。Means for Solving the Problem This problem is solved by the method according to claims 1 to 4.
ナフタリンジカルボン酸異性体は、ジアルキル−アルキ
ル−アシル−およびジアシルナフタリンの酸化の際に生
じる粗酸のナフタリンジカルボン酸異性体は、粗酸を相
応する酸塩化物に変換し、その後分離を行なえば、簡単
に相互間結晶化法、蒸留法および昇化法により互いに分
離しうろことが見出された。分離を行なった後、副産物
を含まずかつ異性体純粋な酸塩化物は、加水分解によシ
ナフタリンジカルボン酸へ戻すか、またはアルコールと
の反応により相応する、時には有利に所望のナフタリン
ジカルボン酸エステルに変換することができる。The naphthalene dicarboxylic acid isomers of the crude acids produced during the oxidation of dialkyl-alkyl-acyl- and diacylnaphthalenes can be obtained by converting the crude acids into the corresponding acid chlorides and subsequent separation. It has been found that they can be easily separated from each other by mutual crystallization, distillation, and elevation methods. After separation, the by-product-free and isomerically pure acid chloride is converted back to the naphthalene dicarboxylic acid by hydrolysis or by reaction with alcohol to form the corresponding, sometimes advantageously, the desired naphthalene dicarboxylic ester. can be converted to .
有利な異性体は、１．５−．２．ろ−、２゜６−および
２，７−ナフタリンジカルボン酸かまたはそれらのエス
テルでアル。Preferred isomers are 1.5-. 2. Al, 6- and 2,7-naphthalene dicarboxylic acids or their esters.
この方法は、−見して当然費用がかかるように思われる
が、実施する場合、共晶および共沸混合物の存在のため
困難となる数度の結晶化お（ろ）
よび／または蒸留による異性体出発物質の分離と比較し
て簡単であることが立証される。Although this process seems understandably expensive, its implementation requires several degrees of crystallization and/or isomerization by distillation, which is difficult due to the presence of eutectics and azeotropes. This proves to be simple compared to the separation of physical starting materials.
異性体分離が、特異な誘導体である酸塩化物において行
なわれ、たとえば酸およびエステルにおいては極めて大
きい費用をかけて部分的に可能であるにすぎないことは
専門家にとっても驚異的である。It is surprising even to experts that isomer separation is carried out in specific derivatives, acid chlorides, and is only partially possible, for example in acids and esters, at great expense.
本発明の他の利点は、この場合同時に酸塩化物からの全
ての望ましくない副産物の分離が達成されることである
。Another advantage of the invention is that in this case separation of all undesired by-products from the acid chloride is achieved at the same time.
本発明の実施は、ジアルキル−、アルキル−アシル−ま
たはジアシルナフタリンの酸化から得られる粗酸を、自
体公知の方法で酸塩化物生成試薬と反応させ、生じた反
応混合物から結晶化および引続く分別真空蒸留ないしは
分別真空昇華、または真空蒸留ないしは真空昇華および
結晶化によシ副産物を含まずかつ異性体純粋なジ酸ジク
ロリＰを分離するようにして行なわれる。引続き水また
はアルコールとの反応により、副生物を含まずかつ異性
体純粋なナフタリンジカルボン酸またはそのエステルが
得られる。The practice of the invention involves reacting the crude acid obtained from the oxidation of dialkyl-, alkyl-acyl- or diacylnaphthalenes with acid chloride-forming reagents in a manner known per se, crystallization and subsequent fractionation from the resulting reaction mixture. Vacuum distillation or fractional vacuum sublimation or vacuum distillation or vacuum sublimation and crystallization are carried out in such a way that by-product-free and isomerically pure diacid dichloride P is separated. Subsequent reaction with water or alcohol gives by-product-free and isomerically pure naphthalene dicarboxylic acid or its ester.
例えば酸塩化物生成試薬の例は、三塩化リン、五塩化リ
ン、オキシ塩化リン、塩化チオニルまたは、塩化オキサ
リル（場合により重金属塩化物添加）である。これらの
試薬は少なくともジ酸クロリケの形成に化学量論的に必
要な量、有利には５〜１５％の過剰量で使用される。Examples of acid chloride generating reagents are phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride, thionyl chloride or oxalyl chloride (optionally with addition of heavy metal chloride). These reagents are used at least in the amount stoichiometrically necessary for the formation of the diacid chlorike, preferably in an excess of 5 to 15%.
この反応は溶液または懸濁液で行なわれ、その際溶剤と
して過剰の液体塩素化剤または反応条件下に不活性の有
機溶剤、たとえばドルオール、キジロールまたはトリク
ロルエチレンが使用される。反応が行なわれた後、反応
生成物は、結晶化および反覆結晶化（溶融結晶化または
溶剤結晶化）および／または真空下での分別蒸留または
分別昇華によるかまたは真空下での蒸留または昇華およ
び引続く結晶化によって副生物を含まずかつ異性体純粋
なナフタリンジカルボン酸ジクロリドに分離される。The reaction is carried out in solution or suspension, using as solvent an excess of liquid chlorinating agent or an organic solvent inert under the reaction conditions, such as doluol, quidyol or trichlorethylene. After the reaction has taken place, the reaction product is processed by crystallization and repeated crystallization (melt crystallization or solvent crystallization) and/or by fractional distillation or sublimation under vacuum or by distillation or sublimation under vacuum and Subsequent crystallization separates by-product-free and isomerically pure naphthalene dicarboxylic acid dichloride.
これらを、溶媒たとえばジメチルスルホキシドまたは、
ジメチルホルムアミドのような溶解助剤が添加されてい
る水またはアルコールド共に煮沸することにより相応す
るナフタリンジカルボン酸またはそのエステルに変える
。These can be dissolved in a solvent such as dimethyl sulfoxide or
It is converted into the corresponding naphthalene dicarboxylic acid or its ester by boiling with water or alcohol to which a solubilizing agent such as dimethylformamide is added.
次の例は、本発明をさらに説明するのに役立つ。この場
合、全ての係表示は重量係表示と解される。The following examples serve to further explain the invention. In this case, all relationship indications are interpreted as weight relationship indications.
実施例
例 １゜
ａ、比較的に異性体純粋なジメチルナフタリン留分（９
２，６％が２．６−ジメチルナフタリンおよび５．２％
が２，７−ジメチルナフタリン）の空気酸化により、（
７４，６％が２，６−ナフタリンジカルボン酸および４
％が２，７−ナフタリンジカルボン酸を有する粗酸を得
る。Example 1゜a, Relatively isomerically pure dimethylnaphthalene fraction (9
2,6% 2,6-dimethylnaphthalene and 5,2%
is 2,7-dimethylnaphthalene) by air oxidation, (
74,6% 2,6-naphthalene dicarboxylic acid and 4
% of 2,7-naphthalene dicarboxylic acid is obtained.
ｂ、粗酸６００ｇ、予備乾燥したドルオール２５００ｍ
１およびジメチルホルムアミドｉＱｍＡ！を装入し、攪
拌および還流下に８０〜９０℃に加熱する。この懸濁液
に、約２時間に塩化チオニル４６０ｍ１を滴加する。約
１時間後反応させ、その際温度を徐々に１１０℃まで上
昇し、透明な褐色溶液が得られ、この溶液から少量の微
粒状沈積物が沈殿する。全反応混合物を熱時（約８０°
Ｃ）に濾過する。−晩中室温に冷却し、沈殿した粗酸塩
化物を分離する。b, 600 g of crude acid, 2500 m of pre-dried doluol
1 and dimethylformamide iQmA! and heated to 80-90°C under stirring and reflux. 460 ml of thionyl chloride are added dropwise to this suspension over a period of about 2 hours. After about 1 hour's reaction, the temperature is gradually increased to 110.degree. C., and a clear brown solution is obtained, from which a small amount of finely divided sediment precipitates. The entire reaction mixture was heated (approximately 80°
C). - Cool to room temperature overnight and separate the precipitated crude acid chloride.
酸塩化物は２，６−ナフタリンジカルボン酸シクロリド
９５．６％および２，７−ナフタリンジカルボン酸シク
ロリド０．５％を主として２−メチル−および２−ホル
ミル−６−ナフタリンカルボン酸クロリドを含有する。The acid chloride contains mainly 2-methyl- and 2-formyl-6-naphthalenecarboxylic acid chlorides, with 95.6% of 2,6-naphthalenedicarboxylic acid cyclolide and 0.5% of 2,7-naphthalenedicarboxylic acid cyclolide.
Ｃ１真空蒸留（３０−５０・１０２Ｐａ、 ２３０℃
）および引続く融解結晶化によりさらに精製する。１９
０℃の融点を有する９９．４％の２゜６−ナフタリンジ
カルボン酸シクロリド６６８Ｊが得られる。C1 vacuum distillation (30-50・102Pa, 230℃
) and further purification by subsequent melt crystallization. 19
99.4% of 2.degree. 6-naphthalene dicarboxylic acid cyclolide 668J having a melting point of 0.degree. C. is obtained.
ｄ、■程すにおいて得られる母液を１２時間００Ｃに冷
却し、かつ沈殿する結晶物を濾過する。d. The mother liquor obtained in step (i) is cooled to 00C for 12 hours and the precipitated crystalline material is filtered.
ものものは、８４．７％の２．７−ナフタリンジカルボ
ン酸シクロリドを含有する。It contains 84.7% of 2,7-naphthalene dicarboxylic acid cyclolide.
汚染物の分離のために、粗酸塩化物を昇華（１０’−２
ｐａ／２００℃）し、その際帯黄色ノ外側帯域および白
色の内側帯域が得られる。帯黄色の外側帯域は主に２，
６−ナフタリンジカルボン酸ジクロリドを含有する。２
，７−ナフタリンジカルボン酸ジクロリＰを含有する白
色の内側帯域を再昇華し、場合により酸成分を分離する
ためにドルオールから再結晶し、その際融点１４６．３
〜１４７．３６Ｃの無色の針状晶が得られる。こうして
合計、９９．９％の２，７−ナフタリンジカルボン酸ジ
クロリド約１６ｇが得られる。゛
ｅ、諸工程において得られる酸塩化物を、そのつどその
重量の２倍の、ジメチルスルホキシドと水から成る混合
物と共に１時間煮沸し、引続き０℃に冷却する。沈殿し
た異性体純粋なナフタリンジカルボン酸を濾過し、メタ
ノールで洗浄しかつ乾燥する。For contaminant separation, crude acid chlorides are sublimated (10'-2
pa/200° C.), a yellowish outer zone and a white inner zone are obtained. The yellowish outer band is mainly 2,
Contains 6-naphthalene dicarboxylic acid dichloride. 2
, 7-naphthalene dicarboxylic acid dichloride P is resublimated and optionally recrystallized from doluol to separate the acid component, with a melting point of 146.3
Colorless needles of ~147.36C are obtained. A total of about 16 g of 99.9% 2,7-naphthalene dicarboxylic acid dichloride are thus obtained. e. The acid chloride obtained in the steps is boiled for 1 hour with in each case twice its weight of a mixture of dimethyl sulfoxide and water and subsequently cooled to 0.degree. The precipitated isomerically pure naphthalene dicarboxylic acid is filtered, washed with methanol and dried.
収量： ９９．８％の２，６−ナフタリンジカルボン酸
２７６ｇ
９９．９％の２，７−ナフタリンジカ
ルボン酸 １２．８ ｇ
例 ２
ａ、、 ２ 、６−シメチルナフタリン７５．４％およ
び２，７−ジメチルナフタリン２４．６ ％からなるジ
メチルナフタリン留分の空気酸化により、２．６−ナフ
タリンジカルボン酸５７．７％および２，７−ナフタリ
ンカルボン酸１８．２％を有する粗酸が得られる。Yield: 276 g 99.8% 2,6-naphthalene dicarboxylic acid 12.8 g 99.9% 2,7-naphthalene dicarboxylic acid Example 2 75.4% a,, 2,6-dimethylnaphthalene and 2, Air oxidation of a dimethylnaphthalene fraction consisting of 24.6% of 7-dimethylnaphthalene gives a crude acid having 57.7% of 2,6-naphthalenedicarboxylic acid and 18.2% of 2,7-naphthalenecarboxylic acid.
ｂ、粗酸６００ｇを、例１と同様に、塩化チオニルと反
応させる。反応混合物から沈殿する粗酸塩化物は：
２．６−ナフタリンジカルボン酸クロリド９４．１％
２．７−ナフタリンジカルボン酸クロリド１．９％
を含有する。b. 600 g of crude acid are reacted analogously to Example 1 with thionyl chloride. The crude acid chloride precipitated from the reaction mixture contains: 94.1% of 2.6-naphthalene dicarboxylic acid chloride 1.9% of 2.7-naphthalene dicarboxylic acid chloride.
Ｃ６粗酸塩化物を真空中で蒸留する（２３０’ｃ；３０
５０．１０２Ｐａ）。The C6 crude acid chloride is distilled in vacuo (230'c; 30
50.102Pa).
２．６−ナフタリンジカルボン酸クロリド９５．３％ ２．７−ナフタリンジカルボン酸クロリド１．８係 を有する酸塩化物混合物が得られる。2.6-naphthalene dicarboxylic acid chloride 95.3% 2.7-Naphthalene dicarboxylic acid chloride Section 1.8 An acid chloride mixture with .
ｄ、工程Ｃからの酸塩化物をドルオールから再結晶する
。その際、９９．６％の２．６−ナフタリンジカルボン
酸クロリド２２８ｇが得られる。d. Recrystallize the acid chloride from step C from doluol. 228 g of 99.6% strength 2,6-naphthalene dicarboxylic acid chloride are obtained.
ｅ、工程すおよびｄからの母液を一緒にし、例１の工程
ｄによって２，６−ナフタリンジカルボン酸クロリドを
単離する。Combine the mother liquors from e, steps a and d and isolate the 2,6-naphthalene dicarboxylic acid chloride according to step d of Example 1.
ｆ、工程ｄおよびｅからのナフタリンジカルボン酸クロ
リドを、例１の工程ｄによって相応する副産物を含まず
かつ異性体純粋なナフタリンジカルボン酸へ変換する。f. The naphthalene dicarboxylic acid chloride from steps d and e is converted into the corresponding by-product-free and isomerically pure naphthalene dicarboxylic acid according to step d of Example 1.
Claims (1)
ナフタリンの異性体混合物の酸化により得られる粗酸混
合物から、副産物を含まずかつ異性体純粋なナフタリン
ジカルボン酸またはナフタリンジカルボン酸エステルの
製造法において、粗酸の異性体混合物をそれぞれの酸塩
化物に変換し、これを相互間結晶化法および／または蒸
留法または昇華法によって、異性体純粋かつ副生物の含
まない酸塩化物に分離し、これを相応する、副生物の含
まずかつ異性体純粋なナフタリンジカルボン酸またはナ
フタリンジカルボン酸エステルに変換することを特徴と
する副産物を含まずかつ異性体純粋なナフタリンジカル
ボン酸またはナフタリンジカルボン酸エステルの製造法
。 ２、２，６−ナフタリンジカルボン酸および２，７−ナ
フタリンジカルボン酸またはそれらのエステルを製造す
る特許請求の範囲第１項記載の方法。 ３、１，５−ナフタリンジカルボン酸またはそのエステ
ルを製造する特許請求の範囲第１項記載の方法。 ４、２，３−ナフタリンジカルボン酸またはそのエステ
ルを製造する特許請求の範囲第１項記載の方法。[Scope of Claims] 1. By-product-free and isomerically pure naphthalene dicarboxylic acid or naphthalene dicarboxylic acid ester from a crude acid mixture obtained by oxidation of an isomer mixture of dialkyl-, alkyl-acyl- or diacylnaphthalene. In the production method, a mixture of crude acid isomers is converted into the respective acid chlorides, which are then converted into isomer-pure and by-product-free acid chlorides by mutual crystallization and/or distillation or sublimation. by-product-free and isomerically pure naphthalene dicarboxylic acid or naphthalene dicarboxylic acid, characterized in that it is separated and converted into the corresponding by-product-free and isomerically pure naphthalene dicarboxylic acid or naphthalene dicarboxylic acid ester. Method for producing esters. A method according to claim 1 for producing 2,2,6-naphthalene dicarboxylic acid and 2,7-naphthalene dicarboxylic acid or esters thereof. The method according to claim 1 for producing 3,1,5-naphthalene dicarboxylic acid or its ester. A method according to claim 1 for producing 4,2,3-naphthalene dicarboxylic acid or an ester thereof.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19863601580 DE3601580A1 (en) | 1986-01-21 | 1986-01-21 | Process for the preparation of isomerically pure naphthalene-dicarboxylic acids or naphthalenedicarboxylates which are free from by-products |
| DE3601580.6 | 1986-01-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62169747A true JPS62169747A (en) | 1987-07-25 |
Family
ID=6292246
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP423487A Pending JPS62169747A (en) | 1986-01-21 | 1987-01-13 | Manufacture of by-product-free and isomerically pure naphthalenedicarboxylic acid or naphthalenedicarboxylic acidester |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPS62169747A (en) |
| DE (1) | DE3601580A1 (en) |
| NL (1) | NL8700118A (en) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3565945A (en) * | 1966-06-24 | 1971-02-23 | Sun Oil Co | Preparation of esters of 2,6- and 2,7-naphthalene dicarboxylic acid |
| GB1246461A (en) * | 1967-12-22 | 1971-09-15 | Sun Oil Co | Preparation of the diacyl halide of 2,6-naphthalene dicarboxylic acid |
-
1986
- 1986-01-21 DE DE19863601580 patent/DE3601580A1/en active Granted
-
1987
- 1987-01-13 JP JP423487A patent/JPS62169747A/en active Pending
- 1987-01-20 NL NL8700118A patent/NL8700118A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| DE3601580C2 (en) | 1990-10-04 |
| NL8700118A (en) | 1987-08-17 |
| DE3601580A1 (en) | 1987-07-23 |
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