JPS621382B2 - - Google Patents
Info
- Publication number
- JPS621382B2 JPS621382B2 JP12813179A JP12813179A JPS621382B2 JP S621382 B2 JPS621382 B2 JP S621382B2 JP 12813179 A JP12813179 A JP 12813179A JP 12813179 A JP12813179 A JP 12813179A JP S621382 B2 JPS621382 B2 JP S621382B2
- Authority
- JP
- Japan
- Prior art keywords
- terephthalate
- monomethyl
- monopotassium
- methanol
- dimethyl terephthalate
- 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
Links
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 51
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 claims description 42
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 39
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 22
- 239000013078 crystal Substances 0.000 claims description 16
- 239000012320 chlorinating reagent Substances 0.000 claims description 13
- -1 Monopotassium terephthalate monomethyl terephthalate Chemical compound 0.000 claims description 12
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 5
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 claims description 5
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims 2
- CVXXHXPNTZBZEL-UHFFFAOYSA-N methyl 4-carbonochloridoylbenzoate Chemical compound COC(=O)C1=CC=C(C(Cl)=O)C=C1 CVXXHXPNTZBZEL-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- DWNDFZTVSFSFTB-UHFFFAOYSA-M potassium;4-methoxycarbonylbenzoate Chemical compound [K+].COC(=O)C1=CC=C(C([O-])=O)C=C1 DWNDFZTVSFSFTB-UHFFFAOYSA-M 0.000 description 7
- REIDAMBAPLIATC-UHFFFAOYSA-M 4-methoxycarbonylbenzoate Chemical compound COC(=O)C1=CC=C(C([O-])=O)C=C1 REIDAMBAPLIATC-UHFFFAOYSA-M 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- LRUDDHYVRFQYCN-UHFFFAOYSA-L dipotassium;terephthalate Chemical compound [K+].[K+].[O-]C(=O)C1=CC=C(C([O-])=O)C=C1 LRUDDHYVRFQYCN-UHFFFAOYSA-L 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005660 chlorination reaction Methods 0.000 description 3
- BPWIVQHIJYRBSR-UHFFFAOYSA-M potassium;hydron;terephthalate Chemical compound [K+].OC(=O)C1=CC=C(C([O-])=O)C=C1 BPWIVQHIJYRBSR-UHFFFAOYSA-M 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000007127 saponification reaction Methods 0.000 description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- UZBQIPPOMKBLAS-UHFFFAOYSA-N diethylazanide Chemical compound CC[N-]CC UZBQIPPOMKBLAS-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- GNBWUEAMCSHHMO-UHFFFAOYSA-N methyl 2-carbonochloridoylbenzoate Chemical compound COC(=O)C1=CC=CC=C1C(Cl)=O GNBWUEAMCSHHMO-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
本発明は医薬や高分子改質剤などの原料として
用いられる高品位のｐ―クロロカルボニル安息香
酸メチルの経済的な製造方法に関するものであ
り、特にテレフタル酸ジメチルをメタノール中で
特定量の水酸化カリウムと反応させることによ
り、高純度のテレフタル酸モノメチルモノカリウ
ムを得、このカリウム塩をカルボン酸に変換させ
ずにそのまま塩素化剤と反応させることにより、
ｐ―クロロカルボニル安息香酸メチルにする方法
に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an economical method for producing high-grade methyl p-chlorocarbonylbenzoate, which is used as a raw material for medicines, polymeric modifiers, etc. By reacting with a specific amount of potassium hydroxide in the reaction mixture, highly pure monomethyl monopotassium terephthalate is obtained, and by reacting this potassium salt with a chlorinating agent as it is without converting it to a carboxylic acid,
The present invention relates to a method for producing methyl p-chlorocarbonylbenzoate.
従来、カルボン酸クロライドは、対応するカル
ボン酸を塩素化する方法によりつくられていた。
したがつてｐ―クロロカルボニル安息香酸メチル
をつくる場合も、まずテレフタル酸モノメチルを
合成し、ついでこれを塩素化する方法が一般的に
採用される合成法である。 Conventionally, carboxylic acid chlorides have been produced by chlorinating the corresponding carboxylic acid.
Therefore, when producing methyl p-chlorocarbonylbenzoate, the commonly employed synthesis method is to first synthesize monomethyl terephthalate and then chlorinate it.
しかしながら、テレフタル酸ジメチルをアルカ
リ金属水酸化物によつてテレフタル酸モノメチル
モノ金属塩にけん化後、酸で処理してテレフタル
酸モノメチルを得ようとする場合には、酸析して
得られるテレフタル酸モノメチルが一般に非常に
微細な粒子になるために、これをロ過・洗浄・乾
燥する操作が困難であるという問題に遭遇する。 However, when attempting to obtain monomethyl terephthalate by saponifying dimethyl terephthalate with an alkali metal hydroxide and then treating it with an acid, the monomethyl terephthalate obtained by acid precipitation is Since the particles generally become very fine, the problem arises in that it is difficult to filter, wash, and dry them.
そこで本発明者らはテレフタル酸モノメチルモ
ノ金属塩を、テレフタル酸ジメチルの部分けん化
により直接高品位の状態で生成させ、これをテレ
フタル酸モノメチルに変換することなくそのまま
塩素化剤と反応させる方法について鋭意検討を進
めた結果適切なけん化条件の設定と適切な塩素化
剤の選定により上記の問題を解決できるとの事実
を見い出し、本発明に到達した。 Therefore, the present inventors have been working diligently on a method of directly producing monometallic monomethyl terephthalate in a high-grade state by partial saponification of dimethyl terephthalate, and directly reacting it with a chlorinating agent without converting it to monomethyl terephthalate. As a result of further investigation, it was discovered that the above problems can be solved by setting appropriate saponification conditions and selecting an appropriate chlorinating agent, and the present invention was achieved.
すなわち本発明は、テレフタル酸ジメチルのメ
タノール溶液に、該テレフタル酸ジメチルに対し
て1.0〜1.5モル倍の水酸化カリウムをメタノール
に溶解した溶液を添加して加温下に前記テレフタ
ル酸ジメチルと水酸化カリウムとを反応させ、生
成したテレフタル酸モノメチルモノカリウムの結
晶をロ別後、次いで塩化チオニル、五塩化リン、
三塩化リン、オキシ塩化リンから選ばれた塩素化
剤と反応させることを特徴とするｐ―クロロカル
ボニル安息香酸メチルの製造法である。 That is, in the present invention, a solution of potassium hydroxide dissolved in methanol in an amount of 1.0 to 1.5 times the molar amount of the dimethyl terephthalate is added to a methanol solution of dimethyl terephthalate, and the dimethyl terephthalate and hydroxide are heated. After reacting with potassium and filtering out the crystals of monopotassium terephthalate produced, thionyl chloride, phosphorus pentachloride,
This is a method for producing methyl p-chlorocarbonylbenzoate, which is characterized by reacting it with a chlorinating agent selected from phosphorus trichloride and phosphorus oxychloride.
ちなみに本発明は以下の重要な事実を見い出し
たことに基づいてなされたものであり、これらの
事実は本発明の特異な効果でもある。 Incidentally, the present invention was made based on the discovery of the following important facts, and these facts are also unique effects of the present invention.
(1) メタノール溶媒に溶解したテレフタル酸ジメ
チルと水酸化カリウムを混合・加熱すると容易
に反応し、テレフタル酸モノメチルモノカリウ
ムを生成する。(1) When dimethyl terephthalate dissolved in methanol solvent and potassium hydroxide are mixed and heated, they easily react and form monopotassium monomethyl terephthalate.
(2) 生成したテレフタル酸モノメチルモノカリウ
ムは熱メタノールに難溶であり、結晶として析
出する。(2) The produced monomethyl monopotassium terephthalate is poorly soluble in hot methanol and precipitates as crystals.
(3) このためにテレフタル酸モノメチルモノカリ
ウムがさらにテレフタル酸ジカリウムにまで分
解する反応は非常に進みにくく、転化率と反応
速度を増大させるためにテレフタル酸ジメチル
に対し等モル以上のアルカリを使用した場合
も、テレフタル酸ジカリウムにまで分解する反
応はわずかしか起らない。(3) For this reason, the reaction in which monopotassium monomethyl terephthalate is further decomposed into dipotassium terephthalate is extremely difficult to proceed, and in order to increase the conversion rate and reaction rate, an alkali in an amount equal to or more than the same molar amount as dimethyl terephthalate was used. Even in this case, only a small number of reactions occur that decompose it into dipotassium terephthalate.
(4) テレフタル酸ジカリウムはわずかであれば副
生してもメタノールに対して溶解性を有するの
で、析出するテレフタル酸モノメチルモノカリ
ウムの結晶にはほとんど混入しない。(4) Even if a small amount of dipotassium terephthalate is produced as a by-product, it is soluble in methanol, so it is hardly mixed into the precipitated crystals of monomethyl monopotassium terephthalate.
(5) このような高純度のテレフタル酸モノメチル
モノカリウムの結晶を高収率で析出させうるの
は、溶媒にメタノールを使用し、アルカリとし
て、水酸化カリウムを用い、しかも水酸化カリ
ウムをテレフタル酸ジメチルに対して1.0〜1.5
モル倍使用する場合に限られる。(5) The reason why it is possible to precipitate such high-purity crystals of monomethyl monopotassium terephthalate in a high yield is by using methanol as a solvent and using potassium hydroxide as an alkali, and in addition, potassium hydroxide is mixed with terephthalic acid. 1.0-1.5 for dimethyl
Limited to cases where twice the mole is used.
(6) すなわち水酸化カリウムの代りにたとえば水
酸化ナトリウムをアルカリとして用いると、メ
タノールへの溶解性が劣るために均一溶液で反
応させることが困難となり、反応速度の低下と
テレフタル酸モノメチルモノ金属塩の純度低下
が起る。(6) In other words, if sodium hydroxide is used as an alkali instead of potassium hydroxide, it becomes difficult to react in a homogeneous solution due to its poor solubility in methanol, resulting in a decrease in the reaction rate and the formation of monometallic monomethyl terephthalate. A decrease in purity occurs.
(7) アルカリとして水酸化カリウムを用いた場合
も、テレフタル酸ジメチルに対する使用モル比
が1.0以下であると反応速度が極端に減少し、
テレフタル酸モノメチルモノカリウムの収率が
大幅に低下するとともに、テレフタル酸モノメ
チルモノカリウムの結晶がテレフタル酸ジメチ
ルで汚染される。一方テレフタル酸ジメチルに
対する使用モル比が1.5以上になると、テレフ
タル酸ジカリウムへの分解が進みやすくなり、
テレフタル酸モノメチルモノカリウムの結晶が
テレフタル酸ジカリウムで汚染されるという不
都合を生じる。(7) Even when potassium hydroxide is used as the alkali, if the molar ratio to dimethyl terephthalate is less than 1.0, the reaction rate will be extremely reduced.
The yield of monopotassium monomethyl terephthalate is significantly reduced, and the crystals of monopotassium monomethyl terephthalate are contaminated with dimethyl terephthalate. On the other hand, if the molar ratio to dimethyl terephthalate is 1.5 or more, the decomposition to dipotassium terephthalate will proceed more easily.
This results in the disadvantage that the crystals of monomethyl monopotassium terephthalate are contaminated with dipotassium terephthalate.
(8) テレフタル酸モノメチルモノカリウムは、塩
化チオニル、五塩化リン、三塩化リン、オキシ
塩化リンから選ばれた塩素化剤と容易に反応
し、ｐ―クロロカルボニル安息香酸メチルにな
る。(8) Monopotassium monomethyl terephthalate easily reacts with a chlorinating agent selected from thionyl chloride, phosphorus pentachloride, phosphorus trichloride, and phosphorus oxychloride to form methyl p-chlorocarbonylbenzoate.
本発明において、出発原料として用いるテレフ
タル酸ジメチルは、ポリエステル繊維・樹脂の原
料として純度99.9％以上の高品位のものが、すで
に大量に製造されており、比較的安価に入手する
ことが可能である。本発明においては、このテレ
フタル酸ジメチルを熱メタノールに溶解し、ここ
へテレフタル酸ジメチルの1.0〜1.5モル倍の水酸
化カリウムをメタノールに溶解した溶液を還流加
熱下で徐々に添加する。添加を開始して数分後
に、テレフタル酸モノメチルモノカリウムの結晶
が析出しはじめる。 In the present invention, dimethyl terephthalate used as a starting material is already produced in large quantities with a purity of 99.9% or higher as a raw material for polyester fibers and resins, and can be obtained at a relatively low cost. . In the present invention, this dimethyl terephthalate is dissolved in hot methanol, and a solution of potassium hydroxide dissolved in methanol in an amount of 1.0 to 1.5 times the mole of dimethyl terephthalate is gradually added thereto under reflux heating. A few minutes after starting the addition, crystals of monopotassium monomethyl terephthalate begin to precipitate.
添加終了後30分程度還流加熱を続けてから冷却
し、生成した結晶をロ別し、少量のメタノールで
これを洗浄する。この結晶はほぼ完全に純粋なテ
レフタル酸モノメチルモノカリウムである。 After the addition is complete, continue heating under reflux for about 30 minutes, then cool, filter out the formed crystals, and wash them with a small amount of methanol. The crystals are almost completely pure monomethyl monopotassium terephthalate.
なおテレフタル酸モノメチルモノカリウムをロ
別したロ液は、過剰のアルカリと、反応で副生す
る水以外の不純物はほとんど含まないので、その
ままあるいは必要に応じて脱水処理を施した後、
テレフタル酸ジメチルのけん化反応の溶媒として
くり返し使用することもできる。 The filtrate obtained by filtering monomethyl monopotassium terephthalate contains almost no impurities other than excess alkali and water produced by the reaction, so it can be used as is or after dehydration if necessary.
It can also be used repeatedly as a solvent for the saponification reaction of dimethyl terephthalate.
このようにして得られたテレフタル酸モノメチ
ルモノカリウムを次に塩化チオニル、三塩化リ
ン、五塩化リン、オキシ塩化リンから選ばれた塩
素化剤と反応させる。 The monomethyl monopotassium terephthalate thus obtained is then reacted with a chlorinating agent selected from thionyl chloride, phosphorus trichloride, phosphorus pentachloride, and phosphorus oxychloride.
塩素化反応は、ベンゼン、四塩化炭素などの溶
媒中で、テレフタル酸モノメチルモノカリウムと
塩素化剤を還流加熱する方法が適当であるが、塩
素化剤が液体の場合は溶媒を用いずに過剰の塩素
化剤と反応させることも可能である。 The appropriate method for the chlorination reaction is to reflux and heat monopotassium terephthalate and the chlorinating agent in a solvent such as benzene or carbon tetrachloride. It is also possible to react with a chlorinating agent.
塩素化反応を終えた反応混合物は、蒸留によつ
て溶媒、過剰の塩素化剤、副生物などを除去し、
ついで残留物から溶媒抽出や蒸留によつて目的物
であるｐ―クロロカルボニル安息香酸メチルを単
離する。さらに必要に応じて再結晶や蒸留などに
よつてｐ―クロロカルボニル安息香酸メチルを精
製する。 After the chlorination reaction, the reaction mixture is distilled to remove the solvent, excess chlorinating agent, byproducts, etc.
The target product, methyl p-chlorocarbonylbenzoate, is then isolated from the residue by solvent extraction or distillation. Furthermore, if necessary, methyl p-chlorocarbonylbenzoate is purified by recrystallization, distillation, or the like.
かくして得られたｐ―クロロカルボニル安息香
酸メチルは医薬や高分子改質剤の原料として広く
有用される。 The thus obtained methyl p-chlorocarbonylbenzoate is widely useful as a raw material for medicines and polymer modifiers.
以下に実施例をあげて本発明を具体的に説明す
る。 The present invention will be specifically explained below with reference to Examples.
実施例 １
テレフタル酸ジメチル9.7ｇ（0.05モル）をメ
タノール130ｇに還流加熱下で溶解し、ここへ85
％水酸化カリウム4.28ｇ（0.065モル）を溶かし
たメタノール溶液13mlを撹拌しながら滴下した。
滴下開始後数分で白色の結晶が析出しはじめた。
滴下終了後30分間還流加熱して冷却し、テレフタ
ル酸モノメチルモノカリウムの結晶をロ別し、メ
タノール20mlで洗浄して乾燥した（収量10.4
ｇ）。Example 1 9.7 g (0.05 mol) of dimethyl terephthalate was dissolved in 130 g of methanol under reflux heating, and 85
13 ml of a methanol solution containing 4.28 g (0.065 mol) of potassium hydroxide was added dropwise with stirring.
White crystals began to precipitate several minutes after the dropwise addition started.
After the dropwise addition was completed, the mixture was heated under reflux for 30 minutes and cooled, and the crystals of monomethyl monopotassium terephthalate were filtered out, washed with 20 ml of methanol, and dried (yield: 10.4
g).
次いでこの結晶を６重量倍の塩化チオニルと２
時間還流加熱し、過剰の塩化チオニルを留去後、
残留分をｎ―ヘキサンで再結晶した。得られたｐ
―クロロカルボニル安息香酸メチルの収量は7.9
ｇ、融点は52〜53℃であつた。 Next, this crystal was mixed with 6 times the weight of thionyl chloride and 2 times the weight of thionyl chloride.
After heating under reflux for an hour and distilling off excess thionyl chloride,
The residue was recrystallized from n-hexane. The obtained p
-Yield of methyl chlorocarbonylbenzoate is 7.9
g, the melting point was 52-53°C.
このものをジエチルアミンと反応させ、ジエチ
ルアミドとしてガスクロマトグラフイーにより求
めた純度は99％であり、テレフタル酸ジアミドと
して検出されるテレフタロイルクロライドの含有
量は１％以下であつた。 This product was reacted with diethylamine, and the purity determined by gas chromatography as diethylamide was 99%, and the content of terephthaloyl chloride detected as terephthalic acid diamide was 1% or less.
比較例 １
実施例１において、85％水酸化カリウムの使用
量を4.28ｇから3.19ｇ（0.0485モル、テレフタル
酸ジメチルに対するモル比0.97）に減らして、同
様に反応させた。メタノールから析出した結晶
（収量8.8ｇ）は、16％ものテレフタル酸ジメチル
を含有しており、塩素化反応に使用しうる純度の
よいテレフタル酸モノメチルモノカリウムの結晶
ではなかつた。Comparative Example 1 In Example 1, the amount of 85% potassium hydroxide used was reduced from 4.28 g to 3.19 g (0.0485 mol, molar ratio to dimethyl terephthalate 0.97), and the reaction was carried out in the same manner. The crystals precipitated from methanol (yield: 8.8 g) contained as much as 16% dimethyl terephthalate, and were not crystals of monopotassium monomethyl terephthalate with good purity that could be used in the chlorination reaction.
比較例 ２
実施例１において、85％水酸化カリウムの使用
量を5.27ｇ（0.08モル、テレフタル酸ジメチルに
対するモル比1.6）に増加して、同様に反応させ
た。メタノールから析出した結晶（収量9.4ｇ）
を実施例１と同様に塩化チオニルで塩素化し、ｎ
―ヘキサンで再結晶した（収量7.2ｇ、融点51〜
52℃）。Comparative Example 2 In Example 1, the amount of 85% potassium hydroxide used was increased to 5.27 g (0.08 mol, molar ratio to dimethyl terephthalate 1.6), and the reaction was carried out in the same manner. Crystals precipitated from methanol (yield 9.4g)
was chlorinated with thionyl chloride in the same manner as in Example 1, and n
- Recrystallized from hexane (yield 7.2g, melting point 51~
52℃).
ジエチルアミンでアミド化し、テレフタル酸ジ
アミドとしてガスクロマトグラフイーにより求め
たテレフタロイルクロライドの含有量は3.9％で
あつた。 The content of terephthaloyl chloride, which was amidated with diethylamine and determined by gas chromatography as terephthalic acid diamide, was 3.9%.
実施例 ２
実施例１において、塩素化剤として塩化チオニ
ルの代りにオキシ塩化リンを使用した。ｐ―クロ
ロカルボニル安息香酸メチルの収量は7.7ｇ、テ
レフタロイルクロライドの含有量は１％以下であ
つた。Example 2 In Example 1, phosphorus oxychloride was used instead of thionyl chloride as the chlorinating agent. The yield of methyl p-chlorocarbonylbenzoate was 7.7 g, and the content of terephthaloyl chloride was 1% or less.
実施例 ３
実施例１において、塩素化剤として塩化チオニ
ルの代りに三塩化リンを使用した。Example 3 In Example 1, phosphorus trichloride was used instead of thionyl chloride as the chlorinating agent.
ｐ―クロロカルボニル安息香酸メチルの収量は
3.5ｇ、テレフタロイルクロライドの含有量は１
％以下であつた。 The yield of methyl p-chlorocarbonylbenzoate is
3.5g, terephthaloyl chloride content is 1
% or less.
実施例 ４
実施例１において、塩素化剤として塩化チオニ
ルの代りに五塩化リンを用い、さらに溶媒として
テレフタル酸モノメチルモノカリウムに対し10重
量倍のベンゼンを使用した。Example 4 In Example 1, phosphorus pentachloride was used as the chlorinating agent instead of thionyl chloride, and benzene was used in an amount of 10 times the weight of monopotassium terephthalate as the solvent.
ｐ―クロロカルボニル安息香酸メチルの収量は
7.7ｇ、テレフタロイルクロライドの含有量は１
％以下であつた。 The yield of methyl p-chlorocarbonylbenzoate is
7.7g, terephthaloyl chloride content is 1
% or less.
Claims (1)
該テレフタル酸ジメチルに対して1.0〜1.5モル倍
の水酸化カリウムをメタノールに溶解した溶液を
添加して加温下に前記テレフタル酸ジメチルと水
酸化カリウムとを反応させ、生成したテレフタル
酸モノメチルモノカリウム塩の結晶をロ別後、次
いで前記塩と、塩化チオニル、五塩化リン、三塩
化リン及びオキシ塩化リンから選ばれる塩素化剤
とを反応させることを特徴とするｐ―クロロカル
ボニル安息香酸メチルの製造法。1 In a methanol solution of dimethyl terephthalate,
Monopotassium terephthalate monomethyl terephthalate is produced by adding a solution of potassium hydroxide dissolved in methanol in an amount of 1.0 to 1.5 times the mole of dimethyl terephthalate and reacting the dimethyl terephthalate and potassium hydroxide under heating. After filtering the salt crystals, the salt is then reacted with a chlorinating agent selected from thionyl chloride, phosphorus pentachloride, phosphorus trichloride and phosphorus oxychloride. Manufacturing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12813179A JPS5651436A (en) | 1979-10-04 | 1979-10-04 | Preparation of p-chlorocarbonylbenzoic acid methyl ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12813179A JPS5651436A (en) | 1979-10-04 | 1979-10-04 | Preparation of p-chlorocarbonylbenzoic acid methyl ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5651436A JPS5651436A (en) | 1981-05-09 |
| JPS621382B2 true JPS621382B2 (en) | 1987-01-13 |
Family
ID=14977157
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12813179A Granted JPS5651436A (en) | 1979-10-04 | 1979-10-04 | Preparation of p-chlorocarbonylbenzoic acid methyl ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5651436A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02160385A (en) * | 1988-12-13 | 1990-06-20 | Riyousei Denso Kk | Connector housing |
-
1979
- 1979-10-04 JP JP12813179A patent/JPS5651436A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02160385A (en) * | 1988-12-13 | 1990-06-20 | Riyousei Denso Kk | Connector housing |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5651436A (en) | 1981-05-09 |
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