JPH0429963A - Production of benzophenones - Google Patents
Production of benzophenonesInfo
- Publication number
- JPH0429963A JPH0429963A JP13272290A JP13272290A JPH0429963A JP H0429963 A JPH0429963 A JP H0429963A JP 13272290 A JP13272290 A JP 13272290A JP 13272290 A JP13272290 A JP 13272290A JP H0429963 A JPH0429963 A JP H0429963A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- carboxylic acid
- added
- benzophenone
- water
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000012965 benzophenone Substances 0.000 title description 8
- 150000008366 benzophenones Chemical class 0.000 title description 8
- 229940100198 alkylating agent Drugs 0.000 claims abstract description 4
- 239000002168 alkylating agent Substances 0.000 claims abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 4
- 229940111759 benzophenone-2 Drugs 0.000 claims description 12
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 7
- 239000003518 caustics Substances 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 239000011591 potassium Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 4
- -1 alkylester compound Chemical class 0.000 abstract description 3
- 230000002152 alkylating effect Effects 0.000 abstract description 2
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 2
- 229940126062 Compound A Drugs 0.000 abstract 5
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 abstract 5
- 239000002253 acid Substances 0.000 abstract 1
- 230000008021 deposition Effects 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 229940008406 diethyl sulfate Drugs 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- IPVMQJMTBBNONT-UHFFFAOYSA-N 2-ethoxy-n,n-diethylaniline Chemical compound CCOC1=CC=CC=C1N(CC)CC IPVMQJMTBBNONT-UHFFFAOYSA-N 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- WXNRYSGJLQFHBR-UHFFFAOYSA-N bis(2,4-dihydroxyphenyl)methanone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1O WXNRYSGJLQFHBR-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、カラーフォーマ−用中間体として有用な２−
アルコキシ−４−ジアルキルアミノ−ベンゾフェノン−
２′−カルボン酸（以下ベンゾフェノン類という）の製
造法に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention provides a 2-
Alkoxy-4-dialkylamino-benzophenone-
The present invention relates to a method for producing 2'-carboxylic acids (hereinafter referred to as benzophenones).
（従来の技術）
本発明に係るベンゾフェノン類の成る種のものは例えば
、特公昭４Ｂ−２１３２９号公報等で既に知られている
化合物である。即ち、２−エトキシ−４−ジエチルアミ
ノ−ベンゾフェノン−２゛−カルボン酸が開示されてい
るが、本発明者らの知見によれば、このベンゾフェノン
類の製造法としては、ジエチルアミノフェネトールと無
水フタル酸とを塩化アルミニウムの存在下に反応する、
いわゆるフリーデルクラフト反応が一般的である。(Prior Art) The benzophenones according to the present invention are, for example, compounds already known from Japanese Patent Publication No. 4B-21329. That is, 2-ethoxy-4-diethylamino-benzophenone-2'-carboxylic acid is disclosed, but according to the knowledge of the present inventors, the method for producing this benzophenone is to use diethylaminophenetol and phthalic anhydride. and in the presence of aluminum chloride,
The so-called Friedel-Crafts reaction is common.
（発明が解決しようとする課題）
しかしながら、この反応方法では、得られるベンゾフェ
ノン類の収率が低く、また塩化アルミニウムの使用に伴
う製造環境の悪化の問題があった。(Problems to be Solved by the Invention) However, with this reaction method, there are problems in that the yield of the obtained benzophenones is low and the production environment is deteriorated due to the use of aluminum chloride.
（課題を解決するための手段）
本発明者らは、上記の課題を解決すべく鋭意検討を行っ
た結果、ベンゾフェノン類の新規な製造法を見い出した
。即ち、本発明は２−ヒドロキシ４−ジアルキルアミノ
−ベンゾフェノン−２−カルボン酸（以下カルボン酸類
という）を脱酸剤としての苛性カリ存在下にアルキル化
剤でアルキル化したのち、加水分解を行うことを特徴と
する２−アルコキシ−４−ジアルキルアミノ−ベンゾフ
ェノン−２゛−カルボン酸の製造法である。(Means for Solving the Problems) The present inventors conducted extensive studies to solve the above problems, and as a result, discovered a novel method for producing benzophenones. That is, the present invention involves alkylating 2-hydroxy 4-dialkylamino-benzophenone-2-carboxylic acid (hereinafter referred to as carboxylic acids) with an alkylating agent in the presence of caustic potassium as a deoxidizing agent, and then hydrolyzing it. This is a characteristic method for producing 2-alkoxy-4-dialkylamino-benzophenone-2'-carboxylic acid.
本発明は、脱酸剤として苛性カリウムを使用することが
大きな特徴であり、この使用により反応濃度を高めるこ
とが可能であり、結果として目的物であるベンゾフェノ
ン類を高純度高収率で得ることができる。A major feature of the present invention is the use of caustic potassium as a deoxidizing agent. By using this, it is possible to increase the reaction concentration, and as a result, the target benzophenones can be obtained with high purity and high yield. I can do it.
本発明のベンゾフェノン類の製造法の概要を示すと、ま
ずカルボン酸類の重量の１．２〜１．８倍の水に苛性カ
リウム２．１モル比（対カルボン酸類）を加え、次にカ
ルボン酸類を加えて溶解する。この溶液に温度２５〜３
５°Ｃに保ちながら、アルキル化剤２．０５モル比（対
カルボン酸＠）を滴下したのち、同温度でアルキル化反
応を行う。次に必要重量の苛性ソーダと水とを加え、１
００°Ｃ近くで数時間かきまぜ加水分解反応を行ったの
ち、酢酸による酸析で目的物を得ることができる。To outline the method for producing benzophenones of the present invention, first, 2.1 molar ratio of caustic potassium (to carboxylic acids) is added to water 1.2 to 1.8 times the weight of carboxylic acids, and then Add and dissolve. This solution has a temperature of 25-3
After dropping an alkylating agent at a molar ratio of 2.05 (to carboxylic acid@) while maintaining the temperature at 5°C, alkylation reaction is carried out at the same temperature. Next, add the required weight of caustic soda and water, and
After performing a hydrolysis reaction by stirring at around 00°C for several hours, the desired product can be obtained by acid precipitation with acetic acid.
（実施例） 以下実施例を挙げて本発明を具体的に説明する。(Example) The present invention will be specifically explained below with reference to Examples.
実施例１
２−エトキシ−４−ジエチルアミノ−ヘンシフエノン−
２゛−カルボン酸の合成
水１００ｎ＋ｊ２に、２−エトキシ−４−ジエチルアミ
ノ−ベンゾフェノン−２゛−カルボン酸８０．４ｇと４
８．７％苛性カリウム水溶液６２．１ ｇとを加え均一
に溶解した。この溶解液に温度２５〜３２゛Ｃに保ちな
がらジエチル硫酸８１．２ ｇを６０分を要して滴下し
、同温度で５時間かきまぜた。次に、同温度に保ちなが
ら４８．７％苛性カリウム水溶液１７、７ ｇを加え、
ジエチル硫酸２３．８ ｇを３０分間で滴下し、同温度
で１０時間かきまぜた。この反応液に、水６０ｍ１と２
８％苛性ソーダ水溶液４４ｇとを加え、９７〜９９“Ｃ
で３時間かきまぜた後、水３２０ｍ！で希釈し、５５〜
６０°Ｃに保ちながら、２９％酢酸水溶液で中和し同温
度で２時間かきまぜた。析出した沈澱を濾過し、ケーキ
を約６０°Ｃの温水６００ｍＩ！、で洗浄したのち８０
°Ｃで乾燥することにより、淡黄色の２−エトキシ４−
ジエチルアミノ−ベンゾフェノン−２′カルボン酸８５
．１ｇ（１８１，９〜１８２．５°Ｃで分解）を得た。Example 1 2-ethoxy-4-diethylamino-hensiphenon-
Synthesis of 2′-carboxylic acid To 100 n+j2 of water, 80.4 g of 2-ethoxy-4-diethylamino-benzophenone-2′-carboxylic acid and 4
62.1 g of an 8.7% aqueous potassium hydroxide solution was added thereto and uniformly dissolved. To this solution, 81.2 g of diethyl sulfuric acid was added dropwise over 60 minutes while maintaining the temperature at 25-32°C, and the mixture was stirred at the same temperature for 5 hours. Next, while maintaining the same temperature, add 17.7 g of a 48.7% caustic potassium aqueous solution.
23.8 g of diethyl sulfate was added dropwise over 30 minutes, and the mixture was stirred at the same temperature for 10 hours. To this reaction solution, add 60 ml of water and 2
Add 44g of 8% caustic soda aqueous solution and heat to 97-99"C.
After stirring for 3 hours, 320m of water! Dilute with 55~
While maintaining the temperature at 60°C, it was neutralized with a 29% acetic acid aqueous solution and stirred at the same temperature for 2 hours. Filter the precipitate and soak the cake in 600ml of warm water at about 60°C! After washing with
By drying at °C, a pale yellow 2-ethoxy 4-
Diethylamino-benzophenone-2'carboxylic acid 85
．． 1 g (decomposed at 181.9-182.5°C) was obtained.
ＮＭＲおよびＩＲによる分析により目的化合物であるこ
とが確認できた。The target compound was confirmed by NMR and IR analysis.
実施例２
２−メトキシ−４−ジブチル−ベンゾフェノン２′−カ
ルボン酸の合成
水９０＋ｎｆｆ１に２−ヒドロキシ−４−ジブチルアミ
ノ−ベンゾフェノン−２′−カルボン酸７３．９ｇと４
８．７％苛性カリウム水溶液４８．２ ｇとを加え、い
ったん６０°Ｃに加温して均一に溶解する。Example 2 Synthesis of 2-methoxy-4-dibutyl-benzophenone-2'-carboxylic acid 73.9 g of 2-hydroxy-4-dibutylamino-benzophenone-2'-carboxylic acid and 4
Add 48.2 g of an 8.7% aqueous solution of potassium hydroxide, and once warm to 60°C to uniformly dissolve.
次に温度３０〜３５°Ｃに保ち、ジメチル硫酸５１．７
ｇを６０分を要して滴下し、４時間かきまぜた。Next, keep the temperature at 30-35°C and dimethyl sulfate 51.7
g was added dropwise over 60 minutes and stirred for 4 hours.
更に、４８．７％苛性カリウム水溶液２４．２ ｇを加
え、３０〜３５°Ｃに保ちながら、ジメチル硫酸２５、
７ ｇを２０分間で加え、同温度で１０時間かえ、９５
〜９８°Ｃで６時間かきまぜた。次に５００へ
ｍｊ２を加え、５０〜５５°Ｃに保ち、２０％酢酸水溶
液１２０ｇを加えて中和し、１時間かきまぜた後、決別
し、濾過ケーキを約６０°Ｃの温水５００ｍＩ！、で洗
浄し、８０°Ｃで乾燥することにより淡黄色の２−メト
キシ−４−ジブチルアミノ−ベンゾフェノン−２′−カ
ルボン酸、７４．５ｇ （ｍ、ｐ。Furthermore, 24.2 g of 48.7% caustic potassium aqueous solution was added, and while maintaining the temperature at 30 to 35°C, 25 g of dimethyl sulfate,
Add 7 g over 20 minutes and leave at the same temperature for 10 hours.95
Stir at ~98°C for 6 hours. Next, add mj2 to 500, keep at 50-55°C, neutralize by adding 120g of 20% acetic acid aqueous solution, stir for 1 hour, separate, and pour the filter cake into 500mI of warm water at about 60°C! , and drying at 80°C to give pale yellow 2-methoxy-4-dibutylamino-benzophenone-2'-carboxylic acid, 74.5 g (m, p.
１６０〜１６２．２゛Ｃ分解）を得た。ＮＭＲおよびＩ
Ｒ分析により目的化合物であることが確認できた。160-162.2°C decomposition) was obtained. NMR and I
The target compound was confirmed by R analysis.
実施例３
２−エトキシ−、ＩＮ−シクロヘキシル−Ｎ−メチル−
ベンゾフェノン−２′−カルボン酸の合成
水５０ｍ１に、２−ヒドロキシ−Ｎ−シクロへキシル−
Ｎ−メチル−ベンゾフェノン−２′−カルボン酸２８．
２ ｇと４８．７％苛性カリウム水液１９、４ ｇとを
加え、−旦６０″Ｃに加温溶解する。Example 3 2-ethoxy-, IN-cyclohexyl-N-methyl-
Synthesis of benzophenone-2'-carboxylic acid To 50 ml of water, add 2-hydroxy-N-cyclohexyl-
N-Methyl-benzophenone-2'-carboxylic acid 28.
2 g and 19.4 g of a 48.7% aqueous potassium hydroxide solution were added, and the mixture was heated and dissolved at 60''C.
２５〜３０°Ｃに保ち、ジエチル硫酸２５．３ ｇを４
０分で滴下した。同温度で４時間かきまぜた後、４８．
７％苛性カリウム水溶液９．７ｇを加え、２５〜３０°
Ｃに保ち、ジエチル硫酸１２．７ ｇを２０分で滴下し
た。３０〜３５°Ｃで１２時間かきまぜた後、９．３％
苛性ソーダ水溶液１２０ｇを加え９８°Ｃで７時間かき
まぜた。水４００ｍｊ２を加え、５５〜６０°Ｃに保ち
、３０％酢酸水溶液１２０ｇで中和し、２時間かきまぜ
た後濾過した。濾過ケーキは５０°Ｃの温水３００ｍｌ
で洗浄し、８０°Ｃで乾燥した。淡黄色の２−エトキシ
−４−Ｎ−シクロへキシル−Ｎ−メチル−ベンゾフェノ
ン−２′カルボン酸２９．０ ｇを得た。融点は１８３
．０〜１８５、６°Ｃで分解した。またＮＭＲおよびＩ
Ｒより目的物であることを確認した。Keep at 25-30°C and add 25.3 g of diethyl sulfate to 4
It was dropped in 0 minutes. After stirring at the same temperature for 4 hours, 48.
Add 9.7 g of 7% caustic potassium aqueous solution and heat at 25-30°
12.7 g of diethyl sulfate was added dropwise over 20 minutes. After stirring at 30-35°C for 12 hours, 9.3%
120 g of caustic soda aqueous solution was added and stirred at 98°C for 7 hours. 400 mj2 of water was added, kept at 55-60°C, neutralized with 120 g of 30% acetic acid aqueous solution, stirred for 2 hours, and then filtered. Filter cake with 300ml of 50°C warm water
and dried at 80°C. 29.0 g of pale yellow 2-ethoxy-4-N-cyclohexyl-N-methyl-benzophenone-2'carboxylic acid was obtained. Melting point is 183
．． 0-185, decomposed at 6°C. Also NMR and I
It was confirmed from R that it was the desired product.
保土谷化学工業株式会社Hodogaya Chemical Industry Co., Ltd.
Claims (1)
ン−２′−カルボン酸を脱酸剤としての苛性カリ存在下
にアルキル化剤でアルキル化したのち、加水分解を行う
ことを特徴とする２−アルコキシ−４−ジアルキルアミ
ノ−ベンゾフェノン−２′−カルボン酸の製造法。2-Alkoxy-4-, which is characterized in that 2-hydroxy-4-dialkylamino-benzophenone-2'-carboxylic acid is alkylated with an alkylating agent in the presence of caustic potassium as a deoxidizing agent, and then hydrolyzed. Method for producing dialkylamino-benzophenone-2'-carboxylic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13272290A JPH0429963A (en) | 1990-05-24 | 1990-05-24 | Production of benzophenones |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13272290A JPH0429963A (en) | 1990-05-24 | 1990-05-24 | Production of benzophenones |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0429963A true JPH0429963A (en) | 1992-01-31 |
Family
ID=15088055
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13272290A Pending JPH0429963A (en) | 1990-05-24 | 1990-05-24 | Production of benzophenones |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0429963A (en) |
-
1990
- 1990-05-24 JP JP13272290A patent/JPH0429963A/en active Pending
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