JPH01117858A - Production of di(hydroxyphenylthio)dioxaheptane - Google Patents
Production of di(hydroxyphenylthio)dioxaheptaneInfo
- Publication number
- JPH01117858A JPH01117858A JP62273405A JP27340587A JPH01117858A JP H01117858 A JPH01117858 A JP H01117858A JP 62273405 A JP62273405 A JP 62273405A JP 27340587 A JP27340587 A JP 27340587A JP H01117858 A JPH01117858 A JP H01117858A
- Authority
- JP
- Japan
- Prior art keywords
- solvent
- dioxaheptane
- hydroxyphenylthio
- methane
- bis
- 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
- CQHWDIMRMOEVRY-UHFFFAOYSA-N 2-[1-hydroperoxy-1-(2-hydroxyphenyl)sulfanylpentyl]sulfanylphenol Chemical compound OC1=C(C=CC=C1)SC(OO)(CCCC)SC1=C(C=CC=C1)O CQHWDIMRMOEVRY-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 239000002904 solvent Substances 0.000 claims abstract description 24
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 9
- 238000010583 slow cooling Methods 0.000 claims abstract description 4
- VMKYTRPNOVFCGZ-UHFFFAOYSA-N 2-sulfanylphenol Chemical compound OC1=CC=CC=C1S VMKYTRPNOVFCGZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 30
- 239000013078 crystal Substances 0.000 abstract description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 13
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 abstract description 12
- 239000002245 particle Substances 0.000 abstract description 8
- 150000001875 compounds Chemical class 0.000 abstract description 7
- 238000001816 cooling Methods 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 7
- BXAVKNRWVKUTLY-UHFFFAOYSA-N 4-sulfanylphenol Chemical compound OC1=CC=C(S)C=C1 BXAVKNRWVKUTLY-UHFFFAOYSA-N 0.000 abstract description 5
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- -1 methanol Chemical compound 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- 239000011780 sodium chloride Substances 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 4
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- NLXGURFLBLRZRO-UHFFFAOYSA-N 1-chloro-2-(2-chloroethoxymethoxy)ethane Chemical compound ClCCOCOCCCl NLXGURFLBLRZRO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- XXXFZKQPYACQLD-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethyl acetate Chemical compound CC(=O)OCCOCCO XXXFZKQPYACQLD-UHFFFAOYSA-N 0.000 description 1
- OVOUKWFJRHALDD-UHFFFAOYSA-N 2-[2-(2-acetyloxyethoxy)ethoxy]ethyl acetate Chemical compound CC(=O)OCCOCCOCCOC(C)=O OVOUKWFJRHALDD-UHFFFAOYSA-N 0.000 description 1
- HZIJXNRGQFAGJR-UHFFFAOYSA-N 2-[2-(2-hydroxyethoxy)ethoxy]ethyl acetate Chemical compound CC(=O)OCCOCCOCCO HZIJXNRGQFAGJR-UHFFFAOYSA-N 0.000 description 1
- DXYGJDUJLDXFOD-UHFFFAOYSA-N 2-[2-[2-(2-acetyloxyethoxy)ethoxy]ethoxy]ethyl acetate Chemical compound CC(=O)OCCOCCOCCOCCOC(C)=O DXYGJDUJLDXFOD-UHFFFAOYSA-N 0.000 description 1
- OZVKHOPICATTIK-UHFFFAOYSA-N 2-[2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]ethyl acetate Chemical compound CC(=O)OCCOCCOCCOCCO OZVKHOPICATTIK-UHFFFAOYSA-N 0.000 description 1
- MBGINZGOPMLHQN-UHFFFAOYSA-N 2-[2-[2-[2-(2-acetyloxyethoxy)ethoxy]ethoxy]ethoxy]ethyl acetate Chemical compound CC(=O)OCCOCCOCCOCCOCCOC(C)=O MBGINZGOPMLHQN-UHFFFAOYSA-N 0.000 description 1
- XPSWWUUYXYTSCW-UHFFFAOYSA-N 2-[2-[2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]ethoxy]ethyl acetate Chemical compound CC(=O)OCCOCCOCCOCCOCCO XPSWWUUYXYTSCW-UHFFFAOYSA-N 0.000 description 1
- JTXMVXSTHSMVQF-UHFFFAOYSA-N 2-acetyloxyethyl acetate Chemical compound CC(=O)OCCOC(C)=O JTXMVXSTHSMVQF-UHFFFAOYSA-N 0.000 description 1
- HXDLWJWIAHWIKI-UHFFFAOYSA-N 2-hydroxyethyl acetate Chemical compound CC(=O)OCCO HXDLWJWIAHWIKI-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical class C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 238000009835 boiling Methods 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
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- UBPGILLNMDGSDS-UHFFFAOYSA-N diethylene glycol diacetate Chemical compound CC(=O)OCCOCCOC(C)=O UBPGILLNMDGSDS-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- KLKFAASOGCDTDT-UHFFFAOYSA-N ethoxymethoxyethane Chemical compound CCOCOCC KLKFAASOGCDTDT-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 210000003608 fece Anatomy 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- UHHKSVZZTYJVEG-UHFFFAOYSA-N oxepane Chemical compound C1CCCOCC1 UHHKSVZZTYJVEG-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/333—Colour developing components therefor, e.g. acidic compounds
- B41M5/3333—Non-macromolecular compounds
- B41M5/3335—Compounds containing phenolic or carboxylic acid groups or metal salts thereof
- B41M5/3336—Sulfur compounds, e.g. sulfones, sulfides, sulfonamides
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
- 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］
本発明はジ（ヒドロキシフェニルチオ）ジオキサヘプタ
ンに関し、詳しくは感熱記録紙用顕色剤として有用な１
．７−ジ（トヒドロキシフェニルチオ）−３，５−ジオ
キサヘプタンの効率的な製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to di(hydroxyphenylthio)dioxaheptane, and more specifically to di(hydroxyphenylthio)dioxaheptane, which is useful as a color developer for thermal recording paper.
．． The present invention relates to an efficient method for producing 7-di(tohydroxyphenylthio)-3,5-dioxaheptane.
［従来の技術］
感熱記録紙用顕色剤として有用な！、７−ジ（トヒドロ
キシフェニルチオ）−３，Ｓ−ジオキサヘプタンは、ト
メルカプトフェノールとビス（２−ハロエトキシ）メタ
ンとを反応させて製造しうろことが知られている。[Prior art] Useful as a color developer for thermal recording paper! , 7-di(tohydroxyphenylthio)-3,S-dioxaheptane is known to be produced by reacting tomercaptophenol and bis(2-haloethoxy)methane.
この製造においては、水酸化ナトリウム等のアルカリと
メタノール等の溶媒を用いて反応を行い、つづいて溶媒
除去工程、晶析工程、分離工程、水洗工程および乾燥工
程等の精製工程を経て、目的物を得る。In this production, a reaction is performed using an alkali such as sodium hydroxide and a solvent such as methanol, followed by a purification process such as a solvent removal process, a crystallization process, a separation process, a water washing process, and a drying process. get.
これらの工程のうちの晶析工程としては、４−メルカブ
トフェノールとビス（２−ハロエトキシ）メタンとの反
応生成物に常温の水を加えて急冷する方法が知られてい
る（特開昭６０−２８９５９号公報）。As a crystallization step among these steps, a method is known in which water at room temperature is added to the reaction product of 4-mercabutophenol and bis(2-haloethoxy)methane to quench it (Japanese Patent Application Laid-open No. 1983-1999). -28959).
しかしながら、急冷によって晶析した！、７−ジ（４−
ヒドロキシフェニルチオ）−３，Ｓジオキサヘプタンの
結晶は微細であり、しかも析出時に副生成物である塩化
ナトリウムなどのアルカリ金属のハロゲン化物や有機物
質の溶けた水を含有して取り込んでしまうため、乾燥し
ても水が完全に除去できない欠点、純度が上がらず着色
しやすい欠点、さらには感熱記録紙の顕色剤として使用
した場合、融点が低下して耐熱性が低下するといういわ
ゆるかぶり現象を生じやすい欠点があった。However, it crystallized upon rapid cooling! , 7-di(4-
The crystals of hydroxyphenylthio)-3,S dioxaheptane are fine, and when they are precipitated, they contain and incorporate alkali metal halides such as sodium chloride, which are by-products, and water in which organic substances are dissolved. , the disadvantage that water cannot be completely removed even when dried, the disadvantage that the purity does not increase and it is easily colored, and the so-called fogging phenomenon that when used as a color developer for thermal recording paper, the melting point decreases and the heat resistance decreases. There was a drawback that it was easy to cause.
この欠点は適当な有機溶媒等を用いて再結晶を行えばあ
る程度は改善されるが、再結晶操作による製品の収率は
非常に大きく低下し、工業的には不利であった。Although this drawback can be improved to some extent by recrystallization using a suitable organic solvent, the yield of the product due to the recrystallization operation is greatly reduced, which is industrially disadvantageous.
［発明が解決しようとする問題点］
この発明は比較的粒径の大きい結晶として、さらに不純
物をほとんど含まない結晶を再結晶させる工程を省略で
きる １．７−ジ（４−ヒドロキシフェニルチオ） −
３，５−ジオキサヘプタンの製造方法を提供することを
目的とする。[Problems to be Solved by the Invention] This invention makes it possible to omit the step of recrystallizing crystals with relatively large particle size and containing almost no impurities. 1.7-di(4-hydroxyphenylthio) -
An object of the present invention is to provide a method for producing 3,5-dioxaheptane.
［問題点を解決するための手段］
本発明者らは前記問題点を解決する方法を鋭意研究の結
果、反応後の反応液の後処理において温水を加えて特定
の速度で非常にゆっくり冷却することにより、これを解
決できることを見出し、本発明をなすに至った。[Means for Solving the Problems] As a result of intensive research into a method for solving the above-mentioned problems, the present inventors found that in post-treatment of the reaction solution after the reaction, hot water is added to cool it very slowly at a specific rate. The inventors have found that this problem can be solved by doing so, and have come up with the present invention.
すなわち、本発明は、アルカリ及び溶媒の存在下で、メ
ルカプトフェノールとビス（ハロエトキシ）メタンとを
反応させて得られる反応生成溶液から溶媒を除去し、つ
いで反応生成物に温水を加えて徐冷することを特徴とす
るジ（ヒドロキシフェニルチオ）ジオキサヘプタンの製
造方法を提供するものである。That is, in the present invention, the solvent is removed from a reaction product solution obtained by reacting mercaptophenol and bis(haloethoxy)methane in the presence of an alkali and a solvent, and then warm water is added to the reaction product to slowly cool it. The present invention provides a method for producing di(hydroxyphenylthio)dioxaheptane characterized by the following.
本発明に用いるアルカリは、アルカリ金属の水酸化物、
炭酸塩、重炭酸塩、例えば、Ｎ ａ ＯＨ５ＫＯＨ，Ｎ
ａ２ＣＯ，、ＮａＨＣＯ３、Ｋ ２ ＣＯｓ、ＫＨＣＯ
，などを好適に使用することができる。The alkali used in the present invention is an alkali metal hydroxide,
Carbonates, bicarbonates, such as N a OH5KOH, N
a2CO,, NaHCO3, K2COs, KHCO
, etc. can be suitably used.
本発明に用いることのできる溶媒は、例えば次の３種に
大別することができる。Solvents that can be used in the present invention can be roughly classified, for example, into the following three types.
（１）炭素数が１〜４のアルコール。(1) Alcohol having 1 to 4 carbon atoms.
例えば、メチルアルコール、エチルアルコール、ｎ−プ
ロピルアルコール、ｉ−プロピルアルコール、ブチルア
ルコールなどが好適に使用することができる。For example, methyl alcohol, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, butyl alcohol, etc. can be suitably used.
（２）式Ｒ−（ＯＣＨｚＣＩｌｉ）ｎ−ＯＲ’で表わさ
れるエチレンオキシド類（式中、Ｒ，Ｒ’−水素原子ま
たは良素数１〜６のアルキル基またはアセトキシ基）。(2) Ethylene oxides represented by the formula R-(OCHzCIli)n-OR' (wherein R,R'-hydrogen atom, alkyl group having 1 to 6 prime numbers, or acetoxy group).
この式に該当する具体的な化合物としては、ｎの数値に
応じ、次のものをそれぞれ使用することができる。As specific compounds corresponding to this formula, the following can be used depending on the value of n.
ｎ＝１の場合の化合物例
エチレングリコール、エチレングリコールモノアルキル
エーテル、エチレングリコールジアルキルエーテル、エ
チレングリコールモノアセテート、エチレングリコール
ジアセテート、エチレングリコールモノアルキルエーテ
ルモノアセテート。Examples of compounds when n=1: ethylene glycol, ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, ethylene glycol monoacetate, ethylene glycol diacetate, ethylene glycol monoalkyl ether monoacetate.
ｎ＝２の場合の化合物例
ジエチレングリコール、ジエチレングリコールモノアル
キルエーテル、ジエチレングリコールジアルキルエーテ
ル、ジエチレングリコールモノアセテート、ジエチレン
グリコールジアセテート、ジエチレングリコールモノア
ルキルエーテル七ノ゛アセテート。Examples of compounds when n=2: diethylene glycol, diethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, diethylene glycol monoacetate, diethylene glycol diacetate, diethylene glycol monoalkyl ether 7-acetate.
ｎ窮３の場合の化合物例
トリエチレングリコール、トリエチレングリコールモノ
アルキルエーテル、トリエチレングリコールジアルキル
エーテル、トリエチレングリコールモノアセテート、ト
リエチレングリコールジアセテート、トリエチレングリ
コールモノアルキルエーテルモノアセテート。Examples of compounds in the case of n3: triethylene glycol, triethylene glycol monoalkyl ether, triethylene glycol dialkyl ether, triethylene glycol monoacetate, triethylene glycol diacetate, triethylene glycol monoalkyl ether monoacetate.
ｎ−４の場合の化合物例
テトラエチレングリコール、テトラエチレングリコール
モノアルキルエーテル、テトラエチレングリコールジア
ルキルエーテル、テトラエチレングリコールモノアセテ
ート、テトラエチレングリコールジアセテート、テトラ
エチレングリコールモノアルキルエーテルモノアセテー
ト。Compound examples for n-4 Tetraethylene glycol, tetraethylene glycol monoalkyl ether, tetraethylene glycol dialkyl ether, tetraethylene glycol monoacetate, tetraethylene glycol diacetate, tetraethylene glycol monoalkyl ether monoacetate.
ｎ＝５の場合の化合物例
ペンタエチレングリコール、ペンタエチレングリコール
モノアルキルエーテル、ペンタエチレングリコールジア
ルキルエーテル、ペンタエチレングリコールモノアセテ
ート、ペンタエチレングリコールジアセテート、ペンタ
エチレングリコールモノアルキルエーテルモノアセテー
ト。Examples of compounds when n=5: pentaethylene glycol, pentaethylene glycol monoalkyl ether, pentaethylene glycol dialkyl ether, pentaethylene glycol monoacetate, pentaethylene glycol diacetate, pentaethylene glycol monoalkyl ether monoacetate.
前記式中の置換基としての炭素数１〜６のアルキル酸は
メチル、エチル、ｎ−プロピル、ｉ−プロピル、ブチル
、ペンチル、ヘキシル等が好適である。The alkyl acid having 1 to 6 carbon atoms as a substituent in the above formula is preferably methyl, ethyl, n-propyl, i-propyl, butyl, pentyl, hexyl, or the like.
（３）炭、素数３〜６の環状エーテル。(3) Carbon, a cyclic ether with a prime number of 3 to 6.
Ｉ；とえば、下記式に示すテトラヒドロフラン、テトラ
ヒドロビラン、オキセパン、ジオキソラン、ジオキサン
、トリオキサン、トリオキサシクロノナンを使用するこ
とができる。I; For example, tetrahydrofuran, tetrahydrobilane, oxepane, dioxolane, dioxane, trioxane, trioxacyclononane shown in the following formula can be used.
一一一−ノ゛
本発明における溶剤の使用量は、４−メルカプトフェノ
ール１モルに対して、４０〜２０００ｍ１１゜好ましく
は、８０〜１０００１００Ｏとすることができる。111-The amount of the solvent used in the present invention can be 40 to 2,000 ml, preferably 80 to 1,000,100 mol per mole of 4-mercaptophenol.
本発明における原料の使用量は、トメルカプトフェノー
ル１モルに対し、ビス（２−ハロエトキシ）メタン０．
２〜２モル、好ましくは、０．４〜１モル、アルカリは
アルカリ金属として０．４〜４モル、好ましくは、０．
８〜２モルを使用することができる。The amount of raw materials used in the present invention is 0.00% bis(2-haloethoxy)methane per 1 mole of tomercaptophenol.
2 to 2 mol, preferably 0.4 to 1 mol, and the alkali is 0.4 to 4 mol, preferably 0.4 to 4 mol as alkali metal.
8 to 2 mol can be used.
原料の仕込み順序に制限はないが、通常はトメルカプト
フェノールとアルカリと溶媒を反応器の採り、これにビ
ス（２−ハロエトキシ）メタンを添加するか又は４−メ
ルカプトフェノールとビス（２−ハロエトキシ）メタン
と溶媒を反応器に採り、これにアルカリを添加するのが
望ましい。There is no restriction on the order in which the raw materials are charged, but usually tomercaptophenol, alkali, and solvent are placed in a reactor, and bis(2-haloethoxy)methane is added to this, or 4-mercaptophenol and bis(2-haloethoxy) Preferably, methane and solvent are placed in a reactor and an alkali is added thereto.
本発明の反応圧力に特に制限はないが、通常は常圧で行
うことができ、反応温度は０〜１５０℃、好ましくは２
０〜１００℃が好適であり、通常反応は０．１〜１２時
間で終了する。The reaction pressure of the present invention is not particularly limited, but it can usually be carried out at normal pressure, and the reaction temperature is 0 to 150°C, preferably 2.
A temperature of 0 to 100°C is suitable, and the reaction is usually completed in 0.1 to 12 hours.
反応終了後、溶媒を留去させる。溶媒の沸点に応じて減
圧又は常圧で加熱して留去させる。After the reaction is completed, the solvent is distilled off. The solvent is distilled off by heating under reduced pressure or normal pressure depending on the boiling point of the solvent.
本発明の方法では、溶媒は一部残して留去することがで
きる。In the method of the present invention, a portion of the solvent can be distilled off.
本発明においては、溶媒の留去の後、温水を添加して撹
拌し、生成物を溶解させる。In the present invention, after the solvent is distilled off, warm water is added and stirred to dissolve the product.
本発明に用いる温水は、温度は４０〜１００°Ｃ１好ま
しくは５０〜９０℃、使用量は、溶媒及び無機物を除い
た後の反応生成物１００ｇ当たり３０〜１０００１００
Ｏ，好ましくは５０〜５００ｍ１である。The temperature of the hot water used in the present invention is 40 to 100°C, preferably 50 to 90°C, and the amount used is 30 to 1,000,100 g per 100 g of the reaction product after removing the solvent and inorganic substances.
O, preferably 50 to 500 ml.
本発明に用いる冷却速度は５〜ｂ
ましくは７〜１５°Ｏ／ｈｒであり、室温程度まで冷却
する。The cooling rate used in the present invention is 5 to 15 degrees O/hr, preferably 7 to 15 degrees O/hr, and the material is cooled to about room temperature.
このゆるやかな冷却方法により得られる結晶は板状で、
粒径は結晶の最大長さを顕微鏡で観察してその平均値で
測定して５０〜５００μｍ、板状の厚さは同じく平均値
５〜１００μｍのものが得られる。The crystals obtained by this slow cooling method are plate-shaped.
The particle size is determined by observing the maximum length of the crystals with a microscope and measuring the average value of 50 to 500 μm, and the plate-like thickness is also obtained with an average value of 5 to 100 μm.
本発明の方法によって得られるジ（ヒドロキシフェニル
チオ）ジオキサヘプタンの純度は高速液体クロマトグラ
フィーによる測定によれば、９３．０〜９９．９重量％
である。The purity of di(hydroxyphenylthio)dioxaheptane obtained by the method of the present invention is 93.0 to 99.9% by weight as determined by high performance liquid chromatography.
It is.
［発明の効果］
本発明によれば、簡単な工程により収率よくジ（ヒドロ
キシフェニルチオ）ジオキサヘプタンを製造することが
できる。その上、粒径が大きく、かつ、純度の高い結晶
を得ることができる利点がある。[Effects of the Invention] According to the present invention, di(hydroxyphenylthio)dioxaheptane can be produced with good yield through simple steps. Moreover, there is an advantage that crystals having a large particle size and high purity can be obtained.
［実施例］ 本発明を実施例によりさらに詳細に説明する。[Example] The present invention will be explained in more detail with reference to Examples.
実施例１
撹拌装置、温度計、ジムロート冷却管、及び滴下ロート
を備えた２１１の４つロフラスコに（−゛メルカプトフ
ェノール１２６．２９、ビス（２−クロルエトキシ）メ
タン８６．５９、及びメタノール１２５ｍ１＋を仕込み
、室温下で混合溶解させＩ；。この溶液を撹拌しながら
、あらかじめ水酸化ナトリウム４２．０９をメタノール
３４５ｍＱにより溶解した溶液を室温下で５０分間に互
って滴下した。Example 1 In a 211 four-neck flask equipped with a stirrer, a thermometer, a Dimroth condenser, and an addition funnel, 126.29 ml of -mercaptophenol, 86.59 ml of bis(2-chloroethoxy)methane, and 125 ml of methanol were charged. While stirring this solution, a solution prepared by dissolving 42.09 m of sodium hydroxide in 345 mQ of methanol was added dropwise to the mixture over a period of 50 minutes at room temperature.
反応混合溶液は、水酸化ナトリウムのメタノール溶液を
滴下している途中に塩化ナトリウムが析出し、次第に不
均一の懸濁状に変化した。Sodium chloride precipitated during the dropwise addition of the methanol solution of sodium hydroxide, and the reaction mixture solution gradually turned into a non-uniform suspension.
引き続き、油浴を用いてフラスコを加熱し、溶媒の還流
下で温度６５〜６８℃で４時間反応させＩこ 。Subsequently, the flask was heated using an oil bath, and the reaction was carried out at a temperature of 65 to 68° C. for 4 hours under reflux of the solvent.
反応終了後、フラスコからジムロート冷却管を取り外し
、クライゼンヘッド、リービッヒ冷却管、および受器を
備えつけ、大気圧下で溶媒を留出させ、２００ｍＡのメ
タノールを回収した。フラスコ内の人糞は、塩化ナトリ
ウムの白色沈澱を含む淡黄色の液体であった。After the reaction was completed, the Dimroth condenser was removed from the flask, and a Claisen head, a Liebig condenser, and a receiver were installed, and the solvent was distilled off under atmospheric pressure to recover 200 mA of methanol. The human feces in the flask was a pale yellow liquid containing a white precipitate of sodium chloride.
ここで得られたメタノールを含む温度７０°Ｃの反応生
成物に、温度６５°Ｃの水２５０ｍＡを添加し撹拌した
ところ、均一に溶解した。引き続き、湯浴の中に入れ、
湯浴の温度を自動温度調節により加熱又は冷却して調節
しながら、４時間かけて一定の冷却速度でフラスコ内温
を２０°Ｃまで冷却した。さらに２０’Ｏで２時間放置
し、完全に晶析させた。なお徐冷中は、温度を均一に保
つため、液をゆっくり撹拌した。When 250 mA of water at a temperature of 65°C was added to the obtained reaction product containing methanol at a temperature of 70°C and stirred, it was uniformly dissolved. Next, put it in a hot water bath,
While adjusting the temperature of the water bath by heating or cooling using automatic temperature control, the internal temperature of the flask was cooled to 20° C. at a constant cooling rate over 4 hours. The mixture was further left at 20'O for 2 hours to completely crystallize. During slow cooling, the liquid was slowly stirred to keep the temperature uniform.
ここで析出しｔ；結晶を減圧下でろ過し、さらに温度２
５°Ｃの２００ｍ１の水で洗浄後、真空乾燥機を用いて
、温度ｓｏ’ｃで８時間乾燥させ、白色の１．７−ジ（
４−ヒドロキシフェニルチオ） −３，５−ジオキサヘ
プタンの結晶１７０．５９を得た。この結晶を高速液体
クロマトグラフィーにより純度を測定した結果、９９．
４重量％であった。At this point, precipitation occurs; the crystals are filtered under reduced pressure, and further heated to 2
After washing with 200 ml of water at 5°C, it was dried in a vacuum dryer at a temperature of SO'C for 8 hours to obtain a white 1,7-di(
170.59 crystals of 4-hydroxyphenylthio)-3,5-dioxaheptane were obtained. The purity of this crystal was measured by high performance liquid chromatography and the purity was found to be 99.
It was 4% by weight.
この収量は、４−メルカプトフェノール基準の収率で９
６．２モル％に相当する。This yield is 9% based on 4-mercaptophenol.
This corresponds to 6.2 mol%.
また顕微鏡による測定の結果、平均粒子径は非常に大き
く、２２３μｍであった。Further, as a result of measurement using a microscope, the average particle diameter was found to be very large, 223 μm.
実施例２
実施例１と同様のフラスコに、トメルカプトフェノール
１２６．２９水酸化ナトリウム４２．０９、及びエチレ
ングリコールモノエチルエーテル５００ｍＱを仕込み、
室温下で混合溶解させた。この溶液を撹拌しながら、ビ
ス（２−クロルエトキシ）メタン８６．５９を室温下で
４０分間に互って滴下した。Example 2 A flask similar to Example 1 was charged with 126.29 mQ of tomercaptophenol, 42.09 mQ of sodium hydroxide, and 500 mQ of ethylene glycol monoethyl ether.
Mix and dissolve at room temperature. While stirring this solution, 86.59 g of bis(2-chloroethoxy)methane was added dropwise over 40 minutes at room temperature.
反応混合溶液は、ビス（２−クロルエトキシ）メタンを
滴下している途中に塩化ナトリウムが析出し、次第に不
均一の懸濁状に変化した。During the dropwise addition of bis(2-chloroethoxy)methane, sodium chloride precipitated from the reaction mixture solution, and the solution gradually turned into a non-uniform suspension.
引き続き、油浴を用いてフラスコを加熱し、温度７０°
Ｃで３時間反応させｔ；。Subsequently, heat the flask using an oil bath until the temperature reaches 70°.
React at C for 3 hours.
反応終了後、実施例１と同様な装置で、溶液の温度８０
℃において、２５〜３０ｍｍＨｇの減圧下で溶媒を留出
させ、１２０ｍ１ｔのエチレングリコールモノエチルエ
ーテルを回収シタ。After the reaction was completed, the temperature of the solution was increased to 80°C using the same apparatus as in Example 1.
℃, the solvent was distilled off under reduced pressure of 25 to 30 mmHg, and 120 ml of ethylene glycol monoethyl ether was recovered.
ここで得られた反応生成物に対して、実施例１・の温度
６５℃の温水２５０ｍ１を３５０ｍ１に増加した以外は
実施例１と同様な操作を行い、白色の１．７−ジ（４−
ヒドロキシフェニルチオ） −３，Ｓ−ジオキサヘプタ
ンの結晶１６０．３９を得た。この結晶を高速液体クロ
マトグラフィーにより純度を測定して、９９．１重量％
を得た。The reaction product obtained here was subjected to the same operation as in Example 1, except that the 250 ml of warm water at a temperature of 65°C in Example 1 was increased to 350 ml, and a white 1,7-di(4-
160.39 crystals of hydroxyphenylthio-3,S-dioxaheptane were obtained. The purity of this crystal was measured by high performance liquid chromatography and was found to be 99.1% by weight.
I got it.
これは、トメルカプトフェノール基準の収率で９０．１
モル％に相当する。この結晶の顕微鏡測定による平均粒
子径は非常に大きく、１９７μｍでありｔ；。This is a yield of 90.1 based on tomercaptophenol.
Corresponds to mol%. The average particle size of these crystals measured using a microscope is very large, 197 μm.
比較例
実施例１と同様の装置を用い、実施例１と同様の仕込み
で同様の操作を行って反応させた。Comparative Example Using the same apparatus as in Example 1, the same preparations and the same operations as in Example 1 were carried out to cause a reaction.
反応終了後、実施例１と同様の装置を用い、大気圧下で
溶媒を留出させ、３９０ｍ１ｌのメタノールを回収した
。After the reaction was completed, the solvent was distilled off under atmospheric pressure using the same apparatus as in Example 1, and 390 ml of methanol was recovered.
その後、７０°Ｃの反応生成物に温度２５℃の水５００
ＩＩｌηを添加し、６５℃から２０℃まで３０分間かけ
て冷却した。この冷却は氷水浴を使用して撹拌しながら
行った。続いて実施例１と同様の操作を行い、１８Ｌ１
ｇの淡黄色の微細結晶を得た。After that, the reaction product at 70°C was mixed with 500 g of water at a temperature of 25°C.
IIlη was added and cooled from 65°C to 20°C over 30 minutes. This cooling was done using an ice water bath with stirring. Subsequently, the same operation as in Example 1 was performed, and 18L1
A pale yellow fine crystal of g was obtained.
この結晶は水、塩化ナトリウムおよび有機不純物成分を
含有しており、高速液体クロマトグラフィによる純度は
８９．４重量％、４−メルカプトフェノール基準の収率
は９５．４モル％であり、結晶の平均粒子径は７μｍで
あった。These crystals contain water, sodium chloride, and organic impurity components, and the purity determined by high-performance liquid chromatography is 89.4% by weight, the yield based on 4-mercaptophenol is 95.4% by mole, and the average particle size of the crystals is 89.4% by weight. The diameter was 7 μm.
この淡黄色の結晶は純度が低いものであったので、メタ
ノール１５容量％とトルエン８５容量％の混合溶媒４０
０ｍＱを用い、再結晶を行った結果、白色結晶１２３．
２９を得た。この再結晶して得た結晶の純度は９８．３
重量％、（−メルカプトフェノール基準の収率は６８．
７モル％であり、平均粒子径は８５μｍであった。These pale yellow crystals were of low purity, so a mixed solvent of 15% by volume methanol and 85% by volume toluene was used.
As a result of recrystallization using 0mQ, white crystals 123.
I got 29. The purity of the crystal obtained by this recrystallization is 98.3
Weight %, (yield based on -mercaptophenol is 68.
The average particle size was 7 mol % and 85 μm.
特許出願人 出光石油化学株式会社 手続主甫正書（自発） 昭和６３年１１月１ 日Patent applicant: Idemitsu Petrochemical Co., Ltd. Procedural master's letter (spontaneous) November 1, 1985
Claims (1)
ルとビス（ハロエトキシ）メタンとを反応させて得られ
る反応生成溶液から溶媒を除去し、ついで反応生成物に
温水を加えて徐冷することを特徴とするジ（ヒドロキシ
フェニルチオ）ジオキサヘプタンの製造方法。 ２ 溶媒の除去が部分的除去である特許請求の範囲第１
項記載のジ（ヒドロキシフェニルチオ）ジオキサヘプタ
ンの製造方法。 ３ 温水の温度が４０〜１００℃である特許請求の範囲
第１項記載のジ（ヒドロキシフェニルチオ）ジオキサヘ
プタンの製造方法。 ４ 徐冷速度が５〜２０℃／時間である特許請求の範囲
第１項記載のジ（ヒドロキシフェニルチオ）ジオキサヘ
プタンの製造方法。[Claims] 1. In the presence of an alkali and a solvent, the solvent is removed from the reaction product solution obtained by reacting mercaptophenol and bis(haloethoxy)methane, and then warm water is added to the reaction product to slowly cool it. A method for producing di(hydroxyphenylthio)dioxaheptane, characterized by: 2 Claim 1 in which the removal of the solvent is partial removal
A method for producing di(hydroxyphenylthio)dioxaheptane as described in Section 1. 3. The method for producing di(hydroxyphenylthio)dioxaheptane according to claim 1, wherein the temperature of the hot water is 40 to 100°C. 4. The method for producing di(hydroxyphenylthio)dioxaheptane according to claim 1, wherein the slow cooling rate is 5 to 20°C/hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62273405A JPH01117858A (en) | 1987-10-30 | 1987-10-30 | Production of di(hydroxyphenylthio)dioxaheptane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62273405A JPH01117858A (en) | 1987-10-30 | 1987-10-30 | Production of di(hydroxyphenylthio)dioxaheptane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01117858A true JPH01117858A (en) | 1989-05-10 |
Family
ID=17527434
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62273405A Pending JPH01117858A (en) | 1987-10-30 | 1987-10-30 | Production of di(hydroxyphenylthio)dioxaheptane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01117858A (en) |
-
1987
- 1987-10-30 JP JP62273405A patent/JPH01117858A/en active Pending
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