JPH0436269A - Production of bis(2-hydroxyethylthiomethyl) ether - Google Patents
Production of bis(2-hydroxyethylthiomethyl) etherInfo
- Publication number
- JPH0436269A JPH0436269A JP13859990A JP13859990A JPH0436269A JP H0436269 A JPH0436269 A JP H0436269A JP 13859990 A JP13859990 A JP 13859990A JP 13859990 A JP13859990 A JP 13859990A JP H0436269 A JPH0436269 A JP H0436269A
- Authority
- JP
- Japan
- Prior art keywords
- solvent
- mercaptoethanol
- ether
- bis
- compound
- 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
- QGECTPPOVMJXOX-UHFFFAOYSA-N 2-(2-hydroxyethylsulfanylmethoxymethylsulfanyl)ethanol Chemical compound OCCSCOCSCCO QGECTPPOVMJXOX-UHFFFAOYSA-N 0.000 title description 10
- 238000004519 manufacturing process Methods 0.000 title description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims abstract description 13
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims abstract description 13
- 125000001424 substituent group Chemical group 0.000 claims abstract description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- -1 2-hydroxyethylthiomethyl Chemical group 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 8
- 238000009835 boiling Methods 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 4
- DJYQPTJGQRXOMR-UHFFFAOYSA-N 1,3,5-trichloro-2-[(2,4,6-trichlorophenoxy)methoxymethoxy]benzene Chemical compound ClC1=CC(Cl)=CC(Cl)=C1OCOCOC1=C(Cl)C=C(Cl)C=C1Cl DJYQPTJGQRXOMR-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000654 additive Substances 0.000 abstract description 2
- 239000007795 chemical reaction product Substances 0.000 abstract description 2
- 239000004848 polyfunctional curative Substances 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 238000007796 conventional method Methods 0.000 description 5
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- HKYGSMOFSFOEIP-UHFFFAOYSA-N dichloro(dichloromethoxy)methane Chemical compound ClC(Cl)OC(Cl)Cl HKYGSMOFSFOEIP-UHFFFAOYSA-N 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 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
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910000102 alkali metal hydride Inorganic materials 0.000 description 1
- 150000008046 alkali metal hydrides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000588 tumorigenic Toxicity 0.000 description 1
- 230000000381 tumorigenic effect Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野コ
本発明はビス（２−ヒドロキシエチルチオメチル）エー
テルの製造方法に関し、更に詳しくは写真用添加剤や写
真用硬膜剤の合成中間体として有用なビス（２−ヒドロ
キシエチルチオメチル）エーテルの製造方法に関する。[Detailed Description of the Invention] [Industrial Field of Application] The present invention relates to a method for producing bis(2-hydroxyethylthiomethyl)ether, more specifically as a synthetic intermediate for photographic additives and photographic hardeners. The present invention relates to a method for producing useful bis(2-hydroxyethylthiomethyl)ether.
［従来の技術〕
ビス（２−ヒドロキシエチルチオメチル）エーテルの製
造法としては、従来、ビスクロルメチルエーテルとメル
カプトエタノールを塩基存在下に反応させる方法か一般
的であった。しかし、このビスクロルメチルエーテルは
、揮発性であるうえ、強い毒性と催腫瘍性を持っている
ことから作業者の健康を害する恐れがあるため、わが国
では労働安全衛生法に基く施行令によって製造等禁止物
質に指定されており、事実上使用する事ができない。[Prior Art] A conventional method for producing bis(2-hydroxyethylthiomethyl) ether has been a method in which bischloromethyl ether and mercaptoethanol are reacted in the presence of a base. However, this bischloromethyl ether is volatile and has strong toxicity and tumor-causing properties, which may harm the health of workers. It is designated as a prohibited substance and cannot be used in practice.
そのため、これにかわる不揮発性でかつ毒性及び催腫瘍
性の低い化合物を用いたビス（２−ヒドロキシエチルチ
オメチル）エーテルの新たな製造方法が必要とされてい
た。Therefore, there has been a need for a new method for producing bis(2-hydroxyethylthiomethyl)ether using a nonvolatile, less toxic and tumorigenic compound.
その方法の一つとして米国特許第３，９５４，８７８号
明細書には、ビス（アリールオキシメチル）エーテルと
メルカプトエタノールを、ジメチルホルムアミド、ジメ
チルスルホキシド、ジメチルアセトアミド、Ｎ−メチル
ピロリドンの様な非プロトン性極性溶媒又はエチルセル
ソルブ、ブタノールの様な高沸点のアルコール中で、塩
基共存下に反応させる方法が開示されている。As one method, U.S. Pat. No. 3,954,878 discloses that bis(aryloxymethyl)ether and mercaptoethanol are combined with aprotic compounds such as dimethylformamide, dimethylsulfoxide, dimethylacetamide, N-methylpyrrolidone, etc. A method is disclosed in which the reaction is carried out in a polar solvent or a high boiling point alcohol such as ethyl cellosolve or butanol in the presence of a base.
［発明の解決しようとする問題点］
しかし、この方法では使用する溶媒が高価であったり、
溶媒の沸点が高いために反応生成物がら溶媒を除去する
のに手間がかかってしまうという問題があった。[Problems to be solved by the invention] However, in this method, the solvent used is expensive,
There has been a problem in that it takes time and effort to remove the solvent from the reaction product because the boiling point of the solvent is high.
［本発明の目的］
従って、本発明の目的は、安価でかつ沸点が低く、生成
物との分離が容易な溶媒を用い、短時間に高い収率でビ
ス（２−ヒドロキシエチルチオメチル）エーテルを得る
製造方法を提供することにある。[Object of the present invention] Therefore, the object of the present invention is to produce bis(2-hydroxyethylthiomethyl) ether in a short time and in high yield using a solvent that is inexpensive, has a low boiling point, and is easily separated from the product. The objective is to provide a manufacturing method that obtains.
［課題を達成するための手段］
即ち、本発明の上記目的は、
一般式［Ｉ］
（式中・Ｒ１・Ｒ２５Ｒ，・Ｒ４・Ｒ１は各々水素原子
あるいは電子吸引性の置換基を表す。）で表される化合
物と、メルカプトエタノールを炭素数３以下の低級アル
コール中、強塩基の共存下に加圧下、反応温度１００℃
以上、１６０℃以下で反応させることによって達成され
た。[Means for Achieving the Object] That is, the above-mentioned object of the present invention is achieved by the general formula [I] (in the formula, ・R1・R25R, ・R4・R1 each represent a hydrogen atom or an electron-withdrawing substituent). The compound represented by and mercaptoethanol are mixed in a lower alcohol having 3 or less carbon atoms under pressure in the coexistence of a strong base at a reaction temperature of 100°C.
The above was achieved by reacting at 160°C or lower.
さらに本発明の詳細な説明する。Further, the present invention will be explained in detail.
一般式［１］において、Ｒｓ 、Ｒ２、Ｒ３、Ｒ４、Ｒ
９は各々水素原子あるいは電子吸引性の置換基を表す。In general formula [1], Rs, R2, R3, R4, R
9 each represents a hydrogen atom or an electron-withdrawing substituent.
置換基の例としては、ハロゲン原子、ニトロ基、シアノ
基、スルホニル基が挙げられる。Examples of substituents include halogen atoms, nitro groups, cyano groups, and sulfonyl groups.
これらのうちで好ましいものはハロゲン原子であり、よ
り好ましくは塩素原子である。Among these, halogen atoms are preferred, and chlorine atoms are more preferred.
次に本発明で用いられる一般式［Ｉ］で表される化合物
の例を示すが、本発明はこれらに限定されるものではな
い。Next, examples of compounds represented by the general formula [I] used in the present invention will be shown, but the present invention is not limited thereto.
１゜
一般式［１］で表される化合物は、公知の方法、例えば
リサーチ・ディスクロージャー １４７巻第１９〜２０
頁（１９１６年）に記載されている方法によって収率よ
く合成することができる。1゜The compound represented by the general formula [1] can be prepared by a known method, for example, Research Disclosure, Vol. 147, No. 19-20.
(1916), it can be synthesized with good yield.
本発明で用いるメルカプトエタノールの量は、一般式［
Ｉ］で表される化合物の２当量以上が必要であり、好ま
しくは２１〜２５当量用いることである。The amount of mercaptoethanol used in the present invention is determined by the general formula [
2 equivalents or more of the compound represented by I] is required, preferably 21 to 25 equivalents.
本発明で用いられる炭素数３以下の低級アルフルとして
、メタノール、エタノール、ｎ−プロパツール、ｌ−プ
ロパツールが挙げられる。これらのうちで好ましいもの
はメタノールあるいはエタノールである。Examples of the lower arfur having 3 or less carbon atoms used in the present invention include methanol, ethanol, n-propanol, and l-propanol. Among these, methanol or ethanol is preferred.
本発明で用いられる強塩基としては、アルカリ金属、ア
ルカリ金属水素化物、アルカリ金属水酸化物あるいはア
ルカリ金属アルコキシドが挙げられるが、好ましくはア
ルカリ金属水酸化物である。Examples of the strong base used in the present invention include alkali metals, alkali metal hydrides, alkali metal hydroxides, and alkali metal alkoxides, and preferably alkali metal hydroxides.
アルカリ金属水酸化物を用いた場合は、あらかじめ、反
応容器内でメルカプトエタノールと反応させ、メルカプ
チドを調整した後、一般式［Ｉ〕で表される化合物を加
え、反応させてもよいし、アルカリ金属水酸化物、メル
カプトエタノール及び一般式［１］で表される化合物を
一緒に反応容器内に入れて反応させてもよい。用いる塩
基の量は、用いるメルカプトエタノールと等量用いるの
が好ましい。When an alkali metal hydroxide is used, it may be reacted with mercaptoethanol in a reaction vessel in advance to prepare mercaptide, and then the compound represented by general formula [I] may be added and reacted. The metal hydroxide, mercaptoethanol, and the compound represented by the general formula [1] may be placed together in a reaction vessel and reacted. The amount of base used is preferably equivalent to the amount of mercaptoethanol used.
本発明において、反応を加圧下に行なうのは必須である
。常圧下の反応では炭素数３以下の低級アルコールを用
いた場合、還流下に反応を行なっても極めて反応が遅く
、実用的な製造には用いることができない。加圧下に反
応を行ない、反応温度を１００℃以上にすることにより
炭素数３以下の低級アルコールを用いた実用的な製造が
可能となった。In the present invention, it is essential to carry out the reaction under pressure. In the reaction under normal pressure, when a lower alcohol having 3 or less carbon atoms is used, the reaction is extremely slow even if the reaction is carried out under reflux, and it cannot be used for practical production. By conducting the reaction under pressure and increasing the reaction temperature to 100° C. or higher, practical production using lower alcohols having 3 or less carbon atoms has become possible.
加える圧力は、反応温度やその他の条件によって変わる
が、１．５ ｋｇ／ｒｆ〜１５ ）ｃｇ／ｒｒｒの圧力
下で反応を行なうのが好ましい。The pressure to be applied varies depending on the reaction temperature and other conditions, but it is preferable to carry out the reaction under a pressure of 1.5 kg/rf to 15) cg/rrr.
反応温度は１００℃以上、１６０℃以下であるか、好ま
しくは１２０℃以上で行うことであり、その場合数時間
で反応が終了する。The reaction temperature is 100°C or higher and 160°C or lower, preferably 120°C or higher, in which case the reaction is completed in several hours.
本発明において生成物の単離は次のようにして行うこと
ができる。まず、反応液から溶媒を常圧あるいは減圧濃
縮によって回収した後、適当量の水に残渣を溶解する。In the present invention, the product can be isolated as follows. First, the solvent is recovered from the reaction solution by concentration under normal pressure or reduced pressure, and then the residue is dissolved in an appropriate amount of water.
これを塩酸等の強酸を用いて酸性とすると、反応混合物
から副生物のフェノールが析出してくる。これを濾過す
ることで副生物のフェノールを容易に除去することがで
きる。When this is made acidic using a strong acid such as hydrochloric acid, the by-product phenol precipitates from the reaction mixture. By filtering this, the by-product phenol can be easily removed.
この水溶液から目的のビス（２−ヒドロキシエチルチオ
メチル）エーテルを抽出によって回収する。The target bis(2-hydroxyethylthiomethyl)ether is recovered from this aqueous solution by extraction.
ビス（２−ヒドロキシエチルチオメチル）エーテルはこ
こで得られた水溶液のままでも次の反応に用いることが
できる。Bis(2-hydroxyethylthiomethyl)ether can be used in the next reaction even in the aqueous solution obtained here.
［実施例］
以下に、本発明の具体的実施例を示すが、本発明はこれ
らによって限定されるものではない。[Examples] Specific examples of the present invention are shown below, but the present invention is not limited thereto.
以下の実施例において生成物の同定はＮＭＲ及びガスク
ロマトグラフィーによって行なった。In the following examples, product identification was carried out by NMR and gas chromatography.
比較例１（従来法）
ビス（２，４，６−トリクロロフエノキシメチル）エー
テル１７４．５ ｇ （０，４モル）、水酸化ナトリウ
ム３３．６ｇ （０，８４モル）、メルカプトエタノー
ル６５．６ｇ （０，１１４モル）を５００ ｍｌのエ
チルセルソルブに添加した後、加熱を始め、攪拌しなが
ら２時間加熱還流させた。その後、常圧下、溶媒のエチ
ルセルソルブを溜去した。約４００ ｍｌ溜去したとこ
ろで水５００ ｍｌを加え、さらに水との共沸によって
約４００ ｍｌ溜去した。さらに水５００ｍ１を加え、
約２００ｍ１溜去してほとんどのエチルセルソルブを除
去した。この時、溶媒の溜去に要した時間は２．５時間
だった。水浴で冷却後、５Ｎ塩酸１７０ｍ１ （塩化水
素０．８５モル）を冷却下激しく攪拌しながら加えた。Comparative Example 1 (Conventional Method) Bis(2,4,6-trichlorophenoxymethyl)ether 174.5 g (0.4 mol), sodium hydroxide 33.6 g (0.84 mol), mercaptoethanol 65. After adding 6 g (0,114 mol) to 500 ml of ethyl cellosolve, heating was started and heated to reflux for 2 hours with stirring. Thereafter, the solvent ethyl cellosolve was distilled off under normal pressure. When about 400 ml was distilled off, 500 ml of water was added, and about 400 ml was further distilled off by azeotropy with water. Add another 500ml of water,
Approximately 200 ml of the solution was distilled to remove most of the ethyl cellosolve. At this time, the time required to distill off the solvent was 2.5 hours. After cooling in a water bath, 170 ml of 5N hydrochloric acid (0.85 mol of hydrogen chloride) was added under cooling and vigorous stirring.
析出した２、４．６−１リクロロフエノールを濾過し、
少量の水で洗浄した。The precipitated 2,4.6-1-lichlorophenol was filtered,
Washed with a small amount of water.
得られた水溶液（約８００ｍ１）を酢酸エチルで抽出（
５００ｍ１を２回）し、乾燥、減圧濃縮すると、ビス（
２−ヒドロキシエチルチオメチル）エーテルの淡黄色オ
イル７２．０ｇ （収率９１％）が得られた。The resulting aqueous solution (approximately 800 ml) was extracted with ethyl acetate (
500ml twice), dried, and concentrated under reduced pressure to obtain bis(
72.0 g (91% yield) of pale yellow oil of 2-hydroxyethylthiomethyl)ether was obtained.
比較例２
ビス（２，４，６−トリクロロフエノキンメチル）エー
テル１７４．５ ｇ （０，４モル）、へ酸化ナトリウ
ム３３．６ｇ （０，８４モル）、メルカプトエタノル
６５．６ｇ （０，８４モル）を５００ ｍｌのエタノ
ールに添加した後、加熱を始め、攪拌しながら １６時
間加熱還流させる。反応液をガスクロマトグラフィで測
定したところ、目的物の生成率は約２０９ｏ程度であり
、他は未反応の原料であった。Comparative Example 2 Bis(2,4,6-trichlorophenoquine methyl)ether 174.5 g (0.4 mol), sodium heoxide 33.6 g (0.84 mol), mercaptoethanol 65.6 g (0 , 84 mol) to 500 ml of ethanol, heating was started and the mixture was heated to reflux for 16 hours with stirring. When the reaction solution was measured by gas chromatography, the production rate of the target product was about 209°, and the rest were unreacted raw materials.
反応溶媒としてメタノール、ｎ−プロパ、ノール、！−
プロパツールを用い、１６時間加熱還流させたものにつ
いても反応液をガスクロマトグラフィーで測定したか、
目的物の生成率は３〜３０％程度だった。Methanol, n-propa, alcohol, etc. as reaction solvents! −
Was the reaction solution heated under reflux for 16 hours measured using gas chromatography using a propatool?
The production rate of the target product was about 3 to 30%.
実施例１
ビス（２４，６−１リクロロフエノキシメチル）エーテ
ル１７４．５ ｇ （０，４モル）、水酸化ナトリウム
３３．６ｇ （０，８４モル）、メルカブトエタノル６
５．６ｇ （０，８４モル）、エタノール５００ ｍｌ
をオ−トクレーブに入れ密封後加熱を始め、８時間、１
００℃で加熱攪拌した。その後、減圧濃縮（３０■ｍＨ
ｇ、 ６０℃゛）によって溶媒のエタノールを溜去し
、乾固させた。この時、溶媒の溜去に要した時間は５０
分だった。残渣を水４００ ｍｌに溶解し、水浴で冷却
後、５Ｎ塩酸１７０ｍ１ （塩化水素０．８５モル）を
冷却下激しく攪拌しながら加えた。析出した２゜４．６
−）リクロロフェノールを濾過し、少量の水で洗浄した
。Example 1 Bis(24,6-1-lichlorophenoxymethyl)ether 174.5 g (0.4 mol), sodium hydroxide 33.6 g (0.84 mol), mercabutoethanol 6
5.6 g (0.84 mol), ethanol 500 ml
Put it in an autoclave, seal it, and start heating it for 8 hours.
The mixture was heated and stirred at 00°C. Then, concentrate under reduced pressure (30 mH
The solvent, ethanol, was distilled off at 60° C. and the mixture was dried. At this time, the time required to distill off the solvent was 50
It was a minute. The residue was dissolved in 400 ml of water, and after cooling in a water bath, 170 ml of 5N hydrochloric acid (0.85 mol of hydrogen chloride) was added with vigorous stirring under cooling. Precipitated 2゜4.6
-) Lichlorophenol was filtered and washed with a small amount of water.
得られた水溶液（約７００ｍ１）を酢酸エチルで抽出（
５００ｍ１を２回）し、乾燥、減圧濃縮すると、ビス（
２−ヒドロキシエチルチオメチル）エーテルの淡黄色オ
イル７４．８ｇ （収率９４％）が得られた。The resulting aqueous solution (approximately 700 ml) was extracted with ethyl acetate (
500ml twice), dried, and concentrated under reduced pressure to obtain bis(
74.8 g (94% yield) of a pale yellow oil of 2-hydroxyethylthiomethyl)ether was obtained.
実施例２
実施例１と同量の原料、溶媒を用い反応温度１４０℃で
１時間反応させた。後処理も実施例１と同様に行ない、
ビス（２−ヒドロキシエチルチオメチル）エーテル７３
．５ｇ （収率９３％）を得た。Example 2 Using the same amounts of raw materials and solvent as in Example 1, a reaction was carried out at a reaction temperature of 140° C. for 1 hour. Post-processing was also carried out in the same manner as in Example 1,
Bis(2-hydroxyethylthiomethyl)ether 73
．． 5g (yield 93%) was obtained.
実施例３
溶媒としてメタノール、ｎ−プロパツール、ｉ−プロパ
ツールを用いた結果を以下の表に示す。Example 3 The results using methanol, n-propatool, and i-propatool as solvents are shown in the table below.
以上の実施例から明らかなように、本発明の方法は、従
来の方法と違って溶媒の除去に特別な操作が不必要であ
り、回収された溶媒の再利用が容易であることもわかる
。As is clear from the above examples, unlike conventional methods, the method of the present invention does not require any special operation to remove the solvent, and the recovered solvent can be easily reused.
又、従来の方法と比較して短時間で収率良く目的物が得
られることがわかる。Furthermore, it can be seen that the target product can be obtained in a shorter time and with better yield than in conventional methods.
［発明の効果］
本発明の方法によれば、従来の方法に比べ、簡便かつ安
価に（２−ヒドロキシエチルチオメチル）エーテルを得
ることができる。[Effects of the Invention] According to the method of the present invention, (2-hydroxyethylthiomethyl)ether can be obtained more easily and at a lower cost than conventional methods.
Claims (1)
々水素原子あるいは電子吸引性の置換基を表す。）で表
される化合物と、メルカプトエタノールを炭素数３以下
の低級アルコール中、強塩基の共存下に加圧下、反応温
度１００℃以上、１６０℃以下で反応させることを特徴
とするビス（２−ヒドロキシエチルチオメチル）エーテ
ルの製造方法。(1) General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1, R_2, R_3, R_4, and R_5 each represent a hydrogen atom or an electron-withdrawing substituent.) Bis(2-hydroxyethylthiomethyl) compound and mercaptoethanol are reacted in a lower alcohol having 3 or less carbon atoms in the presence of a strong base under pressure and at a reaction temperature of 100°C or higher and 160°C or lower. How to make ether.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13859990A JPH0436269A (en) | 1990-05-30 | 1990-05-30 | Production of bis(2-hydroxyethylthiomethyl) ether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13859990A JPH0436269A (en) | 1990-05-30 | 1990-05-30 | Production of bis(2-hydroxyethylthiomethyl) ether |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0436269A true JPH0436269A (en) | 1992-02-06 |
Family
ID=15225859
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13859990A Pending JPH0436269A (en) | 1990-05-30 | 1990-05-30 | Production of bis(2-hydroxyethylthiomethyl) ether |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0436269A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105384668A (en) * | 2014-08-29 | 2016-03-09 | 住友化学株式会社 | Method for preparing ether compound |
-
1990
- 1990-05-30 JP JP13859990A patent/JPH0436269A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105384668A (en) * | 2014-08-29 | 2016-03-09 | 住友化学株式会社 | Method for preparing ether compound |
| JP2016050203A (en) * | 2014-08-29 | 2016-04-11 | 住友化学株式会社 | Method for producing ether compound |
| CN105384668B (en) * | 2014-08-29 | 2018-10-09 | 住友化学株式会社 | The method for being used to prepare ether compound |
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