JPS6121549B2 - - Google Patents
Info
- Publication number
- JPS6121549B2 JPS6121549B2 JP14707879A JP14707879A JPS6121549B2 JP S6121549 B2 JPS6121549 B2 JP S6121549B2 JP 14707879 A JP14707879 A JP 14707879A JP 14707879 A JP14707879 A JP 14707879A JP S6121549 B2 JPS6121549 B2 JP S6121549B2
- Authority
- JP
- Japan
- Prior art keywords
- thiobisphenol
- thiobis
- tert
- butylphenol
- aluminum chloride
- 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
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 22
- BLDLRWQLBOJPEB-UHFFFAOYSA-N 2-(2-hydroxyphenyl)sulfanylphenol Chemical class OC1=CC=CC=C1SC1=CC=CC=C1O BLDLRWQLBOJPEB-UHFFFAOYSA-N 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 239000002635 aromatic organic solvent Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 21
- 238000000034 method Methods 0.000 description 12
- 239000002994 raw material Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000004809 thin layer chromatography Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- -1 2,2'-thiobis(4-sec-butylphenol) Chemical compound 0.000 description 2
- ANJHKVLUGKEZJB-UHFFFAOYSA-N 2,4-ditert-butyl-6-(3,5-ditert-butyl-2-hydroxyphenyl)sulfanylphenol Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(SC=2C(=C(C=C(C=2)C(C)(C)C)C(C)(C)C)O)=C1O ANJHKVLUGKEZJB-UHFFFAOYSA-N 0.000 description 2
- CHNWLKJYOVQXOG-UHFFFAOYSA-N 2-(2-hydroxy-5-methylphenyl)sulfanyl-4-methylphenol Chemical compound CC1=CC=C(O)C(SC=2C(=CC=C(C)C=2)O)=C1 CHNWLKJYOVQXOG-UHFFFAOYSA-N 0.000 description 2
- WQYFETFRIRDUPJ-UHFFFAOYSA-N 2-[2-hydroxy-5-(2,4,4-trimethylpentan-2-yl)phenyl]sulfanyl-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C(SC=2C(=CC=C(C=2)C(C)(C)CC(C)(C)C)O)=C1 WQYFETFRIRDUPJ-UHFFFAOYSA-N 0.000 description 2
- JEBLAEFSCWNZMT-UHFFFAOYSA-N 2-[2-hydroxy-5-(2-methylbutan-2-yl)phenyl]sulfanyl-4-(2-methylbutan-2-yl)phenol Chemical compound CCC(C)(C)C1=CC=C(O)C(SC=2C(=CC=C(C=2)C(C)(C)CC)O)=C1 JEBLAEFSCWNZMT-UHFFFAOYSA-N 0.000 description 2
- KERJVHXRZDUVKQ-UHFFFAOYSA-N 4-tert-butyl-2-(5-tert-butyl-2-hydroxyphenyl)sulfanylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(SC=2C(=CC=C(C=2)C(C)(C)C)O)=C1 KERJVHXRZDUVKQ-UHFFFAOYSA-N 0.000 description 2
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- 150000003462 sulfoxides Chemical class 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- XSVZEASGNTZBRQ-UHFFFAOYSA-N 2-(2-hydroxyphenyl)sulfinylphenol Chemical compound OC1=CC=CC=C1S(=O)C1=CC=CC=C1O XSVZEASGNTZBRQ-UHFFFAOYSA-N 0.000 description 1
- QUWAJPZDCZDTJS-UHFFFAOYSA-N 2-(2-hydroxyphenyl)sulfonylphenol Chemical class OC1=CC=CC=C1S(=O)(=O)C1=CC=CC=C1O QUWAJPZDCZDTJS-UHFFFAOYSA-N 0.000 description 1
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 1
- AYUBHWYUAKTBGU-UHFFFAOYSA-N 2-[2-hydroxy-3,5-bis(2,4,4-trimethylpentan-2-yl)phenyl]sulfanyl-4,6-bis(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC(C(C)(C)CC(C)(C)C)=CC(SC=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)C(C)(C)CC(C)(C)C)O)=C1O AYUBHWYUAKTBGU-UHFFFAOYSA-N 0.000 description 1
- DOYSUFYVCGEEOJ-UHFFFAOYSA-N 2-tert-butyl-6-(3-tert-butyl-2-hydroxyphenyl)sulfanylphenol Chemical compound CC(C)(C)C1=CC=CC(SC=2C(=C(C=CC=2)C(C)(C)C)O)=C1O DOYSUFYVCGEEOJ-UHFFFAOYSA-N 0.000 description 1
- HQRWNPFVXNLBJX-UHFFFAOYSA-N 4-bromo-2-(5-bromo-2-hydroxyphenyl)sulfanylphenol Chemical compound OC1=CC=C(Br)C=C1SC1=CC(Br)=CC=C1O HQRWNPFVXNLBJX-UHFFFAOYSA-N 0.000 description 1
- GZFGOTFRPZRKDS-UHFFFAOYSA-N 4-bromophenol Chemical compound OC1=CC=C(Br)C=C1 GZFGOTFRPZRKDS-UHFFFAOYSA-N 0.000 description 1
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- ISAVYTVYFVQUDY-UHFFFAOYSA-N 4-tert-Octylphenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C=C1 ISAVYTVYFVQUDY-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- QWXNEFAHQSRFQP-UHFFFAOYSA-N CC(C)(C)CC(C)(C)C1=CC(=C(C(=C1)SC2=CC(=CC(=C2O)C(C)(C)C)C(C)(C)CC(C)(C)C)O)C(C)(C)C Chemical compound CC(C)(C)CC(C)(C)C1=CC(=C(C(=C1)SC2=CC(=CC(=C2O)C(C)(C)C)C(C)(C)CC(C)(C)C)O)C(C)(C)C QWXNEFAHQSRFQP-UHFFFAOYSA-N 0.000 description 1
- GVLFJEMGBQFFBM-UHFFFAOYSA-N CCC(C)(C)C(C=C1C(C)(C)C)=CC(SC(C=C(C(C)(C)CC)C=C2C(C)(C)C)=C2O)=C1O Chemical compound CCC(C)(C)C(C=C1C(C)(C)C)=CC(SC(C=C(C(C)(C)CC)C=C2C(C)(C)C)=C2O)=C1O GVLFJEMGBQFFBM-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000020335 dealkylation Effects 0.000 description 1
- 238000006900 dealkylation reaction Methods 0.000 description 1
- 238000007256 debromination reaction Methods 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 238000005695 dehalogenation reaction Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- ANUSOIHIIPAHJV-UHFFFAOYSA-N fenticlor Chemical compound OC1=CC=C(Cl)C=C1SC1=CC(Cl)=CC=C1O ANUSOIHIIPAHJV-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
Description
本発明は耐熱性、難燃性のポリマー原料、ポリ
カーボネート、エポキシ、ポリエステル、フエノ
ール樹脂などのほか架橋剤、農薬、染料などの中
間体として重要な２，2′―チオビスフエノールの
製造法に関する。
さらに詳しくは、２，2′―チオビスフエノール
誘導体を芳香族系有機溶剤中で塩化アルミニウム
と処理することを特徴とする２，2′―チオビスフ
エノールの製造法に関する。
従来、２，2′―チオビスフエノールの製造に関
しては、２，2′―チオビス（４―ハロフエノー
ル）のアルカリ溶液中還元剤を使用した脱ハロゲ
ン化反応により行なわれてきた（J.Am.Chem.
Soc.，67巻、238頁（1945）。たとえば２，2′―チ
オビス（４―ブロモフエノール）を大過剰の水酸
化カリウム水溶液中多量の亜鉛末を使用脱臭素化
反応を行ない、ついで酸析することにより製造す
る方法が知られているが、単離収率は48％と低
い。この方法は４―ブロモフエノールを原料とす
ることからも経済的でなく、しかも多量の亜鉛末
を使用することから工業的に有利な方法ではな
い。また、比較的安価な４―クロロフエノールを
原料とした２，2′―チオビス（４―クロロフエノ
ール）をアルカリ水溶液中ニツケル―アルミニウ
ム合金で脱塩素化反応して製造しているが収率は
30％と極めて低い。このように両者とも収率が極
めて低いことはスルフイド結合が一般にアルカリ
条件下で還元剤に対して安定でなく、いろいろな
副反応が進行することに起因している。
これら公知技術から中性乃至酸性条件下で、し
かも還元剤を使用しない２，2′―チオビスフエノ
ールの工業的な製造法が望まれていた。
本発明者らは工業的有利に２，2′―チオビスフ
エノールを高収率に、高純度で製造できる方法を
目的として鋭意検討した結果第３級アルキル基が
置換した２，2′―チオビスフエノール誘導体を、
芳香族系有機溶剤中塩化アルミニウムと処理する
と、第１級、第２級アルキル基が置換された２，
2′―チオビスフエノール誘導体や、２，2′―チオ
ビスフエノールの酸化同族体である２，2′―スル
フイニイルビスフエノールや２，2′―スルホニル
ビスフエール誘導体では脱アルキル化困難である
のに対して、アルキル基が容易に脱離し、２，
2′―チオビスフエノールを極めて容易に製造でき
ることを見出して本発明を完成するに到つた。
本発明の方法によれば、２，2′―チオビスフエ
ノール誘導体を芳香族系溶剤中で等モル以上の塩
化アルミニウムとかく拌するだけで反応は円滑に
進行し、反応終了後目的物は直接反応混合物から
沈澱するため、工業的に純粋な２，2′―チオビス
フエノールを過によつて容易に単離製造できる
という利点がある。
本発明の方法で用いられる２，2′―チオビスフ
エノール誘導体は、一般式()
（式中、R1およびR2は水素原子または第三級
アルキル基を示し、いずれか一方は必ず第三級ア
ルキル基であつて、ともに第三級アルキル基であ
つてもよい。）で表わされるものである。具体的
にはつぎのような化合物が挙げられるが、これら
に限定されるものではない。
２，2′―チオビス（４―tert―ブチルフエノー
ル）、２，2′―チオビス（６―tert―ブチルフエ
ノール）、２，2′―チオビス（４―tert―アミル
フエノール）、２，2′―チオビス（４―tert―オ
クチルフエノール）、２，2′―チオビス（４，６
―ジ―tert―ブチルフエノール）、２，2′―チオ
ビス（４，６―ジ―tert―オクチルフエノー
ル）、２，2′―チオビス（４―tert―アミル―６
―tert―ブチルフエノール）、２，2′―チオビス
（４―tert―オクチル―６―tert―ブチルフエノー
ル）などを挙げることができる。
本発明の方法で用いられる溶剤は芳香族系有機
溶剤であつて、たとえば、ベンゼン、トルエン、
キシレン、エチルベンゼン、クメン、キシレン、
クロロベンゼン、フエノール、ジフエノール、ジ
フエニルエーテルなどが挙げられる。とくにベン
ゼン、トルエンを用いるのが好ましい。これら溶
剤の使用量は、一般に原料２，2′―チオビスフエ
ノール類１重量部当り１〜10、好ましくは２〜５
重量部である。
本発明の方法において塩化アルミニウムは２，
2′―チオビスフエノール類に対して等モル量使用
するが、通常、少過剰で使用し、1.5〜３倍量の
範囲であつても差支えない。反応温度は０℃以上
であれば何ら問題はない。反応の終点は、たとえ
ばガスクロマトグラフイー、薄層クロマトグラフ
イーまたは高速液体クロマトグラフイーで速かに
かつ簡単な手段で定めることができる。
以上の方法により式()
の２，2′―チオビスフエノールが直接反応混合
物から沈澱として生成するので、これを容易に単
離、しかも公知方法にくらべ著しく高い収率で得
ることができる。
以下、本発明の方法を実施例により詳細に説明
する。
実施例 １
２，2′―チオビス（４―tert―ブチルフエノー
ル）33.1g（0.1モル）と無水塩化アルミニウム
15g（0.11モル）とをベンゼン100mlに溶解させ、
加熱還流を２時間行なつた。60℃まで放冷した後
10％塩酸100mlを加え、５分間かきまぜる。40〜
50℃で下層を分離し、室温に放冷すると沈澱が析
出する。過、水洗乾燥する。収量20g（収率92
％）、融点137〜139℃。
キシレンから再結晶して白色針状結晶の２，
2′―チオビスフエノールを得た。
融点139〜140℃
元素分析
Ｃ(%) Ｈ(%) Ｓ(%)
計算値 66.0 4.61 14.7
測定値 66.7 4.61 14.2
実施例 ２
２，2′―チオビス（４，６―ジ―tert―ブチル
フエノール）44.3g（0.1モル）を使用して実施例
１と全く同様の操作により目的物を得た。
収量19.8g（収率90.5％）、融点136〜138℃
実施例 ３
２，2′―チオビス（４―tert―アミルフエノー
ル）35.4g（0.1モル）と無水塩化アルミニウム
15g（0.11モル）とをトルエン100mlに溶解させ、
50〜60゜に温度を保ちながら４時間かく拌した。
つぎに10％塩酸100mlを加え、同温度で５分間か
きまぜた後40〜50℃で下層を分離し、室温に放冷
すると沈澱が析出する。過、水洗、乾燥する。
収量19.5g（収率89.4％）、融点137〜138℃
実施例 ４
２，2′―チオビス（４―tert―オクチルフエノ
ール）44.3g（0.1モル）と無水塩化アルミニウム
15g（0.11モル）とをベンゼン100mlに溶解させ、
20〜30℃に温度は保ちながら10時間かく拌した。
つぎに10％塩酸100mlを加え、同温度で５分間か
きまぜた後40〜50℃で下層を分離し、室温に放冷
すると沈澱が析出する。過、水洗、乾燥する。
収量20.3g（収率93％）。融点137〜139℃
比較例 １
２，2′―ビス（４―tert―ブチルフエノール）
スルホン36.3g（0.1モル）と無水塩化アルミニウ
ム15g（0.11モル）とをベンゼン100mlに溶解させ
加熱還流を６時間行つた。このときのサンプルを
薄層クロマトグラフイーに展開させたところ、原
料と同じ位置にスポツトがあるのみであつた。
後処理を実施例１と同様に行つて白色鱗片状の
結晶16gを得た。融点は133―135℃で原料との混
融点133―135℃であり、元素分析の結果は次の通
りであつた。
これは原料の２，2′―ビス（４―tert―ブチル
フエノール）スルホンであり目的物は得られなか
つた。
The present invention relates to a method for producing 2,2'-thiobisphenol, which is important as an intermediate for heat-resistant and flame-retardant polymer raw materials such as polycarbonate, epoxy, polyester, and phenolic resins, as well as crosslinking agents, agricultural chemicals, and dyes. More specifically, the present invention relates to a method for producing 2,2'-thiobisphenol, which comprises treating a 2,2'-thiobisphenol derivative with aluminum chloride in an aromatic organic solvent. Conventionally, 2,2'-thiobisphenol has been produced by a dehalogenation reaction using a reducing agent in an alkaline solution of 2,2'-thiobis(4-halophenol) (J.Am. Chem.
Soc., vol. 67, p. 238 (1945). For example, a method is known for producing 2,2'-thiobis(4-bromophenol) by carrying out a debromination reaction using a large amount of zinc powder in a large excess of potassium hydroxide aqueous solution, followed by acid precipitation. , the isolated yield was as low as 48%. This method is not economical because it uses 4-bromophenol as a raw material, and is not industrially advantageous because it uses a large amount of zinc dust. In addition, 2,2'-thiobis(4-chlorophenol) is produced from relatively inexpensive 4-chlorophenol by dechlorination reaction with a nickel-aluminum alloy in an alkaline aqueous solution, but the yield is low.
The rate is extremely low at 30%. The reason why the yields are extremely low in both cases is that sulfide bonds are generally not stable against reducing agents under alkaline conditions, and various side reactions proceed. Based on these known techniques, there has been a desire for an industrial method for producing 2,2'-thiobisphenol under neutral to acidic conditions and without using a reducing agent. The inventors of the present invention have conducted intensive studies with the aim of developing a method that can industrially advantageously produce 2,2'-thiobisphenol in high yield and with high purity. bisphenol derivatives,
When treated with aluminum chloride in an aromatic organic solvent, 2,
Dealkylation is difficult with 2'-thiobisphenol derivatives and 2,2'-sulfinylbisphenol and 2,2'-sulfonylbisphenol derivatives, which are oxidized homologues of 2,2'-thiobisphenol. , the alkyl group is easily eliminated, and 2,
The present invention was completed by discovering that 2'-thiobisphenol can be produced extremely easily. According to the method of the present invention, the reaction proceeds smoothly by simply stirring the 2,2'-thiobisphenol derivative with equimolar or more aluminum chloride in an aromatic solvent, and after the reaction is completed, the target product is directly reacted. Since it is precipitated from a mixture, it has the advantage that industrially pure 2,2'-thiobisphenol can be easily isolated and produced by filtration. The 2,2'-thiobisphenol derivative used in the method of the present invention has the general formula () (In the formula, R 1 and R 2 represent a hydrogen atom or a tertiary alkyl group, and either one is necessarily a tertiary alkyl group, and both may be tertiary alkyl groups.) It is something that can be done. Specifically, the following compounds may be mentioned, but the invention is not limited thereto. 2,2'-thiobis(4-tert-butylphenol), 2,2'-thiobis(6-tert-butylphenol), 2,2'-thiobis(4-tert-amylphenol), 2,2'- Thiobis(4-tert-octylphenol), 2,2′-thiobis(4,6
-di-tert-butylphenol), 2,2'-thiobis(4,6-di-tert-octylphenol), 2,2'-thiobis(4-tert-amyl-6
-tert-butylphenol), 2,2'-thiobis(4-tert-octyl-6-tert-butylphenol), and the like. The solvent used in the method of the present invention is an aromatic organic solvent, such as benzene, toluene,
xylene, ethylbenzene, cumene, xylene,
Examples include chlorobenzene, phenol, diphenol, and diphenyl ether. It is particularly preferable to use benzene and toluene. The amount of these solvents used is generally 1 to 10, preferably 2 to 5, per 1 part by weight of the raw material 2,2'-thiobisphenol.
Parts by weight. In the method of the present invention, aluminum chloride is
Although it is used in an equimolar amount relative to the 2'-thiobisphenol, it is usually used in a slight excess, and may be in the range of 1.5 to 3 times the amount. There is no problem as long as the reaction temperature is 0°C or higher. The end point of the reaction can be determined quickly and easily, for example by gas chromatography, thin layer chromatography or high performance liquid chromatography. Using the above method, the expression () Since the 2,2'-thiobisphenol is formed as a precipitate directly from the reaction mixture, it can be easily isolated and obtained in significantly higher yields than in known methods. Hereinafter, the method of the present invention will be explained in detail with reference to Examples. Example 1 33.1 g (0.1 mol) of 2,2'-thiobis(4-tert-butylphenol) and anhydrous aluminum chloride
Dissolve 15g (0.11mol) in 100ml of benzene,
Heating was carried out under reflux for 2 hours. After cooling down to 60℃
Add 100ml of 10% hydrochloric acid and stir for 5 minutes. 40～
Separate the lower layer at 50°C and allow it to cool to room temperature to form a precipitate. Filter, wash with water and dry. Yield 20g (yield 92
%), melting point 137-139℃. Recrystallized from xylene to produce white needle-like crystals 2,
2′-thiobisphenol was obtained. Melting point 139-140℃ Elemental analysis C(%) H(%) S(%) Calculated value 66.0 4.61 14.7 Measured value 66.7 4.61 14.2 Example 2 2,2'-thiobis(4,6-di-tert-butylphenol) The desired product was obtained in exactly the same manner as in Example 1 using 44.3 g (0.1 mol). Yield 19.8g (yield 90.5%), melting point 136-138℃ Example 3 35.4g (0.1 mol) of 2,2'-thiobis(4-tert-amylphenol) and anhydrous aluminum chloride
Dissolve 15g (0.11mol) in 100ml of toluene,
The mixture was stirred for 4 hours while maintaining the temperature at 50-60°.
Next, 100 ml of 10% hydrochloric acid is added, and after stirring at the same temperature for 5 minutes, the lower layer is separated at 40-50°C, and when it is allowed to cool to room temperature, a precipitate is deposited. Filter, rinse with water, and dry. Yield 19.5g (yield 89.4%), melting point 137-138℃ Example 4 44.3g (0.1 mol) of 2,2'-thiobis(4-tert-octylphenol) and anhydrous aluminum chloride
Dissolve 15g (0.11mol) in 100ml of benzene,
The mixture was stirred for 10 hours while maintaining the temperature at 20-30°C.
Next, 100 ml of 10% hydrochloric acid is added, and after stirring at the same temperature for 5 minutes, the lower layer is separated at 40-50°C, and when it is allowed to cool to room temperature, a precipitate is deposited. Filter, rinse with water, and dry. Yield: 20.3g (93% yield). Melting point 137-139℃ Comparative example 1 2,2'-bis(4-tert-butylphenol)
36.3 g (0.1 mol) of sulfone and 15 g (0.11 mol) of anhydrous aluminum chloride were dissolved in 100 ml of benzene and heated under reflux for 6 hours. When this sample was developed using thin layer chromatography, only a spot was found at the same position as the raw material. Post-treatment was carried out in the same manner as in Example 1 to obtain 16 g of white scaly crystals. The melting point was 133-135°C, and the mixed melting point with the raw material was 133-135°C, and the results of elemental analysis were as follows. This was the raw material 2,2'-bis(4-tert-butylphenol) sulfone, and the desired product could not be obtained.
【表】
比較例 ２
２，2′―ビス（４―tert―オクチルフエノー
ル）スルホキシド45.9g（0.1モル）と無水塩化ア
ルミニウム15g（0.11モル）とをベンゼン100mlを
用い比較例１と同様に行つた。その結果、得られ
た結晶は原料の２，2′―（４―tert―オクチルフ
エノール）スルホキシドであり、融点は171―172
℃であつた。
比較例 ３
２，2′―チオビス（４―クレゾール）24.6g
（0.1モル）と無水塩化アルミニウム15g（0.11モ
ル）およびベンゼン100mlを用い比較例１と同様
に行つた。
その結果、得られた結晶は原料の２，2′―チオ
ビス（４―クレゾール）であり、融点は115―117
℃であつた。
比較例 ４
２，2′―チオビス（４―sec―ブチルフエノー
ル）33.1g（0.1モル）を同様に行つて、褐色油状
物を得た。これは薄層クロマトグラフイーおよび
原料分析の結果から原料の２，2′―チオビス（４
―sec―ブチルフエノール）であることを確認し
た。[Table] Comparative Example 2 45.9 g (0.1 mol) of 2,2'-bis(4-tert-octylphenol) sulfoxide and 15 g (0.11 mol) of anhydrous aluminum chloride were treated in the same manner as in Comparative Example 1 using 100 ml of benzene. . As a result, the obtained crystals were the raw material 2,2'-(4-tert-octylphenol) sulfoxide, with a melting point of 171-172
It was warm at ℃. Comparative example 3 2,2′-thiobis(4-cresol) 24.6g
The same procedure as in Comparative Example 1 was conducted using 15 g (0.11 mol) of anhydrous aluminum chloride and 100 ml of benzene. As a result, the obtained crystals were the raw material 2,2'-thiobis(4-cresol), with a melting point of 115-117
It was warm at ℃. Comparative Example 4 A brown oil was obtained in the same manner using 33.1 g (0.1 mol) of 2,2'-thiobis(4-sec-butylphenol). The results of thin layer chromatography and raw material analysis revealed that the raw material was 2,2'-thiobis(4
-sec-butylphenol).
Claims (1)
アルキル基を示し、いずれか一方は必ず第三級ア
ルキル基であつて、ともに第三級アルキル基であ
つてもよい）で表わされる２，2′―チオビスフエ
ノール誘導体を芳香族系有機溶剤中塩化アルミニ
ウムと処理することを特徴とする式() で表わされる２，2′―チオビスフエノールの製造
法。[Claims] 1 General formula () (In the formula, R 1 and R 2 represent a hydrogen atom or a tertiary alkyl group, and either one is necessarily a tertiary alkyl group, and both may be tertiary alkyl groups) Formula () characterized by treating a 2,2'-thiobisphenol derivative with aluminum chloride in an aromatic organic solvent A method for producing 2,2'-thiobisphenol represented by
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14707879A JPS5671064A (en) | 1979-11-15 | 1979-11-15 | Preparation of 2,2'-thiobisphenol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14707879A JPS5671064A (en) | 1979-11-15 | 1979-11-15 | Preparation of 2,2'-thiobisphenol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5671064A JPS5671064A (en) | 1981-06-13 |
| JPS6121549B2 true JPS6121549B2 (en) | 1986-05-27 |
Family
ID=15421966
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14707879A Granted JPS5671064A (en) | 1979-11-15 | 1979-11-15 | Preparation of 2,2'-thiobisphenol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5671064A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63117558U (en) * | 1987-01-26 | 1988-07-29 | ||
| JPS63166233U (en) * | 1987-04-20 | 1988-10-28 | ||
| JPS6456259U (en) * | 1987-10-05 | 1989-04-07 |
-
1979
- 1979-11-15 JP JP14707879A patent/JPS5671064A/en active Granted
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63117558U (en) * | 1987-01-26 | 1988-07-29 | ||
| JPS63166233U (en) * | 1987-04-20 | 1988-10-28 | ||
| JPS6456259U (en) * | 1987-10-05 | 1989-04-07 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5671064A (en) | 1981-06-13 |
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