JPH075497B2 - Process for producing 6,6'-dihydroxy-3,3,3 ', 3'-tetramethyl-1,1'-spirobiindane - Google Patents
Process for producing 6,6'-dihydroxy-3,3,3 ', 3'-tetramethyl-1,1'-spirobiindaneInfo
- Publication number
- JPH075497B2 JPH075497B2 JP60180500A JP18050085A JPH075497B2 JP H075497 B2 JPH075497 B2 JP H075497B2 JP 60180500 A JP60180500 A JP 60180500A JP 18050085 A JP18050085 A JP 18050085A JP H075497 B2 JPH075497 B2 JP H075497B2
- Authority
- JP
- Japan
- Prior art keywords
- spirobiindane
- dihydroxy
- tetramethyl
- propane
- 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.)
- Expired - Fee Related
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、6,6′−ジヒドロキシ−3,3,3′,3′−テトラ
メチル−1,1′−スピロビインダンの新規な製造方法に
関する。更に詳しくは、2,2−ビス（４−ヒドロキシフ
エニル）プロパンを脂肪族スルホン酸の存在下に加熱処
理することを特徴とする6,6′−ジヒドロキシ−3,3,
3′,3′−テトラメチル−1,1′−スピロビインダンの製
造方法に関する。TECHNICAL FIELD The present invention relates to a novel method for producing 6,6′-dihydroxy-3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindane. . More specifically, 2,6-bis (4-hydroxyphenyl) propane is heat-treated in the presence of an aliphatic sulfonic acid to give 6,6′-dihydroxy-3,3,3,
The present invention relates to a method for producing 3 ', 3'-tetramethyl-1,1'-spirobiindane.
6,6′−ジヒドロキシ−3,3,3′,3′−テトラメチル−1,
1′−スピロビインダンは樹脂原料として極めて有用な
物質である。6,6'-dihydroxy-3,3,3 ', 3'-tetramethyl-1,
1'-spirobiindane is an extremely useful substance as a resin raw material.
（従来技術） 従来、6,6′−ジヒドロキシ−3,3,3′,3′−テトラメチ
ル−1,1′−スピロビインダンの製造方法に関しては、
2,2−ビス（４−ヒドロキシフエニル）プロパンを約
２倍量の硫酸中にて140℃で６時間処理して製造する方
法（米国特許、3,271,463）、2,2−ビス（４−ヒドロ
キシフエニル）プロパンを大過剰の臭化水素酸中にて還
流下、７時間処理して製造する方法（ジャーナル・オブ
・ケミカル・ソサエテイ（J.Chem.SOC.）1962、415）、
また、2,2−ビス（４−ヒドロキシフエニル）プロパン
を濃塩酸と共にオートクレーブ中100℃で24時間処理し
て製造する方法（米国特許、3,271,463）などが知られ
ている。(Prior Art) Conventionally, regarding the method for producing 6,6′-dihydroxy-3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindane,
A method for producing 2,2-bis (4-hydroxyphenyl) propane by treating it in about twice the amount of sulfuric acid at 140 ° C. for 6 hours (US Pat. No. 3,271,463), 2,2-bis (4-hydroxy) (Phenyl) propane in a large excess of hydrobromic acid under reflux for 7 hours to produce (J. Chem. SOC. 1962, 415),
Also known is a method of producing 2,2-bis (4-hydroxyphenyl) propane by treating it with concentrated hydrochloric acid in an autoclave at 100 ° C. for 24 hours (US Pat. No. 3,271,463).
しかしながら、これらの方法は原料である2,2−ビス
（４−ヒドロキシフエニル）プロパンに対して、多量の
硫酸または臭化水素酸を使用し、さらに濃塩酸を使用す
る場合、オートクレーブ中で目的物を製造しているが、
収率が極めて低く、実用的でない。このように公知の製
造方法は硫酸または臭化水素酸を多量に使用するた容積
効率が悪く、廃液の処理等無公害化の処理負荷が大きく
なる。また、腐食に耐える装置が必要などこれらの方法
を実施する上で工業的に合理的でなく製造作業上極めて
因難である。However, these methods use a large amount of sulfuric acid or hydrobromic acid with respect to the raw material 2,2-bis (4-hydroxyphenyl) propane, and when concentrated hydrochloric acid is used, the purpose is to be set in an autoclave. I am manufacturing things,
The yield is extremely low and not practical. As described above, the known manufacturing method uses a large amount of sulfuric acid or hydrobromic acid and has a poor volumetric efficiency, and the processing load for pollution-free processing such as waste liquid processing becomes large. In addition, it is industrially unreasonable to carry out these methods, for example, a device that withstands corrosion is required, and it is extremely difficult in manufacturing work.
（発明が解決しようとする問題点） 本発明の課題は、このような6,6′−ジヒドロキシ−3,
3,3′,3′−テトラメチル−1,1′−スピロビインダンを
製造する従来技術の問題点を解消した全く新規な6,6′
−ジヒドロキシ−3,3,3′,3′−テトラメチル−1,1′−
スピロビインダンの製造方法を提供することである。(Problems to be Solved by the Invention) The object of the present invention is to solve the problem of 6,6′-dihydroxy-3,
A completely new 6,6 'that solves the problems of the prior art for producing 3,3', 3'-tetramethyl-1,1'-spirobiindane
-Dihydroxy-3,3,3 ', 3'-tetramethyl-1,1'-
A method for producing spirobiindane is provided.
（問題点を解決するための手段） 本発明者らは、上記課題を達成すべく鋭意検討した。そ
の結果、原料である2,2−ビス（４−ヒドロキシフエニ
ル）プロパンを、これに対して触媒量の脂肪族スルホン
酸の存在下に加熱処理することにより、合理的かつ効率
良く6,6′−ジヒドロキシ−3,3,3′,3′−テトラメチル
−1,1′−スピロビインダンが得られることを見出し、
本発明を完成するに至つた。(Means for Solving Problems) The inventors of the present invention have diligently studied to achieve the above object. As a result, the raw material 2,2-bis (4-hydroxyphenyl) propane was heat-treated in the presence of a catalytic amount of aliphatic sulfonic acid to the raw material 2,2-bis (4-hydroxyphenyl) propane. It was found that ′ -dihydroxy-3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindane was obtained,
The present invention has been completed.
すなわち、本発明は2,2−ビス（４−ヒドロキシフエニ
ル）プロパンを脂肪族スルホン酸の存在下に加熱処理す
ることを特徴とする、6,6′−ジヒドロキシ−3,3,3′,
3′−テトラメチル−1,1′−スピロビインダンの製造方
法である。That is, the present invention is characterized in that 2,2-bis (4-hydroxyphenyl) propane is heat-treated in the presence of an aliphatic sulfonic acid, 6,6′-dihydroxy-3,3,3 ′,
It is a method for producing 3'-tetramethyl-1,1'-spirobiindane.
本発明の方法で使用する原料は2,2−ビス（４−ヒドロ
キシフエニル）プロパンである。また本発明の方法にお
いて無溶媒または溶媒中のいずれで処理しても良い。使
用する溶媒は芳香族及びハロゲン化炭化水素類で、芳香
族炭化水素溶媒としては例えばベンゼン、トルエン、キ
シレン、エチルベンゼン、トリメチルベンゼン、クロロ
ベンゼン、ブロモベンゼン、アニソール、ナフタリン、
ビフエニル、ジフエニルエーテル等が挙げられる。ハロ
ゲン化炭化水素溶媒としては、例えば1,1−ジクロロエ
タン、四塩化炭素、1,2−ジクロロエタン、1,1,1−トリ
クロロエタン、1,1,2−トリクロロエタン、1,1,1,2−テ
トラクロロエタン、1,1,2,2,−テトラクロロエタン、1,
2−ジクロロエチレン、トリクロロエチレン、テトラク
ロロエチレン等が挙げられる。これら溶媒の使用量は、
特に限定されないが、通常原料に対して１〜10重量倍で
十分である。The raw material used in the method of the present invention is 2,2-bis (4-hydroxyphenyl) propane. In the method of the present invention, the treatment may be carried out with or without a solvent. The solvents used are aromatic and halogenated hydrocarbons, and examples of aromatic hydrocarbon solvents are benzene, toluene, xylene, ethylbenzene, trimethylbenzene, chlorobenzene, bromobenzene, anisole, naphthalene,
Examples thereof include biphenyl and diphenyl ether. Examples of the halogenated hydrocarbon solvent include 1,1-dichloroethane, carbon tetrachloride, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2-trichloroethane, 1,1,1,2-tetrahydrochloride. Chloroethane, 1,1,2,2, -tetrachloroethane, 1,
2-dichloroethylene, trichloroethylene, tetrachloroethylene and the like can be mentioned. The amount of these solvents used is
Although not particularly limited, 1 to 10 times by weight of the raw material is usually sufficient.
本発明の方法で使用する脂肪族スルホン酸としては、一
般式CnH2n＋1SO3H（C1〜C8）で表わされるスルホン酸で
具体的にはCH3SO3H、C2H5SO3H、C4H9SO3H、C5H11SO3H、
C6H13SO3H、C7H15SO3H、C8H17SO3H等が挙げられ、工業
的にはCH3SO3H（メタンスルホン酸）が好ましい。これ
ら脂肪族スルホン酸は原料に対して0.1重量％〜100重量
％使用され、好ましくは１重量％〜20重量％程度が用い
られる。反応温度は通常50℃〜200℃の範囲であるが、
好ましくは60〜160℃の範囲である。反応時間は1/20時
間で行なう。The aliphatic sulfonic acids used in the method of the invention, the general formula C n H 2n + 1 SO 3 H is particularly sulfonic acid represented by (C 1 ~C 8) CH 3 SO 3 H, C 2 H 5 SO 3 H, C 4 H 9 SO 3 H, C 5 H 11 SO 3 H,
C 6 H 13 SO 3 H, C 7 H 15 SO 3 H, C 8 H 17 SO 3 H and the like can be mentioned, and CH 3 SO 3 H (methanesulfonic acid) is industrially preferable. These aliphatic sulfonic acids are used in an amount of 0.1% by weight to 100% by weight, preferably about 1% by weight to 20% by weight, based on the raw materials. The reaction temperature is usually in the range of 50 ° C to 200 ° C,
It is preferably in the range of 60 to 160 ° C. The reaction time is 1/20 hours.
本発明の方法における一般的な実施態様としては2,2−
ビス（４−ヒドロキシフエニル）プロパンと脂肪族スル
ホン酸を装入し、加熱処理する。この反応の終点は高速
液体クロマトグラフイーにより原料の減少を見ながら決
定することが出来る。反応終了後直ちにアルカリ水溶液
を加えアルカリ金属塩として析出させるか、溶媒を留去
しさらに副生するフエノールを減圧蒸留にて留去回収し
アルカリ水溶液を加え、アルカリ金属塩として析出させ
るか、あるいはその析出したアルカリ金属塩を取り出し
鉱酸により中和し、目的物の粗製品を得る。その粗製品
を溶剤により再結を行ない目的物を得る方法がある。A general embodiment of the method of the present invention is 2,2-
Charge bis (4-hydroxyphenyl) propane and aliphatic sulfonic acid and heat-treat. The end point of this reaction can be determined by observing the reduction of the raw materials by high performance liquid chromatography. Immediately after the completion of the reaction, an aqueous alkali solution is added to precipitate as an alkali metal salt, or the solvent is distilled off and the by-product phenol is distilled off and recovered by reduced pressure distillation, and an alkali aqueous solution is added to precipitate it as an alkali metal salt, or The precipitated alkali metal salt is taken out and neutralized with a mineral acid to obtain a target crude product. There is a method in which the crude product is reconstituted with a solvent to obtain the target product.
（作用と効果） 本発明の方法によれば、2,2−ビス（４−ヒドロキシフ
エニル）プロパンを触媒量の脂肪族スルホン酸の存在下
に加熱処理することにより容易に目的物が製造できる。
従つて廃液の処理等の負荷がなく製造作業上合理的かつ
効率良く、目的物が製造出来、工業的に実施する上で極
めて有利な、6,6′−ジヒドロキシ−3,3,3′,3′−テト
ラメチル−1,1′−スピロビインダンの製造方法であ
る。(Action and Effect) According to the method of the present invention, the desired product can be easily produced by heat-treating 2,2-bis (4-hydroxyphenyl) propane in the presence of a catalytic amount of an aliphatic sulfonic acid. .
Therefore, 6,6′-dihydroxy-3,3,3 ′, which is rational and efficient in the manufacturing work without waste liquid treatment, can manufacture the target product, and is extremely advantageous in industrial implementation, It is a method for producing 3'-tetramethyl-1,1'-spirobiindane.
（実施例） 以下、本発明の方法を実施例により更に詳細に説明す
る。(Example) Hereinafter, the method of the present invention will be described in more detail with reference to Examples.
実施例１ １セパラブルフラスコに2,2−ビス（４−ヒドロキシ
フエニル）プロパン250g（1.1モル）とメタンスルホン
酸6.3gを装入し140〜150℃で６時間反応する。反応終了
後直ちに副生するフエノールを減圧蒸留により留去、回
収し、冷却して、IPA150mlを装入し、溶解する。次に９
％NaOH水溶液510g装入するとNa塩結晶が析出する。これ
を過し更に25％IPA水溶液300mlにて80〜83℃で30分間
処理し、冷却、過し、15％IPA水溶液中で塩酸水溶液
により中和する。析出した結晶を別、水洗、乾燥して
ベンゼン中にて共沸により脱水した後、過、乾燥して
6,6′−ジヒドロキシ−3,3,3′,3′−テトラメチル−1,
1′−スピロビインダンの白色結晶を得た。収量79g 実施例２ １セパラブルフラスコに2,2−ビス（４−ヒドロキシ
フエニル）プロパン125g（0.55モル）とメタンスルホン
酸6.3gおよびトルエン250mlを装入し、還流下で８時間
反応する反応終了後冷却し、直ちにトルエンを留去し次
いで副生するフエノールを減圧蒸留にて留去回収し、実
施例１と同様な操作により6,6′−ジヒドロキシ−3,3,
3′,3′−テトラメチル−1,1′−スピロビインダンの白
色結晶を得た。収量38g mp 215〜217℃ 実施例３ １セパラブルフラスコに2,2−ビス（４−ヒドロキシ
フエニル）プロパン125g（0.55モル）とメタンスルホン
酸25gおよびテトラクロロエチレン375mlを装入し還流下
で７時間反応する。反応終了後実施例２と同様な操作に
より6,6′−ジヒドロキシ−3,3,3′,3′−テトラメチル
−1,1′−スピロビインダンの白色結晶を得た。収量36g
mp 215〜217℃ 実施例４ 500mlセパラブルフラスコに2,2−ビス（４−ヒドロキシ
フエニル）プロパン125g（0.55モル）とエタンスルホン
酸3.2gを装入し140〜150℃で６時間反応する。反応終了
後実施例１と同様な操作により6,6′−ジヒドロキシ−
3,3,3′,3′−テトラメチル−1,1′−スピロビインダン
の白色結晶を得た。収量35g mp 215〜217℃ 実施例５ 500mlセパラブルフラスコに2,2−ビス（４−ヒドロキシ
フエニル）プロパン125g（0.55モル）とブタンスルホン
酸3.2gを装入し140〜150℃で６時間反応する。反応終了
後実施例１と同様な操作により6,6′−ジヒドロキシ−
3,3,3′,3′−テトラメチル−1,1′−スピロビインダン
の白色結晶を得た。収量36g mp 215〜217℃ 実施例６ 2lセパラブルフラスコに2,2−ビス（４−ヒドロキシフ
エニル）プロパン500g（2.2モル）とメタンスルホン酸2
5.2gを装入し140〜150℃で８時間反応する。反応終了後
実施例１と同様な操作により6,6′−ジヒドロキシ−3,
3,3′,3′−テトラメチル−1,1′−スピロビインダンの
白色結晶を得た。収量160g mp 215〜217℃Example 1 A 2-separable flask was charged with 250 g (1.1 mol) of 2,2-bis (4-hydroxyphenyl) propane and 6.3 g of methanesulfonic acid and reacted at 140 to 150 ° C. for 6 hours. Immediately after the end of the reaction, the by-product phenol is distilled off under reduced pressure, recovered, cooled, charged with 150 ml of IPA and dissolved. Then 9
When 510 g of an aqueous solution of 10% NaOH is charged, Na salt crystals are precipitated. Then, the mixture is further treated with 300 ml of 25% IPA aqueous solution at 80 to 83 ° C. for 30 minutes, cooled, filtered, and neutralized with a hydrochloric acid aqueous solution in a 15% IPA aqueous solution. The precipitated crystals are separated, washed with water, dried, dehydrated by azeotropic distillation in benzene, then dried and dried.
6,6'-dihydroxy-3,3,3 ', 3'-tetramethyl-1,
White crystals of 1'-spirobiindane were obtained. Yield 79g Example 2 A 2-separable flask was charged with 125 g (0.55 mol) of 2,2-bis (4-hydroxyphenyl) propane, 6.3 g of methanesulfonic acid and 250 ml of toluene and reacted under reflux for 8 hours. After completion of the reaction After cooling, the toluene was immediately distilled off, and the by-produced phenol was distilled off under reduced pressure to recover 6,6′-dihydroxy-3,3,6 'by the same procedure as in Example 1.
White crystals of 3 ', 3'-tetramethyl-1,1'-spirobiindane were obtained. Yield 38 g mp 215-217 ° C. Example 3 A 2-separable flask was charged with 125 g (0.55 mol) of 2,2-bis (4-hydroxyphenyl) propane, 25 g of methanesulfonic acid and 375 ml of tetrachloroethylene under reflux for 7 hours. react. After completion of the reaction, white crystals of 6,6'-dihydroxy-3,3,3 ', 3'-tetramethyl-1,1'-spirobiindane were obtained by the same procedure as in Example 2. Yield 36g
mp 215 to 217 ° C. Example 4 A 500 ml separable flask was charged with 125 g (0.55 mol) of 2,2-bis (4-hydroxyphenyl) propane and 3.2 g of ethanesulfonic acid and reacted at 140 to 150 ° C. for 6 hours. . After completion of the reaction, 6,6'-dihydroxy- was prepared by the same procedure as in Example 1.
White crystals of 3,3,3 ', 3'-tetramethyl-1,1'-spirobiindane were obtained. Yield 35 g mp 215-217 ° C. Example 5 A 500 ml separable flask was charged with 125 g (0.55 mol) of 2,2-bis (4-hydroxyphenyl) propane and 3.2 g of butanesulfonic acid and at 140-150 ° C. for 6 hours. react. After completion of the reaction, 6,6'-dihydroxy- was prepared by the same procedure as in Example 1.
White crystals of 3,3,3 ', 3'-tetramethyl-1,1'-spirobiindane were obtained. Yield 36 g mp 215-217 ° C. Example 6 In a 2 l separable flask, 2,2-bis (4-hydroxyphenyl) propane (500 g, 2.2 mol) and methanesulfonic acid (2)
Charge 5.2 g and react at 140-150 ° C for 8 hours. After completion of the reaction, 6,6'-dihydroxy-3, by the same operation as in Example 1
White crystals of 3,3 ', 3'-tetramethyl-1,1'-spirobiindane were obtained. Yield 160g mp 215 ~ 217 ℃
Claims (1)
ロパンを脂肪族スルホン酸の存在下に加熱処理すること
を特徴とする式（１） で表される、6,6′−ジヒドロキシ−3,3,3′,3′−テト
ラメチル−1,1′−スピロビインダンの製造方法。1. A formula (1) characterized in that 2,2-bis (4-hydroxyphenyl) propane is heat-treated in the presence of an aliphatic sulfonic acid. A method for producing 6,6′-dihydroxy-3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindane represented by
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60180500A JPH075497B2 (en) | 1985-08-19 | 1985-08-19 | Process for producing 6,6'-dihydroxy-3,3,3 ', 3'-tetramethyl-1,1'-spirobiindane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60180500A JPH075497B2 (en) | 1985-08-19 | 1985-08-19 | Process for producing 6,6'-dihydroxy-3,3,3 ', 3'-tetramethyl-1,1'-spirobiindane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6242941A JPS6242941A (en) | 1987-02-24 |
| JPH075497B2 true JPH075497B2 (en) | 1995-01-25 |
Family
ID=16084323
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60180500A Expired - Fee Related JPH075497B2 (en) | 1985-08-19 | 1985-08-19 | Process for producing 6,6'-dihydroxy-3,3,3 ', 3'-tetramethyl-1,1'-spirobiindane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH075497B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5399783A (en) * | 1993-04-12 | 1995-03-21 | Mitsui Toatsu Chemicals, Inc. | Preparation of 6,6'-dihydroxy-3,3,3',3'-tetramethyl-1,1'-spirobiindane |
| CN105669766B (en) * | 2016-03-03 | 2020-03-10 | 中国科学院上海有机化学研究所 | Cyclopentadiene-like compound based on spiro-ring skeleton and its rhodium complex, synthesis method and application |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT999148B (en) * | 1972-11-18 | 1976-02-20 | Basf Ag | PROCESS FOR THE PREPARATION OF I-METHYL 3 MONCALOGEN PHENYLINDANE AND DIHALOGEN I-METHYL 3-PHENYLIN DANI |
| US4064129A (en) * | 1976-09-17 | 1977-12-20 | Harmon Colors Corporation | Process for making quinacridone and its derivatives |
| JPS54132562A (en) * | 1978-04-03 | 1979-10-15 | Sumitomo Chem Co Ltd | Synthesis of m-isopropenylphenol oligomer |
-
1985
- 1985-08-19 JP JP60180500A patent/JPH075497B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6242941A (en) | 1987-02-24 |
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| LAPS | Cancellation because of no payment of annual fees |