JPH03258761A - Bis((4-hydroxy-3-phenyl)phenyl)sulfide and preparation thereof - Google Patents
Bis((4-hydroxy-3-phenyl)phenyl)sulfide and preparation thereofInfo
- Publication number
- JPH03258761A JPH03258761A JP2055005A JP5500590A JPH03258761A JP H03258761 A JPH03258761 A JP H03258761A JP 2055005 A JP2055005 A JP 2055005A JP 5500590 A JP5500590 A JP 5500590A JP H03258761 A JPH03258761 A JP H03258761A
- Authority
- JP
- Japan
- Prior art keywords
- phenyl
- sulfide
- hydroxy
- bis
- formula
- 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.)
- Granted
Links
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 19
- FWMUJAIKEJWSSY-UHFFFAOYSA-N sulfur dichloride Chemical compound ClSCl FWMUJAIKEJWSSY-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000002825 nitriles Chemical class 0.000 claims abstract description 11
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 3
- 125000003118 aryl group Chemical group 0.000 claims abstract description 3
- 235000010292 orthophenyl phenol Nutrition 0.000 claims abstract 4
- -1 (4-hydroxy-3-phenyl)phenyl Chemical group 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 abstract description 15
- 239000002994 raw material Substances 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 3
- RNHKXHKUKJXLAU-UHFFFAOYSA-N 2-(4-methylphenyl)acetonitrile Chemical compound CC1=CC=C(CC#N)C=C1 RNHKXHKUKJXLAU-UHFFFAOYSA-N 0.000 abstract 1
- 239000003905 agrochemical Substances 0.000 abstract 1
- 239000003814 drug Substances 0.000 abstract 1
- 229940079593 drug Drugs 0.000 abstract 1
- 239000003822 epoxy resin Substances 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 239000005011 phenolic resin Substances 0.000 abstract 1
- 229920000515 polycarbonate Polymers 0.000 abstract 1
- 239000004417 polycarbonate Substances 0.000 abstract 1
- 229920000647 polyepoxide Polymers 0.000 abstract 1
- 229920000728 polyester Polymers 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 25
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000003377 acid catalyst Substances 0.000 description 4
- 239000011592 zinc chloride Substances 0.000 description 4
- 235000005074 zinc chloride Nutrition 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- RENMDAKOXSCIGH-UHFFFAOYSA-N Chloroacetonitrile Chemical compound ClCC#N RENMDAKOXSCIGH-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000001103 continuous-wave nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- FMHXHMLHGIPODY-UHFFFAOYSA-N 2,2-dichloropropanenitrile Chemical compound CC(Cl)(Cl)C#N FMHXHMLHGIPODY-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
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- STZZWJCGRKXEFF-UHFFFAOYSA-N Dichloroacetonitrile Chemical compound ClC(Cl)C#N STZZWJCGRKXEFF-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- RFFFKMOABOFIDF-UHFFFAOYSA-N Pentanenitrile Chemical compound CCCCC#N RFFFKMOABOFIDF-UHFFFAOYSA-N 0.000 description 1
- 244000191761 Sida cordifolia Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- JAMNHZBIQDNHMM-UHFFFAOYSA-N pivalonitrile Chemical compound CC(C)(C)C#N JAMNHZBIQDNHMM-UHFFFAOYSA-N 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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
- Low-Molecular Organic Synthesis Reactions Using Catalysts (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、ポリカーボネートポリエステル、エポキシ樹
脂、フェノール樹脂、その他各種ポリマー原料、農医薬
原料として有用なビスフェノール類であるビス（（４−
ヒドロキシ−３−フェニル）フェニル）スルフィドおよ
びその製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to bis((4-
The present invention relates to hydroxy-3-phenyl)phenyl)sulfide and a method for producing the same.
［従来の技術］
このビス（（４−ヒドロキシ−３−フェニル）フェニル
）スルフィドについては、ジャーナル・オブ・ザ・アメ
リカン・ファーマシューティカル・アソシエーション
２１ ５５７−６９ （１９３２）に記載されている。[Prior Art] This bis((4-hydroxy-3-phenyl)phenyl) sulfide is described in the Journal of the American Pharmaceutical Association.
21 557-69 (1932).
この文献では、二硫化炭素を溶媒として低温において、
０−フェニルフェノールと二塩化硫黄を反応させること
により、油状のビス（（４−ヒドロキシ−３−フェニル
）フェニル）スルフィドと称するものを得たとされてい
る。In this document, at low temperature using carbon disulfide as a solvent,
It is said that an oil called bis((4-hydroxy-3-phenyl)phenyl) sulfide was obtained by reacting 0-phenylphenol with sulfur dichloride.
また、本発明者らの追試により、ベンゼン、トルエン、
１．２−ジクロロエタンなど、他の汎用溶媒を用いた
場合においても同様の油状物質が得られた。In addition, additional tests by the inventors revealed that benzene, toluene,
Similar oils were obtained using other common solvents such as 1,2-dichloroethane.
しかしながら、この油状物質を高速液体クロマトグラフ
ィーにより分析した結果、数多くの成分を含む混合物で
あることがわかった。However, analysis of this oily substance by high performance liquid chromatography revealed that it was a mixture containing many components.
このことから、上記油状物質はビス（（４−ヒドロキシ
−３−フェニル）フェニル）スルフィドとは異なる物で
あり、ビス（（４−ヒドロキシ−３−フェニル）フェニ
ル）スルフィドは未だ単離されていない。From this, the above oily substance is different from bis((4-hydroxy-3-phenyl)phenyl) sulfide, and bis((4-hydroxy-3-phenyl)phenyl) sulfide has not yet been isolated. .
したがって、この化合物を利用したポリマーについては
知られていないが、その構造上から予測される性質は極
めて有用であると考えられる。Therefore, although no polymers using this compound are known, the properties predicted from its structure are considered to be extremely useful.
本発明は、上記問題に鑑み成されたものであり、各種ポ
リマー原料として有望なジフェノールであるビス（（４
−ヒドロキシ−３−フェニル）フェニル）スルフィドの
選択的な製造方法を提供するものである。The present invention has been made in view of the above problems, and uses bis((4), a diphenol that is promising as a raw material for various polymers.
-Hydroxy-3-phenyl)phenyl) sulfide is provided.
［課題を解決するための手段］
本発明者らは、上記課題を解決するために鋭意検討した
結果、本発明を完成するに到ったものである。[Means for Solving the Problems] The present inventors have completed the present invention as a result of intensive studies to solve the above problems.
本発明は、式（１）
で表されるビス（（４−ヒドロキシ−３−フェニル）フ
ェニル）スルフィドの提供および０−フェニルフェノー
ルと二塩化硫黄とを反応させる際に、一般式（ｎ）
ｐ。The present invention provides bis((4-hydroxy-3-phenyl)phenyl) sulfide represented by formula (1) and when reacting 0-phenylphenol and sulfur dichloride, the general formula (n) p .
（式中、Ｒ１−Ｒ３は水素原子、ハロゲン原子、炭素数
１〜８の直鎖または分岐のアルキル基、アリール基また
はアラルキル基を示す。）で表されるニトリル類を存在
させることによって、ビス（（４−ヒドロキシ−３−フ
ェニル）フェニル）スルフィドを選択的に製造する方法
である。(In the formula, R1-R3 represent a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, an aryl group, or an aralkyl group.) This is a method for selectively producing ((4-hydroxy-3-phenyl)phenyl)sulfide.
本発明の方法において、このニトリル類の触媒作用はは
っきりしないが、０−フェニルフェノールは水酸基に対
して反応の位置選択性がほとんどないため、通常の条件
で二塩化硫黄を反応させた場合、各種異性体混合物や縮
合物が多量に生成し、目的物が単離できるような組成は
得られなかったのに対し、驚くべきことにニトリル類を
反応系に存在させるとバラ位のみが選択的に結合するこ
とを見出し、本発明を完成した。In the method of the present invention, the catalytic action of this nitrile is not clear, but since 0-phenylphenol has almost no regioselectivity for the reaction with respect to the hydroxyl group, when reacting with sulfur dichloride under normal conditions, various A large amount of isomer mixtures and condensates were produced, and it was not possible to obtain a composition that would allow isolation of the target product. However, surprisingly, when nitriles were present in the reaction system, only the bala position was selectively produced. The present invention was completed based on the discovery that the present invention is capable of binding.
本発明において使用されるニトリル類として例を挙げれ
ば、アセトニトリル、クロロアセトニトリル、ジクロロ
アセトニトリル、プロピオニトリル、２，２−ジクロロ
プロピオニトリル、２．２−ジメチルプロピオニトリル
、ブチロニトリル、４クロロブチロニトリル、イソブチ
ロニトリル、バレロニトリル、ベンゾニトリル、α−ト
ルニトリル、０−トリルアセトニトリル、ｍ−）リルア
セトニトリル、ｐ−）リルアセトニトリル等が挙げられ
、その使用量としては、原料の０−フェニルフェノール
に対して１０モル死程度から溶媒を兼ねた任意の量を使
用することができるが、好ましくは５０モル％〜５００
モル％程度が使用される。Examples of nitriles used in the present invention include acetonitrile, chloroacetonitrile, dichloroacetonitrile, propionitrile, 2,2-dichloropropionitrile, 2,2-dimethylpropionitrile, butyronitrile, 4-chlorobutyro Examples include nitrile, isobutyronitrile, valeronitrile, benzonitrile, α-tolnitrile, 0-tolylacetonitrile, m-)lylacetonitrile, p-)lylacetonitrile, and the amount used is based on the raw material 0-phenylphenol. Any amount can be used that also serves as a solvent, from about 10 mol % to 50 mol %
The mole % range is used.
また、本発明における反応では、酸触媒を併用してもよ
く、酸触媒としては、塩酸、リン酸等の鉱酸類や塩化ア
ルミニウム、塩化亜鉛、塩化鉄なとのルイス酸などが用
いられ、その使用量は０．０１〜１０％（重量％）程度
、好ましくは０．０１〜１％（重量％）程度である。Furthermore, in the reaction of the present invention, an acid catalyst may be used in combination, and examples of the acid catalyst include mineral acids such as hydrochloric acid and phosphoric acid, and Lewis acids such as aluminum chloride, zinc chloride, and iron chloride. The amount used is about 0.01 to 10% (wt%), preferably about 0.01 to 1% (wt%).
本発明のビス（（４−ヒドロキシ−３−フェニル）フェ
ニル）スルフィドは、０−フェニルフェノールと二塩化
硫黄とをニトリル類の存在下において反応させることに
より異性体およびその他の副生物の生成を抑制して効率
よく生成させることができるが、この時使用される０−
フェニルフェノールは、二塩化硫黄に対して２〜５倍モ
ル、好ましくは２．０〜２．５倍モル程度である。The bis((4-hydroxy-3-phenyl)phenyl) sulfide of the present invention suppresses the production of isomers and other by-products by reacting 0-phenylphenol and sulfur dichloride in the presence of nitriles. However, the 0-
Phenylphenol is used in an amount of 2 to 5 times, preferably about 2.0 to 2.5 times, mole relative to sulfur dichloride.
反応の形態としては反応容器に。−フェニルフエノール
、必要により酸触媒、およびニトリル類を仕込み、この
混合物中に二塩化硫黄を滴下していく方法が好ましいが
、特に限定されるものではない。The form of the reaction is in a reaction container. - Phenylphenol, if necessary, an acid catalyst, and a nitrile are charged, and sulfur dichloride is added dropwise into the mixture. This method is preferably, but not particularly limited.
この時、ニトリル類の使用量が、溶媒を兼ね、攪拌が充
分行える量であればよいが、触媒量程度で攪拌が困難な
場合は、反応に関与しない溶剤を使用することは差し支
えない。At this time, the amount of nitrile used may be sufficient as long as it serves as a solvent and is sufficient for stirring, but if stirring is difficult due to the catalytic amount, a solvent that does not participate in the reaction may be used.
この溶剤としては、例えばベンゼン、トルエン、１．２
−ジクロロエタン、１，１．１− トＩＪ クロロエタ
ン、ヘキサン、シクロヘキサン、酢酸等の反応に関与し
ないものであり、その使用量は任意の量でよい。Examples of this solvent include benzene, toluene, 1.2
-Dichloroethane, 1,1.1-IJ It does not participate in the reaction of chloroethane, hexane, cyclohexane, acetic acid, etc., and any amount may be used.
反応温度は、２０°Ｃ以下、好ましくは５〜−１０°Ｃ
の範囲である。The reaction temperature is 20°C or less, preferably 5 to -10°C.
is within the range of
本発明の反応は発熱反応であり、二塩化硫黄の滴下時間
は、反応温度を維持できる速度が望ましい。通常は１〜
１０時間の範囲である。The reaction of the present invention is an exothermic reaction, and the dropwise addition time of sulfur dichloride is preferably such that the reaction temperature can be maintained. Usually 1~
The range is 10 hours.
この様にして得られる反応液から、酸触媒、副生塩酸を
水洗等により充分除去した後、！縮、晶析、再結晶など
任意の方法およびそれらの組み合わせにより、ビス（（
４−ヒドロキシ−３−フェニル）フェニル）スルフィド
を結晶化、精製することができる。After thoroughly removing the acid catalyst and by-product hydrochloric acid from the reaction solution obtained in this way by washing with water, etc. Bis((
4-Hydroxy-3-phenyl)phenyl) sulfide can be crystallized and purified.
次に、本発明を実施例により更に詳細に説明するが、本
発明はこれにより何ら制限されることはない。Next, the present invention will be explained in more detail with reference to examples, but the present invention is not limited thereto.
〔実施例］
実施例１
攪拌器、温度計、滴下ロートを装着した反応容器に、０
−フェニルフェノール３４３．６ｇ（２，０２ｓ＋ｏｌ
）、塩化亜鉛２．３ ｇ （０，５２）及びアセトニト
リル３４３．６ ｇを装入し、撹拌を行いながら〜１０
℃まで冷却する。[Example] Example 1 In a reaction vessel equipped with a stirrer, a thermometer, and a dropping funnel,
-Phenylphenol 343.6g (2,02s+ol
), 2.3 g (0,52) of zinc chloride, and 343.6 g of acetonitrile, and while stirring ~10
Cool to ℃.
さらに攪拌、冷却を続けなから二塩化硫黄１０３ｇ（１
，Ｏｍｏｌ）とアセトニトリル１０３ｇの混合物を滴下
していった。Further stirring and cooling were continued, and 103 g (1
, Omol) and 103 g of acetonitrile was added dropwise.
この時、反応による発熱で温度が上昇しない様に滴下速
度を調整し、３時間で滴下を終了した。At this time, the dropping rate was adjusted so that the temperature would not rise due to heat generated by the reaction, and the dropping was completed in 3 hours.
滴下中の反応温度は−８〜−１０″Ｃであった。The reaction temperature during the dropwise addition was -8 to -10''C.
滴下終了後、温度を〜１０℃に保ったままＩｖｆ開攪拌
を続けた後、反応を終了した。After the dropwise addition was completed, Ivf stirring was continued while the temperature was maintained at ~10°C, and then the reaction was terminated.
この時の全反応生成物に対するビス（（４−ヒドロキシ
−３−フェニル）フェニル）スルフィドと思われる主成
分の含有率は８５．８％であった（高速液体クロマトグ
ラフィーによる。）
この様にして得られた反応液にトルエン５００ｄを装入
し、排水が中性になるまで水洗を行った。The content of the main component, which is believed to be bis((4-hydroxy-3-phenyl)phenyl)sulfide, in the total reaction product was 85.8% (according to high performance liquid chromatography). 500 d of toluene was added to the resulting reaction solution, and the waste water was washed with water until it became neutral.
次いで、この有機層からロータリーエバポレーターによ
って揮発分を除去したところ黄色の油状物質を得た。Then, volatile components were removed from this organic layer using a rotary evaporator to obtain a yellow oily substance.
この油状物質は室温においては大部分が結晶化するもの
であった。This oily substance was mostly crystallized at room temperature.
こうして得られた油状物質をトルエン３５０ ｇに加熱
溶解した後、室温まで徐冷することにより、２８１．２
ｇの白色結晶を得た。このものの高速液体クロマトグ
ラフィーによる純度は９５．７％であった。After heating and dissolving the oily substance obtained in this way in 350 g of toluene, the mixture was slowly cooled to room temperature to obtain 281.2
g white crystals were obtained. The purity of this product by high performance liquid chromatography was 95.7%.
さらに、トルエンによる再結晶を２回行うことにより純
度９８．８％の結晶かえられた（通算収率６５．６％）
。Furthermore, by recrystallizing twice with toluene, crystals with a purity of 98.8% were obtained (total yield 65.6%).
.
以下にその他の分析結果を示す。Other analysis results are shown below.
（１）融点 １２２〜１２３°Ｃ （２）元素分析値 計算値（％） ７７．８４ 測定値（％） ７７．８８ （３） Ｈ−Ｎ Ｍ Ｒ（（ＣＤｊ） ｚｃ。(1) Melting point 122-123°C (2) Elemental analysis values Calculated value (%) 77.84 Measured value (%) 77.88 (3) H-N M R ((CDj) zc.
δ ： ６．９８（２Ｈ，ｄ、 ５
Ｓ
４．８６ ８．６５
４．８２ ８．８２
：Ｔ阿Ｓ） ｐｐｍ
１１Ｘ２． Ｊｓ−６・８．４０ ）７．２３（２
Ｈ，ｄｄ、 ６−ＨＸ２． Ｊｉ−ｓ□８．４１Ｊ
＆−２・２．４７ ）
第１図にＮＭＲ吸収スペクトルを示す。δ: 6.98 (2H, d, 5S 4.86 8.65 4.82 8.82: TAS) ppm 11X2. Js-6・8.40 )7.23(2
H, dd, 6-HX2. Ji-s□8.41J
&-2・2.47) Figure 1 shows the NMR absorption spectrum.
（４） Ｉ Ｒ 第２図に赤外線吸収スペクトルを示す。(4) IR Figure 2 shows the infrared absorption spectrum.
以上の結果より、得られた結晶はビス（（４ヒドロキシ
−３−フェニル）フェニル）スルフィドであることが確
認された。From the above results, it was confirmed that the obtained crystal was bis((4hydroxy-3-phenyl)phenyl)sulfide.
実施例２
反応温度を０〜５°Ｃに変えたほがは、実施例１と全く
同様におこなった。Example 2 The same procedure as in Example 1 was carried out except that the reaction temperature was changed to 0 to 5°C.
この時のビス（（４−ヒドロキシ−３−フェニル）フェ
ニル）スルフィドの含有率は７５．６％であった。The content of bis((4-hydroxy-3-phenyl)phenyl)sulfide at this time was 75.6%.
実施例３
攪拌器、温度計、滴下ロートを装着した反応容器に０−
フェニルフェノール３４．８ ｇ （０，２０５ｍｏｌ
）、塩化亜鉛０．２２ ｇ （０，５χ）及びアセトニ
トリル４．１ｇ（０，１ｓｏｌ）、さらにトルエン３４
．８ ｇを装入し、これに二塩化硫黄１０．３ ｇ （
０，１ｓｏｌ）とトルエン１０．３ ｇの混合物を滴下
して反応を行った。Example 3 A reaction vessel equipped with a stirrer, a thermometer, and a dropping funnel was
Phenylphenol 34.8 g (0,205 mol
), zinc chloride 0.22 g (0.5χ) and acetonitrile 4.1 g (0.1 sol), and toluene 34
．． 8 g of sulfur dichloride (10.3 g of sulfur dichloride (
A mixture of 0.1 sol) and 10.3 g of toluene was added dropwise to carry out the reaction.
反応条件は、実施例１と同様である。The reaction conditions are the same as in Example 1.
この時のビス（（４−ヒドロキシ−３−フェニル）フェ
ニル）スルフィドの含有率は７１，３％であった。The content of bis((4-hydroxy-3-phenyl)phenyl) sulfide at this time was 71.3%.
実施例４
攪拌器、温度計、滴下ロートを装着した反応容器に０−
フェニルフェノール３４．８ ｇ （０，２０５＋＋＋
ｏｌ）、塩化亜鉛０．２２ｇ （０，５％）およびクロ
ロアセトニトリル７．６ ｇ （０，１翔ｏ１）、さら
にトルエン３４．８ ｇを装入し、これに二塩化硫黄１
０．３ ｇ （０，１ｓｏｌ）とトルエン１０．３ ｇ
の混合物を滴下して反応を行った。Example 4 A reaction vessel equipped with a stirrer, a thermometer, and a dropping funnel was
Phenylphenol 34.8 g (0,205+++
ol), 0.22 g (0.5%) of zinc chloride and 7.6 g (0.1 mol) of chloroacetonitrile, as well as 34.8 g of toluene, and 1 sulfur dichloride.
0.3 g (0.1 sol) and toluene 10.3 g
A mixture of these was added dropwise to carry out the reaction.
反応条件は、実施例Ｉと同様である。Reaction conditions are similar to Example I.
この時のビス（（４−ヒドロキシ−３−フェニル）フェ
ニル）スルフィドの含有率は７２．１％であった。The content of bis((4-hydroxy-3-phenyl)phenyl)sulfide at this time was 72.1%.
以上、詳述したように、各種ポリマー原料として有用な
ビス（（４−ヒドロキシ−３−フェニル）フェニル１ス
ルフイドは本発明の方法によって初めて単離することが
できた。As detailed above, bis((4-hydroxy-3-phenyl)phenyl 1-sulfide, which is useful as a raw material for various polymers), could be isolated for the first time by the method of the present invention.
本発明の方法は、ニトリル類を存在させることによって
選択的にバラ位に反応させることができ、その結果、高
収率で目的物を得ることができる。In the method of the present invention, the presence of nitriles allows selective reaction at the distal position, and as a result, the desired product can be obtained in high yield.
第１図は実施例１で得られた化合物のＮＭＲ吸収スペク
トルを示す図であり、第２図は同化合物のＩＲ吸収スペ
クトルを示す図である。FIG. 1 is a diagram showing the NMR absorption spectrum of the compound obtained in Example 1, and FIG. 2 is a diagram showing the IR absorption spectrum of the same compound.
Claims (1)
ェニル）スルフィド。 ２）ｏ−フェニルフェノールと二塩化硫黄を一般式（I
I） ▲数式、化学式、表等があります▼（II） （式中、Ｒ＿１〜Ｒ＿３は水素原子、ハロゲン原子、炭
素数１〜８の直鎖または分岐のアルキル基、アリール基
またはアラルキル基を示す。） で表されるニトリル類の存在下で反応させることを特徴
とするビス（（４−ヒドロキシ−３−フェニル）フェニ
ル）スルフィドの製造方法。[Claims] 1) Bis((4-hydroxy-3-phenyl)phenyl) sulfide represented by the formula (I) ▲There are numerical formulas, chemical formulas, tables, etc.▼(I). 2) O-phenylphenol and sulfur dichloride are combined with the general formula (I
I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, R_1 to R_3 represent a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, an aryl group, or an aralkyl group. .) A method for producing bis((4-hydroxy-3-phenyl)phenyl) sulfide, which comprises reacting in the presence of a nitrile represented by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2055005A JP2807029B2 (en) | 1990-03-08 | 1990-03-08 | Method for producing bis [(4-hydroxy-3-phenyl) phenyl] sulfide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2055005A JP2807029B2 (en) | 1990-03-08 | 1990-03-08 | Method for producing bis [(4-hydroxy-3-phenyl) phenyl] sulfide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03258761A true JPH03258761A (en) | 1991-11-19 |
| JP2807029B2 JP2807029B2 (en) | 1998-09-30 |
Family
ID=12986542
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2055005A Expired - Fee Related JP2807029B2 (en) | 1990-03-08 | 1990-03-08 | Method for producing bis [(4-hydroxy-3-phenyl) phenyl] sulfide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2807029B2 (en) |
-
1990
- 1990-03-08 JP JP2055005A patent/JP2807029B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2807029B2 (en) | 1998-09-30 |
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