JPH02172966A - New organic sulfur compound and production thereof - Google Patents
New organic sulfur compound and production thereofInfo
- Publication number
- JPH02172966A JPH02172966A JP32363788A JP32363788A JPH02172966A JP H02172966 A JPH02172966 A JP H02172966A JP 32363788 A JP32363788 A JP 32363788A JP 32363788 A JP32363788 A JP 32363788A JP H02172966 A JPH02172966 A JP H02172966A
- Authority
- JP
- Japan
- Prior art keywords
- benzyl alcohol
- organic sulfur
- formula
- compound
- general 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.)
- Pending
Links
- 150000002898 organic sulfur compounds Chemical class 0.000 title claims description 16
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- FYWFCRHZXORPFH-UHFFFAOYSA-N (2-sulfanylphenyl)methanol Chemical compound OCC1=CC=CC=C1S FYWFCRHZXORPFH-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000005843 halogen group Chemical group 0.000 claims abstract description 4
- 150000001336 alkenes Chemical class 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 238000006704 dehydrohalogenation reaction Methods 0.000 claims description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N benzyl alcohol Substances OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 abstract description 21
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 abstract description 15
- 150000001875 compounds Chemical class 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 abstract description 5
- 239000011347 resin Substances 0.000 abstract description 5
- 229920005989 resin Polymers 0.000 abstract description 5
- 229920003023 plastic Polymers 0.000 abstract description 3
- 239000004033 plastic Substances 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 2
- 230000003287 optical effect Effects 0.000 abstract description 2
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 238000007334 copolymerization reaction Methods 0.000 abstract 1
- 229940079593 drug Drugs 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 18
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- -1 l -Propatool Natural products 0.000 description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000004440 column chromatography Methods 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical class BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 3
- 235000019445 benzyl alcohol Nutrition 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- 235000019341 magnesium sulphate Nutrition 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- IBYHHJPAARCAIE-UHFFFAOYSA-N 1-bromo-2-chloroethane Chemical compound ClCCBr IBYHHJPAARCAIE-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical class ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000001766 physiological effect Effects 0.000 description 2
- 150000003464 sulfur compounds Chemical class 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- APQIUTYORBAGEZ-UHFFFAOYSA-N 1,1-dibromoethane Chemical compound CC(Br)Br APQIUTYORBAGEZ-UHFFFAOYSA-N 0.000 description 1
- ATWLRNODAYAMQS-UHFFFAOYSA-N 1,1-dibromopropane Chemical compound CCC(Br)Br ATWLRNODAYAMQS-UHFFFAOYSA-N 0.000 description 1
- SEQRDAAUNCRFIT-UHFFFAOYSA-N 1,1-dichlorobutane Chemical compound CCCC(Cl)Cl SEQRDAAUNCRFIT-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 1
- KNKRKFALVUDBJE-UHFFFAOYSA-N 1,2-dichloropropane Chemical compound CC(Cl)CCl KNKRKFALVUDBJE-UHFFFAOYSA-N 0.000 description 1
- YHRUOJUYPBUZOS-UHFFFAOYSA-N 1,3-dichloropropane Chemical compound ClCCCCl YHRUOJUYPBUZOS-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ULTHEAFYOOPTTB-UHFFFAOYSA-N 1,4-dibromobutane Chemical compound BrCCCCBr ULTHEAFYOOPTTB-UHFFFAOYSA-N 0.000 description 1
- KJDRSWPQXHESDQ-UHFFFAOYSA-N 1,4-dichlorobutane Chemical compound ClCCCCCl KJDRSWPQXHESDQ-UHFFFAOYSA-N 0.000 description 1
- SGRHVVLXEBNBDV-UHFFFAOYSA-N 1,6-dibromohexane Chemical compound BrCCCCCCBr SGRHVVLXEBNBDV-UHFFFAOYSA-N 0.000 description 1
- BXXWFOGWXLJPPA-UHFFFAOYSA-N 2,3-dibromobutane Chemical compound CC(Br)C(C)Br BXXWFOGWXLJPPA-UHFFFAOYSA-N 0.000 description 1
- ACRXBKIYQLXFOC-UHFFFAOYSA-N 2-benzyl-N-ethyl-3-phenylpropan-1-amine Chemical compound C=1C=CC=CC=1CC(CNCC)CC1=CC=CC=C1 ACRXBKIYQLXFOC-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- LPNANKDXVBMDKE-UHFFFAOYSA-N 5-bromopent-1-ene Chemical compound BrCCCC=C LPNANKDXVBMDKE-UHFFFAOYSA-N 0.000 description 1
- YKGBNAGNNUEZQC-UHFFFAOYSA-N 6-methyl-n,n-bis(6-methylheptyl)heptan-1-amine Chemical compound CC(C)CCCCCN(CCCCCC(C)C)CCCCCC(C)C YKGBNAGNNUEZQC-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000006911 enzymatic reaction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- MXHTZQSKTCCMFG-UHFFFAOYSA-N n,n-dibenzyl-1-phenylmethanamine Chemical compound C=1C=CC=CC=1CN(CC=1C=CC=CC=1)CC1=CC=CC=C1 MXHTZQSKTCCMFG-UHFFFAOYSA-N 0.000 description 1
- WBGPDYJIPNTOIB-UHFFFAOYSA-N n,n-dibenzylethanamine Chemical compound C=1C=CC=CC=1CN(CC)CC1=CC=CC=C1 WBGPDYJIPNTOIB-UHFFFAOYSA-N 0.000 description 1
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 1
- MSHKXFDHUIFHMD-UHFFFAOYSA-N n-benzyl-n-butylbutan-1-amine Chemical compound CCCCN(CCCC)CC1=CC=CC=C1 MSHKXFDHUIFHMD-UHFFFAOYSA-N 0.000 description 1
- ZWRDBWDXRLPESY-UHFFFAOYSA-N n-benzyl-n-ethylethanamine Chemical compound CCN(CC)CC1=CC=CC=C1 ZWRDBWDXRLPESY-UHFFFAOYSA-N 0.000 description 1
- WYZDCUGWXKHESN-UHFFFAOYSA-N n-benzyl-n-methyl-1-phenylmethanamine Chemical compound C=1C=CC=CC=1CN(C)CC1=CC=CC=C1 WYZDCUGWXKHESN-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- RKBCYCFRFCNLTO-UHFFFAOYSA-N triisopropylamine Chemical compound CC(C)N(C(C)C)C(C)C RKBCYCFRFCNLTO-UHFFFAOYSA-N 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/10—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton
- C07C323/18—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
- C07C323/19—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton with singly-bound oxygen atoms bound to acyclic carbon atoms of the carbon skeleton
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、新規な有機硫黄化合物に関し、より詳細には
重合性のビニル基又はアリル基を有する有機硫黄化合物
で、ラジカル単独もしくは共重合性を有する有機硫黄化
合物ならびにこれらの製造法に関する。Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a novel organic sulfur compound, and more specifically, an organic sulfur compound having a polymerizable vinyl group or an allyl group, which has a radical monopolymerizable or copolymerizable The present invention relates to organic sulfur compounds having the following properties and methods for producing them.
（従来の技術と発明が解決しようとする課題）有機硫黄
化合物は自然界に多数存在し、特に生体内における有機
硫黄化合物は生体の構成要素として多量に含まれるだけ
でなく、その生理作用は重要で、硫黄原子の関与する各
種の酵素反応や生理作用が多数知られている。(Problems to be solved by conventional technology and the invention) Many organic sulfur compounds exist in nature, and in particular, organic sulfur compounds in living organisms are not only contained in large amounts as constituents of living organisms, but also have important physiological effects. A large number of various enzymatic reactions and physiological effects involving sulfur atoms are known.
一方、石炭あるいは石油中にも多量の有機硫黄化合物が
含まれているが、これらの物質は工業的に利用する場合
、各種の好ましくない影響を与えるため、嫌われこそす
れ喜ばれることはなく、むしろ公害の発生源として問題
視されている。On the other hand, coal and petroleum also contain large amounts of organic sulfur compounds, but when used industrially, these substances have various undesirable effects, so they are disliked and not appreciated. Rather, they are viewed as a problem as a source of pollution.
近年、各種の高性能プラスチックス、いわゆるエンジニ
アリングプラスチックスの構成成分として硫黄化合物が
注目され、例えばポリスルホンやポリエーテルスルホン
、ポリフェニレンスルフィド、といった高分子に代表さ
れるように、硫黄原子の特性を十分に利用した高性能高
分子物質を得るために重合性の含硫黄化合物が注目され
て来た。In recent years, sulfur compounds have attracted attention as constituents of various high-performance plastics, so-called engineering plastics. Polymerizable sulfur-containing compounds have attracted attention in order to obtain high-performance polymer materials.
従って、本発明の目的は、医薬品およびその合成中間体
または高機能性樹脂の中間原料として利用可能な有機硫
黄化合物およびその製造法を提供することにある。Therefore, an object of the present invention is to provide an organic sulfur compound that can be used as an intermediate raw material for pharmaceuticals and their synthetic intermediates or highly functional resins, and a method for producing the same.
（課題を解決するための手段）
本発明によれば、一般式（Ｉ）：
（但し、式中には、θ〜７の整数を示す。）で表される
有機硫黄化合物である。(Means for Solving the Problems) According to the present invention, it is an organic sulfur compound represented by the general formula (I): (wherein the formula represents an integer from θ to 7).
また本発明は、この有機硫黄化合物の第一の製造法であ
り、２−メルカプト−ベンジルアルコールと一般式：
Ｘ−（ＣＨｔ）ｍ−Ｘ （ｎ）（但し、式中Ｘ
はハロゲン原子を、またｍは２〜９の整数を示す。）で
表されるジハロゲン化アルカンとを塩基性触媒の存在下
で反応させた後、さらに塩基性触媒の存在下で脱水素化
ハロゲン化することを特徴とする。The present invention also provides a first method for producing this organic sulfur compound, in which 2-mercapto-benzyl alcohol and the general formula:
X-(CHt)m-X (n) (wherein X
represents a halogen atom, and m represents an integer of 2 to 9. ) is reacted with a dihalogenated alkane represented by () in the presence of a basic catalyst, and then further dehydrogenated and halogenated in the presence of a basic catalyst.
また本発明は、このを機硫黄化合物の第二の製造法であ
り、２−メルカプト−ベンジルアルコールと一般式：
Ｘ （ＣＨり ＊ ＣＨ＝ ＣＨｘ （ｍ ）
（但し、式中Ｘはハロゲン原子を、またｋは０〜７の整
数を示す。）で表されるハロゲン化アルケンを塩基性触
媒の存在下で反応させることを特徴とする。The present invention also provides a second method for producing a sulfur compound using 2-mercapto-benzyl alcohol and the general formula:
X (CHri * CH= CHx (m)
(However, in the formula, X represents a halogen atom, and k represents an integer of 0 to 7.) It is characterized by reacting a halogenated alkene represented by the following in the presence of a basic catalyst.
以下本発明をさらに詳細に説明する。The present invention will be explained in more detail below.
本発明の有機硫黄化合物は前記一般式（１）で表すこと
ができ、これらの単量体は、高屈折率を有し、低比重で
あり、また、ラジカル重合性を有する無色透明の液体状
物質であるため取り扱いが容易である。さらに、これら
の単量体は、単独重合あるいは他の重合性単量体との共
重合が可能である。この化合物は、Ｉ Ｒ，ＮＭＲ，元
素分析、屈折率等によって同定することができる。The organic sulfur compound of the present invention can be represented by the above general formula (1), and these monomers have a high refractive index, a low specific gravity, and are in the form of a colorless and transparent liquid that has radical polymerizability. Since it is a substance, it is easy to handle. Furthermore, these monomers can be homopolymerized or copolymerized with other polymerizable monomers. This compound can be identified by IR, NMR, elemental analysis, refractive index, etc.
また本発明の第一の製造法によれば、２−メルカプト−
ベンジルアルコールと前記一般式（ＩＩ）で表されるジ
ハロゲン化アルカンを原料とする。Further, according to the first production method of the present invention, 2-mercapto-
Benzyl alcohol and a dihalogenated alkane represented by the general formula (II) are used as raw materials.
このジハロゲン化アルカンとしては、ジクロロエタン、
ジクロロプロパン、ジクロロブタン、ジブロモエタン、
ジブロモプロパン、ジブロモブタンなどを例示すること
ができる。さらに詳しくは、１．２−ジクロロエタン、
１．２−ジブロモエタン、１−ブロモ−２−クロロエタ
ン、１−７’ロモー３−クロロプロパン、１．３−ジク
ロロプロパン、１゜３−シフ’ロモプロパン、１−７”
ロモー４−１０ロブタン、１，４−ジブロモブタン、１
，４−ジクロロブタン、１．５−ジブロモペンクン、１
．５−ジクロロペンタン、ｌ、６−ジブロモ−ｎ−ヘキ
サン、１゜６−ジクロロヘキサン、１．７−ジブロモへ
ブタン、ｌ・、８−ジブロモオクタンなどからなる群よ
り選ばれる。This dihalogenated alkane includes dichloroethane,
dichloropropane, dichlorobutane, dibromoethane,
Examples include dibromopropane and dibromobutane. More specifically, 1,2-dichloroethane,
1,2-dibromoethane, 1-bromo-2-chloroethane, 1-7' romo-3-chloropropane, 1,3-dichloropropane, 1゜3-shif' romopropane, 1-7''
lomo 4-10butane, 1,4-dibromobutane, 1
, 4-dichlorobutane, 1,5-dibromopencune, 1
．． Selected from the group consisting of 5-dichloropentane, 1,6-dibromo-n-hexane, 1.6-dichlorohexane, 1,7-dibromohebutane, 1., 8-dibromooctane, and the like.
この方法では、２−メルカプト−ベンジルアルコールと
前記例示したようなジハロゲン化アルカンとを原料とし
て、溶媒中で塩基性触媒の存在下、例えば−６０℃以上
の適温で反応させた後、蒸留あるいはカラムクロマトグ
ラフィーなどにより精製し、２−（ハロゲン化アルキル
チオ）−ベンジルアルコールを得る。次に、溶媒中で塩
基性触媒の存在下にて、適温で脱ハロゲン化水素するこ
とにより、２−（ビニルアルキルチオ）ベンジルアルコ
ールを得ることができる。In this method, 2-mercapto-benzyl alcohol and dihalogenated alkanes such as those exemplified above are reacted in a solvent in the presence of a basic catalyst at an appropriate temperature, e.g. It is purified by chromatography or the like to obtain 2-(halogenated alkylthio)-benzyl alcohol. Next, 2-(vinylalkylthio)benzyl alcohol can be obtained by dehydrohalogenation in a solvent in the presence of a basic catalyst at an appropriate temperature.
この製造法において、溶媒としては、アセトニトリル、
酢酸エチル、エタノール、メタノール、テトラヒドロフ
ラン、ジオキサン、クロロホルム、ジクロロメタン、ｌ
−プロパツール、２−プロパノール等が使用できる。In this production method, the solvent is acetonitrile,
Ethyl acetate, ethanol, methanol, tetrahydrofuran, dioxane, chloroform, dichloromethane, l
-Propatool, 2-propanol, etc. can be used.
また塩基性触媒としては、トリエチルアミン、トリメチ
ルアミン、トリノルマルプロピルアミン、トリイソプロ
ピルアミン、トリノルマルブチルアミン、トリイソオク
チルアミン、□トリオクチルアミン、トリエタノールア
ミン、トリベンジルアミン、ベンジルジメチルアミン、
ベンジルジエチルアミン、ジベンジルメチルアミン、ジ
ベンジルジエチルアミン、ジベンジルエチルアミン、ベ
ンジルジノルマルブチルアミン、トリフェニルアミン、
各種ナトリウムアルコキシドなどからなる群より選択さ
れる１種または２種以上を使用できる。In addition, basic catalysts include triethylamine, trimethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisooctylamine, trioctylamine, triethanolamine, tribenzylamine, benzyldimethylamine,
Benzyldiethylamine, dibenzylmethylamine, dibenzyldiethylamine, dibenzylethylamine, benzyl di-n-butylamine, triphenylamine,
One or more selected from the group consisting of various sodium alkoxides can be used.
次に本発明の第二の製造法によれば、２−メルカプト−
ベンジルアルコールと前記一般式（ＩＩＩ）で表される
ハロゲン化アルケンを原料とする。Next, according to the second production method of the present invention, 2-mercapto-
Benzyl alcohol and a halogenated alkene represented by the general formula (III) are used as raw materials.
このハロゲン化アルケンとしては、アリルブロマイド、
アリルクロライド、アリルクロライド、４−ブロモ−１
−ブテン、５−ブロモ−１−ペンテンなどからなる群よ
り選ばれる化合物が挙げられる。As this halogenated alkene, allyl bromide,
Allyl chloride, allyl chloride, 4-bromo-1
Examples include compounds selected from the group consisting of -butene, 5-bromo-1-pentene, and the like.
この方法では、２−メルカプト−ベンジルアルコールと
前記例示したようなハロゲン化アルケンとを原料として
、前記例示したような溶媒中で同様の塩基性触媒の存在
下、例えば−６０℃以上の適温で反応させた後、蒸留あ
るいはカラムクロマトグラフィーなどにより精製し、２
−（ビニルアルキルチオ）−ベンジルアルコールを得る
。In this method, 2-mercapto-benzyl alcohol and a halogenated alkene as exemplified above are used as raw materials and reacted in a solvent as exemplified above in the presence of a similar basic catalyst at an appropriate temperature, e.g., -60°C or higher. After that, it is purified by distillation or column chromatography, etc.
-(vinylalkylthio)-benzyl alcohol is obtained.
なお、一般式（１）においてｋが１以上の有機硫黄化合
物の場合には特に第一の製造法が有効である。Note that the first production method is particularly effective in the case of an organic sulfur compound in which k is 1 or more in general formula (1).
（発明の効果）
本発明の有機硫黄化合物は、重合性の新規な化合物であ
り、医薬品およびその合成中間体としてまたは高機能性
樹脂原料として利用できる。また、本発明の製造法によ
り有機硫黄化合物を高収率で容易に合成することができ
る。さらにこの化合物を重合あるいは共重合して得た樹
脂は透明性、高屈折率など光学的特性に優れており、プ
ラスチックレンズなどに利用できる。(Effects of the Invention) The organic sulfur compound of the present invention is a novel polymerizable compound, and can be used as a pharmaceutical and a synthetic intermediate thereof, or as a raw material for a highly functional resin. Furthermore, organic sulfur compounds can be easily synthesized in high yield by the production method of the present invention. Furthermore, resins obtained by polymerizing or copolymerizing this compound have excellent optical properties such as transparency and high refractive index, and can be used for plastic lenses and the like.
（実施例）
以下実施例により本発明を具体的に説明するが、これは
本発明の範囲を限定するものではない。(Examples) The present invention will be specifically explained below with reference to Examples, but these are not intended to limit the scope of the present invention.
実施例１
２−（ビニルチオ）−ベンジルアルコールの合成滴下ロ
ート、窒素導入管および撹拌機を付した１リツトルの３
ソロフラスコに、０−（ヒドロキシメチル）チオフェノ
ール１４ｇ（１００＋＋＋ｍｏｌ）、トリエチルアミン
１０．１ｇ （１００ｍｍｏｌ）およびアセトニトリル
５０−をとり、滴下ロートよりアセトニトリル２〇−に
溶解させた１、２−ジブロモエタン１８．８ｇ（１００
ｍｍ。Example 1 Synthesis of 2-(vinylthio)-benzyl alcohol 1 liter bottle with dropping funnel, nitrogen inlet tube and stirrer
14 g (100+++ mol) of 0-(hydroxymethyl)thiophenol, 10.1 g (100 mmol) of triethylamine, and 50 mm of acetonitrile were placed in a solo flask, and 18. 8g (100
mm.
ｌ）を滴下した。反応容器内の温度は１０℃を越えない
ように冷却、攪拌を十分に行い、２時間かけて滴下を終
了し、さらに２時間攪拌を続けた後、反応混合液を濾過
し、その濾液を減圧濃縮した。さらに、その残渣を減圧
蒸留することにより、無色透明の液体１８．０ｇ（７３
％）を得た。l) was added dropwise. The temperature inside the reaction vessel was sufficiently cooled and stirred so that it did not exceed 10°C, and the dropwise addition was completed over 2 hours. After continuing stirring for another 2 hours, the reaction mixture was filtered, and the filtrate was depressurized. Concentrated. Furthermore, by distilling the residue under reduced pressure, 18.0 g (73 g) of a colorless and transparent liquid was obtained.
%) was obtained.
次に上述の合成により得られた２−（２−ブロモエチル
チオ）−ベンジルアルコールの脱ハロゲン化水素反応に
よる２−（ビニルチオ）−ベンジルアルコールの合成を
説明する。Next, the synthesis of 2-(vinylthio)-benzyl alcohol by dehydrohalogenation reaction of 2-(2-bromoethylthio)-benzyl alcohol obtained by the above synthesis will be explained.
１００−のナス型フラスコ中、水冷かつ窒素気流下で５
０艷の乾燥エタノールに金属ナトリウムＩｇを加え、良
（攪拌しながら徐々に室温まで戻した。5 in a 100° eggplant-shaped flask under water cooling and nitrogen flow.
Sodium metal Ig was added to 0.0 ml of dry ethanol, and the temperature was gradually warmed to room temperature while stirring.
これに上記法により得られた２−（２−ブロモエチルチ
オ）−ベンジルアルコール２３０■（１０ｎ＋ｍｏｌ）
を加え室温で８時間攪拌した。水を加えた後濃縮し抽出
を行った（ＣＨｚ（Ｊｚ／ａｑ）。有機層を硫酸マグネ
シウムで乾燥後、減圧下で濃縮し、生成物をカラムクロ
マトグラフィーにより単離精製し、２−（ビニルチオ）
ベンジルアルコール１５２ｇ （９７％）を得た。To this was added 230 μ (10 n+mol) of 2-(2-bromoethylthio)-benzyl alcohol obtained by the above method.
was added and stirred at room temperature for 8 hours. After adding water, it was concentrated and extracted (CHz (Jz/aq). The organic layer was dried over magnesium sulfate, concentrated under reduced pressure, and the product was isolated and purified by column chromatography. )
152 g (97%) of benzyl alcohol was obtained.
ｎ ｇ’ ＝ １．６０３４
’Ｈ−ＮＭＲ（ＣＤＣｊ３） ；δ（ｐｐｍ）２．１０
（ｓ、 ｉ Ｈ）、 ４．７３−４．８３ （ｄ、
２ Ｈ）５．００−５．２７ （ｄ、 Ｉ Ｈ）、 ５
．２４−５．３９ （ｄ、 Ｉ Ｈ）６．２６−６．７
０ （ｔ、 Ｉ Ｈ）、 ７．２６−７．４６ （ｍ、
４ Ｈ）Ｉ Ｒ（ｃｒ’）
１５９０ （５ＣＨ＝ＣＨ２）ｍ
３０４０ （−ＣＨ，ＯＨ）
元素分析（％）Ｃ９ＨＩ。Ｏ８
計算値： Ｃ、６５，０６、Ｈｉ ６．０７測定値：
Ｃ； ６４．９７、Ｈ；６．１０実施例２
２−（アリルチオ）−ベンジルアルコールの合成０−（
ヒドロキシメチル）チオフェノールとアリルブロマイド
との反応による２−（アリルチオ）−ベンジルアルコー
ルの合成法を説明する。n g' = 1.6034'H-NMR (CDCj3); δ (ppm) 2.10
(s, i H), 4.73-4.83 (d,
2 H) 5.00-5.27 (d, I H), 5
．． 24-5.39 (d, I H) 6.26-6.7
0 (t, I H), 7.26-7.46 (m,
4H)I R(cr') 1590 (5CH=CH2)m 3040 (-CH,OH) Elemental analysis (%) C9HI. O8 Calculated value: C, 65.06, Hi 6.07 Measured value:
C; 64.97, H; 6.10 Example 2 Synthesis of 2-(allylthio)-benzyl alcohol 0-(
A method for synthesizing 2-(allylthio)-benzyl alcohol by reacting hydroxymethyl)thiophenol and allyl bromide will be described.
滴下ロート、窒素導入管および攪拌機を付した１リツト
ルの３ソロフラスコに、Ｏ−（ヒドロキシメチル）チオ
フェノール１４ｇ（１００ｍ＋＊ｏｌ）、トリエチルア
ミン１０．１ｇ（１００ｍｍｏｌ）およびアセトニトリ
ル５０ＰＲ１をとり、滴下ロートよりアセトニトリル２
０ｍ！に溶解させたアリルブロマイド１２．１ｇ（１０
０ｍｍｏｌ）を滴下した。反応容器内の温度は１０℃を
越えないように冷却、攪拌を十分に行い、２時間かけて
滴下を終了し、さらに８時間攪拌を続けた。水を加えた
後、濃縮し、抽出を行い（ＣＨｚ（ｊｚ／ａＱ） ％有
機層を硫酸マグネシウムで乾燥後、減圧下で濃縮し、生
成物をカラムクロマトグラフィーにより単離精製Ｌ、２
−（アリルチオ）−ベンジルアルコール１６．７ｇ （
９３％）を得た。Into a 1 liter 3-sol flask equipped with a dropping funnel, a nitrogen inlet pipe and a stirrer, 14 g (100 m++ol) of O-(hydroxymethyl)thiophenol, 10.1 g (100 mmol) of triethylamine and acetonitrile 50PR1 were added from the dropping funnel. Acetonitrile 2
0m! 12.1 g of allyl bromide (10
0 mmol) was added dropwise. Sufficient cooling and stirring were performed so that the temperature inside the reaction vessel did not exceed 10° C., and the dropwise addition was completed over 2 hours, and stirring was continued for a further 8 hours. After adding water, it was concentrated and extracted (CHz (jz/aQ)%). The organic layer was dried over magnesium sulfate, concentrated under reduced pressure, and the product was isolated and purified by column chromatography.
-(allylthio)-benzyl alcohol 16.7g (
93%).
０ｇ３・’＝１．５９２０
’ＨＮＭＲ（ＣＤＣｌ２） ； δ（ｐｐｍ）２．１
６ （ｓ、 Ｉ Ｈ）、 ３．４７−３．６１
（ｄ、 ２ Ｈ）４．７５− ４．８３ （ｄ、 ２
Ｈ）、 ４．９２−５．１３ （ｍ、 Ｉ Ｈ）
５．１４− ５．２０ （ｄ、 Ｉ Ｈ）、 ５．
２２−５．９７ （ｍ、 Ｉ Ｈ）７．１４− ７．
５０ （ｍ、 ４ Ｈ）Ｉ Ｒ（ｃ「Ｉ）
１６５０ （−ＣＨｚＣＨ＝ ＣＨｘ）３０４０
（−ＣＨｚＯＨ）
元素分析（％）Ｃ８゜Ｈ１□Ｏ８
計算値： Ｃ；６６．６６ 、Ｈ；６．６６測定値：
Ｃ、６６，６１、Ｈ、６，５６実施例３
２−（３−ブテニルチオ）−ベンジルアルコールの合成
０−（ヒドロキシメチル）チオフェノールと４−プロモ
ー■−ブテンとの反応による２−（３−ブテニルチオ）
−ベンジルアルコールの合成法を説明する。0g3・'=1.5920'HNMR (CDCl2); δ(ppm)2.1
6 (s, IH), 3.47-3.61
(d, 2 H) 4.75- 4.83 (d, 2
H), 4.92-5.13 (m, IH)
5.14-5.20 (d, IH), 5.
22-5.97 (m, I H) 7.14- 7.
50 (m, 4 H) I R (c "I) 1650 (-CHzCH= CHx) 3040
(-CHzOH) Elemental analysis (%) C8°H1□O8 Calculated value: C; 66.66, H; 6.66 Measured value:
C, 66,61, H, 6,56 Example 3 Synthesis of 2-(3-butenylthio)-benzyl alcohol 2-(3- butenylthio)
-Explain the synthesis method of benzyl alcohol.
滴下ロート、窒素導入管および攪拌機を付した１リツト
ルの三ツロフラスコに、０−（ヒドロキシメチル）チオ
フェノール１４ｇ（１００ｍｍｏｌ）、トリエチルアミ
ン１０．１ｇ（１００ｍｍｏｌ）およびアセトニトリル
５０−をとり、滴下ロートよりアセトニトリル２〇−に
溶解させた４−プロモー１−ブテン１３．５ｇ（１００
ｍｍｏｌ）を滴下した。反応容器内の温度は１０℃を越
えないように冷却、攪拌を十分に行い、２時間かけて滴
下を終了し、さらに８時間攪拌を続けた。水を加えた後
、濃縮し、抽出を行い（ＣＨｚＣｊｚ／ａｑ）、有機層
を硫酸マグネシウムで乾燥後、減圧上濃縮し、生成物を
カラムクロマトグラフィーにより単離精製し、２−（３
−ブテニルチオ）−ベンジルアルコール１７．５ｇＣ９
０％）を得た。In a 1 liter three-liter flask equipped with a dropping funnel, a nitrogen inlet tube, and a stirrer, 14 g (100 mmol) of 0-(hydroxymethyl)thiophenol, 10.1 g (100 mmol) of triethylamine, and 50 kg of acetonitrile were placed, and 2 g of acetonitrile was added from the dropping funnel. 13.5 g of 4-promo-1-butene (100
mmol) was added dropwise. Sufficient cooling and stirring were performed so that the temperature inside the reaction vessel did not exceed 10° C., and the dropwise addition was completed over 2 hours, and stirring was continued for a further 8 hours. After adding water, it was concentrated and extracted (CHzCjz/aq). The organic layer was dried over magnesium sulfate, concentrated under reduced pressure, and the product was isolated and purified by column chromatography.
-butenylthio)-benzyl alcohol 17.5gC9
0%) was obtained.
ｎ Ｐ” ＝ １．５８８０
’ Ｈ−ＮＭ Ｒ（ＣＤＩ！、） ；δ（ｐｐｍ）２゜
１４ （ｓ、 Ｌ Ｈ）、 ３．４８−４．０２ （ｍ
、 ４ Ｈ）４．７０−４．８５ （ｄ、２ Ｈ）、
５．０４−５．２０ （ｍ、 Ｉ Ｈ）５．０８−５．
２４ （ｄ、Ｉ Ｈ）、 ５．２９−６．０９ （ｍ、
Ｉ Ｈ）７．１１−７．４９ （ｍ、 ４ Ｈ）Ｉ
Ｒ（ｃｍ−’）
１６５０ （−ＣＨｚＣＨ＝ ＣＨり
３０４０ （−ＣＨｚＯＨ）
元素分析（％） Ｃ＋ ＋ Ｈ＋ ４ＯＳ計算値： Ｃ
；６８．００ 、Ｈ；７．２１測定値： Ｃ； ６７．
９７ 、Ｈｉ ７．２５n P" = 1.5880' H-NMR (CDI!,) ; δ (ppm) 2°14 (s, L H), 3.48-4.02 (m
, 4 H) 4.70-4.85 (d, 2 H),
5.04-5.20 (m, I H) 5.08-5.
24 (d, I H), 5.29-6.09 (m,
I H) 7.11-7.49 (m, 4 H) I
R (cm-') 1650 (-CHzCH= CH 3040 (-CHzOH) Elemental analysis (%) C+ + H+ 4OS calculated value: C
; 68.00, H; 7.21 Measured value: C; 67.
97, Hi 7.25
第１図は本発明実施例１で得た化合物のＩＲチャートで
ある。
第２図は本発明実施例１で得た化合物のＮＭＲチャート
である。FIG. 1 is an IR chart of the compound obtained in Example 1 of the present invention. FIG. 2 is an NMR chart of the compound obtained in Example 1 of the present invention.
Claims (3)
有機硫黄化合物。(1) General formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (However, in the formula, an integer from 0 to 7 is shown.) An organic sulfur compound represented by the following.
Ｘ−（ＣＨ＿２）＿ｍ−Ｘ（II） （但し、式中Ｘはハロゲン原子を、またｍは２〜９の整
数を示す。）で表されるジハロゲン化アルカンとを塩基
性触媒の存在下で反応させた後、さらに塩基性触媒の存
在下で脱ハロゲン化水素することを特徴とする一般式： ▲数式、化学式、表等があります▼（ I ） （但し、式中には、０〜７の整数を示す。）で表される
有機硫黄化合物の製造法。(2) 2-mercapto-benzyl alcohol and general formula:
X-(CH_2)_m-X(II) (wherein, X represents a halogen atom and m represents an integer of 2 to 9) in the presence of a basic catalyst General formula characterized by dehydrohalogenation in the presence of a basic catalyst after the reaction: ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (However, in the formula, 0 to 7 (indicates an integer of ).
Ｘ−（ＣＨ＿２）＿ｋ−ＣＨ＝ＣＨ＿２（III）（但し
、式中Ｘはハロゲン原子を、またｋは０〜７の整数を示
す。）で表されるハロゲン化アルケンを塩基性触媒の存
在下で反応させることを特徴とする一般式： ▲数式、化学式、表等があります▼（ I ） （但し、式中には、０〜７の整数を示す。）で表される
有機硫黄化合物の製造法。(3) 2-mercapto-benzyl alcohol and general formula:
In the presence of a basic catalyst, a halogenated alkene represented by X-(CH_2)_k-CH=CH_2(III) (wherein, General formula characterized by the reaction: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Production of organic sulfur compounds represented by (I) (However, in the formula, an integer from 0 to 7 is shown.) Law.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32363788A JPH02172966A (en) | 1988-12-23 | 1988-12-23 | New organic sulfur compound and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32363788A JPH02172966A (en) | 1988-12-23 | 1988-12-23 | New organic sulfur compound and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02172966A true JPH02172966A (en) | 1990-07-04 |
Family
ID=18156947
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32363788A Pending JPH02172966A (en) | 1988-12-23 | 1988-12-23 | New organic sulfur compound and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02172966A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001040175A1 (en) * | 1999-12-02 | 2001-06-07 | Tokuyama Corporation | Process for production of sulfur compounds |
-
1988
- 1988-12-23 JP JP32363788A patent/JPH02172966A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001040175A1 (en) * | 1999-12-02 | 2001-06-07 | Tokuyama Corporation | Process for production of sulfur compounds |
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