JPH0341064A - 1,8-bis(2-mercaptoethyl)naphthalene, its derivative and production - Google Patents
1,8-bis(2-mercaptoethyl)naphthalene, its derivative and productionInfo
- Publication number
- JPH0341064A JPH0341064A JP17533989A JP17533989A JPH0341064A JP H0341064 A JPH0341064 A JP H0341064A JP 17533989 A JP17533989 A JP 17533989A JP 17533989 A JP17533989 A JP 17533989A JP H0341064 A JPH0341064 A JP H0341064A
- Authority
- JP
- Japan
- Prior art keywords
- bis
- naphthalene
- mercaptoethyl
- formula
- expressed
- 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
- LWEZUEXNOYLGCY-UHFFFAOYSA-N 2-[8-(2-sulfanylethyl)naphthalen-1-yl]ethanethiol Chemical compound C1=CC(CCS)=C2C(CCS)=CC=CC2=C1 LWEZUEXNOYLGCY-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims abstract description 43
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000002252 acyl group Chemical group 0.000 claims abstract description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000005843 halogen group Chemical group 0.000 claims abstract description 4
- -1 2-mercaptoethyl Chemical group 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 8
- 150000002790 naphthalenes Chemical class 0.000 claims description 2
- WPVLFNJWOIPANN-UHFFFAOYSA-N 2-naphthalen-1-ylethanethiol Chemical compound C1=CC=C2C(CCS)=CC=CC2=C1 WPVLFNJWOIPANN-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 16
- 239000003795 chemical substances by application Substances 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 4
- 239000007864 aqueous solution Substances 0.000 abstract description 4
- 239000012299 nitrogen atmosphere Substances 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 2
- 150000001340 alkali metals Chemical group 0.000 abstract description 2
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 2
- 239000000178 monomer Substances 0.000 abstract description 2
- 229920001021 polysulfide Polymers 0.000 abstract description 2
- 239000005077 polysulfide Substances 0.000 abstract description 2
- 150000008117 polysulfides Polymers 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 abstract description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- NYFZLYHJRSCBJK-UHFFFAOYSA-N 1,8-bis(2-bromoethyl)naphthalene Chemical compound C1=CC(CCBr)=C2C(CCBr)=CC=CC2=C1 NYFZLYHJRSCBJK-UHFFFAOYSA-N 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 238000004949 mass spectrometry Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- FTUDIUREWUBVKL-UHFFFAOYSA-N 1,8-bis(ethenyl)naphthalene Chemical compound C1=CC(C=C)=C2C(C=C)=CC=CC2=C1 FTUDIUREWUBVKL-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- NOGFHTGYPKWWRX-UHFFFAOYSA-N 2,2,6,6-tetramethyloxan-4-one Chemical compound CC1(C)CC(=O)CC(C)(C)O1 NOGFHTGYPKWWRX-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- GPXNBMMDNQAKHZ-UHFFFAOYSA-N 2-naphthalen-2-ylethanethiol Chemical compound C1=CC=CC2=CC(CCS)=CC=C21 GPXNBMMDNQAKHZ-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 125000006416 CBr Chemical group BrC* 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 235000006545 Ziziphus mauritiana Nutrition 0.000 description 1
- 240000000038 Ziziphus mauritiana Species 0.000 description 1
- JKNPWHHGFOPCTJ-UHFFFAOYSA-N [8-(sulfanylmethyl)naphthalen-1-yl]methanethiol Chemical group C1=CC(CS)=C2C(CS)=CC=CC2=C1 JKNPWHHGFOPCTJ-UHFFFAOYSA-N 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 150000001266 acyl halides Chemical class 0.000 description 1
- 125000005035 acylthio group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000012746 preparative thin layer chromatography Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、新規化合物である１、８−ビス（２−メルカ
プトエチル）ナフタレン、及びその誘導体並びにこれら
の化合物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 a novel compound, 1,8-bis(2-mercaptoethyl)naphthalene, its derivatives, and a method for producing these compounds.
［従来技術］
ブトメチル基（−ＣＨ，ＳＨ）で置換した１、８−ビス
（メルカプトメチル）ナフタレンはよく知られた化合物
である（日本国特許第９５１３５２号（昭和５４）。[Prior Art] 1,8-bis(mercaptomethyl)naphthalene substituted with a butomethyl group (-CH,SH) is a well-known compound (Japanese Patent No. 951352 (1978)).
Ｃｈｅｍ、Ａｂｓｔｒ、１９７７、Ｖｏ１８６，４３４
４８ｖ） 。Chem, Abstr, 1977, Vo186, 434
48v).
［発明が解決しようとする問題点コ
しかしながら、メルカプトメチル基のメチレン鎖が１個
延長した２−メルカプトエチル基（−〇Ｈ２ＣＨ，ＳＨ
）がナフタレン環のベリ位に置換した１、８−ビス（２
−メルカプトエチル）ナフタレンは、そのメルカプト基
による応用面での幅広い用途が期待されているにも係ら
ず１合成化学上の困難さから現在に至るまで未知化合物
である。[Problems to be solved by the invention] However, the 2-mercaptoethyl group (-〇H2CH,SH
) is substituted at the beri position of the naphthalene ring.
-Mercaptoethyl) naphthalene is an unknown compound until now due to difficulties in synthetic chemistry, although it is expected to have a wide range of applications due to its mercapto group.
すなわち、本発明は、新規化合物の１，８−ビス（２−
メルカプトエチル）ナフタレンとその誘導体、及びこれ
ら化合物の製造方法を提供するものである。That is, the present invention provides novel compounds such as 1,8-bis(2-
(mercaptoethyl)naphthalene and its derivatives, and methods for producing these compounds.
［問題点を解決するための手段］
前記目的を達成する本発明に係る新規化合物の１．８−
ビス（２−メルカプトエチル）ナフタレンは。[Means for solving the problems] 1.8- of the novel compound according to the present invention that achieves the above object
Bis(2-mercaptoethyl)naphthalene.
構造式
（）
％式％
本発明に係る新規化合物の１．８−ビス（２−メルカプ
トエチル）ナフタレン誘導体は、一般式（１）％式％
Ｃ式中、Ｒはアシル基である。）
そして、前記構造式（Ａ）で示される１、８−ビス（２
−メルカプトエチル）ナフタレンは、一般式（ＩＩ）で
示される１、ｌ１ｌ−ビス（２−ハロゲノエチル）ナフ
タレンをチオ尿素で処理することによって製造される。Structural formula () %Formula% The 1,8-bis(2-mercaptoethyl)naphthalene derivative of the new compound according to the present invention has the general formula (1)%Formula%C In the formula, R is an acyl group. ) and 1,8-bis(2
-mercaptoethyl)naphthalene is produced by treating 1,l1l-bis(2-halogenoethyl)naphthalene represented by general formula (II) with thiourea.
ＸＨ，ＣＣＨ□Ｘ
（式中、又はハロゲン原子である。）
また、前記一般式（【）で示される１、８−ビス（２−
メルカプトエチル）ナフタレン誘導体は、前記構造式（
Ａ）で示される１、８−ビス（２−メルカプトエチル）
ナフタレンにエステル化剤を作用させることにより製造
される。XH, CCH □
The mercaptoethyl) naphthalene derivative has the above structural formula (
1,8-bis(2-mercaptoethyl) represented by A)
Manufactured by reacting naphthalene with an esterifying agent.
本発明の１．８−ビス（２−メルカプトエチル）ナフタ
レン（Ａ）の製造方法によれば、まず原料の１．８−ビ
ス（２−ハロゲノエチル）ナフタレン（ＩＩ）をアルコ
ール中でチオ尿素と加熱処理して、１，８−ビス（２−
ハロゲノエチル）ナフタレンのビスイソチウロニウム塩
をつくり１次に、この塩を窒素雰囲気下でアルカリ水溶
液と加熱還流する。この時、水酸化アルカリは約２０倍
量と大過剰に用い、また反応時間は３０分ないし２時間
で充分である６反応後、生じた白濁溶液を有機溶媒で処
理して中性の副生物を除いた後、水溶液中の１，８−ビ
ス（２−メルカプトエチル）ナフタレン−ジアルカリ金
属塩を酸で処理すれば、下記反応式に示すように、［料
分子（ＩＩ）中のハロゲン原子（−Ｘ）が、メルカプト
基（−ＳＨ）に変換された１゜８−ビス（２−メルカプ
トエチル）ナフタレン（Ａ）を得ることができる。According to the method for producing 1,8-bis(2-mercaptoethyl)naphthalene (A) of the present invention, first, the raw material 1,8-bis(2-halogenoethyl)naphthalene (II) is mixed with thiourea in alcohol. After heat treatment, 1,8-bis(2-
First, a bisisothiuronium salt of (halogenoethyl)naphthalene is prepared and then this salt is heated to reflux with an aqueous alkali solution under a nitrogen atmosphere. At this time, the alkali hydroxide is used in a large excess of about 20 times the amount, and the reaction time is sufficient for 30 minutes to 2 hours. 6 After the reaction, the resulting cloudy solution is treated with an organic solvent to remove neutral by-products. If the 1,8-bis(2-mercaptoethyl)naphthalene-dialkali metal salt in the aqueous solution is treated with an acid after removing the halogen atom ( 1°8-bis(2-mercaptoethyl)naphthalene (A) in which -X) is converted to a mercapto group (-SH) can be obtained.
（ｎ）
Ｈ５Ｈ，Ｃ
■
Ｍ；アルカリ金属
Ｈ２ＳＨ
（式中、Ｘはハロゲン原子である。）
なお、１，８−ビス（２−メルカプトエチル）ナフタレ
ン（Ａ）製造の原料となる１、８−ビス（２−ハロゲノ
エチル）ナフタレン（ＩＩ）は、下記反応式に示すよう
に、従来既知化合物の１．８−ジビニルナフタレン（Ｂ
）をハイドロボレーション反応により、１，８−ビス（
２−ヒドロキシエチル）ナフタレン（Ｃ）に変えた後、
ハロゲン化剤で処理することによって製造される。(n) H5H, C M; Alkali metal H2SH (In the formula, Bis(2-halogenoethyl)naphthalene (II) is a conventionally known compound, 1,8-divinylnaphthalene (B), as shown in the reaction formula below.
) to 1,8-bis(
After changing to 2-hydroxyethyl)naphthalene (C),
Manufactured by treatment with a halogenating agent.
（Ｂ）
（Ｃ）
（式中、又はハロゲン原子である。）
次に、得られた１、８−ビス（２−メルカプトエチル）
ナフタレン（Ａ）にアシル化剤などのエステル化剤を作
用させてエステル化反応を行うと、１゜８−ビス（２−
メルカプトエチル）ナフタレンのジエステル誘導体（１
）である１、８−ビス［２−（アシルチオ）エチル］ナ
フタレンが得られる。アシル化剤としては、無水酢酸、
無水安息香酸などのカルボン酸無水物や、塩化アセチル
、塩化ベンゾイルなどのハロゲン化アシルなどが用いら
れる。(B) (C) (in the formula or a halogen atom) Next, the obtained 1,8-bis(2-mercaptoethyl)
When naphthalene (A) is reacted with an esterifying agent such as an acylating agent to perform an esterification reaction, 1°8-bis(2-
mercaptoethyl) naphthalene diester derivative (1
) 1,8-bis[2-(acylthio)ethyl]naphthalene is obtained. As the acylating agent, acetic anhydride,
Carboxylic acid anhydrides such as benzoic anhydride and acyl halides such as acetyl chloride and benzoyl chloride are used.
反応は、ピリジンなどの溶媒中で行なわれ、その反応温
度はアシル化剤の種類により変化するが。The reaction is carried out in a solvent such as pyridine, and the reaction temperature varies depending on the type of acylating agent.
一般には、アシル化剤添加直後が室温ないし５０℃。Generally, the temperature is room temperature to 50°C immediately after adding the acylating agent.
その後の放置温度が０℃〜室温の範囲である。このよう
にして反応を行なうと、反応の進行とともに１反応液は
始めの無色から薄茶色の溶液に変化する０反応終了後に
、この溶液を水で処理すると。The subsequent standing temperature is in the range of 0°C to room temperature. When the reaction is carried out in this manner, as the reaction progresses, the reaction solution changes from an initial colorless color to a light brown solution.After the reaction is completed, this solution is treated with water.
下記反応式に示すように、１，８−ビス（２−メルカプ
トエチル）ナフタレン（Ａ）のメルカプト基（−８Ｈ）
がアシルチオ基（−ＳＲ，Ｒはカルボン酸残基）で置換
された１、８−ビス（２−メルカプトエチル）ナフタレ
ン−ジエステル誘導体（Ｉ）が得られる。As shown in the reaction formula below, the mercapto group (-8H) of 1,8-bis(2-mercaptoethyl)naphthalene (A)
is substituted with an acylthio group (-SR, R is a carboxylic acid residue) to obtain a 1,8-bis(2-mercaptoethyl)naphthalene-diester derivative (I).
（Ａ） （１）（式中、Ｒは
アシル基である。）
本発明で得られた１、８−ビス（２−メルカプトエチル
）ナフタレン（Ａ）およびそのジエステル誘導体である
１、８−ビス［２−（アシルチオ）エチル］ナフタレン
（１）は、いずれも新規化合物である。(A) (1) (In the formula, R is an acyl group.) 1,8-bis(2-mercaptoethyl)naphthalene (A) obtained in the present invention and its diester derivative 1,8-bis [2-(acylthio)ethyl]naphthalene (1) is a new compound.
［発明の効果コ
本発明によれば、新規化合物として、１，８−ビス（２
−メルカプトエチル）ナフタレンおよびそのジエステル
誘導体の１．８− ［２−（アシルチオ）エチル］ナフ
タレンが得られる。[Effects of the Invention] According to the present invention, 1,8-bis(2
-mercaptoethyl)naphthalene and its diester derivative 1,8-[2-(acylthio)ethyl]naphthalene are obtained.
係る化合物は、ポリスルフィドやポリチオエスチル用モ
ノマーとして重要であり、また、界面活性剤や重金属捕
集剤の製造原料としても有用である。Such compounds are important as monomers for polysulfides and polythioethyls, and are also useful as raw materials for producing surfactants and heavy metal scavengers.
かつ、かかる化合物は、従来既知物質の１，８−ジビニ
ルナフタレンから容易に製造することができる。Moreover, such a compound can be easily produced from 1,8-divinylnaphthalene, which is a known substance.
［実施例］ 次に本発明を実施例により、さらに詳細に説明する。[Example] Next, the present invention will be explained in more detail with reference to Examples.
参考例１
１．８−ビス（２−ヒドロキシエチル）ナフタレン（Ｃ
）の製造。Reference example 1 1.8-bis(2-hydroxyethyl)naphthalene (C
)Manufacturing of.
水素化ホウ素ナトリウム２．８８５ ｇと２−メチル−
２−ブテン２１．４ｍ ｆｔを含むテトラヒドロフラン
１６０ｍ２の懸濁液に、氷水浴で冷却下、三沸化ホウ素
エーテル錯体１２．８ｍ ｆｌを１分間で滴下した。2.885 g of sodium borohydride and 2-methyl-
To a suspension in 160 m2 of tetrahydrofuran containing 21.4 m ft of 2-butene, 12.8 m fl of boron triboride ether complex was added dropwise over 1 minute while cooling in an ice-water bath.
添加後、氷水浴を除いて反応液を室温で１．５時間攪拌
した後、再度氷水浴で冷却しながら、１，８−ジビニル
ナフタレン（Ｂ）の結晶５，６６２ ｇを少しずつ添加
した。この混合液を水冷下で２時間。After the addition, the ice-water bath was removed and the reaction solution was stirred at room temperature for 1.5 hours, and then 5,662 g of crystals of 1,8-divinylnaphthalene (B) were added little by little while cooling again in the ice-water bath. This mixture was cooled with water for 2 hours.
次いで室温に温めてｌ晩攪拌した。生じた白濁溶液に、
水冷下で攪拌しながら２０％水酸化ナトリウム水溶液１
２０ｍｕを加えた後、３部過酸化水素水１２０ｍ１をｉ
５分かけて滴下した。添加後、混合液を室温で３５分間
、次いで３５℃の水浴で温めながら１時間攪拌してから
室温に戻し、飽和食塩水を加えて塩化メチレンで抽出し
た。有機層を無水ａｍナトリウムで乾燥して減圧下溶媒
を除去すると、淡黄色の油状物質が得られた。この粗生
成物を、真空乾燥して結晶化させた後、ベンゼンから再
結晶して精製すると、ｌ、８−ビス（２−ヒドロキシエ
チル）ナフタレン（Ｃ）が無色羽毛状結晶として得られ
た（５．３５６ ｇ、収率７９％）。It was then warmed to room temperature and stirred overnight. In the resulting cloudy solution,
20% sodium hydroxide aqueous solution 1 while stirring under water cooling.
After adding 20 mu, add 120 ml of 3 parts hydrogen peroxide solution.
It was added dropwise over 5 minutes. After the addition, the mixture was stirred at room temperature for 35 minutes, then heated in a 35°C water bath for 1 hour, then returned to room temperature, saturated brine was added, and extracted with methylene chloride. The organic layer was dried over anhydrous am sodium and the solvent was removed under reduced pressure to yield a pale yellow oil. This crude product was crystallized by vacuum drying and then purified by recrystallization from benzene to obtain l,8-bis(2-hydroxyethyl)naphthalene (C) as colorless feather-like crystals ( 5.356 g, yield 79%).
園、ｐ、１１２−１１２．５℃。Sono, p, 112-112.5℃.
元素分析：
測定値 Ｃ； ７７．６３． Ｈ； ７．２０計算値
Ｃ；、７７．７５． Ｈ； ７．４６ （Ｃ１４Ｈ，
、Ｏ，）質量分析（ｍ／ ｅ） ： ２１６（Ｍ”
）ＩＲ（Ｎｕｊ ｏ １） ： ｖ ＝３２６０
０１″″″（０−Ｈ）Ｈ−ＮＭＲ（ｃｏｃｕ、）：
δ
＝２．８６ （ｓ、２Ｈ，０Ｈ）
３．４７ （ｔ、Ｊ＝７．７Ｈｚ、４Ｈ，ＡｒＣＨ，−
）３．９０ （ｔ、Ｊ＝７．７Ｈｚ、４Ｈ，−ＣＨ，０
−）７．２６〜７．８１ （ｍ、６Ｈ，ＡｒＨ）参考
例２
１．８−ビス（２−ハロゲノエチル）ナフタレン（ＩＩ
）の製造。Elemental analysis: Measured value C; 77.63. H; 7.20 calculated value
C;, 77.75. H; 7.46 (C14H,
, O,) Mass spectrometry (m/e): 216 (M”
)IR(Nuj o 1) : v =3260
01″″″(0-H)H-NMR (cocu,): δ = 2.86 (s, 2H, 0H) 3.47 (t, J = 7.7Hz, 4H, ArCH, -
)3.90 (t, J=7.7Hz, 4H, -CH,0
-) 7.26 to 7.81 (m, 6H, ArH) Reference Example 2 1.8-bis(2-halogenoethyl)naphthalene (II
)Manufacturing of.
１．８−ビス（２−ヒドロキシエチル）ナフタレン（Ｃ
） １．１０ｇ、 ４８％臭化水素酸水溶液２３５ｍＱ
および濃硫酸数滴を含む混合液を加熱・攪拌した０反応
開始１０分で、原料のジオールの結晶は溶けて透明な溶
液となり、更に２０分後には白濁溶液に変化した１反応
部合物を、激しく沸騰しない程度に加熱して、更に２時
間反応させた後、室温に冷却して塩化メチレンで抽出し
た。有機層を炭酸水素ナトリウム飽和水溶液で洗い、乾
燥して減圧下溶媒を除去すると、薄茶色の油状物質が得
られた。1.8-bis(2-hydroxyethyl)naphthalene (C
) 1.10g, 48% hydrobromic acid aqueous solution 235mQ
A mixed solution containing several drops of concentrated sulfuric acid was heated and stirred. 10 minutes after the start of the reaction, the raw material diol crystals melted and became a transparent solution, and after another 20 minutes, the reaction mixture turned into a cloudy solution. The mixture was heated to such an extent that it did not boil violently and allowed to react for an additional 2 hours, then cooled to room temperature and extracted with methylene chloride. The organic layer was washed with saturated aqueous sodium bicarbonate solution, dried, and the solvent was removed under reduced pressure to obtain a light brown oil.
この粗生成物をヘキサンに溶かし、少量のシルカゲルカ
ラムを用いて極性不純物を除くと、薄黄色結晶が得られ
た。このようにして得られたものを。This crude product was dissolved in hexane and polar impurities were removed using a small amount of silica gel column to obtain pale yellow crystals. What was obtained in this way.
更に究に冷却したヘキサンから再結晶してＩＮすると、
無色結晶の１．８−ビス（２−ブロモエチル）ナフタレ
ン（ＩＩ）が得られた（１．３９６ ｇ、収率８０％）
。Furthermore, when recrystallized from extremely cooled hexane and IN,
Colorless crystals of 1,8-bis(2-bromoethyl)naphthalene (II) were obtained (1.396 g, yield 80%).
.
■、ｐ、６４−６５℃。■, p, 64-65°C.
元素分析：
測定値 Ｃ； ４８．８７． Ｈ； ４．３０計算値
Ｃ； ４９．１５． Ｈ； ４．１３ （Ｃ１４Ｈ１
，Ｂｒ、）質量分析（ｍ／ ｅ ） ： ３４２（Ｍ
” 、Ｃ，，１１１，Ｂｒ、”Ｂｒ１８１）Ｉ Ｒ（Ｎ
ｕ ｊ ｏ ｌ） ： ｔ ＝５９３ａａ−”（
Ｃ−Ｂｒ）’Ｈ−ＮＭＲ（ＣＤ（１，）：
δ＝３．５８ （＋、８Ｈ，＾ｒＣ）！、Ｃ）Ｉ、Ｂｒ
）７．３６〜７．９７ （ｍ、６Ｈ，Ａｒ４＋）実施例
１
１．８−ビス（２−ブロモエチル）ナフタレン（■）２
００ｍ、ｇ、チオ臭素９１ｍｇおよび９５％エタノール
５ｍＱを含む混合液を、攪拌しながら加熱・還流した０
反応開始１５分で原料の臭化物の結晶は完全に溶け５透
明な溶液に変化した。この溶液を、更に１晩加熱・還流
した後溶媒を減圧下除去すると、白色半固体状の１，８
−ビス（２−ブロモエチル）ナフタレンのビスイソチウ
ロニウム塩が得られた。Elemental analysis: Measured value C; 48.87. H; 4.30 calculated value
C; 49.15. H; 4.13 (C14H1
, Br,) Mass spectrometry (m/e): 342 (M
” ,C,,111,Br,”Br181)I R(N
u j o l): t = 593aa-”(
C-Br)'H-NMR (CD(1,): δ=3.58 (+, 8H, ^rC)!, C) I, Br
)7.36-7.97 (m, 6H, Ar4+) Example 1 1.8-bis(2-bromoethyl)naphthalene (■) 2
A mixed solution containing 91 mg of thiobromine and 5 mQ of 95% ethanol was heated and refluxed with stirring.
Fifteen minutes after the start of the reaction, the raw material bromide crystals were completely dissolved and turned into a transparent solution. After heating and refluxing this solution overnight, the solvent was removed under reduced pressure, resulting in a white semi-solid 1,8
A bisisothiuronium salt of -bis(2-bromoethyl)naphthalene was obtained.
この塩に、水酸化カリウム１．２３ｇを水５ｍＱに溶か
した溶液を加え、混合液を窒素雰囲気下で１時間加熱・
還流した０反応終了後、反応液を室温に下げてからベン
ゼンで抽出し、水層部分を、０℃に冷却して激しく攪拌
した２、５Ｎ−塩酸水溶液中に滴下した。生じた白濁溶
液を塩化メチレンで抽出し、抽出液を水洗して乾燥後減
圧下溶媒を除去すると、無色ペースト状の１．８−ビス
（２−メルカプトエチル）ナフタレン（Ａ）が得られた
（６４ｍ ｇ、収率４５％）。A solution of 1.23 g of potassium hydroxide dissolved in 5 mQ of water was added to this salt, and the mixture was heated for 1 hour under a nitrogen atmosphere.
After completion of the refluxing reaction, the reaction solution was cooled to room temperature and extracted with benzene, and the aqueous layer was added dropwise to a 2,5N aqueous hydrochloric acid solution that had been cooled to 0°C and stirred vigorously. The resulting cloudy solution was extracted with methylene chloride, the extract was washed with water, dried, and the solvent was removed under reduced pressure to obtain 1,8-bis(2-mercaptoethyl)naphthalene (A) in the form of a colorless paste ( 64 mg, yield 45%).
元素分析：
測定値 Ｃ； ６７．４９． Ｈ； ６，７０計算値
Ｃ； ６７．７３． Ｈ； ６．５０ （Ｃ，４Ｈ１
，Ｓ２）質量分析（ｍ ／ ｅ ） ： ２４８（Ｍ
” ）Ｉ Ｒ（Ｎ ｅ ａ ｔ ） ： ｖ ＝
２５７０ａｎ−”（Ｓ−Ｈ）１Ｈ−ＮＭＲ（ＣＤ（１，
）：
δ＝１．４７ （ｔ、Ｊ：７．５Ｈｚ、２８，５Ｈ）２
．７５（ｑ、Ｊ＝８．０，７．５）１ｚ、４Ｈ，−ＣＨ
，５−）３．３６（ｔ、、Ｃ８，ＯＨｚ、４Ｈ，ＡｒＣ
Ｈ，）７．２３〜７．８２ （＋、６Ｈ，ＡｒＨ）実施
例２
１．８−ビス（２−メルカプトエチル）ナフタレン（Ａ
）５０ｍｇ、無水酢９１ｍＱおよびピリジン１ｍ党の混
合液を、室温に５日間放置して反応させた。Elemental analysis: Measured value C; 67.49. H; 6,70 calculated value
C; 67.73. H; 6.50 (C, 4H1
, S2) Mass spectrometry (m/e): 248 (M
”) I R(N e at ) : v =
2570an-”(S-H)1H-NMR(CD(1,
): δ=1.47 (t, J: 7.5Hz, 28,5H)2
．． 75 (q, J = 8.0, 7.5) 1z, 4H, -CH
,5-)3.36(t,,C8,OHz,4H,ArC
H,) 7.23-7.82 (+, 6H, ArH) Example 2 1.8-bis(2-mercaptoethyl)naphthalene (A
), 91 mQ of anhydrous vinegar, and 1 mQ of pyridine were left to react at room temperature for 5 days.
反応終了後生じた黄茶色溶液に水と塩化メチレンを加え
て分液した。有機層を希塩酸、次いで炭酸水素ナトリウ
ム水溶液で洗い、乾燥した後溶媒を減圧下除去すると、
淡黄色の油状物質が得られた。After the reaction was completed, water and methylene chloride were added to the resulting yellow-brown solution to separate the solution. The organic layer was washed with dilute hydrochloric acid and then with an aqueous sodium bicarbonate solution, dried, and the solvent was removed under reduced pressure.
A pale yellow oil was obtained.
このようにして得たものを分取薄層クロマトグラフィー
（シリカゲル−ベンゼン）を用いて精製すると、純粋な
１，８−ビス［２−（アセチルチオ）エチル］ナフタレ
ン（１）が得られた（４３ｍｇ、収率
６４％）。The product thus obtained was purified using preparative thin layer chromatography (silica gel-benzene) to obtain pure 1,8-bis[2-(acetylthio)ethyl]naphthalene (1) (43 mg , yield 64%).
（Ｉ）は、精製直後は無色油状物質であるが、冷蔵庫内
に放置すると結晶化した。 ｍ、ｐ、５９ ６０℃。Immediately after purification, (I) was a colorless oily substance, but it crystallized when left in the refrigerator. m, p, 59 60°C.
元素分析：
測定値 Ｃ； ６５．３０． Ｈ；、６．２９計算値
Ｃ； ６５．０５． Ｈ； ６．０７ （Ｃ工ｓ ８２
ｏ ０２ Ｓ２ ）質量分析（ｍ／ ｅ ） ：
３３２（Ｍ” ）ＩＲ（Ｎｅａｔ） ：
ｖ ＝ １６９０−１１３０ ａｍ −１（ＳＣＯＣＨ
３）’Ｈ−ＮＭＲ（ＣＤＣ党、）：Elemental analysis: Measured value C; 65.30. H;, 6.29 calculated value
C; 65.05. H; 6.07 (C engineering s 82
o 02 S2) Mass spectrometry (m/e):
332 (M") IR (Neat): v = 1690-1130 am -1 (SCOCH
3)'H-NMR (CDC Party, ):
Claims (4)
カプトエチル）ナフタレン。 ▲数式、化学式、表等があります▼（Ａ）(1) 1,8-bis(2-mercaptoethyl)naphthalene represented by structural formula (A). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(A)
ルカプトエチル）ナフタレン誘導体。 ▲数式、化学式、表等があります▼（ I ） （式中、Ｒはアシル基である、）(2) 1,8-bis(2-mercaptoethyl)naphthalene derivative represented by general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R is an acyl group.)
ゲノエチル）ナフタレンをチオ尿素で処 理することを特徴とする構造式（Ａ）で示 される１，８−ビス（２−メルカプトエチル）ナフタレ
ンの製造方法。 ▲数式、化学式、表等があります▼（II） ▲数式、化学式、表等があります▼（Ａ） （式中、Ｘはハロゲン原子である。）(3) The 1,8-bis(2-halogenoethyl)naphthalene represented by the general formula (II) is treated with thiourea. Method for producing (mercaptoethyl) naphthalene. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(A) (In the formula, X is a halogen atom.)
カプトエチル）ナフタレンをアシル化剤 で処理することを特徴とする、一般式（ I ）で示され
る１，８−ビス（２−メルカプトエチル）ナフタレン誘
導体の製造方法。 ▲数式、化学式、表等があります▼（Ａ） ▲数式、化学式、表等があります▼（ I ） （式中、Ｒはアシル基である。）(4) 1,8-bis(2-mercaptoethyl)naphthalene represented by structural formula (A) is treated with an acylating agent; A method for producing a 2-mercaptoethyl) naphthalene derivative. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(A) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R is an acyl group.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17533989A JPH0341064A (en) | 1989-07-06 | 1989-07-06 | 1,8-bis(2-mercaptoethyl)naphthalene, its derivative and production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17533989A JPH0341064A (en) | 1989-07-06 | 1989-07-06 | 1,8-bis(2-mercaptoethyl)naphthalene, its derivative and production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0341064A true JPH0341064A (en) | 1991-02-21 |
| JPH0463064B2 JPH0463064B2 (en) | 1992-10-08 |
Family
ID=15994335
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17533989A Granted JPH0341064A (en) | 1989-07-06 | 1989-07-06 | 1,8-bis(2-mercaptoethyl)naphthalene, its derivative and production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0341064A (en) |
-
1989
- 1989-07-06 JP JP17533989A patent/JPH0341064A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0463064B2 (en) | 1992-10-08 |
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