JPH0571593B2 - - Google Patents
Info
- Publication number
- JPH0571593B2 JPH0571593B2 JP30157488A JP30157488A JPH0571593B2 JP H0571593 B2 JPH0571593 B2 JP H0571593B2 JP 30157488 A JP30157488 A JP 30157488A JP 30157488 A JP30157488 A JP 30157488A JP H0571593 B2 JPH0571593 B2 JP H0571593B2
- Authority
- JP
- Japan
- Prior art keywords
- naphthalene
- formula
- cycloocta
- tetrahydro
- dithia
- 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 - Lifetime
Links
- -1 8,10-dithia-8,9,10,11-tetrahydro-7H-cycloocta[de]naphthalene compound Chemical class 0.000 claims description 13
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 18
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 8
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 8
- 229910015900 BF3 Inorganic materials 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- JKNPWHHGFOPCTJ-UHFFFAOYSA-N [8-(sulfanylmethyl)naphthalen-1-yl]methanethiol Chemical compound C1=CC(CS)=C2C(CS)=CC=CC2=C1 JKNPWHHGFOPCTJ-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 150000001728 carbonyl compounds Chemical class 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
〔産業上の利用分野〕
本発明は、新規化合物の８，10−ジチア−８，
９，10，11−テトラヒドロ−7H−シクロオクタ
［de］ナフタレン化合物に関する。
〔従来の技術〕
従来、ナフタレンのペリ位（１，８位）に炭素
数５個のメチレン鎖が環化した、下記構造式のナ
フタレンのペリ環式系化合物８，９，10，11−テ
トラヒドロ−7H−シクロオクタ［de］ナフタレ
ンは、すでに知られている〔T.Kamada，Bull.
Chem.Soc.Jpn.，Vol.52，170（1979）〕。
[Industrial Application Field] The present invention provides a novel compound of 8,10-dithia-8,
This invention relates to a 9,10,11-tetrahydro-7H-cycloocta[de]naphthalene compound. [Prior Art] Conventionally, a pericyclic compound of naphthalene having the following structural formula, 8,9,10,11-tetrahydro, in which a methylene chain having 5 carbon atoms is cyclized at the peri-position (1,8-position) of naphthalene. -7H-cycloocta[de]naphthalene is already known [T. Kamada, Bull.
Chem.Soc.Jpn., Vol.52, 170 (1979)].
本発明は上記従来知られていなかつたペリ炭素
環の炭素原子が部分的に硫黄原子で置換された
８，10−ジチア−８，９，10，11−テトラヒドロ
−7H−シクロオクタ［de］ナフタレン化合物を
提供するものである。
〔課題を解決するための手段〕
本発明に係る新規化合物の８，10−ジチア−
８，９，10，11−テトラヒドロ−7H−シクロオ
クタ［de］ナフタレン化合物は、下記一般式
（）で示される。
The present invention is directed to the above-mentioned previously unknown 8,10-dithia-8,9,10,11-tetrahydro-7H-cycloocta[de]naphthalene compound in which the carbon atoms of the pericarbocyclic ring are partially substituted with sulfur atoms. It provides: [Means for solving the problem] 8,10-dithia-, a novel compound according to the present invention
The 8,9,10,11-tetrahydro-7H-cycloocta[de]naphthalene compound is represented by the following general formula ().
【化】
ただし、（）式中、９位置換基R1はメチル基
であり、R2はエチル基またはフエニル基である。
すなわち本発明に係る新規化合物には下記構造
式の化合物が含まれる。
(イ) ９−エチル−９−メチル−８，10−ジチア−
８，９，10，11−テトラヒドロ−7H−シクロ
オクタ［de］ナフタレンembedded image In formula (), the 9-position substituent R 1 is a methyl group, and R 2 is an ethyl group or a phenyl group. That is, the novel compounds according to the present invention include compounds having the following structural formula. (a) 9-ethyl-9-methyl-8,10-dithia-
8,9,10,11-tetrahydro-7H-cycloocta[de]naphthalene
【式】
(ロ) ９−メチル−９−フエニル−８，10−ジチア
−８，９，10，11−テトラヒドロ−7H−シク
ロオクタ［de］ナフタレン[Formula] (b) 9-methyl-9-phenyl-8,10-dithia-8,9,10,11-tetrahydro-7H-cycloocta[de]naphthalene
【式】
そしてかかる本発明の新規ナフタレン化合物
（）は、下記構造式(A)で示される１，８−ビス
（メルカプトメチル）ナフタレン（鎌田利紘、日
本国特許第951352号（昭54）；CA.1977，86，
43448V）に下記一般式（）で示されるカルボ
ニル化合物と三弗化ホウ素エーテル錯体を作用さ
せることにより製造される。[Formula] And the novel naphthalene compound () of the present invention is 1,8-bis(mercaptomethyl)naphthalene (Toshihiro Kamata, Japanese Patent No. 951352 (1972); CA.1977, 86 ,
43448V) with a carbonyl compound represented by the following general formula () and a boron trifluoride ether complex.
【式】【formula】
【式】
ただし（）式中、R1はメチル基、R2はエチ
ル基またはフエニル基である。
まず、原料の１，８−ビス（メルカプトメチ
ル）ナフタレン(A)とカルボニル化合物（）を、
クロロホルムなどのハロゲン化炭化水素またはテ
トラヒドロフランなどのエーテル類の有機溶媒に
溶かし、次に、この溶液を三弗化ホウ素エーテル
錯体で処理する。すると、三弗化ホウ素エーテル
錯体の作用により、下記反応式に示すように、
１，８−ビス（メルカプトメチル）ナフタレン(A)
の２個のチオール基（−SH）とカルボニル化合
物（）のカルボニル基（Ｃ＝Ｏ）との間でジ
チオケタール化・環化反応が起り、硫黄原子２個
を環内に含むペリ−８−環式系の８，10−ジチア
−８，９，10，11−テトラヒドロ−7H−シクロ
オクタ［de］ナフタレン化合物（）が生成す
る。[Formula] However, in the formula (), R 1 is a methyl group, and R 2 is an ethyl group or a phenyl group. First, the raw materials 1,8-bis(mercaptomethyl)naphthalene (A) and the carbonyl compound () are
It is dissolved in an organic solvent such as a halogenated hydrocarbon such as chloroform or an ether such as tetrahydrofuran, and then this solution is treated with a boron trifluoride ether complex. Then, due to the action of the boron trifluoride ether complex, as shown in the reaction formula below,
1,8-bis(mercaptomethyl)naphthalene (A)
A dithioketalization/cyclization reaction occurs between the two thiol groups (-SH) of the carbonyl compound () and the carbonyl group (C=O) of the carbonyl compound (), resulting in a peri-8-ring containing two sulfur atoms in the ring. An 8,10-dithia-8,9,10,11-tetrahydro-7H-cycloocta[de]naphthalene compound () of the formula system is produced.
【式】【formula】
実施例 １
クロロホルム10mlに１，８−ビス（メルカプト
メチル）ナフタレン110mgと２−ブタノン40mgを
溶かした溶液に、０℃で、三弗化ホウ素エーテル
錯体140mgを添加した。０℃で２時間、次いで室
温で20時間攪拌後、反応液にエーテルと水を加え
て分液した。有機層を、10％水酸化ナトリウムで
２回、続いて水で２回洗つた後乾燥して減圧下溶
媒を除去した。残留物をエタノールから再結晶す
ると、無色結晶の９−エチル−９−メチル−８，
10−ジチア−８，９，10，11−テトラヒドロ−
7H−シクロオクタ［de］ナフタレン（ａ）が
得られた（111mg、収率81％）。
m.p.152−155℃
元素分析：測定値Ｃ；69.85，Ｈ；6.85
計算値Ｃ；70.02，Ｈ；6.61（C16H18S2）
質量分析：274（計算値274）1
H−NMR（CDCl3）：δ＝1.10（ｔ，Ｊ＝7.0Hz，
3H，Ethy1−CH3）
1.65（ｓ，3H，CH3）
2.10（ｑ，Ｊ＝7.0Hz，2H，Ethy1−CH2）
4.43（ｓ，4H，ArCH2）
7.29−7.95（ｍ，6H，ArH）
実施例 ２
１，８−ビス（メルカプトメチル）ナフタレン
110mg、アセトフエノン60mg、およびクロロホル
ム10mlの攪拌溶液に、０℃で、三弗化ホウ素エー
テル錯体140mgを添加した。０℃で２時間、次い
で室温で15時間反応させた後、反応液にエーテル
と水を加えて分液した。有機層を、10％水酸化ナ
トリウムで２回、続いて水で２回洗つた後、乾燥
して減圧下溶媒を除去した。残留物の白色固体を
エタノールから再結晶すると、無色微結晶の９−
メチル−９−フエニル−８，10−ジチア−８，
９，10，11−テトラヒドロ−7H−シクロオクタ
［de］ナフタレン（ｂ）が得られた（95mg、収
率60％）。
m.p.182.5−184.5℃
元素分析：測定値Ｃ；74.59，Ｈ；5.40
計算値Ｃ；74.49，Ｈ；5.63（C20H18S2）
質量分析：322（計算値322）1
H−NMR（CDCl3）：δ＝1.81（ｓ，3H，CH3）
4.23（ｓ，4H，CH2）
7.28−8.22（ｍ，11H，ArH）
〔発明の効果〕
以上述べたように本発明によれば、８，10−ジ
チア−８，９，10，11−テトラヒドロ−7H−シ
クロオクタ［de］ナフタレン化合物として、ペ
リリングの９，９−ジ置換８，10−ジチア−８，
９，10，11−テトラヒドロ−7H−シクロオクタ
［de］ナフタレン（ａ，ｂ）が得られる。
かかる化合物は、文献未載の新しい系列の化合
物であり、新しい骨格の化合物の製造原料として
使用されるほか、ポリスルフイドやポリチオエス
テルのモノマー用原料として、さらに、界面活性
剤や重金属捕集剤の原料としても使用され、産業
上有用である。
Example 1 140 mg of boron trifluoride ether complex was added to a solution of 110 mg of 1,8-bis(mercaptomethyl)naphthalene and 40 mg of 2-butanone dissolved in 10 ml of chloroform at 0°C. After stirring at 0°C for 2 hours and then at room temperature for 20 hours, ether and water were added to the reaction mixture to separate the mixture. The organic layer was washed twice with 10% sodium hydroxide and then twice with water, dried, and the solvent was removed under reduced pressure. Recrystallization of the residue from ethanol yields colorless crystals of 9-ethyl-9-methyl-8,
10-dithia-8,9,10,11-tetrahydro-
7H-cycloocta[de]naphthalene (a) was obtained (111 mg, yield 81%). mp152-155℃ Elemental analysis: Measured value C; 69.85, H; 6.85 Calculated value C; 70.02, H; 6.61 (C 16 H 18 S 2 ) Mass spectrometry: 274 (calculated value 274) 1 H-NMR (CDCl 3 ) : δ=1.10(t, J=7.0Hz,
3H, Ethy1−CH 3 ) 1.65 (s, 3H, CH 3 ) 2.10 (q, J=7.0Hz, 2H, Ethy1−CH 2 ) 4.43 (s, 4H, ArCH 2 ) 7.29−7.95 (m, 6H, ArH ) Example 2 1,8-bis(mercaptomethyl)naphthalene
To a stirred solution of 110 mg of boron trifluoride ether complex, 60 mg of acetophenone, and 10 ml of chloroform at 0°C was added 140 mg of boron trifluoride ether complex. After reacting at 0° C. for 2 hours and then at room temperature for 15 hours, ether and water were added to the reaction solution to separate the layers. The organic layer was washed twice with 10% sodium hydroxide and then twice with water, then dried and the solvent was removed under reduced pressure. The white solid residue was recrystallized from ethanol to give colorless microcrystals of 9-
Methyl-9-phenyl-8,10-dithia-8,
9,10,11-tetrahydro-7H-cycloocta[de]naphthalene (b) was obtained (95 mg, yield 60%). mp182.5−184.5℃ Elemental analysis: Measured value C; 74.59, H; 5.40 Calculated value C; 74.49, H; 5.63 (C 20 H 18 S 2 ) Mass spectrometry: 322 (calculated value 322) 1 H-NMR (CDCl 3 ): δ=1.81 (s, 3H, CH 3 ) 4.23 (s, 4H, CH 2 ) 7.28−8.22 (m, 11H, ArH) [Effects of the Invention] As described above, according to the present invention, 8 , 10-dithia-8,9,10,11-tetrahydro-7H-cycloocta[de]naphthalene compound, 9,9-disubstituted 8,10-dithia-8,
9,10,11-tetrahydro-7H-cycloocta[de]naphthalene (a,b) is obtained. These compounds are a new series of compounds that have not yet been described in literature, and are used as raw materials for producing compounds with new skeletons, as raw materials for polysulfide and polythioester monomers, and as raw materials for surfactants and heavy metal scavengers. It is also used as an industrially useful material.
Claims (1)
−８，９，10，11−テトラヒドロ−7H−シクロ
オクタ［de］ナフタレン化合物。 【式】 ただし、（）式中、R1はメチル基、R2はエチ
ル基またはフエニル基である。[Scope of Claims] 1. 8,10-dithia-8,9,10,11-tetrahydro-7H-cycloocta[de]naphthalene compound represented by the following general formula (). [Formula] However, in the formula (), R 1 is a methyl group, and R 2 is an ethyl group or a phenyl group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30157488A JPH02145582A (en) | 1988-11-29 | 1988-11-29 | 8,10-dithia-8,9,10,11-tetrahydro-7h-cycloocta(de)naphthalene compound and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30157488A JPH02145582A (en) | 1988-11-29 | 1988-11-29 | 8,10-dithia-8,9,10,11-tetrahydro-7h-cycloocta(de)naphthalene compound and production thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02145582A JPH02145582A (en) | 1990-06-05 |
| JPH0571593B2 true JPH0571593B2 (en) | 1993-10-07 |
Family
ID=17898583
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30157488A Granted JPH02145582A (en) | 1988-11-29 | 1988-11-29 | 8,10-dithia-8,9,10,11-tetrahydro-7h-cycloocta(de)naphthalene compound and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02145582A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0538474B1 (en) * | 1991-03-11 | 1997-07-23 | CHLORINE ENGINEERS CORP., Ltd. | Electrolytic vessel for producing hypochlorite |
-
1988
- 1988-11-29 JP JP30157488A patent/JPH02145582A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0538474B1 (en) * | 1991-03-11 | 1997-07-23 | CHLORINE ENGINEERS CORP., Ltd. | Electrolytic vessel for producing hypochlorite |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02145582A (en) | 1990-06-05 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |