JPH0161109B2 - - Google Patents
Info
- Publication number
- JPH0161109B2 JPH0161109B2 JP9209780A JP9209780A JPH0161109B2 JP H0161109 B2 JPH0161109 B2 JP H0161109B2 JP 9209780 A JP9209780 A JP 9209780A JP 9209780 A JP9209780 A JP 9209780A JP H0161109 B2 JPH0161109 B2 JP H0161109B2
- Authority
- JP
- Japan
- Prior art keywords
- azabicyclo
- nonane
- thia
- oxide
- compound
- 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
Links
- 125000003545 alkoxy group Chemical group 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical class CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 description 32
- 238000006243 chemical reaction Methods 0.000 description 18
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 150000007514 bases Chemical class 0.000 description 9
- 239000013078 crystal Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000012312 sodium hydride Substances 0.000 description 4
- 229910000104 sodium hydride Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- -1 methoxy, ethoxy, propoxy, isopropoxy, butoxy, tert-butoxy groups Chemical group 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 230000000202 analgesic effect Effects 0.000 description 2
- 230000001773 anti-convulsant effect Effects 0.000 description 2
- 125000005605 benzo group Chemical group 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- ZFFBIQMNKOJDJE-UHFFFAOYSA-N 2-bromo-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(Br)C(=O)C1=CC=CC=C1 ZFFBIQMNKOJDJE-UHFFFAOYSA-N 0.000 description 1
- XCIZVKSCLVSDHN-UHFFFAOYSA-N 2-ethylquinoline Chemical compound C1=CC=CC2=NC(CC)=CC=C21 XCIZVKSCLVSDHN-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 206010021118 Hypotonia Diseases 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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 239000001961 anticonvulsive agent Substances 0.000 description 1
- 229960003965 antiepileptics Drugs 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- ASGJEMPQQVNTGO-UHFFFAOYSA-N benzene chloroform Chemical compound C(Cl)(Cl)Cl.C1=CC=CC=C1.C1=CC=CC=C1 ASGJEMPQQVNTGO-UHFFFAOYSA-N 0.000 description 1
- WIRUZQNBHNAMAB-UHFFFAOYSA-N benzene;cyclohexane Chemical compound C1CCCCC1.C1=CC=CC=C1 WIRUZQNBHNAMAB-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000036640 muscle relaxation Effects 0.000 description 1
- 239000003158 myorelaxant agent Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012746 preparative thin layer chromatography Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 150000003248 quinolines Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Description
【発明の詳細な説明】
本発明は新規な３，４―ベンゾ―７―チア―２
―アザビシクロ〔３，３，１〕ノナン誘導体に関
する。DETAILED DESCRIPTION OF THE INVENTION The present invention provides novel 3,4-benzo-7-thia-2
-Relating to azabicyclo[3,3,1]nonane derivatives.
本発明の３，４―ベンゾ―７―チア―２―アザ
ビシクロ〔３，３，１〕ノナン誘導体は文献未載
の新規化合物であつて、下記一般式(1)で表わされ
る。 The 3,4-benzo-7-thia-2-azabicyclo[3,3,1]nonane derivative of the present invention is a new compound that has not been described in any literature and is represented by the following general formula (1).
〔式中R1は水素原子又は低級アルキル基を、
R2は低級アルキル基を、R3は水素原子、低級ア
ルキル基、低級アルコキシ基、フエニル低級アル
コキシ基又は水酸基をそれぞれ示す。但しR1が
水素原子を示し且つR2がメチル基を示す場合が
R3は水素原子であつてはならない。〕上記一般式
(1)で表わされる本発明の化合物は優れた抗痙攣作
用、筋弛緩作用、鎮痛作用等を有し、抗痙攣剤、
筋弛緩剤、鎮痛剤等として有用である。 [In the formula, R 1 is a hydrogen atom or a lower alkyl group,
R 2 represents a lower alkyl group, and R 3 represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a phenyl lower alkoxy group, or a hydroxyl group, respectively. However, there are cases where R 1 represents a hydrogen atom and R 2 represents a methyl group.
R 3 must not be a hydrogen atom. ]The above general formula
The compound of the present invention represented by (1) has excellent anticonvulsant action, muscle relaxation action, analgesic action, etc., and is an anticonvulsant,
It is useful as a muscle relaxant, analgesic, etc.
本明細書において、R1，R2及びR3で示される
各基としては、より具体的には夫々次のものを挙
げることができる。 In this specification, more specific examples of each group represented by R 1 , R 2 and R 3 include the following.
低級アルキル基…メチル、エチル、プロピル、
イソプロピル、ブチル、tert―ブチル基等。 Lower alkyl group...methyl, ethyl, propyl,
Isopropyl, butyl, tert-butyl groups, etc.
低級アルコキシ基…メトキシ、エトキシ、プロ
ポキシ、イソプロポキシ、ブトキシ、tert―ブト
キシ基等。 Lower alkoxy groups: methoxy, ethoxy, propoxy, isopropoxy, butoxy, tert-butoxy groups, etc.
フエニル低級アルコキシ基…１―フエニルメト
キシ、２―フエニルエトキシ、３―フエニルプロ
ポキシ、４―フエニルブトキシ、１，１―ジメチ
ル―２―フエニルエトキシ、２―メチル―３―フ
エニルプロポキシ基等。 Phenyl lower alkoxy group...1-phenylmethoxy, 2-phenylethoxy, 3-phenylpropoxy, 4-phenylbutoxy, 1,1-dimethyl-2-phenylethoxy, 2-methyl-3-phenylpropoxy group, etc. .
本発明の化合物のうち代表的なものを以下に掲
げる。 Representative compounds of the present invention are listed below.
Γ １―エチル―３，４―ベンゾ―７―チア―２
―アザビシクロ〔３，３，１〕ノナン―７―オ
キシド
Γ １―プロピル―３，４―ベンゾ―７―チア―
２―アザビシクロ〔３，３，１〕ノナン―７―
オキシド
Γ １―イソプロピル―３，４―ベンゾ―７―チ
ア―２―アザビシクロ〔３，３，１〕ノナン―
７―オキシド
Γ １―tert―ブチル―３，４―ベンゾ―７―チ
ア―２―アザビシクロ〔３，３，１〕ノナン―
７―オキシド
Γ １，２―ジメチル―３，４―ベンゾ―７―チ
ア―２―アザビシクロ〔３，３，１〕ノナン―
７―オキシド
Γ １―エチル―２―メチル―３，４―ベンゾ―
７―チア―２―アザビシクロ〔３，３，１〕ノ
ナン―７―オキシド
Γ １―イソプロピル―２―メチル―３，４―ベ
ンゾ―７―チア―２―アザビシクロ〔３，３，
１〕ノナン―７―オキシド
Γ １―tert―ブチル―２―メチル―３，４―ベ
ンゾ―７―チア―２―アザビシクロ〔３，３，
１〕ノナン―７―オキシド
Γ １，２―ジエチル―３，４―ベンゾ―７―チ
ア―２―アザビシクロ〔３，３，１〕ノナン―
７―オキシド
Γ １―ブチル―２―エチル―３，４―ベンゾ―
７―チア―２―アザビシクロ〔３，３，１〕ノ
ナン―７―オキシド
Γ １，２―ジプロピル―３，４―ベンゾ―７―
チア―２―アザビシクロ〔３，３，１〕ノナン
―７―オキシド
Γ １―ブチル―２―プロピル―３，４―ベンゾ
―７―チア―２―アザビシクロ〔３，３，１〕
ノナン―７―オキシド
Γ １―メチル―２―tert―ブチル―３，４―ベ
ンゾ―７―チア―２―アザビシクロ〔３，３，
１〕ノナン―７―オキシド
Γ １―イソプロピル―２―tert―ブチル―３，
４―ベンゾ―７―チア―２―アザビシクロ
〔３，３，１〕ノナン―７―オキシド
Γ １，２―ジ―tert―ブチル―３，４―ベンゾ
―７―チア―２―アザビシクロ〔３，３，１〕
ノナン―７―オキシド
Γ １―メチル―３，４―（11―メチルベンゾ）
―７―チア―２―アザビシクロ〔３，３，１〕
ノナン―７―オキシド
Γ １―メチル―３，４―（13―メチルベンゾ）
―７―チア―２―アザビシクロ〔３，３，１〕
ノナン―７―オキシド
Γ １―メチル―３，４―（13―メトキシベン
ゾ）―７―チア―２―アザビシクロ〔３，３，
１〕ノナン―７―オキシド
Γ １―エチル―３，４―（10―tert―ブチルベ
ンゾ）―７―チア―２―アザビシクロ〔３，
３，１〕ノナン―７―オキシド
Γ １―プロピル―３，４―（12―エトキシベン
ゾ）―７―チア―２―アザビシクロ〔３，３，
１〕ノナン―７―オキシド
Γ １―tert―ブチル―３，４―（11―プロピル
ベンゾ）―７―チア―２―アザビシクロ〔３，
３，１〕ノナン―７―オキシド
Γ １―ブチル―２―メチル―（11―tert―ブト
キシベンゾ）―７―チア―２―アザビシクロ
〔３，３，１〕ノナン―７―オキシド
Γ １，２―ジメチル―（11―メチルベンゾ）―
７―チア―２―アザビシクロ〔３，３，１〕ノ
ナン―７―オキシド
Γ １―メチル―３，４―〔13―（１―フエニル
メトキシ）ベンゾ〕―７―チア―２―アザビシ
クロ〔３，３，１〕ノナン―７―オキシド
Γ １―エチル―３，４―〔11―（２―フエニル
エトキシ）ベンゾ〕―７―チア―２―アザビシ
クロ〔３，３，１〕ノナン―７―オキシド
Γ １―tert―ブチル―３，４―〔11―（４―フ
エニルブトキシ）ベンゾ）―７―チア―２―ア
ザビシクロ〔３，３，１）ノナン―７―オキシ
ド
Γ １―メチル―３，４―（13―ヒドロキシベン
ゾ）―７―チア―２―アザビシクロ〔３，３，
１〕ノナン―７―オキシド
Γ １―メチル―３，４―（12―ヒドロキシベン
ゾ）―７―チア―２―アザビシクロ〔３，３，
１〕ノナン―７―オキシド
Γ １―メチル―３，４―（11―ヒドロキシベン
ゾ）―７―チア―２―アザビシクロ〔３，３，
１〕ノナン―７―オキシド
Γ １―メチル―３，４―（10―ヒドロキシベン
ゾ）―７―チア―２―アザビシクロ〔３，３，
１〕ノナン―７―オキシド
Γ １，２―ジメチル―３，４―（11―ヒドロキ
シベンゾ）―７―チア―２―アザビシクロ
〔３，３，１〕ノナン―７―オキシド
Γ １―メチル―２―ブチル―３，４―（13―ヒ
ドロキシベンゾ）―７―チア―２―アザビシク
ロ〔３，３，１〕ノナン―７―オキシド
Γ １―ブチル―２―メチル―３，４―（13―ヒ
ドロキシベンゾ）―７―チア―２―アザビシク
ロ〔３，３，１〕ノナン―７―オキシド
Γ １，２―ジエチル―３，４―（12―ヒドロキ
シベンゾ―７―チア―２―アザビシクロ〔３，
３，１〕ノナン―７―オキシド
Γ １―プロピル―３，４―（11―ヒドロキシベ
ンゾ）―７―チア―２―アザビシクロ〔３，
３，１〕ノナン―７―オキシド
本発明の化合物は種々の方法により製造される
が、その好ましい一例を挙げれば下記反応行程式
―１〜３に示す方法に従い製造される。Γ 1-ethyl-3,4-benzo-7-thia-2
-Azabicyclo[3,3,1]nonane-7-oxide Γ 1-propyl-3,4-benzo-7-thia-
2-Azabicyclo[3,3,1]nonane-7-
Oxide Γ 1-isopropyl-3,4-benzo-7-thia-2-azabicyclo[3,3,1]nonane-
7-oxide Γ 1-tert-butyl-3,4-benzo-7-thia-2-azabicyclo[3,3,1]nonane-
7-oxide Γ 1,2-dimethyl-3,4-benzo-7-thia-2-azabicyclo[3,3,1]nonane-
7-oxide Γ 1-ethyl-2-methyl-3,4-benzo-
7-thia-2-azabicyclo[3,3,1]nonane-7-oxide Γ 1-isopropyl-2-methyl-3,4-benzo-7-thia-2-azabicyclo[3,3,
1] Nonane-7-oxide Γ 1-tert-butyl-2-methyl-3,4-benzo-7-thia-2-azabicyclo[3,3,
1] Nonane-7-oxide Γ 1,2-diethyl-3,4-benzo-7-thia-2-azabicyclo[3,3,1]nonane-
7-oxide Γ 1-butyl-2-ethyl-3,4-benzo-
7-thia-2-azabicyclo[3,3,1]nonane-7-oxide Γ 1,2-dipropyl-3,4-benzo-7-
Thia-2-azabicyclo[3,3,1]nonane-7-oxide Γ 1-butyl-2-propyl-3,4-benzo-7-thia-2-azabicyclo[3,3,1]
Nonane-7-oxide Γ 1-methyl-2-tert-butyl-3,4-benzo-7-thia-2-azabicyclo[3,3,
1] Nonane-7-oxide Γ 1-isopropyl-2-tert-butyl-3,
4-Benzo-7-thia-2-azabicyclo[3,3,1]nonane-7-oxide Γ 1,2-di-tert-butyl-3,4-benzo-7-thia-2-azabicyclo[3, 3,1]
Nonane-7-oxide Γ 1-methyl-3,4-(11-methylbenzo)
-7-Chia-2-Azabicyclo [3,3,1]
Nonane-7-oxide Γ 1-methyl-3,4-(13-methylbenzo)
-7-Chia-2-Azabicyclo [3,3,1]
Nonane-7-oxide Γ 1-methyl-3,4-(13-methoxybenzo)-7-thia-2-azabicyclo[3,3,
1] Nonane-7-oxide Γ 1-ethyl-3,4-(10-tert-butylbenzo)-7-thia-2-azabicyclo[3,
3,1] Nonane-7-oxide Γ 1-propyl-3,4-(12-ethoxybenzo)-7-thia-2-azabicyclo[3,3,
1] Nonane-7-oxide Γ 1-tert-butyl-3,4-(11-propylbenzo)-7-thia-2-azabicyclo[3,
3,1] Nonane-7-oxide Γ 1-Butyl-2-methyl-(11-tert-butoxybenzo)-7-thia-2-azabicyclo[3,3,1] Nonane-7-oxide Γ 1,2 -Dimethyl- (11-methylbenzo)-
7-thia-2-azabicyclo[3,3,1]nonane-7-oxide Γ 1-methyl-3,4-[13-(1-phenylmethoxy)benzo]-7-thia-2-azabicyclo[3 ,3,1]nonane-7-oxide Γ 1-ethyl-3,4-[11-(2-phenylethoxy)benzo]-7-thia-2-azabicyclo[3,3,1]nonane-7- Oxide Γ 1-tert-butyl-3,4-[11-(4-phenylbutoxy)benzo)-7-thia-2-azabicyclo[3,3,1)nonane-7-oxide Γ 1-methyl-3,4 -(13-hydroxybenzo)-7-thia-2-azabicyclo[3,3,
1] Nonane-7-oxide Γ 1-methyl-3,4-(12-hydroxybenzo)-7-thia-2-azabicyclo[3,3,
1] Nonane-7-oxide Γ 1-methyl-3,4-(11-hydroxybenzo)-7-thia-2-azabicyclo[3,3,
1] Nonane-7-oxide Γ 1-methyl-3,4-(10-hydroxybenzo)-7-thia-2-azabicyclo[3,3,
1] Nonane-7-oxide Γ 1,2-dimethyl-3,4-(11-hydroxybenzo)-7-thia-2-azabicyclo[3,3,1]nonane-7-oxide Γ 1-methyl-2 -Butyl-3,4-(13-hydroxybenzo)-7-thia-2-azabicyclo[3,3,1]nonane-7-oxide Γ 1-Butyl-2-methyl-3,4-(13-hydroxy benzo)-7-thia-2-azabicyclo[3,3,1]nonane-7-oxide Γ 1,2-diethyl-3,4-(12-hydroxybenzo-7-thia-2-azabicyclo[3,
3,1] Nonane-7-oxide Γ 1-propyl-3,4-(11-hydroxybenzo)-7-thia-2-azabicyclo[3,
3,1] Nonane-7-oxide The compound of the present invention can be produced by various methods, but one preferred example is produced according to the methods shown in Reaction Schemes 1 to 3 below.
反応行程式 １
〔式中R4は水素原子、低級アルキル基、低級
アルコキシ基又はフエニル低級アルコキシ基を示
す。R2は前記に同じ。〕
反応行程式―１によれば、本発明の化合物のう
ちR1が水素原子を示し且つR3が水素原子、低級
アルキル基、低級アルコキシ基又はフエニル低級
アルコキシ基を示す化合物（一般式（1a）の化
合物）は塩基性化合物とジメチルスルホキシドと
の共存下適当な溶媒中にて一般式(2)で表わされる
キノリン誘導体を加熱することにより製造され
る。塩基性化合物としては例えば水素化ナトリウ
ム、カリウムtert―ブトキシド、ｎ―ブチルリチ
ウム、ナトリウムアミド、ナトリウムメトキシド
等を挙げることができる。反応系内に存在させる
べき塩基性化合物の量としては、通常一般式(2)の
化合物に対し少なくとも２倍モル量、好ましくは
３〜７倍モル量、より好ましくは５倍モル量程度
とするのがよい。また反応系内に存在させるべき
ジメチルスルホキシドの量としては、通常一般式
(2)の化合物に対し少なくとも等モル量、好ましく
は過剰量とするのがよい。用いられる溶媒として
は上記反応に不活性なものを広く使用でき、例え
ばテトラヒドロフラン、ジオキサン、ジメチルホ
ルムアミド、ジメチルスルホキシド、ヘキサメチ
ルリン酸トリアミド等を挙げることができる。加
熱温度としては特に限定されず広い範囲内で適宜
選択すればよいが、通常50〜80℃、好ましくは70
℃前後に加熱すればよく、一般に0.5〜５時間で
目的とする一般式（1a）の化合物を収得し得る。Reaction equation 1 [In the formula, R 4 represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a phenyl lower alkoxy group. R 2 is the same as above. ] According to Reaction Scheme-1, compounds of the present invention in which R 1 represents a hydrogen atom and R 3 represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a phenyl lower alkoxy group (general formula (1a) Compound ) is produced by heating a quinoline derivative represented by formula (2) in an appropriate solvent in the coexistence of a basic compound and dimethyl sulfoxide. Examples of the basic compound include sodium hydride, potassium tert-butoxide, n-butyllithium, sodium amide, and sodium methoxide. The amount of the basic compound to be present in the reaction system is usually at least twice the molar amount of the compound of general formula (2), preferably 3 to 7 times the molar amount, and more preferably about 5 times the molar amount. It is better. In addition, the amount of dimethyl sulfoxide that should be present in the reaction system is usually determined by the general formula
The amount is preferably at least equimolar to the compound (2), preferably in excess. A wide variety of solvents can be used that are inert to the above reaction, and examples thereof include tetrahydrofuran, dioxane, dimethylformamide, dimethyl sulfoxide, hexamethylphosphoric triamide, and the like. The heating temperature is not particularly limited and may be selected as appropriate within a wide range, but is usually 50 to 80°C, preferably 70°C.
The desired compound of general formula (1a) can generally be obtained in 0.5 to 5 hours by heating to around 10°C.
本発明では、予め反応系内において塩基性化合
物とジメチルスルホキシドとを上記と同条件下に
加熱し、次いで該反応系内に一般式(2)の化合物を
添加し、この反応溶液を加熱することにより目的
物である一般式（1a）の化合物を製造すること
ができる。 In the present invention, the basic compound and dimethyl sulfoxide are heated in advance in the reaction system under the same conditions as above, then the compound of general formula (2) is added to the reaction system, and the reaction solution is heated. The target compound of general formula (1a) can be produced by the following steps.
反応行程式 ２
〔式中R1′は低級アルキル基を、Ｘはハロゲン
原子をそれぞれ示す。R2及びR4は前記に同じ。〕
反応行程式―２によれば、本発明の化合物のう
ちR1が低級アルキル基を示し且つR3が水素原子、
低級アルキル基、低級アルコキシ基又はフエニル
低級アルコキシ基を示す化合物（一般式（1b）
の化合物）は、一般式（1a）の化合物と一般式
(3)で表わされるハロゲン化アルキルとを反応させ
ることにより製造される。Reaction equation 2 [In the formula, R 1 ' represents a lower alkyl group, and X represents a halogen atom. R 2 and R 4 are the same as above. ] According to Reaction Scheme-2, in the compound of the present invention, R 1 represents a lower alkyl group, R 3 represents a hydrogen atom,
Compounds exhibiting a lower alkyl group, a lower alkoxy group, or a phenyl lower alkoxy group (general formula (1b)
) is a compound of general formula (1a) and a compound of general formula
It is produced by reacting with an alkyl halide represented by (3).
一般式（1a）の化合物と一般式(3)の化合物と
の反応は、例えば塩基性化合物の存在下適当な溶
媒中にて行なうのがよい。用いられる塩基性化合
物としては例えば水素化ナトリウム、カリウム、
ナトリウム、カリウムアミド、ナトリウムアミド
等を挙げることができる。斯かる塩基性化合物は
通常一般式（1a）の化合物に対して少なくとも
等モル量程度、好ましくは等モル〜２倍モル量用
いるのがよい。また溶媒としては例えばジオキサ
ン、ジエチレングリコール、ジメチルエーテル等
のエーテル類、トルエン、キシレン等の芳香族炭
化水素類、ジメチルホルムアミド、ジメチルスル
ホキシド、ヘキサメチルリン酸トリアミド等を挙
げることができる。一般式（1a）の化合物と一
般式(3)の化合物との使用割合としては特に限定が
なく広い範囲内で適宜選択すればよいが、通常前
者に対して後者を少なくとも等モル程度以上、好
ましくは等モル〜２倍モル程度用いるのが良い。
該反応は通常０〜70℃程度、好ましくは50〜60℃
程度付近にて行なわれ、一般に0.5〜12時間程度
で反応は終了する。 The reaction between the compound of general formula (1a) and the compound of general formula (3) is preferably carried out, for example, in the presence of a basic compound in a suitable solvent. Examples of the basic compounds used include sodium hydride, potassium,
Examples include sodium, potassium amide, sodium amide, and the like. Such a basic compound is usually used in an amount of at least equimolar, preferably equimolar to twice the molar amount of the compound of general formula (1a). Examples of the solvent include ethers such as dioxane, diethylene glycol, and dimethyl ether, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethyl sulfoxide, and hexamethylphosphoric triamide. The ratio of the compound of general formula (1a) and the compound of general formula (3) to be used is not particularly limited and may be appropriately selected within a wide range, but usually the latter is preferably at least equimolar to the former. It is preferable to use about equimolar to twice the molar amount.
The reaction is usually carried out at about 0 to 70°C, preferably 50 to 60°C.
The reaction is generally completed in about 0.5 to 12 hours.
反応行程式 ３
〔式中R5は低級アルコキシ基又はフエニル低
級アルコキシ基を示す。R1及びR2は前記に同
じ。〕
反応行程式―３によれば、本発明の化合物のう
ちR3が水酸基を示す化合物（一般式（1d）の化
合物）は一般式（1c）の化合物を加水分解するこ
とにより製造される。Reaction equation 3 [In the formula, R 5 represents a lower alkoxy group or a phenyl lower alkoxy group. R 1 and R 2 are the same as above. ] According to Reaction Scheme-3, among the compounds of the present invention, a compound in which R 3 represents a hydroxyl group (a compound of general formula (1d)) is produced by hydrolyzing a compound of general formula (1c).
一般式（1c）の加水分解は、例えば適当な溶媒
中臭化水素酸を用いて行なわれる。臭化水素酸は
一般に一般式（1c）の化合物に対して過剰量用い
るのがよい。また溶媒としては例えば水、酢酸、
プロピオン酸等の低級脂肪酸、塩酸、硫酸、臭化
水素酸等の鉱酸、ジオキサン、テトラヒドロフラ
ン等のエーテル類、ジメチルホルムアミド、ジメ
チルスルホキシド等を挙げることができる。該加
水分解反応は通常50〜150℃程度、好ましくは80
〜120℃にて行なわれ、一般に３〜12時間程度で
反応は終了する。 Hydrolysis of general formula (1c) is carried out using, for example, hydrobromic acid in a suitable solvent. Hydrobromic acid is generally preferably used in an excess amount relative to the compound of general formula (1c). Examples of solvents include water, acetic acid,
Examples include lower fatty acids such as propionic acid, mineral acids such as hydrochloric acid, sulfuric acid, and hydrobromic acid, ethers such as dioxane and tetrahydrofuran, dimethylformamide, and dimethylsulfoxide. The hydrolysis reaction is usually carried out at a temperature of about 50 to 150°C, preferably 80°C.
The reaction is carried out at ~120°C and generally completes in about 3 to 12 hours.
一般式(1)の化合物は医薬的に許容され得る酸と
容易に酸付加塩を形成させることができる。該酸
としては例えば塩、硫酸、臭化水素酸等の無機
酸、酢酸、マレイン酸、蓚酸、コハク酸等の有機
酸を挙げることができる。また一般式(1)の化合物
のうち、酸性基を有する化合物は医薬的に許容さ
れ得る塩基性化合物と容易に塩を形成させること
ができる。該塩基性化合物としては例えば水酸化
ナトリウム、水酸化カリウム、水酸化カルシウム
等を挙げることができる。本発明では斯かる塩を
も包含される。 The compound of general formula (1) can easily form an acid addition salt with a pharmaceutically acceptable acid. Examples of the acid include salts, inorganic acids such as sulfuric acid and hydrobromic acid, and organic acids such as acetic acid, maleic acid, oxalic acid and succinic acid. Further, among the compounds of general formula (1), a compound having an acidic group can easily form a salt with a pharmaceutically acceptable basic compound. Examples of the basic compound include sodium hydroxide, potassium hydroxide, calcium hydroxide, and the like. The present invention also includes such salts.
斯くして得られる本発明の化合物は、必要なら
ば中和した後通常用いられている分離手段により
容易に単離、精製される。斯かる分離手段として
は沈殿法、抽出法、再結晶法、カラムクロマトグ
ラフイー、プレパラテイブ薄層クロマトグラフイ
ー等を例示できる。 The compound of the present invention thus obtained can be easily isolated and purified by commonly used separation means after neutralization if necessary. Examples of such separation means include precipitation methods, extraction methods, recrystallization methods, column chromatography, preparative thin layer chromatography, and the like.
本発明化合物の製造例を実施例として以下に挙
げる。 Production examples of the compounds of the present invention are listed below as Examples.
実施例 １
窒素気流中、ジメチルスルホキシド100mlに水
素化ナトリウム264ｇを加えて70℃で溶解し、そ
の溶液に２―エチルキノリン3.4ｇを溶解したジ
メチルスルホキシド100mlを滴下し、70℃、４時
間撹拌、冷後水500mlに加えてジクロルメタンで
抽出、水洗、無水硫酸マグネシウムで乾燥後
過、溶媒留去して残渣をシリカゲルカラムクロマ
トグラフイー（クロロホルム）で製精する。ベン
ゼン―クロロホルムより再結晶して無色プリズム
晶の１―エチル―３，４―ベンゾ―７―チア―２
―アザビシクロ〔３，３，１〕ノナン―７―オキ
シド2.19ｇを得る。Example 1 In a nitrogen stream, 264 g of sodium hydride was added to 100 ml of dimethyl sulfoxide and dissolved at 70°C, and 100 ml of dimethyl sulfoxide in which 3.4 g of 2-ethylquinoline was dissolved was added dropwise to the solution, stirred at 70°C for 4 hours, After cooling, add to 500 ml of water, extract with dichloromethane, wash with water, dry over anhydrous magnesium sulfate, filtrate, evaporate the solvent, and purify the residue using silica gel column chromatography (chloroform). Recrystallized from benzene-chloroform to give colorless prismatic crystals of 1-ethyl-3,4-benzo-7-thia-2.
- Obtain 2.19 g of azabicyclo[3,3,1]nonane-7-oxide.
元素分析値
Ｃ Ｈ Ｎ
理論値(%) 66.35 7.28 5.95
実測値(%) 66.14 7.40 5.91
mp.182〜183℃
適当な出発原料を用い実施例１と同様にして、
実施例２〜４の化合物を得る。 Elemental analysis value C H N Theoretical value (%) 66.35 7.28 5.95 Actual value (%) 66.14 7.40 5.91 mp.182-183°C In the same manner as in Example 1 using appropriate starting materials,
Compounds of Examples 2-4 are obtained.
実施例 ２
１―メチル―３，４―（11―メチルベンゾ）―
７―チア―２―アザビシクロ〔３，３，１〕ノ
ナン―７―オキシド
無色針状晶
mp.204〜206℃
実施例 ３
１―メチル―３，４―（13―メチルベンゾ）―
７―チア―２―アザビシクロ〔３，３，１〕ノ
ナン―７―オキシド
無色針状晶
mp.154〜156℃
実施例 ４
１―メチル―３，４―（13―メトキシベンゾ）
―７―チア―２―アザビシクロ〔３，３，１〕
ノナン―７―オキシド
無色針状晶
mp.204〜206℃
実施例 ５
ジメチルホルムアミド50mlと水素化ナトリウム
2.4ｇの混液にジメチルホルムアミドと１―メチ
ル―３，４―ベンゾ―７―チア―２―アザビシク
ロ〔３，３，１〕ノナン―７―オキシド4.42ｇの
溶液を加え、55〜60℃でヨウ化メチル14.2ｇを30
分要して滴下後、２時間撹拌する。冷後、反応液
を氷水（200ml）に入れ、ジクロメタンで抽出す
る。水洗し、無水硫酸マグネシウムで乾燥後、
過、溶媒留去し、析出した結晶をベンゼン―シク
ロヘキサン（１：３）で洗浄し、酢酸エチルより
再結晶して無色針状晶の１，２―ジメチル―３，
４―ベンゾ―７―チア―２―アザビシクロ〔３，
３，１〕ノナン―７―オキシド3.6ｇを得る。Example 2 1-methyl-3,4-(11-methylbenzo)-
7-Thia-2-azabicyclo[3,3,1]nonane-7-oxide Colorless needle crystals mp.204-206℃ Example 3 1-Methyl-3,4-(13-methylbenzo)-
7-Thia-2-azabicyclo[3,3,1]nonane-7-oxide Colorless needle crystals mp.154-156℃ Example 4 1-Methyl-3,4-(13-methoxybenzo)
-7-Chia-2-Azabicyclo [3,3,1]
Nonane-7-oxide Colorless needle crystals mp.204-206℃ Example 5 50ml of dimethylformamide and sodium hydride
A solution of dimethylformamide and 4.42 g of 1-methyl-3,4-benzo-7-thia-2-azabicyclo[3,3,1]nonane-7-oxide was added to 2.4 g of the mixed solution, and iodine was added at 55 to 60°C. 14.2g of methyl chloride 30
After the dropwise addition, the mixture was stirred for 2 hours. After cooling, the reaction solution was poured into ice water (200 ml) and extracted with dichloromethane. After washing with water and drying with anhydrous magnesium sulfate,
The precipitated crystals were washed with benzene-cyclohexane (1:3) and recrystallized from ethyl acetate to give colorless needle-like crystals of 1,2-dimethyl-3,
4-benzo-7-thia-2-azabicyclo[3,
3.6 g of 3,1]nonane-7-oxide is obtained.
元素分析値
Ｃ Ｈ Ｎ
理論値(%) 66.35 7.28 5.95
実測値(%) 66.23 7.43 5.93
mp.138〜140℃
実施例 ６
１―メチル―３，４―（13―ベンジルオキシベ
ンゾ）―７―チア―２―アザビシクロ〔３，３，
１〕ノナン―７―オキシド3.41ｇを酢酸50mlに溶
かし、48％臭化水素酸138mlを加え、撹拌下、100
℃で５時間加熱する。反応混合物を濃縮し10％
NaHCO3でPH７付近にし、クロロホルムで３回
抽出し、水洗、乾燥後、減圧濃縮する。得られた
残渣をエタノールより再結晶し、白色結晶の１―
メチル―３，４―（13―ヒドロキシベンゾ）―７
―チア―２―アザビシクロ〔３，３，１〕ノナン
―７―オキシド0.9ｇを得る。IRスペクトル、
NMRスペクトル及び元素分析値より上記化合物
であると確信する。 Elemental analysis value C H N Theoretical value (%) 66.35 7.28 5.95 Actual value (%) 66.23 7.43 5.93 mp.138-140℃ Example 6 1-Methyl-3,4-(13-benzyloxybenzo)-7-thia -2-Azabicyclo [3,3,
1] Dissolve 3.41 g of nonane-7-oxide in 50 ml of acetic acid, add 138 ml of 48% hydrobromic acid, and add 138 ml of 48% hydrobromic acid.
Heat at ℃ for 5 hours. Concentrate the reaction mixture to 10%
Adjust the pH to around 7 with NaHCO 3 , extract three times with chloroform, wash with water, dry, and concentrate under reduced pressure. The obtained residue was recrystallized from ethanol to obtain white crystals of 1-
Methyl-3,4-(13-hydroxybenzo)-7
0.9 g of -thia-2-azabicyclo[3,3,1]nonane-7-oxide is obtained. IR spectrum,
Based on the NMR spectrum and elemental analysis values, we are confident that this is the above compound.
元素分析値 Ｃ Ｈ Ｎ 理論値(%) 60.76 6.33 5.91 実測値(%) 60.55 6.45 5.87 Elemental analysis value C H N Theoretical value (%) 60.76 6.33 5.91 Actual value (%) 60.55 6.45 5.87
Claims (1)
R2は低級アルキル基を、R3は水素原子、低級ア
ルキル基、低級アルコキシ基、フエニル低級アル
コキシ基又は水酸基をそれぞれ示す。但しR1が
水素原子を示し且つR2がメチル基を示す場合、
R3は水素原子であつてはならない。〕 で表わされる３，４―ベンゾ―７―チア―２―ア
ザビシクロ〔３，３，１〕ノナン誘導体及びその
塩。[Claims] 1. General formula [In the formula, R 1 is a hydrogen atom or a lower alkyl group,
R 2 represents a lower alkyl group, and R 3 represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a phenyl lower alkoxy group, or a hydroxyl group, respectively. However, when R 1 represents a hydrogen atom and R 2 represents a methyl group,
R 3 must not be a hydrogen atom. ] 3,4-benzo-7-thia-2-azabicyclo[3,3,1]nonane derivative and its salt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9209780A JPS5716885A (en) | 1980-07-04 | 1980-07-04 | 3,4-benzo-7-thia-2-azabicyclo 3,3,1 nonane derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9209780A JPS5716885A (en) | 1980-07-04 | 1980-07-04 | 3,4-benzo-7-thia-2-azabicyclo 3,3,1 nonane derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5716885A JPS5716885A (en) | 1982-01-28 |
| JPH0161109B2 true JPH0161109B2 (en) | 1989-12-27 |
Family
ID=14044936
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9209780A Granted JPS5716885A (en) | 1980-07-04 | 1980-07-04 | 3,4-benzo-7-thia-2-azabicyclo 3,3,1 nonane derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5716885A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2522636B2 (en) * | 1993-11-18 | 1996-08-07 | 旭コンクリート工業株式会社 | Manufacturing method for tubular concrete products |
-
1980
- 1980-07-04 JP JP9209780A patent/JPS5716885A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5716885A (en) | 1982-01-28 |
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