JPH0427977B2 - - Google Patents
Info
- Publication number
- JPH0427977B2 JPH0427977B2 JP58112459A JP11245983A JPH0427977B2 JP H0427977 B2 JPH0427977 B2 JP H0427977B2 JP 58112459 A JP58112459 A JP 58112459A JP 11245983 A JP11245983 A JP 11245983A JP H0427977 B2 JPH0427977 B2 JP H0427977B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- general formula
- compound
- formula
- lower alkyl
- 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 carboxymethylphenyl group Chemical group 0.000 claims description 32
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 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
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 238000000034 method Methods 0.000 description 25
- 238000006243 chemical reaction Methods 0.000 description 20
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 150000001412 amines Chemical class 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000003266 anti-allergic effect Effects 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- VVPJUYMCOVDILQ-UHFFFAOYSA-N n-cyclohexyl-3-methylsulfanylpropanamide Chemical compound CSCCC(=O)NC1CCCCC1 VVPJUYMCOVDILQ-UHFFFAOYSA-N 0.000 description 3
- NRHMXMBVLXSSAX-UHFFFAOYSA-N 3-methylsulfanylpropanoyl chloride Chemical compound CSCCC(Cl)=O NRHMXMBVLXSSAX-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- WTZGMOAOGQPMKJ-UHFFFAOYSA-N [3-(cyclohexylamino)-3-oxopropyl]-dimethylsulfanium;4-methylbenzenesulfonate Chemical compound CC1=CC=C(S([O-])(=O)=O)C=C1.C[S+](C)CCC(=O)NC1CCCCC1 WTZGMOAOGQPMKJ-UHFFFAOYSA-N 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000006664 bond formation reaction Methods 0.000 description 2
- PFKFTWBEEFSNDU-UHFFFAOYSA-N carbonyldiimidazole Chemical compound C1=CN=CN1C(=O)N1C=CN=C1 PFKFTWBEEFSNDU-UHFFFAOYSA-N 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- 229940125898 compound 5 Drugs 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- NMPJWUVIRVWNHY-UHFFFAOYSA-N n-(4-acetylphenyl)-3-methylsulfanylpropanamide Chemical compound CSCCC(=O)NC1=CC=C(C(C)=O)C=C1 NMPJWUVIRVWNHY-UHFFFAOYSA-N 0.000 description 2
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OGFAWKRXZLGJSK-UHFFFAOYSA-N 1-(2,4-dihydroxyphenyl)-2-(4-nitrophenyl)ethanone Chemical compound OC1=CC(O)=CC=C1C(=O)CC1=CC=C([N+]([O-])=O)C=C1 OGFAWKRXZLGJSK-UHFFFAOYSA-N 0.000 description 1
- GPRYKVSEZCQIHD-UHFFFAOYSA-N 1-(4-aminophenyl)ethanone Chemical compound CC(=O)C1=CC=C(N)C=C1 GPRYKVSEZCQIHD-UHFFFAOYSA-N 0.000 description 1
- YQTCQNIPQMJNTI-UHFFFAOYSA-N 2,2-dimethylpropan-1-one Chemical group CC(C)(C)[C]=O YQTCQNIPQMJNTI-UHFFFAOYSA-N 0.000 description 1
- AJZDHLHTTJRNQJ-UHFFFAOYSA-N 3-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxy-N-[2-(tetrazol-1-yl)ethyl]benzamide Chemical group N1(N=NN=C1)CCNC(C1=CC(=CC=C1)OC1=NC(=CC(=C1)CN)C(F)(F)F)=O AJZDHLHTTJRNQJ-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 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
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 238000010976 amide bond formation reaction Methods 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 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
- 125000004063 butyryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- PSLIMVZEAPALCD-UHFFFAOYSA-N ethanol;ethoxyethane Chemical compound CCO.CCOCC PSLIMVZEAPALCD-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- IOPLHGOSNCJOOO-UHFFFAOYSA-N methyl 3,4-diaminobenzoate Chemical compound COC(=O)C1=CC=C(N)C(N)=C1 IOPLHGOSNCJOOO-UHFFFAOYSA-N 0.000 description 1
- VUQUOGPMUUJORT-UHFFFAOYSA-N methyl 4-methylbenzenesulfonate Chemical compound COS(=O)(=O)C1=CC=C(C)C=C1 VUQUOGPMUUJORT-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- UXCDUFKZSUBXGM-UHFFFAOYSA-N phosphoric tribromide Chemical compound BrP(Br)(Br)=O UXCDUFKZSUBXGM-UHFFFAOYSA-N 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- ZERULLAPCVRMCO-UHFFFAOYSA-N sulfure de di n-propyle Natural products CCCSCCC ZERULLAPCVRMCO-UHFFFAOYSA-N 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
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
Landscapes
- Furan Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は新規なスルフアイド化合物に関する。
本発明のスルフアイド化合物は下記一般式（）
で表わされる。
［式中R1は低級アルキル基を示し、R2は水素
原子又は低級アルキル基を示す。R3はR2が水素
原子の時、シクロヘキシル基、カルボキシメチル
基、低級アシルフエニル基、テトラゾリルカルバ
モイルフエニル基、カルボキシメチルフエニル
基、３−（２−オキソ−４−ハイドロキシテトラ
ハイドロフリル）オキシフエニル基、低級アルコ
キシカルボニルメチルカルバモイルフエニル基又
は基
The present invention relates to novel sulfide compounds.
The sulfide compound of the present invention has the following general formula ()
It is expressed as [In the formula, R 1 represents a lower alkyl group, and R 2 represents a hydrogen atom or a lower alkyl group. When R 2 is a hydrogen atom, R 3 is a cyclohexyl group, carboxymethyl group, lower acylphenyl group, tetrazolylcarbamoylphenyl group, carboxymethylphenyl group, 3-(2-oxo-4-hydroxytetrahydrofuryl)oxyphenyl group, lower alkoxycarbonylmethylcarbamoylphenyl group or group
【式】（R4は低級アルキル基、ハ
ロゲン原子又は水酸基を示す）を示し、R2が低
級アルキル基の時、フエニル基を示す。更にR2
及びR3は互いに結合してペンタメチレン鎖とな
り、之等の結合する窒素原子と共に複素環基を形
成してもよい。
上記一般式（）中R1，R2，R3及びR4で表わ
される低級アルキル基としては炭素数１〜６のア
ルキル基、例えばメチル、エチル、プロピル、イ
ソプロピル、ブチル、イソブチル、ｔ−ブチル、
ペンチル、ヘキシル基等を例示できる。
一般式（）中R3で表わされる低級アシルフ
エニル基を構成する低級アシル基としては、炭素
数２〜６のアシル基例えばアセチル、プロピオニ
ル、ブチリル、ピバロイル、カプロイル基等を、
低級アルコキシカルボニルメチルカルバモイルフ
エニル基を構成する低級アルコキシカルボニルメ
チルカルバモイル基としては、炭素数４〜９のア
ルコキシカルボニルメチルカルバモイル基例えば
メトキシカルボニルメチルカルバモイル、エトキ
シカルボニルメチルカルバモイル、プロピルオキ
シカルボニルメチルカルバモイル、イソプロピル
オキシカルボニルメチルカルバモイル、ブトキシ
カルボニルメチルカルバモイル、ｔ−ブトキシカ
ルバモイル、ヘキシロキシカルボニルメチルカル
バモイル基等を夫々例示することができる。R4
で示されるハロゲン原子としては、弗素、塩素、
臭素、沃素原子を例示できる。
また上記一般式（）中R2及びR3は互いに結
合してペンタメチレン鎖を形成することができ
る。
本発明の上記一般式（）で表わされるスルフ
アイド化合物は、例えば下記反応式(A)に示す方法
に従い、一般式（）で表わされ抗アレルギー作
用を有するスルホニウム化合物を容易に誘導する
ことができ、かかる抗アレルギー作用を有する医
薬品の合成原料として有用である。
反応式(A)
［各式中R1，R2及びR3は上記に同じ。R6は低
級アルキル基及びＹは酸残基を示す。］
上記反応式(A)に示す反応は、溶媒中または無溶
媒で、約−30〜150℃、好ましくは０〜100℃の温
度条件下に、約0.5〜72時間を要して行なわれる。
溶媒としてはメタノール、エタノール、プロパノ
ール等のアルコール類；アセトニトリル、ニトロ
メタン、ジメチルホルムアミド、ジメチルスルホ
キサイド等の極性溶媒；メチレンクロライド、ク
ロロホルム等のハロゲン化炭化水素；ベンゼン、
トルエン、キシレン等の芳香族炭化水素類；エチ
ルエーテル、プロピルエーテル等のエーテル類；
その他アセトン、石油エーテル、酢酸エチル、水
及びこれら溶媒の混合溶媒等を使用できる。反応
は必要に応じて密閉容器中で行なうことができ
る。また一般式（）で表わされる化合物は、通
常本発明の一般式（）で表わされるスルフアイ
ド化合物に対して、過剰量、好ましくは約１〜４
倍モル量用いられる。上記反応式(A)に示す一般式
（）で表わされるスルホニウム化合物の合成の
詳細は、後記参考例に示す通りである。
以下本発明化合物の製造につき詳述する。
本発明の化合物は種々の方法で製造され、例え
ば下記反応式(B)に示される方法で容易に製造され
る。
反応式(B)
［各式中R1，R2及びR3は上記に同じ。］
上記反応式(B)に示される方法は、一般式（）
で表わされるカルボン酸と、一般式（）で表わ
されるアミンとの、通常のアミド結合生成反応を
利用したものである。上記方法においては一般式
（）のカルボン酸に代えて、そのカルボキシル
基が活性化された化合物を用いてもよく、また一
般式（）のアミンに代えて、そのアミノ基が活
性化された化合物を用いてもよい。之等各原料化
合物を用いたアミド結合生成反応においては、公
知のアミド結合生成反応と同様の反応条件、操作
等を採用することができる。該反応はより詳細に
は以下の各方法のいずれかに従い容易に実施する
ことができる。
(イ) カルボン酸ハライド法；即ち一般式（）の
カルボン酸のハライド化合物に、一般式（）
のアミンを反応させる方法
(ロ) ジシクロヘキシルカルボジイミド法；即ち一
般式（）のカルボン酸とジシクロヘキシルカ
ルボジイミドと一般式（）のアミンとを反応
させる方法
(ハ) カルボニルジイミダゾール法；即ち一般式
（）のカルボン酸にカルボニルジイミダゾー
ルを反応させた後、生成物に一般式（）のア
ミンを反応させる方法
(ニ) カルボン酸無水物法；即ち一般式（）のカ
ルボン酸を例えば無水酢酸等の脱水剤によりカ
ルボン酸無水物とした後、これに一般式（）
のアミンを反応させる方法
(ホ) カルボン酸エステル法；即ち一般式（）の
カルボン酸と、例えば低級アルコール等との反
応により得られるエステルに、一般式（）の
アミンを高温高圧下に反応させる方法
(ヘ) 活性エステル法；即ち一般式（）のカルボ
ン酸を例えばｐ−ニトロフエニルエステル、Ｎ
−ヒドロキシコハク酸イミドエステル等の活性
エステルとした後、これに一般式（）のアミ
ンを反応させる方法
(ト) 混合酸無水物法；即ち一般式（）のカルボ
ン酸に例えばハロカルボン酸アルキルエステル
を反応させて混合酸無水物とし、これに一般式
（）のアミンを反応させる方法
上記(イ)〜(ト)の方法のうちでは、(イ)に示すカルボ
ン酸ハライド法が特に好ましいものである。該カ
ルボン酸ハライド法において、一般式（）のカ
ルボン酸のハライド化合物は、常法に従い一般式
（）のカルボン酸とハロゲン化剤例えば塩化チ
オニル、オキシ塩化リン、オキシ臭化リン、五塩
化リン、五臭化リン等とを無溶媒又は適当な溶媒
中で反応させることにより得られる。該カルボン
酸ハライドと、一般式（）のアミンとの反応
は、好ましくは塩基性化合物、例えばナトリウ
ム、カリウム等のアルカリ金属、これらの水素化
物、これらの水酸化物又はこれらの炭酸塩或いは
ピリジン、モルホリン、ピペリジン、ピペラジ
ン、トリエチルアミン等の存在下、無溶媒或いは
溶媒中、約０〜200℃、好ましくは約０〜100℃の
温度条件下に約0.1〜24時間を要して行なわれる。
一般式（）のアミンは、カルボン酸ハライドに
対し、過剰量使用しても良いが、好ましくは理論
量の約１〜４倍モル量使用するのが良い。溶媒と
しては例えばクロロホルム、メチレンクロライ
ド、四塩化炭素等のハロゲン化炭化水素類；ジオ
キサン、テトラハイドロフラン、ジエチルエーテ
ル、イソプロピルエーテル等のエーテル等；ニト
ロメタン、ジメチルホルムアミド、ジメチルスル
ホキシド等の極性溶媒類；ベンゼン、トルエン、
キシレン等の芳香族炭化水素類；酢酸メチル、酢
酸エチル等のエステル類及び水又はこれらの混合
溶媒等が有利に使用できる。
上記反応式(B)に示す反応に従い得られる一般式
（）の本発明化合物は、通常用いられている分
離手段、例えば沈殿法、抽出法、再結晶法、蒸留
法、カラムクロマトグラフイーまたはプレパラテ
イブ薄層クロマトグラフイー等により容易に単
離、精製することができる。
以下本発明化合物の製造例を実施例として挙
げ、次いで本発明化合物からの抗アレルギー作用
を有するスルホニウム化合物の合成例を参考例と
して挙げ、本発明を更に詳しく説明する。
実施例 １
２−シクロヘキシルカルバモイルエチルメチル
スルフアイド（化合物）の合成
エーテル100mlにシクロヘキシルアミン21.4ｇ
及びトリエチルアミン24.0ｇを溶解させる。これ
に、氷冷下、β−メチルメルカプトプロピオニル
クロライド30.0ｇを加える。室温で２時間撹拌
し、反応液を水洗する。芒硝脱水後、エーテル層
を濃縮し、残渣をシクロヘキサンより再結晶して
２−シクロヘキシルカルバモイルエチルメチルス
ルフアイド（化合物）42.5ｇ（収率97.7％）を
得る。
mp93−94℃
実施例 ２
実施例１と同様の操作により、後記表に示す
化合物４を合成した。
実施例 ３
２−（メチルフエニルカルバモイル）エチルメ
チルスルフアイド（化合物２）のの合成
ベンゼン1000mlにメチルアニリン10.7ｇ及びピ
リジン9.49ｇを溶解させる。これに、氷冷下、β
−メチルカプトプロピオニルクロライド13.9ｇを
加える。室温で１時間撹拌し、反応液を水洗す
る。芒硝脱水後、ベンゼン層を濃縮し、残渣を減
圧蒸留して２−（メチルフエニルカルバモイル）
エチルメチルスルフアイド（化合物２）19.9ｇ
（収率95.2％）を得る。
bp149−150℃／２mmHg
実施例 ４
２−（カルボキシメチルカルバモイル）エチル
メチルスルフアイド（化合物３）の合成
水酸化ナトリウム8.5ｇ及び水100mlにグリシン
7.51ｇを溶解し、氷冷下、β−メチルメルカプト
プロピオニルクロライド13.9ｇを滴下する。同温
度で１時間撹拌する。反応液を塩酸酸性にした
後、酢酸エチルで抽出する。酢酸エチル層を水洗
し、芒硝脱水後、濃縮する。残渣をクロロホルム
より再結晶して２−（カルボキシメチルカルバモ
イル）エチルメチルスルフアイド（化合物３）
16.5ｇ（収率93.2％）を得る。
mp 97−98℃
実施例 ５
実施例４と同様の操作により、後記表に示す
化合物８、11、12、13、14及び15を合成した。
実施例 ６
２−（４−アセチルフエニルカルバモイル）エ
チルメチルスルフアイド（化合物５）の合成
ジメチルホルムアミド20mlに４−アセチルアニ
リン13.5ｇ及びトリエチルアミン15.2ｇを溶解
し、氷冷下β−メチルメルカプトプロピオニルク
ロライド13.9ｇを滴下する。滴下後室温で２時間
撹拌する。反応液を濃縮し、残渣を酢酸エチルで
抽出し、酢酸エチル層を水洗し、芒硝脱水後、濃
縮する。残渣をアセトニトリルより再結晶して、
２−（４−アセチルフエニルカルバモイル）エチ
ルメチルスルフアイド（化合物５）21.8ｇ（収率
92.0％）を得る。
mp 107℃
実施例 ７
実施例６と同様の操作により、後記表に示す
化合物６、７、９及び10を合成した。
参考例 １
ジメチル−２−シクロヘキシルカルバモイルエ
チルスルホニウム ｐ−トルエンスルホネート
の合成
２−シクロヘキシルカルバモイルエチルメチル
スルフアイド2.01ｇをメチレンクロライド30mlに
溶解後、これにｐ−トルエンスルホン酸メチル
5.58ｇを加えて室温で48時間撹拌する。反応液に
エーテルを加え不溶部を取し、エタノール−エ
ーテルより再結晶して、ジメチル−２−シクロヘ
キシルカルバモイルエチルスルホニウムｐ−トル
エンスルホネート3.68ｇ（収率94.8％）を得る。
mp 187−188℃
上記各実施例で得られた化合物（化合物１−
15）の構造と共に、各例における収率（％）並び
に各化合物のmp（℃）と元素分析値又はbp（℃）
と該磁気共鳴スペクトル（NMR）分析結果（δ
値、ppm）を下記表に示す。尚表中元素分析
値における（ ）を付して示した数値は計算値
（％）を、また（ ）を付さないで示した数値は
実測値（％）を示すものとする。またNMRは
DMSO−d6中、TMSを内部標準物質として測定
した値である。[Formula] (R 4 represents a lower alkyl group, a halogen atom or a hydroxyl group), and when R 2 is a lower alkyl group, it represents a phenyl group. Further R 2
and R 3 may be bonded to each other to form a pentamethylene chain, and may form a heterocyclic group together with the nitrogen atom to which they are bonded. In the above general formula (), the lower alkyl group represented by R 1 , R 2 , R 3 and R 4 is an alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl. ,
Examples include pentyl and hexyl groups. The lower acyl group constituting the lower acylphenyl group represented by R 3 in the general formula () includes acyl groups having 2 to 6 carbon atoms, such as acetyl, propionyl, butyryl, pivaloyl, caproyl groups, etc.
Examples of the lower alkoxycarbonylmethylcarbamoyl group constituting the lower alkoxycarbonylmethylcarbamoyl phenyl group include alkoxycarbonylmethylcarbamoyl groups having 4 to 9 carbon atoms, such as methoxycarbonylmethylcarbamoyl, ethoxycarbonylmethylcarbamoyl, propyloxycarbonylmethylcarbamoyl, isopropyloxy Examples include carbonylmethylcarbamoyl, butoxycarbonylmethylcarbamoyl, t-butoxycarbamoyl, hexyloxycarbonylmethylcarbamoyl, and the like. R4
The halogen atoms represented by include fluorine, chlorine,
Examples include bromine and iodine atoms. Furthermore, R 2 and R 3 in the above general formula () can be bonded to each other to form a pentamethylene chain. The sulfide compound represented by the above general formula () of the present invention can be easily derived into a sulfonium compound represented by the general formula () and having an antiallergic effect, for example, according to the method shown in the following reaction formula (A). , is useful as a raw material for the synthesis of pharmaceuticals having such anti-allergic effects. Reaction formula (A) [In each formula, R 1 , R 2 and R 3 are the same as above. R 6 represents a lower alkyl group and Y represents an acid residue. ] The reaction shown in the above reaction formula (A) is carried out in a solvent or without a solvent at a temperature of about -30 to 150°C, preferably 0 to 100°C, for about 0.5 to 72 hours.
Solvents include alcohols such as methanol, ethanol, and propanol; polar solvents such as acetonitrile, nitromethane, dimethylformamide, and dimethyl sulfoxide; halogenated hydrocarbons such as methylene chloride and chloroform; benzene,
Aromatic hydrocarbons such as toluene and xylene; ethers such as ethyl ether and propyl ether;
In addition, acetone, petroleum ether, ethyl acetate, water, a mixed solvent of these solvents, etc. can be used. The reaction can be carried out in a closed container if necessary. Further, the compound represented by the general formula () is usually used in an excess amount, preferably about 1 to 4
Used in twice the molar amount. Details of the synthesis of the sulfonium compound represented by the general formula () shown in the above reaction formula (A) are as shown in the Reference Examples below. The production of the compound of the present invention will be explained in detail below. The compound of the present invention can be produced by various methods, for example, easily produced by the method shown in Reaction Formula (B) below. Reaction formula (B) [In each formula, R 1 , R 2 and R 3 are the same as above. ] The method shown in the above reaction formula (B) is based on the general formula ()
This method utilizes the usual amide bond formation reaction between a carboxylic acid represented by the formula () and an amine represented by the general formula (). In the above method, instead of the carboxylic acid of the general formula (), a compound whose carboxyl group is activated may be used, and in place of the amine of the general formula (), a compound whose amino group is activated may also be used. In the amide bond-forming reaction using each of these raw material compounds, the same reaction conditions, operations, etc. as in known amide bond-forming reactions can be employed. More specifically, this reaction can be easily carried out according to any of the following methods. (a) Carboxylic acid halide method: In other words, a carboxylic acid halide compound of the general formula () is combined with the general formula ().
(b) Dicyclohexylcarbodiimide method; that is, a method of reacting a carboxylic acid of general formula () with dicyclohexylcarbodiimide and an amine of general formula () (c) Carbonyldiimidazole method; that is, a method of reacting a carboxylic acid of general formula () with an amine of general formula () A method in which a carboxylic acid is reacted with carbonyldiimidazole, and then the product is reacted with an amine of the general formula (). After converting it into a carboxylic acid anhydride, it is given the general formula ()
(e) Carboxylic acid ester method: In other words, the ester obtained by reacting the carboxylic acid of the general formula () with, for example, a lower alcohol, is reacted with the amine of the general formula () under high temperature and high pressure. Method (f) Active ester method; that is, carboxylic acid of general formula () is converted into p-nitrophenyl ester, N
- A method in which an active ester such as a hydroxysuccinimide ester is prepared and then reacted with an amine of the general formula (). A method of reacting to form a mixed acid anhydride, which is then reacted with an amine of general formula () Among the methods (a) to (g) above, the carboxylic acid halide method shown in (a) is particularly preferred. . In the carboxylic acid halide method, the carboxylic acid halide compound of the general formula () is prepared by combining the carboxylic acid of the general formula () and a halogenating agent such as thionyl chloride, phosphorus oxychloride, phosphorus oxybromide, phosphorus pentachloride, It can be obtained by reacting phosphorus pentabromide or the like without a solvent or in an appropriate solvent. The reaction between the carboxylic acid halide and the amine of the general formula () is preferably carried out using a basic compound such as an alkali metal such as sodium or potassium, a hydride thereof, a hydroxide thereof or a carbonate thereof, or pyridine, The reaction is carried out in the presence of morpholine, piperidine, piperazine, triethylamine, etc., without a solvent or in a solvent, at a temperature of about 0 to 200°C, preferably about 0 to 100°C, for about 0.1 to 24 hours.
The amine of general formula () may be used in an excess amount relative to the carboxylic acid halide, but it is preferably used in an amount of about 1 to 4 times the theoretical amount. Examples of solvents include halogenated hydrocarbons such as chloroform, methylene chloride, and carbon tetrachloride; ethers such as dioxane, tetrahydrofuran, diethyl ether, and isopropyl ether; polar solvents such as nitromethane, dimethylformamide, and dimethyl sulfoxide; benzene. ,toluene,
Aromatic hydrocarbons such as xylene; esters such as methyl acetate and ethyl acetate; and water or a mixed solvent thereof can be advantageously used. The compound of the present invention of the general formula () obtained according to the reaction shown in the above reaction formula (B) can be obtained by a commonly used separation method such as a precipitation method, an extraction method, a recrystallization method, a distillation method, a column chromatography method, or a preparative method. It can be easily isolated and purified by thin layer chromatography or the like. The present invention will be explained in more detail below by giving examples of the production of the compounds of the present invention as examples, and then giving examples of the synthesis of sulfonium compounds having antiallergic effects from the compounds of the present invention as reference examples. Example 1 Synthesis of 2-cyclohexylcarbamoylethyl methyl sulfide (compound) 21.4 g of cyclohexylamine in 100 ml of ether
and 24.0 g of triethylamine are dissolved. To this, 30.0 g of β-methylmercaptopropionyl chloride is added under ice cooling. Stir at room temperature for 2 hours and wash the reaction solution with water. After dehydrating the sodium sulfate, the ether layer was concentrated, and the residue was recrystallized from cyclohexane to obtain 42.5 g (yield: 97.7%) of 2-cyclohexylcarbamoylethyl methyl sulfide (compound). mp93-94°C Example 2 Compound 4 shown in the table below was synthesized by the same operation as in Example 1. Example 3 Synthesis of 2-(methylphenylcarbamoyl)ethylmethylsulfide (compound 2) 10.7 g of methylaniline and 9.49 g of pyridine are dissolved in 1000 ml of benzene. To this, under ice cooling, β
- Add 13.9 g of methylcaptopropionyl chloride. Stir at room temperature for 1 hour, and wash the reaction solution with water. After dehydrating the sodium sulfate, the benzene layer was concentrated and the residue was distilled under reduced pressure to obtain 2-(methylphenylcarbamoyl).
Ethyl methyl sulfide (compound 2) 19.9g
(yield 95.2%). bp149-150℃/2mmHg Example 4 Synthesis of 2-(carboxymethylcarbamoyl)ethylmethylsulfide (compound 3) Glycine in 8.5g of sodium hydroxide and 100ml of water
7.51 g was dissolved, and 13.9 g of β-methylmercaptopropionyl chloride was added dropwise under ice cooling. Stir at the same temperature for 1 hour. The reaction solution was made acidic with hydrochloric acid, and then extracted with ethyl acetate. The ethyl acetate layer is washed with water, dehydrated with sodium sulfate, and then concentrated. The residue was recrystallized from chloroform to give 2-(carboxymethylcarbamoyl)ethylmethylsulfide (compound 3).
Obtain 16.5 g (93.2% yield). mp 97-98°C Example 5 Compounds 8, 11, 12, 13, 14 and 15 shown in the table below were synthesized by the same operation as in Example 4. Example 6 Synthesis of 2-(4-acetylphenylcarbamoyl)ethylmethylsulfide (compound 5) 13.5 g of 4-acetylaniline and 15.2 g of triethylamine were dissolved in 20 ml of dimethylformamide, and β-methylmercaptopropionyl was dissolved under ice cooling. Add 13.9 g of chloride dropwise. After the addition, the mixture was stirred at room temperature for 2 hours. The reaction solution is concentrated, the residue is extracted with ethyl acetate, the ethyl acetate layer is washed with water, dried with sodium sulfate, and then concentrated. The residue was recrystallized from acetonitrile,
2-(4-acetylphenylcarbamoyl)ethylmethylsulfide (compound 5) 21.8g (yield
92.0%). mp 107°C Example 7 Compounds 6, 7, 9 and 10 shown in the table below were synthesized by the same operation as in Example 6. Reference Example 1 Synthesis of dimethyl-2-cyclohexylcarbamoylethylsulfonium p-toluenesulfonate After dissolving 2.01 g of 2-cyclohexylcarbamoylethyl methyl sulfide in 30 ml of methylene chloride, methyl p-toluenesulfonate was added to this.
Add 5.58g and stir at room temperature for 48 hours. Ether was added to the reaction solution, the insoluble portion was removed, and recrystallized from ethanol-ether to obtain 3.68 g (yield: 94.8%) of dimethyl-2-cyclohexylcarbamoylethylsulfonium p-toluenesulfonate. mp 187-188℃ Compounds obtained in each of the above Examples (Compound 1-
15) structure, as well as the yield (%) in each example, and the mp (°C) and elemental analysis value or bp (°C) of each compound.
and the magnetic resonance spectrum (NMR) analysis results (δ
values, ppm) are shown in the table below. In addition, the numerical values shown in parentheses in the elemental analysis values in the table are calculated values (%), and the numerical values shown without parentheses are actually measured values (%). Also, NMR
This is a value measured in DMSO- d6 using TMS as an internal standard.
【表】【table】
【表】【table】
Claims (1)
原子又は低級アルキル基を示す。R3はR2が水素
原子の時、シクロヘキシル基、カルボキシメチル
基、低級アシルフエニル基、テトラゾリルカルバ
モイルフエニル基、カルボキシメチルフエニル
基、３−（２−オキソ−４−ハイドロキシテトラ
ハイドロフリル）オキシフエニル基、低級アルコ
キシカルボニルメチルカルバモイルフエニル基又
は基 【式】（R4は低級アルキル基、ハ ロゲン原子又は水酸基を示す）を示し、R2が低
級アルキル基の時、フエニル基を示す。更にR2
及びR3は互いに結合してペンタメチレン鎖とな
り、之等の結合する窒素原子と共に複素環基を形
成してもよい。］で表わされるスルフアイド化合
物。[Claims] 1. General formula [In the formula, R 1 represents a lower alkyl group, and R 2 represents a hydrogen atom or a lower alkyl group. When R 2 is a hydrogen atom, R 3 is a cyclohexyl group, carboxymethyl group, lower acylphenyl group, tetrazolylcarbamoylphenyl group, carboxymethylphenyl group, 3-(2-oxo-4-hydroxytetrahydrofuryl)oxyphenyl group, lower alkoxycarbonylmethylcarbamoylphenyl group or group [Formula] (R 4 represents a lower alkyl group, halogen atom or hydroxyl group), and when R 2 is a lower alkyl group, it represents a phenyl group. Further R 2
and R 3 may be bonded to each other to form a pentamethylene chain, and may form a heterocyclic group together with the nitrogen atom to which they are bonded. ] A sulfide compound represented by.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58112459A JPS604163A (en) | 1983-06-21 | 1983-06-21 | Sulfide compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58112459A JPS604163A (en) | 1983-06-21 | 1983-06-21 | Sulfide compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS604163A JPS604163A (en) | 1985-01-10 |
| JPH0427977B2 true JPH0427977B2 (en) | 1992-05-13 |
Family
ID=14587161
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58112459A Granted JPS604163A (en) | 1983-06-21 | 1983-06-21 | Sulfide compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS604163A (en) |
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|---|---|---|---|---|
| EP2998125A1 (en) | 2014-09-18 | 2016-03-23 | Lintec Corporation | Printing sheet and method of manufacturing same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4839467B2 (en) * | 2008-05-13 | 2011-12-21 | 三井金属アクト株式会社 | Automotive door |
| CN108440358B (en) * | 2018-04-10 | 2020-10-09 | 重庆柳江医药科技有限公司 | Preparation method of suplatast tosilate and intermediate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1921841A1 (en) * | 1968-05-06 | 1969-11-20 | Ciba Geigy | Pest repellants |
| JPS5037651A (en) * | 1973-08-06 | 1975-04-08 | ||
| JPS5463044A (en) * | 1977-09-29 | 1979-05-21 | Reckitt & Colmann Prod Ltd | Organic compound |
| JPS5511503A (en) * | 1978-06-05 | 1980-01-26 | Sankyo Co Ltd | Condensed heterocyclic compound |
| JPS5630411A (en) * | 1979-08-21 | 1981-03-27 | Nitto Chem Ind Co Ltd | Preparation of acrylamide polymer |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2998125A1 (en) | 2014-09-18 | 2016-03-23 | Lintec Corporation | Printing sheet and method of manufacturing same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS604163A (en) | 1985-01-10 |
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