JP2004196730A - Novel N-sulfenylpyrrole compound and method for producing the same - Google Patents
Novel N-sulfenylpyrrole compound and method for producing the same Download PDFInfo
- Publication number
- JP2004196730A JP2004196730A JP2002369104A JP2002369104A JP2004196730A JP 2004196730 A JP2004196730 A JP 2004196730A JP 2002369104 A JP2002369104 A JP 2002369104A JP 2002369104 A JP2002369104 A JP 2002369104A JP 2004196730 A JP2004196730 A JP 2004196730A
- Authority
- JP
- Japan
- Prior art keywords
- carbon atoms
- group
- compound
- sulfenylpyrrole
- producing
- 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
- 150000001875 compounds Chemical class 0.000 title claims abstract description 61
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 64
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 26
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 16
- 125000003118 aryl group Chemical group 0.000 claims abstract description 16
- 125000005843 halogen group Chemical group 0.000 claims abstract description 16
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims abstract description 14
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 14
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 12
- -1 sulfenamide compound Chemical class 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims 1
- 238000010586 diagram Methods 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 6
- 229910052794 bromium Inorganic materials 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 4
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 4
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 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 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 4
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 4
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- DWHWPWKPSDLMNS-UHFFFAOYSA-N ethyl 2-aminosulfanylbenzoate Chemical compound CCOC(=O)C1=CC=CC=C1SN DWHWPWKPSDLMNS-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 125000004744 butyloxycarbonyl group Chemical group 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000000417 fungicide Substances 0.000 description 2
- 239000004009 herbicide Substances 0.000 description 2
- 125000005935 hexyloxycarbonyl group Chemical group 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 125000005929 isobutyloxycarbonyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])OC(*)=O 0.000 description 2
- 125000005928 isopropyloxycarbonyl group Chemical group [H]C([H])([H])C([H])(OC(*)=O)C([H])([H])[H] 0.000 description 2
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000001148 pentyloxycarbonyl group Chemical group 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 125000004742 propyloxycarbonyl group Chemical group 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- 125000005023 xylyl group Chemical group 0.000 description 2
- 0 *OC(CC1)OC1O Chemical compound *OC(CC1)OC1O 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- LFDGRWDETVOGDT-UHFFFAOYSA-N 1h-pyrrole;hydrochloride Chemical compound Cl.C=1C=CNC=1 LFDGRWDETVOGDT-UHFFFAOYSA-N 0.000 description 1
- GFISDBXSWQMOND-UHFFFAOYSA-N 2,5-dimethoxyoxolane Chemical compound COC1CCC(OC)O1 GFISDBXSWQMOND-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- DQPBABKTKYNPMH-UHFFFAOYSA-N amino hydrogen sulfate Chemical compound NOS(O)(=O)=O DQPBABKTKYNPMH-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000012156 elution solvent Substances 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- GEUILTLVJDCUJF-UHFFFAOYSA-N methyl 2-aminosulfanylbenzoate Chemical compound COC(=O)C1=CC=CC=C1SN GEUILTLVJDCUJF-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 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
- LOVVSIULYJABJF-UHFFFAOYSA-N s-(2-nitrophenyl)thiohydroxylamine Chemical compound NSC1=CC=CC=C1[N+]([O-])=O LOVVSIULYJABJF-UHFFFAOYSA-N 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical class [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 1
- FWMUJAIKEJWSSY-UHFFFAOYSA-N sulfur dichloride Chemical compound ClSCl FWMUJAIKEJWSSY-UHFFFAOYSA-N 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 229940068492 thiosalicylate Drugs 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Pyrrole Compounds (AREA)
Abstract
【課題】新規なＮ−スルフェニルピロール化合物及びその新規な製造方法の提供。
【解決手段】下記一般式（Ｂ）で表されるＮ−スルフェニルピロール化合物及びその製造方法。
【化１】
（式中、Ｒ２〜Ｒ６は水素原子、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシル基、炭素数２〜７のアルコキシカルボニル基、炭素数６〜１２の芳香族基、ハロゲン原子、ニトロ基、またはシアノ基のいずれかを示す。）
【選択図】なしA novel N-sulfenylpyrrole compound and a novel method for producing the same are provided.
An N-sulfenylpyrrole compound represented by the following general formula (B) and a method for producing the same.
Embedded image
(Wherein, R 2 to R 6 are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxyl group having 1 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, an aromatic group having 6 to 12 carbon atoms) , A halogen atom, a nitro group, or a cyano group.)
[Selection diagram] None
Description
【０００１】
【発明の属する技術分野】
本発明は、新規なＮ−スルフェニルピロール化合物、およびその製造方法に関するものである。さらに詳しくは、新規なＮ−スルフェニルピロール化合物を、スルフェンアミド化合物と2,5-ジアルコキシテトラヒドロフラン化合物を加熱することにより、効率よく製造する方法に関するものである。
【０００２】
【従来の技術】
分子内に窒素−イオウ結合を有するスルフェンアミド化合物は、種々の機能性を持つことが報告されている（非特許文献１）。
たとえば、ゴムの加硫化剤（特許文献１，２）、発芽前処理用除草剤（特許文献３）、殺菌剤（特許文献４）等が知られている。特に、含窒素複素環化合物の窒素上にチオ置換基を有する場合は、殺菌作用を有する化合物として有効であるとされている（特許文献５）。
【０００３】
従来、Ｎ−スルフェニルピロール化合物を製造するには、ピロールとＮ−スルフェニルフタルイミド化合物やＮ−スルフェニルスクシンイミド化合物を塩基性条件下で反応させる方法が行われてきた（非特許文献２）。しかしこの方法においては、５０％水酸化カリウム水溶液中という高濃度のアルカリ性溶液を用いなければならなかった。また、塩化スルフェニル化合物とピロールをカリウムｔ−ブトキシド存在下反応させる製造方法も報告されているが（非特許文献３），出発原料となる塩化スルフェニル化合物は、チオール類またはジスルフィド類に対して、塩素や臭素を反応させるという方法を用いなければ製造できない化合物である。塩素や臭素は有毒な化合物であり、取り扱い上の危険性が高く、反応方法としては、好ましいものではないという問題があった。
【０００４】
【特許文献１】特開昭６４−４８８３１号公報
【特許文献２】米国特許 第２８６６７７７号（１９５５）
【特許文献３】特開昭５３−３１６４３号公報
【特許文献４】特開昭５５−５１０５３号公報
【特許文献５】特開昭５０−２９７４９号公報
【非特許文献１】L. Craine and M. Raban, Chem. Rev., 89, 689-712 (1989).
【非特許文献２】H. M. Gilow, Tetrahedron Lett., 29, 4689-4692 (1986).
【非特許文献３】R. Silvestri, et al., Synth. Commun., 24, 2685-2695 (1994).
【０００５】
【発明が解決しようとする課題】
本発明の課題は、新規なＮ−スルフェニルピロール化合物を提供することである。また、Ｎ−スルフェニルピロール化合物を製造するに際し、通常の方法である強塩基反応条件下で反応を行うこと、又、出発原料製造に塩素や臭素を用いるという条件を用いることなく、工業的に有利な新規な製造方法を提供することである。
【０００６】
【課題を解決するための手段】
本発明者らは、Ｎ−スルフェニルピロール化合物の製造方法について鋭意研究を重ねた結果、スルフェンアミド化合物と2,5-ジアルコキシテトラヒドロフラン化合物を反応をさせれば、Ｎ−チオ置換複素環化合物であるＮ−スルフェニルピロール化合物が収率よく確実に得られることを見い出し、この知見に基づいて本発明を完成するに至った。
【０００７】
すなわち、本発明によれば、以下の発明が提供される。
（１）下記一般式（Ａ）で表されるＮ−スルフェニルピロール化合物。
【化５】
【０００８】
（２）下記一般式（Ｂ）で表されるＮ−スルフェニルピロール化合物を製造する方法において、下記一般式（Ｃ）で表されるスルフェンアミド化合物に、下記一般式（Ｄ）で表される2,5-ジアルコキシテトラヒドロフラン化合物を反応させることを特徴とするＮ−スルフェニルピロール化合物の製造方法。
【化６】
【化７】
【化８】
【０００９】
【発明実施の形態】
本発明の目的化合物であるＮ−スルフェニルピロール化合物は、以下の一般式（Ａ）により示される化合物である。
【化９】
【００１０】
前記化合物（Ａ）の置換基は以下の通りである。
Ｒ１は、炭素数１〜６のアルキル基を示す。アルキル基の具体例としては、メチル、エチル、プロピル、イソプロピル、ブチル、t-ブチル、イソブチル、ペンチル、イソペンチル、ヘキシル、イソヘキシル、シクロプロピル、シクロブチル、シクロペンチル、シクロヘキシル基等が挙げられる。
Ｒ２〜Ｒ５は水素原子、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシル基、炭素数２〜７のアルコキシカルボニル基、炭素数６〜１２の芳香族基、ハロゲン原子、ニトロ基、またはシアノ基のいずれかを示す。
この場合の炭素数１〜６のアルキル基の具体例としては、メチル、エチル、プロピル、イソプロピル、ブチル、t-ブチル、イソブチル、ペンチル、イソペンチル、ヘキシル、イソヘキシル、シクロプロピル、シクロブチル、シクロペンチル、シクロヘキシル基等が挙げられる。
また、炭素数１〜６のアルコキシル基の具体例としては、メトキシ、エトキシ、プロポキシ、イソプロポキシ、シクロプロポキシ、ブトキシ、イソブトキシ、t-ブトキシ、ペンチロキシ、ヘキシロキシ、シクロヘキシロキシル基等が挙げられる。
炭素数２〜７のアルコキシカルボニル基の具体例としては、メトキシカルボニル、エトキシカルボニル、プロポキシカルボニル、イソプロポキシカルボニル、シクロプロポキシカルボニル、ブトキシカルボニル、イソブトキシカルボニル、t-ブトキシカルボニル、ペンチロキシカルボニル、ヘキシロキシカルボニル、シクロヘキシロキシカルボニル基等が挙げられる。
炭素数６〜１２の芳香族基の具体例としては、フェニル基、トリル基、キシリル基、アニシル基、ナフチル基等が挙げられ、これらの芳香族基にはアルキル基、アルコキシル基、ハロゲン原子、ニトロ基、またはシアノ基等の置換基を有していてもよい。
ハロゲン原子の具体例としては、塩素、フッ素、ヨウ素及び臭素が挙げられる。
【００１１】
下記一般式（Ｂ）で表されるＮ−スルフェニルピロール化合物は、下記一般式（Ｃ）で表されるスルフェンアミド化合物に対し、下記一般式（Ｄ）で表される2,5-ジアルコキシテトラヒドロフラン化合物を反応させることいより製造される。
【化１０】
【化１１】
【化１２】
前記化合物（Ｂ）、（Ｃ）の置換基は以下の通りである。
Ｒ２〜Ｒ６は水素原子、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシル基、炭素数２〜７のアルコキシカルボニル基、炭素数６〜１２の芳香族基、ハロゲン原子、ニトロ基、またはシアノ基のいずれかを示す。
この場合の炭素数１〜６のアルキル基の具体例としては、メチル、エチル、プロピル、イソプロピル、ブチル、t-ブチル、イソブチル、ペンチル、イソペンチル、ヘキシル、イソヘキシル、シクロプロピル、シクロブチル、シクロペンチル、シクロヘキシル基等が挙げられる。
また、炭素数１〜６のアルコキシル基の具体例としては、メトキシ、エトキシ、プロポキシ、イソプロポキシ、シクロプロポキシ、ブトキシ、イソブトキシ、t-ブトキシ、ペンチロキシ、ヘキシロキシ、シクロヘキシロキシル基等が挙げられる。
炭素数２〜７のアルコキシカルボニル基の具体例としては、メトキシカルボニル、エトキシカルボニル、プロポキシカルボニル、イソプロポキシカルボニル、シクロプロポキシカルボニル、ブトキシカルボニル、イソブトキシカルボニル、t-ブトキシカルボニル、ペンチロキシカルボニル、ヘキシロキシカルボニル、シクロヘキシロキシカルボニル基等が挙げられる。
炭素数６〜１２の芳香族基の具体例としては、フェニル基、トリル基、キシリル基、アニシル基、ナフチル基等が挙げられ、これらの芳香族基にはアルキル基、アルコキシル基、ハロゲン原子、ニトロ基、またはシアノ基等の置換基を有していてもよい。
ハロゲン原子の具体例としては、塩素、フッ素、ヨウ素及び臭素が挙げられる。
また、前記化合物（Ｄ）の置換基であるＲ７、Ｒ８は、炭素数１〜６のアルキル基を示す。アルキル基の具体例としては、メチル、エチル、プロピル、イソプロピル、ブチル、t-ブチル、イソブチル、ペンチル、イソペンチル、ヘキシル、イソヘキシル、シクロプロピル、シクロブチル、シクロペンチル、シクロヘキシル基等が挙げられる。
前記化合物（Ｃ）、（Ｄ）は公知物質であり、（Ｃ）はチオサリチル酸エステル化合物から、（Ｄ）はジアルコキシジヒドロフラン化合物から製造することができる。
【００１２】
本発明におけるＮ−スルフェニルピロール化合物の製造は、酸の存在下実施される。この場合、酸としては、ベンゼンスルホン酸、p-トルエンスルホン酸、安息香酸、酢酸、プロピオン酸等が使用される。
【００１３】
前記のＮ−スルフェニルピロール化合物の製造方法は、好ましくは反応溶媒の存在下で実施される。
この場合の反応溶媒は、ベンゼン、トルエン、キシレン、クロロベンゼン、ジクロロベンゼン、アニソール等の無極性有機溶媒中で行われる。また、これらの溶媒は単独または混合溶媒の形で使用される。
【００１４】
前記製造方法における温度は５０℃〜１５０℃付近の温度で行うことができるが、あまり低温すぎると反応時間が遅くなり、高すぎると異常な分解反応や副反応が多くなるので、８０℃〜１２０℃の範囲で実施するのが好ましい。
反応時間は反応温度により左右され、一概に定めることはできないが、通常は２〜１０時間で十分である。
【００１５】
前記一般式（Ｃ）で表されるスルフェンアミド化合物の製造方法は、次の通りである。
チオール化合物にヒドロキシルアミン−Ｏ−スルホン酸のようなアミノ化剤を反応させて製造される。
また、前記一般式（Ｄ）で表される2,5-ジアルコキシテトラヒドロフラン化合物の製造方法は、次の通りである。
酢酸カリウム存在下、フランにアルコール類を反応させて2,5-ジアルコキシ-2,5-ジヒドロフラン化合物を製造し、これを水素で還元して製造される。
【００１６】
本発明で得られるＮ−チオ置換複素環化合物の具体例について例示すると、以下の化学式（１）から（３）で示される化合物を挙げることができる。
これらの化合物は、以下に記載する実施例により得られる化合物である。
【化１３】
【００１７】
【実施例】
次に、本発明を実施例により詳細に説明する。
本発明で得られる化合物は、この実施例に挙げた化合物に限定されるものではない。
下記実施例によって製造することにより得られるＮ−スルフェニルピロール化合物は、各種スペクトルと元素分析の結果を主要な判定基準として同定した。
また、製造された化合物（１）〜（３）は、前記で示した化合物（１）〜（３）に対応するもので、その物性値としては、核磁気共鳴スペクトル（１Ｈ−ＮＭＲ，１３Ｃ−ＮＭＲ）、赤外吸収スペクトル（ＩＲ）の順にそれぞれ記した。
【００１８】
実施例１
内容積３０ｍｌのガラス製容器中にスルフェナモイル安息香酸エチル（１００ｍｇ，０．５０７ｍｍｏｌ），2,5-ジメトキシテトラヒドロフラン（２６４ｍｇ，２．０ｍｍｏｌ）およびp-トルエンスルホン酸（１１ｍｇ，０．０６ｍｍｏｌ）をトルエン（５ｍｌ）に溶解させ、８０℃で７分間攪拌し、p-トルエンスルホン酸（１１ｍｇ，０．０６ｍｍｏｌ）を加えてさらに７分間撹拌した。ピリジンを加えてp-トルエンスルホン酸を中和した後、トルエンを減圧下留去させ、粗生成物をシリカゲルクロマトグラフィー（溶出溶媒、塩化メチレン：ヘキサン＝１：１）で精製した。この化合物はヘキサンを用いて再結晶を行うことによりさらに精製することができる。目的生成物の構造式は、化合物（１）のＮ−スルフェニルピロール化合物であることを確認した。
収率 59％；融点 52.2-53.8 ℃. 1H NMR (CDCl3) d 1.43 (3H, t, J = 7.3 Hz), 4.44 (2H, q, J = 7.3 Hz), 6.01 (1H, dd, J = 8.2, 0.9 Hz), 6.37 (2H, t, J = 2.1 Hz), 6.83 (2H, t, J = 2.1 Hz), 7.17 (1H, ddd, J = 7.9, 7.6, 0.9 Hz), 7.36 (1H, ddd, J = 8.2, 7.6, 1.5 Hz), 8.03 (1H, dd, J = 7.9, 1.5 Hz). 13C NMR (CDCl3) d 14.3, 61.8, 122.1, 123.3, 124.8, 127.8, 130.5, 133.6, 148.0, 166.9. IR (KBr) vmax 2990, 2905, 1694, 1564, 1464, 1368, 1316, 1296, 1277, 1184, 1148, 1061, 1042, 727, 606, 507 cm-1. HRMS C13H13NO2S としての計算値: 247.0667. 実測値: 247.0638.
【００１９】
実施例２
実施例１において、2-スルフェナモイル安息香酸エチルの代わりに2-スルフェナモイル安息香酸メチル（１００ｍｇ，０．５５ｍｍｏｌ）を用いて同様な操作を行い、目的生成物を得た。目的生成物の構造式は、化合物（２）のＮ−スルフェニルピロール化合物であることを確認した。
収率 79%；1H NMR (CDCl3) d 3.97 (3H, s), 6.01 (1H, dd, J = 8.5, 0.9 Hz), 6.37 (2H, t, J = 2.1 Hz), 6.83 (2H, t, J = 2.1 Hz), 7.17 (1H, ddd, J = 7.9, 7.3, 0.9 Hz), 735 (1H, ddd, J = 8.5, 7.3, 1.5 Hz), 8.01 (1H, dd, J = 7.9, 1.5 Hz). 13C NMR (CDCl3) d 52.5, 111.8, 122.1, 122.8, 124.8, 127.8, 130.4, 133.7, 148.0, 167.3. IR (KBr) vmax 2957, 1699, 1566, 1429, 1296, 1182, 1144, 1105, 1065, 1038, 961, 608, 523, 496 cm-1.
【００２０】
実施例３
実施例１において、2-スルフェナモイル安息香酸エチルの代わりに2-ニトロベンゼンスルフェンアミド（１００ｍｇ，０．５９ｍｍｏｌ）を用いて同様な操作を行い、ヘキサンから再結晶を行うことにより目的生成物を得た。目的生成物の構造式は、化合物（３）のＮ−スルフェニルピロール化合物であることを確認した。
収率 74%；1H NMR (CDCl3) d 6.01 (1H, dd, J = 8.5, 1.2 Hz), 6.41 (2H, t, J = 2.1 Hz), 6.84 (2H, t, J = 2.1 Hz), 7.30 (1H, ddd, J = 8.5, 7.3, 1.2 Hz), 7.49 (1H, ddd, J = 8.5, 7.3, 1.2 Hz), 8.30 (1H, dd, J = 8.5, 1.2 Hz). 13C NMR (CDCl3) d 112.8, 124.1, 125.5, 126.2, 127.7, 135.3, 141.8, 144.2. IR (KBr) vmax 3096, 1636, 1591, 1568, 1507, 1453, 1339, 1310, 1179, 1069, 1036, 720, 604, 505 cm-1.
【００２１】
【発明の効果】
本発明のＮ−スルフェニルピロール化合物の製造方法は、スルフェンアミド化合物と2,5-ジアルコキシテトラヒドロフラン化合物の反応により、収率よく製造することができる。これは新規な製造方法であり、強塩基や塩素、臭素を用いることなく安全にかつ容易にＮ−スルフェニルピロール化合物を製造することができ、従来のこの種の方法として用いられていた製造方法と比較して優れた方法である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a novel N-sulfenylpyrrole compound and a method for producing the same. More specifically, the present invention relates to a method for efficiently producing a novel N-sulfenylpyrrole compound by heating a sulfenamide compound and a 2,5-dialkoxytetrahydrofuran compound.
[0002]
[Prior art]
It has been reported that sulfenamide compounds having a nitrogen-sulfur bond in a molecule have various functions (Non-Patent Document 1).
For example, vulcanizing agents for rubber (Patent Documents 1 and 2), herbicides for pre-emergence treatment (Patent Document 3), fungicides (Patent Document 4) and the like are known. In particular, when a nitrogen-containing heterocyclic compound has a thio substituent on the nitrogen, it is said to be effective as a compound having a bactericidal action (Patent Document 5).
[0003]
Conventionally, in order to produce an N-sulfenylpyrrole compound, a method of reacting pyrrole with an N-sulfenylphthalimide compound or an N-sulfenylsuccinimide compound under basic conditions has been performed (Non-Patent Document 2). However, in this method, an alkaline solution having a high concentration of 50% aqueous potassium hydroxide had to be used. Further, a production method in which a pyrrole chloride compound is reacted with pyrrole in the presence of potassium t-butoxide has also been reported (Non-Patent Document 3). However, a sulfenyl chloride compound serving as a starting material is required to react with thiols or disulfides. It is a compound that cannot be produced unless a method of reacting chlorine or bromine is used. Chlorine and bromine are toxic compounds, have a high risk of handling, and have a problem that they are not preferable as a reaction method.
[0004]
[Patent Document 1] JP-A-64-48831 [Patent Document 2] U.S. Pat. No. 2,866,777 (1955)
[Patent Document 3] JP-A-53-31643 [Patent Document 4] JP-A-55-51053 [Patent Document 5] JP-A-50-29749 [Non-patent Document 1] L. Craine and M Raban, Chem. Rev., 89 , 689-712 (1989).
[Non-Patent Document 2] HM Gilow, Tetrahedron Lett., 29 , 4689-4692 (1986).
[Non-Patent Document 3] R. Silvestri, et al., Synth. Commun., 24 , 2685-2695 (1994).
[0005]
[Problems to be solved by the invention]
An object of the present invention is to provide a novel N-sulfenylpyrrole compound. Further, in producing an N-sulfenylpyrrole compound, the reaction is carried out under a strong base reaction condition, which is a usual method, and industrially without using a condition that chlorine or bromine is used for producing a starting material, It is to provide an advantageous new manufacturing method.
[0006]
[Means for Solving the Problems]
The present inventors have conducted intensive studies on a method for producing an N-sulfenylpyrrole compound. As a result, if a sulfenamide compound is reacted with a 2,5-dialkoxytetrahydrofuran compound, an N-thio-substituted heterocyclic compound is obtained. It has been found that the N-sulfenylpyrrole compound is reliably obtained with good yield, and based on this finding, the present invention has been completed.
[0007]
That is, according to the present invention, the following inventions are provided.
(1) An N-sulfenylpyrrole compound represented by the following general formula (A).
Embedded image
[0008]
(2) In a method for producing an N-sulfenylpyrrole compound represented by the following general formula (B), a sulfenamide compound represented by the following general formula (C) is represented by the following general formula (D). A method for producing an N-sulfenylpyrrole compound, comprising reacting a 2,5-dialkoxytetrahydrofuran compound.
Embedded image
Embedded image
Embedded image
[0009]
DETAILED DESCRIPTION OF THE INVENTION
The N-sulfenylpyrrole compound as the target compound of the present invention is a compound represented by the following general formula (A).
Embedded image
[0010]
The substituents of the compound (A) are as follows.
R 1 represents an alkyl group having 1 to 6 carbon atoms. Specific examples of the alkyl group include a methyl, ethyl, propyl, isopropyl, butyl, t-butyl, isobutyl, pentyl, isopentyl, hexyl, isohexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl group and the like.
R 2 to R 5 are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxyl group having 1 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, an aromatic group having 6 to 12 carbon atoms, a halogen atom, Indicates either a nitro group or a cyano group.
Specific examples of the alkyl group having 1 to 6 carbon atoms in this case include methyl, ethyl, propyl, isopropyl, butyl, t-butyl, isobutyl, pentyl, isopentyl, hexyl, isohexyl, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl groups And the like.
Specific examples of the alkoxyl group having 1 to 6 carbon atoms include methoxy, ethoxy, propoxy, isopropoxy, cyclopropoxy, butoxy, isobutoxy, t-butoxy, pentoxy, hexyloxy, cyclohexyloxyl and the like.
Specific examples of the alkoxycarbonyl group having 2 to 7 carbon atoms include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, cyclopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, t-butoxycarbonyl, pentoxycarbonyl, hexyloxy Carbonyl and cyclohexyloxycarbonyl groups.
Specific examples of the aromatic group having 6 to 12 carbon atoms include a phenyl group, a tolyl group, a xylyl group, an anisyl group, a naphthyl group, and the like. These aromatic groups include an alkyl group, an alkoxyl group, a halogen atom, It may have a substituent such as a nitro group or a cyano group.
Specific examples of the halogen atom include chlorine, fluorine, iodine and bromine.
[0011]
The N-sulfenylpyrrole compound represented by the following formula (B) is different from the sulfenamide compound represented by the following formula (C) in 2,5-diphenyl compound represented by the following formula (D). It is produced by reacting an alkoxytetrahydrofuran compound.
Embedded image
Embedded image
Embedded image
The substituents of the compounds (B) and (C) are as follows.
R 2 to R 6 are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxyl group having 1 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, an aromatic group having 6 to 12 carbon atoms, a halogen atom, Indicates either a nitro group or a cyano group.
Specific examples of the alkyl group having 1 to 6 carbon atoms in this case include methyl, ethyl, propyl, isopropyl, butyl, t-butyl, isobutyl, pentyl, isopentyl, hexyl, isohexyl, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl groups And the like.
Specific examples of the alkoxyl group having 1 to 6 carbon atoms include methoxy, ethoxy, propoxy, isopropoxy, cyclopropoxy, butoxy, isobutoxy, t-butoxy, pentoxy, hexyloxy, cyclohexyloxyl and the like.
Specific examples of the alkoxycarbonyl group having 2 to 7 carbon atoms include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, cyclopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, t-butoxycarbonyl, pentoxycarbonyl, hexyloxy Carbonyl and cyclohexyloxycarbonyl groups.
Specific examples of the aromatic group having 6 to 12 carbon atoms include a phenyl group, a tolyl group, a xylyl group, an anisyl group, a naphthyl group, and the like. These aromatic groups include an alkyl group, an alkoxyl group, a halogen atom, It may have a substituent such as a nitro group or a cyano group.
Specific examples of the halogen atom include chlorine, fluorine, iodine and bromine.
Further, R 7 and R 8 which are substituents of the compound (D) represent an alkyl group having 1 to 6 carbon atoms. Specific examples of the alkyl group include a methyl, ethyl, propyl, isopropyl, butyl, t-butyl, isobutyl, pentyl, isopentyl, hexyl, isohexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl group and the like.
The compounds (C) and (D) are known substances, and (C) can be produced from a thiosalicylate compound and (D) can be produced from a dialkoxydihydrofuran compound.
[0012]
The production of the N-sulfenylpyrrole compound in the present invention is carried out in the presence of an acid. In this case, benzenesulfonic acid, p-toluenesulfonic acid, benzoic acid, acetic acid, propionic acid and the like are used as the acid.
[0013]
The method for producing the N-sulfenylpyrrole compound is preferably carried out in the presence of a reaction solvent.
The reaction solvent in this case is performed in a nonpolar organic solvent such as benzene, toluene, xylene, chlorobenzene, dichlorobenzene, and anisole. These solvents are used alone or in the form of a mixed solvent.
[0014]
The temperature in the above-mentioned production method can be carried out at a temperature of about 50 ° C. to 150 ° C. However, if the temperature is too low, the reaction time becomes slow, and if it is too high, abnormal decomposition reactions and side reactions increase. It is preferably carried out in the range of ° C.
The reaction time depends on the reaction temperature and cannot be determined unconditionally, but usually 2 to 10 hours is sufficient.
[0015]
The method for producing the sulfenamide compound represented by the general formula (C) is as follows.
It is produced by reacting a thiol compound with an aminating agent such as hydroxylamine-O-sulfonic acid.
The method for producing the 2,5-dialkoxytetrahydrofuran compound represented by the general formula (D) is as follows.
An alcohol is reacted with furan in the presence of potassium acetate to produce a 2,5-dialkoxy-2,5-dihydrofuran compound, which is produced by reducing the compound with hydrogen.
[0016]
Illustrative examples of the N-thio-substituted heterocyclic compound obtained in the present invention include compounds represented by the following chemical formulas (1) to (3).
These compounds are compounds obtained by the examples described below.
Embedded image
[0017]
【Example】
Next, the present invention will be described in detail with reference to examples.
The compounds obtained in the present invention are not limited to the compounds listed in this example.
The N-sulfenylpyrrole compound obtained by manufacturing according to the following examples was identified based on various spectra and the results of elemental analysis as main criteria.
The produced compounds (1) to (3) correspond to the compounds (1) to (3) shown above, and their physical property values are nuclear magnetic resonance spectra ( 1 H-NMR, 13 C-NMR) and an infrared absorption spectrum (IR).
[0018]
Example 1
Ethyl sulfenamoylbenzoate (100 mg, 0.507 mmol), 2,5-dimethoxytetrahydrofuran (264 mg, 2.0 mmol) and p-toluenesulfonic acid (11 mg, 0.06 mmol) were placed in a glass container having an internal volume of 30 ml. 5 ml), stirred at 80 ° C. for 7 minutes, p-toluenesulfonic acid (11 mg, 0.06 mmol) was added, and the mixture was further stirred for 7 minutes. After adding pyridine to neutralize p-toluenesulfonic acid, toluene was distilled off under reduced pressure, and the crude product was purified by silica gel chromatography (elution solvent, methylene chloride: hexane = 1: 1). This compound can be further purified by recrystallization using hexane. The structural formula of the target product was confirmed to be the N-sulfenylpyrrole compound of compound (1).
Yield 59%; melting point 52.2-53.8 ° C. 1 H NMR (CDCl 3 ) d 1.43 (3H, t, J = 7.3 Hz), 4.44 (2H, q, J = 7.3 Hz), 6.01 (1H, dd, J = 8.2, 0.9 Hz), 6.37 (2H, t, J = 2.1 Hz), 6.83 (2H, t, J = 2.1 Hz), 7.17 (1H, ddd, J = 7.9, 7.6, 0.9 Hz), 7.36 (1H , ddd, J = 8.2, 7.6 , 1.5 Hz), 8.03 (1H, dd, J = 7.9, 1.5 Hz). 13 C NMR (CDCl 3) d 14.3, 61.8, 122.1, 123.3, 124.8, 127.8, 130.5, 133.6 , 148.0, 166.9.IR (KBr) v max 2990, 2905, 1694, 1564, 1464, 1368, 1316, 1296, 1277, 1184, 1148, 1061, 1042, 727, 606, 507 cm -1 .HRMS C 13 H Calculated for 13 NO 2 S: 247.0667. Found: 247.0638.
[0019]
Example 2
The same operation as in Example 1 was carried out except that methyl 2-sulfenamoylbenzoate (100 mg, 0.55 mmol) was used instead of ethyl 2-sulfenamoylbenzoate to obtain the desired product. The structural formula of the target product was confirmed to be the N-sulfenylpyrrole compound of compound (2).
79% yield; 1 H NMR (CDCl 3) d 3.97 (3H, s), 6.01 (1H, dd, J = 8.5, 0.9 Hz), 6.37 (2H, t, J = 2.1 Hz), 6.83 (2H, t, J = 2.1 Hz), 7.17 (1H, ddd, J = 7.9, 7.3, 0.9 Hz), 735 (1H, ddd, J = 8.5, 7.3, 1.5 Hz), 8.01 (1H, dd, J = 7.9, 13 C NMR (CDCl 3 ) d 52.5, 111.8, 122.1, 122.8, 124.8, 127.8, 130.4, 133.7, 148.0, 167.3.IR (KBr) v max 2957, 1699, 1566, 1429, 1296, 1182, 1144, 1105, 1065, 1038, 961, 608, 523, 496 cm -1 .
[0020]
Example 3
In Example 1, the same operation was performed using 2-nitrobenzenesulfenamide (100 mg, 0.59 mmol) instead of ethyl 2-sulfenamoylbenzoate, and the target product was obtained by recrystallization from hexane. . The structural formula of the target product was confirmed to be the N-sulfenylpyrrole compound of compound (3).
Yield 74%; 1 H NMR (CDCl 3 ) d 6.01 (1H, dd, J = 8.5, 1.2 Hz), 6.41 (2H, t, J = 2.1 Hz), 6.84 (2H, t, J = 2.1 Hz) , 7.30 (1H, ddd, J = 8.5, 7.3, 1.2 Hz), 7.49 (1H, ddd, J = 8.5, 7.3, 1.2 Hz), 8.30 (1H, dd, J = 8.5, 1.2 Hz). 13 C NMR (CDCl 3 ) d 112.8, 124.1, 125.5, 126.2, 127.7, 135.3, 141.8, 144.2.IR (KBr) v max 3096, 1636, 1591, 1568, 1507, 1453, 1339, 1310, 1179, 1069, 1036, 720 , 604, 505 cm -1 .
[0021]
【The invention's effect】
The method for producing an N-sulfenylpyrrole compound of the present invention can be produced in good yield by reacting a sulfenamide compound with a 2,5-dialkoxytetrahydrofuran compound. This is a novel production method, in which an N-sulfenylpyrrole compound can be produced safely and easily without using a strong base, chlorine or bromine, and a production method used as a conventional method of this kind. This is an excellent method compared to.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002369104A JP4214220B2 (en) | 2002-12-20 | 2002-12-20 | Novel N-sulfenylpyrrole compound and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002369104A JP4214220B2 (en) | 2002-12-20 | 2002-12-20 | Novel N-sulfenylpyrrole compound and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2004196730A true JP2004196730A (en) | 2004-07-15 |
| JP4214220B2 JP4214220B2 (en) | 2009-01-28 |
Family
ID=32765428
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002369104A Expired - Lifetime JP4214220B2 (en) | 2002-12-20 | 2002-12-20 | Novel N-sulfenylpyrrole compound and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4214220B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006225300A (en) * | 2005-02-16 | 2006-08-31 | National Institute Of Advanced Industrial & Technology | Novel N-sulfenylpyrrole compound and method for producing the same |
| JP2006225339A (en) * | 2005-02-18 | 2006-08-31 | National Institute Of Advanced Industrial & Technology | Novel N-sulfenylpyrrole compound and method for producing the same |
| JP2007210937A (en) * | 2006-02-09 | 2007-08-23 | National Institute Of Advanced Industrial & Technology | Novel N-sulfenylbenzotriazole compound and method for producing the same |
| JP2010168316A (en) * | 2009-01-23 | 2010-08-05 | National Institute Of Advanced Industrial Science & Technology | New sulfenamide compound and method for producing the same |
-
2002
- 2002-12-20 JP JP2002369104A patent/JP4214220B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006225300A (en) * | 2005-02-16 | 2006-08-31 | National Institute Of Advanced Industrial & Technology | Novel N-sulfenylpyrrole compound and method for producing the same |
| JP2006225339A (en) * | 2005-02-18 | 2006-08-31 | National Institute Of Advanced Industrial & Technology | Novel N-sulfenylpyrrole compound and method for producing the same |
| JP2007210937A (en) * | 2006-02-09 | 2007-08-23 | National Institute Of Advanced Industrial & Technology | Novel N-sulfenylbenzotriazole compound and method for producing the same |
| JP2010168316A (en) * | 2009-01-23 | 2010-08-05 | National Institute Of Advanced Industrial Science & Technology | New sulfenamide compound and method for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4214220B2 (en) | 2009-01-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4214220B2 (en) | Novel N-sulfenylpyrrole compound and method for producing the same | |
| JP4041881B2 (en) | Novel N-thio-substituted heterocyclic compound and method for producing the same | |
| JP4639382B2 (en) | Novel N-sulfenylbenzotriazole compound and method for producing the same | |
| JP4747359B2 (en) | Novel N-sulfenylpyrrole compound and method for producing the same | |
| JP4729738B2 (en) | Novel N-sulfenylpyrrole compound and method for producing the same | |
| JP4161367B2 (en) | Process for producing 5-substituted oxazole compound and 5-substituted imidazole compound | |
| JP4635178B2 (en) | Novel N-sulfenyl substituted heterocyclic compound and method for producing the same | |
| JP4853911B2 (en) | Method for producing isothiazolopyridin-3-one compound | |
| JP4296268B2 (en) | Novel N-sulfenyl substituted heterocyclic compound and method for producing the same | |
| JP4296267B2 (en) | Novel N-sulfenyl substituted heterocyclic compound and method for producing the same | |
| JP4296266B2 (en) | Novel N-sulfenyl substituted heterocyclic compound and method for producing the same | |
| JP4002972B2 (en) | Method for producing sulfenamide compound | |
| JP4006520B2 (en) | Method for producing sulfenamide compound | |
| JP6590406B2 (en) | Novel pyrrolobenzothiazine compound and method for producing the same | |
| JP2007210938A (en) | Method for producing isothiazolopyridine compound | |
| JP4901481B2 (en) | Method for producing thiocarbamate derivative | |
| JP3896450B2 (en) | Process for producing N-substituted or N, N-disubstituted sulfenamide compounds | |
| JP4273224B2 (en) | Method for producing N-sulfenyl heterocyclic compound | |
| JP4200209B2 (en) | Process for producing 1,2-benzisothiazoline-3-one-1-oxide compound | |
| JP5370990B2 (en) | Novel sulfenamide compound and process for producing the same | |
| JP2000095751A (en) | Sulfenamide compound and its production | |
| JP4982790B2 (en) | Method for producing isothiazolopyridin-3-one compound | |
| Li et al. | Asymmetric synthesis and absolute stereochemistry of 4, 4-bis-(trifluoromethyl) imidazoline based ACAT inhibitors | |
| JP4238314B2 (en) | Novel N-sulfinyl heterocyclic compound and process for producing the same | |
| JP2007210930A (en) | Method for producing pyridinesulfenamide compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20040818 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20080507 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20080602 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20080805 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20080821 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20081007 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4214220 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| EXPY | Cancellation because of completion of term |