JPS62263159A - Pyrazole derivative and production thereof - Google Patents
Pyrazole derivative and production thereofInfo
- Publication number
- JPS62263159A JPS62263159A JP61104383A JP10438386A JPS62263159A JP S62263159 A JPS62263159 A JP S62263159A JP 61104383 A JP61104383 A JP 61104383A JP 10438386 A JP10438386 A JP 10438386A JP S62263159 A JPS62263159 A JP S62263159A
- Authority
- JP
- Japan
- Prior art keywords
- lower alkyl
- formula
- alkyl group
- hydrogen atom
- 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.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 6
- 150000003217 pyrazoles Chemical class 0.000 title claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 21
- -1 alkyl nitrite Chemical compound 0.000 claims abstract description 10
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 6
- CPZPJCBMTQJVEF-UHFFFAOYSA-N 1h-pyrazole-5-sulfonyl chloride Chemical class ClS(=O)(=O)C=1C=CNN=1 CPZPJCBMTQJVEF-UHFFFAOYSA-N 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- JVVRJMXHNUAPHW-UHFFFAOYSA-N 1h-pyrazol-5-amine Chemical class NC=1C=CNN=1 JVVRJMXHNUAPHW-UHFFFAOYSA-N 0.000 claims abstract description 4
- LZDSILRDTDCIQT-UHFFFAOYSA-N dinitrogen trioxide Chemical compound [O-][N+](=O)N=O LZDSILRDTDCIQT-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000012442 inert solvent Substances 0.000 claims abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 12
- 150000008282 halocarbons Chemical class 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 5
- CUDSBWGCGSUXDB-UHFFFAOYSA-N Dibutyl disulfide Chemical group CCCCSSCCCC CUDSBWGCGSUXDB-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 11
- 239000000203 mixture Substances 0.000 abstract description 4
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 abstract description 3
- BKCNDTDWDGQHSD-UHFFFAOYSA-N 2-(tert-butyldisulfanyl)-2-methylpropane Chemical compound CC(C)(C)SSC(C)(C)C BKCNDTDWDGQHSD-UHFFFAOYSA-N 0.000 abstract description 2
- 239000004157 Nitrosyl chloride Substances 0.000 abstract description 2
- 239000003905 agrochemical Substances 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- VPCDQGACGWYTMC-UHFFFAOYSA-N nitrosyl chloride Chemical compound ClN=O VPCDQGACGWYTMC-UHFFFAOYSA-N 0.000 abstract description 2
- 235000019392 nitrosyl chloride Nutrition 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 abstract description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract 1
- FIMJSWFMQJGVAM-UHFFFAOYSA-N chloroform;hydrate Chemical compound O.ClC(Cl)Cl FIMJSWFMQJGVAM-UHFFFAOYSA-N 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 5
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- CYZSLVXXYNYSFL-UHFFFAOYSA-N OC(=O)C=1C=NNC=1S(Cl)(=O)=O Chemical class OC(=O)C=1C=NNC=1S(Cl)(=O)=O CYZSLVXXYNYSFL-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000012954 diazonium Substances 0.000 description 2
- 150000001989 diazonium salts Chemical class 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000005183 environmental health Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
皮ユ上至１［分団
本発明は、４−カルボキシ−５−ターシャリ−ブチルチ
オピラゾール誘導体および、４−カルボキシ−５−クロ
ロスルホニルピラゾール誘導体の製造法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing 4-carboxy-5-tert-butylthiopyrazole derivatives and 4-carboxy-5-chlorosulfonylpyrazole derivatives.
４−カルボキシ−５−ターシャリ−ブチルチオピラゾー
ル誘導体および、４−カルボキシ−５−クロロスルホニ
ルピラゾール誘導体は医薬、農薬等の中間体として有用
である。例えば、特開昭５９−２１９２８１号公報、ヨ
ーロッパ特許公開８７７８０号公報等に記載の除草剤の
中間体として有用である。4-Carboxy-5-tert-butylthiopyrazole derivatives and 4-carboxy-5-chlorosulfonylpyrazole derivatives are useful as intermediates for pharmaceuticals, agricultural chemicals, and the like. For example, it is useful as an intermediate for herbicides described in JP-A-59-219281, European Patent Publication No. 87780, and the like.
ｌ來立技歪
特開昭５９−２１９２８１号公報およびジャーナルオブ
ヘテロサイクリソクケミストリー〇、ＩＩｅｔｅｒｏｃ
ｙｃｌｉｃｃｈｅｍ、 ＋ ２１巻、 １０１７頁（１
９８４年）には５−アミノピラゾール誘導体を原料とす
る５−クロロスルホニルピラゾール誘導体の合成法が記
載されている。Japanese Patent Publication No. 59-219281 and Journal of Heterocyclic Chemistry〇, II eteroc
yclicchem, + vol. 21, p. 1017 (1
(984) describes a method for synthesizing 5-chlorosulfonylpyrazole derivatives using 5-aminopyrazole derivatives as raw materials.
すなわち、５−アミノピラゾール誘導体を亜硝酸ナトリ
ウム等でジアゾニウム塩とし、銅系触媒の存在下、酢酸
中、過剰の二酸化イオウとの反応により５−クロロスル
ホニルピラゾール誘導体を得ている。That is, a 5-aminopyrazole derivative is made into a diazonium salt with sodium nitrite or the like, and a 5-chlorosulfonylpyrazole derivative is obtained by reaction with excess sulfur dioxide in acetic acid in the presence of a copper catalyst.
ｌｈ
Ｈ３
が”ンしようと るロ 占
前記の従来技術では、問題点として、以下のような点が
あげられる。The following problems can be raised with the above-mentioned conventional technology.
■ 触媒に環境衛生上問題を有する銅のような重金属を
用いる必要カーある。■ There is a need to use heavy metals such as copper in catalysts, which pose environmental health problems.
■ スルホニルクロライドを得る、ジアゾニウム塩の分
解工程が必らずしも高収率でない。■ The decomposition step of diazonium salt to obtain sulfonyl chloride does not necessarily have a high yield.
■ 分解工程で多量の酢酸、二酸化イオウを特徴とする
特に上記の■、■において、廃水中に銅あるいは多量の
酢酸が混入しその為の廃水処理が必要になることから工
業的プロセスとしては不充分なものであった。■ The decomposition process is characterized by large amounts of acetic acid and sulfur dioxide. Particularly in the above steps (2) and (3), copper or large amounts of acetic acid may be mixed into the wastewater, which requires wastewater treatment, making it unsuitable as an industrial process. It was sufficient.
Ｉ 占を ンするための および 日の、蝿。I fly for divination and day.
本発明者らは、一般式（■）：
Ｒ１
〔式中Ｒ１は、水素原子または低級アルキル基を示し、
Ｒ１は水素原子または低級アルキ゛ル基を示し、Ｒ３は
低級アルキル基を示す。〕で表わされるピラゾール誘導
体を、ジターシャリ−ブチルジスルフィドの存在下、亜
硝酸アルキル、三二酸化窒素、或いは一酸化窒素等の亜
硝酸供給源と反応させることにより一般式（Ｉ）：（式
中Ｒ＋、Ｒ２およびＲ３は前記同じ意味を示す。〕
で表わされるピラゾール誘導体が得られることを見い出
し、更に一般式（１）で表わされるピラゾール誘導体を
、水または水を含む酢酸もしくはハロゲン化炭化水素等
の不活性溶媒の存在下、塩素と反応させることにより、
一般式（■）−Ｒ′
〔式中Ｒ’、Ｒ”およびＲ３は前記同じ意味を示す。〕
で表わされるクロロスルホニルピラゾール誘導体が得ら
れることを見い出した。（次式参照）Ｒ′
（Ｉｆ）
（Ｉ［Ｉ）
化合物（１）は、化合物（ＩＩ）および化合物（ｎ）に
対し、１〜１０当因、好ましくは２〜５当量のジターシ
ャリ−ブチルジスルフィドを混合し、次いで５０°〜１
５０℃、好ましくは、９０〜１１０℃の反応温度にて、
化合物（ｎ）に対し、０．８〜２．０当量、好ましくは
１〜１．５当量の前記亜硝酸供給源を加え、更に、同温
度にて１５分から２時間攪拌することにより合成される
。The present inventors expressed the general formula (■): R1 [wherein R1 represents a hydrogen atom or a lower alkyl group,
R1 represents a hydrogen atom or a lower alkyl group, and R3 represents a lower alkyl group. ] by reacting the pyrazole derivative represented by the general formula (I): (in the formula R+, R2 and R3 have the same meanings as above.] It has been found that a pyrazole derivative represented by the formula (1) can be obtained, and further, the pyrazole derivative represented by the general formula (1) is treated with water or an acetic acid containing water or an inorganic hydrocarbon such as a halogenated hydrocarbon. By reacting with chlorine in the presence of an active solvent,
It has been found that a chlorosulfonyl pyrazole derivative represented by the general formula (■)-R' [in the formula, R', R'' and R3 have the same meanings as above] can be obtained. (See the following formula) R' (If ) (I [I) Compound (1) is prepared by mixing 1 to 10 equivalents, preferably 2 to 5 equivalents of ditertiary-butyl disulfide to compound (II) and compound (n), and then heating the mixture at 50° to 1
At a reaction temperature of 50°C, preferably 90-110°C,
Synthesized by adding 0.8 to 2.0 equivalents, preferably 1 to 1.5 equivalents of the above nitrous acid source to compound (n), and further stirring at the same temperature for 15 minutes to 2 hours. .
亜硝酸供給源としては、亜硝酸アルキル、三二酸化窒素
、−酸化窒素または塩化ニトロシル等を用いることがで
き、この中ではイソアミルナイトライド、エチルナイト
ライド、ブチルナイトライド等の亜硝酸アルキルが好ま
しい。As the nitrite source, alkyl nitrite, nitrogen sesquioxide, -nitrogen oxide, nitrosyl chloride, etc. can be used, and among these, alkyl nitrite such as isoamyl nitride, ethyl nitride, and butyl nitride are preferred.
また、同反応は、ジターシャリ−ブチルジスルフィドと
、前記亜硝酸供給源との混合物に、化合物（ＩＩ）を加
えることによっても実施される。化合物（，１）は、反
応混合物を減圧蒸留することにより精製することができ
るが、反応混合物を減圧濃縮するだけで、次の反応に用
いることができる。The same reaction can also be carried out by adding compound (II) to a mixture of di-tert-butyl disulfide and the nitrous acid source. Compound (, 1) can be purified by distilling the reaction mixture under reduced pressure, but it can be used in the next reaction simply by concentrating the reaction mixture under reduced pressure.
化合物（Ｉ［［）を得る反応は、化合物（目を、水、希
塩酸、水−酢酸、水−クロロホルムあるいは、水−塩化
メチレン等の不活性溶媒系に溶解あるいはけん濁し、化
合物（１）に対し、３から６当量、好ましくは、３から
４当量の塩素を、−２０〜４０℃、好ましくは、０〜２
０℃にて加えることにより実施される。化合物（ＤＩ）
は、反応混合物を氷水に注ぎ、エーテル、ベンゼン、ク
ロロホルムあるいは、塩化メチレン等の不活性溶媒を用
いて抽出することにより単離することができ、必要な場
合は、更に減圧蒸留により精製することができる。The reaction to obtain compound (I [ 3 to 6 equivalents, preferably 3 to 4 equivalents of chlorine to -20 to 40°C, preferably 0 to 2
This is done by adding at 0°C. Compound (DI)
can be isolated by pouring the reaction mixture into ice water and extracting with an inert solvent such as ether, benzene, chloroform, or methylene chloride, and if necessary, can be further purified by vacuum distillation. can.
１施■
以下に本発明の具体的実施例を示すが、本発明は以下の
実施例に限定されるものではない。EXAMPLE 1 Specific examples of the present invention are shown below, but the present invention is not limited to the following examples.
去ｌ桝土
５−ドブチルチオ−４−エトキシカルボニル−１−メチ
ルピラゾールの合成
５−アミノ−４−エトキシカルボニル−１−メチルピラ
ゾール３．９ｇ及びジターシャリ−ブチルジスルフィド
１２．７ ｇの混合物に、９０−１００℃において、適
度な発泡を保ちつつ、注意深く、イソアミルナイトライ
ド３．２ｇを滴下した。滴下後、９０℃にて、１５分間
攪拌した後、減圧濃縮すると、粗製の目的物４．６ｇを
油状物として得た。Synthesis of 5-dobutylthio-4-ethoxycarbonyl-1-methylpyrazole 90- At 100° C., 3.2 g of isoamyl nitride was carefully added dropwise while maintaining proper foaming. After the dropwise addition, the mixture was stirred at 90° C. for 15 minutes and concentrated under reduced pressure to obtain 4.6 g of the crude target product as an oil.
（沸点、９７℃／ ０．０７ ｍｓＨｇ）１旌±１(Boiling point, 97℃/0.07msHg) 1±1
Claims (3)
、Ｒ＾２は水素原子または低級アルキル基を示し、Ｒ＾
３は低級アルキル基を示す。〕で表わされるピラゾール
誘導体。(1) General formula (I): ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R^1 represents a hydrogen atom or a lower alkyl group, and R^2 represents a hydrogen atom or a lower alkyl group. Show, R^
3 represents a lower alkyl group. ] A pyrazole derivative represented by
、Ｒ＾２は水素原子または低級アルキル基を示し、Ｒ＾
３は低級アルキル基を示す。〕で表わされるアミノピラ
ゾール誘導体をジターシャリーブチルジスルフィドの存
在下、亜硝酸アルキル、三二酸化窒素、または一酸化窒
素等の亜硝酸供給源と反応させることを特徴とする一般
式：▲数式、化学式、表等があります▼（ I ） 〔式中Ｒ＾１は、水素原子または低級アルキル基を示し
、Ｒ＾２は水素原子または低級アルキル基を示し、Ｒ＾
３は低級アルキル基を示す。〕で表わされるピラゾール
誘導体の製造法。(2) General formula (II): ▲Mathematical formulas, chemical formulas, tables, etc.▼(II) [In the formula, R^1 represents a hydrogen atom or a lower alkyl group, and R^2 represents a hydrogen atom or a lower alkyl group. Show, R^
3 represents a lower alkyl group. General formula characterized by reacting the aminopyrazole derivative represented by ] with a nitrite source such as alkyl nitrite, nitrogen sesquioxide, or nitric oxide in the presence of ditertiary butyl disulfide: ▲Mathematical formula, chemical formula, There are tables, etc.▼(I) [In the formula, R^1 represents a hydrogen atom or a lower alkyl group, R^2 represents a hydrogen atom or a lower alkyl group, and R^
3 represents a lower alkyl group. ] A method for producing a pyrazole derivative represented by
、Ｒ＾２は水素原子または低級アルキル基を示し、Ｒ＾
３は低級アルキル基を示す。〕で表わされるピラゾール
誘導体を、水または水を含む酢酸もしくはハロゲン化炭
化水素等の不活性溶媒の存在下、塩素と反応させること
を特徴とする一般式：（III） ▲数式、化学式、表等があります▼（III） 〔式中Ｒ＾１は、水素原子または低級アルキル基を示し
、Ｒ＾２は水素原子または低級アルキル基を示し、Ｒ＾
３は低級アルキル基を示す。〕で表わされるクロロスル
ホニルピラゾール誘導体の製造法。(3) General formula (I): ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R^1 represents a hydrogen atom or a lower alkyl group, and R^2 represents a hydrogen atom or a lower alkyl group. Show, R^
3 represents a lower alkyl group. General formula characterized by reacting a pyrazole derivative represented by ] with chlorine in the presence of water or an inert solvent such as acetic acid containing water or a halogenated hydrocarbon: (III) ▲Mathematical formula, chemical formula, table, etc. ▼(III) [In the formula, R^1 represents a hydrogen atom or a lower alkyl group, R^2 represents a hydrogen atom or a lower alkyl group, and R^
3 represents a lower alkyl group. ] A method for producing a chlorosulfonyl pyrazole derivative represented by
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61104383A JPH0745476B2 (en) | 1986-05-07 | 1986-05-07 | Pyrazole derivative and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61104383A JPH0745476B2 (en) | 1986-05-07 | 1986-05-07 | Pyrazole derivative and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62263159A true JPS62263159A (en) | 1987-11-16 |
| JPH0745476B2 JPH0745476B2 (en) | 1995-05-17 |
Family
ID=14379236
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61104383A Expired - Fee Related JPH0745476B2 (en) | 1986-05-07 | 1986-05-07 | Pyrazole derivative and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0745476B2 (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2829289A1 (en) * | 1978-07-04 | 1980-01-24 | Basf Ag | PYRAZOLAETHER DERIVATIVES |
| JPH0436152A (en) * | 1990-06-01 | 1992-02-06 | Lotte Co Ltd | Flavor composition for chewing gum |
-
1986
- 1986-05-07 JP JP61104383A patent/JPH0745476B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2829289A1 (en) * | 1978-07-04 | 1980-01-24 | Basf Ag | PYRAZOLAETHER DERIVATIVES |
| JPH0436152A (en) * | 1990-06-01 | 1992-02-06 | Lotte Co Ltd | Flavor composition for chewing gum |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0745476B2 (en) | 1995-05-17 |
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