KR830000377B1 - Preparation method of perhydroimidazo thiazole derivative - Google Patents
Preparation method of perhydroimidazo thiazole derivative Download PDFInfo
- Publication number
- KR830000377B1 KR830000377B1 KR1019790001951A KR790001951A KR830000377B1 KR 830000377 B1 KR830000377 B1 KR 830000377B1 KR 1019790001951 A KR1019790001951 A KR 1019790001951A KR 790001951 A KR790001951 A KR 790001951A KR 830000377 B1 KR830000377 B1 KR 830000377B1
- Authority
- KR
- South Korea
- Prior art keywords
- dichlorophenyl
- compound
- carboxylic acid
- perhydroimidazo
- thiazole
- Prior art date
Links
- 238000002360 preparation method Methods 0.000 title description 11
- BXVKVOBCTCUEQD-UHFFFAOYSA-N 3,3a,4,5,6,6a-hexahydro-2h-imidazo[4,5-d][1,3]thiazole Chemical class N1CSC2NCNC21 BXVKVOBCTCUEQD-UHFFFAOYSA-N 0.000 title description 2
- -1 3,5-dichlorophenyl Chemical group 0.000 claims description 38
- 238000004519 manufacturing process Methods 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- ULSZVNJBVJWEJE-UHFFFAOYSA-N thiazolidine-2-carboxylic acid Chemical class OC(=O)C1NCCS1 ULSZVNJBVJWEJE-UHFFFAOYSA-N 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052717 sulfur Chemical group 0.000 claims description 3
- 125000004434 sulfur atom Chemical group 0.000 claims description 3
- YCEKKNMJIZSFCQ-UHFFFAOYSA-N 2,3,5,6,7,7a-hexahydroimidazo[5,1-b][1,3]thiazole Chemical compound S1C2N(CC1)CNC2 YCEKKNMJIZSFCQ-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 description 38
- 238000006243 chemical reaction Methods 0.000 description 25
- 239000000203 mixture Substances 0.000 description 25
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 238000002844 melting Methods 0.000 description 18
- 230000008018 melting Effects 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 238000000921 elemental analysis Methods 0.000 description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- RRFFWUURBRERTJ-UHFFFAOYSA-N 3,7a-dihydro-2h-imidazo[5,1-b][1,3]thiazole-5,7-dione Chemical compound C1CSC2C(=O)NC(=O)N21 RRFFWUURBRERTJ-UHFFFAOYSA-N 0.000 description 9
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- XZGXGPIBEMPYSI-UHFFFAOYSA-N 5-sulfanylidene-3,7a-dihydro-2H-imidazo[5,1-b][1,3]thiazol-7-one Chemical class S1C2N(CC1)C(NC2=O)=S XZGXGPIBEMPYSI-UHFFFAOYSA-N 0.000 description 5
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- GTUDXRQDUASHFT-UHFFFAOYSA-N methyl 2-ethyl-1,3-thiazolidine-2-carboxylate Chemical compound COC(=O)C1(CC)NCCS1 GTUDXRQDUASHFT-UHFFFAOYSA-N 0.000 description 3
- LDPISBPPJFKYQI-UHFFFAOYSA-N methyl 2-methyl-1,3-thiazolidine-2-carboxylate Chemical compound COC(=O)C1(C)NCCS1 LDPISBPPJFKYQI-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
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- FJIQTPGTRICJON-UHFFFAOYSA-N 2-ethyl-1,3-thiazolidine-2-carboxylic acid Chemical compound CCC1(C(O)=O)NCCS1 FJIQTPGTRICJON-UHFFFAOYSA-N 0.000 description 2
- LULAYUGMBFYYEX-UHFFFAOYSA-N 3-chlorobenzoic acid Chemical compound OC(=O)C1=CC=CC(Cl)=C1 LULAYUGMBFYYEX-UHFFFAOYSA-N 0.000 description 2
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- STIPQAUQYAPPPL-UHFFFAOYSA-N ethyl 1,3-thiazolidine-2-carboxylate Chemical compound CCOC(=O)C1NCCS1 STIPQAUQYAPPPL-UHFFFAOYSA-N 0.000 description 2
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- JRJTUKVSRPUZTO-UHFFFAOYSA-N methyl 3-[(3,5-dichlorophenyl)carbamoyl]-2-ethyl-1,3-thiazolidine-2-carboxylate Chemical compound COC(=O)C1(CC)SCCN1C(=O)NC1=CC(Cl)=CC(Cl)=C1 JRJTUKVSRPUZTO-UHFFFAOYSA-N 0.000 description 2
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- 244000052769 pathogen Species 0.000 description 1
- QKFJKGMPGYROCL-UHFFFAOYSA-N phenyl isothiocyanate Chemical compound S=C=NC1=CC=CC=C1 QKFJKGMPGYROCL-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000003389 potentiating effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000003206 sterilizing agent Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
- C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
- C07D513/04—Ortho-condensed systems
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
Abstract
내용 없음.No content.
Description
본 발명은 신규한 퍼하이드로 이미다조 티아졸유도체의 제조에 관한 것이다. 더욱 상세히는 히단토인 유도체인 6-(3,5-디클로로페닐)퍼하이드로 이미다조[5,1-b]티아졸-5,7-디온류 또는 6-(3,5-디클로로페닐)퍼하이드로 이미다조[5,1-b] 티아졸-5-티온-7-온류의 제조에 관한 것으로서, 이것은 뛰어난 살균활성을 나타내는 화합물이다.The present invention relates to the preparation of novel perhydroimidazo thiazole derivatives. More specifically, 6- (3,5-dichlorophenyl) perhydroimidazo [5,1-b] thiazole-5,7-dione or 6- (3,5-dichlorophenyl) perhydro which is a hydantoin derivative The present invention relates to the preparation of imidazo [5,1-b] thiazole-5-thione-7-ones, which is a compound exhibiting excellent bactericidal activity.
3-치환히단토인 유도체에 대하여는 이미 몇개인가의 화합물이 살균효과, 제조효과 등의 생물활성을 갖는다는 것이 보고되고 있다. (OLS 2604989)As for the 3-substituted hydantoin derivatives, it has been reported that some compounds have biological activities such as bactericidal effect and manufacturing effect. (OLS 2604989)
본 발명자들은, 다음 일반식(I)로 표시되는 새로운 히단토인 유도체인 6-(3,5-디클로로페닐)퍼하이드로 이미다조[5,1-b]티아졸-5,7-디온류 또는 6-(3,5-디클로로페닐)퍼하이드로 이미다조[5,1-b]티아졸-5-티온-7-온류가 식물병해에 대해 강력한 살균효과를 갖는 극히 유용한 물질인 것을 발견하였다. 즉, 본 발명은 다음 일반식(I)로 표시되는 화합물의 제법에 관한 것으로,MEANS TO SOLVE THE PROBLEM The present inventors are the 6- (3,5-dichlorophenyl) perhydro imidazo [5,1-b] thiazole-5,7-dione or 6 which are the new hydantoin derivative represented by following General formula (I). It was found that-(3,5-dichlorophenyl) perhydroimidazo [5,1-b] thiazole-5-thione-7- warm is an extremely useful substance with potent bactericidal effects against plant diseases. That is, this invention relates to the manufacturing method of a compound represented by following General formula (I),
일반식General formula
(식중, R은 수소원자 또는 탄소수 1~4의 알킬기를 표시하고, X는 산소원자 또는 유황원자를 표시하며, n은 0,1 또는 2를 표시함)으로 표시되는 6-(3,5-디클로로페닐)퍼하이드로 이미다조[5,1-b]티아졸 유도체의 제조를 목적으로 한다. 알킬기의 구체적인 예로서는, 메틸, 에틸, 푸로필, 부틸기이다.Wherein R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, X represents an oxygen atom or a sulfur atom, and n represents 0, 1 or 2, and is represented by 6- (3,5- It is intended to prepare dichlorophenyl) perhydro imidazo [5,1-b] thiazole derivatives. Specific examples of the alkyl group are methyl, ethyl, fluoropropyl, and butyl groups.
상기 일반식(I)로 표시되는 본 발명의 화합물은, 어느 것도 신규한 화합물로서, 식물병해에 대해서는 강력한 살균효력을 가지고, 더우기 식물에 대한 해로운 작용은 거의 볼 수 없으며, 또 인축 혹은 어류에 대한 독성도 낮다. 본 발명 화합물은, 특히 야채, 과수의 회색곰팡이병, 군핵병, 배의 흑반병, 사과의 반점낙엽병, 양파의 회색부패병 등에 탁월한 효력을 나타내고, 또 벼의 도열병, 호마염고병등에 대해서도 뛰어난 효력을 나타낸다. 또한, 종래, 널리 사용되어온 약제에 대한 내성이 생기고 있는 균에 대해서도 본 발명 화합물을 뛰어난 살균효과를 나타낸다. 상기 일반식(I)로 표시되는 화합물중, 살균효과면에서는 X는 산소, R은 수소 또는 탄소수 1~3의 알킬기이고, n이 0인 경우가 바람직하고, X가 산소원자, R이 수소, 메틸기, 에틸기의 경우가 더욱 바람직하다. 특히 그 중, 살균활성 및 경제적인 면에서는 6-(3,5-디클로로페닐)퍼하이드로 이미다조 [5,1-b]티아졸-5,7-디온 및 7a-메틸-6-(3,5-디클로로페닐)퍼하이드로 이미다조 [5,1-b]티아졸-5,7-디온이 가장 바람직하다.None of the compounds of the present invention represented by the above general formula (I) are novel compounds, and have a strong bactericidal effect against plant diseases, and furthermore, harmful effects on plants are hardly seen, Low toxicity In particular, the compound of the present invention exhibits excellent effects on vegetables, fruit trees, gray mold disease, army nucleus disease, pear plaque, apple spot deciduous disease, onion gray rot, etc. Indicates. In addition, the compound of the present invention exhibits excellent bactericidal effect against bacteria that have developed resistance to a drug which has conventionally been widely used. Among the compounds represented by the general formula (I), in view of bactericidal effect, X is oxygen, R is hydrogen or an alkyl group having 1 to 3 carbon atoms, n is preferably 0, X is an oxygen atom, R is hydrogen, Methyl group and ethyl group are more preferable. Particularly, among them, 6- (3,5-dichlorophenyl) perhydroimidazo [5,1-b] thiazole-5,7-dione and 7a-methyl-6- (3, Most preferred is 5-dichlorophenyl) perhydroimidazo [5,1-b] thiazole-5,7-dione.
본 발명 화합물은, 다음 일반식(Ⅱ)The compound of the present invention is represented by the following general formula (II)
(식중, R은 수소원자 또는 탄소수 1~4의 알킬기를 표시하고, X는 산소원자 또는 유황원자를 표시하고 R'는 수소원자 또는 탄소수 1~5의 저급알킬기를 표시한다)로 표시되는 티아조리딘-2-카르본산 유도체를 축합환화 하므로서 제조된다.Thiazori represented by (wherein R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, X represents an oxygen atom or a sulfur atom and R 'represents a hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms) It is prepared by condensation cyclization of a din-2-carboxylic acid derivative.
이 원료화합물(Ⅱ)은, 2위에 탄소수 1~4의 알킬기가 치환되어 있어도 되는 티아조리딘-2-카르본산 또는 그 저급알킬에스테르와 3,5-디클로로페닐 이소시안산 또는 3,5-디클로로페닐 이소티오시안산을 원료로 해서 제조할 수 있다. 이것을 반응식으로 표시하면 다음과 같다.This raw material compound (II) is thiazolidine-2-carboxylic acid or its lower alkyl ester which may be substituted with a C1-C4 alkyl group at 2nd position, and 3, 5- dichlorophenyl isocyanic acid or 3, 5- dichloro It can manufacture using phenyl isothiocyanic acid as a raw material. If this is expressed as a reaction scheme, it is as follows.
(식중, R,X는 상기 일반식(I)에서 정의된 것과 동일한 의의를 가지며, R'는 수소원자 또는 탄소수 1~5의 알킬기를 표시하고, m은 1또는 2를 표시한다)(Wherein R and X have the same meaning as defined in the general formula (I), R 'represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and m represents 1 or 2)
즉, 티아조리딘-2-카르본산의 저급알킬에스테르를 원료로 하는 경우에는, 이 에스테르와 3,5-디클로로페닐 이소시안산 또는 3,5-디클로로페닐 이소티오시안산을, 벤젠, 톨루엔, 에테르, 디메틸포름 아미드등의 용매중에서 반응시키므로서, 3-(3,5-디클로로페닐 카르바모일)티아조리딘-2-카르본산 에스테르류 또는, 3-(3,5-디클로로페닐 티오카르바모일)티아조리딘-2-카르본산 에스테류류(상기 일반식(Ⅱ)에 있어서 R'=저급알킬기)를 얻는다. 또한 이 반응에 있어서, 반응조건에 따라서는, 상기 3-치환 티아조리딘-2-카르본산 에스테르류(상기 일반식(Ⅱ)에 있어서 R'=저급알킬기)를 거친후 그대로 반응을 계속하므로서, 축합환화 해서 상기 일반식(Ia)에서 표시되는 6-(3,5-디클로로페닐)퍼하이드로 이미다조 [5,1-b]티아졸-5,7-디온류 또는 6-(3,5-디클로로페닐)퍼하이드로 이미다조 [5,1-b]티아졸-5,7-티온-7-온류를 얻을 수 있다. 또, 티아조리딘-2-카르본산을 원료로 하는 경우에는, 이것을 예를들면, 벤젠, 클로로벤젠, 에테르, 디메틸 포름아미드 등의 유기용매와 물과의 혼합용매중에 현탁 또는 용해시켜, 가성소오다, 가성칼리 등의 알칼리의 존재하에, 3,5-디클로로페닐 이소시안산 또는 3,5-디클로로페닐 티오이소시안산과 반응시킨후, 염산, 황산등의 산으로 중화하므로서, 3-(3,5-디클로로페닐 카르바모일)티아조리딘-2-카르본산류 또는 3-(3,5-디클로로페닐 티오카르바모일)티아조리딘-2-카르본산류(상기일반식(Ⅱ)에 있어서, R'=수소원자)를 얻는다.That is, when using the lower alkyl ester of thiazolidine-2-carboxylic acid as a raw material, this ester, 3, 5- dichlorophenyl isocyanic acid, or 3, 5- dichlorophenyl isothiocyanic acid, is selected from benzene, toluene, 3- (3,5-dichlorophenyl carbamoyl) thiazolidine-2-carboxylic acid ester or 3- (3,5-dichlorophenyl thiocarba by reacting in a solvent such as ether or dimethylformamide Moyl) thiazoridin-2-carboxylic acid ester (R '= lower alkyl group in the said General formula (II)) is obtained. In this reaction, depending on the reaction conditions, the reaction is continued as it is after passing through the 3-substituted thiazolidine-2-carboxylic acid esters (R '= lower alkyl group in the general formula (II)), 6- (3,5-dichlorophenyl) perhydroimidazo [5,1-b] thiazole-5,7-diones or 6- (3,5- condensed with cyclization and represented by the general formula (Ia) Dichlorophenyl) perhydro imidazo [5,1-b] thiazole-5,7-thione-7-ones can be obtained. In the case of using thiazoridin-2-carboxylic acid as a raw material, it is suspended or dissolved in a mixed solvent of organic solvents such as benzene, chlorobenzene, ether, dimethyl formamide and water, for example. After reacting with 3,5-dichlorophenyl isocyanic acid or 3,5-dichlorophenyl thioisocyanic acid in the presence of an alkali such as Oda and caustic caustic, and neutralizing with an acid such as hydrochloric acid or sulfuric acid, 3- (3, 5-dichlorophenyl carbamoyl) thiazolidine-2-carboxylic acids or 3- (3,5-dichlorophenyl thiocarbamoyl) thiazolidine-2-carboxylic acids (in the general formula (II) , R '= hydrogen atom).
축합환화 반응은, 이 화합물(Ⅱ)을 염산, 황산 등의 광산의 존재하에 가열하거나, 혹은 아세트산소오다등의 아세트산의 알칼리 금속염의 존재하에 무수아세트산중에서 가열하거나, 더우기는, 나트륨알코크시드 칼륨알코크시드 등의 알칼리금속 알코크시드의 존재하에, 저급알칸올 중에서 반응시키는 것 등에 의해 행하여진다. 이와같이 해서, 6-(3,5-디클로로페닐)퍼하이드로 이미다조 [5,1-b] 티아졸-5,7-디온류 또는 6-(3,5-디클로로페닐)퍼하이드로 이미다조 [5,1-b]티아졸-5-티온-7-온류(Ia)가 얻어진다.The condensation cyclization reaction may be carried out by heating this compound (II) in the presence of a mineral acid such as hydrochloric acid or sulfuric acid, or in acetic anhydride in the presence of an alkali metal salt of acetic acid such as sodium acetate, or, moreover, sodium alkoxide potassium It is carried out by reacting in a lower alkanol in the presence of alkali metal alcocoxides such as alcocoxides. Thus, 6- (3,5-dichlorophenyl) perhydroimidazo [5,1-b] thiazole-5,7-diones or 6- (3,5-dichlorophenyl) perhydroimidazo [5 , 1-b] thiazole-5-thione-7-ones (Ia) are obtained.
이들의 화합물은 재결정, 클로마토그라피등 상법에 따라서 정제된다. 또, 6-(3,5-디클로로페닐)퍼하이드로 이미다조 [5,1-b] 티아졸-5,7-디온-1-옥사이드 혹은 1,1-디옥사이드류 또는 6-(3,5-디클로로페닐)퍼하이드로 이미다조 [5,1-b] 티아졸-5-티온-7-온-1-옥사이드 혹은 1,1-디옥사이드류(Ib)는, 상기 화합물(Ia)을 염화메틸렌 등의 용매에 용해시켜, m-클로로 과안식향산, 과아세트산 등의 산화제로 산화하므로서 얻어진다.These compounds are purified according to conventional methods such as recrystallization and chromatography. 6- (3,5-dichlorophenyl) perhydroimidazo [5,1-b] thiazole-5,7-dione-1-oxide or 1,1-dioxides or 6- (3,5- Dichlorophenyl) perhydro imidazo [5,1-b] thiazole-5-thione-7-one-1-oxide or 1,1-dioxide (Ib) is said compound (Ia), such as methylene chloride It is obtained by dissolving in a solvent and oxidizing with oxidizing agents, such as m-chloro perbenzoic acid and peracetic acid.
본 발명 화합물을 농원예용 살균제로서 사용함에 있어서는, 이 화합물을 그대로 사용하여도 되나, 유효성분의 사용장면에서의 분산을 효과있게 하기 위해, 상법에따라 보조제를 첨가하고, 유제, 수화제, 분제등의 형으로 사용하는 것이 바람직하다.In using the compound of the present invention as an agricultural or horticultural germicide, the compound may be used as it is, but in order to effect dispersion in the use scene of the active ingredient, an auxiliary agent is added according to a conventional method, and an emulsion, a hydrating agent, a powder, etc. It is preferable to use it as a mold.
본 발명 농원예용 살균제에 있어서의 보조제의 하나인 요제로서는, 예를들면 물, 알코올류(메틸알코올, 에틸알코오르, 에틸렌글리코올 등), 케톤류(아세톤, 메틸에티케톤, 시클로헥사논 등), 에테르류(에틸에테르, 디옥산, 셀로솔브류 등), 지방족 탄화수소류(케로신, 등유연료유 등), 방향족 탄화수소류(벤젠, 톨루엔, 크실렌, 솔벤트나프사, 메틸나프탈렌 등), 할로겐화 탄화수소류(디클로로에탄, 트리클로로벤젠, 사염화산소 등) 산아미드류(디메틸포름아미드 등), 에스테르류(아세느산에틸, 아세트산 부틸, 지방산의 글리셀린 에스테르 등), 니트릴류(아세트니트릴류)등이 적당하고, 이들의 1종 또는 2종 이상의 혼합물이 사용된다. 또 중량제로서는, 고령토, 벤토나이트 등의 점토류, 활석, 엽납석 드의 활석류, 규조로, 화이트카아본 등의 산화물 등의 광물성 분말과 대두분, CMC등의 식물성 분말 등이 적당하고, 이들의 1종 또는 2종 이상의 혼합물이 사용된다.Examples of the main agent in the agricultural and horticultural fungicide of the present invention include water, alcohols (methyl alcohol, ethyl alcohol, ethylene glycol, etc.), ketones (acetone, methyl ethiketone, cyclohexanone, etc.). , Ethers (ethyl ether, dioxane, cellosolves, etc.), aliphatic hydrocarbons (kerosene, kerosene fuel oil, etc.), aromatic hydrocarbons (benzene, toluene, xylene, solvent naphtha, methylnaphthalene, etc.), halogenated hydrocarbons Acids (dichloroethane, trichlorobenzene, oxygen tetrachloride, etc.) acid amides (dimethylformamide, etc.), esters (ethyl acetate, butyl acetate, fatty acid glyceline esters, etc.), nitriles (acetnitriles), etc. This is suitable, and 1 type, or 2 or more types thereof is used. As the weighting agent, clays such as kaolin and bentonite, talc, talc and talc, talc, mineral powder such as oxides such as white carbon and vegetable powder such as soy flour and CMC are suitable. One or a mixture of two or more of them is used.
또 계면활성제가 전착제, 분산제, 유화제, 침투제로서 사용된다. 이 계면활성제로서는, 예를들면 비이온계 계면활성제(폴리옥시에틸렌 알킬아릴에테르, 폴리옥시에틸렌솔비탄 모노라우레이트 등), 양이온계 계면활성제(알킬디메틸 벤질암모늄 클로라이드, 알킬피리디늄클로라이드등), 음이온게 계면활성제(알킬벤젠 슬폰산염, 리그닌슬폰산염, 고급알코올 황산염), 양성계면활성제(알킬디메틸 베타인, 도데실아미노에틸글리신 등)등을 들 수 있다. 이들의 게면활성제는, 용도에 따라서 1종 또는 2종 이상의 혼합물로서 사용된다.Moreover, surfactant is used as an electrodeposition agent, a dispersing agent, an emulsifier, and a penetrant. As this surfactant, For example, nonionic surfactant (polyoxyethylene alkylaryl ether, polyoxyethylene sorbitan monolaurate etc.), cationic surfactant (alkyldimethyl benzyl ammonium chloride, alkylpyridinium chloride, etc.), Anionic crab surfactant (alkylbenzene sulfonate, lignin sulfonate, higher alcohol sulfate), an amphoteric surfactant (alkyldimethyl betaine, dodecylamino ethyl glycine etc.) etc. are mentioned. These surfactants are used as 1 type, or 2 or more types of mixtures according to a use.
본 발명 농원예용 살균제를 사용함에 있어, 유제의 형으로 사용하는 경우에는, 본 발명 화합물 10~15부, 용제 10~80부와 계면활성제 3~20부를 적당한 비율로 혼합한 것을 원액으로 하고, 사용시에는 물로 소정농도로 희석하여 이것을 살포 등의 방법에 의해서 시용한다.In the case of using the agricultural and horticultural fungicide of the present invention, when using in the form of an emulsion, a mixture of 10 to 15 parts of the compound of the present invention, 10 to 80 parts of the solvent and 3 to 20 parts of the surfactant at an appropriate ratio is used as a stock solution. The solution is diluted with water to a predetermined concentration and used by spraying or the like.
또 수화제의 형으로 사용하는 경우에는, 본 발명 화합물 5~80부 및 중량제 10~90부와 계면활성 제1~20부를 적당한 비율로 혼합하여 이 혼합물을 유제의 경우와 마찬가지로 물 등으로 희석해서 사용한다.In the case of using in the form of a hydrating agent, 5 to 80 parts of the compound of the present invention, 10 to 90 parts of the weight agent and 1 to 20 parts of the surfactant are mixed in an appropriate ratio, and the mixture is diluted with water or the like as in the case of the emulsion. use.
또 분제의 형으로 사용할 경우에는, 통상, 본 발명 화합물 1~5부를 고령토, 벤트나이토, 활석등의 중량제 95~99부와 균일하게 혼합한 것을 사용한다.Moreover, when using in the form of powder, the thing mix | blended uniformly with 95-99 parts of weight agents, such as kaolin, bent nito, talc, and the like of 1-5 parts of this compound is used normally.
또 본 발명 농원예용 살균제는, 본 유효성분의 살균효과를 저해하는 일이 없는 다른 활성성분, 예를들면 살균제, 살충제, 살비제 등과 혼합해서 상용할 수도 있다.Moreover, the agricultural / horticultural germicide of this invention can also be mixed and mixed with another active ingredient which does not impair the bactericidal effect of this active ingredient, for example, a fungicide, an insecticide, acaricide.
본 발명 농원에용 살균제의 사용량은 경엽 처리인 경우, 250~1500 ppm의 용액을 10α당 50~500ℓ정도이다.In the case of the foliage treatment, the amount of the fungicide for farming of the present invention is about 50 to 500 L per 10α of the solution of 250 to 1500 ppm.
다음에 본 발명 화합물의 제조에, 이것을 함유한 농원에용 살균제의 제제예 및 본 살균제에 의한 방제 시험에를 들어서 본 발명을 더욱 상세히 설명하지만, 본 발명은 이들의 구체예에 예시된 것에 한정되는 것은 아니다. 또한 부는 중량부를 나타낸다.Next, the preparation of the compound of the present invention will be described in more detail with reference to preparation examples of agricultural fungicides containing the same and control tests by the present fungicides, but the present invention is limited to those exemplified in these specific examples. It is not. In addition, a part represents a weight part.
[제조예 1][Production Example 1]
시스테아민염산염 56.6g을 500ml의 에탄올에 용해하고, 이 속에 글리옥실산의 25%수용액 148.1g을 첨가하였다. 1.5시간 가열환류해서 반응을 행하여, 냉각하고, 석출 결정을 여과 선별해서 41.6g(수득율 62.5%)의 티아조리딘-2-카르본산을 얻었다. 융점 : 187~9°(분해)56.6 g of cysteamine hydrochloride was dissolved in 500 ml of ethanol, and 148.1 g of a 25% aqueous solution of glyoxylic acid was added thereto. The mixture was heated and refluxed for 1.5 hours to cool, and the precipitated crystals were filtered out to obtain 41.6 g (yield 62.5%) of thiazolidine-2-carboxylic acid. Melting Point: 187 ~ 9 ° (Decomposition)
얻어진 티아조리딘-2-카르본산 6.66g과 가성소오다2.0g을 100ml의 물에 용해하고, 이 속에 3,5-디클로로페닐 이소시안산 9.40g과 클로로벤젠 50ml의 용액을 첨가하여, 실온에서 2시간 교반해서 반응을 행하였다. 반응후, 에테르를 추출하여, 수상을 농염산으로 중화하였다. 석출결정을 여과선별하여 수세, 건조해서 14.4g(수득율 89.5%)dml 3-(3,5-디클로로페닐 카르바모일)디아조리딘-2-카르본산을 얻었다.6.66 g of the obtained thiazolidine-2-carboxylic acid and 2.0 g of sodium hydroxide were dissolved in 100 ml of water, and a solution of 9.40 g of 3,5-dichlorophenyl isocyanic acid and 50 ml of chlorobenzene was added thereto at room temperature. The reaction was carried out by stirring for 2 hours. After the reaction, ether was extracted and the aqueous phase was neutralized with concentrated hydrochloric acid. The precipitated crystals were filtered, washed with water, and dried to obtain 14.4 g (yield 89.5%) of dml 3- (3,5-dichlorophenyl carbamoyl) diazolidine-2-carboxylic acid.
융점 : 175.5~7.0℃, 원소분석치(괄호내는 계산치)Melting Point: 175.5 ~ 7.0 ℃, Elemental Analysis Value (Calculated Value in Brackets)
C 40.88%(41.14%), H 3.11% (3.14%), N 8.86%*8.72%), Cl 22.24%(22.08%)C 40.88% (41.14%), H 3.11% (3.14%), N 8.86% * 8.72%), Cl 22.24% (22.08%)
얻어진 3-(3,5-디클로로페닐 카르바모일)티아조리딘-2-카르본산 13.0g을 50ml의 농염산 속에 가하여, 120℃로 2시간 가열, 교반하여 반응을 행하였다. 반응후 냉각하여, 석출결정을 여과선별하고, 아세트산에틸-n-헥산혼합용매에서 재결정해서, 10.7g(수득을 86.9%)의 1,1-디옥사이드류 또는 6-(3,5-디클로로페닐)퍼하이드로 이미다조 [5,1-b] 티아졸5,7-디온(화합물 No.1)을 얻었다. 융점 141~2℃, 원소분석치(괄호내는 계산치)13.0 g of obtained 3- (3,5-dichlorophenyl carbamoyl) thiazolidine-2-carboxylic acid was added to 50 ml of concentrated hydrochloric acid, and it heated and stirred at 120 degreeC for 2 hours, and reacted. After the reaction, the mixture was cooled, and the precipitated crystals were filtered out and recrystallized in an ethyl acetate-n-hexane mixed solvent to obtain 10.7 g (86.9% of yield) of 1,1-dioxides or 6- (3,5-dichlorophenyl). Perhydro imidazo [5,1-b] thiazole 5,7-dione (Compound No. 1) was obtained. Melting point 141-2 degrees Celsius, elemental analysis value (calculated value in parenthesis)
C 43.40% (43.58%), H 2.73%(2.66%), N 9.18%(9.24%), Cl 23.25%(23.39%)C 43.40% (43.58%), H 2.73% (2.66%), N 9.18% (9.24%), Cl 23.25% (23.39%)
[제조예 2][Production Example 2]
제조예 1에서 얻은 티아조리딘-2-카르본산 20.0g을 200ml의 20%염산에탄올 용액에 가하여, 2시간 가열환류후, 감압하에 용매를 유거하고, 물을 가한후 포화중조수로 중화하였다. 아세트산에틸로 추출한후, 추출물을 진공증류해서 19.1g(수득율 79.8%)의 티아조리딘-2-카르본산에틸에스테르를 얻었다. 비점 104~5℃/5.5mmHg. 얻어진 티아조리딘-2-카르본산 에틸에스테르 1.61g과 3,5-디클로로페닐 이소티오시안산 2.04g을 20ml의 톨루엔 속에 가해, 90℃로 1시간 가열해서 반응을 행하였다. 반응후 냉각하고 석출결정을 여과 선별하여, 3.11g(수득율 85.1%)의 3-(3,5-디클로로페닐 티오카르바모일)티아조리딘-2-카르본산 에틸에스테르를 얻었다. 융점 : 170.5~1.5℃, 원소분석치(괄호내는 계산치).20.0 g of thiazolidine-2-carboxylic acid obtained in Preparation Example 1 was added to 200 ml of 20% ethanol hydrochloride solution, and after heating under reflux for 2 hours, the solvent was distilled off under reduced pressure, and neutralized with saturated sodium bicarbonate water. After extracting with ethyl acetate, the extract was vacuum distilled to obtain 19.1 g (yield 79.8%) of thiazolidine-2-carboxylic acid ethyl ester. Boiling point 104 ~ 5 ° C / 5.5mmHg. 1.61 g of obtained thiazolidine-2-carboxylic acid ethyl ester and 2.04 g of 3,5-dichlorophenyl isothiocyanic acid were added to 20 ml of toluene, and it heated at 90 degreeC for 1 hour, and reacted. After the reaction, the mixture was cooled and the precipitated crystals were filtered out to obtain 3.11 g (yield 85.1%) of 3- (3,5-dichlorophenyl thiocarbamoyl) thiazolidine-2-carboxylic acid ethyl ester. Melting point: 170.5 ~ 1.5 ° C, elemental analysis value (calculated value in parentheses).
C 42.68% (42.74%), H 3.93%(3.86%), N 7.70%(7.67%), Cl 19.32%(19.41%)C 42.68% (42.74%), H 3.93% (3.86%), N 7.70% (7.67%), Cl 19.32% (19.41%)
얻어진 3-(3,5-디클로로페닐 카르바모일)티아조리딘-2-카르본산 에틸에스테르 2.19g을 20ml의 농염산 속에 가하여, 120℃로 1.5시간 가열교반해서 반응을 행하였다. 반응후 냉각하고, 석출물을 여과선별후, 아세트산에틸-n-헥산혼합 용매에서 재결정해서, 1.43g(수득율 74.7%)의 6-(3,5-디클로로페닐)퍼하이드로 이미다조 [5,1-d] 티아졸-5-티온-7-온(화합물 No.2)을 얻었다.2.19 g of obtained 3- (3,5-dichlorophenyl carbamoyl) thiazolidine-2-carboxylic acid ethyl ester was added to 20 ml of concentrated hydrochloric acid, and the mixture was heated and stirred at 120 ° C. for 1.5 hours to carry out the reaction. After the reaction, the mixture was cooled and the precipitate was filtered and then recrystallized in an ethyl acetate-n-hexane mixed solvent to yield 1.43 g (yield 74.7%) of 6- (3,5-dichlorophenyl) perhydroimidazo [5,1- d] thiazole-5-thione-7-one (compound No. 2) was obtained.
융점 : 149.5~50.5℃ 원소분석치(괄ㅎ호내는 계산치)Melting Point: 149.5 ~ 50.5 ℃ Elemental Analysis Value (Calculated Value in Parenthesis)
C 41.33% (41.39%), H 2.59%(2.53%), N 8.60%(8.78%), Cl 22.51%(22.21%)C 41.33% (41.39%), H 2.59% (2.53%), N 8.60% (8.78%), Cl 22.51% (22.21%)
[제조예 3][Manufacture example 3]
시스테아민염산염 36.6g, 트이에틸아민 32.6g, 피루브산 메틸에스테르 32.9g을 500ml의 에탄올에 가해 2시간 가열환류하여 반응을 행하였다. 반응후 감압하에 용매를 유거하고, 물을 가한후, 아세트산에스테르 추출하였다. 추출물을 진공증류해서 36.6g(수득을 70.4%)의 2-메틸티아조리딘-2-카르본산 메틸에스테르를 얻었다. 비점 : 76℃/2mmHg.36.6 g of cysteamine hydrochloride, 32.6 g of triethylamine and 32.9 g of pyruvic acid methyl ester were added to 500 ml of ethanol, and the mixture was heated and refluxed for 2 hours to carry out the reaction. After the reaction, the solvent was distilled off under reduced pressure, water was added, and then acetate ester was extracted. The extract was vacuum distilled to give 36.6 g (70.4% of yield) of 2-methylthiazolidine-2-carboxylic acid methyl ester. Boiling point: 76 ° C./2 mmHg.
얻어진 2-메틸티아조리딘-2-카르본산 메틸에스테르 3.22g을 가성소오다0.80g, 물20ml의 용액에 가하고, 실온에서 교반하여 2-메틸티아조리딘-2-카르본산의 나트륨염 수용액으로 한후, 3,5-디클로로 이소시안산 3.76g, 클로로벤젠 20ml의 용액을 첨가하고, 실온에서 1.5시간 교반하여 반응을 행하였다. 반응후 에테르로 추득하고, 수상을 농염산으로 중화하였다. 석출결정을 여과선별하고, 수세, 건조하여 5.22g(수아율 77.9%)의 2-메틸-3-(3,5-디클로로페닐 카르바모일)티아조리딘-2-카르본산 5.0g과 아세트산소오다 5mg을 30ml의 무수아세트산 속에 가해, 90℃로 2시간 가열하여 반응을 행하였다. 반응후 감압하에 농축하고, 주수하였다. 석출결정을 아세트산에틸-n-헥산 혼합용매에서 재결정하여 3.92g의 7a-메틸-6-(3,5-디클로로페닐)퍼하이드로 이미다조[5,1-b] 티아졸-5,7-디온(화합물 No.3)을 얻었다.3.22 g of the obtained 2-methylthiazolidine-2-carboxylic acid methyl ester was added to a solution of 0.80 g of caustic sodium and 20 ml of water, and stirred at room temperature to give an aqueous sodium salt solution of 2-methylthiazolidine-2-carboxylic acid. After that, a solution of 3.76 g of 3,5-dichloro isocyanic acid and 20 ml of chlorobenzene was added, followed by stirring at room temperature for 1.5 hours. After the reaction, the mixture was collected with ether, and the aqueous phase was neutralized with concentrated hydrochloric acid. The precipitated crystals were collected by filtration, washed with water and dried to obtain 5.22 g (77.9% of child yield) of 5.0 g of 2-methyl-3- (3,5-dichlorophenyl carbamoyl) thiazolidine-2-carboxylic acid and acetic acid. 5 mg of Oda was added to 30 ml of acetic anhydride, and heated at 90 ° C. for 2 hours to conduct a reaction. After the reaction, the mixture was concentrated under reduced pressure and poured into water. The precipitated crystals were recrystallized from a mixed solvent of ethyl acetate-n-hexane to give 3.92 g of 7a-methyl-6- (3,5-dichlorophenyl) perhydroimidazo [5,1-b] thiazole-5,7-dione. (Compound No. 3) was obtained.
융점 : 110~2℃, 원소분석치(괄호내는 계산치).Melting point: 110 ~ 2 ℃, elemental analysis value (calculated value in parentheses).
C 45.56% (45.44%), H 3.09%(3.18%), N 8.72%(8.83%), Cl 22.20%(22.35%)C 45.56% (45.44%), H 3.09% (3.18%), N 8.72% (8.83%), Cl 22.20% (22.35%)
[제조예 4][Production Example 4]
제조예 3에서 얻는 2-메틸티아조리딘-2-카르본산 메틸에스테르 1.61g과 3,5-디클로로페닐 이소티오시안산 2.04g을 30ml의 톨루엔 속에 가하고, 90℃로 2시간 가열교반하여 반응을 행하였다. 반응후, 감압하에 농축하고, 톨루엔-n-헥산 혼합용매에서 재결정하여, 2.50g(수득율 75.0%)의 7a-메틸-6-(3,5-디클로로페닐)퍼하이드로 이미다조[5,1-b] 티아졸-5-티온-7-온(화합물 No.4)을 얻었다.1.61 g of 2-methylthiazolidine-2-carboxylic acid methyl ester obtained in Production Example 3 and 2.04 g of 3,5-dichlorophenyl isothiocyanic acid were added to 30 ml of toluene, followed by heating and stirring at 90 ° C. for 2 hours. It was done. After the reaction, the mixture was concentrated under reduced pressure, recrystallized from a toluene-n-hexane mixed solvent, and 2.50 g (yield 75.0%) of 7a-methyl-6- (3,5-dichlorophenyl) perhydroimidazo [5,1- b] Thiazol-5-thione-7-one (compound No. 4) was obtained.
융점 160~1℃, 원소분석치(괄호내는 계산치)Melting point 160 ~ 1 ℃, elemental analysis value (calculated value in parentheses)
C 43.36% (43.25%), H 2.95%(3.02%), N 8.36%(8.41%), Cl 21.41%(21.28%)C 43.36% (43.25%), H 2.95% (3.02%), N 8.36% (8.41%), Cl 21.41% (21.28%)
[제조예 5]Production Example 5
제조예 1에서 얻은 화합물No.1 1.52g을 10ml의 염화메틸렌에 용해하여, 이 속에 빙냉하에서, m-클로로과안식향산 1.04g, 염화메틸렌 12.5ml의 용액을 첨가하여, 1시간 가열환류 하였다. 이어서 재차 m-크로로과안식향산 1.04g, 염화메틸렌 12.5ml의 용액을 가하여, 1시간 가열환류하여 반응을 완결시켰다. 반응후, 희가성소오다로 세정하고, 농축후, 아세트산에틸을 전개용매로한 컬럼클로마토그래피로 정제하여 0.50g(수득율 29.8%)의 6-(3,5-디클로로페닐)퍼하이드로 이미다조[5,1-b] 티아졸-5,7-디온-1,1-디옥사이드(화합물 No.5)를 얻었다. 융점 : 176~8℃, 원소분석치(괄호내는 계산치).1.52 g of compound No. 1 obtained in Production Example 1 was dissolved in 10 ml of methylene chloride, and 1.04 g of m-chloroperbenzoic acid and 12.5 ml of methylene chloride were added thereto under ice cooling, and the mixture was heated to reflux for 1 hour. Subsequently, a solution of 1.04 g of m-chloro-benzoic acid and 12.5 ml of methylene chloride was added thereto, and the mixture was heated to reflux for 1 hour to complete the reaction. After the reaction, the mixture was washed with dilute sodium hydroxide, concentrated and purified by column chromatography using ethyl acetate as a developing solvent, and 0.50 g (yield 29.8%) of 6- (3,5-dichlorophenyl) perhydroimidazo. [5,1-b] thiazole-5,7-dione-1,1-dioxide (Compound No. 5) was obtained. Melting point: 176 ~ 8 ℃, elemental analysis value (calculated value in parentheses).
C 40.01% (39.42%), H 2.36%(2.41%), C 8.27%(8.36%), Cl 21.35%(21.16%)C 40.01% (39.42%), H 2.36% (2.41%), C 8.27% (8.36%), Cl 21.35% (21.16%)
[제조예 6][Manufacture example 6]
화합물 No.1 대신에 제조예 3에서 얻은 화합물 No.3 1.52g을 사용하고, 그 외는 제조예 5와 마찬가지로 반응을 행하였다. 반응후, 희가성소오다 용액으로 세정하여, 농축후, 아세트산에틸-n-헥산 혼합용매에서 재결정하여, 1.18g(수득율 67.6%)의 7a-메틸-6-(3,5-디클로로페닐)퍼하이드로 이미다조[5,1-b] 티아졸-5,7-디온-1,1-디옥사이드(화합물 No.6)을 얻었다.Instead of compound No. 1, 1.52 g of compound No. 3 obtained in Production Example 3 was used, and the others were reacted in the same manner as in Production Example 5. After the reaction, the mixture was washed with a dilute sodium hydroxide solution, concentrated, and then recrystallized from a mixed solvent of ethyl acetate-n-hexane to yield 1.18 g (yield 67.6%) of 7a-methyl-6- (3,5-dichlorophenyl) per Hydroimidazo [5,1-b] thiazole-5,7-dione-1,1-dioxide (Compound No. 6) was obtained.
융점 : 190~1℃, 원소분석치(괄호내는 계산치)Melting Point: 190 ~ 1 ℃, Elemental Analysis Value (Calculated Values in Parentheses)
C 41.35% (41.28%), H 2.95%(2.89%), N 7.89%(8.02%), Cl 20.13%(20.31%)C 41.35% (41.28%), H 2.95% (2.89%), N 7.89% (8.02%), Cl 20.13% (20.31%)
[제조예 7][Manufacture example 7]
시스테아민염산염 11.4g, 트리에틸아민 10.1g을 100ml의 에탄올에 용해하고, 이 속에 2-케토낙산 10.2g을 첨가하였다. 30분간 가열환류하여 반응을 행하였다. 냉각후, 석출결정을 여과선별하여, 10.6g(수득율 65.7%)의 2-에틸티아조리딘-2-카르본산을 얻었다. 융점 235~8℃(분해)11.4 g of cysteamine hydrochloride and 10.1 g of triethylamine were dissolved in 100 ml of ethanol, and 10.2 g of 2-ketonoxane was added thereto. The reaction was carried out by refluxing for 30 minutes. After cooling, the precipitated crystals were filtered to obtain 10.6 g (yield 65.7%) of 2-ethylthiazolidine-2-carboxylic acid. Melting Point 235 ~ 8 ℃ (Decomposition)
얻어진 2-에틸-티아조리딘-2-카르본산 10.0g을 200ml의 20%염화수소-메탄올 용액에 가하여, 30분간 가열환류후, 감압하에 용매를 유거하였다. 물을 가한후, 포화중조수로 중화하였다. 아세트산에틸로 추출한후, 추출물을 실리카겔컬럼 클로마토그래피로 정재하여 2.0g(수득율 18.4%)의 2-에틸티아조리딘-2-카르본산 메틸에스 테르를 얻었다. 10.0 g of 2-ethyl-thiazolidine-2-carboxylic acid obtained was added to 200 ml of a 20% hydrogen chloride-methanol solution, and after heating to reflux for 30 minutes, the solvent was distilled off under reduced pressure. Water was added and neutralized with saturated sodium bicarbonate water. After extraction with ethyl acetate, the extract was purified by silica gel column chromatography to obtain 2.0 g (yield 18.4%) of 2-ethylthiazolidine-2-carboxylic acid methyl ester.
얻어진 2-에틸티아조리딘-2-카르본산 메틸에스테르 0.62g과, 3,5-디클로로페닐 이소시안산 0.66g을 10ml의 톨루엔 속에 첨가하여, 실온에서 1시간 교반하였다. 석출결정을 여과선별하여 1.00g(수득율 77.8%)의 2-에틸-3-(3,5-디클로로페닐 카르바모일)티아조리딘-2-카르본산 메틸에스테르를 얻었다.0.62 g of 2-ethylthiazolidine-2-carboxylic acid methyl ester and 0.66 g of 3,5-dichlorophenyl isocyanic acid were added to 10 ml of toluene and stirred at room temperature for 1 hour. The precipitated crystals were filtered to obtain 1.00 g (77.8% yield) of 2-ethyl-3- (3,5-dichlorophenyl carbamoyl) thiazolidine-2-carboxylic acid methyl ester.
융점 : 187~8℃, 원소분석치(괄호내는 계산치)Melting Point: 187 ~ 8 ℃, Elemental Analysis Value (Calculated Value in Brackets)
C 46.48% (46.29%), H 4.35%(4.44%), C 7.50%(7.71%), Cl 19.86%(19.52%)C 46.48% (46.29%), H 4.35% (4.44%), C 7.50% (7.71%), Cl 19.86% (19.52%)
얻어진 2-에틸-3-(3,5-디클로로페닐 카르바모일)티아조리딘-2-카르본산 메틸에스테르 0.70g을 20ml 0.1N의 나트륨 메티라이트 메탄올 용액속에 가하고, 50℃로 20분간 가열하여 반응을 행하였다. 반응후 냉각하고, 석출결정을 여과선별하여 0.16g(수득율 25%)의 7a-에틸-6-(3,5-디클로로페닐)퍼하이드로 이미다조[5,1-b] 티아졸-5,7-디온(화합물 No.7)을 얻었다.0.70 g of the obtained 2-ethyl-3- (3,5-dichlorophenyl carbamoyl) thiazolidine-2-carboxylic acid methyl ester was added to 20 ml 0.1 N sodium methite methanol solution, and heated to 50 DEG C for 20 minutes. The reaction was carried out. After the reaction, the mixture was cooled, and the precipitated crystals were filtered to obtain 0.16 g (25% yield) of 7a-ethyl-6- (3,5-dichlorophenyl) perhydroimidazo [5,1-b] thiazole-5,7 -Dione (compound No. 7) was obtained.
융점 : 138~9℃ 원소분석치(괄호안은 계산치).Melting point: 138 ~ 9 ℃ Elemental analysis (calculated values in parentheses).
C 46.99% (47.14%), H 3.87%(3.65%), N 8.22%(8.46%), Cl 21.41%(21.41%)C 46.99% (47.14%), H 3.87% (3.65%), N 8.22% (8.46%), Cl 21.41% (21.41%)
[제조예 8][Manufacture example 8]
2-케토낙산 대신에 2-케토길초산을 사용하여 제조예 7과 마찬가지로 반응, 후초리를 행하여 2-n-푸로필티아조리딘-2-카르본산(융점 : 222~3℃(분해)), 2-n-푸로필티아조리딘-2-카르본산 메틸에스테르(융점 : 39~40℃), 2-n-푸로필-3-(3,5-디클로로페닐 카르바모일)티아조리딘-2-카르본산 메틸에스테르 융점 : 187~9℃, 원소분석치(괄호안은 계산치)The reaction was carried out in the same manner as in Production Example 7 using 2-ketogilic acid in place of 2-ketobutyric acid, followed by post-treatment to give 2-n-furofilthiazolidine-2-carboxylic acid (melting point: 222 to 3 ° C (decomposition)). , 2-n-furophilthiazoridine-2-carboxylic acid methyl ester (melting point: 39-40 degreeC), 2-n-furophyl-3- (3,5-dichlorophenyl carbamoyl) thiazolidine- 2-carboxylic acid methyl ester melting point: 187 ~ 9 ℃, elemental analysis value (calculated values in parentheses)
C 47.36% (47.75%), H 4.95%(4.81%), N 7.61%(7.42%), Cl 18.53%(18.79%)C 47.36% (47.75%), H 4.95% (4.81%), N 7.61% (7.42%), Cl 18.53% (18.79%)
및 7a-n-푸로필-6-(3,5-디클로로페닐)퍼하이드로 이미다조[5,1-b] 티아졸-3,7-디온 화합물 No.8, 융점 : 145.5~6.5℃, 원소분석(치괄호안은 계산치)And 7a-n-furophil-6- (3,5-dichlorophenyl) perhydroimidazo [5,1-b] thiazole-3,7-dione Compound No. 8, melting point: 145.5 to 6.5 ° C., element Analysis (calculated values in brackets)
C 48.34% (48.70%), H 4.08%(4.09%), N 7.83%(8.11%), Cl 20.28%(20.54%)C 48.34% (48.70%), H 4.08% (4.09%), N 7.83% (8.11%), Cl 20.28% (20.54%)
[제조예 9][Manufacture example 9]
제조예 7에서 얻은 2-에틸티아조리딘-2-카르본산 메틸에스테르 0.33g과 3,5-디클로로페닐 이소티오시안산 0.38g을 5ml의 톨루엔속에 가해 90℃로 2시간 가열하여 반응을 행하였다. 실리카겔컬럼 클로마토그래피로 정제하여 0.15g의 7a-에틸-6-(3,5-디클로로페닐)퍼하이드로 이미다조[5,1-b] 티아졸-5-티온-7-온(화합물 No.9)을 얻었다. 융점 : 139~40℃, 원소분석치(괄호안은 계산치)0.33 g of 2-ethylthiazolidine-2-carboxylic acid methyl ester obtained in Production Example 7 and 0.38 g of 3,5-dichlorophenyl isothiocyanic acid were added to 5 ml of toluene and heated at 90 ° C. for 2 hours to carry out a reaction. . Purified by silica gel column chromatography, 0.15 g of 7a-ethyl-6- (3,5-dichlorophenyl) perhydroimidazo [5,1-b] thiazol-5-thione-7-one (Compound No. 9) was obtained. Melting Point: 139 ~ 40 ℃, Elemental Analysis Value (Calculated Values in Parentheses)
C 44.70% (44.96%), H 3.55%(3.48%), N 8.16%(8.07%), Cl 20.12%(20.42%)C 44.70% (44.96%), H 3.55% (3.48%), N 8.16% (8.07%), Cl 20.12% (20.42%)
[제조예 10][Production Example 10]
2-에틸타아조리딘-2-카르본산 메틸에스테르 대신에 제조예 8에서 얻은 3-n-푸로필 티아조리딘-2-카르본산 메틸에스티르를 사용하여 제조예 9와 마찬가지로 반응후 처리를 행하여서 7a-n-푸로필-6-(3,5-디클로로페닐)퍼하이드로 이미다조[5,1-b] 티아졸-5-티온-7-온(화합물 No.10)을 얻었다.The reaction was carried out in the same manner as in Preparation Example 9, using 3-n-furophyl thiazolidine-2-carboxylic acid methyl ester obtained in Preparation Example 8 instead of 2-ethyltaazoridine-2-carboxylic acid methyl ester. 7a-n-furophil-6- (3,5-dichlorophenyl) perhydroimidazo [5,1-b] thiazole-5-thione-7-one (Compound No. 10) was obtained.
융점 : 153~3.5℃, 원소분석치(괄호안은 계산치)Melting Point: 153 ~ 3.5 ℃, Elemental Analysis Value (Calculated Values in Parentheses)
C 46.81% (46.54%), H 3.90%(3.91%), N 7.91%(7.75%), Cl 19.78%(19.62%)C 46.81% (46.54%), H 3.90% (3.91%), N 7.91% (7.75%), Cl 19.78% (19.62%)
[표 1]TABLE 1
제제예 1Formulation Example 1
화합물 No.1 50부, 활석 45부, 솔포올 8070***(고급알코올 황산 에스테르를 주성분으로 하는 계면활성제) 5부를 균일하게 분쇄 혼합하여 살균제(수화제)를 얻었다.50 parts of compound No. 1, 45 parts of talc, and 5 parts of solfool 8070 *** (surfactant mainly containing a higher alcohol sulfate ester) were uniformly ground and mixed to obtain a disinfectant (hydrating agent).
제제예 2Formulation Example 2
화합물 No.3 40부, 화이트카아본 10부, 규조토 47부, 솔포올 5039(폴리옥시에틸렌 알킬아틸에테르 솔포네이트를 주성분으로 하는 계면 활성제) 3부를 균일하게 분쇄 혼합하여 살균제(수화제)를 얻었다.Compound No. 3 40 parts, white carbon 10 parts, diatomaceous earth 47 parts, solfool 5039 (Surfactant which has a polyoxyethylene alkyl aryl ether sorbonate as a main component) 3 parts was uniformly ground and mixed, and the sterilizing agent (hydrating agent) was obtained.
제제예 3Formulation Example 3
화합물 No.2 30부, 솔포올 3005(비이온 계면활성제와 음이온 계면활성제와의 혼합물) 15부, 크실렌 25부, 디메틸포름아미드 30부를 혼합용해하여 살균제(유제)를 얻었다.Compound No. 2 30 parts, Solfool 3005 (Mixture of nonionic surfactant and anionic surfactant) 15 parts, 25 parts of xylene, and 30 parts of dimethylformamide were mixed and dissolved to obtain a disinfectant (emulsion agent).
제제예 4Formulation Example 4
화합물 No.4 2부와 N,N-카올린크레이(쯔찌야 카올린사 제품) 98부를 혼합 분쇄하여 살균제(유제)를 얻었다.2 parts of compound No. 4 and 98 parts of N, N-kaolin crayfish (manufactured by Tsuchiya Kaolin) were mixed and ground to obtain a disinfectant (emulsion agent).
시험예 1 오이회색곰팡이병 방제효과시험Test Example 1 Cucumber gray mold control effect test
직경 15cm의 비닐포트에 재배한 제 1본열시의 오이(품종 : 사쯔끼 미도리에 수화제(제제예 1에 의해 얻어진 화합물 No.1을 유효성분으로 하는 수화제 및 제제에 1과 마찬가지로해서 얻어진 화합물 No.2내지 10을 유효성분으로 하는 수화제 및 비교약제로서 제제예 1과 마찬가지로 해서 얻어지는 테트라클로로이소프탈로 니트릴을 유효성분으로 하는 수화제)를 물로 희석하여, 1포트당 10ml씩 살포하여, 5시간 풍건하였다. 이어서 이스트글루코오스 액체배지에서 진탕배양한 회색곰팡이병균(포트리티스 시네리아 : Bortrytis cinerea)을 분무접종하고, 접종후 4일간, 23℃의 습실에 유지한 후, 발병상태를 조사하였다. 조사방법은 다음에 따랐다. 즉 발병도는 조사잎의 발병면적비율을 구해서, 그 정도에 따라서 0,1,2,3,4,5의 지수로 분류하고, 각 발병지수에 대응되는 잎의 수 n0,n1,n2,n3,n4,n5를 조사하여 다음식에 의해 산출하였다.Cucumber at the time of the first column cultivated in a vinyl pot having a diameter of 15 cm (variety: Satsuki Midori hydrating agent (Compound No. As a hydrating agent having 2 to 10 as an active ingredient and a comparator, a tetrachloroisophthalonitrile obtained as an active ingredient as an active ingredient) was diluted with water, sprayed 10 ml per pot, and air dried for 5 hours. Subsequently, the fungus was inoculated with gray fungal bacteria (Portritic cinerea) shaken in yeast glucose liquid medium, and maintained in a humidified environment at 23 ° C. for 4 days after inoculation. In other words, the incidence is obtained by calculating the incidence area ratio of irradiated leaves, and classifying them according to the degree into the indices of 0,1,2,3,4,5, and the leaves corresponding to each incidence index. The subject to be n 0, n 1, n 2 , n 3, n 4, n 5 irradiation was calculated from the following equation.
(n은 조사한 전잎수)(n is the number of leaves examined)
방제가는 다음식에 의해 산출하였다.The control value was calculated by the following equation.
결과를 제 2표에 표시한다.The results are shown in the second table.
[표 2]TABLE 2
시험예 2 벼호마엽고병 방제효과 시험Test Example 2 Rice horseshoe leaf disease control effect test
직경 10cm의 질그릇 화분에 재배한 3~4엽기의 벼묘(품종 : 긴난 후우)에 수화제 [제제에 1에 의해 얻어진 화합물 No.1을 유효성분으로 하는 수화제 및 제제예 1과 마찬가지로 해서 얻어진 화합물 No. 2~No.10을 유효성분으로 하는 수화제 및 비교약제로 하여 제제예 1과 마찬가지로 해서 얻어지는 비스(디메틸 티오카르바모임)이황화물을 유효성분으로 하는 수화제]를 물로 희석하여 1포트당 10ml씩 살포하여 5시간 풍건한 후, 습실(온도 27℃, 습도 100%)에 두어, 미리 조제한 호마염고병균(cochliobolus miyabeanus : 왕겨배지에서 25℃ 5일간 배양한 것)의 포자 현탁액을 분무접종하였다. 이것을 다시 습실에 48시간 방치한 후, 발병을 조사하여, 방제효과를 산출하였다.Hydrating agent to 3-4 leaf rice seedlings (variety: nannan hoo) grown in earthenware pots with a diameter of 10 cm [Hydrating agent which uses compound No. 1 obtained in preparation 1 as an active ingredient and compound no. Wetting agent containing bis (dimethyl thiocarbamoim) disulfide as an active ingredient obtained in the same manner as in Formulation Example 1 using a hydrating agent containing 2 to No. 10 as an active ingredient and diluting with water, and spraying 10 ml per pot. After 5 hours of air drying, a spore suspension of cochliobolus miyabeanus (cultivated at 25 ° C. for 5 days in a rice hull medium) was spray-inoculated in a wet room (temperature of 27 ° C. and humidity of 100%). After leaving it in the wet room again for 48 hours, the onset was investigated and the control effect was computed.
결과를 제 3표에 표시한다.The results are shown in Table 3.
[표 3]TABLE 3
*대제약제 : 비스(디메틸티오카르바모일)이황화물* Pharmaceutical: Bis (dimethylthiocarbamoyl) disulfide
시험예 3 강남콩균핵병 방제효과시험Experimental Example 3 Control effect test
직경 15cm의 플라스틱제 포트에 재배한 제3본엽시의 강남콩 (품종 : 긴또끼)에 제제예 1 및 제제예 1과 마찬가지로 해서 얻어진 수화제 형태의 공시약제 및 대조약제를 물로 희석하여, 1포트당 10ml씩 살포하여, 5시간 풍건한 후, 이스트글루코오스 액체배지에서 진탕 배양한 균핵병균(sclerotinia Sclorotionum)을 분무접종하고, 접종후 4일간, 23℃의 습실에 유지한 후, 발병상태를 조사하였다. 조사방법은 시험예 1과 같다. 결과는 제4표에 표시한 바와같다. (대조약제는 2,6-디클로로-4-니트로아니린)10 ml per pot is diluted by diluting the hydrated co-agents and the control agent in water, which are obtained in the same manner as in Preparation Example 1 and Preparation Example 1, in Gangnam beans (variety: ginto), grown in plastic pots with a diameter of 15 cm. After sparging and air drying for 5 hours, Sclerotinia Sclorotionum was inoculated with shaking culture in yeast glucose liquid medium, and maintained for 4 days after the inoculation, and kept in a humidified room at 23 ° C. The investigation method is the same as Test Example 1. The results are shown in Table 4. (Comparative agent is 2,6-dichloro-4-nitroaniline)
[표 4]TABLE 4
시험예 4 항균시험Test Example 4 Antibacterial Test
PDA 배지중에 소정농도가 되도록 각 약액을 혼합하여, 직경 9cm의 실험용기에 부어 넣어서 굳힌다.Each chemical solution is mixed to a predetermined concentration in PDA medium, and poured into an experimental container having a diameter of 9 cm and solidified.
그 후, 각종 병원균을 그 한천 평판위의 중앙부에 접종하고, 25℃로 4일간 배양하였다. 판정은 육안에 의해 생육을 전혀 볼 수 없는 농도를 최소생육 저지농도(MIC)로 하였다. 결과를 제 5표에 표시한다.Thereafter, various pathogens were inoculated at the center of the agar plate and incubated at 25 ° C for 4 days. In the judgment, the concentration at which growth was not seen at all by the naked eye was defined as the minimum growth inhibition concentration (MIC). The results are shown in Table 5.
[표 5] 항균시험결과[MIC(ppm)][Table 5] Antibacterial test results [MIC (ppm)]
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