JPH0219827B2 - - Google Patents
Info
- Publication number
- JPH0219827B2 JPH0219827B2 JP56214520A JP21452081A JPH0219827B2 JP H0219827 B2 JPH0219827 B2 JP H0219827B2 JP 56214520 A JP56214520 A JP 56214520A JP 21452081 A JP21452081 A JP 21452081A JP H0219827 B2 JPH0219827 B2 JP H0219827B2
- Authority
- JP
- Japan
- Prior art keywords
- lower alkyl
- alkyl group
- compound
- ring
- general formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 150000001875 compounds Chemical class 0.000 claims description 26
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 125000004434 sulfur atom Chemical group 0.000 claims description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- -1 p-methylbenzyl Chemical group 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 238000007363 ring formation reaction Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- RHUYHJGZWVXEHW-UHFFFAOYSA-N 1,1-Dimethyhydrazine Chemical compound CN(C)N RHUYHJGZWVXEHW-UHFFFAOYSA-N 0.000 description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229960003237 betaine Drugs 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 238000006798 ring closing metathesis reaction Methods 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 240000008067 Cucumis sativus Species 0.000 description 1
- 235000010799 Cucumis sativus var sativus Nutrition 0.000 description 1
- 244000058871 Echinochloa crus-galli Species 0.000 description 1
- 235000007688 Lycopersicon esculentum Nutrition 0.000 description 1
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical group C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 240000003768 Solanum lycopersicum Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 244000000005 bacterial plant pathogen Species 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000004803 chlorobenzyl group Chemical group 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000009422 growth inhibiting effect Effects 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- DMJJQMYOTLIZHC-UHFFFAOYSA-N methyl N-ethoxycarbothioylcarbamate Chemical compound CCOC(=S)NC(=O)OC DMJJQMYOTLIZHC-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
Landscapes
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
本発明は一般式
（式中、R1は低級アルキル基又は置換基を有
するか有しないベンジル基を示し、R2およびR3
は低級アルキル基を示すか、又はR2とR3とは、
一緒に、それらが結合している窒素原子と共に環
を形成し、Ｘは酸素原子又は硫黄原子を示す。）
で表わされる化合物およびその製法に関するもの
である。
本発明の一般式（）で表わされる化合物は、
いずれも新規な化合物であり、医薬、農薬の中間
体として有用な化合物である。
又そのもの自体、植物や植物病原菌に対して生
育抑制作用を有しており、イネのいもち病、トマ
トえき病、キユウリたんそ病、たちがれ病の防除
又は水田のヒエ、広葉雑草を駆除するのに有用な
化合物である。
前記一般式（）を有する化合物を製造するに
は一般式
（式中、R1，R2，R3およびＸは前述と同意義
を示し、R4は低級アルキル基又はフエニル基を
示す。）で表わされる化合物を塩基の存在下又は
非存在下で加熱閉環せしめることにより容易に製
造することができる。
一般式（）で表わされる化合物は、次に示す
ような共鳴構造を考えることができる。
（式中、R1乃至R3およびＸは前述したものと
同じ。）
実在するのはこれらの化合物の混合物ではな
く、一つの化合物であり、このような化合物はメ
ソイオン化合物と呼ばれている。
（大田正樹他、ノンベンゼノイド・アロマテイ
ツクス、第１巻 117頁、1969年アカデミツクプ
レス刊参照）
一般式（）において、R1は例えばメチル、
エチル、ｎ−プロピル、iso−プロピル、ｎ−ブ
チルのような低級アルキル基又はベンジル、ｐ−
クロロベンジル、ｐ−メチルベンジルのような置
換基を有するか有しないベンジル基を示す。
R2，R3は例えばメチル、エチルのような低級
アルキル基を示すか、又は、R2とR3とは、一緒
に、それらが結合している窒素原子と共に、ピペ
リジン環又はモルホリン環を形成する。
一般式（）で示される化合物の原料として用
いられる化合物（）において、R4は例えばメ
チル、エチルのような低級アルキル基又はフエニ
ル基を示す。
化合物（）から（）への閉環反応において
共存せしめ得る塩基としては、例えば炭酸ナトリ
ウム、炭酸カリウム、などの無機塩基又はトリエ
チルアミン、ジメチルアニリンなどの有機塩基が
あげられる。
一般式（）で表わされる化合物は次式により
製造することができる。
Ｘが酸素原子である場合
Ｘが硫黄原子である場合
（式中、R1，R2，R3およびR4は前述と同意義
を示し、Ｚは臭素又は沃素原子を示す。）
上記の反応で得られる化合物（）は通常単離
する必要はなく、上記）又は）の反応を前述
した閉環反応の条件下におくことにより直接本発
明の目的化合物である化合物（）を得ることが
できる。
化合物（）から化合物（）への閉環反応は
有機溶媒の存在下で実施することが望ましいが、
無溶媒でも反応は進行する。通常80℃から150℃
に加熱することにより閉環反応が進行し、化合物
（）を与える。閉環に必要とされる反応時間は
多くの場合30分から３時間程度で十分である。
次に実施例を示して本発明を具体的に説明する
が本発明はこれらの実施例に限定されるものでは
ない。
実施例 １
エトキシチオカルボニルカルバミン酸メチル
4.9ｇと１，１−ジメチルヒドラジン2.0ｇをメタ
ノール60ml中に溶解させて、約６時間加熱還流
し、溶媒を留去すると粗製のN′−メトキシカル
ボニル−Ｎ，Ｎ−ジメチルヒドラゾノホルムイミ
ジツク酸エチル5.5ｇを油状物として得る。（純品
のIRνLiquid naxcm-1：1760，1650，1610）この油状残
渣を130〜135℃で約１時間さらに加熱撹拌したの
ち冷却し析出する結晶を取し、アセトンで洗滌
すると融点141〜142℃を示す１，１−ジメチル−
３−エトキシ−５−オキソ−１，２，４−トリア
ゾリウム・ベタイン2.14ｇを得る。収率45.53％。
IRNujol naxcm-1：1780（Ｃ＝Ｏ）
実施例 ２〜10
同様にして表の化合物を得た。
The present invention is based on the general formula (In the formula, R 1 represents a lower alkyl group or a benzyl group with or without a substituent, and R 2 and R 3
represents a lower alkyl group, or R 2 and R 3 are
Together, with the nitrogen atom to which they are attached, they form a ring, and X represents an oxygen or sulfur atom. )
The present invention relates to the compound represented by and its manufacturing method. The compound represented by the general formula () of the present invention is
All of these compounds are new and useful as intermediates for pharmaceuticals and agricultural chemicals. In addition, it itself has a growth-inhibiting effect on plants and plant-pathogenic bacteria, and can be used to control rice blast, tomato blight, cucumber blight, and rotting bacterium, and to exterminate barnyard grass and broad-leaved weeds in paddy fields. It is a useful compound for To produce a compound having the above general formula (), use the general formula (In the formula, R 1 , R 2 , R 3 and X have the same meanings as above, and R 4 represents a lower alkyl group or a phenyl group.) Heating the compound represented by It can be easily produced by ring closure. The compound represented by the general formula () can be considered to have a resonance structure as shown below. (In the formula, R 1 to R 3 and X are the same as described above.) What actually exists is not a mixture of these compounds, but a single compound, and such a compound is called a mesoionic compound. (See Masaki Ota et al., Nonbenzenoid Aromatics, Vol. 1, p. 117, published by Academic Press, 1969) In the general formula (), R 1 is, for example, methyl,
Lower alkyl groups such as ethyl, n-propyl, iso-propyl, n-butyl or benzyl, p-
It refers to benzyl groups with or without substituents such as chlorobenzyl and p-methylbenzyl. R 2 and R 3 represent a lower alkyl group such as methyl or ethyl, or R 2 and R 3 together form a piperidine ring or a morpholine ring with the nitrogen atom to which they are bonded. do. In the compound () used as a raw material for the compound represented by the general formula (), R 4 represents, for example, a lower alkyl group such as methyl or ethyl, or a phenyl group. Examples of bases that can coexist in the ring-closing reaction of compound () to () include inorganic bases such as sodium carbonate and potassium carbonate, and organic bases such as triethylamine and dimethylaniline. The compound represented by the general formula () can be produced by the following formula. When X is an oxygen atom When X is a sulfur atom (In the formula, R 1 , R 2 , R 3 and R 4 have the same meanings as above, and Z represents a bromine or iodine atom.) The compound () obtained by the above reaction usually does not need to be isolated. , above) or) under the conditions of the ring-closing reaction described above, the compound (), which is the target compound of the present invention, can be directly obtained. The ring-closing reaction from compound () to compound () is preferably carried out in the presence of an organic solvent, but
The reaction proceeds even without solvent. Normally 80℃ to 150℃
The ring-closing reaction proceeds by heating to give the compound (). The reaction time required for ring closure is often about 30 minutes to 3 hours. Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples. Example 1 Methyl ethoxythiocarbonylcarbamate
4.9 g and 2.0 g of 1,1-dimethylhydrazine were dissolved in 60 ml of methanol, heated under reflux for about 6 hours, and the solvent was distilled off to obtain crude N'-methoxycarbonyl-N,N-dimethylhydrazonoform imidzic. 5.5 g of ethyl acid are obtained as an oil. (Pure product IRν Liquid nax cm -1 : 1760, 1650, 1610) This oily residue was further heated and stirred at 130-135℃ for about 1 hour, then cooled, the precipitated crystals were collected, and washed with acetone, resulting in a melting point of 141~ 1,1-dimethyl- showing 142℃
2.14 g of 3-ethoxy-5-oxo-1,2,4-triazolium betaine are obtained. Yield 45.53%.
IR Nujol nax cm -1 : 1780 (C=O) Examples 2 to 10 The compounds shown in the table were obtained in the same manner.
【表】
実施例 11
１，１−ジメチル−４−エトキシカルボニルチ
オセミカルバジド6.70ｇとヨードメチル5.7ｇを
炭酸カリウム4.8ｇとともにアセトン70ml中に混
和し、約10時間室温にて撹拌し、不溶分を別し
たのち溶媒を留去すると粗製のN′−エトキシカ
ルボニル−Ｎ，Ｎ−ジメチルヒドラゾノチオホル
ムイミジツク酸メチル6.5ｇ（収率91.5％）を油
状物として得る。（純品のIRνLiquid naxcm-1：1740，
1640，1570）この油状残渣を120〜130℃で約１時
間さらに加熱撹拌したのち冷却し、析出する結晶
にベンゼン20mlを加え再結晶すると融点148〜149
℃を示す１，１−ジメチル−３−メチルチオ−５
−オキソ−１，２，４−トリアゾリウム・ベタイ
ン4.6ｇを得る。全収率83.6％。IRνNujol naxcm-1：
1760（Ｃ＝Ｏ）
実施例 12−21
同様にして表の化合物を得た。[Table] Example 11 6.70 g of 1,1-dimethyl-4-ethoxycarbonylthiosemicarbazide and 5.7 g of iodomethyl were mixed in 70 ml of acetone with 4.8 g of potassium carbonate, stirred at room temperature for about 10 hours, and the insoluble matter was separated. Thereafter, the solvent was distilled off to obtain 6.5 g (yield 91.5%) of crude methyl N'-ethoxycarbonyl-N,N-dimethylhydrazonothioformimidinate as an oil. (Pure product IRν Liquid nax cm -1 : 1740,
1640, 1570) This oily residue was further heated and stirred at 120-130°C for about 1 hour, then cooled, and 20 ml of benzene was added to the precipitated crystals to recrystallize, resulting in a melting point of 148-149.
1,1-dimethyl-3-methylthio-5 showing °C
4.6 g of -oxo-1,2,4-triazolium betaine are obtained. Overall yield 83.6%. IRν Nujol nax cm -1 :
1760 (C=O) Example 12-21 The compounds shown in the table were obtained in the same manner.
Claims (1)
するか有しないベンジル基を示し、R2およびR3
は低級アルキル基を示すか、又はR2とR3とは、
一緒に、それらが結合している窒素原子と共に環
を形成し、Ｘは酸素原子又は硫黄原子を示す。）
で表わされる化合物。 ２ 一般式 （式中、R1は低級アルキル基又は置換基を有
するか有しないベンジル基を示し、R2およびR3
は低級アルキル基を示すか、又はR2とR3とは、
一緒に、それらが結合している窒素原子と共に環
を形成し、R4は低級アルキル基又はフエニル基
を示し、Ｘは酸素原子又は硫黄原子を示す。）で
表わされる化合物を加熱閉環することを特徴とす
る一般式 （式中、R1，R2，R3およびＸは前述と同意義
を示す。）で表わされる化合物の製法。[Claims] 1. General formula (In the formula, R 1 represents a lower alkyl group or a benzyl group with or without a substituent, and R 2 and R 3
represents a lower alkyl group, or R 2 and R 3 are
Together, with the nitrogen atom to which they are attached, they form a ring, and X represents an oxygen or sulfur atom. )
A compound represented by 2 General formula (In the formula, R 1 represents a lower alkyl group or a benzyl group with or without a substituent, and R 2 and R 3
represents a lower alkyl group, or R 2 and R 3 are
Together, with the nitrogen atom to which they are attached, they form a ring, R 4 represents a lower alkyl group or a phenyl group, and X represents an oxygen or sulfur atom. ) A general formula characterized by thermally ring-closing a compound represented by A method for producing a compound represented by the formula (wherein R 1 , R 2 , R 3 and X have the same meanings as above).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56214520A JPS58116475A (en) | 1981-12-28 | 1981-12-28 | 1,2,4-triazolium betaine compound and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56214520A JPS58116475A (en) | 1981-12-28 | 1981-12-28 | 1,2,4-triazolium betaine compound and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58116475A JPS58116475A (en) | 1983-07-11 |
| JPH0219827B2 true JPH0219827B2 (en) | 1990-05-07 |
Family
ID=16657076
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56214520A Granted JPS58116475A (en) | 1981-12-28 | 1981-12-28 | 1,2,4-triazolium betaine compound and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58116475A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0565752U (en) * | 1992-02-18 | 1993-08-31 | 株式会社ユニシアジェックス | Reservoir tank device |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3578881B2 (en) * | 1997-01-31 | 2004-10-20 | 富士機工株式会社 | Steering column tilt holding force adjustment mechanism |
| US6489487B1 (en) | 1998-08-03 | 2002-12-03 | Sumitomo Chemical Company, Limited | Triazolone derivatives, use thereof, and intermediates therefor |
| US6602824B1 (en) * | 1999-02-16 | 2003-08-05 | Greener Pastures Development Corp. | Herbicidal composition and a method of using a naturally-occurring organic compound as a herbicide |
| WO2015052103A1 (en) * | 2013-10-11 | 2015-04-16 | Syngenta Participations Ag | Pesticidally active n-iminopyridinium ylide compounds |
-
1981
- 1981-12-28 JP JP56214520A patent/JPS58116475A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0565752U (en) * | 1992-02-18 | 1993-08-31 | 株式会社ユニシアジェックス | Reservoir tank device |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58116475A (en) | 1983-07-11 |
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