JPH0674249B2 - Method for producing substituted nitroguanidines - Google Patents
Method for producing substituted nitroguanidinesInfo
- Publication number
- JPH0674249B2 JPH0674249B2 JP9123790A JP9123790A JPH0674249B2 JP H0674249 B2 JPH0674249 B2 JP H0674249B2 JP 9123790 A JP9123790 A JP 9123790A JP 9123790 A JP9123790 A JP 9123790A JP H0674249 B2 JPH0674249 B2 JP H0674249B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- formula
- reaction
- nitroguanidines
- producing substituted
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- Thiazole And Isothizaole Compounds (AREA)
- Pyridine Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は殺虫性を有する置換ニトログアニジン類の新規
な製造法に関する。TECHNICAL FIELD The present invention relates to a novel method for producing substituted nitroguanidines having insecticidal properties.
従来の技術 本発明による目的物は公知刊行物には未記載の化合物で
ある。本発明者らはさきにこれらの化合物、その製造法
およびこれらの化合物を活性成分とする殺虫剤を内容と
する特許出願を行なった（特願平１−328888号、特開平
３−200768号）。特願平１−328888号（特開平３−2007
68号）には下記の二つの製造法があげられているがいず
れの方法にも欠点がある。これらの欠点をあげるとつぎ
のとおりである。2. Description of the Related Art The object of the present invention is a compound which has not been described in known publications. The present inventors previously filed a patent application containing these compounds, a method for producing the compounds, and an insecticide containing these compounds as active ingredients (Japanese Patent Application No. 1-328888 and Japanese Patent Application Laid-Open No. 3-200768). . Japanese Patent Application No. 1-328888 (JP-A-3-2007)
No. 68) mentions the following two production methods, but each method has drawbacks. The drawbacks are as follows.
製造法1. 反応式 （式中R1は で表わされる基を示す。） で表わされる反応は悪臭を発するメチルメルカプタンが
副生するという欠点がある。Manufacturing method 1. Reaction formula (Where R 1 is Represents a group represented by. The reaction represented by) has a drawback that methyl mercaptan, which emits a foul odor, is by-produced.
製造法2. 反応式 （式中R1は前記と同じ意味を示す。） で表わされる反応は目的物が低収率でしか得られないと
いう欠点がある。Manufacturing method 2. Reaction formula (In the formula, R 1 has the same meaning as described above.) The disadvantage of the reaction is that the desired product can be obtained only in a low yield.
発明が解決しようとする課題 本発明は悪臭を放つメルカプタン類の副生、あるいは目
的物の低収率という従来方法の欠点を克服し、非常に簡
単な操作で、しかも大量に生産し得る、工業的な実施に
有利な置換ニトログアニジン類の新規な製造法を提供す
るためになされたものである。DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention The present invention overcomes the disadvantages of the conventional methods such as a by-product of odorous mercaptans or a low yield of a target substance, can be produced in a large amount with a very simple operation, and can be produced in a large amount. The present invention was made to provide a novel method for producing substituted nitroguanidines which is advantageous for practical implementation.
課題を解決するための手段 本発明者らは置換ニトログアニジン類の製造法について
鋭意研究の結果、置換２−ニトロイミノ−1,3,5−ヘキ
サヒドロトリアジン化合物の酸による開環反応によっ
て、置換ニトログアニジン類を収率良く製造し得ること
を見出し本発明を完成するに至った。Means for Solving the Problems As a result of earnest research on a method for producing substituted nitroguanidines, the present inventors have found that a substituted nitroguanidine-1,3,5-hexahydrotriazine compound is subjected to a ring-opening reaction with an acid to give a substituted nitroguanidine. The inventors have found that guanidines can be produced in high yield and have completed the present invention.
本発明の製造法は下記のようにして実施される。The production method of the present invention is carried out as follows.
反応式 （式中Ｒは低級アルキル基または低級アルケニル基を示
し、R1は で表わされる基を示す。） で表わされる反応で示されるとおり、一般式（Ｉ）で表
わされる化合物を酸の存在下に開環することによって、
一般式（II）で表わされる目的生成物を極めて容易に収
率良く得ることができる。一般式（Ｉ）で表わされる化
合物は本発明と同一出願人による特願平２−24199号
（特開平３−218370号）に開示された方法によって容易
に製造することができる。上記の反応における酸として
は塩酸、硫酸等の鉱酸または酢酸、トルエンスルホン酸
等の有機酸が使用できる。通常過剰量が使用されるが、
好ましくは1.5〜10倍モルが適当である。また溶媒とし
ては水、酢酸、メタノール、エタノール等のアルコール
類、ジクロロメタン、ジクロロエチレン等の塩素化炭化
水素、アセトン、メチルエチルケトン等のケトン類等が
使用でき、単独かまたは適当に混合することにより使用
される。反応温度は20℃からその溶媒の沸騰温度まで任
意に設定できるが、好ましくは40〜110℃の間で行なわ
れる。Reaction formula (In the formula, R represents a lower alkyl group or a lower alkenyl group, and R 1 is Represents a group represented by. ) As shown in the reaction represented by the following formula, by ring-opening the compound represented by the general formula (I) in the presence of an acid,
The target product represented by the general formula (II) can be obtained very easily in good yield. The compound represented by the general formula (I) can be easily produced by the method disclosed in Japanese Patent Application No. 2-24199 (JP-A-3-218370) filed by the same applicant as the present invention. As the acid in the above reaction, a mineral acid such as hydrochloric acid or sulfuric acid, or an organic acid such as acetic acid or toluenesulfonic acid can be used. Usually in excess,
It is preferably 1.5 to 10 times by mole. As the solvent, water, alcohols such as acetic acid, methanol and ethanol, chlorinated hydrocarbons such as dichloromethane and dichloroethylene, ketones such as acetone and methyl ethyl ketone can be used, and they can be used alone or by appropriately mixing them. . The reaction temperature can be arbitrarily set from 20 ° C to the boiling temperature of the solvent, but is preferably 40 to 110 ° C.
次に実施例をあげて本発明の内容を具体的に説明する。Next, the contents of the present invention will be specifically described with reference to examples.
実施例１ １−（２−クロロ−５−ピリジルメチル）−3,5−ジメ
チル−２−ニトロイミノ−1,3,5−ヘキサヒドロトリア
ジン0.5gを酢酸10mlに溶解し、2Nの塩酸を2ml加え、50
〜60℃で30分間加熱攪拌した。放冷後酢酸を減圧下に留
去し、残渣に重曹水を加え、析出した結晶を濾集し、水
洗し、乾燥して目的物であるＮ−（２−クロロ−５−ピ
リジルメチル）−Ｎ′−メチルニトログアニジン0.33g
を得た。Example 1 0.5 g of 1- (2-chloro-5-pyridylmethyl) -3,5-dimethyl-2-nitroimino-1,3,5-hexahydrotriazine was dissolved in 10 ml of acetic acid, 2 ml of 2N hydrochloric acid was added, and 50
The mixture was heated and stirred at -60 ° C for 30 minutes. After allowing to cool, acetic acid was distilled off under reduced pressure, aqueous sodium hydrogen carbonate was added to the residue, and the precipitated crystals were collected by filtration, washed with water, and dried to obtain the desired product, N- (2-chloro-5-pyridylmethyl)-. N'-methylnitroguanidine 0.33g
Got
収率 81％ 融点 157〜158℃ 実施例２ １−（２−クロロ−５−チアゾリルメチル）−3,5−ジ
メチル−２−ニトロイミノ−1,3,5−ヘキサヒドロトリ
アジン0.6g、エタノール5mlおよび1Nの硫酸3mlを30分間
加熱還流した。放冷後重曹水で中和し、減圧下にエタノ
ールを留去し、得られた結晶を濾集し、水洗し、乾燥し
て目的物であるＮ−（２−クロロ−５−チアゾリルメチ
ル）−Ｎ′−メチルニトログアニジン0.48gを得た。Yield 81% Melting point 157-158 ° C Example 2 0.6 g of 1- (2-chloro-5-thiazolylmethyl) -3,5-dimethyl-2-nitroimino-1,3,5-hexahydrotriazine, 5 ml of ethanol and 3 ml of 1N sulfuric acid were heated under reflux for 30 minutes. After cooling, the mixture was neutralized with aqueous sodium hydrogen carbonate, ethanol was distilled off under reduced pressure, and the obtained crystals were collected by filtration, washed with water, and dried to give N- (2-chloro-5-thiazolylmethyl) -of the desired product. 0.48 g of N'-methylnitroguanidine was obtained.
収率 97％ 融点 169〜170℃ 実施例３ １−（２−クロロ−５−ピリジルメチル）−3,5−ジメ
チル−２−ニトロイミノ−1,3,5−ヘキサヒドロトリア
ジン0.5gを20％酢酸30mlに溶解し、50〜60℃で30分間加
熱攪拌した。放冷後重曹水を加えて中和し、析出した結
晶を濾集し、水洗し、乾燥して目的物であるＮ−（２−
クロロ−５−ピリジルメチル）−Ｎ′−メチルニトログ
アニジン0.28gを得た。Yield 97% Melting point 169-170 ° C Example 3 Dissolve 0.5 g of 1- (2-chloro-5-pyridylmethyl) -3,5-dimethyl-2-nitroimino-1,3,5-hexahydrotriazine in 30 ml of 20% acetic acid and at 50-60 ° C for 30 minutes. Heated and stirred. After cooling, sodium bicarbonate water was added to neutralize, and the precipitated crystals were collected by filtration, washed with water, and dried to obtain N- (2-
0.28 g of chloro-5-pyridylmethyl) -N'-methylnitroguanidine was obtained.
収率 69％ 融点 157〜158℃ 効 果 置換２−ニトロイミノ−1,3,5−ヘキサヒドロトリアジ
ン化合物の酸による開環反応によって置換ニトログアニ
ジン類を極めて容易に収率良く得ることができる。Yield 69% Melting point 157-158 ° C Effect The substituted nitroguanidines can be obtained very easily and in good yield by the ring-opening reaction of the substituted 2-nitroimino-1,3,5-hexahydrotriazine compound with an acid.
Claims (1)
し、R1は で表わされる基を示す。） で表わされる化合物を、酸の存在下に開環させることを
特徴とする一般式（II） （式中R1は前記と同じ意味を示す。） で表わされる置換ニトログアニジン類の製造法。1. A general formula (I) (In the formula, R represents a lower alkyl group or a lower alkenyl group, and R 1 is Represents a group represented by. ) The compound represented by the general formula (II) is characterized by ring-opening in the presence of an acid. (In the formula, R 1 has the same meaning as described above.) A method for producing a substituted nitroguanidine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9123790A JPH0674249B2 (en) | 1990-04-05 | 1990-04-05 | Method for producing substituted nitroguanidines |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9123790A JPH0674249B2 (en) | 1990-04-05 | 1990-04-05 | Method for producing substituted nitroguanidines |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03291267A JPH03291267A (en) | 1991-12-20 |
| JPH0674249B2 true JPH0674249B2 (en) | 1994-09-21 |
Family
ID=14020814
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9123790A Expired - Lifetime JPH0674249B2 (en) | 1990-04-05 | 1990-04-05 | Method for producing substituted nitroguanidines |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0674249B2 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW198724B (en) * | 1990-10-24 | 1993-01-21 | Ciba Geigy Ag | |
| DE19712411A1 (en) | 1997-03-25 | 1998-10-01 | Bayer Ag | Process for the preparation of 1,3-disubstituted 2-nitroguanidines |
| US6118007A (en) * | 1997-03-31 | 2000-09-12 | Mitsui Chemicals, Inc. | Preparation process of nitroguanidine derivatives |
| PL338778A1 (en) * | 1997-08-20 | 2000-11-20 | Novartis Ag | Method of obtaining substitution derivatives of 2-nitroguanidine |
| DE19806469A1 (en) * | 1998-02-17 | 1999-08-19 | Bayer Ag | Preparation of 2-nitroguanidine derivatives useful as insecticides and acaricides |
| DE19961604A1 (en) | 1999-12-21 | 2001-07-05 | Bayer Ag | Process for the preparation of 1,3-disubstituted 2-nitroguanidines |
| DE10121652A1 (en) * | 2001-05-03 | 2002-11-07 | Bayer Ag | Process for the preparation of 1,3-disubstituted 2-nitroguanidines |
| CN101379035B (en) | 2006-02-10 | 2011-01-12 | 三井化学株式会社 | Improved method for producing nitroguanidine derivative |
| WO2015002150A1 (en) | 2013-07-03 | 2015-01-08 | 株式会社新日本科学 | Novel compound, organic cation transporter 3 detection agent, and organic cation transporter 3 activity inhibitor |
| CN108610300A (en) * | 2016-12-10 | 2018-10-02 | 海利尔药业集团股份有限公司 | A method of preparing clothianidin |
| CN114014821B (en) * | 2021-11-22 | 2022-10-21 | 江苏中旗科技股份有限公司 | Preparation method of clothianidin |
-
1990
- 1990-04-05 JP JP9123790A patent/JPH0674249B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03291267A (en) | 1991-12-20 |
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