JPS6155909B2 - - Google Patents
Info
- Publication number
- JPS6155909B2 JPS6155909B2 JP8882882A JP8882882A JPS6155909B2 JP S6155909 B2 JPS6155909 B2 JP S6155909B2 JP 8882882 A JP8882882 A JP 8882882A JP 8882882 A JP8882882 A JP 8882882A JP S6155909 B2 JPS6155909 B2 JP S6155909B2
- Authority
- JP
- Japan
- Prior art keywords
- methoxy
- methylaminopyridine
- reaction
- methoxypyridine
- methylamine
- 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
Landscapes
- Pyridine Compounds (AREA)
Description
本発明は、２−メトキシ−６−メチルアミノピ
リジン及びその製造法に関する。
２−メトキシ−６−メチルアミノピリジンは新
規な化合物であり、医薬、農薬などに用いること
のできる物質への中間体として有用である。
本発明の２−メトキシ−６−メチルアミノピリ
ジンは２−ナフチル クロルチオホルメイトと反
応させてＯ−２−ナフチル Ｎ−（６−メトキシ
−２−ピリジル）−Ｎ−メチルチオカーバメート
を製造することができる。こうして得られるＯ−
２−ナフチル Ｎ−（６−メトキシ−２−ピリジ
ル）−Ｎ−メチルチオカーバメートからはこれを
有効成分とする除草剤を調整することができる。
このものはノビエをはじめとする多くの雑草に
対して、極めて優れた除草活性を示すとともに移
植水稲には無害で水田用除草剤として好適であ
る。また、畑地土壌処理によりイネ科雑草−広葉
作物間に優れた選択除草効果を示めし、畑地用除
草剤としても適用性を有する。
本発明の化合物のこのような有用性については
特願昭57−040759号明細書中に開示されている。
本発明の２−メトキシ−６−メチルアミノピリ
ジンは、一般式
The present invention relates to 2-methoxy-6-methylaminopyridine and a method for producing the same. 2-Methoxy-6-methylaminopyridine is a novel compound and is useful as an intermediate for substances that can be used in medicines, agricultural chemicals, and the like. The 2-methoxy-6-methylaminopyridine of the present invention can be reacted with 2-naphthyl chlorothioformate to produce O-2-naphthyl N-(6-methoxy-2-pyridyl)-N-methylthiocarbamate. can. O-
A herbicide containing 2-naphthyl N-(6-methoxy-2-pyridyl)-N-methylthiocarbamate as an active ingredient can be prepared from 2-naphthyl N-(6-methoxy-2-pyridyl)-N-methylthiocarbamate. This product exhibits extremely excellent herbicidal activity against many weeds, including field weeds, and is harmless to transplanted paddy rice, making it suitable as a herbicide for paddy fields. In addition, it shows an excellent selective weeding effect between grass weeds and broad-leaved crops when treated with upland soil, and has applicability as a herbicide for upland fields. Such usefulness of the compounds of the present invention is disclosed in Japanese Patent Application No. 57-040759. The 2-methoxy-6-methylaminopyridine of the present invention has the general formula
【式】（式中Ｘは臭
素原子あるいは塩素原子を示す。）で表わされる
２−ハロ−６−メトキシピリジンとメチルアミン
との反応、一般式Reaction of 2-halo-6-methoxypyridine represented by [Formula] (wherein X represents a bromine atom or a chlorine atom) with methylamine, general formula
【式】（式中Ｘ
は前記に同じ）で表わされる２−ハロ−６−メチ
ルアミノピリジンとナトリウムメチラートとの反
応、２−アミノ−６−メトキシピリジンとヨウ化
メチルとの反応、あるいは２−ハイドロキシ−６
−メチルアミノピリジンとジアゾメタンとの反応
等種々の方法により製造できる。
本発明の方法は２−ハロ−６−メトキシピリジ
ンとメチルアミンとを反応させることを特徴とす
る２−メトキシ−６−メチルアミノピリジンの製
造法を提供するものである。
メチルアミンの使用量は、２−ハロ−６−メト
キシピリジンに対して約２〜約10倍モルである。
反応を円滑に進めるために溶媒を用いる。溶媒と
しては２−ハロ−６−メトキシピリジン、メチル
アミンと反応せず、しかもメチルアミンを溶解す
る水、ベンゼン、アルコール等を挙げることがで
きる。
メチルアミンは常温では気体であり、通常は水
溶液として入手できる。そのため、一般には２−
ハロ−６−メトキシピリジンとメチルアミン水溶
液を反応させるのが簡便である。反応温度は約
100〜約200℃、好ましくは約140〜約180℃であ
り、反応時間は約１〜約20時間が適当である。
次に実施例でもつて本発明を詳細に説明するが
本発明はこれら実施例のみに限定されるものでは
ない。
実施例 １
200mlの電磁撹拌式オートクレーブに２−クロ
ル−６−メトキシピリジン43ｇ、40％−メチルア
ミン水溶液75mlを取り、180℃にて12時間反応さ
せた。反応終了後オートクレーブを冷却し、開缶
して反応液を取り出した。次いで反応液に固体の
水酸化ナトリウムを30ｇ添加後、エーテルで抽出
した。エーテル抽出液を固体の水酸化ナトリウム
で乾燥し、エーテルを留去した。
エーテル留去後の残渣を減圧蒸留し、沸点88〜
92℃／５mmHgの２−メトキシ−６−メチルアミ
ノピリジン18ｇを得た。
赤外線吸収スペクトル（NaCl）
3420（−NH）、2950（Ｃ−Ｈ）、1600、1475、Reaction of 2-halo-6-methylaminopyridine represented by [Formula] (wherein X is the same as above) with sodium methylate, reaction of 2-amino-6-methoxypyridine and methyl iodide, or -Hydroxy-6
- It can be produced by various methods such as reaction of methylaminopyridine and diazomethane. The method of the present invention provides a method for producing 2-methoxy-6-methylaminopyridine, which is characterized by reacting 2-halo-6-methoxypyridine and methylamine. The amount of methylamine used is about 2 to about 10 times the molar amount of 2-halo-6-methoxypyridine.
A solvent is used to facilitate the reaction. Examples of the solvent include water, benzene, alcohol, etc., which do not react with 2-halo-6-methoxypyridine and methylamine, and which dissolve methylamine. Methylamine is a gas at room temperature and is usually available as an aqueous solution. Therefore, generally 2-
It is convenient to react halo-6-methoxypyridine with an aqueous methylamine solution. The reaction temperature is approx.
The temperature is 100 to about 200°C, preferably about 140 to about 180°C, and the reaction time is suitably about 1 to about 20 hours. Next, the present invention will be explained in detail with reference to Examples, but the present invention is not limited to these Examples. Example 1 43 g of 2-chloro-6-methoxypyridine and 75 ml of a 40% aqueous methylamine solution were placed in a 200 ml electromagnetic stirring autoclave and reacted at 180°C for 12 hours. After the reaction was completed, the autoclave was cooled, opened, and the reaction solution was taken out. Next, 30 g of solid sodium hydroxide was added to the reaction solution, followed by extraction with ether. The ether extract was dried over solid sodium hydroxide, and the ether was distilled off. The residue after distilling off the ether is distilled under reduced pressure, and the boiling point is 88~
18 g of 2-methoxy-6-methylaminopyridine was obtained at 92°C/5 mmHg. Infrared absorption spectrum (NaCl) 3420 (-NH), 2950 (C-H), 1600, 1475,
【式】
核磁気共鳴吸収スペクトル（CCl4、内部標準
TMS）
δ 2.86(d)ppm （3H）
δ 3.85（ｓ）〃 （3H）
δ 4.40 〃 （1H）
δ 5.84(d)〃 （1H）
δ 5.94(d)〃 （1H）
δ 7.12（ｔ）〃 （1H）
元素分析（C7H10N2Oとして）結果は以下の通
りであつた。
Ｃ Ｈ Ｎ Ｏ
分析値（％） 60.75 7.22 20.35 11.68
理論値（％） 60.85 7.30 20.27 11.58
GC−MSによる分子量 138
実施例 ２
実施例１と同一の反応装置に２−ブロモ−６−
メトキシピリジン30ｇ、40％−メチルアミン水溶
液75mlを140℃にて18時間反応させた。反応終了
後、実施例１と同一の実験操作を行い２−メトキ
シ−６−メチルアミノピリジン11ｇを得た。
次に本発明化合物から得られる化合物および除
草剤としての使用例を示す。
本発明の方法の目的物質である２−メトキシ−
６−メチルアミノピリジン1.38ｇ及び同量の無水
炭酸カリウムを20mlのアセトン中室温で撹拌、ア
セトン20mlに溶かした２−ナフチル クロルチオ
ホルメイト2.23ｇを加え30分後反応混合物をベン
ゼンで抽出、水洗、乾燥、再結晶してＯ−２−ナ
フチル Ｎ−（６−メトキシ−２−ピリジル）−Ｎ
−メチル−チオカーバメート2.75ｇを得た。
融点 95.5〜97℃
元素分析（C18H16N2O2Sとして）
Ｃ Ｈ Ｎ
分析値（％） 66.42 4.89 8.81
理論値（％） 66.65 4.97 8.64
直径９cmの磁製ポツトに水田土壌を入れ、水を
加えて代かき後、土壌表層に雑草種子を播き、２
葉期の水稲苗（品種、日本晴）を１cmの深さに、
２本２株植とした。翌日２cmの湛水を行い、Ｏ−
２−ナフチル Ｎ−（６−メトキシ−２−ピリジ
ル）−Ｎ−メチルチオカーバメート10％を含む水
和剤をポツト当り10mlの水に希釈して水面に滴下
処理した。その後、温室に静置し薬液処理３週間
後に除草効果および水稲に及ぼした影響を調査し
た。この結果、供試薬量125ｇ／10aで水稲苗に全
く薬害がなく、ノビエ、タマガヤツリ、ホタル
イ、コナギ、キカシグサを100％防除した。[Formula] Nuclear magnetic resonance absorption spectrum (CCl 4 , internal standard
TMS) δ 2.86(d)ppm (3H) δ 3.85(s)〃 (3H) δ 4.40〃 (1H) δ 5.84(d)〃 (1H) δ 5.94(d)〃 (1H) δ 7.12(t)〃 (1H) The results of elemental analysis (as C 7 H 10 N 2 O) were as follows. C H N O Analytical value (%) 60.75 7.22 20.35 11.68 Theoretical value (%) 60.85 7.30 20.27 11.58 Molecular weight by GC-MS 138 Example 2 2-Bromo-6- was added to the same reaction apparatus as Example 1.
30 g of methoxypyridine and 75 ml of a 40% aqueous methylamine solution were reacted at 140°C for 18 hours. After the reaction was completed, the same experimental procedure as in Example 1 was carried out to obtain 11 g of 2-methoxy-6-methylaminopyridine. Next, examples of compounds obtained from the compounds of the present invention and their use as herbicides will be shown. 2-methoxy- which is the target substance of the method of the present invention
1.38 g of 6-methylaminopyridine and the same amount of anhydrous potassium carbonate were stirred in 20 ml of acetone at room temperature, 2.23 g of 2-naphthyl chlorothioformate dissolved in 20 ml of acetone was added, and after 30 minutes the reaction mixture was extracted with benzene and washed with water. , dried and recrystallized to give O-2-naphthyl N-(6-methoxy-2-pyridyl)-N
2.75 g of -methyl-thiocarbamate were obtained. Melting point 95.5-97℃ Elemental analysis (as C 18 H 16 N 2 O 2 S) C H N Analysis value (%) 66.42 4.89 8.81 Theoretical value (%) 66.65 4.97 8.64 Paddy soil was placed in a porcelain pot with a diameter of 9 cm. After adding water and plowing, weed seeds are sown on the soil surface layer.
Paddy rice seedlings (variety, Nipponbare) in the leaf stage are planted at a depth of 1 cm.
Two plants were planted. The next day, the water was flooded to a depth of 2 cm, and O-
A wettable powder containing 10% of 2-naphthyl N-(6-methoxy-2-pyridyl)-N-methylthiocarbamate was diluted in 10 ml of water per pot and dropped onto the water surface. Thereafter, the plants were left in a greenhouse and three weeks after the chemical treatment, the herbicidal effect and the effect on paddy rice were investigated. As a result, the test chemical amount of 125g/10a caused no chemical damage to paddy rice seedlings, and 100% control of wild grass, Japanese cyperus, bulrush, Japanese cypress, and staghorn grass was achieved.
Claims (1)
ハロ−６−メトキシピリジンとメチルアミンを反
応させることを特徴とする２−メトキシ−６−メ
チルアミノピリジンの製造方法。[Claims] 1 2-Methoxy-6-methylaminopyridine. 2 2- represented by the general formula [formula] (wherein X represents a bromine atom or a chlorine atom)
A method for producing 2-methoxy-6-methylaminopyridine, which comprises reacting halo-6-methoxypyridine with methylamine.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8882882A JPS58208272A (en) | 1982-05-27 | 1982-05-27 | 2-methoxy-6-methylaminopyridine and its preparation |
| DE3318560A DE3318560C2 (en) | 1982-05-27 | 1983-05-20 | 2-alkylaminopyridine derivatives and process for their preparation |
| US06/497,408 US4560762A (en) | 1982-05-27 | 1983-05-23 | 2-Alkylaminopyridine derivatives |
| US06/747,298 US4617397A (en) | 1982-05-27 | 1985-06-21 | 2-chloro or bromo-6-C1 C3 -alkylamino-pyridine intermediates |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8882882A JPS58208272A (en) | 1982-05-27 | 1982-05-27 | 2-methoxy-6-methylaminopyridine and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58208272A JPS58208272A (en) | 1983-12-03 |
| JPS6155909B2 true JPS6155909B2 (en) | 1986-11-29 |
Family
ID=13953794
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8882882A Granted JPS58208272A (en) | 1982-05-27 | 1982-05-27 | 2-methoxy-6-methylaminopyridine and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58208272A (en) |
-
1982
- 1982-05-27 JP JP8882882A patent/JPS58208272A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58208272A (en) | 1983-12-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPS5840947B2 (en) | Trifluoromethylpyridoxyphenoxypropionic acid derivative | |
| JPS6341905B2 (en) | ||
| JPS6155909B2 (en) | ||
| US4560762A (en) | 2-Alkylaminopyridine derivatives | |
| JPS6158476B2 (en) | ||
| JPS6155910B2 (en) | ||
| US4617397A (en) | 2-chloro or bromo-6-C1 C3 -alkylamino-pyridine intermediates | |
| JPS632551B2 (en) | ||
| JPH0142257B2 (en) | ||
| JPS6130671B2 (en) | ||
| JPS6344748B2 (en) | ||
| JPS5877848A (en) | Preparation of cyclohexane derivative | |
| JPS632553B2 (en) | ||
| JPS6136485B2 (en) | ||
| JPS632550B2 (en) | ||
| JPS632955B2 (en) | ||
| JPS625432B2 (en) | ||
| JPS6130670B2 (en) | ||
| JPS632554B2 (en) | ||
| JPS5890570A (en) | Oxadiazoline derivative and herbicide | |
| JPS6234756B2 (en) | ||
| JPS5837281B2 (en) | Shinkinadjiyosouzai | |
| JPS632557B2 (en) | ||
| JPS5976045A (en) | Alpha,alpha-dimethylphenylacetic acid anilide derivative, its preparation and herbicide containing the same | |
| JPH0434538B2 (en) |