JPS632552B2 - - Google Patents
Info
- Publication number
- JPS632552B2 JPS632552B2 JP7385783A JP7385783A JPS632552B2 JP S632552 B2 JPS632552 B2 JP S632552B2 JP 7385783 A JP7385783 A JP 7385783A JP 7385783 A JP7385783 A JP 7385783A JP S632552 B2 JPS632552 B2 JP S632552B2
- Authority
- JP
- Japan
- Prior art keywords
- ppm
- formula
- alkylamino
- methoxypyridine
- reaction
- 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
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- 125000003282 alkyl amino group Chemical group 0.000 claims description 3
- 229910052801 chlorine Chemical group 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims 3
- 150000001412 amines Chemical class 0.000 claims 1
- 150000005748 halopyridines Chemical class 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 18
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 6
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 241000196324 Embryophyta Species 0.000 description 5
- 150000003973 alkyl amines Chemical class 0.000 description 5
- QFCMZIPUZKQFQF-UHFFFAOYSA-N n-ethyl-6-methoxypyridin-2-amine Chemical compound CCNC1=CC=CC(OC)=N1 QFCMZIPUZKQFQF-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- -1 N-(6-methoxy-2-pyridyl)thiocarbamate Chemical compound 0.000 description 4
- 241000209094 Oryza Species 0.000 description 4
- 235000007164 Oryza sativa Nutrition 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 230000002363 herbicidal effect Effects 0.000 description 4
- 239000004009 herbicide Substances 0.000 description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 4
- 235000009566 rice Nutrition 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 239000002689 soil Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 229910001956 copper hydroxide Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- ASISNVDDGQPFOB-UHFFFAOYSA-N o-(4-propan-2-ylphenyl) n-ethyl-n-(6-methoxypyridin-2-yl)carbamothioate Chemical compound C=1C=CC(OC)=NC=1N(CC)C(=S)OC1=CC=C(C(C)C)C=C1 ASISNVDDGQPFOB-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- NAMYKGVDVNBCFQ-UHFFFAOYSA-N 2-bromopropane Chemical compound CC(C)Br NAMYKGVDVNBCFQ-UHFFFAOYSA-N 0.000 description 1
- VAVGOGHLNAJECD-UHFFFAOYSA-N 2-chloro-6-methoxypyridine Chemical compound COC1=CC=CC(Cl)=N1 VAVGOGHLNAJECD-UHFFFAOYSA-N 0.000 description 1
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- FZACLMVHJVRFML-UHFFFAOYSA-N 6-bromo-n-propan-2-ylpyridin-2-amine Chemical compound CC(C)NC1=CC=CC(Br)=N1 FZACLMVHJVRFML-UHFFFAOYSA-N 0.000 description 1
- AOQBIRDOCWHWQU-UHFFFAOYSA-N 6-chloro-n-ethylpyridin-2-amine Chemical compound CCNC1=CC=CC(Cl)=N1 AOQBIRDOCWHWQU-UHFFFAOYSA-N 0.000 description 1
- SGHSRDPYZOGYPV-UHFFFAOYSA-N 6-methoxy-n-propan-2-ylpyridin-2-amine Chemical compound COC1=CC=CC(NC(C)C)=N1 SGHSRDPYZOGYPV-UHFFFAOYSA-N 0.000 description 1
- DEUALFRBMNMGDS-UHFFFAOYSA-N 6-methoxypyridin-2-amine Chemical compound COC1=CC=CC(N)=N1 DEUALFRBMNMGDS-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 241000218691 Cupressaceae Species 0.000 description 1
- 241001076438 Oxya japonica Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- GNVMUORYQLCPJZ-UHFFFAOYSA-M Thiocarbamate Chemical compound NC([S-])=O GNVMUORYQLCPJZ-UHFFFAOYSA-M 0.000 description 1
- 241001148683 Zostera marina Species 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 229940120693 copper naphthenate Drugs 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- SEVNKWFHTNVOLD-UHFFFAOYSA-L copper;3-(4-ethylcyclohexyl)propanoate;3-(3-ethylcyclopentyl)propanoate Chemical compound [Cu+2].CCC1CCC(CCC([O-])=O)C1.CCC1CCC(CCC([O-])=O)CC1 SEVNKWFHTNVOLD-UHFFFAOYSA-L 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000012259 ether extract Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 1
- GIKNJMSYQSDBRR-UHFFFAOYSA-N n-propylpyridin-2-amine Chemical compound CCCNC1=CC=CC=N1 GIKNJMSYQSDBRR-UHFFFAOYSA-N 0.000 description 1
- 238000003359 percent control normalization Methods 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000009333 weeding Methods 0.000 description 1
Landscapes
- Pyridine Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
【発明の詳細な説明】 本発明は、一般式[Detailed description of the invention] The present invention is based on the general formula
【式】（式
中Ｒはエチル基、ｎ−プロピル基又はiso−プロ
ピル基を示す。）で表わされる２−アルキルアミ
ノ−６−メトキシピリジン及びその製造法に関す
る。
２−アルキルアミノ−６−メトキシピリジン
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。
先に本発明者らは、本発明化合物の一つの２−
エチルアミノ−６−メトキシピリジンを原料とす
るＯ−４−イソプロピルフエニル Ｎ−エチル−
Ｎ−（６−メトキシ−２−ピリジル）チオカーバ
メートの製造法を提案した。Ｏ−４−イソプロピ
ルフエニル Ｎ−エチル−Ｎ−（６−メトキシ−
２−ピリジル）チオカーバメートを有効成分とす
る除草剤は、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
植水稲には実質的に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し、畑地
用除草剤として適用性を有する。
本発明の２−アルキルアミノ−６−メトキシピ
リジンは、一般式The present invention relates to 2-alkylamino-6-methoxypyridine represented by the formula: (wherein R represents an ethyl group, n-propyl group, or iso-propyl group) and a method for producing the same. 2-Alkylamino-6-methoxypyridine is a novel compound and is useful as an intermediate for substances that can be used in medicines, agricultural chemicals, and the like. Previously, the present inventors discovered that one of the compounds of the present invention, 2-
O-4-isopropylphenyl N-ethyl- from ethylamino-6-methoxypyridine
A method for producing N-(6-methoxy-2-pyridyl)thiocarbamate was proposed. O-4-isopropylphenyl N-ethyl-N-(6-methoxy-
Herbicides containing 2-pyridyl) thiocarbamate as an active ingredient exhibit extremely excellent herbicidal activity against many weeds, including field weeds, and are virtually harmless to transplanted paddy rice, making them suitable as herbicides for paddy fields. It is. In addition, it exhibits 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. The 2-alkylamino-6-methoxypyridine of the present invention has the general formula
【式】（式中Ｒは
前記に同じ、Ｘは臭素原子又は塩素原子を示す。）
で表わされる２−アルキルアミノ−６−ハロピリ
ジン（）とメタノールとの、アルカリ金属水酸
化物存在下の反応、又はナトリウムメチラートと
の反応、一般式[Formula] (In the formula, R is the same as above, and X represents a bromine atom or a chlorine atom.)
The reaction of 2-alkylamino-6-halopyridine () represented by () with methanol in the presence of an alkali metal hydroxide or with sodium methylate, the general formula
【式】（式中Ｘは
前に同じ。）で表わされる２−ハロ−６−メトキ
シピリジン（）とアルキルアミン（エチルアミ
ン、ｎ−プロピルアミン、iso−プロピルアミン）
との反応、２−アミノ−６−メトキシピリジンと
ハロゲン化アルキル（ヨウ化エチル、塩化ｎ−プ
ロピル、臭化iso−プロピル等）との反応等種々
の方法により製造できる。
すなわち、本発明の方法は、
一般式
（式中Ｘは前記に同じ、Ｙはアルキルアミノ基、
又はメトキシ基を示す。）で表わされる２−置換
−６−ハロピリジンにおいて、Ｙがアルキルアミ
ノ基である場合２−アルキルアミノ−６−ハロピ
リジン（）とメタノールをアルカリ金属水酸化
物存在下に反応させること、又はＹがメトキシ基
である場合２−ハロ−６−メトキシピリジン
（）とアルキルアミンを反応させることを特徴
とする２−アルキルアミノ−６−メトキシピリジ
ンの製造方法を提供するものである。
先ず２−アルキルアミノ−６−ハロピリジン
（）とメタノールをアルカリ金属水酸化物存在
下に反応させる方法について述べる。
（式中Ｒ及びＸは前記に同じ）
本方法において、アルカリ金属水酸化物として
は、水酸化リチウム、水酸化ナトリウム、水酸化
カリウム等を挙げることができる。アルカリ金属
水酸化物は２−アルキルアミノ−６−ハロピリジ
ン（）に対して１倍モル以上、好ましくは約２
〜約４倍モルの量で用いる。
反応温度は通常約100〜約220℃、好ましくは約
140〜約200℃である。反応時間は、反応温度、ア
ルカリ金属水酸化物の使用量、その他の条件によ
り変更してよいが、20時間以内に完結させること
ができる。
次に２−ハロ−６−メトキシピリジン（）と
アルキルアミンを反応させる方法について述べ
る。
（式中Ｒ、Ｘ及びＹは前記に同じ）
本方法においてアルキ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２
〜10倍モルである。反応を円滑に進めるために溶
媒を用いることができる。溶媒としては、２−ハ
ロ−６−メトキシピリジン（）と反応せず、し
かもアルキルアミンを溶解する水、アルコール、
ベンゼン等の芳香族炭化水素、ジエチレングリコ
ールジメチルエーテル等の脂肪族エーテル、又は
ジオキサン等の環状エーテルを用いることができ
る。
反応温度は約100〜250℃、好ましくは約140〜
200℃であり、反応は20時間以内に完結させるこ
とができる。また、さらに銅、あるいは硫酸銅、
塩化銅、硝酸銅等の無機酸塩、ナフテン酸銅、酢
酸銅等の有機酸塩、酸化銅等の酸化物、水酸化銅
等の水酸化物の如き銅化合物の存在下での反応は
さらに好ましい。
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−エチルアミノピリジン20gr、メタノール
60mlそして水酸化ナトリウム12grを取り、170℃
にて５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
いで反応液にエーテルを加え、２−エチルアミノ
−６−メトキシピリジンを抽出した。エーテル抽
出液を無水硫酸マグネシウムで乾燥し、エーテル
留去後、減圧蒸留して沸点125〜127℃／20mmHg
の２−エチルアミノ−６−メトキシピリジン
13.9grを得た。
赤外線吸収スペクトル（NaCl）
3420（−NH）、2960（Ｃ−Ｈ）、1600、1460、
核磁気共鳴吸収スペクトル（CDCl3、内部標準
TMS）
δ 1.10（ｔ）ppm（3H）
δ 3.15（mc）ppm（2H）
δ 3.75（ｓ）ppm（3H）
δ 4.30（bs）ppm（1H）
δ 5.78(d)ppm（1H）
δ 5.92(d)ppm（1H）
δ 7.22（ｔ）ppm（1H）
元素分析値（C8H12N2Oとして）
Ｃ Ｈ Ｎ Ｏ
分析値（％） 63.21 7.89 18.36 10.54
理論値（％） 63.13 7.95 18.41 10.51
GC−MSによる分子量 152
実施例 ２
実施例１と同一の反応装置に２−ブロモ−６−
iso−プロピルアミノピリジン20gr、メタノール
70ml、そして水酸化カリウム14grを取り、160℃
にて４時間反応させた。反応終了後、実施例１と
同様の反応操作を行い、沸点127〜128℃／20mm
Hgの２−メトキシ−６−iso−プロピルアミノピ
リジン7.3grを得た。
赤外線吸収スペクトル（NaCl）
3420（−NH）、2960（Ｃ−Ｈ）、1600、1465、
核磁気共鳴吸収スペクトル（CDCl3、内部標準
TMS）
δ 1.20(d)ppm（6H）
δ 3.83（ｓ）ppm（3H）
δ 3.90（mc）ppm（1H）
δ 4.19（bs）ppm（1H）
δ 5.84(d)ppm（1H）
δ 5.98(d)ppm（1H）
δ 7.28（ｔ）ppm（1H）
元素分析値（C9H14N2Oとして）
Ｃ Ｈ Ｎ Ｏ
分析値（％） 65.11 8.43 16.89 9.57
理論値（％） 65.03 8.49 16.85 9.63
GC−MSによる分子量 166
実施例 ３
実施例１と同一の反応装置に２−クロル−６−
メトキシピリジン20gr、ｎ−プロピルアミン
25gr、水80mlを取り、180℃にて５時間反応させ
た。反応終了後、実施例１と同様の反応操作を行
い、沸点90〜91℃／４mmHgの２−メトキシ−ｎ
−プロピルアミノピリジン9.3grを得た。
赤外線吸収スペクトル（NaCl）
3420（−NH）、2950（Ｃ−Ｈ）、1600、1460、
核磁気共鳴吸収スペクトル（CDCl3、内部標準
TMS）
δ 0.90（ｔ）ppm（3H）
δ 1.50（mc）ppm（2H）
δ 3.08（ｑ）ppm（2H）
δ 3.75（ｓ）ppm（3H）
δ 4.50（bs）ppm（1H）
δ 5.78(d)ppm（1H）
δ 5.92(d)ppm（1H）
δ 7.20（ｔ）ppm（1H）
元素分析値（C9H14N2Oとして）
Ｃ Ｈ Ｎ Ｏ
分析値（％） 65.02 8.52 16.78 9.68
理論値（％） 65.03 8.49 16.85 9.63
GC−MSによる分子量 166
次に本発明化合物の一つである２−エチルアミ
ノ−６−メトキシピリジン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。
２−エチルアミノ−６−メトキシピリジン1.52
ｇおよび無水炭酸カリウム1.38ｇをアセトン20ml
に添加し、室温で撹拌しながら、Ｏ−４−イソプ
ロピルフエニルクロルチオホルメイト2.15ｇをア
セトン20mlに溶かして加えた。このまま30分間撹
拌した後、２時間加熱還流した。反応混合物を室
温まで冷却した後、冷水中に注ぎ、生成物をベン
ゼンで抽出した。ベンゼン溶液を水、飽和塩化ナ
トリウム水溶液の順で洗い、無水硫酸マグネシウ
ムで乾燥した後、減圧下でベンゼンを留去した。
残留物をカラムクロマトグラフイー（シリカゲ
ル、ベンゼン展開）で精製してＯ−４−イソプロ
ピルフエニル Ｎ−エチル−Ｎ−（６−メトキシ
−２−ピリジル）チオカーバメート2.67ｇ（収率
81％）を得た。このものの一部をエタノールより
再結晶し、融点53〜54℃の無色結晶を得た。
元素分析（C18H22N2O2Sとして）
Ｃ Ｈ Ｎ
分析値（％） 65.17 6.67 8.63
理論値（％） 65.42 6.71 8.47
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−４
−イソプロピルフエニル Ｎ−エチル−Ｎ−（６
−メトキシ−２−ピリジル）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週間後に除草効果及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、コナギを100％防除した。2-halo-6-methoxypyridine () and alkylamine (ethylamine, n-propylamine, iso-propylamine) represented by [Formula] (in the formula, X is the same as before)
It can be produced by various methods such as reaction with 2-amino-6-methoxypyridine and alkyl halide (ethyl iodide, n-propyl chloride, iso-propyl bromide, etc.). That is, the method of the present invention has the general formula (In the formula, X is the same as above, Y is an alkylamino group,
Or represents a methoxy group. ), when Y is an alkylamino group, 2-alkylamino-6-halopyridine () and methanol are reacted in the presence of an alkali metal hydroxide, or when Y is methoxy The present invention provides a method for producing 2-alkylamino-6-methoxypyridine, which comprises reacting 2-halo-6-methoxypyridine (2) with an alkylamine. First, a method of reacting 2-alkylamino-6-halopyridine (2) and methanol in the presence of an alkali metal hydroxide will be described. (In the formula, R and X are the same as above.) In this method, examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, and the like. The alkali metal hydroxide is used in an amount of at least 1 mole, preferably about 2 times the mole of 2-alkylamino-6-halopyridine ().
It is used in an amount of ~4 times the mole. The reaction temperature is usually about 100 to about 220°C, preferably about
The temperature is 140 to about 200°C. The reaction time may be changed depending on the reaction temperature, the amount of alkali metal hydroxide used, and other conditions, but the reaction can be completed within 20 hours. Next, a method for reacting 2-halo-6-methoxypyridine () with an alkylamine will be described. (In the formula, R, X and Y are the same as above.) In this method, the amount of alkylamine used is 2
-2 for halo-6-methoxypyridine ()
~10 times molar. A solvent can be used to facilitate the reaction. As a solvent, water, alcohol, which does not react with 2-halo-6-methoxypyridine () and dissolves the alkylamine,
Aromatic hydrocarbons such as benzene, aliphatic ethers such as diethylene glycol dimethyl ether, or cyclic ethers such as dioxane can be used. The reaction temperature is about 100~250℃, preferably about 140~
The temperature is 200°C, and the reaction can be completed within 20 hours. In addition, copper or copper sulfate,
The reaction in the presence of copper compounds such as inorganic acid salts such as copper chloride and copper nitrate, organic acid salts such as copper naphthenate and copper acetate, oxides such as copper oxide, and hydroxides such as copper hydroxide is further preferable. 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 20g of 2-chloro-6-ethylaminopyridine and methanol were placed in a 200ml electromagnetic stirring autoclave.
Take 60ml and 12gr of sodium hydroxide, 170℃
The reaction was carried out for 5 hours. After the reaction was completed, the autoclave was cooled, opened, and the reaction solution was taken out. Ether was then added to the reaction solution to extract 2-ethylamino-6-methoxypyridine. The ether extract was dried over anhydrous magnesium sulfate, and after distilling off the ether, it was distilled under reduced pressure to a boiling point of 125-127℃/20mmHg.
2-ethylamino-6-methoxypyridine
Got 13.9gr. Infrared absorption spectrum (NaCl) 3420 (-NH), 2960 (C-H), 1600, 1460, Nuclear magnetic resonance absorption spectrum (CDCl 3 , internal standard
TMS) δ 1.10(t)ppm(3H) δ 3.15(mc)ppm(2H) δ 3.75(s)ppm(3H) δ 4.30(bs)ppm(1H) δ 5.78(d)ppm(1H) δ 5.92( d) ppm (1H) δ 7.22 (t) ppm (1H) Elemental analysis value (as C 8 H 12 N 2 O) C H N O Analysis value (%) 63.21 7.89 18.36 10.54 Theoretical value (%) 63.13 7.95 18.41 10.51 Molecular weight by GC-MS 152 Example 2 2-bromo-6-
iso-propylaminopyridine 20gr, methanol
Take 70ml and 14gr of potassium hydroxide and heat to 160℃
The reaction was carried out for 4 hours. After the reaction was completed, the same reaction operation as in Example 1 was carried out, and the boiling point was 127-128℃/20mm.
7.3 gr of 2-methoxy-6-iso-propylaminopyridine of Hg was obtained. Infrared absorption spectrum (NaCl) 3420 (-NH), 2960 (C-H), 1600, 1465, Nuclear magnetic resonance absorption spectrum (CDCl 3 , internal standard
TMS) δ 1.20(d)ppm(6H) δ 3.83(s)ppm(3H) δ 3.90(mc)ppm(1H) δ 4.19(bs)ppm(1H) δ 5.84(d)ppm(1H) δ 5.98( d) ppm (1H) δ 7.28 (t) ppm (1H) Elemental analysis value (as C 9 H 14 N 2 O) C H N O Analysis value (%) 65.11 8.43 16.89 9.57 Theoretical value (%) 65.03 8.49 16.85 9.63 Molecular weight by GC-MS 166 Example 3 2-chloro-6-
Methoxypyridine 20gr, n-propylamine
25gr and 80ml of water were taken and reacted at 180°C for 5 hours. After the reaction was completed, the same reaction operation as in Example 1 was carried out to obtain 2-methoxy-n with a boiling point of 90-91°C/4 mmHg.
-9.3 gr of propylaminopyridine were obtained. Infrared absorption spectrum (NaCl) 3420 (-NH), 2950 (C-H), 1600, 1460, Nuclear magnetic resonance absorption spectrum (CDCl 3 , internal standard
TMS) δ 0.90 (t) ppm (3H) δ 1.50 (mc) ppm (2H) δ 3.08 (q) ppm (2H) δ 3.75 (s) ppm (3H) δ 4.50 (bs) ppm (1H) δ 5.78( d)ppm(1H) δ 5.92(d)ppm(1H) δ 7.20(t)ppm(1H) Elemental analysis value (as C 9 H 14 N 2 O) C H N O analysis value (%) 65.02 8.52 16.78 9.68 Theoretical value (%) 65.03 8.49 16.85 9.63 Molecular weight by GC-MS 166 Next, a compound obtained from 2-ethylamino-6-methoxypyridine, which is one of the compounds of the present invention, and an example of its use as a herbicide will be shown. 2-ethylamino-6-methoxypyridine 1.52
g and 1.38 g of anhydrous potassium carbonate in 20 ml of acetone.
2.15 g of O-4-isopropylphenylchlorothioformate dissolved in 20 ml of acetone was added while stirring at room temperature. After stirring as it was for 30 minutes, the mixture was heated under reflux for 2 hours. After the reaction mixture was cooled to room temperature, it was poured into cold water and the product was extracted with benzene. The benzene solution was washed with water and a saturated aqueous sodium chloride solution in that order, dried over anhydrous magnesium sulfate, and then benzene was distilled off under reduced pressure.
The residue was purified by column chromatography (silica gel, developed with benzene) to obtain 2.67 g of O-4-isopropylphenyl N-ethyl-N-(6-methoxy-2-pyridyl)thiocarbamate (yield:
81%). A part of this product was recrystallized from ethanol to obtain colorless crystals with a melting point of 53-54°C. Elemental analysis (as C 18 H 22 N 2 O 2 S) C H N Analytical value (%) 65.17 6.67 8.63 Theoretical value (%) 65.42 6.71 8.47 Paddy soil was poured into a porcelain pot with a diameter of 9 cm, water was added, and paddy soil was poured. After that, 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-4
-isopropylphenyl N-ethyl-N-(6
-methoxy-2-pyridyl)thiocarbamate 10
% was diluted in 10 ml of water per pot and dropped onto the water surface. Thereafter, the plants were left in a greenhouse and 3 weeks after treatment with the chemical solution, 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 cypress, and Japanese grasshopper was achieved.
Claims (1)
プロピル基を示す。）で表わされる２−アルキル
アミノ−６−メトキシピリジン。 ２ 一般式 （式中Ｘは臭素原子又は塩素原子、Ｙはアルキル
アミノ基を示す。）で表わされる２−置換−６−
ハロピリジンを、メタノールと反応させることを
特徴とする一般式 （式中Ｒはエチル基、ｎ−プロピル基又はiso−
プロピル基を示す。）で表わされる２−アルキル
アミノ−６−メトキシピリジン類の製造法。 ３ 一般式 （式中Ｘは臭素原子又は塩素原子、Ｙはメトキシ
基を示す。）で表わされる２−置換−６−ハロピ
リジンを、RNH2（式中Ｒはエチル基、ｎ−プロ
ピル基又はiso−プロピル基を示す。）で表わされ
るアミン類と反応させることを特徴とする一般式 （式中Ｒはエチル基、ｎ−プロピル基又はiso−
プロピル基を示す。）で表わされる２−アルキル
アミノ−６−メトキシピリジン類の製造法。[Claims] 1. General formula (In the formula, R is an ethyl group, n-propyl group, or iso-
Indicates a propyl group. ) 2-alkylamino-6-methoxypyridine. 2 General formula (In the formula, X is a bromine atom or a chlorine atom, and Y is an alkylamino group.)
General formula characterized by reacting halopyridine with methanol (In the formula, R is an ethyl group, n-propyl group, or iso-
Indicates a propyl group. ) A method for producing 2-alkylamino-6-methoxypyridines represented by 3 General formula (In the formula, X is a bromine atom or a chlorine atom, and Y is a methoxy group.) A general formula characterized by reacting with amines represented by (In the formula, R is an ethyl group, n-propyl group, or iso-
Indicates a propyl group. ) A method for producing 2-alkylamino-6-methoxypyridines represented by
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7385783A JPS59199675A (en) | 1983-04-28 | 1983-04-28 | 2-alkylamino-6-methoxypyridine 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 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7385783A JPS59199675A (en) | 1983-04-28 | 1983-04-28 | 2-alkylamino-6-methoxypyridine and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59199675A JPS59199675A (en) | 1984-11-12 |
| JPS632552B2 true JPS632552B2 (en) | 1988-01-19 |
Family
ID=13530247
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7385783A Granted JPS59199675A (en) | 1982-05-27 | 1983-04-28 | 2-alkylamino-6-methoxypyridine and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59199675A (en) |
-
1983
- 1983-04-28 JP JP7385783A patent/JPS59199675A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59199675A (en) | 1984-11-12 |
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