JP3084871B2 - N-acyl-O- (3-chloro-2-propenyl) hydroxylamine and method for producing the same - Google Patents
N-acyl-O- (3-chloro-2-propenyl) hydroxylamine and method for producing the sameInfo
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- JP3084871B2 JP3084871B2 JP03353928A JP35392891A JP3084871B2 JP 3084871 B2 JP3084871 B2 JP 3084871B2 JP 03353928 A JP03353928 A JP 03353928A JP 35392891 A JP35392891 A JP 35392891A JP 3084871 B2 JP3084871 B2 JP 3084871B2
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- Prior art keywords
- hydroxylamine
- chcl
- same meaning
- represented
- general formula
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は農医薬、特に除草剤の中
間体として有用なヒドロキシルアミン誘導体に関する。The present invention relates to hydroxylamine derivatives useful as intermediates in agrochemicals, especially herbicides.
【０００２】[0002]
【従来の技術】式Ｈ2 ＮＯＣＨ2 ＣＨ＝ＣＨＣｌで表わ
される３−クロロ−２−プロペニルオキシアミン、特に
そのＥ−体は除草剤の中間体として重要な化合物であ
り、その製造方法が種々検討されていた。BACKGROUND OF THE INVENTION formula H 2 NOCH 2 CH = represented by CHCl 3- chloro-2-propenyloxy amine, in particular the E- body important compounds as intermediates for herbicides, their preparation methods studied It had been.
【０００３】本発明者等はヒドロキサム酸塩と１，３−
ジクロロプロペンとから容易に製造できるヒドロキシル
アミン誘導体が上記オキシアミン製造の有用な中間体と
なることを見い出し、本発明を完成した。[0003] The present inventors have proposed hydroxamic acid salts with 1,3-
The present inventors have found that a hydroxylamine derivative which can be easily produced from dichloropropene can be a useful intermediate for producing the above oxyamine, and have completed the present invention.
【０００４】[0004]
【課題を解決するための手段】本発明は一般式ＲＣＯＮ
ＨＯＣＨ2 ＣＨ＝ＣＨＣｌ（式中、Ｒは低級アルキル基
を示す。）で表わされるヒドロキシルアミン誘導体及び
その製造方法である。本発明の製造方法を反応式で示す
と以下の通りである。 ＲＣＯＯＲ1 ＋ＮＨ2 ＯＨ＋１／ｎＭＯＨ→ＲＣＯＮＨ
Ｏ・１／ｎＭ＋Ｒ1 ＯＨ＋Ｈ2 Ｏ（以下第１工程とい
う。） ＲＣＯＮＨＯ・１／ｎＭ＋ＣｌＣＨ2 ＣＨ＝ＣＨＣｌ→
ＲＣＯＮＨＯＣＨ2 ＣＨ＝ＣＨＣｌ＋１／ｎＭＣｌ（以
下第２工程という。）SUMMARY OF THE INVENTION The present invention relates to a general formula RCON.
A hydroxylamine derivative represented by HOCH 2 CH ＝ CHCl (wherein R represents a lower alkyl group) and a method for producing the same. The reaction method of the production method of the present invention is as follows. RCOOR 1 + NH 2 OH + 1 / nMOH → RCONH
O · 1 / nM + R 1 OH + H 2 O (hereinafter referred to as the first step) RCONHO · 1 / nM + ClCH 2 CH = CHCl →
RCONHOCH 2 CH = CHCl + 1 / nMCl (hereinafter referred to as a second step)
【０００５】第１工程を実施するには硫酸ヒドロキシル
アミン、塩酸ヒドロキシルアミン又はヒドロキシルアミ
ン１モルについてカルボン酸エステル１〜１．５モル、
水１０〜１０００ｍｌさらに要すればアルコールを加え
たものに攪拌しながらアルカリ金属水酸化物又はアルカ
リ土類金属水酸化物を１５〜５０℃で添加する。添加終
了後もしばらく約２０〜４０℃好ましくは２０〜３０℃
で１時間程攪拌を続ける。ヒドロキサム酸塩は水溶液
（又は水−アルコール溶液）として得られるので、要す
ればこのものから常法によりヒドロキサム酸を単離する
ことも可能である。本発明に使用するアルカリ金属水酸
化物は、主にカセイソーダ又はカセイカリであり、通常
２０〜４０ｗｔ％濃度の水溶液として使用する。又アル
カリ土類金属水酸化物としてはカルシウム、バリウム等
が使用され水溶液又は固体の形で使用する。カセイソー
ダ、カセイカリ等はヒドロキシルアミン塩からヒドロキ
シルアミンを遊離させる。又カルボン酸エステル活性化
してヒドロキシルアミンと反応をおこさせる。さらに塩
を生成させるものであることから、アルカリ水溶液とし
て作用させることが好ましく、カルボン酸エステル及び
ヒドロキシルアミン塩の合計モルと等モルあるいは若干
過剰モル作用させる。カルボン酸エステルとヒドロキシ
ルアミン塩のみの混合物にアルカリ水溶液を滴下すると
遊離したヒドロキシルアミンが酸化分解するので、該混
合物中には予め水を存在させておくことが必要であり、
特に水が過少量であればヒドロキシルアミン塩の中和が
遅くなり、結果としてカルボン酸エステルの加水分解が
おこり、過大量であればカルボン酸エステルの加水分解
がおこるので、ヒドロキシルアミン塩１モルに対して１
０〜１０００ｍｌ、好ましくは２０〜２００ｍｌの水を
存在させておく。カルボン酸エステルの量はヒドロキシ
ルアミン塩の１モル当り１．０〜１．５モル、好ましく
は１．１５〜１．３モルであり、過小量の使用は収率の
低下をまねき、過大量の使用は原料コストの増大につな
がり好ましくない。また、反応を行なう際に、水の他に
メタノール、エタノールのような低級アルコールを添加
しておくと、反応系の攪拌が容易になることと生成した
ヒドロキサム酸塩の分解が抑制されることから好都合で
ある。通常ヒドロキシルアミン塩１モルに対して３０〜
３００ｍｌの低級アルコールを添加するのが好ましい。In order to carry out the first step, 1 to 1.5 mol of carboxylic acid ester is added to 1 mol of hydroxylamine sulfate, hydroxylamine hydrochloride or hydroxylamine,
An alkali metal hydroxide or an alkaline earth metal hydroxide is added at 15 to 50 ° C with stirring to 10 to 1000 ml of water and, if necessary, to a mixture containing alcohol. After addition is complete, it is about 20-40 ° C, preferably 20-30 ° C for a while.
And continue stirring for about 1 hour. Since the hydroxamic acid salt is obtained as an aqueous solution (or a water-alcohol solution), the hydroxamic acid can be isolated from the hydroxamic acid by a conventional method, if necessary. The alkali metal hydroxide used in the present invention is mainly caustic soda or caustic potash, and is usually used as an aqueous solution having a concentration of 20 to 40% by weight. As the alkaline earth metal hydroxide, calcium, barium or the like is used, and it is used in the form of an aqueous solution or solid. Caustic soda, caustic potash and the like release hydroxylamine from hydroxylamine salts. The carboxylic acid ester is activated to react with hydroxylamine. Further, since the salt forms a salt, it is preferable to act as an aqueous alkali solution, and to act in an equimolar amount or a slight excess with respect to the total mole of the carboxylic acid ester and the hydroxylamine salt. When an aqueous alkali solution is dropped into a mixture of only a carboxylic acid ester and a hydroxylamine salt, liberated hydroxylamine is oxidatively decomposed, so that it is necessary that water is previously present in the mixture,
In particular, if the amount of water is too small, the neutralization of the hydroxylamine salt is delayed, and as a result, hydrolysis of the carboxylic acid ester occurs.If the amount of water is too large, the hydrolysis of the carboxylic acid ester occurs. 1 for
0-1000 ml, preferably 20-200 ml, of water are present. The amount of the carboxylic acid ester is from 1.0 to 1.5 mol, preferably from 1.15 to 1.3 mol, per mol of the hydroxylamine salt. The use is unfavorable because it leads to an increase in raw material costs. In addition, when a lower alcohol such as methanol or ethanol is added in addition to water during the reaction, the stirring of the reaction system is facilitated and the decomposition of the generated hydroxamic acid salt is suppressed. It is convenient. Usually 30 to 1 mole of hydroxylamine salt
It is preferred to add 300 ml of lower alcohol.
【０００６】第２工程を実施するには第１工程で得られ
たヒドロキサム酸塩の水、低級アルコール又は水−低級
アルコール溶液に１，３−ジクロロプロペンを加え、２
０〜６０℃で攪拌しながら２〜１０時間反応させる。使
用モル比はヒドロキサム酸塩１モルに対し１，３−ジク
ロロプロペンは１〜２モルである。反応終了後、目的物
を単離するにはクロロホルム等の有機溶媒で抽出すれば
よい。また、反応液に塩酸等の鉱酸等を加え、加水分解
させることにより、容易に３−クロロ−２−プロペニル
オキシアミンを得ることができる。In order to carry out the second step, 1,3-dichloropropene is added to a solution of the hydroxamic acid salt obtained in the first step in water, a lower alcohol or a water-lower alcohol solution.
The reaction is carried out for 2 to 10 hours while stirring at 0 to 60 ° C. The molar ratio used is 1 to 2 mol of 1,3-dichloropropene per mol of hydroxamic acid salt. After completion of the reaction, the desired product may be isolated by extraction with an organic solvent such as chloroform. Further, 3-chloro-2-propenyloxyamine can be easily obtained by adding a mineral acid such as hydrochloric acid or the like to the reaction solution and hydrolyzing it.
【０００７】[0007]
【実施例】次に実施例を挙げ、本発明を更に詳細に説明
する。 実施例１ Ｎ−アセチル−Ｏ−（（Ｅ）−３−クロロ−
２−プロペニル）ヒドロキシルアミンの製造 還流冷却器、温度計、攪拌装置を備えた１リットル丸底
フラスコに酢酸メチル９６．３ｇ（１．３モル）メタノ
ール５０ｇ、水５０ｇ、ヒドロキシルアミン硫酸塩（純
度９９．２％）８８．２ｇ（１モル）を入れ、２０℃に
保ち攪拌しながら、２８％水酸化ナトリウム水溶液３２
９ｇ（２．３モル）を滴下し、さらに同温度で１時間攪
拌した。ついで（Ｅ）−１，３−ジクロロプロペン１１
９ｇ（１．０５モル）を加え、温度を５０℃に上げ４時
間攪拌した。反応終了後クロロホルム２００ｍｌで３回
抽出した。抽出液を濃縮液、減圧蒸留により１０６〜１
０８℃、６ｍｍＨｇの無色の留分１３１．７ｇを得た。
この留分は１夜放置すると結晶化した。融点５５〜５７
℃プロトンＮＭＲはこのものがＥ体の目的物であること
を示した。収率８８％。The present invention will be described in more detail with reference to the following examples. Example 1 N-acetyl-O-((E) -3-chloro-
Production of 2-propenyl) hydroxylamine In a 1 liter round bottom flask equipped with a reflux condenser, a thermometer, and a stirrer, 96.3 g (1.3 mol) of methyl acetate, 50 g of methanol, 50 g of water, and hydroxylamine sulfate (purity of 99) 88.2 g (1 mol) was added, and the mixture was stirred at 20 ° C. and stirred at room temperature for 32% aqueous sodium hydroxide solution 32.
9 g (2.3 mol) was added dropwise, and the mixture was further stirred at the same temperature for 1 hour. Then, (E) -1,3-dichloropropene 11
9 g (1.05 mol) was added, the temperature was raised to 50 ° C., and the mixture was stirred for 4 hours. After completion of the reaction, extraction was performed three times with 200 ml of chloroform. The extract was concentrated and concentrated under reduced pressure.
131.7 g of a colorless fraction of 08 ° C. and 6 mmHg was obtained.
This fraction crystallized on standing overnight. 55-57
° C proton NMR showed that this was the desired product of E-form. Yield 88%.
【０００８】参考例 （Ｅ）−３−クロロ−２−プロペ
ニルオキシアミンの製造 実施例１と同様にして得たＮ−アセチル〔（Ｅ）−３−
クロロ−２−プロペニル〕ヒドロキシルアミン１３７．
６ｇを含むアルコール水溶液に３５％塩酸２１３．８ｇ
（２．０５モル）を加えて７０℃で１時間反応させた。
還流が激しくなってきたところで、６４〜８０℃の留分
１０７．７ｇを留出させた。さらに減圧下に４３〜４７
℃、１２５〜９０ｍｍＨｇの留分１５０ｇを留出させ
た。冷却後残液に水４０ｇ、２８％水酸化ナトリウム水
溶液２３７ｇを加えｐＨを９．０とし、ついでトルエン
１００ｇで３回抽出した。抽出液をＨＬＣで分析した結
果、目的物１１９．２ｇ含んでいた。Reference Example Preparation of (E) -3-chloro-2-propenyloxyamine N-acetyl [(E) -3- obtained in the same manner as in Example 1.
Chloro-2-propenyl] hydroxylamine
213.8 g of 35% hydrochloric acid in an aqueous alcohol solution containing 6 g
(2.05 mol) and reacted at 70 ° C. for 1 hour.
When the reflux became intense, 107.7 g of a fraction at 64 to 80 ° C was distilled off. 43-47 under reduced pressure
150 g of a fraction having a temperature of 125 to 90 mmHg was distilled off. After cooling, 40 g of water and 237 g of a 28% aqueous sodium hydroxide solution were added to the remaining solution to adjust the pH to 9.0, and then extracted three times with 100 g of toluene. The extract was analyzed by HLC and found to contain 119.2 g of the desired product.
【０００９】[0009]
【発明の効果】本発明のヒドロキシルアミン誘導体はカ
ルボン酸エステルから容易に製造できる新規化合物であ
り、また、参考例から明らかなように農薬、特に除草剤
の中間体として重要な３−クロロ−２−プロペニルオキ
シアミンに変換できる。The hydroxylamine derivative of the present invention is a novel compound which can be easily produced from a carboxylic acid ester, and, as apparent from the reference examples, 3-chloro-2 which is important as an intermediate for pesticides, especially herbicides. -Can be converted to propenyloxyamine.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 Ｃｈｅｍ．ａｂｓｔｒ．，Ｖｏｌ. 84，ｔｈｅ ａｂｓｔｒｃｔ Ｎｏ. 39251，Ｐａｒｏｎｉｋｙａｎ，Ｇ．Ｍ. ｅｔ ａｌ．，’Ｍｕｔａｇｅｎｉｃ ｅｆｆｅｃｔ ｏｆ ｎｅｗ ｃｈｅｍ ｉｃａｌ ｃｏｍｐｏｕｎｄｓ． ▲Ｉ ＩＩ▼．Ｍｕｔａｇｅｎｉｃ ｅｆｆｅ ｃｔ ｏｆ ｓｏｍｅ ｈｙｄｒｏｘｙ ｌａｍｉｎｅ ｄｅｒｉｖａｔｉｖｅｓ ’，Ｇｅｎｅｔｉｋａ 1975，11 （10），105−110 Ｃｈｅｍ．ａｂｓｔｒ．，Ｖｏｌ. 80，ｔｈｅ ａｂｓｔｒｃｔ Ｎｏ. 47572，Ａｒｏｙａｎ，Ａ．Ａ．ａｎｄ Ｋｈａｃｈａｔｕｒｙａｎ，Ｔ. Ａ．，’Ｓｙｎｔｈｅｓｉｓ ａｎｄ ｓｏｍｅ ｒｅａｃｔｉｏｎｓ ｏｆ ｏ−（３−ｃｈｌｏｒｏ−４−ｍｅｔｈ ｏｘｙｂｅｎｚｙｌ）−ａｎｄ ｏ− （３−ｃｈｌｏｒｏｃｒｏｔｙｌ）ｈｙ ｄｒｏｘｙｌａｍｉｎｅｓ’，Ａｒｍ. Ｋｈｉｍ．Ｚｈ．1973，26（９），758 −762 (58)調査した分野(Int.Cl.7，ＤＢ名) C07C 259/06 ＣＡ（ＳＴＮ) ＣＡＯＬＤ（ＳＴＮ) ＲＥＧＩＳＴＲＹ（ＳＴＮ) ＣＡＳＲＥＡＣＴ（ＳＴＮ) ＭＡＲＰＡＴ（ＳＴＮ)──────────────────────────────────────────────────続 き Continued on the front page (56) Reference Chem. abstr. 84, the abstract No. 39251, Paronikyan, G. et al. M. et al. , 'Mutagenic effect of new chemical compounds. ▲ I II ▼. Mutagenic effect of some hydroxy lamine derivatives', Genetika 1975, 11 (10), 105-110 Chem. abstr. , Vol. 80, the abstract No. 47572, Aroyan, A. et al. A. and Khachaturyan, TA. , 'Synthesis and some reactions of o- (3-chloro-4-methoxybenzyl) -and o- (3-chlorocrotyl) hydroxylamines', Arm. Khim. Zh. 1973, 26 (9), 758-762 (58) Fields investigated (Int. Cl. 7 , DB name) C07C 259/06 CA (STN) CAOLD (STN) REGISTRY (STN) CASREAT (STN) MARPAT (STN)
Claims (3)
ｌ（式中、Ｒは低級アルキル基を示す。）で表わされる
ヒドロキシルアミン誘導体。1. A compound of the general formula RCONHOCH 2 CH ＝ CHC
a hydroxylamine derivative represented by 1 (wherein R represents a lower alkyl group).
Ｒは前記と同じ意味を示し、Ｍはアルカリ金属又はアル
カリ土類金属を、ｎはＭの原子価を示す。）で表わされ
るヒドロキサム酸塩とＣｌＣＨ2 ＣＨ＝ＣＨＣｌで表わ
される１，３−ジクロロプロペンとを反応させることを
特徴とする一般式ＲＣＯＮＨＯＣＨ2 ＣＨ＝ＣＨＣｌ
（式中、Ｒは前記と同じ意味を示す。）で表わされるヒ
ドロキシルアミン誘導体の製造方法。2. The general formula RCONHO · 1 / nM (wherein
R has the same meaning as described above, M represents an alkali metal or an alkaline earth metal, and n represents the valence of M. Formula RCONHOCH 2 CH = CHCl, characterized in that the reaction of 1,3-dichloropropene represented by hydroxamate and ClCH 2 CH = CHCl represented by)
(Wherein, R has the same meaning as described above).
同じ意味を示し、Ｒ1 は低級アルキル基を示す。）で表
わされるカルボン酸エステルとヒドロキシルアミン、硫
酸ヒドロキシルアミン又は塩酸ヒドロキシルアミンとを
アルカリ金属水酸化物又はアルカリ土類金属水酸化物の
水溶液中で反応させ、一般式ＲＣＯＮＨＯ・１／ｎＭ
（式中、Ｒ、Ｍ及びｎは前記と同じ意味を示す。）で表
わされるヒドロキサム塩酸とし、次いでＣｌＣＨ2 ＣＨ
＝ＣＨＣｌで表わされる１，３−ジクロロプロペンを反
応させることを特徴とする一般式ＲＣＯＮＨＯＣＨ2 Ｃ
Ｈ＝ＣＨＣｌ（式中、Ｒは前記と同じ意味を示す。）で
表わされるヒドロキシルアミン誘導体の製造方法。3. A carboxylic acid ester represented by the general formula RCOOR 1 (wherein R has the same meaning as described above, and R 1 represents a lower alkyl group) and hydroxylamine, hydroxylamine sulfate or hydroxylamine hydrochloride. Is reacted in an aqueous solution of an alkali metal hydroxide or an alkaline earth metal hydroxide to obtain a general formula RCONHO.1 / nM
(Wherein, R, M and n have the same meaning as described above), and then ClCH 2 CH
= Formula characterized by reacting 1,3-dichloropropene represented by CHCl RCONHOCH 2 C
A method for producing a hydroxylamine derivative represented by H = CHCl (wherein R has the same meaning as described above).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03353928A JP3084871B2 (en) | 1991-12-19 | 1991-12-19 | N-acyl-O- (3-chloro-2-propenyl) hydroxylamine and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03353928A JP3084871B2 (en) | 1991-12-19 | 1991-12-19 | N-acyl-O- (3-chloro-2-propenyl) hydroxylamine and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05163228A JPH05163228A (en) | 1993-06-29 |
| JP3084871B2 true JP3084871B2 (en) | 2000-09-04 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5777164A (en) * | 1997-04-14 | 1998-07-07 | Eastman Chemical Company | Process for the preparation of high purity O-substituted hydroxylamine derivatives |
| JP2002039836A (en) * | 2000-07-21 | 2002-02-06 | Nippon Soda Co Ltd | Interlayer liquid level controlling method in sequential extraction |
| CN114163350A (en) * | 2021-11-29 | 2022-03-11 | 宁夏汉润生物科技有限公司 | Synthetic method of O-3-chloro-2-propenyl hydroxylamine |
| CN114394916B (en) * | 2021-12-29 | 2023-12-15 | 杭州瑞思新材料有限公司 | Preparation method of O-3-chloro-2-propenyl hydroxylamine |
-
1991
- 1991-12-19 JP JP03353928A patent/JP3084871B2/en not_active Expired - Lifetime
Non-Patent Citations (2)
| Title |
|---|
| Ｃｈｅｍ．ａｂｓｔｒ．，Ｖｏｌ．８０，ｔｈｅ ａｂｓｔｒｃｔ Ｎｏ．４７５７２，Ａｒｏｙａｎ，Ａ．Ａ．ａｎｄ Ｋｈａｃｈａｔｕｒｙａｎ，Ｔ．Ａ．，’Ｓｙｎｔｈｅｓｉｓ ａｎｄ ｓｏｍｅ ｒｅａｃｔｉｏｎｓ ｏｆ ｏ−（３−ｃｈｌｏｒｏ−４−ｍｅｔｈｏｘｙｂｅｎｚｙｌ）−ａｎｄ ｏ−（３−ｃｈｌｏｒｏｃｒｏｔｙｌ）ｈｙｄｒｏｘｙｌａｍｉｎｅｓ’，Ａｒｍ．Ｋｈｉｍ．Ｚｈ．１９７３，２６（９），７５８−７６２ |
| Ｃｈｅｍ．ａｂｓｔｒ．，Ｖｏｌ．８４，ｔｈｅ ａｂｓｔｒｃｔ Ｎｏ．３９２５１，Ｐａｒｏｎｉｋｙａｎ，Ｇ．Ｍ．ｅｔ ａｌ．，’Ｍｕｔａｇｅｎｉｃ ｅｆｆｅｃｔ ｏｆ ｎｅｗ ｃｈｅｍｉｃａｌ ｃｏｍｐｏｕｎｄｓ． ▲ＩＩＩ▼．Ｍｕｔａｇｅｎｉｃ ｅｆｆｅｃｔ ｏｆ ｓｏｍｅ ｈｙｄｒｏｘｙｌａｍｉｎｅ ｄｅｒｉｖａｔｉｖｅｓ’，Ｇｅｎｅｔｉｋａ １９７５，１１（１０），１０５−１１０ |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05163228A (en) | 1993-06-29 |
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