JP3573524B2 - Method for producing hydrazine derivative - Google Patents
Method for producing hydrazine derivative Download PDFInfo
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- JP3573524B2 JP3573524B2 JP11477195A JP11477195A JP3573524B2 JP 3573524 B2 JP3573524 B2 JP 3573524B2 JP 11477195 A JP11477195 A JP 11477195A JP 11477195 A JP11477195 A JP 11477195A JP 3573524 B2 JP3573524 B2 JP 3573524B2
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Description
【0001】
【産業上の利用分野】
本発明は殺虫性ヒドラジン誘導体の製造方法に関するものである。
【0002】
【従来の技術】
特開平5−163266号には本発明におけるヒドラジン誘導体に該当するヒドラジン誘導体の製造方法に関して記載があるが、後記する本発明の製造方法について具体的には記載されていない。
【0003】
【発明が解決しようとする課題】
近年、農薬の製造行程においても、有機溶媒の環境中への放出が少ない等、環境にやさしい方法の開発が求められている。本発明は殺虫性ヒドラジン誘導体の製造方法において、回収、リサイクルが容易である等上記条件を満たし、かつ安価で収率の高い溶媒を用いた方法の開発を目的としたものである。
【0004】
【課題を解決するための手段】
本発明者は上記の目的を達成するため鋭意研究した結果、一般式(1):
【0005】
【化4】
【0006】
[式中、AはCH2 を示し、Bは酸素原子を示し、R1 、R2 、R3 およびR 4 は同じか異なってもよく、水素原子またはメチル基を示し、R5 はハロゲン原子、(C1 〜C4 )アルキル基または(C1 〜C4 )ハロアルキル基を示し、R6 は水素原子、ハロゲン原子、(C1 〜C4 )アルキル基または(C1 〜C4 )ハロアルキル基を示し、R7 は水素原子またはハロゲン原子を示し、R8 、R 9 およびR10はそれぞれ独立して水素原子、ハロゲン原子、ニトロ基、(C1 〜C4 )アルキル基、(C1 〜C4 )ハロアルキル基、(C1 〜C4 )アルコキシ基、(C2 〜C4 )アルケニルオキシ基、(C2 〜C4 )アルキニルオキシ基、(C2 〜C4 )アルケニル基、(C1 〜C4 )ハロアルコキシ基、ハロゲン原子で置換されていてもよいフェニル基を有する(C1 〜C4 )アルコキシ基、または、CF3 、ハロゲンもしくは(C1 〜C2 )アルキル基で置換されていてもよいフェノキシ基を有する(C1 〜C4 )アルコキシ基を示し、R11は(C4 〜C8 )の分岐アルキル基を示す。]で示されるヒドラジン誘導体を製造するのに、一般式(2):
【0007】
【化5】
【0008】
[式中、A、B、R1 、R2 、R3 、R4 、R5 、R6 、R7 およびR11は前記と同義である。]で示されるヒドラジド誘導体をケトン類、エステル類、もしくは芳香族炭化水素を溶媒として、または、それらと水との混合溶液を溶媒として、塩基の存在下、一般式(3):
【0009】
【化6】
【0010】
[式中、R8 、R9 およびR10は前記と同義であり、Xはハロゲン原子を示す。]で示される酸ハロゲン化物と反応させる製造方法がすぐれた方法であることを見い出し、本発明を完成するに至った。
【0011】
一般式(1)、(2)および(3)において、ハロゲン原子としては、例えばフッ素、塩素、臭素または沃素原子が挙げられ、(C1 〜C4 )アルキル基としては、例えばメチル、エチル、n−プロピル、イソプロピル、n−ブチル、イソブチル、sec−ブチル、tert−ブチルが挙げられ、(C2 〜C4 )アルケニル基としては、例えばアリル、2−プロペニル、1−プロペニル、エテニル、2−ブテニル基が挙げられ、(C1 〜C4 )アルコキシ基としては、例えばメトキシ、エトキシ、n−プロポキシ、イソプロポキシ、n−ブトキシ、イソブトキシ、sec−ブトキシまたはtert−ブトキシ基が挙げられ、(C1 〜C4 )ハロアルキル基としては、例えば1−もしくは2−クロロエチル、クロロメチル、ジクロロメチル、ブロモメチル、1−もしくは2−ブロモエチル、フルオロメチル、ジフルオロメチルまたはトリフルオロメチル基などが挙げられ、(C1 〜C4 )ハロアルコキシ基としては、例えば1−もしくは2−ブロモエトキシ、3−ブロモ−n−プロポキシ、2,2,2−もしくは1,1,1−トリフルオロエトキシまたはトリフルオロメトキシ基が挙げられ、(C2 〜C4 )アルケニルオキシ基としては、例えばアリルオキシまたは2−ブテニルオキシ基が挙げられ、(C2 〜C4 )アルキニルオキシ基としては、例えばプロパルギルオキシ基等が挙げられ、ハロゲン原子で置換されていてもよいフェニル基を有する(C1 〜C
4 )アルコキシ基としては、例えば
【0012】
【化7】
【0013】
などが挙げられ、
CF3 、ハロゲンもしくは(C1 〜C2 )アルキル基で置換されていてもよいフェノキシ基を有する(C1 〜C4 )アルコキシ基としては、例えば
【0014】
【化8】
【0015】
が挙げられ、
(C4 〜C8 )分岐アルキル基としては、例えばtert−ブチル、1,2,2−トリメチルプロピル、2,2−ジメチルプロピルまたは1,2,2−トリメチルブチル基が挙げられる。
【0016】
本発明の製造方法で製造されるヒドラジン誘導体において好ましいものは、一般式(1)において、AがCH2 を示し、Bが酸素原子を示し、R1 、R2 、R3 およびR4 が水素原子を示し、R5 が(C1 〜C2 )アルキル基またはハロゲン原子を示し、R6 が水素原子を示し、R7 が水素原子を示し、R8 、R9 およびR10がそれぞれ独立して水素原子、(C1 〜C4 )アルキル基、ハロゲン原子、ニトロ基または(C1 〜C4 )アルコキシ基を示し、R11が(C4 〜C6 )の分岐アルキル基を示すヒドラジン誘導体である。
【0017】
本発明の製造方法で製造されるヒドラジン誘導体においてより好ましいものは、一般式(1)において、AがCH2 を示し、Bが酸素原子を示し、R1 、R2 、R3 およびR4 が水素原子を示し、R5 が(C1 〜C2 )アルキル基を示し、R6 が水素原子を示し、R7 が水素原子を示し、R8 、R9 およびR10がそれぞれ独立して水素原子、メチル基、塩素原子、フッ素原子、ニトロ基またはメトキシ基を示し、R11が(C4 〜C6 )の分岐アルキル基を示すヒドラジン誘導体である。
【0018】
本発明の製造方法で製造されるヒドラジン誘導体で特に好ましいものは、一般式(1)において、AがCH2 を示し、Bが酸素原子を示し、R1 、R2 、R 3 およびR4 が水素原子を示し、R5 が(C1 〜C2 )アルキル基を示し、R 6 が水素原子を示し、R7 が水素原子を示し、R8 、R9 およびR10がこれらが結合しているフェニル基と一緒になって3,5−ジメチルフェニル基、3,5−ジクロロフェニル基または3,5−ジメチル−4−フルオロフェニル基を示し、R11がt−ブチル基、2,2−ジメチルプロピル基または1,2,2−トリメチルプロピル基を示すヒドラジン誘導体である。
【0019】
本発明の製造方法で製造されるヒドラジン誘導体において特に好ましい特定のものは、N−(5−メチルクロマン−6−カルボ)−N′−t−ブチル−N′−(3,5−ジメチルベンゾイル)ヒドラジン、N−(5−メチルクロマン−6−カルボ)−N′−t−ブチル−N′−(3,5−ジメチル−4−フルオロベンゾイル)ヒドラジン、N−(5−メチルクロマン−6−カルボ)−N′−t−ブチル−N′−(3,5−ジクロロベンゾイル)ヒドラジンから選ばれるヒドラジン誘導体である。
【0020】
本発明の製造方法において、反応には一般式(2)の化合物と一般式(3)の化合物とを任意の割合で使用することができるが、好ましくは等モル比かほぼ等モル比で使用する。溶媒としてはケトン類、エステル類、ハロゲノベンゼン類、及びこれらと水との混合溶液を用いる。ケトン類としてはメチルエチルケトン、メチルイソプロピルケトン、メチルイソブチルケトンが挙げられるが、好ましくはメチルイソブチルケトンである。エステル類としては例えば、酢酸エチル、酢酸イソプロピル、酢酸イソブチル、酢酸n−ブチルが挙げられるが、好ましくは酢酸n−ブチルである。ハロゲノベンゼン類としては例えばモノクロロベンゼン、ジクロロベンゼンが挙げられるが、好ましくはモノクロロベンゼンである。
【0021】
溶媒としてより好ましくは、メチルイソブチルケトン、酢酸n−ブチルもしくはこれらと水の混合溶液である。さらに好ましくは酢酸n−ブチルもしくは酢酸n−ブチルと水との混合溶液である。
【0022】
塩基としては例えば、水酸化カリウム、水酸化ナトリウム、炭酸カリウム、炭酸ナトリウム、炭酸水素カリウム、炭酸水素ナトリウムなどの無機塩基、トリエチルアミン、ピリジンなどの有機塩基を使用することができる。塩基の量は化学量論量もしくはそれより過剰に用いることができるが、好ましくは化学量論量かそれより1.0〜5.0倍過剰な量を用いる。反応は、−20℃から溶媒の沸点までの温度範囲で行うことができるが好ましくは−5℃〜70℃の範囲である。N,N′−ジメチルアミノピリジンなどの触媒を反応系中に添加することもできる。
【0023】
一般式(1)の化合物の製造時において、反応混合物は充分な時間攪拌され、ろ過、あるいは抽出、水洗、乾燥、溶媒留去等の過程により目的物が回収される。必要があれば再結晶あるいはカラムクロマトグラフィーにより精製を行うことができる。
【0024】
【実施例】
以下に実施例をあげて本発明を説明するが、本発明はこれらのみに限定されるものではない。
【0025】
製造例1
N−(5−メチルクロマン−6−カルボ)−N′−tert−ブチル−N′−(3,5−ジメチルベンゾイル)ヒドラジンの製造:
N−(5−メチルクロマン−6−カルボ)−N′−tert−ブチルヒドラジンの塩酸水溶液198.9g(N−(5−メチルクロマン−6−カルボ)−N′−tert−ブチルヒドラジン5.31g含有)に酢酸ブチル40.4mlを加え50℃にて炭酸ナトリウム5.5gを発泡に注意して加えた。50℃で攪拌の後、静置し分液した。得られた有機層に5%食塩水20.2mlをくわえ、50℃で攪拌の後静置し分液した。得られた有機層に20%炭酸ナトリウム水溶液6.5gを加え、30℃で3,5−ジメチルベンゾイルクロライド3.40gを滴下した。同温にて2時間攪拌した後、10℃まで冷却し析出した結晶をろ過し、水洗して粗N−(5−メチルクロマン−6−カルボ)−N′−tert−ブチル−N′−(3,5−ジメチルベンゾイル)ヒドラジン8.28gを得た。得られたろ液から分液にて有機層を得た後、減圧下濃縮して(酢酸ブチルを回収して)、オイル0.74gを得た。このオイルと粗N−(5−メチルクロマン−6−カルボ)−N′−tert−ブチル−N′−(3,5−ジメチルベンゾイル)ヒドラジンを合わせてメタノール−水系で再結晶を行い、目的のN−(5−メチルクロマン−6−カルボ)−N′−tert−ブチル−N′−(3,5−ジメチルベンゾイル)ヒドラジン7.18gを得た(純度95.9%、収率86.4%)。
【0026】
1H−NMR(CDCl3 )δ(ppm)
7.37(s,1H),7.06(s,2H),6.98(s,1H),6.48(d,1H,JH =8.3Hz),6.34(d,1H,JH =8.3Hz),4.09(t,2H,JH =5.2Hz),2.56(t,2H,JH =6.6Hz),2.27(s,6H),1.99(m,2H),1.95(s,3H),1.59(s,9H)。
【0027】
製造例2
N−(5−メチルクロマン−6−カルボ)−N′−tert−ブチル−N′−(3,5−ジメチルベンゾイル)ヒドラジンの製造:
N−(5−メチルクロマン−6−カルボ)−N′−tert−ブチルヒドラジンの塩酸水溶液400g(N−(5−メチルクロマン−6−カルボ)−N′−tert−ブチルヒドラジン21.56g含有)にメチルイソブチルケトン123.3mlを加え50℃にて炭酸ナトリウム13.1gを発泡に注意して加えた。50℃で攪拌の後、静置し分液した。得られた有機層に5%食塩水82.2mlをくわえ、50℃で攪拌の後静置し分液した。得られた有機層に10%水酸化ナトリウム水溶液39.5gを加え、室温で3,5−ジメチルベンゾイルクロライド14.3gを滴下した。同温にて2時間攪拌した後、5℃まで冷却し析出した結晶をろ過し、水洗して粗N−(5−メチルクロマン−6−カルボ)−N′−tert−ブチル−N′−(3,5−ジメチルベンゾイル)ヒドラジン8.28gを得た。この粗N−(5−メチルクロマン−6−カルボ)−N′−tert−ブチル−N′−(3,5−ジメチルベンゾイル)ヒドラジンをメタノール−水系で再結晶を行い、乾燥して、目的のN−(5−メチルクロマン−6−カルボ)−N′−tert−ブチル−N′−(3,5−ジメチルベンゾイル)ヒドラジン26.79gを得た(純度95.7%、収率79.1%)。
【0028】
1H−NMR(CDCl3 )δ(ppm)
7.37(s,1H),7.06(s,2H),6.98(s,1H),6.48(d,1H,JH =8.3Hz),6.34(d,1H,JH =8.3Hz),4.09(t,2H,JH =5.2Hz),2.56(t,2H,JH =6.6Hz),2.27(s,6H),1.99(m,2H),1.95(s,3H),1.59(s,9H)。
【0029】
製造例3
N−(5−メチルクロマン−6−カルボ)−N′−tert−ブチル−N′−(3,5−ジメチルベンゾイル)ヒドラジンの製造:
N−(5−メチルクロマン−6−カルボ)−N′−tert−ブチルヒドラジンのモノクロロベンゼン溶液645.1g(N−(5−メチルクロマン−6−カルボ)−N′−tert−ブチルヒドラジン54.4g含有)に4.8%水酸化ナトリウム水溶液258.9gを加え、0〜5℃で3,5−ジメチルベンゾイルクロライド36.0gを滴下した。同温にて3時間攪拌した後、0℃まで冷却し析出した結晶をろ過し、冷却したクロロベンゼンと水で洗浄して粗N−(5−メチルクロマン−6−カルボ)−N′−tert−ブチル−N′−(3,5−ジメチルベンゾイル)ヒドラジン173.51gを得た。この粗N−(5−メチルクロマン−6−カルボ)−N′−tert−ブチル−N′−(3,5−ジメチルベンゾイル)ヒドラジンをメタノール−水系で再結晶を行い、乾燥して、目的のN−(5−メチルクロマン−6−カルボ)−N′−tert−ブチル−N′−(3,5−ジメチルベンゾイル)ヒドラジン82.3gを得た(純度88.0%、収率88.6%)。
【0030】
1H−NMR(CDCl3 )δ(ppm)
7.37(s,1H),7.06(s,2H),6.98(s,1H),6.48(d,1H,JH =8.3Hz),6.34(d,1H,JH =8.3Hz),4.09(t,2H,JH =5.2Hz),2.56(t,2H,JH =6.6Hz),2.27(s,6H),1.99(m,2H),1.95(s,3H),1.59(s,9H)。[0001]
[Industrial applications]
The present invention relates to a method for producing an insecticidal hydrazine derivative.
[0002]
[Prior art]
JP-A-5-163266 describes a method for producing a hydrazine derivative corresponding to the hydrazine derivative in the present invention, but does not specifically describe a production method of the present invention described later.
[0003]
[Problems to be solved by the invention]
In recent years, even in the process of producing pesticides, there is a demand for the development of an environmentally friendly method such as a small release of an organic solvent into the environment. An object of the present invention is to develop a method for producing an insecticidal hydrazine derivative which satisfies the above conditions, such as easy recovery and recycling, and uses a low-cost and high-yield solvent.
[0004]
[Means for Solving the Problems]
The present inventor has conducted intensive studies to achieve the above object, and as a result, general formula (1):
[0005]
Embedded image
[0006]
[Wherein A represents CH 2 , B represents an oxygen atom, R 1 , R 2 , R 3 and R 4 may be the same or different and represent a hydrogen atom or a methyl group, and R 5 represents a halogen atom , (C 1 ~C 4) an alkyl group or a (C 1 ~C 4) haloalkyl group, R 6 is a hydrogen atom, a halogen atom, (C 1 ~C 4) alkyl or (C 1 ~C 4) haloalkyl R 7 represents a hydrogen atom or a halogen atom; R 8 , R 9 and R 10 each independently represent a hydrogen atom, a halogen atom, a nitro group, a (C 1 -C 4 ) alkyl group, a (C 1 -C 4 ) haloalkyl group, (C 1 -C 4 ) alkoxy group, (C 2 -C 4 ) alkenyloxy group, (C 2 -C 4 ) alkynyloxy group, (C 2 -C 4 ) alkenyl group, C 1 ~C 4) Haroarukoki A (C 1 -C 4 ) alkoxy group having a phenyl group which may be substituted with a halogen atom, or a phenoxy which may be substituted with a CF 3 , halogen or (C 1 -C 2 ) alkyl group It represents a (C 1 -C 4 ) alkoxy group having a group, and R 11 represents a (C 4 -C 8 ) branched alkyl group. The hydrazine derivative represented by the general formula (2):
[0007]
Embedded image
[0008]
[In the formula, A, B, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 11 are as defined above. A hydrazide derivative represented by the general formula (3) in the presence of a base, using a ketone, an ester or an aromatic hydrocarbon as a solvent, or a mixed solution thereof with water as a solvent.
[0009]
Embedded image
[0010]
[Wherein, R 8 , R 9 and R 10 have the same meanings as described above, and X represents a halogen atom. ] Has been found to be an excellent method for reacting with an acid halide, and the present invention has been completed.
[0011]
In the general formulas (1), (2) and (3), examples of the halogen atom include a fluorine, chlorine, bromine and iodine atom, and examples of the (C 1 -C 4 ) alkyl group include methyl, ethyl, Examples include n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl. Examples of the (C 2 -C 4 ) alkenyl group include allyl, 2-propenyl, 1-propenyl, ethenyl, and 2-phenyl. And a (C 1 -C 4 ) alkoxy group such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy or tert-butoxy. 1 to C 4 ) Haloalkyl groups include, for example, 1- or 2-chloroethyl, chloromethyl, dichloro Examples thereof include a methyl, bromomethyl, 1- or 2-bromoethyl, fluoromethyl, difluoromethyl or trifluoromethyl group. Examples of the (C 1 -C 4 ) haloalkoxy group include 1- or 2-bromoethoxy, Bromo-n-propoxy, 2,2,2- or 1,1,1-trifluoroethoxy or trifluoromethoxy group is mentioned, and (C 2 -C 4 ) alkenyloxy group includes, for example, allyloxy or 2-butenyloxy And the (C 2 -C 4 ) alkynyloxy group includes, for example, a propargyloxy group and the like, and has a phenyl group which may be substituted by a halogen atom (C 1 -C 4)
4 ) As the alkoxy group, for example,
Embedded image
[0013]
And the like,
CF 3, with a halogen or (C 1 ~C 2) alkyl optionally phenoxy group optionally substituted by a group (C 1 ~C 4) Examples of the alkoxy group, for example, [0014]
Embedded image
[0015]
And
The (C 4 ~C 8) branched alkyl group, for example tert- butyl, 1,2,2-trimethyl propyl, 2,2-dimethylpropyl or 1,2,2-trimethyl-butyl group.
[0016]
In the hydrazine derivative produced by the production method of the present invention, preferred are those in which A represents CH 2 , B represents an oxygen atom, and R 1 , R 2 , R 3, and R 4 are hydrogen in the general formula (1). R 5 represents a (C 1 -C 2 ) alkyl group or a halogen atom, R 6 represents a hydrogen atom, R 7 represents a hydrogen atom, and R 8 , R 9 and R 10 are each independently Te hydrogen atom, (C 1 ~C 4) alkyl group, a halogen atom, a nitro group or a (C 1 ~C 4) alkoxy group, a hydrazine derivative represented R 11 is a branched alkyl group of (C 4 ~C 6) It is.
[0017]
In the hydrazine derivative produced by the production method of the present invention, more preferably, in the general formula (1), A represents CH 2 , B represents an oxygen atom, and R 1 , R 2 , R 3 and R 4 represent R 5 represents a (C 1 -C 2 ) alkyl group; R 6 represents a hydrogen atom; R 7 represents a hydrogen atom; R 8 , R 9 and R 10 each independently represent hydrogen A hydrazine derivative which represents an atom, a methyl group, a chlorine atom, a fluorine atom, a nitro group or a methoxy group, and wherein R 11 represents a (C 4 -C 6 ) branched alkyl group.
[0018]
Particularly preferred hydrazine derivatives produced by the production method of the present invention are those in which A represents CH 2 , B represents an oxygen atom, and R 1 , R 2 , R 3 and R 4 in the general formula (1). R 5 represents a (C 1 -C 2 ) alkyl group, R 6 represents a hydrogen atom, R 7 represents a hydrogen atom, and R 8 , R 9 and R 10 represent a hydrogen atom; Together with a phenyl group present represents a 3,5-dimethylphenyl group, a 3,5-dichlorophenyl group or a 3,5-dimethyl-4-fluorophenyl group, and R 11 is a t-butyl group, 2,2-dimethyl It is a hydrazine derivative showing a propyl group or a 1,2,2-trimethylpropyl group.
[0019]
A particularly preferred specific hydrazine derivative produced by the production method of the present invention is N- (5-methylchroman-6-carbo) -N'-t-butyl-N '-(3,5-dimethylbenzoyl). Hydrazine, N- (5-methylchroman-6-carbo) -N'-t-butyl-N '-(3,5-dimethyl-4-fluorobenzoyl) hydrazine, N- (5-methylchroman-6-carbo) ) Hydrazine derivatives selected from -N'-t-butyl-N '-(3,5-dichlorobenzoyl) hydrazine.
[0020]
In the production method of the present invention, the compound of the general formula (2) and the compound of the general formula (3) can be used in an arbitrary ratio in the reaction, but preferably in an equimolar ratio or an approximately equimolar ratio. I do. As the solvent, ketones, esters, halogenobenzenes, and a mixed solution of these with water are used. Examples of ketones include methyl ethyl ketone, methyl isopropyl ketone, and methyl isobutyl ketone, with methyl isobutyl ketone being preferred. Examples of the esters include ethyl acetate, isopropyl acetate, isobutyl acetate, and n-butyl acetate, and preferably n-butyl acetate. Examples of halogenobenzenes include monochlorobenzene and dichlorobenzene, but monochlorobenzene is preferred.
[0021]
More preferably, the solvent is methyl isobutyl ketone, n-butyl acetate or a mixed solution thereof with water. More preferably, it is n-butyl acetate or a mixed solution of n-butyl acetate and water.
[0022]
As the base, for example, inorganic bases such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium bicarbonate, and sodium bicarbonate, and organic bases such as triethylamine and pyridine can be used. The amount of the base can be used in a stoichiometric amount or in excess thereof, but it is preferable to use a stoichiometric amount or an excess of 1.0 to 5.0 times. The reaction can be carried out in a temperature range from -20 ° C to the boiling point of the solvent, but is preferably in the range of -5 ° C to 70 ° C. A catalyst such as N, N'-dimethylaminopyridine can be added to the reaction system.
[0023]
In the production of the compound of the general formula (1), the reaction mixture is stirred for a sufficient time, and the desired product is recovered by filtration, extraction, washing with water, drying, evaporation of the solvent and the like. If necessary, purification can be performed by recrystallization or column chromatography.
[0024]
【Example】
Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited thereto.
[0025]
Production Example 1
Preparation of N- (5-methylchroman-6-carbo) -N'-tert-butyl-N '-(3,5-dimethylbenzoyl) hydrazine:
198.9 g of an aqueous solution of N- (5-methylchroman-6-carbo) -N'-tert-butylhydrazine in hydrochloric acid (5.31 g of N- (5-methylchroman-6-carbo) -N'-tert-butylhydrazine) 40.4 ml of butyl acetate was added thereto, and 5.5 g of sodium carbonate was added at 50 ° C. while paying attention to foaming. After stirring at 50 ° C., the mixture was allowed to stand and separated. 20.2 ml of a 5% saline solution was added to the obtained organic layer, and the mixture was stirred at 50 ° C., allowed to stand still, and separated. 6.5 g of a 20% aqueous sodium carbonate solution was added to the obtained organic layer, and 3.40 g of 3,5-dimethylbenzoyl chloride was added dropwise at 30 ° C. After stirring at the same temperature for 2 hours, the mixture was cooled to 10 ° C., and the precipitated crystals were filtered, washed with water and crude N- (5-methylchroman-6-carbo) -N′-tert-butyl-N ′-( 8.28 g of 3,5-dimethylbenzoyl) hydrazine was obtained. An organic layer was obtained by liquid separation from the obtained filtrate, and concentrated under reduced pressure (by recovering butyl acetate) to obtain 0.74 g of an oil. This oil and crude N- (5-methylchroman-6-carbo) -N'-tert-butyl-N '-(3,5-dimethylbenzoyl) hydrazine were combined and recrystallized in a methanol-water system to obtain the desired compound. 7.18 g of N- (5-methylchroman-6-carbo) -N'-tert-butyl-N '-(3,5-dimethylbenzoyl) hydrazine was obtained (purity 95.9%, yield 86.4). %).
[0026]
1 H-NMR (CDCl 3 ) δ (ppm)
7.37 (s, 1H), 7.06 (s, 2H), 6.98 (s, 1H), 6.48 (d, 1H, JH = 8.3 Hz), 6.34 (d, 1H) , J H = 8.3Hz), 4.09 (t, 2H, J H = 5.2Hz), 2.56 (t, 2H, J H = 6.6Hz), 2.27 (s, 6H), 1.99 (m, 2H), 1.95 (s, 3H), 1.59 (s, 9H).
[0027]
Production Example 2
Preparation of N- (5-methylchroman-6-carbo) -N'-tert-butyl-N '-(3,5-dimethylbenzoyl) hydrazine:
400 g of an aqueous solution of N- (5-methylchroman-6-carbo) -N'-tert-butylhydrazine in hydrochloric acid (containing 21.56 g of N- (5-methylchroman-6-carbo) -N'-tert-butylhydrazine) To the mixture was added 123.3 ml of methyl isobutyl ketone, and 13.1 g of sodium carbonate was added at 50 ° C. while paying attention to foaming. After stirring at 50 ° C., the mixture was allowed to stand and separated. 82.2 ml of a 5% saline solution was added to the obtained organic layer, and the mixture was stirred at 50 ° C., allowed to stand still, and separated. To the obtained organic layer was added 39.5 g of a 10% aqueous sodium hydroxide solution, and 14.3 g of 3,5-dimethylbenzoyl chloride was added dropwise at room temperature. After stirring at the same temperature for 2 hours, the mixture was cooled to 5 ° C., and the precipitated crystals were filtered, washed with water, and crude N- (5-methylchroman-6-carbo) -N′-tert-butyl-N ′-( 8.28 g of 3,5-dimethylbenzoyl) hydrazine was obtained. The crude N- (5-methylchroman-6-carbo) -N'-tert-butyl-N '-(3,5-dimethylbenzoyl) hydrazine was recrystallized in a methanol-water system, dried, and dried. 26.79 g of N- (5-methylchroman-6-carbo) -N'-tert-butyl-N '-(3,5-dimethylbenzoyl) hydrazine was obtained (purity 95.7%, yield 79.1). %).
[0028]
1 H-NMR (CDCl 3 ) δ (ppm)
7.37 (s, 1H), 7.06 (s, 2H), 6.98 (s, 1H), 6.48 (d, 1H, JH = 8.3 Hz), 6.34 (d, 1H) , J H = 8.3Hz), 4.09 (t, 2H, J H = 5.2Hz), 2.56 (t, 2H, J H = 6.6Hz), 2.27 (s, 6H), 1.99 (m, 2H), 1.95 (s, 3H), 1.59 (s, 9H).
[0029]
Production Example 3
Preparation of N- (5-methylchroman-6-carbo) -N'-tert-butyl-N '-(3,5-dimethylbenzoyl) hydrazine:
645.1 g of a solution of N- (5-methylchroman-6-carbo) -N'-tert-butylhydrazine in monochlorobenzene (N- (5-methylchroman-6-carbo) -N'-tert-butylhydrazine54. 258.9 g of a 4.8% aqueous sodium hydroxide solution was added to the mixture (containing 4 g), and 36.0 g of 3,5-dimethylbenzoyl chloride was added dropwise at 0 to 5 ° C. After stirring at the same temperature for 3 hours, the mixture was cooled to 0 ° C., and the precipitated crystals were filtered, washed with cooled chlorobenzene and water, and crude N- (5-methylchroman-6-carbo) -N′-tert- was obtained. 173.51 g of butyl-N '-(3,5-dimethylbenzoyl) hydrazine were obtained. The crude N- (5-methylchroman-6-carbo) -N'-tert-butyl-N '-(3,5-dimethylbenzoyl) hydrazine was recrystallized in a methanol-water system, dried, and dried. 82.3 g of N- (5-methylchroman-6-carbo) -N'-tert-butyl-N '-(3,5-dimethylbenzoyl) hydrazine were obtained (purity: 88.0%, yield: 88.6). %).
[0030]
1 H-NMR (CDCl 3 ) δ (ppm)
7.37 (s, 1H), 7.06 (s, 2H), 6.98 (s, 1H), 6.48 (d, 1H, JH = 8.3 Hz), 6.34 (d, 1H) , J H = 8.3Hz), 4.09 (t, 2H, J H = 5.2Hz), 2.56 (t, 2H, J H = 6.6Hz), 2.27 (s, 6H), 1.99 (m, 2H), 1.95 (s, 3H), 1.59 (s, 9H).
Claims (3)
で示されるヒドラジン誘導体の製造方法であって、一般式(2):
A method for producing a hydrazine derivative represented by the general formula (2):
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JP11477195A JP3573524B2 (en) | 1995-05-12 | 1995-05-12 | Method for producing hydrazine derivative |
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JP11477195A JP3573524B2 (en) | 1995-05-12 | 1995-05-12 | Method for producing hydrazine derivative |
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JP3573524B2 true JP3573524B2 (en) | 2004-10-06 |
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