JPH02264757A - Production of nitroindoles - Google Patents

Production of nitroindoles

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Publication number
JPH02264757A
JPH02264757A JP8579389A JP8579389A JPH02264757A JP H02264757 A JPH02264757 A JP H02264757A JP 8579389 A JP8579389 A JP 8579389A JP 8579389 A JP8579389 A JP 8579389A JP H02264757 A JPH02264757 A JP H02264757A
Authority
JP
Japan
Prior art keywords
formula
compound
reaction
solvent
nitroindoles
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.)
Pending
Application number
JP8579389A
Other languages
Japanese (ja)
Inventor
Masanori Somei
正徳 染井
Fumio Yamada
山田 文夫
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Steel Chemical and Materials Co Ltd
Original Assignee
Nippon Steel Chemical Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Nippon Steel Chemical Co Ltd filed Critical Nippon Steel Chemical Co Ltd
Priority to JP8579389A priority Critical patent/JPH02264757A/en
Publication of JPH02264757A publication Critical patent/JPH02264757A/en
Pending legal-status Critical Current

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  • Indole Compounds (AREA)

Abstract

PURPOSE:To obtain the subject compound useful as a raw material for pharmaceuticals, agricultural chemicals, electronic materials, etc., in one step and high yield by nitrating an indole compound having-Tl(OCOCF3)2 group at 7 or 4-position in the presence of copper sulfate and sodium nitrite. CONSTITUTION:The objective compound of formula III, formula IV or formula V can be produced by reacting a compound of formula I or II (R1 is H or univalent group such as lower alkyl, aryl, alkoxy and amino; R2 is lower alkyl, aryl, etc.; n is 0-5) in the presence of copper sulfate and sodium nitrite in N,N- dimethylformamide solvent at 80-140 deg.C. The amounts of copper sulfate, sodium nitrite and solvent are respectively 1-10 equivalent, 4-12 equivalent and 5-40 pts.wt. based on the compound of formula I or formula II.

Description

【発明の詳細な説明】 [産業上の利用分野] 本発明は、医薬、農薬、電子材料等の分野においてその
原料や原体として有用なニトロインドール類の製造方法
に関する。
DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing nitroindoles useful as raw materials or bulk materials in the fields of medicines, agricultural chemicals, electronic materials, etc.

[従来の技術] 7−ニトロインドール類ヤ4−ニトロインドール類は、
医薬、農薬、電子材料等の原料として重要である。例え
ば1−ニトロインドール類は現在写真薬の発色材の原料
として用いられており、また、4−二トロインドール類
は医薬の原料として用いられている。そして、これらの
化合物のHa六方法しては、例えば、7−ニトロインド
ールの場合には、■2−ニトロアニリンから合成された
2−二トロフェニルヒドラジンを原料にフィッシャー(
FiSCher)反応によりインドール環を形成し、次
いで脱炭酸反応を行う方法(J、 Am、 Chem、
 Soc、、 80.4261(1958))や、■5
−ニトローβ−ナフトールを出発原料に、開環、転位を
経てインドール環を形成させる方法(Tr、 )los
k、 Tekhriol、 In5t、、 1973.
74)や、■インドールを出発原料とし、インドリンス
ルホン酸塩を経てニトロ化を行うことにより製造する方
法(Chem、 Ber、 95.2205(t962
))が知られている。
[Prior art] 7-nitroindoles and 4-nitroindoles are:
It is important as a raw material for medicines, agricultural chemicals, electronic materials, etc. For example, 1-nitroindoles are currently used as raw materials for coloring materials for photographic drugs, and 4-nitroindoles are used as raw materials for pharmaceuticals. For example, in the case of 7-nitroindole, the Ha6 method for these compounds is as follows:
A method in which an indole ring is formed by a reaction (FiSCher) and then a decarboxylation reaction (J, Am, Chem,
Soc,, 80.4261 (1958)), ■5
- A method of forming an indole ring using nitro β-naphthol as a starting material through ring opening and rearrangement (Tr, )los
K, Tekriol, In5t, 1973.
74), and ■ a method of producing by using indole as a starting material and performing nitration via indoline sulfonate (Chem, Ber, 95.2205 (t962
))It has been known.

また、4−ニトロインドールの場合には、■2,6−シ
ニトロトルエンを原料として三工程で製造する方法(C
hem、 Pharm、 Bull、、 29.314
5(1981)。
In the case of 4-nitroindole, a three-step manufacturing method using 2,6-sinitrotoluene as a raw material (C
hem, Pharm, Bull,, 29.314
5 (1981).

Organic 5ynthesis、 65.146
(t987))が知られている。
Organic 5ynthesis, 65.146
(t987)) is known.

ざらに、先に我々が提案した■7−又は4−位に−TI
(OCOCF3) 2基を有するインドール化合物を原
料に、硝酸銅・三水和物の存在下にN、N−ジメチルホ
ルムアミド−無水酢酸系混合溶媒で各々対応するニトロ
化合物を製造する方法がある(特願昭63−242 、
342号出願)。
Roughly, the ■7- or 4-position that we proposed earlier - TI
(OCOCF3) There is a method of producing corresponding nitro compounds using an indole compound having two groups as a raw material in a mixed solvent of N,N-dimethylformamide and acetic anhydride in the presence of copper nitrate trihydrate (specially Gansho 63-242,
Application No. 342).

しかしながら、これら従来の方法においては原料及び反
応収率において欠点が挙げられている。
However, these conventional methods have drawbacks in terms of raw materials and reaction yield.

すなわち、7−二トロインドールの!!造方法である■
の方法では出発原料及び副原料のコストが高く、フィッ
シャー反応の開環収率が低いことが問題であり、■の方
法では出発原料を合成することが難しく、開環反応及び
転位反応の収率が低いことが問題であり、また、■の方
法ではインドールスルホン塩のニトロ化反応の際に5−
位にニトロ基が導入されるものがその主生成物であり、
7−位のニトロ化の選択性が低いことが問題である。さ
らに、4−ニトロインドールの製造方法である■では出
発原料及び副原料のコストが高く、反応の再現性が難し
いことが問題である。
That is, 7-nitroindole! ! ■ It is a manufacturing method.
The problem with method (2) is that the cost of starting materials and auxiliary materials is high and the ring-opening yield of the Fischer reaction is low, and with method (2), it is difficult to synthesize the starting material and the yield of ring-opening reaction and rearrangement reaction is low. The problem is that the amount of 5-
The main product is one in which a nitro group is introduced into the position,
The problem is that the selectivity for nitration at the 7-position is low. Furthermore, the method (1) for producing 4-nitroindole has problems in that the cost of starting materials and auxiliary materials is high and the reproducibility of the reaction is difficult.

以上の■〜■の方法の問題点を解決すべく、我々が提案
した■の方法は、一応上記■〜■の問題点を解決し・、
その反応収率もこれら■〜■の方法よりも高いが、それ
でも40〜50%程度であり、充分に満足できる結果で
はない。
In order to solve the problems of the above methods ■~■, the method ■ we proposed solves the problems of the above ■~■,
Although the reaction yield is higher than those of methods 1 to 2, it is still only about 40 to 50%, which is not a fully satisfactory result.

[発明が解決しようとする課題] 本発明者らは、上記の問題点を解決すべく研究を重ねた
結果、7−位又は4−位に−Tl(OCOCF3 > 
2基を有するインドール化合物を原料に、1工程で高収
率に、しかも、位置選択的に7−位又は4−位にニトロ
基を有するインドールを製造することができる改良方法
を見い出し、本発明に到達した。
[Problems to be Solved by the Invention] As a result of repeated research to solve the above problems, the present inventors found that -Tl (OCOCF3 >
We have discovered an improved method that can regioselectively produce indole having a nitro group at the 7- or 4-position in one step in a high yield using an indole compound having two groups as a raw material, and the present invention reached.

従って、本発明の目的は、収率良く、しかも、短い製造
工程で7−位又は4−位にニトロ基を有するインドール
類を位置選択的に製造することができる方法を提供する
ことにある。
Therefore, an object of the present invention is to provide a method for regioselectively producing indoles having a nitro group at the 7-position or 4-position in a high yield and in a short production process.

[課題を解決するための手段] すなわら、本発明は、下記一般式[2a1又は[2b1
F3COCO\10COCF3 丁1 H[2b ] (但し、式中Rは1価の基を示し、R2は置換基であり
、nはO又は1〜5の整数を示す)で表される化合物を
中間体として、下記一般式[1al。
[Means for Solving the Problems] In other words, the present invention solves the problems by the following general formula [2a1 or [2b1
F3COCO\10COCF3 D1 H[2b] (However, in the formula, R represents a monovalent group, R2 is a substituent, and n represents O or an integer from 1 to 5) as an intermediate. As, the following general formula [1al.

【1b1又は[1C1 H(1cl (但し、式中R3ハ水素又バーC0R1テI) V)、
R1、R2及びnは前記と同じである〉で表される化合
物を得るニトロインドール化合物類のTIA造方法でお
る。
[1b1 or [1C1 H(1cl (However, in the formula, R3 is hydrogen or C0R1 is V),
This is a TIA production method for nitroindole compounds to obtain a compound represented by R1, R2 and n are the same as above.

本発明方法において、一般式[2a1及び[2blで示
される化合物は、−COR1で示されるカルボニル基を
有するインドール誘導体であり、このR1としては水素
、低級アルキル基、アリール基、アルコキシ基、水酸基
又はアミン基等の1価の基であって、好ましくは炭素数
1〜3のアルキル基が置換したアリール基、炭素数1〜
3のアルコキシ基又はアミノ基が挙げられる。また、置
換基R2は、好ましくは低級アルキル基又はアリール基
であり、nはO又は1〜5の整数である。
In the method of the present invention, the compounds represented by the general formulas [2a1 and [2bl] are indole derivatives having a carbonyl group represented by -COR1, where R1 is hydrogen, a lower alkyl group, an aryl group, an alkoxy group, a hydroxyl group, or A monovalent group such as an amine group, preferably an aryl group substituted with an alkyl group having 1 to 3 carbon atoms, and an aryl group having 1 to 3 carbon atoms.
3, an alkoxy group or an amino group. Further, the substituent R2 is preferably a lower alkyl group or an aryl group, and n is O or an integer of 1 to 5.

一般式[2a1の化合物から得られる一般式[1a]又
は[1b1で示されるニトロインドール類及び一般式[
2b1の化合物から得られる一般式[1c]で示される
ニトロインドール類は、4−位にニトロ基を有する化合
物であり、R3は水素又は−COR1である。そして、
R1、R2及びnは前記と同様のものを示す。
Nitroindoles represented by the general formula [1a] or [1b1 obtained from the compound of the general formula [2a1] and the general formula [
The nitroindoles represented by the general formula [1c] obtained from the compound 2b1 are compounds having a nitro group at the 4-position, and R3 is hydrogen or -COR1. and,
R1, R2 and n are the same as above.

さらに、本発明方法において、中間体である一般式[2
al及び[2b1の化合物の合成は、例えばChem、
 Pharm、  Bull、、 35.3146(1
987)の記載の方法で行うことができる。
Furthermore, in the method of the present invention, an intermediate of the general formula [2
Synthesis of al and [2b1 compounds can be performed, for example, in Chem.
Pharm, Bull, 35.3146 (1
987).

そして、本発明方法において、ニトロインドール類を製
造する場合には、中間体である一般式[2al又は[2
b1の化合物に対して、硫酸銅1〜1゜当量、好ましく
は1〜3当間及び亜硝酸ナトリウム4〜12当母、好ま
しくは6〜10当量と、反応溶媒としてのN、N−ジメ
チルホルムアミド5〜40中4部、好ましくは10〜2
0重量部とを使用し、反応温度は80〜140’C1好
ましくは100〜120″C程度で行うのがよい。
In the method of the present invention, when producing nitroindoles, intermediates of the general formula [2al or [2
1 to 1 equivalents of copper sulfate, preferably 1 to 3 equivalents, and 4 to 12 equivalents, preferably 6 to 10 equivalents of sodium nitrite, and N,N-dimethylformamide as a reaction solvent, relative to the compound b1. 4 parts in 5-40, preferably 10-2
0 parts by weight, and the reaction temperature is preferably about 80 to 140'C, preferably about 100 to 120'C.

反応終了後は、溶媒を留去してハロゲン系有機溶媒で抽
出した後、不溶性の無機物を濾過して飽和食塩水で洗浄
し、硫酸ナトリウムで脱水乾燥させ、次いで溶媒を留去
した後、得られた粗生成物を再結晶やカラムクロマトグ
ラフィー等の手段により精製する。
After the reaction is completed, the solvent is distilled off and extracted with a halogenated organic solvent, and the insoluble inorganic substances are filtered and washed with saturated brine, dehydrated and dried over sodium sulfate, and the solvent is distilled off. The resulting crude product is purified by means such as recrystallization and column chromatography.

なお、一般式[2a1の化合物から上記方法により製造
される一般式[1a1の化合物は、常法に従って酸化脱
水素することにより容易に対応する一般式[1b]の化
合物に変換することができる。
In addition, the compound of general formula [1a1 produced by the above method from the compound of general formula [2a1] can be easily converted into the corresponding compound of general formula [1b] by oxidative dehydrogenation according to a conventional method.

[作 用] 本発明における反応は、銅塩の■価の鋼とベンゼン環と
がπ錯体を形成し、このπ銘体内でニトロソ化が先ず進
行し、次いで生成したニトロソ体が税離し、■価のタリ
ウムによる酸化によりニトロ体が生成し、目的物が1q
られると考えられる。
[Function] In the reaction of the present invention, the steel with a valence of copper salt and the benzene ring form a π complex, nitrosation first proceeds within this π integer, and then the generated nitroso form is separated from tax, and Oxidation with valent thallium produces a nitro body, and the target product is 1q
It is thought that it will be possible.

[実施例] 以下、実施例に基づいて、本発明方法を具体的に説明す
る。
[Example] Hereinafter, the method of the present invention will be specifically explained based on Examples.

なお、当量とあるのは、主原料のはを1当Wとしたどき
の値である。
It should be noted that the term "equivalent" refers to a value based on 1 equivalent W of the main raw material.

実施例1 CO3O4−5820766,1Rg(9,1当M)を
N、N−ジメチルホルムアミド9dに溶解した液にNa
NO2567,5ffig(24当量)を加え、室温下
に15分間攪拌した。得られた溶液中に一般式[2a]
においてR,=CH3、n=0の(1−アセチル−2,
3−ジヒドロインドール−7−イル)タリウムビス(ト
リフルオロアセテート>200.31rIg(1当量)
をN、N−ジメチルホルムアミド2dに溶かした溶液を
加え、攪拌下に100℃で24時間反応させた。
Example 1 Na
NO2567.5ffig (24 equivalents) was added and stirred at room temperature for 15 minutes. In the resulting solution, general formula [2a]
(1-acetyl-2,
3-dihydroindol-7-yl)thallium bis(trifluoroacetate >200.31 rIg (1 equivalent)
A solution prepared by dissolving N,N-dimethylformamide 2d was added thereto, and the mixture was reacted at 100° C. for 24 hours with stirring.

反応終了後、減圧下に溶媒を留去し、得られた残留物に
メタノール−酢酸エチルエステル(5:95゜V/V)
混合溶媒を加え、不溶性の固形物を濾別し除去した。濾
液を飽和食塩水で洗浄した後、無水硫酸ナトリウムで乾
燥し、減圧下に溶媒を留去した。
After the reaction, the solvent was distilled off under reduced pressure, and the resulting residue was mixed with methanol-ethyl acetate (5:95°V/V).
A mixed solvent was added and insoluble solids were filtered and removed. The filtrate was washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure.

このようにして得られた結晶性の残留物を、塩化メチレ
ン−メタノール(99:1.V/V)混合溶媒を展開溶
媒とするシリカゲル分取薄層クロマトグラフィーニヨリ
精製し、Rf (Iao、42〜0.27(7)バンド
より得られた結晶をメタノール−水混合溶媒で再結晶し
、融点114.5〜115℃である無色針状晶の1−ア
セチル−2,3−ジヒドロ−7−二トロインドール59
.9mcJ(収率86%)を得た。
The crystalline residue thus obtained was purified by preparative thin layer chromatography on silica gel using a mixed solvent of methylene chloride and methanol (99:1.V/V) as a developing solvent. The crystals obtained from the ~0.27(7) band were recrystallized from a methanol-water mixed solvent to produce 1-acetyl-2,3-dihydro-7- as colorless needle-like crystals with a melting point of 114.5-115°C. nitro indole 59
.. 9 mcJ (yield 86%) was obtained.

実施例2 1−アセチル−2,3−ジヒドロインドールを原料とし
、Chem Pharm、 Bull、、 35.31
46(1987)の方法に従って(1−アセチル−2,
3−ジヒドロインドール7−イル)タリウムピストリフ
ルオロアセテートを合成し、次いで得られた生成物を単
離精製することなく、上記実施例1と同様にして1−ア
セチル−2,3−ジヒドロインドールから1工程で目的
物を合成した。
Example 2 Using 1-acetyl-2,3-dihydroindole as a raw material, Chem Pharm, Bull, 35.31
46 (1987) (1-acetyl-2,
3-dihydroindol (7-yl) thallium pistriefluoroacetate was synthesized, and then the obtained product was synthesized from 1-acetyl-2,3-dihydroindole in the same manner as in Example 1 above without isolation and purification. The target product was synthesized in one step.

すなわち、1−アセチル−2,3−ジヒドロインドール
84.0mFJをトリフルオロ酢酸1mlに溶解した1
麦、この溶液中に0.88モル濃度のタリウムトリスト
リフルオロ酢酸溶液0.89d(1,5当量)を加え、
室温下に60時間攪拌して反応させた。
That is, 1-acetyl-2,3-dihydroindole 84.0 mFJ was dissolved in 1 ml of trifluoroacetic acid.
wheat, add 0.89 d (1,5 equivalents) of 0.88 molar thallium tristrifluoroacetic acid solution to this solution,
The reaction mixture was stirred at room temperature for 60 hours.

反応終了後、減圧下に溶媒を留去し、jqられた残留物
をN、N〜ジメチルボルムアミド5.0mlに溶解した
。得られた溶液中に、CuSO45t1201 、18
3.7mg(g当量)及びNaNO21、810,3m
y(50当母)をN、N−ジメチルホルムアミド15m
に溶解して得られた溶液を加え、攪拌下に100’Cで
24時間反応させた。
After the reaction was completed, the solvent was distilled off under reduced pressure, and the hydrated residue was dissolved in 5.0 ml of N,N-dimethylbormamide. In the resulting solution, CuSO45t1201,18
3.7 mg (g equivalent) and NaNO21,810.3m
y (50 units) to N,N-dimethylformamide 15m
The solution obtained by dissolving in was added, and the mixture was reacted at 100'C for 24 hours with stirring.

反応終了後、減圧下に溶媒を留去して得られた残留物を
実施例1と同様に処理し、1−アセチル−2,3−ジヒ
ドロ−7−二トロインドール61.8#lび(57,5
%)を得た。
After the reaction, the solvent was distilled off under reduced pressure and the resulting residue was treated in the same manner as in Example 1 to obtain 61.8 #l of 1-acetyl-2,3-dihydro-7-nitroindole ( 57,5
%) was obtained.

実施例3 CuS045H20787、1mff(9,0当量)を
N、N−ジメチルホルムアミド9dに溶解し、得られた
溶液にNaNO2580,2mFJ (24当量)ヲ加
え715分間撹拌した。得られた溶液中に、一般式[2
旧においてR1=H5n=oの(3−ホルミルインドー
ル−4−イル)タリウムビス(トリフルオロアセテート
>201.5777yをN、N−ジメチルホルムアミド
2mlに溶解して得られた溶液を加え、攪拌下に95〜
100’Cで24時間反応させた。
Example 3 1 mff (9.0 equivalents) of CuS045H20787 was dissolved in 9d of N,N-dimethylformamide, and 2 mFJ (24 equivalents) of NaNO2580 was added to the resulting solution and stirred for 715 minutes. In the obtained solution, general formula [2
A solution obtained by dissolving (3-formylindol-4-yl)thallium bis(trifluoroacetate>201.5777y with R1=H5n=o in 2 ml of N,N-dimethylformamide in the previous example) was added, and the mixture was stirred. 95~
The reaction was carried out at 100'C for 24 hours.

反応終了後、減圧下に溶媒を留去し、得られた残留物に
メタノール−酢酸エチルエステル(5:95゜ν/V)
混合溶媒及び飽和食塩水を加え、良く攪拌した後、不溶
性の固形物を濾過して除去し、得られた濾液を分液して
有機層を得、この有機層を無水硫酸ナトリウムで乾燥し
た後、溶媒を留去して残留物を得た。
After the reaction, the solvent was distilled off under reduced pressure, and the resulting residue was mixed with methanol-ethyl acetate (5:95°ν/V).
After adding the mixed solvent and saturated saline and stirring well, insoluble solids were removed by filtration, the resulting filtrate was separated to obtain an organic layer, and this organic layer was dried over anhydrous sodium sulfate. , the solvent was distilled off to obtain a residue.

このようにして得られた残留物を、メタノール−塩化メ
チレン(5: 95. V/V)混合溶媒を展開溶媒と
するシリカゲル分取薄層クロマトグラフィーにより精製
し、融点206〜207℃の4−二トロインドール1.
2IItg(収率2.1%)、3−ホルミルインドール
2.4η(収率4.7%)及び融点196〜198℃の
4−ニトロ−3−ホルミルインドール48.2m!j(
収率72.3%)を得た。
The residue thus obtained was purified by preparative thin layer chromatography on silica gel using a methanol-methylene chloride (5:95.V/V) mixed solvent as a developing solvent to obtain 4- Nitroindole 1.
2IItg (2.1% yield), 2.4η of 3-formylindole (4.7% yield) and 48.2m of 4-nitro-3-formylindole with a melting point of 196-198°C! j(
A yield of 72.3%) was obtained.

実施例4〜13 反応条件を第1表に示すように変化させたほかは、上記
実施例3と同様にして4−ニトロ−3−ホルミルインド
ールを合成した。そのときの反応条(!1及び収率を第
1表に示す。
Examples 4 to 13 4-nitro-3-formylindole was synthesized in the same manner as in Example 3, except that the reaction conditions were changed as shown in Table 1. The reaction conditions (!1) and yields at that time are shown in Table 1.

実施例14 3−ホルミルインドールを原料とし、Chcm、 Ph
arm、 Bull、、 35.3146(t987)
の方法を利用して(3−ホルミルインドール−4−イル
)タリウムビス(1〜リフルオロアセテート)を合成し
、次いで得られた生成物を単離精製することなく、上記
実施例3と同様にして、3−ホルミルインドールから1
工程で目的物を合成した。
Example 14 Using 3-formylindole as a raw material, Chcm, Ph
arm, Bull, 35.3146 (t987)
(3-formylindol-4-yl)thallium bis(1-lifluoroacetate) was synthesized using the method of Example 3 above, and the resulting product was then synthesized in the same manner as in Example 3 above without isolation and purification. , 3-formylindole to 1
The target product was synthesized in the process.

すなわち、3−ホルミルインドール145.8mgをト
ルフルオロ酢酸1dに溶解し、得られた溶液中に0.8
8モル濃度のタリウムトリストリフルオロ酢酸溶液1.
36m(1,2当量)を加え、室温下に24時間攪拌し
て反応させた。
That is, 145.8 mg of 3-formylindole was dissolved in 1 d of trifluoroacetic acid, and 0.8 mg of 3-formylindole was dissolved in 1 d of trifluoroacetic acid.
8 molar thallium tristrifluoroacetic acid solution 1.
36m (1.2 equivalents) was added, and the reaction was stirred at room temperature for 24 hours.

反応終了後、減圧下に溶媒を留去し、jqられた残留物
をN、N−ジメチルホルムアミド6dに溶解し、コhk
−CuS’045H202,280,6mff(g尚早
〉及びNaNO21、694,6mg(24当但)のN
、N−ジメチルホルムアミド26m溶液を加え、攪拌下
に1oo’cで24時間反応させた。
After the reaction was completed, the solvent was distilled off under reduced pressure, and the resulting residue was dissolved in N,N-dimethylformamide 6d.
-N of CuS'045H202,280,6mff (g is too early) and NaNO21,694,6mg (24 for now)
, 26 m of N-dimethylformamide solution was added thereto, and the mixture was allowed to react at 100°C for 24 hours with stirring.

反応終了後、減圧下に溶媒を留去し、(7られた残留物
を実施例3と同様に処理し、4−ニトロ−3−ポルミル
インドール125.0mg(収率65.4%)を19だ
After the reaction was completed, the solvent was distilled off under reduced pressure, and the resulting residue was treated in the same manner as in Example 3 to obtain 125.0 mg (yield 65.4%) of 4-nitro-3-pormylindole. It's 19.

[発明の効果] 本発明方法によれば、入手困難である7−位又は4−位
にニトロ基を有するインドール類を短い工程で、しかも
、位置選択的に収率良く製造することができ、これによ
ってその工業的な製造が可能になり、その製造コストの
大幅な低減を図ることができる。
[Effects of the Invention] According to the method of the present invention, indoles having a nitro group at the 7-position or 4-position, which are difficult to obtain, can be produced in a short process and regioselectively with high yield. This makes it possible to manufacture it industrially, and the manufacturing cost can be significantly reduced.

特許出願人   新日鐵化学株式会社Patent applicant: Nippon Steel Chemical Co., Ltd.

Claims (2)

【特許請求の範囲】[Claims] (1)下記一般式[2a]又は[2b] ▲数式、化学式、表等があります▼[2a] ▲数式、化学式、表等があります▼[2b] (但し、式中R_1は1価の基を示し、R_2は置換基
であり、nは0又は1〜5の整数を示す)で表される化
合物を中間体とし、下記一般式[1a]、[1b]又は
[1c] ▲数式、化学式、表等があります▼[1a] ▲数式、化学式、表等があります▼[1b] ▲数式、化学式、表等があります▼[1c] (但し、式中R_3は水素又は−COR_1であり、R
_1、R_2及びnは前記と同じである)で表される化
合物を得ることを特徴とするニトロインドール類の製造
方法。
(1) The following general formula [2a] or [2b] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [2a] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [2b] (However, in the formula, R_1 is a monovalent group , R_2 is a substituent, n is an integer of 0 or 1 to 5) as an intermediate, and the following general formula [1a], [1b] or [1c] ▲Mathematical formula, chemical formula , tables, etc. ▼ [1a] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [1b] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [1c] (However, R_3 in the formula is hydrogen or -COR_1, and R
_1, R_2 and n are the same as above) A method for producing nitroindoles, characterized by obtaining a compound represented by:
(2)反応は硫酸銅及び亜硝酸ナトリウムの存在下にN
,N−ジメチルホルムアミドを溶媒として行う請求項1
記載のニトロインドール類の製造方法。
(2) The reaction is carried out in the presence of copper sulfate and sodium nitrite.
, N-dimethylformamide as a solvent.Claim 1
A method for producing the described nitroindoles.
JP8579389A 1989-04-06 1989-04-06 Production of nitroindoles Pending JPH02264757A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP8579389A JPH02264757A (en) 1989-04-06 1989-04-06 Production of nitroindoles

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP8579389A JPH02264757A (en) 1989-04-06 1989-04-06 Production of nitroindoles

Publications (1)

Publication Number Publication Date
JPH02264757A true JPH02264757A (en) 1990-10-29

Family

ID=13868766

Family Applications (1)

Application Number Title Priority Date Filing Date
JP8579389A Pending JPH02264757A (en) 1989-04-06 1989-04-06 Production of nitroindoles

Country Status (1)

Country Link
JP (1) JPH02264757A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8889730B2 (en) 2012-04-10 2014-11-18 Pfizer Inc. Indole and indazole compounds that activate AMPK
US9394285B2 (en) 2013-03-15 2016-07-19 Pfizer Inc. Indole and indazole compounds that activate AMPK

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8889730B2 (en) 2012-04-10 2014-11-18 Pfizer Inc. Indole and indazole compounds that activate AMPK
US9394285B2 (en) 2013-03-15 2016-07-19 Pfizer Inc. Indole and indazole compounds that activate AMPK

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