JPS647067B2 - - Google Patents
Info
- Publication number
- JPS647067B2 JPS647067B2 JP56171560A JP17156081A JPS647067B2 JP S647067 B2 JPS647067 B2 JP S647067B2 JP 56171560 A JP56171560 A JP 56171560A JP 17156081 A JP17156081 A JP 17156081A JP S647067 B2 JPS647067 B2 JP S647067B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- general formula
- group
- represented
- hydrogen atom
- 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
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本発明は一般式（）
（式中、R1は水素原子または塩素原子を表わ
す。）
で示される３−アニリノ−４−フルオロベンズア
ルデヒド誘導体およびその製造方法に関する。
本発明化合物である一般式（）で示される３
−アニリノ−４−フルオロベンズアルデヒド誘導
体は例えば一般式
（式中、R1は上記と同じ意味を表わし、R5は
水素原子、シアノ基、エチニル基または１−プロ
ピニル基を表わす。R6は一般式
The present invention is based on the general formula () (In the formula, R 1 represents a hydrogen atom or a chlorine atom.) The present invention relates to a 3-anilino-4-fluorobenzaldehyde derivative represented by the following formula and a method for producing the same. 3 represented by the general formula () which is a compound of the present invention
-Anilino-4-fluorobenzaldehyde derivatives have the general formula (In the formula, R 1 represents the same meaning as above, R 5 represents a hydrogen atom, a cyano group, an ethynyl group, or a 1-propynyl group. R 6 represents the general formula
【式】ま たは[Formula] Ma Taha
【式】（ここに、Ｘは塩素原子また
は臭素原子を表わす。）で示される基を表わす。）
で示される新規な低魚毒性殺虫剤の原料の１つで
あり、極めて重要な中間体である。
本発明は、前記式（）で示されるアルデヒド
と、その製法として一般式（）
（式中、R2およびR3は、ともに低級アルキル
基またはR2とR3が末端で結合しているアルキレ
ン残基を表わす。）
で示されるアセタールと一般式（）
（式中、R1前記と同じ意味を表わし、R4は、
水素原子またはアセチル基を表わす。）
で示されるアニリン誘導体を、塩基と銅あるいは
銅化合物の存在下に反応させた後、保護基をはず
すことによる前記一般式（）で示されるアルデ
ヒドの製造法を提供するものである。
次に本発明化合物の製造方法について詳しく説
明する。
一般式（）で示されるアセタールにおいて置
換基R2およびR3としては、メチル基、エチル基、
ｎ−プロピル基、エチレン残基などが挙げられる
が、もちろんこれらに限定されるものではない。
また、本発明において用いる銅化合物として
は、塩化第一銅、塩化第二銅、臭化第一銅、酸化
第一銅などが挙げられ、塩基としては水酸化アル
カリ、炭酸アルカリなどがよく用いられ、好まし
くは炭酸ナトリウム、炭酸カリウムである。
また、本反応において、必要に応じ溶媒を加え
て行なうこともでき、溶媒としてはピリジン、ジ
メチルホルムアミド、ジメチルアセトアミド、ジ
メチルスルホキシド、２，４，６−トリメチルピ
リジンキノリンなどが挙げられる。
反応温度は、通常100℃〜250℃の範囲、好まし
くは100℃〜180℃の範囲、また溶媒を用いた時は
100℃から使用した溶媒の沸点の範囲である。
また、原料の使用量は一般式（）で示される
アセタール１モルに対し一般式（）で示される
アニリン誘導体が0.5モル〜２モル、好ましくは
１モル〜1.5モルの範囲であり、また塩基は、ア
ニリン誘導体よりやや少なめに用いることが好都
合であり、アニリン誘導体に対し0.8倍モル〜
0.95倍モルの範囲が好ましい。
用いる銅または銅化合物はアセタール１モルに
対し、0.001モル〜0.3モルの範囲であり、好まし
くは0.005〜0.1モルの範囲である。
反応時間は、反応条件によつても異なるが、通
常３〜40時間であり、好ましくは５〜30時間であ
る。
なお、本反応においてアニリン誘導体の酸化を
防ぐために反応を窒素雰囲気中で行なうとより好
都合である。
また、前記一般式（）で示されるアニリン誘
導体において、R4がアセチル基である場合、即
ちアミノ基をアセチル基で保護して用いる場合に
は、生成物としてＮ−アセチルのアセタールが得
られるが、これは水酸化アルカリのアルコール溶
液の存在下に数時間加熱することにより容易に脱
アセチル化することができる。
さらに、以上のようにして得られる生成物を塩
酸、硫酸などの鉱酸で処理することにより、保護
基であるアセタールが容易にはずれ、一般式
（）で示される目的の３−アニリノ−４−フル
オロベンズアルデヒド類が得られる。
次に実施例で本発明をさらに詳細に説明する。
実施例 １
４−クロロアニリン4.59ｇ、３−ブロモ−４−
フルオロベンズアルデヒド−ジエチルアセタール
8.31ｇ、炭酸カリウム4.55ｇ、塩化第一銅1.2ｇお
よびジメチルホルムアミド25mlを反応容器に入
れ、窒素気流下に内温140〜150℃で16時間撹拌し
た。反応液を放冷後、冷却した10％塩酸水150ml
に注ぎ込み30分間撹拌した後、ジエチルエーテル
で４回抽出した。
エーテル層を併せ、食塩水で洗浄した後、硫酸
マグネシウムで乾燥した。次いでエーテルを留去
した後、残渣をシリカゲルを充てんしたカラムク
ロマトグラフイーによつて分離精製したところ、
３−（４−クロロアニリノ）−４−フルオロベンズ
アルデヒド2.6ｇを得た。（収率34.7％）
融点 122〜124℃
実施例 ２
アセトアニリド4.86ｇ、３−ブロモ−４−フル
オロベンズアルデヒド−ジエチルアセタール8.31
ｇ、炭酸カリウム4.55ｇ、銅粉0.48ｇおよびジメ
チルホルムアミド５mlを反応容器に入れ、窒素気
流下に内温150〜160℃で20時間撹拌した。反応液
を放冷後、水酸化カリウムの10％エタノール溶液
60mlを加えて内温80〜90℃で３時間撹拌した。反
応液を冷却後、冷却した15％塩酸水150mlに注ぎ
込み、30分間撹拌した後ジエチルエーテルで４回
抽出した。
エーテル層を併せ食塩水で洗浄し、硫酸マグネ
シウムで乾燥した。次いでエーテルを留去した
後、残渣をシリカゲルを充てんしたカラムクロマ
トグラフイーで分離精製したところ、３−アニリ
ノ−４−フルオロベンズアルデヒド4.4ｇを得た。
（収率68.2％）
融点 91.5℃It represents a group represented by the formula: (wherein, X represents a chlorine atom or a bromine atom). ) It is one of the raw materials for a new low fish toxicity insecticide, and is an extremely important intermediate. The present invention provides an aldehyde represented by the above formula () and a method for producing the aldehyde represented by the general formula (). (In the formula, R 2 and R 3 both represent a lower alkyl group or an alkylene residue in which R 2 and R 3 are bonded at the terminals.) An acetal represented by the general formula () (In the formula, R 1 represents the same meaning as above, and R 4 is
Represents a hydrogen atom or an acetyl group. The present invention provides a method for producing an aldehyde represented by the general formula () by reacting an aniline derivative represented by the formula () with a base in the presence of copper or a copper compound, and then removing the protective group. Next, the method for producing the compound of the present invention will be explained in detail. In the acetal represented by the general formula (), substituents R 2 and R 3 include a methyl group, an ethyl group,
Examples include n-propyl group, ethylene residue, etc., but are not limited to these, of course. Further, examples of the copper compound used in the present invention include cuprous chloride, cupric chloride, cuprous bromide, cuprous oxide, etc., and as the base, alkali hydroxide, alkali carbonate, etc. are often used. , preferably sodium carbonate or potassium carbonate. Further, in this reaction, a solvent may be added if necessary, and examples of the solvent include pyridine, dimethylformamide, dimethylacetamide, dimethylsulfoxide, 2,4,6-trimethylpyridinequinoline, and the like. The reaction temperature is usually in the range of 100°C to 250°C, preferably in the range of 100°C to 180°C, and when a solvent is used.
The range is from 100°C to the boiling point of the solvent used. The amount of raw materials used is 0.5 mol to 2 mol, preferably 1 mol to 1.5 mol, of the aniline derivative represented by the general formula () per 1 mol of the acetal represented by the general formula (), and the base is It is convenient to use it in a slightly smaller amount than the aniline derivative;
A range of 0.95 times the mole is preferred. The amount of copper or copper compound used is in the range of 0.001 mol to 0.3 mol, preferably in the range of 0.005 to 0.1 mol, per 1 mol of acetal. The reaction time varies depending on the reaction conditions, but is usually 3 to 40 hours, preferably 5 to 30 hours. In this reaction, it is more convenient to carry out the reaction in a nitrogen atmosphere in order to prevent oxidation of the aniline derivative. Furthermore, in the aniline derivative represented by the general formula (), when R 4 is an acetyl group, that is, when the amino group is protected with an acetyl group, an acetal of N-acetyl is obtained as a product. , which can be easily deacetylated by heating for several hours in the presence of an alcoholic solution of alkali hydroxide. Furthermore, by treating the product obtained in the above manner with a mineral acid such as hydrochloric acid or sulfuric acid, the acetal protecting group is easily removed, and the desired 3-anilino-4- Fluorobenzaldehydes are obtained. Next, the present invention will be explained in more detail with reference to Examples. Example 1 4.59 g of 4-chloroaniline, 3-bromo-4-
Fluorobenzaldehyde-diethyl acetal
8.31 g, potassium carbonate 4.55 g, cuprous chloride 1.2 g and dimethylformamide 25 ml were placed in a reaction vessel and stirred at an internal temperature of 140 to 150° C. for 16 hours under a nitrogen stream. After cooling the reaction solution, add 150ml of cooled 10% hydrochloric acid water.
After stirring for 30 minutes, the mixture was extracted four times with diethyl ether. The ether layers were combined, washed with brine, and then dried over magnesium sulfate. After distilling off the ether, the residue was separated and purified by column chromatography filled with silica gel.
2.6 g of 3-(4-chloroanilino)-4-fluorobenzaldehyde was obtained. (Yield 34.7%) Melting point 122-124°C Example 2 4.86 g of acetanilide, 8.31 g of 3-bromo-4-fluorobenzaldehyde-diethyl acetal
g, 4.55 g of potassium carbonate, 0.48 g of copper powder, and 5 ml of dimethylformamide were placed in a reaction vessel and stirred at an internal temperature of 150 to 160° C. for 20 hours under a nitrogen stream. After cooling the reaction solution, add a 10% ethanol solution of potassium hydroxide.
60 ml was added and stirred at an internal temperature of 80 to 90°C for 3 hours. After cooling the reaction solution, it was poured into 150 ml of cooled 15% hydrochloric acid water, stirred for 30 minutes, and extracted four times with diethyl ether. The ether layers were combined, washed with brine, and dried over magnesium sulfate. After distilling off the ether, the residue was purified by column chromatography filled with silica gel to obtain 4.4 g of 3-anilino-4-fluorobenzaldehyde.
(Yield 68.2%) Melting point 91.5℃
Claims (1)
す。） で示される３−アニリノ−４−フルオロベンズア
ルデヒド誘導体。 ２ 一般式 （式中、R2およびR3はともに低級アルキル基
または、R2とR3とが末端で結合しているアルキ
レン残基を表わす。） で示されるアセタールと一般式 （式中、R1は水素原子または塩素原子を表わ
し、R4は水素原子またはアセチル基を表わす。） で示されるアニリン誘導体を、塩基と銅あるいは
銅化合物の存在下に反応させた後、保護基をはず
すことを特徴とする一般式 （式中、R1は前記と同じ意味を有する。） で示される３−アニリノ−４−フルオロベンズア
ルデヒド誘導体の製造方法。[Claims] 1. General formula (In the formula, R 1 represents a hydrogen atom or a chlorine atom.) A 3-anilino-4-fluorobenzaldehyde derivative represented by the following. 2 General formula (In the formula, R 2 and R 3 both represent a lower alkyl group or an alkylene residue in which R 2 and R 3 are bonded at the terminals.) An acetal represented by the general formula (In the formula, R 1 represents a hydrogen atom or a chlorine atom, and R 4 represents a hydrogen atom or an acetyl group.) After reacting the aniline derivative represented by the following with a base in the presence of copper or a copper compound, the protected General formula characterized by removing a group (In the formula, R 1 has the same meaning as above.) A method for producing a 3-anilino-4-fluorobenzaldehyde derivative represented by the following.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56171560A JPS5872546A (en) | 1981-10-26 | 1981-10-26 | 2-anilino-4-fluorobenzaldehyde derivative and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56171560A JPS5872546A (en) | 1981-10-26 | 1981-10-26 | 2-anilino-4-fluorobenzaldehyde derivative and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5872546A JPS5872546A (en) | 1983-04-30 |
| JPS647067B2 true JPS647067B2 (en) | 1989-02-07 |
Family
ID=15925394
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56171560A Granted JPS5872546A (en) | 1981-10-26 | 1981-10-26 | 2-anilino-4-fluorobenzaldehyde derivative and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5872546A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2781176B2 (en) * | 1988-02-17 | 1998-07-30 | 株式会社ユニシアジェックス | Actuator |
-
1981
- 1981-10-26 JP JP56171560A patent/JPS5872546A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5872546A (en) | 1983-04-30 |
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