JPS5872546A - 2-anilino-4-fluorobenzaldehyde derivative and its preparation - Google Patents
2-anilino-4-fluorobenzaldehyde derivative and its preparationInfo
- Publication number
- JPS5872546A JPS5872546A JP56171560A JP17156081A JPS5872546A JP S5872546 A JPS5872546 A JP S5872546A JP 56171560 A JP56171560 A JP 56171560A JP 17156081 A JP17156081 A JP 17156081A JP S5872546 A JPS5872546 A JP S5872546A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- group
- general formula
- acetal
- represented
- 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.)
- Granted
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)
Abstract
Description
【発明の詳細な説明】
本発明は一般式（１）
（式中％Ｒ工は水素原子または塩素原子を表わす、）
を示されるＪ−アニリノーダーフルオロペンズアルデヒ
ド誘導体およびその製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a J-anilinoderfluoropenzaldehyde derivative represented by the general formula (1) (in which %R represents a hydrogen atom or a chlorine atom) and a method for producing the same.
本発明化合物であゐ一般式（１）で示される３（式中、
Ｒ２は上記と同じ意味を表わし、穐はたは臭素原子を表
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７つであ勤、
極めて重要攻中間体である。The compound of the present invention is 3 represented by the general formula (1) (wherein,
R2 has the same meaning as above, and represents a bromine atom or a group represented by ).
It is an extremely important offensive intermediate.
本発明は、前記式（１）で示されるアルデヒドと、その
製法として一般式（１）
（式中、Ｒ露およびＲ３Ｆｉ、ともに低級アルキルで示
される１セタールと一般式（１）
（式中、Ｒ工前記と同じ意味を表わし、−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（１）で示さ
れるアルダｋＳＰｅ）Ｉｌ造法を提供するものである。The present invention provides an aldehyde represented by the above formula (1) and a method for producing the aldehyde of the general formula (1) (wherein, R and RFi are both lower alkyl) and a cetal of the general formula (1) (wherein, R represents the same meaning as above, - represents a hydrogen atom or an acetyl group) The above-mentioned method is obtained by reacting an aniline derivative represented by () with a base in the presence of copper or a copper compound, and then removing the protective group. The present invention provides a method for producing AldakSPe)Il represented by the general formula (1).
次に本発明化合物の製造方法について詳しく説明する。Next, the method for producing the compound of the present invention will be explained in detail.
一般式（１）で示されるアセタールにおいて置換基Ｒ３
およびＲ，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衾い。Substituent R3 in the acetal represented by general formula (1)
Examples of and R include a methyl group, an ethyl group, an n-propyl group, an ethylene residue, but are not limited to these.
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、塩化第二鋼、臭化菖−鋼、酸化第一＃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★しくは炭酸ナトリウム、炭酸カリ
ウムである。In addition, examples of the copper compound used in the present invention include cuprous chloride, ferric chloride, steel bromide, #1 oxide, etc., and as the base, alkali hydroxide, alkali carbonate, etc. are often used. , and preferably sodium carbonate or potassium carbonate.
また、本反応において、必４！に応じ溶媒を細見て行な
うこともで！１．溶媒としてはピリジン、−ジメチル＊
ルムアｉｐ、ジメチルアセドアＩＰ、ジメチルスルホキ
シド、−、ダ、６−ドリメチルビリジンキノリンなどが
挙げられる。Also, in this reaction, there must be 4! You can also take a closer look at the solvent depending on the situation! 1. As a solvent, pyridine, -dimethyl*
Examples include Lumua IP, dimethyl acedo IP, dimethyl sulfoxide, -, da, 6-drimethylpyridine quinoline, and the like.
反応温度は、通常７００℃〜−Ｊθ°Ｃの範ＷＭ、好壕
しくは／θρ’ｃ−ｉｔθ℃の範囲、また溶媒を用いた
時はノ０ｏ℃から使用した溶媒の沸点の範■である。The reaction temperature is usually in the range of 700°C to -Jθ°C, preferably /θρ'c-itθ°C, and when a solvent is used, in the range of 0°C to the boiling point of the solvent used. be.
また、原料の使用量は一般式（置）で示されるアセクー
ル７モルに対し一般式（層）で示されるアニリンＩ導体
がＯ０Ｓモルモル上ル、好ましくは１モルへ八Ｊ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、アニリン鱈導体に対し
、ｏ、ｇ倍モル〜０．９ｊ倍モルの範囲が好ましい。In addition, the amount of raw materials to be used is such that the aniline I conductor represented by the general formula (layer) is in the range of 7 moles of acecure represented by the general formula (layer) or more, preferably 1 mole to 8 J moles, and It is convenient to use the base in a slightly smaller amount than the aniline derivative, preferably in a range of 0.g to 0.9j times the aniline conductor.
用いる銅または銅化合物はアセタール１モルに対し０．
００７モル〜０．３モルの範囲であり、好ましくはＯ１
θ０Ｓ〜θ、１モルの範囲である。The amount of copper or copper compound used is 0.0% per mole of acetal.
007 mol to 0.3 mol, preferably O1
The range is θ0S to θ, 1 mole.
反応時間は１反応条件ｅζよっても異なるが、通常Ｊ−
ダρ時間であり、好壕しくは５〜３０時間である。The reaction time varies depending on the reaction conditions eζ, but usually J-
The time is preferably 5 to 30 hours.
なお、本反応においてアニリン誘導体の酸化を防ぐ喪め
に反応を音素雰囲気中で行なうと、より好都合である。In this reaction, it is more convenient to carry out the reaction in a phonetic atmosphere to prevent oxidation of the aniline derivative.
また、前記一般式（ＩＭ）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
アセチル基で保験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
により容具に脱アセチル化す為ことができる。In addition, in the aniline derivative represented by the general formula (IM), when R4 is an acetyl group, that is, when the amino group is used with an acetyl group, the product is N
- An acetal of acetyl is obtained, which can be deacetylated by heating for several hours in the presence of an alcoholic solution of alkali hydroxide.
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Ｋよ〉、保験基であるアセタ
ールが容易にはずれ、一般式（，１）で示される目的の
３−７ニリノーダーフルオロペンスアルデヒド類が得ら
れる。Furthermore, by treating the product obtained in the above manner with a mineral acid such as hydrochloric acid or sulfuric acid, the acetal, which is a protective group, is easily removed and the desired 3 -7 nilinoderfluoropensaldehydes are obtained.
次に実施例で本発明をさらに詳細に鋭門する。Next, the present invention will be explained in further detail in Examples.
実施例／
ダークロロアニリンＵ、１９ｆｉ、！ｌ−ブコモーダー
フルオロベンズアルデヒド−ジエチルアセタールＩＪ／
Ｎ 、炭酸力Ｕウムダ、ｓｓｐ、塩化第−銅／、、２
１およびジメチルホルムアミｒＪｊｙｄを反応容ａＫ入
れ、窒素気流下に内温／ダθ〜ｉｓｏ”ｃで７６時間攪
拌した０反応液を放冷後、冷却した／θチ壇酸水／ｊＯ
ｄに注ぎ込み３０分間攪拌した徒、ジエチルエーテルで
４１回抽出した。Example/Darkloaniline U, 19fi,! l-bucomoder fluorobenzaldehyde-diethyl acetal IJ/
N, carbonic power Uumdah, ssp, cupric chloride/, 2
1 and dimethylformamin rJjyd were placed in a reaction volume aK and stirred for 76 hours under a nitrogen stream at an internal temperature of θ ~ iso''c. The reaction solution was left to cool and then cooled with θ titanic acid water/jO
After stirring for 30 minutes, the mixture was extracted 41 times with diethyl ether.
エーテル層を併せ、＊塩水で洗浄した後、硫酸１ダネシ
ウムで乾燥した０次いでエーテルを留去した後、！ＩＩ
渣をシリカゲルを充てんし九カラムクロマトグラフィー
によって分離精製したところ、′ｊ−（Ｑ−りＱＱアニ
リノ）−ダーフルオロペンズアルデヒドー、ｂｉｔ得た
。（収率３ダ、７チ）
融点 ／コー〜／−ｑ℃
実施例−
アセトアニリドｔ１．ｔｂｌ、３−プロモーｑ−フルオ
ロベンズ１ルデヒドージエチルアセタール１．！／ｊｉ
、炭酸カリウムダＪｊｊｉ、鋼粉θ、ｑｌおよびジメチ
ルホルムアミＩ／１ｊＷ１１を反応容器に入れ、窒素気
流下に内温／１０〜／ｂｏ”ｃで１０時間攪拌した０反
応液を放冷後、水酸化カリウムの／θチエタノール溶液
６θｄを加えて内温１０〜９０℃で３時間攪拌した０反
応液を放冷後、冷却した／３ｆｋ塩酸水塩酸水１１０注
ｌ込み、３０分間攪拌した後ジエチルエーテルでダ回抽
出した。The ether layers were combined, washed with brine, dried over danesium sulfate, and then the ether was distilled off. II
The residue was separated and purified by nine-column chromatography packed with silica gel to obtain 'j-(Q-riQQanilino)-derfluoropenzaldehyde, bit. (Yield: 3 Da, 7 Chi) Melting point /Co~/-q°C Example- Acetanilide t1. tbl, 3-promo q-fluorobenzldehyde diethyl acetal 1. ! /ji
, potassium carbonate, steel powder θ, ql, and dimethylformamide I/1jW11 were placed in a reaction vessel and stirred for 10 hours at an internal temperature of /10~/bo”c under a nitrogen stream. After cooling the reaction solution, water was added. After adding 6θd of /θthiethanol solution of potassium oxide and stirring for 3 hours at an internal temperature of 10 to 90°C, the reaction solution was allowed to cool, and then 110 liters of cooled /3fk hydrochloric acid and hydrochloric acid were poured in, and after stirring for 30 minutes, diethyl Extracted twice with ether.
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０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Ｑｖ）グラ′フィーで分離精
製したところ％３−７ニリノーダーフルオロベンズフル
デヒｙｗ、＊ｇを得た。（収車Ｕ、−優）融点 デ八
ｊ０ＣThe ether layers were combined and washed with brine, dried over magnesium sulfate, and then the ether was distilled off.The residue was separated and purified using a column packed with silica gel. Furdehyyw, *g was obtained. (Collected vehicle U, - excellent) Melting point De8j0C
Claims (2)
ド誘導体。(1) A 3-7=linoda-fluorobenzaldehyde derivative represented by the general formula (wherein R represents a hydrogen atom or a chlorine atom).
、Ｒ１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・−ルと一般式 （式中、Ｒユは水素原子管ｆＦ、け塩素原子を表わし、
Ｒ４は水素原子またけアセチへ基を表わす、） で示されるアニリン銹導体を、塩基と銅あるいは銅化合
物の存在下に反応させた後、保睡基をはずすことを特做
とする−・般式 （式中、Ｒ工は前記と同じ意味を有する。）で示される
３−７ニリノー４−フルオロベンズアルデヒド誘導体の
製造方法。(2) An acetal represented by the general formula (in the formula, s "l and - both represent a lower alkyl group or an alkylene residue in which R1 and R3 are bonded at the terminals) and a general formula (the formula In the middle, R represents a hydrogen atom tube fF, chlorine atom,
R4 represents an acetyl group spanning a hydrogen atom) After reacting the aniline rust conductor represented by the following with a base in the presence of copper or a copper compound, the sleep-retaining group is removed. A method for producing a 3-7 nylino-4-fluorobenzaldehyde derivative represented by the formula (wherein R has the same meaning as above).
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 true JPS5872546A (en) | 1983-04-30 |
| JPS647067B2 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) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5148895A (en) * | 1988-02-17 | 1992-09-22 | Atsugi Motor Parts Company, Limited | Rotary actuator for variable damping force shock absorber |
-
1981
- 1981-10-26 JP JP56171560A patent/JPS5872546A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5148895A (en) * | 1988-02-17 | 1992-09-22 | Atsugi Motor Parts Company, Limited | Rotary actuator for variable damping force shock absorber |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS647067B2 (en) | 1989-02-07 |
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