JPH0336820B2 - - Google Patents
Info
- Publication number
- JPH0336820B2 JPH0336820B2 JP6984782A JP6984782A JPH0336820B2 JP H0336820 B2 JPH0336820 B2 JP H0336820B2 JP 6984782 A JP6984782 A JP 6984782A JP 6984782 A JP6984782 A JP 6984782A JP H0336820 B2 JPH0336820 B2 JP H0336820B2
- Authority
- JP
- Japan
- Prior art keywords
- solution
- water
- mol
- diazonium salt
- added
- 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
- 150000001875 compounds Chemical class 0.000 claims description 10
- 125000005843 halogen group Chemical group 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 125000001188 haloalkyl group Chemical group 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 17
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 13
- 239000012954 diazonium Substances 0.000 description 13
- 150000001989 diazonium salts Chemical class 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 9
- 229960003280 cupric chloride Drugs 0.000 description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 8
- FSPXZKAEHGXEHN-RJRFIUFISA-N (z)-2,4-dichlorobut-2-enal Chemical compound ClC\C=C(/Cl)C=O FSPXZKAEHGXEHN-RJRFIUFISA-N 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000001632 sodium acetate Substances 0.000 description 6
- 235000017281 sodium acetate Nutrition 0.000 description 6
- 235000010288 sodium nitrite Nutrition 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- 239000000284 extract Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 3
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- 235000019341 magnesium sulphate Nutrition 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- BRPSAOUFIJSKOT-UHFFFAOYSA-N 2,3-dichloroaniline Chemical compound NC1=CC=CC(Cl)=C1Cl BRPSAOUFIJSKOT-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VBLXCTYLWZJBKA-UHFFFAOYSA-N 2-(trifluoromethyl)aniline Chemical compound NC1=CC=CC=C1C(F)(F)F VBLXCTYLWZJBKA-UHFFFAOYSA-N 0.000 description 1
- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-UHFFFAOYSA-N 0.000 description 1
- DPJCXCZTLWNFOH-UHFFFAOYSA-N 2-nitroaniline Chemical compound NC1=CC=CC=C1[N+]([O-])=O DPJCXCZTLWNFOH-UHFFFAOYSA-N 0.000 description 1
- YRRQIMILQNHXTB-UHFFFAOYSA-N 3-chloro-4-phenyl-1h-pyrrole Chemical class ClC1=CNC=C1C1=CC=CC=C1 YRRQIMILQNHXTB-UHFFFAOYSA-N 0.000 description 1
- 150000005358 3-phenylpyrroles Chemical class 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000012259 ether extract Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- QJQRNDGUWQVAEV-AAFSJPGBSA-M sodium bisulfite adduct Chemical compound [Na+].[O-]S(=O)(=O)C([C@H]1N(C(C2=C3)=O)C=C(C1)/C=C/C(=O)N(C)C)NC2=CC1=C3OCO1 QJQRNDGUWQVAEV-AAFSJPGBSA-M 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は新規な化合物及びその製造方法に関
し、詳しくは一般式
（式中、Ｘはハロゲン原子、ニトロ基又は低級
ハロアルキル基を、Ｙは水素原子又はハロゲン原
子を、ｎは０、１又は２を示す。）で表わされる
化合物及びその製造方法である。
本発明の化合物は、医薬、農薬又はその中間体
として有用な３−フエニルピロール誘導体の製造
用中間体として有用である。例えば下記反応式に
示す如く、本発明化合物をアンモニアあるいはア
ンモニア水と反応することにより、殺菌剤として
有用な３−フエニル−４−クロロ−ピロール誘導
体が得られる。
本発明化合物は一般式
（式中、Ｘ及びｎは前記と同一の意味を示す。）
で表わされるアニリン類から容易に得られる一般
式
（式中、Ｘ及びｎは前記と同一の意味を示し、
Y1はハロゲン原子を示す。）で表わされるジアゾ
ニウム塩と、一般式 ClCH2CH＝CY2CHO
（）
（式中、Y2は水素原子又はハロゲン原子を示
す。但し、前記Y1又はY2の少くとも一つは塩素
原子を示す。）で表わされるクロトンアルデヒド
類と反応させることにより製造することができ
る。反応は水又は含水溶媒中触媒の存在下10℃〜
30℃で10〜24時間行う。含水溶媒としてはアセト
ン、アセトニトリル、酢酸等が用いられ、触媒と
しては塩化第二銅、臭化第二銅等が用いられる。
通常のメールワイン反応と同様、本発明の方法に
於いても、前記一般式（）で表わされるクロト
ンアルデヒド類を過剰に添加することにより収率
の向上を計ることができる。添加量はジアゾニウ
ム塩に対し、等モル〜10倍モルが好ましい。
反応終了後は適当な有機溶媒で、抽出した後、
溶媒を留去し、残留油状物を減圧蒸留することに
より、本発明化合物を好収率で得ることができ
る。また蒸留して単離することなく未反応のクロ
トンアルデヒド類を減圧留去した後残渣をそのま
ま次の反応に用いることもできる。
又、本発明化合物は蒸留操作において若干の熱
分解が生じ、収率が低下する恐れがあるが、反応
混合物に亜硫酸水素ナトリウムを添加することに
より本発明化合物を亜硫酸水素ナトリウム付加体
として沈澱させて、分離した後、亜硫酸水素ナト
リウムを脱離して本発明化合物を単離することも
できる。
次に実施例を挙げて本発明の製造方法について
更に詳しく説明する。
実施例 １
２，３−ジクロロアニリン8.2ｇ（0.05モル）、
水10ml及び濃塩酸15mlからなる溶液に、亜硝酸ソ
ーダ3.8ｇを水８mlに溶かした溶液を０〜２℃で
滴下した。20分間撹拌した後、過してジアゾニ
ウム塩の水溶液とした。
２，４−ジクロロクロトンアルデヒド4.7ｇ
（0.033モル）とアセトン20mlと、塩化カリウム
9.2ｇの混合液に先に調製したジアゾニウム塩水
溶液を０〜５℃で加えた。飽和酢酸ソーダ水溶液
でPH２に調整し、塩化第二銅１ｇを加えて15〜20
℃で18時間反応させた。反応終了後エーテル30ml
で３回抽出し、飽和食塩水で水洗、硫酸マグネシ
ウムで乾燥後エーテルを留去した。得られた油状
物を蒸留して目的物4.8ｇを得た。
収率45％、融点76℃、沸点140〜148℃／0.3mmHg
実施例 ２
アニリン1.7ｇ（0.018モル）、水８ml及び濃塩
酸６mlからなる溶液に亜硝酸ソーダ1.3ｇを水４
mlに溶かした溶液を滴下し実施例１と同様にして
ジアゾニウム塩水溶液を調製した。
２，４−ジクロルクロトンアルデヒド7.5ｇ
（0.053モル）とアセトン18mlと酢酸ソーダ1.9ｇ
の混合液に、先に調製したジアゾニウム塩水溶液
を０〜５℃で加えた。これに塩化リチウム1.2ｇ、
塩化第二銅0.35ｇを加え15〜20℃で18時間反応さ
せた。反応液からアセトンを留去してエーテル40
mlで２回抽出後、抽出液を硫酸マグネシウムで乾
燥してエーテルを留去した。残留した油状物を蒸
留して目的物1.9ｇを得た。
収率41.4％、沸点96〜97℃／0.15mmHg
実施例 ３
２−クロルアニリン２ｇ（0.0156モル）、水９
ml及び濃塩酸６mlからなる溶液に、亜硝酸ソーダ
1.2ｇを水４mlに溶かした溶液を滴下し、実施例
１と同様にしてジアゾニウム塩水溶液を調製し
た。
２，４−ジクロルクロトンアルデヒド6.5ｇ
（0.0467モル）、アセトン18ml及び酢酸ソーダ1.7
ｇの混合液中に０〜５℃で、先に調製したジアゾ
ニウム塩水溶液を加えた。これに塩化リチウム
0.9ｇ、塩化第二銅0.2ｇを加え、15〜20℃で22時
間反応させた。以下実施例２と同様にして目的物
2.2ｇを得た。
沸点110〜115℃／0.1mmHg、収率49.0％
実施例 ４
２−ニトロアニリン2.3ｇ（0.016モル）、水９
ml、濃塩酸６mlからなる溶液に、亜硝酸ソーダ
1.2ｇを水４mlに溶かした溶液を滴下し、実施例
１と同様にしてジアゾニウム塩水溶液を調製し
た。
２，４−ジクロルクロトンアルデヒド6.7ｇ
（0.0482モル）とアセトン18mlと酢酸ソーダ1.7ｇ
の混合液中に、先に調製したジアゾニウム塩水溶
液を０〜５℃で加えた。これに塩化リチウム１ｇ
及び塩化第二銅0.3ｇを加え15〜20℃で23時間反
応させた。
以下実施例２と同様にして目的物1.4ｇを得た。
沸点155〜168℃／２mmHg、収率31％
実施例 ５
２−アミノベンゾトリフルオライド2.6ｇ
（0.016モル）、水９ml及び濃塩酸６mlからなる溶
液に、亜硝酸ソーダ1.2ｇを水４mlに溶かした溶
液を滴下し、実施例１と同様にしてジアゾニウム
塩水溶液を調製した。
２，４−ジクロルクロトンアルデヒド6.7ｇ
（0.0482モル）とアセトン18ml、酢酸ソーダ２ｇ
の混合液中に、先に調製したジアゾニウム塩水溶
液を０〜５℃で加えた。これに塩化リチウム１ｇ
及び塩化第二銅0.3ｇを加え、15〜20℃で18時間
反応させた。
以下実施例２と同様にして目的物2.3ｇを得た。
収率45.1％、沸点93〜97℃／0.3mmHg
実施例 ６
２，３−ジクロロアニリン4.1ｇ（0.025モル）、
水５mlおよび濃塩酸7.5mlからなる溶液に亜硝酸
ソーダ1.9ｇを水４mlに溶かした溶液を０〜２℃
で滴下した。そのままの温度で20分間撹拌した
後、過してジアゾニウム塩の水溶液とした。こ
のジアゾニウム塩の水溶液を２，４−ジクロロク
ロトンアルデヒド34.755ｇ（0.25モル）、アセト
ン５ml、塩化カリウム1.86ｇ（0.025モル）の混
合物の中に０〜５℃で加え、飽和酢酸ソーダ水溶
液でPHを4.1に調整した後、塩化第二銅0.5ｇ
（0.0037モル）を加えて15〜20℃で５時間反応さ
せた。反応終了後、エーテル30mlで３回抽出し、
エーテル抽出液を飽和食塩水30mlで２回水洗後硫
酸マグネシウムで乾燥後エーテルを留去し、油状
物の蒸留により4.65ｇの２，２，４−トリクロロ
−３−（２，３−ジクロロフルニル）ブチルアル
デヒド（bp140〜148℃／0.3Hg、mp76℃）が得
られた。
収率58％
本発明化合物の代表例を第１表に示す。
The present invention relates to a novel compound and a method for producing the same, in particular, the general formula (wherein, X represents a halogen atom, a nitro group or a lower haloalkyl group, Y represents a hydrogen atom or a halogen atom, and n represents 0, 1 or 2) and a method for producing the same. The compound of the present invention is useful as an intermediate for producing 3-phenylpyrrole derivatives useful as medicines, agricultural chemicals, or intermediates thereof. For example, as shown in the reaction formula below, a 3-phenyl-4-chloro-pyrrole derivative useful as a disinfectant can be obtained by reacting the compound of the present invention with ammonia or aqueous ammonia. The compound of the present invention has the general formula (In the formula, X and n have the same meanings as above.)
General formula easily obtained from anilines represented by (In the formula, X and n have the same meanings as above,
Y 1 represents a halogen atom. ) and the general formula ClCH 2 CH=CY 2 CHO
() (In the formula, Y 2 represents a hydrogen atom or a halogen atom. However, at least one of the above Y 1 or Y 2 represents a chlorine atom.) Produced by reacting with a crotonaldehyde represented by be able to. The reaction takes place at 10°C in the presence of a catalyst in water or a water-containing solvent.
Carry out 10-24 hours at 30 °C. Acetone, acetonitrile, acetic acid, etc. are used as the water-containing solvent, and cupric chloride, cupric bromide, etc. are used as the catalyst.
As in the usual Mehlwein reaction, in the method of the present invention as well, the yield can be improved by adding an excess of crotonaldehyde represented by the general formula (). The amount added is preferably equimolar to 10 times the molar amount of the diazonium salt. After the reaction is complete, extract with a suitable organic solvent,
By distilling off the solvent and distilling the residual oil under reduced pressure, the compound of the present invention can be obtained in a good yield. Alternatively, the unreacted crotonaldehyde can be distilled off under reduced pressure without being isolated by distillation, and the residue can be used as it is in the next reaction. In addition, the compound of the present invention may undergo some thermal decomposition during the distillation operation, which may reduce the yield. However, by adding sodium bisulfite to the reaction mixture, the compound of the present invention can be precipitated as a sodium bisulfite adduct. After separation, the compound of the present invention can also be isolated by removing sodium bisulfite. Next, the manufacturing method of the present invention will be explained in more detail with reference to Examples. Example 1 2,3-dichloroaniline 8.2g (0.05mol),
A solution of 3.8 g of sodium nitrite dissolved in 8 ml of water was added dropwise to a solution of 10 ml of water and 15 ml of concentrated hydrochloric acid at 0 to 2°C. After stirring for 20 minutes, the mixture was filtered to obtain an aqueous solution of diazonium salt. 2,4-dichlorocrotonaldehyde 4.7g
(0.033 mol), 20 ml of acetone, and potassium chloride
The previously prepared diazonium salt aqueous solution was added to 9.2 g of the mixed solution at 0 to 5°C. Adjust the pH to 2 with a saturated aqueous solution of sodium acetate, add 1 g of cupric chloride, and raise the pH to 15-20.
The reaction was allowed to take place at ℃ for 18 hours. After the reaction is complete, add 30 ml of ether.
The extract was extracted three times with water, washed with saturated brine, dried over magnesium sulfate, and then the ether was distilled off. The obtained oil was distilled to obtain 4.8 g of the desired product. Yield 45%, melting point 76℃, boiling point 140-148℃/0.3mmHg Example 2 Add 1.3 g of sodium nitrite to a solution of 1.7 g (0.018 mol) of aniline, 8 ml of water, and 6 ml of concentrated hydrochloric acid.
A diazonium salt aqueous solution was prepared in the same manner as in Example 1 by adding dropwise the solution dissolved in 1 ml. 2,4-dichlorocrotonaldehyde 7.5g
(0.053 mol), acetone 18 ml and sodium acetate 1.9 g
The previously prepared diazonium salt aqueous solution was added to the mixed solution at 0 to 5°C. To this, 1.2g of lithium chloride,
0.35 g of cupric chloride was added and reacted at 15 to 20°C for 18 hours. Distill acetone from the reaction solution to ether 40
After extracting twice with ml, the extract was dried over magnesium sulfate and the ether was distilled off. The remaining oil was distilled to obtain 1.9 g of the desired product. Yield 41.4%, boiling point 96-97℃/0.15mmHg Example 3 2-chloroaniline 2g (0.0156 mol), water 9
ml of sodium nitrite and 6 ml of concentrated hydrochloric acid.
A solution of 1.2 g dissolved in 4 ml of water was added dropwise to prepare a diazonium salt aqueous solution in the same manner as in Example 1. 2,4-dichlorocrotonaldehyde 6.5g
(0.0467 mol), acetone 18 ml and sodium acetate 1.7
The previously prepared diazonium salt aqueous solution was added to the mixture of g at 0 to 5°C. This includes lithium chloride
0.9 g of cupric chloride and 0.2 g of cupric chloride were added, and the mixture was reacted at 15 to 20°C for 22 hours. Hereinafter, in the same manner as in Example 2, the target object
2.2g was obtained. Boiling point 110-115℃/0.1mmHg, yield 49.0% Example 4 2-nitroaniline 2.3 g (0.016 mol), water 9
ml, sodium nitrite to a solution consisting of 6 ml of concentrated hydrochloric acid.
A solution of 1.2 g dissolved in 4 ml of water was added dropwise to prepare a diazonium salt aqueous solution in the same manner as in Example 1. 2,4-dichlorocrotonaldehyde 6.7g
(0.0482 mol), acetone 18 ml and sodium acetate 1.7 g
The previously prepared diazonium salt aqueous solution was added to the mixed solution at 0 to 5°C. Add 1g of lithium chloride to this
Then, 0.3 g of cupric chloride was added and reacted at 15 to 20°C for 23 hours. Thereafter, 1.4 g of the target product was obtained in the same manner as in Example 2. Boiling point 155-168℃/2mmHg, yield 31% Example 5 2-aminobenzotrifluoride 2.6g
(0.016 mol), 9 ml of water, and 6 ml of concentrated hydrochloric acid, a solution of 1.2 g of sodium nitrite dissolved in 4 ml of water was added dropwise to prepare an aqueous diazonium salt solution in the same manner as in Example 1. 2,4-dichlorocrotonaldehyde 6.7g
(0.0482 mol), acetone 18 ml, and sodium acetate 2 g
The previously prepared diazonium salt aqueous solution was added to the mixed solution at 0 to 5°C. Add 1g of lithium chloride to this
and 0.3 g of cupric chloride, and the mixture was reacted at 15 to 20°C for 18 hours. Thereafter, 2.3 g of the target product was obtained in the same manner as in Example 2. Yield 45.1%, boiling point 93-97℃/0.3mmHg Example 6 2,3-dichloroaniline 4.1g (0.025mol),
Add a solution of 1.9 g of sodium nitrite dissolved in 4 ml of water to a solution of 5 ml of water and 7.5 ml of concentrated hydrochloric acid at 0 to 2°C.
It was dripped. After stirring at the same temperature for 20 minutes, the mixture was filtered to obtain an aqueous solution of diazonium salt. This aqueous solution of diazonium salt was added to a mixture of 34.755 g (0.25 mol) of 2,4-dichlorocrotonaldehyde, 5 ml of acetone, and 1.86 g (0.025 mol) of potassium chloride at 0 to 5°C, and the pH was adjusted with a saturated aqueous solution of sodium acetate. After adjusting to 4.1, cupric chloride 0.5g
(0.0037 mol) was added and reacted at 15 to 20°C for 5 hours. After the reaction, extract with 30 ml of ether three times,
The ether extract was washed twice with 30 ml of saturated saline, dried over magnesium sulfate, the ether was distilled off, and the oil was distilled to give 4.65 g of 2,2,4-trichloro-3-(2,3-dichlorofurnyl). ) Butyraldehyde (bp 140-148°C/0.3Hg, mp 76°C) was obtained. Yield: 58% Representative examples of the compounds of the present invention are shown in Table 1.
【表】【table】
Claims (1)
ハロアルキル基を、ｎは０、１又は２を、Ｙは水
素原子又はハロゲン原子を示す。）で表される化
合物。 ２ 一般式 （式中、Ｘはハロゲン原子、ニトロ基又は低級
ハロアルキル基を、ｎは０、１又は２を、Y1は
ハロゲン原子を示す。）で表される化合物と一般
式 （式中、Y2は水素原子又はハロゲン原子を示
す。但し、前記Y1又はY2の少なくとも一つは塩
素原子を示す。）で表されるクロトンアルデヒド
類と反応させることを特徴とする一般式 （式中、Ｘ及びｎは前記と同一の意味を示し、
Ｙは水素原子又はハロゲン原子を示す。）で表さ
れる化合物の製造方法。[Claims] 1. General formula (wherein, X represents a halogen atom, a nitro group or a lower haloalkyl group, n represents 0, 1 or 2, and Y represents a hydrogen atom or a halogen atom). 2 General formula (wherein, X represents a halogen atom, nitro group or lower haloalkyl group, n represents 0, 1 or 2, and Y 1 represents a halogen atom) and the general formula (In the formula, Y 2 represents a hydrogen atom or a halogen atom. However, at least one of Y 1 or Y 2 represents a chlorine atom.) formula (In the formula, X and n have the same meanings as above,
Y represents a hydrogen atom or a halogen atom. ) A method for producing a compound represented by
Priority Applications (11)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6984782A JPS58185535A (en) | 1982-04-26 | 1982-04-26 | Halogeno-3-phenylbutylaldehyde and its preparation |
| US06/485,910 US4471126A (en) | 1982-04-26 | 1983-04-18 | Method for the production of 3-phenylpyrrole |
| KR1019830001722A KR860001335B1 (en) | 1982-04-26 | 1983-04-23 | Process for preparation of 3-phenyl pyroles |
| ES521830A ES8406066A1 (en) | 1982-04-26 | 1983-04-25 | Method for the production of 3-phenylpyrrole derivatives. |
| EP83200592A EP0092890A1 (en) | 1982-04-26 | 1983-04-25 | Method for the production of 3-phenylpyrrole derivatives |
| HU831433A HU190087B (en) | 1982-04-26 | 1983-04-26 | Process for preparing 3-phenyl-pyrrole derivatives |
| HU854800A HU193454B (en) | 1982-04-26 | 1983-04-26 | Process for producing 3-phenyl-butyraldehyde derivatives |
| IL68519A IL68519A (en) | 1982-04-26 | 1983-04-28 | Production of 3-phenylpyrrole derivatives,and novel 2,4-dichloro-3-phenylbutyraldehyde intermediates therefor |
| SU833657406A SU1225479A3 (en) | 1982-04-26 | 1983-10-31 | Method of producing aldehydes |
| ES528633A ES528633A0 (en) | 1982-04-26 | 1984-01-02 | A METHOD FOR THE PREPARATION OF NEW PHENYLBUTYLALDEHYDE DERIVATIVES |
| US06/615,328 US4532363A (en) | 1982-04-26 | 1984-05-30 | Phenylbutyraldehydes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6984782A JPS58185535A (en) | 1982-04-26 | 1982-04-26 | Halogeno-3-phenylbutylaldehyde and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58185535A JPS58185535A (en) | 1983-10-29 |
| JPH0336820B2 true JPH0336820B2 (en) | 1991-06-03 |
Family
ID=13414602
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6984782A Granted JPS58185535A (en) | 1982-04-26 | 1982-04-26 | Halogeno-3-phenylbutylaldehyde and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58185535A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1956274A1 (en) | 2007-02-09 | 2008-08-13 | Carl Freudenberg KG | Installation structure of bore plug |
-
1982
- 1982-04-26 JP JP6984782A patent/JPS58185535A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1956274A1 (en) | 2007-02-09 | 2008-08-13 | Carl Freudenberg KG | Installation structure of bore plug |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58185535A (en) | 1983-10-29 |
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