JPH0747561B2 - Manufacturing method of polychloroalkylphenones - Google Patents
Manufacturing method of polychloroalkylphenonesInfo
- Publication number
- JPH0747561B2 JPH0747561B2 JP61260216A JP26021686A JPH0747561B2 JP H0747561 B2 JPH0747561 B2 JP H0747561B2 JP 61260216 A JP61260216 A JP 61260216A JP 26021686 A JP26021686 A JP 26021686A JP H0747561 B2 JPH0747561 B2 JP H0747561B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- complex
- solution
- water
- solvent
- 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 - Lifetime
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 17
- 238000000354 decomposition reaction Methods 0.000 claims description 13
- 239000012044 organic layer Substances 0.000 claims description 11
- 150000008282 halocarbons Chemical class 0.000 claims description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 150000004816 dichlorobenzenes Chemical class 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 2
- 238000005727 Friedel-Crafts reaction Methods 0.000 claims description 2
- 150000001805 chlorine compounds Chemical class 0.000 claims description 2
- 125000004965 chloroalkyl group Chemical group 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 3
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 229940117389 dichlorobenzene Drugs 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- UBOXGVDOUJQMTN-UHFFFAOYSA-N 1,1,2-trichloroethane Chemical compound ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 2
- -1 2 ' Chemical class 0.000 description 2
- LRXWJPURTZCTEH-UHFFFAOYSA-N 2,2-dichloro-1-(2,4-dichlorophenyl)ethanone Chemical compound ClC(Cl)C(=O)C1=CC=C(Cl)C=C1Cl LRXWJPURTZCTEH-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 230000010933 acylation Effects 0.000 description 2
- 238000005917 acylation reaction Methods 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- XMCRWEBERCXJCH-UHFFFAOYSA-N 1-(2,4-dichlorophenyl)ethanone Chemical compound CC(=O)C1=CC=C(Cl)C=C1Cl XMCRWEBERCXJCH-UHFFFAOYSA-N 0.000 description 1
- CYNFEPKQDJHIMV-UHFFFAOYSA-N 1-(2,5-dichlorophenyl)ethanone Chemical compound CC(=O)C1=CC(Cl)=CC=C1Cl CYNFEPKQDJHIMV-UHFFFAOYSA-N 0.000 description 1
- WBPAOUHWPONFEQ-UHFFFAOYSA-N 1-(3,4-dichlorophenyl)ethanone Chemical compound CC(=O)C1=CC=C(Cl)C(Cl)=C1 WBPAOUHWPONFEQ-UHFFFAOYSA-N 0.000 description 1
- YBUWGLYFFYIIEH-UHFFFAOYSA-N 2,2,2-trichloro-1-(2,4-dichlorophenyl)ethanone Chemical compound ClC(C(=O)C1=C(C=C(C=C1)Cl)Cl)(Cl)Cl YBUWGLYFFYIIEH-UHFFFAOYSA-N 0.000 description 1
- XPNFRMQAKTUXFF-UHFFFAOYSA-N 2,2-dichloro-1-(2,5-dichlorophenyl)ethanone Chemical compound ClC(Cl)C(=O)C1=CC(Cl)=CC=C1Cl XPNFRMQAKTUXFF-UHFFFAOYSA-N 0.000 description 1
- WXCFLJVLTMYQKO-UHFFFAOYSA-N 2,2-dichloro-1-(3,4-dichlorophenyl)ethanone Chemical compound ClC(Cl)C(=O)C1=CC=C(Cl)C(Cl)=C1 WXCFLJVLTMYQKO-UHFFFAOYSA-N 0.000 description 1
- VYWPPRLJNVHPEU-UHFFFAOYSA-N 2-chloro-1-(2,4-dichlorophenyl)ethanone Chemical compound ClCC(=O)C1=CC=C(Cl)C=C1Cl VYWPPRLJNVHPEU-UHFFFAOYSA-N 0.000 description 1
- CXEVBWANBXAQSY-UHFFFAOYSA-N 2-chloro-1-(2,5-dichlorophenyl)ethanone Chemical compound ClCC(=O)C1=CC(Cl)=CC=C1Cl CXEVBWANBXAQSY-UHFFFAOYSA-N 0.000 description 1
- BYTZWANJVUAPNO-UHFFFAOYSA-N 2-chloro-1-(3,4-dichlorophenyl)ethanone Chemical compound ClCC(=O)C1=CC=C(Cl)C(Cl)=C1 BYTZWANJVUAPNO-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は農薬の中間原料として有用な多クロルアルキル
フェノン類の製法に関するものであり、例えば2,2,2′,
4′−テトラクロルアセトフェノンは 等の殺虫剤原料として有用である。DETAILED DESCRIPTION OF THE INVENTION (Industrial field of application) The present invention relates to a process for producing polychloroalkylphenones useful as an intermediate raw material for agricultural chemicals, for example 2,2,2 ′,
4'-tetrachloroacetophenone is It is useful as a raw material for insecticides such as.
（従来技術） モノクロルベンゼンのアシル化は反応性が高く、常温付
近で反応するが、途中で錯体が析出するため通常は溶媒
を用いて反応している。(Prior Art) Acylation of monochlorobenzene is highly reactive and reacts at around room temperature, but usually a solvent is used because a complex is precipitated during the reaction.
ところが、ジクロルベンゼンのアシル化は反応性が低
く、比較的高い反応温度が必要であるため、反応溶媒を
使用せずに反応しても反応完結まで錯体が結晶化しな
い。そのため反応に引続いて反応液に水を加えて錯体分
解し、そこへ溶媒を加えてフェノン類を抽出後、有機層
を蒸留しフェノン類を単離する方法が取られている（Ge
r.Pat.1247289）。However, acylation of dichlorobenzene is low in reactivity and requires a relatively high reaction temperature, so that the complex does not crystallize until completion of the reaction even if the reaction is performed without using a reaction solvent. Therefore, following the reaction, water is added to the reaction solution to decompose the complex, a solvent is added to the solution to extract phenones, and then the organic layer is distilled to isolate the phenones (Ge
r.Pat.1247289).
（発明が解決しようとする問題点） 従来技術では反応液中に水を加えて錯体分解するとき、
途中で内容物が固化し、錯体分解に伴って発生する熱の
除去が困難になる。このため錯体分解温度の上昇により
多クロルアルキルフェノン類のタール化が起り低収率に
なる。又、蒸留で得られる多クロルアルキルフェノンは
青紫色〜赤褐色に着色し低品質になる等工業的製法とし
ては問題があった。(Problems to be Solved by the Invention) In the prior art, when water is added to the reaction solution to decompose the complex,
The contents solidify on the way and it becomes difficult to remove the heat generated by the decomposition of the complex. Therefore, an increase in the complex decomposition temperature causes tar formation of polychloroalkylphenones, resulting in a low yield. Further, the polychloroalkylphenone obtained by distillation has a problem as an industrial production method such that it is colored in blue-purple to reddish brown and has low quality.
本発明は錯体分解時のタール分の副生を抑制し、高品質
の多クロルアルキルフェノンを高収率に得ることを目的
とするものである。An object of the present invention is to suppress the by-product of the tar content at the time of complex decomposition and to obtain a high quality polychloroalkylphenone in a high yield.
（問題点を解決するための手段） 本発明者は前述の問題点を解決するために鋭意検討した
結果、多クロルアルキルフェノン−アルミニウム錯体
（以下錯体と略す）がハロゲン化炭化水素溶媒に良く溶
解することから、錯体を溶解したハロゲン化炭化水素溶
液を水の中に滴下しながら錯体分解することにより、錯
体分解温度を低く制御しタールの副生を大巾に抑制でき
ることを見い出した。又この錯体分解後の有機層をアル
カリ水で洗浄することにより製品の着色を抑制できるこ
とを見い出し本発明に至った。(Means for Solving Problems) As a result of intensive studies for solving the above problems, the present inventor has found that a polychloroalkylphenone-aluminum complex (hereinafter abbreviated as a complex) is well dissolved in a halogenated hydrocarbon solvent. Therefore, it was found that the decomposition temperature of the complex can be controlled to be low and the by-product of tar can be greatly suppressed by decomposing the complex while dropping the halogenated hydrocarbon solution in which the complex is dissolved into water. Further, they have found that coloring of the product can be suppressed by washing the organic layer after the decomposition of the complex with alkaline water, and the present invention has been completed.
即ち本発明は、ジクロルベンゼン類、酸クロライド及び
無水塩化アルミニウムのフリーデルクラフツ反応による
一般式 （ここでＲはC1〜C3のアルキル基又はクロルアルキル基
を示す）で表わされる多クロルアルキルフェノン類の製
造において、溶媒を用いずに反応し、反応後に反応液を
ハロゲン化炭化水素溶媒に溶解した後、その溶液を水の
中に滴下しながら０〜60℃で錯体分解することを特徴と
する多クロルアルキルフェノン類の製法である。That is, the present invention is a general formula based on the Friedel-Crafts reaction of dichlorobenzenes, acid chlorides and anhydrous aluminum chloride. (Wherein R represents a C 1 -C 3 alkyl group or a chloroalkyl group), in the production of polychloroalkylphenones, the reaction is carried out without using a solvent, and the reaction solution is used as a halogenated hydrocarbon solvent after the reaction. Is dissolved in water, and then the solution is dropped into water to undergo complex decomposition at 0 to 60 ° C., which is a method for producing polychloroalkylphenones.
反応時にハロゲン化炭化水素を反応溶媒に用いる方法も
取られるが、反応中副反応が起り錯体分解後の分液不良
になること、副生する塩酸ガスに同伴に溶媒のロスが多
いこと、溶媒中の水分により低収率になる等の不利が有
り工業的には好ましくない。A method in which a halogenated hydrocarbon is used as a reaction solvent at the time of reaction is also used, but a side reaction occurs during the reaction to cause poor liquid separation after decomposition of the complex, and a large amount of solvent is lost due to accompanying hydrochloric acid gas, and the solvent It is not industrially preferable because there are disadvantages such as low yield due to the water content.
本発明に使用されるハロゲン化炭化水素溶媒はC1〜C2の
ハロゲン化炭化水素が好しく、例えばジクロルメタン、
クロロホルム、四塩化炭素、1,1−ジクロルエタン、1,2
−ジクロルエタン、1,1,2−トリクロルエタン、1,1,2,2
−テトラクロルエタン、及びこれらの混合物等が、使用
できる。The halogenated hydrocarbon solvent used in the present invention is preferably a C 1 to C 2 halogenated hydrocarbon, such as dichloromethane,
Chloroform, carbon tetrachloride, 1,1-dichloroethane, 1,2
-Dichloroethane, 1,1,2-trichloroethane, 1,1,2,2
-Tetrachloroethane, mixtures thereof and the like can be used.
ジクロルベンゼン類は一般式 で表されるものである。酸クロライドは一般式RCOClで
表されＲは前述した通りであり、目的とする多クロルア
ルキルフェノンに対応する酸クロライドが使用される。Dichlorobenzenes have the general formula It is represented by. The acid chloride is represented by the general formula RCOCl, R is as described above, and the acid chloride corresponding to the desired polychloroalkylphenone is used.
反応液に溶媒を添加する時期は錯体の凝固点及び溶媒の
沸点によっても異るが、通常は熟成終了後反応液を冷却
しながら溶媒を加えて溶解する方法が好しい。この方法
は溶媒の潜熱を利用して冷却効率を高める点でも有利で
ある。Although the timing of adding the solvent to the reaction solution varies depending on the freezing point of the complex and the boiling point of the solvent, it is usually preferable to add the solvent while cooling the reaction solution after completion of the aging to dissolve it. This method is also advantageous in enhancing the cooling efficiency by utilizing the latent heat of the solvent.
溶媒の使用量は錯体の溶解度によっても異るが、通常は
反応液に対し1/2〜３倍量使用される。錯体分解温度は
０〜60℃、好しくは20〜40℃である。Although the amount of the solvent used varies depending on the solubility of the complex, it is usually used in an amount of 1/2 to 3 times the amount of the reaction solution. The decomposition temperature of the complex is 0 to 60 ° C, preferably 20 to 40 ° C.
錯体分解後の有機層は減圧蒸留で単離されるが、有機層
を直接、又は水洗後に蒸留すると多クロルアルキルフェ
ノンが青紫色〜赤褐色に着色し好しくない。この原因は
明らかでないが蒸留中に酸性成分が生成する所から、酸
の影響が予想される。The organic layer after the decomposition of the complex is isolated by vacuum distillation, but when the organic layer is distilled directly or after washing with water, the polychloroalkylphenone is colored in a blue-purple to reddish brown color, which is not preferable. The cause of this is not clear, but the effect of acid is expected from the fact that acidic components are produced during distillation.
蒸留に先だって有機層をアルカリ水溶液で洗浄すること
により多クロルアルキンフェノンの着色は大巾に改良さ
れ、淡黄色〜黄色になる。By washing the organic layer with an aqueous alkali solution prior to distillation, the coloring of the polychloroalkynephenone is greatly improved and it becomes pale yellow to yellow.
中和に使用されるアルカリはナトリウム及びカリウムの
水酸化物、炭酸塩又は重炭酸塩である。アルカリ濃度は
アルキル基の塩素数によっても異るが0.5〜５％、好し
くは１〜２％である。The alkali used for neutralization is sodium and potassium hydroxide, carbonate or bicarbonate. The alkali concentration varies depending on the number of chlorine in the alkyl group, but is 0.5 to 5%, preferably 1 to 2%.
アルキル基の塩素が２個以上の場合はアルカリ濃度を10
％まで上げると確実に多クロルアルキルフェノンが分解
し低収率になる。If the number of chlorine in the alkyl group is 2 or more, the alkali concentration is 10
%, The polychloroalkylphenone is surely decomposed and the yield becomes low.
アルカリ水の使用量は有機層に対し0.5〜２容積倍の使
用が好しい。中和の温度は常温が好しく、高温では多ク
ロルアルキルフェノンが分解し好しくない。The amount of alkaline water used is preferably 0.5 to 2 times the volume of the organic layer. The neutralization temperature is preferably normal temperature, and at high temperature the polychloroalkylphenone is decomposed, which is not preferable.
中和後は有機層にアルカリ水が若干混入するので、引続
き水洗しこれらを除去した後に蒸留するのが好しい。After neutralization, a small amount of alkaline water is mixed in the organic layer, so it is preferable to continue washing with water, remove these, and then distill.
本発明の多クロルアルキルフェノンとはジクロルベンゼ
ン類より得られるフェノン類であって例えば、２′,4′
−ジクロルアセトフェノン、2,2′,4′−トリクロルア
セトフェノン、2,2,2′,4′−テトラクロルアセトフェ
ノン、2,2,2,2′,4′−ペンタクロルアセトフェノン、
３′,4′−ジクロルアセトフェノン、2,3′,4′−トリ
クロルアセトフェノン、2,2,3′,4′−テトラクロルア
セトフェノン、２′,5′−ジクロルアセトフェノン、2,
2′,5′−トリクロルアセトフェノン、2,2,2′,5′−テ
トラクロルアセトフェノン等である。The polychloroalkylphenone of the present invention is a phenone obtained from dichlorobenzenes such as 2 ', 4'.
-Dichloroacetophenone, 2,2 ', 4'-trichloroacetophenone, 2,2,2', 4'-tetrachloroacetophenone, 2,2,2,2 ', 4'-pentachloroacetophenone,
3 ', 4'-dichloroacetophenone, 2,3', 4'-trichloroacetophenone, 2,2,3 ', 4'-tetrachloroacetophenone, 2', 5'-dichloroacetophenone, 2,
2 ', 5'-trichloroacetophenone, 2,2,2', 5'-tetrachloroacetophenone and the like.
（発明の効果） 本発明の方法により、錯体分解中のタール分の生成を大
巾に抑制すると共に、多クロルアルキルフェノンの着色
を容易に抑制可能とし総収率を向上することができた。(Effects of the Invention) By the method of the present invention, it is possible to significantly suppress the generation of the tar component during the decomposition of the complex, and it is possible to easily suppress the coloring of the polychloroalkylphenone to improve the total yield.
（実施例） 実施例１〜７ 攪拌機、還流冷却器、温度計及び滴下斗を備えた2lセ
パラブルフラスコにジクロルベンゼンと無水塩化アルミ
ニウムを仕込み所定の温度を保持しながら酸クロライド
を滴下反応した。引続き所定の温度で熟成を取り反応を
完結させた。この反応液を40〜80℃まで冷却した後に所
定量のハロゲン化炭素溶媒を滴下し反応液を溶解した。(Examples) Examples 1 to 7 Dichlorobenzene and anhydrous aluminum chloride were charged into a 2 liter separable flask equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel, and acid chloride was reacted dropwise while maintaining a predetermined temperature. . Subsequently, aging was carried out at a predetermined temperature to complete the reaction. After the reaction solution was cooled to 40 to 80 ° C, a predetermined amount of carbon halide solvent was added dropwise to dissolve the reaction solution.
この溶液を滴下ロートに移し、あらかじめ水1400gを仕
込んだ3lセパラブルフラスコに徐々に滴下し、30〜40℃
を保持しながら錯体分解を行った。This solution was transferred to a dropping funnel and gradually added dropwise to a 3 l separable flask charged with 1400 g of water in advance, and 30 to 40 ° C.
Was maintained while complex decomposition was performed.
水層を分離後、有機層に１％苛性ソーダー溶液1400gを
加えて室温にて30分攪拌中和した。同様に有機層を1400
gの水で洗浄後、200〜300mmHgの圧力で脱ハロゲン化炭
化水素を行ない。引続いて４〜15mmHgで多クロルアルキ
ルフェノンの蒸留を行った結果を表−１に示す。After separating the aqueous layer, 1400 g of a 1% caustic soda solution was added to the organic layer and the mixture was neutralized with stirring at room temperature for 30 minutes. Similarly 1400 organic layers
After washing with g water, dehalogenated hydrocarbon is carried out at a pressure of 200 to 300 mmHg. The results of subsequent distillation of polychloroalkylphenone at 4 to 15 mmHg are shown in Table 1.
比較例 実施例−１において、反応液をハロゲン化炭化水素溶媒
を使用せず、反応液に直接水1400gを加え、60〜95℃で
錯体分解した後、クロルベンゼン700gを加えて抽出した
こと、有機層を中和せず水洗のみで蒸留したこと以外は
実施例−１と同様に処理した所、２′,4′−ジクロルア
セトフェノンの収率は63.2％、主留の外観は赤紫色であ
り、タール分は64g/ジクロルベンゼン（モル）であっ
た。 Comparative Example In Example-1, without using a halogenated hydrocarbon solvent in the reaction solution, 1400 g of water was added directly to the reaction solution, and after complex decomposition at 60 to 95 ° C., 700 g of chlorobenzene was added for extraction. After treating in the same manner as in Example 1 except that the organic layer was not washed and distilled only with water, the yield of 2 ', 4'-dichloroacetophenone was 63.2%, and the appearance of the main distillate was reddish purple. Yes, the tar content was 64 g / dichlorobenzene (mol).
Claims (2)
水塩化アルミニウムのフリーデルクラフツ反応による一
般式 （ここでＲはC1〜C3のアルキル基又はクロルアルキル基
を示す）で表わされる多クロルアルキルフェノン類の製
造において、溶媒を用いずに反応し、反応後に反応液を
ハロゲン化炭化水素溶媒に溶解した後、その溶液を水の
中に滴下しながら０〜60℃で錯体分解することを特徴と
する多クロルアルキルフェノン類の製法。1. A general formula by Friedel-Crafts reaction of dichlorobenzenes, acid chlorides and anhydrous aluminum chloride. (Wherein R represents a C 1 -C 3 alkyl group or a chloroalkyl group), in the production of polychloroalkylphenones, the reaction is carried out without using a solvent, and the reaction solution is used as a halogenated hydrocarbon solvent after the reaction. A method for producing polychloroalkylphenones, which comprises dissolving the solution in water, and then complex-decomposing the solution at 0 to 60 ° C. while dropping the solution in water.
ることを特徴とする特許請求の範囲第一項記載の製法。2. The method according to claim 1, wherein the organic layer after the decomposition of the complex is washed with alkaline water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61260216A JPH0747561B2 (en) | 1986-10-31 | 1986-10-31 | Manufacturing method of polychloroalkylphenones |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61260216A JPH0747561B2 (en) | 1986-10-31 | 1986-10-31 | Manufacturing method of polychloroalkylphenones |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63115839A JPS63115839A (en) | 1988-05-20 |
| JPH0747561B2 true JPH0747561B2 (en) | 1995-05-24 |
Family
ID=17344958
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61260216A Expired - Lifetime JPH0747561B2 (en) | 1986-10-31 | 1986-10-31 | Manufacturing method of polychloroalkylphenones |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0747561B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5210313A (en) * | 1992-01-10 | 1993-05-11 | Maxdem Incorporated | Preparation of 2,5-dichlorobenzophenones |
-
1986
- 1986-10-31 JP JP61260216A patent/JPH0747561B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63115839A (en) | 1988-05-20 |
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