JPS6338976B2 - - Google Patents
Info
- Publication number
- JPS6338976B2 JPS6338976B2 JP674081A JP674081A JPS6338976B2 JP S6338976 B2 JPS6338976 B2 JP S6338976B2 JP 674081 A JP674081 A JP 674081A JP 674081 A JP674081 A JP 674081A JP S6338976 B2 JPS6338976 B2 JP S6338976B2
- Authority
- JP
- Japan
- Prior art keywords
- chloroacetophenone
- reaction
- acetophenone
- chloroform
- liquid phase
- 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
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 16
- IMACFCSSMIZSPP-UHFFFAOYSA-N phenacyl chloride Chemical compound ClCC(=O)C1=CC=CC=C1 IMACFCSSMIZSPP-UHFFFAOYSA-N 0.000 claims description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 14
- 239000007791 liquid phase Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 6
- CERJZAHSUZVMCH-UHFFFAOYSA-N 2,2-dichloro-1-phenylethanone Chemical compound ClC(Cl)C(=O)C1=CC=CC=C1 CERJZAHSUZVMCH-UHFFFAOYSA-N 0.000 description 4
- 238000005660 chlorination reaction Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010446 mirabilite Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は、α―クロロアセトフエノンの製造方
法に関し、詳しくは特定の溶媒中でアセトフエノ
ンを液相で塩素化してα―クロロアセトフエノン
を製造する方法に関する。
α―クロロアセトフエノンは種々の農薬、医薬
などの中間原料として有用なものであり、従来は
主として、ベンゼンとクロロ塩化アセチルのフリ
ーデルークラフツ反応によつて製造されていた
が、最近ではクメン法によるフエノール製造の副
生物として得られる安価なアウセトフエノンを原
料として用い、これを液相で塩素化して製造する
ことが試みられている。例えばケミツシエ・ベリ
ヒテ（Chemische Berichte）34 1902（1901）に
は酢酸中での塩素化反応が、またアナーレス・ド
ウ・チミー・エ・ドウ・フイジツク（Annales
de chimie et de physique）14（６）377（1888）
には、二硫化炭素中での塩素化反応がそれぞれ記
載されている。
しかしながら、このような塩素化反応において
は、α，α―ジクロロアセトフエノンが多量に副
生し、原料の損失を来たすと共に、α―クロロア
セトフエノンとα，α―ジクロロアセトフエノン
との分離が難しいために、α―クロロアセトフエ
ノンの収率が低くなり、工業的に難点を抱えてい
る。
本発明者等は、アセトフエノンの液相での塩素
化反応に注目し、種々の溶媒について検討を重ね
たところ、クロロホルム及び塩化メチレンを溶媒
として用いた場合、高収率でかつ高純度のα―ク
ロロアセトフエノンが得られることを見い出し、
本発明を完成した。
すなわち、本発明はクロロホルム又は塩化メチ
レン中で、アセトフエノンを液相で塩素化してα
―クロロアセトフエノンを製造することを特徴と
するα―クロロアセトフエノンの製造方法であ
る。
本発明方法では、一般にアセトフエノンをクロ
ロホルム又は塩化メチレン中に溶解させ、液相で
塩素化してα―クロロアセトフエノンを製造す
る。反応温度は通常−30℃〜溶媒の沸点、望まし
くは−30℃〜60℃、更に望ましくは−20℃〜40℃
であり、溶媒の使用量は通常アセトフエノン１重
量部に対して３〜20倍、望ましくは５〜15倍であ
る。反応は通常、塩素ガスを液相中に通じること
により行なわれ、塩素の使用量はアセトフエノン
に対してほぼ等モルであつて、普通10分〜12時間
で終了する。
反応終了後、反応生成物に溶媒除去、晶析、
過などの通常行なわれる分離操作が施されると、
目的物のα―クロロアセトフエノンを例えば90％
以上の収率で得ることができる。
次に本発明に係る実施例を記載する。
実施例 １
温度計、還流冷却器、撹拌装置、ガス吹込管を
取りつけた四つ口フラスコ中に、5gのアセトフ
エノンと50gのクロロホルム試薬を加えた。撹拌
しながら、20℃で塩素ガスを毎分20mlの割合で、
50分間クロロホルム溶液中に吹き込んで反応させ
た。反応終了後、反応生成物をガスクロマトグラ
フイーにより分析したところ、このものはα―ク
ロロアセトフエノン95.1％、α，α―ジクロロア
セトフエノン3.3％及びその他1.6％を含んでいる
ことがわかつた。
更に、前記反応生成物をチオ硫酸ナトリウム水
溶液で洗浄し、芒硝で乾燥した後溶媒を留去し
た。このものを30℃で晶析し、結晶を別し、少
量の石油エーテルで洗浄して、純度99％のα―ク
ロロアセトフエノン5.9g（収率91.7％）を得た。
実施例 ２
クロロホルム50gを塩化メチレン試薬50gに代
えること以外は、前記実施例１の場合と同様にし
て反応を行ない、反応生成物をガスクロマトグラ
フイーにより分析したところ、α―クロロアセト
フエノン95.8％及びα，α―ジクロロアセトフエ
ノン4.2％を含んでいることがわかつた。
また、この反応生成物を前記実施例１の場合と
同様にして、精製を行ない純度98％のα―クロロ
アセトフエノン5.9g（収率91.7％）を得た。
比較例 １〜６
下記第１表の反応条件を用い、前記実施例１の
場合と同様に反応させ（塩素の使用量は実施例１
の場合と同じ）、精製処理して第２表の反応生成
物及び目的物を得た。
The present invention relates to a method for producing α-chloroacetophenone, and more particularly to a method for producing α-chloroacetophenone by chlorinating acetophenone in a liquid phase in a specific solvent. α-Chloroacetophenone is useful as an intermediate raw material for various agricultural chemicals and medicines, and has traditionally been produced mainly by the Friedel-Crafts reaction of benzene and chloroacetyl chloride, but recently it has been produced using the cumene method. Attempts have been made to use cheap ausetophenone, which is obtained as a by-product of phenol production, as a raw material and to chlorinate it in the liquid phase. For example, Chemische Berichte 34 1902 (1901) describes the chlorination reaction in acetic acid;
de chimie et de physique) 14 (6) 377 (1888)
describes the chlorination reaction in carbon disulfide. However, in such a chlorination reaction, a large amount of α,α-dichloroacetophenone is produced as a by-product, resulting in a loss of raw materials, and the relationship between α-chloroacetophenone and α,α-dichloroacetophenone is Due to the difficulty of separation, the yield of α-chloroacetophenone is low, which is an industrial problem. The present inventors focused on the chlorination reaction of acetophenone in the liquid phase and repeatedly investigated various solvents, and found that when chloroform and methylene chloride were used as solvents, high yield and high purity α- discovered that chloroacetophenone could be obtained,
The invention has been completed. That is, the present invention chlorinates acetophenone in the liquid phase in chloroform or methylene chloride to obtain α
- A method for producing α-chloroacetophenone, characterized by producing chloroacetophenone. In the process of the present invention, acetophenone is generally dissolved in chloroform or methylene chloride and chlorinated in the liquid phase to produce α-chloroacetophenone. The reaction temperature is usually -30°C to the boiling point of the solvent, preferably -30°C to 60°C, more preferably -20°C to 40°C.
The amount of the solvent used is usually 3 to 20 times, preferably 5 to 15 times, relative to 1 part by weight of acetophenone. The reaction is usually carried out by passing chlorine gas into the liquid phase, the amount of chlorine used is approximately equimolar to the amount of acetophenone, and the reaction is normally completed in 10 minutes to 12 hours. After the reaction is completed, the reaction product is subjected to solvent removal, crystallization,
After normal separation operations such as filtration,
For example, 90% of the target α-chloroacetophenone
It can be obtained with a yield higher than that. Next, examples according to the present invention will be described. Example 1 5 g of acetophenone and 50 g of chloroform reagent were added to a four-necked flask equipped with a thermometer, reflux condenser, stirrer, and gas blowing tube. While stirring, add chlorine gas at a rate of 20 ml per minute at 20°C.
The mixture was reacted by bubbling into a chloroform solution for 50 minutes. After the reaction was completed, the reaction product was analyzed by gas chromatography and was found to contain 95.1% α-chloroacetophenone, 3.3% α,α-dichloroacetophenone, and 1.6% other substances. . Further, the reaction product was washed with an aqueous sodium thiosulfate solution, dried over Glauber's salt, and then the solvent was distilled off. This product was crystallized at 30°C, and the crystals were separated and washed with a small amount of petroleum ether to obtain 5.9 g of α-chloroacetophenone (yield: 91.7%) with a purity of 99%. Example 2 The reaction was carried out in the same manner as in Example 1 above, except that 50 g of chloroform was replaced with 50 g of methylene chloride reagent, and the reaction product was analyzed by gas chromatography and found to be 95.8% α-chloroacetophenone. It was found that it contained 4.2% of α,α-dichloroacetophenone. Further, this reaction product was purified in the same manner as in Example 1 to obtain 5.9 g of α-chloroacetophenone with a purity of 98% (yield: 91.7%). Comparative Examples 1 to 6 Using the reaction conditions shown in Table 1 below, the reaction was carried out in the same manner as in Example 1 (the amount of chlorine used was the same as in Example 1).
(same as in the case of ), and purification was performed to obtain the reaction products and target products shown in Table 2.
【表】【table】
Claims (1)
フエノンを液相で塩素化してα―クロロアセトフ
エノンを製造することを特徴とするα―クロロア
セトフエノンの製造方法。1. A method for producing α-chloroacetophenone, which comprises producing α-chloroacetophenone by chlorinating acetophenone in a liquid phase in chloroform or methylene chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP674081A JPS57120545A (en) | 1981-01-20 | 1981-01-20 | Preparation of alpha-chloroacetophenone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP674081A JPS57120545A (en) | 1981-01-20 | 1981-01-20 | Preparation of alpha-chloroacetophenone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57120545A JPS57120545A (en) | 1982-07-27 |
| JPS6338976B2 true JPS6338976B2 (en) | 1988-08-03 |
Family
ID=11646603
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP674081A Granted JPS57120545A (en) | 1981-01-20 | 1981-01-20 | Preparation of alpha-chloroacetophenone |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57120545A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4598486B2 (en) * | 2004-11-17 | 2010-12-15 | 三井化学株式会社 | Method for producing 1,5-diaminonaphthalene |
| RU2644778C1 (en) * | 2017-04-17 | 2018-02-14 | Федеральное Государственное Бюджетное Учреждение Науки Институт Химии Коми Научного Центра Уральского Отделения Российской Академии Наук | METHOD OF α-CHLORACETOPHENONE SYNTHESIS (VERSIONS) |
-
1981
- 1981-01-20 JP JP674081A patent/JPS57120545A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57120545A (en) | 1982-07-27 |
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