JPS63170333A - Production of alpha-haloisobutyrophenones - Google Patents
Production of alpha-haloisobutyrophenonesInfo
- Publication number
- JPS63170333A JPS63170333A JP62002789A JP278987A JPS63170333A JP S63170333 A JPS63170333 A JP S63170333A JP 62002789 A JP62002789 A JP 62002789A JP 278987 A JP278987 A JP 278987A JP S63170333 A JPS63170333 A JP S63170333A
- Authority
- JP
- Japan
- Prior art keywords
- alpha
- benzene
- chloride
- aluminum chloride
- haloisobutyric
- 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.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 28
- 150000004820 halides Chemical class 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims description 4
- 238000006482 condensation reaction Methods 0.000 claims 1
- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 15
- 150000001555 benzenes Chemical class 0.000 abstract description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 abstract description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 4
- DTZKVZKYSZUBAG-UHFFFAOYSA-N 2-chloro-2-methylpropanoyl chloride Chemical compound CC(C)(Cl)C(Cl)=O DTZKVZKYSZUBAG-UHFFFAOYSA-N 0.000 abstract description 3
- YOCIJWAHRAJQFT-UHFFFAOYSA-N 2-bromo-2-methylpropanoyl bromide Chemical compound CC(C)(Br)C(Br)=O YOCIJWAHRAJQFT-UHFFFAOYSA-N 0.000 abstract description 2
- VUNWOWKGBXOBGY-UHFFFAOYSA-N 2-bromo-2-methylpropanoyl chloride Chemical compound CC(C)(Br)C(Cl)=O VUNWOWKGBXOBGY-UHFFFAOYSA-N 0.000 abstract description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003905 agrochemical Substances 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003505 polymerization initiator Substances 0.000 abstract description 2
- 239000008096 xylene Substances 0.000 abstract description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 abstract 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 abstract 1
- 229940079593 drug Drugs 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 3
- KJCFAQDTHMIAAN-UHFFFAOYSA-N 2-methyl-1-phenylprop-2-en-1-one Chemical compound CC(=C)C(=O)C1=CC=CC=C1 KJCFAQDTHMIAAN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 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 1
- NUJHTYRNHYOUKO-UHFFFAOYSA-N 2-chloro-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(Cl)C(=O)C1=CC=CC=C1 NUJHTYRNHYOUKO-UHFFFAOYSA-N 0.000 description 1
- BEKNOGMQVKBMQN-UHFFFAOYSA-N 2-methyl-2,3-dihydroinden-1-one Chemical compound C1=CC=C2C(=O)C(C)CC2=C1 BEKNOGMQVKBMQN-UHFFFAOYSA-N 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 235000009827 Prunus armeniaca Nutrition 0.000 description 1
- 244000018633 Prunus armeniaca Species 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- ULKGULQGPBMIJU-UHFFFAOYSA-N benzene;hydron;bromide Chemical compound Br.C1=CC=CC=C1 ULKGULQGPBMIJU-UHFFFAOYSA-N 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- -1 oxygen-substituted benzenes Chemical class 0.000 description 1
- 239000002994 raw material Substances 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
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、α−ハロイソブチロフェノン類の製法に関す
る。本発明の方法で得られるα−ハロイソブチロフェノ
ン類は、医農薬中間体或いは不飽和化合物の重合開始剤
の合成中間体（特開昭５８−２０３９３４）として有用
である。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for producing α-haloisobutyrophenones. The α-haloisobutyrophenones obtained by the method of the present invention are useful as intermediates for pharmaceuticals and agricultural chemicals or synthetic intermediates for polymerization initiators for unsaturated compounds (Japanese Patent Laid-Open No. 58-203934).
（従来技術及び問題点）
ベンゼン誘導体とα−ハロイソ酪酸ハライドとの反応に
ついては、例えばオーク（Ｏｌａｈ）によるフリーデル
ークラフツアンドリレイテドリアクションズ（Ｆｒｉｅ
ｄｅｌ−Ｃｒａｆｔｓ ａｎｄ ｒｅｌａｔｅｄ ｒｅ
ａｃｔｉｏｎｓ）第ｎ１巻、第２１頁（１９６４年）に
記載されている。しかしながら、上記反応では、主生成
物としてα−ハロイソプチロフエノンではなく、メチル
イソダノン及びわずかのイソプロペニルフェニルケトン
が得られたのみであった。(Prior Art and Problems) Regarding the reaction between benzene derivatives and α-haloisobutyric acid halides, for example, the Friedel-Crafts and Related Reactions by Olah et al.
del-Crafts and related re
actions) Volume n1, Page 21 (1964). However, in the above reaction, only methylisodanone and a small amount of isopropenylphenyl ketone were obtained instead of α-haloisoptilofhenone as the main product.
（問題を解決するための手段）
本発明の目的は、上記反応において従来技術では得られ
なかった０−ハロイソブチロフェノンの選択性を改善し
て収率良く目的物を得る方法を提供することである。(Means for Solving the Problems) An object of the present invention is to provide a method for obtaining the target product in high yield by improving the selectivity of 0-haloisobutyrophenone, which could not be obtained with the conventional techniques, in the above reaction. be.
本発明者等は、反応選択性に関し、α−ハロイソ酪酸ハ
ライドと塩化アルミニウムの比率（モル比）に着目し、
鋭意検討したところ、α−ハロイソ酪酸ハライドに対し
塩化アルミニウムを０．８モル倍から１．１モル倍用い
ることにより選択的にａ−ハロイソブチロフェノンか得
られることがわかり、本発明に至った。Regarding reaction selectivity, the present inventors focused on the ratio (molar ratio) of α-haloisobutyric acid halide and aluminum chloride,
After extensive investigation, it was found that a-haloisobutyrophenone could be selectively obtained by using aluminum chloride in an amount of 0.8 to 1.1 times the mole of α-haloisobutyric acid halide, leading to the present invention.
すなわち、本発明者等は、０−ハロイソ酪酸ハライドに
対する塩化アルミニウムのモル比と得られる生成物分布
について詳細に検討し、表に示した如くモル比が１．１
モル倍を越えると急激にα−ハロイソブチロフェノンの
生成比率が減り、メチルインダノン及びイソプロペニル
フェニルケトンの生成比率が増加することを見出した。That is, the present inventors investigated in detail the molar ratio of aluminum chloride to 0-haloisobutyric acid halide and the resulting product distribution, and as shown in the table, the molar ratio was 1.1.
It has been found that when the molar ratio is exceeded, the production ratio of α-haloisobutyrophenone rapidly decreases, and the production ratio of methyl indanone and isopropenylphenyl ketone increases.
またモル比が０．８モル倍未満の場合は、α−ハロイソ
ブチロフェノンが得られるものの十分な収率が得られな
くなる。If the molar ratio is less than 0.8 times, α-haloisobutyrophenone can be obtained, but a sufficient yield will not be obtained.
本発明において、ベンゼン誘導体の好適な例としては、
ベンゼン、トルエン、キシレンなどのアルキル置換ベン
ゼン、アニソール、フェノール、カテコールなどの酸素
置換ベンゼン、塩化ベンゼン、臭化ベンゼン、などのハ
ロゲン置換ベンゼンを挙げることができる。またα−ハ
ロイソ酪酸ハライドとしては、α−クロロイソ酪酸クロ
リド、α−ブロモイソ酪酸クロリド、α−ブロモイソ酪
酸プロミドなどが例示る。ベンゼン誘導、体それ自体を
反応溶媒として過剰に用いることもできるが、ニトロベ
ンゼン、四塩化炭素等の不活性溶媒を共存させても構わ
ない。In the present invention, preferred examples of benzene derivatives include:
Examples include alkyl-substituted benzenes such as benzene, toluene and xylene; oxygen-substituted benzenes such as anisole, phenol and catechol; and halogen-substituted benzenes such as chlorinated benzene and bromide benzene. Further, examples of the α-haloisobutyric acid halide include α-chloroisobutyric acid chloride, α-bromoisobutyric acid chloride, α-bromoisobutyric acid bromide, and the like. Although the benzene derivative itself can be used in excess as a reaction solvent, an inert solvent such as nitrobenzene or carbon tetrachloride may also be present.
反応温度は、特に限定されるものではないが、好ましく
は、１０°Ｃから５０°Ｃの範囲である。また原料の添
加順序もベンゼン誘導体と塩化アルミニウムの混合系に
ａ−ハロイソ酪酸ハライドを滴下しても良くベンゼン誘
導体とα−ハロイソ酪酸ハライドの混合系に塩化アルミ
ニウムを添加しても構わない。いずれの場合も添加後、
数時間の熟成を行った方が好結果が得られる。The reaction temperature is not particularly limited, but is preferably in the range of 10°C to 50°C. Regarding the addition order of the raw materials, a-haloisobutyric acid halide may be added dropwise to a mixed system of benzene derivatives and aluminum chloride, or aluminum chloride may be added to a mixed system of benzene derivatives and α-haloisobutyric acid halide. In either case, after addition,
Better results can be obtained by aging for several hours.
このようにして得られた反応液を常法に従って塩分解し
、必要に応じて抽出、脱溶媒あるいは、蒸留等により単
離精製することがてきる。The reaction solution thus obtained can be subjected to salt decomposition according to a conventional method and, if necessary, isolated and purified by extraction, removal of solvent, distillation, etc.
（発明の効果）
本発明の方法により、従来上記フリーデルクラフッ反応
において得ることができなかったα−７１０イソブチロ
フエノンを塩化アルミニウムの添加量をコントロールす
ることにより、高純度及び高収率で得ることが可能にな
った。(Effects of the Invention) By the method of the present invention, α-710 isobutylophenone, which could not be obtained conventionally in the Friedel-Crach reaction, can be obtained with high purity and high yield by controlling the amount of aluminum chloride added. It is now possible to obtain.
実施例１゜
ベンゼン３５０ｍ１中に無水塩化アルミニウム９４．６
ｇ（０，７１モル）を分散させ１５°Ｃから２０°Ｃを
保ちながら、α−タロロイソ酪酸クロリド１００ｇ（０
，７１モル）のベンゼン溶液（４００ｍｌ）を約２５分
かけて滴下した。滴下終了後、２５°Ｃを保ち６時間熟
成し、反応液を２Ｎ塩酸水溶液と氷の混合液に添加し、
塩分解を行った。上層を分液した後、溶媒を除去し１１
７．４ｇのα−クロロイソブチロフェノンが得られた（
収率９０．０％）。このものをガスクロマトグラフィー
により分析したところ、９９．４％の純度であった。Example 1 94.6 ml of anhydrous aluminum chloride in 350 ml of benzene
100 g (0.71 mol) of α-taloloyisobutyric acid chloride was dispersed and maintained at 15°C to 20°C.
, 71 mol) in benzene (400 ml) was added dropwise over about 25 minutes. After completion of the dropwise addition, the mixture was maintained at 25°C and aged for 6 hours, and the reaction solution was added to a mixture of 2N hydrochloric acid aqueous solution and ice.
Salt decomposition was performed. After separating the upper layer, the solvent was removed and 11
7.4 g of α-chloroisobutyrophenone was obtained (
yield 90.0%). This product was analyzed by gas chromatography and found to have a purity of 99.4%.
実施例２
α−クロロイソ酪酸クロリド１００ｇのベンゼン’
（７００ｍｌ）溶液に１５°Ｃから２０°Ｃを保ちな
がら無水塩化アルミニウムを少量ずつ約２５分かけて添
加した。２５°Ｃで６時間熟成した後、実施例１と同様
の方法で処理し、９９．２％のａ−クロロイソブチロフ
ェノン１０８．５ｇが得られた（収率８３％）。Example 2 100 g of α-chloroisobutyric acid chloride in benzene'
(700 ml) Anhydrous aluminum chloride was added little by little to the solution over about 25 minutes while maintaining the temperature at 15°C to 20°C. After aging at 25°C for 6 hours, it was treated in the same manner as in Example 1 to obtain 108.5 g of 99.2% a-chloroisobutyrophenone (yield: 83%).
以下実施例１と同様の方法で塩化アルミニウム／α−ク
ロロイソ酪酸クロリド（モル比）を変えて反応を行った
実施例及び比較例を表に示す。Examples and comparative examples in which the reaction was carried out in the same manner as in Example 1 by changing the molar ratio of aluminum chloride/α-chloroisobutyric acid chloride are shown in the table below.
杏apricot
Claims (1)
イソ酪酸ハライドとの縮合反応においてα−ハロイソ酪
酸ハライドに対し、０．８モル倍から１．１モル倍の塩
化アルミニウムを用いることを特徴とするα−ハロイソ
ブチロフェノン類の製法。α- characterized in that aluminum chloride is used in a condensation reaction between a benzene derivative and α-haloisobutyric acid halide in the presence of aluminum chloride in an amount of 0.8 to 1.1 times the mole of α-haloisobutyric acid halide. Process for producing haloisobutyrophenones.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62002789A JPS63170333A (en) | 1987-01-09 | 1987-01-09 | Production of alpha-haloisobutyrophenones |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62002789A JPS63170333A (en) | 1987-01-09 | 1987-01-09 | Production of alpha-haloisobutyrophenones |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63170333A true JPS63170333A (en) | 1988-07-14 |
Family
ID=11539123
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62002789A Pending JPS63170333A (en) | 1987-01-09 | 1987-01-09 | Production of alpha-haloisobutyrophenones |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63170333A (en) |
-
1987
- 1987-01-09 JP JP62002789A patent/JPS63170333A/en active Pending
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