JPH0240340A - Production of halobenzophenone derivative - Google Patents
Production of halobenzophenone derivativeInfo
- Publication number
- JPH0240340A JPH0240340A JP18678988A JP18678988A JPH0240340A JP H0240340 A JPH0240340 A JP H0240340A JP 18678988 A JP18678988 A JP 18678988A JP 18678988 A JP18678988 A JP 18678988A JP H0240340 A JPH0240340 A JP H0240340A
- Authority
- JP
- Japan
- Prior art keywords
- nitric acid
- reaction
- specific gravity
- ethylene
- aqueous solution
- 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 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 30
- 230000005484 gravity Effects 0.000 claims abstract description 22
- 239000007864 aqueous solution Substances 0.000 claims abstract description 17
- 239000000126 substance Substances 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 43
- 239000005977 Ethylene Substances 0.000 abstract description 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 12
- 239000003960 organic solvent Substances 0.000 abstract description 10
- 150000001875 compounds Chemical class 0.000 abstract description 7
- 229920000642 polymer Polymers 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 239000000178 monomer Substances 0.000 abstract description 4
- 230000001590 oxidative effect Effects 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 4
- 150000002828 nitro derivatives Chemical class 0.000 abstract description 2
- 229920001643 poly(ether ketone) Polymers 0.000 abstract description 2
- 150000002576 ketones Chemical class 0.000 abstract 1
- 229920006295 polythiol Polymers 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- 239000002994 raw material Substances 0.000 description 18
- 239000000243 solution Substances 0.000 description 7
- -1 aliphatic halogenated hydrocarbon Chemical class 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 238000011403 purification operation Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OKISUZLXOYGIFP-UHFFFAOYSA-N 4,4'-dichlorobenzophenone Chemical compound C1=CC(Cl)=CC=C1C(=O)C1=CC=C(Cl)C=C1 OKISUZLXOYGIFP-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- VLTYTTRXESKBKI-UHFFFAOYSA-N (2,4-dichlorophenyl)-phenylmethanone Chemical compound ClC1=CC(Cl)=CC=C1C(=O)C1=CC=CC=C1 VLTYTTRXESKBKI-UHFFFAOYSA-N 0.000 description 1
- IEAUXBMXWDAYID-UHFFFAOYSA-N 1-chloro-4-[1-(4-chlorophenyl)ethenyl]benzene Chemical group C1=CC(Cl)=CC=C1C(=C)C1=CC=C(Cl)C=C1 IEAUXBMXWDAYID-UHFFFAOYSA-N 0.000 description 1
- WELCIURRBCOJDX-UHFFFAOYSA-N 1-chloro-4-[2-(4-chlorophenyl)ethenyl]benzene Chemical group C1=CC(Cl)=CC=C1C=CC1=CC=C(Cl)C=C1 WELCIURRBCOJDX-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- UCNVFOCBFJOQAL-UHFFFAOYSA-N DDE Chemical group C=1C=C(Cl)C=CC=1C(=C(Cl)Cl)C1=CC=C(Cl)C=C1 UCNVFOCBFJOQAL-UHFFFAOYSA-N 0.000 description 1
- 241001590997 Moolgarda engeli Species 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- LFABNOYDEODDFX-UHFFFAOYSA-N bis(4-bromophenyl)methanone Chemical compound C1=CC(Br)=CC=C1C(=O)C1=CC=C(Br)C=C1 LFABNOYDEODDFX-UHFFFAOYSA-N 0.000 description 1
- 125000004799 bromophenyl group Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000000068 chlorophenyl group Chemical group 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization 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
- 238000005516 engineering process Methods 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000001207 fluorophenyl group Chemical group 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000005059 halophenyl group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 125000002346 iodo group Chemical group I* 0.000 description 1
- 125000006303 iodophenyl group Chemical group 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、耐熱性高分子のモノマーとして利用されるハ
ロベンゾフェノン誘導体の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method for producing halobenzophenone derivatives used as monomers for heat-resistant polymers.
従来の技術
ハロベンゾフェノン誘導体は、ポリエーテルケトン類や
ポリチオエーテルケトン類等の耐熱性高分子のモノマー
として最近特に注目されており、それを安価に得る製造
方法の開発が強＜Ｆ！ｊ、よれている、従来ハロベンゾ
フェノン誘導体の製造方法として、例えば、Ｊ、 Ｆｏ
ｒｒｅｓｔ ｅｔ ａｌ、、Ｊ、 Ｃｈｅｍ。Conventional Technology Halobenzophenone derivatives have recently attracted particular attention as monomers for heat-resistant polymers such as polyetherketones and polythioetherketones, and the development of a manufacturing method to obtain them at low cost is highly desirable. J, as a method for producing conventional halobenzophenone derivatives that are twisted, for example, J, Fo
rrest et al., J. Chem.
Ｓｏｃ、 、 Ｐ、３３３（１９４６）や、１１．Ｌ、
Ｂｒａｄｌｏｗ ｅｔ ａｔ、、 Ｊ。Soc, P, 333 (1946), 11. L,
Bradlow et at, J.
＾ｎｃｒ、ｃｈｅｎ、ｓｏｃ、、 ６９．ｐ、６６２（
１９４７）には、１，１−ジクロロ−２，２−ビス（４
−クロロフェニル）エチレンをクロム酸により酸化する
方法が記載されている。^ncr, chen, soc,, 69. p, 662 (
(1947), 1,1-dichloro-2,2-bis(4
A method for oxidizing ethylene (-chlorophenyl) with chromic acid is described.
よた、Ｏ，Ｇ、 Ｂａｃｋｃｂａｒｇ、Ｊ、Ｌ、Ｃ，Ｈ
ａｒａｉｓ、 Ｊ、Ｃｈａｍ。Yota, O, G, Backcbarg, J, L, C, H
arais, J., Cham.
Ｓｏｃ、、Ｐ、 ８０３ （１９４５）及び特開昭５８
−１２６８２９公報には、有機溶媒の使用の下に、１．
１−ジクロ１ｙ−２，２−ビス（４−クロロフェニル）
エチレンを硝酸により酸化する方法が記載されており、
そして有機溶媒として、前者の刊行物に記載の場合は酢
酸が使用され、後者の刊行物の場合は脂肪族ハロゲン化
炭化水素か使用されている。Soc, P. 803 (1945) and JP-A-1983
Publication No.-126829 discloses that 1.
1-dichloro1y-2,2-bis(4-chlorophenyl)
A method for oxidizing ethylene with nitric acid is described,
As the organic solvent, acetic acid is used in the case described in the former publication, and an aliphatic halogenated hydrocarbon is used in the latter publication.
発明か解決しようとする課題
しかしながら、ハロベンゾフェノン誘導体を製造する」
１記従来の方法は、種々の問題点を有していた。即ち、
クロムｔｉｈ化による方法は、反応において多量のクロ
ム酸を消費することに加えて、廃液処理などの環境問題
に対処する必要があり、多額の費用を要する為、工業的
に実施するのは困難な状況にあった。However, the problem to be solved by the invention is to produce halobenzophenone derivatives.
1. The conventional methods had various problems. That is,
The method based on chromium tihing consumes a large amount of chromic acid in the reaction, and in addition, it is necessary to deal with environmental problems such as waste liquid treatment, and it requires a large amount of cost, so it is difficult to implement it industrially. I was in a situation.
また、硝酸酸化による方法は、有機溶媒を反応にｆ・を
用するため、有機溶媒回収のために多大なエネルギーを
要するほか、環境問題についても問題を残している。例
えは、脂肪族ハロゲン化炭化水素溶媒を使用する場合に
は、環境に対する影響が懸念されており、将来、規制が
強化されることが確実となっているという問題がある。Further, the method using nitric acid oxidation uses f. in an organic solvent for the reaction, and therefore requires a large amount of energy to recover the organic solvent, and also has environmental problems. For example, when using aliphatic halogenated hydrocarbon solvents, there are concerns about their impact on the environment, and there is a problem in that regulations are certain to be tightened in the future.
したがって、硝酸酸化による方法の場合も、有機溶媒を
使用する為に、経済的な観点から、或いは環境問題とい
う点から、実用上問題がある。なお、１．１−ジクロロ
−２，２−ビス（４−クロロフェニル）エチレンの硝酸
酸化において、有機溶媒を使用しないと、ニトロ化物が
生成し、目的とする４、４°−ジクロロペンゾフエノン
の収率が低いことが明らかとなっているため＜ ０．０
． Ｂａｃｋｅｂｅｒａ、Ｊ、１．、Ｃ。Therefore, even in the case of the method using nitric acid oxidation, since an organic solvent is used, there are practical problems from an economic point of view or an environmental point of view. In addition, in the nitric acid oxidation of 1,1-dichloro-2,2-bis(4-chlorophenyl)ethylene, if an organic solvent is not used, a nitrate will be produced, and the target 4,4°-dichloropenzophenone will not be produced. < 0.0 as it is clear that the yield is low
．． Backebera, J., 1. ,C.
Ｈａｒａｉｓ、 Ｊ、 ＣｈａＩｌ、Ｓｏｃ、、Ｐ、１
１０３［１９４５） ） 、従来、硝酸酸化による方法
においては、有機溶媒の使用が不可欠であった。Harais, J., ChaIl,Soc,,P,1
103 [1945)), conventional methods using nitric acid oxidation have required the use of organic solvents.
したがって、本発明は、上記の如き現状に鑑みてなされ
たものである。したがって、本発明の目的は、従来の技
術における上記のような問題点のない、ハロベンゾフェ
ノン誘導体の新規な製造方法を提供することにある。Therefore, the present invention has been made in view of the above-mentioned current situation. Therefore, an object of the present invention is to provide a novel method for producing halobenzophenone derivatives that does not have the above-mentioned problems in the conventional techniques.
課題を解決するための手段
本発明者等は、ハロベンゾフェノン誘導体の製造法に関
し、従来使用されている反応原料とは異なる物質を使用
する、未だ技術的に開示されていない新規な方法につい
て検討した結果、下記一般式（Ｉ＞
（式中、Ｘ及びＹは同一でも異なってもよく、それぞれ
Ｆ、ＣＩ、Ｂｒまたは■を表わし、ｍは１〜４の整数を
表わし、ｎは０〜４の整数を表わす）で表わされる化合
物を反応原料として使用し、特定の比重の硝酸水溶液を
用いて酸化を行うことにより、下記一般式（ｎ）
（式中、Ｘ、Ｙ、ｍ及びｎは、それぞれ前記に同じ）
で表わされるハロベンゾフェノン誘導体が、ニトロ化合
物を殆ど生成させることなく、短時間かう高収率で得ら
れることを見出し、本発明を完成するに至った。Means for Solving the Problems The present inventors have investigated a novel method for producing halobenzophenone derivatives, which has not yet been technically disclosed, and uses a substance different from the reaction raw materials conventionally used. As a result, the following general formula (I> (wherein, X and Y may be the same or different, each represents F, CI, Br or (representing an integer) is used as a reaction raw material, and by performing oxidation using a nitric acid aqueous solution of a specific specific gravity, the following general formula (n) (wherein, X, Y, m and n are each The present inventors have discovered that a halobenzophenone derivative represented by (same as above) can be obtained in a high yield in a short period of time without generating almost any nitro compound, and have completed the present invention.
即ち５本発明は、前記一般式（Ｉ＞で表わされる化合物
を、比重（於２０℃） １．３５以下の硝酸水溶液によ
り酸化することによって、前記一般式（ＩＩ）で表わさ
れるハロベンゾフェノン誘導体を製造することを’４！
ｔ＠とする。したがって、本発明は有機溶媒を用いるこ
となく、反応原料と硝酸水溶液という最も革純な反応系
で反応が行われるという特徴を有している。That is, 5 the present invention provides a halobenzophenone derivative represented by the general formula (II) by oxidizing the compound represented by the general formula (I>) with an aqueous nitric acid solution having a specific gravity (at 20°C) of 1.35 or less. '4 to manufacture!
Let it be t@. Therefore, the present invention is characterized in that the reaction is carried out in the purest reaction system of a reaction raw material and an aqueous nitric acid solution without using an organic solvent.
本発明において反応原料とする前記一般式（Ｉ＞で表さ
れる化合物とは、１，１．−ジ（ハロフェニル）エチレ
ン、または１−（ハロフェニル）−１−フェニルエチレ
ンであり、ここでハロフェニルとは、Ｆ。In the present invention, the compound represented by the general formula (I>) used as a reaction raw material is 1,1.-di(halophenyl)ethylene or 1-(halophenyl)-1-phenylethylene, where halophenyl Is F.
ＣＩ、Ｂｒ及び工より選択されたハロゲン原子を１〜４
個を有するフェニル基を意味する。従ってその種類は多
岐にわたるが、本発明の目的化合物であるハロベンゾフ
ェノン誘導体の耐熱性高分子用モノマーとしての用途を
考慮するとき、本発明において使用される反応原料とし
ては、１，１−ジ（モノハロフェニル）エチレン類が好
ましい。具体的には
１．１−ジ（フルオロフェニル）エチレン、１−（ブロ
モフェニル）−１−（フルオロフェニル）エチレン、
１−（クロロフェニル）−１−（フルオロフェニル）エ
チレン、
１−（フルオロフェニル）−１−（ヨードフェニル）エ
チレン、
１１−ジ（クロロフェニル）エチレン、１−（ブロモフ
ェニル）−１−（クロロフェニル）エチレン、
１−（クロロフェニル）−１−（ヨードフェニル）エチ
レン
１．１−ジ（ブロモフェニル）エチレン、１−（ブロモ
フェニル）−１−（ヨー１４フエニル）エチレン
１．１−ジ（ヨードフェニル）エチレン、の各々の異性
体があげられる。1 to 4 halogen atoms selected from CI, Br and Engineering
means a phenyl group having . Therefore, there are a wide variety of types, but when considering the use of halobenzophenone derivatives, which are the target compounds of the present invention, as monomers for heat-resistant polymers, the reaction raw materials used in the present invention include 1,1-di( Monohalophenyl)ethylenes are preferred. Specifically, 1.1-di(fluorophenyl)ethylene, 1-(bromophenyl)-1-(fluorophenyl)ethylene, 1-(chlorophenyl)-1-(fluorophenyl)ethylene, 1-(fluorophenyl) -1-(iodophenyl)ethylene, 11-di(chlorophenyl)ethylene, 1-(bromophenyl)-1-(chlorophenyl)ethylene, 1-(chlorophenyl)-1-(iodophenyl)ethylene 1.1-di( Bromophenyl)ethylene, 1-(bromophenyl)-1-(io14phenyl)ethylene, and 1,1-di(iodophenyl)ethylene.
上記例示した化合物のエチレン骨格が本発明の方法によ
り酸化され、各々の反応原料から対応するベンゾフェノ
ン誘導体が得られる９本発明の方法によって得られる上
記一般式（ＩＩ）で表わされるへロペンゾフエノン誘導
体の代表的なものとしては、４，４°−ジクロロベンゾ
フェノン、２．４−ジクロロベンゾフェノン、４，４゛
−ジブロモベンゾフェノン等があげられる。The ethylene skeleton of the above-exemplified compounds is oxidized by the method of the present invention, and the corresponding benzophenone derivatives are obtained from each reaction raw material. 9. Representative of the heropenzophenone derivatives represented by the above general formula (II) obtained by the method of the present invention. Examples include 4,4°-dichlorobenzophenone, 2,4-dichlorobenzophenone, and 4,4′-dibromobenzophenone.
また、本発明に於いて使用される硝酸水溶液は、比重（
於２０℃）が１．３５以下でなければならない。In addition, the nitric acid aqueous solution used in the present invention has a specific gravity (
(at 20°C) must be 1.35 or less.
比重が１．３５よりも大きいと、副反応であるニトロ化
か起り易くなる。一方比重が１．０付近になると反応性
が著しく低下するので、比重は１．０以上であることが
望ましい、より好ましい硝酸水溶液の比重く於２０°Ｃ
）は、１．０５ないし１．２５の範囲である。When the specific gravity is greater than 1.35, nitration, which is a side reaction, tends to occur. On the other hand, when the specific gravity is around 1.0, the reactivity decreases significantly, so it is desirable that the specific gravity is 1.0 or more.
) ranges from 1.05 to 1.25.
反応温度は、０°Ｃ〜１５０℃の範囲であるが、硝酸水
溶液の比重が大きい場合は低温側で、また、硝酸水溶液
の比重が小さい場合は高温側で反応させる方が好ましい
。The reaction temperature is in the range of 0° C. to 150° C., but it is preferable to carry out the reaction at a low temperature side when the specific gravity of the nitric acid aqueous solution is high, and at a high temperature side when the specific gravity of the nitric acid aqueous solution is low.
反応時間、及び反応原料と硝酸水溶液との比率について
は、用いる硝酸水溶液の比重と反応温度とによっても異
なるが、反応時間は、通常、１分間〜１００時間の範囲
であり、好ましくは、５分間〜５０時間の範囲である。The reaction time and the ratio of the reaction raw material to the nitric acid aqueous solution vary depending on the specific gravity of the nitric acid aqueous solution used and the reaction temperature, but the reaction time is usually in the range of 1 minute to 100 hours, preferably 5 minutes. ~50 hours.
また、反応原料と硝酸水溶液との比率は、反応原料／硝
酸水溶液＝Ｏ，ＯＯ１〜５０（重量比）の範囲であるか
、好ましくは、反応原料／硝酸水溶液＝０．００５〜５
（重量比）の範囲である。Further, the ratio of the reaction raw material to the nitric acid aqueous solution is in the range of reaction raw material/nitric acid aqueous solution = O, OO 1 to 50 (weight ratio), or preferably, reaction raw material / nitric acid aqueous solution = 0.005 to 5.
(weight ratio).
なお、反応時に於ける圧力は、特に限定はされないが、
通常、常圧下、或いは加圧下にて行われる。また、反応
は、酸素雰囲気下や空気雰囲気下、若しくは不活性ガス
雰囲気下の何れに於いても行うことができ、特に制限は
されない、更に、反応様式についても、四分式、連続式
の何れを採用することも可能である。Note that the pressure during the reaction is not particularly limited, but
Usually, it is carried out under normal pressure or under increased pressure. In addition, the reaction can be carried out under an oxygen atmosphere, an air atmosphere, or an inert gas atmosphere, and there is no particular restriction. Furthermore, the reaction mode can be either a four-part type or a continuous type. It is also possible to adopt
本発明によると、例えば４，４゛−ジクロロベンゾフェ
ノンが主生成物の場合など、反応生成物によっては、反
応終了後、反応液を単に冷却、炉別するだけで、ハロベ
ンゾフェノン類を結晶として分離・回収できるため、反
応後の分離・精製操作が容易であるという利点がある。According to the present invention, depending on the reaction product, for example, when 4,4'-dichlorobenzophenone is the main product, halobenzophenones can be separated as crystals by simply cooling and furnace-separating the reaction solution after the completion of the reaction.・Since it can be recovered, it has the advantage that separation and purification operations after the reaction are easy.
そして、以上の操作に、洗浄・有機溶媒による抽出、晶
析、減圧蒸溜などの通常の分離・精製操作を適宜組合せ
れば、より窩純度の反応生成物を得ることができる。If the above operations are appropriately combined with ordinary separation and purification operations such as washing, extraction with an organic solvent, crystallization, and distillation under reduced pressure, a reaction product with higher purity can be obtained.
実施例
以下に、実施例を示して本発明を更に説明するが、本発
明はこれらの実施例に限定されるものではない。なお、
以下の実施例および比較例における転化率および収率は
それぞれ下記式により算出したものである。EXAMPLES The present invention will be further explained below with reference to Examples, but the present invention is not limited to these Examples. In addition,
The conversion rates and yields in the following Examples and Comparative Examples were calculated using the following formulas.
仕込み原料（モル）
一残存原料（モル）
転化率（％） ＝ ｘ１００仕
込み原料（モル）
生成！ｌｌ７（モル）
収率（％）＝
×１００
仕込み原料（モル）
実施例１
撹拌機を備えた２００ ｍｌのフラスコに、１．１−ビ
ス（４−クロロフェニル）エチレンを５．０ 、、そし
て比重１．２０の硝酸を８５ｍ１仕込み〔反応原料／硝
酸水溶液＝０．０４９ （重量比）〕、混合物を９４
℃に加熱した後、窒素雰囲気下で激しく撹拌しながら３
時間反応を続けた。その後、反応液を冷却し、析出した
結晶をジクロロメタンで抽出した。ジクロロメタン層を
十分に水洗した後、ガスクロマトグラフィーで分析、定
量したところ、１．１−ビス（４−クロロフェニル）エ
チレン転化率は８８４２％、４．４’−ジクロロベンゾ
フェノン収率は６０．０％であった。Charged raw material (mol) 1 remaining raw material (mol) Conversion rate (%) = x100 Charged raw material (mol) Production! 17 (mol) Yield (%) = ×100 Raw materials (mol) Example 1 In a 200 ml flask equipped with a stirrer, 1.1-bis(4-chlorophenyl)ethylene was added at a concentration of 5.0, and the specific gravity was Pour 85ml of 1.20% nitric acid [reaction raw material/nitric acid aqueous solution = 0.049 (weight ratio)], and add 94ml of the mixture.
After heating to 3°C with vigorous stirring under nitrogen atmosphere,
The reaction continued for hours. Thereafter, the reaction solution was cooled, and the precipitated crystals were extracted with dichloromethane. After thoroughly washing the dichloromethane layer with water, it was analyzed and quantified by gas chromatography, and the conversion rate of 1.1-bis(4-chlorophenyl)ethylene was 8842%, and the yield of 4.4'-dichlorobenzophenone was 60.0%. Met.
実施例２
撹拌機を備えた２００ ｍｌのフラスコに、１．１−ビ
ス（４−クロロフェニル）エチレンを５．Ｏｇ、そして
比重１．１０の硝酸を８５ｍ１仕込み〔反応原料／硝酸
水溶液＝Ｏ，ＯＳ・３ （重量比）〕、混合物を８５℃
に加熱した後、窒素雰囲気下で激しく撹拌しながら６時
間反応を続けた。その後、反応液を冷却し、析出した結
晶をジクロロメタンで抽出した。ジクロロメタン層を十
分に水洗した後、ガスクロマトグラフィーで分析、定量
したところ、１．１−ビス（４−クロロフェニル）エチ
レン転化率は８４．６％、４．４’−ジクロロベンゾフ
ェノン収率は７４．１％であった。Example 2 In a 200 ml flask equipped with a stirrer, 5.5% of 1.1-bis(4-chlorophenyl)ethylene was added. Charge Og and 85 ml of nitric acid with a specific gravity of 1.10 [reaction raw material/nitric acid aqueous solution = O, OS・3 (weight ratio)], and heat the mixture at 85°C.
The reaction was continued for 6 hours with vigorous stirring under a nitrogen atmosphere. Thereafter, the reaction solution was cooled, and the precipitated crystals were extracted with dichloromethane. After thoroughly washing the dichloromethane layer with water, it was analyzed and quantified by gas chromatography, and the conversion rate of 1.1-bis(4-chlorophenyl)ethylene was 84.6%, and the yield of 4.4'-dichlorobenzophenone was 74. It was 1%.
比較例
撹拌機を備えた２００ ｒｏｆのフラスコに、１．１−
ビス（４−クロロフェニル）エチレンを５．０ｇ、そし
て比重１．４２の硝酸水溶液を８５ｍ１仕込み〔反応原
料／硝酸水ｆ＃液＝０．０４１ （重量比）〕、混合
物を８０℃に加熱した後、窒素雰囲気下で激しく撹拌し
ながら１時間量反応を続けた。その後、反応液を冷却し
、析出しな結晶をジクロロメタンで抽出した。Comparative Example In a 200 rof flask equipped with a stirrer, 1.1-
After charging 5.0 g of bis(4-chlorophenyl)ethylene and 85 ml of a nitric acid aqueous solution with a specific gravity of 1.42 [reaction raw material/nitric acid aqueous f# liquid = 0.041 (weight ratio)] and heating the mixture to 80°C. The reaction was continued for 1 hour under a nitrogen atmosphere with vigorous stirring. Thereafter, the reaction solution was cooled, and precipitated crystals were extracted with dichloromethane.
ジクロロメタン層を十分に水洗した後、カスクロマトグ
ラフィーで分析、定量したところ、１，１−ビス（４−
クロロフェニル）エチレン転化率は９８．０％、４．４
′−ジクロロベンゾフェノン収率は９．４％であり、主
生成物は４，４゛−ジクロロベンゾフェノンのニトロ化
物であった。After thoroughly washing the dichloromethane layer with water, analysis and quantitative analysis using gas chromatography revealed that 1,1-bis(4-
Chlorophenyl) ethylene conversion rate is 98.0%, 4.4
The yield of '-dichlorobenzophenone was 9.4%, and the main product was a nitrated product of 4,4'-dichlorobenzophenone.
発明の効果
実施例１〜２と比較例とを比べて明らかなように、本発
明の方法は、転化率及び目的生成物の収率が著しく高い
、そして、本発明によれば、反応原料である前記一般式
（Ｉ）で表わされる１、１−ジ（ハロフェニル）エチレ
ンまたは１−（ハロフェニル）−１−エチレンと、硝酸
水溶液とよりなる、最も単純な反応系により、簡便かつ
極めて高収率で前記一般式＜ＩＩ）で表されるへロペン
ゾフエノン誘導体を製造することができる。しかも、本
発明においては、有機溶媒を反応系に用いていないため
、以後の分離・精製操作も簡便かつ経済的であるという
利点も有する。したがって、本発明によれば、へロペン
ゾフェノン誘導体を工業的に有利に製造することが可能
である。Effects of the Invention As is clear from comparing Examples 1 and 2 with Comparative Examples, the method of the present invention has a significantly high conversion rate and a yield of the target product, and according to the present invention, the reaction raw material is The simplest reaction system consisting of 1,1-di(halophenyl)ethylene or 1-(halophenyl)-1-ethylene represented by the above-mentioned general formula (I) and an aqueous nitric acid solution enables simple and extremely high yields. The heropenzophenone derivative represented by the above general formula <II) can be produced. Moreover, in the present invention, since no organic solvent is used in the reaction system, the subsequent separation and purification operations are also advantageous in that they are simple and economical. Therefore, according to the present invention, it is possible to industrially advantageously produce heropenzophenone derivatives.
特許出願人 呉羽化学工業株式会社
代理人 弁理士 液部 剛
手続補正書
（自発）
平成元年４月６ 日
特許庁長官 吉 １）文 毅 殿
１、事件の表示
昭和６３年 特許願 第１８６７８９号２、発明の名称
へロペンゾフエノン誘導体の製造方法
代表者
児玉 俊一部
４、代理人
住所
〒１０１
東京都千代田区神田錦町１丁目８番５号６、補正の内容
（１） 明細書第７頁第２０行目の「異性体があげら
れる。」の次に下記の記載を挿入する。Patent Applicant Kureha Chemical Industry Co., Ltd. Agent Patent Attorney Tsuyoshi Liquidbe Procedural Amendment (spontaneous) April 6, 1989 Director General of the Patent Office Yoshi 1) Takeshi Moon 1, Indication of Case 1986 Patent Application No. 186789 2. Name of the invention Process for producing lopenzophenone derivatives Representative Shun Kodama Part 4 Address of agent 1-8-5-6 Kanda Nishiki-cho, Chiyoda-ku, Tokyo 101 Contents of amendment (1) Description page 7 No. 20 Insert the following statement next to "Isomers are included." in line 1.
「即ち、上記のブロモフェニル、クロロフェニル、フロ
ロフェニル、およびヨードフェニルとはＢｒ、Ｃｌ５Ｆ
およびＩ原子がフェニル基上のいずれの位置に結合した
ものであってもよいことを意味する。」
（２） 同第８頁第１３行目から第１４行目の「比重
は１．０以上であることが望ましい。より」を削除する
。"That is, the above bromophenyl, chlorophenyl, fluorophenyl, and iodophenyl are Br, Cl5F
and means that the I atom may be bonded to any position on the phenyl group. ” (2) Delete “It is desirable that the specific gravity is 1.0 or more.” from lines 13 to 14 on page 8.
（３） 同第８真下から第５行目の「０℃〜１５０℃
」の次に［好ましくは３０〜１２０℃」を挿入する。(3) “0°C to 150°C” on the 5th line from the bottom of No. 8
” followed by “preferably 30 to 120°C”.
（５）同第９頁第７行目の「（重量比）」の次に「更に
好ましくは０．０１〜１（重量比）」を加入する。(5) Add "more preferably 0.01 to 1 (weight ratio)" next to "(weight ratio)" on page 9, line 7.
（６） 同第１１頁第１行目の「比重１．２０の硝酸
」を「比重１．２０ （於２０℃）の硝酸水溶液」に補
正する。(6) Correct "nitric acid with a specific gravity of 1.20" in the first line of page 11 to "nitric acid aqueous solution with a specific gravity of 1.20 (at 20°C)".
（７） 同第１１頁下から第７行目の「比重１．１０
の硝酸」を「比重１．１０ （於２０℃）の硝酸水溶液
」に補正する。(7) “Specific gravity 1.10” on page 11, line 7 from the bottom
of nitric acid" is corrected to "nitric acid aqueous solution with a specific gravity of 1.10 (at 20°C)."
（８） 同第１２頁第６行目の「比重１．４２Ｊを「
比重１．４２ （於２０℃）」に補正する。(8) "Specific gravity 1.42J" on page 12, line 6 of the same
Correct the specific gravity to 1.42 (at 20°C).
以上
（４） 同第９頁第４行目の「範囲である。」を「範
囲であり１、更に好ましくは、１時間〜１０時間である
。」に補正する。Above (4) "It is a range." on the 4th line of page 9 is corrected to "It is a range of 1, more preferably 1 hour to 10 hours."
Claims (1)
Ｆ、Ｃｌ、ＢｒまたはＩを表わし、ｍは１〜４の整数を
表わし、ｎは０〜４の整数を表わす）で表わされる化合
物を比重（於２０℃）１．３５以下の硝酸水溶液により
酸化することを特徴とする下記一般式（II） ▲数式、化学式、表等があります▼（II） （式中、Ｘ、Ｙ、ｍ及びｎは、それぞれ前記に同じ） で表わされるハロベンゾフェノン誘導体の製造方法。(1) The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, X and Y may be the same or different and each represents F, Cl, Br or I, and m is (representing an integer of 1 to 4, n represents an integer of 0 to 4) is oxidized with a nitric acid aqueous solution having a specific gravity (at 20°C) of 1.35 or less, according to the following general formula (II). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) A method for producing a halobenzophenone derivative represented by (in the formula, X, Y, m, and n are each the same as above).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18678988A JPH0240340A (en) | 1988-07-28 | 1988-07-28 | Production of halobenzophenone derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18678988A JPH0240340A (en) | 1988-07-28 | 1988-07-28 | Production of halobenzophenone derivative |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0240340A true JPH0240340A (en) | 1990-02-09 |
Family
ID=16194615
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18678988A Pending JPH0240340A (en) | 1988-07-28 | 1988-07-28 | Production of halobenzophenone derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0240340A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6329648A (en) * | 1986-07-19 | 1988-02-08 | 松下電工株式会社 | Production of deodorant |
| US5592791A (en) * | 1995-05-24 | 1997-01-14 | Radix Sytems, Inc. | Active controller for the attenuation of mechanical vibrations |
| US5819484A (en) * | 1995-07-28 | 1998-10-13 | Kar; Ramapada | Building structure with friction based supplementary damping in its bracing system for dissipating seismic energy |
-
1988
- 1988-07-28 JP JP18678988A patent/JPH0240340A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6329648A (en) * | 1986-07-19 | 1988-02-08 | 松下電工株式会社 | Production of deodorant |
| JPH0351187B2 (en) * | 1986-07-19 | 1991-08-06 | Matsushita Electric Works Ltd | |
| US5592791A (en) * | 1995-05-24 | 1997-01-14 | Radix Sytems, Inc. | Active controller for the attenuation of mechanical vibrations |
| US5819484A (en) * | 1995-07-28 | 1998-10-13 | Kar; Ramapada | Building structure with friction based supplementary damping in its bracing system for dissipating seismic energy |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US2870206A (en) | Preparation of benzophenone-azine | |
| GB1062482A (en) | High quality phthalic acids | |
| JPH0240340A (en) | Production of halobenzophenone derivative | |
| JP2000309558A (en) | Production of 2-adamanthyl(meth)acrylate compound | |
| JPS5925779B2 (en) | Isomerization method for stereoisomeric alicyclic diamines | |
| JPS62241926A (en) | Production of polysilane | |
| KR940011421A (en) | Continuous Production Method of Aromatic Aldehyde | |
| JPH0240339A (en) | Production of halobenzophenone derivative | |
| JPS6121455B2 (en) | ||
| JPS62108839A (en) | Production of 3-fluorobenzoic acid compound | |
| US3978118A (en) | Process for converting styrene or polystyrene to nitrobenzoic acids | |
| JPH0327338A (en) | Production of bis(2-hydroxyhexafluoro-2-propyl)-benzene derivative | |
| JP2003055288A (en) | Method for distilling oxystyrene derivative | |
| US3963751A (en) | Chlorination of butadiene sulfone to 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide | |
| JPH0625079A (en) | Production of aromatic tetracarboxylic acid | |
| GB1511181A (en) | Preparation of terephthalic acid by oxidation of p-xylene | |
| US3978117A (en) | Process for converting styrene bottoms to nitrobenzoic acids | |
| US4388251A (en) | Method for preparing 2-chlorobenzoyl chloride | |
| JPS6030297B2 (en) | Method for producing 1,1,3-trisubstituted-3-phenylindanes | |
| JPS6284093A (en) | Group v metal ethane dithiolate complex and production thereof | |
| JPS5940151B2 (en) | Method for producing 1-phthalazinone | |
| JPH0827041A (en) | Production of divinylbenzene | |
| JPS6261989A (en) | Production of aromatic titanocene compound | |
| JPS5940809B2 (en) | Method for producing P-methylacetophenone | |
| JPS59219286A (en) | Novel bicycloorthoester compound |