JPH02117635A - Production of benzophenones - Google Patents
Production of benzophenonesInfo
- Publication number
- JPH02117635A JPH02117635A JP63269423A JP26942388A JPH02117635A JP H02117635 A JPH02117635 A JP H02117635A JP 63269423 A JP63269423 A JP 63269423A JP 26942388 A JP26942388 A JP 26942388A JP H02117635 A JPH02117635 A JP H02117635A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- condensation reaction
- carbon tetrachloride
- dehydrohalogenation
- aromatic compound
- 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
- 239000012965 benzophenone Substances 0.000 title claims abstract description 12
- 150000008366 benzophenones Chemical class 0.000 title claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims abstract description 34
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000001491 aromatic compounds Chemical class 0.000 claims abstract description 12
- 238000006704 dehydrohalogenation reaction Methods 0.000 claims abstract description 12
- 229910000323 aluminium silicate Inorganic materials 0.000 claims abstract description 10
- 238000006482 condensation reaction Methods 0.000 claims abstract description 9
- 239000007809 chemical reaction catalyst Substances 0.000 claims abstract description 5
- 239000003377 acid catalyst Substances 0.000 claims abstract description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 5
- 238000000034 method Methods 0.000 abstract description 14
- 239000002994 raw material Substances 0.000 abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 9
- 239000003054 catalyst Substances 0.000 abstract description 8
- 239000010457 zeolite Substances 0.000 abstract description 8
- 229910021536 Zeolite Inorganic materials 0.000 abstract description 7
- -1 mono-substituted benzene Chemical class 0.000 abstract description 7
- YLCPDXXGHPHTFJ-UHFFFAOYSA-N diphenylmethanone;dihydrochloride Chemical class Cl.Cl.C=1C=CC=CC=1C(=O)C1=CC=CC=C1 YLCPDXXGHPHTFJ-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000377 silicon dioxide Substances 0.000 abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 3
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 230000001413 cellular effect Effects 0.000 abstract 1
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 10
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- RLUFBDIRFJGKLY-UHFFFAOYSA-N (2,3-dichlorophenyl)-phenylmethanone Chemical compound ClC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1Cl RLUFBDIRFJGKLY-UHFFFAOYSA-N 0.000 description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052680 mordenite Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 101100514056 Rhodobacter capsulatus modD gene Proteins 0.000 description 2
- 150000001555 benzenes Chemical class 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- GOYDNIKZWGIXJT-UHFFFAOYSA-N 1,2-difluorobenzene Chemical compound FC1=CC=CC=C1F GOYDNIKZWGIXJT-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 101150096839 Fcmr gene Proteins 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000007033 dehydrochlorination reaction Methods 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 150000004816 dichlorobenzenes Chemical class 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- OPTDDWCXQQYKGU-UHFFFAOYSA-N diphenyldichloromethane Chemical compound C=1C=CC=CC=1C(Cl)(Cl)C1=CC=CC=C1 OPTDDWCXQQYKGU-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- 239000008096 xylene 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
- 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、ベンゾフェノン類の製造方法に関し、詳しく
は芳香族化合物と四塩化炭素を脱ハロゲン化水素縮合さ
せベンゾフェノンジクロライド類とし、ついで加水分解
してベンゾフェノン類を製造する方法において、脱ハロ
ゲン化水素縮合反応触媒として結晶性アルミノシリケー
トを用いることを特徴とするベンゾフェノン類の製造方
法に関する。Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a method for producing benzophenones, and more specifically, dehydrohalogenation condensation of an aromatic compound and carbon tetrachloride to produce benzophenone dichlorides, followed by hydrolysis. The present invention relates to a method for producing benzophenones, characterized in that a crystalline aluminosilicate is used as a dehydrohalogenation condensation reaction catalyst.
（従来の技術）
芳香族化合物と四塩化炭素を無水塩化アルミニウムを用
いフリーデルクラフッ反応を行わせ、ついで、加水分解
してベンゾフェノンを得る方法は古くから知られている
。例えば、Ｏｒｇａｎｉｃ ５ｙｎｔｈｅｓｉｓ Ｃｏ
１１． Ｖｏｌ、 １ 、９５ （１９４８）には、無
水塩化アルミニウムの存在下にベンゼンと四塩化炭素よ
りベンゾフェノンを合成する方法が、ケミカルアフスト
ラクｌ−，７１，４８０６６には、無水塩化アルミニウ
ムを用い、ハロゲン化ベンゼンと四塩化炭素より２．４
”−ジクロロベンゾフェノンおよび４，４゛−ジクロロ
ベンゾフェノンを略１：１で合成する方法等が記載され
ている。また、特開昭５８−１３１９２５号公報には、
ｍ−ジクロロヘンゼンと四塩化炭素より塩化アルミニウ
ムの存在下に２．２’、４４°−テトラクロロベンゾフ
ェノンジクロリドを製造する方法が記載されている。(Prior Art) A method has long been known in which an aromatic compound and carbon tetrachloride are subjected to a Friedel-Crach reaction using anhydrous aluminum chloride, and then hydrolyzed to obtain benzophenone. For example, Organic 5ynthesis Co.
11. Vol. 1, 95 (1948) describes a method for synthesizing benzophenone from benzene and carbon tetrachloride in the presence of anhydrous aluminum chloride, and Chemical Afstrak L-, 71, 48066 describes a method for synthesizing benzophenone from benzene and carbon tetrachloride in the presence of anhydrous aluminum chloride. 2.4 from benzene and carbon tetrachloride
A method for synthesizing ``-dichlorobenzophenone and 4,4''-dichlorobenzophenone in a ratio of approximately 1:1 is described.In addition, JP-A-58-131925 discloses,
A method for preparing 2.2',44°-tetrachlorobenzophenone dichloride from m-dichlorohenzene and carbon tetrachloride in the presence of aluminum chloride is described.
（発明が解決しようとする課題）
しかしながら、従来の技術は、無水塩化アルミニウム等
のフリーデルクラフッ反応触媒を原料芳香族化合物に対
して等モル以上必要とし、使用塩化アルミニウムの再使
用は困難であり、処理も大変である。また、モノ置換ベ
ンゼンから特に有用な異性体である４、４°置換ベンゾ
フエノンを選択的に合成することができない等の問題点
を有している。(Problem to be solved by the invention) However, the conventional technology requires at least the same mole of Friedel-Crach reaction catalyst such as anhydrous aluminum chloride to the raw material aromatic compound, and it is difficult to reuse the used aluminum chloride. Yes, and it is difficult to process. Further, it has problems such as the inability to selectively synthesize 4,4°-substituted benzophenone, which is a particularly useful isomer, from monosubstituted benzene.
（課題を解決するための手段）
本発明者らは、芳香族化合物と四塩化炭素より前述の問
題点を解決し工業的に製造する方法について鋭意検討を
加えた結果、芳香族化合物と四塩化炭素より脱ハロゲン
化水素縮合によりベンゾフェノンジクロライド類とし、
ついで加水分解することによりベンゾフェノンを得る方
法において、脱ハロゲン化水素縮合反応触媒として、結
晶性アルミノシリケートが適用できることを見出し、本
発明を完成したものである。(Means for Solving the Problems) The present inventors have conducted intensive studies on a method for industrially producing aromatic compounds and carbon tetrachloride to solve the above-mentioned problems. Benzophenone dichlorides are produced by dehydrohalogenation condensation from carbon,
In a method for obtaining benzophenone by subsequent hydrolysis, the inventors have discovered that crystalline aluminosilicate can be used as a dehydrohalogenation condensation reaction catalyst, and have completed the present invention.
本発明に用いられる芳香族化合物としては、ベンゼンお
よび置換ベンゼン等が挙げられ、具体的には、ベンゼン
、トルエン、キシレン等のアルキルベンゼン、クロロベ
ンゼン、フルオロベンゼン、ジクロロベンゼン、ジフル
オロベンゼン等のハロゲン化ベンゼン等を挙げることが
できる。Aromatic compounds used in the present invention include benzene and substituted benzenes, and specifically include benzene, alkylbenzenes such as toluene and xylene, halogenated benzenes such as chlorobenzene, fluorobenzene, dichlorobenzene, and difluorobenzene, etc. can be mentioned.
特にモノ置換ベンゼン、例えば、クロロベンゼンを芳香
族化合物原料として用いた場合は、工業的に有用な４．
４°−ジクロロ異性体を高い選択率で得ることができる
。In particular, when monosubstituted benzene, such as chlorobenzene, is used as a raw material for aromatic compounds, industrially useful 4.
The 4°-dichloro isomer can be obtained with high selectivity.
本発明に用いる結晶性アルミノシリケートとしては、有
効細孔径が６Å以上のものが好ましく、シリカ／アルミ
ナモル比としては４以上、２００以下が好ましい。これ
ら結晶性アルミノシリケートの代表例としては、Ｙ型ゼ
オライト、モルデナイト、β型ゼオライト、ＺＳＭ−４
、ＺＳＭ−１２、Ｌ型ゼオライト、ダメリナイト等を挙
げることができる。The crystalline aluminosilicate used in the present invention preferably has an effective pore diameter of 6 Å or more, and a silica/alumina molar ratio of 4 or more and 200 or less. Representative examples of these crystalline aluminosilicates include Y-type zeolite, mordenite, β-type zeolite, and ZSM-4.
, ZSM-12, L-type zeolite, damelinite, and the like.
これら結晶性アルミノシリケートゼオライトは、水素カ
チオンあるいは多価金属カチオン等でイオン交換し、活
性化されて用いられる。水素カチオンが特に好ましい。These crystalline aluminosilicate zeolites are used after being activated by ion exchange with hydrogen cations or polyvalent metal cations. Particularly preferred are hydrogen cations.
さらに、ＩＢ族、■族、■族、■族の金属成分を含有さ
せてもよい。Furthermore, a metal component of group IB, group ①, group ①, or group ② may be contained.
本発明に用いられる反応条件としては、通常、１００〜
５００°Ｃ１好ましくは２００〜４５０°Ｃ１さらに好
ましくは３００〜４００°Ｃの反応温度、原料芳香族化
合物／四塩化炭素のモル比としては０．１〜１００、好
ましくは１〜５０が用いられる。さらに、反応系に窒素
等の不活性ガスあるいは希釈剤としてトリクロロベンゼ
ン等を加えてもよい。原料供給速度としては、重量時間
空間速度（ＷＨ３Ｖ）で０．０５〜２０ｈｒ−’、好ま
しくは０．１〜１０ｈｒ−’が用いられる。The reaction conditions used in the present invention are usually 100-
The reaction temperature is 500°C, preferably 200 to 450°C, more preferably 300 to 400°C, and the molar ratio of raw material aromatic compound/carbon tetrachloride is 0.1 to 100, preferably 1 to 50. Furthermore, an inert gas such as nitrogen or trichlorobenzene as a diluent may be added to the reaction system. As the raw material supply rate, a weight hourly space velocity (WH3V) of 0.05 to 20 hr-', preferably 0.1 to 10 hr-' is used.
原料中に含まれる少量の水分の存在は、脱ハロゲン化水
素縮合とつづいて加水分解を一段で実施できる利点もあ
るが、多量の水分の存在は、安息香酸等の副生を生じ好
ましくない。脱ハロゲン化水素縮合反応時の水分量とし
ては１１０００ｐｐ以下、好ましくは５００ｐｐｍ以下
にするべきである。The presence of a small amount of water contained in the raw material has the advantage that dehydrohalogenation condensation and subsequent hydrolysis can be carried out in one step, but the presence of a large amount of water is undesirable because it causes by-products such as benzoic acid. The amount of water during the dehydrohalogenation condensation reaction should be 11,000 ppm or less, preferably 500 ppm or less.
脱ハロゲン化水素縮合につづいての加水分解反応は、触
媒として前述の結晶性アルミノシリケートを用いること
もできるし、通常の酸触媒等で行うこともできる。反応
条件としては、ベンゾフェノンジクロライド類を別個に
加水分解する場合は、生成ベンゾフェノンジクロライド
に対し等モル以上の水を添加し、通常は１００°Ｃ前後
の温度で実施される。The hydrolysis reaction following the dehydrohalogenation condensation can be carried out using the above-mentioned crystalline aluminosilicate as a catalyst, or can be carried out using a conventional acid catalyst. As for the reaction conditions, when benzophenone dichlorides are separately hydrolyzed, water is added in an amount equal to or more than equimolar amount to the produced benzophenone dichloride, and the reaction is usually carried out at a temperature of about 100°C.
（発明の効果）
本発明の方法によれば、芳香族化合物と四塩化炭素より
脱塩化水素縮合し、ついで加水分解することによりベン
ゾフェノン類を製造するに際し、塩化アルミニウム等の
可溶性触媒を用いることなく固体触媒で実施できるため
、触媒の分離が容易であるし、触媒は繰り返し再使用が
可能である等工業的利点は大である。さらに、モノ置換
ベンゼンを芳香族化合物として用いた場合は、工業的に
有用な４，４゛−異性体比率が高く得られる等の利点も
有している。(Effects of the Invention) According to the method of the present invention, benzophenones can be produced by dehydrochlorination condensation from an aromatic compound and carbon tetrachloride, followed by hydrolysis, without using a soluble catalyst such as aluminum chloride. Since it can be carried out using a solid catalyst, the catalyst can be easily separated, and the catalyst can be repeatedly reused, which has great industrial advantages. Furthermore, when monosubstituted benzene is used as the aromatic compound, it also has the advantage that a high 4,4'-isomer ratio, which is industrially useful, can be obtained.
（実施例）
以下、実施例を挙げて本発明を具体的に示すが、本発明
は、これに限定されるものではない。(Example) Hereinafter, the present invention will be specifically illustrated with reference to Examples, but the present invention is not limited thereto.
実施例１ 市販のモルデナイトゼオライト（東ソ製 Ｓｉｎ。Example 1 Commercially available mordenite zeolite (Sin manufactured by Toso.
／ Ａｊｌ！ ２０３＝２０ ）を常法によりＨ゛交換
、８〜１２メツシユに成型したものをＩＯＭφ×３００
ｍｌの石英製反応管に５ｇ充填し、管状電気炉により
４００°Ｃに加熱し、窒素ガスをＩＡ／Ｈｒで通気し加
熱脱水後、３３０ ’Ｃに温度を設定し、クロロベンゼ
ン／四塩化炭素＝ ２０ ／ １モルの原料を２．５ｃ
ｃ／Ｈｒで供給した。通液後５時間目の溜出反応液を採
取し、ガスクロマトグラフにより分析した結果、４，４
”−ジクロロベンゾフェノンの収率は１５ｍｏｌχ、２
，４′−ジクロロベンゾフェノンの収率は１．２ｍｏｌ
χであった。ただし、収率は四塩化炭素基準である。す
なわち、四塩化炭素を１００ｍｏｌＸとしたときの収率
をｍｏｌχで示した。/Ajl! 203=20) was exchanged with H by the usual method and molded into 8 to 12 meshes to IOMφ×300.
ml of quartz reaction tube was filled with 5 g, heated to 400°C in a tubular electric furnace, nitrogen gas was passed through IA/Hr, heated and dehydrated, the temperature was set at 330'C, and chlorobenzene/carbon tetrachloride = 20/2.5c of 1 mole of raw material
It was supplied at c/hr. The distilled reaction solution was collected 5 hours after passing and analyzed by gas chromatography.
”-The yield of dichlorobenzophenone is 15 molχ, 2
, the yield of 4'-dichlorobenzophenone is 1.2 mol
It was χ. However, the yield is based on carbon tetrachloride. That is, the yield is expressed in molχ when carbon tetrachloride is 100molX.
実施例２
実施例１と同様に、ただし、触媒として脱アルミモルデ
ナイト（ＳｉＯ□／ Ａｊ２ｚＯｓ ＝９６） １０
ｇを用い、クロロベンゼン／四塩化炭素モル比４の原
料を２．５ｃｃ／Ｈｒで供給しまた。反応温度は３４０
°Ｃで行った。その結果、ジクロロベンゾフェノンの選
択率は８０％で、４，４°−ジクロロベンゾフェノンの
収率は１６ｍｏｌχ、２，４゛−ジクロロベンゾフェノ
ンの収率は２ｍｏｌχであった。Example 2 Same as Example 1, except that dealuminated mordenite (SiO□/Aj2zOs = 96) was used as a catalyst 10
A raw material with a chlorobenzene/carbon tetrachloride molar ratio of 4 was supplied at a rate of 2.5 cc/Hr. The reaction temperature is 340
Performed at °C. As a result, the selectivity of dichlorobenzophenone was 80%, the yield of 4,4[deg.]-dichlorobenzophenone was 16 mol[chi], and the yield of 2,4[deg.]-dichlorobenzophenone was 2 mol[chi].
実施例３
実施例１と同様に、ただし、触媒として市販のＹ型ゼオ
ライト（ＳｉＯｚ／ Ａ ｌ ｚ（ｈ ＝ ５ 、 ２
）を常法にしたがいＮＨ４Ｃｆ水溶液でプロトン交換
したものを用いた。その結果、４．４”−ジクロロベン
ゾフェノンの収率は８ｍｏｌχ、２，４”−ジクロロベ
ンゾフェノンの収率は５ｍｏｌＸであった。なお、ジク
ロロベンゾフェノンの選択率は８５％であった。Example 3 Same as Example 1, except that commercially available Y-type zeolite (SiOz/Alz (h = 5, 2
) was proton-exchanged with an aqueous NH4Cf solution according to a conventional method. As a result, the yield of 4.4"-dichlorobenzophenone was 8 molX, and the yield of 2,4"-dichlorobenzophenone was 5 molX. Note that the selectivity of dichlorobenzophenone was 85%.
実施例４
実施例２と同様に、ただし、触媒として脱アルミモルデ
ナイトをさらに硝酸銅水溶液で銅交換した触媒（銅交換
率６０％）を用いて行った。その結果、４．４゛−ジク
ロロベンゾフェノンの収率は１３ｍｏｌχ、その他のジ
クロロベンゼン異性体の収率はＩＯｍｏ１％であった。Example 4 The same procedure as in Example 2 was carried out, except that a catalyst in which dealuminated mordenite was further copper-exchanged with an aqueous copper nitrate solution (copper exchange rate 60%) was used. As a result, the yield of 4.4'-dichlorobenzophenone was 13 molχ, and the yield of other dichlorobenzene isomers was 10mol%.
実施例５
実施例１と同様に、ただし、原料とＬ７てベンゼン／四
塩化炭素モル比２０を用い、反応温度３５０″Ｃで行っ
た。その結果、ジベンヅフエノンの収率は２０ｍｏｌχ
、選択率８．７％であった。Example 5 The same procedure as in Example 1 was carried out, except that the raw materials and L7 were used at a benzene/carbon tetrachloride molar ratio of 20, and the reaction temperature was 350"C. As a result, the yield of dibenduphenone was 20 molχ
, the selectivity was 8.7%.
実施例６
実施例１と同様に、ただし、触媒として、米国特許筒３
，３０８．０６９号記載の方法にしたがって、テトラエ
チルアンモニウムハイドロキサイド１０％水溶液５００
ｇを茎留水２５０ｇに熔解させた液に、アルミン酸ソー
ダ１９．９ｇを攪拌上混合し、ついでシリカパウダー１
６９ｇを混合した。この原料混合物を１ｆ！、のテフロ
ンコーティング製オートクレーブに仕込み、１５０ ’
Ｃで２００ ｒｐｍ （Ｄｆｌ拌下に６日間水熱合成し
、ベータ型ゼオライトを得た。このものを１規定硝酸を
用い、室温で約４時間処理し、濾過、水洗、乾燥し、水
素型ゼオライト（ＳｉＯｚ／ Ａｊ２ｚＯｆｆ＝ ６５
）としたものを用いた。その結果、ジクロロベンゾフ
ェノンの選択率は８６％で、４．４”−ジクロロベンゾ
フェノンの収率は２２ｍｏｌχであった。Example 6 Same as Example 1, except that U.S. Pat.
, 308.069, a 10% aqueous solution of tetraethylammonium hydroxide 500
19.9 g of sodium aluminate was mixed with 19.9 g of silica powder dissolved in 250 g of distilled water, and then 1 silica powder was added.
69g were mixed. 1f of this raw material mixture! , in a Teflon-coated autoclave for 150'
Hydrothermal synthesis was carried out for 6 days at 200 rpm (Dfl) to obtain beta-type zeolite. This product was treated with 1N nitric acid at room temperature for about 4 hours, filtered, washed with water, and dried to obtain hydrogen-type zeolite. (SiOz/Aj2zOff=65
) was used. As a result, the selectivity of dichlorobenzophenone was 86%, and the yield of 4.4''-dichlorobenzophenone was 22 molχ.
ほか１名1 other person
Claims (1)
ン化水素縮合反応させ、ついで加水分解することにより
ベンゾフェノン類を製造するに際し、脱ハロゲン化水素
縮合反応触媒として結晶性アルミノシリケートを用いる
ことを特徴とするベンゾフェノン類の製造方法。Use of crystalline aluminosilicate as a dehydrohalogenation condensation reaction catalyst when producing benzophenones by subjecting an aromatic compound and carbon tetrachloride to a dehydrohalogenation condensation reaction in the presence of an acid catalyst, followed by hydrolysis. A method for producing benzophenones, characterized by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63269423A JPH02117635A (en) | 1988-10-27 | 1988-10-27 | Production of benzophenones |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63269423A JPH02117635A (en) | 1988-10-27 | 1988-10-27 | Production of benzophenones |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02117635A true JPH02117635A (en) | 1990-05-02 |
Family
ID=17472215
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63269423A Pending JPH02117635A (en) | 1988-10-27 | 1988-10-27 | Production of benzophenones |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02117635A (en) |
-
1988
- 1988-10-27 JP JP63269423A patent/JPH02117635A/en active Pending
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