JPH0557971B2 - - Google Patents
Info
- Publication number
- JPH0557971B2 JPH0557971B2 JP59041929A JP4192984A JPH0557971B2 JP H0557971 B2 JPH0557971 B2 JP H0557971B2 JP 59041929 A JP59041929 A JP 59041929A JP 4192984 A JP4192984 A JP 4192984A JP H0557971 B2 JPH0557971 B2 JP H0557971B2
- Authority
- JP
- Japan
- Prior art keywords
- halogenated
- zeolite
- catalyst
- chloride
- acylating agent
- 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 - Fee Related
Links
- 239000010457 zeolite Substances 0.000 claims description 24
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 23
- 229910021536 Zeolite Inorganic materials 0.000 claims description 22
- 150000001555 benzenes Chemical class 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims description 8
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical group CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 5
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 claims description 4
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 3
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 claims description 2
- 239000012346 acetyl chloride Substances 0.000 claims description 2
- FBCCMZVIWNDFMO-UHFFFAOYSA-N dichloroacetyl chloride Chemical compound ClC(Cl)C(Cl)=O FBCCMZVIWNDFMO-UHFFFAOYSA-N 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 15
- 238000005658 halogenation reaction Methods 0.000 description 11
- 230000026030 halogenation Effects 0.000 description 8
- 239000002994 raw material Substances 0.000 description 6
- 230000002140 halogenating effect Effects 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 150000004820 halides Chemical class 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 239000002841 Lewis acid Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 150000007517 lewis acids Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- -1 acetic acid halides Chemical class 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- IBSQPLPBRSHTTG-UHFFFAOYSA-N 1-chloro-2-methylbenzene Chemical compound CC1=CC=CC=C1Cl IBSQPLPBRSHTTG-UHFFFAOYSA-N 0.000 description 1
- NPDACUSDTOMAMK-UHFFFAOYSA-N 4-Chlorotoluene Chemical compound CC1=CC=C(Cl)C=C1 NPDACUSDTOMAMK-UHFFFAOYSA-N 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-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
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- FXXACINHVKSMDR-UHFFFAOYSA-N acetyl bromide Chemical compound CC(Br)=O FXXACINHVKSMDR-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229940065287 selenium compound Drugs 0.000 description 1
- 150000003343 selenium compounds Chemical class 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- GVIJJXMXTUZIOD-UHFFFAOYSA-N thianthrene Chemical compound C1=CC=C2SC3=CC=CC=C3SC2=C1 GVIJJXMXTUZIOD-UHFFFAOYSA-N 0.000 description 1
- PVFOMCVHYWHZJE-UHFFFAOYSA-N trichloroacetyl chloride Chemical compound ClC(=O)C(Cl)(Cl)Cl PVFOMCVHYWHZJE-UHFFFAOYSA-N 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
Description
本発明は、ハロゲン化ベンゼン類の製造方法、
さらに詳しくいえば新規な触媒を用いて核置換ベ
ンゼン類をハロゲン化し、良好な選択率でｐ−ハ
ロゲン化核置換ベンゼン類を製造する方法に関す
るものである。
ベンゼン類の核ハロゲン化物は、医薬、農薬な
どの製造原料として使用されているが、その中で
特に需要が多いのは置換基に対してｐ位がハロゲ
ン化された核置換ベンゼン類であるので、ｐ−ハ
ロゲン化の選択率を上げるために種々の研究が行
われている。
従来、アルキルベンゼン類のハロゲン化方法と
しては、塩化アンチモン、塩化第二鉄、塩化アル
ミニウムなどのルイス酸触媒の存在下で、塩素ガ
スのようなハロゲンを用いてハロゲン化する方法
が一般に行われているが、この方法によると主と
してｏ−クロロアルキルベンゼンが生成し、さら
にｍ−クロロ化物、多クロロ化物なども副生する
ため、ｐ−クロロアルキルベンゼンの収率を40％
以上にすることは不可能であつた。そのため、ｐ
−クロロアルキルベンゼンの選択率を増大させる
べく、種々の触媒の開発研究が行われ、これまで
にもいくつか提案されている。
例えばルイス酸と硫黄又はセレンから成る触媒
を用いて45〜52％の収率でｐ−クロロ化物を得る
方法、ルイス酸とチアンスレンから成る触媒を用
いて55〜60％の収率でｐ−クロロ化物を得る方法
（特開昭52−19630号公報）、ルイス酸とフエノキ
サチン化合物から成る触媒系を用いて52〜60％の
収率でｐ−クロロ化物を得る方法（特開昭57−
175133号公報）などが知られている。
他方、クロロベンゼンの塩素化に関しては、硫
化鉄触媒の存在下、塩素を作用させて60〜70％の
収率でｐ−ジクロロベンゼンを得る方法（特開昭
50−64231号公報）、セレン又はセレン化合物を触
媒として塩素を作用させ、72％の収率でｐ−ジク
ロロベンゼンを得る方法（特公昭50−34010号公
報）などが知られている。
しかしながら、これらの方法はいずれもｐ−ハ
ロゲン化物に対する選択率は低く、ｐ−ハロゲン
化ベンゼン類の製造方法としては必ずしも満足し
うるものとはいえなかつた。
本発明者らは、このような従来方法の欠点を克
服し、高い選択率でｐ−ハロゲン化核置換ベンゼ
ン類を製造しうる方法を開発するために、鋭意研
究を重ねた結果、ある種のゼオライトを特定のア
シル化剤で処理したものを触媒として用いること
によりその目的を達成しうることを見出し、この
知見に基づいて本発明をなすに至つた。
すなわち、本発明は、触媒の存在下、一般式
（式中のＲは低級アルキル基、低級アルコキシ
基又はハロゲン原子である）
で表わされる核置換ベンゼン類を液相でハロゲン
化して、一般式
（式中のＲは前記と同じ意味をもち、Ｘはハロ
ゲン原子である）
で表わされるハロゲン化ベンゼン類を製造するに
当り、触媒として、低級脂肪族カルボン酸又はハ
ロゲン化低級脂肪族カルボン酸の官能性誘導体か
らなるアシル化剤（以下低級アシル化剤というこ
ともある）で処理した、SiO2／Al2O3モル比３〜
８、細孔径６〜10Åのゼオライトを用いることを
特徴とするハロゲン化核置換ベンゼン類の製造方
法を提供するものである。
本発明方法における一般式(1)で示される原料化
合物中の、核置換基Ｒの例としては、直鎖状及び
分枝鎖状アルキル基あるいはこのアルキル基を含
むアルコキシ基を挙げることができるが、特に炭
素数１〜４のアルキル基又はそれを含む低級アル
コキシ基が好ましい。またＲがハロゲン原子の例
としては、フツ素原子、塩素原子、臭素原子を挙
げることができる。
次に、本発明方法においては、触媒として、
SiO2／Al2O3のモル比が３〜８の範囲にあり、細
孔径が６〜10Åの範囲にあるゼオライトを、低級
アシル化剤で処理したものを用いることが必要で
ある。SiO2／Al2O3のモル比や細孔径が前記の範
囲外にあるゼオライトを用いた場合は、ｐ−ハロ
ゲン化物の選択率が著しく低下する。
このような条件に適合したゼオライトの代表的
なものとしてはＬ型ゼオライトがあるが、これは
酸化ケイ素（SiO2）：酸化アルミニウム（Al2O3）
のモル比が４：１ないし８：１の組成を有し、細
孔径約７〜10Åの結晶性アルミナシリケートであ
る。前記の条件に適合したゼオライトの他の例と
しては、SiO2：Al2O3のモル比が３：１ないし
７：１の組成を有し、細孔径約６〜９ÅのＹ型ゼ
オライトを挙げることができる。
本発明における触媒としては、これらと同一の
Ｘ線回折スペクトルを有する合成ゼオライト、天
然ゼオライトも用いることができる。また、これ
らのゼオライト中に含まれるイオン交換可能なカ
チオンは、通常ナトリウム又はカリウムである
が、それ以外のカチオンを含むものでもよい。こ
のようなカチオンとしては、例えば周期表Ａ
族、Ａ族、Ａ族、Ａ族、Ａ族の金属イオ
ン又はプロトンを挙げることができる。これらの
カチオンは１種含まれていてもよいし、また２種
以上含まれていてもよい。
本発明方法においては、このゼオライトを低級
脂肪族カルボン酸又はハロゲン化低級脂肪族カル
ボン酸の官能性誘導体からなるアシル化剤（低級
アシル化剤）で処理したものが用いられるが、こ
の処理はハロゲン化での使用に先立つてあらかじ
め施してもよいし、またハロゲン化反応時に反応
系内に低級アシル化剤とゼオライトを同時に添加
して行つてもよい。
あらかじめ処理する場合には、例えばゼオライ
ト粉末を溶媒に懸濁させ、低級アシル化剤を加え
たのち、溶媒及び過剰の低級アシル化剤を留去
し、減圧乾燥することによつて行われる。この
際、溶媒を用いずに、低級アシル化剤の中に直接
ゼオライト粉末を加え、過剰分を留去してもよ
い。
他方、反応時に処理する場合には、ハロゲン化
装置内に装入した原料の核置換ベンゼン類にゼオ
ライト粉末を懸濁させ、これに低級アシル化剤を
加えて、沸点以下の温度、好ましくは室温から
100℃までの温度でかきまぜたのち、そのまま後
続のハロゲン化を行う。
これらの低級アシル化剤の処理は、いずれか一
方を行うだけで十分であるが、所望ならばその両
方を行うこともできる。
この際に低級アシル化剤として用いられる低級
脂肪族カルボン酸又はハロゲン化低級脂肪族カル
ボン酸の官能性誘導体としては、無水酢酸、酢酸
ハライド例えばアセチルクロリド、アセチルブロ
ミドなど、ハロゲン化酢酸ハライド例えばクロロ
アセチルクロリド、ジクロロアセチルクロリド、
トリクロロアセチルクロリド及び対応するブロミ
ドなど、トリフルオロ酢酸無水物、ギ酸誘導体例
えばオルソギ酸メチルなどを挙げることができ
る。このアシル化剤として塩化ベンゾイルのよう
な大きい分子のものを用いた場合には、ｐ−ハロ
ゲン化物の選択率の向上は得られない。このアシ
ル化剤の使用量としては、ゼオライトに基づき１
重量％以上あれば十分である。
本発明方法に従つて核置換ベンゼンのハロゲン
化を行うには、例えば低級アシル化剤で処理した
ゼオライトを原料化合物１モル当り0.01〜10ｇ好
ましくは0.1〜７ｇの割合で混合し、沸点以下の
温度でかきまぜながら液相でハロゲン化剤を導入
する。この際、所望に応じ反応溶媒を使用するこ
ともできる。ハロゲン化剤としては、芳香環のハ
ロゲン化に慣用されているものが用いられるが、
好ましいのは塩素、臭素、スルフリルクロリドな
どである。これらは、所望に応じ窒素のような不
活性ガスで希釈して用いることもできる。また、
ハロゲン化の実用的な反応温度は０℃以上、反応
混合物の沸点以下の温度である。この反応は減圧
下、加圧下のいずれでで行つてもよいが通常は常
圧下で行われる。
本発明方法によれば、核置換ベンゼン類のハロ
ゲン化において、ｏ−位のハロゲン化を抑制し、
ｐ−位のハロゲン化を選択的かつ効率よく行うこ
とができる上に、側鎖ハロゲン化物や多核ハロゲ
ン化物のような副生物の生成を極めて少量に抑え
ることができ、利用度の高いｐ−ハロゲン化核置
換ベンゼン類を高い収率で得ることができるとい
う利点がある。
また、本発明方法によれば、モノハロゲン化ベ
ンゼンを原料としてｐ−ジハロゲン化ベンゼンを
製造する場合に、ベンゼンからモノハロゲン化ベ
ンゼンを製造し、これをさらにハロゲン化してｐ
−ジハロゲン化ベンゼンとする工程を同一反応装
置内で連続して行うことができるので有利であ
る。
さらに、本発明方法は、反応及びその後に行う
後処理操作が簡単であり、触媒の再使用も可能で
あるなどｐ−ハロゲン化核置換ベンゼン類の工業
的製法として好適である。
次に実施例によつて本発明をさらに詳細に説明
する。
実施例 １
冷却管、温度計、かきまぜ機及び吹込み管を備
えた200ml容量の反応フラスコに、Ｌ型ゼオライ
ト（東洋曹達〓製、商品名TSZ−504）５ｇとト
ルエン92.1ｇ（１モル）を入れ、クロロアセチル
クロリド0.5ｇを加えて、50℃に維持し、窒素ガ
スを導入しながら30分間かきまぜる。続いて、反
応温度を50℃に保ち、塩素ガスを毎時0.25モルの
割合で４時間吹き込んで反応させる。反応終了
後、得られた反応生成物を、ガスクロマトグラフ
イーにより分析したところ、トルエンの反応率98
％、ｏ−クロロトルエン／ｐ−クロロトルエン生
成比（以下ｏ／ｐ比と略す）0.312であつた。
実施例 ２
クロロアセチルクロリドの添加量を0.25ｇとす
る以外は実施例１と同様の実験を繰り返したとこ
ろ、トルエンの反応率は90.1％、ｏ／ｐ比は
0.338であつた。
実施例 ３
原料としてトルエンの代りに種々のベンゼン類
を用い、実施例１と同様にして70℃においてハロ
ゲン化を行つた。その結果を第１表に示す。
The present invention provides a method for producing halogenated benzenes,
More specifically, the present invention relates to a method for producing p-halogenated nuclear-substituted benzenes with good selectivity by halogenating nuclear-substituted benzenes using a novel catalyst. Nuclear halides of benzenes are used as raw materials for the production of medicines, agricultural chemicals, etc. Among them, the ones in particular demand are nuclear-substituted benzenes in which the p-position relative to the substituent is halogenated. , various studies have been conducted to increase the selectivity of p-halogenation. Conventionally, the method for halogenating alkylbenzenes is to use a halogen such as chlorine gas in the presence of a Lewis acid catalyst such as antimony chloride, ferric chloride, or aluminum chloride. However, according to this method, mainly o-chloroalkylbenzene is produced, and m-chloride and polychloride are also produced as by-products, so the yield of p-chloroalkylbenzene is reduced to 40%.
It was impossible to do more. Therefore, p
- In order to increase the selectivity of chloroalkylbenzene, various catalyst development studies have been conducted, and several proposals have been made so far. For example, a method of obtaining p-chloride with a yield of 45-52% using a catalyst consisting of a Lewis acid and sulfur or selenium, and a method of obtaining p-chloride with a yield of 55-60% using a catalyst consisting of a Lewis acid and thianthrene. A method for obtaining p-chloride with a yield of 52 to 60% using a catalyst system consisting of a Lewis acid and a phenoxatin compound (Japanese Patent Application Laid-open No. 1963-1983).
175133) are known. On the other hand, regarding the chlorination of chlorobenzene, a method for obtaining p-dichlorobenzene with a yield of 60 to 70% by reacting chlorine in the presence of an iron sulfide catalyst (Japanese Patent Application Laid-open No.
50-64231), and a method for obtaining p-dichlorobenzene with a yield of 72% by reacting chlorine with selenium or a selenium compound as a catalyst (Japanese Patent Publication No. 50-34010). However, all of these methods have low selectivity to p-halides, and cannot be said to be necessarily satisfactory as a method for producing p-halogenated benzenes. The present inventors have conducted extensive research in order to overcome the drawbacks of such conventional methods and to develop a method capable of producing p-halogenated nucleus-substituted benzenes with high selectivity. The inventors have discovered that the objective can be achieved by using a zeolite treated with a specific acylating agent as a catalyst, and based on this knowledge, the present invention has been accomplished. That is, in the presence of a catalyst, the present invention provides (R in the formula is a lower alkyl group, a lower alkoxy group, or a halogen atom) is halogenated in a liquid phase, and the general formula (In the formula, R has the same meaning as above, and X is a halogen atom.) In producing the halogenated benzenes represented by the formula, a lower aliphatic carboxylic acid or a halogenated lower aliphatic carboxylic acid is used as a catalyst. SiO 2 /Al 2 O 3 molar ratio of 3 to 3 treated with an acylating agent (hereinafter also referred to as lower acylating agent) consisting of a functional derivative
8. The present invention provides a method for producing benzenes having a halogenated nucleus, which is characterized by using a zeolite having a pore diameter of 6 to 10 Å. Examples of the nuclear substituent R in the raw material compound represented by general formula (1) in the method of the present invention include linear and branched alkyl groups, and alkoxy groups containing this alkyl group. In particular, an alkyl group having 1 to 4 carbon atoms or a lower alkoxy group containing the same is preferable. Examples of a halogen atom for R include a fluorine atom, a chlorine atom, and a bromine atom. Next, in the method of the present invention, as a catalyst,
It is necessary to use a zeolite having a molar ratio of SiO 2 /Al 2 O 3 in the range of 3 to 8 and a pore diameter in the range of 6 to 10 Å, which has been treated with a lower acylating agent. When a zeolite having a SiO 2 /Al 2 O 3 molar ratio or a pore diameter outside the above range is used, the selectivity of p-halides is significantly reduced. A typical zeolite that meets these conditions is L-type zeolite, which is composed of silicon oxide (SiO 2 ):aluminum oxide (Al 2 O 3 ).
It is a crystalline alumina silicate having a composition with a molar ratio of 4:1 to 8:1 and a pore diameter of about 7 to 10 Å. Another example of a zeolite that meets the above conditions is a Y-type zeolite having a SiO 2 :Al 2 O 3 molar ratio of 3:1 to 7:1 and a pore size of about 6 to 9 Å. be able to. As the catalyst in the present invention, synthetic zeolites and natural zeolites having the same X-ray diffraction spectra as these can also be used. Further, the ion-exchangeable cations contained in these zeolites are usually sodium or potassium, but they may also contain other cations. Such cations include, for example, periodic table A
Mention may be made of metal ions or protons of Group A, Group A, Group A, Group A, Group A. One type of these cations may be contained, or two or more types may be contained. In the method of the present invention, this zeolite is treated with an acylating agent (lower acylating agent) consisting of a lower aliphatic carboxylic acid or a functional derivative of a halogenated lower aliphatic carboxylic acid. It may be applied in advance prior to use in the halogenation reaction, or the lower acylating agent and the zeolite may be added simultaneously to the reaction system during the halogenation reaction. In the case of pre-treatment, for example, the zeolite powder is suspended in a solvent, a lower acylating agent is added thereto, the solvent and excess lower acylating agent are distilled off, and the suspension is dried under reduced pressure. At this time, the zeolite powder may be directly added to the lower acylating agent without using a solvent, and the excess amount may be distilled off. On the other hand, when processing during the reaction, zeolite powder is suspended in nuclear-substituted benzenes as a raw material charged into a halogenation apparatus, a lower acylating agent is added thereto, and the mixture is heated at a temperature below the boiling point, preferably at room temperature. from
After stirring at a temperature of up to 100°C, the subsequent halogenation is carried out as it is. It is sufficient to perform either one of these treatments with the lower acylating agent, but if desired, both can be performed. In this case, the functional derivatives of lower aliphatic carboxylic acids or halogenated lower aliphatic carboxylic acids used as lower acylating agents include acetic anhydride, acetic acid halides such as acetyl chloride, acetyl bromide, halogenated acetic halides such as chloroacetyl chloride, dichloroacetyl chloride,
Mention may be made of trifluoroacetic anhydride, formic acid derivatives such as methyl orthoformate, etc., such as trichloroacetyl chloride and the corresponding bromides. If a large molecule such as benzoyl chloride is used as the acylating agent, no improvement in the selectivity of p-halides can be obtained. The amount of this acylating agent used is 1% based on the zeolite.
It is sufficient if it is at least % by weight. In order to halogenate nuclear-substituted benzene according to the method of the present invention, for example, zeolite treated with a lower acylating agent is mixed at a ratio of 0.01 to 10 g, preferably 0.1 to 7 g, per 1 mole of the raw material compound, and the mixture is heated at a temperature below the boiling point. Introduce the halogenating agent in the liquid phase while stirring. At this time, a reaction solvent may be used if desired. As the halogenating agent, those commonly used for halogenating aromatic rings are used.
Preferred are chlorine, bromine, sulfuryl chloride and the like. These can also be used after being diluted with an inert gas such as nitrogen, if desired. Also,
The practical reaction temperature for halogenation is 0° C. or higher and lower than the boiling point of the reaction mixture. This reaction may be carried out either under reduced pressure or increased pressure, but is usually carried out under normal pressure. According to the method of the present invention, in the halogenation of nuclear-substituted benzenes, halogenation at the o-position is suppressed,
In addition to being able to selectively and efficiently halogenate the p-position, the production of by-products such as side chain halides and polynuclear halides can be suppressed to extremely small amounts, making it possible to halogenate p-halogens, which are highly utilized. It has the advantage of being able to obtain substituted benzenes in high yield. Furthermore, according to the method of the present invention, when producing p-dihalogenated benzene using monohalogenated benzene as a raw material, monohalogenated benzene is produced from benzene, and this is further halogenated to produce p-dihalogenated benzene.
It is advantageous that the steps to form -dihalogenated benzene can be carried out continuously in the same reactor. Further, the method of the present invention is suitable as an industrial method for producing p-halogenated nucleus-substituted benzenes because the reaction and subsequent post-treatment operations are simple, and the catalyst can be reused. Next, the present invention will be explained in more detail with reference to Examples. Example 1 5 g of L-type zeolite (manufactured by Toyo Soda, trade name TSZ-504) and 92.1 g (1 mol) of toluene were placed in a 200 ml reaction flask equipped with a cooling tube, a thermometer, a stirrer, and a blowing tube. Add 0.5 g of chloroacetyl chloride, maintain the temperature at 50°C, and stir for 30 minutes while introducing nitrogen gas. Subsequently, the reaction temperature was maintained at 50°C, and chlorine gas was blown in at a rate of 0.25 mol/hour for 4 hours to cause the reaction. After the reaction was completed, the reaction product obtained was analyzed by gas chromatography, and the reaction rate of toluene was 98.
%, o-chlorotoluene/p-chlorotoluene production ratio (hereinafter abbreviated as o/p ratio) was 0.312. Example 2 The same experiment as Example 1 was repeated except that the amount of chloroacetyl chloride added was 0.25 g, and the reaction rate of toluene was 90.1% and the O/P ratio was
It was 0.338. Example 3 Halogenation was carried out at 70° C. in the same manner as in Example 1, using various benzenes instead of toluene as raw materials. The results are shown in Table 1.
【表】
実施例 ４
塩素ガスの代りにスルフリルクロリド35.2ｇ
（1.002モル）を４時間で滴下し、３時間熟成する
ことにより、実施例１と同様にして70℃において
ハロゲン化を行つたところ、トルエンの反応率は
99.4％、ｏ／ｐ比は0.293であつた。
実施例 ５
種々の異なつたアシル化剤を用い、反応温度を
70℃とした以外は実施例１と同様にしてハロゲン
化を行つた。その結果を第２表に示す。
なお、比較のために、無処理ゼオライト及びベ
ンゾイルクロリドで処理したゼオライトを用いた
場合の結果も併記した。[Table] Example 4 35.2g of sulfuryl chloride instead of chlorine gas
(1.002 mol) was added dropwise over 4 hours and aged for 3 hours to carry out halogenation at 70°C in the same manner as in Example 1. The reaction rate of toluene was
The o/p ratio was 99.4% and 0.293. Example 5 Using various different acylating agents and adjusting the reaction temperature
Halogenation was carried out in the same manner as in Example 1 except that the temperature was 70°C. The results are shown in Table 2. For comparison, results using untreated zeolite and zeolite treated with benzoyl chloride are also shown.
【表】
実施例 ６
実施例１の終了後反応混合物から触媒を回収
し、それを用いて実施例１と同様の実験を繰り返
したところ、反応は正常に行われ、この場合の反
応率は98.2％、ｏ／ｐ比は0.320であつた。[Table] Example 6 After the completion of Example 1, the catalyst was recovered from the reaction mixture, and the same experiment as in Example 1 was repeated using it. The reaction was carried out normally, and the reaction rate in this case was 98.2. %, and the o/p ratio was 0.320.
Claims (1)
基又はハロゲン原子である） で表わされる核置換ベンゼン類を液相でハロゲン
化して、一般式 （式中のＲは前記と同じ意味をもち、Ｘはハロ
ゲン原子である） で表わされるハロゲン化ベンゼン類を製造いする
に当り、触媒として、低級脂肪族カルボン酸又は
ハロゲン化低級脂肪族カルボン酸の官能性誘導体
からなるアシル化剤で処理した、SiO2／Al2O3モ
ル比３〜８、細孔径６〜10Åのゼオライトを用い
ることを特徴とするハロゲン化核置換ベンゼン類
の製造方法。 ２ アシル化剤が、無水酢酸、アセチルクロリ
ド、クロロアセチルクロリド、ジクロロアセチル
クロリド、トリフルオロ酢酸無水物又はオルソギ
酸メチルである特許請求の範囲第１項記載の方
法。 ３ ゼオライトがＬ型ゼオライト又はＹ型ゼオラ
イトである特許請求の範囲第１項又は第２項記載
の方法。[Claims] 1. In the presence of a catalyst, the general formula (R in the formula is a lower alkyl group, a lower alkoxy group, or a halogen atom) is halogenated in a liquid phase, and the general formula (In the formula, R has the same meaning as above, and X is a halogen atom.) In producing the halogenated benzenes represented by the formula, a lower aliphatic carboxylic acid or a halogenated lower aliphatic carboxylic acid is used as a catalyst. 1. A method for producing benzenes substituted with a halogenated nucleus, characterized by using a zeolite treated with an acylating agent consisting of a functional derivative of the following, having a SiO 2 /Al 2 O 3 molar ratio of 3 to 8 and a pore diameter of 6 to 10 Å. 2. The method according to claim 1, wherein the acylating agent is acetic anhydride, acetyl chloride, chloroacetyl chloride, dichloroacetyl chloride, trifluoroacetic anhydride or methyl orthoformate. 3. The method according to claim 1 or 2, wherein the zeolite is L-type zeolite or Y-type zeolite.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59041929A JPS60188333A (en) | 1984-03-07 | 1984-03-07 | Production of halogenated benzene |
| EP85101707A EP0154236B1 (en) | 1984-03-07 | 1985-02-15 | Process for producing a halobenzene |
| DE8585101707T DE3561389D1 (en) | 1984-03-07 | 1985-02-15 | Process for producing a halobenzene |
| CA000474550A CA1262920A (en) | 1984-03-07 | 1985-02-18 | Process for producing a halobenzene |
| KR1019850001359A KR900003295B1 (en) | 1984-03-07 | 1985-03-05 | Process for producing a halobenzene |
| US07/057,650 US4831199A (en) | 1984-03-07 | 1987-06-09 | Process for producing a halobenzene |
| US07/323,845 US4942268A (en) | 1984-03-07 | 1989-03-15 | Process for producing a halobenzene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59041929A JPS60188333A (en) | 1984-03-07 | 1984-03-07 | Production of halogenated benzene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60188333A JPS60188333A (en) | 1985-09-25 |
| JPH0557971B2 true JPH0557971B2 (en) | 1993-08-25 |
Family
ID=12621924
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59041929A Granted JPS60188333A (en) | 1984-03-07 | 1984-03-07 | Production of halogenated benzene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60188333A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2598581B2 (en) * | 1991-06-17 | 1997-04-09 | 株式会社トクヤマ | Method for producing aromatic halide |
| AU2007278224C1 (en) * | 2006-07-24 | 2012-06-21 | Grünenthal GmbH | Preparation of (2R,3R)-3-(3-methoxyphenyl)-N,N,2-trimethylpentanamine |
-
1984
- 1984-03-07 JP JP59041929A patent/JPS60188333A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60188333A (en) | 1985-09-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0248931B1 (en) | Process for producing p-chlorobenzenes | |
| US4822933A (en) | Process for producing a chlorohalobenzene | |
| KR900003295B1 (en) | Process for producing a halobenzene | |
| EP0112722B1 (en) | Process for preparation of nuclear halides of monoalkylbenzenes | |
| JPH0557971B2 (en) | ||
| JP4913962B2 (en) | Process for producing phenylethynylphthalic anhydride derivative | |
| JPH10158202A (en) | Production of diphenylethane bromide | |
| US5872291A (en) | Process for producing benzoyl chlorides | |
| JPH0557972B2 (en) | ||
| US4740641A (en) | Producing a halogenated benzene derivative using zeolite catalyst treated with alkali solution of pH 11 or more | |
| JPS60125251A (en) | Catalyst for halogenating nucleus of alkylbenzene | |
| JPH0627079B2 (en) | Method for producing halogenated benzenes | |
| JPH01149740A (en) | Production of 4,4'-dibromobiphenyl | |
| KR880000200B1 (en) | Process for the preparation of p-chlorobenzene | |
| JPH0225896B2 (en) | ||
| JPS59144722A (en) | Preparation of alkylbenzene nucleus halide | |
| JP2742275B2 (en) | Method for producing p-chlorohalogenobenzene | |
| CA2080204A1 (en) | Process for the free-radical chlorination or bromination of methyl aromatic compounds | |
| JPH02200647A (en) | Preparation of 4-chloro-4'-halogenodiphenyls | |
| JPH0327334A (en) | Production of 2,5-dihalogenated benzotrichlorides | |
| JPS6239138B2 (en) | ||
| JPS6327054B2 (en) | ||
| JPH03261733A (en) | Production of nucleus-chlorinated diphenylmethane | |
| JPS6334129B2 (en) | ||
| JPS5883638A (en) | Preparation of nucleus-chlorinated alkylbenzene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |