JPS6021129B2 - Method for producing 1-bromo-3,5-dichlorobenzene - Google Patents
Method for producing 1-bromo-3,5-dichlorobenzeneInfo
- Publication number
- JPS6021129B2 JPS6021129B2 JP51122591A JP12259176A JPS6021129B2 JP S6021129 B2 JPS6021129 B2 JP S6021129B2 JP 51122591 A JP51122591 A JP 51122591A JP 12259176 A JP12259176 A JP 12259176A JP S6021129 B2 JPS6021129 B2 JP S6021129B2
- Authority
- JP
- Japan
- Prior art keywords
- dichlorobenzene
- reaction
- bromo
- target product
- furomo
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- DZHFFMWJXJBBRG-UHFFFAOYSA-N 1-bromo-3,5-dichlorobenzene Chemical compound ClC1=CC(Cl)=CC(Br)=C1 DZHFFMWJXJBBRG-UHFFFAOYSA-N 0.000 title claims description 11
- HVKCZUVMQPUWSX-UHFFFAOYSA-N 1-bromo-2,3-dichlorobenzene Chemical compound ClC1=CC=CC(Br)=C1Cl HVKCZUVMQPUWSX-UHFFFAOYSA-N 0.000 claims description 14
- -1 aluminum halide Chemical class 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 7
- 229940117389 dichlorobenzene Drugs 0.000 description 24
- 239000000047 product Substances 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000007788 liquid Substances 0.000 description 14
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 12
- 239000010779 crude oil Substances 0.000 description 10
- CSOWEPYJECMZOB-UHFFFAOYSA-N 1,2-dibromo-3,4-dichlorobenzene Chemical compound ClC1=CC=C(Br)C(Br)=C1Cl CSOWEPYJECMZOB-UHFFFAOYSA-N 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 238000006317 isomerization reaction Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 150000004816 dichlorobenzenes Chemical class 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- ISHYFWKKWKXXPL-UHFFFAOYSA-N 1-bromo-2,4-dichlorobenzene Chemical compound ClC1=CC=C(Br)C(Cl)=C1 ISHYFWKKWKXXPL-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XMLDCMHIIUWWPP-UHFFFAOYSA-N 1,2-dibromo-4,5-dichlorobenzene Chemical compound ClC1=CC(Br)=C(Br)C=C1Cl XMLDCMHIIUWWPP-UHFFFAOYSA-N 0.000 description 1
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 1
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 description 1
- DGJPEYHWCWGMFF-UHFFFAOYSA-N 1,4-dibromo-2,5-dichlorobenzene Chemical compound ClC1=CC(Br)=C(Cl)C=C1Br DGJPEYHWCWGMFF-UHFFFAOYSA-N 0.000 description 1
- AIYBGLGSFXUJDS-UHFFFAOYSA-N 1,5-dibromo-2,4-dichlorobenzene Chemical compound ClC1=CC(Cl)=C(Br)C=C1Br AIYBGLGSFXUJDS-UHFFFAOYSA-N 0.000 description 1
- WRXIPCQPHZMXOO-UHFFFAOYSA-N 3,5-dichlorobenzenethiol Chemical compound SC1=CC(Cl)=CC(Cl)=C1 WRXIPCQPHZMXOO-UHFFFAOYSA-N 0.000 description 1
- VPOMSPZBQMDLTM-UHFFFAOYSA-N 3,5-dichlorophenol Chemical compound OC1=CC(Cl)=CC(Cl)=C1 VPOMSPZBQMDLTM-UHFFFAOYSA-N 0.000 description 1
- CFPZDVAZISWERM-UHFFFAOYSA-N 4-bromo-1,2-dichlorobenzene Chemical compound ClC1=CC=C(Br)C=C1Cl CFPZDVAZISWERM-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- PUGUQINMNYINPK-UHFFFAOYSA-N tert-butyl 4-(2-chloroacetyl)piperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(C(=O)CCl)CC1 PUGUQINMNYINPK-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
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
本発明はモノブロモジクロロベンゼンを１−ブロモ−３
．５ージクロロベンゼンに異性化する方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention provides monobromodichlorobenzene with 1-bromo-3
．． This invention relates to a method for isomerizing to 5-dichlorobenzene.
１ーフロモー３．５ージクロロベンゼンは合成化学上貴
重な化合物であって、例えば３，５ージクロロフエノー
ル、３．５ージクロロチオフエノ−ル、１−アルコキシ
−３．５−ジクロロベンゼン、３．５ージクロロアニリ
ン、３．５ージクロロベンゾニトリルなどに容易に誘導
でき、農薬、染料、医薬などの中間原料として有用であ
る。1-Flomo-3,5-dichlorobenzene is a valuable compound in synthetic chemistry, such as 3,5-dichlorophenol, 3,5-dichlorothiophenol, 1-alkoxy-3,5-dichlorobenzene, It can be easily derived into .5-dichloroaniline, 3.5-dichlorobenzonitrile, etc., and is useful as an intermediate raw material for agricultural chemicals, dyes, medicines, etc.
しかしながら、このものの工業上有利な合成方法は未だ
確立されていない現状である。本発明は従来の実験室的
な製造方法とは異なり、工業的実施上有利な１ーフロモ
ー３．５ージクロロベンゼンの製造方法である。However, an industrially advantageous synthesis method for this product has not yet been established. The present invention is a method for producing 1-fromo-3,5-dichlorobenzene that is advantageous for industrial implementation, unlike conventional laboratory production methods.
本願発明は、ハロゲン化アルミニウムの存在下にモノブ
ロモジクロロベンゼンを８０ｑｏ以上に加熱して異性化
することを特徴とする１−ブロモー３，５一ジクロロべ
ンゼンの製造方法である。本発明におては通常、実質的
に１−フロモ−３．５ージクロロベンゼンでないモノプ
ロモジクロロベンゼン原料中にハロゲン化アルミニウム
を懸濁させ、澄拝しながら加熱して異性化反応を行なう
。The present invention is a method for producing 1-bromo-3,5-dichlorobenzene, which is characterized in that monobromodichlorobenzene is isomerized by heating to 80 qo or higher in the presence of aluminum halide. In the present invention, aluminum halide is usually suspended in a raw material of monopromodichlorobenzene that is not substantially 1-furomo-3,5-dichlorobenzene, and the isomerization reaction is carried out by heating under clear conditions.
更に適量のジクロロベンゼンをも存在させて反応を行な
うときは通常、ジクロロベンゼン及びモノブロモジクロ
ロベンゼン原料中にハロゲン化アルミニウムを懸濁させ
、鷹梓下に加熱した反応を行なう。本発明の出発原料で
あるモノプロモジクロロベンゼンは例えば次のようにし
て容易に製造できる。When carrying out the reaction in the presence of an appropriate amount of dichlorobenzene, the reaction is usually carried out by suspending aluminum halide in the dichlorobenzene and monobromodichlorobenzene raw materials and heating the mixture under high pressure. Monopromodichlorobenzene, which is the starting material of the present invention, can be easily produced, for example, as follows.
有機合成品の中間原料として多量に使用されているオル
ソ、メタ及びパラジクロロベンゼン或はこれらの混合物
を塩化アルミニウム、塩化第２鉄、鉄分などの存在下に
０〜１００℃で臭素化したり、ブロモベンゼンを同条件
下で塩素化したり、或はジクロロベンゼンとジブロモジ
クロロベンゼンとを同条件下で反応させたりすれば１〜
５時間の反応処理で１ーブロモー２．４−ジクロロベン
ゼン、１−フロモー２．５ージクロロベンゼン、１ーフ
ロモー３．４−ジクロロベンゼンなどが高収率で得られ
る。本発明に用いるハロゲン化アルミニウムとしては無
水塩化アルミニウム、無水臭化アルミニウム、その混合
物などがあげられ、前二者が作用上、経済上好適である
。Ortho-, meta-, and para-dichlorobenzene, which are used in large amounts as intermediate raw materials for organic synthetic products, or mixtures thereof, are brominated at 0 to 100°C in the presence of aluminum chloride, ferric chloride, iron, etc., or bromobenzene is If chlorinated under the same conditions, or dichlorobenzene and dibromodichlorobenzene are reacted under the same conditions, 1-
After 5 hours of reaction treatment, 1-bromo-2,4-dichlorobenzene, 1-fromo-2,5-dichlorobenzene, 1-fromo-3,4-dichlorobenzene, etc. can be obtained in high yield. Examples of the aluminum halide used in the present invention include anhydrous aluminum chloride, anhydrous aluminum bromide, and mixtures thereof, with the former two being preferred from an operational and economic standpoint.
モノブロモジクロロベンゼン原料に対するハロゲン化ア
ルミニウムの使用量は反応条件の相違によって一概にい
えないが、普通前者１０堰重量部に対し、後者２〜１０
の重量部使用する。本発明の異性化反応は常圧では一般
に８０〜１８０℃、望ましくは１２０〜１７０００で行
ない、この場合、通常０．５〜５餌時間で終了する。Although the amount of aluminum halide to be used for the monobromodichlorobenzene raw material cannot be determined unconditionally due to differences in reaction conditions, it is usually 10 parts by weight of the former and 2 to 10 parts by weight of the latter.
Use parts by weight. The isomerization reaction of the present invention is generally carried out at a temperature of 80 to 180 DEG C., preferably 120 to 17,000 at normal pressure, and is usually completed in 0.5 to 5 feeding times.
反応温度が低きに過ぎても、高さに過ぎても反応速度、
反応目的物の収量、系外に排除すべき反応副生物の発生
量などの点から望ましくない。後記実施例にも見られる
ように、原料モノブロモジクロロベンゼンとして１−ブ
ロモー２，４ージクロロベンゼンを用いた場合短かい反
応時間で、かつ比較的緩和な条件で目的物の生成率が高
いが、１−ブロモ−３，４ージクロロベンゼンを２０％
以上含有するものを用いた場合、目的物の生成率が低く
、前者の場合に比べて工業的実施上不利である。前記異
性化反応においては、１．５ージブロモー２，４ージク
ロロベンゼン、１．４−ジプロモ−２．５ージクロロベ
ンゼン、１．２ージブロモ−４．５ージクロロベンゼン
などの各種ジブロモジクロロベンゼン類が生成し、この
ものが反応生成物中に例えば１５〜３０％以上含有され
るが、前記異性化反応に際して適量のジクロロベンゼン
を存在させたときは各種ジブロモジクロロベンゼン類の
生成を抑制でき、かつ原料モノブロモジクロロベンゼン
に対する目的物１−フロモ−３．５−ジクロロベンゼン
の収率を向上させることができる。Even if the reaction temperature is too low or too high, the reaction rate,
This is undesirable from the viewpoint of the yield of the reaction target product and the amount of reaction by-products that should be removed from the system. As seen in the examples below, when 1-bromo-2,4-dichlorobenzene is used as the raw material monobromodichlorobenzene, the yield of the target product is high in a short reaction time and under relatively mild conditions; 20% 1-bromo-3,4-dichlorobenzene
When those containing the above are used, the yield of the target product is low, which is disadvantageous in industrial practice compared to the former case. In the isomerization reaction, various dibromodichlorobenzenes such as 1,5-dibromo-2,4-dichlorobenzene, 1,4-dibromo-2,5-dichlorobenzene, and 1,2-dibromo-4,5-dichlorobenzene are used. The reaction product contains, for example, 15 to 30% or more of this substance, but when an appropriate amount of dichlorobenzene is present during the isomerization reaction, the formation of various dibromodichlorobenzenes can be suppressed, and the raw material It is possible to improve the yield of the target product 1-furomo-3,5-dichlorobenzene relative to monobromodichlorobenzene.
本発明の異性化反応を行うことにより、目的物１−ブロ
モ−３．５−ジクロロベンゼン、目的物以外の各種モノ
ブロモジクロロベンゼン類、各種ジクロロベンゼン類、
各種ジブロモジクロロベンゼン類及びその他化合物を含
有する反応生成物が得られる。By performing the isomerization reaction of the present invention, the target product 1-bromo-3,5-dichlorobenzene, various monobromodichlorobenzenes other than the target product, various dichlorobenzenes,
Reaction products containing various dibromodichlorobenzenes and other compounds are obtained.
この反応生成物は通常放冷したのち水中に投入、洗浄し
、得られた液状物を室温乃至それ以下に冷却すると目的
物が析出する。This reaction product is usually allowed to cool and then poured into water for washing. When the obtained liquid is cooled to room temperature or lower, the target product is precipitated.
また液状物を油相と水相とに分離し、この油相を必要あ
れば乾燥剤によって脱水処理し、蒸留を行う。前記蒸留
によれば初留分として各種ジクロロベンゼン類及び後留
分として各種ジプロモジクロロベンゼン類が分離でき、
主留分をあつめて、室温乃至それ以下に冷却すると１ー
ブロモー３．５ージクロロベンゼンが析出する。このも
のを炉過すれば目的物である１ーブロモー３．５ージク
ロロベンゼン固形状物が得られる。炉液は分離できなか
った１−ブロモ−３．５ージクロロベンゼン、１ーフロ
モー３．５ージクロロベンゼン以外のモノブロモジクロ
ロベンゼン類などを含有するものである。前記反応生成
物中の各種モノブロモジクロロベンゼン類及び各種ジク
ロロベソゼン類は前記異性化反応に与かるものであり、
また各種ジブロモジクロロベンゼン類も異性化反応系に
おいて目的物１−ブロモ−３．５−ジクロロベンゼンに
誘導できる。Further, the liquid substance is separated into an oil phase and an aqueous phase, and if necessary, this oil phase is dehydrated using a desiccant and distilled. According to the above distillation, various dichlorobenzenes can be separated as the first distillate and various dibromodichlorobenzenes as the after distillate,
When the main fractions are collected and cooled to room temperature or lower, 1-bromo-3,5-dichlorobenzene is precipitated. If this product is filtered in a furnace, the target product, 1-bromo-3,5-dichlorobenzene solid, can be obtained. The furnace liquid contains 1-bromo-3.5-dichlorobenzene and monobromodichlorobenzenes other than 1-bromo-3.5-dichlorobenzene that could not be separated. Various monobromodichlorobenzenes and various dichlorobesozenes in the reaction product participate in the isomerization reaction,
Further, various dibromodichlorobenzenes can also be induced into the target product 1-bromo-3,5-dichlorobenzene in the isomerization reaction system.
従って、これらの創生物はすべて本発明の前記工程に循
環使用することができる。そのときの本発明の実施は工
業的に非常に有利なものである。本発明によって得られ
る１−フロモ−３．５−ジクロロベンゼンは前述のよう
に合成化学上貴重なものであり、多種化合物に議導する
ことができる。Therefore, all these created organisms can be reused in the above steps of the present invention. The implementation of the present invention in that case is industrially very advantageous. As mentioned above, 1-furomo-3,5-dichlorobenzene obtained by the present invention is valuable in terms of synthetic chemistry, and can be converted into a wide variety of compounds.
特に求核置換試薬との反応による臭素置換によって簡易
に所望化合物を生成できる点に注目されるものである。
例えば１ーフロモー３．５ージクロロベンゼンとアンモ
ニア水とを塩化第１鋼の存在下に加圧、加熱することに
より、収率よく３．５−ジクロロアニリンを生成させる
ことができる。以下に本発明の実施例を記載する。実施
例 １
下記第１−１表に示す条件に従って、鷹梓器、温度計及
び冷却管を備えた４つ口フラスコ中に原料及び無水ハロ
ゲン化アルミニウムを入れ、凝拝しながら加熱し、それ
ぞれの反応時間維持して反応を行ない、反応物を放冷し
た後水中に投入、洗浄し、得られた液状物を分液漏斗に
よって油層と水層とに分離し、油層を無水塩化カルシウ
ムで脱水して粗製油状物を得た。In particular, it is noteworthy that a desired compound can be easily produced by bromine substitution through reaction with a nucleophilic substitution reagent.
For example, 3.5-dichloroaniline can be produced in good yield by pressurizing and heating 1-fromo-3.5-dichlorobenzene and aqueous ammonia in the presence of No. 1 steel chloride. Examples of the present invention will be described below. Example 1 According to the conditions shown in Table 1-1 below, raw materials and anhydrous aluminum halide were placed in a four-necked flask equipped with a thermometer, a thermometer, and a cooling tube, and heated while stirring. The reaction was carried out while maintaining the reaction time, and after cooling the reactant, it was poured into water and washed. The obtained liquid was separated into an oil layer and an aqueous layer using a separatory funnel, and the oil layer was dehydrated with anhydrous calcium chloride. A crude oil was obtained.
Ｍ．１〜４のそれぞれの粗製油状物の組成をガスクロマ
トグラフィ一によって分析し、第１一２表の結果を得た
。M. The composition of each of the crude oils Nos. 1 to 4 was analyzed by gas chromatography, and the results shown in Tables 1-2 were obtained.
恥．１〜４のいずれの場合も目的物１−フロモー３．５
−ジクロロベンゼン（表中では３．劫本と略す）の他に
、ジクロロベンゼン類（表中ではＤＣＢと略す）、１−
フロモ−３．５−ジクロロベンゼン以外のモノプロモジ
クロロベンゼン類すなわち、１−フロモー２．４−ジク
ロロベンゼン、１−フロモ−２．５−ジクロロベンゼン
、１ーフロモ−３．４−ジクｏｏベンゼン、１ーフロモ
−２．３−ジクロロベンゼン及び１−フロモ−２．６−
ジクロロベンゼン（表中ではＭ旧ＣＢと略す）、ジブロ
モジクロロベンゼン類（表中ではＤＢＣＢと略す）など
が含まれていることが判った。Ｍ．１〜４のそれぞれの
粗製油状物を１３０〜１３７℃／６０脚Ｈｇで減圧蒸留
し、初留分としてのジクロロベンゼン類を分離した後主
留分を取り出し、室温乃至それ以下にまで冷却して目的
物を晶折ごせた。shame. In any case of 1 to 4, object 1-fromo 3.5
- In addition to dichlorobenzene (abbreviated as 3.Korubon in the table), dichlorobenzenes (abbreviated as DCB in the table), 1-
Monopromodichlorobenzenes other than furomo-3,5-dichlorobenzene, i.e., 1-furomo-2,4-dichlorobenzene, 1-furomo-2,5-dichlorobenzene, 1-furomo-3,4-dichlorobenzene, 1 -furomo-2,3-dichlorobenzene and 1-furomo-2,6-
It was found that dichlorobenzene (abbreviated as M old CB in the table), dibromodichlorobenzenes (abbreviated as DBCB in the table), etc. were contained. M. The crude oils of each of Nos. 1 to 4 were distilled under reduced pressure at 130 to 137°C/60 feet of Hg, and after separating the dichlorobenzenes as the first distillate, the main fraction was taken out and cooled to room temperature or lower. I was able to break down the target.
この晶析生成物を炉遇して、目的物である純度９５％以
上の１−フロモ−３．５−ジクロロベンゼン固形状物を
得た。炉液は分離できなかった１ーブロモー３．５ージ
クロロベンゼーン、１ーブロモ−３．５ージクロロベン
ゼン以外のモノブロモジクロロベンゼンからなり、更に
痕跡量のジブロモジクロロベンゼン類などを含有するも
のであった。第１一１表第１−２表
実施例 ２
下記第２一１表に示す条件に従って、瀦梓器、温度計及
び冷却管を備えた４つ口フラスコ中にジクロロベンゼン
及び無水ハロゲン化アルミニウムを入れ、蝿拝しながら
加熱し、そほへモノブロモジクロロベンゼンを滴下漏斗
より添加し、それぞれの加熱温度にそれぞれの反応時間
維持して反応を行ない、以下実施例１の場合と同様の操
作を経て粗製油状物を得た。This crystallized product was treated in a furnace to obtain the desired solid 1-furomo-3.5-dichlorobenzene with a purity of 95% or more. The furnace liquid consisted of monobromodichlorobenzenes other than 1-bromo-3.5-dichlorobenzene and 1-bromo-3.5-dichlorobenzene, which could not be separated, and also contained traces of dibromodichlorobenzenes. . Table 1-1 Table 1-2 Example 2 According to the conditions shown in Table 2-1 below, dichlorobenzene and anhydrous aluminum halide were placed in a four-necked flask equipped with a strainer, a thermometer, and a cooling tube. Add monobromodichlorobenzene to it from the dropping funnel, maintain each reaction time at each heating temperature, and conduct the reaction in the same manner as in Example 1. A crude oil was obtained.
恥．５〜１１のそれぞれの粗製油状物の組成について実
施例１の場合と同様の方法で分析し、第２−２表結果を
得た。shame. The composition of each of the crude oils Nos. 5 to 11 was analyzed in the same manner as in Example 1, and the results were obtained in Table 2-2.
表中の略号は実施例１の場合と同様である。Ｍ．５〜１
１のそれぞれの粗製油状物について実施例１の場合と同
様の操作を経て、第２−２表に示す初蟹分ジクロロベン
ゼン、目的物及び炉液を得た。The abbreviations in the table are the same as in Example 1. M. 5-1
Each of the crude oils in Example 1 was subjected to the same operations as in Example 1 to obtain the initial dichlorobenzene, the target product, and the furnace liquid shown in Table 2-2.
第２−１表
第２−２表
実施例 ３
下記第３−１表に示す条件に従って、前記実施例２の場
合と同様の４つ口フラスコ中にジクロロベンゼン及び無
水ハロゲン化アルミニウムを入れ、燈拝しながら加熱し
、そこへモノブロモジクロロベンゼンと前記実施例２で
得られた副生物（製造Ｎｏ．１２の場合は前記実施例２
の製造Ｎｏ．５で得られた炉液の一部、製造Ｎｏ．１３
の場合は前記実施例２の製造Ｎｏ．７で得られた初留分
ＤＣＢと炉液との混合液の全部、製造Ｎｏ．１４の場合
は前記実施例２の製造Ｎｏ．９で得られた初留分ＤＣＢ
と炉液との混合液の全部製造Ｍ．１５の場合は前記実施
例２の製造Ｍ．１１で得られた炉液の一部）との混合物
を滴下漏斗より添加し、それぞれの加熱温度にそれぞれ
の反応時間維持して反応を行ない、以下実施例１の場合
と同様の操作を経て粗製油状物を得た。Table 2-1 Table 2-2 Example 3 According to the conditions shown in Table 3-1 below, dichlorobenzene and anhydrous aluminum halide were placed in the same four-necked flask as in Example 2, and a light was placed. Heat while stirring, and add monobromodichlorobenzene and the by-product obtained in Example 2 (in the case of Production No. 12, add
Manufacturing No. A part of the furnace liquid obtained in Step No. 5, Production No. 13
In the case of production No. of Example 2 above. All of the mixed liquid of the first distillate DCB obtained in Step 7 and the furnace liquid, Production No. In the case of No. 14, production No. 14 of Example 2 is used. First distillate DCB obtained in step 9
Complete production of mixed liquid of and furnace liquidM. In the case of 15, the production M. A mixture with a portion of the furnace liquid obtained in step 11) was added from the dropping funnel, and the reaction was carried out by maintaining each reaction time at each heating temperature. An oil was obtained.
Ｎｏ．１２〜１５のそれぞれの粗製油状物の組成につい
て実施例１の場合と同様の方法で分析し、第３−２表の
結果を得た。No. The composition of each of the crude oils Nos. 12 to 15 was analyzed in the same manner as in Example 1, and the results shown in Table 3-2 were obtained.
表中の略号は実施例１の場合と同様である。Ｎｏ．１２
〜１５のそれぞれの粗製油状物について実施例１の場合
と同様の操作を経て、第３−２表に示す初留分ジクロロ
ベンゼン、目的物及び炉液を得た。The abbreviations in the table are the same as in Example 1. No. 12
The first distillate dichlorobenzene, the target product, and the furnace liquid shown in Table 3-2 were obtained by carrying out the same operations as in Example 1 for each of the crude oils No. 1 to 15.
第３−１表
第３−２表
実施例 ４
下記第４一１表に示す条件に従って前記実施例１の場合
とほぼ同様にして第１回目の異性化反応を行ない、反応
物を放冷後水洗して粗製油状物を得た。Table 3-1 Table 3-2 Example 4 The first isomerization reaction was carried out in substantially the same manner as in Example 1 according to the conditions shown in Table 4-1 below, and the reaction product was left to cool. A crude oil was obtained by washing with water.
Ｎｏ．１６〜１７のそれぞれの粗製油状物を１３０〜１
３７０／６０脚Ｈｇで減圧蒸留して主留分を取り出し、
目的物を晶折ごせて純度９５％以上の１−フロモ−３．
５−ジクロロベンゼン固形状物を得た。前記実施例１の
場合と同様に炉液及び初留分は主としてそれぞれモノブ
ロモジクロロベンゼン及びジクロロベンゼンからなり、
後留分は主としてジブロモジクロロベンゼンからなるも
のであって、その反応の結果を第４−２表に示す。前記
炉液、初蟹分及び後蟹分すなわち残分をリサィクルして
新しい原料と混合して次回の反応を行ない、それを繰り
返した。定常状態における反応の条件及び結果をそれぞ
れ第４−３又は４−４表に示す。第４−１表第４−２表
第４−３表
第４−４表No. 130 to 1 of each crude oil of 16 to 17
Distill the main fraction under reduced pressure at 370/60 Hg,
1-Flomo-3 with a purity of 95% or more by crystallizing the target product.
A solid 5-dichlorobenzene was obtained. As in the case of Example 1, the furnace liquid and the first distillate mainly consisted of monobromodichlorobenzene and dichlorobenzene, respectively,
The after-distillate mainly consists of dibromodichlorobenzene, and the results of the reaction are shown in Table 4-2. The reactor liquid, the initial and post-cracking fractions, that is, the residue, were recycled and mixed with new raw materials for the next reaction, and the process was repeated. The reaction conditions and results in steady state are shown in Tables 4-3 and 4-4, respectively. Table 4-1 Table 4-2 Table 4-3 Table 4-4
Claims (1)
ロロベンゼンを８０℃以上に加熱して異性化することを
特徴とする１−ブロモ−３．５−ジクロロベンゼンの製
造方法。1. A method for producing 1-bromo-3,5-dichlorobenzene, which comprises isomerizing monobromodichlorobenzene by heating it to 80° C. or higher in the presence of aluminum halide.
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP51122591A JPS6021129B2 (en) | 1976-10-12 | 1976-10-12 | Method for producing 1-bromo-3,5-dichlorobenzene |
| GB34738/77A GB1535697A (en) | 1976-08-25 | 1977-08-18 | Process for producing 1-bromo-3,5-dichlorobenzene |
| DE19772737797 DE2737797A1 (en) | 1976-08-25 | 1977-08-22 | PROCESS FOR MANUFACTURING 1-BROMO-3,5-DICHLOROBENZENE |
| CA285,263A CA1078410A (en) | 1976-08-25 | 1977-08-23 | Process for producing 1-bromo-3,5-dichlorobenzene |
| FR7725834A FR2362807A1 (en) | 1976-08-25 | 1977-08-24 | PROCESS FOR PREPARING BROMO-1-DICHLORO-3,5-BENZENE BY SPECIAL ISOMERIZATION OF MONOBROMODICHLOROBENZENE |
| CH1036377A CH631953A5 (en) | 1976-08-25 | 1977-08-24 | METHOD FOR PRODUCING 1-BROM-3,5-DICHLORBENZOL. |
| NLAANVRAGE7709373,A NL188899C (en) | 1976-08-25 | 1977-08-25 | PROCESS FOR THE PREPARATION OF 1-BROME-3,5-DICHLOROBENZENE. |
| IT26959/77A IT1085018B (en) | 1976-08-25 | 1977-08-25 | PROCEDURE FOR THE PRODUCTION OF 1-BROMO-3,5-DICHLOROBENZENE |
| US06/206,392 US4347390A (en) | 1976-08-25 | 1980-11-13 | Process for producing 1-bromo-3,5-dichlorobenzene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP51122591A JPS6021129B2 (en) | 1976-10-12 | 1976-10-12 | Method for producing 1-bromo-3,5-dichlorobenzene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5356623A JPS5356623A (en) | 1978-05-23 |
| JPS6021129B2 true JPS6021129B2 (en) | 1985-05-25 |
Family
ID=14839705
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP51122591A Expired JPS6021129B2 (en) | 1976-08-25 | 1976-10-12 | Method for producing 1-bromo-3,5-dichlorobenzene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6021129B2 (en) |
-
1976
- 1976-10-12 JP JP51122591A patent/JPS6021129B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5356623A (en) | 1978-05-23 |
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