JPS63297336A - Bromination of aromatic ether - Google Patents
Bromination of aromatic etherInfo
- Publication number
- JPS63297336A JPS63297336A JP12984587A JP12984587A JPS63297336A JP S63297336 A JPS63297336 A JP S63297336A JP 12984587 A JP12984587 A JP 12984587A JP 12984587 A JP12984587 A JP 12984587A JP S63297336 A JPS63297336 A JP S63297336A
- Authority
- JP
- Japan
- Prior art keywords
- solvent
- brominating agent
- aromatic ether
- group
- reaction
- 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.)
- Granted
Links
- 150000008378 aryl ethers Chemical class 0.000 title claims abstract description 15
- 230000031709 bromination Effects 0.000 title description 5
- 238000005893 bromination reaction Methods 0.000 title description 5
- 125000005210 alkyl ammonium group Chemical group 0.000 claims abstract description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 abstract description 15
- 239000002904 solvent Substances 0.000 abstract description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 9
- 239000003795 chemical substances by application Substances 0.000 abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 7
- 125000000217 alkyl group Chemical group 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 abstract description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- GPWHDDKQSYOYBF-UHFFFAOYSA-N ac1l2u0q Chemical compound Br[Br-]Br GPWHDDKQSYOYBF-UHFFFAOYSA-N 0.000 abstract description 3
- 230000009257 reactivity Effects 0.000 abstract description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 abstract description 2
- 239000004009 herbicide Substances 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 abstract description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 abstract description 2
- 239000002917 insecticide Substances 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- -1 gold halide Chemical class 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 2
- 235000010216 calcium carbonate Nutrition 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical group ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- FGIBLIQLKYAGPD-UHFFFAOYSA-N [7-(bromomethyl)-2,6-dimethyl-3,5-dioxopyrazolo[1,2-a]pyrazol-1-yl]methyl-trimethylazanium Chemical compound C[N+](C)(C)CC1=C(C)C(=O)N2C(=O)C(C)=C(CBr)N21 FGIBLIQLKYAGPD-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- QSRFYFHZPSGRQX-UHFFFAOYSA-N benzyl(tributyl)azanium Chemical compound CCCC[N+](CCCC)(CCCC)CC1=CC=CC=C1 QSRFYFHZPSGRQX-UHFFFAOYSA-N 0.000 description 1
- VBQDSLGFSUGBBE-UHFFFAOYSA-N benzyl(triethyl)azanium Chemical compound CC[N+](CC)(CC)CC1=CC=CC=C1 VBQDSLGFSUGBBE-UHFFFAOYSA-N 0.000 description 1
- YOUGRGFIHBUKRS-UHFFFAOYSA-N benzyl(trimethyl)azanium Chemical compound C[N+](C)(C)CC1=CC=CC=C1 YOUGRGFIHBUKRS-UHFFFAOYSA-N 0.000 description 1
- OQESKQAHRXOSMS-UHFFFAOYSA-N benzyltrimethylammonium tribromide Chemical compound Br[Br-]Br.C[N+](C)(C)CC1=CC=CC=C1 OQESKQAHRXOSMS-UHFFFAOYSA-N 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
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 description 1
- 229910000020 calcium bicarbonate Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
［発明の目的］
（産業上の利用分野）
本発明は、芳香族エーテルの芳香環をブロモ化する方法
に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Industrial Application Field) The present invention relates to a method for brominating an aromatic ring of an aromatic ether.
（従来の技術及びその問題点）
芳香族エーテルのブロモ化体は、種々の医薬、除草剤、
殺菌剤等の製造原料として有用である（例えば、西独特
許第２４ ０２ ６７２号公報、同第２４ ２０ ４３
９号公輯、同第２２ ５５ ４３９号公報及び特開昭６
２−３３１０４号公報）。(Prior art and its problems) Brominated aromatic ethers are used in various medicines, herbicides,
It is useful as a raw material for producing fungicides, etc. (for example, West German Patent No. 24 02 672, West German Patent No. 24 20 43).
Publication No. 9, Publication No. 22 55 439, and JP-A-6
2-33104).
一般に、芳香族エーテルの核へのブロモ化は、金屑ハロ
ゲン化物やヨウ素などの触媒の共存下に臭素を作用させ
ることにより行われている。Generally, bromination of an aromatic ether into a nucleus is carried out by the action of bromine in the presence of a catalyst such as a gold halide or iodine.
これらの手段を用いて芳香族エーテルのブロモ化を行う
と、これらの化合物ではフェノール類などと異なり、芳
香環のブロモ化に対する活性が低下しているため、効率
よく目的物を得ることができない。When aromatic ethers are brominated using these methods, unlike phenols and the like, these compounds have reduced activity for bromination of the aromatic ring, so it is not possible to efficiently obtain the desired product.
そこで、本発明者らは、従来の芳香族エーテルのブロモ
化方法を改良すべく鋭意研究を重ねた結果、ブロモ化剤
としてベンジルトリ低級アルキルアンモニウムトリブロ
ミドを用いることにより、芳香環がブロモ化された目的
化合物が好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。Therefore, the present inventors conducted extensive research to improve the conventional method for brominating aromatic ethers, and as a result, the aromatic ring was brominated by using benzyl tri-lower alkyl ammonium tribromide as the brominating agent. The inventors discovered that the target compound could be obtained in good yield and completed the present invention.
［発明の構成］
（問題点を解決するための手段）
本発明は、芳香族エーテルをベンジルトリ低級アルキル
アンモニウムトリブロミドで処理することを特徴とする
芳香族エーテルのブロモ化方法に関するものである。[Structure of the Invention] (Means for Solving the Problems) The present invention relates to a method for brominating an aromatic ether, which is characterized by treating the aromatic ether with benzyl tri-lower alkyl ammonium tribromide.
本発明に用いられる芳香族エーテルとしては、芳香環の
少なくとも一つの位置が非置換のものであれば特に制限
はない、かかる芳香族エーテルの芳香１１の置換基とし
ては、例えば、メチル基、エチル基、プロピル基、イソ
プロピル基、ブチル基、イソブチル基、５ｅｃ−ブチル
基、ｔｅｒｔ−ブチル基、ペンチル基、ヘキシル基等の
アルキル基ニジクロヘキシル基等のシクロアルキル基；
メトキシ基、エトキシ基、プロポキシ基、イソプロポキ
シ基、ブトキシ基、イソブトキシ基、 ５ｅｃ−ブトキ
シ基、ｔｅｒｔ−ブトキシ基等の他のアルコキシ基；フ
ッ素原子、塩素原子、臭素原子等のハロゲン原子などが
挙げられる。The aromatic ether used in the present invention is not particularly limited as long as at least one position on the aromatic ring is unsubstituted.Substituents for aroma 11 of such an aromatic ether include, for example, methyl group, ethyl group, etc. a cycloalkyl group such as a dichlorohexyl group;
Other alkoxy groups such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, 5ec-butoxy group, tert-butoxy group; halogen atoms such as fluorine atom, chlorine atom, bromine atom, etc. It will be done.
本発明に用いるベンジルトリ低級アルキルアンモニウム
トリブロミドは、
次式（１）：
％式％（）
（式中、Ｒ，、Ｒ２及びＲ３は、同−又は相異なる低級
アルキル基を表す。）
で示される化合物である。The benzyl tri-lower alkylammonium tribromide used in the present invention is represented by the following formula (1): % formula % (in the formula, R, , R2 and R3 represent the same or different lower alkyl groups) It is a compound.
前記式（１）の定義において、低級アルキル基とは、炭
素数１〜６のアルキル基であり、例えば、メチル基、エ
チル基、プロピル基、イソプロピル基、ブチル基、ペン
チル基、ヘキシル基などが挙げられる。In the definition of the above formula (1), the lower alkyl group is an alkyl group having 1 to 6 carbon atoms, such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, pentyl group, hexyl group, etc. Can be mentioned.
本発明に用いる溶媒は、特に制限はなく、前記式（Ｉ）
で示されるブロモ化剤を溶解するものであれば如何なる
ものでもよい、特に、ハロゲン化アルキル溶媒、例えば
塩化メチレン、クロロホルム、トリクレン、ジクロルエ
チレン等は非常に高い溶解性を有し反応溶媒として最適
である。また、この溶媒中に低級アルコール、例えばメ
タノール、エタノール、プロピルアルコール、イソプロ
ピルアルコール等を混入するとブロモ化剤の反応性が著
しく高まる。特にメタノールはその効果が著しい、ハロ
ゲン化アルキル溶媒とアルコールの混合比は特に制限は
ないが、通常ｌ：５〜１０：１、好ましくはｌ：１〜５
：１である。The solvent used in the present invention is not particularly limited, and has the formula (I)
Any solvent may be used as long as it dissolves the brominating agent represented by .In particular, halogenated alkyl solvents such as methylene chloride, chloroform, trichlorethylene, dichloroethylene, etc. have very high solubility and are suitable as reaction solvents. It is. Furthermore, when a lower alcohol such as methanol, ethanol, propyl alcohol, isopropyl alcohol, etc. is mixed into this solvent, the reactivity of the brominating agent increases significantly. In particular, methanol has a remarkable effect.The mixing ratio of halogenated alkyl solvent and alcohol is not particularly limited, but is usually 1:5 to 10:1, preferably 1:1 to 5.
:1.
また基質に対してブロモ化剤は理論量で十分であり過剰
に加える必要はない。Further, the stoichiometric amount of the brominating agent is sufficient for the substrate, and there is no need to add it in excess.
更に反応性を高めるためには塩基共存下で反応を行って
もよいが、使用する塩基はブロモ化後、副生ずる臭化水
素をトラップする目的で使用される。従ってわずかの溶
解度があればよく、その意味においては炭酸カルシウム
、炭酸水素カルシウム、炭酸ナトリウム、炭酸水素ナト
リウム、炭酸カリウム、炭酸水素カリウム等のアルカリ
金属又はアルカリ土類金属の炭酸塩又は炭酸水素塩が有
効である。かかる塩基の使用量はブロモ化剤（Ｉ）と当
量であれば十分であるが多くても反応に影響を与えない
。In order to further increase the reactivity, the reaction may be carried out in the presence of a base, but the base used is used for the purpose of trapping hydrogen bromide produced as a by-product after bromination. Therefore, only a slight solubility is required, and in this sense, carbonates or hydrogen carbonates of alkali metals or alkaline earth metals such as calcium carbonate, calcium hydrogen carbonate, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, etc. It is valid. The amount of the base to be used is sufficient as long as it is equivalent to the amount of the brominating agent (I), but even if the amount is large, the reaction will not be affected.
（発明の実施例）
以下、合成例及び実施例により本発明を更に詳細に説明
するが、これらの実施例は本発明の範囲を何ら制限する
ものではない。(Examples of the Invention) Hereinafter, the present invention will be explained in more detail with reference to Synthesis Examples and Examples, but these Examples are not intended to limit the scope of the present invention in any way.
合成例１ ベンジルトリメチルアンモニウムトリプロミ
ド（ＢＴＭＡＢ ｒｓ ）の合成ベンジルトリメチルア
ンモニウムクロリド１１ 、１ ｇ （６０ｍ＋ｏｏｌ
）とＮａＢｒＯ３４，５ｇ（３０１１ＥＩＯＩ）を水１
００ｍ１に溶解し、臭化水素酸（４７％）１８０ｓｍｌ
を室温下で加えてゆくと即ちに結晶が析出した。塩化メ
チレン５０−で４回抽出した。有機層を硫酸マグネシウ
ムで乾燥後、溶媒を留去した。得られた粗結晶を塩化メ
チレン／エーテル（１０：１）の混合溶媒で再結晶した
。Synthesis Example 1 Synthesis of benzyltrimethylammonium tripromide (BTMAB rs ) Benzyltrimethylammonium chloride 11, 1 g (60m+ool
) and NaBrO34.5g (3011EIOI) in water 1
00ml dissolved in 180sml of hydrobromic acid (47%)
was added at room temperature, crystals were immediately precipitated. Extracted four times with 50 methylene chloride. After drying the organic layer with magnesium sulfate, the solvent was distilled off. The obtained crude crystals were recrystallized from a mixed solvent of methylene chloride/ether (10:1).
収量：１８．２ｇ（収率７８％）
ｍ、ｐ、１００〜ｌｏ１”０
合成例２ ベンジルトリエチルアンモニウムトリプロミ
ド（ＢＴＥＡＢｒｓ ）ｃ７）合成ベンジルトリメチル
アンモニウムクロリドに代えてベンジルトリエチルアン
モニウムクロ１．Ｉ Ｆｌ ３ 、７ ｇ （６０ｍｍ
ｏｌ）を用いて合成例１と同様に行った。Yield: 18.2g (yield 78%) m, p, 100~lo1''0 Synthesis Example 2 Benzyltriethylammonium tripromide (BTEABrs) c7) Synthesis Benzyltriethylammonium chloride replaced with benzyltrimethylammonium chloride 1.I Fl 3 , 7g (60mm
The same procedure as in Synthesis Example 1 was carried out using ol).
収量：２１．３ｇ（収率８２％）
ｍ、ｐ、１０２〜１０３℃
合成例３ ベンジルトリブチルアンモニウムトリプロミ
ド（ＢＴＢＡＢｒ３）（１）合成ベンジルトリメチルア
ンモニウムクロリドに代えてペンジルトリブチルアンモ
ニウムクロリド１８ 、７ ｇ （６０ｍｍｏｌ）を用
いて合成例１と同様に行った。Yield: 21.3 g (yield 82%) m, p, 102-103°C Synthesis Example 3 Benzyltributylammonium tripromide (BTBABr3) (1) Synthesis Penzyltributylammonium chloride 18.7 g instead of benzyltrimethylammonium chloride (60 mmol) was carried out in the same manner as in Synthesis Example 1.
収量：１９．２ｇ（収率６２％）
ｍ、ｐ、９１〜９２℃
実施例１４−ブロモアニソールの合成
アニソール ０．４ ｇ （４ｍ’ｍｏｌ）の塩化メチ
レン５０ｍ１溶液にメタノール２０−を添加しＢＴＭＡ
Ｂｒ３１．７ｇ（４，４ｍｍｏｌ）を加え室温で２時間
攪拌した０反応終了時にはＢＴＭＡＢｒ３のオレンジ色
がほぼ消失する０反応後、溶媒を留去した後、５％亜硫
酸水素ナトリウム水溶液２０−を加え、未反応のＢ Ｔ
Ｍ Ａ Ｂ ｒ ｓを分解した後、内容物をエーテル
４０ａＪで２回抽出し、次いで溶媒を留去して４−ブロ
モアニツールｏ、７ａｇ（収１１９％）を得た。Yield: 19.2 g (yield 62%) m, p, 91-92°C Example 14 - Synthesis of bromoanisole Methanol 20- was added to a solution of 0.4 g (4 m'mol) of anisole in 50 ml of methylene chloride to prepare BTMA.
Added 31.7 g (4.4 mmol) of Br and stirred at room temperature for 2 hours. At the end of the reaction, the orange color of BTMABr3 almost disappeared. After the reaction, the solvent was distilled off, and 5% aqueous sodium hydrogen sulfite solution was added. Unreacted B T
After decomposing M A B r s, the contents were extracted twice with ether 40aJ, and then the solvent was distilled off to obtain 4-bromoanitool o, 7ag (yield 119%).
ｂ、ｐ、２１３℃７７６０ｍ■）Ｉｇ
実施例２ 各種芳香族エーテルのブロモ化原料のアニソ
ールに代えて以下に示す原料を用いて実施例１と同様に
行った。結果を表に示す。b, p, 213° C. 7760 m) Ig Example 2 The same procedure as in Example 1 was carried out using the raw materials shown below in place of anisole as the raw material for bromination of various aromatic ethers. The results are shown in the table.
［発明の効果］
本発明によれば、ブロモ芳香族エーテルを好収率で提供
することができる。[Effects of the Invention] According to the present invention, bromoaromatic ether can be provided in good yield.
Claims (1)
ムトリブロミドで処理することを特徴とする芳香族エー
テルのブロモ化方法。A method for brominating aromatic ethers, which comprises treating aromatic ethers with benzyl tri-lower alkyl ammonium tribromide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12984587A JPS63297336A (en) | 1987-05-28 | 1987-05-28 | Bromination of aromatic ether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12984587A JPS63297336A (en) | 1987-05-28 | 1987-05-28 | Bromination of aromatic ether |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63297336A true JPS63297336A (en) | 1988-12-05 |
| JPH0470294B2 JPH0470294B2 (en) | 1992-11-10 |
Family
ID=15019657
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12984587A Granted JPS63297336A (en) | 1987-05-28 | 1987-05-28 | Bromination of aromatic ether |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63297336A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111348990A (en) * | 2020-04-15 | 2020-06-30 | 北京格林凯默科技有限公司 | Preparation method of p-bromophenyl alkyl ether |
-
1987
- 1987-05-28 JP JP12984587A patent/JPS63297336A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111348990A (en) * | 2020-04-15 | 2020-06-30 | 北京格林凯默科技有限公司 | Preparation method of p-bromophenyl alkyl ether |
| CN111348990B (en) * | 2020-04-15 | 2022-11-18 | 北京格林凯默科技有限公司 | Preparation method of p-bromophenyl alkyl ether |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0470294B2 (en) | 1992-11-10 |
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