JPS62298562A - Production of bromoaniline or such - Google Patents
Production of bromoaniline or suchInfo
- Publication number
- JPS62298562A JPS62298562A JP13930986A JP13930986A JPS62298562A JP S62298562 A JPS62298562 A JP S62298562A JP 13930986 A JP13930986 A JP 13930986A JP 13930986 A JP13930986 A JP 13930986A JP S62298562 A JPS62298562 A JP S62298562A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- compound
- promosuccinimide
- polar solvent
- trifluoromethylaniline
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- ILCQYORZHHFLNL-UHFFFAOYSA-N n-bromoaniline Chemical compound BrNC1=CC=CC=C1 ILCQYORZHHFLNL-UHFFFAOYSA-N 0.000 title claims description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 239000002798 polar solvent Substances 0.000 claims abstract description 8
- 125000001188 haloalkyl group Chemical group 0.000 claims abstract description 6
- 125000003277 amino group Chemical group 0.000 claims abstract description 3
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 3
- 125000004438 haloalkoxy group Chemical group 0.000 claims abstract description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 3
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 claims 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims 1
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 claims 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 claims 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 claims 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims 1
- -1 aniline compound Chemical class 0.000 abstract description 6
- HRYILSDLIGTCOP-UHFFFAOYSA-N N-benzoylurea Chemical compound NC(=O)NC(=O)C1=CC=CC=C1 HRYILSDLIGTCOP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 3
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 abstract 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 abstract 2
- 229910052736 halogen Inorganic materials 0.000 abstract 2
- 150000002367 halogens Chemical class 0.000 abstract 2
- 229940079593 drug Drugs 0.000 abstract 1
- 230000000855 fungicidal effect Effects 0.000 abstract 1
- 239000000417 fungicide Substances 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 8
- 229910052794 bromium Inorganic materials 0.000 description 7
- 150000001448 anilines Chemical group 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- SLFVYFOEHHLHDW-UHFFFAOYSA-N n-(trifluoromethyl)aniline Chemical compound FC(F)(F)NC1=CC=CC=C1 SLFVYFOEHHLHDW-UHFFFAOYSA-N 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- XWHRORSQEQYOKG-UHFFFAOYSA-N 2-bromo-6-fluoro-3-(trifluoromethyl)aniline Chemical compound NC1=C(F)C=CC(C(F)(F)F)=C1Br XWHRORSQEQYOKG-UHFFFAOYSA-N 0.000 description 2
- DRKWGMXFFCPZLW-UHFFFAOYSA-N 2-fluoro-5-(trifluoromethyl)aniline Chemical compound NC1=CC(C(F)(F)F)=CC=C1F DRKWGMXFFCPZLW-UHFFFAOYSA-N 0.000 description 2
- UQRLKWGPEVNVHT-UHFFFAOYSA-N 3,5-dichloroaniline Chemical compound NC1=CC(Cl)=CC(Cl)=C1 UQRLKWGPEVNVHT-UHFFFAOYSA-N 0.000 description 2
- UYVDMCXPDGRLEC-UHFFFAOYSA-N 4-bromo-2-fluoro-5-(trifluoromethyl)aniline Chemical compound NC1=CC(C(F)(F)F)=C(Br)C=C1F UYVDMCXPDGRLEC-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 241000238631 Hexapoda Species 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000031709 bromination Effects 0.000 description 2
- 238000005893 bromination reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000009422 growth inhibiting effect Effects 0.000 description 2
- 239000002917 insecticide Substances 0.000 description 2
- KXHORCXSQZTQQI-UHFFFAOYSA-N n-(fluoromethyl)aniline Chemical compound FCNC1=CC=CC=C1 KXHORCXSQZTQQI-UHFFFAOYSA-N 0.000 description 2
- BYODQNZIFLYIPV-UHFFFAOYSA-N n-fluoro-3-(trifluoromethyl)aniline Chemical compound FNC1=CC=CC(C(F)(F)F)=C1 BYODQNZIFLYIPV-UHFFFAOYSA-N 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- YNOOQIUSYGWMSS-UHFFFAOYSA-N 2,5-difluoroaniline Chemical compound NC1=CC(F)=CC=C1F YNOOQIUSYGWMSS-UHFFFAOYSA-N 0.000 description 1
- VBLXCTYLWZJBKA-UHFFFAOYSA-N 2-(trifluoromethyl)aniline Chemical compound NC1=CC=CC=C1C(F)(F)F VBLXCTYLWZJBKA-UHFFFAOYSA-N 0.000 description 1
- IQHSSYROJYPFDV-UHFFFAOYSA-N 2-bromo-1,3-dichloro-5-(trifluoromethyl)benzene Chemical group FC(F)(F)C1=CC(Cl)=C(Br)C(Cl)=C1 IQHSSYROJYPFDV-UHFFFAOYSA-N 0.000 description 1
- HQUWXEXDIIWBBY-UHFFFAOYSA-N 2-fluoro-5-(trifluoromethoxy)aniline Chemical compound NC1=CC(OC(F)(F)F)=CC=C1F HQUWXEXDIIWBBY-UHFFFAOYSA-N 0.000 description 1
- FTZQXOJYPFINKJ-UHFFFAOYSA-N 2-fluoroaniline Chemical compound NC1=CC=CC=C1F FTZQXOJYPFINKJ-UHFFFAOYSA-N 0.000 description 1
- SADHVOSOZBAAGL-UHFFFAOYSA-N 3-(trifluoromethoxy)aniline Chemical compound NC1=CC=CC(OC(F)(F)F)=C1 SADHVOSOZBAAGL-UHFFFAOYSA-N 0.000 description 1
- VIUDTWATMPPKEL-UHFFFAOYSA-N 3-(trifluoromethyl)aniline Chemical compound NC1=CC=CC(C(F)(F)F)=C1 VIUDTWATMPPKEL-UHFFFAOYSA-N 0.000 description 1
- XWBTZHDDWRNOQH-UHFFFAOYSA-N 3-chloro-2-fluoroaniline Chemical compound NC1=CC=CC(Cl)=C1F XWBTZHDDWRNOQH-UHFFFAOYSA-N 0.000 description 1
- PNPCRKVUWYDDST-UHFFFAOYSA-N 3-chloroaniline Chemical compound NC1=CC=CC(Cl)=C1 PNPCRKVUWYDDST-UHFFFAOYSA-N 0.000 description 1
- GZRMNMGWNKSANY-UHFFFAOYSA-N 4-bromo-2-fluoroaniline Chemical compound NC1=CC=C(Br)C=C1F GZRMNMGWNKSANY-UHFFFAOYSA-N 0.000 description 1
- QOPGULWHAXFEIP-UHFFFAOYSA-N 4-bromo-3,5-dichloroaniline Chemical compound NC1=CC(Cl)=C(Br)C(Cl)=C1 QOPGULWHAXFEIP-UHFFFAOYSA-N 0.000 description 1
- JCYROOANFKVAIB-UHFFFAOYSA-N 5-chloro-2-fluoroaniline Chemical compound NC1=CC(Cl)=CC=C1F JCYROOANFKVAIB-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、強い昆虫生育抑制作用を有するベンゾイルウ
レア系殺虫剤の中間体として、又医薬の有用な中間体と
して用いられるブロモアニリン類の工業的に有利な製造
法に関する。Detailed Description of the Invention [Field of Industrial Application] The present invention is directed to the industrial application of bromoanilines, which are used as intermediates for benzoyl urea insecticides that have a strong insect growth inhibitory effect, and as useful intermediates for pharmaceuticals. This invention relates to an advantageous manufacturing method.
従来、アニリン類のパラ位をブロム化する方法としては
、アニリン類をアセドアニライドに誘導した後、臭素で
ブロム化する方法が古くから知られている。Conventionally, as a method for brominating the para-position of anilines, a method has long been known in which anilines are induced into acedoanilide and then brominated with bromine.
又、ブロム化剤として、Ｎ−プロモサクシンイミドを用
いるアニリン類のブロム化方法も例えば、米国特許第３
９９２１８９号で知られている。Furthermore, a method for brominating anilines using N-promosuccinimide as a brominating agent is also described, for example, in U.S. Pat.
It is known as No. 992189.
この特許では２−フルオロアニリンと等モルのＮ−プロ
モサクシンイミドを塩化メチレン中、０℃で反応させ、
４−ブロモ−２−フルオロアニリンを９６％の収率で得
ている。In this patent, 2-fluoroaniline and equimolar amounts of N-promosuccinimide are reacted in methylene chloride at 0°C,
4-Bromo-2-fluoroaniline is obtained with a yield of 96%.
しかし、特にアミン基に対するメタ位に置換基を有する
了ニリン類を前記の慣用的方法で。However, in particular, the compounds having a substituent in the meta-position relative to the amine group can be treated in the conventional manner as described above.
メタ置換アセドアニライドに誘導し、臭素でブロム化を
行う場合、目的とするパラ位のブロム体の他に、オルソ
位ブロム体、ジブロム体等ノ副生物が多量に生成し、分
離精製が困難である。When a meta-substituted acedoanilide is derived and brominated with bromine, large amounts of by-products such as ortho-bromine and dibromine are produced in addition to the desired para-bromine, making separation and purification difficult. .
又、ブロム化後、アセチル基を切断することが必要であ
る為、製造工程が長い欠点を有する。Furthermore, since it is necessary to cleave the acetyl group after bromination, it has the disadvantage that the manufacturing process is long.
さらに１米国特許第３９９２１８９号の方法において特
にメタ位に置換基を有する了ニリン類とＮ−プロモサク
シンイミドとを塩化メチレン中で反応させ、ブロム化す
る場合は、目的とするパラ位のブロム体の他にオルソ位
ブロム体がかなり副生ずる欠点を有する。例えば、２−
フルオロ−５−トリフルオロメチルアニリンと等モルの
Ｎ−プロモサクシンイミドを塩化メチレン中で反応させ
たところ、目的とする、４−ブロモ−２−フルオロ−５
−トリフルオロメチルアニリンは５１，２％の収率でし
か得られず、６−ブロモ−２−フルオロ−５−トリフル
オロメチルアニリンが４６．２％副生じ１選択性が低か
った。Furthermore, in the method of 1 U.S. Pat. No. 3,992,189, when bromination is carried out by reacting a phosphoniline having a substituent at the meta position with N-promosuccinimide in methylene chloride, the target bromine compound at the para position is In addition, it has the disadvantage that a considerable amount of ortho-bromine is produced as a by-product. For example, 2-
When fluoro-5-trifluoromethylaniline and equimolar amounts of N-promosuccinimide were reacted in methylene chloride, the desired 4-bromo-2-fluoro-5
-Trifluoromethylaniline was obtained in a yield of only 51.2%, and 6-bromo-2-fluoro-5-trifluoromethylaniline was produced as a by-product at 46.2%. 1 Selectivity was low.
この様に、特にメタ位に置換基を有するアニリン類をブ
ロム化する場合、従来の方法では、選択性が低く、分離
精製が困難であり、工業的に有利でない。本発明の方法
は、アニリン類のパラ位を選択的にブロム化する工業的
に有利な方法を提供するものである。As described above, when brominating anilines having a substituent at the meta position, the conventional methods have low selectivity and are difficult to separate and purify, and are not industrially advantageous. The method of the present invention provides an industrially advantageous method for selectively brominating the para-position of anilines.
本発明者らはアニＩＪン類のパラ位を選択的にブロム化
する工業的に有利な製造法を鋭意検討した結果、式
（式中、Ｒ１は水素原子、ハロゲン原子又はハロアルキ
ル基を、Ｒ２は水素原子、ハロゲン原子又はハロアルキ
ル基を、ルは、水素原子、ハロゲン原子、ハロアルキル
基又はハロアルコキシ基を示す。）で表わされる化合物
をＮ−プロモサクシンイミドと極性溶媒中で反応させる
ことによりアミン基に対するパラ位が選択的にブロム化
された一般式
（式中、Ｒ１、Ｒ２およびＲ３は前記と同じ意味を有す
る）
で表わされるブロモアニリン類を工業的に有利に製造す
る方法を見い出した。The present inventors have intensively investigated an industrially advantageous production method for selectively brominating the para-position of amines, and found that represents a hydrogen atom, a halogen atom, or a haloalkyl group, and R represents a hydrogen atom, a halogen atom, a haloalkyl group, or a haloalkoxy group) with N-promosuccinimide in a polar solvent to produce an amine. We have found an industrially advantageous method for producing bromoanilines represented by the general formula (wherein R1, R2 and R3 have the same meanings as above) in which the para-position of the group is selectively brominated.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明の反応は式（１）の化合物を極性溶媒に溶解し、
好ましくは一２０〜５０℃の温度に調整し、式（１）の
化合物と好ましくは等モルのＮ−プロモサクシンイミド
を上記極性溶媒に溶解した溶液を好ましくは一２０〜５
０℃にて、３０〜１２０分で滴下する。滴下終了後、同
温度にて３０〜１２０分反応させることにより式（２）
の化合物を高収率で得ることができる。あるいは式（１
）の化合物を極性溶媒に溶解させ、好１しくは一２０〜
５０℃の温度に調整し、式（１）の化合物と好ましくは
等モルのＮ−プロモサクシンイミドを同温度にて３０〜
１２０分で添加し、添加終了後、同温にて、３０〜１２
０分反応させることにより式（２）の化合物を高収率で
得ることができる。The reaction of the present invention involves dissolving the compound of formula (1) in a polar solvent,
Preferably, the temperature is adjusted to -20 to 50°C, and a solution of the compound of formula (1) and preferably equimolar N-promosuccinimide dissolved in the above polar solvent is preferably heated to -20 to -50°C.
Add dropwise over 30 to 120 minutes at 0°C. After completing the dropwise addition, the formula (2) is obtained by reacting at the same temperature for 30 to 120 minutes.
can be obtained in high yield. Or the formula (1
) is dissolved in a polar solvent, preferably from 1 to 20
The temperature was adjusted to 50°C, and the compound of formula (1) and preferably equimolar amount of N-promosuccinimide were added at the same temperature for 30~
It was added for 120 minutes, and after the addition was completed, it was heated at the same temperature for 30 to 12 minutes.
By reacting for 0 minutes, the compound of formula (2) can be obtained in high yield.
本発明で式（２）の化合物の原料である式（１）の化合
物としては、例えば２−フルオロ−５−トリフルオロメ
チルアニリン、３−クロロ−２−フルオロアニリン、５
−クロロ−２−フルオロアニリン、２−フルオロ−５−
トリフルオロメトキシアニリン、３，５−ジクロロアニ
リン、３−トリフルオロメチルアニリン、２−トリフル
オロメチルアニリン、２−１０ロー５−トリフルオロメ
チルアニリン、３−クロロアニリン、３−トリフルオロ
メトキシアニリン、２．５−ジフルオロアニリン、２−
フルオロ−５−テトラフルオロエトキシアニリンなどが
挙げられる。Examples of the compound of formula (1) which is a raw material for the compound of formula (2) in the present invention include 2-fluoro-5-trifluoromethylaniline, 3-chloro-2-fluoroaniline, 5
-chloro-2-fluoroaniline, 2-fluoro-5-
Trifluoromethoxyaniline, 3,5-dichloroaniline, 3-trifluoromethylaniline, 2-trifluoromethylaniline, 2-10-5-trifluoromethylaniline, 3-chloroaniline, 3-trifluoromethoxyaniline, 2 .5-difluoroaniline, 2-
Examples include fluoro-5-tetrafluoroethoxyaniline.
本発明は、強い昆虫生育抑制作用を有するベンゾイルウ
レア系殺虫剤の中間体として、又。The present invention can also be used as an intermediate for benzoyl urea insecticides having a strong insect growth inhibiting effect.
医薬の有用な中間体として用いられるブロモアニリン類
を工業的に有利に製造できる。Bromoanilines, which are used as useful intermediates for pharmaceuticals, can be advantageously produced industrially.
以下に実施例を挙げて本発明を説明するが、本発明は、
この実施例によって限定されるものではない。The present invention will be explained below with reference to Examples.
The invention is not limited to this example.
実施例１゜
１７．９ ｇｒ （０，１モル）の２−フルオロ−５−
トリフルオロメチルアニリンの５０ ｍｌ Ｎ、Ｎ−ジ
メチルホルムアミド溶液Ｋ、１７．８ ｇｒ（０，１モ
ル） ノＮ−プロモサクシンイミドのｓｏｍｌＮ、Ｎ−
ジメチルホルムアミド溶液を室温にて１時間かけて滴下
した。滴下終了後、３０分攪拌した後、水にあけ、エー
テル抽出し、冷水にて洗浄後エーテルを留去し、２５．
８ ｇｒの油状物質を得た。ガスクロ分析の結果、４−
フロモー２−フルオロ−５−） リフルオロメチルアニ
リンが９１．６％及ヒ６− フＣ１モー２−フルオロ−
５−） ＩＪフルオロメチルアニリンが４．０％の生成
比率であった。この油状物質を減圧下で蒸留しｂ３３〜
３５１３０〜１３２℃の沸点を有する４−ブロモー２−
フルオロ−５−トリフルオロメチルアニリン２３．２ｇ
ｒを４た。Example 1 17.9 gr (0.1 mol) of 2-fluoro-5-
50 ml of trifluoromethylaniline in N,N-dimethylformamide solution K, 17.8 gr (0,1 mol) soml of N-promosuccinimide, N,N-
A dimethylformamide solution was added dropwise at room temperature over 1 hour. After the dropwise addition was completed, the mixture was stirred for 30 minutes, poured into water, extracted with ether, washed with cold water, and the ether was distilled off. 25.
8 gr of oil was obtained. As a result of gas chromatography, 4-
2-fluoro-5-) 91.6% of fluoromethylaniline and 6-fluoro-2-fluoro-
5-) The production ratio of IJ fluoromethylaniline was 4.0%. This oily substance is distilled under reduced pressure b33~
4-bromo 2- with a boiling point of 35130-132°C
Fluoro-5-trifluoromethylaniline 23.2g
I got 4 r.
構造はＮＭＲスペクトルにより確認した。The structure was confirmed by NMR spectrum.
ＮＭＲ（ＣＤｃｔｘ ） ；δｐｐｍ ７．１８ （ｄ
、Ｊ＝ｌ ＩＨｚ 、 ＩＨ）６．９９ （ｄ 、
Ｊ＝９Ｈｚ 、 ＩＨ）３．９６（ｓ、２Ｈ）
比較例１゜
３．６ ｇｒ （０，０２モル）の２−フルオロ−５−
トリフルオロメチルアニリンと２．５ｇｒの無水酢酸を
酢酸４０ｍＩ中で室温にて２時間攪拌してアセチルアミ
ノ体とした後、１）２〜１）５℃にて、１）．２ｇｒの
臭素を６時間かけて滴下した。滴下終了後、さらに同温
度にて２時間攪拌した抜水にあけ、ベンゼン抽出し、水
洗後ベンゼンを減圧留去し、濃縮物を得た。濃縮物に３
０ｍ１のエタノールと１０ｍ１の濃塩酸な〕えて２時間
加熱還流後１０％水酸化ナトリウム溶液で中和し、ベン
ゼン抽出し、水洗後ベンゼンを減圧留去し、５．２ ｇ
ｒの油状物質を得た。ガスクロ分析の結果、４−ブロモ
−２−フＡ／ 、ｔ Ｏ−５−トリフルオロメチルアニ
リンが７４．４％及び６−ブロモー２−フルオロ−５−
トリフルオロメチルアニリンが１５，２％の生成比率で
あった。NMR (CDctx); δppm 7.18 (d
, J=l IHz, IH)6.99 (d,
J=9Hz, IH) 3.96 (s, 2H) Comparative Example 1゜3.6 gr (0.02 mol) of 2-fluoro-5-
Trifluoromethylaniline and 2.5g of acetic anhydride were stirred in 40ml of acetic acid at room temperature for 2 hours to form an acetylamino compound, and then 1). 2 gr of bromine was added dropwise over 6 hours. After the dropwise addition was completed, the mixture was further stirred at the same temperature for 2 hours, drained with water, extracted with benzene, washed with water, and the benzene was distilled off under reduced pressure to obtain a concentrate. 3 for concentrate
0 ml of ethanol and 10 ml of concentrated hydrochloric acid], heated under reflux for 2 hours, neutralized with 10% sodium hydroxide solution, extracted with benzene, washed with water, and distilled off the benzene under reduced pressure. 5.2 g
An oily substance of r was obtained. As a result of gas chromatography analysis, 4-bromo-2-phA/,tO-5-trifluoromethylaniline was 74.4% and 6-bromo-2-fluoro-5-
The production ratio of trifluoromethylaniline was 15.2%.
比較例２゜
１７．９ ｇｒ （０，１％ル）の２ ７／ｌｚオｏ
５−）リフルオロメチルアニリンの１００ｍ１塩化メ
チレン溶液に１７．８ｇｒ（０，１モル）のＮ−プロモ
サクシンイミドを室温にて、１時間かけて雄刃ａした。Comparative example 2゜17.9 gr (0.1% l) 27/lz o
5-) 17.8 gr (0.1 mol) of N-promosuccinimide was added to a 100 ml methylene chloride solution of trifluoromethylaniline at room temperature over a period of 1 hour.
添加後、３０分攪拌した後、水にあけ、有機層を冷水に
て洗浄後、塩化メチレンを留去し、２５．８ｇｒの油状
物質を得た。ガスクロ分析の結果、４−ブロモー２−フ
ルオロ−５−トリフルオロメチルアニリンが５１．２％
及び６−ブロモ−２−フルオロ−５−トリフルオロメチ
ルアニリン力４６．２％の生成比率であった。After the addition, the mixture was stirred for 30 minutes, poured into water, and after washing the organic layer with cold water, methylene chloride was distilled off to obtain 25.8 gr of an oily substance. As a result of gas chromatography, 4-bromo-2-fluoro-5-trifluoromethylaniline was 51.2%.
The production ratio of 6-bromo-2-fluoro-5-trifluoromethylaniline was 46.2%.
実施例２゜
１６．２ｇｒ （０，１モル）の３．５−ジクロロアニ
リンの５０ｍ１Ｎ、Ｎ−ジメチルホルムアミド溶液に１
７．８ｇｒ（０，１モル）のＮ−プロモサクシンイミド
の５０ ｍｌ Ｎ、Ｎ−ジメチルホルムアミド溶液を室
温にて、１時間かけて滴下した。滴下終了後、３０分攪
拌した後、水にあけ析出した結晶を戸別し、水洗したの
ち乾燥し、４−ブロモ−３，５−ジクロロアニリン２３
．Ｏｇｒを無色結晶（ｍ−ｐ、１２９〜１３０°Ｃ）と
して得た。Example 2 A solution of 16.2 gr (0.1 mol) of 3,5-dichloroaniline in 50 ml of N, N-dimethylformamide
A solution of 7.8 gr (0.1 mol) of N-promosuccinimide in 50 ml of N,N-dimethylformamide was added dropwise at room temperature over 1 hour. After the addition was completed, the mixture was stirred for 30 minutes, poured into water, and the precipitated crystals were separated, washed with water, and dried to give 4-bromo-3,5-dichloroaniline 23
．． Ogr was obtained as colorless crystals (m-p, 129-130°C).
構造はＮＭＲスペクトルにより確認した。The structure was confirmed by NMR spectrum.
ＮＭＲ，（ＣＤＣｔ３） ：δｐｐｍ ６．３０ （ｓ
、 ２Ｈ）３．５６ （ｂｒ、 ｓ 、 ２Ｈ）
実施例３〜実施例１６゜
前記実施例の場合と同様にして下記式（１）の化合物を
臭素化し、第１表の結果を得た。NMR, (CDCt3): δppm 6.30 (s
, 2H) 3.56 (br, s, 2H) Examples 3 to 16 The compound of the following formula (1) was brominated in the same manner as in the above examples, and the results shown in Table 1 were obtained.
＊ガスクロ面積比。*Gas chromatography area ratio.
ガスクロ分析条件Gas chromatography analysis conditions
Claims (3)
キル基をＲ＾２は水素原子、ハロゲン原子又はハロアル
キル基を、Ｒ＾３は水素原子、ハロゲン原子、ハロアル
キル基又はハロアルコキシ基を示す） で表わされる化合物をＮ−プロモサクシンイミドと極性
溶媒中で反応させ、アミノ基に対するパラ位を選択的に
ブロム化することを特徴とする一般式 ▲数式、化学式、表等があります▼（２） （式中、Ｒ＾１、Ｒ＾２およびＲ＾３は前記と同じ意味
を有する） で表わされるブロモアニリン類の製造法。(1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1) (In the formula, R^1 is a hydrogen atom, a halogen atom, or a haloalkyl group; ^3 represents a hydrogen atom, a halogen atom, a haloalkyl group, or a haloalkoxy group) is reacted with N-promosuccinimide in a polar solvent to selectively bromate the para-position to the amino group. Characteristic general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (2) (In the formula, R^1, R^2 and R^3 have the same meanings as above) Production method of bromoanilines .
ルのＮ−プロモサクシンイミドを使用する特許請求の範
囲第１項記載の方法。(2) The method according to claim 1, wherein N-promosuccinimide is used as the brominating agent in an equimolar amount relative to the compound of formula (1).
Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトア
ミド、Ｎ−メチルピロリドン、アセトニトリル、プロピ
レンカーボネート、エチレングリコール、Ｎ−メチルホ
ルムアミド、Ｎ−メチルアセトアミド、スルホラン又は
ニトロベンゼンを使用する特許請求の範囲第１項記載の
方法。(3) As a polar solvent, dimethyl sulfoxide, N,
Claim 1 in which N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, acetonitrile, propylene carbonate, ethylene glycol, N-methylformamide, N-methylacetamide, sulfolane or nitrobenzene is used. Method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13930986A JPS62298562A (en) | 1986-06-17 | 1986-06-17 | Production of bromoaniline or such |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13930986A JPS62298562A (en) | 1986-06-17 | 1986-06-17 | Production of bromoaniline or such |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62298562A true JPS62298562A (en) | 1987-12-25 |
Family
ID=15242296
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13930986A Pending JPS62298562A (en) | 1986-06-17 | 1986-06-17 | Production of bromoaniline or such |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62298562A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0315862A2 (en) * | 1987-11-09 | 1989-05-17 | Bayer Ag | Aromatically fluorinated fluoromethoxy- and fluoromethylthio-amino benzenes and their preparation |
| JPH01168651A (en) * | 1987-12-01 | 1989-07-04 | Bayer Ag | Alkoxyaniline containing fluorine atom in aromatic nucleus or side chain and production thereof |
| WO1997018197A1 (en) * | 1995-11-16 | 1997-05-22 | Hoechst Marion Roussel | New process for the preparation of phenylimidazolidine derivatives |
| KR100418355B1 (en) * | 2000-12-28 | 2004-02-11 | 이석우 | Process for preparing aryl bromide derivatives |
| WO2007107820A3 (en) * | 2006-03-17 | 2007-11-22 | Miteni Spa | Process for the preparation of 1-bromo-3-trifluoromethoxybenzene |
-
1986
- 1986-06-17 JP JP13930986A patent/JPS62298562A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01149755A (en) * | 1987-11-02 | 1989-06-12 | Bayer Ag | Fluoromethoxy-aminobenzenes and fluoromethylthio-aminobenzenes containing fluorine in aromatic nucleus and production thereof |
| EP0315862A2 (en) * | 1987-11-09 | 1989-05-17 | Bayer Ag | Aromatically fluorinated fluoromethoxy- and fluoromethylthio-amino benzenes and their preparation |
| EP0315862A3 (en) * | 1987-11-09 | 1990-02-07 | Bayer Ag | Aromatically fluorinated fluoromethoxy- and fluoromethylthio-amino benzenes and their preparation |
| JPH01168651A (en) * | 1987-12-01 | 1989-07-04 | Bayer Ag | Alkoxyaniline containing fluorine atom in aromatic nucleus or side chain and production thereof |
| WO1997018197A1 (en) * | 1995-11-16 | 1997-05-22 | Hoechst Marion Roussel | New process for the preparation of phenylimidazolidine derivatives |
| FR2741346A1 (en) * | 1995-11-16 | 1997-05-23 | Roussel Uclaf | NOVEL PROCESS FOR THE PREPARATION OF PHENYLIMIDAZOLIDINE DERIVATIVES |
| KR100418355B1 (en) * | 2000-12-28 | 2004-02-11 | 이석우 | Process for preparing aryl bromide derivatives |
| WO2007107820A3 (en) * | 2006-03-17 | 2007-11-22 | Miteni Spa | Process for the preparation of 1-bromo-3-trifluoromethoxybenzene |
| JP2009530260A (en) * | 2006-03-17 | 2009-08-27 | ミテーニ ソチエタ ペル アツィオーニ | Process for producing 1-bromo-3-trifluoromethoxybenzene |
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