JPH02221233A - Bromination of methyl group bonded to aromatic nucleus - Google Patents
Bromination of methyl group bonded to aromatic nucleusInfo
- Publication number
- JPH02221233A JPH02221233A JP4359489A JP4359489A JPH02221233A JP H02221233 A JPH02221233 A JP H02221233A JP 4359489 A JP4359489 A JP 4359489A JP 4359489 A JP4359489 A JP 4359489A JP H02221233 A JPH02221233 A JP H02221233A
- Authority
- JP
- Japan
- Prior art keywords
- methyl group
- aromatic nucleus
- group
- brominating agent
- bonded
- 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
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 title claims abstract description 36
- 125000003118 aryl group Chemical group 0.000 title claims abstract description 23
- 238000005893 bromination reaction Methods 0.000 title description 18
- 230000031709 bromination Effects 0.000 title description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 150000001491 aromatic compounds Chemical class 0.000 claims abstract description 15
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 12
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract 4
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 125000006575 electron-withdrawing group Chemical group 0.000 claims description 9
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- FEWDXGMBVQULLN-UHFFFAOYSA-N 1-hydroxy-2-phenyl-1,5,6,7-tetrahydro-4H-benzimidazol-4-one Chemical compound ON1C=2CCCC(=O)C=2N=C1C1=CC=CC=C1 FEWDXGMBVQULLN-UHFFFAOYSA-N 0.000 claims description 2
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 claims description 2
- 125000001246 bromo group Chemical group Br* 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 11
- 239000006227 byproduct Substances 0.000 abstract description 7
- 238000007796 conventional method Methods 0.000 abstract description 3
- 239000012442 inert solvent Substances 0.000 abstract description 2
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- 150000002431 hydrogen Chemical class 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 30
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 12
- 238000003756 stirring Methods 0.000 description 8
- VOLRSQPSJGXRNJ-UHFFFAOYSA-N 4-nitrobenzyl bromide Chemical compound [O-][N+](=O)C1=CC=C(CBr)C=C1 VOLRSQPSJGXRNJ-UHFFFAOYSA-N 0.000 description 7
- 238000004817 gas chromatography Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 6
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 5
- ZPTVNYMJQHSSEA-UHFFFAOYSA-N 4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1 ZPTVNYMJQHSSEA-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- PLAZTCDQAHEYBI-UHFFFAOYSA-N 2-nitrotoluene Chemical compound CC1=CC=CC=C1[N+]([O-])=O PLAZTCDQAHEYBI-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- MKHFRSNFHCJQIQ-UHFFFAOYSA-N 1-(dibromomethyl)-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(C(Br)Br)C=C1 MKHFRSNFHCJQIQ-UHFFFAOYSA-N 0.000 description 2
- CAHQGWAXKLQREW-UHFFFAOYSA-N Benzal chloride Chemical compound ClC(Cl)C1=CC=CC=C1 CAHQGWAXKLQREW-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- IGBSAAYMSMEDQY-UHFFFAOYSA-N carboxy hydrogen carbonate;2-propan-2-ylperoxypropane Chemical compound OC(=O)OC(O)=O.CC(C)OOC(C)C IGBSAAYMSMEDQY-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- FUNUTBJJKQIVSY-UHFFFAOYSA-N 2,4-Dichlorotoluene Chemical compound CC1=CC=C(Cl)C=C1Cl FUNUTBJJKQIVSY-UHFFFAOYSA-N 0.000 description 1
- ORHGCDXPUFGVFD-UHFFFAOYSA-N 2,4-dichloro-1-(dibromomethyl)benzene Chemical compound ClC1=CC=C(C(Br)Br)C(Cl)=C1 ORHGCDXPUFGVFD-UHFFFAOYSA-N 0.000 description 1
- CQQSQBRPAJSTFB-UHFFFAOYSA-N 4-(bromomethyl)benzoic acid Chemical compound OC(=O)C1=CC=C(CBr)C=C1 CQQSQBRPAJSTFB-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- FUMLKAFCVQJVEZ-UHFFFAOYSA-N [bromo(nitro)methyl]benzene Chemical compound [O-][N+](=O)C(Br)C1=CC=CC=C1 FUMLKAFCVQJVEZ-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000005079 alkoxycarbonylmethyl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- -1 bromine radicals Chemical class 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- VLZLOWPYUQHHCG-UHFFFAOYSA-N nitromethylbenzene Chemical compound [O-][N+](=O)CC1=CC=CC=C1 VLZLOWPYUQHHCG-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000004742 propyloxycarbonyl group Chemical group 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000012258 stirred mixture Substances 0.000 description 1
- 238000006467 substitution reaction 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〕
本発明は芳香核に結合するメチル基の臭素化方法に関す
るものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for brominating a methyl group bonded to an aromatic nucleus.
芳香核に結合するメチル基を臭素化する方法は知られて
いる。この場合、芳香核にメチル基とともに、電子吸引
基が結合しているとそのメチル基の臭素化は著しく困難
になる０例えば、電子吸引基であるニトロ基を有するオ
ルトニトロトルエンを臭素化する場合、ボンベ中で１０
０−１６０”Ｃで臭素化を行うと、得られる臭素化物の
収率はわずかであるか又は臭素化生成物は分解を起し樹
脂化してしまう（Ｈｏｕｂａｎ−１１ａｙｌ；５／ ４
巻、５３３４−５３３７Ｐ）、また、オルトニトロトル
エンに可視光線を照射しながら臭素化すると、その臭素
化は著しく低収率でしか進まない（Ｊｏｈｎ Ｒ，Ｓａ
ｍｐｅｙ；：Ｊ、Ａｍ、 Ｃｈｅｗ、Ｓｏｃ、ｙ６２，
１８３９）。Methods for brominating methyl groups attached to aromatic nuclei are known. In this case, if an electron-withdrawing group is bonded to the aromatic nucleus together with a methyl group, bromination of the methyl group becomes extremely difficult. 10 in the cylinder
When bromination is carried out at 0-160"C, the yield of the brominated product obtained is small or the brominated product decomposes and becomes a resin (Houban-11ayl; 5/4
Vol. 5334-5337P), and when orthonitrotoluene is brominated while irradiated with visible light, the bromination proceeds only in extremely low yields (John R, Sa.
mpey;:J, Am, Chew, Soc, y62,
1839).
一方、有機溶媒を使用したオルトニトロトルエンのメチ
ル基の臭素化では、ジベンゾイルパーオキサイド又はジ
イソプロピルパーオキシドジカーボネートを添加下、あ
るいは赤外又は可視光線照射下に臭素を用いる方法が知
られている（ Ｇｅｔ 、 ０ｆｆｅｎ、 ２，６１４
，４８５ （ＶＥＲ））。On the other hand, for the bromination of the methyl group of orthonitrotoluene using an organic solvent, methods using bromine with the addition of dibenzoyl peroxide or diisopropyl peroxide dicarbonate, or under irradiation with infrared or visible light are known ( Get, 0ffen, 2,614
, 485 (VER)).
さらに、溶媒と水を用いた２相系で、オルトニトロトル
エンのメチル基を臭素により臭素化する方法において、
アルカリ存在下に光を照射する方法（Ｇａｒ、 ０ｆｆ
ｅｎ、 ２，７４９，８００ （チバ・ガイギー）〕及
び光あるいはジイソプロピルパーオキシドジカーボネー
トを使用する方法（Ｇｅｒ、（Ｅａｓｔ）ＤＯ１５０，
１９７（ＶＥＤ） ）が知られている。Furthermore, in a method of brominating the methyl group of orthonitrotoluene with bromine in a two-phase system using a solvent and water,
Method of irradiating light in the presence of alkali (Gar, 0ff
en, 2,749,800 (Ciba Geigy)] and a method using light or diisopropyl peroxide dicarbonate (Ger, (East) DO150,
197 (VED)) is known.
その他、バラ−ニトロトルエンに、臭素を１００°−２
５０℃で反応させることにより、対応するベンジルブロ
マイド及びベンザルブロマイドを得る方法が知られ゛〔
いる（Ｅｕｒ、 Ｐｓｔ、 Ａｐｐｌ、 ＥＰ ４５，
４３１（Ｂａｙｓｒ Ａ−Ｇ）特開昭５０−８９，３３
７（日本化薬）〕。In addition, bromine is added to nitrotoluene at 100°-2
A method for obtaining the corresponding benzyl bromide and benzal bromide by reacting at 50°C is known.
(Eur, Pst, Appl, EP 45,
431 (Baysr A-G) JP-A-1989-89, 33
7 (Nippon Kayaku)].
前記したように、電子吸引基を有するメチル化芳香族化
合物のメチル基の臭素化は非常に困難であり、高い温度
や光照射、さらには有機過酸化物等の高コストのラジカ
ル発生剤を用いて行われている。このような方法により
、ブロムラジカルを生成し、芳香核に結合するメチル基
を臭素化する場合、酸素や生成臭化水素により、著しく
反応が阻害されることが知られている。また、低い反応
温度では、ブロムラジカルによるメチル基の置換速度は
小さく１反応の進行は著しく遅くなる。As mentioned above, bromination of the methyl group of a methylated aromatic compound having an electron-withdrawing group is extremely difficult and requires high temperatures, light irradiation, and even expensive radical generators such as organic peroxides. It is being done. It is known that when a bromine radical is generated and a methyl group bonded to an aromatic nucleus is brominated by such a method, the reaction is significantly inhibited by oxygen and generated hydrogen bromide. Furthermore, at low reaction temperatures, the rate of substitution of methyl groups by bromine radicals is low and the progress of one reaction is significantly slowed down.
（発明の課題）
従って、本発明は、芳香族核に結合するメチル基、特に
、電子吸引基を有する芳香核に結合するメチル基を、低
温度でかつ収率よく臭素化する方法を提供することをそ
の課題とする。(Problem of the Invention) Therefore, the present invention provides a method for brominating a methyl group bonded to an aromatic nucleus, particularly a methyl group bonded to an aromatic nucleus having an electron-withdrawing group, at low temperature and in good yield. That is the issue.
本発明者らは、前記課題を解決すべく鋭意研究を重ねた
結果、メチル基を有する芳香族化合物を、過酸化水素水
の存在下、臭素化剤と反応させる時に、そのメチル基を
、低温度でかつ容易に臭素化し得ることを見出し、本発
明を完成するに至った。As a result of intensive research to solve the above problems, the present inventors have found that when an aromatic compound having a methyl group is reacted with a brominating agent in the presence of hydrogen peroxide, the methyl group is reduced. It was discovered that bromination can be easily carried out at low temperatures, leading to the completion of the present invention.
即ち１本発明によれば、芳香核に結合するメチル基を臭
素化するに際し、該原料メチル化芳香族化合物を、過酸
化水素水の存在下、臭素化剤と反応させることを特徴と
する芳香核に結合するメチル基の臭素化方法が提供され
る。Namely, according to the present invention, when brominating the methyl group bonded to the aromatic nucleus, the aromatic compound is characterized in that the raw material methylated aromatic compound is reacted with a brominating agent in the presence of aqueous hydrogen peroxide. A method for brominating a methyl group attached to a nucleus is provided.
本発明による臭素化反応は１次の一般式で表わされる。The bromination reaction according to the present invention is represented by the following general formula.
（１）臭素化剤としてＢｒ、を用いる場合（２）臭素化
剤として）ｌＢｒを用いる場合（なお、前記式中、 Ａ
ｒは芳香核を示す）即ち、本発明の臭素化反応では、過
酸化水素が反応剤として関与し、臭素化副生物としては
水が生成するのみである。(1) When Br is used as the brominating agent (2) When lBr is used as the brominating agent (in the above formula, A
(r indicates an aromatic nucleus) That is, in the bromination reaction of the present invention, hydrogen peroxide is involved as a reactant, and only water is produced as a bromination by-product.
一方、従来の臭素化反応は、次の一般式で表わされる。On the other hand, the conventional bromination reaction is represented by the following general formula.
Ａｒ −ＣＨ，＋ Ｂｒ、→Ａｒ−ＣＨ２Ｂｒ＋）ｌＢ
ｒ （Ｖ）Ａｒ ＣＨｉ＋２Ｂｒｚ→Ａｒ
−ＣＨＢｒ、 ＋ ２ＨＢｒ （ＶＩ ）即ち、
従来の臭素化方法では、副生物としてＨｅｒが生成する
。Ar −CH, + Br, →Ar−CH2Br+)lB
r (V)Ar CHi+2Brz→Ar
-CHBr, +2HBr (VI), i.e.
Conventional bromination methods produce Her as a by-product.
前記した本発明の方法と従来の方法における反応式を検
討してわかるように、本発明の場合、副生物は水であっ
て臭化水素を生成しないことから。As can be seen by examining the reaction formulas of the method of the present invention and the conventional method described above, in the case of the present invention, the by-product is water and hydrogen bromide is not produced.
臭素化剤の使用量は従来の半量ですむ上、副生する臭化
水素の捕集及びその処理が必要でなくなり、工業的に非
常に有利である。The amount of brominating agent used is half of the conventional amount, and there is no need to collect and treat by-product hydrogen bromide, which is very advantageous industrially.
本発明で用いる原料は、メチル基を有する芳香族化合物
である。この場合、芳香核としては、ベンゼン核の他、
ナフタレン核やアントラセン核等の縮合核も包含される
。芳香核には、炭化水素基や、アルコキシカルボニルメ
チル基等を有することができるが、本発明の場合、芳香
核に結合するメチル基の臭素化に悪影響を与えるとされ
ている電子吸引基１例えば、ニトロ基、シアノ基、カル
ボキシル基、アルコキシカルボニル基、ハロゲン原子等
を有することができる。前記アルコキシカルボニル基と
しては、例えば、メトキシカルボニル基、エトキシカル
ボニル基、プロポキシカルボニル等が挙げられ、ハロゲ
ン原子としては、塩素、臭素、ヨウ素、フッ素が挙げら
れる。芳香核に結合する電子吸引基の数は特に制約され
ず、複数個、例えば２〜３個であることができる。また
、芳香核に結合するメチル基も複数個であることができ
る。The raw material used in the present invention is an aromatic compound having a methyl group. In this case, as the aromatic nucleus, in addition to the benzene nucleus,
Condensation nuclei such as naphthalene nuclei and anthracene nuclei are also included. The aromatic nucleus can have a hydrocarbon group, an alkoxycarbonylmethyl group, etc., but in the case of the present invention, an electron-withdrawing group 1, which is said to have an adverse effect on the bromination of the methyl group bonded to the aromatic nucleus, is used. , a nitro group, a cyano group, a carboxyl group, an alkoxycarbonyl group, a halogen atom, etc. Examples of the alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, and examples of the halogen atom include chlorine, bromine, iodine, and fluorine. The number of electron-withdrawing groups bonded to the aromatic nucleus is not particularly limited, and may be plural, for example 2 to 3. Moreover, the number of methyl groups bonded to the aromatic nucleus can be plural.
本発明で用いる臭素化剤としては、従来公知のものが用
いられ、このようなものには、例えば、臭素（Ｂｒ、’
）の他、臭化水素酸、臭化水素等が挙げられる。臭素化
剤は１反応系に対して、−度に添加し得る他、少量づつ
徐々に滴下することができる。As the brominating agent used in the present invention, conventionally known ones are used, and such agents include, for example, bromine (Br, '
), hydrobromic acid, hydrogen bromide, etc. The brominating agent can be added at a time to one reaction system, or can be gradually added dropwise in small amounts.
本発明の臭素化反応は、過酸化水素水とメチル化芳香族
化合物との撹拌混合物中に臭素化剤を添加することによ
り好まし〈実施することができる。The bromination reaction of the present invention can be preferably carried out by adding a bromination agent to a stirred mixture of hydrogen peroxide and a methylated aromatic compound.
この場合、反応温度は０〜９０℃、好ましくは３０−５
０℃である。過酸化水素水の濃度は特に制約されないが
、２〜６０重量％、好ましくは３〜３５重量％である。In this case, the reaction temperature is 0 to 90°C, preferably 30-5°C.
It is 0°C. The concentration of the hydrogen peroxide solution is not particularly limited, but is 2 to 60% by weight, preferably 3 to 35% by weight.
過酸化水素水の使用割合は、それに含まれる過酸化水素
が、メチル化芳香族化合物のメチル基を臭素化するに必
要な量以上であればよい、一般には。In general, the proportion of hydrogen peroxide used is sufficient as long as the amount of hydrogen peroxide contained therein is at least the amount necessary to bromine the methyl group of the methylated aromatic compound.
過酸化水素水の量は、Ｈ，０□換算で、臭素化すべきメ
チル基１個に対して０．１〜１０モル、好ましくは０．
５〜５モルの割合である。The amount of hydrogen peroxide solution is 0.1 to 10 mol, preferably 0.1 to 10 mol per methyl group to be brominated, in terms of H,0□.
The proportion is 5 to 5 moles.
本発明を実施する場合、必要に応じ、反応系には不活性
有機溶媒を添加することができる。このような不活性溶
媒として、ベンゼン、クロロベンゼン、ブロムベンゼン
、ニトロベンゼンのようなメチル基を有しない芳香族化
合物や、ジクロルメタン、クロロホルム、ジクロルエタ
ン、テトラクロロエタンのようなハロゲン化炭化水素が
挙げられ、特にジクロルメタンの使用が好ましい、不活
性有機溶媒の使用量は、原料メチル化芳香族化合物１重
量部に対して、０〜１００重量部、好ましくは５−３０
重量部の割合である９本発明における臭素化反応は、過
酸化水素水層と、芳香族化合物を含む有機相の２相系で
行われるため、反応混合物を゛連続的によく撹拌するこ
とによって１円滑し二進行させることができる。When carrying out the present invention, an inert organic solvent can be added to the reaction system if necessary. Such inert solvents include aromatic compounds without methyl groups such as benzene, chlorobenzene, bromobenzene, and nitrobenzene, and halogenated hydrocarbons such as dichloromethane, chloroform, dichloroethane, and tetrachloroethane, especially dichloromethane. The amount of the inert organic solvent used is preferably 0 to 100 parts by weight, preferably 5 to 30 parts by weight, per 1 part by weight of the starting methylated aromatic compound.
The bromination reaction in the present invention is carried out in a two-phase system consisting of an aqueous hydrogen peroxide layer and an organic phase containing an aromatic compound. 1. It can be made smooth and 2. It can be made to progress.
次に本発明を実施によってさらに詳細に説明する。 Next, the present invention will be explained in more detail by way of implementation.
実施例１
ρ−ニトロトルエン１５ｇ（０，１１モル）、ジクロロ
メタン１８〇−及び３０％過酸化水素水５６ｍ（０，０
５モル）を撹拌しながら、還流下に臭素８．８ｇ （０
，０５５モル）を含むジクロルメタン溶液１５−を３０
分間で滴下する。Example 1 15 g (0.11 mol) of ρ-nitrotoluene, 180 g of dichloromethane, and 56 m (0.0 mol) of 30% hydrogen peroxide
8.8 g (0.5 mol) of bromine was added under reflux while stirring
,055 mol) in dichloromethane solution containing 15-30
Drip in minutes.
この後２時間、還流下に反応させる０反応の進行状況は
ガスクロマトグラフィーによりチエツクすることにより
終点を決めることができる。反応終了後、ジクロロメタ
ン層を分液し、水洗後、無水硫酸ナトリウムで脱水乾燥
し、減圧下に濃縮すると２２．９ｇの淡黄色油状物を得
る。このものは、ガスクロマトグラフィーにより、ｐ−
ニトロトルエン１０．２％、Ｐ−ニトロベンジルブロマ
イド７５．１％及びｐ−ニトロベンザルブロマイド１４
．４％の面積比を示した。ｐ−ニトロベンジルブロマイ
ドの純度は７３．７％であり、純収率７１．０％を得た
。After this, the reaction is carried out under reflux for 2 hours. The progress of the reaction can be checked by gas chromatography to determine the end point. After the reaction, the dichloromethane layer is separated, washed with water, dehydrated and dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain 22.9 g of a pale yellow oil. This product was determined by gas chromatography to be p-
Nitrotoluene 10.2%, p-nitrobenzyl bromide 75.1% and p-nitrobenzyl bromide 14
．． It showed an area ratio of 4%. The purity of p-nitrobenzyl bromide was 73.7%, giving a pure yield of 71.0%.
実施例２
°２，４−ジクロロトルエン８．Ｉｇ（０，０５モル）
、ジクロロメタン９０−１水２５−及び３５％過酸化水
素水２．５−（０，０２９モル）を含む混合液に、撹拌
還流下、臭素４゜４ｇ（０，０２８モル）を１時間かけ
て滴下し、さらに５時間反応績行後、冷却し、ジクロロ
メタン層を分液する。得られた有機層を水洗し、無水硫
酸ナトリウムで脱水、乾燥する０次に、減圧下で溶媒を
除去すると１２．５ｇの無色油状物を得る。このものは
、ガスクロマトグラフィーにより、２，４−ジクロロト
ルエン２．０％、２，４−ジクロロベンザルブロマイド
６．３％及び２，４−ベンジルブロマイド９１．３％の
面積比を示した。Example 2 °2,4-dichlorotoluene8. Ig (0.05 mol)
To a mixed solution containing 90-1 dichloromethane, 25-1 water, and 2.5-(0,029 mol) 35% hydrogen peroxide solution, 4.4 g (0,028 mol) of bromine was added over 1 hour under stirring and reflux. The mixture was added dropwise and the reaction was allowed to proceed for an additional 5 hours, after which it was cooled and the dichloromethane layer was separated. The obtained organic layer is washed with water, dehydrated with anhydrous sodium sulfate, and dried. Next, the solvent is removed under reduced pressure to obtain 12.5 g of a colorless oil. This product showed an area ratio of 2.0% of 2,4-dichlorotoluene, 6.3% of 2,4-dichlorobenzalbromide, and 91.3% of 2,4-benzyl bromide by gas chromatography.
実施例３
Ｐ−メチル安息香酸７．５ｇ（０，０５５モル）に、ジ
クロロメタン９０ｍ１及び水２５＋ｓＱを加えて加熱し
、ｐ−メチル安息香酸を溶解した後に過酸化水素水２．
５ｍ （０゜０２９モル）を加え、還流下に撹拌しなが
ら臭素４．４ｇ（０，０２８モル）を含むジクロメタン
ｔｏｄｌ液を４５分間で滴下する０滴下と共に結晶が析
出してくるが、約２時間還流下に撹拌した後に結晶を熱
濾過すると、白色の結晶９．４ｇを得る。このものは、
ガスクロマトグラフィーにより、ｐ−ブロムメチル安息
香酸９６．４％及びＰ−メチル安息香酸３．１％の面積
比を示した。Example 3 90 ml of dichloromethane and 25+ sQ of water were added to 7.5 g (0,055 mol) of p-methylbenzoic acid and heated to dissolve the p-methylbenzoic acid, followed by 2.5 g (0,055 mol) of hydrogen peroxide solution.
5m (0.029 mol) was added, and while stirring under reflux, a dichloromethane todl solution containing 4.4 g (0.028 mol) of bromine was added dropwise over 45 minutes. Crystals precipitated with the addition of 0 drops, but about 2. Hot filtration of the crystals after stirring under reflux for an hour gives 9.4 g of white crystals. This thing is
Gas chromatography showed an area ratio of 96.4% p-bromomethylbenzoic acid and 3.1% p-methylbenzoic acid.
実施例４
ｐ−ニトロトルエン６゜９ｇ（０，０５モル）、ジクロ
ロメタン７０ｍ及び３５％過酸化水素水５．２ｄ （０
，２０１モル）を加熱し、還流撹拌しながら４７％臭化
水素酸１３．９ｇ（Ｏ，Ｏａモル）を１時間３０分で滴
下する。その後、４時間、還流撹拌下に反応を続行し、
冷却後、水３０−を加え、有機層を分液する。有機層は
無水硫酸ナトリウムで脱水乾燥後、減圧下に濃縮すると
、１３゜１ｇの淡黄色油状物を得る。このものは、ガス
クロマトグラフィーにより、Ｐ−ニトロベンジルブロマ
イド４６．２％、Ｐ−ニトロベンザルブロマイド５３．
８％の面積比を示した。また、このものは、定量分析に
より、それぞれＰ−ニトロベンジルブロマイド５．１８
ｇ（０，０２４モル）、Ｐ−ニトロベンザルブロマイド
７．７ｇ（０，０２６モル）を含むことが確認された。Example 4 6.9 g (0.05 mol) of p-nitrotoluene, 70 m of dichloromethane and 5.2 d (0.0 mol) of 35% hydrogen peroxide
, 201 mol) was heated, and 13.9 g (O, Oa mol) of 47% hydrobromic acid was added dropwise over 1 hour and 30 minutes while stirring under reflux. Thereafter, the reaction was continued under reflux stirring for 4 hours,
After cooling, 30% of water is added and the organic layer is separated. The organic layer was dehydrated and dried over anhydrous sodium sulfate and concentrated under reduced pressure to obtain 13.1 g of a pale yellow oil. This product was determined by gas chromatography to contain 46.2% P-nitrobenzyl bromide and 53% P-nitrobenzyl bromide.
It showed an area ratio of 8%. In addition, quantitative analysis revealed that this product contained 5.18% of P-nitrobenzyl bromide, respectively.
g (0,024 mol), and 7.7 g (0,026 mol) of P-nitrobenzal bromide.
実施例５
Ｐ−ニトロトルエン６．９ｇ（０，０５モル）、ベンゼ
ン９〇−及び３５％過酸化水素水５．３ｇ（０，０５５
モル）の混合液を温度３５〜４０℃に保ちながら、撹拌
下に４７％臭化水素酸８．６ｇ（０，０５モル）を３０
分間で滴下する。その後。Example 5 6.9 g (0,05 mol) of P-nitrotoluene, 90-benzene and 5.3 g (0,055 mol) of 35% hydrogen peroxide
8.6 g (0.05 mol) of 47% hydrobromic acid was added to 30% of the mixture of 47% hydrobromic acid (0.05 mol) while keeping the temperature between 35 and 40°C while stirring.
Drip in minutes. after that.
４時間、同温度で撹拌し、水５０ｍＱを加え、有機層を
分液する。得られた有機層を無水硫酸ナトリウムで脱水
乾燥し、減圧下に濃縮すると、 １４．５ｇの淡黄色油
状物を得る。このものは、ガスクロマトグラフィーによ
り、ｐ−ニトロベンジルブロマイド５６．９％、ｐ−ニ
トロベンザルブロマイド３．６％、ｐ−ニトロトルエン
３８．９％を示した。このものは、定量分析により、Ｐ
−ニトロベンジルブロマイド６．０ｇ（０゜０２８モル
）含有することが確認された。Stir at the same temperature for 4 hours, add 50 mQ of water, and separate the organic layer. The obtained organic layer is dehydrated and dried over anhydrous sodium sulfate and concentrated under reduced pressure to obtain 14.5 g of a pale yellow oil. Gas chromatography showed that this product contained 56.9% p-nitrobenzyl bromide, 3.6% p-nitrobenzal bromide, and 38.9% p-nitrotoluene. Quantitative analysis revealed that P
- It was confirmed that it contained 6.0 g (0.028 mol) of nitrobenzyl bromide.
次に１本発明によって得られる代表的な反応結果を表−
１に示す、物質の確認はガスクロマトグラフおよびＮＭ
Ｒにより行なった。Next, a table shows typical reaction results obtained by the present invention.
Confirmation of the substance shown in 1 is done by gas chromatography and NM.
This was done using R.
本発明によれば、芳香核に結合するメチル基を低温度に
おいて収率よく臭素化することができる。According to the present invention, a methyl group bonded to an aromatic nucleus can be brominated with good yield at low temperature.
しかも、本発明では、臭素化反応による副生物は水のみ
であり、臭素化剤の臭素原子は全てメチル基と反応させ
ることができる。従って１本発明は、臭化水素を副生す
る従来法とは異なり、臭化水素の捕集及びその処理が必
要とされず、かつ臭素化剤の使用量は半分ですむため工
業的に非常に有利である。Moreover, in the present invention, the only byproduct resulting from the bromination reaction is water, and all of the bromine atoms in the brominating agent can be reacted with methyl groups. Therefore, unlike the conventional method that produces hydrogen bromide as a by-product, the present invention does not require the collection and treatment of hydrogen bromide, and the amount of brominating agent used is only half, making it extremely industrially possible. It is advantageous for
その上、本発明では、メチル基とともに、電子吸引基を
有する芳香族化合物のメチル基の臭素化に対しても非常
に有利に適用することができる。Furthermore, the present invention can be very advantageously applied to the bromination of methyl groups as well as methyl groups of aromatic compounds having electron-withdrawing groups.
ニトロ基やカルボキシル基、ハロゲン原子、シアノ基、
アルコキシカルボニル基等の電子吸引基を有するベンジ
ルクロライドやベンザルクロライドは、対応するベンジ
ルアルコールやベンズアルデヒドを製造するための反応
原料として適用されるものであるが１本発明は、このよ
うなベンジルクロライドやベンザルクロライドの製造法
として極めで有用なものである。Nitro group, carboxyl group, halogen atom, cyano group,
Benzyl chloride and benzal chloride having an electron-withdrawing group such as an alkoxycarbonyl group are used as reaction raw materials for producing the corresponding benzyl alcohol and benzaldehyde. This is an extremely useful method for producing benzal chloride.
特許出願人 三光化学工業株式会社Patent applicant: Sanko Chemical Industry Co., Ltd.
Claims (5)
該原料メチル化芳香族化合物を、過酸化水素水の存在化
、臭素化剤と反応させることを特徴とする芳香核に結合
するメチル基の臭素化方法。(1) When brominating the methyl group bonded to the aromatic nucleus,
A method for brominating a methyl group bonded to an aromatic nucleus, which comprises reacting the raw material methylated aromatic compound with a brominating agent in the presence of hydrogen peroxide solution.
ゲン原子、シアノ基、カルボキシル基及びアルコキシカ
ルボニル基の中から選ばれる少なくとも１個の電子吸引
基を有する請求項１の方法。(2) The method according to claim 1, wherein the aromatic nucleus has at least one electron-withdrawing group selected from a nitro group, a halogen atom, a cyano group, a carboxyl group, and an alkoxycarbonyl group in addition to a methyl group.
ロゲン原子、シアノ基、カルボキシル基及びアルコキシ
カルボニル基の中から選ばれる少なくとも１個の電子吸
引基を有するメチルベンゼンを用い、対応するベンジル
ブロマイド及び／又はベンザルブロマイドを生成させる
請求項１の方法。(3) Using methylbenzene having at least one electron-withdrawing group selected from a nitro group, a halogen atom, a cyano group, a carboxyl group, and an alkoxycarbonyl group as the raw material methylated aromatic compound, the corresponding benzyl bromide and 2. The method of claim 1, wherein benzalbromide is produced.
１〜３のいずれかの方法。(4) The method according to any one of claims 1 to 3, wherein the brominating agent is bromine or hydrobromic acid.
４のいずれかの方法。(5) Claims 1 to 1 in which the reaction is carried out in the presence of an inert organic solvent.
Any of the 4 methods.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1043594A JP2688657B2 (en) | 1989-02-23 | 1989-02-23 | Method for bromination of methyl group bonded to aromatic nucleus |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1043594A JP2688657B2 (en) | 1989-02-23 | 1989-02-23 | Method for bromination of methyl group bonded to aromatic nucleus |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02221233A true JPH02221233A (en) | 1990-09-04 |
| JP2688657B2 JP2688657B2 (en) | 1997-12-10 |
Family
ID=12668126
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1043594A Expired - Fee Related JP2688657B2 (en) | 1989-02-23 | 1989-02-23 | Method for bromination of methyl group bonded to aromatic nucleus |
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| Country | Link |
|---|---|
| JP (1) | JP2688657B2 (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998046562A1 (en) * | 1997-04-11 | 1998-10-22 | Istituto Luso Farmaco D'italia S.P.A. | A process for the preparation of 4-bromomethyl diphenyl compounds |
| WO1999006339A1 (en) * | 1997-07-30 | 1999-02-11 | Basf Aktiengesellschaft | Method for preparing substituted benzyl bromides |
| WO1999033788A3 (en) * | 1997-12-29 | 1999-09-02 | Great Lakes Chem Konstanz Gmbh | Method for producing aromatic bromomethyl biphenyl compounds |
| WO2000053564A3 (en) * | 1999-03-12 | 2000-12-28 | Albemarle Corp | Benzylic halogenation of alkylbenzoic acid esters |
| JP2002284755A (en) * | 2001-03-26 | 2002-10-03 | Kanto Denka Kogyo Co Ltd | New fluorine-containing anthracene compound and method for manufacturing the same |
| WO2005023785A1 (en) * | 2003-09-04 | 2005-03-17 | Sumitomo Chemical Company, Limited | Process for producing 2'-(1h-tetrazol-5-yl)biphenyl-4-carbaldehyde |
| WO2010052536A1 (en) * | 2008-11-06 | 2010-05-14 | Council Of Scientific & Industrial Research | An improved process for the preparation of para-nitrobenzyl bromide |
| CN102791678A (en) * | 2009-12-16 | 2012-11-21 | 赛诺菲 | Process for the preparation of 4-bromomethyl-[1,1'-biphenyl]-2'-carbonitrile |
| WO2015146561A1 (en) * | 2014-03-26 | 2015-10-01 | 住友精化株式会社 | Method for producing brominated aromatic ester compound |
| CN113620879A (en) * | 2021-06-16 | 2021-11-09 | 浙江禾本科技股份有限公司 | Synthesis of 2[ (N-4-chlorphenyl) -1H-pyrazol-3-yloxymethyl ] nitrobenzene |
| CN114369029A (en) * | 2022-01-05 | 2022-04-19 | 江苏丰山集团股份有限公司 | Preparation method of o-nitrobenzyl bromide |
| CN114773204A (en) * | 2022-05-24 | 2022-07-22 | 浙江禾本科技股份有限公司 | Method for continuously preparing benzyl bromide derivative |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4954301A (en) * | 1972-06-06 | 1974-05-27 |
-
1989
- 1989-02-23 JP JP1043594A patent/JP2688657B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4954301A (en) * | 1972-06-06 | 1974-05-27 |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998046562A1 (en) * | 1997-04-11 | 1998-10-22 | Istituto Luso Farmaco D'italia S.P.A. | A process for the preparation of 4-bromomethyl diphenyl compounds |
| WO1999006339A1 (en) * | 1997-07-30 | 1999-02-11 | Basf Aktiengesellschaft | Method for preparing substituted benzyl bromides |
| WO1999033788A3 (en) * | 1997-12-29 | 1999-09-02 | Great Lakes Chem Konstanz Gmbh | Method for producing aromatic bromomethyl biphenyl compounds |
| WO2000053564A3 (en) * | 1999-03-12 | 2000-12-28 | Albemarle Corp | Benzylic halogenation of alkylbenzoic acid esters |
| JP2002284755A (en) * | 2001-03-26 | 2002-10-03 | Kanto Denka Kogyo Co Ltd | New fluorine-containing anthracene compound and method for manufacturing the same |
| WO2005023785A1 (en) * | 2003-09-04 | 2005-03-17 | Sumitomo Chemical Company, Limited | Process for producing 2'-(1h-tetrazol-5-yl)biphenyl-4-carbaldehyde |
| WO2010052536A1 (en) * | 2008-11-06 | 2010-05-14 | Council Of Scientific & Industrial Research | An improved process for the preparation of para-nitrobenzyl bromide |
| CN102791678A (en) * | 2009-12-16 | 2012-11-21 | 赛诺菲 | Process for the preparation of 4-bromomethyl-[1,1'-biphenyl]-2'-carbonitrile |
| WO2015146561A1 (en) * | 2014-03-26 | 2015-10-01 | 住友精化株式会社 | Method for producing brominated aromatic ester compound |
| JPWO2015146561A1 (en) * | 2014-03-26 | 2017-04-13 | 住友精化株式会社 | Method for producing brominated aromatic ester compound |
| CN113620879A (en) * | 2021-06-16 | 2021-11-09 | 浙江禾本科技股份有限公司 | Synthesis of 2[ (N-4-chlorphenyl) -1H-pyrazol-3-yloxymethyl ] nitrobenzene |
| CN113620879B (en) * | 2021-06-16 | 2023-05-05 | 浙江禾本科技股份有限公司 | Synthesis of 2[ (N-4-chlorophenyl) -1H-pyrazol-3-yloxymethyl ] nitrobenzene |
| CN114369029A (en) * | 2022-01-05 | 2022-04-19 | 江苏丰山集团股份有限公司 | Preparation method of o-nitrobenzyl bromide |
| CN114773204A (en) * | 2022-05-24 | 2022-07-22 | 浙江禾本科技股份有限公司 | Method for continuously preparing benzyl bromide derivative |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2688657B2 (en) | 1997-12-10 |
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