JPH04282327A - Production of bis(bromomethyl) aromatic hydrocarbon - Google Patents
Production of bis(bromomethyl) aromatic hydrocarbonInfo
- Publication number
- JPH04282327A JPH04282327A JP4635391A JP4635391A JPH04282327A JP H04282327 A JPH04282327 A JP H04282327A JP 4635391 A JP4635391 A JP 4635391A JP 4635391 A JP4635391 A JP 4635391A JP H04282327 A JPH04282327 A JP H04282327A
- Authority
- JP
- Japan
- Prior art keywords
- bis
- bromomethyl
- dimethylnaphthalene
- aromatic hydrocarbon
- aromatic hydrocarbons
- 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
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims description 13
- 125000005997 bromomethyl group Chemical group 0.000 title claims description 11
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 17
- -1 dimethyl aromatic hydrocarbon Chemical class 0.000 claims abstract description 17
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 4
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 abstract description 9
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 abstract description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 abstract description 6
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 abstract description 6
- QNLZIZAQLLYXTC-UHFFFAOYSA-N 1,2-dimethylnaphthalene Chemical compound C1=CC=CC2=C(C)C(C)=CC=C21 QNLZIZAQLLYXTC-UHFFFAOYSA-N 0.000 abstract description 5
- 239000006227 byproduct Substances 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 abstract description 3
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 abstract description 3
- RBZMSGOBSOCYHR-UHFFFAOYSA-N 1,4-bis(bromomethyl)benzene Chemical compound BrCC1=CC=C(CBr)C=C1 RBZMSGOBSOCYHR-UHFFFAOYSA-N 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 239000008096 xylene Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 2
- 229940126062 Compound A Drugs 0.000 abstract 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- YGYNBBAUIYTWBF-UHFFFAOYSA-N 2,6-dimethylnaphthalene Chemical compound C1=C(C)C=CC2=CC(C)=CC=C21 YGYNBBAUIYTWBF-UHFFFAOYSA-N 0.000 description 12
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 10
- WWGUMAYGTYQSGA-UHFFFAOYSA-N 2,3-dimethylnaphthalene Chemical compound C1=CC=C2C=C(C)C(C)=CC2=C1 WWGUMAYGTYQSGA-UHFFFAOYSA-N 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- RZTDESRVPFKCBH-UHFFFAOYSA-N 1-methyl-4-(4-methylphenyl)benzene Chemical group C1=CC(C)=CC=C1C1=CC=C(C)C=C1 RZTDESRVPFKCBH-UHFFFAOYSA-N 0.000 description 4
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 4
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 4
- APQSQLNWAIULLK-UHFFFAOYSA-N 1,4-dimethylnaphthalene Chemical compound C1=CC=C2C(C)=CC=C(C)C2=C1 APQSQLNWAIULLK-UHFFFAOYSA-N 0.000 description 3
- JRHSGFPVPTWMND-UHFFFAOYSA-N 2,6-bis(bromomethyl)naphthalene Chemical compound C1=C(CBr)C=CC2=CC(CBr)=CC=C21 JRHSGFPVPTWMND-UHFFFAOYSA-N 0.000 description 3
- QHJMFSMPSZREIF-UHFFFAOYSA-N 1,3-dimethylnaphthalene Chemical compound C1=CC=CC2=CC(C)=CC(C)=C21 QHJMFSMPSZREIF-UHFFFAOYSA-N 0.000 description 2
- 239000005967 1,4-Dimethylnaphthalene Substances 0.000 description 2
- CBMXCNPQDUJNHT-UHFFFAOYSA-N 1,6-dimethylnaphthalene Chemical compound CC1=CC=CC2=CC(C)=CC=C21 CBMXCNPQDUJNHT-UHFFFAOYSA-N 0.000 description 2
- XAABPYINPXYOLM-UHFFFAOYSA-N 1,8-dimethylnaphthalene Chemical compound C1=CC(C)=C2C(C)=CC=CC2=C1 XAABPYINPXYOLM-UHFFFAOYSA-N 0.000 description 2
- CFDDCSMNZFPVTH-UHFFFAOYSA-N 2,7-dimethylanthracene Chemical compound C1=CC(C)=CC2=CC3=CC(C)=CC=C3C=C21 CFDDCSMNZFPVTH-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229960002317 succinimide Drugs 0.000 description 2
- UZHZQZOMHXNQBJ-UHFFFAOYSA-N 1,4-bis(bromomethyl)naphthalene Chemical compound C1=CC=C2C(CBr)=CC=C(CBr)C2=C1 UZHZQZOMHXNQBJ-UHFFFAOYSA-N 0.000 description 1
- GCZOMCDXYFMAGP-UHFFFAOYSA-N 1,8-bis(bromomethyl)naphthalene Chemical compound C1=CC(CBr)=C2C(CBr)=CC=CC2=C1 GCZOMCDXYFMAGP-UHFFFAOYSA-N 0.000 description 1
- HMUGRILXVBKBID-UHFFFAOYSA-N 1-(bromomethyl)-4-[4-(bromomethyl)phenyl]benzene Chemical group C1=CC(CBr)=CC=C1C1=CC=C(CBr)C=C1 HMUGRILXVBKBID-UHFFFAOYSA-N 0.000 description 1
- HSFRODBENVJLHS-UHFFFAOYSA-N 2,3-bis(bromomethyl)naphthalene Chemical compound C1=CC=C2C=C(CBr)C(CBr)=CC2=C1 HSFRODBENVJLHS-UHFFFAOYSA-N 0.000 description 1
- LRQYSMQNJLZKPS-UHFFFAOYSA-N 2,7-dimethylnaphthalene Chemical compound C1=CC(C)=CC2=CC(C)=CC=C21 LRQYSMQNJLZKPS-UHFFFAOYSA-N 0.000 description 1
- ZLZYZWBZSRVLDB-UHFFFAOYSA-N 2,9-dimethylanthracene Chemical compound C1=CC=CC2=C(C)C3=CC(C)=CC=C3C=C21 ZLZYZWBZSRVLDB-UHFFFAOYSA-N 0.000 description 1
- ZRPAUEVGEGEPFQ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2 ZRPAUEVGEGEPFQ-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 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
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001454 anthracenes Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 150000004074 biphenyls Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229940078552 o-xylene Drugs 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、高分子、色素、耐熱性
高分子及び新機能材料の原料として有用なビス（ブロモ
メチル）芳香族炭化水素の製造法に関するものである。TECHNICAL FIELD The present invention relates to a method for producing bis(bromomethyl) aromatic hydrocarbons useful as raw materials for polymers, dyes, heat-resistant polymers, and new functional materials.
【０００２】0002
【従来の技術】ビス（ブロモメチル）芳香族炭化水素の
製造法としては、一般にジメチル芳香族炭化水素と臭素
を光照射下で反応させる製造法が知られている。又、ダ
ブリュー・ベェーナー、ジャーナル、オルガニック、ケ
ミストー（Ｊ．Ｏｒｇ．Ｃｈｅｍ．）、第１７巻、５２
３頁、１９５２年及びジェ・ディークマン等、同、第２
８巻、２７１９頁、１９６３年には、２，３−ジメチル
ナフタレン、２，６−ジメチルナフタレン等のジメチル
芳香族炭化水素とＮ−ブロモ− コハク酸イミドを触媒
量の過酸化ベンゾイル、アゾビスイソブチロニトリル等
のラジカル開始剤の存在下、加熱反応させるビス（ブロ
モメチル）芳香族炭化水素の製造法が知られている。2. Description of the Related Art A generally known method for producing bis(bromomethyl) aromatic hydrocarbons is a method in which dimethyl aromatic hydrocarbons and bromine are reacted under light irradiation. Also, W. Boehner, Journal, Organic, Chemistry (J.Org.Chem.), Volume 17, 52
3, 1952 and J. Diekmann et al., vol.
8, p. 2719, 1963, dimethyl aromatic hydrocarbons such as 2,3-dimethylnaphthalene and 2,6-dimethylnaphthalene and N-bromo-succinimide were combined with catalytic amounts of benzoyl peroxide and azobisisomer. A method for producing bis(bromomethyl) aromatic hydrocarbons is known in which a heating reaction is carried out in the presence of a radical initiator such as butyronitrile.
【０００３】0003
【発明が解決しようとする課題】しかし、上記何れの製
造法もビス（ジブロモメチル）芳香族炭化水素、ビス（
トリブロモメチル）芳香族炭化水素、ジブロモメチル−
メチル芳香族炭化水素、芳香核置換臭素化物等の副生成
物が生成し、ビス（ブロモメチル）芳香族炭化水素の選
択率及び収率が低い。[Problems to be Solved by the Invention] However, in all of the above production methods, bis(dibromomethyl) aromatic hydrocarbons, bis(dibromomethyl)
tribromomethyl) aromatic hydrocarbon, dibromomethyl-
By-products such as methyl aromatic hydrocarbons and aromatic nucleus-substituted bromides are produced, and the selectivity and yield of bis(bromomethyl) aromatic hydrocarbons are low.
【０００４】0004
【課題を解決するための手段】本発明者らは、上記課題
を解決すべく鋭意努力検討の結果、上記副生成物を画期
的に抑制できるビス（ブロモメチル）芳香族炭化水素の
製造法を見出し本発明を完成するに至った。即ち、本発
明は、ジメチル芳香族炭化水素とＮ−ブロモ− コハク
酸イミドを、有機溶媒中光を照射し反応させることを特
徴とするビス（ブロモメチル） 芳香族炭化水素の製造
法に関するものである。[Means for Solving the Problems] As a result of intensive efforts and studies to solve the above problems, the present inventors have developed a method for producing bis(bromomethyl) aromatic hydrocarbons that can dramatically suppress the above-mentioned by-products. Heading: The present invention has been completed. That is, the present invention relates to a method for producing bis(bromomethyl) aromatic hydrocarbons, which is characterized by reacting dimethyl aromatic hydrocarbons and N-bromo-succinimide by irradiating light in an organic solvent. .
【０００５】以下、本発明を詳細に説明する。ジメチル
芳香族炭化水素としては、ｏ−キシレン、ｍ−キシレン
、ｐ−キシレン等のキシレン類、１，２−ジメチルナフ
タレン、１，３−ジメチルナフタレン、１，４−ジメチ
ルナフタレン、１，５−ジメチルナフタレン、１，６−
ジメチルナフタレン、１，８−ジメチルナフタレン、２
，３−ジメチルナフタレン、２，６−ジメチルナフタレ
ン、２，７−ジメチルナフタレン等のジメチルナフタレ
ン類、４，４ ´− ジメチルビフェニル等のビフェニ
ル類、２，７−ジメチルアントラセン、６，１０− ジ
メチルアントラセン等のアントラセン類が挙げられる。[0005] The present invention will be explained in detail below. Examples of dimethyl aromatic hydrocarbons include xylenes such as o-xylene, m-xylene, and p-xylene, 1,2-dimethylnaphthalene, 1,3-dimethylnaphthalene, 1,4-dimethylnaphthalene, and 1,5-dimethyl. Naphthalene, 1,6-
Dimethylnaphthalene, 1,8-dimethylnaphthalene, 2
, 3-dimethylnaphthalene, 2,6-dimethylnaphthalene, dimethylnaphthalenes such as 2,7-dimethylnaphthalene, biphenyls such as 4,4′-dimethylbiphenyl, 2,7-dimethylanthracene, 6,10-dimethylanthracene Examples include anthracenes such as.
【０００６】Ｎ−ブロモ− コハク酸イミドの使用量と
しては、ジメチル芳香族炭化水素に対して通常１．８〜
３．０モル倍、好ましくは２．０〜２．５モル倍が良い
。反応温度としては、通常０〜８０℃、好ましくは１０
〜４０℃が良い。照射する光としては、通常２５０ｎｍ
以上の波長の光、好ましくは３１０ｎｍ以上の波長の光
、より好ましくは３９０ｎｍ以上の波長の光が良い。[0006] The amount of N-bromo-succinimide used is usually 1.8 to 1.8 to
It is preferably 3.0 times by mole, preferably 2.0 to 2.5 times by mole. The reaction temperature is usually 0 to 80°C, preferably 10°C.
~40℃ is good. The light to be irradiated is usually 250 nm.
Light having a wavelength of 310 nm or more, preferably 310 nm or more, more preferably 390 nm or more is preferable.
【０００７】照射する光の波長が３９０ｎｍより短くな
るにつれ、有機溶媒の分解による副反応等が増加しビス
（ブロモメチル） 芳香族炭化水素の収率が低下する。
有機溶媒は、着色の強いもの及びジメチル芳香族炭化水
素を溶解しにくいものは好ましくない。使用される有機
溶媒としては、例えばアセトン、四塩化炭素、ベンゼン
、アセトニトリル、デカリン等が挙げられる。As the wavelength of the irradiated light becomes shorter than 390 nm, side reactions due to decomposition of the organic solvent increase and the yield of bis(bromomethyl) aromatic hydrocarbons decreases. It is not preferable to use organic solvents that are strongly colored or that are difficult to dissolve dimethyl aromatic hydrocarbons. Examples of the organic solvent used include acetone, carbon tetrachloride, benzene, acetonitrile, decalin, and the like.
【０００８】反応後の操作を考慮すると、生成するコハ
ク酸イミドが析出し、ろ過し易いベンゼン溶媒等が好ま
しい。有機溶媒の使用量としては、特に制限はないが通
常ジメチル芳香族炭化水素の濃度として０．００１〜０
．５Ｍ、好ましくは０．０１〜０．１Ｍが良い。[0008] Considering the operations after the reaction, a benzene solvent or the like is preferred because the produced succinimide precipitates out and is easy to filter. There is no particular limit to the amount of organic solvent used, but the concentration of dimethyl aromatic hydrocarbon is usually 0.001 to 0.
．． 5M, preferably 0.01-0.1M.
【０００９】[0009]
【発明の効果】本発明方法に従うと、ジメチル芳香族炭
化水素からビス（ブロモメチル） 芳香族炭化水素を高
い収率で得ることができるうえ、副生成物の生成が少な
いため、精製工程を必要とせず工業的製造法として好適
である。[Effects of the Invention] According to the method of the present invention, bis(bromomethyl) aromatic hydrocarbons can be obtained from dimethyl aromatic hydrocarbons in a high yield, and since little by-products are produced, there is no need for a purification step. It is suitable as an industrial manufacturing method.
【００１０】0010
【実施例】以下、実施例を挙げ本発明を更に詳細に説明
するが、本発明はこれらに限定されるものではない。
実施例１
ベンゼン７０ｍＬ、２，６−ジメチルナフタレン５４６
ｇ（０．０５モル／Ｌ）、Ｎ−ブロモ− コハク酸イミ
ド１．３７ｇ（０．１１モル／Ｌ）を１００ｍＬの二口
フラスコに仕込み、窒素気流下、２００ワット超高圧水
銀燈（Ｓｈｉｍａｄｚｕ−Ｂａｕｓｃｈ−Ｌｏｍｂ）
の光をグラスフィルター（東芝製 Ｌ−３９）を使用し
て３９０ｎｍ以上の波長として外部照射し、２０℃で２
時間反応させた。[Examples] The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited thereto. Example 1 Benzene 70mL, 2,6-dimethylnaphthalene 546
g (0.05 mol/L) and 1.37 g (0.11 mol/L) of N-bromo-succinimide were charged into a 100 mL two-necked flask, and heated with a 200 watt ultra-high pressure mercury lamp (Shimadzu-Bausch lamp) under a nitrogen stream. -Lomb)
The light was externally irradiated with a wavelength of 390 nm or more using a glass filter (L-39 manufactured by Toshiba), and was heated at 20°C.
Allowed time to react.
【００１１】次に、反応液より溶媒を約半量留去した後
析出したコハク酸イミドをろ過し、更にベンゼン３０ｍ
Ｌで２回洗浄した。このろ液と洗液を合わせ減圧乾固し
、淡褐色の結晶１．１０ｇを得た。このものをガスクロ
マトグラフィ分析したところ、原料２，６−ジメチルナ
フタレンの転化率は１００％、目的物２，６−ビス（モ
ノブロモメチル）ナフタレンの収率は１００％であった
。Next, about half of the solvent was distilled off from the reaction solution, and the precipitated succinimide was filtered, and then 30 ml of benzene was added.
Washed twice with L. The filtrate and washing liquid were combined and dried under reduced pressure to obtain 1.10 g of pale brown crystals. Gas chromatography analysis of this product revealed that the conversion rate of the raw material 2,6-dimethylnaphthalene was 100% and the yield of the target product 2,6-bis(monobromomethyl)naphthalene was 100%.
【００１２】融点、赤外線吸収スペクトル、核磁気共鳴
スペクトル及び質量分析の結果を以下に示す。
融点 １４６．２〜１４６．７℃
ＮＭＲ（ＣＤＣｌ３，ｐｐｍ）：δ ４．１０（ｓ，４
Ｈ）， ７．１８ 〜７．３７（ｍ，６Ｈ）ＩＲ（ｎｕ
ｊｏｌ） ：８２７，８９６，１２０８ｃｍ−１ＭＳ（
ｍ／ｅ） ：３１６（４）， ３１４（２９）， ３１
２（１５，Ｍ ＋ ）， ２３５（１００）， ２３３
（９９）， １５４（９１）
実施例２〜５
有機溶媒を代えた他は、実施例１と同様に反応及び操作
を行った。The results of melting point, infrared absorption spectrum, nuclear magnetic resonance spectrum and mass spectrometry are shown below. Melting point 146.2-146.7°C NMR (CDCl3, ppm): δ 4.10 (s, 4
H), 7.18 ~ 7.37 (m, 6H) IR (nu
jol) :827,896,1208cm-1MS(
m/e) :316(4), 314(29), 31
2 (15, M + ), 235 (100), 233
(99), 154(91) Examples 2 to 5 Reactions and operations were carried out in the same manner as in Example 1, except that the organic solvent was changed.
【００１３】原料２，６−ジメチルナフタレンの転化率
及び目的物２，６−ビス（モノブロモメチル）ナフタレ
ンの収率を第１表に示す。Table 1 shows the conversion rate of the raw material 2,6-dimethylnaphthalene and the yield of the target product 2,6-bis(monobromomethyl)naphthalene.
【００１４】[0014]
【表 １】
第１表 ─────────
─────────────────────
実施例 溶媒
転化率（％） 収率（％）
───────────────────────
─────── 実施例２
デカリン １８
１７ 実施例３ アセ
トニトリル １００ ８８
実施例４ アセトン
１００ １００
実施例５ 四塩化炭素
１００ １００ ────
─────────────────────────
─実施例６〜１０
原料２，６−ジメチルナフタレンを他の原料であるジメ
チル芳香族炭化水素に代えた他は、実施例１と同様に反
応及び操作を行った。[Table 1]
Table 1 ──────────
──────────────────────
Example Solvent
Conversion rate (%) Yield (%)
────────────────────────
─────── Example 2
Decalin 18
17 Example 3 Acetonitrile 100 88
Example 4 Acetone
100 100
Example 5 Carbon tetrachloride
100 100 ────
──────────────────────────
- Examples 6 to 10 The reactions and operations were carried out in the same manner as in Example 1, except that the raw material 2,6-dimethylnaphthalene was replaced with another raw material, dimethyl aromatic hydrocarbon.
【００１５】目的物であるビス（ブロモメチル）芳香族
炭化水素の収率を第２表に示す。Table 2 shows the yield of the target bis(bromomethyl) aromatic hydrocarbon.
【００１６】[0016]
【表 ２】
第２表 ───────────
──────────────────────
実施例 原料
転化率（％） 収率（％
） ────────────────────
───────────── 実施例６
ｐ−キシレン
１００ １００ 実施例７
４，４ ´− ジメチルビフェニル １００
１００ 実施例８ １，
４−ジメチルナフタレン １００
１００ 実施例９ １，８−ジ
メチルナフタレン １００
１００ 実施例１０ ２，３−ジメチ
ルナフタレン １００
１００ ──────────────────
───────────────以下に、各目的物の融
点、赤外線吸収スペクトル、核磁気共鳴スペクトル及び
質量分析の結果等を示す。[Table 2]
Table 2 ────────────
──────────────────────
Examples Raw materials
Conversion rate (%) Yield (%
) ────────────────────
───────────── Example 6
p-xylene
100 100 Example 7
4,4′-dimethylbiphenyl 100
100 Example 8 1,
4-dimethylnaphthalene 100
100 Example 9 1,8-dimethylnaphthalene 100
100 Example 10 2,3-dimethylnaphthalene 100
100 ──────────────────
────────────────The melting point, infrared absorption spectrum, nuclear magnetic resonance spectrum, and mass spectrometry results of each target product are shown below.
【００１７】（Ｉ）１，４−ビス（ブロモメチル）ベン
ゼンＭＳ（ｍ／ｅ） ：２６６（７．１）， ２６４（
１４）， ２６２（７．３，Ｍ＋ ）， １８５（１０
０）， １８３（１００），１０４（５８）（ＩＩ）４
，４ ´− ビス（ブロモメチル）ビフェニルＮＭＲ（
ＣＤＣｌ３，ｐｐｍ）：δ ４．５３（ｓ，４Ｈ），７
．４６（ｄ，４Ｈ，Ｊ ＝８．５４Ｈｚ），７．５４（
ｄ，４Ｈ，Ｊ＝８．５４Ｈｚ）ＭＳ（ｍ／ｅ） ：３４
２（８．３）， ３４０（１８）， ３３８（９．２，
Ｍ ＋ ）， ２６１（９９）， ２５９（１００）
（ＩＩＩ） １，４− ビス（ブロモメチル）ナフタレ
ン融点 １３７．２〜１３７．７℃
ＮＭＲ（ＣＤＣｌ３，ｐｐｍ）：δ ４．３３（ｓ，４
Ｈ）， ６．８３（ｓ，２Ｈ）， ７，２７（ｄ，２Ｈ
）， ７．９３（ｄ，２Ｈ）
ＩＲ（ｎｕｊｏｌ） ：７５６，７６４，１２０４ｃｍ
−１ＭＳ（ｍ／ｅ） ：３１６（１１）， ３１４（２
３）， ３１２（１２，Ｍ ＋ ）， ２３５（９０）
， ２３３（９１）， １５４（１００）（ＩＶ） １
，８−ビス（ブロモメチル）ナフタレン融点 １２６
．２〜１２６．８℃
ＮＭＲ（ＣＤＣｌ３，ｐｐｍ）：δ ５．３０（ｓ，４
Ｈ）， ７．４５（ｄｄ，２Ｈ）， ７，６２（ｄｄ，
２Ｈ）， ７．８８（ｄｄ，２Ｈ）ＩＲ（ｎｕｊｏｌ）
：７６１，８１６，８２２，１２０８ｃｍ−１ＭＳ（
ｍ／ｅ） ：３１６（１０）， ３１４（２２）， ３
１２（１１，Ｍ ＋ ）， ２３５（９７）， ２３３
（１００）， １５３（３５）（Ｖ） ２，３−ビス（
ブロモメチル）ナフタレン融点 １２５．１〜１２５
．７℃
ＮＭＲ（ＣＤＣｌ３，ｐｐｍ）：δ ４．５０（ｓ，４
Ｈ）， ７．１７（ｄ，２Ｈ）， ７，２５（ｓ，２Ｈ
）， ７．３８（ｄ，２Ｈ）
ＩＲ（ｎｕｊｏｌ） ：７５３，８９１，１２０４ｃｍ
−１ＭＳ（ｍ／ｅ） ：３１６（１６）， ３１４（３
３）， ３１２（１７，Ｍ ＋ ）， ２３５（９７）
， ２３３（１００）， １５４（７１）実施例１１
有機溶媒を四塩化炭素、グラスフィルターを使用せず光
の波長を３１０ｎｍ以上とした他は、実施例１と同様に
反応及び操作を行った。(I) 1,4-bis(bromomethyl)benzene MS (m/e): 266 (7.1), 264 (
14), 262 (7.3, M+), 185 (10
0), 183 (100), 104 (58) (II) 4
,4'-bis(bromomethyl)biphenyl NMR (
CDCl3, ppm): δ 4.53 (s, 4H), 7
．． 46 (d, 4H, J = 8.54Hz), 7.54 (
d, 4H, J=8.54Hz) MS (m/e): 34
2 (8.3), 340 (18), 338 (9.2,
M + ), 261 (99), 259 (100) (III) 1,4-bis(bromomethyl)naphthalene Melting point 137.2-137.7°C NMR (CDCl3, ppm): δ 4.33 (s, 4
H), 6.83 (s, 2H), 7,27 (d, 2H
), 7.93 (d, 2H) IR (nujol): 756,764,1204cm
-1MS (m/e): 316 (11), 314 (2
3), 312 (12, M + ), 235 (90)
, 233(91), 154(100)(IV) 1
,8-bis(bromomethyl)naphthalene Melting point 126
．． 2-126.8°C NMR (CDCl3, ppm): δ 5.30 (s, 4
H), 7.45 (dd, 2H), 7,62 (dd,
2H), 7.88(dd, 2H)IR(nujol)
:761,816,822,1208cm-1MS(
m/e) :316(10), 314(22), 3
12 (11, M + ), 235 (97), 233
(100), 153(35)(V) 2,3-bis(
Bromomethyl)naphthalene Melting point 125.1-125
．． 7°C NMR (CDCl3, ppm): δ 4.50 (s, 4
H), 7.17(d,2H), 7,25(s,2H
), 7.38 (d, 2H) IR (nujol): 753,891,1204cm
-1MS (m/e): 316 (16), 314 (3
3), 312 (17, M + ), 235 (97)
, 233(100), 154(71) Example 11 The reaction and operation were carried out in the same manner as in Example 1, except that the organic solvent was carbon tetrachloride, a glass filter was not used, and the wavelength of light was 310 nm or more.
【００１８】目的物２，６−ジ（モノブロモメチル）ナ
フタレンの収率は８３％であり、四塩化炭素の一部が分
解して反応したと考えられるクロロメチル体及び２，２
，２−トリクロロエチル体の生成が認められた。The yield of the target product 2,6-di(monobromomethyl)naphthalene was 83%, and the chloromethyl compound and 2,2
, 2-trichloroethyl compound was observed.
Claims (3)
− コハク酸イミドを、有機溶媒中光を照射し反応させ
ることを特徴とするビス（ブロモメチル） 芳香族炭化
水素の製造法。1. A method for producing bis(bromomethyl) aromatic hydrocarbons, which comprises reacting dimethyl aromatic hydrocarbons and N-bromo-succinimide by irradiating them with light in an organic solvent.
１記載の製造法。2. The manufacturing method according to claim 1, wherein the wavelength of the light is 390 nm.
載の製造法。3. The method according to claim 1, wherein the organic solvent is benzene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4635391A JPH04282327A (en) | 1991-03-12 | 1991-03-12 | Production of bis(bromomethyl) aromatic hydrocarbon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4635391A JPH04282327A (en) | 1991-03-12 | 1991-03-12 | Production of bis(bromomethyl) aromatic hydrocarbon |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04282327A true JPH04282327A (en) | 1992-10-07 |
Family
ID=12744784
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4635391A Pending JPH04282327A (en) | 1991-03-12 | 1991-03-12 | Production of bis(bromomethyl) aromatic hydrocarbon |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04282327A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1705168A1 (en) * | 2005-03-21 | 2006-09-27 | Helm AG | Improved process for side-chain bromination of alkyl-benzenes |
| JP2006290765A (en) * | 2005-04-07 | 2006-10-26 | Shiratori Pharmaceutical Co Ltd | Method for producing 7-alkyl-10-hydroxycamptothecin |
| WO2007054963A2 (en) * | 2005-09-30 | 2007-05-18 | Cadila Healthcare Limited | A process for the preparation of pure anastrozole |
-
1991
- 1991-03-12 JP JP4635391A patent/JPH04282327A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1705168A1 (en) * | 2005-03-21 | 2006-09-27 | Helm AG | Improved process for side-chain bromination of alkyl-benzenes |
| JP2006290765A (en) * | 2005-04-07 | 2006-10-26 | Shiratori Pharmaceutical Co Ltd | Method for producing 7-alkyl-10-hydroxycamptothecin |
| JP4652875B2 (en) * | 2005-04-07 | 2011-03-16 | 白鳥製薬株式会社 | Process for producing 7-alkyl-10-hydroxycamptothecins |
| WO2007054963A2 (en) * | 2005-09-30 | 2007-05-18 | Cadila Healthcare Limited | A process for the preparation of pure anastrozole |
| WO2007054963A3 (en) * | 2005-09-30 | 2007-11-29 | Cadila Healthcare Ltd | A process for the preparation of pure anastrozole |
| EP2397472A1 (en) * | 2005-09-30 | 2011-12-21 | Cadila Healthcare Limited | A process for the preparation of a benzylbromide intermediates |
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