JPH04128243A - Production of 1,2-bis(3,4-dimethylphenyl)ethane - Google Patents
Production of 1,2-bis(3,4-dimethylphenyl)ethaneInfo
- Publication number
- JPH04128243A JPH04128243A JP2246846A JP24684690A JPH04128243A JP H04128243 A JPH04128243 A JP H04128243A JP 2246846 A JP2246846 A JP 2246846A JP 24684690 A JP24684690 A JP 24684690A JP H04128243 A JPH04128243 A JP H04128243A
- Authority
- JP
- Japan
- Prior art keywords
- dimethylphenyl
- bis
- ethane
- mixture
- content
- 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
- MOPBWASVAUDDTC-UHFFFAOYSA-N 4-[2-(3,4-dimethylphenyl)ethyl]-1,2-dimethylbenzene Chemical compound C1=C(C)C(C)=CC=C1CCC1=CC=C(C)C(C)=C1 MOPBWASVAUDDTC-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000000203 mixture Substances 0.000 claims abstract description 38
- DQAZLNHCFTUZEN-UHFFFAOYSA-N 1-[1-(2,3-dimethylphenyl)ethyl]-2,3-dimethylbenzene Chemical compound C=1C=CC(C)=C(C)C=1C(C)C1=CC=CC(C)=C1C DQAZLNHCFTUZEN-UHFFFAOYSA-N 0.000 claims abstract description 27
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 16
- 229910001510 metal chloride Inorganic materials 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 9
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 35
- -1 3,4-dimethylphenyl Chemical group 0.000 claims description 16
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 3
- 239000002699 waste material Substances 0.000 abstract description 6
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 3
- BAVMXDNHWGQCSR-UHFFFAOYSA-N 1-[2-(2,3-dimethylphenyl)ethyl]-2,3-dimethylbenzene Chemical compound CC1=CC=CC(CCC=2C(=C(C)C=CC=2)C)=C1C BAVMXDNHWGQCSR-UHFFFAOYSA-N 0.000 abstract 5
- 229940078552 o-xylene Drugs 0.000 abstract 4
- 239000011541 reaction mixture Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 239000012043 crude product Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- NCSVCMFDHINRJE-UHFFFAOYSA-N 4-[1-(3,4-dimethylphenyl)ethyl]-1,2-dimethylbenzene Chemical compound C=1C=C(C)C(C)=CC=1C(C)C1=CC=C(C)C(C)=C1 NCSVCMFDHINRJE-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000013076 target substance Substances 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- BOXVSFHSLKQLNZ-UHFFFAOYSA-K dysprosium(iii) chloride Chemical compound Cl[Dy](Cl)Cl BOXVSFHSLKQLNZ-UHFFFAOYSA-K 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- BHXBZLPMVFUQBQ-UHFFFAOYSA-K samarium(iii) chloride Chemical compound Cl[Sm](Cl)Cl BHXBZLPMVFUQBQ-UHFFFAOYSA-K 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- ILOTUXNTERMOJL-UHFFFAOYSA-K thulium(iii) chloride Chemical compound Cl[Tm](Cl)Cl ILOTUXNTERMOJL-UHFFFAOYSA-K 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- PYOOBRULIYNHJR-UHFFFAOYSA-K trichloroholmium Chemical compound Cl[Ho](Cl)Cl PYOOBRULIYNHJR-UHFFFAOYSA-K 0.000 description 1
- CKLHRQNQYIJFFX-UHFFFAOYSA-K ytterbium(III) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Yb+3] CKLHRQNQYIJFFX-UHFFFAOYSA-K 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、１．２−ビス（３，４−ジメチルフェニル）
エタンの製造方法、詳しくは、実際上廃粟物を全く生じ
ることなく１．２−ビス（３，４−ジメチルフェニル）
エタンを製造し得る方法に関する。[Detailed description of the invention] [Industrial application field] The present invention provides 1,2-bis(3,4-dimethylphenyl)
A method for producing ethane, in detail, 1,2-bis(3,4-dimethylphenyl) without actually producing any waste.
The present invention relates to a method by which ethane can be produced.
〔従来の技術及び発明が解決しようとする課題〕１．２
−ビス（３，４−ジメチルフェニル）エタンは、トリメ
リット酸の合成原料、感熱記録材料用の増感剤等として
有用な化合物であり、オルソキシレンとジクロルエタン
とを塩化アルミニウム等の金属塩化物の存在下に反応さ
せる、フリーゾルタラフッ反応によって合成されること
が知られている。[Problems to be solved by conventional technology and invention] 1.2
-Bis(3,4-dimethylphenyl)ethane is a compound useful as a raw material for the synthesis of trimellitic acid and a sensitizer for heat-sensitive recording materials. It is known that it can be synthesized by a free-solat fluorine reaction in the presence of
例えば、特公昭４６−２９１３７号公報には、オルソキ
シレンとジクロルエタンとを塩化アルミニウムまたは塩
化第二鉄の存在下に反応させることにより、収率的７０
〜８０％で目的の１，２−ビス（３，４−ジメチルフェ
ニル）エタンが得られることが記載されている。For example, Japanese Patent Publication No. 46-29137 discloses that ortho-xylene and dichloroethane are reacted in the presence of aluminum chloride or ferric chloride to achieve a yield of 70%.
It is described that the desired 1,2-bis(3,4-dimethylphenyl)ethane can be obtained at a concentration of 80%.
しかしながら、本発明者等の検討によれば、このような
方法で得られた生成物は、異性体あるいはメチル基の転
移した生成物である、１．２−ビス（２，３−ジメチル
フェニル）エタン、１． ２−ビス（２，４−ジメチル
フェニル）エタン、１゜２−ビス（３，５−ジメチルフ
ェニル）エタン、１−（２，３−ジメチルフェニル）−
２−（３゜４−ジメチルフェニル）エタン、１−（３，
４−ジメチルフェニル）−２−（３，５−ジメチルフェ
ニル）エタン等の他のビス（ジメチルフェニル）エタン
類を多量に含有しており、目的の１．２ビス（３，４−
ジメチルフェニル）エタンの生成率は生成物中の約６０
重量％程度にすぎないことが明らかとなった。However, according to the studies of the present inventors, the product obtained by such a method is an isomer or a product with a methyl group transferred, 1,2-bis(2,3-dimethylphenyl). Ethane, 1. 2-bis(2,4-dimethylphenyl)ethane, 1゜2-bis(3,5-dimethylphenyl)ethane, 1-(2,3-dimethylphenyl)-
2-(3゜4-dimethylphenyl)ethane, 1-(3,
It contains a large amount of other bis(dimethylphenyl)ethanes such as 4-dimethylphenyl)-2-(3,5-dimethylphenyl)ethane, and the target 1.2bis(3,4-
The production rate of dimethylphenyl)ethane is approximately 60% in the product.
It became clear that the amount was only about % by weight.
従って、このような不純物を多量に含む反応生成物から
高純度の１．２−ビス（３，４−ジメチルフェニル）エ
タンを得るためには、再結晶、精密蒸留等の分離操作が
必要となるが、目的物と不純物とは極めて類似した化学
構造を有するため、反応生成物から１．２−ビス（３，
４−ジメチルフェニル）エタンを完全に分離することは
困難であり、また、生成物中には約４０重量％の不純物
が含まれることとあいまって、ビス（ジメチルフェニル
）エタン混合物を主成分とする多量の廃棄物がＢＥじる
こととなり、実用上大きな問題となっていた。Therefore, in order to obtain highly pure 1,2-bis(3,4-dimethylphenyl)ethane from a reaction product containing a large amount of such impurities, separation operations such as recrystallization and precision distillation are required. However, since the target product and the impurity have extremely similar chemical structures, 1,2-bis(3,
It is difficult to completely separate 4-dimethylphenyl)ethane, and the product contains about 40% by weight of impurities, so the main component is a mixture of bis(dimethylphenyl)ethane. This resulted in a large amount of waste being subjected to BE, which was a big problem in practice.
このため、廃棄物の少ない、より合理的な１゜、２−ビ
ス（３，４−ジメチルフェニル）エタンの製造方法を見
いだすことが強（望まれていた。Therefore, it has been strongly desired to find a more rational method for producing 1°, 2-bis(3,4-dimethylphenyl)ethane that produces less waste.
本発明者等は、上記現状に鑑み鋭意検討を重ねた結果、
１．２−ビス（３，４−ジメチルフェニル）エタンの含
有率の低いビス（ジメチルフェニル）エタン混合物とオ
ルソキシレンとを金属塩化物の存在下に反応させること
により、該混合物中の１．２−ビス（３，４−ジメチル
フェニル）エタンの含有率が著しく増加することを見い
だし本発明に到達した。As a result of extensive studies in view of the above-mentioned current situation, the inventors of the present invention have found that
By reacting a bis(dimethylphenyl)ethane mixture with a low content of 1.2-bis(3,4-dimethylphenyl)ethane and ortho-xylene in the presence of a metal chloride, the 1.2 The present invention was achieved by discovering that the content of -bis(3,4-dimethylphenyl)ethane increases significantly.
即ち、本発明は、１．２−ビス（３，４−ジメチルフェ
ニル）エタン以外のビス（ジメチルフェニル）エタン混
合物するビス（ジメチルフェニル）エタン混合物とオル
ソキシレンとを金属塩化物の存在下に反応させ、ビス（
ジメチルフェニル）エタン混合物中の１，２−ビス（３
，４−ジメチルフェニル）エタンの含有率を高め、その
後、該ビス（ジメチルフェニル）エタン混合物から１゜
２−ビス（３，４−ジメチルフェニル）エタンを回収す
ることを特徴とする１、２−ビス（３，４−ジメチルフ
ェニル）エタンの製造方法を提供するものである。That is, the present invention involves reacting a mixture of bis(dimethylphenyl)ethane other than 1,2-bis(3,4-dimethylphenyl)ethane with ortho-xylene in the presence of a metal chloride. and screw (
1,2-bis(3) in dimethylphenyl)ethane mixture
,4-dimethylphenyl)ethane, and then recovering 1°2-bis(3,4-dimethylphenyl)ethane from the bis(dimethylphenyl)ethane mixture. A method for producing bis(3,4-dimethylphenyl)ethane is provided.
以下、本発明の１．２−ビス（３，４−ジメチルフェニ
ル）エタンの製造方法についてさらに詳細に説明する。Hereinafter, the method for producing 1,2-bis(3,4-dimethylphenyl)ethane of the present invention will be explained in more detail.
本発明で原料として用いられるビス（ジメチルフェニル
）エタン混合物は、本発明の目的物である１、２−ビス
（３，４−ジメチルフェニル）エタンの他に、１．２−
ビス（２，３−ジメチルフェニル）エタン、１．２−ビ
ス（２，４−ジメチルフェニル）エタン、１．２−ビス
（３，５−ジメチルフェニル）エタン、１−（２，３−
ジメチルフェニル）−２−（３，４−ジメチルフェニル
）エタン、１−（３，４−ジメチルフェニル）−２−（
３，５−ジメチルフェニル）エタン等の他のビス（ジメ
チルフェニル）エタン化合物の一種または二種以上を含
有するものである。The bis(dimethylphenyl)ethane mixture used as a raw material in the present invention includes 1,2-bis(3,4-dimethylphenyl)ethane, which is the object of the present invention, and 1,2-bis(3,4-dimethylphenyl)ethane.
Bis(2,3-dimethylphenyl)ethane, 1.2-bis(2,4-dimethylphenyl)ethane, 1.2-bis(3,5-dimethylphenyl)ethane, 1-(2,3-
dimethylphenyl)-2-(3,4-dimethylphenyl)ethane, 1-(3,4-dimethylphenyl)-2-(
It contains one or more other bis(dimethylphenyl)ethane compounds such as 3,5-dimethylphenyl)ethane.
該混合物中の１．２−ビス（３，４−ジメチルフェニル
）エタンの含有率が約５０重量％以上、より好ましくは
約５５重量％以上であれば、晶析等の分離操作により高
純度の目的物が容易に得られるが、その含有率が約４０
重量％未満の場合には、再結晶等の分離操作によって高
純度の目的物を得ることは極めて困難であり、このよう
なビス（ジメチルフェニル）エタン混合物から目的の１
゜２−ビス（３，４−ジメチルフェニル）エタンを回収
するためには、その含有率を約５０重量％以上まで高め
る必要がある。If the content of 1,2-bis(3,4-dimethylphenyl)ethane in the mixture is about 50% by weight or more, more preferably about 55% by weight or more, high purity can be obtained by a separation operation such as crystallization. The target product is easily obtained, but its content is about 40%
If the amount is less than % by weight, it is extremely difficult to obtain a highly pure target product by separation operations such as recrystallization, and the target product cannot be obtained from such a bis(dimethylphenyl)ethane mixture.
In order to recover 2-bis(3,4-dimethylphenyl)ethane, it is necessary to increase its content to about 50% by weight or more.
このような、１．２−ビス（３，４−ジメチルフェニル
）エタンの含有率の低いビス（ジメチルフェニル）エタ
ン混合物としては、１，２−ビス（３，４−ジメチルフ
ェニル）エタンを回収した後の残渣である１、２−ビス
（３，４−ジメチルフェニル）エタンの含有率の低いビ
ス（ジメチルフェニル）エタン混合物を、原料として繰
り返し使用することができるので、実際上廃棄物を全く
生じることなく１．２−ビス（３，４−ジメチルフェニ
ル）エタンを製造することができる。As such a bis(dimethylphenyl)ethane mixture with a low content of 1,2-bis(3,4-dimethylphenyl)ethane, 1,2-bis(3,4-dimethylphenyl)ethane was recovered. The resulting residue, a bis(dimethylphenyl)ethane mixture with a low content of 1,2-bis(3,4-dimethylphenyl)ethane, can be used repeatedly as a raw material, so virtually no waste is generated. 1,2-bis(3,4-dimethylphenyl)ethane can be produced without any
本発明では、１．２−ビス（３，４−ジメチルフェニル
）エタンの含有率の低いビス（ジメチルフェニル）エタ
ン混合物とオルソキシレンとを、金属塩化物の存在下に
反応させることによって、該混合物中の１，２−ビス（
３，４−ジメチルフェニル）エタンの含有率が著しく向
上するが、その理由としては、オルソキシレンとビス（
ジメチルフェニル）エタンのジメチルフェニル基との交
換が主要な原因であると推定される。In the present invention, by reacting a bis(dimethylphenyl)ethane mixture with a low content of 1,2-bis(3,4-dimethylphenyl)ethane and ortho-xylene in the presence of a metal chloride, the mixture is 1,2-bis(
The content of 3,4-dimethylphenyl)ethane increases significantly, and the reason for this is that ortho-xylene and bis(
The exchange of dimethylphenyl)ethane with dimethylphenyl group is presumed to be the main cause.
オルソキシレンの使用量は、ビス（ジメチルフェニル）
エタン１００重量部に対して、５０重量部以上、より好
ましくは１００重量部以上であることが１．２−ビス（
３，４−ジメチルフェニル）エタンの含有率を高めるた
めに好ましい。また、使用量の上限は特に制限を受けな
いが、あまりに多量に用いてもその含有率はそれ以上改
善できず、かえって目的物の収量が低下するだけなので
、−船釣には約５００重量部以下とすることが好ましい
また、オルソキシレンとともにジクロルエタンを存在さ
せることによって、ビス（ジメチルフェニル）エタン混
合物中の目的物の含有率が向上するばかりでなく、オル
ソキシレンとジクロルエタンとの反応による目的物の製
造を同時に行なうことも可能である。The amount of orthoxylene used is bis(dimethylphenyl)
The amount of 1,2-bis(
Preferable for increasing the content of 3,4-dimethylphenyl)ethane. In addition, although there is no particular upper limit on the amount used, if too much is used, the content cannot be improved any further and the yield of the target product is reduced, so - approximately 500 parts by weight for boat fishing. The following is preferable. Furthermore, by having dichloroethane present together with ortho-xylene, not only the content of the target substance in the bis(dimethylphenyl)ethane mixture is improved, but also the content of the target substance by the reaction between ortho-xylene and dichloroethane is improved. It is also possible to carry out the manufacturing at the same time.
本発明で用いられる金属塩化物としては、塩化亜鉛、塩
化カドミウム、塩化カルシウム、塩化バリウム、塩化マ
グネシウム、塩化アルミニウム、塩化ジルコニウム、塩
化鉄、塩化第一錫、塩化第二錫、４塩化チタン、３塩化
サマリウム、３塩化ジスプロシウム、３塩化ホルミウム
、３塩化ツリウム、３塩化イツテルビウム、３塩化ルテ
ニウム等があげられ、また、これらの数種を併用しても
よい。これらの金属塩化物の内、特に、塩化アルミニウ
ムが好ましい。The metal chlorides used in the present invention include zinc chloride, cadmium chloride, calcium chloride, barium chloride, magnesium chloride, aluminum chloride, zirconium chloride, iron chloride, stannous chloride, tin chloride, titanium tetrachloride, Examples include samarium chloride, dysprosium trichloride, holmium trichloride, thulium trichloride, ytterbium trichloride, ruthenium trichloride, and several of these may be used in combination. Among these metal chlorides, aluminum chloride is particularly preferred.
これらの金属塩化物の使用量は、ビス（ジメチルフェニ
ル）エタン１００重量部に対して、好ましくは０．１〜
２０重量部、より好ましくは０゜５〜１０重量部である
。The amount of these metal chlorides used is preferably 0.1 to 100 parts by weight of bis(dimethylphenyl)ethane.
The amount is 20 parts by weight, more preferably 0.5 to 10 parts by weight.
また、本発明の方法は、加熱下に行なうことが好ましく
、−ｉには、４０〜１５０℃の範囲、より好ましくは５
０〜１００”Ｃの範囲で行なわれる。Further, the method of the present invention is preferably carried out under heating, and -i is in the range of 40 to 150 °C, more preferably 5
It is carried out in the range of 0 to 100''C.
反応終了後に目的物を分離する方法は特に制限を受けな
いが、例えば、水を加えて金属塩化物を分解した後、有
機層をとり、脱溶媒後、再結晶することにより高純度の
目的物を単離することができる。The method of separating the target product after the reaction is not particularly limited, but for example, after adding water to decompose the metal chloride, taking the organic layer, removing the solvent, and recrystallizing it, the target product can be isolated with high purity. can be isolated.
以下、具体的な実施例によって本発明を更に詳細に説明
するが、本発明は以下の実施例によって制限を受けるも
のではない。EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to specific examples, but the present invention is not limited by the following examples.
参考例 １
オルソキシレン及び１．２−ジクロルエタンからの１．
２−ビス（３，４−ジメチルフェニル）エタンの製造
温度針、気密かきまぜ機及び冷却器を備えた１ｆ容１の
三つロフラスコに、乾燥オルソキシレン７９０ｇ及び１
，２−ジクロルエタン１３４ｇをとり、窒素ガスで充分
に置換した後、無水塩化アルミニウム５．４ｇを添加し
、８０°Ｃで４時間撹拌した。Reference Example 1 1. from ortho-xylene and 1,2-dichloroethane.
Preparation of 2-bis(3,4-dimethylphenyl)ethane 790 g of dry ortho-xylene and
, 2-dichloroethane was taken, and after the atmosphere was sufficiently replaced with nitrogen gas, 5.4 g of anhydrous aluminum chloride was added, and the mixture was stirred at 80°C for 4 hours.
冷却後、水洗、乾燥し、次いで１２０°Ｃ，１０ｍ１ｇ
の条件で１時間脱溶剤し、下記表−１に示す組成の白色
固体の粗生成物２６６．８ｇ （相数率８１％）を得た
。After cooling, wash with water, dry, then 120°C, 10ml/g
The solvent was removed for 1 hour under these conditions to obtain 266.8 g (phase ratio: 81%) of a white solid crude product having the composition shown in Table 1 below.
この粗生成物を、
イソプロピルアルコールを用
いて再結晶して、目的物である１、２−ビス（３゜４−
ジメチルフェニル）エタン１２５ｇ（純度９９％）を得
た。This crude product was recrystallized using isopropyl alcohol to obtain the target product, 1,2-bis(3゜4-
125 g (purity 99%) of dimethylphenyl)ethane was obtained.
残渣をガスクロマトグラムにより分析したところ、その
組成は下記表−２に示す通りであった。When the residue was analyzed by gas chromatography, its composition was as shown in Table 2 below.
表−２
実施例 １
ビス（ジメチルフェニル）エタン混合物からの１゜２−
ビス（３，４−ジメチルフェニル）エタンの製造
参考例１で得た下記表−２に示す組成を有するビス（ジ
メチルフェニル）エタン混合物（残渣）１４０ ｇ、オ
ルソキシレン１４０ｇ及び無水塩化アルミニウム７．７
ｇをとり、窒素気流下、８０°Ｃで６時間撹拌した。冷
却後、オルソキシレン７００ｇを加え、６規定塩酸で洗
浄後、蒸留水でさらに洗浄した。Table 2 Example 1 1゜2- from bis(dimethylphenyl)ethane mixture
Production of bis(3,4-dimethylphenyl)ethane 140 g of the bis(dimethylphenyl)ethane mixture (residue) having the composition shown in Table 2 below obtained in Reference Example 1, 140 g of ortho-xylene, and 7.7 g of anhydrous aluminum chloride.
The mixture was stirred at 80°C for 6 hours under a nitrogen stream. After cooling, 700 g of ortho-xylene was added, and the mixture was washed with 6N hydrochloric acid and further washed with distilled water.
油水分離後、キシレン層を脱溶剤し、下記表−３に示す
組成を有する白色固体の粗生成物１３４゜８ｇ（相数率
９６％）を得た。After oil and water separation, the xylene layer was desolvented to obtain 134.8 g (phase ratio: 96%) of a white solid crude product having the composition shown in Table 3 below.
表−３
この粗生成物を、イソプロピルアルコールを用いて再結
晶して、目的物である１、 ２−ビス（３゜４−ジメ
チルフェニル）エタン６６ ｇ （純度９９％）を得た
。Table 3 This crude product was recrystallized using isopropyl alcohol to obtain 66 g (purity 99%) of 1,2-bis(3°4-dimethylphenyl)ethane, which was the target product.
残渣をガスクロマトグラムにより分析したところ、その
組成は下記表−４に示す通りであった。When the residue was analyzed by gas chromatography, its composition was as shown in Table 4 below.
実施例 ２
ビス（ジメチルフェニル）エタン混合物、゛ジクロルエ
タン及びオルソキシレンからの１．２−ビス（３，４−
ジメチルフェニル）エタンの製造実施例１で得た上記表
−４の組成を有するビス（ジメチルフェニル）エタン混
合物（残渣）６０ｇ、１．２−ジクロルエタン２８．５
ｇ、オルソキシレン２６３ｇ及び無水塩化アルミニウム
２゜２ｇをとり、窒素気流下、８０°Ｃで５時間撹拌し
た。冷却後、６規定塩酸で洗浄後、蒸留水でさらに洗浄
した９ 油水分離後、キシレン層を脱溶剤し、下記表−
５に示す組成を有する白色固体の粗性放物１０９．４ｇ
（粒数率８５％）を得た。Example 2 1,2-bis(3,4-
Production of dimethylphenyl)ethane 60 g of the bis(dimethylphenyl)ethane mixture (residue) having the composition shown in Table 4 obtained in Example 1, 28.5 g of 1,2-dichloroethane
263 g of ortho-xylene and 2.2 g of anhydrous aluminum chloride were taken and stirred at 80° C. for 5 hours under a nitrogen stream. After cooling, the mixture was washed with 6N hydrochloric acid and further washed with distilled water.9 After oil and water separation, the xylene layer was desolvented and
109.4 g of a crude white solid having the composition shown in 5.
(Particle number ratio 85%) was obtained.
この粗生成物を、トルエン／メタノール（１：４）を用
いて再結晶して、目的物である１、２ビス（３４−ジメ
チルフェニル）エタン５１ｇ（純度９９％）を得た。This crude product was recrystallized using toluene/methanol (1:4) to obtain 51 g (purity 99%) of 1,2-bis(34-dimethylphenyl)ethane, which was the desired product.
本発明の方法によれば、１．２−ビス（３，４ジメチル
フエニル）エタンを回収した後の１゜２−ビス（３，４
−ジメチルフェニル）エタンの含有率の低いビス（ジメ
チルフェニル）エタン混合物を原料として、再度１．２
−ビス（３，４ジメチルフエニル）エタンを製造するこ
とが可能となり、実際上廃棄物を全く生じることなく１
゜２−ビス（３，４−ジメチルフェニル）エタンを製造
することができる。According to the method of the present invention, 1°2-bis(3,4 dimethylphenyl)ethane is recovered after recovering 1.2-bis(3,4 dimethylphenyl)ethane.
- Using a bis(dimethylphenyl)ethane mixture with a low content of dimethylphenyl)ethane as a raw material, 1.2
-It is now possible to produce bis(3,4 dimethylphenyl)ethane, with virtually no waste produced at all.
2-bis(3,4-dimethylphenyl)ethane can be produced.
Claims (7)
ン以外のビス（ジメチルフェニル）エタンを含有するビ
ス（ジメチルフェニル）エタン混合物とオルソキシレン
とを金属塩化物の存在下に反応させ、ビス（ジメチルフ
ェニル）エタン混合物中の１，２−ビス（３，４−ジメ
チルフェニル）エタンの含有率を高め、その後、該ビス
（ジメチルフェニル）エタン混合物から１，２−ビス（
３，４−ジメチルフェニル）エタンを回収することを特
徴とする１，２−ビス（３，４−ジメチルフェニル）エ
タンの製造方法。(1) Reacting a bis(dimethylphenyl)ethane mixture containing bis(dimethylphenyl)ethane other than 1,2-bis(3,4-dimethylphenyl)ethane with ortho-xylene in the presence of a metal chloride, The content of 1,2-bis(3,4-dimethylphenyl)ethane in the bis(dimethylphenyl)ethane mixture is increased, and then 1,2-bis(
A method for producing 1,2-bis(3,4-dimethylphenyl)ethane, which comprises recovering 3,4-dimethylphenyl)ethane.
２−ビス（３，４−ジメチルフェニル）エタンの含有率
が０〜４０重量％である請求項（１）記載の製造方法。(2) 1 in a bis(dimethylphenyl)ethane mixture,
The method according to claim 1, wherein the content of 2-bis(3,4-dimethylphenyl)ethane is 0 to 40% by weight.
２−ビス（３，４−ジメチルフェニル）エタンの含有率
を５０重量％以上まで高める請求項（１）記載の製造方
法。(3) 1 in a bis(dimethylphenyl)ethane mixture,
The manufacturing method according to claim 1, wherein the content of 2-bis(3,4-dimethylphenyl)ethane is increased to 50% by weight or more.
ニル）エタン混合物１００重量部に対し、５０重量部以
上である請求項（１）記載の製造方法。(4) The method according to claim 1, wherein the amount of orthoxylene used is 50 parts by weight or more based on 100 parts by weight of the bis(dimethylphenyl)ethane mixture.
）エタン混合物１００重量部に対し、０．１〜２０重量
部である請求項（１）記載の製造方法。(5) The method according to claim 1, wherein the amount of the metal chloride used is 0.1 to 20 parts by weight based on 100 parts by weight of the bis(dimethylphenyl)ethane mixture.
）記載の製造方法。(6) Claim (1) wherein the metal chloride is aluminum chloride
) manufacturing method described.
キシレンとを反応させる際に、１，２−ジクロルエタン
を共存させることを特徴とする請求項（１）記載の製造
方法。(7) The production method according to claim (1), wherein 1,2-dichloroethane is allowed to coexist when the bis(dimethylphenyl)ethane mixture and orthoxylene are reacted.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2246846A JP2792609B2 (en) | 1990-09-17 | 1990-09-17 | Method for producing 1,2-bis (3,4-dimethylphenyl) ethane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2246846A JP2792609B2 (en) | 1990-09-17 | 1990-09-17 | Method for producing 1,2-bis (3,4-dimethylphenyl) ethane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04128243A true JPH04128243A (en) | 1992-04-28 |
| JP2792609B2 JP2792609B2 (en) | 1998-09-03 |
Family
ID=17154582
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2246846A Expired - Fee Related JP2792609B2 (en) | 1990-09-17 | 1990-09-17 | Method for producing 1,2-bis (3,4-dimethylphenyl) ethane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2792609B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5859302A (en) * | 1996-10-28 | 1999-01-12 | Albemarle Corporation | Processes employing reusable aluminum catalysts |
| CN1046698C (en) * | 1996-05-10 | 1999-11-24 | 江苏省化工研究所 | Production method for 1,2-(3,3',4,4'-tetramethyl-dibenzene) ethane |
| US6096680A (en) * | 1996-10-28 | 2000-08-01 | Albemarle Corporation | Liquid clathrate compositions |
-
1990
- 1990-09-17 JP JP2246846A patent/JP2792609B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1046698C (en) * | 1996-05-10 | 1999-11-24 | 江苏省化工研究所 | Production method for 1,2-(3,3',4,4'-tetramethyl-dibenzene) ethane |
| US5859302A (en) * | 1996-10-28 | 1999-01-12 | Albemarle Corporation | Processes employing reusable aluminum catalysts |
| US6096680A (en) * | 1996-10-28 | 2000-08-01 | Albemarle Corporation | Liquid clathrate compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2792609B2 (en) | 1998-09-03 |
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