JPH02129133A - Production of alpha,alpha-dichloro-diphenylmethanes - Google Patents
Production of alpha,alpha-dichloro-diphenylmethanesInfo
- Publication number
- JPH02129133A JPH02129133A JP63281200A JP28120088A JPH02129133A JP H02129133 A JPH02129133 A JP H02129133A JP 63281200 A JP63281200 A JP 63281200A JP 28120088 A JP28120088 A JP 28120088A JP H02129133 A JPH02129133 A JP H02129133A
- Authority
- JP
- Japan
- Prior art keywords
- diphenylmethane
- alpha
- dichloro
- reaction
- general formula
- 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 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000460 chlorine Substances 0.000 claims abstract description 15
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 4
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 12
- 125000001424 substituent group Chemical group 0.000 claims description 11
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 claims 1
- OPTDDWCXQQYKGU-UHFFFAOYSA-N diphenyldichloromethane Chemical compound C=1C=CC=CC=1C(Cl)(Cl)C1=CC=CC=C1 OPTDDWCXQQYKGU-UHFFFAOYSA-N 0.000 abstract description 8
- 239000007810 chemical reaction solvent Substances 0.000 abstract description 6
- 239000006227 byproduct Substances 0.000 abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 4
- 125000000217 alkyl group Chemical group 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 125000006840 diphenylmethane group Chemical class 0.000 abstract description 4
- 125000003118 aryl group Chemical group 0.000 abstract description 3
- 239000000178 monomer Substances 0.000 abstract description 2
- 229920000515 polycarbonate Polymers 0.000 abstract description 2
- 239000004417 polycarbonate Substances 0.000 abstract description 2
- 239000011347 resin Substances 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 abstract description 2
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- 239000000047 product Substances 0.000 description 10
- 239000007795 chemical reaction product Substances 0.000 description 7
- 238000004817 gas chromatography Methods 0.000 description 6
- HZAWPPRBCALFRN-UHFFFAOYSA-N 1-methyl-4-[(4-methylphenyl)methyl]benzene Chemical compound C1=CC(C)=CC=C1CC1=CC=C(C)C=C1 HZAWPPRBCALFRN-UHFFFAOYSA-N 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2,2'-azo-bis-isobutyronitrile Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZDVDCDLBOLSVGM-UHFFFAOYSA-N [chloro(phenyl)methyl]benzene Chemical compound C=1C=CC=CC=1C(Cl)C1=CC=CC=C1 ZDVDCDLBOLSVGM-UHFFFAOYSA-N 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical group [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 1
- NPOGRKGIBGKRNI-UHFFFAOYSA-N 1-benzyl-4-chlorobenzene Chemical compound C1=CC(Cl)=CC=C1CC1=CC=CC=C1 NPOGRKGIBGKRNI-UHFFFAOYSA-N 0.000 description 1
- ADCBAIUWZPOIMC-UHFFFAOYSA-N 1-benzyl-4-fluorobenzene Chemical compound C1=CC(F)=CC=C1CC1=CC=CC=C1 ADCBAIUWZPOIMC-UHFFFAOYSA-N 0.000 description 1
- SIYISNUJKMAQBV-UHFFFAOYSA-N 1-benzyl-4-methylbenzene Chemical compound C1=CC(C)=CC=C1CC1=CC=CC=C1 SIYISNUJKMAQBV-UHFFFAOYSA-N 0.000 description 1
- AGPLQTQFIZBOLI-UHFFFAOYSA-N 1-benzyl-4-phenylbenzene Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1CC1=CC=CC=C1 AGPLQTQFIZBOLI-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229940054021 anxiolytics diphenylmethane derivative Drugs 0.000 description 1
- -1 carbon tetrachloride Chemical compound 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- AYOOGWWGECJQPI-NSHDSACASA-N n-[(1s)-1-(5-fluoropyrimidin-2-yl)ethyl]-3-(3-propan-2-yloxy-1h-pyrazol-5-yl)imidazo[4,5-b]pyridin-5-amine Chemical compound N1C(OC(C)C)=CC(N2C3=NC(N[C@@H](C)C=4N=CC(F)=CN=4)=CC=C3N=C2)=N1 AYOOGWWGECJQPI-NSHDSACASA-N 0.000 description 1
- XULSCZPZVQIMFM-IPZQJPLYSA-N odevixibat Chemical compound C12=CC(SC)=C(OCC(=O)N[C@@H](C(=O)N[C@@H](CC)C(O)=O)C=3C=CC(O)=CC=3)C=C2S(=O)(=O)NC(CCCC)(CCCC)CN1C1=CC=CC=C1 XULSCZPZVQIMFM-IPZQJPLYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 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
- Catalysts (AREA)
- 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」
本発明はポリカーボネート等の機能性樹脂等のモノマー
の中間体として有用なα、α−ジクロロ−ジフェニルメ
タン類を高収率で製造し得る製造法に間するものである
。Detailed Description of the Invention "Industrial Application Field" The present invention is a method for producing α,α-dichloro-diphenylmethane in high yield, which is useful as an intermediate for monomers such as functional resins such as polycarbonate. It is something that takes place in between.
「従来の技術」
従来、α、α−ジクロロージフェニルメタン類の製造方
法としては、ヘンシフエノン類と五塩化リンを反応させ
る方法が知られている。"Prior Art" Conventionally, as a method for producing α,α-dichlorodiphenylmethanes, a method of reacting hensifenones and phosphorus pentachloride is known.
：Ｂｅｒ、 ２９． ２９９４（１８９６））。:Ber, 29. 2994 (1896)).
又、ドイツ特許第２５３３９８８号（１９７７）には、
触媒に有機リン化合物を用いて、ヘンシフエノン類と塩
化チオニルを反応させる方法が記されている。Also, in German Patent No. 2533988 (1977),
A method is described in which hensiphenones and thionyl chloride are reacted using an organic phosphorus compound as a catalyst.
しかし乍ら、前者の場合、五塩化リンが容易に昇華し且
つ加水分解され易い為、取扱いが非常に困雅である。ざ
らには、オキシ塩化リンが多量に副生ずる為その処理に
多大な労力を要し・工業的方法としては問題がある。However, in the former case, handling is very difficult because phosphorus pentachloride easily sublimates and is easily hydrolyzed. Moreover, since a large amount of phosphorus oxychloride is produced as a by-product, it requires a great deal of effort to process and is problematic as an industrial method.
又、後者の場合には、塩化チオニルが加水分解し易く、
し・かも過剰に使用する為、回収して再使用する必要が
あり、工業的製法とは言い難い。In addition, in the latter case, thionyl chloride is easily hydrolyzed,
Moreover, since it is used in excess, it must be collected and reused, so it cannot be called an industrial manufacturing method.
一方、ジフェニルメタンと塩素を四塩化炭素等の塩素に
不活性な反応溶媒存在下、触媒にａ 、 α′−アゾ
ビスイソブチロニトリルを用いてα、α−ジクロロ−ジ
フェニルメタンを得ている方法がハンカリー特許第２９
９８９号（１９８４）に記されている。On the other hand, there is a method in which diphenylmethane and chlorine are reacted in the presence of a reaction solvent inert to chlorine such as carbon tetrachloride, and α,α-dichloro-diphenylmethane is obtained using a, α′-azobisisobutyronitrile as a catalyst. Hunkery Patent No. 29
No. 989 (1984).
しかしγら、本性によれば目的物の収＄は約３３％と極
めて低く、又反応溶媒を回収する必要がありこの方法も
工業的製法とし・では問題がある。However, according to the nature of γ et al., the yield of the target product is extremely low at about 33%, and it is necessary to recover the reaction solvent, so this method also has problems as an industrial production method.
「発明の解決しようとする問題点」
本発明の目的は、従来技術が有していた前述の問題点を
解決しようとするものである。"Problems to be Solved by the Invention" An object of the present invention is to solve the above-mentioned problems that the prior art had.
「問題点を解決するための手段」
本発明者等は、前述の問題点を解決すべく鋭意研究を重
ねた結果本発明を完成するに至ったものである。"Means for Solving the Problems" The present inventors have completed the present invention as a result of extensive research in order to solve the above-mentioned problems.
即ち、下記一般式一（１）で示されるジフェニルメタン
類を触媒の存在下に塩素と反応させて下記一般式−（２
）で示されるα、α−ジクロロ−ジフェニルメタン類を
製造する際、反応を無溶媒下で１テなうことを特徴とす
るα、α−ジクロロ−ジフェニルメタン類の製造法を提
供するものである。That is, diphenylmethane represented by the following general formula (1) is reacted with chlorine in the presence of a catalyst to form the following general formula - (2).
The present invention provides a method for producing α,α-dichloro-diphenylmethanes, which is characterized in that the reaction is carried out one time in the absence of a solvent.
一般式＝（１）
「但し、Ｒｌ、Ｒ２，Ｒ３，Ｒ４は各々水素原子、ハロ
ゲン原子、アルキル基、アルコキシ基、ンクロアルキル
基、アルケニル基、アリール基、アラルキル基を示し、
各々同一であっても異なっていてもよく、又水素原子、
ハロゲン原子以外のＲ１，Ｒ２，Ｒ３，Ｒ４て表わされ
る置換基もざらに置換基を有していてもよい。」一般式
−（２）
「但し、Ｒ１，Ｒ２，Ｒ３，Ｒ４は前記と同し會味を表
わす。」
即ち、本発明によれば、驚くべき事ここは、高反応率、
高転化率てα、α−ジクロロ−ジフェニルメタン類が得
られるという事である。General formula = (1) "However, Rl, R2, R3, R4 each represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkyl group, an alkenyl group, an aryl group, an aralkyl group,
Each may be the same or different, and hydrogen atoms,
The substituents represented by R1, R2, R3, and R4 other than the halogen atoms may also have other substituents. ”General formula-(2) “However, R1, R2, R3, and R4 represent the same relationships as above.” That is, according to the present invention, surprisingly, a high reaction rate,
This means that α,α-dichloro-diphenylmethanes can be obtained at a high conversion rate.
本発明に於いて採用される一般式−（１）て示されるジ
フェニルメタン類としては、ジフェニルメタン、ジフェ
ニルメタン誘導体が挙げられろ。The diphenylmethanes represented by the general formula (1) employed in the present invention include diphenylmethane and diphenylmethane derivatives.
ここにジフェニルメタン誘導体としては、母体となるジ
フェニルメタンの一方の又は両方のベンゼン環に少なく
とも一個以上の実質的に塩素に不活性な置換基を有する
核置換ジフェニルメタンを意味する。The diphenylmethane derivative herein means a nuclear-substituted diphenylmethane having at least one substituent substantially inert to chlorine on one or both benzene rings of the base diphenylmethane.
この置換基が複数個である場合、各々の置換基は同一で
あってもまたは異なるものてあっでもよい。When there is a plurality of substituents, each substituent may be the same or different.
ここで実質的に不活性な置換基とは、反応に実質的に支
Ｉ′ｔを生じることのない置換基を意味し、例えば、ア
ルキル基、アルコキシ基、シクロアルキル基、アルケニ
ル基、アリール基、アラルキル基等の炭化水素基、ハロ
ゲン置換アルキル基、ハロゲン置換アルコキシ基、ハロ
ゲン置換アリール基等のハロゲン置換炭（ヒ水素基等を
挙げろことが出来る。The term "substantially inert substituent" as used herein means a substituent that does not substantially produce a support I't in the reaction, such as an alkyl group, an alkoxy group, a cycloalkyl group, an alkenyl group, an aryl group. , hydrocarbon groups such as aralkyl groups, halogen-substituted carbon groups such as halogen-substituted alkyl groups, halogen-substituted alkoxy groups, and halogen-substituted aryl groups (arsenic groups, etc.).
又、置換基の位置としては特に制限はないが、反応性の
点より２−、Ｇ−，２′−及び６′位以外の位置に置換
されているものが好ましく、特に同一の置換基が４−．
４′−位に置換されているものが好適である。There is no particular restriction on the position of the substituent, but from the viewpoint of reactivity, it is preferable that it is substituted at a position other than the 2-, G-, 2'-, and 6'-positions, especially when the same substituents are 4-.
Those substituted at the 4'-position are preferred.
本発明において、前記のジフェニルメタン類の具体例と
しては下記化合物を例記する事が出来るがこれによって
同等限定されるものではない。In the present invention, the following compounds can be mentioned as specific examples of the above-mentioned diphenylmethanes, but the compounds are not equally limited by these.
ジフェニルメタン、４−メチル−ジフェニルメタン、４
，４′−ジメチル−ジフェニルメタン、３．４．４′−
１リメチルージフエニルメタン、３．４．３′、４’−
テトラメチル−ジフェニルメタン、４−フェニル−ジフ
ェニルメタン、４．４′ −ジフェニル−ジフェニルメ
タン、４−とニル−ジフェニルメタン、４．４′−ジビ
ニル−ジフェニルメタン、４−シクロヘキシル−ジフェ
ニルメタン、４゜４′−ジシクロヘキシル−ジフェニル
メタン、４−クロロ−ジフェニルメタン、４．４′ジク
ロロ−ジフェニルメタン、４−フルオロ−ジフェニルメ
タン、４．４′−ジフルオロ−ジフェニルメタン等が挙
げられる。diphenylmethane, 4-methyl-diphenylmethane, 4
, 4'-dimethyl-diphenylmethane, 3.4.4'-
1-limethyl-diphenylmethane, 3.4.3',4'-
Tetramethyl-diphenylmethane, 4-phenyl-diphenylmethane, 4.4'-diphenyl-diphenylmethane, 4-andyl-diphenylmethane, 4.4'-divinyl-diphenylmethane, 4-cyclohexyl-diphenylmethane, 4゜4'-dicyclohexyl-diphenylmethane , 4-chloro-diphenylmethane, 4.4'-dichloro-diphenylmethane, 4-fluoro-diphenylmethane, 4.4'-difluoro-diphenylmethane and the like.
これらの中でもジフェニルメタン、４．４′−ジメチル
−ジフェニルメタン、４，４′ジフェニル−ジフェニル
メタン、４．４′ジクロロ（またはジフルオロ）−ジフ
ェニルメタン等が好適である。Among these, diphenylmethane, 4,4'-dimethyl-diphenylmethane, 4,4'-diphenyl-diphenylmethane, 4,4'-dichloro (or difluoro)-diphenylmethane and the like are preferred.
本発明に於いては、ジフェニルメタン類に対する触媒の
α、α′−アゾビスイソブチロニトリルの使用モル比は
０．００１〜０．２好ましくは０．００２〜０． １特
に好ましくは０．００３〜０．０３である。In the present invention, the molar ratio of α, α'-azobisisobutyronitrile used as a catalyst to diphenylmethane is 0.001 to 0.2, preferably 0.002 to 0.0. 1, particularly preferably from 0.003 to 0.03.
使用モル比がこの量より少ないと反応率、選沢率が低下
し好ましくない。又この量より多くても同等利点はない
。If the molar ratio used is less than this amount, the reaction rate and selection rate will decrease, which is not preferable. Moreover, even if the amount is larger than this amount, there is no equivalent advantage.
本発明に於いては、ジフェニルメタン類に対する塩素の
モル比は２．０〜１Ｏ９０、好ましくは２．０〜５．０
、特に好ましくは２．１〜３．０である。二〇モル比よ
り少ないと反応率が低下し好ましくなく又このモル比よ
り多くても同等利点はない。In the present invention, the molar ratio of chlorine to diphenylmethane is 2.0 to 1O90, preferably 2.0 to 5.0.
, particularly preferably from 2.1 to 3.0. If the molar ratio is less than 20, the reaction rate decreases, which is undesirable, and if the molar ratio is greater than this, there is no equivalent advantage.
本発明に於ける反応温度は使用するジフェニルメタン類
の融点により左右される。The reaction temperature in the present invention depends on the melting point of the diphenylmethane used.
反応温度としては０〜３００℃の温度が採用されるが、
好ましくは２０〜２００℃である。As the reaction temperature, a temperature of 0 to 300°C is adopted,
Preferably it is 20-200°C.
この温度より低いと反応時間が延びるとともに転（ヒ率
も低下するため好ましくない。又この温度より高い温度
では副反応が起こり好ましくない。If the temperature is lower than this temperature, the reaction time will be prolonged and the conversion ratio will also be reduced, which is undesirable. If the temperature is higher than this temperature, side reactions will occur, which is undesirable.
本発明に於ける反応圧は通常々圧下に実施されるが必要
ならば加圧下に実施することもできる。The reaction pressure in the present invention is usually carried out under pressure, but it can also be carried out under increased pressure if necessary.
本発明に於ける反応溶媒として塩素に不活性な有機溶媒
を使用する事もてきるが同等利点はない。Although organic solvents inert to chlorine can be used as reaction solvents in the present invention, they do not have the same advantages.
本発明の方法の概略を示せば次のようになる。まず原料
のジフェニルメタン類をその融点以上に加熱して溶融後
触媒を添加し、充分々散させたのち所定の温度まで昇温
し、この温度を保ちながら所定量の塩素を導入する。The outline of the method of the present invention is as follows. First, the raw material diphenylmethane is heated above its melting point to melt it, then a catalyst is added, and after being sufficiently dispersed, the temperature is raised to a predetermined temperature, and while maintaining this temperature, a predetermined amount of chlorine is introduced.
反応完結後反応生成物から目的物を公知方法により分離
回収する。After the reaction is completed, the target product is separated and recovered from the reaction product by a known method.
「発明の効果」
本発明の方法：こよれば、反応溶媒を使用しないため生
産効率が高く、又副生物は塩酸であり簡単に処理が可能
である。更に従来になく高反応率、高ｉｆ！＋沢率て実
施し得ろことから生産性が極めて高く、且つ未精製品で
もその使用目的によっては充分純粋であり、従来法に比
し経済上著しく有利なα、α−ジクロロ−ジフェニルメ
タン類を製造し得るという優れた効果を有する。"Effects of the Invention" The method of the present invention: According to this method, production efficiency is high because no reaction solvent is used, and the by-product is hydrochloric acid, which can be easily treated. Furthermore, it has an unprecedented high reaction rate and high if! + Productivity is extremely high because it can be carried out at a high yield rate, and even unrefined products are sufficiently pure depending on the purpose of use, producing α,α-dichloro-diphenylmethane, which is economically advantageous compared to conventional methods. It has the excellent effect of being able to
「実方ｖｉす」
以下実施例を示し本発明の詳細な説明するが本発明の範
囲が実施例に記載の態様に限定されるものではない。EXAMPLES The present invention will be described in detail below with reference to Examples, but the scope of the present invention is not limited to the embodiments described in the Examples.
実施例−１
撹拌装置、温度計、塩素導入管、先端を水酸化ナトリウ
ム水溶液に導いである冷却コンデンサーを備えた５００
ｍ１容量の４０フラスコにジフェニルメタン１６８ｇｒ
（１，０モル）、α、α′−アゾビスイソブチロニト
リル１．０ ｇｒ （０，００６モル）を仕込、内温
を９０℃に昇温した後、内、星を９０〜９５℃に保ちな
がら、塩素１５６ｇｒ （２，２モル）を８時間を要し
て導入した。Example-1 500 equipped with a stirring device, a thermometer, a chlorine introduction tube, and a cooling condenser whose tip is led to an aqueous sodium hydroxide solution.
168 gr of diphenylmethane in a 40 flask with a volume of ml
(1.0 mol), α, α'-azobisisobutyronitrile 1.0 gr (0,006 mol), and after raising the internal temperature to 90°C, the inner temperature was heated to 90-95°C. 156 gr (2.2 mol) of chlorine were introduced over a period of 8 hours while maintaining the temperature.
その後同温度下に３０分後援拌を行ない反応を完結させ
た後、導入管より窒素ガスを通気して系内に残存する塩
素及び副生塩１ヒ水素を系外に除いた。Thereafter, the reaction was completed by stirring at the same temperature for 30 minutes, and then nitrogen gas was passed through the inlet tube to remove the chlorine and by-product salt monoarsenic remaining in the system.
得られた反応生成物は２３２ｇｒであった。The reaction product obtained was 232 gr.
これを更に減圧下に蒸留して精製し目的物のα、α−ジ
クロロ−ジフェニルメタンを２１３ｇｒ得た。これは使
用したジフェニルメタンに対して９０．０％の収率に相
当する。このもののガスクロマトグラフィーによる純度
は９７．０％であった。This was further purified by distillation under reduced pressure to obtain 213 gr of the target product, α,α-dichloro-diphenylmethane. This corresponds to a yield of 90.0% based on the diphenylmethane used. The purity of this product by gas chromatography was 97.0%.
実施例−２
反応温度を１５０’（？＋こした以外は実施作り−１と
同様に行い反応生成物２３５ｇｒを得た。Example 2 The same procedure as in Example 1 was carried out except that the reaction temperature was raised to 150' (?+) to obtain 235 gr of a reaction product.
更にこれを蒸留してα、ａ−ジクロロ−ジフェニルメタ
ン２１８ｇｒを得た。これは使用したジフェニルメタン
に対して９２％の収率に相当しこのもののガスクロマト
グラフィーによる純度は９６．３％であった。This was further distilled to obtain 218 gr of α,a-dichloro-diphenylmethane. This corresponds to a yield of 92% based on the diphenylmethane used, and the purity of this product as determined by gas chromatography was 96.3%.
実施例−３
塩素の導入量を２１３ｇｒ （３，０モル）ここかえた
以外は実施例−１と同様に１テない反応生成物を２３７
ｇｒ得た。更にこれを蒸留してα、α−ジクロロ−ジフ
ェニルメタン２０１ｇｒを得た。これは使用したジフェ
ニルメタンに対して８５％の収率に相当し、又このもの
のガスクロマトグラフィーによる純度は９５．７％であ
った。Example-3 The same reaction product as in Example-1 was used except that the amount of chlorine introduced was changed to 213 gr (3.0 mol).
I got gr. This was further distilled to obtain 201 gr of α,α-dichloro-diphenylmethane. This corresponds to a yield of 85% based on the diphenylmethane used, and the purity of this product as determined by gas chromatography was 95.7%.
実施例−４
α、α′−７ゾビスイソブチロニトリルを５．０ｇｒ
（０，０３モル）用いた以外は実施例−１と同様に行な
い反応生成物２３３ｇｒを得た。Example-4 5.0g of α,α′-7zobisisobutyronitrile
(0.03 mol) was used in the same manner as in Example 1 to obtain 233 gr of a reaction product.
これを蒸留しα、α−ジクロロ−ジフェニルメタン２１
３ｇｒをえた。これは使用したジフェニルメタンに対し
て９０゜０％の収率に相当しこのもののガスクロマトグ
ラフィー純度は９５．０％であった。This was distilled and α,α-dichloro-diphenylmethane 21
I got 3 gr. This corresponds to a yield of 90.0% based on the diphenylmethane used, and the gas chromatographic purity of this product was 95.0%.
実施例−５
実施ηリ−１のジフェニルメタンを４．４′−ジメチル
−ジフェニルメタン１９６ｇｒ （１，０モル）にかえ
た以外は実施例−１と同様：こ反応し反応生成物２４０
ｇｒを濤た。これを蒸留し４．４′−ジメチル−α α
−ジクロロ−ジフェニルメタン２２５ｇｒを得た。Example-5 Same as Example-1 except that the diphenylmethane in Example η-1 was changed to 196 gr (1.0 mol) of 4,4'-dimethyl-diphenylmethane: The reaction product 240
I got gr. This was distilled to give 4.4'-dimethyl-α α
225 gr of -dichloro-diphenylmethane were obtained.
これは使用した４、４′−ジメチル−ジフェニルメタン
に対して８５．０％の収率に相当する。又、このものの
ガスクロマトグラフィーによる純度は９６．５％であっ
た。This corresponds to a yield of 85.0% based on the 4,4'-dimethyl-diphenylmethane used. Further, the purity of this product as determined by gas chromatography was 96.5%.
実施例−６
実施η１１−１におけるジフェニルメタンに替えて４，
４′−ジクロロ−ジフェニルメタンを２３７ｇｒ （１
，０モル）用いた以外は実施例−１と同様に行ない反応
生成物２７０ｇｒを得た。更にこれを蒸留して４．４′
−ジクロロ−α、α−ジクロロジフェニルメタン！
２４５ｇｒを得た。これは使用した４、４−ジクロロ−
ジフェニルメタンに文Ｊして８０゜０％の収率に相当す
る。このもののガスクロマトグラフィーによる純度は９
７．４％てあった。Example-6 In place of diphenylmethane in Example η11-1, 4,
237 gr of 4'-dichloro-diphenylmethane (1
, 0 mol) was used in the same manner as in Example 1 to obtain 270 gr of a reaction product. Furthermore, this was distilled to 4.4'
-dichloro-α,α-dichlorodiphenylmethane! Obtained 245 gr. This is the 4,4-dichloro-
This corresponds to a yield of 80.0% based on diphenylmethane. The purity of this substance by gas chromatography is 9
It was 7.4%.
比較例
反応時に四塩化炭素３００ｍ１を併用し７更にこれを蒸
留してα−クロロ−ジフェニルメタンとα、α−ジクロ
ロ−ジフェニルメタンの混合物１９０ｇを得た。Comparative Example During the reaction, 300 ml of carbon tetrachloride was used in combination.7 This was further distilled to obtain 190 g of a mixture of α-chloro-diphenylmethane and α,α-dichloro-diphenylmethane.
これは使用したジフェニルメタンに対して８０％の収率
に相当するがこの物のガスクロマトグラフィーによる純
度は３０％であり７０％はα−クロロ−ジフェニルメタ
ンであった。This corresponds to a yield of 80% based on the diphenylmethane used, but the purity of this product by gas chromatography was 30%, and 70% was α-chloro-diphenylmethane.
Claims (1)
類を触媒の存在下、塩素と反応させて下記一般式−（２
）で示されるα，α−ジクロロ−ジフェニルメタン類を
製造する際、反応を無溶媒条件下で行なうことを特徴と
するα，α−ジクロロ−ジフェニルメタン類の製造法。 一般式−（１） ▲数式、化学式、表等があります▼ 「但し、Ｒ１、Ｒ２、Ｒ３、Ｒ４は各々水素原子、ハロ
ゲン原子、アルキル基、アルコキシ基、シクロアルキル
基、アルケニル基、アリール基、アラルキル基を示し、
各々同一であっても異なっていてもよく、又水素原子、
ハロゲン原子以外のＲ１、Ｒ２、Ｒ３、Ｒ４で表わされ
る置換基もさらに置換基を有していてもよい。 」 一般式−（２） ▲数式、化学式、表等があります▼ 「但し、Ｒ１、Ｒ２、Ｒ３、Ｒ４は前記と同し意味を表
わす。」 （２）触媒がα，α′−アゾビスイソブチロニトリルで
ある請求項（１）記載の製造法。 （３）触媒の使用モル比が一般式−（１）で示されるジ
フェニルメタン類に対して０．００１〜０．２の範囲で
ある請求項（１）及び（２）のいずれかに記載の製造法
。 （４）塩素の使用モル比が一般式−（１）で示されるジ
フェニルメタン類に対して２．０〜 １０．０の範囲である請求項（１）記載の製造法。 （５）反応温度が０〜３００℃の範囲である請求項（１
）記載の製造法。[Scope of Claims] (1) Diphenylmethane represented by the following general formula -(1) is reacted with chlorine in the presence of a catalyst to produce a diphenylmethane represented by the following general formula -(2).
) A method for producing α,α-dichloro-diphenylmethanes, characterized in that the reaction is carried out under solvent-free conditions. General Formula - (1) ▲ Numerical formulas, chemical formulas, tables, etc. Indicates an aralkyl group,
Each may be the same or different, and hydrogen atoms,
The substituents represented by R1, R2, R3, and R4 other than the halogen atom may also have a further substituent. ” General formula - (2) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ ``However, R1, R2, R3, and R4 have the same meanings as above.'' (2) The catalyst is The manufacturing method according to claim (1), which is butyronitrile. (3) The production according to any one of claims (1) and (2), wherein the molar ratio of the catalyst used to the diphenylmethane represented by general formula -(1) is in the range of 0.001 to 0.2. Law. (4) The method according to claim (1), wherein the molar ratio of chlorine to the diphenylmethane represented by general formula -(1) is in the range of 2.0 to 10.0. (5) Claim (1) wherein the reaction temperature is in the range of 0 to 300°C.
) Manufacturing method described.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63281200A JPH02129133A (en) | 1988-11-09 | 1988-11-09 | Production of alpha,alpha-dichloro-diphenylmethanes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63281200A JPH02129133A (en) | 1988-11-09 | 1988-11-09 | Production of alpha,alpha-dichloro-diphenylmethanes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02129133A true JPH02129133A (en) | 1990-05-17 |
Family
ID=17635742
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63281200A Pending JPH02129133A (en) | 1988-11-09 | 1988-11-09 | Production of alpha,alpha-dichloro-diphenylmethanes |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02129133A (en) |
-
1988
- 1988-11-09 JP JP63281200A patent/JPH02129133A/en active Pending
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