JPH0136467B2 - - Google Patents
Info
- Publication number
- JPH0136467B2 JPH0136467B2 JP56107712A JP10771281A JPH0136467B2 JP H0136467 B2 JPH0136467 B2 JP H0136467B2 JP 56107712 A JP56107712 A JP 56107712A JP 10771281 A JP10771281 A JP 10771281A JP H0136467 B2 JPH0136467 B2 JP H0136467B2
- Authority
- JP
- Japan
- Prior art keywords
- trifluoromethylpyridine
- reaction
- lutidine
- picoline
- reactor
- 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.)
- Expired
Links
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 claims description 20
- ATRQECRSCHYSNP-UHFFFAOYSA-N 2-(trifluoromethyl)pyridine Chemical class FC(F)(F)C1=CC=CC=N1 ATRQECRSCHYSNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 15
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 claims description 14
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 14
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 14
- 239000003085 diluting agent Substances 0.000 claims description 12
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 claims description 11
- 239000000460 chlorine Substances 0.000 claims description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- HPYNZHMRTTWQTB-UHFFFAOYSA-N dimethylpyridine Natural products CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 229910021594 Copper(II) fluoride Inorganic materials 0.000 claims description 5
- GWFAVIIMQDUCRA-UHFFFAOYSA-L copper(ii) fluoride Chemical compound [F-].[F-].[Cu+2] GWFAVIIMQDUCRA-UHFFFAOYSA-L 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 150000003222 pyridines Chemical class 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 16
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 14
- 239000002994 raw material Substances 0.000 description 14
- -1 pyridine compound Chemical class 0.000 description 12
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 11
- 239000000203 mixture Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- HWWYDZCSSYKIAD-UHFFFAOYSA-N 3,5-dimethylpyridine Chemical compound CC1=CN=CC(C)=C1 HWWYDZCSSYKIAD-UHFFFAOYSA-N 0.000 description 6
- JYYNAJVZFGKDEQ-UHFFFAOYSA-N 2,4-Dimethylpyridine Chemical compound CC1=CC=NC(C)=C1 JYYNAJVZFGKDEQ-UHFFFAOYSA-N 0.000 description 4
- XWKFPIODWVPXLX-UHFFFAOYSA-N 2,5-dimethylpyridine Chemical compound CC1=CC=C(C)N=C1 XWKFPIODWVPXLX-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 4
- 229960003280 cupric chloride Drugs 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 229910001026 inconel Inorganic materials 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 239000013067 intermediate product Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- KAQJMEHRXVENSF-UHFFFAOYSA-N 2-(trichloromethyl)pyridine Chemical class ClC(Cl)(Cl)C1=CC=CC=N1 KAQJMEHRXVENSF-UHFFFAOYSA-N 0.000 description 2
- GBNPVXZNWBWNEN-UHFFFAOYSA-N 2-chloro-4-(trifluoromethyl)pyridine Chemical compound FC(F)(F)C1=CC=NC(Cl)=C1 GBNPVXZNWBWNEN-UHFFFAOYSA-N 0.000 description 2
- ADVQMCQMDHBTHJ-UHFFFAOYSA-N 2-chloro-6-(trifluoromethyl)pyridine Chemical compound FC(F)(F)C1=CC=CC(Cl)=N1 ADVQMCQMDHBTHJ-UHFFFAOYSA-N 0.000 description 2
- RQEOYYWUVYZZLL-UHFFFAOYSA-N 3,5-bis(trifluoromethyl)pyridine Chemical compound FC(F)(F)C1=CN=CC(C(F)(F)F)=C1 RQEOYYWUVYZZLL-UHFFFAOYSA-N 0.000 description 2
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 229910021593 Copper(I) fluoride Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000003682 fluorination reaction Methods 0.000 description 2
- 150000002222 fluorine compounds Chemical class 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- UGCSPKPEHQEOSR-UHFFFAOYSA-N 1,1,2,2-tetrachloro-1,2-difluoroethane Chemical compound FC(Cl)(Cl)C(F)(Cl)Cl UGCSPKPEHQEOSR-UHFFFAOYSA-N 0.000 description 1
- ODNBVEIAQAZNNM-UHFFFAOYSA-N 1-(6-chloroimidazo[1,2-b]pyridazin-3-yl)ethanone Chemical compound C1=CC(Cl)=NN2C(C(=O)C)=CN=C21 ODNBVEIAQAZNNM-UHFFFAOYSA-N 0.000 description 1
- OIWWGZUWYQHWIU-UHFFFAOYSA-N 2,3,5-trichloro-4,6-bis(trifluoromethyl)pyridine Chemical compound FC(F)(F)C1=NC(Cl)=C(Cl)C(C(F)(F)F)=C1Cl OIWWGZUWYQHWIU-UHFFFAOYSA-N 0.000 description 1
- NZFDZFJVWFDFQV-UHFFFAOYSA-N 2,4-bis(trifluoromethyl)pyridine Chemical compound FC(F)(F)C1=CC=NC(C(F)(F)F)=C1 NZFDZFJVWFDFQV-UHFFFAOYSA-N 0.000 description 1
- YPDVFTXBESQIPJ-UHFFFAOYSA-N 2,6-bis(trifluoromethyl)pyridine Chemical compound FC(F)(F)C1=CC=CC(C(F)(F)F)=N1 YPDVFTXBESQIPJ-UHFFFAOYSA-N 0.000 description 1
- KVNQWVYYVLCZKK-UHFFFAOYSA-N 2,6-dichloro-4-(trifluoromethyl)pyridine Chemical compound FC(F)(F)C1=CC(Cl)=NC(Cl)=C1 KVNQWVYYVLCZKK-UHFFFAOYSA-N 0.000 description 1
- UJJMLGJZQGGQAZ-UHFFFAOYSA-N 2-(fluoromethyl)pyridine Chemical class FCC1=CC=CC=N1 UJJMLGJZQGGQAZ-UHFFFAOYSA-N 0.000 description 1
- PZJLRLKOOIIRNI-UHFFFAOYSA-N 2-chloro-4,6-bis(trifluoromethyl)pyridine Chemical compound FC(F)(F)C1=CC(Cl)=NC(C(F)(F)F)=C1 PZJLRLKOOIIRNI-UHFFFAOYSA-N 0.000 description 1
- YNYROPYZSZBORI-UHFFFAOYSA-N 3-chloro-4-(trifluoromethyl)pyridine Chemical compound FC(F)(F)C1=CC=NC=C1Cl YNYROPYZSZBORI-UHFFFAOYSA-N 0.000 description 1
- IIYVNMXPYWIJBL-UHFFFAOYSA-N 4-(trifluoromethyl)pyridine Chemical compound FC(F)(F)C1=CC=NC=C1 IIYVNMXPYWIJBL-UHFFFAOYSA-N 0.000 description 1
- GUNJVIDCYZYFGV-UHFFFAOYSA-K Antimony trifluoride Inorganic materials F[Sb](F)F GUNJVIDCYZYFGV-UHFFFAOYSA-K 0.000 description 1
- 229910016509 CuF 2 Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- JZZBOEVFOPPWSG-UHFFFAOYSA-N [N].CC1=CC=CC=N1 Chemical compound [N].CC1=CC=CC=N1 JZZBOEVFOPPWSG-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012025 fluorinating agent Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011282 treatment Methods 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
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Pyridine Compounds (AREA)
Description
【発明の詳細な説明】
本発明はα−ピコリン、γ−ピコリン又はルチ
ジンから直接トリフルオロメチルピリジン類を製
造する方法に関し、詳しくは触媒及び希釈剤の存
在下にα−ピコリン、γ−ピコリン又はルチジン
（以下ピリジン化合物と略称する）と塩素及び無
水弗化水素とを気相で反応させて、α或はγ−ト
リフルオロメチルピリジン、ビストリフルオロメ
チルピリジン又はそれらのピリジン核の塩素化物
（以下トリフルオロメチルピリジン類と略称する）
を製造する方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing trifluoromethylpyridines directly from α-picoline, γ-picoline or lutidine. Lutidine (hereinafter abbreviated as pyridine compound) is reacted with chlorine and anhydrous hydrogen fluoride to form α- or γ-trifluoromethylpyridine, bistrifluoromethylpyridine, or chlorinated products of their pyridine nuclei (hereinafter trifluoromethylpyridine). (abbreviated as fluoromethylpyridines)
Relating to a method of manufacturing.
前記トリフルオロメチルピリジン類は除草剤、
殺虫剤などの原料として有用な化合物である。 The trifluoromethylpyridines are herbicides,
It is a compound useful as a raw material for insecticides, etc.
トリフルオロメチルピリジン類の製造法として
は、(1)ピリジン化合物を液相で紫外線の照射下に
塩素ガスと反応させたり、或は希釈剤の存在下に
高温で気相にて塩素ガスと反応させたりして、対
応するトリクロロメチルピリジン類を生成させ、
次いで、(2)これらトリクロロメチルピリジン類を
液相で無水弗化水素又は三弗化アンチモンと反応
させて製造する方法が知られている。しかしなが
ら、この方法の塩素化反応では多くの種類の副生
物が発生して目的化合物の分離が困難であり、ま
た弗素化反応では反応に長時間を要する他、高価
な弗素化剤の使用或は加圧下での反応が必要にな
り、工業的には望ましくない。 The methods for producing trifluoromethylpyridines include (1) reacting a pyridine compound with chlorine gas in the liquid phase under ultraviolet irradiation, or reacting with chlorine gas in the gas phase at high temperature in the presence of a diluent; to generate the corresponding trichloromethylpyridines,
Next, (2) a method of producing trichloromethylpyridines by reacting them with anhydrous hydrogen fluoride or antimony trifluoride in a liquid phase is known. However, the chlorination reaction of this method generates many types of by-products, making it difficult to separate the target compound.Furthermore, the fluorination reaction requires a long time, and requires the use of expensive fluorinating agents. This requires reaction under pressure, which is industrially undesirable.
本発明は、触媒及び希釈剤の存在下にピリジン
化合物と塩素及び無水弗化水素とを気相で接触反
応させると、単独工程でかつ短時間に、トリフル
オロメチルピリジン類が生成することの知見にも
とずいている。 The present invention is based on the knowledge that trifluoromethylpyridines are produced in a single step and in a short time when a pyridine compound is catalytically reacted with chlorine and anhydrous hydrogen fluoride in the gas phase in the presence of a catalyst and a diluent. It is based on
即ち、本発明は、弗化銅を含む触媒及び希釈剤
の存在下に、α−ピコリン、γ−ピコリン又はル
チジンと塩素及び無水弗化水素とを気相で反応さ
せてα−トリフルオロメチルピリジン、γ−トリ
フルオロメチルピリジン、ビストリフルオロメチ
ルピリジン又はそれらのピリジン核の塩素化物の
トリフルオロメチルピリジン類を製造することを
特徴とする、トリフルオロメチルピリジン類の製
造方法である。 That is, the present invention produces α-trifluoromethylpyridine by reacting α-picoline, γ-picoline, or lutidine with chlorine and anhydrous hydrogen fluoride in the gas phase in the presence of a catalyst and diluent containing copper fluoride. , γ-trifluoromethylpyridine, bistrifluoromethylpyridine, or trifluoromethylpyridines of chlorinated products of their pyridine nuclei.
本発明で触媒として使用される弗化銅として
は、弗化第一銅（CuF）、弗化第二銅（CuF2）又
はそれらの混合物が挙げられ、その使用量は、反
応条件により一概に規定できないが、普通、原料
のピリジン化合物１モルに対して0.001〜３モル
である。通常、この触媒は活性炭、活性アルミナ
などの担体と混合し、適当な大きさの粒状、ペレ
ツト状に成型してから、原料物質、希釈剤、反応
生成物を含むガス流中に固定床又は流動床として
存在させる。また触媒は弗化銅の型態で直接、反
応管に入れて存在させる方法もあるが、工業的に
は、前記金属元素の酸化物、塩化物、水酸化物、
炭酸塩などの型態で、或はそれらの水和物の型態
で反応管に入れ、無水弗化水素と反応させて弗化
物に変換させることによつて存在させる方法が有
利である。例えばアルミナの担体に塩化第二銅を
担持させた成型物を反応管に入れ、予め無水弗化
水素を導入して200〜600℃で反応させ、前記金属
元素の弗化物に変換させてから本発明に係る反応
を行なう。 Copper fluoride used as a catalyst in the present invention includes cuprous fluoride (CuF), cupric fluoride (CuF 2 ), or a mixture thereof, and the amount used generally depends on the reaction conditions. Although it cannot be specified, it is usually 0.001 to 3 moles per mole of the raw material pyridine compound. Usually, this catalyst is mixed with a carrier such as activated carbon or activated alumina, formed into granules or pellets of appropriate size, and then placed in a fixed bed or fluidized bed in a gas stream containing raw materials, diluent, and reaction products. Let it exist as a floor. There is also a method in which the catalyst is placed directly in the reaction tube in the form of copper fluoride, but industrially, oxides, chlorides, hydroxides,
Advantageously, they are present in the form of carbonates or their hydrates by introducing them into a reaction tube and converting them into fluorides by reaction with anhydrous hydrogen fluoride. For example, a molded product in which cupric chloride is supported on an alumina carrier is placed in a reaction tube, and anhydrous hydrogen fluoride is introduced in advance and reacted at 200 to 600°C to convert it into a fluoride of the metal element. carrying out the reaction according to the invention;
希釈剤としては四塩化炭素、クロロホルム、塩
化メチレン、Ｆ−112（CFCl2・CFCl2）、Ｆ−113
（CF2Cl・CFCl2）などのハロゲン化炭化水素の有
機溶媒、窒素、ヘリウム、アルゴンなどの不活性
気体が使用でき、これら希釈剤は燃焼、炭化、タ
ール状副生物の生成などを抑制する機能を有する
ものである。 Diluents include carbon tetrachloride, chloroform, methylene chloride, F-112 (CFCl 2 / CFCl 2 ), F-113
Organic solvents for halogenated hydrocarbons such as (CF 2 Cl/CFCl 2 ) and inert gases such as nitrogen, helium, and argon can be used, and these diluents suppress combustion, carbonization, and the formation of tar-like byproducts. It has a function.
本発明の実施に当つては、原料物質及び希釈剤
を別々に反応器へ供給できる他、これらの混合状
態でも供給でき、また、これらを同時に又は順次
に、或は一括又は分割して供給できる。例えばピ
リジン化合物と希釈剤との混合物、或は塩素と無
水弗化水素との混合物を別々に供給する。 In carrying out the present invention, the raw materials and diluent can be supplied to the reactor separately, or they can be supplied in a mixed state, and they can be supplied simultaneously or sequentially, all at once or in parts. . For example, a mixture of a pyridine compound and a diluent or a mixture of chlorine and anhydrous hydrogen fluoride are fed separately.
塩素及び無水弗化水素の使用量は原料のピリジ
ン化合物の種類、目的物の種類、反応装置などの
違いによつて一概に規定できないが、一般に原料
のピリジン化合物１モル当りそれぞれ3.5〜15モ
ル及び３〜20モルである。希釈剤の使用量は普
通、原料のピリジン化合物１モル当り３〜70モル
である。反応温度は一般に350〜600℃であり、反
応混合物の反応帯域における滞留時間は普通１〜
60秒である。 The amount of chlorine and anhydrous hydrogen fluoride to be used cannot be absolutely specified depending on the type of pyridine compound used as a raw material, the type of target product, the reaction equipment, etc., but generally it is 3.5 to 15 mol and 15 mol, respectively, per 1 mol of pyridine compound used as a raw material. It is 3 to 20 moles. The amount of diluent used is usually 3 to 70 moles per mole of starting pyridine compound. The reaction temperature is generally 350-600°C, and the residence time of the reaction mixture in the reaction zone is usually 1-600°C.
It is 60 seconds.
通常、反応器からはトリフルオロメチルピリジ
ン類を主成分とする生成弗素化物、未反応の弗化
水素及び塩素、中間生成物、副生塩化水素、更に
は希釈剤を含有するガス状物質が排出されるが、
適当な冷却、凝縮装置を経てトリフルオロメチル
ピリジン類は液体混合物として採取される。液体
混合物には一般に、α−ピコリンを原料とする場
合にはα−トリフルオロメチルピリジンの他に、
２−クロロ、２，４−ジクロロ、２，５−ジクロ
ロ、２，３，５−トリクロロ−６−トリフルオロ
メチルピリジンなどのα−トリフルオロメチルピ
リジンの核塩素化物が含まれる。γ−ピコリンを
原料とする場合にはγ−トリフルオロメチルピリ
ジンの他に、２−クロロ、２，６−ジクロロ−４
−トリフルオロメチルピリジンなどのその核塩素
化物が含まれる。ルチジンを原料とする場合に
は、このルチジン自体が異性体、たとえば２，４
−ルチジン、２，５−ルチジン、２，６−ルチジ
ン、３，５−ルチジンなどを有しているので、ど
れを原料とするかによつて生成物も異なつてく
る。例えば２，４−ルチジンを原料とする場合に
は２，４−ビストリフルオロメチルピリジンの他
に、６−クロロ、５，６−ジクロロ、３，５，６
−トリクロロ−２，４−ビストリフルオロメチル
ピリジンなどのその核塩素化物が含まれ、３，５
−ルチジンを原料とする場合には３，５−ビスト
リフルオロメチルピリジンの他に、２−クロロ、
２，６−ジクロロ、２，４，６−トリクロロ−
３，５−ビストリフルオロメチルピリジンなどの
その核塩素化物が含まれ、２，６−ルチジンを原
料とする場合には、２，６−ビストリフルオロメ
チルピリジンの他に、４−クロロ、３，４−ジク
ロロ、３，４，５−トリクロロ−２，６−ビスト
リフルオロメチルピリジンなどのその核塩素化物
が含まれる。 Normally, gaseous substances containing produced fluorides mainly composed of trifluoromethylpyridines, unreacted hydrogen fluoride and chlorine, intermediate products, by-product hydrogen chloride, and diluents are discharged from the reactor. However,
Trifluoromethylpyridines are collected as a liquid mixture through appropriate cooling and condensation equipment. In addition to α-trifluoromethylpyridine, the liquid mixture generally contains, when α-picoline is the raw material,
Nuclear chlorides of α-trifluoromethylpyridine such as 2-chloro, 2,4-dichloro, 2,5-dichloro, 2,3,5-trichloro-6-trifluoromethylpyridine are included. When using γ-picoline as a raw material, in addition to γ-trifluoromethylpyridine, 2-chloro, 2,6-dichloro-4
-Includes its nuclear chlorinated products such as trifluoromethylpyridine. When lutidine is used as a raw material, this lutidine itself is an isomer, for example, 2,4
-lutidine, 2,5-lutidine, 2,6-lutidine, 3,5-lutidine, etc., so the products will differ depending on which one is used as the raw material. For example, when 2,4-lutidine is used as a raw material, in addition to 2,4-bistrifluoromethylpyridine, 6-chloro, 5,6-dichloro, 3,5,6
- including its nuclear chlorinated products such as trichloro-2,4-bistrifluoromethylpyridine, 3,5
- When using lutidine as a raw material, in addition to 3,5-bistrifluoromethylpyridine, 2-chloro,
2,6-dichloro, 2,4,6-trichloro-
It includes its nuclear chlorinated products such as 3,5-bistrifluoromethylpyridine, and when 2,6-lutidine is used as a raw material, in addition to 2,6-bistrifluoromethylpyridine, 4-chloro, 3,4 - dichloro, 3,4,5-trichloro-2,6-bistrifluoromethylpyridine, and its nuclear chlorinated products.
本発明方法によれば、トリフルオロメチルピリ
ジン類は例えば75％以上の生成率で得られる。採
取した液体混合物中に、目的のトリフルオロメチ
ルピリジン類の生成迄達していない中間生成物が
含まれているときには、これら中間生成物は未反
応原料、又は希釈剤と共に分離、回収し、反応帯
域へ循環使用することができる。更に上記のトリ
フルオロメチルピリジン類には抽出、蒸留、晶析
などの通常の精製処理が加えられることによつ
て、例えば２−クロロ−６−トリフルオロメチル
ピリジン、２−クロロ−４−トリフルオロメチル
ピリジン、６−クロロ−２，４−ビストリフルオ
ロメチルピリジン、２，６−ジクロロ−３，５−
ビストリフルオロメチルピリジンなどの単一化合
物を高純度で得ることができる。 According to the method of the present invention, trifluoromethylpyridines can be obtained at a production rate of, for example, 75% or more. If the collected liquid mixture contains intermediate products that have not reached the level of production of the target trifluoromethylpyridines, these intermediate products are separated and collected together with unreacted raw materials or diluent, and then transferred to the reaction zone. Can be used for circulation. Furthermore, the above trifluoromethylpyridines are subjected to ordinary purification treatments such as extraction, distillation, and crystallization to produce, for example, 2-chloro-6-trifluoromethylpyridine, 2-chloro-4-trifluoromethylpyridine, etc. Methylpyridine, 6-chloro-2,4-bistrifluoromethylpyridine, 2,6-dichloro-3,5-
Single compounds such as bistrifluoromethylpyridine can be obtained in high purity.
次に本発明方法の実施例を記載するが、本発明
方法の範囲はこれらの記載によつて何ら限定され
るものでない。 Next, examples of the method of the present invention will be described, but the scope of the method of the present invention is not limited by these descriptions.
実施例 １
反応器として、反応部が内径80mm、高さ1000mm
であり、かつ触媒充填部が底部から高さ500mmで
ある触媒流動床を有するインコネル製堅型反応器
を設置し、反応器底部に内径20mm、長さ1500mmの
インコネル製予熱管を２本接続し、反応管及び予
熱管を温度制御できるように、その外部を電熱器
及び断熱材で覆つた。Example 1 As a reactor, the reaction part has an inner diameter of 80 mm and a height of 1000 mm.
An Inconel rigid reactor with a catalyst fluidized bed was installed, and the catalyst filling part was 500 mm in height from the bottom, and two Inconel preheating tubes with an inner diameter of 20 mm and a length of 1500 mm were connected to the bottom of the reactor. In order to control the temperature of the reaction tube and preheating tube, the outside of the tube was covered with an electric heater and a heat insulating material.
塩化第二銅を粒径105〜210メツシユの活性炭に
担持（重量比67：1000）したもの（1870ｇ）を予
め弗素化触媒充填部に充填し、200℃で無水弗化
水素を10N／分の割合にて導入して触媒を活性
化した。 Cupric chloride supported on activated carbon with a particle size of 105 to 210 mesh (weight ratio 67:1000) (1870 g) was packed in advance into the fluorination catalyst packing section, and anhydrous hydrogen fluoride was added at 10 N/min at 200°C. The catalyst was activated.
反応器を420℃に加熱し、200ｇ／時間のα−ピ
コリンとα−ピコリンの５倍モルの窒素ガスとを
一方の予熱管を通じ、またα−ピコリンの７倍モ
ルの無水弗化水素とα−ピコリンの５倍モルの塩
素ガスとを他方の予熱管を通じ、それぞれ反応器
に導入して５時間にわたつて反応させた。反応混
合物の器内滞留時間は約8.2秒であつた。 The reactor was heated to 420°C, and 200 g/hour of α-picoline and 5 times the mole of α-picoline nitrogen gas were passed through one preheating tube, and anhydrous hydrogen fluoride and α - Chlorine gas in an amount 5 times the mole of picoline was introduced into the reactor through the other preheating tube and reacted for 5 hours. The residence time of the reaction mixture in the vessel was approximately 8.2 seconds.
反応器より排出するガスは、冷縮塔、水洗塔を
通じて捕集し、捕集された反応物をアンモニア水
で中和後、水蒸気蒸留を行なつて、油状物2250ｇ
を得た。 The gas discharged from the reactor is collected through a cooling tower and a water washing tower, and the collected reactants are neutralized with aqueous ammonia and steam distilled to produce 2250 g of oily material.
I got it.
この油状物を昇温ガスクロマトグラフイーによ
り分析したところ、その組成は２−トリフルオロ
メチルピリジン10.6％、６−クロロ−２−トリフ
ルオロメチルピリジン41.2％、４，６−ジクロロ
−２−トリフルオロメチルピリジン4.6％及びク
ロロ−２−パークロロフルオロメチルピリジン類
など43.6％であつた。 Analysis of this oil by heating gas chromatography revealed that its composition was 10.6% 2-trifluoromethylpyridine, 41.2% 6-chloro-2-trifluoromethylpyridine, 4,6-dichloro-2-trifluoromethyl The content was 4.6% pyridine and 43.6% chloro-2-perchlorofluoromethylpyridines.
実施例 ２
反応器として、反応部が内径100mm、高さ2300
mmであり、かつ触媒充填部が底部から高さ800mm
である触媒流動床を有するインコネル製堅型反応
器を設置し、反応器底部に内径20mm、長さ1500mm
のインコネル製予熱管を２本接続し、反応管及び
予熱管を温度制御できるように、その外部を電熱
器及び断熱材で覆つた。Example 2 As a reactor, the reaction part has an inner diameter of 100 mm and a height of 2300 mm.
mm, and the height of the catalyst filling part is 800 mm from the bottom.
An Inconel rigid reactor with a catalyst fluidized bed was installed at the bottom of the reactor with an inner diameter of 20 mm and a length of 1500 mm.
Two Inconel preheating tubes were connected, and the outside of the reaction tube and preheating tube was covered with an electric heater and a heat insulating material so that the temperature of the reaction tube and the preheating tube could be controlled.
塩化第二銅を粒径105〜255μの三弗化アルミニ
ウムに担持（重量44：1000）したもの（3800ｇ）
を予め弗素化処理されたものを触媒充填部に充填
し、反応器を340〜400℃に加熱した。250ｇ／時
間のγ−ピコリンとγ−ピコリンの５倍モルの窒
素ガスとを一方の予熱管を通じ、またγ−ピコリ
ンの５倍モルの無水弗化水素及び塩素ガスを他方
の予熱管を通じ、それぞれ反応器に導入して６時
間にわたつて反応させた。反応混合物の器内滞留
時間は約27〜30であつた。 Cupric chloride supported on aluminum trifluoride (weight 44:1000) with particle size 105-255μ (3800g)
was previously fluorinated and filled into the catalyst filling section, and the reactor was heated to 340 to 400°C. 250 g/hour of γ-picoline and 5 times the mole of nitrogen gas of γ-picoline were passed through one preheating tube, and anhydrous hydrogen fluoride and chlorine gas of 5 times the mole of γ-picoline were passed through the other preheating tube. The mixture was introduced into a reactor and reacted for 6 hours. The residence time of the reaction mixture in the vessel was approximately 27-30 minutes.
反応器より排出するガスは、冷縮塔、水洗塔を
通じて捕集し、捕集された反応物をアンモニア水
で中和後、水蒸気蒸留を行なつて、油状物2350ｇ
を得た。 The gas discharged from the reactor is collected through a cooling tower and a water washing tower, and the collected reactants are neutralized with aqueous ammonia and steam distilled to produce 2350 g of oily material.
I got it.
この油状物を昇温ガスクロマトグラフイーによ
り分析したところ、その組成は４−トリフルオロ
メチルピリジン19.2％、２−クロロ−４−トリフ
ルオロメチルピリジン47.6％、３−クロロ−４−
トリフルオロメチルピリジン2.8％、２，６−ジ
クロロ−４−トリフルオロメチルピリジン16.2％
及びクロロ−４−パークロロフルオロメチルピリ
ジン類など14.2％であつた。 Analysis of this oil by temperature-rising gas chromatography revealed that its composition was 19.2% 4-trifluoromethylpyridine, 47.6% 2-chloro-4-trifluoromethylpyridine, and 3-chloro-4-trifluoromethylpyridine.
Trifluoromethylpyridine 2.8%, 2,6-dichloro-4-trifluoromethylpyridine 16.2%
and 14.2% of chloro-4-perchlorofluoromethylpyridines.
実施例 ３
反応器として実施例１で用いたものと同様のも
のを使用した。触媒として塩化第二銅を粒径105
〜255μの三弗化アルミニウムに担持（重量比
67：1000）したもの（1500ｇ）を予め弗素化処理
されたものを触媒充填部に充填した。反応器を
420℃に加熱し、３，５−ルチジンを140ｇ／時間
及び３，５−ルチジンの６倍モルの窒素ガスを一
方の予熱管を通じ、また、３，５−ルチジンの10
倍モルの無水弗化水素及び同８倍モルの塩素ガス
を他方の予熱管を通じて２時間反応させた。反応
混合物の器内滞留時間は約10秒であつた。前記実
施例１の場合と同様にして油状物を得、通常の精
留、晶析手段によつて処理して２−クロロ−３，
５−ビス（トリフルオロメチル）ピリジン390ｇ
を得た。Example 3 A reactor similar to that used in Example 1 was used. Particle size 105 with cupric chloride as a catalyst
Supported on ~255μ aluminum trifluoride (weight ratio
67:1000) (1500 g) which had been previously fluorinated was charged into the catalyst filling section. reactor
Heating to 420°C, 140 g/hour of 3,5-lutidine and 6 times the mole of 3,5-lutidine nitrogen gas was passed through one preheating tube, and 10 g/hour of 3,5-lutidine
Two times the mole of anhydrous hydrogen fluoride and eight times the same mole of chlorine gas were reacted for 2 hours through the other preheating tube. The residence time of the reaction mixture in the vessel was about 10 seconds. An oily substance was obtained in the same manner as in Example 1, and treated by conventional rectification and crystallization means to obtain 2-chloro-3,
390g of 5-bis(trifluoromethyl)pyridine
I got it.
Claims (1)
−ピコリン、γ−ピコリン又はルチジンと塩素及
び無水弗化水素とを気相で反応させて、α−トリ
フルオロメチルピリジン、γ−トリフルオロメチ
ルピリジン、ビストリフルオロメチルピリジン又
はそれらのピリジン核の塩素化物のトリフルオロ
メチルピリジン類を製造することを特徴とする、
トリフルオロメチルピリジン類の製造方法。1 In the presence of a catalyst and diluent containing copper fluoride, α
- Reacting picoline, γ-picoline or lutidine with chlorine and anhydrous hydrogen fluoride in the gas phase to produce α-trifluoromethylpyridine, γ-trifluoromethylpyridine, bistrifluoromethylpyridine or chlorinated pyridine nuclei thereof. characterized by producing trifluoromethylpyridines of
A method for producing trifluoromethylpyridines.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56107712A JPS5810569A (en) | 1981-07-10 | 1981-07-10 | Preparation of trifluoromethylpyridine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56107712A JPS5810569A (en) | 1981-07-10 | 1981-07-10 | Preparation of trifluoromethylpyridine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5810569A JPS5810569A (en) | 1983-01-21 |
| JPH0136467B2 true JPH0136467B2 (en) | 1989-07-31 |
Family
ID=14466028
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56107712A Granted JPS5810569A (en) | 1981-07-10 | 1981-07-10 | Preparation of trifluoromethylpyridine |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5810569A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102006059710A1 (en) * | 2006-12-18 | 2008-06-19 | Freie Universität Berlin | Substituted 4-hydroxypyridines |
| WO2019134477A1 (en) * | 2018-01-05 | 2019-07-11 | 浙江省化工研究院有限公司 | Method for preparation of 2-chloro-5-trifluoromethylpyridine |
| JP2021118993A (en) * | 2018-04-23 | 2021-08-12 | 石原産業株式会社 | Internal, fluidized bed reaction apparatus, and method for manufacturing trifluoromethyl pyridine-based compound |
-
1981
- 1981-07-10 JP JP56107712A patent/JPS5810569A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5810569A (en) | 1983-01-21 |
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