JPH0816101B2 - Process for producing 3,5-dichloropyridine - Google Patents
Process for producing 3,5-dichloropyridineInfo
- Publication number
- JPH0816101B2 JPH0816101B2 JP27878387A JP27878387A JPH0816101B2 JP H0816101 B2 JPH0816101 B2 JP H0816101B2 JP 27878387 A JP27878387 A JP 27878387A JP 27878387 A JP27878387 A JP 27878387A JP H0816101 B2 JPH0816101 B2 JP H0816101B2
- Authority
- JP
- Japan
- Prior art keywords
- producing
- dichloropyridine
- reaction
- catalyst
- trichloropyridine
- 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 - Fee Related
Links
- WPGHPGAUFIJVJF-UHFFFAOYSA-N 3,5-dichloropyridine Chemical compound ClC1=CN=CC(Cl)=C1 WPGHPGAUFIJVJF-UHFFFAOYSA-N 0.000 title claims description 6
- 238000000034 method Methods 0.000 title description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- CNLIIAKAAMFCJG-UHFFFAOYSA-N 2,3,5-trichloropyridine Chemical compound ClC1=CN=C(Cl)C(Cl)=C1 CNLIIAKAAMFCJG-UHFFFAOYSA-N 0.000 claims description 6
- FATBKZJZAHWCSL-UHFFFAOYSA-N 2,3,5,6-tetrachloropyridine Chemical compound ClC1=CC(Cl)=C(Cl)N=C1Cl FATBKZJZAHWCSL-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- DNDPLEAVNVOOQZ-UHFFFAOYSA-N 2,3,4,5,6-pentachloropyridine Chemical compound ClC1=NC(Cl)=C(Cl)C(Cl)=C1Cl DNDPLEAVNVOOQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 150000003222 pyridines Chemical class 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 3
- 239000001632 sodium acetate Substances 0.000 description 3
- 235000017281 sodium acetate Nutrition 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000007868 Raney catalyst Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- PVMNPAUTCMBOMO-UHFFFAOYSA-N 4-chloropyridine Chemical compound ClC1=CC=NC=C1 PVMNPAUTCMBOMO-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910001361 White metal Inorganic materials 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010969 white metal Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/006—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by hydrogenation of aromatic hydroxy compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、農・医薬中間体として有用な3,5−ジクロ
ロピリジンを製造する方法に関する。TECHNICAL FIELD The present invention relates to a method for producing 3,5-dichloropyridine which is useful as an agricultural / pharmaceutical intermediate.
（従来技術） 3,5−ジクロロピリジン（以下3,5-DCP）の製造法とし
ては、ピリジンもしくはピリジン塩酸塩の液相塩素化に
より製造する方法（特開61-249965）やピリジンの気相
塩素化により製造する方法（特開58-206564）などがあ
る。(Prior Art) As a method for producing 3,5-dichloropyridine (hereinafter, 3,5-DCP), a method for producing by liquid phase chlorination of pyridine or pyridine hydrochloride (JP-A-61-249965) or a vapor phase of pyridine There is a method of producing by chlorination (JP-A-58-206564) and the like.
（発明が解決しようとする問題点） しかしながら、上記方法においては目的物である3,5-
DCPはピリジン多塩素化物の混合物として得られ、さら
に反応収率も10〜15％と非常に低いという欠点があっ
た。このために、更に目的物の精製に蒸留等の操作を用
いざるを得ず、煩雑になると共に収率の一層の低下は避
けえなかった。(Problems to be Solved by the Invention) However, in the above-mentioned method, 3,5-
DCP was obtained as a mixture of pyridine polychlorinated compounds, and the reaction yield was 10-15%, which was very low. For this reason, an operation such as distillation has to be used for further purification of the target product, which is complicated and further reduction of the yield cannot be avoided.
（問題点を解決するための手段） 発明者等は、2,3,5−トリクロロピリジン（以下TCPY
という）,2,3,5,6−テトラクロロピリジン（以下TECPと
いう）,2,3,4,5,6−ペンタクロロピリジン（以下PCPと
いう）から選ばれる一種以上の塩素化ピリジンを用いて
収率の良い3,5-DCPの製造法を鋭意検討した結果、本発
明に至った。即ち、本発明は、TCPY,TECP,PCPから選ば
れる一種以上の塩素化ピリジンを触媒の存在下、水素と
反応させることを特徴とする3,5-DCPの製造法を提供す
るものである。TCPY,PCPの水素化分解法については従来
例がなく、TECPについてもTCPY製造を目的とする本出願
人の先願（特願62-108564）に例があるだけである。(Means for Solving Problems) The inventors have found that 2,3,5-trichloropyridine (hereinafter TCPY)
, 2,3,5,6-tetrachloropyridine (hereinafter TECP), 2,3,4,5,6-pentachloropyridine (hereinafter PCP) As a result of extensive studies on a method for producing 3,5-DCP having a high yield, the present invention has been accomplished. That is, the present invention provides a method for producing 3,5-DCP, which comprises reacting one or more chlorinated pyridines selected from TCPY, TECP and PCP with hydrogen in the presence of a catalyst. There is no conventional example for the hydrogenolysis method of TCPY and PCP, and there is only an example of TECP in the applicant's earlier application (Japanese Patent Application No. 62-108564) for the purpose of TCPY production.
上記触媒としては、パラジウム，白金，ルテニウム，
ロジウムなどの白金属，又はラネーニッケル，ラネー銅
等のラネー系触媒である。Examples of the catalyst include palladium, platinum, ruthenium,
It is a white metal such as rhodium or a Raney catalyst such as Raney nickel or Raney copper.
これらの触媒は炭素，シリカ等の担体に担持されたも
のでもよい。These catalysts may be supported on a carrier such as carbon or silica.
又、この様な本発明の触媒の含水率が高いと、更に水
添が進みモノクロロピリジンあるいはピリジンにまで変
化する傾向が高くなる。従って触媒中の水分は10wt％以
下、更には２〜3wt％以下である事が好ましい。In addition, when the water content of the catalyst of the present invention is high, the hydrogenation further proceeds, and the tendency to change to monochloropyridine or pyridine increases. Therefore, the water content in the catalyst is preferably 10 wt% or less, more preferably 2-3 wt% or less.
本発明の方法を行うのに溶媒の使用は必ずしも必要で
はないが、ヘキサン，ヘプタンのような炭化水素類，メ
タノール，エタノール，イソプロピルアルコールのよう
なアルコール類，ギ酸，酢酸のような有機酸，酢酸エチ
ルのようなエステルなどを使用してもよい。その量は水
素化分解するピリジン塩素化物を溶解させるに足る量で
良く、通常水素化分解するピリジン塩素化物に対して0.
5〜４重量倍用いられる。The use of a solvent is not always necessary to carry out the method of the present invention, but hydrocarbons such as hexane and heptane, alcohols such as methanol, ethanol and isopropyl alcohol, organic acids such as formic acid and acetic acid, acetic acid. Esters such as ethyl may be used. The amount may be an amount sufficient to dissolve the hydrolyzed pyridine chloride, and is usually 0.
It is used 5 to 4 times by weight.
なお酢酸ナトリウム，トリエチルアミン，炭酸ナトリ
ウムなどの塩基の添加によって反応は促進される。The reaction is promoted by adding a base such as sodium acetate, triethylamine, sodium carbonate.
反応温度は、実質的に反応が進行する最低温度以上、
及びある程度の選択性を保ちかつ工業的に容易に実施で
きる温度範囲で適時選択される。通常は０℃〜200℃，
好ましくは30〜150℃の間で行われる。The reaction temperature is at least the minimum temperature at which the reaction proceeds,
And, it is properly selected within a temperature range in which a certain degree of selectivity is maintained and which can be industrially easily carried out. Normally 0 ℃ ~ 200 ℃,
It is preferably carried out between 30 and 150 ° C.
圧力は、常圧，加圧どちらかにおいても実施できる。 The pressure can be either normal pressure or increased pressure.
反応後の後処理法としては、触媒を過、又はデカン
テーションで除去（これは再使用する）した後、溶媒を
留去し、水洗浄により塩基物を分離除去した後、分留に
より精製する方法が効率的である。As a post-treatment method after the reaction, the catalyst is removed by excess or decantation (which is reused), the solvent is distilled off, the base substance is separated and removed by washing with water, and then purified by fractional distillation. The method is efficient.
（発明の効果） 本発明の方法によれば、簡便なプロセスにより反応・
後処理が実施でき、また極めて高い選択率で目的とする
3,5−ジクロロピリジンを製造することができる。(Effects of the Invention) According to the method of the present invention, the reaction
Post-treatment can be carried out, and the target is extremely high.
3,5-Dichloropyridine can be produced.
（実施例１） 還流管，水素ガス吹き込み管，温度計及び攪拌器を備
えた500mlの四つ口フラスコに2,3,5−トリクロロピリジ
ン86.7g（0.48モル）、酢酸ナトリウム39.4g（0.48モ
ル），炭素上パラジウム５重量％の触媒（水分１％以
下）2.0g、及び酢酸300.0gを仕込み、50℃に加温した。
50℃を維持しながらガス吹き込み管より水素ガスを１
/Hの速度で10時間連続的に吹き込み水素化分解を行っ
た。反応後の組成は、3,5−ジクロロピリジン31％、原
料である2,3,5−トリクロロピリジン68％、その他１％
であった。(Example 1) 86.7 g (0.48 mol) of 2,3,5-trichloropyridine and 39.4 g (0.48 mol) of sodium acetate were placed in a 500 ml four-necked flask equipped with a reflux tube, a hydrogen gas blowing tube, a thermometer and a stirrer. ), 2.0 g of a catalyst containing 5% by weight of palladium on carbon (water content of 1% or less), and 300.0 g of acetic acid were charged, and the mixture was heated to 50 ° C.
While maintaining 50 ℃, add 1 hydrogen gas from the gas blowing pipe.
Blow-off hydrocracking was continuously carried out at a rate of / H for 10 hours. After the reaction, the composition was 31,5-dichloropyridine 31%, raw material 2,3,5-trichloropyridine 68%, other 1%
Met.
（実施例２） 前記実施例１において2,3,5−トリクロロピリジンの
代わりに2,3,5,6−テトラクロロピリジン86.7g（0.4モ
ル）を使用すること、酢酸ナトリウム32.8g（0.4モル）
を使用すること、及び反応時間を20時間にすることを除
いては、実施例１の場合と同様に反応処理した。反応後
の組成は、3,5−ジクロロピリジン18％、2,3,5−トリク
ロロピリジン20％、原料である2,3,5,6−テトラクロロ
ピリジン60％、その他２％であった。 Example 2 86.7 g (0.4 mol) of 2,3,5,6-tetrachloropyridine was used in place of 2,3,5-trichloropyridine in Example 1, and 32.8 g (0.4 mol) of sodium acetate was used. )
Was used and the reaction time was the same as in Example 1, except that the reaction time was 20 hours. The composition after the reaction was 18% 3,5-dichloropyridine, 20% 2,3,5-trichloropyridine, 60% 2,3,5,6-tetrachloropyridine as a raw material, and 2% other.
Claims (1)
トラクロロピリジン,2,3,4,5,6−ペンタクロロピリジン
から選ばれる一種以上の塩素化ピリジンを触媒の存在
下、水素と反応させることを特徴とする3,5−ジクロロ
ピリジンの製造法。1. A catalyst for one or more chlorinated pyridines selected from 2,3,5-trichloropyridine, 2,3,5,6-tetrachloropyridine and 2,3,4,5,6-pentachloropyridine. A method for producing 3,5-dichloropyridine, which comprises reacting with hydrogen in the presence of
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27878387A JPH0816101B2 (en) | 1987-11-04 | 1987-11-04 | Process for producing 3,5-dichloropyridine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27878387A JPH0816101B2 (en) | 1987-11-04 | 1987-11-04 | Process for producing 3,5-dichloropyridine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01121268A JPH01121268A (en) | 1989-05-12 |
| JPH0816101B2 true JPH0816101B2 (en) | 1996-02-21 |
Family
ID=17602115
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27878387A Expired - Fee Related JPH0816101B2 (en) | 1987-11-04 | 1987-11-04 | Process for producing 3,5-dichloropyridine |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0816101B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105642280A (en) * | 2016-03-17 | 2016-06-08 | 西安凯立新材料股份有限公司 | Catalyst for use in continuous production of 2,3-dichloropyridine, and preparation method and application thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000003989A1 (en) | 1998-07-15 | 2000-01-27 | Reilly Industries, Inc. | Dechlorination of pyridines in acidic, zinc-containing mediums |
| GB9916809D0 (en) * | 1999-07-16 | 1999-09-22 | Zeneca Ltd | Chemical process |
-
1987
- 1987-11-04 JP JP27878387A patent/JPH0816101B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105642280A (en) * | 2016-03-17 | 2016-06-08 | 西安凯立新材料股份有限公司 | Catalyst for use in continuous production of 2,3-dichloropyridine, and preparation method and application thereof |
| CN105642280B (en) * | 2016-03-17 | 2018-07-31 | 西安凯立新材料股份有限公司 | Continuous production 2,3- dichloropyridine catalyst and its preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01121268A (en) | 1989-05-12 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |