JPS6153344B2 - - Google Patents
Info
- Publication number
- JPS6153344B2 JPS6153344B2 JP58241398A JP24139883A JPS6153344B2 JP S6153344 B2 JPS6153344 B2 JP S6153344B2 JP 58241398 A JP58241398 A JP 58241398A JP 24139883 A JP24139883 A JP 24139883A JP S6153344 B2 JPS6153344 B2 JP S6153344B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- cyanopyridine
- catalyst
- hydrogen
- pyridine methanol
- 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
- 239000003054 catalyst Substances 0.000 claims description 20
- 238000005984 hydrogenation reaction Methods 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- FFNVQNRYTPFDDP-UHFFFAOYSA-N 2-cyanopyridine Chemical compound N#CC1=CC=CC=N1 FFNVQNRYTPFDDP-UHFFFAOYSA-N 0.000 claims description 12
- 230000002378 acidificating effect Effects 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- PTMBWNZJOQBTBK-UHFFFAOYSA-N pyridin-4-ylmethanol Chemical compound OCC1=CC=NC=C1 PTMBWNZJOQBTBK-UHFFFAOYSA-N 0.000 claims description 6
- 229910000510 noble metal Inorganic materials 0.000 claims description 5
- GPHQHTOMRSGBNZ-UHFFFAOYSA-N pyridine-4-carbonitrile Chemical compound N#CC1=CC=NC=C1 GPHQHTOMRSGBNZ-UHFFFAOYSA-N 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 claims description 3
- SHNUBALDGXWUJI-UHFFFAOYSA-N pyridin-2-ylmethanol Chemical compound OCC1=CC=CC=N1 SHNUBALDGXWUJI-UHFFFAOYSA-N 0.000 description 15
- 229910000564 Raney nickel Inorganic materials 0.000 description 8
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- WOXFMYVTSLAQMO-UHFFFAOYSA-N 2-Pyridinemethanamine Chemical compound NCC1=CC=CC=N1 WOXFMYVTSLAQMO-UHFFFAOYSA-N 0.000 description 2
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- VRWLBMGRSLQKSU-UHFFFAOYSA-N methanol;pyridine Chemical compound OC.C1=CC=NC=C1 VRWLBMGRSLQKSU-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- CFZKDDTWZYUZKS-UHFFFAOYSA-N picoline N-oxide Chemical compound CC1=CC=CC=[N+]1[O-] CFZKDDTWZYUZKS-UHFFFAOYSA-N 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- TXQWFIVRZNOPCK-UHFFFAOYSA-N pyridin-4-ylmethanamine Chemical compound NCC1=CC=NC=C1 TXQWFIVRZNOPCK-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring 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
- Pyridine Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】
本発明はシアノピリジンからピリジンメタノー
ルまたはその塩を製造する方法に関する。さらに
詳しくは、２−または４−シアノピリジンを水素
化触媒（貴金属水素化触媒を除く）の存在下、酸
性水溶液中で接触水素還元せしめ、２−または４
−ピリジンメタノールまたはその塩を製造する方
法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing pyridine methanol or a salt thereof from cyanopyridine. More specifically, 2- or 4-cyanopyridine is subjected to catalytic hydrogen reduction in an acidic aqueous solution in the presence of a hydrogenation catalyst (excluding noble metal hydrogenation catalysts), and
- A method for producing pyridine methanol or a salt thereof.
かかるピリジンメタノールは医薬中間体などに
使用されており有用である。従来、その製法とし
て、α−アセトキシメチルピリジンを加水分解す
る方法が知られている（O.Bullitt、J.Am.Chem.
Soc.76 1370（1954））。 Such pyridine methanol is useful as it is used in pharmaceutical intermediates and the like. Conventionally, a method of hydrolyzing α-acetoxymethylpyridine has been known as its production method (O. Bullitt, J. Am. Chem.
Soc. 76 1370 (1954)).
これは出発原料にα−ピコリンを用い、これを
過酸化水素で２−ピコリン−Ｎ−オキサイドに
し、ついで無水酢酸を作用させ、２−（α−アセ
トキシメチル）ピリジンにし、これを加水分解し
て２−ピリジンメタノールを製造するという長い
工程を経なければならず、工業的に有利な製法と
はいえない。 This uses α-picoline as a starting material, converts it into 2-picoline-N-oxide with hydrogen peroxide, then reacts with acetic anhydride to form 2-(α-acetoxymethyl)pyridine, which is then hydrolyzed. It is not an industrially advantageous production method because it requires a long process to produce 2-pyridine methanol.
本発明者らは上記のごとき実情に鑑み鋭意研究
を重ねた結果、２−または４−シアノピリジンを
水素化触媒（貴金属水素化触媒を除く）の存在
下、酸性水溶液中で反応温度50℃以下で接触水素
還元せしめることにより、２−または４−ピリジ
ンメタノール（以下、ピリジンメタノールとい
う）またはその塩を短い工程で、容易に、収率よ
く製造する方法を見出した。しかも２−または４
−シアノピリジン（以下シアノピリジンという）
はα−またはγ−ピリコンのアンモ酸化により容
易にえられるものである。 The present inventors conducted extensive research in view of the above circumstances, and found that 2- or 4-cyanopyridine was reacted in an acidic aqueous solution at a temperature of 50°C or less in the presence of a hydrogenation catalyst (excluding noble metal hydrogenation catalysts). We have found a method for producing 2- or 4-pyridinemethanol (hereinafter referred to as pyridinemethanol) or its salts easily and in high yield in a short process by catalytic hydrogen reduction. And 2- or 4
-Cyanopyridine (hereinafter referred to as cyanopyridine)
is easily obtained by ammoxidation of α- or γ-pyricone.
本発明に用いる水素化触媒（貴金属水素化触媒
を除く）としては、通常使用される水素化触媒
（貴金属水素化触媒を除く）があげられるが、具
体例としてはラネーニツケル合金を常法により展
開したラネーニツケル触媒があげられる。 As the hydrogenation catalyst (excluding noble metal hydrogenation catalysts) used in the present invention, commonly used hydrogenation catalysts (excluding noble metal hydrogenation catalysts) can be mentioned. Raney nickel catalyst is mentioned.
前記水素化触媒がラネーニツケル触媒のばあい
には、触媒価格が安価で、工業的に使用しやす
く、かつ反応収率が高い。 When the hydrogenation catalyst is a Raney-nickel catalyst, the catalyst price is low, it is easy to use industrially, and the reaction yield is high.
なお本発明において、水素化触媒（貴金属水素
化触媒を除く）は酸性水溶液中で使用されるた
め、たとえばラネーニツケル触媒のようなもの
は、強酸性条件下で使用すると、ニツケルが溶解
するので使用しがたいと一般的に考えられていた
が、本発明者らは鋭意研究を重ねた結果、意外に
も本発明においてはラネーニツケル触媒を好適に
使用しうることを見出した。 In the present invention, hydrogenation catalysts (excluding precious metal hydrogenation catalysts) are used in an acidic aqueous solution, so if a Raney nickel catalyst is used under strongly acidic conditions, nickel will dissolve, so it should not be used. Although it was generally thought that the Raney nickel catalyst was difficult to use, as a result of extensive research, the present inventors unexpectedly discovered that the Raney nickel catalyst can be suitably used in the present invention.
前記水素化触媒の使用量はシアノピリジンに対
して、ラネーニツケル触媒では５〜50重量％の範
囲が、反応効率、触媒効率などの面から好まし
い。 The hydrogenation catalyst is preferably used in an amount of 5 to 50% by weight of the Raney-nickel catalyst based on the cyanopyridine from the viewpoint of reaction efficiency and catalyst efficiency.
本発明に用いる酸性水溶液としては、塩酸、硫
酸などを水で希釈したものがあげられるが、これ
らに限定されるものではない。酸性水溶液として
用いる酸の使用量は、シアノピリジンに対して１
〜10倍のモルの範囲が好ましく、水の使用量は、
酸に対して重量で0.5〜10倍の範囲が好ましい。
酸性水溶液として用いる酸の使用量が１倍モル未
満になると、水素還元が進み難く、収率がわるく
なる傾向が生じ、10倍モルをこえると、生成した
ピリジンメタノールの酸塩からピリジンメタノー
ルを単離する際に使用する中和剤の量が多くな
り、さらに中和で多量の無機塩が生成し、ピリジ
ンメタノールの分離工程が繁雑となり好ましくな
い。 The acidic aqueous solution used in the present invention includes, but is not limited to, hydrochloric acid, sulfuric acid, etc. diluted with water. The amount of acid used as the acidic aqueous solution is 1 to cyanopyridine.
~10 times the molar range is preferred, and the amount of water used is
It is preferably in a range of 0.5 to 10 times the weight of the acid.
When the amount of acid used in the acidic aqueous solution is less than 1 mole, hydrogen reduction tends to be difficult to proceed and the yield tends to be poor, and when it exceeds 10 times the mole, pyridine methanol is simply converted from the acid salt of pyridine methanol produced. The amount of neutralizing agent used during separation increases, and furthermore, a large amount of inorganic salts are generated during neutralization, making the separation process of pyridine methanol complicated, which is not preferable.
本発明ではシアノピリジンが酸性水溶液中で接
触水素還元されるが、その反応温度としては、シ
アノピリジンが酸性水溶液中で加水分解されず、
かつ生産性が良好な温度、すなわち50℃以下が好
ましく、さらに好ましくは０〜40℃であり、反応
圧としては常圧以上あればよいが、反応速度や操
作のしやすさから考えて水素分圧５〜100気圧の
範囲が好ましい。このような反応条件では通常１
〜５時間で反応が終了する。 In the present invention, cyanopyridine is catalytically reduced with hydrogen in an acidic aqueous solution, but the reaction temperature is such that cyanopyridine is not hydrolyzed in the acidic aqueous solution.
The temperature is preferably 50°C or lower, more preferably 0 to 40°C, at which productivity is good, and the reaction pressure is normal pressure or higher, but from the viewpoint of reaction speed and ease of operation, the hydrogen content is The pressure range is preferably from 5 to 100 atmospheres. Under such reaction conditions, usually 1
The reaction is complete in ~5 hours.
反応生成物であるピリジンメタノール酸付加塩
を含有する反応液から濾過により水素化触媒を除
去したのち、濾液をアルカルでPH２程度にし、水
を留去し、適当な有機溶媒で抽出する。この抽出
液を濃縮・冷却するとピリジンメタノール塩とし
て取得できる。また、濾液をアルカリ性にしたの
ち有機溶媒で抽出し、えられた油層を蒸留してピ
リジンメタノールとして取得してもよい。 After removing the hydrogenation catalyst by filtration from the reaction solution containing the reaction product pyridine methanol acid addition salt, the filtrate is brought to a pH of about 2 with an alkal, water is distilled off, and extracted with a suitable organic solvent. When this extract is concentrated and cooled, it can be obtained as pyridine methanol salt. Alternatively, the filtrate may be made alkaline and then extracted with an organic solvent, and the resulting oil layer may be distilled to obtain pyridine methanol.
本発明の製法によると、ピリジンメタノールが
短い工程で、容易に、収率よく、シアノピリジン
を出発原料としてえられる。 According to the production method of the present invention, pyridine methanol can be obtained easily and in good yield in a short process using cyanopyridine as a starting material.
つぎに本発明の製法を実施例にもとづき説明す
るが、本発明はそれらに限定されるものではな
い。 Next, the manufacturing method of the present invention will be explained based on Examples, but the present invention is not limited thereto.
実施例 １
容量３の電磁撹拌式オートクレーブに２−シ
アノピリジン312ｇ、濃硫酸750ｇ、水630ｇおよ
びラネーニツケル触媒62ｇを仕込み、それに水素
を導入し、20気圧、30℃で反応させた。反応が進
行するにつれて水素圧が減少するので、逐次水素
を追加した。2.5時間反応させると水素の吸収は
なくなり、反応は終了した。Example 1 A 3-capacity electromagnetic stirring autoclave was charged with 312 g of 2-cyanopyridine, 750 g of concentrated sulfuric acid, 630 g of water, and 62 g of Raney nickel catalyst, hydrogen was introduced therein, and a reaction was carried out at 20 atmospheres and 30°C. Hydrogen was added sequentially as the hydrogen pressure decreased as the reaction progressed. After 2.5 hours of reaction, hydrogen absorption ceased and the reaction was completed.
えられた反応物を濾過して触媒を濾別し、濾液
を荷性ソーダで中和し、ついでブタノールで抽出
した。そののち、えられた抽層を蒸留し、b.
p.165℃（100mmHg）の留分を捕集したところ、
GC純度99.8％の２−ピリジンメタノール226ｇ
（収率69.1％）をえた。また副生成物の２−アミ
ノメチルピリジン49ｇ（収率15.1％）をえた。 The resulting reaction product was filtered to remove the catalyst, the filtrate was neutralized with sodium chloride, and then extracted with butanol. After that, the extracted extract is distilled, and b.
When the fraction at p.165℃ (100mmHg) was collected,
226g of 2-pyridine methanol with GC purity of 99.8%
(yield 69.1%). Additionally, 49 g (yield 15.1%) of 2-aminomethylpyridine was obtained as a by-product.
２−アミノメチルピリジンは亜硝酸ソーダによ
りジアゾ化して２−ピリジンメタノールに転換す
ることができ、この方法によりえられた２−ピリ
ジンメタノール47ｇを加えると合計収率83.5％に
達した。 2-Aminomethylpyridine could be converted into 2-pyridinemethanol by diazotization with sodium nitrite, and when 47 g of 2-pyridinemethanol obtained by this method was added, a total yield of 83.5% was reached.
実施例 ２
容量３の電磁撹拌式オークレーブに４−シア
ノピリジン312ｇ、濃硫酸450ｇ、水630ｇおよび
ラネーニツケル触媒62ｇを仕込み、それに水素を
導入し、10気圧、30℃で反応させた。Example 2 312 g of 4-cyanopyridine, 450 g of concentrated sulfuric acid, 630 g of water, and 62 g of Raney nickel catalyst were placed in a magnetically stirred oaklave with a capacity of 3. Hydrogen was introduced into the mixture and the mixture was reacted at 10 atm and 30°C.
反応が進行するにつれて水素圧が減少するので
逐次水素を追加した。２時間反応させると水素の
吸収はなくなり、反応は終了した。 Since the hydrogen pressure decreased as the reaction progressed, hydrogen was added successively. After 2 hours of reaction, hydrogen absorption ceased and the reaction was completed.
以下、実施例１と同様にして処理したところ、
４−ピリジンメタノール266ｇ（収率81.3％）お
よび４−アミノメチルピリジン35ｇ（収率10.8
％）がえられた。 The following treatment was carried out in the same manner as in Example 1.
266 g of 4-pyridinemethanol (yield 81.3%) and 35 g of 4-aminomethylpyridine (yield 10.8%)
%) was obtained.
Claims (1)
（貴金属水素化触媒を除く）の存在下、酸性水溶
液中で反応温度50℃以下で接触水素還元せしめる
ことを特徴とする２−または４−ピリジンメタノ
ールまたはその塩の製法。 ２ 前記水素化触媒がラネーラツケル触媒である
特許請求の範囲第１項記載の製法。[Claims] 1. Catalytic hydrogen reduction of 2- or 4-cyanopyridine in the presence of a hydrogenation catalyst (excluding a noble metal hydrogenation catalyst) in an acidic aqueous solution at a reaction temperature of 50°C or less. 2 - or a method for producing 4-pyridine methanol or a salt thereof. 2. The method according to claim 1, wherein the hydrogenation catalyst is a Raney-Rachel catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58241398A JPS60132959A (en) | 1983-12-21 | 1983-12-21 | Preparation of pyridinemethanol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58241398A JPS60132959A (en) | 1983-12-21 | 1983-12-21 | Preparation of pyridinemethanol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60132959A JPS60132959A (en) | 1985-07-16 |
| JPS6153344B2 true JPS6153344B2 (en) | 1986-11-17 |
Family
ID=17073683
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58241398A Granted JPS60132959A (en) | 1983-12-21 | 1983-12-21 | Preparation of pyridinemethanol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60132959A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01134073U (en) * | 1988-03-05 | 1989-09-12 | ||
| JPH0231846U (en) * | 1988-08-19 | 1990-02-28 |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4684541B2 (en) * | 2003-06-25 | 2011-05-18 | 広栄化学工業株式会社 | Method for producing 4-pyridinemethanol |
| JP2005200367A (en) * | 2004-01-16 | 2005-07-28 | Koei Chem Co Ltd | Method for producing pyridine methanols |
| JP2008231078A (en) * | 2007-03-23 | 2008-10-02 | Tama Kagaku Kogyo Kk | Method for producing 3-hydroxymethylpyridine |
-
1983
- 1983-12-21 JP JP58241398A patent/JPS60132959A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01134073U (en) * | 1988-03-05 | 1989-09-12 | ||
| JPH0231846U (en) * | 1988-08-19 | 1990-02-28 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60132959A (en) | 1985-07-16 |
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