JP2767458B2 - Method for producing piperazines - Google Patents
Method for producing piperazinesInfo
- Publication number
- JP2767458B2 JP2767458B2 JP1116730A JP11673089A JP2767458B2 JP 2767458 B2 JP2767458 B2 JP 2767458B2 JP 1116730 A JP1116730 A JP 1116730A JP 11673089 A JP11673089 A JP 11673089A JP 2767458 B2 JP2767458 B2 JP 2767458B2
- Authority
- JP
- Japan
- Prior art keywords
- piperazines
- catalyst
- reaction
- group
- present
- 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
- 150000004885 piperazines Chemical class 0.000 title claims description 18
- 238000004519 manufacturing process Methods 0.000 title description 5
- 239000003054 catalyst Substances 0.000 claims description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 claims description 12
- 150000003216 pyrazines Chemical class 0.000 claims description 10
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 238000005984 hydrogenation reaction Methods 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000007868 Raney catalyst Substances 0.000 description 5
- 229910000564 Raney nickel Inorganic materials 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- OXQOBQJCDNLAPO-UHFFFAOYSA-N 2,3-Dimethylpyrazine Chemical compound CC1=NC=CN=C1C OXQOBQJCDNLAPO-UHFFFAOYSA-N 0.000 description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- CAWHJQAVHZEVTJ-UHFFFAOYSA-N methylpyrazine Chemical compound CC1=CN=CC=N1 CAWHJQAVHZEVTJ-UHFFFAOYSA-N 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- JOMNTHCQHJPVAZ-UHFFFAOYSA-N 2-methylpiperazine Chemical compound CC1CNCCN1 JOMNTHCQHJPVAZ-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- LCZUOKDVTBMCMX-UHFFFAOYSA-N 2,5-Dimethylpyrazine Chemical compound CC1=CN=C(C)C=N1 LCZUOKDVTBMCMX-UHFFFAOYSA-N 0.000 description 2
- 239000001934 2,5-dimethylpyrazine Substances 0.000 description 2
- HJFZAYHYIWGLNL-UHFFFAOYSA-N 2,6-Dimethylpyrazine Chemical compound CC1=CN=CC(C)=N1 HJFZAYHYIWGLNL-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- KVFIJIWMDBAGDP-UHFFFAOYSA-N ethylpyrazine Chemical compound CCC1=CN=CC=N1 KVFIJIWMDBAGDP-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011403 purification operation Methods 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- -1 alkyl pyrazines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000003965 capillary gas chromatography Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011005 laboratory method Methods 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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)
Description
【発明の詳細な説明】 「産業上の利用分野」 本発明は、ピラジン類の接触還元反応によるピペラジ
ン類の製造法に関し、更に詳しくは、ピラジン又はピラ
ジン核に置換基を有するピラジンを核水素化し、高純度
の相当するピペラジン類を製造する方法に関するもので
ある。Description: FIELD OF THE INVENTION The present invention relates to a method for producing piperazines by catalytic reduction of pyrazines, and more particularly, to hydrogenation of pyrazine or pyrazine having a substituent on the pyrazine nucleus. And a process for producing the corresponding piperazines of high purity.
「従来技術及び発明が解決しようとする課題」 従来、ピラジン類を還元反応し、相当するピペラジン
類を合成する方法としては、エタノール中金属ナトリウ
ムを作用させて、発生する水素で核還元する方法（J.Pr
akt.Chem.,51,449（1895）等）が有るが、この方法は実
験室的方法であるため、安全面等で工業的な製造法でな
い。又触媒としてニッケル、白金等の金属の用いて2,5
−ジメチルピラジンを気相で水添核還元する方法（Comp
t.Rend.,190,798（1930））があるが、収率が低く工業
的な方法とは言い難い。[Problems to be Solved by the Prior Art and the Invention] Conventionally, as a method of reducing pyrazines and synthesizing the corresponding piperazines, a method of reacting metal sodium in ethanol to reduce nuclei with generated hydrogen ( J.Pr
akt. Chem., 51 , 449 (1895)), but this method is a laboratory method and is not an industrial production method in terms of safety and the like. Also, using metals such as nickel and platinum as catalysts
-Method for hydrogenating dimethylpyrazine in the gas phase (Comp
t.Rend., 190, 798 (1930 )) it is, it is hard to say that industrial process low yield.
一方、ラネーニッケル、ラネーコバルト、還元ニッケ
ル、ロジウム、パラジウム等の水素化触媒を用いて、ア
ルキルピラジン類を触媒還元する方法（USP.2,843,58
9）が知られている。しかしながら、この方法では、ピ
ペラジン類と沸点が非常に近接した副生成物が生成し、
蒸留等の通常の精製操作では、この副生成物とピペラジ
ン類との分離が極めて困難なために、高純度のピペラジ
ン類が容易に得られないという欠点がある。On the other hand, a method of catalytically reducing alkyl pyrazines using a hydrogenation catalyst such as Raney nickel, Raney cobalt, reduced nickel, rhodium, palladium (USP. 2,843,58
9) is known. However, this method produces by-products whose boiling points are very close to those of piperazines,
In ordinary purification operations such as distillation, it is extremely difficult to separate this by-product from piperazines, so that there is a drawback that high-purity piperazines cannot be easily obtained.
最近、医農薬、電子材料分野ではきわめて高純度のピ
ペラジン類が要求されており、この従来方法は、かかる
要求を満足せしめるものとは言いがたい。Recently, extremely high-purity piperazines have been required in the fields of medicine, agricultural chemicals and electronic materials, and this conventional method cannot be said to satisfy such requirements.
本発明の目的は、ピペラジン類の近似沸点物の副生を
抑制することのできるピペラジン類の製造方法を提供す
ることにある。An object of the present invention is to provide a method for producing piperazines which can suppress by-produced products having a similar boiling point to piperazines.
「課題を解決するための手段」 本発明者らは、かかる目的を達成すべく、ピラジン類の
工業的により有利な接触還元方法について鋭意検討した
結果、アンモニア共存下でピラジン類の接触還元を行な
うことにより、ピペラジン類の近似した沸点を有する物
質の副生が従来方法よりも極めて少なくすることができ
ることを見出し本発明を完成した。"Means for Solving the Problems" The present inventors have conducted intensive studies on an industrially more advantageous catalytic reduction method of pyrazines in order to achieve the object, and as a result, carry out catalytic reduction of pyrazines in the presence of ammonia. As a result, it has been found that by-products of piperazines having a similar boiling point can be extremely reduced as compared with the conventional method, and the present invention has been completed.
即ち本発明は、ピラジン類を水素化触媒の存在下水素
で接触還元をしてピペラジン類を製造するにあたり、ア
ンモニアを共存せしめることを特徴とするピペラジン類
の製造方法である。That is, the present invention is a method for producing piperazines, which comprises producing ammonia by catalytic reduction of pyrazines with hydrogen in the presence of a hydrogenation catalyst, thereby producing ammonia.
本発明のピラジン類としては、一般式（Ｉ）： （式中、R1、R2、R3及びR4は、水素原子、炭素数１乃至
６個のアルキル基、炭素数３乃至６個のシクロアルキル
基、アリール基又はベンジル基、フェネチル基を示す）
で表されるピラジン類が挙げられ、具体的には、ピラジ
ン、メチルピラジン、2,3−ジメチルピラジン、2,5−ジ
メチルピラジン、2,6−ジメチルピラジン、エチルピラ
ジン等を例示できる。As the pyrazines of the present invention, general formula (I): (Wherein, R 1 , R 2 , R 3 and R 4 represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an aryl group or a benzyl group, or a phenethyl group) Show)
And specific examples thereof include pyrazine, methylpyrazine, 2,3-dimethylpyrazine, 2,5-dimethylpyrazine, 2,6-dimethylpyrazine, ethylpyrazine and the like.
本発明における水素化触媒としては、ニッケルコバル
ト、鉄、銅、パラジウム、ロジウム、ルテニウム、白金
等の遷移金属を用いた接触還元用触媒であり、具体的に
はラネー型触媒、安定化触媒あるいは貴金属触媒等が用
いられる。ラネー型触媒としては、ラネーニッケル、ラ
ネーコバルト、ラネー鉄、ラネー銅、安定化触媒として
安定化ニッケル、安定化コバルト、又貴金属触媒として
はパラジウム、ロジウム、ルテニウム、白金又はこれら
の化合物があげられるが、触媒コストの面からラネーニ
ッケル、ラネーコバルト、安定化ニッケルが好ましい。
又その使用量は、原料ピラジン類に対し0.5重量％以上
であれば本発明の実施を防げるものではないが、必要以
上に触媒を添加することは経済性からみて好ましいもの
ではなく、通常約２乃至20重量％が好ましい範囲であ
る。The hydrogenation catalyst in the present invention is a catalyst for catalytic reduction using a transition metal such as nickel cobalt, iron, copper, palladium, rhodium, ruthenium, and platinum, and specifically, a Raney-type catalyst, a stabilizing catalyst or a noble metal. A catalyst or the like is used. Examples of the Raney-type catalyst include Raney nickel, Raney cobalt, Raney iron, Raney copper, stabilized nickel and stabilized cobalt as the stabilizing catalyst, and palladium, rhodium, ruthenium, platinum and compounds thereof as the noble metal catalyst, Raney nickel, Raney cobalt and stabilized nickel are preferred from the viewpoint of catalyst cost.
If the amount is 0.5% by weight or more based on the amount of the starting pyrazine, the practice of the present invention is not prevented. However, it is not preferable to add a catalyst more than necessary from the viewpoint of economy, and usually about 2%. To 20% by weight is a preferable range.
本発明のアンモニアは、ガス状、液状あるいは水溶液
のいずれの形態でも使用でき、その使用量は原料ピラジ
ン類に対し１乃至50重量％、好ましくは５乃至20重量％
である。The ammonia of the present invention can be used in any form of gaseous, liquid or aqueous solution, and its use amount is 1 to 50% by weight, preferably 5 to 20% by weight based on the starting pyrazines.
It is.
本発明において、水素を理論量以上使用すれば還元反
応は完結する。In the present invention, if hydrogen is used in a stoichiometric amount or more, the reduction reaction is completed.
本発明方法を実施するためには、ピペラジン類が一般
的に結晶性の固体であるために適当な溶媒を使用するの
が望ましい。そのための溶媒としては水、アルコール類
やジオキサン、テトラヒドロフラン等のピペラジンを溶
解しうる不活性溶媒が用いられる。中でも水及びアルコ
ール類が廉価で好ましい溶媒である。溶媒の使用量は、
原料ピペラジン類に対して0.3乃至10倍容量が用いられ
る。しかし反応効率や除熱効果等を考慮して、好ましく
は約0.5乃至３倍容量である。In order to carry out the process of the present invention, it is desirable to use a suitable solvent since piperazines are generally crystalline solids. As a solvent therefor, an inert solvent capable of dissolving water, alcohols, piperazine such as dioxane and tetrahydrofuran is used. Among them, water and alcohols are inexpensive and preferable solvents. The amount of solvent used is
0.3 to 10 times the volume of the starting piperazine is used. However, the volume is preferably about 0.5 to 3 times in consideration of reaction efficiency and heat removal effect.
反応は、通常オートクレーブのような耐圧容器中で行
う。反応圧力は10乃至100Kg/cm2一般的には20乃至70Kg/
cm2が好ましい。反応温度は、用いる触媒により異なる
が60乃至200℃、好ましくは100乃至150℃で本発明の反
応が円滑に進行することができる。The reaction is usually performed in a pressure vessel such as an autoclave. The reaction pressure is 10 to 100 Kg / cm 2 is generally 20 to 70 Kg /
cm 2 is preferred. Although the reaction temperature varies depending on the catalyst used, the reaction of the present invention can proceed smoothly at 60 to 200 ° C, preferably 100 to 150 ° C.
後処理操作として、水添反応終了後、反応液をトーオ
クレーブより取り出し、触媒を濾別後、蒸留等の通常の
精製操作により高純度のピペラジン類を得ることができ
る。As a post-treatment operation, after completion of the hydrogenation reaction, the reaction solution is taken out from the toe clave, the catalyst is separated by filtration, and high-purity piperazines can be obtained by ordinary purification operations such as distillation.
「発明の効果」 本発明を実施することによりピペラジン類の近似沸点
物の副生を従来方法に比べて格段に抑制することができ
るために後処理工程による精製が困難になるといったこ
ともなく、容易に高純度のピペラジン類たとえば純度9
9.9％以上という高純度品を得ることができる。"Effect of the Invention" By performing the present invention, by-produced by-products of the approximate boiling point of piperazines can be significantly suppressed as compared with the conventional method, so that purification by the post-treatment step does not become difficult, Easily high-purity piperazines such as purity 9
High purity products of 9.9% or more can be obtained.
次に、本発明をさらに詳しく説明するために実施例に
より説明する。Next, the present invention will be described in further detail with reference to examples.
実施例１ 撹拌機付きステンレス製１のオートクレーブに２−
メチルピラジン94g、市販のラネーニッケル9.4g及び溶
媒としてイソプロパノール100gを仕込み、オートクレー
ブの上部空間部分を水素置換した後アンモニアガス9.4g
を圧入した。その後、反応温度穂140℃で水素を供給し
ながら、反応圧力50Kg/cm2に保ち水添反応を行ったとこ
ろ、１時間30分で理論量の100％の水素が消費された。
その後室温まで冷却後、反応液を取り出し触媒を濾別
し、蒸留により目的の２−メチルピペラジンガスクロ純
度（キャピラリーガスクロマトグラフィによる。以下同
様）99.99％品を得た。収率92.0％,bp106℃/135mmHg 実施例２〜10 実施例１と同様に第１表に示す条件下にピラジン類の
接触還元反応を行い、得られた結果を第１表に示す。Example 1 2-Stainless Steel Autoclave with Stirrer
After charging 94 g of methylpyrazine, 9.4 g of commercially available Raney nickel and 100 g of isopropanol as a solvent, and replacing the upper space of the autoclave with hydrogen, 9.4 g of ammonia gas was added.
Was press-fitted. Thereafter, a hydrogenation reaction was carried out while maintaining the reaction pressure at 50 kg / cm 2 while supplying hydrogen at a reaction temperature of 140 ° C., and 100% of the theoretical amount of hydrogen was consumed in 1 hour and 30 minutes.
Then, after cooling to room temperature, the reaction solution was taken out and the catalyst was separated by filtration, and 99.99% of the desired 2-methylpiperazine gas chromatographically purified (by capillary gas chromatography; the same applies hereinafter) was obtained by distillation. Yield 92.0%, bp 106 ° C./135 mmHg Examples 2 to 10 The catalytic reduction reaction of pyrazines was carried out in the same manner as in Example 1 under the conditions shown in Table 1, and the results obtained are shown in Table 1.
比較例１ 実施例１と同一条件下、ただしアンモニアを共存させ
ずにピラジンの接触還元反応を行ない、同一方法で反応
液を冷却、濾過、蒸留したところ、得られた２−メチル
ピペラジンのガスクロ純度は98.9％であった。収率92.0
％ 比較例２ ラネーニッケルのかわりに市販のパラジウム触媒（活
性炭担体）4.7gを用いた以外は比較例１と同様にして反
応、後処理を行なったところ、得られた２−メチルピペ
ラジンのガスクロ純度は97.8％であった。収率90.7％ Comparative Example 1 A catalytic reduction reaction of pyrazine was carried out under the same conditions as in Example 1 except that no ammonia was present, and the reaction solution was cooled, filtered and distilled by the same method. The gas chromatographic purity of the obtained 2-methylpiperazine Was 98.9%. 92.0 yield
Comparative Example 2 The reaction and post-treatment were performed in the same manner as in Comparative Example 1 except that 4.7 g of a commercially available palladium catalyst (activated carbon carrier) was used instead of Raney nickel, and the gas chromatographic purity of the obtained 2-methylpiperazine was 97.8%. 90.7% yield
Claims (2)
触還元をしてピペラジン類を製造するにあたり、アンモ
ニアを共存せしめることを特徴とするピペラジン類の製
造方法。1. A process for producing piperazines, which comprises subjecting pyrazines to catalytic reduction with hydrogen in the presence of a hydrogenation catalyst to produce piperazines, wherein ammonia is allowed to coexist.
個のアルキル基、炭素数３乃至６個のシクロアルキル
基、アリール基又はベンジル基、フェネチル基を示す）
で表されるピラジン類であることを特徴とする請求項１
記載の方法。2. A compound of the formula (I): (Wherein, R 1 , R 2 , R 3 and R 4 are a hydrogen atom, a carbon number of 1 to 6)
Alkyl group, cycloalkyl group having 3 to 6 carbon atoms, aryl group or benzyl group, phenethyl group)
2. A pyrazine represented by the formula:
The described method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1116730A JP2767458B2 (en) | 1989-05-09 | 1989-05-09 | Method for producing piperazines |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1116730A JP2767458B2 (en) | 1989-05-09 | 1989-05-09 | Method for producing piperazines |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02295981A JPH02295981A (en) | 1990-12-06 |
| JP2767458B2 true JP2767458B2 (en) | 1998-06-18 |
Family
ID=14694374
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1116730A Expired - Fee Related JP2767458B2 (en) | 1989-05-09 | 1989-05-09 | Method for producing piperazines |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2767458B2 (en) |
-
1989
- 1989-05-09 JP JP1116730A patent/JP2767458B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02295981A (en) | 1990-12-06 |
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