JPH0674256B2 - Method for producing pyrazines - Google Patents
Method for producing pyrazinesInfo
- Publication number
- JPH0674256B2 JPH0674256B2 JP61314502A JP31450286A JPH0674256B2 JP H0674256 B2 JPH0674256 B2 JP H0674256B2 JP 61314502 A JP61314502 A JP 61314502A JP 31450286 A JP31450286 A JP 31450286A JP H0674256 B2 JPH0674256 B2 JP H0674256B2
- Authority
- JP
- Japan
- Prior art keywords
- diamines
- catalyst
- pyrazines
- general formula
- alkanolamines
- 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 - Lifetime
Links
- 150000003216 pyrazines Chemical class 0.000 title description 21
- 238000004519 manufacturing process Methods 0.000 title description 7
- 150000004985 diamines Chemical class 0.000 claims description 36
- 239000003054 catalyst Substances 0.000 claims description 23
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- 229940102253 isopropanolamine Drugs 0.000 claims description 8
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 7
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 claims description 5
- 238000006297 dehydration reaction Methods 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- GHWVXCQZPNWFRO-UHFFFAOYSA-N butane-2,3-diamine Chemical compound CC(N)C(C)N GHWVXCQZPNWFRO-UHFFFAOYSA-N 0.000 claims description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims description 2
- ULEAQRIQMIQDPJ-UHFFFAOYSA-N butane-1,2-diamine Chemical compound CCC(N)CN ULEAQRIQMIQDPJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- 238000007363 ring formation reaction Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 9
- CAWHJQAVHZEVTJ-UHFFFAOYSA-N methylpyrazine Chemical compound CC1=CN=CC=N1 CAWHJQAVHZEVTJ-UHFFFAOYSA-N 0.000 description 9
- 150000002009 diols Chemical class 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- LCZUOKDVTBMCMX-UHFFFAOYSA-N 2,5-Dimethylpyrazine Chemical compound CC1=CN=C(C)C=N1 LCZUOKDVTBMCMX-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- GFCDJPPBUCXJSC-UHFFFAOYSA-N [O-2].[Zn+2].[Cu]=O Chemical compound [O-2].[Zn+2].[Cu]=O GFCDJPPBUCXJSC-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- KODLUXHSIZOKTG-UHFFFAOYSA-N 1-aminobutan-2-ol Chemical compound CCC(O)CN KODLUXHSIZOKTG-UHFFFAOYSA-N 0.000 description 1
- 239000001934 2,5-dimethylpyrazine Substances 0.000 description 1
- JCBPETKZIGVZRE-UHFFFAOYSA-N 2-aminobutan-1-ol Chemical compound CCC(N)CO JCBPETKZIGVZRE-UHFFFAOYSA-N 0.000 description 1
- BKMMTJMQCTUHRP-UHFFFAOYSA-N 2-aminopropan-1-ol Chemical compound CC(N)CO BKMMTJMQCTUHRP-UHFFFAOYSA-N 0.000 description 1
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- RNCXCPUOPDATPU-UHFFFAOYSA-N chromium(3+) oxocopper oxygen(2-) Chemical compound [O-2].[Cr+3].[Cu]=O.[O-2].[O-2].[Cr+3] RNCXCPUOPDATPU-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- -1 gold metal compounds Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 150000004885 piperazines Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium 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
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明はピペラジン類の製造方法に関する。TECHNICAL FIELD The present invention relates to a method for producing piperazines.
ピラジン類は香料、医薬、農薬等の中間体として有用で
ある。Pyrazines are useful as intermediates for perfumes, pharmaceuticals, agricultural chemicals and the like.
従来技術と本発明が解決しようとする問題点 従来ピラジン類の製造方法としては （１）ピペラジンの脱水素による方法（特開昭60−1694
68号公報） （２）プロピレングリコールのごときジオール類とエチ
レンジアミンのごときジアミン類を原料として脱水素、
脱水反応する方法（特公昭55−50024号公報） （３）アルカノールアミンを環化脱水素する方法（特開
昭60−258168号公報）などが知られているが、アルカノ
ールアミン類とジアミン類の環化縮合によるピラジン類
の製造法は知られていない。さらに（２）に示したジオ
ール類とジアミン類を出発原料とするピラジン類の合成
法においては、ジオール類とジアミン類の環化縮合反応
と、ジアミン類同志の環化縮合反応による２種類のピラ
ジン類の生成が期待できるが、実際にはジオール類とジ
アミン類の反応によるメチルピラジンが優先的に生成
し、ジアミン類同志の環化縮合によるピラジンはほとん
ど生成しない。Problems to be Solved by the Prior Art and the Present Invention Conventional methods for producing pyrazines include (1) a method by dehydrogenation of piperazine (Japanese Patent Laid-Open No. 60-1694
No. 68) (2) Dehydrogenation using diols such as propylene glycol and diamines such as ethylenediamine as raw materials,
A method of dehydration reaction (Japanese Patent Publication No. 5550024) (3) A method of cyclodehydrogenating an alkanolamine (Japanese Patent Laid-Open No. 60-258168) and the like are known. There is no known method for producing pyrazines by cyclocondensation. Further, in the method for synthesizing pyrazines starting from diols and diamines shown in (2), two types of pyrazines are prepared by a cyclization condensation reaction of diols and diamines and a cyclization condensation reaction of diamines. Although the formation of compounds can be expected, actually, methylpyrazine is preferentially produced by the reaction of diols and diamines, and pyrazine is hardly produced by the cyclocondensation of diamines.
本発明者らはアルカノールアミン類とジアミン類を脱
水、脱水素触媒の存在下気相接触反応させるピラジン類
の新規な製造法を見出しさらにはその方法によりアルカ
ノールアミン類同志の環化縮合による反応、アルカノー
ルアミン類とジアミン類の反応さらにはジアミン類同志
の環化縮合という３種類の反応が同時におこり、複数個
のピラジン類が同時に生成するとともに、これらピラジ
ン類の生成比率を自由に制御出来ることも見出し本発明
を完成するにいたった。The present inventors have found a novel method for producing pyrazines by dehydrating alkanolamines and diamines and subjecting them to gas phase catalytic reaction in the presence of a dehydrogenation catalyst, and further by the method, reaction by cyclization condensation of alkanolamines. The reaction of alkanolamines and diamines, and further the three types of reactions of cyclocondensation of diamines occur simultaneously, and a plurality of pyrazines are simultaneously produced, and the production ratio of these pyrazines can be freely controlled. Heading The present invention has been completed.
問題点を解決するための手段 本発明は、脱水、脱水素能を有する触媒の存在下、一般
式（Ｉ） （式中、R1およびR2は水素又は炭素数１乃３の炭化水素
基を示す） で示されるアルカノールアミン類と一般式（II） （式中、R3およびR4は水素又は炭素数１乃至３の炭化水
素基を示す） で示されるジアミン類を気相接触反応せしめるピラジン
類の新規な製造する方法に関する。Means for Solving the Problems The present invention provides a compound of the general formula (I) in the presence of a catalyst having dehydration and dehydrogenation ability. (Wherein R 1 and R 2 represent hydrogen or a hydrocarbon group having 1 to 3 carbon atoms) and a general formula (II) (Wherein R 3 and R 4 represent hydrogen or a hydrocarbon group having 1 to 3 carbon atoms) and a novel method for producing pyrazines by gas phase catalytic reaction of diamines.
本発明における脱水、脱水素能を有する触媒とはシリカ
ーアルミナ、ゼオライト、亜鉛系、銅系、パラジウム
系、白金系等があげられるが、好ましくは銅および／ま
たは亜鉛を主要成分とする触媒であり、具体的には酸化
銅および／または酸化亜鉛を主要成分として含む触媒で
ある。該触媒は他の金属化合物を含有していてもよく例
えばクロム、バリウム、カルシウム、マンガン、スズ、
セリウム、ジルコニア、ビスマス、トリウム、チタン、
アルミニウム、マグネシウムなどの１種もしくは２種以
上の金金属化合物があげられるが、これら以外の金属化
合物を用いることも出来る。触媒の特に好ましい具体例
としては酸化亜鉛、酸化銅−酸化クロム、酸化銅−酸化
亜鉛などがあげられる。又、該触媒は担体としてシカ
リ、ゼオライト、シリカアルミナ、けいそう土、シリコ
ンカーバイド、アルミナなどを用いることも可能であ
る。The catalyst having dehydration and dehydrogenation ability in the present invention includes silica-alumina, zeolite, zinc-based, copper-based, palladium-based, platinum-based and the like, but is preferably a catalyst containing copper and / or zinc as a main component. Yes, specifically, a catalyst containing copper oxide and / or zinc oxide as a main component. The catalyst may contain other metal compounds such as chromium, barium, calcium, manganese, tin,
Cerium, zirconia, bismuth, thorium, titanium,
One or more gold metal compounds such as aluminum and magnesium can be used, but metal compounds other than these can also be used. Particularly preferred specific examples of the catalyst include zinc oxide, copper oxide-chromium oxide, copper oxide-zinc oxide and the like. In addition, as the carrier, shikari, zeolite, silica-alumina, diatomaceous earth, silicon carbide, alumina and the like can be used as the catalyst.
本発明中一般式〔Ｉ〕でされるアルカノールアミン類
（以下、アルカノールアミン類（Ｉ）という）の具体例
としてはエタノールアミン、イソプロパノールアミン、
２−アミノ−１−プロパノール、１−アミノ−２−ブタ
ノールあるいは２−アミノ−１−ブタノール等があげら
れる。一般式〔II〕で示されるジアミン類（以下、ジア
ミン類（II）という）の具体例としてはエチレンジアミ
ン、1,2−ジアミノプロパン、1,2−ジアミノブタンある
いは2,3−ジアミノブタン等があげられる。アルカノー
ルアミン類（Ｉ）とジアミン類（II）の混合比率は自由
に変えることが出来るが、好ましくは10対１乃至１対10
である。Specific examples of the alkanolamines represented by the general formula [I] in the present invention (hereinafter referred to as alkanolamines (I)) include ethanolamine, isopropanolamine,
2-amino-1-propanol, 1-amino-2-butanol, 2-amino-1-butanol and the like can be mentioned. Specific examples of the diamines represented by the general formula [II] (hereinafter referred to as diamines (II)) include ethylenediamine, 1,2-diaminopropane, 1,2-diaminobutane, and 2,3-diaminobutane. To be The mixing ratio of the alkanolamines (I) and the diamines (II) can be freely changed, but is preferably 10: 1 to 1:10.
Is.
本発明により生成するピラジン類としてはアルカノー
ルアミン類（Ｉ）の環化縮合による一般式（III） （式中、R1およびR2は前記に同じ） で表わされるピラジン類 アルカノールアミン類（Ｉ）とジアミン類（II）との
環化縮合による一般式（IV） （式中、R1,R2,R3およびR4は前記に同じ） で表わされるピラジン類ならびに ジアミン類（II）の環化縮合による一般式（Ｖ） （式中、R3およびR4は前記に同じ） で表わされるピラジン類があげられる。The pyrazines produced by the present invention are represented by the general formula (III) obtained by cyclocondensation of alkanolamines (I). (In the formula, R 1 and R 2 are the same as above) Pyrazines represented by the general formula (IV) by cyclization condensation of alkanolamines (I) and diamines (II) (Wherein R 1 , R 2 , R 3 and R 4 are the same as defined above) and the general formula (V) by cyclization condensation of pyrazines and diamines (II) (In the formula, R 3 and R 4 are the same as above).
生成するピラジン類の比率は、アルカノールアミン類
（Ｉ）とジアミン類（II）の混合比率を変えることによ
って自由に制御出来る。具体的にはアルカノールアミン
類（Ｉ）の混合比を大きくすると、一般式（III）のピ
ラジン類が多く生成し、ジアミン類（II）の混合比を大
きくすると一般式（Ｖ）のピラジン類が多く生成する。The ratio of the pyrazines formed can be freely controlled by changing the mixing ratio of the alkanolamines (I) and the diamines (II). Specifically, when the mixing ratio of the alkanolamines (I) is increased, a large amount of pyrazines of the general formula (III) is produced, and when the mixing ratio of the diamines (II) is increased, the pyrazines of the general formula (V) are generated. Generate a lot.
本発明における反応温度は200乃至600℃であり、好まし
くは250乃至500℃である。The reaction temperature in the present invention is 200 to 600 ° C, preferably 250 to 500 ° C.
本発明においてアルカノールアミン類〔Ｉ〕、ジアミン
類〔II〕を反応させる際、希釈剤として水、ベンゼン、
窒素、水素、アンモニア等を使用することも出来る。When the alkanolamines [I] and the diamines [II] are reacted in the present invention, water, benzene,
Nitrogen, hydrogen, ammonia, etc. can also be used.
本発明を実施するには通常触媒を充填し且つ所定の温度
に保持した固定床又は流動床反応器に原料ガスを導入し
て触媒と接触させればよい。触媒との接触時間も広範囲
に変化させることが出来、空間速度は50乃至20000Hr-1
好ましくは100乃至5000Hr-1である。In order to carry out the present invention, a raw material gas may be introduced into a fixed bed or fluidized bed reactor which is usually filled with a catalyst and kept at a predetermined temperature and brought into contact with the catalyst. The contact time with the catalyst can also be changed over a wide range, and the space velocity is 50 to 20000 Hr -1.
It is preferably 100 to 5000 Hr -1 .
尚本発明における収率は下記基準で計算した。一般式
〔Ｉ〕のアルカノールアミン類〔Ｉ〕の環化縮合による
ピラジン類 一般式〔Ｉ〕，〔II〕のアルカノールアミン類〔Ｉ〕と
ジアミン類〔II〕の環化縮によるピラジン類 一般式〔II〕のジアミン類〔II〕の環化縮合によるピラ
ジン類 発明の効果 本発明はアルカノールアミン類〔Ｉ〕とジアミン類〔I
I〕の気相接触反応によるピラジン類の新規な製造法に
関するものであり、本発明を例えば原料としてイソプロ
パノールアミン、エチレンジアミンを用いて実施すれ
ば、蒸留によって容易に分離可能な、ピラジン、メチル
ピラジン、2,5−ジメチルピラジンの３種類のピラジン
類が同時に製造出来る利点がある。The yield in the present invention was calculated based on the following criteria. Pyrazines by cyclocondensation of alkanolamines [I] of the general formula [I] Pyrazines by cyclization of alkanolamines [I] of general formulas [I] and [II] and diamines [II] Pyrazines by cyclocondensation of diamines of general formula [II] [II] EFFECT OF THE INVENTION The present invention is directed to alkanolamines [I] and diamines [I].
I) relates to a novel method for producing pyrazines by a gas phase catalytic reaction, and if the present invention is carried out using, for example, isopropanolamine or ethylenediamine as a raw material, it is easily separable by distillation, pyrazine, methylpyrazine, There is an advantage that three types of pyrazines such as 2,5-dimethylpyrazine can be simultaneously produced.
実施例−１ 硝酸亜鉛182gを含む水溶液と25％アンモニア水100gとを
混合し沈殿物を得た。得られた沈殿物を過、水洗後、
110℃で乾燥し400℃で３時間焼成して酸化亜鉛触媒を得
た。得られた触媒を内径14mmφのパイレックス製反応管
に6g充填し400℃に保持した。この反応器にイソプロパ
ノールアミン2.6g/Hr、エチレンジアミン2.6g/Hr、H2O
1.2g/Hrをガス状で１時間反応させ、反応液をガスクロ
マトグラフィーで分析したところ2.5−ジメチルピラジ
ン収率27.8％、メチルピラジン収率28.8％、ピラジン収
率24.0％を得た。Example 1 An aqueous solution containing 182 g of zinc nitrate and 100 g of 25% aqueous ammonia were mixed to obtain a precipitate. After the obtained precipitate is washed with water,
It was dried at 110 ° C and calcined at 400 ° C for 3 hours to obtain a zinc oxide catalyst. 6 g of the obtained catalyst was filled in a Pyrex reaction tube having an inner diameter of 14 mmφ and kept at 400 ° C. In this reactor, isopropanolamine 2.6 g / Hr, ethylenediamine 2.6 g / Hr, H 2 O
When 1.2 g / Hr was reacted in a gaseous state for 1 hour and the reaction solution was analyzed by gas chromatography, 2.5-dimethylpyrazine yield 27.8%, methylpyrazine yield 28.8% and pyrazine yield 24.0% were obtained.
実施例−２ 他の原料として硝酸銅65gを用いる以外は実施例−１と
同様な方法で触媒を調製し酸化銅−酸化亜鉛触媒（重量
比30:70）を得た。この触媒6gを実施例−１と同じ反応
器に充填し350℃に保持したところにイソプロパノール
アミン3.4g/Hr、エチレンアミン1.4g/Hr、H2O2.0g/Hrの
混合物をガス状で通したところ、2,5−メチルピラジン
収率27.5％、メチルピラジン収率41.9％、ピラジン収率
19.8％を得た。Example-2 A catalyst was prepared in the same manner as in Example-1 except that 65 g of copper nitrate was used as another raw material to obtain a copper oxide-zinc oxide catalyst (weight ratio 30:70). 6 g of this catalyst was charged into the same reactor as in Example-1 and kept at 350 ° C., and then a mixture of 3.4 g / Hr of isopropanolamine, 1.4 g / Hr of ethyleneamine, and 2.0 g / Hr of H 2 O was passed in a gaseous state. As a result, the yield of 2,5-methylpyrazine was 27.5%, the yield of methylpyrazine was 41.9%, and the yield of pyrazine was
I got 19.8%.
実施例３〜５ 実施例−２と同様な方法で得た下記に示す触媒に用い
て、イソプロパノールアミン1.8g/Hr、エチレンジアミ
ン3.0g/Hr、H2O1.2g/Hrの混合ガス流す以外は実施例−
１に従って反応したところ表−１の結果を得た。Examples 3 to 5 Except that a mixed gas of isopropanolamine 1.8 g / Hr, ethylenediamine 3.0 g / Hr, and H 2 O 1.2 g / Hr was used by using the catalyst shown below obtained in the same manner as in Example-2. Example-
When the reaction was performed according to 1, the results shown in Table 1 were obtained.
実施例６〜７ 実施例−２と同様な方法で得た下記に示す触媒を用い
て、イソプロパノールアミン2.1g/Hr、2,3−ジアミノブ
タン2.4g/Hr、H2O1.0g/Hrの混合ガスを流す以外は実施
例−２に従って反応したところ表−２の結果を得た。 Examples 6 to 7 Isopropanolamine 2.1 g / Hr, 2,3-diaminobutane 2.4 g / Hr, H 2 O 1.0 g / Hr were prepared using the catalyst shown below obtained in the same manner as in Example-2. When the reaction was performed according to Example-2 except that the mixed gas was flowed, the results shown in Table-2 were obtained.
Claims (6)
般式（Ｉ） （式中R1およびR2は水素又は炭素数１乃至３の炭化水素
基を示す） で示されるアルカノールアミン類と一般式（II） （式中R3およびR4は水素又は炭素数１乃至３の炭化水素
基を示す） で示されるジアミン類を気相接触反応せしめることを特
徴とするピラジン類の製造方法。1. The formula (I) in the presence of a catalyst having dehydration and dehydrogenation ability. (Wherein R 1 and R 2 represent hydrogen or a hydrocarbon group having 1 to 3 carbon atoms) and the general formula (II) (Wherein R 3 and R 4 represent hydrogen or a hydrocarbon group having 1 to 3 carbon atoms), and the diamines are subjected to a gas phase catalytic reaction to produce a pyrazine.
または亜鉛を主要成分とする触媒である特許請求の範囲
第１項記載の方法。2. A catalyst having dehydration and dehydrogenation ability is copper and / or
The method according to claim 1, which is a catalyst containing zinc as a main component.
媒が酸化銅および／または酸化亜鉛を主要成分とする触
媒である特許請求の範囲第２項記載の方法。3. The method according to claim 2, wherein the catalyst containing copper and / or zinc as a main component is a catalyst containing copper oxide and / or zinc oxide as a main component.
類がエタノールアミン、イソプロパノールアミンまたは
２−アミノ−１−ププロパノールである特許請求の範囲
第1,2または３項記載の方法。4. The method according to claim 1, 2 or 3, wherein the alkanolamine represented by the general formula (I) is ethanolamine, isopropanolamine or 2-amino-1-pupropanol.
レンジアミン、1,2−ジアミンプロパン、1,2−ジアミノ
ブタンまたは2,3−ジアミノブタンである特許請求の範
囲第1,2または３項記載の方法。5. The diamines represented by the general formula (II) are ethylenediamine, 1,2-diaminepropane, 1,2-diaminobutane or 2,3-diaminobutane. Method described in section.
アミンおよびジアミン類がエチレンジアミンである特許
請求の範囲第１項,2または３項記載の方法。6. The method according to claim 1, 2 or 3, wherein the alkanolamines are isopropanolamine and the diamines are ethylenediamine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61314502A JPH0674256B2 (en) | 1986-12-24 | 1986-12-24 | Method for producing pyrazines |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61314502A JPH0674256B2 (en) | 1986-12-24 | 1986-12-24 | Method for producing pyrazines |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63162678A JPS63162678A (en) | 1988-07-06 |
| JPH0674256B2 true JPH0674256B2 (en) | 1994-09-21 |
Family
ID=18054062
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61314502A Expired - Lifetime JPH0674256B2 (en) | 1986-12-24 | 1986-12-24 | Method for producing pyrazines |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0674256B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4873777B2 (en) * | 2000-12-04 | 2012-02-08 | 広栄化学工業株式会社 | Process for producing β-picoline |
| JP5271721B2 (en) * | 2008-01-23 | 2013-08-21 | 株式会社半導体エネルギー研究所 | Method for producing triarylpyrazine derivative |
-
1986
- 1986-12-24 JP JP61314502A patent/JPH0674256B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63162678A (en) | 1988-07-06 |
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