JPH0674255B2 - Process for producing compound containing pyrazine nucleus - Google Patents
Process for producing compound containing pyrazine nucleusInfo
- Publication number
- JPH0674255B2 JPH0674255B2 JP61138441A JP13844186A JPH0674255B2 JP H0674255 B2 JPH0674255 B2 JP H0674255B2 JP 61138441 A JP61138441 A JP 61138441A JP 13844186 A JP13844186 A JP 13844186A JP H0674255 B2 JPH0674255 B2 JP H0674255B2
- Authority
- JP
- Japan
- Prior art keywords
- general formula
- zinc
- present
- catalyst
- main component
- 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
- 238000000034 method Methods 0.000 title claims description 11
- 150000003216 pyrazines Chemical class 0.000 title claims description 10
- 150000001875 compounds Chemical class 0.000 title claims description 9
- 239000003054 catalyst Substances 0.000 claims description 18
- 150000004985 diamines Chemical class 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 3
- GHWVXCQZPNWFRO-UHFFFAOYSA-N butane-2,3-diamine Chemical compound CC(N)C(C)N GHWVXCQZPNWFRO-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 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
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- 238000006555 catalytic reaction Methods 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VEPOHXYIFQMVHW-XOZOLZJESA-N 2,3-dihydroxybutanedioic acid (2S,3S)-3,4-dimethyl-2-phenylmorpholine Chemical compound OC(C(O)C(O)=O)C(O)=O.C[C@H]1[C@@H](OCCN1C)c1ccccc1 VEPOHXYIFQMVHW-XOZOLZJESA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- FINHMKGKINIASC-UHFFFAOYSA-N Tetramethylpyrazine Chemical compound CC1=NC(C)=C(C)N=C1C FINHMKGKINIASC-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
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 239000000017 hydrogel Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 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
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- 239000005909 Kieselgur Substances 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
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- GXDVEXJTVGRLNW-UHFFFAOYSA-N [Cr].[Cu] Chemical compound [Cr].[Cu] GXDVEXJTVGRLNW-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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 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
- 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
- 239000007795 chemical reaction product Substances 0.000 description 1
- -1 chromium Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 150000001880 copper compounds Chemical class 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
- MYJQGGALXPHWLV-UHFFFAOYSA-N cyclopentane-1,2-diamine Chemical compound NC1CCCC1N MYJQGGALXPHWLV-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000000543 intermediate 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
- 239000005297 pyrex Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 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
- 239000007858 starting material 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
- 239000010457 zeolite Substances 0.000 description 1
- 150000003752 zinc compounds 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
- Catalysts (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 本発明はピラジン核を含有する化合物の製造方法に関し
さらに詳しくはジアミン類を銅および／または亜鉛を主
要成分とする触媒の存在下、気相反応させてピラジン核
を含有する化合物の製造方法である。TECHNICAL FIELD The present invention relates to a process for producing a compound containing a pyrazine nucleus, more specifically, a diamine is reacted in a gas phase in the presence of a catalyst containing copper and / or zinc as a main component. And a method for producing a compound containing a pyrazine nucleus.
ピラジン類は香料、医薬、農薬の中間体として有用であ
る。Pyrazines are useful as intermediates for fragrances, medicines and agricultural chemicals.
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）エチ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、脱水素反応する方法（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目的
物によってはこれらは有効な方法であるが、原料の入手
難あるいは目的物の種類によって使いわけしなければな
らない。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) dehydration and dehydrogenation reaction using diols such as ethylene glycol and diamines such as ethylenediamine as raw materials (Japanese Patent Publication No. 5550024), and (3) cyclodehydrogenation of alkanolamines. There are known methods (Japanese Patent Laid-Open No. 60-258168) and the like, which are effective methods depending on the intended product, but they must be used properly depending on the difficulty of obtaining the raw materials or the type of the intended product.
又、主生成物以外の副生成物が出来る場合があり、副生
成物は通常位置異性体の場合が多く、ピラジン類の位置
異性体は分離が困難でありそれぞれの方法に一長一短が
あった。Further, there are cases where by-products other than the main product are produced, and by-products are usually regioisomers in many cases, and regioisomers of pyrazines are difficult to separate, and each method has advantages and disadvantages.
問題点を解決するための手段 本発明者らは、これらの点について鋭意検討した結果、
ジアミン類を銅および／または亜鉛を主要成分とする触
媒存在下、気相反応させることによりピラジン核を有す
る化合物が生成することを見出し本発明を完成させた。
特に本出願方法は一般式 で示されるフェナジンのごとき縮合環をもつピラジン誘
導体の合成法として好ましい。Means for Solving Problems As a result of diligent study on these points,
The present invention has been completed by finding that a compound having a pyrazine nucleus is produced by reacting a diamine in the gas phase in the presence of a catalyst containing copper and / or zinc as a main component.
In particular, this application method Is preferred as a method for synthesizing a pyrazine derivative having a condensed ring such as phenazine.
本発明は一般式 （式中R1,R2は水素又は炭素数１乃至６の炭化水素基を
示す） もしくは一般式 （式中R3は炭素数３乃至４の炭化水素残基、（Ｈ）はＣ
−Ｃ間が一重結合のときは水素が存在し２重結合ときは
水素がないことを示す） であらわされるジアミン類を銅および／または亜鉛を主
要成分とする触媒の存在下気相接触反応せしめることを
特徴とする一般式 （式中R1,R2は前記と同じ） もしくは一般式 （式中R3は前記と同じ） で示されるピラジン核を含有する化合物の製造法に関す
るものである。The present invention has the general formula (Wherein R 1 and R 2 represent hydrogen or a hydrocarbon group having 1 to 6 carbon atoms) or the general formula (In the formula, R 3 is a hydrocarbon residue having 3 to 4 carbon atoms, (H) is C
When C is a single bond, hydrogen is present, and when a double bond is present, hydrogen is absent.) A diamine represented by is reacted in the gas phase in the presence of a catalyst containing copper and / or zinc as a main component. General formula characterized by (Wherein R 1 and R 2 are the same as above) or the general formula (Wherein R 3 is the same as the above), and to a method for producing a compound containing a pyrazine nucleus.
本発明に於ける銅および／または亜鉛を主要成分とする
触媒としては銅化合物又は亜鉛化合物を含む触媒であれ
ばよいが、酸化物が好ましい。The catalyst containing copper and / or zinc as a main component in the present invention may be a catalyst containing a copper compound or a zinc compound, but an oxide is preferable.
又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、ビスマス、ト
リウム、チタン、アルミニウム、シリカ、などの１種も
しくは２種以上の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。該触媒の特に好
ましい具体例としては酸化銅、銅−クロム、酸化銅−酸
化亜鉛などがあげられる。It may also contain other metal compounds such as chromium,
Examples thereof include one or more metal compounds such as barium, calcium, manganese, tin, bismuth, thorium, titanium, aluminum and silica, but metal compounds other than these can also be used. Particularly preferred specific examples of the catalyst include copper oxide, copper-chromium, copper oxide-zinc oxide and the like.
又該触媒は担体としてシリカ、ゼオライト、シリカアル
ミナ、けいそう土、シリコンカーバイトなどを用いるこ
とも可能である。本発明中一般式（Ｉ）に示されるジア
ミン類としては、エチレンジアミン、2,3−ジアミノブ
タンなどがあげられる。The catalyst may use silica, zeolite, silica-alumina, diatomaceous earth, silicon carbide or the like as a carrier. Examples of the diamines represented by the general formula (I) in the present invention include ethylenediamine and 2,3-diaminobutane.
一般式（II）で示されるジアミンとしては、ｏ−フェニ
レンジアミン、1,2−ジアミノシクロペンタンなどがあ
げられる。Examples of the diamine represented by the general formula (II) include o-phenylenediamine and 1,2-diaminocyclopentane.
本発明に於ける反応温度は200℃乃至500℃であり好しく
は250乃至400℃である。The reaction temperature in the present invention is 200 to 500 ° C, preferably 250 to 400 ° C.
本発明に於て、一般式（Ｉ），（II）で示されるジアミ
ン類を反応させる際、希釈剤として水，ベンゼン，ピリ
ジン，窒素，水素，アンモニアなど反応に関与しない化
合物を使用することが出来る。In the present invention, when the diamines represented by the general formulas (I) and (II) are reacted, it is preferable to use compounds such as water, benzene, pyridine, nitrogen, hydrogen, and ammonia that do not participate in the reaction as diluents. I can.
本発明を実施するには、通常触媒を充填し且つ所定の反
応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2000
0Hr-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 reaction temperature and brought into contact with the catalyst. The contact time with the catalyst can be changed over a wide range, and the space velocity is 50 to 2000.
It is 0 Hr -1 , preferably 100 to 5000 Hr -1 .
本発明で得られた反応物は、常法に従って例えば蒸留等
によって分離精製が可能である。The reaction product obtained in the present invention can be separated and purified by a conventional method such as distillation.
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
混合しヒドロゲルを得た。Example 1 An aqueous solution containing 182 g of zinc nitrate and 100 g of 25% aqueous ammonia were mixed to obtain a hydrogel.
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12mmのパイレックス製反応管に6g充填し400℃に保持
した。The obtained precipitate was washed with water, dried at 110 ° C., and calcined at 400 ° C. for 3 hours to obtain a zinc oxide catalyst. 6 g of a Pyrex reaction tube having an inner diameter of 12 mm was filled with the obtained catalyst and kept at 400 ° C.
この反応器にエチレンジアミン4.8gHr,H2O1g/Hrをガス
状で２時間反応させたところピラジンを収率48％で得
た。When ethylenediamine 4.8 g Hr and H 2 O 1 g / Hr were reacted in a gaseous state for 2 hours in this reactor, pyrazine was obtained in a yield of 48%.
実施例２ 硝酸銅46g,硝酸亜鉛128gを含む水溶液に約25％アンモニ
ア水84gを加え、pH7としヒドロゲルを得た。得られた沈
殿物を過、水洗後80℃で乾燥し、500℃で５時間焼成
して、酸化銅−酸化亜鉛触媒（重量比30:70）を得た。Example 2 To an aqueous solution containing 46 g of copper nitrate and 128 g of zinc nitrate, 84 g of about 25% ammonia water was added to adjust the pH to 7 to obtain a hydrogel. The obtained precipitate was washed with water, dried at 80 ° C., and calcined at 500 ° C. for 5 hours to obtain a copper oxide-zinc oxide catalyst (weight ratio 30:70).
この触媒6gを実施例１と同じ反応器に充填し400℃に保
持したところｏ−フェニレンジアミン4.6g/Hr,アンモニ
ア1.5/Hr,ベンゼン5g/Hrの混合物をガス状で通したと
ころ、フェナジンを収率51％で得た。When 6 g of this catalyst was charged in the same reactor as in Example 1 and kept at 400 ° C., a mixture of 4.6 g / Hr of o-phenylenediamine, 1.5 / Hr of ammonia, and 5 g / Hr of benzene was passed in a gaseous state, and phenazine was found Obtained with a yield of 51%.
実施例３〜５ 実施例１と同一方法で下記に示す触媒を用いて1,2−ジ
アミノプロパン0.07モル/Hr,H2O0.04モル/Hrで流したと
ころ表−１の結果を得た。Examples 3 to 5 In the same manner as in Example 1, using the catalyst shown below and flowing 1,2-diaminopropane 0.07 mol / Hr, H 2 O 0.04 mol / Hr, the results shown in Table 1 were obtained. .
実施例６ 2,3−ジアミノブタン3g/Hr,H2O3.0g/Hrを原料とする以
外は、実施例１に従って反応したところ、2,3,5,6−テ
トラメチルピラジンを収率45％で得た。 Example 6 The reaction was carried out according to Example 1 except that 3 g / Hr of 2,3-diaminobutane and 3.0 g / Hr of H 2 O were used as starting materials, and yielded 2,3,5,6-tetramethylpyrazine in a yield of 45. Earned in%.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０７Ｄ 241/46 8615−4Ｃ ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 5 Identification code Office reference number FI technical display location C07D 241/46 8615-4C
Claims (4)
を示す） もしくは一般式 （式中R3は炭素数３乃至４の炭化水素残基、（Ｈ）はＣ
−Ｃ間が単結合のときは水素が存在し２重結合のときは
水素がないことを示す） であらわされるジアミン類を銅および／または亜鉛を主
要成分とする触媒の存在下気相接触反応せしめることを
特徴とする一般式 （式中R1,R2は前記と同じ） もしくは一般式 （式中R3は前記と同じ） でされるピラジン核を含有する化合物の製造法1. A general formula (Wherein R 1 and R 2 represent hydrogen or a hydrocarbon group having 1 to 6 carbon atoms) or the general formula (In the formula, R 3 is a hydrocarbon residue having 3 to 4 carbon atoms, (H) is C
When C is a single bond, hydrogen is present, and when it is a double bond, hydrogen is absent.) A diamine represented by the formula) is present in the presence of a catalyst containing copper and / or zinc as a main component in the presence of a gas phase catalytic reaction. General formula characterized by (Wherein R 1 and R 2 are the same as above) or the general formula (Wherein R 3 is the same as above) and a method for producing a compound containing a pyrazine nucleus
ジアミン、1,2−ジアミノプロパン、ジアミノブタンで
ある特許請求の範囲第１項記載の方法2. The method according to claim 1, wherein the compound represented by the general formula (I) is ethylenediamine, 1,2-diaminopropane or diaminobutane.
ニレンジアミンである特許請求の範囲の第１項記載の方
法3. The method according to claim 1, wherein the compound represented by the general formula (II) is o-phenylenediamine.
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１項記載の方法4. The method according to claim 1, 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61138441A JPH0674255B2 (en) | 1986-06-13 | 1986-06-13 | Process for producing compound containing pyrazine nucleus |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61138441A JPH0674255B2 (en) | 1986-06-13 | 1986-06-13 | Process for producing compound containing pyrazine nucleus |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62294668A JPS62294668A (en) | 1987-12-22 |
| JPH0674255B2 true JPH0674255B2 (en) | 1994-09-21 |
Family
ID=15222065
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61138441A Expired - Lifetime JPH0674255B2 (en) | 1986-06-13 | 1986-06-13 | Process for producing compound containing pyrazine nucleus |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0674255B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113816912B (en) * | 2021-08-30 | 2023-02-28 | 上海日异生物科技有限公司 | Preparation method of phenazine |
-
1986
- 1986-06-13 JP JP61138441A patent/JPH0674255B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62294668A (en) | 1987-12-22 |
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