JPS6128671B2 - - Google Patents
Info
- Publication number
- JPS6128671B2 JPS6128671B2 JP5271276A JP5271276A JPS6128671B2 JP S6128671 B2 JPS6128671 B2 JP S6128671B2 JP 5271276 A JP5271276 A JP 5271276A JP 5271276 A JP5271276 A JP 5271276A JP S6128671 B2 JPS6128671 B2 JP S6128671B2
- Authority
- JP
- Japan
- Prior art keywords
- compound
- dihydropyrazine
- pyrazine
- same
- metal oxide
- 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
- -1 dihydropyrazine compound Chemical class 0.000 claims description 16
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 claims description 6
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Natural products C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical group CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 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 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 150000004706 metal oxides Chemical class 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000003205 fragrance Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000796 flavoring agent Substances 0.000 description 2
- 235000019634 flavors Nutrition 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 150000003216 pyrazines Chemical class 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 244000061176 Nicotiana tabacum Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 244000299461 Theobroma cacao Species 0.000 description 1
- 235000009470 Theobroma cacao Nutrition 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- XMFOQHDPRMAJNU-UHFFFAOYSA-N lead(ii,iv) oxide Chemical compound O1[Pb]O[Pb]11O[Pb]O1 XMFOQHDPRMAJNU-UHFFFAOYSA-N 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Description
本発明は一般式
（但しR1，R2，R3，R4は同一又は異なつて水
素原子、炭素数１〜４のアルキル基又はアルケニ
ル基を意味し、或はR1とR2またはR3とR4が一緒
になつてｎ−ブチレン基を意味する。）
を有するジヒドロピラジン化合物（）を脱水素
して対応する一般式
（但しR1，R2，R3，R4は前記と同じ）を有するピ
ラジン化合物（）を製造する方法に関する。
ピラジン化合物（）は農薬、医薬品合成中間
体及び香料として有用で特に従来の調合ではどう
しても得られなかつたこうばしさをこれらピラジ
ン化合物（）の微量の配合によつて賦与するこ
とができるのでコーヒー、ココア、ナツツ類、タ
バコ、人造肉等向のフレーバとして有用であり、
又香粧品用香料としても最近注目されている。
ピラジン化合物（）の製法としてはジヒドロ
ピラジン化合物（）を塩基性媒体中で加熱する
方法〔薬誌、78、229（1958）；Agr.Biol.Chem.
37(6)，1509（1973）〕が知られている。これらの
方法では収率が低く、本発明者らが追試したとこ
ろその収率は40％止りに過ぎなかつた。又この両
方法では不都合な副反応生成物が多量に生じた
り、又可成りの未反応原料が残存するため製品の
純度は低くかつ製品が経日すると着色したり、異
臭を発するので、これら方法は香料分野における
製造法としては不適当である。
又ピペラジンの気相脱水素法でつくる方法
（U.S.P.2，400398）もあるが、この方法にはピペ
ラジンが高価であることの難点がある。
α−ジアミン化合物とα−エポキシド化合物を
触媒の存在下で気相で反応させる方法（特開昭49
−101391）では目的の単一のピラジン化合物
（）を得ることは困難である。
本発明者はジヒドロピラジン化合物（）を塩
基性の不活性溶媒中金属酸化物と反応せしめるこ
とにより99.9％の高純度のピラジン化合物（）
を80％以上の高収率で得て本発明に成功した。
出発原料のジヒドロピラジン化合物（）はα
−ジカルボニル化合物とα−ジアミンの縮合によ
つて得られるものである。
金属酸化物としてはマンガン、銅、鉛の酸化物
が使用でき、二酸化マンガン、酸化第二銅、四三
酸化鉛が適当である。
反応媒体にはメタノール、エタノール、エチレ
ングリコール等が使用できジヒドロピラジン化合
物（）に対して重量で５〜50倍なるべく10〜20
倍使用した方がよい。
ジヒドロピラジン化合物（）と金属酸化物と
の反応を酸性条件下で行うと生成物は黒褐色の樹
脂状物となり、又中性条件下では反応は進行しな
い。塩基性条件下で行うと前記の如き好結果が得
られる。
ジヒドロピラジン化合物（）と金属酸化物と
を１：1.5〜４のモル比で溶媒の還流下に２〜８
時間保持することにより目的のピラジン化合物
（）を得ることができる。
実施例 １〜12
ジヒドロピラジン化合物（）（Ag）のエタノ
ール（Bml）溶液に水酸化カリウム（Cg）と金
属酸化物（Dg）を加え、Ｅ時間加熱還流後沈殿
を濾去し、濾液よりそれが1/4容量になるまでエ
タノールを留去し、残留物とその４倍容量のベン
ゼン、飽和食塩水とを混合し、ベンゼン層を分取
し、ベンゼンを留取後残留物を減圧蒸留し、Ｆ
℃／ＧmmHgの留分を得る。これについてガスク
ロマトグラム、質量スペクトル、赤外線吸収スペ
クトル及び核磁気共鳴吸収スペクトルを試べ化合
物（）に対応するピラジン化合物（）である
ことを確認する。以上の処理によるデータを第１
表及び第２表に示した。
The present invention is based on the general formula (However, R 1 , R 2 , R 3 , and R 4 are the same or different and mean a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkenyl group, or R 1 and R 2 or R 3 and R 4 are ) which together mean n-butylene group) are dehydrogenated to form the corresponding general formula (However, R 1 , R 2 , R 3 , and R 4 are the same as above). Pyrazine compounds () are useful as agricultural chemicals, pharmaceutical synthesis intermediates, and fragrances, and in particular, the combination of small amounts of these pyrazine compounds () can impart a flavor that cannot be obtained with conventional formulations, so coffee, cocoa, etc. , useful as a flavor for nuts, tobacco, artificial meat, etc.
It has also recently attracted attention as a fragrance for cosmetics. The method for producing pyrazine compound () is to heat dihydropyrazine compound () in a basic medium [Yakushu, 78 , 229 (1958); Agr.Biol.Chem.
37 (6), 1509 (1973)] is known. These methods have low yields, and when the present inventors conducted additional tests, the yields were only 40%. In addition, both of these methods produce a large amount of undesirable side reaction products, and a considerable amount of unreacted raw materials remain, resulting in low product purity and the product becoming colored and emitting a strange odor over time. is unsuitable as a manufacturing method in the fragrance field. There is also a method of producing it by gas phase dehydrogenation of piperazine (USP 2, 400398), but this method has the disadvantage that piperazine is expensive. A method of reacting an α-diamine compound and an α-epoxide compound in the gas phase in the presence of a catalyst (Japanese Unexamined Patent Publication No. 49
-101391), it is difficult to obtain the desired single pyrazine compound (). The present inventor has developed a pyrazine compound () with a high purity of 99.9% by reacting the dihydropyrazine compound () with a metal oxide in a basic inert solvent.
The present invention was successful in obtaining the following with a high yield of over 80%. The starting material dihydropyrazine compound () is α
- It is obtained by condensation of a dicarbonyl compound and α-diamine. As the metal oxide, oxides of manganese, copper, and lead can be used, and manganese dioxide, cupric oxide, and trilead tetroxide are suitable. Methanol, ethanol, ethylene glycol, etc. can be used as the reaction medium, preferably 10 to 20 times the weight of the dihydropyrazine compound ().
It is better to use twice as much. When the reaction between the dihydropyrazine compound () and the metal oxide is carried out under acidic conditions, the product becomes a blackish brown resin, and the reaction does not proceed under neutral conditions. When carried out under basic conditions, the above-mentioned good results can be obtained. A dihydropyrazine compound () and a metal oxide are mixed in a molar ratio of 1:1.5 to 4 under refluxing of a solvent.
By holding for a certain period of time, the desired pyrazine compound () can be obtained. Examples 1 to 12 Potassium hydroxide (Cg) and metal oxide (Dg) were added to an ethanol (Bml) solution of dihydropyrazine compound (Ag), and after heating under reflux for E hours, the precipitate was removed by filtration, and the precipitate was removed from the filtrate. Distill the ethanol until it becomes 1/4 volume, mix the residue with 4 times the volume of benzene and saturated saline, separate the benzene layer, distill off the benzene, and then distill the residue under reduced pressure. ,F
A fraction of °C/GmmHg is obtained. A gas chromatogram, a mass spectrum, an infrared absorption spectrum and a nuclear magnetic resonance absorption spectrum were examined for this, and it was confirmed that it was a pyrazine compound () corresponding to the compound (). The data resulting from the above processing is
It is shown in Table and Table 2.
【表】【table】
【表】【table】
Claims (1)
素原子、炭素数１〜４のアルキル基はアルケニル
基を意味し、或はR1とR2またはR3とR4が一緒に
なつてｎ−ブチレン基を意味する）を有するジヒ
ドロピラジン化合物（）とマンガン、銅又は酸
化物を塩基性溶媒中で加熱することを特徴とする 一般式 （但しR1，R2，R3，R4は上記と同じ） を有するピラジン化合物（）の製法。[Claims] 1. General formula (However, R 1 , R 2 , R 3 , and R 4 are the same or different, and represent a hydrogen atom, and an alkyl group having 1 to 4 carbon atoms means an alkenyl group, or R 1 and R 2 or R 3 and R 4 A dihydropyrazine compound (2) having (together meaning an n-butylene group) and a manganese, copper or oxide are heated in a basic solvent. (However, R 1 , R 2 , R 3 , and R 4 are the same as above.) A method for producing a pyrazine compound ( ).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5271276A JPS52136182A (en) | 1976-05-07 | 1976-05-07 | Production of pyradine compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5271276A JPS52136182A (en) | 1976-05-07 | 1976-05-07 | Production of pyradine compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS52136182A JPS52136182A (en) | 1977-11-14 |
| JPS6128671B2 true JPS6128671B2 (en) | 1986-07-01 |
Family
ID=12922501
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5271276A Granted JPS52136182A (en) | 1976-05-07 | 1976-05-07 | Production of pyradine compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS52136182A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11773904B2 (en) | 2019-05-21 | 2023-10-03 | Osaka Fuji Corporation | Ball bearing and method for manufacturing same |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5015157A (en) * | 1990-01-10 | 1991-05-14 | Dennis Pinkerton | Pump with multi-port discharge |
| DE10022361C1 (en) | 2000-05-08 | 2001-05-23 | Haarmann & Reimer Gmbh | Preparation of 2-ethyl-3-methyl-1,4-diazine |
-
1976
- 1976-05-07 JP JP5271276A patent/JPS52136182A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11773904B2 (en) | 2019-05-21 | 2023-10-03 | Osaka Fuji Corporation | Ball bearing and method for manufacturing same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS52136182A (en) | 1977-11-14 |
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