JPS5811901B2 - Method for producing quinazolone derivatives - Google Patents
Method for producing quinazolone derivativesInfo
- Publication number
- JPS5811901B2 JPS5811901B2 JP11565674A JP11565674A JPS5811901B2 JP S5811901 B2 JPS5811901 B2 JP S5811901B2 JP 11565674 A JP11565674 A JP 11565674A JP 11565674 A JP11565674 A JP 11565674A JP S5811901 B2 JPS5811901 B2 JP S5811901B2
- Authority
- JP
- Japan
- Prior art keywords
- producing
- parts
- quinazoline
- group
- pyrimide
- 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
Landscapes
- Nitrogen Condensed Heterocyclic Rings (AREA)
Description
【発明の詳細な説明】
本発明は、キナゾロン誘導体の製造法に関するものであ
り、更に詳しくは、６，１４−ジヒドロピリド〔２，１
−ｂ〕ピリド〔１´、２´：１，２〕ピリミド〔４，５
−ｇ〕キナゾリン−７，１５−ジオン類の製造法に関す
るものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing quinazolone derivatives.
-b]Pyrido[1',2':1,2]Pyrimide[4,5
-g] This relates to a method for producing quinazoline-7,15-diones.
即ち、本発明は、一般式
（式中Ｒ１はメチル基、エチル基などのアルキル基を示
す。That is, the present invention relates to the general formula (wherein R1 represents an alkyl group such as a methyl group or an ethyl group).
）で示される１、４− ビス（アルコキシカルボニル）
−２，５−ジアミノ−１，４−シクロヘキサジエン類を
溶媒中、酸の存在下で、一般式
（式中Ｒ２〜Ｒ４は水素又はメチル基、エチル基などの
アルキル基を示す。) 1,4-bis(alkoxycarbonyl)
-2,5-diamino-1,4-cyclohexadiene in a solvent in the presence of an acid to form a compound of the general formula (wherein R2 to R4 represent hydrogen or an alkyl group such as a methyl group or an ethyl group).
）で示される２−アミノピリジン類と反応させ、−般式 （式中Ｒ２〜Ｒ４は前記したものと同じ。) is reacted with 2-aminopyridines represented by - general formula (In the formula, R2 to R4 are the same as described above.
）で示される６、１４−ジヒドロピリド〔２，１−ｂ〕
ピリド〔１´、２´：１，２〕ピリミド〔４，５−ｇ〕
キナゾリン−７，１５−ジオン類を製造することを特徴
とするキナゾリン誘導体の製造法を提供するものである
。) 6,14-dihydropyrido [2,1-b]
Pyrido [1', 2':1,2] Pyrimide [4,5-g]
The present invention provides a method for producing quinazoline derivatives, which is characterized by producing quinazoline-7,15-diones.
本発明の反応式をＲ１が−Ｃ２Ｈ３，Ｒ２〜Ｒ４が水素
である場合について示せは、次のとおりである。The reaction formula of the present invention when R1 is -C2H3 and R2 to R4 are hydrogen is as follows.
本発明で用いられる溶媒としては、出発物質及び生成物
に対して不活性なものであれば特に厳密な限定を必要と
はしないが、特に酢酸、Ｎ−メチル−２−ピロリドン、
ジメチルスルホキシド、ジメチルアセトアミド、ジメチ
ルホルムアミドなどのような比較的極性の強い溶媒が好
ましい。The solvent used in the present invention is not particularly limited as long as it is inert to the starting materials and products, but in particular acetic acid, N-methyl-2-pyrrolidone,
Relatively polar solvents such as dimethyl sulfoxide, dimethylacetamide, dimethylformamide, etc. are preferred.
また、これらの溶媒の使用量は、出発物質の総数の３〜
２０重量倍、好ましくは５〜１５重量倍である。In addition, the amount of these solvents used is 3 to 3 of the total number of starting materials.
It is 20 times by weight, preferably 5 to 15 times by weight.
本発明に用いられる縮合剤としての酸は、硫酸、塩酸、
ｐ−トルエンスルホン酸、酢酸などが好ましい。Acids used as condensing agents in the present invention include sulfuric acid, hydrochloric acid,
Preferred are p-toluenesulfonic acid, acetic acid, and the like.
また、その使用量は、出発物質である１゜４−ビス（ア
ルコキシカルボニル）−２，５−ジアミノ−１，４−シ
クロヘキサジエン類１モルに対して０．０５〜０．２モ
ルが適当である。Further, the appropriate amount to be used is 0.05 to 0.2 mol per 1 mol of 1゜4-bis(alkoxycarbonyl)-2,5-diamino-1,4-cyclohexadiene as the starting material. be.
特に酢酸を使用する場合は、その量を増加させることに
より、縮合触媒としての使用のほかに、溶媒としての効
果をも得られる。Particularly when acetic acid is used, by increasing its amount, it can be used not only as a condensation catalyst but also as a solvent.
本発明の反応は、上記した条件の下では１００〜２００
℃で約３時間以上加熱することによって容易に進行する
。The reaction of the present invention has a reaction rate of 100 to 200 under the conditions described above.
The process can be easily carried out by heating at ℃ for about 3 hours or more.
本発明により得られる６、１４−ジヒドロピリド〔２，
１−ｂ〕ピリド〔１´、２´：１，２〕ピリミド〔４，
５−ｇ〕キナゾリン−７，１５−ジオン類は白色結晶で
、融点は３００℃以上である。6,14-dihydropyride [2,
1-b] Pyrido [1', 2':1,2] Pyrimide [4,
5-g] Quinazoline-7,15-diones are white crystals with a melting point of 300°C or higher.
また、このものはアルコール、アセトン、ｎ−ヘキサン
、ベンゼン等の一般の有機溶媒にはほとんど不溶である
が、希硫酸には溶解する。Further, this product is almost insoluble in general organic solvents such as alcohol, acetone, n-hexane, and benzene, but it is soluble in dilute sulfuric acid.
本発明により得られるキナゾロン誘導体、６゜１４−ジ
ヒドロピリド〔２，１−ｂ〕ピリド〔１′。Quinazolone derivative obtained according to the present invention, 6°14-dihydropyrido[2,1-b]pyrido[1'.
２´：１，２〕ピリミド〔４，５−ｇ〕キナゾリン−７
，１５−ジオン類は有用な中間体であって、これを有機
溶媒中、空気またはニトロベンゼン−ｍ−スルホン酸ナ
トリウムのような酸化剤の存在下で酸化することにより
、赤色顔料として有用なピリド〔２，１−ｂ〕ピリド〔
１´、２´：１，２〕ピリミド〔４，５−ｇ〕キナゾリ
ン７．１５−ジオン類を製造することができる。2′:1,2]pyrimide[4,5-g]quinazoline-7
, 15-diones are useful intermediates that can be oxidized in an organic solvent in the presence of air or an oxidizing agent such as sodium nitrobenzene-m-sulfonate to form pyridos useful as red pigments. 2,1-b] pyrido [
1', 2': 1,2]pyrimido[4,5-g]quinazoline 7,15-diones can be produced.
次に本発明を実施例により説明するが、本発明はこれに
よって限定されるものではない。Next, the present invention will be explained by examples, but the present invention is not limited thereto.
実施例中、単に部とあるのは重量部を示す。In the examples, parts simply indicate parts by weight.
実施例 １
１．４−ビス（エトキシカルボニル）−２，５−ジアミ
ノ−１，４−シクロヘキサジエン５部と２−アミノピリ
ジン５部及び氷酢酸５０容量部とをフラスコに装入し、
窒素雰囲気下に１０時間加熱還流させた。Example 1 A flask was charged with 5 parts of 1.4-bis(ethoxycarbonyl)-2,5-diamino-1,4-cyclohexadiene, 5 parts of 2-aminopyridine, and 50 parts by volume of glacial acetic acid,
The mixture was heated under reflux for 10 hours under a nitrogen atmosphere.
次いで内容物を室温まで冷却し、生成した白色結晶を濾
過し、得られたケーキを酢酸とメタノールで充分洗浄し
たのち、６０℃で乾燥したところ、１．５ｇの白色結晶
が得られた。The contents were then cooled to room temperature, the white crystals formed were filtered, the resulting cake was thoroughly washed with acetic acid and methanol, and then dried at 60°C to obtain 1.5 g of white crystals.
この生成物の特性は次のとおりである。The properties of this product are as follows.
また、この生成物の赤外線吸収スペクトルは、１６７２
ｃｍ−１と１６３０ｃｍ−１にそれぞれＣ＝Ｏ及びＣ＝
Ｎ伸縮に起因すると思われる吸収があり、１５７０ｃｍ
−１・１５３０ｃｍ−１・１４９０ｃｍ−１に縮合環の
伸縮に起因すると思われる吸収が、更に１４２０ｃｍ−
１にシクロヘキサジエン環のＣＨ変角、及び７７０ｃｍ
−１に芳香核プロトンの面外変角振動に基づく特性吸収
が存在する。In addition, the infrared absorption spectrum of this product is 1672
C=O and C= at cm-1 and 1630 cm-1, respectively
There is absorption that is thought to be due to N expansion and contraction, and the height is 1570 cm.
-1・1530cm−1・1490cm−1, there is an absorption at 1420cm−1 that is thought to be caused by the expansion and contraction of the condensed ring.
1, CH bending angle of cyclohexadiene ring, and 770 cm
-1, there is a characteristic absorption based on the out-of-plane bending vibration of aromatic nucleus protons.
従って、この生成物は、６，１４−ジヒドロピリド〔２
，１−ｂ〕ピリド（１´、２´：１，２〕ピリミド〔４
，５−ｇ〕キナゾリン−７，１５−ジオンであるものと
推定される。Therefore, this product is 6,14-dihydropyrido [2
, 1-b] Pyrido (1', 2': 1, 2) Pyrimide [4
, 5-g] quinazoline-7,15-dione.
紫外線吸収スペクトルを測定したところ、２４０ｎｍと
３２２ｎｍとに特性吸収が認められ、また、ＮＭＲスペ
クトルをトリフルオル酢酸中で測定した結果は、次のと
おりであった。When an ultraviolet absorption spectrum was measured, characteristic absorption was observed at 240 nm and 322 nm, and an NMR spectrum was measured in trifluoroacetic acid, and the results were as follows.
以上の元素分析、赤外線吸収スペクトル、紫外線吸収ス
ペクトル更にＮＭＲスペクトルの結果よりこの生成物は
、６，１４−ジヒドロピリド〔２゜１−ｂ〕ピリド〔１
´、２´：１，２〕ピリミド〔４゜５−ｇ〕キナゾリン
−７，１５−ジオンであることが確認された。From the results of the above elemental analysis, infrared absorption spectrum, ultraviolet absorption spectrum, and NMR spectrum, this product was found to be 6,14-dihydropyrido[2゜1-b]pyrid[1
',2':1,2]pyrimide[4°5-g]quinazoline-7,15-dione was confirmed.
実施例 ２
１．４−ビス（エトキシカルボニル）−２，５−ジアミ
ノ−１，４−シクロヘキサジエン５部と２−アミノ−３
−メチルピリジン５部及び酢酸５０容量部とをフラスコ
に装入し、実施例１に準じて反応させ、処理した結果、
１．０ｇの白色結晶が得られた。Example 2 5 parts of 1,4-bis(ethoxycarbonyl)-2,5-diamino-1,4-cyclohexadiene and 2-amino-3
- 5 parts of methylpyridine and 50 parts by volume of acetic acid were charged into a flask and reacted and treated according to Example 1. As a result,
1.0 g of white crystals were obtained.
この生成物の融点は３００℃以上であり、また元素分析
の結果は次のとおりであった。The melting point of this product was 300°C or higher, and the results of elemental analysis were as follows.
以上の元素分析の結果及び赤外線吸収スペクトル及びＮ
ＭＲスペクトルの結果から、この生成物は６，１４−ジ
ヒドロ−４，１２−ジメチルピリド〔２，１−ｂ〕ピリ
ド〔１´、２´：１，２〕ピリミド〔４，５−ｇ〕キナ
ゾリン−７，１５−ジオンであることが確認された。Results of the above elemental analysis, infrared absorption spectrum and N
According to the results of the MR spectrum, this product is 6,14-dihydro-4,12-dimethylpyrido[2,1-b]pyrido[1',2':1,2]pyrimide[4,5-g]quinazoline- It was confirmed to be 7,15-dione.
実施例 ３
１．４−ビス（エトキシカルボニル）−２，５−ジアミ
ノ−１，４−シクロヘキサジエン５部、２−アミノピリ
ジン５部、ｐ−トルエンスルホン酸０．５部及びｎ−メ
チル−２−ピロリドン５０容量部とをフラスコに装入し
、窒素雰囲気下に３時間加熱還流させた。Example 3 1,4-bis(ethoxycarbonyl)-2,5-diamino-1,4-cyclohexadiene 5 parts, 2-aminopyridine 5 parts, p-toluenesulfonic acid 0.5 part and n-methyl-2 - 50 parts by volume of pyrrolidone were placed in a flask and heated under reflux for 3 hours under a nitrogen atmosphere.
次いで内容物を室温まで冷却し、生成した結晶を濾別し
、得られたケーキを熱酢酸で洗浄して乾燥したところ、
実施例１で得た生成物と同様の生成物２０ｇが得られた
。The contents were then cooled to room temperature, the formed crystals were filtered off, and the resulting cake was washed with hot acetic acid and dried.
20 g of a product similar to that obtained in Example 1 was obtained.
実施例 ４
１．４−ビス（エトキシカルボニル）−２，５−ジアミ
ノ−１，４−シクロヘキサジエン５部と２−アミノ−５
−メチルピリジン５部及び氷酢酸５０容量部とをフラス
コに装入し、実施例１に準じて反応させ、処理した結果
、６，１４−ジヒドロ−２，１０−ジメチル−ピリド〔
２，１−ｂ〕ピリド〔１´、２´：１，２〕ピリミド〔
４，５−ｇ〕キナゾリン−７，１５−ジオン１．５ｇが
得られた。Example 4 5 parts of 1,4-bis(ethoxycarbonyl)-2,5-diamino-1,4-cyclohexadiene and 2-amino-5
- 5 parts of methylpyridine and 50 parts by volume of glacial acetic acid were charged into a flask and reacted according to Example 1. As a result of the treatment, 6,14-dihydro-2,10-dimethyl-pyrid [
2,1-b] Pyrido [1', 2':1,2] Pyrimide [
4,5-g] Quinazoline-7,15-dione (1.5 g) was obtained.
この生成物の元素分析の結果は、次のとおりであった。The results of elemental analysis of this product were as follows.
Claims (1)
す。 ）で示される１、４−ビス（アルコキシカルボニル）−
２，５−ジアミノ−１，４−シクロヘキサジエン類を溶
媒中酸の存在下で、一般式 （式中Ｒ２〜Ｒ４は水素又はメチル基、エチル基などの
アルキル基を示す。 ）で示される２−アミノピリジン類と反応させ、一般式 （式中Ｒ２〜Ｒ４は水素又はメチル基、エチル基などの
アルキル基を示す。 ）で示される６、１４−ジヒドロピリド〔２，１−ｂ〕
ピリド〔１’、２’：１，２〕ピリミド〔４，５−ｇ〕
キナゾリン−７，１５−ジオン類を製造することを特徴
とするキナゾロン誘導体の製造法。[Scope of Claims] 1 1,4-bis(alkoxycarbonyl)- represented by the general formula (wherein R1 represents an alkyl group such as a methyl group or an ethyl group)
2,5-diamino-1,4-cyclohexadiene in a solvent in the presence of an acid, 2 represented by the general formula (wherein R2 to R4 represent hydrogen or an alkyl group such as a methyl group or an ethyl group) -6,14-dihydropyride [2,1-b] represented by the general formula (wherein R2 to R4 represent hydrogen or an alkyl group such as a methyl group or an ethyl group) by reacting with an aminopyridine.
Pyrido[1',2':1,2]pyrimide[4,5-g]
1. A method for producing quinazolone derivatives, which comprises producing quinazoline-7,15-diones.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11565674A JPS5811901B2 (en) | 1974-10-09 | 1974-10-09 | Method for producing quinazolone derivatives |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11565674A JPS5811901B2 (en) | 1974-10-09 | 1974-10-09 | Method for producing quinazolone derivatives |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5142723A JPS5142723A (en) | 1976-04-12 |
| JPS5811901B2 true JPS5811901B2 (en) | 1983-03-05 |
Family
ID=14668033
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11565674A Expired JPS5811901B2 (en) | 1974-10-09 | 1974-10-09 | Method for producing quinazolone derivatives |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5811901B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0685640B2 (en) * | 1984-07-11 | 1994-10-26 | 株式会社日立製作所 | AC generator |
-
1974
- 1974-10-09 JP JP11565674A patent/JPS5811901B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5142723A (en) | 1976-04-12 |
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