Benzylamine → HCID 178507216, Verbindung

HRID 1386128

Reaktionsgleichung

Reaktionsgleichung von HRID 1386128
[NH2:1][C:2]1[CH:7]=[C:6]([NH2:8])[C:5]([C:9]#[N:10])=[CH:4][N:3]=1.[CH2:11](NC1C2N=CC=CC=2N=CN=1)C1C=CC=CC=1.C(N)C1C=CC=CC=1.C([O-])([O-])OCC.C(OC(=O)C)(=O)C.[SH-:50]>C(O)=O>[NH2:1][C:2]1[N:3]=[CH:4][C:5]2[C:9](=[S:50])[NH:10][CH:11]=[N:8][C:6]=2[CH:7]=1

Komponenten

7

Edukt 5

HCID 7504BenzylamineHCID 2958964,6-DiaminonicotinonitrileHCID 5047209HydrosulfideHCID 5328272N-benzylpyrido[3,2-d]pyrimidin-4-amineHCID 86583744Ethyl orthoformate acetic anhydride

Produkt 1

HCID 178507216HCID 178507216, Verbindung

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 284Formic AcidLösungsmittel

Versuchsvorschrift

2,4-Diamino-5-cyanopyridine can be cyclized directly to many 4-benzylaminopyridopyrimidine derivatives by treatment with the benzylamine and formic acid at high temperature. For less nucleophilic amines 2,4-diamino-5-cyanopyridine is converted via ethyl orthoformate/acetic anhydride treatment, followed by cyclization with hydrosulfide ion in anhydrous conditions, to give 7-amino-4-thiono-3H-pyrido[4,3-d]pyrimidine. S-Alkylation and displacement with an appropriate amine gives the desired product. If R4 is not amino, the amine can be acylated, or reductively alkylated. Alternatively 2,4-diamino-5-cyanopyridine can be hydrolysed to the corresponding amide, and this species can be cyclized to 7-amino-4-oxo-3H-pyrido[4,3-d]pyrimidine with orthoformate. Diazotization of the 7-amine and replacement with fluorine allows for introduction of other amine and alkoxide nucleophiles at the end of the synthesis after the C4 substituent has been introduced in the usual manner. Diazotization and replacement of the amine with bromide allows for Stille couplings at the 7-position.

Quellen und Nachweise

ORD-Eintrag
ord-28a54f39906049b9b4f78fce7649d3db
Quelldatensatz
uspto-grants-2001_07
Patentnummer
US06265410B1

Verknüpfte Notizen

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