Hydrazine → [1,2,5]Thiadiazolo[3,4-b]pyrazine-5,6-diamine

HRID 974222Notes

Reaction equation

HRID 974222 reaction equation
C1(=O)[N:5]([C:6]2[C:11]([N:12]3C(=O)C4=CC=CC=C4C3=O)=[N:10][C:9]3=[N:23][S:24][N:25]=[C:8]3[N:7]=2)C(=O)C2=CC=CC=C12.NN>>[NH2:12][C:11]1[C:6]([NH2:5])=[N:7][C:8]2=[N:25][S:24][N:23]=[C:9]2[N:10]=1

Participants

3

Reactant 2

HCID 9321HydrazineHCID 14495955HCID 14495955, compound

Product 1

HCID 312908[1,2,5]Thiadiazolo[3,4-b]pyrazine-5,6-diamine

Procedure

The cyclization reaction of o-diaminobenzene (compound II) in an aqueous solution of glyoxal and sodium hydrogen sulfite gives quinoxaline (compound III; See R. G. Jones et al., Org. Syn. Collective Vol. IV, page 824). Quinoxaline is in turn oxidized by an aqueous solution of potassium permanganate to produce 2,3-pyrazinedicarboxylic acid (compound IV; See R. G. Jones et al., Org. Syn. Collective Vol. IV, page 824). 2,3-pyrazinedicarboxylic acid is then chlorinated with phosphorus pentachloride at 300° C. to produce 2,3,5,6-tetrachloropyrazine (compound V; See C. G. Allison et al., J. Chem. Soc. (C), 1970, page 1023). The reaction of 2,3,5,6-tetrachloropyrazine with ammonium chloride at a temperature of 120° C. gives 2,3-diamino-5,6-dichloropyrazine (compound VI; See Palamidess et al., Ed. Sc. XXI-fasc, 11, 1966, page 810). The cyclization reaction of 2,3-diamino-5,6-dichloropyrazine with thionyl chloride in the presence of pyridine in xylene produces 5,6-dichloro-[1,2,5]thiadiazolo[3,4-b]pyrazine (compound VII; See Y. C. Tong, J. Heterocyclic Chem., 12, 1975, page 451 ) The 5,6-dichloro-[1,2,5]thiadiazolo[3,4-b]pyrazine is reacted with potassium phthalimide in the presence of dimethyl formamide (DMF) at a temperature of 60° C. to produce 5,6-diphtalimido-[1,2,5]thiadiazolo[3,4-b]pyrazine (compound VIII; See Example 1). The 5,6-diphthalimido-[1,2,5]thiadiazolo[3,4-b]pyrazine is then reacted with an aqueous solution of hydrazine at 0° C. to produce 5,6-diamino-[1,2,5]thiadiazolo[3,4-b]pyrazine (compound IX; See Example 2). Finally the cyclization reaction of 5,6-diamino[1,2,5]thiadiazolo[3,4-b]pyrazine with thionyl chloride in the presence of pyridine in methylene chloride gives bis[1,2,5]thiadiazolo[3,4-b: 3',4'-e]pyrazine (compound I; See Example 3).

Sources & evidence

ORD record
ord-db3ae699fcbf4201afb9819875971245
Source dataset
uspto-grants-1991_11
Patent number
US05068328

Reaction notes

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