1-Isopropylhydrazine hydrochloride → 8-Bromo-2-(2-isopropyl-5-methyl-2H-[1,2,4]triazol-3-yl)-4,5-dihydro-6-oxa-3-thia-1-aza-benzo[e]azulene

HRID 708269Notes

Reaction equation

HRID 708269 reaction equation
[Br:1][C:2]1[CH:18]=[CH:17][C:5]2[C:6]3[N:7]=[C:8]([C:14]([NH2:16])=O)[S:9][C:10]=3[CH2:11][CH2:12][O:13][C:4]=2[CH:3]=1.CO[C:21](OC)(N(C)C)[CH3:22].Cl.[CH:29]([NH:32][NH2:33])([CH3:31])[CH3:30]>C1(C)C=CC=CC=1>[Br:1][C:2]1[CH:18]=[CH:17][C:5]2[C:6]3[N:7]=[C:8]([C:14]4[N:32]([CH:29]([CH3:31])[CH3:30])[N:33]=[C:21]([CH3:22])[N:16]=4)[S:9][C:10]=3[CH2:11][CH2:12][O:13][C:4]=2[CH:3]=1

Participants

5

Reactant 3

HCID 855731-Isopropylhydrazine hydrochlorideHCID 878351,1-Dimethoxyethyl(dimethyl)amineHCID 670505308-Bromo-4,5-dihydro-6-oxa-3-thia-1-aza-benzo[e]azulene-2-carboxylic acid amide

Product 1

HCID 582039088-Bromo-2-(2-isopropyl-5-methyl-2H-[1,2,4]triazol-3-yl)-4,5-dihydro-6-oxa-3-thia-1-aza-benzo[e]azuleneYield 92.5%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
95 °C

Procedure

To a solution of 8-Bromo-4,5-dihydro-6-oxa-3-thia-1-aza-benzo[e]azulene-2-carboxylic acid amide (9.040 g, 0.02780 mol) in Toluene (150 mL) was added dimethylacetamide-dimethylacetal (12.38 mL, 0.08340 mol). The reaction was stirred at 95° C. for 4 hours. The toluene was then removed in vacuo and the crude was carried forward without further purification. The crude material was redissolved in acetic acid (90 mL). Isopropylhydrazine hydrochloride (3.689 g, 0.03336 mol) was added and the reaction was stirred at room temperature overnight. The acetic acid was then removed in vacuo. The crude material was triturated in isopropyl alcohol, and filtered to give 8-Bromo-2-(2-isopropyl-5-methyl-2H-[1,2,4]triazol-3-yl)-4,5-dihydro-6-oxa-3-thia-1-aza-benzo[e]azulene as a light yellow solid (10.422 g). MS(ESI+) 405.0/407.0

Workup

  1. customThe toluene was then removed in vacuo
  2. customthe crude was carried forward without further purification
  3. dissolutionThe crude material was redissolved in acetic acid (90 mL)
  4. stirringthe reaction was stirred at room temperature overnight
  5. customThe acetic acid was then removed in vacuo
  6. customThe crude material was triturated in isopropyl alcohol
  7. filtrationfiltered

Sources & evidence

ORD record
ord-958f25b24fb34a22bed8cd955c4ac502
Source dataset
uspto-grants-2015_11
Patent number
US09175009B2

Reaction notes

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