Triethylamine → HCID 178503946, compound

HRID 1498103Notes

Reaction equation

HRID 1498103 reaction equation
[Br:1][C:2]1[CH:18]=[CH:17][C:5]2[C:6]3[N:10]([CH2:11][CH2:12][O:13][C:4]=2[CH:3]=1)[CH:9]=[C:8]([C:14]([OH:16])=O)[N:7]=3.C(Cl)(=O)C(Cl)=O.[C:25]([O:29][C:30]([NH:32][C:33](=[NH:36])[S:34][CH3:35])=[O:31])([CH3:28])([CH3:27])[CH3:26].C(N(CC)CC)C>C(Cl)Cl.CN(C)C=O.O>[C:25]([O:29][C:30](=[O:31])[NH:32]/[C:33](=[N:36]\[C:14]([C:8]1[N:7]=[C:6]2[N:10]([CH2:11][CH2:12][O:13][C:4]3[CH:3]=[C:2]([Br:1])[CH:18]=[CH:17][C:5]=32)[CH:9]=1)=[O:16])/[S:34][CH3:35])([CH3:28])([CH3:26])[CH3:27]

Participants

8

Reactant 4

HCID 8471TriethylamineHCID 65578Oxalyl chlorideHCID 582043519-Bromo-5,6-dihydrobenzo[F]imidazo[1,2-D][1,4]oxazepine-2-carboxylic acidHCID 137319820tert-butyl N-[(methylsulfanyl)methanimidoyl]carbamate

Product 1

HCID 178503946HCID 178503946, compoundYield 50.4%

Reagents, catalysts & solvents 3

HCID 6228DimethylformamideCatalystHCID 962WaterSolventHCID 6344DichloromethaneSolvent3×

Procedure

To a solution of 8-Bromo-4,5-dihydro-6-oxa-1,3a-diaza-benzo[e]azulene-2-carboxylic acid (0.839 g, 0.00271 mol) and oxalyl chloride (2M in DCM, 1.36 mL, 0.002714 mol), in methylene chloride (16.70 mL) under nitrogen atmosphere was added 1 drop of N,N-dimethylformamide. The solution was stirred at room temperature for 2 h. The reaction was concentrated in vacuo and the acid chloride was redissolved in methylene chloride (9.0 mL). The solution was added dropwise to a solution of N-tertbutoxycarbonyl-S-methylpseudothiourea (0.5164 g, 0.002714 mol) and triethylamine (1.173 mL, 0.008414 mol) in methylene chloride (9.0 mL). The reaction was stirred at room temperature for 1.5 h. Methylene chloride and water were added and the mixture was extracted 3× with methylene chloride. Saturated sodium carbonate was then added and the mixture was extracted with chloroform. The organic layers were combined and concentrated. The product was redissolved in methylene chloride and methanol and filtered. The filtrate was collected, concentrated and dry loaded onto silica gel and purified by flash chromatography (0-15% MeOH in DCM) to give {[(E)-8-Bromo-4,5-dihydro-6-oxa-1,3a-diaza-benzo[e]azulene-2-carbonylimino]-methylthiomethyl}-carbamic acid tert-butyl ester (658 mg) as an off-white solid. MS(ESI+) 481.0/483.0

Workup

  1. concentrationThe reaction was concentrated in vacuo
  2. dissolutionthe acid chloride was redissolved in methylene chloride (9.0 mL)
  3. stirringThe reaction was stirred at room temperature for 1.5 h
  4. extractionthe mixture was extracted 3× with methylene chloride
  5. additionSaturated sodium carbonate was then added
  6. extractionthe mixture was extracted with chloroform
  7. concentrationconcentrated
  8. dissolutionThe product was redissolved in methylene chloride
  9. filtrationmethanol and filtered
  10. customThe filtrate was collected
  11. concentrationconcentrated
  12. customdry
  13. custompurified by flash chromatography (0-15% MeOH in DCM)

Sources & evidence

ORD record
ord-19072a79bb3f477db7863e85f5612f38
Source dataset
uspto-grants-2015_12
Patent number
US09198918B2

Reaction notes

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