Dimethylcarbamoyl Chloride → HCID 89610413, compound

HRID 1507719Notes

Reaction equation

HRID 1507719 reaction equation
[CH3:1][N:2]([CH3:6])[C:3](Cl)=[O:4].[CH3:7][N:8]([CH3:31])[C:9]([C:11]1[N:15]([C:16]2[CH:21]=[CH:20][C:19]([O:22][CH3:23])=[CH:18][CH:17]=2)[C:14]([C:24]([O:26][CH2:27][CH3:28])=[O:25])=[C:13]([OH:29])[C:12]=1[OH:30])=[O:10].C([O-])([O-])=O.[K+].[K+]>CC#N>[CH3:31][N:8]([CH3:7])[C:9]([C:11]1[N:15]([C:16]2[CH:17]=[CH:18][C:19]([O:22][CH3:23])=[CH:20][CH:21]=2)[C:14]([C:24]([O:26][CH2:27][CH3:28])=[O:25])=[C:13]([OH:29])[C:12]=1[O:30][C:3](=[O:4])[N:2]([CH3:6])[CH3:1])=[O:10]

Participants

5

Reactant 3

HCID 6598Dimethylcarbamoyl ChlorideHCID 11430Potassium CarbonateHCID 71576576HCID 71576576, compound

Product 1

HCID 89610413HCID 89610413, compoundYield 6%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

Dimethylcarbamic chloride (163 μL, 1.77 mmol) was added dropwise to a stirred suspension of ethyl 5-(dimethylcarbamoyl)-3,4-dihydroxy-1-(4-methoxyphenyl)-1H-pyrrole-2-carboxylate (UL1-012) (494 mg, 1.42 mmol) and K2CO3 (255 mg, 1.85 mmol) in MeCN (8 mL). The resulting mixture was stirred at RT for 24 h then partitioned between water (30 mL) and DCM (20 mL) the aqueous layer was extracted with DCM (2×20 mL), the combined organics were dried (MgSO4), filtered and solvents removed in vacuo to give an orange oil. The residue was purified by silica gel chromatography (12 g, 0-10% MeOH (+1% NH3) in DCM) to afford ethyl 5-(dimethylcarbamoyl)-4-((dimethylcarbamoyl)oxy)-3-hydroxy-1-(4-methoxyphenyl)-1H-pyrrole-2-carboxylate (UL1-066) (35 mg, 6%) as a white solid: m/z 420 (M+H)+ (ES+). 1H NMR (400 MHz, DMSO-d6) δ: 8.85 (s, 1H), 7.16-7.06 (m, 2H), 6.95-6.86 (m, 2H), 4.00 (q, J=7.1 Hz, 2H), 3.77 (s, 3H), 2.98 (s, 3H), 2.88 (s, 3H), 2.78 (s, 3H), 2.69 (s, 3H), 1.00 (t, J=7.1 Hz, 3H).

Workup

  1. customthen partitioned between water (30 mL) and DCM (20 mL) the aqueous layer
  2. extractionwas extracted with DCM (2×20 mL)
  3. dry with materialthe combined organics were dried (MgSO4)
  4. filtrationfiltered
  5. customsolvents removed in vacuo
  6. customto give an orange oil
  7. customThe residue was purified by silica gel chromatography (12 g, 0-10% MeOH (+1% NH3) in DCM)

Sources & evidence

ORD record
ord-1cae17e240f641b7ad9a724b82edb72a
Source dataset
uspto-grants-2015_12
Patent number
US09221756B2

Reaction notes

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