Sulfamic Acid → HCID 86749556, compound

HRID 260166Notes

Reaction equation

HRID 260166 reaction equation
[NH2:1][C:2]1[CH:3]=[C:4]([NH:9][C:10](=[O:16])[O:11][C:12]([CH3:15])([CH3:14])[CH3:13])[CH:5]=[C:6]([I:8])[CH:7]=1.N([O-])=O.[Na+].S(=O)(=O)(O)N.[N-:26]=[N+:27]=[N-].[Na+]>CO.Cl.O.C(Cl)(Cl)Cl>[N:1]([C:2]1[CH:3]=[C:4]([NH:9][C:10](=[O:16])[O:11][C:12]([CH3:13])([CH3:15])[CH3:14])[CH:5]=[C:6]([I:8])[CH:7]=1)=[N+:26]=[N-:27]

Participants

9

Reactant 4

HCID 5987Sulfamic AcidHCID 33557Sodium AzideHCID 23668193Sodium NitriteHCID 57166986HCID 57166986, compound

Product 1

HCID 86749556HCID 86749556, compoundYield 86.3%

Reagents, catalysts & solvents 4

HCID 313Hydrochloric AcidSolventHCID 887MethanolSolventHCID 962WaterSolventHCID 6212ChloroformSolvent

Conditions

Temperature
0 °C

Procedure

A stirred solution of 3-amino-5-iodophenylcarbamic acid, 1,1-dimethylethyl ester (A-2, 4.32 g, 13.0 mmol) in methanol (115 mL) and 1 N aqueous HCl (115 mL) is cooled to 0° C., add 1.2 M aqueous NaNO2 (12.9 mL). The reaction mixture is stirred at 0° C. for 25 min, then sulfamic acid (1.26 g, 13.0 mmol) is added followed by sodium azide (1.01 g, 15.6 mmol) in water (6 mL). Stirring is continued at 0° C. for thirty minutes and then the reaction mixture is poured into chloroform (400 mL). The phases are separated and the aqueous phase is extracted with chloroform (2×150 mL). The combined organics are dried (MgSO4), filtered and concentrated. The organic residue is purified by flash chromatography using 20% ethyl acetate in hexane as the eluent to afford 4.04 g of 3-azido-5-iodophenylcarbamic acid, 1,1 -dimethylethyl ester (A-3) as an orange colored oil. This material is used immediately in the next reaction, Step A-4. IR (liquid)3308, 2981, 2119, 2105, 1709, 1691, 1599, 1580, 1537, 1528, 1456, 1451, 1414, 1367, 1276, 1257, 1244, 1160 cm-1 ; 1H NMR (CDCl3) δ7.47 (s, 1 H), 7.09 (t, 1 H, J=2 Hz), 7.01 (t, 3 H, J=2 Hz), 6.00 (bs, 1 H), 1.51 (s, 9 H); 13C NMR (CDCl3) δ152.0, 141.5, 140.4, 123.2, 122.0, 108.1, 94.2, 81.2, 28.0; Mass Spec (70eV, EI) m/z 360 (parent), 304, 276, 248, 232, 205, 149, 131, 105, 77, 57 (base), 40. Exact mass calculated for C11H13IN4O2 : 360.0085. Found: 360.0051.

Workup

  1. stirringStirring
  2. waitis continued at 0° C. for thirty minutes
  3. customThe phases are separated
  4. extractionthe aqueous phase is extracted with chloroform (2×150 mL)
  5. dry with materialThe combined organics are dried (MgSO4)
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customThe organic residue is purified by flash chromatography

Sources & evidence

ORD record
ord-1f3ca7075b924467b3ac2c3f2024f46e
Source dataset
uspto-grants-1996_06
Patent number
US05525742

Reaction notes

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