Bicarbonate Ion → HCID 22402759, compound

HRID 260167Notes

Reaction equation

HRID 260167 reaction equation
[N:1]([C:4]1[CH:5]=[C:6]([NH:11]C(=O)OC(C)(C)C)[CH:7]=[C:8]([I:10])[CH:9]=1)=[N+:2]=[N-:3].FC(F)(F)C(O)=O.C(=O)(O)[O-]>ClCCl>[N:1]([C:4]1[CH:5]=[C:6]([CH:7]=[C:8]([I:10])[CH:9]=1)[NH2:11])=[N+:2]=[N-:3]

Participants

5

Reactant 3

HCID 769Bicarbonate IonHCID 6422Trifluoroacetic acidHCID 86749556HCID 86749556, compound

Product 1

HCID 22402759HCID 22402759, compoundYield 83.4%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

Step A-4. To a stirred solution of 3-azido-5-iodophenylcarbamic acid, 1,1-dimethylethyl ester (A-3, 4.03 g, 11.2 mmol) in dichloromethane (13 mL) is added trifluoroacetic acid (13 mL). The reaction mixture is stirred at 20°-25° C. for 30 minutes and then carefully poured into a stirred mixture of saturated aqueous bicarbonate (300 mL) and dichloromethane (300 mL). The phases are separated and the organics are dried (MgSO4), filtered and concentrated. The residue is purified by medium pressure liquid chromatography using 20% ethyl acetate in hexane as the eluent to afford 2.43 g of 3-azido-5-iodoaniline (A-4) which is used immediately in the next reaction, CHART B, Step B-1. A small analytical sample is recrystallized from ethyl acetate in hexane. Mp=89°-91° C. IR (mull) 3402, 3299, 2954, 2925, 2869, 2135, 2119, 1596, 1581, 1572, 1570, 1463, 1149, 1304, 1246, 987, 842, 826 cm-1 ; 1H NMR (CDCl3) δ6.79 (t, 1 H, J=2 Hz), 6.75 (t, 1 H, J=3 Hz), 6.23 (t, 1 H, J=2 Hz), 3.75 (bs, 2 H); 13C NMR(CDCl3) δ148.5, 141.9, 120.3, 117.7, 104.6, 94.9; Mass Spec (70eV, EI) m/z 260 (parent), 232, 205, 165, 127, 116, 105 (base), 78, 66, 541, 37; Exact mass calculated for C6H5IN4 : 259.9561. Found: 259.9573. Analysis calculated for C6H5IN4 ; C, 27.71; H, 1.90; N, 21.55; Found C, 27.67; H, 1.90; N, 21.66.

Workup

  1. customThe phases are separated
  2. dry with materialthe organics are dried (MgSO4)
  3. filtrationfiltered
  4. concentrationconcentrated
  5. customThe residue is purified by medium pressure liquid chromatography

Sources & evidence

ORD record
ord-edb61625fee14126b8827c8588583be6
Source dataset
uspto-grants-1996_06
Patent number
US05525742

Reaction notes

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