m-Toluidine → HCID 11175937, compound

HRID 1247465Notes

Reaction equation

HRID 1247465 reaction equation
[O:1]=[C:2]1[C:10]2[C:5](=[C:6]([C:11]3[S:15][C:14](C(O)=O)=[CH:13][CH:12]=3)[CH:7]=[CH:8][CH:9]=2)[CH2:4][NH:3]1.C([N:21]([CH2:24]C)CC)C.C1(P(N=[N+]=[N-])(C2C=CC=CC=2)=[O:33])C=CC=CC=1.[CH3:43][C:44]1[CH:45]=[C:46]([CH:48]=[CH:49][CH:50]=1)[NH2:47]>CN(C=O)C.O>[CH3:43][C:44]1[CH:45]=[C:46]([NH:47][C:24]([NH:21][C:14]2[S:15][C:11]([C:6]3[CH:7]=[CH:8][CH:9]=[C:10]4[C:5]=3[CH2:4][NH:3][C:2]4=[O:1])=[CH:12][CH:13]=2)=[O:33])[CH:48]=[CH:49][CH:50]=1

Participants

7

Reactant 4

HCID 7934m-ToluidineHCID 8471TriethylamineHCID 199401P,P-Diphenylphosphinic azideHCID 21907496HCID 21907496, compound

Product 1

HCID 11175937HCID 11175937, compoundYield 13%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent

Conditions

Temperature
80 °C

Procedure

A solution of Example 127B (70 mg, 0.27 mmol) and triethylamine (0.046 mL, 0.32 mmol) in DMF (8 mL) was treated with diphenylphosphorylazide (0.072 mL, 0.32 mmol), heated to 80° C. for 2 hours, cooled to room temperature, and treated with 3-methylaniline (0.03 mL, 0.27 mL). The resulting mixture was heated to 80° C. for 2 hours, cooled to room temperature, diluted with water, and extracted with dichloromethane and ethyl acetate. The combined extracts were dried (MgSO4), filtered, and concentrated. The concentrate was purified by silica gel chromatography, with 3% methanol/dichloromethane to give the desired product (13% yield). 1H NMR (300 MHz, DMSO-d6) δ 2.29 (s, 3H), 4.58 (s, 2H), 6.63 (d, 1H, J =4.2 Hz), 6.82 (d, 1H, J=6.9 Hz), 7.14–7.27 (m, 3H), 7.34 (s, 1H), 7.48–7.58 (m, 2H), 7.75–7.79 (m, 1H), 8.73 (s, 1H), 8.77 (s, 1H), 9.86 (s, 1H); MS (ESI(+)) m/e 364.0 (M+H)+.

Workup

  1. temperaturecooled to room temperature
  2. temperatureThe resulting mixture was heated to 80° C. for 2 hours
  3. temperaturecooled to room temperature
  4. extractionextracted with dichloromethane and ethyl acetate
  5. dry with materialThe combined extracts were dried (MgSO4)
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customThe concentrate was purified by silica gel chromatography, with 3% methanol/dichloromethane

Sources & evidence

ORD record
ord-8c89493f63cc4063badd05da2fddaf20
Source dataset
uspto-grants-2006_10
Patent number
US07129260B2

Reaction notes

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