Dimethyl Sulfate → HCID 53253553, compound

HRID 1464882Notes

Reaction equation

HRID 1464882 reaction equation
[Br:1][C:2]1[CH:14]=[CH:13][CH:12]=[CH:11][C:3]=1[NH:4][C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1.[CH2:15]1OCCOCCOCCOCCOC1.[H-].[Na+].S(OC)(OC)(=O)=O.[K+].[Br-]>C(COC)OC.C1COCC1>[Br:1][C:2]1[CH:14]=[CH:13][CH:12]=[CH:11][C:3]=1[N:4]([CH3:15])[C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1

Participants

8

Reactant 5

HCID 6497Dimethyl SulfateHCID 24758Sodium hydride2×HCID 3633615-Crown-5HCID 253877Potassium BromideHCID 64257872-Bromodiphenylamine

Product 1

HCID 53253553HCID 53253553, compound

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 80711,2-DimethoxyethaneSolvent

Conditions

Temperature
0 °C

Procedure

A flame-dried two-neck round bottom flask was charged with 2-bromo-N-phenylaniline (3 g, 12.2 mmol), 0.1 mL 15-crown-5, 200 mL dry THF and 50 mL dimethoxyethane under argon. The solution was cooled to 0° C. in an ice bath, 0.6 g of a 60 wt % dispersion of NaH in mineral oil (0.36 g NaH, 15 mmol) was added to the reaction mixture in small portions under argon and 1.4 mL dimethyl sulfate (1.89 g, 15 mmol) was added via syringe. After refluxing for 20 h under argon the reaction was poured carefully onto 500 g ice and extracted with Et2O (5×50 mL). The organic layers were combined, washed thoroughly with saturated sodium bicarbonate (3×25 mL), brine and water, dried over MgSO4 and the solvent evaporated under reduced pressure. The resulting oil was purified by flash column chromatography using gradient elution, starting with 100% hexanes and progressing to 30% dichloromethane in hexanes to yield 2.5 g (80%)-of a clear oil. 1H NMR (400 MHz, CHCl3) δ 3.22 (s, 3H), 6.56 (d, J=7.6 Hz, 2H), 6.75 (t, J=7.6 Hz, 1H), 7.15 (m, 3H), 7.25 (dd, J=8.0 Hz, J=2.0 Hz, 1H), 7.32 (td, J=7.6 Hz, J=1.2 Hz, 1H), 7.66 (dd, J=8.0 Hz, J=1.6 Hz, 1H). 13C NMR (100 MHz, CHCl3) δ 39.1, 113.5, 117.8, 124.4, 127.9, 128.4, 129.1, 129.2, 130.6, 134.3, 147.0, 148.7. HRMS (ESI) calc for C13H12BrN [M+H]+ 262.0226, found 262.0234. IR (KBr plate) 654 (s), 691 (s), 748 (s), 872 (s), 1139 (s), 1137 (s), 1273 (s), 1346 (s), 1438 (m), 1467 (s), 1499 (s), 1580 (s), 1601 (s), 2813 (m), 2824 (s), 3058 (m), 3089 (m) cm−1.

Workup

  1. temperatureAfter refluxing for 20 h under argon the reaction
  2. extractionextracted with Et2O (5×50 mL)
  3. washwashed thoroughly with saturated sodium bicarbonate (3×25 mL), brine and water
  4. dry with materialdried over MgSO4
  5. customthe solvent evaporated under reduced pressure
  6. customThe resulting oil was purified by flash column chromatography
  7. washelution
  8. customto yield 2.5 g (80%)

Sources & evidence

ORD record
ord-9d79118d34cf4d8789f18c0764a3de03
Source dataset
uspto-grants-2015_04
Patent number
US08999722B2

Reaction notes

Loading…