tert-Butanol → Tert-butyl 7-cyano-2-naphthylcarbamate

HRID 2238422Notes

Reaction equation

HRID 2238422 reaction equation
[C:1]([C:3]1[CH:12]=[C:11]2[C:6]([CH:7]=[CH:8][C:9](C(O)=O)=[CH:10]2)=[CH:5][CH:4]=1)#[N:2].P(N=[N+]=[N-])(=O)([O:24][C:25]1C=CC=CC=1)OC1C=CC=CC=1.CC[N:37](CC)CC.[CH3:42][C:43]([OH:46])([CH3:45])[CH3:44]>>[C:1]([C:3]1[CH:12]=[C:11]2[C:6]([CH:7]=[CH:8][C:9]([NH:37][C:25](=[O:24])[O:46][C:43]([CH3:45])([CH3:44])[CH3:42])=[CH:10]2)=[CH:5][CH:4]=1)#[N:2]

Participants

5

Reactant 4

HCID 6386tert-ButanolHCID 8471TriethylamineHCID 123414Diphenylphosphoryl azideHCID 15392240HCID 15392240, compound

Product 1

HCID 44549667Tert-butyl 7-cyano-2-naphthylcarbamateYield 85%

Procedure

A solution of acid 192 (6.60 g, 23 mmol), diphenyl phosphorazidate (7.71 g, 28 mmol) and Et3N (5.19 g, 51 mmol) in t-BuOH (50 mL) was heated under reflux for 6 h. The mixture was partitioned between EtOAc and brine. The EtOAc layer was dried and filtered through silica gel. Chromatography eluting with CH2Cl2/petroleum ether/MeOH (25:24:1) followed by recrystallization (CH2Cl2/petroleum ether) gave tert-butyl 7-cyano-2-naphthylcarbamate (193) (5.30 g, 85%) as colorless needles. A sample was recrystallised (EtOAc/n-hexane): mp 126-128° C.; 1H NMR (CDCl3) δ 8.13 (s, 1H), 8.07 (s, 1H), 7.82 (d, J=8.1 Hz, 1H), 7.80 (d, J=8.1 Hz, 1H), 7.51-7.48 (m, 2H), 6.71 (br s, 1H), 1.56 (s, 9H); 13C NMR δ 152.5, 137.5, 133.4, 133.1, 131.0, 128.9, 128.8, 124.9, 122.0, 119.3, 114.4, 110.0, 81.3, 28.3. Anal. (C16H16N2O2) C, H, N.

Workup

  1. temperatureunder reflux for 6 h
  2. customThe mixture was partitioned between EtOAc and brine
  3. dry with materialThe EtOAc layer was dried
  4. filtrationfiltered through silica gel
  5. washChromatography eluting with CH2Cl2/petroleum ether/MeOH (25:24:1)
  6. customfollowed by recrystallization (CH2Cl2/petroleum ether)

Sources & evidence

ORD record
ord-3873354fd726455e88d8800d4bd96cd4
Source dataset
uspto-grants-2010_05
Patent number
US07718688B2

Reaction notes

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