Hydrochloric Acid → HCID 54040210, compound

HRID 2257435Notes

Reaction equation

HRID 2257435 reaction equation
[CH3:1][C@H:2]([O:9][C:10]1[CH:15]=[CH:14][C:13]([O:16]C(=O)C2C=CC=CC=2)=[CH:12][C:11]=1[N+:25]([O-:27])=[O:26])[CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH3:8].O[Li].O.Cl>CO.O.[OH-].[Na+]>[CH3:1][C@H:2]([O:9][C:10]1[CH:15]=[CH:14][C:13]([OH:16])=[CH:12][C:11]=1[N+:25]([O-:27])=[O:26])[CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH3:8]

Participants

7

Reactant 3

HCID 313Hydrochloric AcidHCID 168937Lithium hydroxide, monohydrateHCID 54374222HCID 54374222, compound

Product 1

HCID 54040210HCID 54040210, compound

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 962WaterSolventHCID 14798Sodium HydroxideSolvent

Procedure

To a solution of 5.3 mmol of ester 10 in 40 ml of methanol and 15 ml of water, 22 mmol of LiOH·H2O was added. The reaction mixture was stirred vigorously at room temperature for 14-22 h until no starting material was detected by TLC. The solution was diluted with 65 ml of 3.5% (wt/wt) NaOH solution, acidified by adding concentrated HCl with ice and extracted several times with ethyl ether. The combined organic layers were dried over anhydrous MgSO4 and the solvent removed. The phenol were purified by flash chromatography with hexanes/ethyl acetate [90:10] to give (S)-4-(1-methyl-heptyloxy)-3-nitro-phenol (Compound 11, Scheme I, R2 =(S)-OCH(CH3)C6H13) in 89-98% yield as an orange liquid: Rf [hexanes/ethyl acetate 85/15]: 0.24; 1H NMR (300 MHz, CDCl3): δ 0.84(t, 3H, J=6.8 Hz), 1.16-1.48(m, 8H), 1.27(d, 3H, J=6.1 Hz), 1.56(m, 1H), 1.72(m, 1H), 4.35(m, 1H), 5.44(broad s, 1H), 6.94(d, 1H, J=9 Hz), 7.01(dd, 1H, J=2.8 Hz, J=9 Hz), 7.28(d, 1H, J=2.8 Hz); 13C NMR (300 MHz, CDCl3): δ 13.98, 19.49, 22.50, 25.19, 29.15, 31.66, 36.19, 77.57, 112.03, 118.50, 121.44, 140.98, 145.81, 148.84; Mass spectrum, m/z(rel.intensity): 267(M+ 0.3), 156(8), 155(100), 71(9) 57(20), 55(16), 43(29).

Workup

  1. extractionextracted several times with ethyl ether
  2. dry with materialThe combined organic layers were dried over anhydrous MgSO4
  3. customthe solvent removed
  4. customThe phenol were purified by flash chromatography with hexanes/ethyl acetate [90:10]

Sources & evidence

ORD record
ord-13fd872d403f4305b28accd38643ed51
Source dataset
uspto-grants-1997_08
Patent number
US05658493

Reaction notes

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