Bromine → 5-tert-Butyl-2-methyl-4-thiocyanato-phenol

HRID 1003856Notes

Reaction equation

[C:1]([C:5]1[CH:6]=[CH:7][C:8]([CH3:12])=[C:9]([OH:11])[CH:10]=1)([CH3:4])([CH3:3])[CH3:2].[S:13](C#N)[C:14]#[N:15].[Na].[Br-].[Na+].BrBr>CO>[C:1]([C:5]1[C:6]([S:13][C:14]#[N:15])=[CH:7][C:8]([CH3:12])=[C:9]([OH:11])[CH:10]=1)([CH3:4])([CH3:3])[CH3:2]

Participants

Conditions

Temperature: 40 °C

Procedure

In a 5 L flask were placed 350 g (2.13 mol) of 5-tert-butyl-2-methyl-phenol, sodium thiocyanide (555 g, 6.85 mol) and MeOH (1400 mL), and the resulting mixture cooled to 7° C. A solution of sodium bromide (214 g, 2.08 mol), bromine (126 mL, 2.38 mol), and MeOH (1800 mL) was added slowly and the temperature raised to 40° C. over a period of 30 minutes. The precipitants were filtered and the filtrate concentrated by half. Saturated sodium carbonate (3.5 L) and H2O (4.5 L) were added. The mixture was extracted with EtOAc (3 L), and the organic layers were combined and concentrated. To this residue were added t-butylmethyl ether (500 mL) and hexanes (500 mL), and the mixture was allowed to stand for 17 hours at -5° C. The precipitants were filtered to give the title compound, m.p. 99-102° C. 1H NMR (CDCl3) δ 1.46 (s, 9 H), 2.22 (s, 3 H), 5.01 (s, 1 H), 6.89 (s, 1 H), 7.49 (s, 1 H).

Workup

customIn a 5 L flask were placed
filtrationThe precipitants were filtered
concentrationthe filtrate concentrated by half
additionSaturated sodium carbonate (3.5 L) and H2O (4.5 L) were added
extractionThe mixture was extracted with EtOAc (3 L)
concentrationconcentrated
additionTo this residue were added t-butylmethyl ether (500 mL) and hexanes (500 mL)
filtrationThe precipitants were filtered

Sources & evidence

ORD record: ord-1df6aa95a5ac41bf9a2e2630edf4febe
Source dataset: uspto-grants-2000_04
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US06046355

Reaction notes

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