2-methylsulfanylphenol

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Phenol (4.0 g, 0.043 moles), para-(methylthio)phenol (6.0 g, 0.043 moles), and catalyst (2.0 g, Examples 32 and 33 in Table below) were combined and heated under nitrogen for the times and at the temperatures indicated. The mixtures were cooled to room temperature and filtered. The solid catalyst was washed several times with ether. The filtrate and ether washings were combined, and volatiles were removed on a rotary flash evaporator. GC analysis indicated the presence of phenol, ortho-(methylthio)phenol, para-(methylthio)phenol, and di-(methylthio)phenols. Yields of ortho-(methylthio)phenol are given in the Table below. heated under nitrogen for the times and at the temperatures filtered The solid catalyst was washed several times with ether volatiles were removed on a rotary flash evaporator

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The mixture was cooled to room temperature and filtered. The catalyst was washed several times with ether and allowed to dry. The filtrate and ether washings were combined, and volatiles were removed on a rotary flash evaporator. GC analysis indicated the presence of phenol (5.3 g. 42% recovered), ortho(methylthio)phenol (5.2 g. 41% yield), para-(methylthio)phenol (2.0 g, and di-(methylthio)phenols (2.0 g). filtered The catalyst was washed several times with ether to dry volatiles were removed on a rotary flash evaporator

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The reaction was again repeated using identical amounts of phenol and methyl disulfide and 2.8 g of the solid H ELZ-20 catalyst recovered from the first repetition. The mixture was heated for 4 hours at which time the temperature was 179° C. After work-up as before, GC analysis indicated the presence of phenol (5.7 g, 46% recovered), ortho-(methylthio)phenol (5.1 g, 41% yield), para-(methylthio)phenol (2.7 g), and di-(methylthio)phenols (2.4 g). recovered from the first repetition The mixture was heated for 4 hours at which time the temperature was 179° C

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Phenol (12.5 g, 0.13 moles), methyl disulfide (8.4 g, 0.089 moles), and H ELZ-20 (2.5 g) were combined and heated under nitrogen at reflux for 3 hours during which the temperature increased to 180° C. and GC analysis indicated no further increase in the amount of ortho-(methylthio)phenol. Methyl mercaptan was allowed to escape continuously. The mixture was cooled to room temperature and filtered. The catalyst was washed several times with ether and allowed to dry leaving solid weighing 3.2 g. The filtrate and ether washings were combined, and volatiles were removed on a rotary flash evaporator leaving 15.2 g of liquid. GC analysis indicated the presence of phenol (5.3 g, 43% recovered), ortho-(methylthio)phenol (5.1 g, 41% yield), para-(methylthio)phenol (2.3 g), and di(methylthio)phenols (2.2 g).

Conditions: temp:105.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2-Methylsulfanyl-phenol (2.00 g, 14.29 mmol), 2-bromo-2-methyl-propionic acid, ethyl ester (28 g, 142.8 mmol) and powdered K2CO3 (4.93 g, 35.7 mmol) were mixed (no solvent) and stirred at 105° C. for 8 hrs. After cooling, water and CHCl3 were added. The CHCl3 was separated, dried (MgSO4) and concentrated. Xylene was added and concentrated in vacuo (4 times) to remove the bromo ester. The resulting oil was chromatographed on silica, eluting with CH2Cl2 to obtain the title compound (2.30 g, 63% yield). After cooling The CHCl3 was separated dried (MgSO4) concentrated Xylene was added concentrated in vacuo (4 times) to remove the bromo ester The resulting oil was chromatographed on silica eluting with CH2Cl2

Conditions: temp:105.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2-Methylsulfanyl-phenol (2.00 g, 14.29 mmol), 2-bromo-2-methyl-propionic acid, ethyl ester (28 g, 142.8 mmol) and powdered K2CO3 (4.93 g, 35.7 mmol) were mixed (no solvent) and stirred at 105° C. for 8 hrs. After cooling, water and CHCl3 were added. The CHCl3 was separated, dried (MgSO4) and concentrated. Xylene was added and concentrated in vacuo (4 times) to remove the bromo ester. The resulting oil was chromatographed on silica, eluting with CH2Cl2 to obtain the title compound (2.30 g, 63% yield). After cooling The CHCl3 was separated dried (MgSO4) concentrated Xylene was added concentrated in vacuo (4 times) to remove the bromo ester The resulting oil was chromatographed on silica eluting with CH2Cl2