2-ethylsulfanylphenol

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:200.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To phenol (35.3 g, 0.37 moles) was added 10.6 g of zirconium n-propoxide in n-propanol consisting of 21.6% zirconium (0.025 mole) and 10.8% free n-propanol. The mixture was distilled at atmospheric pressure removing n-propanol. Ethyl disulfide (30.6 g, 0.25 moles) was added, and the mixture was heated under nitrogen while ethyl mercaptan was removed continuously by distillation. Heating was continued for a total of 6.5 hours during which temperature slowly increased to 200° C. Distillation of the mixture at 0.5 mm mercury to a maximum head temperature of 84° C. yielded 31.7 g of distillate. GC analysis indicated the distillate contained 12.4 g of phenol (35% recovered) and 15.9 g of ortho-(ethylthio)phenol (41% yield). The mixture was distilled at atmospheric pressure removing n-propanol was removed continuously by distillation Heating was continued for a total of 6.5 hours during which temperature Distillation of the mixture at 0.5 mm mercury to a maximum head temperature of 84° C. yielded 31.7 g of distillate

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

Procedure: A similar run using phenol (142 g, 1.51 moles), toluene (150 ml), zirconium tetrachloride (6.0 g, 0.026 moles), and ethyl disulfide (62.0 g, 0.50 moles) gave ortho-(ethylthio)phenol (36.0 g, 46% yield).

Conditions: temp:150.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of phenol (87.5 g, 0.93 moles), xylene (100 ml), and zirconium tetrachloride (6.0 g, 0.026 moles) was heated to reflux under a slow nitrogen stream. The xylene was distilled through a 10 inch Vigreux column. The distillation was continued over a 2 hour period until the reaction mixture reached 177° C. Approximately 10 g of phenol was distilled with the xylene. The reaction mass was cooled to 150° C., and ethyl disulfide (62.0 g, 0.50 moles) was added. The reaction mixture was heated to 152° C., then heated slowly over a 5 hour period to 180° C., and finally held at 180° C. for an additional 10 hours. Ethyl mercaptan was removed continuously by distillation. The reaction mixture was cooled to 100° C., then vacuum distilled at 100 mm mercury until the pot temperature reached 200° C. to give 70.8 g of distillate. GC analysis indicated the distillate contained 34.0 g of ortho-(ethylthio)phenol (44% yield). was heated to reflux under a slow nitrogen stream The xylene was distilled through a 10 inch Vigreux column The distillation reached 177° C Approximately 10 g of phenol was distilled with the xylene The reaction mixture was heated to 152° C. heated slowly over a 5 hour period to 180° C. finally held at 180° C. for an additional 10 hours Ethyl mercaptan was removed continuously by distillation The reaction mixture was cooled to 100° C. vacuum distilled at 100 mm mercury until the pot temperature reached 200° C. to give 70.8 g of distillate

Conditions: temp:156.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Zirconium tetrachloride (23.4 g, 0.1 mole) was added to phenol (141.2 g, 1.5 moles). The mixture was slowly heated to 156° C. under nitrogen and maintained at this temperature overnight while allowing HCl to escape. The mixture was cooled to ca. 100° C. and ethyl disulfide (122.3 g, 1 mole) was added. The mixture was heated under nitrogen while ethyl mercaptan was removed continuously by distillation. Heating was continued for a total of 7 hours during which temperature slowly increased to 198° C. Distillation of the mixture at 0.4 mm mercury to a maximum head temperature of 101° C. yielded 134.7 g of distillate. GC analysis indicated the distillate contained 53.4 g of phenol (38% recovered) and 63.7 g of ortho-(ethylthio)phenol (41% yield). Fractional distillation through a 5 inch Vigreux column yielded, after removal of phenol, a main fraction of 99.2% pure ortho-(ethylthio)phenol distilling at 125°-127° C. at 30 mm mercury. maintained at this temperature overnight The mixture was cooled to ca. 100° C. was removed continuously by distillation Heating was continued for a total of 7 hours during which temperature slowly increased to 198° C Distillation of the mixture at 0.4 mm mercury to a maximum head temperature of 101° C. yielded 134.7 g of distillate

Conditions: temp:195.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Zirconium phenoxide (4.0 g, 0.0086 moles) was added to phenol (8.9 g, 0.095 moles) and ethyl disulfide (10.5 g, 0.086 moles). The mixture was heated under nitrogen for 6.5 hours during which the temperature slowly increased to 195° C. Ethyl mercaptan was removed continuously by distillation. The mixture was distilled at 0.4 mm mercury to a maximum head temperature of 102° C. yielding 12.2 g of distillate. Gas chromatographic (GC) analysis indicated the distillate contained 5.0 g of ortho-(ethylthio)phenol (38% yield). The mixture was heated under nitrogen for 6.5 hours during which the temperature Ethyl mercaptan was removed continuously by distillation The mixture was distilled at 0.4 mm mercury to a maximum head temperature of 102° C. yielding 12.2 g of distillate

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