2,4-dimethylpentan-3-one

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: 2,4-dimethyl-3-pentanone (330 g, 2.89M) in chloroform (800 ml) was cooled in an ice water bath to 10° C. and bromine (462 g, 2.89M) was added slowly over 3 hours. After the addition, a slow stream of nitrogen was introduced to the mixture and HBr gas was slowly evolved from the flask. The nitrogen was left bubbling over a weekend to remove all of the HBr produced and then sodium carbonate (5 g) was added. The reaction mixture was then filtered through Celite and the chloroform removed using a rotary evaporator. Distillation of the crude product using a 1′ (2.54 cm) vigreux gave essentially pure 2-bromo-2,4-dimethyl-3-pentanone (478 g, 2.47M) b.pt. 50-52° C./10 mb (1000 Nm−2). After the addition The nitrogen was left bubbling over a weekend to remove all of the HBr produced The reaction mixture was then filtered through Celite the chloroform removed a rotary evaporator Distillation of the crude product

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

Procedure: Reaction between 2,4-dimethyl-3-pentanone (1.2.4.3), trimethylsilyl chloride, and base gave 2,4-dimethyl-3-trimethysilyloxy-2-pentene (1.2.4.4) which was reacted with 1-fluoropyridinium triflate (1.2.4.5) to form 2,4-dimethyl-2-fluoro-3-pentanone (1.2.4.6). This product was reacted with (CH3)3S(O)+I- to form the title compound (1.2.4.2). ##STR31##

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

Procedure: 1,1-Diisopropyl-6-(5-norbornen-2-yl)hexanol (yield: 85%) was obtained in the same manner as in Synthesis Example 1, except that diisopropyl ketone and 1-chloro-5-(5-norbornen-2-yl)pentane were used in place of acetone and 1-chloro-4-(5-norbornen-2-yl)butane, respectively.

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

Procedure: 1,1-Diisopropyl-6-(5-norbornen-2-yl)hexanol (yield: 85%) was obtained in the same manner as in Synthesis Example 1, except that diisopropyl ketone and 1-chloro-5-(5-norbornen-2-yl)pentane were used in place of acetone and 1-chloro-4-(5-norbornen-2-yl)butane, respectively.

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

Procedure: To a stirred solution of 28.3 ml. (0.2 mole) 2,4-dimethyl-3-pentanone in 100 ml. chloroform was added dropwise 10.3 ml. (0.2 mole) bromine in 30 ml. of the same solvent. The resulting mixture was stirred for a few minutes, the solvent evaporated in vacuo, the residue taken up in 100 ml. ethanol. Water, 50 ml., and 10 M sodium hydroxide, 50 ml., added. The resulting mixture was stirred at reflux for one hour, diluted with 200 ml. water and extracted with 3×50 ml. ethyl ether. The extracts were dried (MgSO4) evaporated to dryness and the residue distilled to obtain 15.95 g. (61%) of the hydroxy-ketone, b.p. 60°-62° C./18 mm. the solvent evaporated in vacuo , added The resulting mixture was stirred at reflux for one hour diluted with 200 ml water and extracted with 3×50 ml The extracts were dried (MgSO4) evaporated to dryness the residue distilled to obtain 15.95 g

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

Procedure: To a stirred solution of 28.3 ml. (0.2 mole) 2,4-dimethyl-3-pentanone in 100 ml. chloroform was added dropwise 10.3 ml. (0.2 mole) bromine in 30 ml. of the same solvent. The resulting mixture was stirred for a few minutes, the solvent evaporated in vacuo, the residue taken up in 100 ml. ethanol. Water, 50 ml., and 10M sodium hydroxide, 50 ml., added. The resulting mixture was stirred at reflux for one hour, diluted with 200 ml. water and extracted with 3×50 ml. ethyl ether. The extracts were dried (MgSO4) evaporated to dryness and the residue distilled to obtain 15.95 g. (61%) of the hydroxy-ketone, b.p. 60°-62° C./18 mm. the solvent evaporated in vacuo , added The resulting mixture was stirred at reflux for one hour diluted with 200 ml water and extracted with 3×50 ml The extracts were dried (MgSO4) evaporated to dryness the residue distilled to obtain 15.95 g

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

Procedure: To a stirred solution of 28.3 ml. (0.2 mole) 2,4-dimethyl-3-pentanone in 100 ml. chloroform was added dropwise 10.3 ml. (0.2 mole) bromine in 30 ml. of the same solvent. The resulting mixture was stirred for a few minutes, the solvent evaporated in vacuo, the residue taken up in 100 ml. ethanol. Water, 50 ml., and 10M sodium hydroxide, 50 ml., added. The resulting mixture was stirred at reflux for one hour, diluted with 200 ml. water and extracted with 3×50 ml. ethyl ether. The extracts were dried (MgSO4) evaporated to dryness and the residue distilled to obtain 15.95 g. (61%) of the hydroxy-ketone, b.p. 60°-62° C./18 mm. the solvent evaporated in vacuo , added The resulting mixture was stirred at reflux for one hour diluted with 200 ml water and extracted with 3×50 ml The extracts were dried (MgSO4) evaporated to dryness the residue distilled to obtain 15.95 g