2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To 300 mL toluene in an 500 mL flask with condenser under a nitrogen atmosphere were added 30 g (120 mmol) di(trimethylolpropane), 4, 45.6 mL (38.9 g, 300 mmol) acrolein diethyl acetal, and 1.5 g (6 mmol) pyridinium p-toluenesulfonate. The mixture was refluxed for 4 hours, then cooled to room temperature, and 0.67 g (6 mmol) potassium tert-butoxide added. The toluene was removed by evaporation under reduced pressure, and the residue distilled in a Kugelrohr apparatus (pressure 1-3 mbar, pot temperature 142-180° C.) to give 35.35 g (91% yield) of crude di[(5-ethyl-2-vinyl-[1,3]dioxan-5-yl)methyl]ether, 5, as a light yellow oil. The crude product, 30 g, was purified by chromatography on 1 Kg Merck Silica Gel 60 in a 2 L glass fritted funnel, eluting with 20:80 ethyl acetate/heptane, to give 27.8 g (71% yield) of purer product, which was re-purified by a second chromatography on 1 Kg MERCK® Silica Gel 60 in a 2 L glass fritted funnel, eluting with 10:90 ethyl acetate/heptane, to give 16.44 g (42% yield) of essentially pure di[(5-ethyl-2-vinyl-1,3dioxan-5-yl)methyl]ether. This material was used in the photoisomerization. The mixture was refluxed for 4 hours The toluene was removed by evaporation under reduced pressure the residue distilled in a Kugelrohr apparatus (pressure 1-3 mbar, pot temperature 142-180° C.)

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To 300 mL toluene in an 500 mL flask with condenser under a nitrogen atmosphere were added 30 g (120 mmol) di(trimethylolpropane), 4, 45.6 mL (38.9 g, 300 mmol) acrolein diethyl acetal, and 1.5 g (6 mmol) pyridinium p-toluenesulfonate. The mixture was refluxed for 4 hours, then cooled to room temperature, and 0.67 g (6 mmol) potassium tert-butoxide added. The toluene was removed by evaporation under reduced pressure, and the residue distilled in a Kugelrohr apparatus (pressure 1-3 mbar, pot temperature 142-180° C.) to give 35.35 g (91% yield) of crude di[(5-ethyl-2-vinyl-[1,3]dioxan-5-yl)methyl]ether, 5, as a light yellow oil. The crude product, 30 g, was purified by chromatography on 1 Kg Merck Silica Gel 60 in a 2 L glass fritted funnel, eluting with 20:80 ethyl acetate/heptane, to give 27.8 g (71% yield) of purer product, which was re-purified by a second chromatography on 1 Kg MERCK® Silica Gel 60 in a 2 L glass fritted funnel, eluting with 10:90 ethyl acetate/heptane, to give 16.44 g (42% yield) of essentially pure di[(5-ethyl-2-vinyl-1,3dioxan-5-yl)methyl]ether. This material was used in the photoisomerization. The mixture was refluxed for 4 hours The toluene was removed by evaporation under reduced pressure the residue distilled in a Kugelrohr apparatus (pressure 1-3 mbar, pot temperature 142-180° C.)

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: DE 10 2010 033 844 A1 likewise concerns a process for obtaining ditrimethylolpropane from the secondary streams of trimethylolpropane preparation. This involves dissolving the high-boiling fractions and residues obtained in water and catalytically hydrogenating the aqueous solution in the presence of an acidic compound to split formaldehyde-containing acetals. After removal of solids, the aqueous hydrogenated material is then contacted both with basic and with acidic ion exchangers. A trimethylolpropane-enriched product stream is distilled out of the aqueous eluate, and ditrimethylolpropane remains as the distillation residue. In order that ditrimethylolpropane is obtained in sufficient quality in the distillation residue, in the process according to DE 10 2010 033 844 A1, the treatment of the aqueous hydrogenated material both with basic and with acidic ion exchangers is absolutely necessary. This involves dissolving the high-boiling fractions and residues to split formaldehyde- containing acetals After removal of solids A trimethylolpropane-enriched product stream is distilled out of the aqueous eluate, and ditrimethylolpropane

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: DE 10 2010 033 844 A1 likewise concerns a process for obtaining ditrimethylolpropane from the secondary streams of trimethylolpropane preparation. This involves dissolving the high-boiling fractions and residues obtained in water and catalytically hydrogenating the aqueous solution in the presence of an acidic compound to split formaldehyde-containing acetals. After removal of solids, the aqueous hydrogenated material is then contacted both with basic and with acidic ion exchangers. A trimethylolpropane-enriched product stream is distilled out of the aqueous eluate, and ditrimethylolpropane remains as the distillation residue. In order that ditrimethylolpropane is obtained in sufficient quality in the distillation residue, in the process according to DE 10 2010 033 844 A1, the treatment of the aqueous hydrogenated material both with basic and with acidic ion exchangers is absolutely necessary. This involves dissolving the high-boiling fractions and residues to split formaldehyde- containing acetals After removal of solids A trimethylolpropane-enriched product stream is distilled out of the aqueous eluate, and ditrimethylolpropane

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To 300 mL toluene in an 500 mL flask with condenser under a nitrogen atmosphere were added 30 g (120 mmol) di(trimethylolpropane), 4, 45.6 mL (38.9 g, 300 mmol) acrolein diethyl acetal, and 1.5 g (6 mmol) pyridinium p-toluenesulfonate. The mixture was refluxed for 4 hours, then cooled to room temperature, and 0.67 g (6 mmol) potassium tert-butoxide added. The toluene was removed by evaporation under reduced pressure, and the residue distilled in a Kugelrohr apparatus (pressure 1-3 mbar, pot temperature 142-180° C.) to give 35.35 g (91% yield) of crude di[(5-ethyl-2-vinyl-[1,3]dioxan-5-yl)methyl]ether, 5, as a light yellow oil. The crude product, 30 g, was purified by chromatography on 1 Kg Merck Silica Gel 60 in a 2 L glass fritted funnel, eluting with 20:80 ethyl acetate/heptane, to give 27.8 g (71% yield) of purer product, which was re-purified by a second chromatography on 1 Kg MERCK® Silica Gel 60 in a 2 L glass fritted funnel, eluting with 10:90 ethyl acetate/heptane, to give 16.44 g (42% yield) of essentially pure di[(5-ethyl-2-vinyl-1,3dioxan-5-yl)methyl]ether. This material was used in the photoisomerization. The mixture was refluxed for 4 hours The toluene was removed by evaporation under reduced pressure the residue distilled in a Kugelrohr apparatus (pressure 1-3 mbar, pot temperature 142-180° C.)

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: DE 10 2010 033 844 A1 likewise concerns a process for obtaining ditrimethylolpropane from the secondary streams of trimethylolpropane preparation. This involves dissolving the high-boiling fractions and residues obtained in water and catalytically hydrogenating the aqueous solution in the presence of an acidic compound to split formaldehyde-containing acetals. After removal of solids, the aqueous hydrogenated material is then contacted both with basic and with acidic ion exchangers. A trimethylolpropane-enriched product stream is distilled out of the aqueous eluate, and ditrimethylolpropane remains as the distillation residue. In order that ditrimethylolpropane is obtained in sufficient quality in the distillation residue, in the process according to DE 10 2010 033 844 A1, the treatment of the aqueous hydrogenated material both with basic and with acidic ion exchangers is absolutely necessary. This involves dissolving the high-boiling fractions and residues to split formaldehyde- containing acetals After removal of solids A trimethylolpropane-enriched product stream is distilled out of the aqueous eluate, and ditrimethylolpropane