Formaldehyde → 3,3-Bis(hydroxymethyl)-2-butanone

Temperature

12.5 °C

2-Butanone (216 g, 3.0 mol) and 30% formalin (600 g, 6.0 mol) were added simultaneously, but separately, to an aqueous calcium hydroxide solution (1.89 g, 0.255 mol) in a 3-liter flask during a 5-min. period. The solution was stirred vigorously for 6 hr at 10-15° C. Another portion of calcium hydroxide (0.4 g, 0.0054 mol) was added and the reaction mixture stirred another 6 hr at ambient conditions. Subsequently, the solution was filtered and neutralized with dry ice. The solution was concentrated at reduced pressure to yield a cloudy syrup containing insoluble calcium carbonate. The viscous product was dissolved in a minimum amount of ethyl acetate and filtered to remove traces of calcium carbonate, and the ethyl acetate was removed in vacuo to yield a water white liquid. The residue was slurried in 3 liters of ligroin and the mixture heated to boiling with good stirring for 10 min. The solution/suspension was allowed to cool/settle for 2 hr., after which time the ligroin was decanted from the liquid product. This procedure was repeated once more except that the solution was allowed to stand overnight in a freezer. The ligroin was decanted and the solid recovered. The 3,3-Bis(hydroxymethyl)-2-butanone was used without further purification. Analytical samples were prepared by recrystallization from chloroform and petroleum ether; m.p. 60° C.; 753 g, 95% of theoretical yield; H-NMR spectra were consistent.

1. stirringthe reaction mixture stirred another 6 hr at ambient conditions
2. filtrationSubsequently, the solution was filtered
3. concentrationThe solution was concentrated at reduced pressure
4. customto yield a cloudy syrup
5. filtrationfiltered
6. customto remove traces of calcium carbonate
7. customthe ethyl acetate was removed in vacuo
8. customto yield a water white liquid
9. temperaturethe mixture heated
10. stirringwith good stirring for 10 min
11. temperatureto cool/settle for 2 hr
12. custom, after which time the ligroin was decanted from the liquid product
13. waitto stand overnight in a freezer
14. customThe ligroin was decanted
15. customthe solid recovered
16. customThe 3,3-Bis(hydroxymethyl)-2-butanone was used without further purification
17. customAnalytical samples were prepared by recrystallization from chloroform and petroleum ether

ORD record

ord-afc5c1d4b705449598a226f499e50c7d

Source dataset

uspto-grants-2002_10

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US06458521B1