Water → 3,5-Dimethyl-1-hexyn-3-ol

温度

80 °C

A solution of 12.6 g of 3,5-dimethyl-1-hexyn-3-ol (Aldrich Chemical Co.)(o.1 mole) and 1.5 g of t-butyl peroctoate dissolved in 35 g of denatured ethanol was added dropwise over 3.1 hours to a stirred solution containing 21.2 g of sodium hypophosphite monohydrate (0.2 mole), 40 g of denatured ethanol and 20 g of deionized water. The temperature was maintained at 80° C. throughout the addition. After completion of the addition, heating at 79°-80° C. was continued for 4.8 hours longer. A fine white precipitate formed in the reaction mixture during the addition and post heating. The reaction mixture was cooled and the precipitate was filtered off using a sintered glass funnel. The precipitate was washed on the funnel several times with fresh ethanol, air dried on the funnel for 2 hours and finally was dried in a vacuum oven at 1 mm Hg and 60° C. for 24 hours. Dry weight of the precipitate was 21.8 g, a white solid. The filtrate was concentrated on a rotary evaporator and then dried in a vacuum oven at 1 mm Hg at 60° C. for 22 hours to leave 9.6 g of a brittle, puffy, white solid. The precipitate was analyzed by 13C and 31P NMR and was identified as nearly pure disodium 3,5-dimethylhexyl-3-ol-1,1-diphosphinate, the product resulting from 1,1-diaddition of hypophosphite to the acetylenic bond of 3,5-dimethyl-1-hexyn-3-ol. Phosphorous 31NMR analysis of the dried filtrate from the reaction showed that about half of it was unreacted hypophosphite and the remaining half was organophosphorous compounds, probably 1,2-diadduct of hypophosphite to the acetylenic compound. Neglecting organophosphorous compounds in the filtrate, the yield of the main product was 72.2%.

1. additionwas added dropwise over 3.1 hours to a stirred solution
2. additionAfter completion of the addition
3. temperatureheating at 79°-80° C.
4. customA fine white precipitate formed in the reaction mixture during the addition and post
5. temperatureheating
6. temperatureThe reaction mixture was cooled
7. filtrationthe precipitate was filtered off
8. washThe precipitate was washed on the funnel several times with fresh ethanol, air
9. customdried on the funnel for 2 hours
10. customfinally was dried in a vacuum oven at 1 mm Hg and 60° C. for 24 hours
11. customDry weight of the precipitate
12. concentrationThe filtrate was concentrated on a rotary evaporator
13. customdried in a vacuum oven at 1 mm Hg at 60° C. for 22 hours
14. customto leave 9.6 g of a brittle

ORDレコード

ord-585f24c4aefa49eba0feceacc7779b89

出典データセット

uspto-grants-1997_07

DOI

10.6084/m9.figshare.5104873.v1

特許番号

US05647995