Ammonia → HCID 12400614, compound

Temperature

-78 °C

Liquid ammonia (520 mL) was condensed in a three-necked flask which was fitted with a cold finger and overhead stirrer and kept at -78° C. with a dry ice/isopropanol bath. A solution of 1-methoxy-4-hydroxymethyl-benzene (50 g, 329 mmol) in tetrahydrofuran (140 mL) was added to the reaction flask followed by the addition of small pieces of lithium wire (10.3 g, 1.48 mol) over a period of about 15 min. The reaction mixture was stirred an additional 30 min at -78° C. and then quenched by the slow addition of absolute ethanol (400 mL). After the reaction was completely quenched (white color), it was allowed to warm to room temperature overnight. This allowed most of the NH3 to evaporate. The residue was partitioned between water and diethyl ether, the organic layer collected, dried over anhydrous MgSO4, filtered and evaporated at reduced pressure. The residue, which still contained some water, was dissolved in methylene chloride, dried over anhydrous MgSO4, filtered and evaporated at reduced pressure to give crude 1-methoxy-4-(2-hydroxyethyl)-cyclohexa-1,4-diene (1) as an oil (40.3 g), which was used in the next step without further purification. This crude product was contaminated with the over-reduced product, 1-methoxy-4-(2-hydroxyethyl)-cyclohex-1-ene (2). Compound (1): 1H NMR δ (CDCl3) 2.12 (1H, br s), 2.28 (2H, t, J=7.5 Hz), 2.78 (4H, br s), 3.58 (3H, s), 3.73 (2H, t, J=7.5 Hz), 4.68 (1H, br s), 5.55 (1H, br s).

1. customcondensed in a three-necked flask which
2. customwas fitted with a cold finger and overhead stirrer
3. customkept at -78° C. with a dry ice/isopropanol bath
4. customquenched by the slow addition of absolute ethanol (400 mL)
5. customAfter the reaction was completely quenched (white color), it
6. temperatureto warm to room temperature overnight
7. customto evaporate
8. customThe residue was partitioned between water and diethyl ether
9. customthe organic layer collected
10. dry with materialdried over anhydrous MgSO4
11. filtrationfiltered
12. customevaporated at reduced pressure
13. dissolutionwas dissolved in methylene chloride
14. dry with materialdried over anhydrous MgSO4
15. filtrationfiltered
16. customevaporated at reduced pressure

ORD record

ord-c745a918d2f4453da204e272b62f0fdf

Source dataset

uspto-grants-1995_11

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US05470849