تفاعل #449854

معادلة التفاعل

triethylamine

tetrahydrofuran

2-adamantanone

2,2,2-trifluoroethyl-4-chloro-3-methoxybenzoate

THF

→

adamantylidene adamantane

ظروف التفاعل

المعالجة

1. 1
   workup.ADDITIONCare should be taken, as this addition
2. 2
   أخرىA moderate exotherm resulted in a reddish-brown mixture which
3. 3
   workup.STIRRINGAfter 15 minutes stirring
4. 4
   درجة الحرارةThe mixture was then refluxed for 2 hours
5. 5
   درجة الحرارةReflux
6. 6
   workup.WAITwas continued overnight for 16 hours
7. 7
   أخرىThe solvents were rotary evaporated from the cooled reaction mixture
8. 8
   أخرىto yield a brown-black gum
9. 9
   أخرىThis gum was triturated with hexanes, 100 mL, and ethyl acetate, 20 mL
10. 10
    أخرىThe yellow-orange supernate was decanted
11. 11
    workup.WAITAfter 10 minutes of agitation, triethylamine and methanol, 5 mL each
12. 12
    workup.ADDITIONwere added
13. 13
    أخرىThe combined decanted supernates
14. 14
    أخرىwere rotary evaporated to a light yellow, semisolid paste
15. 15
    workup.ADDITIONThe mixture was treated with hot hexanes, 50 mL
16. 16
    ترشيحfiltered
17. 17
    درجة الحرارةwarm
18. 18
    أخرىto remove some insolubles
19. 19
    أخرىThe residue obtained
20. 20
    أخرىafter rotary evaporation of the filtrate
21. 21
    غسيلThe column was eluted with hexanes

الإجراء التجريبي

Titanium trichloride, 7.9 g (51.3 mmol), was weighed into a round-bottomed flask in a glove bag under an argon atmosphere. Freshly distilled tetrahydrofuran (from LAH), 60 mL, was added quickly under argon flow. Care should be taken, as this addition can be exothermic. The purple suspension was stirred vigorously so as to break up the solid adhering to the walls of the flask. After 15 minutes, zinc dust, 5.2 g, was added all at once under argon with continued stirring. A moderate exotherm resulted in a reddish-brown mixture which did not contain black suspended solids. After 15 minutes stirring, the triethylamine, 11 mL, was added with exclusion of air. The mixture was then refluxed for 2 hours. A solution of 2-adamantanone, 3.0 g (20 mmol), and 2,2,2-trifluoroethyl-4-chloro-3-methoxybenzoate, 2.6 g (10 mmol) in dry THF, 30 mL, was added dropwise to the refluxing brown mixture over approximately 65 minutes. Reflux was continued overnight for 16 hours. The solvents were rotary evaporated from the cooled reaction mixture to yield a brown-black gum. This gum was triturated with hexanes, 100 mL, and ethyl acetate, 20 mL. The yellow-orange supernate was decanted and the trituration procedure was repeated. After 10 minutes of agitation, triethylamine and methanol, 5 mL each, were added. The gum began to stiffen and eventually became a lumpy solid. The solid was broken up and the supernate decanted. One final trituration was accomplished with 20% ethyl acetate-hexanes. The combined decanted supernates were rotary evaporated to a light yellow, semisolid paste. The mixture was treated with hot hexanes, 50 mL, and filtered warm to remove some insolubles. The residue obtained after rotary evaporation of the filtrate was applied to a 2.1×20 cm column of activity I aluminum oxide as a slurry in a small amount of warm hexanes. The column was eluted with hexanes to obtain adamantylidene adamantane. The elution was continued with 10% dichloromethane-hexanes to obtain an oil which contained two major mid Rf, UV-active components. The oil was taken up in a small amount of hot hexanes. A crystalline, colorless solid, weighing 0.71 g and having a melting point of 108°-112° C., precipitated out upon cooling.

المصدر