반응 #6061

반응 방정식

methoxylamine hydrochloride

t-Butyldimethylsilyl chloride

3,3-Bis(hydroxymethyl)-1,1-dimethoxycyclobutane

3.3-Bis(hydroxymethyl)-1,1-dimethoxycyclobutane

hydrochloric acid

hydroxide

→

title compound

수율 20.0%

3,3-Bis(((1,1-dimethylethyl)dimethylsilyl)oxymethyl)cyclobutanone-O-methyl oxime

수율 20.0%

용매

pyridine

THF

반응 조건

후처리

1. 1
   여과then filtered
2. 2
   농축concentrated in vacuo
3. 3
   세척The residue was washed with THF
4. 4
   workup.DISSOLUTIONdissolved in 30 mL of anhydrous pyridine
5. 5
   workup.STIRRINGstirring continued overnight
6. 6
   기타The bulk of the solvent was evaporated in vacuo at 35°-40° C.
7. 7
   workup.DISSOLUTIONthe concentrate dissolved in 200 mL of methylene chloride
8. 8
   세척The methylene chloride solution was washed with 100 mL of water
9. 9
   건조dried over anhydrous magnesium sulfate
10. 10
    여과filtered
11. 11
    농축concentrated in vacuo
12. 12
    기타The residue was purified on a 1.5×50 cm silica gel column
13. 13
    세척eluted @ 5 psi with 200 mL of hexane

실험 절차

3,3-Bis(hydroxymethyl)-1,1-dimethoxycyclobutane (1.35 g, 7.65 mmol) from Step A and 3.8 mL of 2M aqueous hydrochloric acid solution were added to 60 mL of THF and the reaction mixture was stirred at ambient temperature for 0.5 h, under a nitrogen atmosphere. The reaction mixture was neutralized by the addition of a strongly basic hydroxide resin then filtered and concentrated in vacuo. The residue was washed with THF and dissolved in 30 mL of anhydrous pyridine. To this solution was added 767 mg (9.2 mmol) of methoxylamine hydrochloride and the resultant solution was stirred for ~20 h at ambient temperature, under a nitrogen atmosphere. t-Butyldimethylsilyl chloride (3.5 g, 23 mmol) and 60 mL of anhydrous pyridine were then added and stirring continued overnight. The bulk of the solvent was evaporated in vacuo at 35°-40° C. and the concentrate dissolved in 200 mL of methylene chloride. The methylene chloride solution was washed with 100 mL of water, dried over anhydrous magnesium sulfate, filtered and concentrated in vacuo. The residue was purified on a 1.5×50 cm silica gel column eluted @ 5 psi with 200 mL of hexane, followed by 200 mL of 2% acetone in hexane, followed by 200 mL of 3% acetone in hexane, followed by 200 mL of 4% acetone in hexane and finally 200 mL of 10% acetone in hexane, to give 583 mg (20% yield) of the title compound; MS DCI-NH3M/Z: 388 (M+H)+ ; 1H NMR (CDCl3) δ 0.04 (s, 12H), 0.87 (s, 18H), 2.61 (d, 4H), 3.58 (s, 4H), 3.82 (s, 3H).

출처