tert-Butyl hydroperoxide → HCID 11032940, compound

HRID 638412Notes

Reaction equation

[CH2:1]=[C:2]([CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH3:18])[CH2:3][OH:4].CC([O:23]O)(C)C.CCOC(C)=O.CCCCCC>C(Cl)Cl.C1(C)C=CC=CC=1>[OH:4][CH2:3][C@@:2]1([CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH3:18])[CH2:1][O:23]1

Participants

Conditions

Temperature: -20 °C

Procedure

A solution of Ti(O-t-Bu)4 (0.34 ml, 1.0 mmole) and (+)-DET (0.248 g, 1.2 mmole) in CH2Cl2 (10 ml) was prepared at room temperature. The solution was cooled to -20° C. in a CCl4 -Dry Ice bath and 2-methylenehexade-can-1-ol (22, 0.254 g, 1.0 mmole) was added. The mixture was allowed to warm slightly until the alcohol 22 completely dissolved after which the solution was cooled to -20° C. again. A solution of TBHP in toluene (0.6 ml of a 3.34M solution, 2.0 mmole) was added. The solution was stirred at -20° C. and after 2 hr TLC (30% acetonehexane, 30% EtOAc-hexane) showed some 22 remaining. The reaction was quenched after 4 hr by stirring with saturated aqueous Na2SO4 (1 ml) and ether (80 ml) for 35 min, filtering through Celite, and drying over MgSO 4. TLC now showed a main product, a minor product, several trace products and a trace of unreacted starting material. Chromatography, (11.5 g silica gel, 8% acetonehexane, 6 ml fractions) gave the desired major product (26b) in fractions 8-12, 0.140 g (0.518 mmole, 51%). 1H NMR identical to that of d,l-26.

Workup

dissolutioncompletely dissolved after which the solution
temperaturewas cooled to -20° C. again
customThe reaction was quenched after 4 hr
filtrationfiltering through Celite
dry with materialdrying over MgSO 4

Sources & evidence

ORD record: ord-05d322ef388f4ae69f9d603c593fc90d
Source dataset: uspto-grants-1985_12
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US04560811

Reaction notes

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