A convenient procedure for transformation of tertiary cyclopropanols into 5-substituted isoxazoles

Synlett

Volumn , Issue 20, 2006, Pages 3427-3430

  Churykau, Dzmitry H ^a   Kulinkovich, Oleg G ^a  

^a BELARUSIAN STATE UNIVERSITY   (Belarus)

Author keywords

nitrosoketones; Cyclopropanols; Isoxazoles; Isoxazolines; Nitrosation

Indexed keywords

5 ETHOXY 5 HEXYL DELTA 2 ISOXAZOLINE; 5 HEXYL 5 HYDROXY DELTA 2 ISOXAZOLINE; 5 HYDROXY DELTA 2 ISOXAZOLINE DERIVATIVE; BETA NITROSOKETONE DERIVATIVE; CYCLOPROPANOL DERIVATIVE; ISOXAZOLE DERIVATIVE; KETONE DERIVATIVE; METHANOL; PROPANOL; UNCLASSIFIED DRUG;

ARTICLE;

EID: 33846528988     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-2006-956475     Document Type: Article

References (31)

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22. Cyclopropanols 1a-h were synthesized by the reductive cyclopropanation of the corresponding esters with ethylmagnesium bromide (compounds 1a-g) or propylmagnesium bromide (1h) in the presence of titanium(IV) isopropoxide (see ref. 1).
23. Utilization of amyl nitrite that was stored in a refrigerator for more than two weeks led to a significant reduction of the reaction rate and to a decrease in the yields of products.
24. After crystallization from MeOH pure E isomer was obtained.
25. Preparation of β-Nitrosoketones 2; Typical Procedure: Freshly prepared amyl nitrite (17 mL, 124 mmol) was added at 5 °C under Ar atmosphere to a solution of 1a (4.9 g, 31 mmol) in anhyd benzene (5 mL) in one portion. The mixture was stirred for 3 h and was kept at r.t. until the reaction was completed as monitored by TLC (2-3 d, see ref. 20). The mixture was concentrated in vacuo and was used for the preparation of isoxazoles without further purification. In order to obtain solid samples of 2a (as a mixture of Z and E isomers), the residue was diluted with petroleum ether, cooled and the crystals were filtered off. Single E isomer of 2a (3.45 g, 20.2 mmol, 65%) was obtained by the crystallization from hot MeOH as a yellowish solid (mp 86-87 °C).
26. 2 (163.61): C, 44.05; H, 6.16. Found: C, 43.90; H, 5.89.
27. Bellamy, L. J. Advances in Infrared Group Frequencies; Methuen & Co. Ltd.: Bungay/Suffolk, 1968.
28. 2, PE-EtOAc as eluent) as a yellowish oil (4.4 g, 91%).
29. 3 (185.22): C, 58.36; H, 8.16. Found: C, 58.60; H, 8.01.
30. 2 (171.24): C, 63.13; H, 10.01. Found: C, 63.28; H, 9.75.
31. The reaction proceeded less smoothly under elevated temperatures or in the presence of acidic or basic catalysts.