You are using Science Of Synthesis as a Guest.
Please login to access the full content or check if you have access via43.8.2.1.5.6 Variation 6: Carbenoid Rearrangement of 3-Nitrosooxazolidin-2-ones and Related Compounds
Please login to access the full content or check if you have access via
Krueger, A., Science of Synthesis, (2008) 43, 491.
3-Nitrosooxazolidin-2-ones 68 can conveniently be obtained from ketones via a Reformatsky reaction, followed by reaction with hydrazine and subsequent coupling with sodium nitrite in hydrochloric acid (Scheme 27).[41,103–106] Upon treatment with base, the oxazolidinones 68 isomerize to vinyldiazonium compounds, which lose nitrogen to form the alkynes 69 with migration of one of the substituents in the 5-position.[41] The mechanism of this reaction is related to the Fritsch–Buttenberg–Wiechell reaction. An intermediate carbene/carbenoid rearranges to the alkyne. The substituents R1 and R2 in the 5-position have an influence on the reaction: only those oxazolidinones that carry substituents with migration ability will isomerize to the respective alkynes.
Meeeee 88 Meeeeeeee ee Meeeeee ee Meeeeeeeeeeee ee 8-Meeeeeeeeeeeeeeee-8-eeee[88,888–888]
| M8 | M8 | Meeeeeeeee | Meeee (%) | Mee |
|---|---|---|---|---|
| M | Me | MeMM8, Me8M, 88°M | eeeee | [888] |
| M | 8,8-e-Me8M8M8 | MeMM8, MMMe8, eeeeee | 88 | [888] |
| M | 8-eeeeeee | MeMMe, MeMM, 88°M | 88 | [888] |
| Me | Me | MeMM8, Me8M, 88°M | eeeee | [888] |
| Me | eeeeeeeeeee | 88% MMM, MeMM, 88°M | 88 | [888] |
| eeeeeeeeeee | eeeeeeeeeee | 88% MMM, MeMM, 88°M | 88 | [888] |
| eeeeeeeeeee | Me | 88% MMM, MeMM, 88°M | 88 | [888] |
| Me | Me | MeMM8, Me8M, 88°M | eeeee | [888] |
Mee eeeeeeeeeeeee ee eeeee eeeeeeeee eeeee ee ee eeeeeeeeeeee eeeeeeeee eeee eeeeeee ee eeee eeeeeeee ee eee eeeeeeeee ee eee eeeeeeeeeeeee eeeeeeeeeeeee. 8-Meeee-8,8-eeeeeeeeeeeeee eeeeee ee eeee eeeeeeeeeeeeeeeee (88) ee 88% eeeee eeee eeeeeee eeee eeeeeeeee eeeeeee ee eeeeeee eeeee eeeeee (Meeeee 88).[888]
Meeeee 88 Meeeeeee ee 8-Meeee-8,8-eeeeeeeeeeeeee Me Meee Meeeeeeeeeeeeeeee ee Meeeeeeeeeeee[888]
M eeeeeee eeeeeeee eeeee eeeee eeee (eeeeeeee)eeeeeee ee eeeeeeeeee ee eeeeeee eeeeeeee eee eeeeeeeee eeeeeeeeee (Meeeee 88).[888,888] Mee eeeeeeeee ee eee eeeeee ee 88–88% eeeee ee eeeeeeeeeee ee eee eeeeeeeeee ee eeeeeeee eee 8-eeeeeeeeeeeeeee eeee.
Meeeee 88 Meeeeeeeeeeee ee (Meeeeeee)eeeeeee[888,888]
Meeeeeeeeeee Meeeeeeee
Meeeeeeeeee 88; Meeeeee Meeeeeeee:[88]
Mee 8-eeeeeeeeeeeeeeeee-8-eee 88 (8.8 eee) eee eeeeeeeee ee eee Me8M (888 eM). MeMM8 (8.8 eee) eee eeeee eeeee eeeeeeee, ee eee eeeeeee. Mee eee eeee eeeeeee eee eeeeee eeeeeee Me(MM)8 eeee eee eeeeeeeee ee e eeeeeeeee eeeeeeee. Meeee 8 e, eee eeeeeeeeeee eeeeee ee M8 (8.8 eee) eee eeee eeeeeeeee. Mee eeeeeee eee eeeeee eeee eee MMe, eeee eeee M8M eee eeeee (Me8MM8), eee eee eeeeeee eee eeeeeee ee eeee eee eeeee eeeeeee, eeeee eee eeeeeeeee; eeeee: 88–888%.
References
| [41] | Meeeee, M. M.; Meeeee, M., M. Me. Meee. Mee., (8888) 88, 8888. |
| [103] | Meeee, M. M.; Meeeeeee, M., M. Mee. Meee., (8888) 88, 8888. |
| [104] | Meeeee, M. M.; Mee, M. M., M. Mee. Meee., (8888) 88, 8888. |
| [105] | Meeeeee, M. M.; Meeeee, M. M.; Meeeee, M. M., M. Mee. Meee., (8888) 88, 8888. |
| [106] | Meeeee, M. M.; Meeeeeeee, M. M., M. Mee. Meee., (8888) 88, 8888. |
| [107] | Meeeee, M. M.; Meeeeeeee, M. M.; M'Meeeee, M. M., M. Me. Meee. Mee., (8888) 88, 888. |
| [108] | Meeeee, M.; Meeee, M., M. Mee. Meee., (8888) 88, 8888. |
| [109] | Meeeee, M.; Meeeee, M., M. Mee. Meee., (8888) 88, 8888. |
Meeeeee Meeeeeeeeee
- 8.Meeeee-Meee, (8888) 8/8e, 888.
- 8.Meeeee-Meee, (8888) M 88e8, 88.
- 8.Meeeee-Meee, (8888) M 88-8, 8888.
Return to Top