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Please login to access the full content or check if you have access via14.4.3.1.1.2.1.1.2 Variation 2: Condensation of 2-Hydroxyphenyl Ketones with Acyl Chlorides
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Williams, A. C.; Camp, N., Science of Synthesis, (2003) 14, 450.
Examples of the condensation of 2-hydroxyphenyl ketones with acyl chlorides to give 4H-1-benzopyran-4-ones are given in Schemes 101–103. Condensation of a 2-hydroxyphenyl ketone with a benzoyl chloride using potassium tert-butoxide gives an intermediate 1-(2-hydroxyphenyl)-3-arylpropane-1,3-dione 302; on refluxing with sulfuric acid in acetic acid, 302 gives the 2-aryl-4H-1-benzopyran-4-one 303 in poor to moderate yield. An analogous reaction using lithium hexamethylsilazanide as the base gives intermediate 304 and final cyclization product 305 in excellent yield. Condensation of 1-(2-hydroxy-4-methoxyphenyl)-4-phenylbutan-1-one with 3,4-dimethoxybenzoyl chloride gives 1-[2-(3,4-dimethoxybenzoyloxy)-4-methoxyphenyl]-4-phenylbutan-1-one (306), which cyclizes to give 2-(3,4-dimethoxyphenyl)-7-methoxy-3-(2-phenylethyl)-4H-1-benzopyran-4-one (307); similarly a 1-(2,4-dihydroxyphenyl)-2-benzimidazol-2-ylethanone gives 308 as an intermediate, which cyclizes to 309 on treatment with hydrochloric acid in ethanol. Other examples of the condensation of 2-hydroxyphenyl ketones with benzoyl or acyl chlorides include the formation of 310–320.
Meeeee 888 8M-8-Meeeeeeeee-8-eeee ee Meeeeeeeeeee ee 8-Meeeeeeeeeeee Meeeeee eeee Meee Meeeeeeee[888,888–888,888,888,888–888]
Meeeee 888 8M-8-Meeeeeeeee-8-eeee ee Meeeeeeeeeee ee 8-Meeeeeeeeeeee Meeeeee eeee Meee Meeeeeeee[888,888–888,888,888,888–888]
Meeeee 888 8M-8-Meeeeeeeee-8-eeee ee Meeeeeeeeeee ee 8-Meeeeeeeeeeee Meeeeee eeee Meee Meeeeeeee[888,888–888,888,888,888–888]
Meeeeeeeeeee Meeeeeeeee
8-Meeeeee-8-eeeeee-8M-8-eeeeeeeeee-8-eee (888, M8 = MMe; M8 = M8 = M8 = M8 = M8 = M); Meeeeee Meeeeeeee:[888]
e-MeMM (888.8 e, 8.8 eee) eee eeeeee ee e 8-M, eeeee-eeeeee eeeee-eeeeeeee eeeee eeeeeeee eeee e M8 eeeee, eeeeeeee eeeeee, eeeeeeeee eeeeeeeeeee, eee eeeeeeee. Mee MMM (888 eM) eee eeeee eee eee eeeeeee eeeeee ee 8–8°M eeee eeeeeeee. M eeee ee 8-(8-eeeeeee-8-eeeeeeeeeeeee)eeeeeeee (888 e, 8.8 eee) ee eee MMM eee eeeee eeeeee ee eee eeeeeeee eeeeee eeee e eeeeee ee 88 eee, eeeeeeeeeee eee eeeeeeeeeee eeeee 8°M. Mee eee eeee eee eeeeeee eee eee eeeeeee eeeeeee ee ee eee 88 eee, eeee eeeeeeee ee 8–8°M. Meeeeee eeeeeeee (888.8 e, 888 eM, 8.88 eee) eee eeeee eeeeeeee eeee 88 eee eeeeee eeeeeeeeeee eee eeeeeeeeeee eeeee 8°M, eeee eee eeeeeee eeeeeee ee ee eee e eeeeeee 8 e. Mee eeeeeee eee eeeeeeee ee 8–8°M eee e-MeMM (888.8 e, 8.8 eee) eeeee, ee e eeeeee ee eeeee eee eeeeeeeeeee eeee ee 88°M. M eeeeee eeeeeeeee eee eeeeeeee eee eee eeeeeee eeeeee eeeee eeeeee eeeeeeeee, eeee eeeeee ee ee eee eeeeeee eeee 8 M MMe ee eM 8. Mee eeeeeee eee eeeeeeeeeeee ee eeee e eeeeeee eeeee eee (888 e), eeeee eee eeeeeeeee ee MM8Me8 (888 eM), eee eee eeeeeee eeeeeee eeeeee eeeeeeeeeeee eeee 8% ee MeMMM8 (8 × 888 eM), eeeee (8 × 888 eM), eee M8M (888 eM). Mee eeeeeee eeeeee eeee eeeee (Me8MM8) eee eeeeeeeeee ee eeee ee eee (888 e), eeeee eee eeeeeeeeeeeeee (MeMM) ee eeeeee 8-(8-eeeeeee-8-eeeeeeeeeeeee)-8-eeeeeeeeeeeee-8,8-eeeee (888, M8 = MMe; M8 = M8 = M8 = M8 = M8 = M); eeeee: 888.8 e (88.8%). Meee eeeeeeee eee eeeeeeeee ee eeeeeee MeMM (888 eM) eee eeeee M8MM8 (88 eM) eeeee, eeee eee eeeeeee eeeeee eeeee eeeeee eee 8.8 e, eee eee eee eeee eeeeee eeeeeeeee eeee eeeeeee eee (8–8 M) eee M8M (8 M). Mee eeeeeee eee eeeeeee eeeeeeeeee eee 88 eee eeee eeeeeeeeeeee eeeeeeeee. Mee eeeeeeeeeee eee eeeeeee ee eeeeeeeeee eee eeeeee eeee M8M (8–8 M) eee eeee eeeee ee 88°M ee eeeeee e eeeee eeeee eeeee; eeeee: 888 e (88%); eeeeeee eeeee eeee 8-(8-eeeeeee-8-eeeeeeeeeeeee)eeeeeeee: 88%; ee 888–888°M. Meeeeeeeeeeeeeeee (eMeMM) eeee e eeeeee eeeeeeeeeee eeeee; ee 888–888°M.
8-Meeeeee-8-(8-eeeeeeeeeee)-8M-8-eeeeeeeeee-8-eee (888, M8 = M8 = M8 = M8 = M8 = M; M8 = MM; M8 = MM8); Meeeeee Meeeeeeee:[888]
M 8 M eeee ee MeMMMM ee MMM (88 eM, 88 eeee) eee eeeee ee e eeee-eeeeeee eeee ee 8-(8,8-eeeeeeeeeeeeeee)eeeeeeee (8.88 e, 88 eeee) ee MMM eeeee eeeee ee −88°M eeee 88 eee. Mee eeeeeee eee eeeeeee ee −88°M eee 8 e eeee ee −88°M eee e eeeeeee 8 e, eeee eeeeeeee ee −88°M eee e eeee ee 8-eeeeeeeeeeee eeeeeeee (8.8 e, 88 eeee) ee MMM (88 eM) eeeee eeee 88 eee. Meeeeeee eee eeeeeeeee ee −88°M eee e eeeeeee 88 eee, eeee ee ee eee 8 e, eeee eee eeeeeee eeeeee eeee e eeeeeee ee eee eeeee (888 e) eee MMe (88 eM). Me eee eeeeeeeee eeee MMMe8 (8 × 88 eM) eee eee eeeeeeee eeeeeeee eeeee (Me8MM8), eeee eee eeeeeee eeeeeee. Mee eeeeeee eee eeeee eeee eeeeeee MeMM (888 eM) eee eeeee M8MM8 (8.8 eM) eee eeeeee ee 88–888°M eee 8 e. Mee eeeeeee eee eeeeeeeeeeee ee 88% ee eee eeeeeeee eeeeee eeee eeeeee eeee eee eeeee (888 eM). Mee eeeeeee eee eeeeeeee ee eeeeeeeeee, eeeeee eeee M8M, eee eeeee; eeeee: 8.88 e (88%). Meeeeeeeeeee eeee eeeeeeee eeeee ee eeeeeeee ee eeeeeeeeeeeeeeeee (eeeeeee).
Meeeee 8-Mee-8-(8,8,8-eeeeeeeeeeeeeeee)-8M-8-eeeeeeeeee-8-eeeeeeeeeee (888, M8 = M8 = M8 = M; M8 = M8 = M8 = MMe; M8 = Me); Meeeeee Meeeeeeee:[888]
M eeeeeee ee eeeeee 8-(8-eeeeeeeeeeeee)-8-eeeeeeeeeeeee (888 ee, 8 eeee), Me (88 ee, 8 eeee), eee MeMM (88 eM), eee eee MMe8 eee eeeeee ee 88–88°M eeeee eee ee eee Me eee eeeeeeeee (∼8 e). Mee eeeeeee eee eeeeeee eeeee eeeeeee eeeeeeee eee eeeeeee (88 eM) eee 8,8,8-eeeeeeeeeeeeeeeee eeeeeeee (888 ee, 8 eeee) eeeee ee eee eeeeeee. Mee eeeeeee eee eeeeee eeeee eeeeee eee 8 e, eeee eeeeee ee ee eee eeeeeee eeee 88% (e/e) ee MeMM (88 eM), eeee eeeeeeeee eeee MMMe8 (8 × 88 eM). Mee eeeeeeee eeeeeee eeeeeeee eeee eeeeee eeee eeeee (8 × 88 eM) eee eeeee (Me8MM8), eeee eee eeeeeee eeeeeee eeeee eeeeeee eeeeeeee. Meeeeeeeeeee ee eee eeeeeee ee eeeeeeeeeeeeee (eeeeee eee, eeeeee/MeMMe eeeeeeee 88:8 ee 8:8) eeee eee eeeeeee; eeeee: 888 ee (88%); ee 88–88°M.
Meeeeeeeeee 8M-8-Meeeeeeeee-8-eeee 888; Meeeeee Meeeeeeee:[888]
MMM (8.88 e, 88 eeee) eee eeeee ee e eeee ee eee eeeeeeeeeee 8-(8-eeeeeeeeeeeee)eeeeeeee 888 (88 eeee) eee eee eeeeeeeeeee eeee eeeeeeee (88.8 eeee) ee eeeee eeeeeeee (88 eM). Mee eeeeeee eee eeeeeee ee 88–88°M eee 8–88 e, eeeeee ee ee, eeeeee eeee 8 M MMe eeeeeeeeee eee, eee eeeeeeeee eeee MeMMe. Mee eeeeeeee eeeeeeee eeee eeeeee eeee M8M, eeeee (Me8MM8), eee eeeeeeeeee ee eeeeeee ee eeeee. Mee eeeee eeeeeee eee eeeeeeee ee eeeee eeeeeeeeeeeeee [eeeeeeeee eeeee (ee 88–88°M)/MeMMe] eeeeeeee ee eeeeeeeeeeeeeeeee ee eeeeeee eee eeeeeee; eeeee: 88–88%.
8-Meee-8-eeeeeee-8M-8-eeeeeeeeee-8-eeee 888; Meeeeee Meeeeeeee:[888]
Me e eeee ee 8-(8,8-eeeeeeeeeeeeeee)eeeeeeee ee eee eeeeeee (8 eM·eeee−8) eee eeeee eeeee M8MM8 (8 eeeee). Mee eeee eee eeeeeee ee ee eee 88 eee eeee eee eeeee eeeeeeee (8 eeeee) eeeee, eee eee eeeeeee eeeeee eeeee eeeeee, eeee eeeeeeee, eee 88 e. Meeee eeeeeee ee ee, M8M eee eeeee eee eee eeeeeee eeeeeeeeee. Mee eeeeeee eee eeeeeeeee eeee MeMMe, eee eeeeeee eeeeee eeee M8M eee eeeee, eee eee eeeeeee eeeeeee. Meeeeeeeeeee ee eee eeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, eeeeee/MeMMe 8:8) eeeeeeee eee eeeeeee; eeeee: 88–88%.
Meeeeeeeeee 8-Meeeeee-8-(8-eeeeeeeeeeeee)-8-eee-8M-8-eeeeeeeeee-8-eeeeeeeeee 888; Meeeeee Meeeeeeee:[888]
Mee eeee eeeeeeee eeeee 888 (8 ee 88 eeee) eee eeeee eeeeeeee ee e eeeeeee eeeeeeeeee ee eee eeeeeeeeeee 8-(8,8-eeeeeeeeeeeeeee)-8-(8-eeeeeeeeeeeee)eeeeeeee 888 (8 eeee), eeeee M8MM8 (8.88 e, 88 eeee), eee MMMM (8.88 e, 8 eeee) ee eeeee eeeeeee (88 eM) eeeee eeeee ee ee. Meeee eeeeeeee eee 8 e ee ee, eee eeeeeee eee eeeeee ee ee eee eeee ee 88°M eee 88–88 e, eeee eeeeeee ee eeee ee ee. Mee eeeee eee eeeeeee ee eeeeeeeeee eee eeeeeeeee ee M8M (888 eM) eee eee eeeeeeeee eeee eeeeeeeeeee eeee 8 M MMe eee eeeeeeeee eeee MeMMe (8 × 88 eM). Mee eeeeeeee eeeeeeee eeee eeeeee eeee M8M (888 eM), eeeee (MeMM8), eee eeeeeeee eeee eee eeeeeee eeeeeeee eeee eee eeeee eeeeeeeeee. Meeeeeeeeee ee eeee eeeeeee eeee ee eeeeee eee eeee eee eeeeeeeee ee MeMM (888 eM) eee eeeeeee eeee ee 8.8 M MMMM8 (88 eM) eee eeeeeee (88 eM), eee eeeeeee ee ee eee 88 e. Mee eeeeeee eeeeeeee eeee eeeeeee eeeee eeeeeee eeeeeeee, eee M8M (88 eM) eee eeeee, eee eeee eee eeeeeeeeeee eeee eee MMe eee eeeeeeeee eeee MeMMe (88 eM). Mee MeMMe eeeeeee eee eeeeee eeee M8M (88 eM), eeeee (MeMM8), eee eeeeeeeeeeee ee eeee ee eeeeee eee. Meeeeeeeeeee ee eeeee eeeeeeeeeeeeee (eeeeee eee, eeeeeeee MM8Me8 ee MM8Me8/eeeeeee 8:8) eeeeeeee ee eeeeeeeeeeeeeeeee (eeeeeee/Me8M 8:8) eeeeeeee eee eeeeeee; eeeee: 88–88%.
References
[417] | Meeeee, M, M.; Mee Me Meeee, M., Mee. M. Mee. Meee., (8888) 88, 888. |
[446] | Meee, M. M.; Meee, M. M.; Meeeeeee, M. M.; Meee, M. M.; Meeeee, M. M., M. Mee. Meee., (8888) 88, 8888. |
[447] | Meee, M.; Meeee, M.; Meeeeeee, M.-M.; Meeeeeeeee, M., Meeeeee, (8888), 8888. |
[448] | Meeeeee, M.; Meeeeeeeeee, M.; Meee, M. M.; Meeeeee, M. M., M. Mee. Meee., (8888) 88, 888. |
[450] | Meeeeee, M.; Meeeeeeeeee, M., M. Mee. Meee., (8888) 88, 8888. |
[467] | Me-Meeeeee, M.; Meeeeeeeee, M.; Meeeeeeee, M., Meeeeeeee, (8888), 888. |
[489] | Meeee, M. M.; Meeeee, M. M.; Meee, M. M.; Meeeee, M. M.; Meeee, M.; Meeeee, M., Meeeee M. Meee., Meee. M, (8888) 88, 8888. |
[490] | Meeee, M.; Meeeeeeeeeeee, M. M., Meeeee M. Meee., Meee. M, (8888) 88, 888. |
[491] | Meeeeee, M. M.; Meeee, M. M.; Meeeeeee, M. M., Meeeee M. Meee., Meee. M, (8888) 88, 888. |
[492] | Mee, M. M.; Mee, M. M. M., Meeeee M. Meee., Meee. M, (8888) 88, 888. |
[493] | Meee, M.-M.; Meeeeeee, M. M.; Meeeeee, M.; Meeeeeee, M.; Meeeee, M.; Meeee, M.; Me Meeee, M., Meeeeee Mee. Meee., (8888), 8888. |
[494] | Meee, M. M.; Meeeeee, M.; Meeeeeeeee, M. M. M., Meeeee M. Meee., Meee. M, (8888) 88, 888. |
[495] | Meee, M. M. M.; Meeeee, M., Meeeee M. Meee., Meee. M, (8888) 88, 888. |
[496] | Meee, Me Meee, M.; Meeeeee, M.; Mee, M.; Meeeeee, M.; Meeee, M.; Meeeeeee, M., Meeeeeeee, (8888), 888. |
[497] | Meeeee, M. M.; Meeeeeeeee, M. M. M.; Meeeeeeeeeeeee, M., Meeeee M. Meee., Meee. M, (8888) 88, 888. |
Meeeeee Meeeeeeeeee
- 8.Meeeee-Meee, (8888) 8/8e8, 8888.