Fluoride-Catalyzed Nucleophilic Perfluoroalkylations of Acetylenic Ketones or Aldehydes

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Title:Fluoride-Catalyzed Nucleophilic Perfluoroalkylations of Acetylenic Ketones or Aldehydes
Creators:
Manandhar, Sudha
Singh, Rajendra P.
Shreeve, Jean'ne M.
Journal or Publication Title:
Collection of Czechoslovak Chemical Communications, 67, 9, pp. 1296-1304
Uncontrolled Keywords:Nucleophilic additions, Fluoride, Perfluoroakylations, Ketones, Trimethyl(perfluoroalkyl)silanes, Alkynes, Aldehydes

Abstract

Reactions of 4-phenylbut-3-yn-2-one (<strong>1a</strong>) and phenylpropynal (<strong>1b</strong>) with trimethyl(perfluoroalkyl)silanes (Me<sub>3</sub>SiR<sub>f</sub>) (R<sub>f</sub> = CF<sub>3</sub>, C<sub>2</sub>F<sub>5</sub>, n-C<sub>6</sub>F<sub>13</sub>, n-C<sub>7</sub>F<sub>15</sub>, n-C<sub>8</sub>F<sub>17</sub>) in the presence of catalytic amounts of cesium fluoride (CsF) have been studied. Compounds <strong>1a</strong>, <strong>1b</strong> were reacted with 0.5 equivalent excess of Me<sub>3</sub>SiR<sub>f </sub>in ethylene glycol dimethyl ether (monoglyme) at 25 °C for R<sub>f</sub> = CF<sub>3</sub>, C<sub>2</sub>F<sub>5</sub> and at 50 °C for R<sub>f</sub> = n-C<sub>6</sub>F<sub>13</sub>, n-C<sub>7</sub>F<sub>15</sub>, n-C<sub>8</sub>F<sub>17</sub> to give the corresponding perfluoroalkylated alcohols in good yields after acid hydrolysis. The new compounds were characterized by IR, NMR (<sup>1</sup>H, <sup>19</sup>F, <sup>13</sup>C), MS and elemental analysis. In these reactions, tetrabutylammonium fluoride (TBAF) is also effective as the fluoride catalyst. The alcohols with CF<sub>3</sub> or C<sub>2</sub>F<sub>5</sub> are viscous liquids whereas those with n-C<sub>6</sub>F<sub>13</sub>, n-C<sub>7</sub>F<sub>15</sub> or n-C<sub>8</sub>F<sub>17</sub> are solids. They are soluble in common organic solvents and stable to air and moisture. <p>

Title:Fluoride-Catalyzed Nucleophilic Perfluoroalkylations of Acetylenic Ketones or Aldehydes
Creators:
Manandhar, Sudha
Singh, Rajendra P.
Shreeve, Jean'ne M.
Uncontrolled Keywords:Nucleophilic additions, Fluoride, Perfluoroakylations, Ketones, Trimethyl(perfluoroalkyl)silanes, Alkynes, Aldehydes
Divisions:Life and Chemical Sciences > Institute of Organic Chemistry and Biochemistry > Collection of Czechoslovak Chemical Communications
Journal or Publication Title:Collection of Czechoslovak Chemical Communications
Volume:67
Number:9
Page Range:pp. 1296-1304
ISSN:0010-0765
E-ISSN:1212-6950
Publisher:Institute of Organic Chemistry and Biochemistry
Related URLs:
URLURL Type
http://dx.doi.org/10.1135/cccc20021296UNSPECIFIED
ID Code:1993
Item Type:Article
Deposited On:06 Feb 2009 17:14
Last Modified:06 Feb 2009 16:14

Citation

Manandhar, Sudha; Singh, Rajendra P.; Shreeve, Jean'ne M. (2002) Fluoride-Catalyzed Nucleophilic Perfluoroalkylations of Acetylenic Ketones or Aldehydes. Collection of Czechoslovak Chemical Communications, 67 (9). pp. 1296-1304. ISSN 0010-0765

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