Unique Dialkylsulfonio-Methylation of the 7,8-C2B9H12(-) Ion to the 9-R2S-CH2-7,8-C2B9H11 Zwitterions by Formaldehyde and Dialkyl Sulfides. General Synthesis of the Compounds 10-R2E-7,8-C2B9H11 (E = O, S)

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Title:Unique Dialkylsulfonio-Methylation of the 7,8-C2B9H12(-) Ion to the 9-R2S-CH2-7,8-C2B9H11 Zwitterions by Formaldehyde and Dialkyl Sulfides. General Synthesis of the Compounds 10-R2E-7,8-C2B9H11 (E = O, S)
Creators:
Plešek, Jaromír
Jelínek, Tomáš
Mareš, František
Heřmánek, Stanislav
Journal or Publication Title:
Collection of Czechoslovak Chemical Communications, 58, 7, pp. 1534-1547

Abstract

Dialkylsulfonio-methylation has been observed on the treatment of the 7,8-C<sub>2</sub>B<sub>9</sub>H<sub>12</sub><sup>(-)</sup> ion with formaldehyde and dialkyl sulfides in aqueous acidic medium. Four zwitterions of the type 9-R<sub>2</sub>S-CH<sub>2</sub>-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>11</sub> were formed with dimethyl and diethyl sulfide, tetrahydrothiophene and thioxane. In contrast, dialkyl ethers (diethyl ether, tetrahydrofuran, dioxane) afforded low amounts of the 10-R<sub>2</sub>O-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>11</sub> zwitterions, with the carborane 4,5- C<sub>2</sub>B<sub>7</sub>H<sub>13</sub> being the principal product. Using acetaldehyde instead of formaldehyde, moderate yields of the 10-R<sub>2</sub>O- and high yields of the 10-R<sub>2</sub>S-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>11</sub> derivatives were obtained. With tertiary amines, only corresponding ammonium salts precipitated. Possible reaction pathways for these transformations are discussed and compared with the specific degradation of the 7,8-C<sub>2</sub>B<sub>9</sub>H<sub>12</sub><sup>(-)</sup> ion to the <i>arachno</i>-4,5- C<sub>2</sub>B<sub>7</sub>H<sub>13</sub> carborane.

Title:Unique Dialkylsulfonio-Methylation of the 7,8-C2B9H12(-) Ion to the 9-R2S-CH2-7,8-C2B9H11 Zwitterions by Formaldehyde and Dialkyl Sulfides. General Synthesis of the Compounds 10-R2E-7,8-C2B9H11 (E = O, S)
Creators:
Plešek, Jaromír
Jelínek, Tomáš
Mareš, František
Heřmánek, Stanislav
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:58
Number:7
Page Range:pp. 1534-1547
ISSN:0010-0765
E-ISSN:1212-6950
Publisher:Institute of Organic Chemistry and Biochemistry
Related URLs:
URLURL Type
http://dx.doi.org/10.1135/cccc19931534UNSPECIFIED
ID Code:273
Item Type:Article
Deposited On:06 Feb 2009 16:59
Last Modified:06 Feb 2009 15:59

Citation

Plešek, Jaromír; Jelínek, Tomáš; Mareš, František; Heřmánek, Stanislav (1993) Unique Dialkylsulfonio-Methylation of the 7,8-C2B9H12(-) Ion to the 9-R2S-CH2-7,8-C2B9H11 Zwitterions by Formaldehyde and Dialkyl Sulfides. General Synthesis of the Compounds 10-R2E-7,8-C2B9H11 (E = O, S). Collection of Czechoslovak Chemical Communications, 58 (7). pp. 1534-1547. ISSN 0010-0765

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