The Influence of HCl Concentration on the Rate of the Hydrolysis–Condensation Reaction of Phenyltrichlorosilane and the Yield of (Tetrahydroxy)(Tetraphenyl)Cyclotetrasiloxanes, Synthesis of All Its Geometrical Isomers and Thermal Self-Condensation of Them under “Pseudo”-Equilibrium Conditions
The rate of hydrolysis–condensation reaction of phenyltrichlorosilane in water-acetone solutions and the product yields were shown to significantly depend on the concentration of HCl (C<sub>HCl</sub>) in the solutions. The main product of the reaction was all-<i>cis-</i>(tetr...
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MDPI AG
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doaj-bd21446ee2b34dbb86f9f028ea26a9db2021-07-23T13:57:00ZengMDPI AGMolecules1420-30492021-07-01264383438310.3390/molecules26144383The Influence of HCl Concentration on the Rate of the Hydrolysis–Condensation Reaction of Phenyltrichlorosilane and the Yield of (Tetrahydroxy)(Tetraphenyl)Cyclotetrasiloxanes, Synthesis of All Its Geometrical Isomers and Thermal Self-Condensation of Them under “Pseudo”-Equilibrium ConditionsIrina M. Petrova0Yury I. Lyakhovetsky1Nikolai S. Ikonnikov2Nataliya N. Makarova3A.N. Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences, 28 Vavilov St., 119991 Moscow, RussiaA.N. Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences, 28 Vavilov St., 119991 Moscow, RussiaA.N. Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences, 28 Vavilov St., 119991 Moscow, RussiaA.N. Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences, 28 Vavilov St., 119991 Moscow, RussiaThe rate of hydrolysis–condensation reaction of phenyltrichlorosilane in water-acetone solutions and the product yields were shown to significantly depend on the concentration of HCl (C<sub>HCl</sub>) in the solutions. The main product of the reaction was all-<i>cis-</i>(tetrahydroxy)(tetraphenyl)cyclotetrasiloxane. This was different from the earlier published results of analogous reactions of <i>m</i>-tolylSiCl<sub>3</sub>, <i>m</i>-ClPhSiCl<sub>3</sub>, and <i>α</i>-naphtylSiCl, in which some products of other types were formed. For example, <i>trans</i>-1,1,3,3-tetrahydroxy-1,3-di-<i>α</i>-naphtyldisiloxane was obtained in the case of <i>α</i>-naphtylSiCl<sub>3</sub>. All-<i>cis-</i>(tetrahydroxy)(tetraphenyl)cyclotetrasiloxane was treated in acetone with HCl to give the other three geometric isomers (<i>cis-cis-trans</i>-, <i>cis-trans-</i>, and all-<i>trans-</i>). The thermal self-condensation of these four isomers under “pseudo”-equilibrium conditions (under atmospheric pressure) was investigated in different solvents, in quartz or molybdenum glass flasks. The compositions of the products were monitored by APCI-MS and <sup>29</sup>Si NMR spectroscopy. It was shown that all-<i>cis</i>- and <i>cis-cis-trans</i>-isomers in toluene or anisole mostly gave the cage-like Ph-T<sub>8,10,12,14</sub> and uncompleted cage-like Ph-T<sub>10,12</sub>OSi(HO)Ph compounds. In contrast to these two isomers, the <i>cis-trans</i>–isomer in toluene mainly formed dimers with the loss of one or two molecules of water. However, in acetonitrile, significant amounts of Ph-T<sub>10,12</sub> and Ph-T<sub>10,12</sub>OSi(HO)Ph species were formed along with the dimers. All-<i>trans</i>-isomer did not enter into the reaction at all.https://www.mdpi.com/1420-3049/26/14/4383hydrolysis-condensationself-condensation“pseudo”-equilibrium conditionsphenyltrichlorosilaneisomers of (tetrahydroxy)(tetraphenyl)tetrasiloxanecage-like compounds |
| collection |
DOAJ |
| language |
English |
| format |
Article |
| sources |
DOAJ |
| author |
Irina M. Petrova Yury I. Lyakhovetsky Nikolai S. Ikonnikov Nataliya N. Makarova |
| spellingShingle |
Irina M. Petrova Yury I. Lyakhovetsky Nikolai S. Ikonnikov Nataliya N. Makarova The Influence of HCl Concentration on the Rate of the Hydrolysis–Condensation Reaction of Phenyltrichlorosilane and the Yield of (Tetrahydroxy)(Tetraphenyl)Cyclotetrasiloxanes, Synthesis of All Its Geometrical Isomers and Thermal Self-Condensation of Them under “Pseudo”-Equilibrium Conditions Molecules hydrolysis-condensation self-condensation “pseudo”-equilibrium conditions phenyltrichlorosilane isomers of (tetrahydroxy)(tetraphenyl)tetrasiloxane cage-like compounds |
| author_facet |
Irina M. Petrova Yury I. Lyakhovetsky Nikolai S. Ikonnikov Nataliya N. Makarova |
| author_sort |
Irina M. Petrova |
| title |
The Influence of HCl Concentration on the Rate of the Hydrolysis–Condensation Reaction of Phenyltrichlorosilane and the Yield of (Tetrahydroxy)(Tetraphenyl)Cyclotetrasiloxanes, Synthesis of All Its Geometrical Isomers and Thermal Self-Condensation of Them under “Pseudo”-Equilibrium Conditions |
| title_short |
The Influence of HCl Concentration on the Rate of the Hydrolysis–Condensation Reaction of Phenyltrichlorosilane and the Yield of (Tetrahydroxy)(Tetraphenyl)Cyclotetrasiloxanes, Synthesis of All Its Geometrical Isomers and Thermal Self-Condensation of Them under “Pseudo”-Equilibrium Conditions |
| title_full |
The Influence of HCl Concentration on the Rate of the Hydrolysis–Condensation Reaction of Phenyltrichlorosilane and the Yield of (Tetrahydroxy)(Tetraphenyl)Cyclotetrasiloxanes, Synthesis of All Its Geometrical Isomers and Thermal Self-Condensation of Them under “Pseudo”-Equilibrium Conditions |
| title_fullStr |
The Influence of HCl Concentration on the Rate of the Hydrolysis–Condensation Reaction of Phenyltrichlorosilane and the Yield of (Tetrahydroxy)(Tetraphenyl)Cyclotetrasiloxanes, Synthesis of All Its Geometrical Isomers and Thermal Self-Condensation of Them under “Pseudo”-Equilibrium Conditions |
| title_full_unstemmed |
The Influence of HCl Concentration on the Rate of the Hydrolysis–Condensation Reaction of Phenyltrichlorosilane and the Yield of (Tetrahydroxy)(Tetraphenyl)Cyclotetrasiloxanes, Synthesis of All Its Geometrical Isomers and Thermal Self-Condensation of Them under “Pseudo”-Equilibrium Conditions |
| title_sort |
influence of hcl concentration on the rate of the hydrolysis–condensation reaction of phenyltrichlorosilane and the yield of (tetrahydroxy)(tetraphenyl)cyclotetrasiloxanes, synthesis of all its geometrical isomers and thermal self-condensation of them under “pseudo”-equilibrium conditions |
| publisher |
MDPI AG |
| series |
Molecules |
| issn |
1420-3049 |
| publishDate |
2021-07-01 |
| description |
The rate of hydrolysis–condensation reaction of phenyltrichlorosilane in water-acetone solutions and the product yields were shown to significantly depend on the concentration of HCl (C<sub>HCl</sub>) in the solutions. The main product of the reaction was all-<i>cis-</i>(tetrahydroxy)(tetraphenyl)cyclotetrasiloxane. This was different from the earlier published results of analogous reactions of <i>m</i>-tolylSiCl<sub>3</sub>, <i>m</i>-ClPhSiCl<sub>3</sub>, and <i>α</i>-naphtylSiCl, in which some products of other types were formed. For example, <i>trans</i>-1,1,3,3-tetrahydroxy-1,3-di-<i>α</i>-naphtyldisiloxane was obtained in the case of <i>α</i>-naphtylSiCl<sub>3</sub>. All-<i>cis-</i>(tetrahydroxy)(tetraphenyl)cyclotetrasiloxane was treated in acetone with HCl to give the other three geometric isomers (<i>cis-cis-trans</i>-, <i>cis-trans-</i>, and all-<i>trans-</i>). The thermal self-condensation of these four isomers under “pseudo”-equilibrium conditions (under atmospheric pressure) was investigated in different solvents, in quartz or molybdenum glass flasks. The compositions of the products were monitored by APCI-MS and <sup>29</sup>Si NMR spectroscopy. It was shown that all-<i>cis</i>- and <i>cis-cis-trans</i>-isomers in toluene or anisole mostly gave the cage-like Ph-T<sub>8,10,12,14</sub> and uncompleted cage-like Ph-T<sub>10,12</sub>OSi(HO)Ph compounds. In contrast to these two isomers, the <i>cis-trans</i>–isomer in toluene mainly formed dimers with the loss of one or two molecules of water. However, in acetonitrile, significant amounts of Ph-T<sub>10,12</sub> and Ph-T<sub>10,12</sub>OSi(HO)Ph species were formed along with the dimers. All-<i>trans</i>-isomer did not enter into the reaction at all. |
| topic |
hydrolysis-condensation self-condensation “pseudo”-equilibrium conditions phenyltrichlorosilane isomers of (tetrahydroxy)(tetraphenyl)tetrasiloxane cage-like compounds |
| url |
https://www.mdpi.com/1420-3049/26/14/4383 |
| work_keys_str_mv |
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