Reactions of Dimethyl Sulfite with Diorganotin Oxides. One-Pot Synthesis of Methoxydiorganotin Methanesulfonates through the Arbuzov Rearrangement, Spectroscopic Characterization of These Compounds an
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- 作者：Suraj P. Narula ; Sukhjeevan Kaur ; Ravi Shankar ; Sushma Verma ; Paloth Venugopalan ; Surinder K. Sharma ; and Raj K. Chadha
- 刊名：Inorganic Chemistry
- 出版年：1999
- 出版时间：October 18, 1999
- 年：1999
- 卷：38
- 期：21
- 页码：4777 - 4783
- 全文大小：114K
- 年卷期：v.38,no.21(October 18, 1999)
- ISSN：1520-510X
文摘
One-pot reactions of diorganotin oxides, R2SnO, with dimethyl sulfite under reflux conditions (125-127 
C)proceed via the Arbuzov rearrangement at the sulfur center, yielding the corresponding methoxydiorganotinmethanesulfonates, R2Sn(OMe)OS(O)2Me [R = n-Pr (1), n-Bu (2), i-Bu (3), c-Hx (4)], as white, hygroscopicsolids. These compounds react with 
-diketones [acetylacetone (Hacac), benzoylacetone (Hbzac), and dibenzoylmethane (Hbzbz)] to afford mixed-ligand organotin derivatives, R2Sn(X)OS(O)2Me [X = acac, R = n-Pr (5),n-Bu (6); X = bzac, R = n-Pr (7), n-Bu (8); X = bzbz, R = n-Pr (9), n-Bu (10), i-Bu (11)]. Selective hydrolysisof the Sn-OMe bond in 1-3 occurs, resulting in the isolation of (
-hydroxo)diorganotin methanesulfonates,R2Sn(OH)OS(O)2Me [R = n-Pr (12), n-Bu (13), i-Bu (14)]. All the compounds are characterized by elementalanalyses and IR, multinuclear (1H, 13C, and 119Sn) NMR, and mass spectra. Unequivocal evidence of the presenceof the methanesulfonate group is provided by the X-ray crystal structures of 6, 10, and 13. [For 6: trigonal spacegroup R
(No. 148), a = 28.664(1) Å, c = 13.056(1)Å, Z = 18. For 10: triclinic space group P
(No. 2), a =13.056(3) Å, b = 14.062(3) Å, c = 16.282(3) Å, Z = 4. For 13: triclinic space group P (No. 2), a = 9.089(2)Å, b = 12.040(2) Å, c =13.894(2) Å, Z = 2]. For 6 and 10, the solid-state structural analyses reveal dimericstructures with a bridging bidentate methanesulfonate group forming a centrosymmetric eight-membered ring.Compound 13 possesses a polymeric sheet structure with repeating 20-membered macrocycles (including twofour-membered [Sn(OH)]2 rings) by virtue of the bridging bidentate methanesulfonate groups. A search for apossible pathway to give Arbuzov-rearranged products 1-4 leads us to speculate that there is an initial catalytictransformation of dimethyl sulfite to methyl methanesulfonate via intermediate compounds, Bu2Sn(OMe)2 (A)and [Bu2SnOMe]2O (B). A and B subsequently react with methyl methanesulfonate to give 1-4.
C)proceed via the Arbuzov rearrangement at the sulfur center, yielding the corresponding methoxydiorganotinmethanesulfonates, R2Sn(OMe)OS(O)2Me [R = n-Pr (1), n-Bu (2), i-Bu (3), c-Hx (4)], as white, hygroscopicsolids. These compounds react with -diketones [acetylacetone (Hacac), benzoylacetone (Hbzac), and dibenzoylmethane (Hbzbz)] to afford mixed-ligand organotin derivatives, R2Sn(X)OS(O)2Me [X = acac, R = n-Pr (5),n-Bu (6); X = bzac, R = n-Pr (7), n-Bu (8); X = bzbz, R = n-Pr (9), n-Bu (10), i-Bu (11)]. Selective hydrolysisof the Sn-OMe bond in 1-3 occurs, resulting in the isolation of (-hydroxo)diorganotin methanesulfonates,R2Sn(OH)OS(O)2Me [R = n-Pr (12), n-Bu (13), i-Bu (14)]. All the compounds are characterized by elementalanalyses and IR, multinuclear (1H, 13C, and 119Sn) NMR, and mass spectra. Unequivocal evidence of the presenceof the methanesulfonate group is provided by the X-ray crystal structures of 6, 10, and 13. [For 6: trigonal spacegroup R (No. 148), a = 28.664(1) Å, c = 13.056(1)Å, Z = 18. For 10: triclinic space group P (No. 2), a =13.056(3) Å, b = 14.062(3) Å, c = 16.282(3) Å, Z = 4. For 13: triclinic space group P (No. 2), a = 9.089(2)Å, b = 12.040(2) Å, c =13.894(2) Å, Z = 2]. For 6 and 10, the solid-state structural analyses reveal dimericstructures with a bridging bidentate methanesulfonate group forming a centrosymmetric eight-membered ring.Compound 13 possesses a polymeric sheet structure with repeating 20-membered macrocycles (including twofour-membered [Sn(OH)]2 rings) by virtue of the bridging bidentate methanesulfonate groups. A search for apossible pathway to give Arbuzov-rearranged products 1-4 leads us to speculate that there is an initial catalytictransformation of dimethyl sulfite to methyl methanesulfonate via intermediate compounds, Bu2Sn(OMe)2 (A)and [Bu2SnOMe]2O (B). A and B subsequently react with methyl methanesulfonate to give 1-4.