Reactions of Tetraethyltin With Organic Acids

Abstract

This paper reports the cleavage of ethyl groups from tetraethyltin by organic acids whose ionization constants range between 10-1 and 10-10. SUMMARY 1. Cleavage reactions of tetraethyltin were studied. 2. The following previously unreported compounds were prepared: triethyltin monochloroacetate, dichloroacetate, ß-naphthyl mercaptide, phenyl mercaptide, n-heptyl mercaptide, and n-hexyl mercaptide.Philadelphia 4, Pennsylvania

Synthesis, Characterization and Biological Activity of Organotin Derivatives of 2-Thionaphthalene, Including the Crystal Structures of (Naphthalenethiolato-S)triphenyltin(IV) and Bis(naphthalenethiolato-S)dimethyltin(IV)

“…For comparison, the 119 Sn chemical shifts of related four-coordinate species are: Ph 3 SnSMe Ϫ 69, Me 3 SnSMe 90, (Bz 3 Sn) 2 S 27, Me 2 Sn(SMe) 2 144, Sn(SPh) 4 44 ppm. 30 Mössbauer data for 1-7 are all consistent with tin in the + 4 oxidation state (IS: 1.12-1.50 mm s Ϫ 1 ) while the Mössbauer QS data reflect the simple tetrahedral coordination Ϫ 1260 (3) 2606 (9) 1365 (2) C (12) Ϫ 1863 (3) 3208 (9) 1641 (2) C (13) Ϫ 2561 (3) 1796 (9) 1596 (2) C (14) Ϫ 3201 (4) 2377 (10) 1877 (3) C (15) Ϫ 3854 (4) 981 (13) 1831 (3) C (16) Ϫ 3931 (4) Ϫ 1058 (12) 1500 (3) C (17) Ϫ 3333 (4) Ϫ 1663 (10) 1218 (3) C (18) Ϫ 2635 (3) Ϫ 283 (9) 1260 (2) C (19) Ϫ 1995 (4) Ϫ 849 (10) 986 (3) C (20) Ϫ 1326 (4) 532 (9) 1035 ( sphere about tin (1.46-2.09 mm s Ϫ 1 ). 29 The smallest QS occurs for 1 (1.46 mm s Ϫ 1 ) in which the dipole created by the four aryl groups is smaller than in the other, less symmetrical alkyltin compounds, while the largest QS (2.29 mm s Ϫ 1 ) occurs for polar 7.…”

“…15 Solvents were dried by standard procedures. 16 Spectra were recorded on the following instruments: JEOL GX270 ( 1 H, 13 C NMR), and GX400 ( 119 Sn NMR), Hitachi model 270-50 spectrometer (IR; as = asymmetric; sm = symmetric; s = strong; sh = sharp; shd = shoulder; m = medium; w = weak; v = very), MAT 8500 (70 eV EI mass spectra, courtesy of the University of Bayreuth, Germany; quoted fragments are based on 120 Sn). NMR spectra were recorded in CDCl 3 unless indicated otherwise.…”

“…[4][5][6] Most of the metallo-organic mercaptans are known for their fungicidal activities, 7,8 while organotins in general are known for their toxicity and widespread biological activity. 9,10 Tetraorganotin compounds react with thiols and thiophenols to cleave the Sn-C bond with the formation of Sn-S bonds [11][12][13] The products obtained by such reactions are non-uniform and yields are only moderate. Sn-S heterocycles are formed when the thiolysis of diorganotin dihalides is carried out with 1 mol of dithiol instead of 2 mol of monothiol.…”

SN2 and E2 Branching of Main-Group-Metal Alkyl Intermediates in Alkane CH Oxidation: Mechanistic Investigation Using Isotopically Labeled Main-Group-Metal Alkyls

“…Et 3 Sn-(TFA) was generated in situ by addition of Et 4 Sn to HTFA. 26 The resulting solution of Et 3 Sn(TFA) was stable for a few hours and only underwent slow protonolysis to generate Et 2 Sn(TFA) 2 ). An important advantage of this approach, in addition to generating EtTl(TFA) 2 , is the ease of synthesis of a wide range of organotin (R n SnX 4−n ) reagents that give ready access to a wide range of RTl(TFA) 2 intermediates for future study.…”

“…37 Triethyltin trifluoroacetate, Et 3 Sn(TFA), was prepared by addition of a known amount of tetraethyltin to trifluoroacetic acid, as has been previously described, and used in situ. 26 Ethyl iodide-1,1-d 2 (H 3 C-CD 2 I) and isopropyl iodide were purchased from Sigma-Aldrich and used as received. Ethyl iodide-2,2,2-d 3 (D 3 C-CH 2 I) was purchased from Cambridge Isotopes and used as received.…”