65212-09-1Relevant articles and documents
Group 13 metal carbochalcogenoato complexes: Synthesis, X-ray structure analysis, and reactions
Nakata, Norio,Kato, Shinzi,Niyomura, Osamu,Ebihara, Masahiro
, (2018/11/23)
A series of alkali metal tetrakis(carbochalcogenoato)-gallates and -indates M[M′(EOCR)4](solv.) (M?=?alkali metal; M′?=?Ga, In; E?=?S, Se) and tris(carbodithioato)aluminum, -gallates and -indates M′ (SSCR)3 (M′?=?Al, Ga, In) were prepared by the reactions of alkali metal carbochalcogenate with metal trihalogenides (M′X3; M′?=?Al, Ga, In; X?=?Cl, Br) and by those of piperidinium carbodithioates or carbodithioic and carboselenoic acids with M′X3, respectively. An X-ray molecular structure analysis revealed that they have an acetone molecule as a crystal solvent. The reactions of the potassium complexes K[M′ (EOCR)4](H2O) (E?=?S, Se) with methanol and primary and secondary amines gave the corresponding methyl ester and amides in good yields, while the reactions with iodomethane and iodine gave S- and Se-methyl chalcogenoesters RCOEMe (E?=?S, Se) in good yields. Similar reactions of the tris(carbodithioato)gallates and -indates led to the corresponding O-methyl thioesters, thioamides, and S-methyl dithioesters in moderate to good yields. Oxidation of the tetrakis- and tris-derivatives with iodine afforded the corresponding diacyl dichalcogenides (RCOE)2 (E?=?S, Se) and di(carbothioyl) disulfides in quantitative yields. These reactions appeared to occur on the carbonyl or selenium atom of the tetrakis compounds and on the sulfide sulfur or thiocarbonyl carbon atom of the tris-compounds, respectively. A possible mechanism for these I2-oxidation reactions is discussed.
Synthesis, structures, and some reactions of [(Thioacyl)thio]- and (Acylseleno)antimony and -bismuth derivatives ((RCSS)xMR 3-x1 and (RCOSe)xMR3-x1 with M=Sb, Bi and x=1-3)
Kimura, Mitsutoshi,Iwata, Akiyuki,Itoh, Masahiro,Yamada, Kazuki,Kimura, Tsutomu,Sugiura, Noriyuki,Ishida, Masaru,Kato, Shinzi
, p. 747 - 783 (2007/10/03)
A series of [(thioacyl)thio]- and (acylseleno)antimony and [(thioacyl)thio]- and (acylseleno)bismuth, i.e., (RCSS)xMR 3-x1 and (RCOSe)xMR3-x1 (M = Sb, Bi, R1 = aryl, x = 1 - 3), were synthesized in moderate to good yields by treating piperidinium or sodium carbodithioates and -selenoates with antimony and bismuth halides. Crystal structures of (4-MeC 6H4CSS)2Sb(4-MeC6H4) (9b′), (4-MeOC6H4COSe)2Sb(4-MeC 6H4) (12c′), (4-MeOC6H 4COS)2Bi(4-MeC6H4) (15c′), and (4-MeOC6H4CSS)2BiPh (18c) along with (4-MeC6H4COS)2SbPh (6b) and (4-MeC 6H4COS)3Sb (7b) were determined (Figs. 1 and 2). These compounds have a distorted square pyramidal structure, where the aryl or carbothioato (=acylthio) ligand at the central Sb- or Bi-atom is perpendicular to the plane that includes the two carbodithioato (=(thioacyl)thio), carboselenato (=acylseleno), or carbothioato ligand and exist as an enantiomorph pair. Despite the large atomic radii, the C=S...Sb distances in (RCSS)2MR1 (M = As, Sb, Bi; R1 = aryl) and the C=O...Sb distances in (RCOS)xMR3-x 1 (M = As, Sb, Bi; x = 2, 3) are comparable to or shorter than those of the corresponding arsenic derivatives (Tables 2 and 3). A molecular-orbital calculation performed on the model compounds (MeC(E)E1) 3-xMMex (M = As, Sb, Bi; E = O, S; E1 = S, Se; x = 1, 2) at the RHF/LANL2DZ level supported this shortening of C=E...Sb distances (Table 4). Natural-bond-orbital (NBO) analyses of the model compounds also revealed that two types of orbital interactions nS → σ*MC and nS → σ* MS(1) play a role in the (thioacyl)thio derivatives (MeCSS) 3-xMMex (x = 1, 2) (Table 5). In the acylthio- MeCOSMMe2 (M = As, Sb, Bi), nO → σ* MC contributes predominantly to the orbital interactions, but in MeCOSeSbMe2, none of nO → σ*MC and nO → σ*MSe contributes to the orbital interactions. The nS → σ*MC and nS → σ*MS(1) orbital interactions in the (thioacyl)thio derivatives are greater than those of nO → σ*MC and nO → σ*ME in the acylthio and acylseleno derivatives (MeCOE)3-xMMex (E = S, Se; M = As, Sb, Bi; x = 1, 2). The reactions of RCOSeSbPh2 (R = 4-MeC6H4) with piperidine led to the formation of piperidinium diphenylselenoxoantimonate(1-) (=piperidinium diphenylstibinoselenoite) (H2NC5H10) +Ph2SbSe-, along with the corresponding N-acylpiperidine (Table 6). Similar reactions of the bis-derivatives (RCOSe)2SbR1 (R, R1 = 4-MeC6H 4) with piperidine gave the novel di(piperidinium) phenyldiselenoxoantimonate(2-) (=di(piperidinium) phenylstibonodiselenoite), [(H2NC5H10)+] 2(PhSbSe2)2-, in which the negative charges are delocalized on the SbSe2 moiety (Table 6). Treatment of RCOSeSbR21 (R, R1=4-MeC6H 4) with N-halosuccinimides indicated the formation of Se-(halocyclohexyl) arenecarboselenoates (Table 8). Pyrolysis of bis(acylseleno)arylbismuth at 150° gave Se-aryl carboselenoates in moderate to good yields (Table 9).
A facile method for β-selenoglycoside synthesis using β-p-methylbenzoyl selenoglycoside as the selenating unit
Kawai, Yumiko,Ando, Hiromune,Ozeki, Hideya,Koketsu, Mamoru,Ishihara, Hideharu
, p. 4653 - 4656 (2007/10/03)
(Chemical Equation Presented) The reaction between α-glycosyl bromides and potassium p-methylselenobenzoate yields β-p-methylbenzoyl selenoglycosides. The acyl selenoglycosides were activated by the action of a secondary amine and Cs2CO3 to produce an anomeric selenolate anion, which reacted in situ with various electrophiles to yield novel selenoglycosides while retaining the anomeric stereochemistry.
