3481-62-7Relevant academic research and scientific papers
Metal-free three-component synthesis of thioamides from β-nitrostyrenes, amines and elemental sulfur
Peng, Ling,Ma, Li,Ran, Ying,Chen, Yunfeng,Zeng, Zhigang
supporting information, (2021/05/05)
A metal-free C[dbnd]C bond cleavage reaction of β-nitrostyrenes in the presence of elemental sulfur and secondary amines/amides is described. Elemental sulfur serves as both a raw material and an oxidant for C[dbnd]C bond cleavage, and secondary amines or amides are both feasible nitrogen sources. Besides mild reaction condition and simple work-up procedure, the method provided thioamides with good to excellent yields.
Mixed bases mediated synthesis of thioamides in water
Li, Jiao,Ren, Xuanhe,Li, Ganzhong,Liang, Helong,Zhao, Yajie,Wang, Zhiwu,Li, Heng,Yuan, Bingxin
, p. 229 - 237 (2020/02/20)
A mixed bases mediated protocol is developed to synthesize thioamides from N-aryl or N-alkylamide, aldehyde and elemental sulfur in water. This reaction requires no addition of external oxidant and avoids large excess of amides. Various functional groups
Willgerodt-Kindler reaction at room temperature: Synthesis of thioamides from aromatic aldehydes and cyclic secondary amines
Kale, Arun D.,Tayade, Yogesh A.,Mahale, Sachin D.,Patil, Rahul D.,Dalal, Dipak S.
, (2019/09/12)
A simple method for the synthesis of thioamide derivatives in DMSO at room temperature and at 120 °C has been developed. Total 27 compounds were prepared under both conditions via a one-pot, three component reaction between substituted aromatic aldehydes,
Base-Controlled Three Component Reactions of Amines, Elemental Sulfur, and Styrenes: Synthesis of Thioamides under Metal-Free Conditions
Zhang, Pingshun,Chen, Wanzhi,Liu, Miaochang,Wu, Huayue
, p. 14269 - 14276 (2018/11/25)
Three component reactions of olefins, amines, and sulfur were studied. Thioamidation of styrenes is base-controlled, and 2-phenylethanethioamides and benzothioamides were obtained selectively in the presence of two different bases. This protocol offers a simple and efficient procedure for the synthesis of thioamides.
Copper-catalyzed chemoselective cross-coupling reaction of thioamides and α-diazocarbonyl compounds: Synthesis of enaminones
Pal, Arpal,Koduri, Naga D.,Wang, Zhiguo,Quiroz, Erika Lopez,Chong, Alexandra,Vuong, Matthew,Rajagopal, Nisha,Nguyen, Michael,Roberts, Kenneth P.,Hussaini, Syed R.
supporting information, p. 586 - 589 (2017/01/16)
The development of operationally simple and cost-effective methods for C[sbnd]C bond formation reactions are highly important in pharmaceutical, agrochemical and material research. In this article we describe the first copper-catalyzed cross-coupling reaction of thioamides with acceptor/acceptor-substituted and acceptor-only substituted α-diazocarbonyl compounds to yield enaminones. The reaction shows broad substrate scope in terms of thioamides and diazocarbonyl compounds. Primary, secondary and tertiary thioamides all give enanminones when reacted with α-diazodiesters, α-diazoketoesters, α-diazodiketones, α-diazoketoamides, α-diazoesteramides, α-diazoketosulfones and α-diazomonoketones.
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).
Facile preparation of amides from thioamides by ceric ammonium nitrate
Movassagh, Barahman,Meibodi, Forhatosadat,Sobhani, Shahin
, p. 1296 - 1298 (2007/10/03)
Ceric ammonium nitrate (CAN) is found to be a good oxidizing agent which converts thioamides into their oxygen analogues in aqueous acetic acid under very mild conditions.
Thioacylsulfanylarsines (RCS2)xAsPh3-x, x = 1-3: Synthesis, structures, natural bond order analyses and reactions with piperidine
Tani, Kazuyasu,Hanabusa, Shin-Ichi,Kato, Shinzi,Mutoh, Shin-Ya,Suzuki, Shun-Ichi,Ishida, Masaru
, p. 518 - 527 (2007/10/03)
A series of thioacylsulfanylarsines ((RCS2)AsPh2, (RCS2)2AsPh, (RCS2)3As) were synthesized by treating piperidinium dithiocarboxylates with Ph2AsCl, PhAsCl2 or AsCl3, respectively and characterized. Their molecular structures were determined by X-ray crystallography and compared with those of the corresponding acylsulfanyl derivatives ((RCOS)AsPh2, (RCOS)2AsPh, (RCOS)3As). They exist as monomers, and the environment around the arsenic atoms is distorted tetrahedral with one lone pair at the apex. The structure of the mono(dithiocarboxylate) is different from that of the corresponding thiocarboxylic acid derivative, while the bis and tris derivatives showed similar structure to the corresponding thiocarboxylic acid derivatives ((RCOS)2AsPh, (RCOS)3As), respectively. The new compounds showed intramolecular interactions between the thiocarbonyl sulfur and the central arsenic atom. NBO (Natural Bond Orbital) analyses performed on the model compounds (CH3CS2)As(CH3)2 and (CH3CS21)-(CH3CS22 )AsCH3 at the RHF/LANL2DZ level of theory showed the presence of interactions between the non-bonding orbitals on the thiocarbonyl sulfur (ns) and the σ*MS orbitals together with that between the ns and the σ*MC orbitals for the former compound; for the latter the presence of both orbital interactions between ns and σ*MS1 and between ns and σ*MS2 are present. The reaction of the mono(dithiocarboxylate) derivative (R = 4-CH3-C6H4) with piperidine in ethanol gave piperidinium diphenyldithioarsinate along with the corresponding N-thioacyl- or N-acyl-piperidine. A similar reaction of the bis(dithiocarboxylate) derivative (R = 4-CH3C6H4) gave the novel di(piperidinium) phenyltrithioarsonate in which two anion charges are delocalized on the AsS3 moiety and a cyclic phenylarsine sulfide tetramer (PhAsS)4. The diphenyldithioarsinate and phenyltrithioarsonate salts exist as a dimer and a polymer, respectively, in which 12-membered rings are formed by intermolecular N-H ... S hydrogen bonds.
A new versatile one-pot synthesis of functionalized thioamides from Grignards, carbon disulfide and amines
Katritzky,Moutou,Yang
, p. 1497 - 1505 (2007/10/02)
The one-pot successive reactions of Grignard reagents with carbon disulfide and amines mediated by 1-trifluoromethylsulfonylbenzotriazole or triflic anhydride, provide an attractive and general route to thioamides. A wide variety of amines (primary alkyl, arylalkyl, secondary alkyl, cyclic amines, aniline, N-substituted anilines, heterocyclic amidines, amino alcohols, amino ethers, amino acetals, amino ketones, amino esters, amino amides (peptides), aminoalkenes, and diamines) and Grignards (primary alkyl, arylalkyl, aryl, secondary alkyl and tertiary alkyl) can be used, and thioamides are generally formed in good to moderate yields.
Se-Aryl Alkane- or Arenecarboselenothioates: Synthesis and Some Reactions
Kato, Shinzi,Yasui, Eiji,Terashima, Kiyomitsu,Ishihara, Hideharu,Murai, Toshiaki
, p. 3931 - 3942 (2007/10/02)
A series of Se-aryl carboselenothioates 3 (RCSSeAr, R=alkyl, aryl) were synthesized and characterized from the reaction of bis(thioacyl) sulfides 1 with sodium areneselenolates.The thionselenolesters 3 are stable (liquid or crystals) both thermally and to moisture.Reactions of 3 with aliphatic primary and secondary amines gave the corresponding ammonium carbodithioates 8 together with diphenyl diselenide 7.In contrast, treatment with aromatic amines or sodium alcoholates afforded the corresponding thioamides or O-alkyl or O-aryl thionoesters in good yields.The oxidation of 3 with m-chloroperbenzoic acid gave the corresponding sulfides 12 and acyl arylseleno sulfides 13 which are formed by a rearrangement of the ArSe group to the thiocarbonyl sulfur atom.
