Reactions of Iso(thio)cyanates with Dialanes: Cycloaddition, Reductive Coupling, or Cleavage of the C=S or C=O Bond was written by Dodonov, Vladimir A.;Chen, Weixing;Liu, Li;Sokolov, Vladimir G.;Baranov, Evgeny V.;Skatova, Alexandra A.;Zhao, Yanxia;Wu, Biao;Yang, Xiao-Juan;Fedushkin, Igor L.. And the article was included in Inorganic Chemistry in 2021.Application In Synthesis of Isopropylisothiocyanate The following contents are mentioned in the article:
The dialanes [(dpp-Bian)Al-Al(dpp-Bian)] (1) and [(dpp-dad)Al(THF)-(THF)Al(dpp-dad)] (2) (dpp-Bian = 1,2-[(2,6-iPr2C6H3)NC]2C12H6, dpp-dad = [(2,6-iPr2C6H3)NC(CH3)]2) react with some isothiocyanates, isocyanates, and diphenylketene via [2 + 4] cycloaddition of the C=O or C=S bond across the C=C-N-Al fragment to afford complexes [L(X=C-Y)Al-Al(X=C-Y)L] with an intact Al-Al single bond (L = dpp-Bian, X = PhN, Y = O (3); L = dpp-Bian, X = Ph2C, Y = O (4); L = dpp-dad, X = BnN, Y = S (6); L = dpp-dad, X = tBuN, Y = O (7); L = dpp-dad, X = iPrN, Y = S (8); and L = dpp-dad, X = CyN, Y = S (9)). A mixed C=N and C=O mode cycloadduct, [(dpp-Bian)(TosN=C-O)Al-Al(TosN-C=O)(dpp-Bian)] (5), was obtained in the reaction of 1 with tosylisocyanate. Heating the solution of 3 resulted in a thermal transformation and a change of the cycloaddition mode from C=O to C=N to give the product [(dpp-Bian)(PhN-C=O)Al(O)Al(PhN-C=O)(dpp-Bian)] (10). The reduction of 7 and 8 with Na yielded the products [Na(THF)n]2[(dpp-dad-H)(X=C-Y)Al]2 (X = iPrN, Y = S, n = 2 (12) and X = tBuN, Y = O, n = 3 (13)) in which one of the Me groups of the backbone of the initial dpp-dad ligand was dehydrogenated. When 2 was reacted with the bulky adamantyl isocyanate AdNCO, the C-C coupling of two substrates occurred to form [(dpp-dad)Al(O=C-NAd)2Al(dpp-dad)] (14) in which the coupled dianionic oxamide ligand bridged two Al atoms in a μ,η4-N,O/N,O mode. Moreover, in the presence of 2.0 equiv of Na metal, precursor 2 reacts with tBuNCS, p-TolylNCS, or Me3SiNCO, possibly through the reduced AlI intermediate, to yield the sulfur- or oxygen-bridged dimer [Na(solv)n]2[(dpp-dad)Al(μ-E)]2 (E = S, solv = THF, n = 3 (15) and E = O, solv = DME, n = 2 (16)) upon C=S or C=O bond cleavage. Dialane 1 reacts with dimethylsulfone to give a Lewis adduct [(dpp-Bian)(Me2SO2)Al]2 (17), which releases dimethylsulfone upon heating. The diamagnetic compounds 3–10 and 12–17 were characterized by NMR and IR spectroscopy. The mol. structures of 3–17 were established by single-crystal X-ray diffraction anal. Electronic structures of the compounds and possible isomers were examined by DFT calculations This study involved multiple reactions and reactants, such as Isopropylisothiocyanate (cas: 2253-73-8Application In Synthesis of Isopropylisothiocyanate).
Isopropylisothiocyanate (cas: 2253-73-8) belongs to esters. Volatile esters with characteristic odours are used in synthetic flavours, perfumes, and cosmetics. Certain volatile esters are used as solvents for lacquers, paints, and varnishes. Esters are more polar than ethers but less polar than alcohols. They participate in hydrogen bonds as hydrogen-bond acceptors, but cannot act as hydrogen-bond donors, unlike their parent alcohols. This ability to participate in hydrogen bonding confers some water-solubility.Application In Synthesis of Isopropylisothiocyanate
Referemce:
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics