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  • 3-Aza-1-metalla-1,3-dienes, of chromium and tungsten  (1)
  • 5-Aza-1-metalla-1,3,5-trienes, cyclization to 2H-pyrroles  (1)
  • Addition of alkynes to thiocarbene ligands  (1)
  • 1
    ISSN: 0009-2940
    Keywords: Thiocarbene complexes of chromium and tungsten ; Addition of alkynes to thiocarbene ligands ; β-(Thioalkenyl)carbene complexes, preparation ; Disengagement of ligands of silica gel ; Thioenol ether, preparation ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Organic Syntheses via Transition Metal Complexes, 41 1. - Thioenol Ethers by Insertion of Alkynes into M = C Bonds of Thiocarbene Complexes and Disengagement of Ligands on Silica GelA first example of reactions between alkynes and thiocarbene complexes is described. Et2N—C=C—CCH3 (2) adds to (alkylthio)phenylcarbene complexes LnM=C(SR)C6H5 (1) [LnM = Cr(CO)5. W(WO)5; R=CH2CH=CH2, CH2C6H5, c-C6H11, t-C4H9, C6H5] with insertion of the C=C into the M=C bond to form stereoselectively [(E)-β-(alkylthio)alkenyl]aminocarbene complexes LnM=C(NEt2) - C(CH3)=C(SR)C6H5 [(E)-3a-g]. With tungsten, but not with chromium, small amounts of indanone derivatives 4-6 were also obtained. We describe a straightforward and efficient method for the disengagement of ligands from carbene chromium complexes 3 on silica gel. Metal residues remain attached to the solid phase, and products are isolated by elution. Depending on the reaction conditions, different thioenol ethers 7-9 were obtained. Thus (E)-3a-d on silica gel at ambient temperature under the influence of air give β-(alkylthio)propenamides O=C(NEt2)-C(CH3)=C(SR)C6H5 [(E)-] and β-(alkylthio)propenals O=CH-C(CH3) = C(SR)C6H5 [(E)-8]. Thermolysis of 3 on silica gel in the absence of oxygen leads to the formation of aldehydes 8 and 3-(alkylthio)-1-indanones 5. Thermolysis of 3 on silca gel in the presence of sulfur yields β-(alkylthio)propenethioamides 9 as the only products.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0009-2940
    Keywords: Aminocarbene complexes, of chromium and tungsten ; 3-Aza-1-metalla-1,3-dienes, of chromium and tungsten ; 5-Aza-1-metalla-1,3,5-trienes, cyclization to 2H-pyrroles ; 2H-Pyrrole complexes, of chromium and tungsten ; Pyrroles, syntheses by metal-induced [3 + 2] cycloaddition reactions ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Organic Syntheses via Transition Metal Complexes, 551). - 5-Aza-1-metalla-1,3,5-trienes of Chromium and Tungsten, and Their Cyclization to 2H-Pyrrole Complexes5-Aza-1-metalla-1,3,5-trienes 5 and 6 [LnM = C - C = C - N = C, a: LnM = Cr(CO)5, b: W(CO)5] are obtained in two steps from aminocarbene complexes 1 [LnM = C(NH2)Ph, a: LnM = Cr(CO)5, b: W(CO)5]. The first step involves the condensation of 1 with benzaldehyde (2) in the prescence of TiCl4/Et3N to give 3-aza-1-metalla-1,3-dienes 3 (LnM = C - N = C). 3 adds to the 1-aminoalkyne 4 to give 5 and 6 by a chain extension of two carbon atoms. The trans isomers 5 are formed as the major products and are stable both in the solid state and in solution. The cis isomers 6 undergo a novel-type cyclization to give 2H-pyrrole complexes 8. Triene 5b was characterized by an X-ray analysis.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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