Isopropyl N-Arylmalonamates. Synthesis, Structure, Conformation and Reactions with Carbon Disulfide

2006 ◽  
Vol 71 (1) ◽  
pp. 59-76 ◽  
Author(s):  
Wolf-Dieter Rudorf ◽  
Dušan Loos ◽  
Joanna Wybraniec ◽  
Naďa Prónayová ◽  
Ryszard Gawinecki ◽  
...  
Keyword(s):  
Molecular Structure ◽  
Hydrogen Bonding ◽  
Carbon Disulfide ◽  
Aromatic Amines ◽  
Alkylating Agent ◽  
Sodium Hydride ◽  
Open Chain ◽  
Ketene Dithioacetals ◽  
Correlation Analyses ◽  
C Nmr

Acylation of aromatic amines 1 with diisopropyl malonate (2) leads to a mixture of isopropyl N-arylmalonamates 3 and malonanilides 4. The reaction of 3 with carbon disulfide in the presence of sodium hydride gives disodium salts 5. Treatment of 5 with an alkylating agent yields the open-chain or cyclic ketene dithioacetals 6, 7 or 8. The molecular structure, hydrogen bonding and preferential conformation of the isopropyl N-arylmalonamates 3, 6 and 7 were investigated using correlation analyses of IR, 13C NMR and AM1 semiempirical data.

scholarly journals Application of Commercially Available Anhydrous Potassium Fluoride for a Convenient Synthesis of Ketene Dithioacetals

1999 ◽  
Vol 23 (8) ◽  
pp. 492-493
Author(s):  
Sabir H. Mashraqui ◽  
Harini Hariharasubrahmanian
Keyword(s):  
Carbon Disulfide ◽  
Alkylating Agent ◽  
Potassium Fluoride ◽  
Solid Support ◽  
Ambient Conditions ◽  
Ketene Dithioacetals ◽  
Convenient Synthesis ◽  
Active Methylene Compounds ◽  
Active Methylene

Commercially available anhydrous KF without activation or solid support promotes condensation between active methylene compounds, carbon disulfide and an alkylating agent in dry DMF to allow the preparation of a variety of ketene dithioacetals in fair to good yields under ambient conditions.

Reaktionen von 2-Methyl-1H-benzimidazol mit Schwefelkohlenstoff und Phenylisothiocyanat. Kristall- und Molekülstruktur von 1,1′ -Carbonothioyl-bis(2-methyl-1H-benzimidazol) und 2-Methyl-1-(ethoxycarbonylmethylthio-phenylimino)-1H-benzimidazol / Reactions of 2-Methyl-1 H-benzimidazole with Carbon Disulfide and Phenyl Isothiocyanate. Molecular and Crystal Structures of 1,1′-Carbonothioyl-bis(2-methyl-1 H-benzimidazole) and 2-Methyl-1-(ethoxycarbonylmethylthio-phenylimino)-1 H-benzimidazole

1995 ◽  
Vol 50 (5) ◽  
pp. 837-843 ◽  
Author(s):  
Wolfgang Dölling ◽  
Helmut Hartungb ◽  
Matthias Biedermann
Keyword(s):  
Crystal Structures ◽  
Methyl Iodide ◽  
Carbon Disulfide ◽  
Alkylating Agent ◽  
Sodium Hydride ◽  
Phenyl Isothiocyanate ◽  
Reaction Products ◽  
X Ray ◽  
Molecular And Crystal Structures

Abstract 2-Methyl-1 H-benzimidazole 1 reacts in the presence of two equivalents of sodium hydride in dry DMSO with carbon disulfide to methyl 2-methylbenzimidazole-1-dithiocarboxylate 3 using methyl iodide as alkylating agent, whereas using 1,2-dibromoethane 1,1′-carbonothioyl bis(2-methyl-1 H-benzimidazole) 5 is formed. Compound 1 reacts with phenyl isothiocyanate in the presence of one equivalent of sodium hydride in dry DMF after alkylation to 2-methyl-1-( alkylthio-phenylimino)-1 H-benzimidazoles 6a, 6b. Reaction products 5 and 6b have been identified and structurally characterized by X-ray analysis.

scholarly journals Reaktionen von Derivaten der (Diphenylmethylen-amino)-essigsäure mit Schwefelkohlenstoff und Phenylisothiocyanat sowie Kristall- und Molekülstruktur des 2-(Diphenylmethylen-amino)-2-(1,3-dithian-2-yliden)-essigsäuremethylesters / Reactions of the Derivatives of (Diphenylmethylene-amino) Acetic Acid with Carbon Disulfide and Phenyl Isothiocyanate and Crystal and Molecular Structure of Methyl 2-(Diphenylmethylene-amino)-2-(1,3-dithiane-2-ylidene) Acetate

1993 ◽  
Vol 48 (4) ◽  
pp. 493-504 ◽  
Author(s):  
Wolfgang Dölling ◽  
Klaus Frost ◽  
Frank Heinemann ◽  
Helmut Hartung
Keyword(s):  
Molecular Structure ◽  
Acetic Acid ◽  
Carbon Disulfide ◽  
Structure Determination ◽  
Phase Transfer ◽  
Crystal And Molecular Structure ◽  
Phenyl Isothiocyanate ◽  
X Ray ◽  
Ketene Dithioacetals ◽  
Derivatives Of

Derivatives of (diphenylmethylene-amino) acetic acid 1-3 react in the presence of bases (NaH, t-BuONa) or under phase transfer conditions with carbon disulfide to give the corresponding ketene dithioacetals 4-11 after alkylation. Phenyl isothiocyanate and dicyclohexyl carbodiimide give rise to ketene-S,N- and N,N-acetals. Methyl 2-(diphenylmethyleneamino)-2-(1,3-dithiane-2-ylidene) acetate (7) was characterized by an X-ray structure determination. The compound has a 2-aza-1,3-butadiene fragment containing two well localized double bonds. The C=N-C=C group is significantly non-planar, the relevant torsion angle amounts to -103.5(3)°.

scholarly journals Vibrational Resonant Inelastic X-Ray Scattering Inliquid Acetic Acid: A Ruler for Molecular Chain Lengths

2020 ◽  
Author(s):  
Viktoriia Savchenko ◽  
Iulia-Emilia Brumboiu ◽  
Victor Kimberg ◽  
Michael Odelius ◽  
Pavel Krasnov ◽  
...  
Keyword(s):  
Molecular Structure ◽  
Hydrogen Bonding ◽  
Acetic Acid ◽  
Molecular Chain ◽  
X Ray ◽  
X Ray Scattering ◽  
Localized Excitations ◽  
Vibrational Excitations ◽  
Chain Lengths ◽  
Ray Scattering

Abstract Quenching of vibrational excitations in resonant inelastic X-ray scattering (RIXS) spectra of liquid acetic acid is observed. At the oxygen core resonance associated with localized excitations at the O-H bond, the spectra lack the typical progressionof vibrational excitations observed in RIXS spectra of comparable systems. We interpret this phenomenon as due to strong rehybridization of the unoccupied molecular orbitals as a result of hydrogen bonding. This allows us to address the molecular structure of the liquid, and to determine a lower limit for the average molecular chain length.

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