32502-05-9Relevant academic research and scientific papers
Crystal Chemistry of Some (Alkoxyohenyl)propiolic Acids. The Role of Oxygen and Hydrogen Atoms in Determining Stack Structures of Planar Aromatic Compounds
Desiraju, Gautam R.,Kishan, K. V. Radha
, p. 4838 - 4843 (2007/10/02)
Crystal structures of planar oxygenated aromatic compounds are determined by an interplay of C...H interactions which steer to herringbone structures, characterized by adjacent inclined molecules, and C-H...O interactions, which being lateral, steer to stacked-sheet structures with short axes of 3.8-4.2 Angstroem.The number of hydrogen and oxygen atoms in the molecule seems to determine which of these two preferences is exercised, a smaller number of hydrogens and a greater number of oxygens leading to the stack structure.Accordingly, if an alkoxycinnamic acid has a stack structure, the corresponding phenylpropiolic acid will, in all likelihood, have the same structure.This is exemplified by the pair of nearly isomorphous compounds 3,4-(methylenedioxy)cinnamic acid and propiolic acid.The structure of the latter is triclinic, P, Z = 2, a = 3.807(2) Angstroem, b = 10.297(2) Angstroem, c = 10.995(3) Angstroem, α = 84.07(2) deg, β = 96.46(3) deg, γ = 98.13(3) deg.Even if a cinnamic acid does not have a 4-Angstroem structure, the removal of two hydrogen atoms to give the propiolic acid could result in the stack structure for the latter.Accordingly, (3,4-dimethoxyphenyl)propiolic acid is triclinic, P, Z = 2, a = 3.891(1) Angstroem, b = 11.361(3) Angstroem, c = 12.089(4) Angstroem, α = 112.50(2) deg, β = 92.53(3) deg, γ = 96.12(3) deg.A large number of oxygen atoms acting as C-H...O bond acceptors can lead to a stack structure for significantly nonplanar molecules.An example is (3,4,5-trimethoxyphenyl)propiolic acid which is monoclinic, P21/n, Z = 4, a = 20.806(6) Angstroem, b = 14.159(3) Angstroem, c = 3.942(5) Angstroem, β = 94.79(7) deg.In contrast, (4-methoxyphenyl)propiolic acid, which does not have the critical number of oxygen atoms, does not have a 4-Angstroem stack structure being triclinic, P, Z = 2, with a = 10.767(3) Angstroem, b = 8.494(3) Angstroem, c = 7.499(2) Angstroem, α = 99.01(2) deg, β = 125.62(2) deg, γ = 112.42(2) deg.The crystal structures of these and other phenylpropiolic acids are closely paralleled by their solid-state thermal reactivities.Acids with a 4-Angstroem stack structure participate in an intermolecular Diels-Alder reaction to give derivatives of 1-phenylnaphthalene-2,3-dicarboxylic acid anhydride, while those with short axes greater than 4.2 Angstroem are unreactive.The products of these reactions may be rationalized by assuming that adjacent double and triple bonds, within a threshold distance of ca. 4.5 Angstroem in the crystal, are potentially reactive.In general, any crystalline phenylpropiolic acid may be expected to form Diels-Alder products upon heating if the triple bonds are sufficiently close for topochemical reaction.The formation of these lignan derivatives from acetylenic precursors under mild conditions could be of biosynthetic significance.
A NEW ROUTE TO 1-PHENYLNAPHTHALENES BY CYCLOADDITION: A SIMPLE AND SELECTIVE SYNTHESIS OF SOME NAPHTHALENE LIGNAN LACTONES
Takano, Seiichi,Otaki, Shizuo,Ogasawara, Kunio
, p. 1659 - 1660 (2007/10/02)
2-(2-Dithianyl)benzhydrols (2 a-c) undergo facile cycloaddition reaction with maleic anhydride under thermal conditions to give 1-phenyl-naphthalenes (7 a-c) in one step.The naphthalenes (7 a-c) have been converted into the naphthalene lignan lactones, (9 a-c) and (10 a-c).
