Preparation and X-Ray Crystal Structure of 3-(4-(Dimethylamino)phenyl)-2-(phenylamino)isoquinolin-1(2H)-one, 3-(4-Methoxyphenyl)-2-(phenylamino)isoquinolin-1(2H)-one, and 2-Methyl-N′-(4-methylbenzoyl)-N′-phenylbenzohydrazide from Polylithiated 2-methylbenzoic Acid Phenylhydrazide and Methyl 4-dimethylaminobenzoate, Methyl 4-methoxybenzoate, or Methyl 4-methylbenzoate

Abstract

2-Methylbenzoic acid phenylhydrazide was polylithiated with excess lithium diisopropylamide, and the resulting polylithiated intermediate was condensed with methyl 4-dimethylaminobenzoate or methyl 4-methoxybenzoate to afford C-acylated intermediates that were immediately acid cyclized to afford 3-(4-(dimethylamino)-phenyl)-2-(phenylamino)isoquinolin-1(2H)-one C₂₃H₂₁N₃O or 3-(4-methoxyphenyl)-2-(phenylamino)isoquinolin-1(2H)-one C₂₂H₁₈N₂O₂. The polylithiated intermediate underwent N-acylation when it was condensed with methyl 4-methylbenzoate to give 2-methyl-N′-(4-methylbenzoyl)-N′-phenylbenzohydrazide C₂₂H₂₀N₂O₂. Crystals of C₂₃H₂₁N₃O 4a are triclinic, P $\overline{1}$, a = 9.138(2) Å, b = 10.519(2) Å, c = 11.082(2) Å, α = 91.55(3)°, β = 108.92(3)°, γ = 111.16(3)°, Z = 2, V = 927.1(3) Å³, R ₁ = 0.0711 and wR ₂ = 0.1828 for reflections with I > 2σ(I); crystals of C₂₂H₁₈N₂O₂ 4b are monoclinic, P2₁/c, a = 8.821(1) Å, b = 13.276(2) Å, c = 15.482(3) Å, β = 105.271(4)°, Z = 4, V = 1748.9(5) Å³, R ₁ = 0.0416 and wR ₂ = 0.1030 for reflections with I > 2σ(I); crystals of C₂₂H₂₀N₂O₂ 3 are orthorhombic, Pbca, a = 13.505(3) Å, b = 9.733(2) Å, c = 28.601(6) Å, Z = 8, V = 3759.4(13) Å³, R ₁ = 0.1683 and wR ₂ = 0.3526 for reflections with I > 2σ(I).

Index Abstract

X-ray crystal analysis was important for the confirmation of the structure of 3-(4-(dimethylamino)phenyl)-2-(phenylamino)isoquinolin-1(2H)-one C₂₃H₂₁N₃O 4a, 3-(4-methoxyphenyl)-2-(phenylamino)isoquinolin-1(2H)-one C₂₂H₁₈N₂O₂ 4b, and 2-methyl-N′-(4-methylbenzoyl)-N′-phenylbenzohydrazide C₂₂H₂₀N₂O₂ 3 prepared from polylithiated 2-methylbenzoicacid phenylhydrazide and methyl 4-dimethylaminobenzoate, methyl 4-methoxybenzoate, or methyl 4-methylbenzoate. Crystals of C₂₃H₂₁N₃O 4a are triclinic, P $\overline{1}$, a = 9.138(2) Å, b = 10.519(2) Å, c = 11.082(2) Å, α = 91.55(3)°, β = 108.92(3)°, γ = 111.16(3)°, Z = 2, V = 927.1(3) Å³, R ₁ = 0.0711 and wR ₂ = 0.1828 for reflections with I > 2σ(I); crystals of C₂₂H₁₈N₂O₂ 4b are monoclinic, P2₁/c, a = 8.821(1) Å, b = 13.276(2) Å, c = 15.482(3) Å, β = 105.271(4)°, Z = 4, V = 1748.9(5) Å³, R ₁ = 0.0416 and wR ₂ = 0.1030 for reflections with I > 2σ(I); crystals of C₂₂H₂₀N₂O₂ 3 are orthorhombic, Pbca, a = 13.505(3) Å, b = 9.733(2) Å, c = 28.601(6) Å, Z = 8, V = 3759.4(13) Å³, R ₁ = 0.1683 and wR ₂ = 0.3526 for reflections with I > 2σ(I).