Pseudoacids. II. 2-Acylbenzoic Acid Derivatives

1998 ◽  
Vol 54 (3) ◽  
pp. 264-276 ◽  
Author(s):  
E. J. Valente ◽  
S. B. Martin ◽  
L. D. Sullivan
Keyword(s):  
Bond Length ◽  
Tertiary Amide ◽  
Derivatives Of

Structures of derivatives of cyclic o-acylbenzoic acids, including the chloride, endo- and exocyclic amides, esters and anhydrides, are examined. 3-Chloro-1(3H)-isobenzofuranone (1), orthorhombic, Pbca, a = 11.616 (5), b = 8.120 (3), c = 15.640 (9) Å; 3-methoxy-3-phenyl-1(3H)-isobenzofuranone (3), orthorhombic, P212121, a = 6.923 (2), b = 8.291 (4), c = 21.551 (8) Å; 3-hydroxy-3-phenyl-N-propyl-1(3H)-isoindolone (4), orthorhombic, P212121, a = 8.662 (4), b = 9.551 (7), c = 17.649 (14) Å; 3-(N-morpholino)-1(3H)-isobenzofuranone (5), triclinic, P1¯, a = 6.172 (4), b = 11.163 (7), c = 17.33 (2) Å, α = 105.91 (6), β = 99.85 (6), γ = 97.57 (5)°; 3-(2′-benzoylbenzoyloxy)-3-phenyl-1(3H)-isobenzofuranone (7), triclinic, P1¯, a = 9.694 (3), b = 10.505 (4), c = 11.163 (4) Å, α = 80.58 (3), β = 80.41 (3), γ = 76.49 (3)°; bis[1(3H)-isobenzofuranone-3-yl]ether (8), monoclinic, I2/a, a = 15.31 (2), b = 6.111 (12), c = 28.30 (5) Å, β = 101.61 (12)°. An open oxoacid tertiary amide is also described: N-morpholino 2′-benzoylbenzamide (6): monoclinic, P21/c, a = 6.844 (4), b = 15.696 (8), c = 14.154 (7) Å, β = 99.43 (4)°. Pseudoacid derivatives form planar isobenzofuran and isoindole rings, and the former aldehyde/ketone carbon–heteroatom endocyclic and exocyclic bond distances show bond length variations which correlate with the relative basicities of the attached groups. Structures of both endocyclic and exocyclic nitrogen pseudoamides are reported as well as examples of the normal–pseudoanhydride and the dipseudoanhydride.

scholarly journals Microwave-assisted synthesis of biologically active amide derivatives of naphthenic acids under neat conditions

2018 ◽  
Vol 37 (1) ◽  
pp. 13 ◽  
Author(s):  
Ljubica Grbović ◽  
Bojana Radovan Vasiljević ◽  
Ksenija Pavlović ◽  
Timea Hajnal-Jafari ◽  
Simonida Đurić ◽  
...  
Keyword(s):  
Naphthenic Acid ◽  
Growth Stimulation ◽  
Naphthenic Acids ◽  
Biologically Active ◽  
Microwave Assisted Synthesis ◽  
Tertiary Amide ◽  
Amide Derivatives ◽  
Temperature Heating ◽  
Derivatives Of ◽  
Solvent Free Synthesis

Within the field of green chemistry, a noticeable results were obtained in the solvent-free synthesis of amide derivatives of naphthenic acids under microwave irradiation. Naphthenic acid amides, anilides, and morpholides were synthesized directly from free carboxylic acids and amines in the absence of solvent and catalyst under high-temperature heating in a closed-vessel system of microwave reactor. With this new and efficient method, different primary, secondary, and tertiary amide derivatives of naphthenic acids were obtained in good to excellent yields. Synthesized derivatives were assayed as plant rooting agents for their stimulative effects on the formation of adventitious roots in sunflower cuttings and susceptibility for growth stimulation of Pseudomonas sp. strains.

scholarly journals On differences in substituent effects in substituted ethene and acetylene derivatives and their boranyl analogs

2020 ◽  
Vol 32 (1) ◽  
pp. 285-296
Author(s):  
Mirosław Jabłoński ◽  
Tadeusz M. Krygowski
Keyword(s):  
Bond Length ◽  
Triple Bond ◽  
Wide Spectrum ◽  
Substituent Effects ◽  
Triple Bonds ◽  
External Perturbations ◽  
Substituent Constants ◽  
The Impact ◽  
Derivatives Of ◽  
Acetylene Derivatives

AbstractThis article is the first attempt to present different influence of substituent effects on double and triple bonds and, conversely, to present the impact of these bonds on the electronic structure of substituents. For this purpose, quantum-mechanical calculations were made for X-substituted derivatives of ethene and acetylene with 27 diverse substituents representing a wide spectrum of electronic properties, from strongly electron-accepting to strongly electron-donating ones. In addition to these systems, their boranyl derivatives are also investigated. It turns out that the Hammett substituent constants do not correctly describe changes in the CC bond length in any of the considered family of systems. However, the relationships with the CB bond length are significantly better. It is shown that the triple bond in acetylene derivatives is much more resistant to external perturbations than the double bond in the analogs containing an ethene unit. As a consequence, in acetylene derivatives, the substituent effects on CC bond length are about half of the substituent effects in ethene derivatives. We suggest that the observed lack of a clear linear correlation between the length of the CC triple bond in acetylene derivatives and the value of electron density on this bond is due to the disturbing additional interaction between the structure of the X substituent in the xy plane and the π bond being in the same plane in the acetylene unit—on the contrary, this interaction is not possible in ethene analogs.

Concerning the conformational preferences of the 2-cyano derivatives of oxane, thiane, and selenane

2010 ◽  
Vol 88 (8) ◽  
pp. 831-838 ◽  
Author(s):  
Michael H. Benn ◽  
Yan Yan Huang ◽  
Frank Johannsen ◽  
Michael O’Reilly ◽  
Masood Parvez ◽  
...  
Keyword(s):  
Bond Length ◽  
Cyano Group ◽  
Lone Pair ◽  
Nbo Analysis ◽  
Orbital Interaction ◽  
Anomeric Effect ◽  
Model Compounds ◽  
Conformational Preferences ◽  
Lone Pair Electrons ◽  
Derivatives Of

This paper investigates the origin of the anomalous anomeric effect in merosinigrin, a 2-cyanothiane in which the cyano group is axial as expected for the anomeric effect, but in which bond distances are opposite to that expected from the nS→[Formula: see text] orbital interaction, which underlies the classical anomeric effect. The model compounds, 2-cyanooxane, 2-cyanothiane, and 2-cyanoselenane, were synthesized and studied both experimentally and computationally. Both the thia and selena systems displayed an even higher preference for the axial conformation than the oxa system but also exhibited the bond length anomalies found previously in merosinigren. Natural bond order (NBO) analysis of the B3LYP/6–311+G(3df,2p) wave functions of the axial and equatorial forms of the three systems confirmed a weakening of the n→σ* orbital interaction in the O, S, and Se series, and a strengthening of a σ–π*(CN) interaction that explains the bond length reversals observed in the S and Se systems. It also revealed a new mechanism, n→π*, namely, a through-space interaction between the nonbonded lone pair electrons of the heteroatom and the π* orbital of the cyano group, which selects for the axial conformation.

Directed ortho Metalation Studies on Podocarpic Acid Derivatives: Advantageous Use of a LICKOR Base

1991 ◽  
Vol 44 (10) ◽  
pp. 1465 ◽  
Author(s):  
RC Cambie ◽  
PI Higgs ◽  
KC Lee ◽  
MR Metzler ◽  
PS Rutledge ◽  
...  
Keyword(s):  
Amide Group ◽  
Dynamic Features ◽  
Tertiary Amide ◽  
Ortho Metalation ◽  
Derivatives Of ◽  
Oxazoline Derivatives

Methyl 13-(N,N- diethylcarbamoyl )-12-methoxypodocarpa-8,11,13-trien-19-oate (2), 13-(N,N- diethylcarbamoyl )-12,19-dimethoxypodocarpa-8,11,13-triene (8) and N,N-diethyl-2-methoxy-4,5-dimethylbenzamide (15) were prepared for studies involving lithiation directed ortho to the tertiary amide group, in which the use of a LICKOR base was advantageous. Some dynamic features of the n.m.r. spectra of the amides are discussed. Oxazoline derivatives of both tile monocyclic and diterpenoid compounds were synthesized.

ChemInform Abstract: Metal-Assisted Reactions. Part 29. Structure and Hydrogenolysis of C-N Bonds in Derivatives of Aromatic Amines. Bond Length and Electronegativity Changes from X-Ray Crystallographic Data.

ChemInform ◽  
2010 ◽  
Vol 32 (45) ◽  
pp. no-no
Author(s):  
Amadeu F. Brigas ◽  
William Clegg ◽  
Christopher J. Dillon ◽  
Custodia F. C. Fonseca ◽  
Robert A. W. Johnstone
Keyword(s):  
Bond Length ◽  
Aromatic Amines ◽  
Crystallographic Data ◽  
X Ray ◽  
Derivatives Of

scholarly journals Calculating energy derivatives for quantum chemistry on a quantum computer

2019 ◽  
Vol 5 (1) ◽  
Author(s):  
Thomas E. O’Brien ◽  
Bruno Senjean ◽  
Ramiro Sagastizabal ◽  
Xavier Bonet-Monroig ◽  
Alicja Dutkiewicz ◽  
...  
Keyword(s):  
Bond Length ◽  
Quantum Computer ◽  
Survey Methods ◽  
Geometry Optimization ◽  
Equilibrium Bond Length ◽  
Molecular Systems ◽  
Energy Derivatives ◽  
Quantum Processor ◽  
Dynamics Simulations ◽  
Derivatives Of

AbstractModeling chemical reactions and complicated molecular systems has been proposed as the “killer application” of a future quantum computer. Accurate calculations of derivatives of molecular eigenenergies are essential toward this end, allowing for geometry optimization, transition state searches, predictions of the response to an applied electric or magnetic field, and molecular dynamics simulations. In this work, we survey methods to calculate energy derivatives, and present two new methods: one based on quantum phase estimation, the other on a low-order response approximation. We calculate asymptotic error bounds and approximate computational scalings for the methods presented. Implementing these methods, we perform geometry optimization on an experimental quantum processor, estimating the equilibrium bond length of the dihydrogen molecule to within $$0.014$$0.014 Å of the full configuration interaction value. Within the same experiment, we estimate the polarizability of the H$${}_{2}$$2 molecule, finding agreement at the equilibrium bond length to within $$0.06$$0.06 a.u. ($$2 \%$$2% relative error).

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