's Amides (1970) PDF

ISBN-10: 0470771232

ISBN-13: 9780470771235

ISBN-10: 0471980498

ISBN-13: 9780471980490

Chapter 1 Molecular and digital constitution of the amide workforce (pages 1–72): M. B. Robin, F. A. Bovey and Harold Basch
Chapter 2 Synthesis of amides (pages 73–185): A. L. J. Beckwith
Chapter three Acid?base and complexing homes of amides (pages 187–243): R. B. Homer and C. D. Johnson
Chapter four Rearrangement and removal of the amido crew (pages 245–288): Joseph F. Bieron and Frank J. Dinan
Chapter five Photochemistry of the amido crew (pages 289–308): Ionel Rosenthal
Chapter 6 Radiation chemistry of amides (pages 309–334): Owen H. Wheeler
Chapter 7 Chemistry of imidic compounds (pages 335–381): Owen H. Wheeler and Oscar Rosado
Chapter eight The chemistry of thioamides (pages 383–475): W. Walter and J. Voss
Chapter nine The chemistry of the thiohydrazide workforce (pages 477–514): W. Walter and ok. J. Reubke
Chapter 10 The chemistry of hydrazides (pages 515–600): Hans Paulsen and Dieter Stoye
Chapter eleven organic formation and reactions of the amido team (pages 601–684): J. E. Reimann and R. U. Byerrum
Chapter 12 Directing and activating results of the amido team (pages 685–729): J. A. Shafer
Chapter thirteen Reactions of the carboxamide team (pages 731–857): Brian G. Challis and Judith A. Challis

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Sample text

Molccular and clectronic structure of thc amide group 23 with A and €3 othcr than H, corrcsponds to cp' = 180". Whcn A = 13, wc may supposc that, assuming a threc-fold potential barrier, there will be in addition to this trans conformcr, two equally populated mirror-image gauche conformcrs, corresponding to cp' = 60". When A # B, as in a polypeptidc chain, these gauche conformers will in gcncral be unequally populated. It should be notcd that the minima usually assurncd in polypeptidc conformational energy calculations differ from these by k 60", and that furthermore, rp' for thc a-helix is ca.

Of the five bands of the amide group, the W band is least controversial, with all investigators agreeing to a singlet-singlet n --z T* (10a’ -> 3a”) assignment. T h e presence of this band in amides was only barely hinted at for a long time, until Litman and Schellman133 pointed out that by going from the usual hydroxylic solvents to 54 M. B. Robin, F. A. Bovey, and Harold Basch non-polar hydrocarbons, the W band is red shifted, whereas the adjacent absorption is blue shifted, thus uncovering the W-band profile.

However, the population analysis of the D*( 1la’) and n* (3a”) virtual orbitals shows that in the BADZ + 3p basis both of the MO’S are computed to be almost 100% Rydberg. A). In the same table are shown the results of SCF calculations performed directly on the upper-state triplets corresponding to thc singlet states of interest. The triplet-state SCF wave functions are readily obtainable, and if we make the presumption that triplet and singlet configurations differ only in the spin parts of their wave functions, then the space wave functions of the triplet (Table 8) will be the same as that of the singlet.

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Amides (1970)

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