Über die Stereochemie der Hydrogenolyse von N-Benzyl-Bindungen I. Die Hydrogenolyse von Derivaten der 2-Amino-2-phenyl-propionsäure.

The stereochemistry of the hydrogenolysis of benzyl-N bonds was studied using S(+)-2-dimethylamino-2-phenyl-propionic acid (I) and its derivatives, and R(?)-2-anilino-2-phenyl-propionic acid (II). The configuration of I was confirmed, that of II established by ORD. measurements, after transformation of the phenyl into cyclohexyl groups. On a palladium catalyst the hydrogenolysis of I, its methyl and ethyl esters and its amide proceeded with 72 to 99% inversion of configuration, that of II with at least 66% inversion. The ester of the quaternary ammonium derivative of I gave as much inversion as retention (= racemisation).     

NMR of Terminal Oxygen. Part 14. Kinetically stabilized simple enols containing methylated uracil groups: Application of a 17O-NMR test of H-bonding

In the crystalline N,N′-dimethylated uracil derivatives 2a , b , the kinetically stabilized enol group forms an H-bond with O? C(4), as demonstrated by increased shielding of specifically labelled 2a and 2b in the ¹⁷O-NMR spectra (Δδ(¹⁷O)(C(4)—O) ? ?30 ppm); absence of dilution and solvent effects show that the H-bridge is intra-molecular, forming an eight-membered chelate ring. The (apparent) shielding effect Δδ(¹⁷O) in 2a, b is larger than that in salicylamide. The strong H-bond explains why the enols 2 , in spite of the absence of steric hindrance, are kinetically stabilized.     

1,2-Shift of a Carboxyl Group in a Wagner-Meerwein Rearrangement

On treatment with HSO₃F in SO₂C1F at 0°, 3-hydroxy-2,2-dimethyl-3-phenyl-propionic acid ( 1a ) is transformed into 2-phenyl-3-methyl-2-butenoic acid ( 2a ) (isolated yield: 40–44%). Using monolabelled [3-¹³C]- 1a ( 1a *) and doubly labelled [1,3-¹³C₂]- 1a ( 1a **), the migration of HOOC (or a mechanistically equivalent group) was proved; a cross experiment established the intramolecular character of the rearrangement. By following the reaction at low temperature in an NMR. spectrometer, the formation of intermediates and side products was demonstrated.     

Echange d'oxygène lors de la substitution électrophile des phénols

In the bromodesulfonation of sodium 2, 6-dibromophenol-4-sulfonate (I) and similar compounds, the relatively stable quinoloid intermediate II exchanges its carbonyl oxygen with that of H₂¹⁸O by an addition-elimination process. The exchange is slower than the formation of the product III; it is roughly comparable to the exchange velocity of quinones of similar structure. By reversibility of the electrophilic additon step, ¹⁸O is incorporated into the starting phenol I. In electrophilic substitutions with shorter life-time of the quinoloid intermediate, the oxygen exchange is difficult or impossible to observe.     

The Nitrosation of Primary Aliphatic Diazocarbonyl Compounds: Formation of α-carbonyl nitrile oxides. Preliminary communication

Aqueous nitrosation of primary α-carbonyl diazo compounds (ethyl diazoacetate, diazoacetone, diazoacetophenones) yields α-carbonyl nitrile oxides, R? CO? CNO; their formation is demonstrated by 1,3-dipolar addition reactions.     

La migration de groupes carboxamides lors de la transposition benzilique d'amides α,β-dicarbonylés. 24e Communication sur les réductones et les composés tricarbonylés-1,2,3 [1]

Under the conditions of the benzilic acid rearrangement, α,β-diketobutyryl-di-phenylamide (Ia) and -N-methylanilide (Ib) are transformed into tartronic acid derivatives (VI), which decarboxylate to lactamides VII. It is proved by ¹⁴-labelling of Ia, that the reaction takes place by carbonamide group migration. The reaction was followed kinetically by polarography at a fixed potential; at low pH the velocity is proportional to [OH^?], at higher pH it becomes independent of [OH^?], which is explained by complete transformation of I into its hydrate-anion. The equilibrium between I and its hydrate was measured by UV.-spectroscopy.     

Optical rotatory dispersion and circular dichroism. LXXV. Circular dichroism of some aryl-amino acids

CD. curves have been recorded for α-aryl-α-amino acids, esters and amides related to α-phenylglycine, α-phenyl-alanine and their N-dimethyl derivatives, and for the corresponding α-cyclohexyl-α-amino acids and esters. Compounds with the (S)-configuration at the single asymmetric carbon atom give strong positive Cotton effects near 220 nm. The conformations of the acids are discussed and compared with those of other α-amino acids.     

Unambiguous Proof for Alcoxycarbonyl-group Migration in Wagner-Meerwein Rearrangements

In HSO₃F/SO₂ClF the β-hydroxy esters Ph-CHOH-CMe₂-COOR ( 1 , R?Me, Et) are doubly protonated, then transformed into the fluorosulfates 7 and (partly) into the fluorides 8. At ?15°, both 7 and 8 undergo a rearrangement, forming derivatives of Me₂C?C(Ph)COOR ( 2 ). By labelling 1 with ¹³C, singly (¹³C(3)) and doubly (¹³C(1,3)), it could be shown that exclusively the ROOC groups undergo a 1,2-shift. Compound 2 is also formed in HSO₃F/SO₂ClF from the isomeric Me₂COH-CHPh-COOR ( 3 ) by elimination, and less easily from the α-hydroxy ester Ph-CMe₂-CHOH-COOR (5) via a phenyl 1,2-shift. Another isomer, Ph-C(OH)Me-CHMe-COOR (4) gives products different from 2 . Using more acidic systems containing SbF₅, the free carbenium ions 13 (Ph-CH⁺-CMe₂-COOR) can be stabilized; they do not form 2 , possibly because of complexation of the ester group with SbF₅. The energy profile and the mechanism of the rearrangement 1 → 2 are discussed.     

Crystallographic Studies of Clathrate Hydrates. Part I

Low-temperature neutron and X-ray diffraction studies show the gas hydrates of oxygen and nitrogen to be structure II (Fd3m), as recently found also for the hydrates of the small argon and krypton molecules. New lattice parameters of three structure I and 14 structure II hydrates from powder X-ray diffraction at 170 K are reported. The thermal expansion coefficient of tetrahydrofuran hydrate was determined from X-ray diffraction at some 50 temperatures between 18 and 263 K and found to be three times as great as for ice near 100 K and 30% higher near 250 K. Lattice parameters qf 40 type II clathrate hydrates are compared at 0°C and found to lie within 0.10 Å of 17.30 Å.     

Groupes de départ inhabituels lors de cyclisations dans la série des quinoxalines,II [1]

Quinoxaline-3-ketones substituted by different groups in position 2 (I) are easily cyclized by hydroxylamine and phenylhydrazine to form isoxazolo[4, 5-b] quinoxalines (II) and pyrazolo [3, 4-b] quinoxalines (III) respectively. The reactions proceed via the oximes resp. phenylhydrazones. Groups displaced are not only the customary leaving groups of aromatic S_N2 reactions (halogens, OH), but likewise H, COOH, CONH₂, CO-Ar, and, less easily, benzyl groups; methyl and phenyl groups were not displaced. The displacement of hydride ion in the presence of excess of hydroxylamine resp. phenylhydrazine is explained in terms of an extension of the theory of osazone formation.