Diastereospecific ring cleavage of bornane-2,3-dione in the Bucherer-Bergs reaction

A novel regio- and diastereospecific ring cleavage of bornane-2,3-dione (camphor quinone) under Bucherer-Bergs reaction conditions has been investigated. The simplicity of this transformation provides a novel and straightforward synthetic pathway to enantiopure derivatives of cyclopentane carboxylic acid as well as functionalized hydantoins in just two steps, starting from inexpensive and easily available camphor.     

Substituent effects on carbon-13 NMR chemical shifts of side chain carbonyl carbons of 4-substituted 1-naphthamides

Substituent induced¹³C NMR chemical shifts of side chain carbonyl carbons of several 4-substituted 1-naphthamides have been measured in DMSO-d ₆ solvent. Analysis of the substituent induced chemical shifts by the DSP equation gave the regression equation. Both {ie207-1} and {ie207-2} values were negative. The negative sign on {ie207-3} term indicates the operation of a reverse substituent effect and that π-polarisation is the important mechanism for the transmission of substituent effects by inductive effect. Theperi-hydrogen interaction in naphthamides forces the amide group out of the plane of the naphthalene ring.     

13C and 1H chemical shifts in 2-benzylidene[3]ferrocenophane-1,3-diones. Elucidation of the substituent dependence of carbonyl chemical shifts in different carbonyl derivatives

The ¹³C and ¹H chemical shifts of the ferrocene moiety, as well as the carbonyl carbons and styrene moiety, of substituted 2-benzylidene[3]ferrocenophane-1,3-diones have been assigned. Correlations of ¹³C substituent chemical shifts of both carbonyl carbons with the Hammett constants have been found, and the effect of the transmission of substituent effects on these chemical shifts through the styrene moiety is discussed. An explanation is given for the different sensitivities of the carbonyl carbon chemical shifts to the electronic effect of substituents in mono- and dicarbonyl derivatives.     

Synthesis of 4-substituted 5,6-diphenylmorpholine-2,3-diones with two or three chiral centers

Chiral α-aminoalcohols obtained by stereoselective reduction of α-iminoketones have been condensed with oxalyl chloride to afford 4-substituted 5,6-diphenylmorpholine-2,3-diones having two or three chiral centers.     

Photolysis of Matrix-Isolated 4-R-1,2,4-triazoline-3,5-diones: Identification of Aziridine-2,3-dione Transients

Matrix-isolated 4-methyl-1,2,4-triazolinedione 1a and 4-phenyl-1,2,4-triazolinedione 1b were photolyzed at lambda >/= 335 nm and lambda >/= 310 nm, respectively. The reactions induced by photolysis were monitored by FT-IR spectroscopy. The isocyanates 2a and 2b are always the more abundant products with carbon monoxide. Methyl- and phenylaziridine-2,3-diones (3a and 3b) were detected as minor, but well-identified reaction products. The IR experimental absorption bands were assigned by comparison with literature data and with simulated infrared spectra obtained by ab initio calculation at the 6-31G level. Stable at the matrix temperature (10 K), 3a and 3b photolyzed to isocyanates and CO when irradiated at lambda >/= 230 nm. Irradiation of 2b at this wavelength induces its decomposition. The kinetic data show that the rate constant process 1a --> 2a is faster than the 1a --> 3a process (3.29 x 10(-)(3 )and 2.35 x 10(-)(4)min(-)(1) respectively).     

Regio- and stereocontrolled metal-mediated carbonyl propargylation or allenylation of enantiomerically pure azetidine-2,3-diones: synthesis of highly functionalized 3-substituted 3-hydroxy-beta-lactams

Regio- and stereocontrolled metal-mediated Barbier-type reactions of azetidine-2,3-diones with differently substituted propargyl bromides offer an efficient asymmetric entry to densely functionalized 3-propargyl- (or allenyl-) substituted 3-hydroxy-beta-lactams.     

N-Methyl chemical shifts in some 2-, 3- and 4-substituted N-methylpyridinium salts

The chemical shifts of the N-methyl group in a series of 2-, 3- and 4-substituted N-methylpyridinium salts have been measured in DMSO solution. The shift is primarily affected by resonance interaction between the substituent and aza group, and the results suggest that the resonance effect from a 2-substituent is at least as great as from the corresponding 4-substituent.     

Facile synthesis of 3-substituted quinazoline-2,4-dione and 2,3-di-substituted quinazolinone derivatives

3-Substituted quinazoline-2,4(1H,3H)-dione and 2,3-di-substituted quinazolineone derivatives attract considerable interest due to their pharmacological properties. In this paper, we report the synthesis of N-substituted-3-nitrophthalimide derivatives II?CIII, the reactions of phthalimide III with amines, hydrazines, and amino acid derivatives to synthesise a small library of 3-substituted-5-nitroquinazoline-2,4(1H,3H)-diones IV?CXIV and 2,3-di-substituted-6-nitro-quinazolineones XVIII?CXIX.     

Substituent and solvent effects on the 19F chemical shifts of 3- and 4-XCH2-substituted fluorobenzenes

Substituent effects on the ¹⁹F chemical shifts of a series of 3- and 4-XCH₂-substituted fluorobenzenes have been studied in five different solvents (dimethyl sulphoxide, acetone, chloroform, carbon tetrachloride and benzene). The results show that in both series substituent effects (other than inductive effects) contribute in at least some cases to the overall shifts, but that these showed little solvent dependence. The meta series showed a proportionately greater solvent dependence than the para series, and this is attributed to the greater importance of ‘through solvent’ direct field effects in the former.     

Effect of substituents on NMR chemical shifts of carboxylic acid esters and nitriles

Conclusions It was shown that the chemical shifts in the NMR spectra of carboxylic acid esters and nitriles can be estimated using the equation for substituted methanes.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1169–1171, May, 1977.The authors express their gratitude to R. G. Gainullina and T. A. Zyablikova for taking the spectra.     

A study of the 17O carbonyl chemical shifts in substituted benzaldehydes

An analysis of 17O carbonyl chemical shifts of 50 substituted benzaldehydes leads to an empirical equation, delta(cal)(17O) = 564.0 + (sigma)(delta)o + (sigma)(delta)m + (sigma)(delta)p + C, for calculating 17O chemical shifts. This equation is based on a linear regression analysis using 11 substituent parameters and leads to good conformity with the expected data.     

Effects of some phosphorus substituents on the carbon-13 chemical shifts of alkyl chains

The carbon-13 NMR spectra of 16 aliphatic phosphorus compounds with -PCl₂, -P(OCH₃)₂, -P(CH₃)₂ or -PS(CH₃)₂ groups were determined and interpreted on the basis of the usual α, β-deshielding and γ-shielding effects. The α-effects of all the groups were quite large (15 to 30 ppm), though the β-effects were small (0 to 3 ppm). The γ-effects were also small (0·2 to 1·6 ppm), but of significance in suggesting reduced steric compression relative to that found for methyl and most of the common organic functional groups. This may be attributed to the greater length of the C? P bond. The phosphorus-31 NMR spectra of these compounds also show the existence of interaction with γ-carbons by exhibiting small additive upfield shifts.     

The effect of solvents on the 13C NMR chemical shifts of the carbonyl carbon and the rotational barriers of N,N-dimethylbenzamide

The ¹³C solvent induced chemical shifts (SICS) of the carbonyl carbon and the thermodynamic barriers to rotation about the C? N bond of N,N-dimethylbenzamide are linearly related to the solvent parameter, E_T(30). A multi-parametric solvent parameter approach indicates that the SICS are influenced equally by polar effects and hydrogen-bond donor effects. Rotational barriers for N,N-dimethylbenzamide may, in principle, be determined by measurement of the ¹³C chemical shift of the carbonyl carbon in a particular solvent.     

A 17O NMR study. On the correlation of ionization potentials and 17O chemical shifts in 4-substituted pyridine-N-oxides and 4-substituted N-(benzylidene)phenylamine-N-oxides

The approximate linear correlation between first ionization potentials and ¹⁷O chemical shifts for 4-substituted pyridine-N-oxides and 4-substituted N-(benzylidene)phenylamine-N-oxides is presented. The obtained results are used to estimate the ¹⁷O chemical shift in 4-N,N-dimethyl pyridine-N-oxide. The obtained results are discussed in relation to similar correlations in substituted benzenes and pyridines. The linear correlation between oxygen atomic net charge and ¹⁷O chemical shift for 4-substituted pyridine-N-oxides and 4-substituted N-(benzylidene)phenylamine-N-oxides is also presented.