Acyl derivatives systems

Alkoxy titanium acylate derivatives coordinated with a phosphite diester (phosphonate diester) can be prepared by reaction of a tetraalkyl titanate and an equal molar amount of a carboxyUc acid, such as methacrylic acid or isostearic acid, and a phosphite or phosphonate diester, such as dibutyl hydrogen phosphite (103). These materials reduce the viscosity of a composite system, improve... 

Similarly, no systematic study of the IR spectra of the pyridopyridazines has been recorded, but the spectra of the [2,3-d] derivatives have been discussed <68AJCl29l). The diones of this series have also been studied <69MI21501), and IR used to distinguish between the structure (303) and the possible isomeric formulation (304) <74JHC35l). The IR spectra of some of the azodicarboxylic ester adducts <79X2027) have been recorded, whilst in the benzo fused systems some problems with the structure of acyl derivatives in the pyridazino[4,5-6]quinoline series have been resolved with the help of IR spectroscopy <71BSF906, 72BSF1588). 

The reaction of ADC compounds with carbenes and their precursors has already been discussed in Section IV,A- In general, the heterocyclic products are not the result of 1,2-addition but of 1,4-addition of the carbene to the —N=N—C=0 system.1 Thus the ADC compound reacts as a 4n unit in a cheletropic reaction leading to the formation of 1,3,4-oxadiazolines. Recent applications include the preparation of spiro-1,3,4-oxadiazolines from cyclic diazoketones and DEAZD as shown in Eq. (14),133 and the synthesis of the acyl derivatives 85 from the pyridinium salts 86.134 The acyl derivatives 85 are readily converted into a-hydroxyketones by a sequence of hydrolysis and reduction reactions. 

Azido derivatives of furazans have proved to be particularly useful for the synthesis of heterocyclic systems. Thus, by 1,3-dipolar addition of l-azido(4-amino-l,2,5-oxadiazol-3-yl)aldoxime 186 to propargyl alcohol and phenylacetyl-ene, bicyclic 4-amino-l,2,5-oxadiazol-3-yl(4-R-l,2,3-triazol-l-yl)ketoximes 187 were obtained (Equation 34) which in reaction with acetic anhydride afforded the corresponding 0-acyl derivatives <2003RJ0574>. 

The most frequently used acyl derivatives, i.e., benzoates and cinnamates substituted in the 4-position, are listed in Table 7. The analysis of the stereochemistry of the bichromophoric system including a benzoate (cinnamate) chromophore is greatly simplified by its preference for s-trans conformation at the C(0)-0 bond, in which the carbonyl group is staggered ca. 30° to either side of the carbinyl C H bond. Consequently the direction of the electric dipole moment of the charge-transfer transition is approximately parallel to the C(H)-Q bond (Figure 16). 

The conformational properties of the amide system in N-acyl heterocyclic derivatives may nevertheless be characterized by further peculiarities. Differences must be anticipated between N-acyl derivatives of conjugated and nonconjugated heterocycles. 

Comparison of the conformational behavior of different C = X substituents seems necessary either to acquire a more general knowledge of s-cis/ s-trans isomerism in heterocyclic systems or for a better understanding of the behavior of acyl derivatives. 

The synthesis of this ring system may be achieved by building the triazole onto a preformed pyrimidine ring. Cyclocondensation of ketoesters 330 with O-methylisourea (331) gave the pyrimidine 332, whose acylation gave the /V-acyl derivative 333, which can be cyclized with hydrazines to give 334 (89GEP3839711) (Scheme 64). 

O-Acyl derivatives of thiohydroxamic esters (Barton esters) react with benzynes to afford a tricyclic thiophene ring system thus the pyridine derivative 30 gives benzo[4,5]thieno[2,3-A pyridines 31 (Scheme 14) <2002JOC3409, CHEC-III(3.11.3.3)900>. 

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