Bonding schemes

Category Ih cyclizations effect closure of the C2 C3 bond. Scheme 3.1 depicts retrosynthetic transformations corresponding to syntheses in category lb. Included are three variations of the intramolecular aldol condensation and reductive coupling of o,/V-diacylanilines,... 

The main features are the molecular ions as the base peak and the M-t-1 ions arising from another species. For 2-aminothiazole the m/e 73 ion (M-HCN) is shifted to m/e 75 in the spectrum of the dideuteroamino derivative and, therefore, largely arises via rupture of 2-3 and 4-5 bonds (Scheme 18). This fragmentation process could involve the kind of intermediates postulated in photochemical rearrangements (see Chapter III, Section IX.3.B). The other fragments fit well the general pattern of fragmentation proposed by Clarke (136). 

TT-bonding (Scheme 84) (463). A series of simple thiazole complexes has... 

The tetrahedral network can be considered the idealized stmcture of vitreous siUca. Disorder is present but the basic bonding scheme is still intact. An additional level of disorder occurs because the atomic arrangement can deviate from the hiUy bonded, stoichiometric form through the introduction of intrinsic (stmctural) defects and impurities. These perturbations in the stmcture have significant effects on many of the physical properties. A key concern is whether any of these defects breaks the Si—O bonds that hold the tetrahedral network together. Fracturing these links produces a less viscous stmcture which can respond more readily to thermal and mechanical changes. 

Because all of these structures share the same short-range bonding scheme, the density differences iadicate that vitreous siUca has a substantial iaterstitial volume and can be compacted. 

Diazo compounds react with alkenes to afford A -pyrazolines, which in turn izomerize to A -pyrazolines if there is a hydrogen atom a to the N=N bond (Scheme 54). In those cases where two possible ways of isomerization exist, the more acidic hydrogen migrates preferentially. The alkene configuration is conserved on the A -pyrazoline (stereospecificity) but the regioselectivity depends on the substituents of both the alkene and the diazo compound. 

Nitrile oxides react with a wide variety of alkenic compounds and this reaction may be complicated by dimerization of the nitrile oxide to furoxan in the presence of unreactive double bonds (Scheme 98). 

Acid treatment or thermolysis of aziridinyl phenyl ketone oxime generated a 2-isoxazoline (74JAP(K)74i 17462), while treatment of a diphenylcyclopropene (486) with NOCl generated a 2-isoxazoline in contrast to dialkylcyclopropene (487) which produced addition across the double bond (Scheme 126) (73MI41605). 

The bonding scheme is also consistent with the observed lengthening of the H-H distance to about 84-90pm in the complexes (as... 

Compound 104 could not be obtained from 103, and a hypothesis about its formation considered the (homolytic or heterolytic) cleavage of the O—N bond (Scheme 43) (68TL2417). The sensitized reaction didnotgive adifferentresult the author supposed that the reaction involved the excited triplet state of the molecule. When the reaction was carried out in methanol, 104 was obtained in 8% yield... 

Uracil dimers were studied at the MP2 level using the 6-3IG basis with modified polarization functions. Eleven low-energy minima were located Seven of them are H-bonded, one is T-shaped, and three correspond to various stacked arrangements. The most stable structure was found to be the H-bonded dimer with two Ni-H O2-H bonds (Scheme 85) [98JPC(A)6921]. 

Moreover, with a change of solvent, a new tautomeric form can arise owing to formation of intermolecular hydrogen bonds in place of the previously existent intramolecular hydrogen bonds. This situation is characteristic, for example, for pyrimidine derivatives 49, for which the use of polar (DMSO, DMF, MeOH, HMPT) solvents or specifically solvating cosolvents (S) (e.g., a small amount of water or A-methylpyrrolidinone) leads to the appearance of ylidene tautomer 49b with the p-quinonoid disposition of the double bonds (Scheme 18) [88KGS521 90UK457]. 

The synthesis of aziridines through reactions between nitrenes or nitrenoids and alkenes involves the simultaneous (though often asynchronous vide supra) formation of two new C-N bonds. The most obvious other alternative synthetic analysis would be simultaneous formation of one C-N bond and one C-C bond (Scheme 4.26). Thus, reactions between carbenes or carbene equivalents and imines comprise an increasingly useful method for aziridination. In addition to carbenes and carbenoids, ylides have also been used to effect aziridinations of imines in all classes of this reaction type the mechanism frequently involves a stepwise, addition-elimination process, rather than a synchronous bond-forming event. 

A common reaction sequence is shown in the schemes printed above. The sulfosuccinate monoesters are produced by a two-step reaction. In the first step 1 mol of maleic anhydride is reacted with a hydroxyl group-bearing component. In the second step the monoester is reacted with sodium sulfite (or sodium bisulfite) to form the disodium alkyl sulfosuccinate. At the so-called halfester stage, there are two possibilities for an electrophilic attack [61] (Michael-type reaction) at the double bond (Scheme 6). Reactivity differences between the two vinylic carbons should be very small, so that probably an exclusive formation of one single regioisomer can be excluded. 

An alternative pathway to impart diversity at the C-3 position of the pyrazinone scaffold is possible via the hnkage of the triazole moiety to the core using a C - C bond (Scheme 27). The C-3 acetylenic pyrazinone... 

The lobes of electron density outside the C-O vector thus offer cr-donor lone-pair character. Surprisingly, carbon monoxide does not form particularly stable complexes with BF3 or with main group metals such as potassium or magnesium. Yet transition-metal complexes with carbon monoxide are known by the thousand. In all cases, the CO ligands are bound to the metal through the carbon atom and the complexes are called carbonyls. Furthermore, the metals occur most usually in low formal oxidation states. Dewar, Chatt and Duncanson have described a bonding scheme for the metal - CO interaction that successfully accounts for the formation and properties of these transition-metal carbonyls. 

CpFe(CO)[FcC(NCy)2] results in rapid exchange of CO at 25 °C. Heating this solution to 80 °C results in the partial formation of the carbamoyl species by a formal CO insertion into an Fe-N bond (Scheme 136). ... 

Cp =7j -C5Me5) d(S-S)=199.7 pm [65]). These properties maybe explained in terms of the large contribution of resonance structure B, which has some extent of double bond character in the S-S bond (Scheme 36). 

---