Synthesis, Properties, and Reactions

Benzylidene acetals can be formed under essentially neutral conditions using the bis-sulphonium ion (62) obtained by methylation of benzaldehyde ethylene dithioacetal with methyl fluorosulphonate (Magic Methyl ). Thus, methyl -d-glucopyranoside afforded a 4,6-0-benzylidene derivative (25%) when treated with (62) in pyridine. In the absence of an acid catalyst, it is unlikely that the thermodynamically favoured acetal would be obtained in high yield. 

Collins et al. have reported details of their interesting work on the photochemical rearrangement of 2-nitrobenzylidene acetals. Derivatives of methyl 4,6-0-(2-nitrobenzylidene)glycopyranosides rearranged upon u.v.-irradiation in methanol to give the corresponding 4- and 6-(2-nitrosobenzoates), which were converted into the 4- and 6-(2-nitrobenzoates) on oxidation with trifluoroperacetic acid. 2 Thus, methyl 2,3-di-0-acetyl-4,6-0-(2-nitrobenzylidene)-a- and -jS-D- 

The ozonolysis of benzylidene acetals to give benzoylated compounds is discussed in Chapter 6. 

The concentrations of acetic acid and acetic anhydride used in the acid-catalysed acetolysis of 1,2-0-isopropylidenealdofuranoses have been shown to influence the proportions of acyclic by-products formed (see Vol. 7, p. 46). The formation of acyclic compounds can be suppressed by decreasing the concentration of acetic anhydride, although the configuration of the starting material also affects the outcome of acetolysis.  

Acetonation of D-ribose and D-arabinose using ethyl (or methyl) isopropenyl ether in DMF containing a trace of toluene-p-sulphonic acid has been reported. D-Ribose yielded principally 3,4-O-isopropylidene-jS-D-ribopyranose, together with other minor products such as 2,3-O-isopropylidene-D-ribofuranose, and D-arabinose gave mostly 3,4-0-isopropylidene-)3-D-arabinopyranose and some l,2 3,4-diacetal. D-Fucose and 6-0-methyl-D-galactose afforded 3,4-0-isopro-pylidene derivatives, in 40—60% yield, on treatment with acetone and anhydrous cupric sulphate. D-Ribose also yielded a 3,4-0-isopropylidene derivative (15—20%) on similar treatment, whereas 4,6-0-isopropylidene-D-glucose was obtained in low yield when D-glucose reacted in the presence of DMF. 

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Baiocchi Synthesis, properties and reactions of indazolones 78S633... 

Synthesis, properties, and reactions of cyclic trisulfides and their oxides 980PP551. 

Synthesis, Properties, and Reactions of Carbene Complexes of Silver 203... 

The Synthesis, Properties, and Reactions of Several Steroidal a-Oximino and a-Diazoketones, University Microfilms, Ann Arbor, Mich., Order No. 65-3941 Dissertation Abstr., (11) 25, 6246 (1965). 

We make no attempt to list the individual hydrazonoyl halides of type 2-4 described in the literature rather, we shall endeavor to give a broad general review of the synthesis, properties, and reactions of such halides. Furthermore, we sometimes found it necessary to question the mechanisms of some of the reactions and the structures of some of the products outlined herein. The literature was surveyed up to the middle of 1993. The hitherto-reported hydrazonoyl halides of types 2-4 are listed in Table I. 

Huttner, G. Knoll, K. RP-bridged metal carbonyl clusters Synthesis, properties, and reactions, Angew. Chem., Int. Ed. Engl 1987, 26, 743 Angew. Chem. 1987, 99, 765. 

Another possible explanation for enhanced stabilities of perfluoro-alkyltransition metal compounds concerns possible multiple bonding between the metal and the fluorocarbon group 230). Whatever the reason, a large number of fluorocarbon derivatives of the transition metals have now been described, and a study of their synthesis, properties, and reactions constitutes an important new branch of organotransition metal chemistry. Fluoroalkyltransition metal compounds were first described in 1959 J 8), while perfluoroary 1-transition metal derivatives were discovered in 1963 201, 234). Some typical syntheses of fluorocarbon-transition, metal compounds are shown below ... 

In a very comprehensive study by Finn and co-workers the synthesis, properties and reactions of several titanium-substituted ylides are described. The complexes were prepared from titanium alkoxides and (Me2N)3P=CH2 (scheme 9). The structure of one of the complexes was determined crystallographically which showed it to exist as a chloride bridged dimer (53). The ylidic P-C distance and /pc coupling constant are charactersitic of a P-C single bond which, together with the six-coordinate nature of the Ti centres, verify the zwitterionic nature of the species in both the solid state and in solution. The titanium ylide... 

The synthesis, properties, and reactions of A -phosphorins have been reviewed. Whereas the 4-alkoxystannabenzoles (176 R = alkyl) react with phosphorus tribromide to give the phosphorin (177), the corresponding reaction of the 4-hydroxy-derivatives (176 R = H) fails to give recognizable products. Methyl-lithium adds to the phosphorus atom of (177 R = H) to give the phosphine (178) after quenching with water. ... 

Synthesis, properties and reactions of l//-indazol-3-ols and l,2-dihydro-3//-indazol-3-ones , Baiocchi, L., Corsi, G. and Palazzo, G., Synthesis, 1978,... 

Pioneering investigations by Bdhme et al. into the synthesis, properties and reactions of preformed iminium salts have provided much of the basis for their recent applications in organic synthesis. These and related investigations are described in his extensive review on Methyleneiminium Salts , covering woric up to the early 1970s. 

III, Elsevier, 2007. Each of these sets has an extensive listing of references on organometallic compounds that have been structurally characterized by X-ray, electron, or neutron diffraction. A useful reference to literature sources on the synthesis, properties, and reactions of specific organometallic compounds is J. Buckingham and J. E. Macintyre, editors. Dictionary of Organometallic Compounds, Chapman and HaU, London, 1984, to which supplementary volumes have also been published. The series Advances in Organometallic Chemistry, Academic Press, San Diego, provides valuable review articles. 

The methods of synthesis, properties, and reactions of j8-chloro-a/3-unsaturated aldehydes have been reviewed.In a recent innovation 8-chloro-a 8-unsaturated aldehydes are available through Vilsmeier formylation of ketones. ... 

J. Foropoulos Jr., D. D. DesMarteau, Inorg. Chem. 1984, 23, 3720-3723. Synthesis, properties, and reactions of bis((trilluoromethyl)sulfonyl) imide, (CFsSOiljNH. 

Co, Rh and Ir - The synthesis, properties and reactions of (T]5-bicyclo[3.2.01hcpta-l,3-dienyl)(il -COD)cobalt(I) have been reported, including the X-ray crystal structure of the tetraphenylcyclobutadiene complex, (17), the product of its reaction with diphenylethyne. The reaction of [(Ti5-C5H4R)Co( n -COD)] with 1,6-cyclodecadiyne afforded the (q. C5H4R)cobalt-capped cyclobutadiene superphane. The yield of the reaction was reported to vary with the substituent R. 

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