Tris- methyl benzoate

Eupe and Majewski attempted to determine by experiment the influence of the relative positions of osmophores on each other in the same molecule. In the case of the three methyl tri-azo-benzoates no great difference in the type of odour exists, only a difference in the strengths, the para compound being the strongest and the ortho the weakest. Of the three methoxy-acetophenones, as another example, the meta isomer is almost odourless in comparison with the ortho and para. 

Triphenylcarbinol has been obtained by the reaction between phenylmagnesium bromide and benzophenone,1 methyl benzoate, or phosgene 8 by action of phenylsodium upon benzophenone, benzoyl chloride, ethyl chlorocarbonate, or ethyl benzoate 4 by hydrolysis of triphenylchloromethane 5 and by oxidation of tri-phenylmethane.6... 

Although the reaction with thiosulfate and with iodide ions may be a mere reduction of the halide, the reaction with sodium benzoate would appear to be a radical dissociation induced by the attack of a negative ion. The fate of the benzoate ion is unknown. Tris-( -nitrophenyl)-methyl benzoate is a stable substance which does not dissociate into radicals.23... 

A maximum in the DP and a minimum in the specific conductivity, both at a ratio of [additive]/ [A1C13] ranging from 0.8 to 1.0 (in EtCl at -78.5°) were also reported for a large range of additives , comprising various alcohols, acetone, methyl benzoate, acetic acid, 1-dodecanethiol, and tri-n-butylamine [66]. For all these additives no details are given, so that it is not known whether the relevant curves have more than one turning point. 

Esters are also reduced by sodium aluminum hydride (yields 95-97%) [<9<9] and by lithium trimethoxyaluminum hydride (2 mol per mol of the ester) [94] but not by lithium tris tert-butoxy)aluminum hydride [96], Another complex hydride, sodium bis(2-methoxyethoxy)aluminum hydride, reduces esters in benzene or toluene solutions (1.1 -1.2 mol per ester group) at 80° in 15-90 minutes in 66-98% yields [969], Magnesium aluminum hydride (in the form of its tetrakistetrahydrofuranate) reduced methyl benzoate to benzyl alcohol in 58% yield on refluxing for 2 hours in tetrahydrofuran [59]. 

Pentacarbonyl(methoxymethyl-methylene)chromium, 83 Tri-p,-carbonylhexacarbonyldiiron, 320 Tricarbonyl(methyl benzoate)chromium, 19... 

Chiralcel OJ Cellulose tris(4-methyl benzoate) Aryl methyl esters, aryl methoxy esters ... 

Decomposition of methanesulphonyl azide in aromatic solvents (methyl benzoate or benzotrifluoride), in the presence of transition metal compounds (e.g. copper(ri) acetylacetonate, manganese(ii) acetylacetonate, di-cobalt octacarbonyl, tri-iron dodecacarbonyl, and iron pentacarbonyl) led to a marked decrease in the aromatic substitution product compared with thermolysis, and, with the iron carbonyls, to an increased yield of methanesulphonamide . In addition, the aromatic substitution products shifted from mainly ortAo-substitution with no additives to mainly w ia-substitution in the presence of the additives mentioned above. 

CrFeN09P2C45H3i, Chromate(l -)hydrido-nonacarbonyliron-, p.-nitrido-bis(tri-phenylphosphorus)(l -(-), 26 338 CrFeN209P4C,iH i, Chromate(2-), nona-carbonyliron-, bis[p.-nitrido-bis(tri-phenylphosphorus)(l +)], 26 339 CrNOsCwH, Chromium, (benzoyl isocyan-ide)dicarbonyl(T -methyl benzoate)-, 26 32... 

This isotherm model has been used successfully to accoimt for the adsorption behavior of numerous compounds, particularly (but not only) pairs of enantiomers on different chiral stationary phases. For example, Zhou et ah [28] foimd that the competitive isotherms of two homologous peptides, kallidin and bradyki-nine are well described by the bi-Langmuir model (see Figure 4.3). However, most examples of applications of the bi-Langmuir isotherm are found with enantiomers. lire N-benzoyl derivatives of several amino acids were separated on bovine serum albumin immobilized on silica [26]. Figure 4.25c compares the competitive isotherms measured by frontal analysis with the racemic (1 1) mixture of N-benzoyl-D and L-alanine, and with the single-component isotherms of these compounds determined by ECP [29]. Charton et al. foimd that the competitive adsorption isotherms of the enantiomers of ketoprofen on cellulose tris-(4-methyl benzoate) are well accounted for by a bi-Langmuir isotherm [30]. Fornstedt et al. obtained the same results for several jS-blockers (amino-alcohols) on immobilized Cel-7A, a protein [31,32]. 

SMB parameters Cellulose tris(p-methyl- benzoate) beads Poly(N-acryloyl-amino acid ester) silica CSP Cellulose tris(p-methylbenzoate) coated on silica (Chiralcel OJ) Amylose tris(3,5-dimethylphenyl-carbamate) coated on silica (Chiralpak AD)... 

Figure 8.8. Separation of a test mixture on a 50 cm x 50 p.ni column packed with 1.5 )xm Spherisorb ODS-1 with a mobile phase of 70 % (v/v) acetonitrile in a 10 mM pH 9 TRIS buffer at 25° C and voltage 30 kV. Compounds 1 = acetone 2 = benzyl alcohol 3 = dimethyl phthalate 4 = acetophenone 5 = anisole 6 = methyl benzoate 7 = toluene and 8 = phenyl benzoate.

Myrcenol Phenoxyethyl propionate Piperonyl acetone Prenyl benzoate 3,5,5-Trimethylhexyl acetate fragrance, herbal compositons Tri methyl benzyl alcohol fragrance, herbal fragrances 2,4-Hexadienol fragrance, household prods. 

C1O3C9H4, Chromium, (if -benzene)tri-carbonyl-, 28 139 CrOgCioHg, Chromium, (fi -anisole)tricarbonyl-, 28 137 CrOjCiiHg, Chromium, tricarbonyl(>r -methyl benzoate)-, 28 139 CrjBrgCs, Chromate(3—X nonabromodi-, tricesium, 26 379... 

Reactions of the same carbonyl ylide intermediate with aldehydes are even more fruitful. The Rh2(OAc)2 catalyzed reaction proceeds at room temperature in the presence of 2 mol% of the catalyst, but the diastereoselectivity is disappointingly low (endo/exo = 49 51, Scheme 11.56). However, when 10 mol% of the cocatalyst Yb(OTf)3 is added, the reaction becomes highly exo-selective (endo/ exo = 3 97) (198). Suga has extended this Lewis acid catalyzed carbonyl ylide cycloaddition reaction to catalyzed asymmetric versions. The chiral cocatalyst employed is ytterbium(III) tris(5)-1,1 -binaphthyl-2,2 -diyl phosphonate, Yb[(S) BNP]3 (10 mol%). In the reaction of methyl o-(diazoacetyl)benzoate with benzyloxyacetaldehyde in the presence of Rh2(OAc)2 (2 mol%) at room temperature with the chiral Yb catalyst, the diastereoselectivity is low (endo/exo = 57 43) and the enantiopurity of the endo-cycloadduct is 52% ee. 

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