Azidations 2- benzoate

Lithium acetate ammonium sulfate azide benzoate borate (meta-) bromate bromide carbonate chlorate chloride... 

Reactions of substituted cumyl benzoates in 50 50 trifluoroethanol-water show no effect of [NaN3] on the rate between 0 and 0.5 M. The product ratio, however, is highly dependent on the cumyl substituent. Electron-releasing substituents favor azide formation whereas electron-withdrawing substituents result in solvent capture. Formu-... 

In the original work (72), the authors stated that heating of 42 with excess sodium iodide did not result in further exchange. The extensive studies of Stevens and co-workers (96, 97) on the displacement reactions of compounds much related to 40, indicate that the C-4 sulfonate group can indeed be displaced by various nucleophiles. In fact compound 42 and its C-4 epimer (43) (d-threo) have been subjected to displacement reactions with benzoate (38), acetate and azide (98) ions to give the corresponding C-4 inverted products. 

Treatment of 51 with an excess of sodium benzoate in DMF resulted in substitution and elimination, to yield the cyclohexene derivative (228, 36%). The yield was low, but 228 was later shown to be a useful compound for synthesis of carba-oligosaccharides. <9-Deacylation of228 and successive benzylidenation and acetylation gave the alkene 229, which was oxidized with a peroxy acid to give a single epoxide (230) in 60% yield. Treatment of 230 with sodium azide and ammonium chloride in aqueous 2-methoxyeth-anol gave the azide (231,55%) as the major product this was converted into a hydroxyvalidamine derivative in the usual manner. On the other hand, an elimination reaction of the methanesulfonate of 231 with DBU in toluene gave the protected precursor (232, 87%) of 203. 

Figure 10 Capillary ion analysis of 30 anions 1 = thiosulfate, 2 = bromide, 3 = chloride, 4 = sulfate, 5 = nitrite, 6 = nitrate, 7 = molybdate, 8 = azide, 9 = tungstate, 10 = monofluorophosphate, 11 = chlorate, 12 = citrate, 13 = fluoride, 14 = formate, 15 = phosphate, 16 = phosphite, 17 = chlorite, 18 = galactarate, 19 = carbonate, 20 = acetate, 21 = ethanesulphonate, 22 = propionate, 23 = propanesulphonate, 24 = butyrate, 25 = butanesulphonate, 26 = valerate, 27 = benzoate, 28 = D-glutamate, 29 = pentane-sulphonate and 30 = D-gluconate. Experimental conditions fused silica capillary, 60 cm (Ld 52 cm) x 50 p i.d., voltage 30 kV, indirect UV detection at 254 nm, 5 mM chromate, 0.5 mM NICE-Pak OFM Anion-BT, adjusted to pH 8.0, with 100 mM NaOH. (From Jones, W. R. and Jandik, R, /. Chromatogr., 546, 445,1991. With permission.)...

Copper catalyzes the decomposition of sulphonyl azides in benzene very slowly. When methanesulphonyl azide was boiled under reflux in benzene solution in the presence of an excess of freshly reduced copper powder, some decomposition occurred to give methanesulphonamide and azide was recovered 78>. Transition metal complexes have been found to exert a marked effect upon the yields of products and isomer ratios formed in the thermal decomposition of methanesulphonyl azide in methyl benzoate and in benzotrifluoride 36>. These results will be discussed in detail in the section on the properties of sulphonyl nitrenes and singlet and triplet behaviour. A sulphonyl nitrene-iron complex has recently been isolated 37> and more on this species will be reported soon. 

Lead arsenates, 74 797 Lead azide, 70 727-729 74 792 Lead babbitt, 3 52, 52t arsenic addition to, 3 271 Lead-base babbitts, 24 797 Lead-based paint, 74 765 Lead-based paint remediation, 18 75 Lead-based pigments, 79 386. See also Lead chromate pigments Lead benzoate, 74 794 Lead bisilicate, 74 796 Lead blast furnace, 74 737 Lead borate, 74 797 Lead bromide, 74 785 Lead bullion, 74 742, 745... 

Sodium azide, 13 597 Sodium azidodithiocarbonate, 4 827 Sodium bentonite, 6 696 Sodium bentonites, 6 664—665 Sodium benzoate... 

Benzhy dr azide.1—24 g. (0-15 mole) of ethyl benzoate (p. 141) are heated for six hours under a small reflux condenser on the water bath with 9 g. of hydrazine hydrate.2 The solid crystalline cake which is formed on cooling is, after some time, filtered as dry as possible at the pump and washed with a little ice-cold methyl alcohol. If the yield is too small the filtrate is concentrated and heated again. 

Kurita et al. reacted a-azidocinnamate 327 with benzoyl chloride (Scheme 119) to form benzoate 328, which upon conversion of the azide group into an iminophosphorane (329) underwent an aza-Wittig cyclization to yield 1,3-benzoxazepine (330) (92CC81). 

Displacement reactions on methyl 6-deoxy-2,3-0-isopropylidene-a-D-(L)-mannopyranoside 4-sulphonates with ionic nucleopliiles such as acetate benzoate azide and thiobenzoate > take place... 

Differential triflate reactivities as just described similarly gave access to the regioisomeric tricunines 6 and from a single precursor, the unsymmetrical diazido sugar 89 (Figure 14). Action of sodium azide upon the diepoxide (readily prepared from had been known known to give mainly the symmetrical counterpart 88 (35), but was now found (53) to yield additionally the (partial) anti-FUrst — Plattner product, on a practical scale. Sequential displacements in its ditriflate, with azide followed by benzoate and in reverse order, furnished 2,3,3 - and 2,3,2 -triazido D-manno.D-manno derivatives, respectively, which were used to prepare 65 and by standard manipulations. The tetraamine was synthesized via double displacement, with azide, from the ditriflate of 88 (53). 

Several types of corrosion inhibitors have been investigated in the last 20 years [53-55] these include calcium and sodium nitrites, sodium benzoate, sodium/potassium chromate, sodium salts of silicates and phosphates, stannous chloride, hydrazine hydrate, sodium fluorophosphate, permanganate, aniline and related compounds, alkalis, azides, ferrocyanide, EDTA and many chelating compounds. However, in terms of field practice and research data, nitrite-based compounds occupy a dominant position. 

Figure 2.5. Nucleophile selectivities determined from product analysis for the reactions of ring-suhstituted 1-phenylethyl derivatives (X-l-Y) with azide ion, acetate ion and methanol in 50 50 (v/v) water/trifluoroethanol. The selectivities are plotted against the appropriate Hammett substituent constant or a. Leaving group Y ( ) ring-suhstituted benzoates ( ) chloride (T) dimethyl sulfide (A) tosylate.

All nuclear nucleophilic substitutions on derivatives of compound 4 have involved the replacement of a substituent at position 7 (the equivalent of the y -position in pyridine). In the 7-chloro derivative 244, replacement is possible by methoxide ion,151 by ammonia (with some rearrangement)192 and by amines,151 and by thiourea to give the sulfide (245).151 Substituted 7-chloro derivatives undergo replacement by benzyl oxide ion to give a 7-benzyloxy derivative155,220 and by azide,153 hydrazine,216 hydrosulfide (to give the 7-thione166), and methyl thiolate.220 Some of these compounds carry D-ribofuranosyl benzoate substituents on N-2 or N-3, and methoxide ion... 

Figure 25-12 Isocratic HPLC separation of a mixture of aromatic compounds at 1.0 mL/min on a 0.46 x 25 cm Hypersil ODS column (C,8 on 5-jxm silica) at ambient temperature ( 22 C) (1) benzyl alcohol (2) phenol (3) 3, 4 -dimethoxyacetophenone (4) benzoin (5) ethyl benzoate (6) toluene (7) 2,6-dimethoxytoluene (8) o-methoxybiphenyl. Eluent consisted ot aqueous buffer (designated A) and acetonitrile (designated B). The notation 90% B in the first chromatogram means 10 vol% A and 90 vol% B. The buffer contained 25 mM KH2P04 plus 0.1 g/L sodium azide adjusted to pH 3.5 with HCI.

As in the pyranoside series, the substitution at C-2 of furanoside derivatives is also difficult (87], Treatment of the 2-imidazylate ester of a benzyl 5-deoxy-a-D-hexofurano-side derivative with tetrabutylammonium azide or benzoate in refluxing toluene led to the formation of substitution products in 82 and 53% yields, respectively [88] (Scheme 11). 

Cleavage of epoxides The epoxide 1 is cleaved by N3Si(CH3)3 and a catalytic amount of ZnCl2 to the hydroxy azide 2 in 90% yield. The corresponding benzoate (3) on hydrogenation undergoes O — N benzoyl transfer to provide 4 in 95% ee. 

H. Stamm also measured the solubilities of the salts of the alkalies in liquid ammonia —potassium hydroxide, nitrate, sulphate, chromate, oxalate, perchlorate, persulphate, chloride, bromide, iodide, carbonate, and chlorate rubidium chloride, bromide, and sulphate esesium chloride, iodide, carbonate, and sulphate lithium chloride and sulphate sodium phosphate, phosphite, hypophosphite, fluoride, chloride, iodide, bromate, perchlorate, periodate, hyponitrire, nitrite, nitrate, azide, dithionate, chromate, carbonate, oxalate, benzoate, phtnalate, isophthalate ammonium, chloride, chlorate, bromide, iodide, perchlorate, sulphate, sulphite, chromate, molybdate, nitrate, dithionate, thiosulphate, persulphate, thiocyanate, phosphate, phosphite, hypophosphite, arsenate, arsenite, amidosulphonate, ferrocyanide, carbonate, benzoate, methionate, phenylacetate, picrate, salicylate, phenylpropionate, benzoldisulphonate, benzolsulphonate, phthalate, trimesmate, mellitate, aliphatic dicarboxylates, tartrate, fumarate, and maleinate and phenol. 

The cyclic sulfates undergo ring opening with a wide variety of nucleophiles, such as hydride, azide, fluoride, benzoate, amines, and Grignard reagents. The reaction of an amidine with a cyclic sulfate provides an expeditious entry to chiral imidazolines 21 and 1,2-diamines (Scheme 9.27).169... 

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