N-Butyl fluoride

The proximity of carbon-carbon double or triple bonds, as in allylic and propargylic systems has little impact upon a fluorine substituent s chemical shift (Scheme 3.69). Note that one would not intuitively expect allyl fluoride and n-butyl fluoride to have such similar chemical shifts. 

Considerable effort has been made in the area of snail control in utilizing slow-release incorporated tri-n-butyl fluoride within elastomeric substrates.Using mostly rubber-type substrates, at least five different formulations are cited in controlling seven species of snails under a variety of conditions. Although all of these are physically entrapped, a variety of shapes and densities are now available to allow quite a range of use in the field. The citations in reference 26 showed complete control under a variety of conditions for periods up to 19 months long. 

A/ HE, 0.1 M NaF, pH 5. THE, 25°, 2 days, 77% yield. In this substrate, a mixture of products resulted from the attempted cleavage of the t-butyl-dimethylsilyl ether with tetra-n-butylammonium fluoride, the reagent generally used. ... 

Fluorides and 0x0 compounds of Ru and Os have already been mentioned, and salts such as (R4N)[Ru04l, (R = n-propyl, n-butyl) are useful reagents to oxidize a variety of organic materials without attacking double or allylic bonds,... 

Various organic extractants may be used, including butyl and amyl alcohols, di-isopropyl ether, tri-n-butyl phosphate, and tri-2-ethylhexyl phosphate. The fluoride remains with the... 

Phase-transfer catalysis can be used to mimic high dilution reaction conditions and has been utilized to good effect in the synthesis of large ring lactones [67J. Macrocyclic nitrolactones have also been obtained by rearrangement of 2-(3-hydroxy-propyI)-2-nitrocycloalkanones using a stoichiometric amount of tetra-n-butyl-ammonium fluoride [68]. 

Optimum yields of (3-vinyl-y-butyrolactols from the Pd(II) promoted reaction of vinyl triflates with Z-but-2-en-l,4-diol (Scheme 6.33) are attained when tetra-n-butylammonium chloride is added (47]. The lactol is conveniently oxidized to the lactone with celite-supported silver carbonate. The corresponding arylbutyrolactols are obtained in high yield (70-80%) from an analogous reaction of iodoarenes with the enediol. The yields of 2-alkenyl-2,5-dihydrofurans, resulting from the Pd(0) catalysed reaction of cyclic alkynylcarbonates with acrylic esters via tandem C-C and C-0 bond forming reactions, are enhanced by the presence of tetra-n-butyl-ammonium fluoride (e.g. Scheme 6.33) (48]. 

E-2-bromomethyleneglutaric esters (>70%) have been obtained from the corresponding 2-bromo-2-bromomethylglutarates using a 25% excess tetra-n-butyl-ammonium fluoride in HMPA [24], A similar procedure converts dimethyl 2-bromo-2-bromomethylsuccinate into dimethyl Z-2-bromomethylenefumarate [25], whereas methyl 2,2-bis(bromomethyl)ethanoate yields the 2-bromomethyl-propenoate when reacted with aqueous sodium hydroxide in the presence of benzyl-triethylammonium chloride [26]. No hydrolysis of the ester is evident at 0°C, but becomes apparent at 25 °C. 

N-Sulphonyl azoles are deprotected by a stoichiometric amount of tetra-n-butyl-ammonium fluoride in THF in good yields (>70%) [19]. 

Epoxidation of ot.fl-unsaturated ketones by hydrogen peroxide or /-butyl peroxide is promoted by the addition of tetra-n-butylammonium fluoride [10], whereas the corresponding reaction with 1,4-disubstituted but-2-en-l,4-diones is catalysed by quaternary ammonium iodides [11], Oxiranes are also produced by the catalysed reaction of /-butyl peroxide with a,f)-unsaturated sulphonates under basic conditions [12]. 

Von Runge and Triebs used a solution of dinitrogen pentoxide in chloroform for the N-nitration of both amides and imides. Solutions of dinitrogen pentoxide in chlorinated solvents are not neutral nitrating agents when amides and imides are nitrated - the presence of acidic N-H protons in these substrates leads to the formation of nitric acid. Sodium fluoride acts like a base towards nitric acid and so its addition to these reactions can increase product yield. Sodium acetate has been used for the same purpose during the nitration of n-butyl-V, V -dimethylurea. The effectiveness of dinitrogen pentoxide for the V-nitration of ureas is further illustrated by its use in the conversion of 2-imidazolidinone to N, V -dinitro-2-imidazolidinone in 90 % yield. In the presence of sodium fluoride the yield for this reaction exceeds 90 %. 

The only measured enthalpy of vaporization is for n-butyl lithium, 107.1 2.9 kJmoU, from which the constant b(Li) in equation 4 is derived as 85 kJmoU. This is a hefty value compared to fc(OH) = 29, b(—S(0)2—) = 53 and b(CY) = 11 kJmoU. However, the oligomeric states of the organolithium liquid and gas phases are not known with certainty. This is reminiscent of problems for hydrogen-bonded species such as carboxylic acids and hydrogen fluoride. 

Tri-n-butyl-tin(IV) fluoride, cetyltrimethylammoniumbromide, cationic, anionic, and non-ionic surfactants... 

Micellar systems (i.e.,. Shenoy 1984 Ohlendorf Brunn) as well as other colloidal systems (polyphosphates (Hunston), tri-n-butyl-tin-fluoride, e.g. Dunn Evans) come under the heading surfactants . It is necessary to differentiate soaps into anionic, cationic, and non-ionic types. Among the anionic types one can find, for instance, alkali metals and ammonium salts consisting of various fatty acids, which were... 

Dunn P, Oldfield D (1970) Tri-n-butyl-tin-fluoride. A novel coordination polymer in solution J Macromol Sci A4 1157... 

Acetimidoyl Fluoride N-Butyl-ehloro-fluoro- ElOb,. 635 (ClFC = CF, + R-NH,) C6Hl0CIF2O4P... 

They chose the TBDMS derivatives for reducing the polarity of hydroxyl groups of hydroxy fatty acid PNB esters because the TBDMS derivatives were resistant to hydrolysis, stable in common organic solvents, and changed the adsorption TLC and RP-HPLC retention of PNB hydroxy fatty acids more than smaller siloxy groups and because the TBDMS groups could easily be removed by fluoride ions (sodium fluoride or tetra-n-butyl ammonium fluoride) to free... 

NMO NMP Nu PPA PCC PDC phen Phth PPE PPTS Red-Al SEM Sia2BH TAS TBAF TBDMS TBDMS-C1 TBHP TCE TCNE TES Tf TFA TFAA THF THP TIPBS-C1 TIPS-C1 TMEDA TMS TMS-C1 TMS-CN Tol TosMIC TPP Tr Ts TTFA TTN N-methylmorpholine N-oxide jV-methyl-2-pyrrolidone nucleophile polyphosphoric acid pyridinium chlorochromate pyridinium dichromate 1,10-phenanthroline phthaloyl polyphosphate ester pyridinium p-toluenesulfonate sodium bis(methoxyethoxy)aluminum dihydride (3-trimethylsilylethoxy methyl disiamylborane tris(diethylamino)sulfonium tetra-n-butylammonium fluoride f-butyldimethylsilyl f-butyldimethylsilyl chloride f-butyl hydroperoxide 2,2,2-trichloroethanol tetracyanoethylene triethylsilyl triflyl (trifluoromethanesulfonyl) trifluoroacetic acid trifluoroacetic anhydride tetrahydrofuran tetrahydropyranyl 2,4,6-triisopropylbenzenesulfonyl chloride 1,3-dichloro-1,1,3,3-tetraisopropyldisiloxane tetramethylethylenediamine [ 1,2-bis(dimethylamino)ethane] trimethylsilyl trimethylsilyl chloride trimethylsilyl cyanide tolyl tosylmethyl isocyanide meso-tetraphenylporphyrin trityl (triphenylmethyl) tosyl (p-toluenesulfonyl) thallium trifluoroacetate thallium(III) nitrate... 

The. S n reactions between HF and protonated methyl, ethyl, isopropyl, and /-butyl fluorides in the gas phase have been examined at the MP2/6-31+- -G(d,p) level of theory.112 113 The reaction of CH3FH+ clearly occurs via back-side attack as the transition state for this process is of lower energy than the transition state for frontside attack. The EtFH+ can react via a more stable back-side. S N2 reaction or an. S n 1 reaction via front-side attack since the. S N 1 pathway is 4.4 kJmol-1 lower in energy. No. S n2 path could be found for i-PrFH+ and the front- and back-side pathways had equal activation energies for /-BuFH+, which effectively reacts by an. S N1 mechanism. The conclusion is that the preference for back-side attack is reduced as the size of... 

Moreover, the formation of enoxy-silanes via silylation of ketones127 by means of N-methyl-N-TMS-acetamide (1 72) in presence of sodium trimethylsilanolate (173) was reported in 1969 and since then, the use of silylating reagents in presence of a catalyst has found wide appreciation and growing utilization as shown in recent papers128-132 (Scheme 27). Diacetyl (181) can be converted by trifluoromethylsul-fonic acid-TMS-ester (182) into 2,3-bis(trimethylsiloxy)-l, 3-butadiene (7treatment with ethyl TMS acetate (7 5)/tetrakis(n-butyl)amine fluoride l-trimethylsiloxy-2-methyl-styrene (i<56)130. Cyclohexanone reacts with the combination dimethyl-TMS-amine (18 7)/p-toluenesulfonic acid to 1-trimethylsiloxy-l-cyclohexene (iSS)131. Similarly, acetylacetone plus phenyl-triethylsilyl-sulfide (189) afford 2-triethylsiloxy-2-pentene-4-one (790)132. ... 

However, an efficient synthesis of the spirovetivane-sesquiterpene a-Vetispirene 392 was achieved initiating the cleavage of the silicon-cyclopropane carbon bond of 160 by fluoride ion. This was effected with anhydrous tetra-n-butyl ammonium fluoride in THF solution containing acetone at reflux temperature for 10 hr. The pentadienyl anion 387 thus generated experienced highly regioselective addition of acetone at the... 

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