Boron trifluoride reactivity

Boron trifluoride is a colourless, reactive gas which can be prepared by heating boron tnoxide and fluorspar with concentrated sulphuric acid. 

From these results it appears that the 5-position of thiazole is two to three more reactive than the 4-position, that methylation in the 2-position enhances the rate of nitration by a factor of 15 in the 5-position and of 8 in the 4-position, that this last factor is 10 and 14 for 2-Et and 2-t-Bu groups, respectively. Asato (374) and Dou (375) arrived at the same figure for the orientation of the nitration of 2-methyl and 2-propylthiazole Asato used nitronium fluoroborate and the dinitrogen tetroxide-boron trifluoride complex at room temperature, and Dou used sulfonitric acid at 70°C (Table T54). About the same proportion of 4-and 5-isomers was obtained in the nitration of 2-methoxythiazole by Friedmann (376). Recently, Katritzky et al. (377) presented the first kinetic studies of electrophilic substitution in thiazoles the nitration of thiazoles and thiazolones (Table 1-55). The reaction was followed spec-trophotometrically and performed at different acidities by varying the... 

Fluorochloro, fluorobromo, and fluoroiodoalkanes react selectively with aromatics under boron trifluoride catalysis to provide chloro-, bromo- and iodoalkylated products (48). The higher reactivity of the C—F bond over C—Cl, C—Br, and C—I bonds under Lewis acid catalysis results in the observed products. 

Cationic polymerization of coal-tar fractions has been commercially achieved through the use of strong protic acids, as well as various Lewis acids. Sulfuric acid was the first polymerization catalyst (11). More recent technology has focused on the Friedel-Crafts polymerization of coal fractions to yield resins with higher softening points and better color. Typical Lewis acid catalysts used in these processes are aluminum chloride, boron trifluoride, and various boron trifluoride complexes (12). Cmde feedstocks typically contain 25—75% reactive components and may be refined prior to polymerization (eg, acid or alkali treatment) to remove sulfur and other undesired components. Table 1 illustrates the typical components found in coal-tar fractions and their corresponding properties. 

The 12-ketone is generally less reactive than 3-, 6- and 7-ketones but more reactive than the 11-ketone. 12-Ethylene ketals are readily prepared by the usual procedures and the 12-ketone can be selectively ketalized in the presence of a 20-ketone bearing a 17a-hydrogen or 17a-hydroxyl substituent [(81)- (82)]. ° The procedure of choice for this reaction utihzes ethylene glycol and boron trifluoride-ether complex at room temperature. 

The dimethyl acetal (94) is readily prepared from the 22-aldehyde (93) by direct reaction with methanol in the presence of hydrogen chloride. Ena-mines (95) are formed without a catalyst even with the poorly reactive piperidine and morpholine.Enol acetates (96) are prepared by refluxing with acetic anhydride-sodium acetate or by exchange with isopropenyl acetate in pyridine.Reaction with acetic anhydride catalyzed by boron trifluoride-etherate or perchloric acid gives the aldehyde diacetate. 

B-Homosteroids have also been prepared by acid-catalyzed reaction of diazomethane with a,/5-unsaturated ketones. 3/ -Hydroxycholest-5-en-7-one acetate (57) reacts with diazomethane in the presence of concentrated fluoroboric acid, boron trifluoride etherate or aluminum chloride to give 3yS-hydroxy-B-homo-cholest-5-en-7a-one acetate (67). The 7a-keto group is reported to be chemically less reactive than an 11-keto group. 

Addition of 15-crown-5 to the higher-order cuprate led to a reagent that is totally unrcac-tive towards 2-phenylpropanal even at room temperature18. If, however, boron trifluoride-diethyl ether complex was added as additional ingredient, the reactivity was restored and, furthermore, the Cram selectivity increased to 90 10 (Table 4). Analogous results could be obtained by placing the crown-ether effect within the cuprate itself, as in reagent 10. 

Benzylzinc requires activation by copper(l) cyanidc/boron trifluoride-diethyl ether complex for rapid carbonyl addition29. Little information is available on the reactivity of benzyltitani-um derivatives30,31. 

The Lewis acid, boron trifluoride, enhances selectivity, but not reactivity. 

Phenyllithium and phenylcopper boron trifluoride yield different diastereomers of the reaction products, i.c., the sense of asymmetric induction is a function of the metal. These results are rationalized on the basis of antiperiplanar 6 and synperiplanar 8 reactive enoate conformations for additions of the copper and lithium reagents, respectively. 

Olivier and Berger335, who measured the first-order rate coefficients for the aluminium chloride-catalysed reaction of 4-nitroben2yl chloride with excess aromatic (solvent) at 30 °C and obtained the rate coefficients (lO5/ ) PhCI, 1.40 PhH, 7.50 PhMe, 17.5. These results demonstrated the electrophilic nature of the reaction and also the unselective nature of the electrophile which has been confirmed many times since. That the electrophile in these reactions is not the simple and intuitively expected free carbonium ion was indicated by the observation by Calloway that the reactivity of alkyl halides was in the order RF > RC1 > RBr > RI, which is the reverse of that for acylation by acyl halides336. The low selectivity (and high steric hindrance) of the reaction was further demonstrated by Condon337 who measured the relative rates at 40 °C, by the competition method, of isopropylation of toluene and isopropylbenzene with propene catalyzed by boron trifluoride etherate (or aluminium chloride) these were as follows PhMe, 2.09 (1.10) PhEt, 1.73 (1.81) Ph-iPr, (1.69) Ph-tBu, 1.23 (1.40). The isomer distribution in the reactions337,338 yielded partial rate factors of 2.37 /mMe, 1.80 /pMe, 4.72 /, 0.35 / , 2.2 / Pr, 2.55337 339. 

Benkeser et a/.431 measured the relative rates of acetylation of alkylferrocenes using acetic anhydride catalysed by boron trifluoride etherate, in dichloromethane at 0 and 25 °C. The relative reactivities are given in Table 115, and are interesting... 

There have not been any accidents recorded that have mentioned metal halides (except with interhalogens , which are very reactive anyway). Nevertheless, it seems important that calcium should not be in contact with such halides without taking any precautions. It was noticed that calcium starts glowing when it is heated with boron trifluoride. 

Lewis acids such as zinc chloride, boron trifluoride, tin tetrachloride, aluminum chloride, methylaluminum dichloride, and diethylaluminum chloride catalyze Diels-Alder reactions.22 The catalytic effect is the result of coordination of the Lewis acid with the dienophile. The complexed dienophile is more electrophilic and more reactive toward electron-rich dienes. The mechanism of the addition is believed to be concerted and enhanced regio- and stereoselectivity is often observed.23... 

Thallium(III), particularly as the trifluoroacetate salt, is also a reactive electrophilic metallating species, and a variety of synthetic schemes based on arylthallium intermediates have been devised.75 Arylthallium compounds are converted to chlorides or bromides by reaction with the appropriate cupric halide.76 Reaction with potassium iodide gives aryl iodides.77 Fluorides are prepared by successive treatment with potassium fluoride and boron trifluoride.78 Procedures for converting arylthallium compounds to nitriles and phenols have also been described.79... 

Lead tetraacetate can effect oxidation of carbonyl groups, leading to formation of a-acetoxy ketones,215 but the yields are seldom high. Boron trifluoride can be used to catalyze these oxidations. It is presumed to function by catalyzing the formation of the enol, which is thought to be the reactive species.216 With unsymmetrical ketones, products from oxidation at both a-methylene groups are found.217... 

Polyepichlorohydrin and dimethylamine Polymerisation of epichlorohydrin in carbon tetrachloride with boron trifluoride/ether catalyst, then reaction with dimethylamine. Applied to cotton by exhaust method or pad-dry. Scheme 10.65 Good yields with direct dyes using only 2 g/l salt. Excellent build-up with most reactive dyes only 10% of normal salt usage needed for low-reactivity dyes and none for highly reactive types. Washing fastness very good but light fastness impaired. 

Another differential reaction is copolymerization. An equi-molar mixture of styrene and methyl methacrylate gives copolymers of different composition depending on the initiator. The radical chains started by benzoyl peroxide are 51 % polystyrene, the cationic chains from stannic chloride or boron trifluoride etherate are 100% polystyrene, and the anionic chains from sodium or potassium are more than 99 % polymethyl methacrylate.444 The radicals attack either monomer indiscriminately, the carbanions prefer methyl methacrylate and the carbonium ions prefer styrene. As can be seen from the data of Table XIV, the reactivity of a radical varies considerably with its structure, and it is worth considering whether this variability would be enough to make a radical derived from sodium or potassium give 99 % polymethyl methacrylate.446 If so, the alkali metal intitiated polymerization would not need to be a carbanionic chain reaction. However, the polymer initiated by triphenylmethyl sodium is also about 99% polymethyl methacrylate, whereas tert-butyl peroxide and >-chlorobenzoyl peroxide give 49 to 51 % styrene in the initial polymer.445... 

The reactivity of acylzirconocene chlorides towards carbon electrophiles is very low, and no reaction takes place with aldehydes at ambient temperature. In the reaction described in Scheme 5.12, addition of a silver salt gave the expected product, albeit in low yield (22—34%). The yield was improved to 79% by the use of a stoichiometric amount of boron trifluoride etherate (BF3OEt2) (1 equivalent with respect to the acylzirconocene chloride) at 0 °C. Other Lewis acids, such as chlorotitanium derivatives, zinc chloride, aluminum trichloride, etc., are less efficient. Neither ketones nor acid chlorides react with acylzirconocene chlorides. In Table 5.1, BF3 OEt2-mediated reactions of acylzirconocene chlorides with aldehydes in CH2C12 are listed. 

Examples Sodium Titanium tetrachloride Boron trifluoride Acetic anhydride Examples Most organic and inorganic materials are not water reactive... 

Juri and Bartsch (1979) have studied the coupling of 4-t-butylbenzene-diazonium tetrafluoroborate with N,N-dimethylaniline in 1,2-dichloroethane solution. The addition of one equivalent (based on diazonium salt) of 18-crown-6 caused the rate constant to drop by a factor of 10, indicating that complexed diazonium is less reactive than the free cation. Benzenediazonium tetrafluoroborate complexes of crown ethers are photochemically more stable than the free salt. The decomposition into fluorobenzene and boron trifluoride is strongly inhibited but no explanation has been given (Bartsch et al., 1977). 

The boron trifluoride alkyl fluoride (chloride) complexes gave no evidence of alkylcarbonium ion formation. It must, however, be emphasized that (a) the physical investigation of the binary system was carried out at such low temperatures (generally below —100°) that ionization of the halides could hardly be expected (with exception of highly reactive tertiary halides) (b) the methods used could not he relied on to detect a small ionization equilibrium even if it existed. 

When the chiral molybdenum Ti-allyl-substituted enone 147 was treated with lithium dimethylcuprate, formation of adduct 148 with fair selectivity was observed (Scheme 6.29) [69]. Interestingly, higher selectivities were obtained in the presence of boron trifluoride etherate. It is assumed that Lewis acid coordination induces the s-trans reactive conformation 149 [64]. Consequently, nucleophile attack anti to the molybdenum fragment should afford the major diastereomer 148. 

Hydrolysis of the ethyl ester proceeded smoothly using hydrochloric acid in acetic acid to give carboxylic acid 69 in 88% yield (Scheme 4.9). Previously, amines were allowed to react with the carboxylic acid core in hot DMSO to deliver the C7 products however, the difluoroborate 70, derived from the carboxylic acid 69, greatly increased the reactivity of the C7 position. Consequently, the displacement of the C7-F with amines was accomplished at lower temperature (Baker et al., 2004 Cecchetti et al., 1996 Domalaga et al., 1993 Ellsworth et al., 2005a,b Hu et al., 2003). In this event, the carboxylic acid was allowed to react with boron trifluoride to deliver difluroboronate 70 in excellent yield. The thus afforded borate ester reacted with A -methylpiperidine in DMSO in the presence of triethylamine at ambient temperature to furnish ( —)-ofloxacin (1, levofloxacin) in 56% yield. 

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