Nitriles boron trifluoride complex

Wear nitrile rubber gloves, laboratory coat, eye protection, and, if necessary, a self-contained breathing apparatus. Cover the spill with a 1 1 1 mixture by weight of sodium carbonate or calcium carbonate, clay cat litter (bentonite), and sand. When the boron trifluoride complex has been absorbed, scoop the mixture into a plastic pail and, in the fume hood, very slowly add the mixture to a pail of cold water. Allow to stand for 24 hours. Test the pH of the solution and neutralize if necessary with sodium carbonate. Decant the solution to the drain. Treat the solid residue as normal refuse.5... 

A solution of 3 g of the nitrile, water (5 moles per mole of nitrile), and 20 g of boron trifluoride-acetic acid complex is heated (mantle or oil bath) at 115-120° for 10 minutes. The solution is cooled in an ice bath with stirring and is carefully made alkaline by the slow addition of 6 A sodium hydroxide (about 100 ml). The mixture is then extracted three times with 100-ml portions of 1 1 ether-ethyl acetate, the extracts are dried over anhydrous sodium sulfate, and the solvent is evaporated on a rotary evaporator to yield the desired amide. The product may be recrystallized from water or aqueous methanol. Examples are given in Table 7.1. 

Kurabayashi and Grundmann have reported the preparation of the 1,2,4-oxadiazoles (34) from 1,3,5-triazine and aryl nitrile oxides in the presence of boron trifluoride. The mechanism has not been fully elucidated, but it is most likely that the initial stage is the formation of the complex (33) (78BCJ1484). 

Intramolecular acylation has been used frequently. Houben-Hoesch cyclization of 1 -/ -cyanoethylpyrrole (2a) gives l-oxo-2,3-dihydropyrrolizine (3a).9-17 Difficulties occur because polymerization of the nitrile (2a) can be a side reaction. Addition of boron trifluoride [3a (33%)]11 or its ethyl ether complex [3a (60-80%)]15 has been recommended. Treatment of nitrile 2a with a molten aluminum chloride-potassium chloride-sodium chloride mixture yields 70% of ketone 3a but the experimental conditions are highly critical.13 A reproducible procedure that is based mainly on Clemo s specification9,10 gave 22% of ketone 3a.17 Purification of 3a should be carried out in an efficient fume hood because it appears to induce analgesia.1 ... 

Reduction of esters, nitriles, and amides. These groups are rapidly reduced by horanc-dimcthyl sulfide in refluxing THF (b.p. 67°) if the dimethyl sulfide (b.p. 38°) is removed as liberated. Under these conditions, the reagent is comparable to uncomplexed diborane. Reduction of secondary and tertiary amides is best effected in the presence of boron trifluoride etherate otherwise, excess reagent is utilized for formation of complexes with the products. 

In consideration of conceivable strategies for the more direct construction of these derivatives, nitriles can be regarded as simple starting materials with which the 3+2 cycloaddition of acylcarbenes would, in a formal sense, provide the desired oxazoles. Oxazoles, in fact, have previously been obtained by the reaction of diazocarbonyl compounds with nitriles through the use of boron trifluoride etherate as a Lewis acid promoter. Other methods for attaining oxazoles involve thermal, photochemical, or metal-catalyzed conditions.12 Several recent studies have indicated that many types of rhodium-catalyzed reactions of diazocarbonyl compounds proceed via formation of electrophilic rhodium carbene complexes as key intermediates rather than free carbenes or other types of reactive intermediates.13 If this postulate holds for the reactions described here, then the mechanism outlined in Scheme 2 may be proposed, in which the carbene complex 3 and the adduct 4 are formed as intermediates.14... 

Low temperature (-50 C) H and F NMR spectra of a- or -substituted ketones, esters and nitriles complexed to boron trifluoride showed that boron coordinates preferentially at the most basic and least-hindered base when more than one coordination site is present in the ligand. Ordinarily a relative measure of chemical shifts for each type of complex would be derived from the spectra of a number of model complexes. For example, F chemical shifts for BF3 complexes of ketones (acetone), esters (methyl acetate), nitriles (acetonitrile) and ethers (diethyl ether) were measured as 149 p.p.m., 150 p.p.m., 144 p.p.m. and 156 p.p.m., respectively. Inspection of the resonance frequency and relative intensities of each peak would then reveal Ae types and ratios of the complexes present in solution. 

Other Lewis acids, such as boron trifluoride-diethyl ether complex, titanium(IV) fluoride, and triethyloxonium tetrafluoroborate, were far less effective. a, -Unsaturated esters and nitriles cannot be cyclopropanated in this manner. 

Boron trifluoride forms a range of complexes with ethers, nitriles and amines. It is commercially available as the adduct Et20 BF3 (12.11). Being a liquid at 298 K, it is a convenient means of handling BF3 which has many applications as a catalyst in organic reactions, e.g. in Friedel-Crafts alkylations and acylations. 

Thicker epoxy-based coatings, highly flexibllized with amine-reactive nitrile liquid polymer, have been described by Mendelsohn (50) in which the flexibilizing hardener is comprised of an admixture of ATBN, fatty polyamide and boron trifluoride/amine complex. This coating ages well at 100°C and has excellent toughness/ flex with good abrasion and vibration absorption properties. 

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