1.1.1- Trifluorides amines

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. 

Lewis acid or base complexes (boron trifluoride amine complex) Long pot life Tendency to exotherm... 

However, boron trifluoride amine complexes are used to polymerize epoxies, especially the cycloaliphatic type. The cured product has very good electrical properties but relatively poor adhesive properties as indicated above. 

For some electrical and electronic adhesive applications it may be advantageous to use CTBN modified epoxide adhesives in place of unmodified epoxides because of the enhanced tensile shear strengths achieved. The tensile shear strengths for a boron trifluoride amine complex cured DGEBA-type epoxide modified with various amounts of CTBN on solvent-cleaned cold-rolled steel are shown in Table 10.3. 

For the one-part systems diglycidyl ethers of bisphenol and diglycidyl ethers of resorcinol have been utilised with hardeners such as dicyan-diamide, aromatic substituted ureas and boron trifluoride amine complexes. For further information on component mounting with epoxides the reader is referred to an excellent review by Marshall. ... 

Fischer, R. F, Polyesters from epoxides and anhydrides,/. Polym. Sci., 44, 155,1960. Bouillon, Nelly, Pascault,/. R, and Tighzert, L., Epoxy prepolymers cured with boron trifluoride amine complexes. 1. Influence of the amine on the curing, Maferomol. Chem., 191, 1403, 1990. 

Other crosslinkers such as aromatic amines, dicyandiamide, dihydrazides, and boron trifluoride amine complexes give stable formulations at room temperature and only eine when heated at elevated temperatures. These cme systems are the basis for one part epoxy adhesives. Crosslinkers such as polysulfides and polyamides can be used to increase the flexibility of the adhesive bonds. Other eomponents that may be added to modify the properties of the adhesives are diluents, flexibilizers, modifiers, fillers, and reinforcing agents. 

Boron trifluoride amine complexes can be used in one part epo adhesives as they are stable at room temperature and must be heated to initiate cme. These cures are termed latent curing systems and the boron triflouride acts as a catalyst. Dicyandiamide (DICY) is frequently used in these cme systems for construction and metal to metal adhesion. 

Aqueous mineral acids react with BF to yield the hydrates of BF or the hydroxyfluoroboric acids, fluoroboric acid, or boric acid. Solution in aqueous alkali gives the soluble salts of the hydroxyfluoroboric acids, fluoroboric acids, or boric acid. Boron trifluoride, slightly soluble in many organic solvents including saturated hydrocarbons (qv), halogenated hydrocarbons, and aromatic compounds, easily polymerizes unsaturated compounds such as butylenes (qv), styrene (qv), or vinyl esters, as well as easily cleaved cycHc molecules such as tetrahydrofuran (see Furan derivatives). Other molecules containing electron-donating atoms such as O, S, N, P, etc, eg, alcohols, acids, amines, phosphines, and ethers, may dissolve BF to produce soluble adducts. 

Boron trifluoride catalyst may be recovered by distillation, chemical reactions, or a combination of these methods. Ammonia or amines are frequently added to the spent catalyst to form stable coordination compounds that can be separated from the reaction products. Subsequent treatment with sulfuric acid releases boron trifluoride. An organic compound may be added that forms an adduct more stable than that formed by the desired product and boron trifluoride. In another procedure, a fluoride is added to the reaction products to precipitate the boron trifluoride which is then released by heating. Selective solvents may also be employed in recovery procedures (see Catalysts,regeneration). 

Many perfluoroaUphatic ethers and tertiary amines have been prepared by electrochemical fluorination (1 6), direct fluorination using elemental fluorine (7—9), or, in a few cases, by fluorination using cobalt trifluoride (10). Examples of lower molecular weight materials are shown in Table 1. In addition to these, there are three commercial classes of perfluoropolyethers prepared by anionic polymerization of hexafluoropropene oxide [428-59-1] (11,12), photooxidation of hexafluoropropene [116-15-4] or tetrafluoroethene [116-14-3] (13,14), or by anionic ring-opening polymeriza tion of tetrafluorooxetane [765-63-9] followed by direct fluorination (15). 

Primary nitroparaffins react with two moles of formaldehyde and two moles of amines to yield 2-nitro-l,3-propanediamines. With excess formaldehyde, Mannich bases from primary nitroparaffins and primary amines can react further to give nitro-substituted cycHc derivatives, such as tetrahydro-l,3-oxa2iaes or hexahydropyrimidines (38,39). Pyrolysis of salts of Mannich bases, particularly of the boron trifluoride complex (40), yields nitro olefins by loss of the amine moiety. Closely related to the Mannich reaction is the formation of sodium 2-nitrobutane-1-sulfonate [76794-27-9] by warming 1-nitropropane with formaldehyde and sodium sulfite (41). 

Aromatic amines form addition compounds and complexes with many inorganic substances, such as ziac chloride, copper chloride, uranium tetrachloride, or boron trifluoride. Various metals react with the amino group to form metal anilides and hydrochloric, sulfuric, or phosphoric acid salts of aniline are important intermediates in the dye industry. 

Catalytic curing agents initiate resin homopolymerization, either cationic or anionic, as a consequence of using a Lewis acid or base in the curing process. The Lewis acid catalysts frequently employed are complexes of boron trifluoride with amines or ethers. 

Complexes of boron trifluoride and amines such as monoethylamine are of interest because of the very long pot lives possible. The disadvantages of these complexes are their hygroscopic nature and the corrosive effects of BF3 liberated during cure. 

Notable examples of general synthetic procedures in Volume 47 include the synthesis of aromatic aldehydes (from dichloro-methyl methyl ether), aliphatic aldehydes (from alkyl halides and trimethylamine oxide and by oxidation of alcohols using dimethyl sulfoxide, dicyclohexylcarbodiimide, and pyridinum trifluoro-acetate the latter method is particularly useful since the conditions are so mild), carbethoxycycloalkanones (from sodium hydride, diethyl carbonate, and the cycloalkanone), m-dialkylbenzenes (from the />-isomer by isomerization with hydrogen fluoride and boron trifluoride), and the deamination of amines (by conversion to the nitrosoamide and thermolysis to the ester). Other general methods are represented by the synthesis of 1 J-difluoroolefins (from sodium chlorodifluoroacetate, triphenyl phosphine, and an aldehyde or ketone), the nitration of aromatic rings (with ni-tronium tetrafluoroborate), the reductive methylation of aromatic nitro compounds (with formaldehyde and hydrogen), the synthesis of dialkyl ketones (from carboxylic acids and iron powder), and the preparation of 1-substituted cyclopropanols (from the condensation of a 1,3-dichloro-2-propanol derivative and ethyl-... 

The pharmaceutical interest in the tricyclic structure of dibenz[6,/]oxepins with various side chains in position 10(11) stimulated a search for a convenient method for the introduction of functional groups into this position. It has been shown that nucleophilic attack at the carbonyl group in the 10-position of the dibenzoxepin structure renders the system susceptible to water elimination. Formally, the hydroxy group in the enol form is replaced by nucleophiles such as amines or thiols. The Lewis acids boron trifluoride-diethyl ether complex and titanium(IV) chloride have been used as catalysts. 

Preparation. Its prepn was first carried out by the action of metals as F acceptors on N trifluoride in a flow reactor at 375°, conversion 42—62%, yield 62—71% (Ref 1). It has also been prepd by the passage of N trifluoride thru a fluidized bed of powd C at 400—500°, conversion 38%, yield 77% (Refs 3 3a) or by the oxidn of difluor-amine (Ref 6)... 

Hlasta and Deng have developed a two-step solid-phase method for the decoration of azoles at C-2 [188]. First, imidazole was loaded onto a polystyrene-bound carbamyl chloride via a benzaldehyde bridge (Fig. 40). The 2-substi-tuted imidazole was efficiently cleaved in good yields in the presence of various nucleophiles (i.e., water, alcohols, and amines), trifluoroacetic acid, and boron trifluoride under microwave irradiation in a closed vessel at 120 °C for 5 min. 

Note It is reported that the use of chlorobenzene as solvent is essential when the reagent is to be used to detect aromatic amines [1]. In the case of steroids, penicillins, diuretics and alkaloids the reaction should be accelerated and intensified by spraying afterwards with dimethylsulfoxide (DMSO) or dimethylformamide (DMF), indeed this step makes it possible to detect some substances when this would not otherwise be possible [5,9-11] this latter treatment can, like heating, cause color changes [5,9]. Penicillins and diuretics only exhibit weak reactions if not treated afterwards with DMF [10, 11]. Steroids alone also yield colored derivatives with DMSO [9]. Tlreatment afterwards with diluted sulfuric acid (c = 2 mol/L) also leads to an improvement in detection sensitivity in the case of a range of alkaloids. In the case of pyrrolizidine alkaloids it is possible to use o-chloranil as an alternative detection reagent however, in this case it is recommended that the plate be treated afterwards with a solution of 2 g 4-(dimethyl-amino)-benzaldehyde and 2 ml boron trifluoride etherate in 100 ml anhydrous ethanol because otherwise the colors initially produced with o-chloranil rapidly fade [12]. 

On the theoretical side, study of the dissociation of addition compounds of amines with trimethylborane, boron trifluoride, and borane provide a new quantitative approach to steric strains. These studies quickly removed doubts as to the importance of steric effects in chemical behavior. 

Compound (1) phosphorylates phosphate monoesters and alcohols, although with the latter a considerable excess of alcohol is necessary to obtain satisfactory yields. In the absence of mercuric ions the milder phosphorylating species (3) can be isolated which converts monoalkyl phosphates to pyrophosphate diesters in good yield but does not react appreciably with alcohols unless catalytic amounts of boron trifluoride are added. Amine salts of (3) are converted to phosphoramidates on heating. In the presence of silver ions, O-esters of thiophosphoric acid behave as phosphorylating agents and a very mild and convenient procedure suitable for preparing labile unsymmetrical pyrophosphate diesters, such as the... 

The reactions of boron trifluoride adducts of ammonia,and primary, secondary, and tertiary amines with phosphorus pentachloride have been studied and in the first two cases acyclic phosphazenes were obtained. With the ammonia-adduct, a previously characterized phosphazene salt was obtained ... 

Most dinitroanilines are synthesized from a precursor which is nitrated and subsequently aminated to yield the desired product. In the case of trifluralin, 4-chlorobenzo-trifluoride (PCBT) is dinitrated to yield 4-chloro-3,5-dinitro-a,a,a-triflurotoluene (Dinitro PCBT),... 

Several nitro compounds are soluble in chlorine trifluoride, but the solutions are extremely shock-sensitive. These include trinitrotoluene, hexanitrobiphenyl, hexanitrodiphenyl-amine, -sulfide or -ether. Highly chlorinated compounds behave similarly. 

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