Ethers complex

Beryllium Hydride. BeryUium hydride [13597-97-2] is an amorphous, colorless, highly toxic polymeric soHd (H = 18.3%) that is stable to water but hydroly2ed by acid (8). It is insoluble in organic solvents but reacts with tertiary amines at 160°C to form stable adducts, eg, (R3N-BeH2 )2 (9). It is prepared by continuous thermal decomposition of a di-/-butylberylhum-ethyl ether complex in a boiling hydrocarbon (10). 

Examination of possible systems for boron isotope separation resulted in the selection of the multistage exchange-distillation of boron trifluoride—dimethyl ether complex, BF3 -0(CH3 )2, as a method for B production (21,22). Isotope fractionation in this process is achieved by the distillation of the complex at reduced pressure, ie, 20 kPa (150 torr), in a tapered cascade of multiplate columns. Although the process involves reflux by evaporation and condensation, the isotope separation is a result of exchange between the Hquid and gaseous phases. 

Kawakami, Suzuki and Yamashita showed that compound 7, among many others, could be polymerized to derivatives of the corresponding open-chained species by treatment with boron trifluoride ether complex. Yamashita and Kawakami formed these same sorts of materials by heating the glycols and paraformaldehyde in the presence of toluenesulfonic acid. This led to prepolymers which were then thermally depolymerized to afford the cyclic oligomers which were separated by fractional distillation. 

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 boron trifluoride-ether complex has been employed mainly in the opening of 5,6-epoxides. This reaction was first studied by Henbest and Wrigley and affords products depending on the nature and stereochemistry of the... 

Alkyl silyl ethers are cleaved by a variety of reagents Whether the silicon-oxygen or the carbon-oxygen bond is cleaved depends on the nature of the reagent used Treatment of alkoxysilanes with electrophilic reagents like antimony tri-fluonde, 40% hydrofluonc acid, or a boron tnfluonde-ether complex results in the cleavage of the silicon-oxygen bond to form mono-, di-, and tnfluorosiloxanes or silanes [19, 20, 21) (equations 18-20)... 

On treatment with a potassium fluoridc-orown ether complex, alkyl 1,2,2,2-tetrachloroethyl carbonates are cleaved at the carbonyl group-oxygen bond to give high yields of alkyl fluoioformates [ 15] (equation 25)... 

In addition to the perfluoroalkylzinc compounds, the zinc reagent formed from 1,1,1-trifluorotrichloroethane has received considerable attention. This zinc compound was first reported as a stable ether complex [56]. Later, the DMF complex was isolated and the structure was determined by X-ray diffraction and shown to be monomeric [57] (equation 50). This zinc reagent undergoes a variety of functionalization reactions, and some typical examples are illustrated in Table 2 [47, 58, 59, 60, 61] The alcohol products (Table 2) can be converted to AiCF=CXCF3 (X = Cl, F) by further reaction with diethylaminosulfur trifluoride (DAST) and l,8-diazabicyclo[5 4.0]undec-7-ene (DBU) [60]... 

Figure 4.11 Molecular structures of typical crown-ether complexes with alkali metal cations (a) sodium-water-benzo-I5-crown-5 showing pentagonal-pyramidal coordination of Na by 6 oxygen atoms (b) 18-crown-6-potassium-ethyl acetoacetate enolate showing unsymmelrical coordination of K by 8 oxygen atoms and (c) the RbNCS ion pair coordinated by dibenzo-I8-crown-6 to give seven-fold coordination about Rb.

Reaction of Na2Se and Na2Sc2 with Se in the presence of ethanolic solutions of tetraalkyl-ammonium halides and catalytic amounts of I2 yields dark green or black crystalline polyselenides (jc = 3,5-9) depending on the conditions used and the particular cation selected. Tetraphenylphosphonium salts and crown ether complexes of alkali or alkaline earth cations in dimethylformamide solution can also be used. " )... 

What effect does the solvent have on the structure, charges and reactivity of Grignards Compare geometries, atomic charges and electrostatic potential maps of the diethyl ether complex to that of methylmagnesium chloride itself. How does solvent-magnesium bond formation affect the reactivity of the methyl group Explain. 

Electrostatic potential map for methylmagnesium chloride-diethyl ether complex shows negatively-charged regions (in red) and positively-charged regions (in blue). 

Fig. 3.3 H NMR and X-ray crystallography study of the bis-ether complex 28. [Denmark, S.E. Edwards, ).P. Wilson, S.R.J. Am. Chem. Soc. 1992, 114, 2592. Reprinted with permission from The American Chemical Society]...

Problem 18.15 l 15-Crown-5 and 12-crown-4 ethers complex Na+ and Li+, respectively. Make models of these crown ethers, and compare the sizes of the cavities. 

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. 

Alternatively, diazomcthanc can be added to thioxanthylium perchlorate (4) over 30 minutes at 0°C, and the reaction solution then poured into propan-2-ol. After concentration, the residue is dissolved in acetic anhydride and treated with boron trifluoride-diethyl ether complex at 0 C, to provide dibenzo[6,/]thiepin in 55 % overall yield16 (cf. Houben-Weyl, Vol. 10/4, p 834). 

In acid solution 1-acyl-1//-azepines and alkyl l//-azepine-l-carboxylates undergo rapid aromatization to A-arylcarbamates,115,139,142 whereas 1/Z-azepine-l-carbonitrile suffers quantitative rearrangement and hydrolysis to phenylurea.163 Rearrangement of ethyl l//-azepine-l-carboxylate to ethyl A-phenylcarbamate is also rapid (5 min) and quantitative with boron trifluoride-diethyl ether complex in benzene.245... 

The dehydrogenation of 2,3-dihydro- and 2,5-dihydro-l//-l-benzazepines to 3//-l-benz-azepincs with heterocyclic enamines in the presence of boron trifluoride diethyl ether complex has been achieved in moderate yields (30-35%).241 In contrast, electrochemical oxidation of 2,5-dihydro-1 H- -benzazepines in buffered acetic acid solution furnishes initially 5//-l-benz-azepines in 35-45% yield.242... 

Indole and dimethyl acetylenedicarboxylate yield 2-(indol-3-yl)-2,3-dihydro-l//-l-ben-zazepine (mp 240-242 C) by addition of indole to the initially formed l//-l-benzazepinc,21 whereas 1,3-dimethylindole (10, R = H) fails to react with the diester under a variety of conditions.145 However, in the presence of boron trifluoride-diethyl ether complex at room tem-... 

The reaction of benzopentathiepin with alkenes [(fl-but- -ene, ( )-hex-3-ene, cyclopentene or cyclohexene] in the presence of the boron trifluoride-diethyl ether complex results in the formation of 3,4-dihydro-l,2,5-benzotrithiepins, e.g. formation of 3.407... 

In addition to the boron trifluoride-diethyl ether complex, chlorotrimcthylsilanc also shows a rate accelerating effect on cuprate addition reactions this effect emerges only if tetrahydrofuran is used as the reaction solvent. No significant difference in rate and diastereoselectivity is observed in diethyl ether as reaction solvent when addition of the cuprate, prepared from butyllithium and copper(I) bromide-dimethylsulfide complex, is performed in the presence or absence of chlorotrimethylsilane17. If, however, the reaction is performed in tetrahydrofuran, the reaction rate is accelerated in the presence of chlorotrimethylsilane and the diastereofacial selectivity increases to a ratio of 88 12 17. In contrast to the reaction in diethyl ether, the O-silylated product is predominantly formed in tetrahydrofuran. The alcohol product is only formed to a low extent and showed a diastereomeric ratio of 55 45, which is similar to the result obtained in the absence of chlorotrimethylsilane. This discrepancy indicates that the selective pathway leading to the O-silylated product is totally different and several times faster than the unselective pathway" which leads to the unsilylated alcohol adduct. A slight further increase in the Cram selectivity was achieved when 18-crown-6 was used in order to increase the steric bulk of the reagent. 

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. 

The alkynyl reagent 9 was recently introduced for the dia stereoselective synthesis of tertiary propargylic alcohols144. 9 can be prepared as a solid 1 1 complex with tetrahydrofuran by treatment of 9-methoxy-9-borabicyclo[3.3.1]nonane with (trimethylsilylethynyl)lithium, followed by addition of boron trifluoride-diethyl ether complex. The nucleophilic addition of reagent 9 to (R)-2-methoxy-2-methylhexanal (10) afforded a mixture of the diastereomers 11 with a considerable preference to the nonchelation-controlled (3S,4R)-isomer144. 

For the monoprotected a-amino aldehydes, the best results in yield and stereoselectivity were obtained under kinetic control conditions which gave the expected sw-com pounds. The addition of tin(lV) chloride did not result in increased syn selectivity, and the use of boron trifluoride diethyl ether complex did not provide the ann -isomer as the major product. 

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