Borane, dichloro

The two redistribution products, monochlorodiborane and dichloro-borane, could be isolated by low-temperature gas chromatography (216). Monochlorodiborane, although comparatively stable for a short time at room temperature, slowly reequilibrates, exchanging chlorine and hydrogen atoms as shown in Fig. 9. During the disproportionation according to Eq. (61)... 

The reaction of trialkylboranes with A-chloro- or A-(benzoyloxy)alkylamines afforded secondary amines via an anisotropic 1,2-shift of the alkyl group from boron atom to nitrogen in the B-N complex intermediate.519-521 Alkylation of A-chlorodimethylamine with primary trialkylboranes to give A,A-dimethylalkylamines was conducted in the presence of galvinoxyl to avoid the formation of alkyl chlorides via free radical process.522,523 A convenient approach to mixed secondary amines is alkylation of alkyl azides with relatively unhindered trialkylboranes in refluxing xylene followed by hydrolysis with water. The reaction smoothly took place at low temperature when trialkylboranes were replaced by alkyl(dichloro)boranes (Equation (108)).524 Intramolecular amination furnished cyclic amines (Equation (109)).400,525-528... 

Unfortunately, those single source precursors which are farthest advanced towards application are liquid at room temperature, and attempts to grow crystals at low temperatures have failed, so far. However, reliable insights into the relevant geometric/structural features have been gained by quantum mechanic calculations. Some theoretical work concerning single source preciursors has been done by Marian et al., who combined experimental and ab initio techniques to study the structural properties of l-(dichloroboryl)-l-(trichlorosilyl)ethane (TSDE, cf. Eq. 6) and (trichlorosilylamino)dichloro-borane (TADB, cf. Eq. 1) [43, 44]. 

The replacement of tin by boron in l,l-dimethyl-2,3,4,5-tetraarylstannoles (104) by reaction with aryl(dichloro)boranes provides pentaarylboroles (5) or (6). Stannoles (104) are obtained from the lithium reagent (86) by the addition of stoichiometric amount of dichloro(dimethyl)tin <86JA379>. 

A sulfoxide deoxygenation method consists of treatment with dichloro-borane (142), The substitution of two hydrogen atoms of borane by chlorine appears to impart the boron with a hardness compatible with the sulfoxide oxygen. 

However, they are too slow to react with 9-BBN. Catecholborane and pinacolborane react with fluoroolefins in the presence of a transition metal catalyst. However, reactive boranes, such as dichloroborane-methyl sulpfide readily react with mono, and disubstituted terminal perfluoroaUcenes in the presence of BCI3. The latter coordinates to Me2S and releases the free dichloro-borane, which instantaneously hydroborates theperfluoroalkenes. Oxidation under alkaline conditions furnishes the primary alcohol in >98% regioselectivity (eq 8). Alternatively, the free dichloroborane prepared via Matteson s protocol can also be used for the hydroboration of fluoroolefins. 

P-Chirogenic diphosphine 19, which rhodium-chelate complex forms a seven-membered ring (rare case for P-stereogenic ligand), was also prepared in reasonable yield (68%) using the wide chemistry of secondary phosphine borane [37]. Deprotonation of the enantiomerically enriched ferf-butylmethylphos-phine-borane 88 (Scheme 15) followed by quenching with a,a -dichloro-o-xylene and recrystallization afforded optically active diphosphine-borane 89 (precursor of free phosphine 19). 

Simlilar conclusions are indicated for the reaction product obtained from dichloro-acetonitrile and trichloroborane. For the product obtained from chloroacetonitrile and trichloroborane, however, a nitrile-borane structure is found which, according to the authors 481, might depend critically on the reaction conditions. 

Isomeric with non-classical triboretanes of type 3 (Schemes 3.2-3 and 3.2-5) are triboraficyclo] 1.1,0 butanes of type 13 (Scheme 3.2-8). The first derivative 13a was obtained when 4b was reacted with dichloro(trimethylsilylmethyl)borane [19]. 

Miscellaneous spectral studies include e.s.r. spectra of chloro-phosphines (2)6 and vibrational spectra of various phosphines.6-8 N.m.r. studies include those of borane complexes of aryldichlorophosphines,9 and studies of the conformation of dichloro-(isopropyl)phosphine (3)10 and dichloro(ethyl)phosphine (4).10 These phosphines have the preferred conformations shown. Conformation has also been the theme of electron-diffraction work on the anhydride (5), which appears to have a staggered conformation.11 The electronic implications of a relatively short P—O bond and wide POP angle have been discussed.11... 

HYDRO ALUM [NATION Dichlorobis-(cyclopcntadienyl)titanium. Dichloro-his(cyclopentadicnyl)zirconium. Lithium aluminum hydride-I)ichlorobis(cyclo-pentadienyi)zirconium. Borane-Di-metliyl sulfide. 

Borane Dichloro-drifluoro-cihenyl)-ElOa. 517 (Educt)... 

The synthesis of 1 starts with the reaction of dichloro(dimethylamino)borane with the Grignard reagent from 2,5-dibromohexane, and includes a resolution with (S)-prolinol. 

Dibromoborane-Dimethyl sulfide, 92 Dichloro(dimethylamino)borane, 120 Diisobutylaluminum hydride-Boron trifluoride etherate, 116 Diisopinocampheylborane, 117, 182 Diisopinocampheylmethoxyborane, 86 Dimesitylmethylborane, 8 Dimethoxy[l-trimethylsilyl-l,2-buta-dienyl]borane, 218 (R,R)- and (S,S)-frans-2,5-Dimethyl-borolanes, 119... 

Methylammonium perchlorate, 0498 Methyl azide, 0458 Methyl 2-azidobenzoate, 2934 f Methylbenzene, see Toluene, 2787 4-Methylbenzyl chloride, 2954 Methylbis( 2-peroxo)rhenium oxide hydrate, 0494b Methylborondichloride, see Dichloro(methyl)borane, 0425b Methylborylene, 0424... 

AT-Formylnor-reticuline, on treatment with 2,3-dichloro-5,6-dicyano-l,4-benzoquinone in methanol, is oxidized to the 4-methoxy-compound (35), which can be cyclized to N-norbisnorargemonine (36) (converted by N- and O-methylation into argemonine) by mineral acid or to the isopavine N-formyl-northalidine (37) by treatment with methanesulphonic acid in acetonitrile. The N-formyl compounds can be reduced to AT-methyl by borane or converted into the secondary bases by hydrazinolysis.69... 

The reaction of triboracyclobutanide 36 in [D8]THF with methyl trifluoromethanesulfonate in an NMR tube at —90 °C affords a mixture of C-boryldiboracyclopropane 37 and compound 38 in a 3 1 ratio. Compound 36 reacts with dichloro(trimethylsilylmethyl)borane to give a product mixture, from which compound 39 (yield 50%) can be separated by crystallization (Scheme 2) <2003AGE671>. 

The unsymmetrically substituted triboracyclobutanide 62 was obtained by reaction of compound 61 with dichloro-(trimethylsilylmethyl)borane and then with lithium (Equation 11) <2003AGE669>. 

Reaction of l,2-dichloro-l,2-bis(dimethylamino)diborane(4) with N-dilithio bis- or tris(amino)borane derivatives resulted in several derivatives of the system named in the heading, according to the following equation ... 

The selective preparation of various chlorophosphines used as building blocks for the preparation of polyfunctional phosphines is achieved using dichloro (diethylamino)phosphine (Et2NPCl2). Alkylation of this phosphine with organozinc halides furnishes, after borane treatment, protected aminodi-organophosphines. These in turn can be converted to the corresponding... 

Preparation of 4-acetoxybutylzinc iodide and its addition to dichloro(diethylamino)phosphine preparation of di(4-acetoxybutyl) (diethylamino)-phosphine-borane complex10... 

A new class of boron compounds has been prepared by the reaction of pentacarbonyliron with dichloro(dimethylamino)borane to form (CO)4FeBN(CH3)2, a borylene complex.10 The mono- and dihaloamino-boranes can be prepared from the corresponding tris(amino)borane.11,12 Pyrolysis of the tris(primary amino)borane B(NHR)3 yields the borazine B3(NHR)3N3R3.3... 

Dichloro(phenyl)borane is a clear liquid. It is sensitive to water, hydrolyzing to di hydroxy (phenyl) borane C6H5B(OH)2. 

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