Phosphites trimethylphosphite

Phosphite Trimethylphosphite (CH30)3P CH3O P -0CH3 OCHs... 

For these reasons, higher concentrations of alkoxide were used, firstly to increase the initial rate and secondly to pre-erve alkalinity throughout the reaction. With two equivalents of alkoxide, high yields of trialkyl phosphite were obtained within 1-2 h. at 25°. Again, the yield decreased with time owing to the subsequent oxidation, e.g. 82% trimethylphosphite and 76% tri-ethylphosphite after 1 h. 

However, it was not generally possible to obtain trisubstituted compounds from phosphines (except for trimethylphosphine 19)), while the phosphites give the trisubstituted derivatives 131) easily. Later Bigorgne 19) described all the possible substitution derivatives of carbonyl nickel with trimethylphosphite and triethylphosphite. 

If the substituting ligands have n acceptor properties, more than two carbonyl ligands can be replaced in simple thermal processes. We demonstrated that treatment of complexes 78 with trimethylphosphite at room temperature affords the trisphosphite-substituted complexes 85 105). When M equals Mo and W the remaining carbonyl ligand may be replaced by heating in neat trimethylphosphite [Eq. (70)]. The phosphite ligands in... 

Polymerization by Ionic Catalysts. Attempts to polymerize monomer I with ionic catalysts such as trimethylphosphite or boron trifluoride-etherate at room temperature did not succeed. No reaction was visible in either case despite the fact that it has been reported that trialkyl phosphites react vigorously with sulfur at room temperature (21). However, even in that specific instance, no polymerization was observed. The use of an anionic initiator such as n-butyllithium did not produce polymer either. In this case, however, a reaction did occur, as evidenced by the discoloration of the monomer solution. 

Transition metal compounds can be replaced by other substances, for example, by phosphites. Thus, 2-substituted 4-trifluoromethyl-5-fluoro-l,3-oxazole-2,4-dienes 9 were obtained by the reaction of 4,4-bis(trifluoromethyl)-N-acylimine 10 with trimethylphosphite (71CB1826, 74CB1448). The reaction occurs via the intermediate formation of 5-substituted 3,3-bis(trifluoromethyl)-2,2-dihydro-1,4,2-oxazaphos-pharol-4-ene 11 (Scheme 15). 

Breakdown of 18 affords olefin 13, trimethylphosphite, and carbon dioxide. It is also possible that ylide 18 is generated directly via nucleophilic attack on carbene 12 by phosphite. Evidence for an ylide intermediate has been obtained from trapping experiments with trithiocarbonates and benzaldehyde.3... 

Tris(trimethylsilyl)phosphites, analogous to trialkylphosphites, undergo Perkow reaction with a-halo carbonyl compounds to give vinyl phosphates.223 Reaction of a-chloroketone 19 with trimethylphosphite produces dimethyl enol phosphate 20, which is further converted to b is [trimethyls ilyl] esters 21 using MeaSiBr. 21 is also produced directly from a-chloroketone 19 on reacting with P(SiMe3)3. 

AI3-60394 EINECS 204471-5 Fosforyn trojmetylowy HSDB 1007 NSC 6513 Phosphorous acid, trimethyl ester Trimethoxytosfin Trimethoxyphosphine Trimethyl phosphite Trimethyltosfit Trimethylphosphite UN2329. Uqukt bp = 111.5° d = 1.0518 4m = 251, 257, 263 nm (s 575, 631, 457, EtCH) slightly soluble in CCI4, very soluble in EtOH, EtzO. 

In hydrolysis with trialkylphosphites, a first order in phosphite and a second order in water were determined [138]. These observations provide evidence that the reaction proceeds via a concerted mechanism with the participation of two water molecules. In Scheme 2.107, two alternative routes for hydrolysis of trimethylphosphite are illustrated. 

The hydrolysis is autocatalytic because of the acidic properties of the diorganohydrogenphosphites (HASPOs), organodihydrogenphosphites, and H3PO3 formed (Scheme 2.120) [157]. This cascading effect was evidenced by the addition of diethyl hydrogen phosphite to a trimethylphosphite/water system or by addition of basic compounds, such as hydrotalcite, as an acid scavenger [158]. 

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