Phosphites allyl

The product when, carefully distilled in CO2 usually exploded (Ref 5). A prepn from dimethyl phosphite, allyl alcohol ... 

SAFETY PROFILE Poison by ingestion and inhalation. A corrosive irritant to skin, eyes (at 2 ppm), and mucous membranes. Potentially explosive reaction with chlorobenzene + sodium, dimethyl sulfoxide, molten sodium, chromyl chloride, nitric acid, sodium peroxide, oxygen (above 100°C), tetravinyl lead. Reacts with carboxylic acids (e.g., acetic acid) to form violently unstable products. Violent reaction or ignition with Al, chromium pentafluoride, diallyl phosphite + allyl alcohol, F2, hexafluoroisopropylideneaminolithium, hydroxylamine, iodine chloride, PbOa, HNO2, organic matter, potassium, selenium dioxide, sulfur acids (e.g., sulfuric acid. 

Janecki, T, and Bodalski, R., A convenient method for the synthesis of substituted 2-methoxycarbonyl-and 2-cyanoallylphosphonates. The allyl phosphite-allyl phosphonate rearrangement, Synthesis, 799, 1990. 

Ally I Bromide. 3 Br0mo-I-propene 3-bromopro-pylene bromallylene. CjH5Br mol wt 120.99. C 29.78%, H 4.17%, Br 66.05%. CHi—CHCH2Br Prepd from hydro-bromic acid and allyl alcohol O. Kamm, C. S, Marvel. Org Syn. coll. vol. 1, 27 (2nd ed., 1941) from tri phenyl phosphite, allyl alcohol and benzyl bromide Landauer. Rydon, J. 

Diallylsulfonium salts undergo intramolecular allylic rearrangement with strong bases to yield 1,5-dienes after reductive desulfurization. The straight-chain 1,5-dienes may be obtained by double sulfur extrusion with concomitant allylic rearrangements from diallyl disulfides. The first step is achieved with phosphines or phosphites, the second with benzyne. This procedure is especially suitable for the synthesis of acid sensitive olefins and has been used in oligoisoprene synthesis (G.M. Blackburn, 1969). 

The dimethyl allylphosphonate 352 is prepared by the reaction of allylic acetates with trimethyl phosphite[221]. 

Carboxylic acids react with butadiene as alkali metal carboxylates. A mixture of isomeric 1- and 3-acetoxyoctadienes (39 and 40) is formed by the reaction of acetic acid[13]. The reaction is very slow in acetic acid alone. It is accelerated by forming acetate by the addition of a base[40]. Addition of an equal amount of triethylamine achieved complete conversion at 80 C after 2 h. AcONa or AcOK also can be used as a base. Trimethylolpropane phosphite (TMPP) completely eliminates the formation of 1,3,7-octatriene, and the acetoxyocta-dienes 39 and 40 are obtained in 81% and 9% yields by using N.N.N M -tetramethyl-l,3-diaminobutane at 50 in a 2 h reaction. These two isomers undergo Pd-catalyzed allylic rearrangement with each other. 

Vulcanisation can be effected by diamines, polyamines and lead compounds such as lead oxides and basic lead phosphite. The homopolymer vulcanisate is similar to butyl rubber in such characteristics as low air permeability, low resilience, excellent ozone resistance, good heat resistance and good weathering resistance. In addition the polyepichlorohydrins have good flame resistance. The copolymers have more resilience and lower brittle points but air impermeability and oil resistance are not so good. The inclusion of allyl glycidyl ether in the polymerisation recipe produces a sulphur-curable elastomer primarily of interest because of its better resistance to sour gas than conventional epichlorhydrin rubbers. 

With acyl halides, the corresponding acyl phosphonates are obtained. Furthermore allylic and acetylenic halides, as well as a-halogenated carboxylic esters and dihalides, can be used as starting materials. If substituents R and R are different, a mixture of products may be obtained, because the reaction product RX 5 can further react with phosphite 1 that is still present ... 

The photo-Arbuzov rearrangement of allyl-, benzyl- and naphtylmethyl-phosphites (Scheme 13), first developed by Bentrude et al. [20], found applications in the preparation of phosphonates (70-90%) [38]. Arylphosphonates have been shown to act as protein tyrosine kinase inhibitors [39] or non-hy-drolyzable analogs of phosphorylated tyrosine residues [40]. 

An allylic sulfenate, like 199, is known to be in equilibrium with allylic sulfoxide, like 196, although its concentration is usually low . Various allylic sulfoxides can be prepared by treatment of allylic alcohols with arenesulfenyl chlorides . Evans and coworkers prepared various allylic alcohols by treating the corresponding allylic sulfoxides with trimethyl phosphite. For example, the carbanion from a cycloalkenyl sulfoxide 201 was readily alkylated at the a-position by treatment with alkyl halide. The resulting alkylated derivative 202 was then treated with trimethyl phosphite and 3-substituted cycloalkenol was obtained. Alkylation of acyclic allylic sulfoxide 204 gave... 

Although the interception of allylic sulfenates in the manner described by equation 11 was first observed by Abbott and Stirling ", the general value of this transformation and its remarkable synthetic potential has been recognized by Evans and coworkers , who have also introduced the previously used trimethyl phosphite as a preferable trapping agent. An early review of the synthetic utility of the reversible allylic sulfoxide-sulfenate rearrangement has also been published by Evans and Andrews . 

Since Pd complexes are well-known catalysts for enantioselective allylic substitution reactions, here the catalytic behaviour of palladium NPs for this reaction is examined (Scheme 1). One example involving a chiral phosphite with a carbohydrate backbone, able to coordinate firmly at the surface of NPs together with oxygen atoms capable to interact weakly with this surface, is presented. In particular. 

Since carbohydrates constitute an inexpensive and highly modular chiral source for preparing chiral ligands," Claver et al. have reported the use of a series of thioether-phosphite" and thioether-phosphinite furanoside ligands" in the test palladium-catalysed allylic substitution reaction. In the first type of ligand, a systematic variation of the donor group attached to the carbon atom C5 indicated that the presence of a bulky phosphite functionality had a positive effect on the enantioselectivity. Indeed, the enantioselectivity was controlled mainly by the phosphite moiety. This was confirmed by the use of a ligand... 

The allyl sulfoxide-allyl sulfenate rearrangement can be used to prepare allylic alcohols.275 The reaction is carried out in the presence of a reagent, such as phenylthi-olate or trimethyl phosphite, that reacts with the sulfenate to cleave the S—O bond. 

The smaller p -tert-butyl-calix [4] arenes have a rich coordination chemistry as well (65). Of these, however, only the upper-rim modified calixarenes seem to support metal complexes with confined binding sites (66), except in those cases where the lower-rim substituents form an appended cavity. Thus, Matt and coworkers have reported (67) a pocket-shaped calix[4]arene ligand L2 bearing two lower-rim [([Pg.410]

The allylic acetate 47 can be isomerized to 48 by the palladium catalyst. When Pd(acac)2 and PPh3 were used, 47 was converted at 90°C for 12 hours into a 3.9 1 mixture of 47 and 48. But the ratio remained 17 1 when tris(o-methylphenyl)phosphite (52) was used. 

Some of these coupling reactions can be made catalytic if hydrogen is eliminated and combines with the anion, thus leaving the nickel complex in the zero-valent state. Allylation of alkynes or of strained olefins with allylic acetates and nickel complexes with phosphites has been achieved (example 38, Table III). 

If the insertion step following oxidative addition occurs on one of the two fragments resulting from oxidative addition, an intramolecular catalytic reaction (C—O — C—C rearrangement) takes place (example 40, Table III). It is interesting to note that two different products—2,6- and 3,6-heptadienoic acids—can be obtained from allyl 3-butenoate. Their ratio can be controlled by adding 1 mole of the appropriate phosphine or phosphite to bis(cyclooctadiene)nickel or similar complex. Bulky ligands favor the 2,6 isomer. It is thus possible to drive the reaction toward two different types of H elimination, namely, from the a or y carbon atoms. 

Baker has also reported the reaction of butadiene with phenylhydra-zones leading to azoalkenes (example 14, Table IV). This is also a Grig-nard-type reaction which is catalytic. Analogous results were obtained with methylhydrazones (136). A wider scope was recently attained by causing allylic esters to react with phenylhydrazones in the presence of zero-valent nickel complexes having trialkyl phosphites (example 15, Table IV). 

An allylic phosphorus ester rearrangement to form a new C-P bond has been reported under photochemical conditions.179 Under irradiation in the presence of 9,10-dicyanoanthracene, an allylic phosphite ester undergoes rearrangement to form the corresponding allyl-icphosphonite ester (Equation 4.40). Benzophenone serves only poorly as a photosensitizer in this reaction. 

A PHOX analogue containing a P-O bond, the TADDOL-derived phosphite oxa-zoline catalyst 20a (Fig. 29.8) has been used in the hydrogenation of a number of substituted styrenes, as well as in asymmetric allylic alkylation [19]. However,... 

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