Tris phosphites rearrangement

Allyl phosphite rearrangements, 138-142 Aluminum-phosphorus cubane, 60-61 Aluminum tris(methyl methylphosphonate),... 

Bis(2-Chloroethyl) 2-Chloroethylphosphonate. The commercial product, Albright Wilson s Antiblaze 78, is a mixture having various related higher boiling diphosphonates. This product is made by the Arbuzov rearrangement of tris(2-chloroethyl) phosphite [140-08-9] ... 

Allyloxypyrimidine largely resists rearrangement even at 200°C. However, ally lie cyclopentenyl 2-pyrimidinyl ethers (852) can be rearranged on catalysis by tetrakis(tri-isopropyl phosphite)palla-dium, a Pd(0)-complex (Scheme 68). 

Such condensation reactions are also promoted by certain trTvalent phosphorus compounds, e.g. triphenyl phosphite (2) or diphenyl ethylphosphonite (3), or to a lesser extent by pFosphonate esters, e.g. diphenyl n-butylphosphonate (3). "Bates reagent," p-oxobi s[tri s(cTi methyl ami no)phosphoni urn] bi s-tetra-f1uoroborate (2) may also be used to activate the carboxyl function towards amide bond formation during peptide synthesis (4) and to bring about the Beckmann rearrangement of ketoximes (F). 

Using the nickel-tri(o-phenylphenyl)phosphite catalyst, the composition of the reaction product is markedly dependent on the extent of conversion of the butadiene. With a conversion of less than 85°, 1,2-divinylcyclo-butane (DVCB) is obtained in a yield of up to 40° At higher conversions DVCB catalytically rearranges to COD and VCH ( Table VI)... 

Fig. 2. The Cope rearrangement of DVCB (84). I, Thermal rearrangement at 80°C II, catalytic rearrangement with nickel-tri(o-phenylphenyl)phosphite (0.2 M solution), 24° C.

The three-st synthesis (Figure 13) comprises the additiai of ethylene oxide to phosphorus trichloride, subsequent thermal Arbuscw rearrangement of tris-2-chloroethyl phosphite, and, finally, the eliminaticxi of hydrogen chloride (23). Ihe final dehydrochlorination is advantageously carried out as a continous process using basic eiluminum oxide (24). 

If the reaction between prop-2-ynol and PCI3 (3 1 ratio) is carried out in the absence of a tertiary amine, the liberated HCl dealkylates the tris(prop-2-ynyl) phosphite before it is able to undergo rearrangement, and the product is bis(prop-2-ynyl) hydrogenphospho-nate. ... 

Amino-l-nitro-l,2,4-triazole (581), obtained by nitration of 5-amino-triazole with acetyl nitrate, rearranges, on heating, to the nitramino-triazole (582). ° The combined action of sodium hydroxide, potassium iodide, tri-ethylamine, and sodium dihydrogen phosphite on the chloro-nitro-triazole (583) results in a mixture of the rearranged triazole (584), 3-chloro-l,2,4-triazole, and the coupled product (585). The stable betaine (586) has been prepared by treatment of 4-phenyl-1,2,4-triazole with phenacyl bromide, followed by tri-ethylamine. The meso-ionic triazolium thiolate (537 X = S) reacts with chlorine to form the dichloride (587 X = SCU), which has been converted into the betaine (588) by the action of diethyl bromomalonate in the presence of triethylamine. ... 

First obtained is tris(2-chloroethyl) phosphite, which undergoes an Arbuzov rearrangement to give bis(2-chloroethyl) 2-chloroethylphosphonate. This product reacts with thionyl chloride in the presence of a suitable... 

Arbuzov Polycondensation. To date industrial applications have been limited to production of oligomeric flame retardants, such as the conversion of tris(2-chloroethyl) phosphite to a mixture of its intramolecular Arbuzov rearrangement product, bis(2-chloroethyl) 2-chloroethylphosphonate and its oligomeric in-termolecular Arbuzov products (108,109), where x = 2-6 ... 

Room temperature imidazolium ionic liquids have been shown to be useful solvents for the Michaelis-Arbuzov rearrangement, sometimes allowing the reaction to be performed at room temperature in a short period of tirne. Halolactones, which are the products of halolactonisation of y,5-unsaturated acids, have been shown to be dehalogenated by trialkyphosphites in the presence of water. This makes a useful alternative to the commonly used reduction by tributyltin hydride. The reactions of dibromoethane and dibromopropane with silyl phosphites have been studied. Mono and diphosphonoalkanes (37) and (38) were prepared and their chemical properties were studied. In the reaction of trifluoromethylated P-alkoxyketones with tris(trimethylsilyl)phosphite, a mixture of the 1,2- and 1,4-adducts (39) and (40) is produced. 

The mixed oligomerization of allene and butadiene (1 10) in the presence of nickel(o) tris(2-biphenylyl) phosphite affords the ten-membered ring [2+2+2] cycloadducts 284 and 285 in a combined yield of 69 %. Heating of the cycloadducts at 150 °C gives 4-methylene-c -divinylcyclohexane 286 as the result of a thermal Cope rearrangement . ... 

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