Rearrangement Arbuzov

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] ... 

An alkyl group can also migrate from oxygen to nitrogen or phosphorus [I, 72] (Michaelis-Arbuzov rearrangement) With this methodology, tetrafluoro-pyndine phosphonates and phosphmates can be obtained [75, 74], Chlorine fluoride... 

Nucleophilic substitution of the halogen atom of halogenomethylisoxazoles proceeds readily this reaction does not differ essentially from that of benzyl halides. One should note the successful hydrolysis of 4-chloromethyl- and 4-(chlorobenzyl)-isoxazoles by freshly precipitated lead oxide, a reagent seldom used in organic chemistry. Other halides, ethers, and esters of the isoxazole series have been obtained from 3- and 4-halogenomethylisoxazoles, and 3-chloro-methylisoxazole has been reported in the Arbuzov rearrangement. Panizzi has used dichloromethylisoxazole derivatives to synthesize isoxazole-3- and isoxazole-5-aldehydes/ ... 

Bentrude et al. [20] reported the first photo-Arbuzov rearrangement of arylethylphosphites (Scheme 4). The direct photolysis of arylethylphosphites... 

Scheme 5 Photo-Arbuzov rearrangement of arylethylphosphites via a short-lived singlet proximate radical pair mechanism. Reprinted with permission from [22]. Copyright 2001 American Chemical Society...

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]. 

Lutsenko, I.F. and Kraits, Z.S., Arbuzov rearrangement of vinyl esters of phosphorous and phenyl phosphonous acids, Dokl. Akad. Nauk S.S.S.R., 132, 612, 1960. 

Kiddle, J.J. and Gurley, A.F., Microwave irradiation in organophosphorus chemistry 1 The Michaelis-Arbuzov rearrangement, Phosph., Sulf, Silic. Relat. Elem., 160, 195, 2000. 

Benzoic acid (271) when reacted with PCI3 yielded an adduct (272) which underwent an Arbuzov rearrangement to the phosphoryl compound (273), which eliminated 3HC1 to give benzoylphosphonic anhydride (274). Addition of water to the reaction mixture converted the anhydride (274) into benzoylphosphonic acid (275), which underwent... 

Also known as the Michaelis-Arbuzov rearrangement. For reviews, see Petrov Dogadina lonin Garibina Leonov Russ. Chem. Rev. 1983,52. 1030-1035 Bhaltacharya Thyagarajan Chem. Rev. 1981, 81.415-430. For related reviews, see Shokol Kozhushko Russ. Chem. Rev. 1985, 53, 98-104 Brill Landon Chem. Rev. 1984,84, 577-585. 

Polyfluoroalkyl fluorosulfates are formed on reacting dialkyl sulfites with chlorine monofluoride, presumably via an Arbuzov rearrangement.93... 

Disubstituted pyrylium salts reacted with NaOP(OR )2 to give 4H-pyranylphosphonates (217),263-265 which are hydrolyzed to the corresponding phosphoric acids 217 (R1 = H).263-265 The condensed acid 218 was prepared in the same way.259 If a mixture of P(OBu)3 and Bui is used in place of NaOP(OBu)2, the Arbuzov rearrangement gives the same products.2641... 

Methoxy(methyl)(trifluoromethyl)phosphane (1) undergoes an Arbuzov rearrangement with iodomethane to give dimelhyl(trifluoromethyl)phosphane oxide (2). The reaction does not follow an intramolecular 1,2-shift mechanism, but rather occurs by the normal Arbuzov addition-substitution mechanism, as demonstrated by the reaction of 1 with iodomethane-phosphane oxide 2 containing a deuterated methyl group. 

Keywords alkyl chloride, trialkyl phosphite, alumina, microwave irradiation, Arbuzov rearrangement, dialkyl alkylphosphonate... 

The protected methyl glycoside 3 is converted to the corresponding aldehyde by Swern oxidation using oxalyl chloride activated DMSO. Further reaction with triethyl phosphonoacetate and sodium hydride -known as the Horner-Wadsworth-Emmons reaction - provides selectively the trans et /Tun saturated ester 4 in 72 % yield. This valuable alternative to the Wittig olefination protocol uses phosphonate esters as substrates which are readily available from alkyl halides and trialkyl phosphites via the Arbuzov rearrangement.9 co2Et Reaction of the phosphonate with a suitable base gives the... 

The reaction of functionalized iminium salts 4 derived from aziridines with trimethylphosphite gives aminophosphonates 11 by a Michaelis-Arbuzov rearrangement. This reaction is general(6 ). 

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