Thiophosphite

The HHT of ethyl glycinate 25 also reacted quantitatively with aliphatic phosphites under comparable conditions to give the corresponding aliphatic glyphosate triester 26, which was identical in all respects to the corresponding Mannich product (31). The product mixture from diethyl thiophosphite was much mote complex and led to dramatically lower yields (27). 

Phosphites, however, undergo a cheletropic reaction with acyclic ADC compounds to give 1,2,3,4-oxaphosphadiazoles (Eq. 15).139 Thiophosphites react similarly.140... 

Michael addition in the absence of any catalytic agent has been reported for dialkyl and diaryl phosphites and thiophosphites with a-cyanoacrylate esters and a-cyanoacrylic acid.444 Yields of the conjugate addition products were moderate to good. The regiochemistry of this process is the opposite of that previously reported for similar additions to ketene acetals, the latter presumably proceeding by initial protonation of the distal olefinic carbon site.445... 

Zwierzak, A., Cyclic organophosphorus compounds. 1. Synthesis and infrared spectral studies of cyclic hydrogen phosphites and thiophosphites, Can. 

An anionic ligand effect in iron porphyrin complex-catalyzed competitive epoxidations of cis- and frawi-stilbenes by BU4NHSO5 has been studied in detail . Oxidation of the thiophosphite to the thiophosphate in solid phase oligonucleotide synthesis using BU4NHSO5 was also reported. ... 

Triethylamine, A 138 Triethy thiophosphate, Al l Triethyl thiophosphite, A 1 0 TrJf 1 uoroacetic acid, AAi l... 

Four main types of antioxidants are commonly used in polypropylene stabilizer systems although many other types of chemical compounds have been suggested. These types include hindered phenolics, thiodi-propionate esters, aryl phosphites, and ultraviolet absorbers such as the hydroxybenzophenones and benzotriazoles. Other chemicals which have been reported include aromatic amines such as p-phenylenediamine, hydrocarbon borates, aminophenols, Zn and other metal dithiocarbamates, thiophosphates, and thiophosphites, mercaptals, chromium salt complexes, tin-sulfur compounds, triazoles, silicone polymers, carbon black, nickel phenolates, thiurams, oxamides, metal stearates, Cu, Zn, Cd, and Pb salts of benzimidazoles, succinic acid anhydride, and others. The polymeric phenolic phosphites described here are another type. 

Thiophosphite ion, even upon irradiation, only attacks the halogen atom of Me2C(Cl)N02 in an S 2 attack on the halogen188. With azide anion as nucleophile, only low yields of substitution products have been obtained287,288. Much more effective nitrogen--centred nucleophiles in photostimulated reactions with a-halo nitroalkanes are the anions of nitroimidazoles186 and imidazoles187. With the ambident 4(5)-nitroimidazole anion, the 4-isomer is exclusively formed, with no indication of the 5-isomer (equation 72). 

Dialkylphosphite ions have been shown to undergo S l reactions with different haloni-tro substrates117. The analogous thiophosphite ions117 react by this mechanism only with p-nitrobenzyl or p-nitrocumyl chlorides, but undergo X-philic reactions with 2-chloro-2-nitropropane. 

Phosphorus combines directly with sulphur in various proportions to give sulphides, the formulae of some of which resemble those of the oxides. It also gives oxysulphides, thiophosphites, thiophosphates and the corresponding acids. The latter salts may be made by the action of alkalies or alkali sulphides on phosphorus sulphides. 

Thiophosphites.—These salts may be regarded as derived from mono-, H3PS02, di-, H3PS20, and tri-thiophosphorous acids, H3PS3. They were prepared, with other products, by heating metals with a mixture of sulphur and phosphorus, e.g. AgsPS3, or metallic sulphides... 

Phosphorous hydrides, such as phosphites, (R0)2P(0)H, thiophosphites, (RO)2P(S)H, and phosphinates, R(R0)P(0)H, have received considerable attention in the recent years as nontoxic alternative to tin hydrides commonly used in radical chain reactions. 

Ghromous Thiophosphite, Cr3(PS3)2, is prepared by heating metallic ehromium with a mixture of sulphur and red phosphorus to a cherry-red heat in a closed vessel for twenty hours. It yields black, hexagonal, microscopic crystals, possessing metallic lustre. 

Conversion of thiophosphite to its Na salt, followed by thermolysis, yields PHj quantitatively ... 

The thiophosphite (27) with acetyl chloride gave mainly the Arbuzov product (28) in methylene chloride, but the substitution product (29) was the main product in hexane or without solvent, probably because the intermediate is a phosphorane in the latter case. 2-Acetylphenyl alkylphosphonamidites, phosphorodiamidites, or phos-phoramidites (30) upon heating gave different cyclisation products (31)-(33) dependant on the substituents on phosphorus, and on the amount of amine hydrochlorides present in (30). ... 

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