Tri-isopropyl phosphite

Di-isopropyl hydrogen phosphite is a colourless mobile liquid, which, unlike triethyl and tri-isopropyl phosphite, is completely miscible with water, due undoubtedly to the polar P=0 group. 

Simpson and Burt have studied the same reactions in the presence of various amounts of ethanol and have plotted graphs of phosphonate (81 R = Ph) and phenyl acetylene produced against moles of alcohol added. Acetylene in the product reached a maximum (around 60%) when two moles of ethanol were added and stayed fairly constant beyond this, which suggests that the attack-on-halogen contribution to the mechanism is approximately 60%. The rest of the reaction presumably follows some other mechanism and the authors suggest the addition-elimination route (79) in view of the isolation of the phosphonate (83) from the reaction of tri(isopropyl) phosphite with the bromoacetylene (84). 

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). 

Distal ring-opening is also observed in the intramolecular 3+2 cycloaddition reaction of a 3-pentenone diphenylmethylenecyclopropane derivative in the presence of bis(diben-zylideneacetone)palladium/tri-isopropyl phosphite catalyst, affording regioselectively a diphenylmethylene pentalenone system (equation 360)424. Similarly, thermal cyclization of... 

The success of cycloisomerization reactions of this type is critically dependent on factors that influence the conformational mobility of the side chain bearing the alkene moiety. Additionally, functional groups which are able to serve as ligands at palladium may also be of importance. As an example, neither the (E)- nor the (Z)-crotonate derivative ( -IS or (Z)-13 gives rise to the formation of bicyclic products on treatment with bis(dibenzylideneacetone)palladium/tri-isopropyl phosphite. Instead, the corresponding isomeric substituted butadienes, methyl (2E or 2Z,6 )-7,8-dimethylnona-2,6,8-trienoate (14) and methyl (2E or 2Z)-8-methyl-7-methyl-enenona-2,8-dienoate (15), are formed. 

See Tributyl phosphate Aibrite TEP. See Triethyl phosphite Aibrite TiOP. See Triisooctyl phosphite Aibrite TiPP. See Tri isopropyl phosphite Aibrite TKPP. See Tetrapotassium pyrophosphate... 

An unusual conversion of a nitrocyclopropyl group into a nitrile is brought about by tri-isopropyl phosphite [133] ... 

Put tri(isopropyl)phosphite (1.11 g, 5.34 mmol) into the flask using a syringe by puncturing the septum on the reaction flask. A yellow solution should form. 

Allylic esters and alk-l-ynes in the presence of Ni° catalysts react under mild conditions to give alk-l-en-4-ynes (46) in satisfactory yield, although catalyst turnover numbers are low (ca. 50)." The yield appears to be dependent on the ligand around the metal, with tri-isopropyl phosphite being the best ligand. Allylic halides give only very low yields. 

The preference for the formation of diphosphonates in reactions between trialkyl phosphites and periluoro-(l,2-dichlorocycloalkenes) has been discussed in terms of the ability of a dialkyl phosphonate group to stabilize an adjacent carbanionic site and steric effects have been invoked to account for the fact that a small amount of monophosphonate is present in the product from perfluoro-(l,2-dichloro(grclopentene) and tri-isopropyl phosphite. PoIyfluorocyclobut-1-enyl phosphonates have been obtained as the main products in y-ray-induced reactions between dialkyl phosphites and poly-fluorocyclobutenes. ... 

Alkynes are poor dienophiles in the Diels- Alder reaction decomposition occurs by an attempted thermal intramolecular Diels-Alder reaction of dienynes at 160 °C. In contrast, the Ni-catalysed [4+2] cycloaddition of the dienyne 50 proceeded smoothly at room temperature using tri(hexafluoro)isopropyl phosphite to give 51, which was converted to the yohimbine skeleton 52 [15]. The same reaction is catalysed by RhCl(Ph3P)3 in trifluoroethanol [16]. Intramolecular Diels-Alder reactions of the 6,8-dieneyne 53 and the 1,3,8-triene 55, efficiently catalysed by [Rh(dppe)(CH2CH2)2]SbF6 at room temperature, gave 54 and 56 [17],... 

Triisopropylbenzene Triisopropyl borate Triisopropyl phosphate Triisopropyl phosphite Tri isopropyl vanadate... 

NdC4jHj9, Neodymium, tris(2,6-dwert-butyl-4-methylphenoxo)-, 27 167 O3PC3H, Trimethyl phosphite, cobalt and rhodium complexes, 28 283,284 iron complexes, 28 171, 29 158 nickel complex, 28 101 O3PCJH15, Triethyl phosphite, iron complexes, 28 171, 29 159 nickel complex, 28 101 nickel, palladium, and platinum complexes, 28 104-106 03PC,H2i, Isopropyl phosphite, nickel complex, 28 101... 

Irgastab SN-55 Ciba-Geigy Corp., USA Tri(/j-propylphenyl-phosphite) (0.1-1.0) A-Isopropyl-A -phenyl phenylene) diamine-1,4 (up to 1)... 

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