1.1.3.3- tetrakis propane

FIGURE 6.32 Configurationally different spiro tetramers 44a and 44b formed by spiro tetramerization of l,3-bis(5-tocopheryl)propane (43) in a 15 1 ratio in agreement with theory. Reduction of each of the tetramers provides c s-l,2-c s-4,5-tetrakis(5-tocopheryl)cyclohexane (45). The dashed lines separate the two former units of 43, indicating where bond formation during the spiro oligomerization process occurred. 

Tetrakis(picolyl)propane-l,3-diamine and its butane-1,4-diamine analogue each contain two terdentate chelating units and can thus provide the groups L on both iron atoms, giving further bridging (see also Section 5.4.S.4.3 below). ... 

SYNTHESIS OF (45, 55)-[(f -l,5-CYCLOOCTADIENE)- 2-(2-PHEN YL-5-METHYL, 5-DIHYDRO-OXAZOL-4-YL)-1,3-DIPHENYL-2-DIPHENYLPHOSPHINITE-PROPANE IRIDIUM(I)]-TETRAKIS[3,5-BIS(TRIFLUOROMETHYL)PHENYL]BORATE... 

Cyclooctadiene)- 2-(2-phenyl-5-methyl-4,5-dihydro-oxazol-4-yl)-l,3-diphenyl-2-diphenylphosphimte-propane mdium(l)]-tetrakis[3,5-bis(tri-fluoromethyl)phenyl]borate (1.72mg, l.Opmol). The catalyst is available from Strem Chemicals, Inc. (catalogue no. 77-5020). 

C65H70Oi2P2S4-4Na> Benzenesulfonic acid, 4,4,4",4 "-[( 1,3-dime thyl-1,3-propan-ediyl)bis[phosphinidynebis(4,l-phenylene-3,l-propanediyl)]]tetrakis-, tetrasodium salt, [S-(R, )]-, [169829-24-7], 32 34-35, 32 34-36... 

Michael P. Doyle, William R. Winchester, Marina N. Protopopova, Amy P. Kazala, and Larry J. Westrum 13 (1 R,5S)-(-)-6,6-DIMETHYL-3-OXABICYCLO[3.10]HEXAN-2-ONE. HIGHLY ENANTIOSELECTIVE INTRAMOLECULAR CYCLO-PROPANATION CATALYZED BY DIRHODIUM(II) TETRAKIS[METHYL 2-PYRROLIDONE-5(R)-CARBOXYLATEl... 

Co = Catechol oxidase He = Hemocyanin Tyr = Tyrosinase MePy2 = Al,Al-bis(2-pyridylethyl)methylamine TACN = l,3,5-triazocyclononane TMPA = Tris[(2-pyridyl) methyljamine XYL-O = Q ,Q -bis[Al,Al-bis(2-pyridylethyl) amino]-m-xylene-2-olate XYL = Q ,Q -bis[A, Al-bis(2-pyri-dylethyl)amino]-m-xylene XYL-R = Meta substituted a,a -bis[Al,Al-bis(2-pyridylethyl)amtno]-m-xylene N3 = N,N, Al -Tetrakis-(2-pyridin-2-yl-ethyl)-propane-1,2-diamine N4 = Al,Al,Al, Al -Tetrakis-(2-pyridin-2-yl-ethyl)-butane-1,2-diamine N5 = Al,Al,Al, Al -Tetrakis-(2-pyridin-2-yl-... 

The prefixes, di, tri, tetra, etc., will be used before simple expressions (for example, diethylbutanetriol) and the prefixes bis, tris, tetrakis, etc., before complex expressions. Examples bis(methylamino)propane CH3NH(CH2)sNHCH3 bis(dimethylamino)-... 

A screening of ruthenium(II) carboxylates and several ruthenium(II) chloride complexes has identified tetrakis(trifluoroacetato)diruthenium as an excellent catalyst for the cyclo-propanation of cyclooctene with ethyl diazoacetate (60°C, excess of alkene, 0.75 mol% of catalyst yield of ethyl bicyclo[6.1,0]nonane-9-carboxylate 99% endojexo 1.65)." With several other ruthenium(II) complexes, ring-opening metathesis polymerization of cyclooctene competes strongly with the cyclopropanation reaction. 

The binuclear iron(III) complex [Fe2(HPTP)(p-OH)(N03)2](C104)2 (1) with HPTP = A W,7W,-tetrakis(2-pyridyl methyl)-2-hydroxy-1,3-diamino-propane [5], reacts with H2O2 to yield a blue species [6], The crystal structure of (1) and its interaction with montmorillonites (MMT) has been reported [7]. The occlusion of [Fe2(HPTP)(p-OH)] complexes in new families of hexagonal mesoporous materials such as MCM-41 and HMS will be described elsewhere [8], Related HPTB complexes, with benzimidazole instead of pyridine, have their tripodal N atoms tmns to strong basic peroxo-ligands, the benzimidazole ligands perpendicular to the Fc203 plane and tmns to each other on every iron [9]. 

The A(A(Af ,A ,-tetrakis(2-pyridyl-methyl)-2-hydroxy-l,3-diamino-propane was prepared by crushing para-chloropicoline (0.097 mol) and mixing it with 2-hydroxy-1,3-diamino-propane (0.016 mmol) [5-6]. The mixture is heated to 170-180°C for 1 hour, till gas formation stops. After cooling the red glassy structure is diluted with HCl (150 ml, 4M), thus a blue precipitate arises. After filtration the precipitate is washed several times with acetone. The precipitate is then dissolved in water and neutralised with a diluted ammonia solution. The white precipitate is recrystallised in acetone and crushed to a fine powder and then dried under vacumn. To an ethanolic solution with Fe(N03)3.6H20 (0.31 g) the HPTP (0.3 g) is added. The precipitate of binuclear iron complex is collected. 

Fig. 64. Two tetramers. Left, is the [Mn40j(tphpn)2] tetramer. Right, [Mnl (2-OH picpn)2l tphpn = iV,iV,iY, iV,-tetrakis(pyridylmethyl)-l,3-diaminopropan-2-ol. 20Hpicpn is the Schiff-base condensation product of pyridine-2-carboxaldehyde with 1,3-diamino-propan-2-ol. [Reproduced with permission from (334) and (333), respectively. Copyright 1991 and 1996 the American Chemical Society, respectively.]...

Asymmetric cyclopropanation. The ability to effect ligand exchange between rhodium(II) acetate and various amides has lead to a search for novel, chiral rhodium(II) catalysts for enantioselective cyclopropanation with diazo carbonyl compounds. The most promising to date are prepared from methyl (S)- or (R)-pyroglutamate (1), [dirhodium(ll) tetrakis(methyl 2-pyrrolidone-5-carboxylate)]. Thus these complexes, Rh2[(S)- or (R)-l]4, effect intramolecular cyclopropanation of allylic diazoacetates (2) to give the cyclo-propanated y-lactones 3 in 65 S 94% ee (equation 1). In general, the enantioselectivity is higher in cyclopropanation of (Z)-alkenes. 

Ethylidenebis (4,6-di-t-butylphenol) 2,2 -Methylenebis (6-t-butyl-4-methylphenol) Octadecyl 3,5-di-t-butyl-4-hydroxyhydroci nnamate Pentaerythrityl tetrakis [3-(3, 5 -di-t-butyl-4-hydroxyphenyl) propionate] Stearyl lauryl thiodipropionate Styrenated diphenylamine 4,4 -Thiobis-6-(t-butyl-m-cresol) 2,4,6-Tri-t-butylphenyl 2-butyl-2-ethyl-1,3-propanediol phosphite Tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate Zinc diisobutyidithiocarbamate antioxidant, after-sun treatments Ascorbyl methylsilanol pectinate antioxidant, alkyd resins 1,1,3-Tris (hydroxyphenyl) propane antioxidant, alkyds Drometrizole antioxidant, animal feed BHT... 

---