Titanium acetyl complexes

Cp2TiCl2 reacts with sodium acetyl salicylate or sodium salicylate in dry benzene to give bis-Cp diaspirin and disalicylate titanium(iv) complexes.1571 The molecular structure of Cp2Ti(sal) containing the dianionic salicylato... 

To prepare the a anomer (60) of the aminonucleoside [ namely, 9-(3-amino-3-deoxy-)8-D-ribofuranosyl)-iV , lV -dimethyladenine], 9-(3-ac-etamido-3-deoxy-a-D-arabinofuranosyl) -JV , iV -dimethyl-2- (methylthio) -adenine (59) was prepared by condensation of the titanium chloride complex of 3-acetamido-l-0-acetyl-2,5-di-0-benzoyl-3-deoxy-arabinofuranose with iV ,iV -dimethyl-2-(methylthio)adenine, followed by desulfurization and de-O-acylation. The inversion of the hydroxyl group on C-2 by way of its methylsulfonyl ester then gave the desired a anomer (60) of the aminonucleoside, isolated as its vanillylidene derivative. " The A-acetyl... 

The intense reddish-brown color of the acetylacetone titanium complexes impart a yellow discoloration to white inks. This discoloration is accentuated when the inks are used to print substrates that contain phenol-based antioxidants. The phenoHc compounds react with the organic titanate to form a highly colored titanium phenolate. Replacement of 0.25 to 0.75 moles of acetylacetone with a malonic acid dialkyl ester, such as diethyl malonate, gives a titanium complex that maintains the performance advantages of the acetyl acetone titanium complexes, but which is only slightly yellow in color (505). These complexes still form highly colored titanium phenolates. 

In other examples, also involving propargyl carbonates, the parent derivative 86 was first coupled with 87 - obtained by reaction of 5-octyne with the titanium diiso-propoxide - propene complex at -50 °C, providing the titanated vinylallene 88, which on hydrolysis furnished the vinylallenes 89 in good yield [29]. Carbonate 90 in the presence of a Pd° catalyst readily decarboxylated and yielded the allenylpalladium intermediate 91, which could be coupled with various vinyl derivatives to afford the vinylallenes 92. Since X represents a functional group (ester, acetyl), functionalized vinylallenes are available by this route [30]. 

Cyanation of aldehydes and ketones is an important chemical process for C C bond formation." " Trimethylsilyl cyanide and/or HCN are commonly used as cyanide sources. The intrinsic toxicity and instability of these reagents are problematic in their applications. Acetyl cyanide and cyanoformates were used as cyanide sources in the enantioselective cyanation of aldehydes catalyzed by a chiral Ti complex and Lewis base (Scheme 5.31)." The Lewis base was necessary for the good yields and selectivities of these reactions. The desired products were obtained in the presence of 10mol% triethyl amine and 5mol% chiral titanium catalyst (Figure 5.14). Various aliphatic and aromatic aldehydes could be used in these reactions. 

While the first two allow the isolation of the reaction products, the third does not. When a Lewis acid is mixed with an acyl halide, a donor-acceptor complex RCOX. .. MtX , or full ionisation by halide ion transfer, to give RCO MtX +i, or both, take place. The extent of ionisation depends mostly on the nature and strength of the Lewis acid used Thus, for example, acetyl halides react with stannic chloride and titanium tetrachloride to give mostly the coordination complex while with antimony pentachloride, pen-tafluoride and boron fluoride they give the conesponding acylium salts. Many of these... 

Many soluble catalysts are known which will polymerize ethylene and butadiene. High activity soluble catalysts are employed commercially for diene polymerization but most soluble types are inefficient for olefin polymerization. A few are crystalline and of known structure such as blue (7r-C5H5)2TiCl. AlEtaCl [49] and red [(tt-CsHs )2TiAlEt2 ] 2 [50]. The complex (tt-CsHs )2TiCl2. AlEt2Cl polymerizes ethylene rapidly but decomposes quickly to the much less active blue trivalent titanium complex. Soluble catalysts are obtained from titanium alkoxides or acetyl acetonates with aluminium trialkyls and these polymerize ethylene and butadiene. Several active species have been identified, dependent on the temperature of formation and the Al/Ti ratio. Reduction to the trivalent state is slow and incomplete and maximum activity for ethylene polymerization occurs at about 25% reduction to Ti [51]. 

Muzzarelli et al. (2000) described a method for coating prosthetic articles with chitosan-oxychitin. Plates of titanium (Ti) and its alloys were plasma sprayed with hydroxyapatite and glass layers, and subsequently a chitosan coat was deposited on the plasma-sprayed layers using chitosan acetate. These layers were treated with 6-oxychitin to form a polyelectrolytic complex. This complex was optionally contacted with l-ethyl-3-(3-dimethylami-nopropyl) carbodiimide at 4°C for 2 hours to form amide links between the two polysaccharides, or acetylation with acetic anhydride in methanol to obtain a chitin film. In all cases, the modified coats were insoluble, uniformly flat, and smooth. Prosthetic materials coated with chitosan-oxychitin were capable of provoking colonization by cells, osteogenesis, and osteointegration. 

Friedel-Crafts reaction catalysts like anhydrous aluminum chloride are readily soluble in the nitroalkanes. Solutions containing up to 50% aluminum chloride are easily prepared in nitroalkane solvents. These catalytically active complexes, AICI3-RNO2, can be isolated and used in solvents other than the nitroalkane. The reactants in the Friedel-Crafts reaction are often soluble in the nitroalkane reaction medium. Other catalysts like boron trifluoride (BF3), titanium tetrachloride (TiCl4), and stannic tetrachloride (SnCl4) are also soluble in the nitroalkane solvents. Reaction types which use nitroparaffins as solvents include alkylation of aromatics, acetylation of aromatics, halogenations, nitrations, and the reaction of olefins and hydrogen sulfide to yield mercaptans. 

Other works by the same group on the cyanation of a-ketoesters with acetyl cyanide revealed that, when using a ketone as substrate, a chiral base such as cinchonidine became responsible for enantioselection instead of the chiral titanium(iv) salen complex (Scheme 7.18), leading to the corresponding tertiary cyanohydrins in good enantioselectivities of up to 82% ee. ... 

The widely used asymmetrical epoxidation of allylic alcohols developed by Katsuki and Sharpless employs tert-batyl hydroperoxide (TBHP), enantiomerically pure tartaric acid esters, and isopropyl titanium(TV) (6). Similar results were obtained using TBHP and vanadyl acetyl acetonate VO(acac>2 and hexacarbonyl molybdenum [7,8]. The drawback of these reactions are their restriction to allylic alcohols, which is required as anchor group for the formation of the intermediate complex. 

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