Tanning reaction

Inspired by the use of chiral imidazolidinones as highly enantioselective catalysts for Diels-Alder, 1,3-dipolar cycloaddition and Friedel-Crafts reactions, Tan et have synthesized a series of novel chiral imidazolines and examined their application in MBH reactions. Up to 54% ee and high yields were obtained by using stoichiometric amounts of imidazoline 175 for the MBH reactions of various aromatic aldehydes with unactivated acrylates. Furthermore, the imidazolines were also suitable promoters for reactions between aromatic aldehydes and alkyl vinyl ketone. Using 50 mol.% of imidazoline 176, which bears a chiral methylnaphthyl group, afforded adducts in high yield with up to 78% ee (Scheme 2.86). These chiral imidazolines are readily prepared from commercially available amino alcohols and can be easily recovered for reuse without loss of product enantioselectivity. 

Not all workers, however, are convinced of the validity of the accepted mechanisms for these types of reactions. Tan et al have studied a phase transfer catalysed Williamson ether synthesis by electrochemical methods including cyclic voltammetry [23], and came to the conclusion that... 

Gaseous Effluents. Twenty percent of the carbon disulfide used in xanthation is converted into hydrogen sulfide (or equivalents) by the regeneration reactions. Ninety to 95% of this hydrogen sulfide is recoverable by scmbbers that yield sodium hydrogen sulfide for the tanning or pulp industries, or for conversion back to sulfur. Up to 60% of the carbon disulfide is recyclable by condensation from rich streams, but costly carbon-bed... 

Transparent, homogeneous hybrids using a 50 50 PVAc-to-TEOS mixture and an acid-catalyzed reaction have been produced and characterized by dsc and dms (46). Dsc indicated only a slight increase in the T of the hybrid with incorporation of sihca. Dynamic mechanical tan 8 responses indicate a strong interaction between the organic and inorganic phases and, hence, weU-dispersed phases that lead to high modulus mbbery plateaus. 

Control of chromium penetration, essential to permit tannage of the center of the hide, is accompHshed by pH adjustment. At a pH > 3.0 the reactivity of the hide to the chromium complex is greatiy increased. The pH is therefore raised gradually to the desired point by addition of a mild alkah, usually sodium bicarbonate. The chemistry of chrome tanning involves competing reactions that must be controlled for satisfactory results. 

Chrome Tanning. The original chrome tanning was a two-bath process. The unhaired hides, delimed and bated, were treated with a solution of sodium bichromate [10588-01-9]. The amount of bichromate used was about 3—5% based on the weight of the hides. The bichromate was absorbed or adsorbed into the hide, the solution drained, and the hides refloated. Sodium bisulfite was added and two important reactions resulted in the formation of a basic chromium and coUoidal sulfur in the hide. This gave a chrome taimage and also helped to fiH the hide with the soHd sulfur. This cmde system, which continued in the industry in some types of leather for over 50 years, is obsolete. 

Lithium Acetylide. Lithium acetyhde—ethylenediamine complex [50475-76-8], LiCM7H -112X01120112X112, is obtained as colodess-to-light-tan, free-flowing crystals from the reaction of /V-lithoethylenediamine and acetylene in an appropriate solvent (131). The complex decomposes slowly above 40°O to lithium carbide and ethylenediamine. Lithium acetyhde—ethylenediamine is very soluble in primary amines, ethylenediamine, and dimethyl sulfoxide. It is slightly soluble in ether, THF, and secondary and tertiary amines, and is insoluble in hydrocarbons. 

Sihcon nitride occurs in two forms, a-Si N and P-Si N. Pure Si N is white, but the colors of commercial materials may be tan, gray, or black because of residual siUcon or impurities. Si N may be prepared by nitriding siUcon powder at 1200—1400°C or, for extremely fine-grained Si N, by the reaction of SiCl or SiH and N2 or NH (see also Advanced ceramics). 

OxazoHdines, formed by reaction of alkanolamines with aldehydes, ate useful as leather tanning agents and ate effective curing agents for proteins, phenoHc resins, moisture-cure urethanes, etc. They also find use as antimicrobial agents. 

Dynamic techniques are used to determine storage and loss moduli, G and G respectively, and the loss tangent, tan 5. Some instmments are sensitive enough for the study of Hquids and can be used to measure the dynamic viscosity T 7 Measurements are made as a function of temperature, time, or frequency, and results can be used to determine transitions and chemical reactions as well as the properties noted above. Dynamic mechanical techniques for sohds can be grouped into three main areas free vibration, resonance-forced vibrations, and nonresonance-forced vibrations. Dynamic techniques have been described in detail (242,251,255,266,269—279). A number of instmments are Hsted in Table 8. Related ASTM standards are Hsted in Table 9. 

The Rheometric Scientific RDA II dynamic analy2er is designed for characteri2ation of polymer melts and soHds in the form of rectangular bars. It makes computer-controUed measurements of dynamic shear viscosity, elastic modulus, loss modulus, tan 5, and linear thermal expansion coefficient over a temperature range of ambient to 600°C (—150°C optional) at frequencies 10 -500 rad/s. It is particularly useful for the characteri2ation of materials that experience considerable changes in properties because of thermal transitions or chemical reactions. 

Tantalum Nitrides. Tantalum nitride [12033-62-4] TaN, is produced by direct synthesis of the elements at 1100°C. Very pure TaN has been produced by spontaneous reaction of lithium amide, L1NH2, and TaCl ( )- The compound is often added to cermets in 3—18 wt %. Ta N [12033-94-2] is used as a red pigment in plastics and paints (78). 

How does this unlocking occur Figure 19.1 shows a dislocation which cannot glide because a precipitate blocks its path. The glide force rb per unit length, is balanced by the reaction /o from the precipitate. But unless the dislocation hits the precipitate at its mid-plane (an unlikely event) there is a component of force left over. It is the component ib tan 0, which tries to push the dislocation out of its slip plane. 

To the cooled reaction mixture, 200 ml. of water is added carefully with stirring. Potassium carbonate is added with continued stirring until the water layer is saturated the mixture is now transferred to a separatory funnel and extracted three times with 60-ml. portions of ether. The combined ether extracts are dried over solid sodium hydroxide and are then transferred to a simple distillation apparatus. Distillation is commenced with a steam bath as source of heat when most of the ether has been removed, the steam bath is replaced by a flame. Distillation is continued until most of the piperidine (b.p. 106°) has been removed. The cooled residue in the distillation flask is recrystallized from petroleum ether (boiling range 30-60°) with the use of charcoal. There is obtained 30.0 g. (71%) of N-/3-naphthyl-piperidine as tan crystals, m.p. 52-56°. An additional recrystallization from the same solvent gives crystals, m.p. 56-58°, with about 10% loss in weight (Note 6). 

The other class of primary antioxidants are the phenols (hindered phenols, hindered bisphenols, hindered thiobisphenols, polyhydroxy phenols) (Fig. 34). Phenolic antioxidants are generally used when the discolouration of the amine antioxidants cannot be tolerated. Phenols may produce coloured reaction products (yellow, tan or pink) but the discolouration is significantly less than produced with amines. 

Tan et al. investigated polymers made from bis-benzocyclobutenes [13-15]. As the benzocyclobutane is analogous to tbe dien, tbe Diels-Alder addition takes place. This reaction is applied to the preparation of polyimides. The advantage of this system is that the resultant polymer is oxidized to form thermally stable aromatic polyimides (Fig. 7). 

Formaldehyde has been rated as a possible carcinogen by the United States Occupational Safety and Health Act (OSHA) rules and should be handled with due caution. It is also a strong lacrymator and choking respiratory irritant. It irritates the skin, eyes, and mucous membranes [76]. Since it is used for tanning leather, it is obvious that fonnaldehyde has a high potential for reactions with proteins. Formaldehyde gas is flammable and most formalin solutions contain significant amounts of methanol, which is also volatile, toxic, and flammable. 

The scale-up of exothermic processes is greatly enhanced through the use of the coefficient of thermal stability. Kafarov [2] defined this as the ratio of the slope (tan ttj) of the line representing the heat removal (due to the heat transfer medium and changes in enthalpy) to the slope (tan ttj) of the line representing heat generation (by the reaction) at the intersection of the two lines when plotted on the T versus Q coordinates. This is expressed as... 

An iinportaiit compound is the mixed methyl-raetl lene derivative of bis(cylopentadlenyl)tan-takjm(V) piepared by the following sequence of high-yield reactions ... 

The reaction of 17 g (0.177 mole) of 2-cycIohexene-l-one under the conditions previously described gives about 29 g of tan solid on cooling. Several recrystallizations may be necessary to remove a small amount of isomer formed. The pure product has mp 138-141°. 

Melting points were taken at Intervals in order to gain an idea of the extent of reaction. The final residue was boiled with alcohol but since the solid exhibited insufficient solubility in the hot solvent, the mixture was filtered. The residue consisted of tan crystals, MP about 220°-221 G, and the filtrate on cooling gave an additional crop of tan crystals, MP about 219°-221°C. The two materials were identical and consisted of diphenimide. 

About 23 g (0.095 mol) of 1-ethyl-6,7 methylenedioxy-4(1H)-oxocinnoline-3concentrated hydrochloric acid and 200 ml of acetic acid. The resultant reaction mixture was heated under reflux for IB hours. The excess acids were removed under vacuum, and the residue was taken up in 150 ml of a 5% sodium bicarbonate solution. The resultant solution was treated with 5 g of charcoal and filtered. The filtrate was made acidic by the addition of hydrochloric acid and the resulting precipitate was removed by filtration. 23 g, representing a yield of 91.6% of 1-ethyl-6,7-methylenedioxy-4(1H)-oxocinnoline-3<arboxylic acid as light tan crystals which melted at 261°C to 262°C with decomposition were recovered. 

A solution of 10.0 grams of purified S-methyl ether of 2-thio-5-fluorouracil, MP 230° to 237°C, in 150 ml of concentrated aqueous hydrochloric acid (containing approximately 37% by weight HCI) was refluxed under nitrogen for 4 hours. The reaction mixture was then evaporated in vacuo. The crystalline brownish residue was recrystallized from water. The resulting recrystallized product was further purified by sublimation in vacuo at 190° to 200°C (bath temperature)/0.1 mm pressure. There was obtained 5-fluorouracil, in the form of colorless or pinkish-tan crystals, MP 282° to 283°C (with decomposition). 

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