Chloroformate resin

The chloroformate resin is readily prepared immediately before use and hence its stability to long-term storage has not been explored. However, no special precautions were needed in handling the resin and no stability problems were observed during the course of this work. The FT-IR spectrum of sampled beads showed no sign of a hydroxyl signal. 

A solid-phase Ugi-Reissert reaction on chloroformate resin, has been reported. The product, the ot-carbamoylated isoquinoline 230, is released by oxidative cleavage (Scheme 33a). Interestingly, the enamide moiety in the adduct can be exploited to perform this process in tandem with a Povarov MCR [189, 190]. In this way, by interaction of dihydroisoquinoline 231 with aldehydes, anilines and a suitable Lewis acid catalyst, the polyheterocyclic system 232 was prepared (Scheme 33b). The Zhu group devised an innovative approach for the synthesis of this class of compounds. They employed the heterocyclic amine 233, which was oxidized in situ to the dihydroisoquinoline 234 with IBX, to undergo the classic Ugi reaction. Remarkably, all the components are chemically compatible, allowing the sequence to proceed as a true MCR (Scheme 33c) [191]. 

The synthesis of this scaffold requires a set of diverse anthranilic acids 71, of which only a few are commercially available. A variety of these was prepared by nucleophilic substitution of 2-chlorobenzoic acid 70 with a range of primary amines (alkyl, benzyl, phenyl). These anthranilic acids 71 were bound to a polysty-rene/triethyleneglycol chloroformate resin through the amine group (72). Amidation of the carboxylic acid function gave 73 and reaction at 125 °C in DMF gave the cyclized product 74 (Scheme 20) [33]. 

NaOH Cannizzaro s reaction < yellow resin > chloroform on heating Cannizzaro s reaction yellow coloration... 

SAN resins show considerable resistance to solvents and are insoluble in carbon tetrachloride, ethyl alcohol, gasoline, and hydrocarbon solvents. They are swelled by solvents such as ben2ene, ether, and toluene. Polar solvents such as acetone, chloroform, dioxane, methyl ethyl ketone, and pyridine will dissolve SAN (14). The interactions of various solvents and SAN copolymers containing up to 52% acrylonitrile have been studied along with their thermodynamic parameters, ie, the second virial coefficient, free-energy parameter, expansion factor, and intrinsic viscosity (15). 

Pyrrole is a colorless, slightly hygroscopic Hquid which, if fresh, emits an odor like that of chloroform. However, it darkens on exposure to air and eventually produces a dark brown resin. It can be preserved by excluding air from the storage container, preferably by displacement with ammonia to prevent acid-catalyzed polymerization. A review of the physical and theoretical aspects of pyrrole is found in Reference 4. Some physical properties of pyrrole are Hsted in Table 1. 

Succinic acid is absorbed from aqueous solutions by anion-exchange resins or active carbon (9—11). Succinic anhydride forms rhombic pyramidal or bipyramidal crystals. It is relatively insoluble in ether, but soluble in boiling chloroform and ethyl acetate. Succinic anhydride reacts with water and alcohols, giving the acid and monoesters, respectively. 

The physical piopeities of ethyl chloiide aie hsted in Table 1. At 0°C, 100 g ethyl chloride dissolve 0.07 g water and 100 g water dissolve 0.447 g ethyl chloride. The solubihty of water in ethyl chloride increases sharply with temperature to 0.36 g/100 g at 50°C. Ethyl chloride dissolves many organic substances, such as fats, oils, resins, and waxes, and it is also a solvent for sulfur and phosphoms. It is miscible with methyl and ethyl alcohols, diethyl ether, ethyl acetate, methylene chloride, chloroform, carbon tetrachloride, and benzene. Butane, ethyl nitrite, and 2-methylbutane each have been reported to form a binary azeotrope with ethyl chloride, but the accuracy of this data is uncertain (1). 

Nearly all of the benzyl chloride [100-44-7], henzal chloride [98-87-3], and hen zotrichl oride /P< -(97-i manufactured is converted to other chemical intermediates or products by reactions involving the chlorine substituents of the side chain. Each of the compounds has a single primary use that consumes a large portion of the compound produced. Benzyl chloride is utilized in the manufacture of benzyl butyl phthalate, a vinyl resin plasticizer benzal chloride is hydrolyzed to benzaldehyde hen zotrichl oride is converted to benzoyl chloride. Benzyl chloride is also hydrolyzed to benzyl alcohol, which is used in the photographic industry, in perfumes (as esters), and in peptide synthesis by conversion to benzyl chloroformate [501-53-1] (see Benzyl ALCOHOL AND p-PHENETHYL ALCOHOL CARBONIC AND CARBONOCm ORIDIC ESTERS). 

The resin is fairly soluble in aleohol, ether and chloroform and is decomposed by nitric acid. It becomes thermoplastic at temperatures above 150°C and decomposes at a temperature rather below 300°C, yielding an oil of amber and leaving a residue known as amber colophony or amber pitch. 

The methacrylic backbone structure makes the spherical Toyopearl particles rigid, which in turn allows linear pressure flow curves up to nearly 120 psi (<10 bar), as seen in Fig. 4.45. Toyopearl HW resins are highly resistant to chemical and microbial attack and are stable over a wide pH range (pH 2-12 for operation, and from pH 1 to 13 for routine cleaning and sanitization). Toyopearl HW resins are compatible with solvents such as methanol, ethanol, acetone, isopropanol, -propanol, and chloroform. Toyopearl HW media have been used with harsh denaturants such as guanidine chloride, sodium dodecyl sulfate, and urea with no loss of efficiency or resolution (40). Studies in which Toyopearl HW media were exposed to 50% trifluoroacetic acid at 40°C for 4 weeks revealed no change in the retention of various proteins. Similarly, the repeated exposure of Toyopearl HW-55S to 0.1 N NaOH did not change retention times or efficiencies for marker compounds (41). 

Figures 13.25-13.28 show the ultrahigh resolution separations in chloroform of polystyrene standards, polytetramethylene glycol, urethanes and isocyanates, and epoxy resins, respectively. Multiple column sets of anywhere from two to six columns in series have been used for well over a year with no apparent loss of efficiency. The 500- and 10 -A gels can easily tolerate 15,000 psi or more. In fact, the limiting factor in the number of columns that can be used in series is generally the pump or injector in the FIPLC system. A pump capable of 10,000 psi operation should allow the use of a column bank of 10-12 50-cm columns with a total plate count of 500,000 or more.

FIGURE 13.28 Different epoxy resins run in chloroform, analysis times of 160 min, and column temperature maintained at 50°C. 

This Fmoc analog is prepared from the chloroformate, O-succinimide, or p-nitrophenyl carbonate and is cleaved with 10% piperidine in 1 1 6M guanidine/IPA. It was designed to interact strongly on a column of porous graphitized carbon so as to aid in the purification of peptides after cleavage from the resin. 

After consecutive elutions with pure benzene, and benzene containing increasing proportions of chloroform, 0.748 g of 1 -diethyl amino ethyl-reserpine is isolated in the form of a resin. The crystalline acid bitartrate prepared in ethyl acetate melts at 145°-150°C, with decomposition. 

To a solution of 20 parts of thiamine hydrochloride in 30 parts of water is added an aqueous solution of sodium hydroxide (7.2 parts of NaOH in 30 parts of water), and the mixture is cooled with water. The mixture is allowed to stand for 30 minutes, 60 parts of chloroform is added, followed by a solution of 30 parts of crude sodium tetrahydrofurfurylthiosulfate in 30 parts of water, and the whole is stirred for 30 minutes. The chloroform layer is separated and the aqueous layer is extracted twice with 20 parts of chloroform. All the chloroform solutions are combined and shaken with 50 parts of 5% hydrochloric acid. The acid solution is decolorized and neutralized with alkali carbonate, whereupon thiamine tetrahydrofurfuryl disulfide separates out in the resinous state but soon solidifies [MP 129 (decomp.)]. The yield is 16 parts. Recrystallization from ethyl acetate gives colorless prisms melting at 132°C (decomp.). 

Purification of the activation products (PMs). The methylamine activation product dissolved in methanol is purified by chromatography, first on a column of silica gel using a mixed solvent of chloroform/ethanol, followed by reversed-phase HPLC on a column of divinylbenzene resin (such as Jordi Reversed-Phase and Hamilton PRP-1) using various solvent systems suitable for the target substance (for example, acetonitrile/water containing 0.15% acetic acid). 

Dichlorodibenzo- -dioxin. 2-Bromo-4-chlorophenol (31 grams, 0.15 mole) and solid potassium hydroxide (8.4 grams, 0.13 mole) were dissolved in methanol and evaporated to dryness under reduced pressure. The residue was mixed with 50 ml of bEEE, 0.5 ml of ethylene diacetate, and 200 mg of copper catalyst. The turbid mixture was stirred and heated at 200°C for 15 hours. Cooling produced a thick slurry which was transferred into the 500-ml reservoir of a liquid chromatographic column (1.5 X 25 cm) packed with acetate ion exchange resin (Bio-Rad, AG1-X2, 200-400 mesh). The product was eluted from the column with 3 liters of chloroform. After evaporation, the residue was heated at 170°C/2 mm for 14 hours in a 300-cc Nestor-Faust sublimer. The identity of the sublimed product (14 grams, 74% yield) was confirmed by mass spectrometry and x-ray diffraction. Product purity was estimated at 99- -% by GLC (electron capture detector). 

A PET oligomer isolation method has utilised chloroform extraction in a Parr bomb lined with a Teflon-TFE fluoro-carbon resin [40]. The analytics of fluoropolymer processing aids (combustion analysis, XRF, EUR, 19F NMR, OM) have recently been described [29]. Combustion analysis (Parr Oxygen Bomb Calorimeter) can be used for quantitative analysis... 

Polyester resins Chloroform-di, acetone-dg, DMSO-dg Ambient... 

Peroxidic groups in oxidized polyolefins have frequently been employed as sources of free radicals to allow grafting of vinyl monomers to polyolefins (2f[). Some of the products from the gas reactions also have interesting potential as reactive sites. For example, chloroformate groups are well known to react with alcohols, and amines 2J[). Thus chloroformate groups could be useful for example in coupling highly oriented polyolefin fibres to resins such as epoxy based systems. 

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