Crystallization following carbon treatment

Scheme 9.28). Despite the modest enantioselectivity, we knew from our previous work that upgrade of enantiomeric purity was possible via preferential removal of the less soluble racemic material by crystallization. In this manner, after a carbon treatment to achieve acceptable levels of residual rhodium, racemic 1 was removed by partial crystallization, followed by subsequent isolation of 1 as a crystalline solid in 72% yield from 22, and in 98.5% ee. 

Grayish-white metal hody-centered cubic crystalline structure density 19.3 g/cm3 melts at 3,422°C vaporizes at 5,555°C vapor pressure 1 torr at 3,990°C electrical resistivity 5.5 microhm-cm at 20°C modulus of elasticity about 50 to 57 x lO psi (single crystal) Poisson s ratio 0.17 magnetic sus-ceptibilty +59 x 10-6 thermal neutron absorption cross section 19.2 + 1.0 barns (2,200m/sec) velocity of sound, about 13,000 ft/sec insoluble in water practically insoluble in most acids and alkabes dissolves slowly in hot concentrated nitric acid dissolves in saturated aqueous solution of sodium chlorate and basic solution of potassium ferricyanide also solubibzed by fusion with sodium hydroxide or sodium carbonate in the presence of potassium nitrate followed by treatment with water... 

Chemically related to barium, radium is recovered from its ores by addition of barium salt, followed by treatment as fur recovery of barium, usually as the sulfate. The sulfates of barium and of radium are insoluble in most chemicals, so they arc transformed into carbonate or sulfide, both of which are readily soluble in HC1. Separation from barium is accomplished by fractional crystallization of the chlorides (or bromides, or hydroxides). Dry, concentrated radium salts are preserved in sealed glass tubes, which are periodically opened by experienced workers to relieve the pressure, The glass tubes are kept m lead shields,... 

This is where the synthesis of nano-sized molecular sieves is carried out in the template matrix within confined spaces. This is an ideal synthetic route if the space size and uniformity favor the crystallization, and the as-synthesized product is easily isolated from the templates. Mesoporous molecular sieves with uniform mesopore structures can be adopted as the template, such as MCM-41. In 2000, Schmidt et al.[127] first proposed such a route to synthesize ZSM-5 nanocrystals. The synthesis procedure consisted of the impregnation of mesoporous carbon black with reaction solution, followed by treatment with steam at 150 °C, and the combustion of carbon black. Compared with other methods, the advantage of this one is that the nano-sized product is easily isolated and the yield is relatively higher. However, it also has some drawbacks. First, there is a high requirement for the preparation of carbon black as the template matrix, i.e., the mesopore sizes in carbon black must be uniform. Second, the crystallization must be performed in the mesopores, not on the extra surfaces of the carbon black. Third, a large amount of carbon black will be consumed (about four-times that of the nanozeolite product). All of these factors affect the further development of this route to some degree. 

In operations that do not include a stage of distillation or crystallization, ion-exchange resins have been employed to remove inorganic compounds, alkalinity, or acidity not adsorbable by activated carbon. In general, the use of the ion-exchanger should follow the treatment with carbon, especially if the carbon contains any appreciable amount of soluble inorganic compounds. 

To explore the difficulties in practical implementation of the above concepts, mixed matrix membranes, with 20% molecular sieves (by volume), were prepared by solution deposition on top of a porous ceramic support. The ceramic supports used were Anodise membrane filters which had 200 A pores that open into 2000 A pores and offer negligible resistance to gas flow. Initially the molecular sieve media, zeolites (4A crystals) or carbon molecular sieves, was dispersed in the solvent, dichloromethane, to remove entrapped air. After two hours, Matrimid was added to the mixture, and the solution was stirred for four hours. The solutions used varied in polymer content from 1-5 wt %. The solution was then deposited on top of the ceramic support, and the solvent was evaporated in a controlled manner. The membranes were then dried overnight at 90°C under vacuum. This was followed by a reactive intercalation post treatment technique 15) to eliminate defects. This technique involves imbibing a reactive monomer (e.g. diamine) from an inert solvent (e.g. heptane) into any micro defects. Next, a second reactive monomer (e.g. acid chloride) was introduced to reactively close defects by forming a low permeability polymer. The membranes were dried again to remove the inert solvent. Individual membrane thickness was determined by weight gain and varied from 5 to 25 Jim. 

The reaction conditions were optimized to afford clean coupling of enol tosylate 32 using only a slight excess of amide 24 (1.05equiv) at 100 °C, 5mol% Pd2(dba)3/ dppb catalyst, and a toluene/tert-amyl alcohol solvent system. Even under the harsh reaction conditions required for complete conversion of the tosylate (100 °C, 20 h) no detectable E/Z isomerization was seen, providing further proof that the hindered nature of the enamide aids stability to isomerization. Treatment of the mixture with activated carbon (Darco KB-B) at the end of the reaction followed by isolation of the product by crystallization, afforded enamide 22 in 92% isolated yield. 

D-Glucosamine hydrochloride (25 g.) and 6.1 g. of sodium carbonate are dissolved in 50 ml. of water. Then, 25 ml. of ethyl acetoacetate is added, followed by enough acetone to make the liquid homogeneous. The mixture is kept for four days and is then evaporated to dryness under diminished pressure. The residue is recrystallized from water, with treatment with Norit, and the crystals are dried over anhydrous calcium chloride yield, 10.8 g. m. p., 141-142°.58... 

A variation of the CD process for PbSe involved deposition of a basic lead carbonate followed by selenization of this film with selenosulphate [64]. White films of what was identified by XRD as 6PbC03-3Pb(0H)2-Pb0 (denoted here as Pb—OH—C) were slowly formed over a few days from selenosulphate-free solutions that contained a colloidal phase and that were open to air (they did not form in closed, degassed solutions). CO2 was necessary for film formation—other than sparse deposits, no film formation occurred of hydrated lead oxide under any conditions attempted in this study. Treatment of these films with selenosulphate solution resulted in complete conversion to PbSe at room temperature after 6 min. The selenization process of this film was followed by XRD, and it was seen to proceed by a breakdown of the large Pb—OH—C crystals to an essentially amorphous phase of PbSe with crystallization of this phase to give finally large (ca. 200 nm) PbSe crystals covered with smaller (15-20 nm) ones as well as some amorphous material. 

HaS or HI, so as to form lead carbonate, sulfide or iodide oidy on the surface without penetration into the crystal (Ref 22). This treatment will unquestionably reduce the efficiency of LA because it will be contaminated by inert materials l)Solubiliry of LA in water or in 50% alcohol was detd as described in item VII F tinder Lead Azide Plant Analytical Procedures In addn to above listed tests, the various LA s were loaded in M47 caps as intermediate chges together with NOLNo 130 as a primary chge and RDX as a base chge and subjected to the following tests given in the Purchase Description PA-PD-202, with Rev 1 dated 30 Sept 1952 and Amend 1 dated 27 Jan 1953 ... 

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