Atmosphere nitrogen

Figure Bl.20.6. Short-range adliesion of a mica-mica contact as a fiinction of the relative crystallographic orientation of the mica surfaces, measured in a dry nitrogen atmosphere. With penuission from [94].

Many organolithium compounds may be prepared by the interaction of lithium with an alkyl chloride or bromide or with an aryl bromide in dry ethereal solution In a nitrogen atmosphere ... 

If preferred, the apparatiaa depicted in Fig. II, 7, 13 may be used. This enables an oxygen-free nitrogen atmosphere to be maintained in the apparatus and leads to the best yield of phenyl-lithium. 

As pointed out in Note 1 a nitrogen atmosphere is preferred for the preparation of organolithium compounds. In the present example exclusion of oxygen is attained fairly satisfactorily by keeping the solution at the reflux point throughout an atmosphere of ether vapour is thus maintained. 

The mercury-sealed stirrer may be replaced by a Kyrides stirrer (Fig. II, 7, 12) formed from a P.V.C. gland and lubricated with a mixture of vaseline and light paraffin. The continuous passage of nitrogen may be dispensed with if a fairly wide tube dipping into a little mercury is connected to the top of the condenser the latter serves to retain the nitrogen atmosphere. 

The reaction mixture in ethyl acetate is then transferred to a 100-ml reactor, purged under a nitrogen atmosphere, 340 mg of Lil is added, and the whole mass is then heated, with mechanical stirring, on an oil bath, up to ethyl acetate reflux temperature. The heating is continued for 5 hours, until the disappearance of the epoxide (II), as evidenced by the thin-layer chromatography. 

The benzoic acid derivative 457 is formed by the carbonylation of iodoben-zene in aqueous DMF (1 1) without using a phosphine ligand at room temperature and 1 atm[311]. As optimum conditions for the technical synthesis of the anthranilic acid derivative 458, it has been found that A-acetyl protection, which has a chelating effect, is important[312]. Phase-transfer catalysis is combined with the Pd-catalyzed carbonylation of halides[3l3]. Carbonylation of 1,1-dibromoalkenes in the presence of a phase-transfer catalyst gives the gem-inal dicarboxylic acid 459. Use of a polar solvent is important[314]. Interestingly, addition of trimethylsilyl chloride (2 equiv.) increased yield of the lactone 460 remarkabiy[3l5]. Formate esters as a CO source and NaOR are used for the carbonylation of aryl iodides under a nitrogen atmosphere without using CO[316]. Chlorobenzene coordinated by Cr(CO)j is carbonylated with ethyl formate[3l7]. 

A stirred solution of o-methylpivalanilide (50 mmol) in dry THE (100 ml) was maintained at 15°C under a nitrogen atmosphere. A 1.5 M solution of n-butyllithium in hexane (3 equiv.) was added dropwise. The solution was then maintained at room temperature for 16h. The solution was cooled in an ice-bath and treated with 2 N HCl (60 ml). The organic layer was separated and the aqueous layer was further extracted with benzene. The combined layers were dried (MgS04). The product was obtained in 87% yield and recrystallized from ether-cyclohexane. 

To achieve the very low initial fluorine concentration in the LaMar fluorination process initially a helium or nitrogen atmosphere is used in the reactor and fluorine is bled slowly into the system. If pure fluorine is used as the incoming gas, a concentration of fluorine may be approached asymptotically over any time period (Fig. 3). It is possible to approach asymptotically any fluorine partial pressure in this manner. The very low initial concentrations of fluorine in the system greatiy decreases the probabiUty of simultaneous fluorine coUisions on the same molecules or on adjacent reaction sites. 

Process. Any standard precursor material can be used, but the preferred material is wet spun Courtaulds special acrylic fiber (SAF), oxidized by RK Carbon Fibers Co. to form 6K Panox B oxidized polyacrylonitrile (PAN) fiber (OPF). This OPF is treated ia a nitrogen atmosphere at 450—750°C, preferably 525—595°C, to give fibers having between 69—70% C, 19% N density less than 2.5 g/mL and a specific resistivity under 10 ° ohm-cm. If crimp is desired, the fibers are first knit iato a sock before heat treating and then de-knit. Controlled carbonization of precursor filaments results ia a linear Dow fiber (LDF), whereas controlled carbonization of knit precursor fibers results ia a curly carbonaceous fiber (EDF). At higher carbonizing temperatures of 1000—1400°C the fibers become electrically conductive (22). 

The characteristic times for waste destmction to an efficiency of 99.99%, for water in a nitrogen atmosphere, where the residue is a typical hydrocarbon breaking into two large fragments, eg, / -butane decomposing into two ethyl radicals would be droplet heatup, 0.073 s droplet evaporation,... 

The most overlooked hazard and contaminant is water (99). Water reacts with isocyanates at room temperature to yield both ureas and large quantities of carbon dioxide. The presence of water or moisture can produce a sufficient amount of CO2 to overpressurize and mpture containers. As Httle as 30 mL of water can result in 40 L of carbon dioxide which could result in pressures of up to 300 kPa (40 psi). For these reasons, the use of dry nitrogen atmospheres is recommended during handling. If a plant air system must be used, purification equipment, such as oil traps and drying beds, should be installed between the source and the isocyanate vessel. 

The reactor charge is heated to 140°C under a nitrogen atmosphere and the monomer charge and initiator charge are added uniformly over three hours while maintaining 140 2°C. After the additions are complete, this temperature is maintained for two more hours, then the product is cooled and packaged. A clear, viscous solution of about 58% polymer is obtained (63). 

In a vacuum, uncoated molybdenum metal has an unlimited life at high temperatures. This is also tme under the vacuum-like conditions of outer space. Pure hydrogen, argon, and hehum atmospheres are completely inert to molybdenum at all temperatures, whereas water vapor, sulfur dioxide, and nitrous and nitric oxides have an oxidizing action at elevated temperatures. Molybdenum is relatively inert to carbon dioxide, ammonia, and nitrogen atmospheres up to about 1100°C a superficial nitride film may be formed at higher temperatures in the latter two gases. Hydrocarbons and carbon monoxide may carburize molybdenum at temperatures above 1100°C. 

Manufacture is either by reaction of molten sodium with methyl alcohol or by the reaction of methyl alcohol with sodium amalgam obtained from the electrolysis of brine in a Castner mercury cell (78). Both these methods produce a solution of sodium methylate in methanol and the product is offered in two forms a 30% solution in methanol, and a soHd, which is a dry, free-flowing white powder obtained by evaporating the methanol. The direct production of dry sodium methylate has been carried out by the introduction of methanol vapors to molten sodium in a heavy duty agitating reactor. The sohd is supphed in polyethylene bags contained in airtight dmms filled in a nitrogen atmosphere. 

In an alternative industrial process, resorcinol [108-46-3] is autoclaved with ammonia for 2—6 h at 200—230°C under a pressurized nitrogen atmosphere, 2.2—3.5 MPa (22—35 atm). Diammonium phosphate, ammonium molybdate, ammonium sulfite, or arsenic pentoxide maybe used as a catalyst to give yields of 60—94% with 85—90% selectivity for 3-aminophenol (67,68). A vapor-phase system operating at 320°C using a siUcon dioxide catalyst impregnated with gallium sesquioxide gives a 26—31% conversion of resorcinol with a 96—99% selectivity for 3-aminophenol (69). 

Any sihcate that forms thermally and chemically stable residual compounds as its oxygen content is reduced provides a suitable source of siUcon for this reaction. A typical process consists of alternating aluminum, siUca, and graphite plates separated by 2—4-cm thick graphite spacers stacked in a graphite-lined alumina tube and heated to 1400°C for 12 h in a nitrogen atmosphere. After cooling for approximately 6 h the fibers are removed. 

Emmerich Method. This method is for determination of trace amounts of reducing sugars in pure sucrose and white and refined sugars with reducing sugar content up to 0.15%. The test is carried out in a nitrogen atmosphere and is based on the reduction of 3,6-dinitrophthahc acid. 

Sulfurization of unsaturated compounds and meicaptans is normally carried out at atmospheric pressure, in a mild or stainless steel, batch-reaction vessel equipped with an overhead condenser, nitrogen atmosphere, an agitator, heating media capable of 120—215°C temperatures and a scmbber (typically caustic bleach or diethanolamine) capable of handling hydrogen sulfide. If the reaction iavolves the use of H2S as a reactant or the olefin or mercaptan is a low boiling material, a stainless steel pressurized vessel is recommended. 

Eor many polymeri2ations, MEHQ need not be removed instead, polymeri2ation initiators are added. Vinyhdene chloride from which the inhibitor has been removed should be refrigerated in the dark at —10° C, under a nitrogen atmosphere, and in a nickel-lined or baked phenolic-lined storage tank. If not used within one day, it should be reinhibited. 

Pentaphenylbismuth is a violet-colored, crystalline compound that decomposes spontaneously after standing for several days in a dry nitrogen atmosphere. With a variety of agents, eg, hydrohahc acids, halogens, and triphenylboron, one phenyl group is cleaved to form quaternary bismuth compounds. 

Methylene chloride vapor reacts at 300—400°C with a mixture of siHcon and reduced copper under a nitrogen atmosphere to give a mixture of organosiHcon derivatives (11). 

Hydrolysis. Heating 1,2-dichloroethane with excess water at 60°C in a nitrogen atmosphere produces some hydrogen chloride. The rate of evolution is dependent on the temperature and volume of the aqueous phase. Hydrolysis at 160—175°C and 1.5 MPa (15 atm) in the presence of an acid... 

Dimethyl carbonate is available from Aldrich Chemical Company, Inc. The checkers dried the tetrahydrofuran Immediately before use by distillation from the sodium ketyl of benzophenone under a nitrogen atmosphere. The submitters purchased sodium hydride (50% oil dispersion) from Alfa Products, Morton/Thiokol, Inc. The checkers used 12.24 g of a 50% dispersion of sodium hydride in mineral oil obtained from the same supplier. The dispersion was washed with three portions of pentane to remove the mineral oil and the remaining sodium hydride was allowed to dry under nitrogen. 

---