Distillate yields from COED

Table XI. Chemical Weight Percent Yields from COED Distillates...

In a suitably adapted glass reaction vessel were placed anhyd Na CO, (42.5 g, 0.4 tnol) and anhyd bis(2-methoxymethyl) ether (diglyme) (75 niL). To (he stirred slln ry was added pcrfluoro(2-propoxypropanoyl fluoride) (96 g, 0.29 mol). Within a few min a slow exothermic reaction occurred, and the temperature rose to about 60 C. The substrate, removed from the reaction flask by distillation during the reaction, was collected in a cold trap and returned to the reaction flask. The mixture was then heated to 140 C for. 10 min. after which time the reaction was complete. The crude product was purilied by distillation yield 75.6 g (98%) bp 35 36 C. 

Use of a co-amine is embodied in an improved procedure for the preparation of A -octalin. A mixture of 0.2 mole of naphthalene and 250 ml. each of ethylamine and dimethylamine is placed in a flask fitted with a dry ice condenser, 1.65 g.-atoms of lithium wire cut in half-centimeter pieces is added all at once, and the mixture is stirred magnetically for 14 hrs. The solvent mixture is allowed to evaporate and the grayish white residue (containing excess lithium) is decomposed by cautious addition of about 100 ml. of water with cooling. The precipitated product is collected and the filtrate extracted with ether distillation affords 19-20 g. of hydrocarbon found by VPC analysis to contEiin 80% of A "-octalin and 20% of A -octalin. Isolation of the major product in pure form is accomplished by reaction of the mixture with bis-3-methyl-2-butylborane, which adds selectively to the less hindered A -isomer. Oxidation of the product with hydrogen peroxide to convert the adduct into an easily separated alcohol, followed by distillation, affords A" " -octalin of 99% purity in yield from naphthalene of 50-54%,... 

The analysis of basil oil has been reviewed [49-53]. Extraction of basil leaves with CO2 containing ethanol as an extrainer has been reported [13]. At pressures of 200 bar and 40°C an extract was obtained which was subsequently fractionated at 56 bar and 15°C to yield 1.3% of oil. This was from a batch of leaf which had a steam-distilled yield of only 0.5%. The CO2 extraction of basil was first reported by Pekhov and his co-workers at KNIIPP in Russia [54], who compared it to the steam-distilled oil of East Indian basil Ocimum gratissimum). 

The conversion of methanol and ammonia to methylamines is achieved over dehydration catalysts operated in the temperature range 300450°C and 0.12 MPa pressure. The reactions are exothermic, and excess ammonia is used to control the product distribution. The dehydration catalysts are generally promoted Si-Al composites. The promoters include molybdenum sulfide and silver phosphate [68]. In the commercial Leonard process, a gas-phase downflow catalytic reactor operating at about 350°C and 0.62 MPa is used [69]. Recovery of the desired product is achieved throu a series of four distillation and extractive distillation columns. Unwanted product is recycled, suppressing further formation of the undesired component in the reactor. A very small amount of methanol is lost to CO and H2, and yields from the commercial process based on methanol and anunonia are >97% [70]. 

The w cod when distilled in Europe yields from 7 co 9 per cent, of oil, hut, whether this is due to better methods of distillation or to an after devrloprueut of oil in the wood is a matter of uncertainty. 

Homogeneous rhodium-catalyzed hydroformylation (135,136) of propene to -butyraldehyde (qv) was commercialized in 1976. -Butyraldehyde is a key intermediate in the synthesis of 2-ethyIhexanol, an important plasticizer alcohol. Hydroformylation is carried out at <2 MPa (<290 psi) at 100°C. A large excess of triphenyl phosphine contributes to catalyst life and high selectivity for -butyraldehyde (>10 1) yielding few side products (137). Normally, product separation from the catalyst [Rh(P(C2H2)3)3(CO)H] [17185-29-4] is achieved by distillation. 

Sasol Fischer-Tropsch Process. 1-Propanol is one of the products from Sasol s Fischer-Tropsch process (7). Coal (qv) is gasified ia Lurgi reactors to produce synthesis gas (H2/CO). After separation from gas Hquids and purification, the synthesis gas is fed iato the Sasol Synthol plant where it is entrained with a powdered iron-based catalyst within the fluid-bed reactors. The exothermic Fischer-Tropsch reaction produces a mixture of hydrocarbons (qv) and oxygenates. The condensation products from the process consist of hydrocarbon Hquids and an aqueous stream that contains a mixture of ketones (qv) and alcohols. The ketones and alcohols are recovered and most of the alcohols are used for the blending of high octane gasoline. Some of the alcohol streams are further purified by distillation to yield pure 1-propanol and ethanol ia a multiunit plant, which has a total capacity of 25,000-30,000 t/yr (see Coal conversion processes, gasification). 

The catalyst, 3-benzyl-5-(2-hydroxyethyl )-4-methyl-l, 3-thiazoHum chloride, is supplied by Fluka AG, Buchs, Switzerland, and by Tridom Chemical, Inc., Hauppauge, New York. The thiazolium salt may also be prepared as described below by benzylation of 5-(2-hydroxyethyl)-4-methyl-l,3-thiazole which is commercially available from E. Merck, Darmstadt, West Germany, and Columbia Organic Chemicals Co., Inc., Columbia, SC. The acetonitrile used by the checkers was dried over Linde 3A molecular sieves and distilled under nitrogen, bp 77-78°C. The same yield of thiazolium salt was obtained by the checkers when benzyl chloride and acetonitrile from commercial sources were used without purification. 

Satisfactory sebacoyl chloride can be purchased from the Eastman Kodak Co., Rochester, New York. The submitters prepared it as follows. A mixture of 150 g. (0.74 mole) of sebacic acid and 150 ml. of thionyl chloride is heated in a water bath at 60°. The acid gradually goes into solution with evolution of sulfur dioxide and hydrogen chloride. When gas evolution ceases, the mixture is distilled as rapidly as possible under reduced pressure. The yield of sebacoyl chloride, b.p. 171-175°/15 mm., is about 140 g. (79%). Caution1 Toward the end of the distillation, spontaneous decomposition of the residue with formation of a voluminous black foam frequently occurs. 

The submitters used THF that was freshly distilled over Na/K alloy NMP was distilled over CaH2. The checkers used commercially available anhydrous THF and NMP obtained from Aldrich Chemical Co. There appears to be a slight increase in yield when THF distilled from sodium/benzophenone ketyl is used instead of the commercial THF. All other solvents used were of reagent grade quality and were used without further purification. 

Co. and 20 mM nitrite in water, pH 3, 25 C, 60 min reaction], it was nitrosated to yield 3.62 mM 2,6-dimethyl-N-nitrosomorpho-line (DMNM), which was a 10% greater yield than that for a similar nitrosation of morpholine to give NMOR. This indicated a slightly larger rate constant for DMNM than for NMOR formation (3). Crude DMM is a 2 1 mixture of the cis and trans isomers ( 0). GC analysis of the product of the kinetic run showed that the 2 isomers were nitrosated at similar rates. Cis-DMNM [retention time (RT), 320 sec] was well separated from NMOR (RT, 430 sec), but trans-DMNM (RT, 405 sec) was not. Accordingly, we prepared pure cis-DMM, b.p. 133 C, by spinning-band fractional distillation of crude DMM and used it in the analytical procedure. The RT of N-nitrosopyrrolidine (NPYR) was 390 sec. 

In some cases we may benefit from adopting a semi-continuous mode of operation, e.g. to a batch of one reactant we continuously feed the other reactant, while removing a volatile product continuously. An example where this is advantageous is the production of ethyl-4-pentenoate, CH2=(CH2)3(CO)OEt from allyl alcohol and triethyl orthoacetate, CHs-CfOEt). Continuous addition of allyl alcohol to a batch of triethyl orthoacetate and continuous removal of the produced ethylalcohol (and. some allyl alcohol) by distillation resulted in high yields of the dersired ester ethyl-4-pentenoate. By contrast, if allyl alcohol and triethyl orthoacetate were reacted in a batch-wise manner the product consisted of a 1 1 mixture of the desired ester and the undesired ester (Anderson, 2000, p 279 Bollyn and Wright, 1998). 

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