Acids water, adding

A soln. of Nal and Na-acetate in acetic acid-water added at 0° with stirring to a soln. of l,2-epoxy-3-diazirine-5a-androstan-17j -ol in acetic acid, and the product isolated after 24 hrs. at 0° product. Y ca. 60%. F. e. s. P. Borrevang, R. T. Ra-pala et al., Tetrah. Let. 1968, 4905. 

A soln. of GrOg in acetic acid-water added at 75° with gentle stirring to a soln. of pivaloin in H2S04-acetic acid-water, and the hot mixture poured on ice immediately after the reaction has subsided pivalil. Y 87%. M. S. Newman and A. Arkell, J. Org. Ghem. 24, 385 (1959). 

A soln. of 3/9-acetoxy-5,6-seco-5- 0X0 -6- cholestanecarboxylic acid chloride in acetone stirred and treated with aq. NaNs, after 10 min. more water added, after an additional 10 min. the resulting crude acid azide isolated, dissolved in acetic acid, water added, and heated on a steam bath until N2-evolution ceases 3,5-6-azacholestadiene. Y 96%. 

Anhydrous Na-acetate and Zn-dust added with vigorous stirring at 80° to a soln. of ethyl 4,6-dioxo-5-methylheptanoate in glacial acetic acid, then a soln. of ethyl oximinomalonate in acetic acid-water added dr op wise at 95°, and refluxed 1 hr. on a water bath 2,3-dimelhyl-4- (2-ethoxycarbonylethyl) -5-... 

The sea water is first treated with chlorine in acid solution (sulphuric acid is added) and very dilute bromine is obtained by blowing air through the solution. This is mixed with sulphur dioxide and the gases passed up a tower down which water trickles ... 

CH2(0H)CH(0H)CH2(0H) + HCOOH reaches about 100°, losing carbon dioxide and giving glyceryl monoformate (B). On further heating, particularly if more oxalic acid is added, the mono formate is hydrolysed (the necessary water being provided both by the oxalic acid and by the first reaction), and consequently a distillate of aqueous formic acid is obtained. 

Method A, Prepare approximately 90% sulphuric acid by adding 25 ml. of the concentrated acid cautiously with gentle shaking to 5 mh of water. 

Beckmann Rearrangement. Prepare the 85% sulphuric acid by adding 50 ml. of the concentrated acid cautiously to 10 ml. of water, stirring the mixture meanwhile, and then cool the diluted acid in ice-water. Place 16 ml. of the cold acid in a 500 ml. beaker, add 8 g, of the pure oxime, and warm the mixture cautiously until effervescence begins, and then at once remove the heat. A vigorous reaction occurs, and is soon complete. Repeat this operation with another 8 g. of the oxime in a second beaker the reaction is too vigorous to be carried out with larger quantities. 

To obtain the free acid, dissolve the potassium salt in 50 ml. of cold water, filter the solution if a small undissolved residue remains, and then boil the clear solution gently whilst dilute sulphuric acid is added until the separation of the acid is complete. Cool the solution and filter off the pale orange-coloured crystals of the benzilic acid wash the crystals on the filter with some hot distilled water, drain well, and then dry in a desiccator. Yield of crude acid, 4 g. Recrystallise from benzene (about 50 ml.) to which a small quantity of animal charcoal has been added, filtering the boiling solution through a preheated funnel fitted w ith a fluted filter-paper, as the benzilic acid readily crystallises as the solution cools alternatively, recrystallise from much hot water. The benzilic acid is obtained as colourless crystals, m.p. 150°. 

Amino-4 -methylthiazole slowly decomposes on storage to a red viscous mass. It can be stored as the nitrate, which is readily deposited as pink crystals when dilute nitric acid is added to a cold ethanolic solution of the thiazole. The nitrate can be recrystallised from ethanol, although a faint pink colour persists. Alternatively, water can be added dropwise to a boiling suspension of the nitrate in acetone until the solution is just clear charcoal is now added and the solution, when boiled for a short time, filtered and cooled, deposits the colourless crystalline nitrate, m.p. 192-194° (immersed at 185°). The thiazole can be regenerated by decomposing the nitrate with aqueous sodium hydroxide, and extracting the free base with ether as before. 

IsoValeric acid. Prepare dilute sulphuric acid by adding 140 ml. of concentrated sulphuric acid cautiously and with stirring to 85 ml. of water cool and add 80 g. (99 ml.) of redistilled woamyl alcohol. Place a solution of 200 g. of crystallised sodium dicliromate in 400 ml. of water in a 1-litre (or 1-5 litre) round-bottomed flask and attach an efficient reflux condenser. Add the sulphuric acid solution of the isoamyl alcohol in amaU portions through the top of the condenser shake the apparatus vigorously after each addition. No heating is required as the heat of the reaction will suffice to keep the mixture hot. It is important to shake the flask well immediately after each addition and not to add a further portion of alcohol until the previous one has reacted if the reaction should become violent, immerse the flask momentarily in ice water. The addition occupies 2-2-5 hours. When all the isoamyl alcohol has been introduced, reflux the mixture gently for 30 minutes, and then allow to cool. Arrange the flask for distillation (compare Fig. II, 13, 3, but with the thermometer omitted) and collect about 350 ml. of distillate. The latter consists of a mixture of water, isovaleric acid and isoamyl isovalerate. Add 30 g. of potassium not sodium) hydroxide pellets to the distillate and shake until dissolved. Transfer to a separatory funnel and remove the upper layer of ester (16 g.). Treat the aqueous layer contained in a beaker with 30 ml. of dilute sulphuric acid (1 1 by volume) and extract the liberated isovaleric acid with two... 

To isolate the p-hydroxybenzaldehyde, filter the residue from the steam distillation while hot through a fluted filter paper in order to remove resinous matter, and extract the cold filtrate with ether. Distil off the ether, and recrystallise the yellow solid from hot water to which some aqueous sulphurous acid is added. The yield of p-hydroxybenzaldehyde (colourless crystals), m.p. 116°, is 2-3 g. 

Added 112 grams sassafras oil. Shake for a couple of minutes. You get an orangish emulsion. Clears within 15 minutes forming two layers, bottom layer oil, top layer acetic acid, eugenol + the other solubles. Separated the oil from the others, washed the oil layer 2x with fresh C//-/2O. Weight after acetic acid water washes 101.5 (-10.5 grams). 

To 200 ml of 48% hydrobromic acid was added 0.40 mol of phosphorus tribromide (note 1). The mixture was agitated vigorously, while the temperature was kept between 20 and 30 0 by cooling in a water-bath at 10-15 0. After about 1 h the lower layer had disappeared completely. The solution was cooled to 0°C, then 0.40 mol of ammonium bromide, 0.10 mol (note 2) of copper(I) bromide (commercial product),... 

To a mixture of 25 ml of water and 3 ml of 95% sulfuric acid were added 40 ml of DMSO. The mixture was cooled to 10°C and 0.20 mol of l-ethoxy-l,4-hexadiyne (see Chapter III, Exp. 51) was added with vigorous stirring in 15 min. During this addition, which was exothermic, the temperature of the mixture was kept between 20 and 25 0. After the addition stirring was continued for 30 min at 3S C, then 150 ml of water were added and six extractions with diethyl ether were carried out. The combined extracts were washed with water and dried over magnesium sulfate. Evaporation of the solvent in a water-pump vacuum, followed by distillation through a 25-cm... 

In a widely used industnal process the mixture of ethylene and propene that is obtained by dehydrogenation of natural gas is passed into concentrated sulfunc acid Water is added and the solution IS heated to hydrolyze the alkyl hydrogen sulfate The product is almost exclusively a sin gle alcohol Is this alcohol ethanol 1 propanol or 2 propanoH Why is this particular one formed almost exclusively" ... 

Thus when acetic acid is added to pure water the ra tio of acetate ion to acetic acid is... 

Now think about what happens when the same amount of acetic acid is added to water that is buffered at pH = 7 0 Before doing the calculation let us recognize that it is the [CH3C02 ]/[CH3C02H] ratio m which we are interested and do a little alge braic manipulation Because... 

Although acetic acid and water are not beheved to form an azeotrope, acetic acid is hard to separate from aqueous mixtures. Because a number of common hydrocarbons such as heptane or isooctane form azeotropes with formic acid, one of these hydrocarbons can be added to the reactor oxidate permitting separation of formic acid. Water is decanted in a separator from the condensate. Much greater quantities of formic acid are produced from naphtha than from butane, hence formic acid recovery is more extensive in such plants. Through judicious recycling of the less desirable oxygenates, nearly all major impurities can be oxidized to acetic acid. Final acetic acid purification follows much the same treatments as are used in acetaldehyde oxidation. Acid quahty equivalent to the best analytical grade can be produced in tank car quantities without difficulties. 

Another example of manufacture in this series is the sulfonation of an aminonaphthalenesulfonic acid, followed by selected desulfonation, to make 6-amino-l,3-naphthalenedisulfonic acid (21). Thus, 2-amino-l-naphthalenesulfonic acid made by amination of 2-hydroxy-1-naphthalenesulfonic acid is added to 20 wt % oleum at ca 35°C. At this temperature, 65 wt % oleum is added and the charge is stirred for 2 h, is then slowly heated to 100°C and is maintained for 12 h to produce 6-amino-l,3,5-naphthalenetrisulfonic acid. The mass is diluted with water and maintained for 3 h at 105°C to remove the sulfo group adjacent to the amino group. After cooling to ca 20°C and filtration, 6-amino-l,3-naphthalenedisulfonic acid is obtained in 80% yield (55). 

The reaction solution is flushed under reduced pressure after it is sent out from the column, to remove CO2 gas formed as a by-product. The water formed is then removed from the reaction solution by a2eotropic distillation with BN, and most of the resultant reaction solution is recycled to the reaction column as the circulating solution. Part of the circulating solution is taken out from the reaction system and processed further to obtain DBO. The catalyst is first filtered, then BN, C H OH, and by-products are removed from the resultant solution. Purified DBO is thus obtained. The catalyst, BN, and C4H2OH are recovered and recycled to the circulating solution. After the make-up C H OH and nitric acid are added, the circulating solution is pressuri2ed and fed back to the reaction column. 

Thermal Process. In the manufacture of phosphoric acid from elemental phosphoms, white (yellow) phosphoms is burned in excess air, the resulting phosphoms pentoxide is hydrated, heats of combustion and hydration are removed, and the phosphoric acid mist collected. Within limits, the concentration of the product acid is controlled by the quantity of water added and the cooling capabiUties. Various process schemes deal with the problems of high combustion-zone temperatures, the reactivity of hot phosphoms pentoxide, the corrosive nature of hot phosphoric acid, and the difficulty of collecting fine phosphoric acid mist. The principal process types (Fig. 3) include the wetted-waH, water-cooled, or air-cooled combustion chamber, depending on the method used to protect the combustion chamber wall. 

Analysis for Poly(Ethylene Oxide). Another special analytical method takes advantage of the fact that poly(ethylene oxide) forms a water-insoluble association compound with poly(acryhc acid). This reaction can be used in the analysis of the concentration of poly(ethylene oxide) in a dilute aqueous solution. Ereshly prepared poly(acryhc acid) is added to a solution of unknown poly(ethylene oxide) concentration. A precipitate forms, and its concentration can be measured turbidimetricaHy. Using appropriate caUbration standards, the precipitate concentration can then be converted to concentration of poly(ethylene oxide). The optimum resin concentration in the unknown sample is 0.2—0.4 ppm. Therefore, it is necessary to dilute more concentrated solutions to this range before analysis (97). Low concentrations of poly(ethylene oxide) in water may also be determined by viscometry (98) or by complexation with KI and then titration with Na2S202 (99). 

---