Acetic acid from petroleum oils

Twenty-five years ago the only oxygenated aliphatics produced in important quantities were ethyl and n-butyl alcohols and acetone made by the fermentation of molasses and grain, glycerol made from fats and oils, and methanol and acetic acid made by the pyrolysis of wood. In 1927 the production of acetic acid (from acetylene) and methanol (from synthesis gas) was begun, both made fundamentally from coal. All these oxygenated products are still made from the old raw materials by the same or similar processes, but the amount so made has changed very little in the past quarter century. Nearly all the tremendous growth in the production of this class of compounds has come from petroleum hydrocarbons. 

Method 1. Dissolve 25 0 g. of salicylaldehyde (Section IV,122) in 215 ml. of 2N sodium hydroxide solution, add 12 05 g. of hydroxylamine hydrochloride, and warm the mixture for 30 minutes on a water bath. Acidify with acetic acid and cool in ice the salicylaldoxime separates as a congealed oil. Recrystalhae from chloroform - light petroleum (b.p. 40-60°). The yield of salicylaldoxime (colourless crystals, m.p. 57°) is 5 g. 

The Phenox process (254) removes phenol (qv) from the efduent from catalytic cracking in the petroleum industry. Extraction of phenols from ammoniacal coke-oven Hquor may show a small profit. Acetic acid can be recovered by extraction from dilute waste streams (255). Oils are recovered by extraction from oily wastewater from petroleum and petrochemical operations. Solvent extraction is employed commercially for the removal of valuable... 

Carboxylic acids having 6—24 carbon atoms are commonly known as fatty acids. Shorter-chain acids, such as formic, acetic, and propionic acid, are not classified as fatty acids and are produced synthetically from petroleum sources (see Acetic acid Formic acid and derivatives Oxo process). Fatty acids are produced primarily from natural fats and oils through a series of unit operations. Clay bleaching and acid washing are sometimes also included with the above operations in the manufacture of fatty acids for the removal of impurities prior to subsequent processing. 

The identification of camphene is best carried out by its conversion into isobomeol under the influence of acetic acid in the presence of sulphuric acid. In order to effect this conversion, 100 grams of the fraction containing the terpene in substantial quantity are mixed with 250 grains of glacial acetic acid and 10 grams of 50 per cent, sulphuric acid. Tne mixture is heated for two to three hours on a water-bath to a temperature of 50° to 60°. At first the liquid separates into two layers, bat soon becomes homogeneous and takes on a pale red colour. Excess of water is added, and the oil which is precipitated, and which contains the isobomeol in the form of its acetate, is well washed with water repeatedly. It is then saponified by heating with alcoholic potash solution on a water-bath. The liquid is then evaporated and extracted with water, and the residue recrystallised from petroleum ether. 

Camphene forms a well-defined nitrite, and a nitroso-nitrite, when treated in the following manner A well-cooled solution of camphene in petroleum ether is mixed with a saturated solution of sodium nitrite, and dilute acetic acid is added. The mixture is well stirred, being kept cool all the time. Camphene nitrosonitrite, CuHi NjOj, separates and on recrystallisation forms crystals which decompose at about 149°. The petroleum ether solution, which has been filtered off from this compound, is shaken with a concentrated solution of pK)tassium hydroxide, which removes camphene nitrosite, CjQHigNjOj, in the form of its potassium salt. When this is decomposed with acids it yields the free nitrosite. This compound is a greenish oil, with a pleasant odour, easily decomposing when heated to 50°. 

Dissolve 71 g. of P-methylnaphthalene in 460 g. (283 ml.) of A.B. carbon tetrachloride and place the solution in a 1 -litre three-necked flask equipped with a mechanical stirrer and reflux condenser. Introduce 89 g. of JV-bromosuccinimide through the third neck, close the latter with a stopper, and reflux the mixture with stirring for 16 hours. Filter ofiT the succinimide and remove the solvent under reduced pressure on a water bath. Dissolve the residual brown oil (largely 2-bromomethyl naphthalene) in 300 ml. of A.R. chloroform, and add it to a rapidly stirred solution of 84 g. of hexamine in 150 ml. of A.R. chloroform contained in a 2-litre three-necked flask, fitted with a reflux condenser, mechanical stirrer and dropping funnel maintain the rate of addition so that the mixture refluxes vigorously. A white solid separates almost immediately. Heat the mixture to reflux for 30 minutes, cool and filter. Wash the crystalline hexaminium bromide with two 100 ml. portions of light petroleum, b.p. 40-60°, and dry the yield of solid, m.p. 175-176°, is 147 g. Reflux the hexaminium salt for 2 hours with 760 ml. of 60 per cent, acetic acid, add 160 ml. of concentrated hydrochloric acid, continue the refluxing for 5 minutes more, and cool. Extract the aldehyde from the solution with ether, evaporate the ether, and recrystallise the residue from hot -hexane. The yield of p-naphthaldehyde, m.p. 69-60°, is 60 g. 

To 16.3 g Na in 210 ml ethanol add 93 g ethyl-acetoacetate (ethyl-3-oxo-butanoate), heat to boil and add dropwise 92 g (II) over 20 minutes. Stir and reflux five hours and cool to precipitate. Filter, wash with ethanol and dissolve precipitate in 800 ml water. Cool to 0° C and slowly add 80 ml ice cold concentrated HC1 to precipitate. Filter, wash with water and ligroin to get about 108 g 6-carbethoxy-4,5-dihydro-olivetol (ID) (reciystallize from petroleum ether). To 104 g (III) in 260 ml glacial acetic acid at room temperature with good stirring, add dropwise over one hour 69 ml Bromine. Heat-four to five hours at 60° C, cool and add 300 ml water and let stand twelve hours. Oil separates which will precipitate on agitation and... 

The 4b-methyl-ip-(2-formylethyl)-2p-formyl-2-(2-cyanoethyl)-4p,7a-dihydroxyperhydrophenanthrene ip-methyl acetal 2p,4p-lactol methyl ether 7a-acetate (360 mg) was stirred in 3 ml of ether. Upon the addition of 9 ml of 70% aqueous acetic acid the crystals dissolved immediately. The solution was allowed to stand at room temperature for 16 h and was then extracted with ether. The extract was washed thoroughly with water and aqueous sodium bicarbonate, dried over magnesium sulfate and concentrated to dryness under reduced pressure, yielding 337 mg of oil. On trituration with ether there was obtained 305 mg of crystals of 4b-methyl-ip-(2-formylethyl)-2p-formyl-2-(2-cyanoethyl)-4p,7a-dihydroxyperhydrophenanthrene 2p,4p-lactol methyl ether 7a-acetate as platelets, melting point 85°-105°C after recrystallizations from benzene-petroleum ether. 

The reaction mixture was then cooled and poured into 2 L of ice/water. The resulting mixture was acidified with 10% HCI and extracted with ethyl acetate (3 times 1 L). The combined ethyl acetate extract was extracted with 1 N NH4OH (3 times 1 L) and the combined aqueous basic extract washed with ethyl acetate (2 L), cooled to 0° to 5°C, acidified slowly to a pH below 1.0 with concentrated HCI and extracted with ethyl acetate (4 times 2 L). The combined ethyl acetate extract was dried (MgS04) and evaporated under vacuum to a light yellow oil slightly contaminated with diethyl succinate (477 g, 80% yield). An analytical sample of 3-ethoxycarbonyl-4-(3,4-dichlorophenyl)-4-phenylbut-3-enoic acid was crystallized from petroleum ether (melting point 128°-130°C). 

Methyl 2-(3 -Phenyl-2 -propen-r-oyl)phenyl Tellurium3 A stirred mixture of 12 g (46 mmol) of 2-acetylphenyl methyl tellurium, 17.6 m/(18.4 g, 170 mmol) of benzaldehyde, 88 mlof acetic acid, and 35 ml of piperidine is heated under reflux for 6 h. The mixture is then steam-distilled to remove unreacted benzaldehyde. The resultant red oil is separated by extraction with chloroform, the extract is evaporated, and the residue is fractionally distilled under vacuum. The fraction boiling above 200°/0.1 torr is collected and redistilled to give a condensate that should solidify. This solid is recrystallized several times from a mixture of petroleum ether and benzene yield 3.2 g (20%) m.p. 102-104° (from heptane/benzenc). 

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