Isopropyl alcohols

Physical properties of isopropyl alcohol are characteristic of polar compounds because of the presence of the polar hydroxyl, —OH, group. Isopropyl alcohol is completely miscible ia water and readily soluble ia a number of common organic solvents such as acids, esters, and ketones. It has solubiUty properties similar to those of ethyl alcohol (qv). There is a competition between these two products for many solvent appHcations. Isopropyl alcohol has a slight, pleasant odor resembling a mixture of ethyl alcohol and acetone, but unlike ethyl alcohol, isopropyl alcohol has a bitter, unpotable taste. 

Physical and chemical properties of isopropyl alcohol reflect its secondary hydroxyl functionaHty. For example, its boiling and flash poiats are lower than / -propyl alcohol [71-25-8], whereas its vapor pressure and freezing poiat are significantly higher. Isopropyl alcohol bods only 4°C higher than ethyl alcohol. 

Kirk-Othmer Encyclopedia of Chemical Technology (4th Edition) 

Component CAS Registry Number Bp°, °C Azeotrope bp, °C Isopropyl alcohol composition, wt % 

Chemical properties of isopropyl alcohol are determined by its functional hydroxyl group in the secondary position. Except for the production of acetone, most isopropyl alcohol chemistry involves the introduction of the isopropyl or isopropoxy group into other organic molecules by the breaking of the C—OH or the O—H bond in the isopropyl alcohol molecule. 

Isopropanol was one of the first petrochemicals to be produced on a large scale and is still widely nsed as a solvent and chemical intermediate. Originally, pro-dnetion was by direct catalytic hydration of propylene in the liquid phase  

Concentrated 70-98% snlfuric acid was used as the catalyst at a low pressure and temperature. The reaction mechanism involved the sulfate monoester intermediate, which was then hydrolyzed to isopropanol. The proeess is similar to the production of ethanol from ethylene, although the hydration step beeomes easier as the carbon number of the olefin inereases. The acid strength reqnired for effective operation deereases from more than 90% for ethylene hydration to abont 70% for propylene hydration. 

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An example of a reaction which does produce a byproduct is the production of acetone from isopropyl alcohol, which produces a hydrogen byproduct ... 

Figure 10.3a shows a simplified fiowsheet for the production of isopropyl alcohol by the direct hydration of propylene. Different reactor technologies are available for the process, and separation and recycle systems vary, but Fig. 10.3a is representative. Propylene... 

Figure 10.3 Outline flowsheet for the production of isopropyl alcohol by direct hydration of propylene. (From Smith and Petela, Chem. Eng., 513 24, 1991 reproduced by permission of the Institution of Chemical Engineers.)...

In general, the best way to deal with a feed impurity is to purify the feed before it enters the process. Let us return to the isopropyl alcohol process from Fig. 10.3. Propylene is fed to the process containing propane as a feed impurity. In Fig. 10.3 the propane is removed from the process using a purge. This causes waste of... 

C5H10O2, CHjCOOPr. Colourless liquid with a fragrant odour b.p. 88 C. Manufactured by leading propene into hot ethanoic acid containing sulphuric acid, or by heating isopropyl alcohol with ethanoic and sulphuric acids. Used as a solvent for cellulose nitrate and various gums. 

Aldehydes form addition products at the double bond of the carbonyl (>C 0) group, and hydrolysis gives secondary alcohols. Thus acetaldehyde gives isopropyl alcohol ... 

Mix 40 g. (51 ml.) of isopropyl alcohol with 460 g. (310 ml.) of constant boiling point hydrobromic acid in a 500 ml. distilling flask, attach a double surface (or long Liebig) condenser and distil slowly (1-2 drops per second) until about half of the liquid has passed over. Separate the lower alkyl bromide layer (70 g.), and redistil the aqueous layer when a further 7 g. of the crude bromide will be obtained (1). Shake the crude bromide in a separatory funnel successively with an equal volume of concentrated hydrochloric acid (2), water, 5 per cent, sodium bicarbonate solution, and water, and dry with anhydrous calcium chloride. Distil from a 100 ml. flask the isopropyl bromide passes over constantly at 59°. The yield is 66 g. 

The residue in the flask may be mixed with the aqueous layer of the first distillate, 40 g. of isopropyl alcohol added, and the slow distillation repeated. The yield of crude isopropyl bromide in the second distillation is only slightly less than that obtained in the original preparation. Subsequently most of the residual hydrobromic acid may be recovered by distillation as the constant boiling point acid (126°). 

A further quantity of wopropyl iodide, only slightly less than that obtained in the first distillation, may be prepared by combining the residues in the distilling flask, adding 30 g. (38 ml.) of isopropyl alcohol, and repeating the distillation. Finally, the residues should be distUled and the 67 per cent, constant boiling point acid recovered. 

Acetone is reduced by amalgamated magnesium largely to a bimolecu lar reduction product, tetramethylethylene glycol or plnacol (CHjjjClOHjClOHjiCHj), some isopropyl alcohol is also formed ... 

Place a mixture of 53 g. of A.R. lactic acid (85-88 per cent, acid), 75 g. (85-5 ml.) of commercial anhydrous isopropyl alcohol, 300 ml. of benzene and 20 g. of Zeo-Karb 225/H (1) in a 700 ml. bolt-head flask, equipped with an automatic water separator (e.g., a large modified Dean and Stark apparatus with a stopcock at the lower end, see Fig. Ill, 126, 1) carrying an efficient reflux condenser at its upper end, and a mercury-sealed stirrer (alternatively, the hquid-sealed stirrer shown in Fig. 11,7,11, c. may be used). Reflux the mixture, with stirring, on a steam bath for 5 hours or until water no longer collects in appreciable amount in the water separator run off the water from time to time. Filter off the resin at the pump and wash it with two 25 ml. portions of benzene. Shake the combined filtrate and washings with about 5 g. of precipit-ated calcium... 

If desired, the alcohol may be identified as the 3 5-dinitrobenzoate (Section 111,27) it is then best to repeat the experiment on a larger scale and to replace the dilute hydrochloric acid by dilute sulphuric acid. It must, however, be pointed out that the reaction is not always so simple as indicated in the above equation. Olefine formation and rearrangement of the alcohol sometimes occur thus n-prop3 lamine yields n-propyl alcohol, isopropyl alcohol and propylene. 

The reagent is conveniently stored as a solution in isopropyl alcohol. The molten (or solid) alkoxide is weighed out after distillation into a glass-stoppered bottle or flask and is dissolved in sufficient dry isopropyl alcohol to give a one molar solution. This solution may be kept without appreciable deterioration provided the glass stopper is sealed with paraffin wax or cellophane tape. Crystals of aluminium isopropoxide separate on standing, but these may be redissolved by warming the mixture to 65-70°. 

For many reductions it is not necessary to distil the reagent. Dilute the dark solution, prepared as above to the point marked with an asterisk, to 1 htre with dry isopropyl alcohol this gives an approximately one molar solution. Alternatively, prepare the quantity necessary for the reduction, using the appropriate proportions of the reagents. 

Prepare a solution of aluminium isopropoxide from 23 -5 g. of aluminium, 0-5 g. of mercuric chloride and 250 ml. of dry isopropyl alcohol ... 

The above test will detect 1 part of acetone in 500-1000 parts of isopropyl alcohol. The reagent should not be kept for more than 1-2 months since it deteriorates upon keeping. 

Place 35 ml. of a M solution of aluminium tsopropoxide or 7 g. of solid aluminium tsopropoxide, 450 ml. of dry isopropyl alcohol and 21 g. of purified benzaldehyde (Section IV,115) in a 1 litre round-bottomed flask. Fit a short reflux condenser (no water in the cooling jacket) or better a Hahn condenser (2) (containing a 1 cm. layer of ethyl alcohol in the iimer tube) to the flask and arrange for slow distillation from a water bath at the rate of 3-6 drops per minute. Continue the heating until a negative test for acetone is obtained after 5 minutes of total reflux (6-9 hours) if the volume of the mixture falls below 200 ml. during the reduction, add more isopropyl alcohol. Remove the reflux or Hahn condenser and distil off (Fig. II, 13, 3) most of the isopropyl alcohol under atmospheric pressure from a suitable oil bath. Hydrolyse the... 

A modified Hahn condenser, a form of partial condenser, is illustrated in Fig. VI, 12, 1 it is best constructed of Pyrex glass. The dimensions given are only approximate and may be varied slightly. The inside clearance should be approximately 0-3 cm. a water jacket should be fitted over the central portion of the side arm by moans of rubber stoppers. Alternatively, the side arm may have a length of about 10 cm. and a condenser fitted to this in the usual manner. An approximately 1 cm. layer of absolute alcohol is placed in the inner condensing tube and the top of the tube is connected to a reflux condenser. The outside of the condenser below the side arm should be insulated with asbestos cloth or paper. The refluxing mixture boils the ethyl alcohol in the inner tube, most of the isopropyl alcohol is returned to the flask and the acetone distils over. 

Recovery of the wopropyl alcohol. It is not usually economical to recover the isopropyl alcohol because of its lo v cost. However, if the alcohol is to be recovered, great care must be exercised particularly if it has been allowed to stand for several days peroxides are readily formed in the impure acetone - isopropyl alcohol mixtures. Test first for peroxides by adding 0-6 ml. of the isopropyl alcohol to 1 ml. of 10 per cent, potassium iodide solution acidified with 0-6 ml. of dilute (1 5) hydrochloric acid and mixed with a few drops of starch solution if a blue (or blue-black) coloration appears in one minute, the test is positive. One convenient method of removing the peroxides is to reflux each one litre of recovered isopropyl alcohol with 10-15 g. of solid stannous chloride for half an hour. Test for peroxides with a portion of the cooled solution if iodine is liberated, add further 5 g. portions of stannous chloride followed by refluxing for half-hour periods until the test is negative. Then add about 200 g. of quicklime, reflux for 4 hours, and distil (Fig. II, 47, 2) discard the first portion of the distillate until the test for acetone is negative (Crotyl Alcohol, Note 1). Peroxides generally redevelop in tliis purified isopropyl alcohol in several days. 

After 3 hours the stirring is stopped and the solution allowed to settle. By this time just about all the foil will have turned to dust, which is going to make the next step of vacuum filtration very difficult because it will plug up the filter paper in a second. So the chemist lets it settle, then pours off the liquid through the vacuum filtration setup (see methodology section). The flask is rinsed with lOOmL methanol, the methanol poured through the grey filter cake and the filter cake discarded. All of the filtrate is placed in a flask and vacuum distilled to remove all the methanol, isopropyl alcohol and water which will leave the chemist with oil and junk in the bottom of the flask. 

Sodium hydride (9.3 g, 0.22 mol) was washed with petroleum ether and DMSO (200 ml) was added and the mixture was heated to 100°C. A solution of diethyl malonate (35.2 g, 0.22mol) in DMSO (50 ml) was then added and stirred for 10 min to give a clear solution. A solution of 4-bromo-3-nitrobenzophenone (30.6 g, 0.10 mol) in DMSO (100 ml) was added and the resulting dark solution kept at 100 C for 1 h. The solution was poured into water (3 1) and extracted (2x) with ether. The extract was washed with water, dried (NajSOj and concentrated in vacuo to give an oil which crystallized. The solid was recrystallized from isopropyl alcohol to give 35.4 g (92% yield) of the product. 

Organic chemists have devised a number of shortcuts to speed the writing of structural formulas Sometimes we leave out unshared electron pairs but only when we are sure enough m our ability to count electrons to know when they are present and when they re not We ve already mentioned representing covalent bonds by dashes In condensed structural formulas we leave out some many or all of the covalent bonds and use sub scripts to indicate the number of identical groups attached to a particular atom These successive levels of simplification are illustrated as shown for isopropyl alcohol ( rub bmg alcohol )... 

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