Alcohol-free

Add 1 ml. of the alcohol-free ether to 0-1-0-15 g. of finely-powdered anhydrous zinc chloride and 0 5 g. of pure 3 5-dinitrobenzoyl chloride (Section 111,27,1) contained in a test-tube attach a small water condenser and reflux gently for 1 hour. Treat the reaction product with 10 ml. of 1-5N sodium carbonate solution, heat and stir the mixture for 1 minute upon a boiling water bath, allow to cool, and filter at the pump. Wash the precipitate with 5 ml. of 1 5N sodium carbonate solution and twice with 6 ml. of ether. Dry on a porous tile or upon a pad of filter paper. Transfer the crude ester to a test-tube and boil it with 10 ml. of chloroform or carbon tetrachloride filter the hot solution, if necessary. If the ester does not separate on cooling, evaporate to dryness on a water bath, and recrystallise the residue from 2-3 ml. of either of the above solvents. Determine the melting point of the resulting 3 5 dinitro benzoate (Section 111,27). 

Phenylhydrazones (compare Section III,74,C). Dissolve 0-5 g, of colourless phenylhydrazine hydrochloride and 0 8 g. of sodium acetate in 5 ml. of water, and add a solution of 0-2-0-4 g. of the aldehyde (or ketone) in a little alcohol (free from aldehydes and ketones). Shake the mixture until a clear solution is obtained and add a little more alcohol, if necessary. Warm on a water bath for 10-15 minutes and cool. Filter ofiF the crystalline derivative, and recrystalhse it from dilute alcohol or water sometimes benzene or light petroleum (b.p. 60-80°) may be used. 

Alcohol distillation Alcohol fractionation Alcohol free beer... 

Solvents. The most widely used solvent is deionized water primarily because it is cheap and readily available. Other solvents include ethanol, propjdene glycol or butylene glycol, sorbitol, and ethoxylated nonionic surfactants. There is a trend in styling products toward alcohol-free formulas. This may have consumer appeal, but limits the formulator to using water-soluble polymers, and requires additional solvents to solubilize the fragrance and higher levels of preservatives. 

Jojoba. Jojoba oil [61789-91-1] is obtained from the seeds of the jojoba plant grown in semiarid regions of Costa Rica, Israel, Mexico, and the United States. The oil is made up of ca 80 wt % of esters of eicos-ll-enoic and docos-13-enoic acids, and eicos-ll- -l-ol, and docos-13- -l-ol, ca 17 wt % of other hquid esters, with the balance being free alcohols, free acids, and steroids. Jojoba oil is used primarily in the formulation of cosmetics. Hydrogenated jojoba oil is a wax used in candles and other low volume specialty apphcations. 

After-Shaves. After-shave preparations serve the same function as and are formulated similarly to skin asttingents. After-shave balms are hydro-alcohoHc or alcohol-free emulsions that supply soothing iagredients, for example, witch ha2el, and em ollients, for example, decyl oleate [3687-46-5] to the skin. Menthol, which provides a cooling sensation, is a common constituent of after-shaves. 

Hydrolysis of the ester is achieved by refluxing in aqueous N or 2N NaOH solution until the insoluble ester dissolves. The solution is then cooled, and the alcohol is extracted into a suitable solvent, e.g. ether, toluene or alcohol-free chloroform. The extract is dried (CaS04, MgS04) and distilled, then fractionally distilled if liquid or recrystallised if solid. (The p-nitrobenzoic acid can be recovered by acidification of the aqueous layer.) In most cases where the alcohol to be purified can be readily extracted fi-om ethanol, the hydrolysis of the ester is best achieved with N or 2N ethanolic NaOH or 85% aqueous ethanolic N NaOH. The former is prepared by dissolving the necessary alkali in a minimum volume of water and diluting with absolute alcohol. The ethanolic solution is refluxed for one to two hours and hydrolysis is complete when an aliquot gives a clear solution on dilution with four or five times its volume of water. The bulk of the ethanol is distilled off and the residue is... 

Other derivatives can be prepared by reaction of the alcohol with an acid anhydride. For example, phthalic or 3-nitrophthalic anhydride (I mol) and the alcohol (Imol) are refluxed for half to one hour in a non-hydroxylic solvent, e.g. toluene or alcohol-free chloroform, and then cooled. The phthalate ester crystallises out, is precipitated by the addition of low boiling petroleum ether or is isolated by ev toration of the solvent. It is recrystallised from water, 50% aqueous ethanol, toluene or low boiling petroleum ether. Such an ester has a characteristic melting point and the alcohol can be recovered by acid or alkaline hydrolysis. 

Of the alkyl esters, methyl esters are the most useful because of their rapid hydrolysis. The acid is refluxed with one or two equivalents of methanol in excess alcohol-free chloroform (or dichloromethane) containing about O.lg of p-toluenesulfonic acid (as catalyst), using a Dean-Stark apparatus. (The water formed by the... 

Liquid aliphatic halides are obtained alcohol-free by distillation from phosphorus pentoxide. They are stored in dark bottles to prevent oxidation and, in some cases, the formation of phosgene. 

The submitters employed alcohol-free potassium ferf-butoxide, purchased from K K Laboratories, without further purification the checkers employed comparable material taken from a freshly opened bottle purchased from MSA Research Corporation. The submitters report that among approximately ten different bottles of commercial potassium terf-butoxide used, only material from one bottle failed to form the tricarbonate in this procedure. The defective material in this one bottle was an extremely fine powder that failed to dissolve when... 

If an alcohol-free solution of diazomcthane is required, absolute ether should be used throughout this preparation. 

The dihydroxyacetone side chain is conveniently protected by forming 17a,20 20,21-bismethylenedioxy compounds (BMD) (92). Formation of llf -ethers as by-products from 11 -hydroxycompounds (91) can be limited by using formalin with a low methanol content, or better with paraformaldehyde as a source of alcohol-free formaldehyde. ... 

The present occasion seems opportune to direct attention to the fact that one of the most familiar, most leadily procurable and most cheaply produced of all oiganic materials is placed beyond the reach of many students by the heavy duty levied upon it. May I, in the name of teachers of organic chemistry, appeal to the Board of Inland Revenue, on behalf of scientific and technical education, to provide institutions for higher education in science with a limited quantity of pure alcohol free of duty, thereby placing schools of chemistry in this country in the same position as those on the Continent ... 

An alcohol-free solution of diazomethane in ether is prepared as in Chapter 17, Section III. This solution is approximately 0.5 M in diazomethane and may be standardized by titration as follows benzoic acid (0.6 g, approx. 0.005 mole) is weighed accurately into an Erlenmeyer flask and suspended in 5 ml of ether. The diazomethane solution (approx. 5 ml) is added from a buret with swirling, care being taken that an excess of unreacted benzoic acid remains (the yellow color of the diazomethane should be completely discharged). The excess benzoic acid is now titrated with standard 0.2 N sodium hydroxide solution, and the concentration of diazomethane is calculated. 

For the preparation of an alcohol-free ethereal solution of diazomethane, the generating flask is charged with 35 ml of diethylene glycol monoethyl ether, 10 ml of ether, and a solution of 6 g of potassium hydroxide in 10 ml of water. The flask is heated in a water bath at 70°, and a solution of 21.4 g of Diazald in 140 ml of ether is added over 20 minutes with occasional shaking of the flask. The distillate is collected as above and the yield is the same. 

Chloro-10-(3-dirrethylaminopropyl)-10-hydroxythiaxanthene, 3.34 g (0.01 mol) obtained as described was dissolved in 15 ml of dry, alcohol-free chloroform. Acetyl chloride,... 

To a suspension of 25.0 g of 11/3,17a,21-trihydroxy-6,16a-dimethyl-4,6-pregnadiene-3,20-dione in 1.5 liters of alcohol-free chloroform cooled to about 5°C in an ice bath is added with constant stirring 750 ml of cold, concentrated hydrochloric acid and then 750 ml of formalin (low in methanol). The mixture is removed from the ice bath and stirred at room temperature for 7 hours. The layers are separated and the aqueous phase is back-extracted twice with chloroform. The combined organic layers are washed twice with a 5% solution of sodium bicarbonate, and twice with a saturated salt solution. The solution is dried over magnesium sulfate and evaporated to dryness under reduced pressure. 

A solution of the amide chloride (4.6 g) in dry, alcohol-free chloroform (20 ml) was added slowly to a solution of trimethylsilyl 6-amino-penicillanate (7.2 g) and triethylamine (3.5 ml) in dry, alcohol-free chloroform (50 ml) with stirring and cooling to -70°C. The temperature was raised to 0°C during 1V4 hours. The solution was evaporated to dryness in vacua and the residue was triturated with dry ether (200 ml). The precipitate was filtered off and washed with dry ether. The filtrate was diluted with ether (200 ml). 2-Butanol (2.8 ml) was added dropwise with stirring and cooling to0°C. The stirring was continued for A hour at 0°C, whereupon the precipitate was filtered off, washed with ether and dried. It was a white, amorphous powder, soluble in water. 

To a stirred suspension of 6-aminopenicillanic acid (540 g) in dry alcohol-free chloroform (3.75 liters) was added dry triethylamine (697 ml), and the mixture stirred for 10 minutes at room temperature. It was then cooled in a bath of crushed Ice while a solution of 2,6-dimethoxybenzoyl chloride (500 g) in dry alcohol-free chloroform (3.75 liters) was added in a steady stream over 20 minutes. When all the acid chloride had been added the cooling bath was removed and the mixture stirred for 1 hour at room temperature. The mixture was stirred vigorously and sufficient dilute hydrochloride acid (2.3 liters of 0.87 N) was added to give an aqueous layer of pH 2.5. The mixture was filtered, the layers separated, and only the chloroform layer was retained. 

As it is difficult to prepare ter /-butyl alcohol free from water, 84 g. of the constant boiling mixture of the alcohol and water can be used. This mixture boils at 8o°, contains 88.24 per cent alcohol when the distillation is carried out at 760 mm., and can be readily obtained by distilling a sample of the dilute alcohol. 

The dry calcium malonate is placed in a 3-I. round-bottomed flask with sufficient (750-1000 cc.) alcohol-free ether (Note 3) to make a paste which can be stirred. The flask is surrounded by an ice bath, and the well-stirred salt is treated with 1 cc. of 12 N hydrochloric acid for each gram of salt. After the acid has been added slowly through a dropping funnel, the solution is transferred to a continuous extractor (Note 4) and extracted with ether until no more malonic acid is obtained. The product, as obtained from the undried ether solution by concentration, filtration, and drying in the air, melts at 130° or higher and is sufficiently pure for most purposes. The yield is 415-440 g. (77-82 per cent of the theoretical amount). 

The apparatus consists of a 3-]. three-necked flask fitted with a mercury-sealed mechanical stirrer, a reflux condenser, a dropping funnel, and a thermometer which reaches almost to the bottom of the flask. Five hundred grams of potassium hydroxide pellets (85 per cent potassium hydroxide) (7.5 moles) and 750 cc. of commercial absolute methyl alcohol (free from acetone) are placed in the flask and stirring begun. The bulk of the alkali dissolves in a few minutes, with the evolution of heat. The flask is now surrounded by an ample cold-water bath, and, when the internal temperature drops to 6o°, addition of a mixture of 360 g. (353 cc., 3 moles) of -tolualdehyde (Note 1), 300 cc. of formalin (3.9 moles) (Note 2), and 300 cc. of absolute methyl alcohol is begun at such a rate that the internal temperature remains at 60-70°. This addition requires about fifteen minutes. The internal temperature is then maintained at 60-70° for three hours, after which the reflux condenser is replaced by a downward condenser, and the methyl alcohol distilled with the aid of a brine bath until the internal temperature reaches ioi°. Nine hundred cubic centimeters of cold water is then added to the warm residue, and the mixture cooled. The resulting two layers are separated at once (Note 3), and the aqueous layer extracted with three 200-cc. portions of benzene. The combined oil and extracts are washed with five or six 50-cc. portions of water (Note 4), and the combined washings extracted... 

C. Provide frequent mouth care with normal saline or alcohol-free mouthwash. 

However, alcohol-free solutions of diazomethane146 must be used to avoid destruction of the intermediate sulfene and a stronger base such as 1,5-diazabicyclo [4.3.0] non-5-ene is required for the final dehydrohalogenation step to obtain sulfones 19a,d. 

C. A. Sanz and G. A. Pope. Alcohol-free chemical flooding from surfactant screening to coreflood design. In Proceedings Volume, pages 117-128. SPE Oilfield Chem Int Symp (San Antonio, TX, 2/14-2/17), 1995. 

Parazzini, F., La Vecchia, C., Riundi, R., Pampallona, S., Regallo, M., Scanni, A., Methylxanthine alcohol-free diet and fibrocystic breast disease A factorial clinical trial, Surgery, 99, 576, 1986. 

Extemporaneous production of pediatric dosage forms is commonly undertaken in hospitals. Without the sophisticated formulation capabilities of pharmaceutical manufacturers, alcohol-based vehicles have been recommended for extemporaneous preparation of liquid dosage forms [73]. There is a critical need to conduct research studies to assist the pharmacist in replacing current formulations with stable, alcohol-free preparations [74]. 

Glycerites are glycerin-extracted preparations and are alcohol-free. Although glycerin tastes sweet, it is not considered a sugar. Although glycerin is considered a poor solvent for many of the active... 

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