Phenol

“ Chemical Analysis.—Carbolic acid may be separated from mixture with organic substances by distillation with dilute sulphuric acid, from urine by agitation with ether. Bromine water, as recommended by Landolt, gives a bulky yellowish precipitate of tribromo-phenol. The precipitate should then be collected, well washed, and gently warmed in a test tube with sodium-amalgam and water. The liquid poured into a dish and acidulated, will, if phenol be present, give the characteristic odour of that substance, and it may be seen floating in the liquid as an oily fluid. ”

“ Phenol dissolves, and forms a clear mixture. Were any phenol present in the wood creosote, the increase in the volume of the glycerine solution, if in a graduated tube, would distinctly indicate the percentage of phenol present.
4. Solubility in benzine. Wood creosote entirely soluble. Phenol is insoluble.
5. A 1 per cent, solution of wood creosote. Take of this 10 cubic centimeters, add 1 drop of a test solution of ferric chloride; an evanescent blue color is formed, passing quickly into a red color. Phenol gives a permanent blue color. ”

“ Natural phenol is recovered in practically all European countries and in Japan. Germany and the United Kingdom are the principal producers and have also been the leading exporters. Synthetic phenol was made in Germany as early as 1900, and during the World War. Plants for synthetic phenol recently installed are now in operation in Germany, Great Britain, Belgium, and Italy.
Table 60 shows the average annual world production of phenol in recent years by countries. Half of the total was produced in the United States. ”

“ Distil over 15 to 20 c.c. Divide the distillate into three portions a, b and c.
4. Add to (a) 0.5 c.c. Millon's reagent and boil.
Red colour = phenol. [Pg 288]
5. Add to (b) about 0.5 c.c. ferric chloride solution. Violet colour = phenol.
(If the distillate be acid the reaction will be negative.)
6. Add to (c) bromine water. Crystalline white ppt. of tribromo-phenol = phenol.
Note.—If both indol and phenol appear to be present in cultivations of the same organism, it is well to separate them before testing. This may be done in the following manner:
1. ”

“ A colorless liquid, which may become reddish.
Dosage: 0.05 Cc. or 1 minim (U.S.P.) .
Unguentum Phenolis (Ung. Phenol.) , Ointment of Phenol, U.S.P. (Ointment of Carbolic Acid) .—Liquefied phenol (2.25%) in ointment.
Phenol Iodatum (Phenol Iodat.) , Iodized Phenol, N.F. (Acidum Carbolicum Iodatum, N.F. III) .—Iodine (20%) and phenol (60%) in glycerin.
*Phenolphthaleinum (Phenolphthal.) , Phenolphthalein, U.S.P.
White or nearly white, odorless, tasteless powder. Almost insoluble in water; soluble in alcohol (1:13) .
Action and Uses: Mild but efficient cathartic. ”

“ The original letters patent is worded as follows: 10 kilos each of crude phenol and sulphuric acid (66° Bé.) are heated with stirring for two hours at 105°-106°C., cooled to about 35°C., and 463 kilos 30 per cent. formaldehyde added during three hours, the temperature thereby not exceeding 35°C.; the stirring is continued for a couple of hours after the final addition of formaldehyde. This yields about 24 kilos of the crude condensation product. On a commercial scale, however, cresol (cresylic acid) is substituted for phenol. ”

“ Prior to the afternoon recess, Doctor, we were discussing the phenol problem. Now, in this connection, did you at any time propose experiments to be conducted at Buchenwald concerning the tolerance of serum or sera containing phenol? That is, did you propose that in 1942 or 1943 at any time?
Defendant Mrugowsky: No. No such suggestions were made and they were not necessary, because in Germany every serum contains phenol. In the German serum industry there is no serum produced without phenol. I am speaking of the sera for therapeutic purposes, not vaccines. ”

“ Substitution of the Benzene Ring.—As a general rule, homologues and mono-derivatives of benzene react more readily with substituting agents than the parent hydrocarbon; for example, phenol is converted into tribromphenol by the action of bromine water, and into the nitrophenols by dilute nitric acid; similar activity characterizes aniline. Not only does the substituent group modify the readiness with which the derivative is attacked, but also the nature of the product. ”

“ Baekeland turned his attention to the phenol condensation products, working gradually up from test tubes to ton vats according to his motto: "Make your mistakes on a small scale and your profits on a large scale." He found that when equal weights of phenol and formaldehyde were mixed and warmed in the presence of an alkaline catalytic agent the solution separated into two layers, the upper aqueous and the lower a resinous precipitate. This resin was soft, viscous and soluble in alcohol or acetone. ”

“ If now these phenol bodies are contained in the plant and animal juices constituting our foods they must be contained in those that are short lived in largest amount, and it should be possible to bring on old age much more rapidly by feeding short lived plants. For this purpose I used first oat straw, but I found this did not produce the desired effect. On further consideration it seemed 55unlikely that it should: for the ripe, and therefore dead, straw would contain only the resin and neither aldehyde nor phenol. ”

“ It is the most important resin material in this group.
Phenyl phenols.
Both ortho and para phenyl phenol are commercially produced and are used to some extent in resins to replace phenol. The ortho isomer is a white solid boiling at 284° C. and melting at about 56° C. It is used chiefly as a germicide, though small quantities are used in resins.
Para phenyl phenol is a white solid melting at about 165° C. and boiling at 322° C. Commercial production was reported for the first time in 1933. The output has increased each year since and the selling price has gradually declined. ”

“ A portion of the symmetrical chloride was brought together with somewhat more than double the molecular amount of phenol. The mixture was placed in a good-sized test-tube and the temperature gradually raised by means of a sulphuric acid bath.
As soon as the phenol melts, some slight action occurs, as is indicated by the fact that the mixture assumes a bright red color. No appreciable amount of hydrochloric acid gas is evolved however, until the liquid mixture has reached a temperature of about 115°. At this point the gas is freely evolved, and the action is complete at a temperature of 125°. ”

“ A number of these condensation products are derivatives of diphenylamine or hydroxybenzyl alcohols. When the latter are heated, either by themselves or in presence of acids, anhydrides and polymerisation products are formed producing hard, brittle, fusible substances, insoluble in water but fairly soluble in organic solvents. The same substances are formed when phenols are condensed with formaldehyde, especially in the presence of acid contact substances and excess of phenol by sufficiently long heating at certain temperatures. ”

“ Similarly, the replacement of hydrogen by a water-residue, hydroxyl, gives rise to a phenol. The group of carbon, oxygen, and hydrogen atoms which confers the property of acidity upon an organic compound is a half-molecule of oxalic acid—it is known as the carboxyl group. Thus benzoic acid is the carboxyl-derivative of benzene, and the phthalic acid with which we are now concerned is a dicarboxyl-derivative of benzene. It is related to benzoic acid in the same way that diamidobenzene is related to aniline. ”

“ First, it illustrates the fact that the published formulas of the “ethical” proprietaries are not always reliable. The Campho-Phenique Company has been very willing to give out a formula, purporting their product to be 51 per cent. camphor and 49 per cent. phenol (carbolic acid) . Now, these two drugs will make a liquid mixture, and any druggist can make it, and the mixture will have about the same consistency and appearance as Campho-Phenique. ”

“ When, however, the concentration has reached the value represented by the point y, two liquid layers will be formed, the one solution having the composition represented by y, the other that represented by y′. The system is now univariant, and on further addition of phenol, the composition of the two liquid phases will remain unchanged, but their relative amounts will alter. The phase richer in phenol will increase in amount; that richer in water will decrease, and ultimately disappear, and there will remain the solution y′. ”

“ The phenols of naphthalene are called naphthols—they bear the same relationship to naphthalene that carbolic acid bears to benzene. Owing to the structure of the naphthalene molecule there are two isomeric naphthols, whereas there is only one phenol. ”

“ If we treat phenol with nitric acid under proper conditions, we get a yellow dye called picric acid, which is trinitro-phenol C6H2 (NO2) 3OH; you see this is no aniline dye; it is not a basic colour, for it would saturate, i.e. destroy the basicity of bases. Again, by oxidising phenol with oxalic acid and vitriol, we get a colour dyeing silk orange, namely, Aurin, HO.C [C6H4 (OH) ] 3. This is also an acid or phenolic dye, as a glance at its formula will show you. Its compound atom bristles, so to say, with phenol-residues, as some of the aniline dyes do with aniline residue-groups. ”

“ It must be always borne in mind that, with regard to statistics generally, the term “carbolic acid” is not used by coroners, juries, or medical men, in a strictly chemical sense, the term being made to include disinfecting fluids which are almost wholly composed of the cresols, and contain scarcely any phenol. In this article, with regard to symptoms and pathological appearances, it is only occasionally possible to state whether the pure medicinal crystalline phenol or a mixture of tar-acids was the cause of poisoning. ”

“ In Germany all serums which are obtained from animals, mostly horses, are mixed with 0.5 percent of phenol and carbolic acid—in order to preserve them—i. e., to 400 cubic centimeters I added a concentration of two cubic centimeters of phenol acid. This amount is, of course, far above the tolerance of human beings. Carbolic acid is one of the strongest acids we possess. When treating people with gas gangrene serums a number of deaths occurred. We discussed whether we were dealing with cases of serum death, resulting from the serum, or whether death was caused by the phenol added. ”

“ The occurrence of hydroxyl, whether the substance belong to the simpler chain carbon series or to the aromatic carbon compounds, appears to usually endow the substance with more or less active and frequently poisonous properties, as, for example, in the alcohols, and as in hydroxylamine. It is also found that among the aromatic bodies the toxic action is likely to increase with the number of hydroxyls: thus phenol has one hydroxyl, resorcin two, and phloroglucin three; and the toxic power is strictly in the same order, for, of the three, phenol is least and phloroglucin most poisonous. ”

“ In the developing bath 1 per cent. of resorcine is usually sufficient to use. It develops an orange with Primuline.
Developer F (Bayer) is a mixture of resorcine and soda ash. It requires 11⁄2 per cent, to make a developing bath.
Phenol, better known as carbolic acid, finds a use as a developer. It is dissolved in caustic soda, 10 lb. phenol, 15 lb. caustic soda lye of 70° Tw., and 60 gallons of water. Generally 1 per cent. is sufficient to use as a developer. It is often called yellow developer.
Naphthylamine ether is used as a developer for blues in conjunction with the Diamine blacks. ”

“ In the early days of the phenol-formaldehyde resin industry (1909-16) there was considerable uneasiness about the supply of phenol. World production was not large and Germany and England controlled most of it. The output of the United States was almost entirely for medicinal use, although our potential production was large (see p. 111) . This situation caused many research workers to study the resins made from other tar acids, principally meta and para cresols and the xylenols. The investigations resulted in many new types of resins and in modifications of the phenol-formaldehyde type. ”

“ It dissolves in water, 15 parts of water dissolving about one part of phenol at 16–17° C., but it is miscible in all proportions at about 70° C.; it is volatile in steam, and is readily soluble in alcohol, ether, benzene, carbon bisulphide, chloroform and glacial acetic acid. It is also readily soluble in solutions of the caustic alkalis, slightly soluble in aqueous ammonia solution, and almost insoluble in sodium carbonate solution. When exposed in the moist condition to the air it gradually acquires a red colour. ”

“ If a hydroxyl is substituted for a hydrogen atom in the aromatic hydrocarbons, the action of sulphuric acid is greatly facilitated; thus, by merely mixing phenol with sulphuric acid, the sulphonic acid is at once formed, whereby, in the cold, o-phenolsulphonic acid prevails which on heating for some time to 100°-110° C. is completely converted into p-phenolsulphonic acid. In the absence of free sulphuric acid the conversion of o- into p-phenolsulphonic acid is brought about by heating the aqueous solution. ”

“ I then tried various additions to the green oat straw with the object of finding some substance capable of uniting with and destroying the phenol. This I have at last succeeded in finding; and I am now in possession of a reagent which will so far destroy any of these phenols contained in food, that old age is indefinitely arrested. This as you will see places a dreadful responsibility in my hands. This is not the Secret of Perpetual Youth exactly, for I cannot so far restore youth to the aged—I can only arrest decay. By feeding this antidote to a baby it may remain a baby forever. ”