September, 1926
Iil‘DCSTRIAL A X D ELVGINEERIAVGCHEMISTRY
will become accustomed to use these to lacquer or enamel household furniture, as the active operation will be complete within a half hour. Thus has the paint and varnish industry emerged, after
949
five hundred years of stagnation, into a whirlwind of discoveries and inventions, and it is not within the knowledge of any man to say what will be next in the line of useful paint and varnish materials.
The Evolution of Synthetic Medicinal Chemicals’ By H. V. Arny COLUMRU I ~X I X
ERSITY
COLLEGE OF P 7 1 i R M 4 C Y N E \ \ ’ I ‘ O R K .
HEN the writer entered the retail drug business in
W
1884, about the only prescribed medicinal substance that could be called a synthetic organic chemical was chloral hydrate. It is true that phenol was being made synthetically, and so was salicylic acid, but these substances had been introduced into medicine from quasi-natural sources, whereas chloral hydrate was marketed from the Liebreich pharmacy as a novel hypnotic, even though chloral itself had been described by Liebig thirty-six years earlier.’.* Synthetic medicinal chemicals may therefore be considered as creations of the half-century during which the A b r E R I C A N CHEMICAL SOCIETYhas existed, and the entire remarkable progress made in this field of synthetic chemicals may be included in the recollections of many of us who are still interested in this field. Upon the shelves of the drug store just mentioned were also two other bottles which excited the interest of the pharmaceutical apprentice. One was labeled “croton chloral hydrate” (now known as butyl chloral hydrate),2 which enjoyed for a while some vogue as a hypnotic, coming into use on the wave of popularity of chloral hydrate; the other was labeled “propylamine” (now known as trimethylamine), which was employed by a former owner of the pharmacy as the chief ingredient of a rheumatism remedy which he marketed. The first of the synthetic organic medicaments which came into use during the writer’s experience was iodol. Antipyrine followed shortly and behind it came acetanilide masquerading under the copyrighted name of “antifebrin,” and in their train a horde of substitutes, some of distinct merit and others fraudulent imitations. This is true of almost all the pioneers in the groups of organic synthetics enumerated below. The followers of the typical chemicals were either honestly conceived irnprovcments over the original product or were merely the inferior outputs of competing houses. A study of the groups of synthetic chemicals which will be discussed in this paper shows the interesting fact that the six years 1884 to 1890 were not only the beginning years of what we now call synthetic organics, but were also the years when most of our present-day groups of organic synthetics had their beginnings. This can best be shown by a n enumeration of the groups with the date of introduction of the type chemical heading the list. Aseptol (18%) and other phenol derivatives Beta-naphthol (1884) and other naphthol derivatives Iodol (1886) and other iodoform substitutes Antipyrine (1885) and other synthetic antipyretics Salol (1886) and other salicylic compounds Sulfonal (1888) and other synthetic hypnotics Methylene blue (1890) and other antiseptic dyestuffs Eucaine (1894) and other alkaloidal synthetics Guaiacol carbonate (1902) and other creosote derivatives 1
Received June 2, 1926.
* Numbers in text refer to bibliography
a t end of article
N Y
Arsphenamine (1909) and other arseno- and metallo-organics Epinephrine and other glandular chemicals Hexamethylenetetramine and other miscellaneous chemicals
Phenol Derivatives Phenol3 has been known as a valuable antiseptic for over fifty years, while phenolsulfonates were employed as watersoluble antiseptics as far back as 1870.4 The first product. however, marketed as under a coined name was asept01,~ a solution of o-phenolsulfonic acid. This was followed in 1889 by soziodo1,e which was marketed as metallic salts of iodo-p-phenolsulfonic acid; and in 1893 aluminum pphenolsulfonate under the name s o ~ o l . ~ The accidental discovery in 1906 of the purgative action of phenolphthaleinS has transferred its main value from a n indicator to the field of medicine, and of late years phenolsulfonephthaleing has become the standard diagnostic reagent for determining the efficiency of kidney functionation. Naphthol Derivatives I n 1884 beta-naphthol10 was recommended as a skin and intestinal antiseptic, and for several years following there was considerable controversy as to the relative value of it and its rivals, such as alpha-naphthol and the so-called hydro-naphthol. Beta-naphthol has enjoyed continued esteem in dermatological practice, but its popularity as an intestinal antiseptic has been lessened because of its peppery taste. Derivatives such as benxo-naphthol, or beta-naphtho1 benzoate,” betol, or beta-naphthol salicylate,12 and asaprol, or calcium beta-naphthol m o n o ~ u l f o n a t e ~have ~ some vogue because of their mild taste. Iodoform Substitutes Iodoform14 has been used as a n antiseptic since 1868, and the only drawback to its use is its persistent odor. The first odorless substitute appeared in 1885 under the name of i0d0l.l~ This substance is tetra-iodopyrol and enjoyed much popularity until the appearance in 1890 of a r i ~ t o l , ’ ~ or dithymol diiodide, the lavish advertising of which caused it to become the foremost iodoform substitute. Synthetic Antipyretics With the introduction of antipyrine or phenyldimethyl paraxolon in 1889’ the era of synthetic organic chemicals might be said to have fairly begun. The three groups just discussed are either chemicals discovered in routine research with medical uses later discovered or modifications of such chemicals designed to remove their objectionable features. Antipyrine, however, was a new product, the medical uses of which were published almost simultaneously with its discovery, and since Knorr’s remarkable success investigators the world over have been attempting the synthesis of chemicals with their medical uses directly in mind. Rivals of this immensely successful antipyretic sprang up in large numbers. Some, like antifebrin or acetanilide,lg
’
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ILVDL'S'TRIAL A S D EiLTGIAVEERINGCHEMISTRY
were old chemicals with newly discovered medicinal value; others, like exalgin or a ~ e t o - t o l u i d i d ewere , ~ ~ chemical modifications of the medicament in popular use; still others were pharmaceutical mixtures masquerading as definite chemicals. Among the legitimate antipyrine derivatives may be cited benzopyrine, or antipyrine benzoate,20 salipyrine, or antipyrine salicylate,21 iodopyrine, or monoiodoantipyrine,22 and pyramidone or dimethylamin~antipyrine.~~ I n 1887 appeared phenacetin, or acetophenetidine,?4 the forerunner of a different group of synthetic antipyretics. Phenacetin was speedily followed by methacetin, the monoacetyl compound of methylated a m i d o p h e n ~ lby ; ~ ~hydracetine or acetphenylhydrazine,zGand by phenacoll hydrochloride, or amidoacet~phenetidine.~~
VOl. 18, KO. 9
urinary antiseptic. -4bout the same time that methylene blue was first discussed medicinally, pyoktanin4* was recommended as an antiseptic. The use of scarlet red49 in burns and ulcers began around 1912; while treatment of wounds during the World War brought to light the value of acriflavine,jOproflavine, 51 and brilliant green.52 Alkaloidal Synthetics
This heading is chosen in preference to the phrase "synthetic alkaloids," since the latter would be in part misleading. I n this heterogeneous group the first places chronologically belong to apomorphine, first made in 1869 by Matthiessen and Wright53 and to homatropine, first made in 1880 by Ladenburg. 54 From this viewpoint apomorphine might Salicylic Derivatives be considered as our oldest synthetic medicament, since its remarkable emetic properties were discovered during the The value of salicylic acid and salicylates in rheumatism investigations immediately following its original preparation. has been known since 1875, so the acid may be considered I n the eighties, however, it was merely considered as an as one of the earlier synthetic chemicals. However, we interesting derivative of the plant base, morphine, rather again find the situation where the chemical was both isolated than as a synthetic chemical. I n considering this class, and synthetized before its medicinal value was generally three distinct types immediately come to mind: ( a ) chemicals known, and it was not until 1886, with the introduction of made by slightly modifying natural alkaloids; ( b ) substitutes salol or phenyl salicylate,28 that a synthetic salicylate in for natural alkaloids made from alkaloidal material; (c) the modern sense was brought to the attention of prescribing synthetic chemicals having action similar to natural alphysicians. Salol was soon followed by salophen or acetyl- kaloids but not necessarily having similar chemical compop-amido sal01,29 and by cresalol, or cresol ~alicylate.~OAs- sition. As illustrations of the first two types may be cited pirin, or acetylsalicylic the most popular of the salicyl apomorphine and homatropine, respectively, whereas the nuderivatives, appeared in 1899, and this was followed by merous cocaine substitutes afford examples of the third type. novaspirin or methylenecitrylsalicylic acid.32 This paragraph Apomorphine is obtained by the chemical dehydration would be incomplete without reference to the fine work of of morphine, and it is interesting to recall that this supposedly Hirschfelder on the derivatives of saligenin, or o-salicyl simple chemical change converts the narcotic morphine alcoho1,33 a number of which have distinct medicinal value. into the emetic apomorphine. Other modified morphine derivatives are heroin or diacetyl morphine,55 the manuSynthetic Hypnotics facture of which is now prohibited in this country, and dionine ils mentioned before, chloral hydrate was a largely used or ethyl m0rphine.5~ A quinine derivative, euquinine, hypnotic in the early eighties and shared with the bromides or quinine ethyl carbonate,S7 enjoys popularity because highest popularity among this class of medicaments. In of its absence of taste; while more or less satisfactory attempts 1888, however, there appeared a new claimant for leadership to utilize cupreine, the alkaloid of the Cuprea barks, have in the form of sulfonal or diethylsulfone dimethylmetha1ie,~4 resulted in the marketing of optochin, or ethyl hydrocupreine,ja the first of a long series of synthetic hypnotics that are being vuzin, or iso-octyl hydro~upreine,~g and eucuprin, or isoput upon the market even to this day. Sulfonal was one amyl hydrocupreine.Go of a trio, the other two chemicals being trional, or diethylThe homatropine type of alkaloidal synthetics is of dissulfone methylethylmethane,35 and tetronal, or diethyl- tinct interest because the chemicals falling under this head sulfone d i e t h ~ l m e t h a n e . ~These ~ hypnotics were used are products which are an improvement upon nature. Xtenormously during the late nineties and during the first ropine, or tropine tropate. has certain properties which render decade of this century, and their use mas not entirely free it unsatisfactory as a mydriatic; hence Ladenburg in his from the evil consequences of habit-forming character. classic work, split the tropine from atropine and then, comTurning from the mercaptan derivatives, prescribing bining it with other acids, found the most satisfactory physicians became interested in compounds of barbituric product was tropine mandelate or homatropine. The acid and other urea derivatives. Among these may be cocaine derivative, eckaine, cited in the next group might cited veronal or barbital, or diethylmalonyl~rea,~~ luminal be considered as belonging to this group. or phenobarbital or phenylethyl barbituric dial, The third group of alkaloidal synthetics are chiefly cocaine or diallyl barbituric a ~ i d , ~adaiin, 9 or carbromal, or bromo- substitutes, devised for the purpose of providing local anesdiethylacetyl carbamide,40 bromural or monobrom-iso- thetics free from the harmful habit-forming properties of ~ a l e r y l u r e a ,iodival ~~ or iodo-iso-~alerylurea,~~ and nirvanol coca alkaloid. The earliest of these were the eucaines, or phenylethyl hydantoin.43 beta-eucaine or the hydrochloride of trimethylbenzoyl Two chloral derivatives that are worthy of notice are hydroxypiperidine6l and alpha-eucaine or the hydrochloride chloralamide, the condensation product of chloral with form- of benzoylmethyl tetramethyl oxypiperidine carboxylic amide,44 ural, or chloral ret than,^^ while chloretone, or methyl ester.G2 Around 1906, alypine or benzoyldimethyl trichloro butanol,46is of distinct interest as one of the earlier aminomethyldimethyl aminobutane,63 and stovaine, or organic synthetics produced in the United States. benzoyldimethyl aminoethylpropanol,G4 appeared on the market; while within the past decade such cocaine substiAntiseptic Dyes tutes as eckaine, or benzoyl hydroxypropyl nov-ecgonidine This class affords another illustration of chemicals long ester;Gj anesthesine or benzocaine or ethylamino benzoate;66 used for technical purposes eventually finding their way butyn or p-aminobenzoyl-y-dinormalbutyl-aminopropanol into medicine. The medicinal value of methylene blue47 sulfate,67 phenacaine, or holocaine, or ethenyl-p-diethoxywas first suggested around 1890 when i t was recommended diphenylamidine chloride;'j8procaine, or novocaine, or p as an anodyne. Its largest use in medicine today is as a aminobenzoyl diethylaminoethanol chloride;69 and butesin,
September, 1926
I S D V S T R I A L A N D E-:GI-VVRERISG CHEMISTRY
the butyl ester of p-aminobenzoic acid,jOhave found favor among prescribing physicians. The brilliant investigations of Macht about 1918 confirmed the fact that the anesthetic properties of cocaine were due to its benzoyl group and brought about the medical nse of benzyl alcohol and its esters, notably the benzoate. It is interesting that the pharmacological properties of papaverine, the opium alkaloid, is largely due to the presence of a benzoyl group. Eucatropine, or euphthalmine, or pheiiylglycolylmethy1vinyldiacetonealkamine h y d r ~ c h l o r i d e ,is~ ~the combination of mandelic acid and a base similar to that found in betaeucaine. Its properties are mydriatic rather than anesthetic; hence its trade name. Whether the gout remedies, atophan or cinchophen or phenylquinoline carboxylic acid,’* and novatophan, or ethylmethyl atophan,j3 should be included in this group is a matter of opinion. 4 s quinoline derivatives, however, they seem to belong properly a t this place. I n fact, in some respects these chemicals may be considered as the best illustrations of alkaloidal synthetics. Creosote Derivatives
Creosote has been used in medicine since 1862. Since about 1888, its active constituent, guaiacol, has been upon the market and is much used as a pulmonary and intestinal antiseptic. The fact that it is a liquid and possesses a characteristic odor and a more or less irritating effect upon the stomach suggested to chemists the task of preparing creosote products in solid and tasteless form. Among these may be cited benzosol, or guaiacol benzoate;j4 duotal, or guaiacol carbonate,?: creosotal, or creosote carbonate;j6 thiacol, or potassium guaiacol sulfonate;??and calcreose, or calcium creosotate.7b Arseno- and Metallo-Organics
Cacodylates were seriously considered in medicine around 1900, but the real introduction of arseno-organics may be said to date from the time of the epoch-making researches of Ehrlich on salvarsan, or arsphenamine’g when the era of intravenous medication really began. Arsphenamine was followed by neoarsphenamine, or neosalvarsan, while recently tryparsamide, or the sodium salt of phenylglycineamido-p-arsonic acid,bl has received favorable attention. Antimony preparations have been subjects of careful study by English investigators, especially as remedies for spirochetal diseases. Among the few placed upon the market is stibacetin, or p-acetylaminophenyl stibinate.’j2 h number of mercuro-organics are now employed as antiseptics and autosyphilitics. The most popular of these are mercurochrome or dibromoxymercury fluorescein,83 mercurophen, or sodium oxymercury-nitrophenolate,*4and mercurosal, or disodium hydroxymercuri salicylacetate.8j Glandular Products
This heading brings us to a field in which synthetic chemistry has merely made a beginning. Away hack in IS57 Boudault, the French pharmacist, prepared pepsin upon a commercial scale, while pancreatin began to be prescribed somewhere around 1873. These two enzymes are, however, mixtures of principles extracted from natural sources. The first glandular product to be used in medicine of a quality akin to a definite chemical was adrenaline, or epinephrine or inethylaminoethanol catechol,86 and the levogyrate variety is now made synthetically. A similar synthetic product is tyramine, the hydrochloride of the base p-hydroxy phenylethylamine,67which was isolated from ergot by Barger and which was first made synthetically by him. We should perhaps consider this substance among the alkaloidal syn-
951
thetics, but its close chemical relation to epinephrine suggests its discussion a t this time. Tethelin,&8isolated by Robertson from the anterior lobe of the pituitary body, is a glandular product of which little is known chemically, and the same may be said of that valuable agent in the treatment of diabetes, insulin.89 On the other hand, Kendall’s study of the thyroid gland brought about the isolation of thyroxin or t,riiododihydrooxindolepropionicacid, although the synthesis of this substance has not yet been accomplished. Miscellaneous
A number of useful synthetic medicinals do not, lend themselves to places in the foregoing groups and are yet worthy of passing notice. Thus hexamethylenetetramine, described by organic chemists back in the sixties, came into medical use around 1900 as a uric acid solvent and urinary antiseptic under bhe trade name of u r ~ t r o p i n e . ~Oil ~ of chaulmoogra, prescribed largely as a leprosy remedy by Dr. Isadore Dyer of New Orleans in the nineties, is now utilized intravenously in the form of the ethyl ethers of its charact,eristic a ~ i d s . 9 ~Behenic acid from oil of hen is now utilized medicinally in the form of bromine and iodine compounds. Calioben or saiodin, the calcium salt of monoiodobehenic acid,93 and as sabromin, or calbroben, or calcium dibr0mobenate.9~ During the World War, after the CarrellDakin solut’ionhad obtained great vogue as a wound dressing, Dr. Dakin devised for the same purpose stable chlorinated organic substances known as chloramine-T, or sodiump-toluene sulfonechloramide9~ and dichloramine-?’, or p toluene sulfonedichloramide.96 Conclusion
The foregoing review of the past fifty years of synthetic organic medicaments enumerates almost one hundred organics that have proved of distinct value in the treatment and cure of disease. The next fifty years will show even greater trend toward the use of organic synthetics as medicines and it behooves us American chemists to do our part in developing this field of human endeavor. Bibliography 1-Chloral: Liebig, A m . J . Pharm., 4, 351 (1833); Liebreich, Pharm. J . , [2] 11, 150 (1869). 2-Croton chloral hydrate: Hofmann, I b i d . , [ 2 ] 11, 720 (1870); Kraemer a n d Pinner, A n n . Chem., 151, 37 (1871). 3-Phenol: Calvert, Chem. N e z o s , 17, 69 (1868). 4-Phenolsiilfonates: Procter, A m . J . Pharm., 41, 131 (1870). 5-Aseptol: Serrant, Proc. A m . Pharm. Assoc., 34, 563 (1886). 6-Soziodol: Larmuth, I b i d . , 37, 630 (1889). 7-Sozol: Schaeges. I b i d . , 41, 531 (1893). 8-Phenolphthalein: Brasch, Pharm. Ztg., 61, 668 (1906). 9-Phenolsulfonephthalein: Anon, J . A m . M e d . Assoc., 62, 297 (1914). 10-Beta-naphthol: Anon, Proc. A m . Pharm. Assoc., 32, 246 (1884). 11-Benzo-naphthol: Yvon a n d Berlioz, I b i d . , 40, 956 (1892). 12-Betol: Robert, Arch. Pharm., 216, 703 (1888). 13-Asaprol: Stackler, A m . J . Pharm., 64, 517 (1892). 14-Iodoform: Anon, Proc. A m . Pharm. Assoc., 16, 206 (1868). 15-Iodol: Ciamician and Silber, Ber., 18, 1766 (1885). 16-Aristol: Goldman, Proc. A m . Pharm. .lssoc., 38, 624 (1890). 17-Antipyrine: Knorr, Ber., 17, 2032 (1884). 18-Antifebrin: Cahn a n d Hepp, A m . Druggist, 15, 209 (1886). 19-Exalgin: Dujardin-Beaumetz, A m . J . Phnrm., 61, 243 (1889). 2O--Renzopyrine: Cressati, Proc. A m . Pharm. .Assoc., 40, 1047 (1892). 21-Saiipyrine: Schulvien, Pharm. Z t g . , 35, 395 (1890). 22-Iodopyrine: Dtiroy, Proc. A m . Pharm. A s s o c , 40, 1049 (1892). 23-Pyramidone: U. S. Patent 579,412 (1897). 24-Phenacetin: Anon, Phorm. J . , 131 18, 264 (1887). 25-Methacetin: Weller, Pharm. Z t g . , 34, 419 (1889). 29-Hydracetine: Guttmann, Proc. .Am. Pharm. Asssoc., 38, 690 (1890). 27-Phenacoll: Schering, U. S. Patent 543.214 (1896). 28-Salol: Nencki, A m . Druggist, 15, 226 (1888). 29-Salophen: Anon, Proc. A m . Pharm. Assoc., 40, 1027 (1892). 30-Cresalol: Anon, I b i d . , 44, 474 (1896). Bayer, U. S. Patent 644,077 (1900). 31-Aspirin:
INDUSTRIAL AND ENGINEERING CHEMISTRY
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32-Novaspirin: Rayer, U. S. Patent 858,142 (1907). 33-Saligenin: Hirschfelder, Ind. Eng. Chem., 15, 457 (1923). 34-Sulfonal: Baumann, Ber., 19, 2808 (18%). 3 e T r i o n a l : l‘romm, A n n . , 263, 150 (1889). 36-Tetronal: Baumann a n d Kast, Z . physiol. Chem., 14, 64 (1890). 37-Veronal: Bayer, U. S. Patent 782,739 (1905). 38-Luminal: U. S. Patent 1,025,872 (1912). U. S. Patent 1,042,265 (1912). 39-Dial: I O - A d a l i n : Bayer, U.S. Patent 983,425 (1911). U. S. Patent 914,518 (1909). 41-Bromural: 42-Iodival: Ernert, Pharm. ZentraZhaZle, 49, 873 (1905). 43-Nirvanol: Anon, Yearbook, Am. Pharm. Assoc., 7, 162 (1918). 44-Chloralamide: Rabon, A m . Druggisl, 18, 190 (1889). 4 6 U r a l : Poppi, Chemist and Druggist, 34, 406 (1889). 4B-Chloretone: Anon, A m . Druggist, 36, 12 (1900). 47-Methylene blue: Ehrlich and Leppmann, Proc. A m . Phaum. Assoc., 38, 689 (1890). 48-Pyoktanin: Merck, A m . J . Pharm., 6 2 , 295 (1890). 4 9 4 c a r l e t red: Anon, Drug. Circ., 66, 201 (1912). 5 h A c r i f l a v i n e : Browning, A m . Druggist, 66, 400 (1917). 51-Proflavine: Pearson, A m . J. Pharm., 90, 428 (1918). 52-Brilliant green: Browning (see 50). 53-Apomorphine: Matthiessen a n d Wright, Proc. A m . Phaum. Assoc., 17, 260 (1869). 54-Homatropine: Ladenburg, Ber., 13, 1340 (1880). &&Heroin: Dresen, Proc. A m . Pharm. Assoc., 47, 735 (1899). 5 6 D i o n i n e : Anon, Ibid., 49, 630 (1901). 57-Euquinine: Merck, U. S. Patent 585,068 (1897). 58-Optochin: Oliver, Yearbook, Am. Pharm. Assoc., 6, 377 (1916). 59-Vuzin: Schaeffer, I b i d . , 7, 522 (1918). 60-Eucuprin: Bylsma, 2. exptl. Med., 11, 257 (1920); C. A , , 15, 1575 (1921). 61-Beta-eucaine: Merling, Pvoc. A m . Pharm. Assoc., 46, 727 (1894). 62-Alpha-eucaine: Merling, I b i d . 63-Alypine: Bayer, U. S. Patent 808,748 (1906). 64-Stovaine: Poulenc, U. S. Patents 828,846; 829,262; and 829,374 (1906). 6,+Eckaine: Wichura, J . SOC.Chem. Ind., 38, 598 (1919). 6 6 A n e s t h e s i n e : Hirschfelder, Ind. Eng. Chem., 15, 456 (1923).
Vol. 18, No. 9
67-Butyn: Abbott, U. S. Patent 1,358,751 (1920). 68-Phenacaine: Anon, Yearbook, Am. Pharm. Assoc., 9, 177 (1920). 69-Novocaine: Anon, Ibid., 3, 650 (1914). 7O-Butesin: Abbott, U. S. Patent 1,440,652 (1923). Anon, New a n d Non-Official Remedies, 1924, p. 60. 71-Eucatropine: 72-Atophan: Nicolaier and Dohrn, Deut. Arch. kZin. Med.. 93, 231 (1908); C. A , , 2 , 2832 (1908). 73-Novatophan: Schering, U. S. Patent 1,045,759 (1912). 74-Benzosol: Anon, Chemist and Druggist, 37, 102 (1890). 75--Duotal: Ehlert, Pharm. Rev., 20, 211 (1902). Anon, Proc. A m . Pharm. Assoc., 42, 715 (1594). 76-Creosotal: 77-Thiacol: Roche, U.S. Patent 650,218 (1901). 78-Calcreose: Maltbie, U. S. Patent 1,047,961 (1912). 79-Salvarsan: Ehrlich, Ber., 42, 17 (1909). 8 G N e o s a l v a r s a n : Anon, J . A m . Med. Assoc., 69, 323 (1912). 81-Tryparsamide: Jacobs and Heidelberger, J . A m . Chem. Soc., 4 1 1587 (1919). 82-Stibacetin: Fargher, J . Soc. Chem. Ind., 39, 333R (1920). 83-Mercurochrome: Young, White, and Swartz, J . A m . Med. Assoc., 73, 1483 (1919). 84-Mercurophen: Schamberg, Kolmer, a n d Raiziss, I b i d . , 68, 1458 (1917). 85-Mercurosal: Rowe, J . A m . Pharm. Assoc., 12, 8 (1923); 14, 317 (1925). 8 6 A d r e n a l i n e : Takamini, A m . J . Pharm., 73, 523 (1901); Abel, Ibid., 76, 301 (1903); Anon, Pharm. Ztg., 62, 466 (1907); Flaecher, Proc. A m . Pharm. Assoc., 67, 404 (1909). 87-Tyramine: Barger, J . Chem. SOC.(London), 96, 1123 (1909). 88-Tethelin: Robertson, J . B i d . Chem., 24, 397 (1916). 89-Insulin: Banting a n d Best, J . Soc. Chem. I n d . , 41, 537R (1922). Q&Thyroxin: Kendall, Yearbook, Am. Pharm. Assoc., 7,312 (1918); 8, 503 (1919). 91-Urotropine: Nicolaier, Proc. A m . Pharm. Assoc., 44, 494 (1896). 92-Chaulmoogra esters: Dean and Wrenshall, J . A m . Chem. Soc., 42, 2626 (1920). 93-Calioben: Bayer, U. S. Patent 839,509 (1906). 94-Sabromin: Bayer, U. S. Patent 848,230 (1907). 95 a n d 96-Chloramines: Dakin, Cohen, Daufresne, a n d Kenyon, Proc. Roy. Soc. London, ( B ) ,89, 232 (1916); C. A . , 10, 2912 (1916).
Influence of Chemistry on Ceramics’ By Ross C. Purdy 252s
NORTH
HIGHST..COLUMBUS, OUIO
UCH of fable, romance, and drama has been told of
*M
the beginning of clay and glass working. The claim that ceramics is the “oldest of the arts” is plausible but not certain. Bricks with straw and the potter’s craft are mentioned in prehistoric records. Recent excavations prove for man of the early centuries a high degree of ski11 and considerable knowledge of compounding for quality and color. The story of Pallisy sacrificing his flammable possessions to gain a n effect in enamels and that of TT’edgewood discovering potter’s flint in the dust prepared for treating the eyes of his horse typify the legends of the beginning of ceramics. Varying properties in the body of the ware and differing color effects were produced in clay and glass long before the chemistry of the elements was known. As in metallurgy, men for several centuries have fashioned useful and decorative ceramic wares of distinctive merit from minerals by empiricism of scientific caliber. They could neither analyze nor synthesize in any other than the most simple cut-and-try empirical manner. The wonder of it all is that no record has been found of the experiments made and mixtures used, for these early ceramists were anything but quacks; they were real scientists. Highly educational would be the stories of how they discovered the way to work minerals and ores into usable condition and how t o compound them to obtain such perfection in form, quality, and decoration. These stories would, 1
Received August 4, 1926
no doubt, shame most of the present-day ceramic experimenters on the score of resourcefulness and imagination. They did not have means of knowing what ceramic workers in other parts of the world were accomplishing, and quite evidently not one of them thought he could afford to tell the world his secrets. There was neither means nor incentive to exchange information. The museum samples of the wonderful ware occasionally made in clay and glass in the years prior to the development of chemical knowledge and methods have given rise to the notion by many collectors that these specimens represent a lost art. It is often said that modern ceramists cannot reproduce the properties, tints, and decorative processes of some of these ancient museum samples. Such statements are folly. Chemistry of materials and material-compounding is a knoivledge so generally possessed, and the methods and equipment so finely developed, that ceramic wares which rival in every way the finest that man has ever made are produced today in carload lots. The most direct answer to a query regarding the influence of chemistry on industrial ceramics is that, rather than now and then one skilled in synthetic impericism, today a n accurate knowledge of mineral compositions and properties and of what is produced when mixtures of silicate minerals are heated to a degree of fusion, is quite general. The shop-trained ceramist can and usually does know more about the chemistry of materials and mat erial-compounding required for specified properties than did the best informed ceramist of fifty years
.
