October, 1927
INDUSTRIAL AND ENGINEERING CHEMISTRY
joint may be used. The Van Stone joint is desirable if frequent taking down will be necessary, as the stainless irons tend to seize in threaded joints. Stainless iron tubing, because of its high oxidation resistance, is eminently suitable for construction of recuperators, heat exchangers, etc. The question of castings is an important one. Actually, all the types described above may be cast, but it is difficult to produce sound castings free from blowholes and porosities with the extremely low carbon of the stainless irons. The usual carbon content of stainless castings will run from 0.25 to 0.40 per cent; and obviously much higher carbon may be used when hardness is desirable, as for parts to resist wear and abrasion. With high carbon the alloys are really steels and require careful annealing before becoming machinable. Further,
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since the molten alloy is somewhat viscid and gummy, intricate castings with small sections are difficult to produce; also larger-sized castings, as may be made from steel, are still an impossibility. Probably the easiest cast and the most successful alloy for casting purposes is Type 5. Physical properties of such material (annealed) are given in Table I [Castings (a)].This is a moderately soft material, but has a low ductility. The Type 3 analysis, with 16-18 per cent chromium and 0.30 to 0.35 per cent carbon, has also been successfully cast, although it is slightly more difficult to obtain sound castings. Castings of this alloy have the advantage of greater toughness and strength. The physical properties of these castings are shown in Table I [Castings ( b ) ] .
Mothproofing Fabrics and Furs’ A Consideration of the Procedures That Have Been Proposed by Others and a Description of a New Process By Lloyd E. Jackson and Helen E. Wassell MELLON INSTITUTE OF INDUSTRIA&RESEARCH, UNIVSRSITY O F PITTSBURGH, PITTSBURGH, PA.
The authors have recently completed a comprehensive investigation of possible moth-repelling chemicals, in which the discovery was made that the cinchona alkaloids, as well as their derivatives, are particularly effective moth repellents. The fact that they can be prepared to be soluble in a wide variety of appropriate vehicles makes it possible to use some one or more of these substances under almost any condition encountered in the production and use of materials susceptible to moth attack. A process in which one of the cinchona alkaloids is employed has been in successful commercial use for more than a year in the dry-cleaning industry. Processes utilizing the cinchona alkaloids are adaptable to many other
industries in which the clothes-moth is a destructive nuisance. Products of the cinchona alkaloids have been shown to meet criteria of excellence heretofore unsatisfied by other moth repellents. They are inodorous; they adhere to the materials to which they are applied: they can be put on evenly like a dyestuff: they are not apparent on the materials treated; they do not dust off: they do not affect undesirably the physical properties of textile fibers; they can be made soluble in inexpensive organic solvents, such as petroleum naphtha, as well as in water: they are nontoxic to human beings: they are valuable clothes-moth repellents; and they are economical to use industrially.
...... . . ...... UCH has been written about the destructiveness of the clothes-moth, but only a rough estimate can be made of the damage caused by this common pest. Clothes-moths are continually engaged in their work of destruction in many parts of the world. There are, in fact, many records of their vast damage since the beginning of history, in writings concerning European, ilsiatic, African, and other countries. Dependable data on the losses caused by clothes-moths are unobtainable, because these insects do their destruction in so many different places, such as homes, mills, storehouses. stores, etc. The annual loss, in the United States alone, due to injurious insects of all kinds is conservatively placed a t two billion dollars.2 There is little doubt that millions of dollars of this loss are attributable to the clothes-moth. Many methods have been proposed for controlling clothesmoths. During the last fifty years more than forty patents have been issued in the United States on procedures of combating the pest. Various methods of control are mentioned in textbooks, government bulletins, trade journals, and household magazines.3 Many of these procedures have become
M
’
Received March 28, 1927. Fernald, “Applied Entomology,” p. 34. SSee, for example, Smith, “Our Insect Friends and Enemies,” p. 241; Packard, “A Guide to the Study of Insects,” p. 347; Cornstock, “Manual for Study of Insects,” p. 257; Hygeia, 3, 642 (1925); A m . Dyestuf Reptr., 14, 151 (1925); Bur. Chemistry, Farmers’ Bull. 1363; Texlzle Colorist, 48, 89 (1926). 2
common knowledge, and some of them are the bases of commercial products; but most of the methods are either ineffective or a t least inefficient in repelling clothes-moths. ’ Often the substances used to combat clothes-moths have some undesirable characteristic, such as malodor; or they affect adversely the physical properties of the materials treated. The use of most materials recommended for controlling clothesmoths depends upon the production of a vapor which is toxic or otherwise offensive to the insects. The clothes-moth readily adapts itself to its food. The presence of comparatively large quantities of any one or more of a large variety of chemicals in its natural food of wool or feathers does not curtail its voracious appetite. It is generally known that petroleum distillates, such as gasoline and naphtha, destroy clothes-moths. For this reason it has been a practice of the housewife to have moth-infested wearing apparel, furniture, and other household articles drycleaned to destroy clothes-moths in them. Such treatment exterminates the insects, but it does not prevent other clothesmoths from entering the materials later, to continue the destruction that was temporarily curbed. Early in 1921 a group of dry-cleaners and dyers, organized as the hlundatechnical Society of America, established a Multiple Industrial Fellowship in Mellon Institute of Industrial Research for the purpose of investigating problems pertaining to the garment-renovation industry. Because the inadequacy of dry-cleaning for clothes-moth control was
INDUSTRIAL '*.!ID ENGINEERING C l i E M l S T K Y
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recogriiied by the society, research on clot.lres-motli repelling substances was started by the Fellowship in tlic fall of 1922. A substance was specified which would be soluble in drycleaning fluid, aud which could be put into clothes-moth iniested or atbackable materials after tho dry-cleaning fluid had evaporated. In consequence (JS t,liis investigation, a series of related products of t,he einchona alltaloidu bas 1)een fr~ninlt,o Fulfil not only t,lle clothes-moth repelling requirements of tlie drycleatmr and dyer, hut t h e of other indust,ries H S well. T h e study OF the produck has also been extended with tlic idea of making them generrtlly applicablc in h o m e s , warehouses, mills, stores, and factories where materials areexposed to clothesm o t h a t t a c k . The 1: x pi: r i iiic n t a1 work has covered four and a half years, during wliich t i m e tlic 14ot,i1cs-inoth repelling properties OF a large number of substrinces have heen given atteution hg the I"el1owsliip. Pisure I-Moth
Incubation Cupboards
Criteria of Excellence of Mothproofing
Before act,ual remwci, on mothproofiug agents vias undertaktm by the Fellowship, definite criteria OF excellence were decided upon and adopted as the objective of the investigstion. The standard WRF ma,& such tliat all the objections to t,he coinrnonly used clot,hes-moth cont,rolling materials would he oycrconie by the satisfactory conclusion of the research program. Moth repellcnbs that have heen proposed in the past are objectional~lefor one reason or another. Odor,ous materials are commonly used. It is the vapor from most of them substaliees that destroys or repels the moth. Large yrimt,it,ies OF tlie substances are usually required. Many of the products that have heen recommended do not adliere to the material that is to bc probected. To use others effectively, it is necessary to place the materials and tire repellent in closed containers or cupboards, in order to corifirie tlie moth-repelling fumes to a small sp the effect,desircd. With repellents of iiiis type ticahle to distrihut,e them evenly over t,he material to be protectcri. I.'urthernrore, it is not always convenient,, or e:m:n possible, t,o use them in closed cupboards. Still other iiuhst,ances used for clot,hes-niot.hcont.ro1, wlricli depend for &e(,ti\mtess on tieing dust,ed onto the mabcri:als t.o be protected, have t,lie object,iunnble propert,y of being visible on and diffimlt to remove from the materials treated. Some of tlie substances that bare heen recommcndcd affect tlie physical properbies of the materiirk treated in t.hat. the tensile strengt,li is lowered, colors are changed, and the general appearance is altcrrd. I'roliably the most objectionable property oF certiLin mot,h repellents is their toxicity toward human beings; for example, such poisonous substances as arsenic compounds liave heen actunlly t t s ~ l . Weber is employed as a solvent for many of the materials offered as moth-repellents. Under many conditions water is not a suif,abic solvent for the purpose. Water caiwes wool
Vol. 19, No. 10
to slnink; liardens the Icather of fur; spots vaniished surfaces; looscris glued joints in wooden Furniture; water-spot,s silk linings of wool or Fur gamrcnbs; removes pleats and other creases pressed into wool fabrics; impairs the shape of wool garmenbs, and destroys the our1 and sliape of such feather articles as ~ilumes;it does not have the peiietrating properties OF most organic solvents; and, last!?, it is devoid of the specific insecticidal (larvacidal) properties of niany organic solvents, as, for example, carbon tetrachloride or petroleum naphtha. hlindful of such objeet.ions to the niotli repellents that have IJWW recommendecl, the criteris of excellence for the moth repelleiit that was to be developed were defined as follows: (1) I t must be inodorous. (2) I t must adhere evenly to the fiber treated like a dyestuff.
( 3 ) It must l e unrecognirsble on the fiber. (4) It must not dust off. (5) It must not affect adversely the physical propcrties of the textile fibers. (e) It must be soluble in inexpensive organic solvents, such as petroleum naphtha, as well as in water. (7) It inust have no untoward physiological action; tbat is, it must be non-toxic to human beings. (X) I t must repel clothes-moths. ($1) I t s Cost must be rcasom.ble lnm thc iiidustribl viewpoint. investigational Plan
Upon undertaking the search For such a desirable mot,hproofiiig agent, t,ho literature was found to reveal little in-
formation regarding i,lie toxicology of viirinus cheniicals with respect to clothes-moths. Reports were located regarding sncli substances as Martins' yellow dyestuff (sodium, calcium, or ammonium salt of dinitronaplithol), which have heen claimed to liave moth-repelling properties.' Certain Anorides such as sodium fluoride, ammonium-aluminurn fluoride, and salts of hydrogen fluosilicic acid, as well as other acids and their salts, such as phosphotungstic, fluotitanic, antimonytungsiic, phosphomolybdic, tungstic, uranic, colloidal sificic, colloidal stannic, molybdic, and antimonic acid, were found in a patcnt on protecting wool from clothes-moths.' Some rrsii1t.s of work on the nioth-proofing qualities OF various dyest.uffs have heen published recently.6 Many of tlie materials mentioned were tried during the miirse OF ilie writers' work on mothproofing. Fluorides of organic bases were propared and investigated for mothproofing properhs. Organic compounds s i m h to Martius' yellow were prepared with the ohject of increasing toximty. Such compounds as the 1,2 and 1,4-hydronaphthoquinonesand nitronaplithalenes were tried, to determine, if possihle, which of tlie mdicsls, the hydroxyl or the nitro, is the more act,ive for repelling mot,hs. According to some authorities on pharmacology, both groups increase toxicity to human h e w s , hut tile writers found tha,t neit,her radical seems to he toxic to clothes-moths. A number of the naphthylarninesulFonic acids were studied, and beta-naphthylamine was used as a base to prepare a hydrofluoride. Atbempts were made to use tri- and tetra-oxynapbtlralenes, hut these substances were Found to be too unstable for application as mothproofing agents. NapJiQiyl fluoride was prepared and tried without success. I n order to make tlie food of the clotiies-motlis unattractive to them, hittersubstances, such a3 aloes and ethyl phthalate, were tried on wool, which was then exposed to the insects. Certain alkaloids were chosen for study on account 4
l'rih;mdhingcn des Verein
Z U Hrfoidrruns ~
des Cewerbffrisses, 1921;
n z t ; I i h . Wisi., Ind. Hondd, IS,350 (19211; Ibid., 19, 378 (1922). I British I'atcni 173.5316 (1921). I Tmjiii
C d w i , % t49, , 89 (1927).
INDUSTRIAL A N D ENGINEERING CHEMISTRY
October, 1927
of their bitterness and also because they form salts with such acids as hydrofluoric acid. Although bitterness and the property of forming a hydrofluoride did not prove to be the essentials needed to produce a mothproofing compound, the choice of substances for trial based on this hypothesis finally led to the discovery of a series of compounds that have strong moth-repelling properties. Nost of the bitter substances and hydrofluorides proved to be ineffective mothproofing agents. The conclusion of a German zoologist, that substances are moth-repellent that produce inflammation and irritation in the intestinal tract of the clothes-moth larvae, led to the study of substances that are known t o cause this condition in the human body. Various organic purgatives, magnesium sulfate, sodium sulfate, and acid salts were tried on the strength of this hypothesis, but none of them proved to be effective moth repellents. T a b l e I-Substances Acetamine Acetophenetidin Acid acetylsalicylic Aldol Aloin Alpha-naphthol Alpha-naphthylamine hydrofluoride Alpha-nitronaphthaiene Aluminum acetate Aluminum fluoride Aluminum palmitate Amarine Ammonium fluoride Ammonium phosphate Anthracene Anthraquinone Antipyrine Benzidine hydrofluoride Betaine hydrochloride Beta-naphthoquinone Beta-naphthylamine Beta-naDhthvl - - benzoate Beta-naphthyl methyl ether Beta-naphthyl salicylate Bismuthal Cerium oleate Cinchonicine hydrochloride. Cinchoriicine oleate Cinchonidine hydrochloride Cinchonidine hvdrofluoride Cinchonidine oleate Cinchonidine sulfate Cinchonine hydrochloride
E x a m i n e d f o r Moth-Repelling Properties Phosphine R N Cinchonine hydrofluorPhosphine G N ide Potassium alum Cinchonine oleate Cinchonine sulfate Creatine Crotonaldehyde 1,s-Dihydroxynaphthalene-3,6-disulfonic acid ride Quinicine oleate Dinitrobenzoic acid Quinidine hydrochloDinitronaphthalene Diphenylguanidine ride Ditolylguanidine Qyireidine hydrofluorElaterin Quinidine oleate Ethyl phthalate Quinidine sulfate G" salt Quinine hydrochloride Hexachloroethane Quinine oleate Hydrazine hydrofluorQuinine sulfate ide Quinoidicine oleate(&\ Hydrazine sulfate Quinoidicine oleate Hydroquinone uinoidine hydrochlo1.4 - HydronaDhtharide quinone 8 Hydroxyquinoline Quinoidine oleate@) uinoline hydrofluorLanthanum oleate ide Magnesium oleate Magnesium sulfate Quinoline salicylate Metaldehyde Q uinoline : sulfate Salicin Naphthalene tetrachloSodLum benzoate ride Naphthyl fluoride Sodium bicarbonate h'aphthylhydrazine Sodium carbonate Sodium fluoride hydrofluoride 1-Xitro-2-naphthol Sodium phosphate Nitronaphthylamine Tannin Tartar emetic Nitroso-beta-naphthol Tetraldon Numoquin hydrochloride Thiocarbanalide Thorium oleate Paraldehyde Vusin hydrochloride Pepper - alcoholic extract of black pepper Phenetidine hydro5uoride I
COMBINATIONS O F CHEMICALS A N D
COMPOUNDS
Aluminum fluoride, aluminum sulfate, ammonium fluoride, and sulfuric acid in water Aluminum soap solution in naphtha followed b y ammonia in naphtha Ammonium molybdate, nitric acid, and sodium phosphate in water Hydrazine sulfate in water, followed by ammonium fluoride in water Hydrazine sulfate, ammonium fluoride, and dry-cleaning soap in naphtha Hydrazine sulfate, magnesium sulfate, and ammonium fluoride in water Hydrofluoric acid, Glauber's salt, and sulfuric acid in water Magnesium sulfate in water, followed by ammonium fluoride in water Magnesium sulfate, followed b y sodium fluoride in water Naphthylhydrazine hydrofluoride mixed with dry-cleaning soap in naphtha Potassium silicate, Glauber's salt, and sulfuric acid i n water Quinidine hydrofluoride mixed with dry-cleaning soap in naphtha Quinidine sulfate mixed with dry-cleaning soap in naphtha Stannic acid, Glauber's salt, and sulfuric acid in water Tannin in water, followed b y tartar emetic in water Tannin in acetone followed by antimony oleate in naphtha Tungstic acid, Glauber's salt, and sulfuric acid in water a Quinoidicine is a mixture of quinatoxins prepared from quinoidine. b Quinoidine is a mixture of alkaloids occurring in the mother liquors from the preparation of quinine sulfate and is obtained by precipitation with caustic soda.
Another basis of attack was to investigate substances that have germicidal and antiseptic properties. A large number of substances that are known to be toxic to bacteria and other forms of lower life, but non-toxic to human beings in quantities such as would be used for treating wool, etc., were chosen for trial as moth repellents. The property of local anesthesia was made the basis for selecting still other materials, such
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as alkylated cinchona alkaloids. Other chemicals were tried because they are astringents. On the basis of these hypotheses a long list of chemicals was decided upon for investigation. As the work progressed, mixtures of various chemicals were also studied. The chemicals chosen for examination are listed in Table I. Experimental
Before the mothproofing properties of the chemicals could be determined, a supply of clothes-moths had to be propagated. Note-The clothes-moth used in most of the experiments was Taneola biselliella, commonly known as the webbing or Southern clothesmoth. The black carpet beetle, Allagenus $iceus, was also used.
The first plan was to incubate them in small glass jars at about 30" C. Larvae obtained from moth-infested materials were transferred to pieces of woolen cloth and then incubated, but the method was not successful even after several months' trial. With the next procedure better results were obtained. Moth-infested garments were placed in burlap sacks, which were then kept near a steam radiator during cool weather, and moths were seen to thrive under this crude method of culture. Somewhat later a wooden cupboard was constructed containing six large drawers to take the place of the burlap bags. The cupboard was kept in a steam-heated room and was sumlied with an auxiliarv" thermostat-controlled electrical heating unit to keep i t warm during cold nights. Each drawer was fitted with a top of fine-mesh wire to prevent the escape of moth flies, and was stocked with moth-infested m a t e r i a 1s . p$$m ' Woolen test pieces treated with the different chemicals u n d e r investigation were placed in the drawers for observation. Varnalene Woolen c l o t h with a Carbon heavy pile or nap was chosen fetmch'oride for the test pieces. During t h e i n v e s t i g a t i o n many different pieces of woolen cloth were purchased for the Longrtime purpose, and a piece of the burninq oil cloth from each purchase was placed in one of the moth cupboards as a blank or control to make sure that the untreated cloth I w o u l d be e a t e n by the Carbo,, Kerosene larvae. I n each case the ktmchlorideblank pieces were attacked. The pieces of cloth for all F i g u r e 2-Relative P e n e t r a b i l i t y the tests were cut to about pofe l lVarious Vehicles f o r M o t h Reents 6 by 5 inches. PRELIMINARY TEsTs-The preliminary test of any chemical or mixture of chemicals consisted of preparing a solution usually 0.25 per cent in a volatile solvent. Then three test pieces of woolen cloth were either sprayed with or immersed in this solubion, and then allowed to dry. When t h d t e s t pieces were sprayed, they were treated with just enough solution to dampen the material; and when they were immersed they were removed from the solution and tightly wrung or extracted. When the pieces were dry one of them was washed with soap and water, another was dry-cleaned, and the third was left per se-i. e., it was given no further treatment. Finally, the test pieces were placed in one of the moth cupboards. Every 2 or 3 weeks all the moth cupboards were
0
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COWXKMATORY Tnsrs--hil the chemicals and mixtures of chemicals chosen for the investigation were studied in the way described. Most of them were soon eliminated, because they did not show moth-repelling properties. When a cliemical passed the “special test,” confirmatory tests were made. Clothes-moth flies were allowed to deposit eggs on woolen t e s t pieces which had been treated with t.he mothrepelling cliemical, and then the test pieces were incubated to determine whether the eggs would develop. Live, healthy clothes-moth larvae were placed and confined on other test pieces treated with the chemical. If the chemical passed all the tests mentioned, it was then subjected to sub-commereial tests to determine its adant.abilitv to technical requirements. The described lahoratorv urocedure for ascertainins the effectiveriess of moth repelling requires more than a year for its complete application. It includes conditions comparable with the natural conditions undcr wliich the clothesmoth lives as well as seven art,ificial conditions. Experience in the work with clothes-moths has taught that the determinaiion of tho mothproofing effect,iveness of any substance should embrace check determinations, because often, when a single test for the effect,ivenessof a substance is positive, a check test under the same, or slightly different, conditions is negative. h substance was considered an effective moth repellent only when it gave positive results under all logical conditions. FURTIIER 8 T U D Y OX’ CINCAOSA l!LLKALOIDS-~f a.11 the chemicals and mixt,iires of cliemicalv studied, only one group of cioscly related substances has const;tiitiy tests. These substances are the cinchona alkaloids arid their derivatives.’ Quinidine as the sulfate was mie of the first of the group studied, and it showed marked mothproofing properties. The original test pieces of wool treated with an alcoholic solution of quinidine sulfate liave withstood moth attack during the past four years in bhe moth-stocked cupboards where they are still under observation. Since tlic discovery of the moth-repelling properties OS quinidine sulfate, the repellent properties of the other cinchona alkaloids, cinchona alkaloid derivatives, and their compounds have been thoroughly investigated, and it has been demonstrated that they all repel clothes-moth attack when the materials that are to be protected are impregnated with any one or more of them. The commonly known cinchona alkaloids and their compounds are not readily soluble in inert and inexpensive organic solvents, such as petroleum naphtha. Because it is known that many fatty acidsaltsof other substances are sohble in such solvents, fatty acid compounds of the cinchona alkaloids were prepared and tried for mothproofing qualities. They were not olily soluble in petroleum naphtha, but they were among the most effective salts of all for repelling clothcs-mothq. Many s a h of the cinchona alkaloids are known and d e scribed in the literature. During this investigation, I~on~ever, Figure 3-Spray Procedure Used in Mothproofins Uphdlstered, FUIIIILYIC a iiurnber of the fatty acid salts of these alkaloids were prepared for the first time. These salts, which will be described If these test, pieces showed moth damage before the cud of in detail in a later paper, are amorphous, vi,seous substances 6 months, another series of test pieces was prepared in the of the nature of soaps. They are iiisoluble in water, but are same maimer, except tirat, a douhle-stren@,h solution NRS variously soluble in organic solvents. The alkaloids form used. monobasic and dibasic salts with the fatty ncids. I n a mono111 both the special t.ests and the preliminiiry tests the chembasic salt the tatty acid radical probably is attached to the ical or mixture of chemicals used for treittiiig was not rejected tertiary nitrogen of the quinuclidiiie portion of the alkaloid. as an ineffective moth-repelling a,gcirt when the test pieces I n tlie dibasic salts fatty acid radicals are probably attached L wit,h wader or petroleum n a p h t . 1 were ~ wliicli bad ~ P C J ~~-asIieil to both nitrogen atoms of the alkaloid. The st.ructure of damaged by clothes-motlis. In such histances tlie obvious the salts may be indicated graphically by the following conclusion was drawn tliat lnmidcring or dry-cleaning, as Sorniulas: the case might be, removed the mot,hproofiiigagent and that the mothproofing subst,ance was effwtivtr only SO lorn as the ? The use of cinchoiis slknloidr and their d e i i v r t i v e e as insectifuges is ciniiired in the wrilem’l;. S. Patent 1,616,843 (February 1, 1027). materials treatrd were iiot clmined.
inspected tu determiiie if aiiy of the test pieces had been attacked by the larvae. ISy having three test pieces treated in this manner, it was possible to obtain in tlie prr’liminary test ioformat,ion regarding the effects of x-ashiiig nnd drycleaning. \\%xiever the per se test picoe was attacked, tlie test was repeated witli new test pieces dreated witli a solution of doubk the origirial strength. If the washed or dr)icieaned pieces vere seen to be damaged, the tcst was continued on the reiuaiiiing t,est pieces in the series. This scheme of douhling and redoubling the strength of the solution a.nd treating new scries of test pieces when oue set was damaged was continued u6til moth larvae would not eat the test piece or until an 8 per cent solution was reached, if tlie chemical was soluble in ally suitable solvent up to that percentage. IS the chemical was not soluble up to 8 per cent, it was tried up to the limit of ita solubility. I n a few cases the tria.1 of some of tlie eheiuicals was discontinued before an 8 per cent solution was reached, because in the higher concentrations they were observed to stain light-colored materials. SPECIAL Tnsrs-Whenever a per se test piece remained in the moth cupboard for 6 months or more without being damaged, so-called “special tents” were started on another series of six test pieces treated vitli the same strength solution. Before being placed in the moth cupboards, one of the test pieces was brushed with a still brush, just, as garments, furniture, rugs, etc., are often hrw~lied;a second piece was thoroi~gl~ly vacuuin-elc:iiicd; a third piece was held in a jet of steniri for soveral minutes; a fourth pinee was spotted &h foods, such as butt,er, beef broth, sugar sirup, milk, etc.; a fifth piece %-asdry-cleaued; and the sixth piece vas washed in soap and wnter. These t,est pieces covered practically evcry condition to which a niot.h-repelling agent worrld bo subjected on woolens, fur, or feathers in the hands of the consumer. If they reina.ined in the moth ciipboard without showing damRge for arrotlier 6 months, the chemical with which these pieces were treated was regarded as possessing moth-repelling propert,ies in the strength of solution used.
”
I
I
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October, 1927
1179
Industrial Application of New Process
H C/cH\C/N\cH I1
HzC
CHI
CHR
CHI
CHz
The cinchona alkaloids, their derivatives, and compounds were the only substances which laboratory investigation indi\CH/ ‘\c/ C H O d I? / cated to have sufficient moth-repelling effectiveness for com/\ mercial application. Of these, the most inexpensive materials H R’ are desirable from a commercial viewpoint. Quinoidine is Monobasic Salt the least expensive of the cinchona alkaloid products. Its commercial use as a moth repellent is limited, however, beH R’ cause it is so dark that it noticeably colors materials treated with its solutions. I n this respect quinoidine does not satisfy the criteria of excellence. Considering the cost per unit volume of treating fluid and compliance with these criteria, quinidine salts have so far proved to be the most economical A to use industrially. H R’ When the laboratory investigation of the chemicals was Dibasic Salt made all that was desired then was a solvent that would dissolve the chemical and completely evaporate after it had I n these formulas R represents either hydrogen or a radical carried the chemical on to the test pieces. When consideration was accorded to the commercial aspects of the proband R’ represents a fatty acid radical. When some of the cinchona alkaloids, notably cinchonine, lem, however, a study was made to find the most suitable were heated on a steam bath for several hours with an ex- vehicle for practical purposes. Initial cost, evaporation loss, cess of a fatty acid, more than sufficient fatty acid combined fire hazard, and penetration were given attention. I n some with the alkaloid than is required to form a dibasic salt, sug- cases, such as treating woolens in the process of manufacture gesting the possibility of the formation of a condensation either water or petroleum naphtha would be the most useful product on the secondary alcohol radical between the quin- solvent. For treating woolens in the form of garments, rugs, furniture, etc., in dry-cleaning plants and in the home, some uclidine and quinoline rings. The cinchona alkaloids have properties which make them of the so-called “dry” solvents, which include most of the attach themselves’to a woolen fiber like a dyestuff. A dye- organic solvents, are more suitable than water. It happens that the cinchona alkaloids can be converted stuff may be acidic or basic. The cinchona alkaloids are basic. A test was made to determine if a quinidine hydro- into many different salts that are soluble in a variety of solchloride bath becomes “exhausted” when a piece of woolen vents. They can be prepared to be soluble in water or in cloth is steeped in it. The procedure was similar to that used any of the “dry” solvents, and therefore the problem was to for applying a basic dyestuff. A piece of woolen cloth was find the most suitable “dry” solvent. When the moth-resteeped in a 0.5 per cent solution of quinidine hydrochloride by pelling solution is applied by spraying, penetrational power weight of material. Quinidine was determined in an aliquot of is an all-important requirement for the vehicle. I n order to the ‘quinidine hydrochloride solution before and after the wool determine the relative value of various solvents in this respect, was steeped in it. The original solution contained 0.1565 some of them were colored with a dyestuff and the colored gram of quinidine. After 31.3 grams of wool had been steeped solutions were sprayed onto pieces of white woolen cloth, in it for 30 minutes at 90’ C., it contained only 0.0640 gram one-half of which was protected by means of a sheet of steel. of quinidine, indicating that approximately 0.003 gram of The extent of the creeping due to surface tension or capillarity quinidine was deposited on each gram of wool. This test was observed. I n some cases the colored liquid did not creep revealed that the quinidine hydrochloride bath exhausts it- into the protected part of the cloth, in others the liquid crept into the part protected by the steel plate various distances self in the same manner as a dye bath.8 Although following the classification mentioned for select- up to as much as 5 inches. This test revealed that the least ing possible moth repellents has led to the discovery of the volatile solvents are the best creepers, and therefore would moth-repelling properties of the cinchona alkaloids, this char- carry the moth-repelling chemical into the seams and peneacteristic is not based on any one of the properties mentioned, trate into deep pile fabrics in a much more efficient manner but is probably due to a combination of properties. The than water or the more volatile organic solvents. Some of cinchona alkaloids come within more of the bases for choosing the results of these tests are shown in Figure 1. It will be moth repellents mentioned than any of the other chemicals observed in the illustration that the least volatile substances, investigated. They are as follows: (1) salt-forming organic such as naphtha, long-time burning oil, and kerosene, have chemicals, (2) bitter substances, (3) intestinal irritants, (4) the best creeping properties. The most useful “dry” vehicle germicides and antiseptics, and (5) astringents. Some of is a special heavy petroleum naphtha,g which is sufficiently their derivatives are also (6) local anesthetics. I n thera- volatile that it evaporates in a short time from materials peutics quinidine enjoys a good reputation for its beneficial treated therewith. Also, it has great creeping or penetrataction on the heart. All the cinchona alkaloids are well ing power, its initial cost is low, and the fire hazard is comknown for their specific action on malarial parasites and as parable with that of kerosene. A vehicle of this kind is suitantipyretics. Many chemicals coming under any one of able for spraying or for an immersion bath. the classes into which the cinchona alkaloids fall were not I n addition to the laboratory investigation, practical tests found to be moth repelling. For example, such bitter sub- have been made with cinchona alkaloid products which have stances as aloin and ethyl phthalate were not observed to be consisted of treatingmoth-infested clothing,rugs,and furniture moth repellents. Astringents such as alum and tannin and with cinchona alkaloid compounds dissolved in such solvents germicides such as aldol and phosphine G N (acridine as water, petroleum naphtha, and carbon tetrachloride, the dye) were not moth repelling. Yet with these and other last-named because it is non-flammable. Clothes-moths were properties combined in the cinchona alkaloids the desired destroyed and did not reenter articles treated by immersion result is obtained. in these solutions, followed by centrifugal extracting, drying, and exposure to the insects. Similar results were ob8 The investigation of this phase of the use of cinchona alkaloids is still I
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i n progress, and the results will be reported in a subsequent paper.
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See specifications in article by Jackson, THIS JOURNAL, 18, 237 (1926).
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INDUSTRIAL A X D ENGINEERING CHEiMISTRY
tained with articles sprayed with petroleum naphtha solutions. Furniture, rugs, and hangings were treated in mothinfested homes to determine the effectiveness of the various ways of using the cinchona alkaloids as moth repellents. The conclusion drawn from a number of tests of this nature was that the cinchona alkaloids or their compounds in either water or petroleum naphtha solution are commercially suitable for treating materials by immersion in or by spraying with the solution. Since this conclusion was drawn over a year ago, more than 4000 gallons of cinchona alkaloid solutions have been applied to articles of wearing apparel, furniture, etc., under commercial conditions in the dry-cleaning plants of members of the Mundatechnical Society. hfany of the articles treated were moth-infested when received. They were all guaranteed to be mothproofed and free from moths after treatment. Not one complaint has been made by any of the many owners of the articles treated. Four thousand gallons of the solution are sufficient to treat 160,000 pounds of wool. feathers, or fur. The plants in which the work was
Vol. 19, No. 10
done are located in eight large cities of the eastern, southern, and midwestern parts of the United States, and this successful and extensive use of the process in several sections of the country indicates its adaptability in the dry-cleaning industry. The utility of the process in other fields is apparent. As a spraying solution for household use the value of high flashpoint petroleum naphtha solutions of the cinchona alkaloids is obvious. The process can readily be made applicable for meeting the mothproofing requirements of a wide range of wool, feather, and fur industries, inasmuch as some of the many compounds and derivatives of the cinchona alkaloids are soluble and therefore usable in almost any solvent desired. The process can be readily adapted to treating upholstering materials, felts, blankets, comforts, mattresses, suitings, etc. For the past year the process has been successfully applied commercially in the dry-cleaning and dyeing industry. The process will be made available to other interested branches of technology just as soon as commercialization plans are concluded.
Possible Use of Shale Oil, as a Wood Preservative’ Toxicity of Pyridine and Quinoline to Fomes annosus By Arthur M . Sowder SCHOOL OF FORESTRY, UNIVERSITY OF IDAHO, Moscow, IDAHO
The toxicities of pyridine and quinoline have been oils contain from 1.855 to ACH year t h e wood determined by the Petri dish and sawdust methods. 1.501 per cent total nitrogen. preservation industry The results indicate that pyridine can play no imWeiss4 has shown that a becomes of greater important part in influencing the availability of shale oil concentration of 0.10 per Cent portance, owing to the ecoas a wood preservative. The toxicity of quinoline to quinoline in nutrient agar is nomic conditions caused by wood-destroying fungi compares favorably with the toxic to Penicillium. The the steadily increasing prices toxicities of creosol, phenol, and mercuric chloride. toxicity of quinoline apparof structural timber due to the If shale oil contains from 2.43 to 3.06 per cent quinoline, e n t 1y compares favorably threatened shortage of this there is reason to believe that it will inhibit the growth with pure phenol, creosol, and material. Close utilization of wood-destroying fungi when injected into wood at mercuric chloride. No data is a n aid in alleviating a future the rate of 12 pounds of oil per cubic foot of wood. dealing with the toxicity of wood famine and wood prespyridine to wood-destroying ervation is one way to effect fungi are known to the writer. this closer utilization. Pyridine6r6 is a colorless, mobile liquid, having a characWood preservatives are substances injected into wood through various processes to prevent or inhibit the destruc- teristic penetrating odor and the empirical formula CsH5N. tion of the wood by decay or by infestations of marine borers, It is readily soluble in water in all proportions, basic to litwhite ants, beetles, etc. For general use a good preservative mus, has a specific gravity of 0.9779, and boils at 115” C. should be cheap, available, efficient, easily handled, and not Quinoline, having the empirical formula C ~ H T Nis, sparingly injurious to the mechanical properties of wood or increase soluble in water but readily soluble in alcohol and ether. its inflammability to too high a degree. Since the shale oil It is dark brown in color and has a penetrating odor and industry seems to have vast possibilities, the question arises burning taste. The specific gravity of quinoline is 1.081 and as to whether or not this oil fulfils the requirements of a wood i t boils at 239’ C. Both pyridine and quinoline are found in coal-tar creosotes and stand somewhat in the same relation preservative. Oil-bearing shales occur in various parts of the United to each other as do phenol and naphthalene. States in enormous quantities, but the largest deposits are Methods found in the Rocky Mountain states. It is estimated2 that Colorado alone has enough shale to produce 58 billion barrels There are two common methods’ of determining the effecof oil. Data showing the composition of shale oils are rela- tiveness of a wood preservative-(1) actual service of treated tively meager, but according to Franks3 shale oil, especially timber, and (2) laboratory tests. Service tests, although that obtained from Colorado, contains relatively large amounts always desirable, are often impractical as they frequently of nitrogen and some of this nitrogen a t least possibly occurs require from 10 to 15 years to get the final results. Labin the form of pyridine and quinoline. The exact amounts oratory tests, on the other hand, permit the determination of pyridine and quinoline present in shale oil are not known, of the relative toxicity to wood-destroying fungi within a but Franks’ analyses show that the crude Colorado shale J . Soc. Chem. Ind., 30, 1348 (1911).
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Received May 31, 1927. 2 Alderson, “The Shale Oil Industry,” 1920. a Quart. Cola School Mtnes, 16, 1 (1921). 1
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Lunge, “Coal Tar and Ammonia,” Gurney & Jackson, London, 1900. Sudborough, “Organic Chemistry.” Richards, Proc. A m . Wood Preservers’ dssocn., 19, 127 (19231.
