UNIVERSITY OF CALIFORNIA PUBLICATIONS COLLEGE OF AGRICULTURE AGRICULTURAL EXPERIMENT STATION BERKELEY, CALIFORNIA PHENOLIC INSECTICIDES AND FUNGICIDES BY GEO. P. GRAY BULLETIN No. 269 Berkeley, Calif., April, 1916 UNIVERSITY OF CALIFORNIA PRESS BERKELEY 1916 Benjamin Ide Wheeler, President of the University. EXPERIMENT STATION STAFF HEADS OP DIVISIONS Thomas Forsyth Hunt, Director. Edward J. Wickson, Horticulture (Emeritus). Herbert J. Webber, Director Citrus Experiment Station; Plant Breeding. Hubert E. Van Norman, Vice-Director; Dairy Management. William A. Setchell, Botany. Myer E. Jaffa, Nutrition. Robert H. Loughridge, Soil Chemistry and Physics (Emeritus). Charles W. Woodworth, Entomology. Ralph E. Smith, Plant Pathology. J. Eliot Coit, Citriculture. John W. Gilmore, Agronomy. Charles F. Shaw, Soil Technology. John W. Gregg, Landscape Gardening and Floriculture. Frederic T. Bioletti, Viticulture and Enology. Warren T. Clarke, Agricultural Extension. John S. Burd, Agricultural Chemistry. Charles B. Lipman, Soil Chemistry and Bacteriology. Clarence M. Haring, Veterinary Science and Bacteriology. Ernest B. Babcock, Genetics. Gordon H. True, Animal Husbandry. James T. Barrett, Plant Pathology. Fritz W. Woll, Animal Nutrition. A. V. Stubenrauch, Pomology. Walter Mulford, Forestry. W. P. Kelley, Agricultural Chemistry. H. J. Quayle, Entomology. D. T. Mason, Forestry. J. B. Davidson, Agricultural Engineering. Elwood Mead, Rural Institutions. H. S. Reed, Plant Physiology. William G. Hummel, Agricultural Education. Leon M. Davis, Dairy Industry. John E. Dougherty, Poultry Husbandry. S. S. Rogers, Olericulture. Frank Adams, Irrigation Practice. David N. Morgan, Assistant to the Director. Mrs. D. L. Bunnell, Librarian. division of entomology C. W. Woodworth E. O. Essig W. B. Herms S. B. Freeborn E. C. Van Dyke E. P. Van Duzee Geo. A. Coleman M. R. Miller Geo. P. Gray E. R. de Ong INTRODUCTION This bulletin is a report of such examinations and analyses as were made of the samples of phenolic insecticides and fungicides collected during the fiscal years July 1, 1911, to June 30, 1913, with comments, description of methods of examination and information concerning these products that seem of interest. The work was done under the authority of the California Insecticide Law of 1911 (California Statutes of 1911, Chapter 653). Part I is a general discussion of phenolic insecticides and fungi- cides, classification of the materials found on the market, description, properties and uses of the refined phenols in common use, description, properties and uses of the crude phenols and compounded remedies. The especial points brought out in the discussion are : (1) All of the cresols are more active fungicides than phenol, the higher boiling cresols (especially meta-cresol) are more active as fungicides than the lower-boiling cresols. (2) Commercial cresol is usually a mixture of the three cresols. (3) A specially prepared high-boiling cresol would be of par- ticular value in the preparation of disinfectants. (4) "Coal-tar Creosote," "Crude Carbolic Acid," and "Creosote Oil" are practically synonymous terms as commercially used in the United States. The general term "Crude Phenols" is applied to the above in the author's classification. Large quantities of the mixed residues from all sorts of tars are sold under the above names, as well as under the names of many proprietary Lice-killers, etc. (5) It is thought that the use of the word "Creosote" should be restricted to the phenol-bearing distillates, heavier than water, ob- tained by the distillation of a tar or a tar-like substance. So-called "Oil-tar Creosote," if the above is correct, is an adulterant when added to crude phenols, and is a substitute when sold in place of them. (6) Crude Cresylic Acid is a more appropriate term to be applied to the liquid commonly sold as Crude Carbolic Acid, with emphasis on the word "Crude." The source of the crude phenols should be re- stricted to the light oils, designating the phenol-bearing heavy oils as creosotes. (7) Dependable phenolic insecticides and fungicides, especially the soluble and emulsifiable ones, possess many distinct features of advantage over other materials used for the same purpose. If products of this sort and the crude materials from which they are made could [329] 330 UNIVERSITY OF CALIFORNIA EXPERIMENT STATION be standardized and supplied of reasonable uniformity from season to season, it is thought that they might be extended to a far wider field of usefulness than at present. Part II is a classification of the samples examined and a tabulation of the results of the determination of their phenolic contents, with comments. From the results of examination of the 176 samples listed in the tables and a study of the situation, the following conclusions and ob- servations are made concerning such materials as are offered for sale in the state : (1) The refined phenols are of good quality. (2) A very unsatisfactory condition exists in regard to the crude phenols. The amount of phenols found in the samples analysed varied from 4.9 to 38.4 per cent. A variation of 15 to 18 per cent, from the amount of phenols stated on the label is a matter of frequent oc- currence. (3) The phenols are not necessarily the most active insecticidal constituents of the non-em ulsifiable preparations but are probably the most active as fungicides. Analyses of the samples of this group indi- cate a decided opportunity for improvement. (4) The emulsifiable preparations made up with fatty soap emulsi- fier are fairly satisfactory in conforming to guarantee, although the variation in total phenols is rather remarkable, ranging from 4.1 per cent, to 71.86 per cent. (5) The emulsifiable preparations made up similar to the above but containing rosin soap or a mixed rosin and fatty soap, most fre- quently known as ' ' carbolic sheep dips, ' ' is the group with the greatest number of representatives. In these the phenolic content varied from 3.8 per cent, to 25.2 per cent. Of the dips stating percentages of active ingredients, more than one third were not within 5 per cent, of the guarantee. This state of affairs indicates the need of a more accurate knowledge of the composition of the products on the part of some of the manufacturers. (6) The soluble preparations of the type represented by the Liquor Cresolis Compositus of the U. S. Pharmacopoeia are fairly reliable in conforming to the guarantee of phenols. (7) Manufacturers and dealers are not accused of wilfully making or selling low-grade or non-standard products, but it appears that material has often been guaranteed and sold with but slight knowledge of its composition. The blame must be shared with the producers of the raw materials who have shown great hesitancy in giving specific guarantees for their output. PHENOLIC INSECTICIDES AND FUNGICIDES 331 (8) Amendments to the Insecticide Law have done away with the requirement of stating the percentage of active ingredients in an in- secticide or fungicide. This lends encouragement to the promoter of worthless or non-standard proprietary preparations and the sellers of heterogeneous by-products of uncertain composition. The most serious result of the amendments is, however, that the accomplishment of the standardization of insecticides and fungicides, so much to be desired by the consumer and the conscientious producer, is greatly impeded. Part III describes qualitative methods most frequently used in the Insecticide Laboratory for the examination of phenolic insecticides and fungicides, and gives references to methods for their complete examination which are in use by the U. S. Department of Agriculture. Apparatus used in the determination of total phenols by Chapin's method is illustrated, including some new apparatus and conveniences developed during the progress of the work. An index of samples is appended giving the laboratory number of each compounded and proprietary remedy examined and the table in which listed. The different names applied to the crude and refined phenols are also indexed, showing the number of the table in which the material is listed. The headings of the tables referred to are made to correspond to the classification suggested in Part I, so that the author's classification of any particular sample may be readily ascertained. PHENOLIC INSECTICIDES AND FUNGICIDES By GEO. P. GRAY Part I GENERAL DISCUSSION PAGE Quality of Standard Insecticides and Fungicides 332 Quality of Phenolic Insecticides and Fungicides ! 333 Active Ingredients 333 Definitions 333 Classification 334 Refined Phenols, Description and Properties 335 Phenol 335 Cresol 335 Uses of the Refined Phenols 336 Crude Phenols, Description and Properties 337 Uses of the Crude Phenols 339 Compounded and Proprietary Remedies 339 Uses of the Emulsifiable Phenolic Liquids 344 This bulletin is a report of such examination and analyses as were made of the samples of phenolic insecticides and fungicides collected during the fiscal years, July 1, 1911, to June 30, 1913, with com- ments, description of methods of examination and information con- cerning these products. The samples were taken by authorized depu- ties of the Director of the Agricultural Experiment Station of the University of California and examined in the Insecticide Laboratory acting under the authority of the California Insecticide Law of 1911 (California Statutes of 1911, Chapter 653). Not all of the samples collected have been analyzed on account of duplication and the small size of some of the samples. It is thought, however, that a sufficient number have been analyzed to fairly repre- sent this class of insecticides and fungicides offered for sale in the state during the period of inspection. QUALITY OF STANDARD INSECTICIDES AND FUNGICIDES The standard and more important insecticides and fungicides in general use in the state are the arsenicals, cyanides, sulfur and sulfur compounds, petroleum oils, tobacco preparations, and Bordeaux mix- ture. With comparatively few exceptions, the above have been found [332] PHENOLIC INSECTICIDES AND FUNGICIDES 333 to be free from adulteration, and it is believed that the consumers of the state are being supplied with materials of worth and reliability. This is particularly true of the arsenicals, due no doubt in part to the fact that the Federal Insecticide Law of 1910 fixes a standard for lead arsenate and Paris green, that California has had in operation a Paris green law since 1901, and that this station has been particu- larly active in the investigation of the composition and suitability of other arsenicals. QUALITY OF PHENOLIC INSECTICIDES AND FUNGICIDES It is to be regretted that similarly favorable comment cannot be made upon many of the insecticides and fungicides listed in this bulle- tin, more especially upon the crude materials. Preliminary examina- tion of the samples of the latter class of substances showed wide varia- tions in composition in some cases, in which to all appearances the materials were alike and bore similar names. Consequently, samples were obtained from wholesale and retail dealers in different parts of the state for analysis. This collection contained so many different brands that complete analyses were not attempted. Attention was given to qualitative tests to indicate the nature of the substance and to quantitative determination of the total phenols (or tar acids) present. (Description of methods of examination are given in Part III of this bulletin). ACTIVE INGREDIENTS It is not contended that the phenols are the only active ingredients of this class, as indeed the oils, naphthalene, anthracene, pyridin, etc., have decided value in destroying or repelling insects. It is thought, however, that the phenols are the most active and are undoubtedly the most valuable in a commercial way, so that if any constituent is below guarantee, this is likely to be the one for commercial reasons. DEFINITIONS The Phenols This name is given to a certain group of organic substances other- wise known as the hydroxyl derivatives of the benzene series. The simplest phenol is known as phenol or carbolic acid. Other phenols are of common occurence and are collectively known as the phenols, the group taking its name from the simplest member of the group. When the word "phenol" is used in the singular without qualifi- cation, the definite chemical substance (C 6 H 5 OH), or hydroxyben- zene, commonly called carbolic acid, is meant. When the word 334 UNIVERSITY OF CALIFORNIA EXPERIMENT STATION "phenols" (plural) is used, the phenol group is meant, spoken of in commercial language as "tar acids." CLASSIFICATION Considerable confusion exists in the nomenclature of the phenols in general, and of phenolic insecticides and fungicides in particular. The names of definite chemical substances are often confused with familiar trade names of compounded preparations. Even pharmacists have sold to inspectors of this office compounded articles under the definite name of one of the phenols. In order to clear up some of these points, a tentative classification of the phenolic insecticides and fungicides, so far as known to this office, is suggested below. Comments are solicited by interested parties, suggesting changes or additions that may seem advisable. Following this is given a more detailed description of the different substances with information concerning their derivation or compound- ing, and uses. In a preliminary examination of the compounded and proprietary remedies they were separated into classes arranged according to the table as given below. The classification of any particular compound listed in this bulletin may be ascertained by reference to the index of samples, which gives the sample number and the table in which it is listed. 1 CLASSIFICATION OF PHENOLIC INSECTICIDES AND FUNGICIDES I. Eefined Phenols: 1. Phenol. (C 6 H 5 OH). Commonly called Carbolic Acid, and occasionally called Phenic, or Phenylic Acid. Chemically known as Hydroxybenz-ene (or -ol), Benzo-phenol, or Phenyl Hydroxide. 2. Cresol. (C 6 H 4 CH 3 OH). (Ortho, meta, para and mixtures). Commonly called Cresylic Acid or Kresylic Acid, and occasionally called Kresol or Cresylol. Chemically known as Hydroxytolu-ene (or -ol), or Methylhydroxybenz- ene (or -ol). 3. Higher Phenols. II. Crude Phenols: 1. Coal-tar Creosote ] Commercial terms applied to mixed re- 2. Creosote Oil j> sides from tar refineries containing 3. Crude Carbolic Acid I variable amounts of phenols. 4. Wood-tar Creosote (infrequently used as an insecticide). i The classification of the emulsifiable liquids may not be strictly accurate in respect to the soap employed, as many of these contain a mixture of fatty and rosin soap. If a good test for rosin was obtained, the compound was placed in the rosin soap class; if the test was negative or faint, it was placed in the fatty soap class. PHENOLIC INSECTICIDES AND FUNGICIDES 335 III. Compounded and Proprietary Remedies: 1. Liquids A. Insoluble in water (a) Non-emulsifiable (1) With Tar Oil Solvent (2) With Petroleum Solvent (3) Mixtures of (1) and (2) (b) Emulsifiable (1) With Fatty Soap Emulsifier (2) With Rosin Soap Emulsifier (3) With Mixed Soap Emulsifier B. Soluble in Water 2. Solids and Semi-solids A. Ointments B. Powders C. Soaps. REFINED PHENOLS The phenols in most common use as insecticides and fungicides are phenol and cresol. A discussion of the properties and composition of these two can be found in any work on organic chemistry. A few words on this topic may not be out of place at this time. Phenol or Carbolic Acid Phenol when in a pure state is a white solid at ordinary tempera- tures, forming long needle-shaped crystals when crystallized from a suitable solvent. It melts, however, at a temperature slightly above 42° C. (108° F.) so that on a very hot day it will be a liquid. A small amount of moisture or cresol lowers the melting point so that as purchased it is in liquid form unless very pure. The solid absorbs moisture from the air and under the combined influence of air, light, and moisture, it often turns to a reddish or pink color. Cresol or Cresylic Acid The most evident physical property distinguishing cresol from phenol is that cresol is a liquid at ordinary temperatures while phenol is a solid. The odor of cresol is somewhat like that of phenol and is not at all unpleasant. There are three kinds of cresols, known as ortho, meta, and para cresol, commercial cresol being a mixture of the three. Their separation would be a difficult commercial operation, possibly excepting the partial separation of ortho cresol which has a lower boiling point than the others. 336 UNIVERSITY OP CALIFORNIA — EXPERIMENT STATION USES OF THE BEFINED PHENOLS Phenol The principal use of phenol pertinent to the topic is as an anti- septic and disinfectant, although its use as such is somewhat limited on account of the difficulty of making a uniform mixture with water, its poisonous nature, and causticity. The Cresols have been found to be more efficient, less poisonous, and less caustic, although less soluble in water. The solubility defect has been remedied by the use of the soluble and emulsifiable preparations described on succeeding pages. Solutions of phenol in kerosene or other solvent are on the market as proprietary compounds. Cresol Cresol is the active and most valuable germicidal constituent of the crude phenols and is usually the only representative of the phenol family to be found in any considerable quantity in crude carbolic acid and creosote. It is used to fortify the compounded phenolic preparations which have been made from the crude phenols. It is also used in the prepara- tion of the higher grade soluble and emulsifiable "dips" and disin- fectants. It is used quite extensively as an ingredient in the preparation of ointments, salves, and in antiseptic and insecticidal soaps. More recently cresol finds a very useful field in the preparation of emulsifiers for the various petroleum oils to be used as insecticide sprays. It is used as a necessary ingredient in making up the more satisfactory "miscible oils." The formula given by Penny 2 for the preparation of his emulsifier or "soap solution" calls for the use of "carbolic acid," the grade known as "Liquid crude, one hundred per cent, straw color." The preceding commercial term is rather mis- leading, as one not familiar with commercial language might infer a product essentially carbolic acid of great purity. As a matter of fact, this commodity is only a very good grade of mixed phenols and sometimes may be very largely cresol. This grade of ' ' carbolic acid, ' ' however, has been found by Penny to be satisfactory in the prepara- tion of a great variety of miscible oils. Many liquid soaps are now on the market, some of which contain as high as twenty-five per cent, cresol. 2 Del. Agr. Exp. Sta., Bull. 75, p. 7, 1906. PHENOLIC INSECTICIDES AND FUNGICIDES 337 CRUDE PHENOLS There appears to be no very definite distinction between the pro- ducts sold under the names of coal-tar creosote, creosote oil, and crude carbolic acid. Sadtler 3 expresses the situation thus: "The name 'Kreosot' was first applied by Reichenbach, in 1832, to the character- istic antiseptic principle contained in wood-tar (C. Rice, Amer. Journ. Pharm., 1894, 167). Carbolic acid was discovered soon after by Runge in coal-tar, and was long confused with the wood-tar principle : and the crude carbolic acid from coal-tar is still known as 'Coal-tar creosote.' Somewhat similar products are now obtained from other sources, so that much confusion has arisen. The term ' creosote ' when used without qualification, ought to be understood as signifying the product from wood-tar, but it is better to describe Reichenbach 's sub- stance as 'wood-tar creosote,' and employ the unqualified word 'creo- sote' in a generic sense as meaning the mixed phenols and phenoloid bodies obtained from wood-tar, coal-tar, blast-furnace-tar, shale-oil, bone-oil, or other sources. The term 'creosote' should be restricted to the phenolic 4 " derivatives from the above or similar sources, the crude products from which they are derived being the corresponding 'creosote oils.' Coal-Tar Creosote Oil* "Coal-tar creosote oil commonly consists of that portion of coal- tar which distills between 200° and 300°, together with the residual oils from the manufacture of crude carbolic acid, naphthalene, and anthracene. This description, however, applies especially to the best- managed works. In some works every residue which cannot be used for any other purpose finds its way into the creosote oil well." The manufacturers' agents admit that insofar as trade usage is concerned, there is no well defined distinction between the products commonly sold under the names Coal-tar Creosote, Creosote Oil, and Crude Carbolic Acid. In some cases, however, there seems to be this distinction: the crude carbolic acid may have been derived from a certain fraction resulting from the distillation of coal-tar which is lighter than water and therefore may contain a greater proportion of the lighter oils than the creosote oils which may have been ob- tained from the fractions which are heavier than water. s Allen 's Commercial Organic Analysis, 4th Ed., Vol. Ill, 346. 4 Italics by the author. * Loc. cit., page 365. 338 UNIVERSITY OF CALIFORNIA EXPERIMENT STATION It is believed that the above is the only distinction which is made, but this distinction would not be applicable to products from works described by Sadtler in which "every residue which cannot be used for any other purpose finds its way into the creosote oil well. ' ' The Forest Service of the United States Department of Agricul- ture has made an extended study of commercial creosotes and a circu- lar has been issued giving a summary of the work up to 1912. 5 In this circular definitions and terms are suggested in order to differen- tiate between the various creosotes. The general term "creosote" is defined as " a distillate heavier than water obtained by the distillation of a tar or a tar-like substance." The term "oil-tar creosote" is in- cluded in the definitions and is the only one to which exception might be taken. While the meaning is perfectly clear to those conversant with the subject, it is thought that the word "creosote" applied to such a product is misleading. In fact this oil-gas tar distillate does not appear to be entitled to the name "creosote" at all, for the rea- son that the phenols and phenoloid bodies are entirely lacking in the tars produced from oil. The phenol group is held to be an essential and characteristic antiseptic principle of all creosotes. Some such term as "oil-tar distillate" would seem to be more appropriate. Crude Carbolic Acid There can be no place for the continued use of this term except out of respect for old age. It is a matter of common knowledge, to those who have looked into the question, that "crude carbolic acid 1 ' contains no carbolic acid (phenol), or at most only a trace. The only phenols present are cresylic acid (cresol) and the higher phenols. This commodity, as commonly sold in this state, and doubtless else- where, may be more properly referred to as " crude cresylic acid. ' ' As expressed by one of the manufacturers' agents dealing in creo- sotes, if the prospective customer is interested in a liquid for use as a shingle stain or wood preservative, he asks for creosote and creosote is sold to him. If the customer desires to disinfect his premises or rid his poultry of vermin, he asks for crude carbolic acid and obtains the latter. But it all comes out of the same tank ! It is perfectly evident that in many cases the temptation to sell under one name or other as a crude phenol ' ' every residue which can- not be used for any other purpose" is too great to be overcome. And this uncertain and variable mixture, whether good or bad, in its original form, or after "doctoring," masquerades under hundreds of s Winslow, C. P., U. S. D. A. Forest Service, Circ. 206, 1912. PHENOLIC INSECTICIDES AND FUNGICIDES 339 fanciful names and finally falls into the hands of the unsuspecting consumer. USES OF THE CRUDE PHENOLS As a Fungicide According to the Forest Service of the United States Department of Agriculture, 6 "By far the largest consumption of creosote in this country is in the treatment of wood to prevent the development of wood-destroying fungi. In 1910 approximately 63,266,271 gallons of creosote was used in the United States for this purpose of which 18,184,355 gallons was of domestic production and 45,081,916 gallons imported. ' ' The use of creosote as indicated ahove clearly establishes its status as a fungicide and hence it comes under the supervision of the Cali- fornia Insecticide and Fungicide Law of 1911. Little attention, however, has been given to this phase of the sub- ject, but it may properly become one of the activities of the Insecti- cide Laboratory in the future. As a Disinfectant Large quantities of the crude phenols are annually consumed as a general disinfectant about drains, closets, cesspools, and the like, and in the disinfection of stables. Their use for this purpose is being dis- continued to a large extent in favor of the more refined products, as the crude materials have been found to be so unreliable. As an Insecticide They are also used quite extensively for the destruction of lice and vermin in poultry houses and stables, in this case being sold as crude carbolic acid, but perhaps more frequently under a trade name as a ' ' Lice Killer, ' ' containing some added substance such as carbon bisul- fide and very often a petroleum oil. Another, and perhaps the largest market aside from the wood- preserving industry, is in the preparation of the so-called carbolic sheep dips and similarly prepared disinfectants. COMPOUNDED AND PKOPRIETARY EEMEDIES Non-Emulsifiable Liquids; Insoluble in Water (III-l-Aa) This group is of lesser importance than those following, although the number of brands listed is fully as great. As indicated in the outline of classification, this group has been found to consist of three subdivisions, depending upon the kind of solvent or vehicle. G Forest Service U. S. Department of Agriculture, Circ. 206. 340 UNIVERSITY OF CALIFORNIA- —EXPERIMENT STATION 1. With Tar Oil Solvent. Many of these compounds appear to be by-products of oil refineries and some of these might be classified as crude phenols except for their trade names which bring them under the above heading. Certain mixtures resulting from the distillation of various tars are often sold as insecticides under trade names. Carbon bisulfide, sulfur, or petro- leum distillates are sometimes added to increase their ' ' strength ' ' and all-around usefulness. Naphthalene is usually present in large quanti- ties. Such mixtures as these are best known as "So and So's" Lice Killer. Their extended use and the number of brands sold in the state speak well of their value as lice killers. This may in part be ac- counted for by the fact that lice and mites are especially susceptible to the action of oils of whatever nature. And so it may be considered that all of these oils are of value in the destruction of vermin that infest animals. When the phenols are present in appreciable quanti- ties the liquid has an added value as a disinfectant. This constituent is such a variable quantity, however, that great reliance cannot be placed in them as disinfectants. The phenols are also undoubtedly of value as an insecticide if present. 2. With Petroleum Solvent : A number of brands of this class were found upon the market, widely advertised as deodorizers, insecticides, and disinfectants. The principal ingredient of most of these is kerosene, in which varying quantities of phenol are dissolved. The solubility of phenol in kero- sene is not great and so a number of substances such as benzene, carbon tetra-chlorid, etc., are added to retain the phenol in solution. Nitro- benzene (oil of mirbane) is almost invariably a constituent of these mixtures and probably has value as an insecticide as well as a pleasant odor. Some contain oil of citronella which is a repellent to insects but to man has a pleasant odor. These products are usually clear and transparent, ranging in color from almost colorless to a light brown. 3. Mixtures of 1 and 2 : This subdivision has been added to accommodate the mixtures of tar oils and petroleum oils, the first consisting for the most part of hydrocarbons of the benzene series and the latter of hydrocarbons of the paraffin series. Inasmuch as the present examination of the phenolic insecticides and fungicides is concerned chiefly with their phenolic content, the analyses of the non-emulsifiable liquids, insoluble in water, were not separately tabulated according to the three subdivisions given in the classification, but are all given in one table. When opportunity PHENOLIC INSECTICIDES AND FUNGICIDES 341 offers, this question may be taken up more fully in an effort to classify the liquids of this group according to their respective solvents. Emulsifiable Liquids; Insoluble in Water (III-l-Ab) The majority of the emulsifiable phenolic liquids are produced from the crude phenols arid therefore contain hydrocarbon oils chiefly of the benzene series. It may be that some of them also contain oils from petroleum in which case another division would be necessary. The fact was not evident by the methods used and hence this division is not made in the classification. The only distinction made was on account of the kind of soap used as the emulsifying agent. In the examination of these a straight rosin soap Avas occasionally indicated but more often a mixed soap of rosin and fatty acids was evident as the emulsifier. A smaller proportion was found in which rosin was entirely absent. Pine tar is used as an ingredient in some of the dips and such a dip would give a test for rosin and the soap would be classified as a rosin soap if the pine tar were present in sufficient quantity to give a good test for rosin. Those compounds, then, classi- fied in subdivision 1 of this group with rosin soap emulsifier may not all belong strictly to this group, but many should come in a third group composed of those compounds in which a mixture of rosin and fatty soap is the emulsifying agent. This group will accordingly be discussed as a whole without attempt to differentiate between the emulsifying agent. Such mixtures are most often spoken of as ' ' Carbolic Sheep Dips, ' ' although other names are applied when intended for use for other purposes than for the dipping of sheep. A rosin soap or a mixture of a rosin and fatty soap is thought to be a better emulsifying agent than a fatty soap alone — hence the greater proportion containing rosin. For the sake of brevity in the following discussion, the compounds of this group will be spoken of as "dips." These "dips" may be made by first combining the proper amounts of a solution of lye with rosin or a suitable animal or vegetable oil or fat, or a mixture of rosin and oil or fat, to form a liquid soap. There is then added the required amount of crude phenols with stirring and heat. (The crude phenols may have been purchased under the name of coal-tar creosote, creosote oil, or crude carbolic acid). The soap, aided by the phenols present, is completely dissolved by the coal-tar oils and other constituents of the crude phenols at the concentration used in preparation. There results a homogeneous, thick, dark brown fluid, of a type closely allied to the miscible petro- leum oils which have recently come into the market. If the phenolic 842 UNIVERSITY OF CALIFORNIA EXPERIMENT STATION content of the crude phenols is insufficient to produce a finished pro- duct of the desired strength, the required amount of pure cresol may be added during the process in order to bring the dip up to mark in respect to phenols. When such a compound is diluted with water the oils are in part thrown out of solution, but immediately form an emulsion due to the action of the soap present. These emulsions vary in color from almost milky Avhite to a brown, reddish or greenish color, depending upon the composition of the crude materials used in preparation. An almost perfect emulsion may be made from a good dip, in which the oils are evenly distributed throughout the liquid in very minute globules. In a diluted carefully made dip no oil should separate from the emulsion and rise to the surface except after prolonged standing. Before the passage of regulatory measures by the Federal Govern- ment and by some of the states, no great difficulty was experienced in the commercial manufacture and sale of these dips and disinfectants as the public is very apt to judge the "strength" of such a compound by the vileness of its odor and the latter quality is not usually lacking in such mixtures, whether efficient or valueless. The smell of a prep- aration, however, is no index of its efficiency as an insecticide or fungicide. The comparative ease of manufacture and small cost of such com- pounds offer a convenient and lucrative outlet for no small amount of the products of coal-tar refineries and when not taken advantage of to the detriment of the product marketed, has been a source of great benefit to the general public. A dependable dip of this sort possesses many distinct features of advantage over other materials used for the same purposes. Liquids Soluble in "Water. (III-l-B) This group in general represents a higher grade and more ex- pensive product than the former and a group of more definite com- position. The Liquor Cresolis Compositus (Compound Solution of Cresol), recognized by the United States Pharmacopoeia as an offi- cinal preparation, may be taken as an example of this type. This compound is composed of equal parts of cresol and potash-linseed-oil soap. Lysol is probably the most widely known and extensively adver- tised proprietary representative of this group. In fact, the word lysol is often confused with the word cresol. These soluble phenolic compounds have the great advantage of being readily soluble in water and usually contain a high percentage of PHENOLIC INSECTICIDES AND FUNGICIDES 343 phenols, usually cresols. They are preparations very similar in com- position to the officinal preparation with perhaps fish oil soap present, instead of the linseed oil soap specified in the former. This group is characterized by the absence of the tar oils, pure cresol being used in their preparation. Cresol and the other phenols are acted upon by the alkalies forming compounds which are soluble in water, so that when a compound of this nature is diluted with water, there is no oil to be freed and emulsified by the soap. McBryde 7 has made a study of this class of compounds and con- cludes that "(1) Liquor cresolis compositus is strongly germicidal for the following micro-organisms: Bacillus pyocyaneus, B. cholerae suis, B. coli communis, B.. typhosus, B. tuberculosis, and Staphylococcus pyogenes aureus. "(2) The germicidal efficiency of liquor cresolis compositus increases with the boiling point of the cresol it contains, and solutions of liquor cresolis compositus made from the higher-boiling cresols — i.e., cresols which approxi- mate paracresol and metacresol — are both much stronger germicides than liquor cresolis compositus made from a low-boiling cresol, which approximates ortho- cresol. "(3) Liquor cresolis compositus made from commercial cresols may be expected to vary somewhat in germicidal efficiency, owing to variations in the boiling points of the cresols it contains. This variation, however, does not render it unreliable as a disinfectant, as a solution of liquor cresolis com- positus made from the lowest-boiling and least-active cresol was found to possess stronger germicidal properties than carbolic acid. " (4) The germicidal value of liquor cresolis compositus made from cresol which boils at a temperature approximating orthocresol (187° to 189° C.) is nearly one and one-half times greater than carbolic acid." Solids and Semi-Solids Ointments. (III-2-A) There appears to be very little of such sold in the state as only one sample came in for inspection. Powders. (III-2-B) Various powdered substances such as slaked lime, borax, kiesel- guhr, calcium sulfite, blast furnace slag and others are said to be used for the absorption of crude carbolic acid. Their use, however, is limited and their efficiency not very great. Soaps. (III-2-C) Soaps containing phenols have quite an extended use on dogs and other pet animals for the eradication of fleas and lice. 7 U. S. Dept. Agr., Bur. Animal Ind., Bull. 100, 1907. 344 UNIVERSITY OF CALIFORNIA EXPERIMENT STATION USES OF THE EMULSIFIABLE PHENOLIC LIQUIDS As a Fungicide According to amendment Number Two to the rules and regulations for carrying out the provisions of the United States Insecticide Act of 1910, the Insecticide Board of the United States Department of Agriculture has made the following definition of the term ' ' fungi : ' ' 8 ' ' The term ' fungi ' as used in the act and these regulations, is under- stood to mean all nonchlorophyll-bearing plants of a lower order than mosses and liverworts (i.e., nonchlorophyll-bearing thallophytes). comprising rusts, smuts, molds, yeasts, bacteria, etc." This interpretation of the meaning of the word fungi would neces- sitate making the statement that the use of the so-called carbolic dips and disinfectants as fungicides is very extensive. Preparations of this sort with high and dependable phenolic content are very valuable bactericides. The phenols being of the cresol type, they are even better than phenol for the destruction of bacteria and have the ad- vantage over the latter in being miscible with water in any desired strength and of possessing marked detergent properties. The veter- inarian and stockman find use for them as an antiseptic wash for wounds and ulcers and the disinfection of surgical instruments. An important manufacturer has advocated the use of a dip in a bath for swine claiming thereby to prevent the introduction of hog cholera, this latter claim being to some extent held by veterinarians. As an Insecticide It is claimed by some that a properly made dip of this kind is more efficient for the destruction of the mite causing scabies in sheep than either tobacco or lime-sulfur dips. This view is not held by the of- ficials in California who have charge of the eradication of sheep scab. It is thought that their views are perhaps to a certain extent the con- sequence of experience with improperly made dips. A number of widely used remedies for the destruction of the mange mite are essentially of the type of compounds under discussion. Essig 9 considers that ' ' the most satisfactory of all the sprays used in combating the citrus mealy bug is the carbolic acid emulsion." The preparation recommended is made as follows: Crude Carbolic Acid 5 gals. Whale Oil Soap 40 lbs. Water (Hot) 40 gals. s Amendment 3 to Circ. 34, Office of the Sec, U. S. Dept. Agr. » Pomona College Journal of Entomology, Vol. II, No. 3, p. 252, 1910. Mo. Bull., Calif. State Com. of Hort., Vol. Ill, No. 2, p. 82, 1914. PHENOLIC INSECTICIDES AND FUNGICIDES 345 ''The 40 gallons of water are first poured into the cooking kettle and allowed to boil. While the water is getting hot, the whale soap is cut into fine pieces so as to make it dissolve easily, and added to the water. When the soap is all dissolved in the hot water, the carbolic acid is added, and all is allowed to boil for a short time to insure thorough mixing." The above mixture could have been called "sheep dip" if intended for use in dipping sheep, or if the article has been made up for sale in concentrated form, any of the names listed in table 5 might be applied to it. If the soap were composed partly of rosin, any name in table 6 would be equally applicable. Various preparations of this class have been successfully used for the eradication of insects affecting the date palm, more especially for the dipping of the young imported shoots. Horticulturists and entomologists have occasionally recommended similar preparations for the control of insects and fungi infesting vegetation, but their use in this connection has been comparatively limited, as the results accomplished have not been uniform. At present the use of these is not recommended to any great extent, except as noted above for the control of the citrus mealy bug and insects affect- ing the date palm. In talking with men who have experimented with the use of emulsifiable phenolic insecticides there is usually the same comment made that good results are sometimes obtained but often the results are valueless. Frequently oil-tar residues 10 are sold under the name of crude carbolic acid. Specimens have been examined by this lab- oratory which appear to be saturated solutions of naphthalene to which has been sparingly added enough cresol bearing creosote to give it a "flavor" of phenols. Furthermore, the crude carbolic acids are too often adulterated with petroleum distillates. It is therefore not to be wondered at that the material at times refuses to emulsify or if it does emulsify, the results are erratic. It seems that this condition of affairs may be easily accounted for by the study of results of analyses reported in this bulletin. The favorable results reported by Essig may be accounted for by the possibility that he was unusually fortunate in securing good specimens of crude carbolic acid. If products of this sort and the crude materials from which they are made could be standardized and materials of reasonable depend- ability could be purchased from season to season, it is thought that the coal-tar products in general might be extended to a far wider field of usefulness than at present. io See Oil-tar Creosote, p. 338. 346 UNIVERSITY OP CALIFORNIA EXPERIMENT STATION Part II CLASSIFICATION AND TABULATION OF THE RESULTS OF ANALYSIS OF SAMPLES TAKEN IN FISCAL YEAR 1911-1912-1913, AND COMMENTS No. Obtained from 1037 Brunswig Drug Co., Los Angeles. 1040 Brunswig Drug Co., Los Angeles. 1070 Western Wholesale Drug Co., Los Angeles. 1423 Kirk, Geary & Co., Sacramento. TABLE I Description of Samples (Taken in fiscal year 1911-1912) Manufacturer Unknown Unknown Unknown The Hoffman LaRoche Chemi- cal Works, New York. Brand Liquefied Carbolic Acid. Carbolic Acid, White Crys- tals. Carbolic Acid. Roche-Cryst, 40/42°, U. S. P. TABLE 11 Description of Samples (Taken in fiscal year 1911-1912) No. Obtained from Manufacturer Brand 523 California Drug & Chem Co., Los Angeles. ical Unknown Braucco Cresol. Taken in fiscal year 1912-1913) 1608 Hatzfeld & Parsons, Santa Ana. Unknown Cresol. 2509 California Drug & Chem Co., Los Angeles. ical Unknown Acid Cresylic. 2571 Western Wholesale Drug Los Angeles. Co., Unknown Cresol. (U. S. P.) 2585 Brunswig Drug Co., Los Angeles. Unknown Cresol. U. S. P. so-cal coal-tar Creosote. 3052 Crystal Drug Store, Oroville. Unknown Cresol. 3353 Coffin-Redington Co., San Francisco. Unknown Cresol. 3366 Langley & Michaels, San Francisco. Unknown Cresol. (Cresylic Acid) PHENOLIC INSECTICIDES AND FUNGICIDES IU7 TABLE I I. Eefined Phenols 1. Phenol or Carbolic Acid Guaranteed Absolute Phenol Found Absolute Phenol Gu; arar itee No. Above > Below Remarks % % % % 1037 91.65 Liquefied, Colorless. 1040 98.61 Mostly white crystals, some liquid. 1070 96.0 (U.S. P.) 98.99 2.99 Pink Crystals. 1423 96.0 99.34 3.34 Loose crystals. TABLE II I. Refined Phenols 2. Cresol or Cresylic Acid r Phenol A Cresol Total Phenols Found Total Phenols Guarantee A So. Above Below % % % % % % 523 95-99 95-99 98.0 3.0 Remarks 1608 2509 2571 2585 3052 3353 3366 5.2 95- -99 95-99 95- -99 95-99 100.00 95, ,00 95.00 95-99 95-99 90 .2 95.4 48.48 96.75 1 ,75 93.49 99.35 4, ,35 48.27 97.17 2 , 17 98.68 3 .28 Mislabeled 1 51 Mislabeled 1 1 Samples No. 1608 and 3052 are not cresylic acids nor cresol, but are compounds similar to "liquor cresolis compositus." Both are soluble in water, faintly alkaline and contain an oily soap. 348 UNIVERSITY OF CALIFORNIA- -EXPERIMENT STATION TABLE III Description of Samples (Taken in fiscal year 1911-1912) No. Obtained from 521 California Drug & Chemical Co., Los Angeles. 522 California Drug & Chemical Co., Los Angeles. 567 Western Wholesale Drug Co., Los Angeles. 708 Bean Spray Pump Co., San Jose. 1042 Brunswig Drug Co., Los Angeles. 1056 Sun Drug Co., Los Angeles. 1130 Coffin Redington Co., San Francisco. 1232 Braun-Knecht-Heimann Co., San Francisco. 1424 Kirk, Geary & Co., Sacramento. 2502 California Drug & Chemical Co., Los Angeles. 2503 California Drug & Chemical Co., Los Angeles. 2545 Aggeler & Musser Seed Co., Los Angeles. 2550 Western Wholesale Drug Co., Los Angeles. 2566 Western Wholesale Drug Co., Los Angeles. 3035 C. C. Rubel, Marysville. 3037 Stuck's Pharmacy, Marysville. 3062 J. E. Sangster, Oroville. 3082 Orr's Drug Store, Willows. 3102 The Willows Pharmacy, Willows. 3111 Oscar Robinson, Colusa. 3123 John F. Fouch, Williams. 3185 Ed. F. Johnson, Gilroy. 3209 The Owl Drug Co., San Francisco. 3229 Coffin Redington Co., San Francisco. 3345 Braun-Knecht-Heimann Co.. San Francisco. 3365 Langley & Michaels Co., San Francisco. Brunswig Drug Co., Los Angeles. Manufacturer Blagden & Waugh Blagden & Waugh Blagden & Waugh W. P. Fuller & Co. (Agent). San Francisco Unknown Unknown Unknown Unknown Unknown Unknown Unknown Unknown Unknown Unknown Unknown Unknown Unknown Unknown Unknown Unknown Unknown Unknown Unknown Unknown Unknown Unknown Carbon Paint & Creosote Co Brand 7?c-10% Crude Carbolic Acid. 15%-25% Crude Carbolic Acid. "Western" Crude Carbolic- Acid. Crude Carbolic. Crude Carbolic Acid. Carbolic Acid, Crude. Carbolic Acid, Crude. Crude Carbolic Acid. Crude Carbolic Acid. Crude Carbolic Acid. Crude Carbolic Acid. Crude Carbolic Acid. Creosote Oil. Acid Carbolic, Crude. Acid Carbolic, Crude. Acid Carbolic. Crude. Acid Carbolic, Crude. Acid Carbolic, Crude. Acid Carbolic, Crude. Acid Carbolic, Crude. Acid Carbolic, Crude. Acid Carbolic, Crude. Acid Carbolic, Crude. Acid Carbolic, Crude. Acid Carbolic, Crude. Acid Carbolic, Crude. Acid Carbolic, Crude. PHENOLIC INSECTICIDES AND FUNGICIDES !U9 II. Crude Phenols TABLE III 1. Coal-tar Creosote 1 Commercial terms applied to mixed residues 2. Creosote Oil. I from tar refineries containing variable 3. Crude Carbolic Acid amounts of phenols. Guaranteed A Found Total Phenols % Guarantee Phenol Cresol 7c Total Phenols No. r ' "\ Above Below % % Remarks .V.! 1 7-10 7-10 15-25 7-10 11.0 22.4 13.0 12.7 11.6 4.0 7.4 6.0 522 567 708 1042 1056 19.6 17.5 1130 1232 12.4 1424 38.4 2502 7-10 15-25 11.0 27.6 11.2 4.00 12.6 2503 2545 2550 15-18 15-18 17.4 2.4 2566 7-10 7-10 9.2 2.2 3035 15- -20 20-25 35-45 5.2 29.8 3037 15- -20 20-25 35-45 17.0 18.0 3062 15- -20 20-25 35-45 18.2 16.8 3082 15- -20 20-25 35-45 17.6 17.4 3102 15- -20 20-25 35-45 20.4 14.6 3111 15- -20 20-25 35-45 18.0 17.0 3123 15- -20 20-25 35-45 18.0 17.0 3185 15- -20 20-25 35-45 18.0 17.0 3209 25- -30 25-30 17.8 7.2 3229 21 .0 25.0 46.0 18.2 27.8 3345 7-10 7-10 12.2 5.2 3365 17 .6 8.25 25.85 11.6 14.25 15 -20 10-12 25-32 4.9 20.1 Unofficial 350 UNIVERSITY OF CALIFORNIA — EXPERIMENT STATION TABLE IV Description of Samples (Taken in fiscal year 1911-1912) No. Obtained from Manufacturer Germo Manufacturing Co., Germo Manufacturing Co., Los Angeles. Los Angeles. 21 Winters Pharmacy, Spratt's Patent (America), Winters. ltd. 53 Red Raven Drug Co., Inc., H. Clay Glover, D. V. S., San Francisco. New York. 84 Rossi Drug Co., Dr. G. W. Clayton, San Francisco. Chicago. 155 White Cross Drug Co., Petaluma Incubator Co., Santa Ana. Petaluma. 163 Star Drug Co., Geo. H. Lee, Santa Monica. Omaha, Nebr. 212 Hardman's Drug Store, F. C. Sturtevant, Riverside. Hartford, Conn. 237 Aitken's Pharmacy, The G. E. Conkey Co., Calexico. Cleveland, Ohio. 238 Aitken's Pharmacy Geo. H. Lee, Calexico. Omaha, Nebr. 253 City Drug Co., Sacramento Chemical Co., Lemoore. Sacramento. 263 Wright Bros., Gold Coin Chemical Works, Selma. St. Paul, Minn. 274 Fabian-Grunauer Co., Carpenter-Morten Co., Tracy, Boston, Mass. 275 Fabian-Grunauer Co., Manhattan Food Co., Tracy. Oakland. 446 Osgood's Drug Store, Oakland. F. S. Burch Co. 714 The Manufacturer, West Disinfecting Co., San Francisco. San Francisco. 901 The Manufacturer. Oregon Wood Distilling Co. Linnton, Oregon. 1002 The Manufacturer. Geo. H. Lee, Omaha, Nebr. 1004 The Manufacturer. Henry Albers Co., Los Angeles. 1059 The Manufacturer. West Coast Mill, (Thompkins & Co.) Los Angeles. 1063 The Manufacturer. West Coast Mill, (Thompkins & Co.) Los Angeles. 1503 The Manufacturer. Petaluma Incubator Co., Petaluma. 1515 The Manufacturer, Geo. H. Lee Co., Los Angeles. Omaha, Nebr. 2104 The Manufacturer. Kirk, Geary & Co., Sacramento. 2246 Geo. H. Croley Co., F. C. Sturtevant Co., San Francisco. Hartford, Conn. Brand Germo. Spratt's Eczema and Mange Cure. Glover's Imperial Mange Remedy. Clayton's Mange Remedy. Creosozone. Lee's Lice Killer. Creo-Carbo. Conkey' s Fly Knocker. Flyo-Curo. No-Fly. Gold Coin Lice Killer. Cow-Ease. Fly Keep Off. Sanford's Lice Killer. Kill-Bug. Orwood Lice Killer. Lee's Lice Killer Alber's Liquid Lice Killer. W. C. Lice Killer. Flyfoe. Creosozone Liquid Lice Killer. Lee's Lice Killer. Fornolice. The Sturtevant Lice Paint. PHENOLIC INSECTICIDES AND FUNGICIDES nr>i TABLE IV III. Compounded and Proprietary Remedies 1. Liquids A. Insoluble in water (a) Non-emulsifiable Guaranteed A Found Total Phenols Guarantee K Phenol Cresol Total Phenols No. Above Below % % % % % % 3.8 0.6 7.6 1.0 0.4 21 53 84 155 163 7.2 22.8 o jo 237 2.2 238 2.4 253 0.4 263 6.6 274 10.8 275 1.4 446 0.8 714 10.0 10. 13.1 3.1 901 4.0 1002 6. 8.8 2.8 1004 12.0 3.13 15. 13 19.4 4.27 1059 1.4 1063 1.4 1503 (1) 9.1 1515 6 .0 1.26 4.74 2104 7- -10 18.0 11.0 2246 6 .0 14.82 8.82 (1) Creosotum 81.2%. Remarks 352 UNIVERSITY OF CALIFORNIA EXPERIMENT STATION TABLE IV— (Continued) Description of Samples (Taken in fiscal year 1911-1912) No. Obtained from 2547 Aggeler & Musser Seed Go., Los Angeles. 2603 The Manufacturer. 2611 Thompkins & Co., Los Angeles. 2615 Thompkins & Co., Los Angeles. 2620 Thompkins & Co., Los Angeles. Manufacturer Unknown Henry Albers Co., Los Angeles. West Coast Mill (Thompkins & Co.), Los Angeles. West Coast Mill (Thompkins & Co.), Los Angeles. West Coast Mill (Thompkins & Co.), Los Angeles. Brand A & M Lice Killer. Alber's Liquid Lice Killer. Scalefoe. West Coast Lice Killer. Flyfoe. No. Obtained from 215 Hardman's Drug Store, Riverside. 717 Catfon Bell & Co., San Francisco. 1011 The Manufacturer. 23 75 The Manufacturer. 2594 Brunswig Drug Co. Los, Angeles. TABLE V Description of Samples (Taken in fiscal year 1911-1912) Manufacturer Dr. David Roberts Veterinary Co., Waukesha, Wisconsin. Morris Little & Son, Doncaster, England. McStay Supply Company, Los Angeles. (Taken in fiscal year 1912-1913) Standard Chemical Co., Oakland. Unknown Brand Dr. David Roberts' Germ Killer. Little's Improved Fluid Dip. Stayco Sheep Dip. Ideal Stock Dip. Cre-aseptol. TABLE VI Description of Samples (Taken in fiscal year 1911-1912) No. Obtained from Manufacturer Brand 1 The Manufacturer. George H. Aspinwall, Jersey City, N. J. Phenocide. 35 California Pharmacy, Dr. G. W. Clayton, Ceoline Dog W San Francisco. Chicago, 111. PHENOLIC INSECTICIDES AND FUNGICIDES 353 TABLE YV— (Continued) 111. Compounded and Proprietary Remedies 1. Liquids A. Insoluble in water (a) Non-emulsifiable Guaranteed No. Phenol % Cresol % Total Phenols % Found Total Phenols % 2547 12.00 3.13 15.13 1.70 2603 12.00 3.13 15.13 19.08 2611 18.5 18.5 2.12 2615 1.02 2620 3.13 3.13 1.86 Guarantee , A > Above Below % % 13.43 3.95 16.38 1.27 Remarks TABLE V III. Compounded and Proprietary Eemedies 1. Liquids A. Insoluble in water (b) Emulsiftable (1) With Fatty Soap Emulsifier Guaranteed Phenol % Cresol % Total Phenols % Found Total Phenols % Guarantee A No. Above % Below % Remarks 215 62.5 717 17.0 16.6 0.4 1011 2375 2594 70.0 36.0 (1) 70.0 36.0 4.1 71.86 35.68 1.86 0.32 (1) Crude Carbolic Acid — 25.0% No. 1 35 TABLE VI III. Compounded and Proprietary Eemedies 1. Liquids A. Insoluble in water (b) Emulsiftable (2) With Bosin Soap Emulsifier Guaranteed A Phenol Cresol % % Total Phenols % Found Total Phenols % 9.4 14.0 Guarantee Above Below % % Remarks 354 UNIVERSITY OF CALIFORNIA EXPERIMENT STATION TABLE VI— (Continued) Description of Samples (Taken in fiscal year 1911-1912) No. Obtained from 59 Bass-Hueter Paint Co., San Francisco. 66 Edwin Val Schmidt, San Francisco. 86 Rossi Drug Co., San Francisco. 89 Rossi Drug Co., San Francisco. 121 Lacey & Hartsough, San Diego. 182 Barritt Drug Co., Long Beach. 186 Oakford Drug Co., Long Beach. 194 Jacob Jesson, Ontario. 197 Collins Pharmacy, Uplands. 200 Alhambra Drug Store, Alhambra. 259 Reliable Pharmacy, Kingsburg. 261 Reliable Pharmacy, Kingsburg. 273 Fabian-Grunauer Co., Tracy. 422 Clayton Square Drug Store, East Oakland. 435 Bowman Drug Co., Oakland. 450 Osgoods Drug Store, Oakland. 456 Bowman Drug Co., Oakland. 493 Trumball Seed Co., San Francisco. 496 Trumball Seed Co., San Francisco. 497 Trumball Seed Co., San Francisco. 546 California Drug & Chemical Co., Los Angeles. 712 West Disinfecting Co., San Francisco. 713 West Disinfecting Co., San Francisco. 718 Catton, Bell & Co., San Francisco. 719 Catton, Bell & Co., San Francisco. Manufacturer National Chemical Co., San Francisco. The Sulpho-Napthol Co., Boston, Mass. Dr. A. C. Daniels, Inc., Boston, Mass. Johnson & Johnson, New Brunswick, N. J. Wm. Pearson (Merck & Co., Agents), New York. West Disinfecting Co., New York. Park, Davis & Co., Detroit, Mich. Zenner Disinfectant Co., Detroit, Mich. Dr. Hess & Clark, Ashland, Ohio. Sharp & Dohme, Baltimore, Md. Security Remedy Co., Minneapolis, Minn. Stockmen's Supply Co.. Fresno. Scott & Gilbert Co., San Francisco. Park, Davis & Co., Detroit, Mich. Bowman & Co., Oakland. Merton & Co., Sole Agents, San Francisco. Morris, Little & Son, Doncaster, England. Coulson Poultry & Stock Food Co., Petaluma. The G. E. Conkey Co., Cleveland, Ohio. The G. E. Conkey Co., Cleveland, Ohio. California Drug and Chemical Co., Los Angeles. West Disinfecting Co. West Disinfecting Co. Morris, Little & Son. Doncaster, England. Morris, Little & Son., Doncaster, England. Brand Creofect. Cabot's Sulpho-Napthol. Carbo-Negus. Red Cross Sanitary Fluid. Creolin-Pearson. "C N" Disinfectant. Kreso. Zenoleum. Dr. Hess' Dip and Disin- fectant. Sanax Disinfecting Fluid. Security Carbolized Disin- fectant. Stockmen's Antiseptic Dip. S & G Poultry Lice Killer. Kreso Dip No. 1. Creophene. Merton's Phenolene. Little's Soluble Phenyl. . Cresolene. Conkey's Lice Liquid. Noxicide. Cresylol. Chloro-naptholeum. Chloro-naptholeum Dip. Little's Special Fluid Dip. Little's Soluble Phenyle. PHENOLIC INSECTICIDES AND FUNGICIDES 355 TABLE VI— (Continued) III. Compounded and Proprietary Remedies 1. Liquids A. Insoluble in water (b) Emulsifiable (2) With Eosin Soap Emulsifier Guaranteed A Found Total Phenols % 10.8 14.2 14.4 23.2 17.4 3.8 25.2 14.4 14.2 15.8 16.2 12.0 16.2 19.4 12.4 12.2 12.4 11.8 8.2 12.6 17.6 20.49 14.6 10.87 12.6 Guarantee A Phenol Cr % 12 esol % T« Phe 18- 26 10 12 20 jtal nols % No. 59 Above Below 0.4 5.61 4.0 1.13 7.4 Remarks 66 86 89 121 182 186 194 197 200 259 261 273 422 435 450 456 493 496 497 546 -20 .1 .6 .0 .0 712 713 718 719 .00 :J56 UNIVERSITY OF CALIFORNIA EXPERIMENT STATION TABLE VI— {Continued) Description of Samples (Taken in fiscal year 1911-1912) No. Obtained from 722 Sulpho-Napthol Co., Los Angeles. (By mail). 1045 Brunswig Drug Co., Los Angeles. 1061 Thcmpkins & Co., Los Angeles. 1068 The Manufacturer. 1074 Western Wholesale Drug Co Los Angeles. 1114 Langley & Michaels, San Francisco. 1132 The Manufacturer. 1137 The Manufacturer. 1138 The Manufacturer. 1145 The Manufacturer. 1236 Scott & Gilbert, San Francisco. 1237 Scott & Gilbert, San Francisco. 1239 Scott & Gilbert, San Francisco. 1253 The Manufacturer. 1254 The Manufacturer. 1255 The Manufacturer. 1256 The Manufacturer. 1257 The Manufacturer. 1271 The Manufacturer. 1520 The Manufacturer. 1629 White Cross Drug Co., Santa Ana. 1666 Halsell Drug Co., Huntington Beach. 1720 Mullinix's Store, Anaheim. 2030 N. L. A. Cody, Merced. 2043 W. W. W. Hunter, Madera. Manufacturer Unknown Unknown West Coast Mill (Thompkins & Co.), Los Angeles. Germo Manufacturing Co. of California, Los Angeles. Unknown National Aniline & Chemical Co. Coffin-Redington Co., San Francisco. The Owl Drug Co., San Francisco. The Owl Drug Co., San Francisco. The Owl Drug Co., San Fi'ancisco. California Compounding Co., San Jose. California Compounding Co., San Jose. California Compounding Co., San Jose. W. P. Fuller & Co., San Francisco. W. P. Fuller & Co., San Francisco. W. P. Fuller & Co., San Francisco. W. P. Fuller & Co., San Francisco. W. P. Fuller & Co., San Francisco. Shumate's Pharmacy, Inc., San Francisco. Geo. H. Lee Co., Omaha, Nebr. Western Wholesale Drug Co., Los Angeles. Park, Davis & Co., Detroit, Mich. Park, Davis & Co., Detroit, Mich. Unknown Morris, Little & Son, Doncaster, England. Brand Carbo-Napthol. Sheep Dip. Germioe. Germo-Carbolene. Imperial Sheep Dip. Cresolite Sheep Dip. Creofenol Dip. The Owl Drug Co. Sheep Dip. The Owl's Soluble Phenyl. Todco Mange Remedy. S & G Sheep Dip. S & G Lice Killer. S & G Chicken Dip & Lice Killer. Fuller's Carbolic Tree Spray. Fuller's Carbolic Rose and Vine Spray. Fuller's Carbolic Hop Spray. Fuller's Carbolic Sheep Dip and Cattle Wash. Fuller's Carbolic Poultry Spray. Shumate's Phenyle. Lee's Sheep Dip. Sheep Dip. Sheep Dip. Sheep Dip. Sheep Dip. Little's Sheep Dip. PHENOLIC INSECTICIDES AND FUNGICIDES INS- TABLE VI— (Continued) III. Compounded and Proprietary Remedies 1. Liquids A. Insoluble in water (b) Emulsifiable (2) With Rosin Soap Emulsifter Guaranteed A Found Total Phenols % Guarantee A Total Phenols % No. Phenol Cresol % % Above Below % % Remarks 722 13.6 Unofficial 1045 1061 8.0 16.0 1068 7.4 1074 22.0 20.4 1.6 1114 15.2 1132 20.0 1137 14.6 1138 14.2 1145 15.8 1236 15.0 15.0 17.0 2.0 1237 15.0 15,0 18.8 3.8 1239 15.0 15.0 19.0 4.U 1253 9.1 9.2 0.1^ 1254 9.1 9.4 0.3 1255 . 9.1 9.4 0.3 1256 9.1 9.0 0.1 1257 9.1 9.0 0.1 1271 27. 1 26.0 1.0 > 1520 5.7 1629 22.0 17.4 4.6 1666 18.0 19.4 1.4 1720 16-22 16.4 0.4 2030 16-17 16-17 16.16 0.16 2043 13.28 iPhenyle, 27%. 358 UNIVERSITY OF CALIFORNIA EXPERIMENT STATION TABLE VI— (Continued) Description of Samples (Taken in fiscal year 1911-1912) No. Obtained from Manufacturer 2062 Toda Bros., Security Remedy Co., Farmington. Minneapolis, Minn. 2077 Hotel Drug Co., Stockton. Unknown 2082 Royce & Youngman, Royce & Youngman, Sacramento. Sacramento. 2125 P. Flatow & Son, Sharp & Dohme, Alameda. Baltimore, Md. 2137 Kennet Drug Store, Morris, Little & Son, Kennet. Doncaster, England. 2163 The Manufacturer. Merton & Co., San Francisco. 2165 The Manufacturer, American Druggists' Syndi- San Francisco. cate, New York. 2176 The Manufacturer. W. P. Fuller & Co., San Francisco. 2177 The Manufacturer. \V. 1'. Fuller & Co., San Francisco. 2178 The Manufacturer. \Y. P. Fuller & Co., San Francisco. 2179 The Manufacturer. W. P. Fuller & Co., San Francisco. 2180 The Manufacturer. W. P. Fuller & Co., San Francisco. 2196 The Manufacturer, The Owl Drug Co., San Francisco. San Francisco. 2248 Catton, Bell & Co., Morris, Little & Son, San Francisco. Doncaster, England. 2250 The Manufacturer. Robinson Chemical Works, San Francisco. 2508 The Manufacturer. California Drug & Chemical Co., Los Angeles. 2556 Western Wholesale Drug Co., Los Angeles. Unknown 2584 Brunswig Drug Co., Los Angeles. Unknown 2610 Thompkins & Co., West Coast Mill (Thompkins Los Angeles. & Co.), Los Angeles. 2624 The Manufacturer. Purolene Disinfecting Co., Los Angeles. 2622 The Manufacturer, Germo Manufacturing Co. of Los Angeles. California, Los Angeles. 2633 The Manufacturer. Sun Drug Co., Los Angeles. 2653 The Manufacturer. Los Angeles Chemical Co., Los Angeles. 2673 The Manufacturer. Thomas Drug Store, Azusa. 3066 E. C. Whiting, Oroville. Unknown Brand Security Carbolized Disin- fectant. Sheep Dip. San-i-tin or Sheep Dip. Sheep Dip. Sheep Dip. Merton's Phenolene. A. D. S. Kresano. Fuller's Carbolic Tree Spray. Fuller's Carbolic Hop Spray. Fuller's Carbolic Rose and Vine Spray. Fuller's Carbolic Poultry Spray. Fuller's Carbolic Sheep Dip and Cattle Wash. Todco Mange Remedy. Little's Soluble Phenyle. Palo Alto Sheep Dip & Disinfectant. Cresylol. Imperial Sheep Dip. Creol Dip. Germfoe. Koltarcre. Germo Carbolene. Sun Mealy Bug Spray. Emulsion Disinfectant. 77 Dip. Disinfecting Fluid. Sheep Dip. PHENOLIC INSECTICIDES AND FUNGICIDES 159 TABLE VI— (Continued) III. Compounded and Proprietary Remedies 1. Liquids A. Insoluble in water (b) Emulsifiable (2) With Bosin Soap Emulsifier Guaranteed r Phenol % Cre 15 15 15 A sol % Total Phenols % 22.0 22.0 17.0 15-16 20.0 9.1 9.1 9.1 9.1 9.1 15-17 20.0 15.0 18.0 22.0 15.0 18-20 9.0 18.5 17.0 Found Total Phenols % 5.46 15.36 14.75 16.2 10.68 13.04 6.30 10.58 10.8 11.1 10.5 10.8 14.72 11.48 15.74 17.14 18.46 15.62 14.08 17.18 10.8 6.6 17.2 16.86 21.90 Guarantee A No 2062 Above Below % % 6.64 7.25 0.8 4.32 6.96 1.48 1.7 2.0 1.4 1.7 0.28 8.52 0.74 0.86 3.54 0.62 0.82 2.4 1.3 0.14 Remarks 2077 label 2082 2125 2137 2163 -16 2165 2176 2177 2178 2179 2180 2196 2248 -17 2250 2508 .0 2556 2584 2610 2624 2622 2633 2653 2673 3066 360 UNIVERSITY OF CALIFORNIA EXPERIMENT STATION TABLE VI— (Continued) Description of Samples (Taken in fiscal year 1911-1912) No. Obtained from Manufacturer 3076 The Lee Pharmacy, Chico. Unknown 3138 J. R. Shelton, Woodland. Unknown 3161 Corner Drug Store, Woodland. Unknown 3203 The Owl Drug Co., San Francisco. Unknown 3217 The Owl Drug Co., San Francisco. Unknown 3224 Coffin Redington Co., San Francisco. Unknown 3253 Scott & Gilbert Co., San Francisco. Unknown 3254 Scott & Gilbert Co., San Francisco. Unknown 3292 The Manufacturer. Shumate's Pharmacy San Francisco. 3376 Langley & Michaels Co., San Francisco. Unknown 3377 Langley & Michaels Co., Unknown Brand Sheep Dip. Sheep Dip. Sheep Dip. The Owl's Soluble Phenyl. Sheep Dip. Creo Fenol Sheep Dip. S & G Sheep Dip. S & G Chicken Dip. Shumate's Phenyl. Cresoleum. Cresolite Sheep Dip. San Francisco. No. Obtained from 70 C. F. Fuller, San Francisco. 71 C. F. Fuller, San Francisco. 88 Rossi Drug Co., San Francisco. 1022 Brunswig Drug Co. Los Angeles. TABLE VII Description of Samples (Taken in fiscal year 1911-1912) Manufacturer Hance Brothers & White, Philadelphia, Penn. Entrepot special de produits Hygeniques, Paris. Lehn & Fink, New York. Unknown 1626 White Cross Drug Co., Santa Ana. 2094 Kirk, Geary & Co., Sacramento. 3256 Central Drug Co., San Francisco. 3386 Langley & Michaels Co., San Francisco. (Taken in fiscal year 1912-1913) Unknown Kirk, Geary & Co., Sacramento. H. K. Mulford Co., Philadelphia, Penn. Unknown Brand Phenol Sodique. Veritable Phenol-Baboeuf. Lysol. Cre-aseptol. Solution Cresol Compound. Kasol. Liq. Cresolis Comp. Cresolis Compound. Liquor Cresolis Compositus. PHENOETC INSECTICIDES AND FUNGICIDES 361 TABLE VI— {Continued) III. Compounded and Proprietary Remedies 1. Liquids A. Insoluble in water (b) Emulsifiable (2) With Rosin Soap Emulsifier Guaranteed Total No. 3076 Phenol % Cresol % Phenols % 3138 16-17 16-17 3161 22.0 3203 15-17 15-17 3217 15-17 15-17 3224 22.0 3253 15.0 15.0 3254 15.0 15.0 3292 27. l 3376 16-17 16-17 3377 'Phenyle" 27%. 16-17 16-17 Found Total Phenols % Guarantee A Above % Below % 10.04 15.46 0.54 24.40 2.40 14.6 0.4 13.86 1.14 16.76 5.24 17.30 2.30 18.50 3.50 17.3 9.7 14.58 1.42 14.70 1.30 TABLE VII III. Compounded and Proprietary Remedies 1. Liquids B. Soluble in water .. Guaranteed Phenol % A Cresol % Total Phenols % Found Total Phenols % Guarantee A No. Above Below % % 70 None 71 7.2 88 52.6 1022 35.2 1626 50.0 50.0 46.5 3.5 2094 50.0 50.0 48.84 1.16 3256 45.0 45.0 47.54 2.54 3386 50.0 50.0 48.66 1.34 Remarks Remarks 362 UNIVERSITY OF CALIFORNIA EXPERIMENT STATION TABLE VIII III. Compounded and Proprietary Kemedies 2. Solids and Semi-Solids A. Ointments No. 233 Cresylic Ointment obtained from Dunaway's Pharmacy, El Centre Manu- facturer, Buchan's Soap Corporation, New York. Found Total Phenols 13 . 0% TABLE IX III. Compounded and Proprietary Remedies Guarantee 2. Solids and Semi-Solids B. Powders Total A No. 25 1448 Phenol % Guaranteed Cresol Phenols % % Found Cresol % 0.36 1.05 Above % . Below % Remarks TABLE X Other Samples Examined Users' Samples (submitted in fiscal year 1911-12) No. Sender Material 823 L. P. Spiers, Carbolic Acid for spraying San Jose purposes 826 Bean Spray Pump Co., Crude Carbolic Acid San Jose 827 Charles Keane, State Veterinarian, Little's Improved Fluid Sacramento. Dip Found Total Phenols % 18.4 17.1 16.8 Pine Tar. (Sample taken in fiscal year 1911-12) 542 Obtained from California Drug & Chemical Co., Tjos Angeles 7.2 PHENOLIC INSECTICIDES AND FUNGICIDES 363 TABLE JX Description of Samples (Taken in fiscal year 1911-1912) No. Obtained from Manufacturer Brand 25 The Manufacturer. Langley & Michaels Co., Carbolic Powder or Carbo- San Francisco. lated Lime. 1448 Kirk, Geary & Co., Unknown Compound Carbolic Powder. Sacramento. COMMENTS ON THE RESULTS OF ANALYSIS Tables 1 and 2 Examination of the refined phenols showed them to be of good quality (with one exception) so far as analyzed in the laboratory, even exceeding the guarantee in most cases. Table 3 The amount of total phenols found in the samples of crude phenols varies from 4.9 per cent, to 38.4 per cent. This state of affairs would not be so serious if the correct per cent, of phenols were stated on the label, or even a close approximation, so that the quantity used could be varied according to the strength. But when there is a variation of nearly 30 per cent, from the guarantee, as was found in one sample, and a frequent variation of 15 to 18 per cent., a very unsatisfactory condition must be admitted to exist in regard to the crude phenols. Table 4 These compounds present a very inviting field for research to the chemist, composed as they are of so many substances of difficult separation and identification. In many of these the oils and sub- stances other than phenols are evidently the most active as insecticides, 364 UNIVERSITY OF CALIFORNIA EXPERIMENT STATION so that the determination of the phenols can not be construed as a comparison of their efficiency. Inasmuch as the percentage of phenols was declared in many of such preparations, this constituent was de- termined and may serve as an index of their reliability in other respects, where the composition is given. A large number of them being by-products from the oil and coal-tar refineries it is to be ex- pected that the composition would vary greatly in respect to one of the more valuable commercial products of the refineries: namely, the phenols. Of the eleven samples with labels stating the percentage of active constituents, one stated creosotum as an active constituent which in itself is a very uncertain compound, six were above guar- antee, and four below guarantee. In this group then, there is decided room for improvement. Table 5 Of the preparations listed in this table, one containing an unusu- ally high phenolic content was found to be even above the guarantee ; two were only very slightly below, but well within the 5 per cent, limit; one is passable on account of an indefinite guarantee of crude carbolic acid ; and one had no statement of active ingredients but was found to have an unusually high phenolic content. These, then, are fairly satisfactory in conforming to guarantee, although the variation in total phenols is rather remarkable, ranging from 4.1 per cent, to 71.86 per cent. Table 6 Thirty-nine samples of this group without guarantee were 1 ex- amined. The percentage of total phenols varied from 3.8 per cent, to 25.2 per cent. Forty-nine samples were examined which bore labels stating the percentage of active constituents. Of these latter, twenty were up to standard in phenolic content and twenty-nine below. A 5 per cent, deficiency was allowed in the law before it was amended, without being considered a case of misbranding. This provision takes out eleven of the twenty-nine from those in the below-grade class and places them in the class with those above guarantee. On this basis a little over one-third of the forty-nine guaranteed samples were therefore not within 5 per cent, of the guaranteed amount of total phenols. Extended comment on these results is unnecessary. It seems evi- dent that the manufacturers of the dips which were found to be below guarantee had no extended knowledge of the composition of their products. PHENOLIC INSECTICIDES AND FUNGICIDES 365 Table 7 These preparations may be said to be fairly satisfactory in con- forming to the guarantee. Where variations occurred, they were not usually great. With one or two exceptions the discrepancies may be accounted for by the cresylic acid used in making up the compound. For instance, if sample number 1626, Table 7, had been made up from a cresylic acid similar to sample number 2571, Table 2, using 50 per cent, of this acid supposed to be 100 per cent, pure, the resultant com- pound would upon analysis show only 46.74 per cent, total phenols. This may be remedied by a more thorough knowledge of the raw materials that go to make up the finished product. Table 8 One sample only of cresylic ointment was taken by the inspectors. This sample appeared to be a satisfactory product although no state- ment was made of the per cent, of its active ingredients. Table 9 Very little attention was given to examination of the powders. Those samples examined appear to be scarcely worthy of the name. WHO IS TO BLAME? Those manufacturers and dealers whose wares are shown to be dependable are to be congratulated. The others are not accused of willfully making or selling low-grade or non-standard products, but it appears that material often has been guaranteed and sold with but slight knowledge of its composition. The fault does not lie entirely with the dealers, but the blame must be shared with the producers in other states who have shown hesitancy in giving specific guarantees for their output; if a guar- antee has been given, it may not have had very close relationship to facts. An instance came to the notice of the office, where the manufac- turer of a carbolic dip had been in difficulty with certain officials in charge of the enforcement of an insecticide law, concerning the phenolic content of his dip. He had made up his dip with a coal-tar creosote guaranteed to him to contain a high percentage of phenols and had calculated the phenolic content of the finished dip upon the basis of the guarantee. Analysis showed his product to be far short of the supposed amount of phenols. Investigation disclosed the fact that different shipments of the creosote he was using varied greatly. 366 UNIVERSITY OF CALIFORNIA — EXPERIMENT STATION An analysis of a sample of one shipment showed 20 per cent, less phenols than was claimed. It is therefore only a matter of course that this manufacturer of sheep dip could not make a standard product without first having analyzed each separate lot of raw materials or having purchased from firms whose guarantees are reliable. This manufacturer was legally responsible for the composition of his products, morally the responsibility must be largely shared by the producer of the raw material. Circumstances of this kind will continue to occur as long as the producers of raw materials do not furnish a standard and dependable article to their distributors. A BACKWARD STEP IN INSECTICIDE LEGISLATION It seems very unfortunate that the necessity of stating the per- centages of active ingredients on insecticide labels was removed by amendments to the law. This appears to be decidedly a backward step in insecticide legislation. It lends encouragement to the pro- moter of worthless proprietary preparations and the sellers of hetero- geneous by-products of uncertain composition. It greatly impedes the accomplishment of the standardization of insecticides and fungi- cides which is so much to be desired by the consumer and the con- scientious producer. The label on a package of crude carbolic acid may now venture no more information than that the article is crude; but how crude may only be a matter of conjecture unless the dealer voluntarily gives more definite information. PHENOLIC INSECTICIDES AND FUNGICIDES 367 Part III METHODS OF EXAMINATION AND DESCRIPTION OF APPARATUS QUANTITATIVE METHODS Phenol The percentage of absolute phenol in samples of refined phenol was determined by Koppescharr's method as modified by Allen. 1 In brief the method consists in precipitating the phenol from dilute aqueous or alcoholic solution with bromine in the form of tribrom- phenol. Cresol and Mixed Phenols The bromination method as applied to phenol is not suitable for the determination of cresol for the reason that the latter does not give a uniform product with bromine. As previously pointed out, cresol is the principal phenolic substance or tar acid usually found in the crude phenols and in the compounded and proprietary remedies. Hence some other method must be used for the determination of the phenols in the above. The method of Chapin 2 was adopted as being the best available one for this purpose. The method is equally applicable to cresols, crude phenols, and to the larger proportion of the compounded and proprietary remedies. The amount of the sample taken for analysis must of course be varied so that the volume of phenols will not exceed the capacity of the measuring tube. Slight modifications are neces- sary in the preliminary treatment of some of the materials before distillation. Complete Examination Those who may be interested in the methods for a complete ex- amination of phenolic insecticides and fungicides will be introduced to the literature on the subject by looking up the references cited throughout the text. Particular reference may be made to the fol- 1 Sutton, Volumetric Analysis, 10th edition, p. 415. 2 U. S. Dept. Agr., Bur. Animal Ind., Bull. 107, 1908. 368 UNIVERSITY OF CALIFORNIA EXPERIMENT STATION lowing publications, in which are given the most important methods in use by the Government : U. S. Department of Agriculture, Bureau of Animal Industry, Bulletins 100 and 107 and Circular 167 ; Forest Service, Circulars 112, 191, and 206 ; Treasury Department, Public Health and Marine-Hospital Service of the U. S., Hygienic Labora tory, Bulletin 82. QUALITATIVE TESTS Eosin Rosin may be easily detected by applying the Liebermann-Storch test 3 to the original material. The test as applied in the Insecticide Laboratory is as follows: A glass rod is dipped into the sample to be tested and several smears of varying quantities of the material are made on a white porcelain test plate ; two or three drops of acetic anhydride are added to each smear and lastly a drop of concentrated sulfuric acid. If rosin, rosin oil, or pine-tar is present a peculiar fugitive violet or purple color appears on the plate. Very often the test shows up better when made upon the smallest trace of the material. The most desirable quantity to produce the characteristic test seems to vary with 11k 1 character of the sample. The test therefore is made upon different quantities of the material and there is usually one or two spots which show up more distinctly than the rest. As pointed out by Chapin, the character of the soap employed in making a dip may be judged by observing the residue in the flask after the first distillation in a current of steam. The author found it convenient for this purpose to pour the residue into a large volume of cold water. The residue from a straight rosin soap immediately granulates into solid particles of nearly pure rosin, while the residue from a mixed rosin and fatty or oily soap will be a semi-solid, a thick or thin liquid, depending upon the nature and proportions of the soap acids present. Behavior with Water Unknown liquids are very simply classified into emulsifiable, non- emulsifiable, and soluble by stirring a small quantity of the sample with water. Some idea of the excess alkalinity of the emulsifiable and soluble compounds may be gained by testing at this point with litmus paper. •-* U. S. Dept of Agr., Bur. Chem., Bull. 109, Revised, p. 13. PHENOLIC INSECTICIDES AND FUNGICIDES 369 Nitrobenzene or Oil of Mirbane This substance may be identified by first converting it into aniline and then applying the well-known phenylisocyanide test. The procedure adopted for the identification of nitro-benzene in kerosene solution is as follows: The nitro-benzene is extracted from the kerosene by shaking with alcohol. The alcohol is evaporated off and the nitro-benzene converted into aniline hydrochloride by adding a pinch of zinc powder and a few cubic centimeters of concentrated hydrochloric acid and warming. The acid solution is filtered and to the filtrate is added alcoholic potash and a few drops of chloroform. The characteristic odor of phenylisocyanide is easily recognized upon warming the mixture. SULFONATION TEST* Hydrocarbons of the benzene series may be distinguished from those of the paraffin series by the fact that the former are acted upon by hot concentrated sulfuric acid forming water-soluble compounds, while those of the paraffin series are unaffected by this treatment. The test is not strictly quantitative but does give a very good indica- tion of the nature and source of an oil. Dimethyl Sulfate Test 5 This test is somewhat simpler than the preceding, but has the same end in view, viz. : to determine whether the sample is of coal-tar origin or whether it is in part or wholly derived from oil-gas-tar or tars of other origin, or is mixed with petroleum oils. APPAEATUS With the exception of the phenol measuring tube, the apparatus necessary for performing an analysis by the methods herein referred to are to be found in any well-equipped laboratory or can be pro- cured from the stock of the chemical supply houses on short notice. The phenol measuring tube is easily made and calibrated by a glass blower. The determination of the phenols can be made by any one who is at all familiar with laboratory technique. The processes are somewhat tedious, however, and when a number of analyses are to be made, the work becomes burdensome. In order to facilitate the work, some new apparatus has been developed in the Insecticide Lab- oratory, a description of which may be of interest to those who have 4 Batemann, U. S. Dept. of Agr., Forest Service, Circular 112; also Circulars 191 and 206. • r > Chapin, IT. S. Dept. of Agr., Bur. Animal Ind., Circular 167. 370 UNIVERSITY OF CALIFORNIA EXPERIMENT STATION a number of analyses to make as a matter of routine. The new ap- paratus described is a steam distillation battery, a mechanical shaker, and a small device for holding flasks in the water bath. Illustrations are given, however, showing each step in Chapin's method for the determination of total phenols. In order to conduct the analyses without delays several samples were carried through at one time, the various processes being usually conducted in sets of either three or six, depending upon the time con- sumed and the nature of the process. The number of samples treated Fiji'. 1. — Steam Distillation Battery simultaneously in the different operations may be ascertained by reference to the cuts showing the different steps. The Steam Distillation Battery Chapin's method involves the distillation of the acidified sample in a current of steam until the distillate amounts to at least 800 cc. This operation usually requires considerably more than an hour's time. The apparatus shown in figure 1 has been arranged and found to be of great assistance in the determination of the phenols by this method. Incidentally it is also used whenever a process calls for PHENOLIC INSECTICIDES AND FUNGICIDES 371 steam distillation, being especially useful in the determination of nicotine. The fixed support for the condensers and distillation flasks was suggested in an article by Crossley. 6 The idea adapted to the needs of this laboratory is as follows : The support is fastened to the bench by means of foot plates and screws. To increase its rigidity, the upper part of the frame is fastened by braces to the wall. Ordinary %-inch gas pipe and the necessary couplings were selected as suitable materials for its construction. The rack consists of: First, two up- rights placed 50 inches apart. These uprights are made up of a piece of pipe 16 inches long, screwed into a foot plate at one end and into a T at the other, there being also screwed into this T a longer pipe of 24 inches surmounted by a three-way coupling to accommo- date the upper horizontal pipe and the wall brace. (The upright at the right is not shown in the cut.) Second, two horizontal pipes 50 inches long, one connecting the upper ends of the two uprights, the other, connected to the T's in the uprights. Four T's are inserted into each horizontal pipe at corresponding intervals of 10 inches to receive the shorter verticals. Third, connecting the opposite T's in the two horizontal pipes are four vertical pipes 24 inches in length. To the completed rack can be attached the required flasks, con- densers, and other apparatus by means of the ordinary clamps and clamp fasteners. The water supply for the condensers is brought up to the rack in a horizontal pipe running the length of the rack, at- tached to it by means of clamp fasteners, and having pet-cocks at convenient intervals. A drain pipe is also supported on the rack in the same way. The supply of steam is generated in a copper tank of about four gallons capacity provided with a water-glass marked off at intervals to show the amount of water in the tank. A glass tube about three feet in length is inserted through a stopper held in an opening in the top of the boiler and extends nearly to the bottom of the boiler. The function of this tube is to act as a safety valve and to give a general idea of the pressure in the apparatus by observing the height of the water in the tube. The steam is conducted along the upper length of the rack in a i^-inch pipe insulated by about % inch of asbestos paper which is applied wet in thin layers and subsequently dried. To the outer end of the steam pipe is attached an elbow and a pipe lead- ing to the drain. At this end there is also a valve which is useful for draining the condensed steam from the pipe when the apparatus is 6 A Simple Form of Laboratory Support. T. Linsey Crossley. Journ. Ind. Eng. Chem., Vol. 4, No. 11, p. 846. 372 UNIVERSITY OF CALIFORNIA EXPERIMENT STATION being warmed up and is also of use in relieving the pressure in the apparatus whenever necessary. The steam is distributed from this pipe to the distillation flasks through pet-cocks placed at intervals of ten inches. Connection is made between the pet-cocks and the glass tubes which conduct the steam into the flasks by means of short pieces of rubber tubing. The arrangement described above eliminates many sources of in- convenience often encountered in the usual manner of conducting steam distillations. The use of rubber tubing is reduced to a mini- mum, the short pieces used being easily replaced when necessary at slight expense. The capacity of the burner employed was sufficient for three simultaneous distillations only, but the fourth condenser was found to be of convenience in allowing a sample to be prepared ready for analysis and the flasks, etc., to be attached to it ready for turning in the steam whenever one distillation has been completed. The Mechanical Shaker A part of Chapin's method that requires no small amount of both manual labor and time is the shaking of the large separatory funnels five minutes, three times, at intervals of half an hour. In the analysis of a few occasional samples this objection is not serious, but when a considerable number of samples are to be run through as a matter of daily routine, the busy analyst must seek some device to overcome this difficulty. Search was made in the catalogs of the chemical sup- ply houses and no shaker was found listed which gave promise of being entirely satisfactory for the purpose in view. The author had previously used a "home-made" mechanical shaker in the cereal lab- oratory of the University while working under the direction of Dr. G. W. Shaw. This shaker was so readily adaptable to hold a great variety of glassware and could be constructed sufficiently strong for most kinds of work, that it was thought a similar apparatus could be made to accommodate a number of the large separatory funnels used in the process under discussion. Mr. E. J. Hoff, Mechanician, U. S. Irrigation Investigations, kindly agreed to construct a shaker similar to the one in use in the cereal laboratory, but of larger capacity, and offered many valuable sug- gestions in its construction. After the construction of the shaker many contrivances were made by the author and promptly discarded before a suitable manner of holding the funnels in the box was found. Simple devices were finally evolved, however, which permitted the easy insertion and withdrawal of the funnels and held them securely PHENOLIC INSECTICIDES AND FUNGICIDES 373 in place without the use of screws, springs, or clamps. The shaker which has given excellent service in the Insecticide Laboratory for some three years is illustrated in Figure 2. It is represented as carry- ing a load of six two-liter separatory funnels, each containing 800 cc. of the distillate from a phenol determination, 200 grams of salt, and 150 cc. of benzene for the extraction of the phenols from the brine. The apparatus consists of : First, sl plain well-made box, 5 X 16 X 30 inches inside dimensions. This box is suspended at one end by means of two chains attached to the corners. The other end of the box is supported from the bench by means of an iron bar, % inch thick, 1 inch wide, bent twice at right angles. The bar is about 37 Fig. 2. — Mechanical Shaker, general view with load. inches long and the bends are made about 9% inches from either end, making two legs of equal length and a longer length capable of span- ning the outside width of the box. The longer length is laid flat upon the bench and secured thereto by means of lag-screws passing through loosely fitting holes in the bar. The lag-screws are not entirely screwed down in order to allow the bar to be rocked back and forth. The bench is protected from wear by iron washers around the screws and beneath the bar. The free ends of the legs are hinged to vertical plates attached to the two corners of the box, extending about an inch below the bottom thereof. Second, a % horsepower motor. Third, belts and pulleys for the transmission of power and reduction of speed, and a crank for converting the circular motion of the motor into vibratory motion. This can be accomplished by anyone of a 374 UNIVERSITY OF CALIFORNIA EXPERIMENT STATION mechanical turn of mind and the arrangements would be greatly different to meet the various requirements of the work in hand and the convenient location of motor and shaker. It would be a waste of space to describe these contrivances other than to state that the speed of the motor has been geared down to produce a speed in the shaker of 120 to 130 vibrations per minute, and the crank so arranged that the length of vibration is 3 inches. The criticism that may be made to many of the mechanical shakers that are offered for sale is that the motions produced are too regular and simple to ensure a thorough contact of two immiscible liquids. The particular point of advantage claimed for the one described above is that it produces a variety of motions abundantly sufficient to churn the two liquids into intimate contact. One end of the box being supported from below and the other end being suspended, it Fig. 3. — Device for holding steins of separatory funnels in place in the shaker. is evident that any point in one end of the box must travel through an arc the reverse of any point at the opposite end during an oscilla- tion. The manner of fastening the iron box support to the bench also adds to the complexity of motion. When the legs of the bar are in a vertical position the horizontal part lies flat upon the bench, but is partly turned on edge as the apparatus is moved back and forth. The corresponding end of the box is therefore slightly raised and lowered during each oscillation. The stems of the separatory funnels are held in place in the box of the shaker by the device which is separately shown in Figure 3. This rack fits snugly into the bottom of the box and is removable to permit the insertion of holding arrangements for other glassware. The wooden strips for the slots are placed iy 2 inches apart and pieces of %-inch ordinary white rubber tubing are tacked along the inner sides of the slots. (The block supporting the funnel in the cut is not PHENOLIC INSECTICIDES AND FUNGICIDES 375 Fig. 4. — Detail of the construction of saddle for holding the necks of the separatory funnels in place in the shaker. a part of the rack, but is merely present to hold the funnel in place while being photographed.) In practice the necks of the funnels are held in place by means of saddles placed at intervals along the edges of the box, details of which are indicated in Figure 4. These saddles are made by screwing pairs of right-angled hooks into the edge of the box, each hook being two inches distant from its mate. The ends of the hooks are slipped through holes cut in the side of a piece of rubber tubing of sufficient length to allow it to sag between the pairs of hooks and rest upon the edge of the box. This device offers a firm rest to the necks of the funnels and holds them with surpris- Fig. 5. — Rack holding six large separatory funnels during an interval between the three extractions with benzene. 376 UNIVERSITY OF CALIFORNIA EXPERIMENT STATION ing tenacity, from being thrown out by the motion of the shaker. The horizontal slots (Figure 3) care for the other ends of the funnels with equal efficiency. The slot arrangement for holding the stems allows for a considerable variation in the length and size of the stems as is usually found in purchasing different lots. Water Bath and Condenser Figure 6 represents the water bath and condenser used in distilling off the excess benzene used in the extraction of the phenols. Special i i Fig.. 6. — Distilling off the excess of benzene accumulated in the three extractions. mention is made of this illustration to call attention to the location of the condenser on the edge of the table, the location of the receiving flasks below the table, and the manner of holding the flasks in the water bath. Danger of fire through breakage of the receiving flasks, or un- condensed vapor being carried to the flame, is greatly lessened by placing the receiving flasks below the table. PHENOLIC INSECTICIDES AND FUNGICIDES 377 Device for Holding Flasks in Place in a Water Bath Figure 7 pictures a 500 cc. Erlenmeyer flask with its dress on, ready to be placed in a water bath. The flask is dressed for the oc- casion by slipping over its neck three rings of the water bath ; follow- ing the smaller ring there comes a hollow truncated cone, whose lower diameter is of a size to fit the groove of the smaller ring, the upper diameter being just large enough to pass over the lip of the flask. The Fig. 7. — A convenient arrangement for holding flasks in place in a water bath. cone (shown at the right of the cut) is of the proper height to allow an ordinary wooden test tube holder to snap around the neck of the flask below the lip. The weight of the flask and contents can thus be supported upon the rings of the bath and the necessity of the usual "forest" of ring-stands, clamps and attachments is entirely removed. The author acknowledges the valuable assistance of his associate, Mr. M. R. Miller, who made the photographs used to illustrate the ap- paratus shown in this part of the bulletin. 378 UNIVERSITY OF CALIFORNIA — EXPERIMENT STATION Fig. 8. — Tne transier oi tiie pnenols tioin aqueous to benzene solution after distilling off the excess of benzene. Fig. 9. — The final measurement of the phenols in the tubes designed by Chapin. The two tubes at the right of the cut are shown containing a measured volume of sodium hydroxide solution and one or two cc. of benzene, ready to receive the phenols for final measurement.) PHENOLIC INSECTICIDES AND PUNGIC1DKS 379 INDEX OF SAMPLES The author's classification of the samples herein listed may be ascertained by referring to the heading of the table in which the analysis of the sample is listed. The headings of the tables have been made to correspond to the scheme of classification shown in part I. Acid, Carbolic Acid, Carbolic, Crude Acid, Cresylic A. D. S. Kresano A & M Lice Killer Alber's Liquid Lice Killer Braucco Cresol Cabot's Sulpho-Napthol Carbolated Lime Carbolic Acid, Crude Carbolic Acid Carbolic Powders Carbolic Powder, Compound ... Carbo-Napthol Carbo Negus Ceoline Dog Wash Chloro-Naptholeum Chloro-Naptholeum Dip Clayton's Mange Eemedy Coal-tar Creosote Conkey's Fly Knocker Conkey's Lice Liquid "C N" Disinfectant Cow-Ease Cre-aseptol Cre-aseptol Creo-Carbo Oreofect Creofenol Dip Creo Fenol Sheep Dip Creol Dip Creolin-Pearson Creophene Creosote, Coal-tar Creosote Oil Creosozone Creosozone Liquid Lice Killer Cresylic Acid Cresylic Ointment Sample No. Tab 1 3 2 2165 6 2547 4 004, 2603 4 523 2 66 6 25 9 3 1 9 1448 9 722 6 86 6 35 6 712 6 713 6 84 4 3 237 4 496 6 182 6 274 4 1022 7 2594 5 212 4 59 6 1132 6 3224 6 2584 6 121 6 435 6 3 3 155 4 1503 4 2 233 8 380 UNIVERSITY OP CALIFORNIA EXPERIMENT STATION Cresylol Cresol Compound, Solution Cresolene Cresoleum Cresolis Compound Cresolite Sheep Dip Cresol Crude Carbolic Acid Dips Disinfectants Dog Wash, Ceolene Emulsion Disinfectant Flyfoe Flyo-Curo Fly Keep Off Fornolice Fuller's Carbolic — Hop Spray Poultry Spray Kose & Vine Spray Sheep Dip & Cattle Wash Tree Spray Germfoe Germ Killer, Dr. David Roberts' Germo Germo-Carbolene Glover's Imperial Mange Remedy Gold Coin Lice Killer Hess Dip and Disinfectant, Dr Ideal Stock Dip Imperial Sheep Dip Kasol Kill-Bug Koltarcre Kresano, A. D. S Kreso Kreso Dip No. 1 Lee's Lice Killer 163, Lee's Sheep Dip Lice Killers Lice Liquid, Conkey's Lice Paint Liquor Cresolis Compositus Liq. Cresolis Comp. (Kasol) Little's Improved Fluid Dip Little's Improved Fluid Dip Little's Sheep Dip Little's Soluble Phenyle 456, Little's Special Fluid Dip Sample No. Table 546, 2508 6 1626 7 493 6 3376 6 3256 7 1114, 3377 6 2 3 5, 6 4, 5, 6, 7 35 6 2653 6 1063, 2620 4 238 4 275 4 2104 4 1255, 2177 6 1257, 2179 6 1254, 2178 6 1256, 2180 6 1253, 2176 6 1061, 2610 6 215 5 4 1068, 2622 6 53 4 263 4 197 6 2375 5 1074, 2556 6 2094 7 714 4 2624 6 2165 6 186 6 422 6 1002, 1515 4 1520 6 4, 6 496 6 2246 4 3386 7 2094 7 717 5 827 10 2043 6 719, 2248 6 718 6 PHENOLIC INSECTICIDES AND FUNGICIDES 381 Sample No. Table Lysol 88 7 Mange Cure, Spratt's Eczema and 21 4 Mange Remedy, Clayton's 84 4 Mange Eemedy, Glover's Imperial 53 4 Mange Remedy, Todco 1145, 2196 ' 6 Mealy Bug Spray, Sun 2633 6 Merton's Phenolene 450, 2163 6 No-Fly 253 4 Noxicide 497 6 Ointment, Cresylic 233 8 Orwood Lice Killer 901 4 Owl Drug Co. Dip 1137 6 Owl's Soluble Phenyl 1138, 3203 6 Palo Alto Sheep Dip and Disinfectant 2250 6 Phenocide 1 6 Phenolene, Merton's 450, 2163 6 Phenol 1 Phenol Sodique 70 7 Phenyl, The Owl's Soluble 1138, 3203 6 Phenyl, Shumate's 1271, 3292 6 Phenyle, Little's Soluble 456, 719, 2248 6 Pine-tar 542 10 Red Cross Sanitary Fluid 89 6 Roberts' Germ Killer, Dr. David 215 5 Sanax Disinfecting Fluid 200 6 Sanford's Lice Killer 446 4 San-i-tin or Sheep Dip 2082 6 Scalefoe 2611 4 Security Carbolized Disinfectant 259, 2062 6 77 Dip. Disinfecting Fluid 2673 6 S & G Chicken Dip 3254 6 S & G Chicken Dip and Lice Killer 1239 6 S & G Lice Killer 1237 6 S & G Poultry Lice Killer 273 6 S & G Sheep Dip 1236, 3253 6 Sheep Dips 5, 6 Shumate's Phenyl 1271, 3292 6 Spratt's Eczema and Mange Cure 21 4 Stayco Sheep Dip 1011 5 Stockmen's Antiseptic Dip 261 6 Sturtevant Lice Paint 2246 4 Sulpho-Napthol, Cabot's 66 6 Sun Mealy Bug Spray 2633 6 Tar, Pine 542 10 Todco Mange Remedy 1145, 2196 6 Users' Samples 10 Veritable Phenol-Baboeuf 71 7 W. C. Lice Killer 1059 4 West Coast Lice Killer 2615 4 Zenoleum 194 6 STATION PUBLICATIONS AVAILABLE FOR DISTRIBUTION Appendix to Viticultural REPORTS 1897. Resistant Vines, their Selection, Adaptation, and Grafting. Report for 1896. 1902. Report of the Agricultural Experiment Station for 1898-1901. 1903. Report of the Agricultural Experiment Station for 1901-03. 1904. Twenty-second Report of the Agricultural Experiment Station for 1903-04. 1914. Report of the College of Agriculture and the Agricultural Experiment Station, July, 1913-June, 1914. 1915. Report of the College of Agriculture and the Agricultural Experiment Station, July, 1914-June, 1915. BULLETINS No. 246 248 No. 168. 169. 174. 178. 184. 185. 195. 203. 207. 208. 212. 213. 216. 220. 225. 227. 230. 234. 241. 242. 244. Observations on Some Vine Diseases in Sonoma Count/. Tolerance of the Sugar Beet for Alkali. A New Wine-Cooling Machine. Mosquito Control. Report of the Plant Pathologist to July 1, 1906. Report of Progress in Cereal Investi- gations. The California Grape Root-worm. Report of the Plant Pathologist to July 1, 1909. The Control of the Argentine Ant. The Late Blight of Celery. California White Wheats. The Principles of Wine-making. A Progress Report upon Soil and Climatic Factors Influencing the Composition of Wheat. Dosage Tables. Tolerance of Eucalyptus for Alkali. Grape Vinegar. Enological Investigations. Red Spiders and Mites of Citrus Trees. Vine Pruning in California. Part I. Humus in California Soils. Utilization of Waste Oranges. 249. 250. 251. 252. 253. 254. 255. 256. 257. 258. 261. 262. 263. 264. 265. 266. 267. 268. 269. Vine Pruning in California. Part II. The Economic Value of Pacific Coast Kelps. Stock Poisoning Plants of California. The Loquat. Utilization of the Nitrogen and Or- ganic Matter in Septic and Imhoff Tank Sludges. Deterioration of Lumber. Irrigation and Soil Conditions in the Sierra Nevada Foothills, California. The Avocado in California. The Citricola Scale. Value of Barley for Cows fed Alfalfa. New Dosage Tables . Mealy Bugs of Citrus Trees. Melaxuma of the Walnut, "Juglans regia." Citrus Diseases of Florida and Cuba compared with those of California. Size Grade for Ripe Olives. The Calibration of the Leakage Meter. Cottony Rot of Lemons in California. A Spotting of Citrus Fruits Due to the Action of Oil Liberated from the Rind. Experiments with Stocks for Citrus. Growing and Grafting Olive Seedlings. Phenolic Insecticides and Fungicides. No. CIRCULARS No. 65. The California Insecticide Law. 69. The Extermination of Morning-Glory. 70. Observations on the Status of Corn Growing in California. 76. Hot Room Callusing. 82. The Common Ground Squirrels of California. 100. Pruning Frosted Citrus Trees. 106. Directions for using Anti-Hog-Cholera Serum. 107. Spraying Walnut Trees for Blight and Aphis Control. 108. Grape Juice. 109. Community or Local Extension Work by the High School Agricultural De- partment. 110. Green Manuring in California. 111. The Use of Lime and Gypsum on Cali- fornia Soils. 113. Correspondence Courses in Agriculture. 114. Increasing the Duty of Water. 115. Grafting Vinifera Vineyards. 117. The Selection and Cost of a Small Pumping Plant. 118. The County Farm Bureau 119. Winery Directions. 121. Some Things the Prospective Settler Should Know. 122. The Management of Strawberry Soils in Pajaro Valley. 124. Alfalfa Silage for Fattening Steers. 125. 126. 127. 128. 129. 130. 131. 132. 133. 134. 135. 136. 137. 138. 139. 140. 142. 143. 144. 145. 146. 147. 148. 149. Aphids on Grain and Cantaloupes. Spraying for the Grape Leaf Hopper. House Fumigation. Insecticide Formulas. The Control of Citrus Insects. Cabbage Growing in California. Spraying for Control of Walnut Aphis. When to Vaccinate against Hog Cholera. County Farm Advisor. Control of Raisin Insects. Official Tests of Dairy Cows. Melilotus Indica. Wood Decay in Orchard Trees. The Silo in California Agriculture. The Generation of Hydrocyanic Acid Gas in Fumigation by Portable Ma- chines. The Practical Application of Improved Methods of Fermentation in Califor- nia Wineries during 1913 and 1914. Standard Insecticides and Fungicides versus Secret Preparations. Practical and Inexpensive Poultry Ap- pliances. Control of Grasshoppers in Imperial Valley. Oidium or Powdery Mildew of the Vine. Suggestions to Poultrymen concerning Cbicken Pox. Jellies and Marmalades from Citrus Fruits. Tomato Growing in California. "Lungworms." Lawn Making in California