MAY, 1939
INDUSTRIAL AND ENGINEERING CHEMISTRY
2-Methyl-2-nitrobutane was identified by its boiling point (149.8' C. a t 752.3 mm.) and by its insolubility in a sodium hydroxide solution. 3-Methyl-Z-nitrobutane, boiling a t 154' C. (746.2 mm.), was identified by the fact that it formed a blue pseudonitrole when treated with an alcoholic solution of sodium hydroxide and sodium nitrite with subsequent neutralization of the solution. The analysis of the mixture containing 2-methyl-1-nitrobutane and 3-methyl-1-nitrobutane involved the reduction of the mixture to the amines. The amine fraction of boiling range 94-97' C. was collected and converted to the hydrochlorides. The melting point of the hydrochloride mixture was compared to the melting point of known mixtures of the hydrochlorides of 2-methyl-1-butylamine and 3-methyl-lbutylamine.
and 2-methyl-1-nitropropane are present. The amounts of each component of the mixture could not be determined.
Preparation of Amine Hydrochlorides I n order to determine the amounts of the hydrochlorides of 2-methyl-1-butylamine and of 3-methyl-1-butylamine present, a melting point-composition curve was prepared from the pure compounds. sec-Butyl alcohol was converted to the bromide by the use of bromine in the presence of phosphorus (3) and purified by rectification. The sec-butyl bromide was converted to the nitrile according to the procedure of Hass and Marshall (6). The yield was very poor. The nitrile was purified by rectification. The fraction boiling a t 123-125' C. was collected.
Mixture Containing 2-Nitrobutane and 2-Methyl-1-nitropropane A fraction of the distillate within the range of the boiling point of Z-nitrobutane and 2-methyl-1-nitropropane was reduced to the amines with iron and hydrochloric acid. The amines were rectified and the fraction of boiling range 6162.2' C. was collected. The phenylthiourea derivative melted a t 100-101' C. This proves the presence of 2-nitrobutane in the original mixture. Another portion of the nitrobutane mixture was rectified, and the fraction boiling a t 77-81.6' C. (100 mm.) was collected. This material was dissolved in sodium hydroxide, and a slight excess of the calculated amount of sodium nitrite was added. The solution was made acid with sulfuric acid. The aqueous solution was blue. This color was due to the pseudonitrole of 2-nitrobutane which was known to be present. The aqueous solution was extracted with ether, and the ether extract shaken with an aqueous solution of sodium hydroxide. The ether layer remained blue in color, but the aqueous layer was orange-red. The orange-red color of the aqueous solution is characteristic of the sodium salts of the
**O
2 I
I
I80 __
IO
PO 30 40 50 60 70 80 90 PER CENT PMETHYL-I-BUTYLAMINE HYDROCHLORIDE
100
FIGURE1. COMPOSITION-MELTING POINTCURVE FOR %AND 3-METHYL-1-BUTYLAMINE HYDROCHLORIDE
nitrolic acids. Demole (,%') showed that the nitrolic acid derived from 2-methyl-1-nitropropane yields isobutyric acid upon treatment with sulfuric acid. Upon treatment with sulfuric acid the orange-red aqueous layer gave a distinct odor of isobutyric acid, which confirmed the presence of 2methyl-1-nitropropane. From the boiling point of the fraction and the color reaction it is believed that 2-nitrobutane
649
MIXTURE of:
2-METHYL-I-NITROPROPANE
2-N ITROBU TAN E
I
60
I
I
I
120
180
240
I
300
M LS. OF DISTILLATE
FIGURE 2. RECTIFICATION CURVEOF THE PRODUCT OBTAINED BY NITRATING ISOPENTANE AT 420 C. O
The nitrile was reduced to the corresponding amine by the method of Adams and Marvel (1). After unreacted sodium was destroyed, the reaction mixture was steam-distilled. The distillate was made acid with hydrochloric acid and evaporated to dryness. The salt was taken up with a sodium hydroxide solution. The alkaline solution was extracted with ether, and the ether extract was dried over anhydrous potassium carbonate. The ether was stripped from the amine in a modified Podbielniak column, and the amine was rectified. The fraction of boiling range 94-96.5" C. was collected. The amine was dissolved in ether and treated with dry hydrogen chloride in the cold. The amine hydrochloride was filtered off and dissolved in a small amount of anhydrous butyl alcohol. The solution was filtered, and the 2-methyl-lbutylamine hydrochloride was reprecipitated by the addition of dry ether. The melting point of the salt was 180-181" C. The melting point given in the literature is 176" C. (9). The hydrochloride of isoamylamine (3-methyl-1-butylamine) was prepared in a manner similar to that just described. The conversion of the isobutyl bromide to the nitrile was less than that obtained in the previous preparation. The phenylthiourea derivative of the isoamylamine was prepared. Its melting point was 103.6' C. The melting point in the literature is 102' C. (IO). The remainder of the amine was converted to the hydrochloride by the method previously described. The melting point of the isoamylamine hydrochloride was 218-219' C. Ten samples of mixtures of the two amine hydrochlorides were weighed out and mixed, and five melting points of each mixture were taken with calibrated Fisher short-stem thermometers (7). The curve shown in Figure 1 was obtained
INDUSTRIAL AND ENGINEERING CHEMISTRY
650
by plotting the average melting point against the percentage composition. Isopentane was nitrated a t 380” C. The average yield per pass, based upon the nitric acid reacting, was 17.5 per cent. The average mole ratio of hydrocarbon to acid was 1.71. At 420” C. t h e average yield per pass was 23.5 per cent, and the average mole ratio of hydrocarbon to acid was 4.73. The approximate percentage composition of the material obtained by nitrating isopentane a t the two temperatures is as follows:
Nitromethane Nitroethane 2-Nitropropane 2-Meth 1 1 nitropropane 2-Nitrog%m
380 OC. 6 6 6
} 12
$20
c.
380
420
o c .
o c .
19
2 6 11
2-Methyl-2-nitrobutane 3-Methyl-2-nitrobutane 2-Methyl-1-nitrobutane
27
11
14 16 28
10
3-Methyl-1-nitrobutane
13
13
The materials used were ordinary c. P. concentrated (68 per cent) nitric acid and 97 per cent c. P. isopentane obtained from the Phillips Petroleum Company.
VOL. 31, NO. 5
Thanks are hereby extended to the Commercial Solvents Corporation for defraying the expenses of this investigation, and for furnishing the nitroparaffins used.
Literature Cited (1) Adams, R., and Marvel, C. S., J . Am. Chem. SOC.,42, 310 (1920). ( 2 ) Demole, E.,Ann., 175, 142 (1875). (3) Goshorn, R. H., and Degering, E. F., Proc. Indiana Acad. Sci., 45, 139 (1936). ENG. (4) Hass, H. B., Hodge, E. B., and Vanderbilt, B. M.. IND. CHEM.,28, 339 (1936). ( 5 ) Hass, H. B., and Marshall, J. R., Ibid., 23, 352 (1931). (6) Hass, H. B., and Patterson, J. A., Ibid., 30, 67 (1938). (7) Hass, H. B., and Weber, Paul, IND.ENG.CHIM., Anal. Ed., 7 , 231 (1935). 30, (8) McCleary, R. F., and Degering, E. F., IND.ENG. CHEM., 64 (1938). Marchwald, W., Ber., 37, 1048 (1904). Shriner, R. L., and Fuson, R. C., “Systematic Identification of Organic Compounds”, p. 119, New York, John Wiley & Sons, 1935.
(j:;
CORRESPONDENCE Deposition of Gold on Fabrics SIR: In the article on “Chemistry in 1938” [ ~ N D .ENG.CHEM., 31,3 (1939) 1 reference is made on page 5 to a novelty which may become of commercial interest in the production of new fabrics. The discovery has to do with a new process by which a film of gold of nearly colloidal thickness can be deposited on a fabric. According to the information, the fabric is dipped into an organic compound of gold which breaks up into its constituent parts when slightly heated. This information is far too scanty for us to pass judgment on the commercial importance of such a development. However, the basic principle of this discovery is not only not new from a purely scientificstandpoint, but a complete book devoted entirely to this method of dyeing was published nearly one hundred and fifty years ago (“An Essay on Combustion, with a View to a New Art of Dyeing and Painting”, by Mrs. FuIhame, published by J. Cooper in London in 1794). The preface of this book, which deserves greater recognition than it has so far obtained, states: “The possibility of making cloth of gold, silver, and other metals, by chymical processes, occurred to me in the year 1780. . . .Though I was, after some considerable time, able to make small bits of cloth of gold, and silver, yet I did not think them worthy of public attention; but by persevering I at length succeeded in making pieces of gold cloth, as large as my finances would admit.” The following are quotations of experiments discussed by Mrs. Fulhame :
this experiment, which was repeated times without number, or demonstrates the necessity of water in these reductions in a more convincing manner. This piece, viewed by transmitted light, had a purple colour with a considerable tinge of blue; and the margin of the reduced gold was fringed with purple (page 49). A piece of silk was immersed in a solution of nitromuriate of gold in water, suspended in the glass funnel, and exposed, while wet, to vapour of sulphur, formed by a burning match; no sooner did the vapour touch the silk, than the reduction commenced; and in a few seconds the whole piece was covered with a splendid coat of reduced gold, permanent, and retentive of its lustre; but had a few specks of a dull violet hue. The silk viewed by transmitted light appeared of a beautiful blue colour; and being removed from the vapour, and suspended in the air, began in about ten minutes to exhale a vapour, which continued about two hours, and smelled acid, and pungent. Another piece of silk, dipped in the same solution of gold, and dried, was wetted with alcohol, and exposed to the same vapour: the silk acquired a brownish hue; and a small white metallic film appeared on its lower end, where the alcohol most abounded: the silk was then wetted with water, and replaced in the vapour; instantly a lively purple with a bright pellicle of reduced gold appeared (page 70). A piece of silk, which was immersed in a solution of nitro-muriate of gold in distilled water, and suspended in the air twelve hours to dry, was divided into three parts. One of these was exposed to a stream of phosphorated hydrogen gas: the silk became brown, and its margins, which happened to touch the sides of the phial, acquired a violet tinge: but no reduction took place. Another of these parts was wetted with alcohol, and exposed to the gas; but no signs of reduction could be perceived. The remaining part was wetted with water, and was no sooner exposed to the gas, than the reduction commenced over the whole silk, which was soon covered with a bright coat of reduced gold (page 114).
I dipped a piece of silk in the solution of phosphorus, when the ether evaporated, and the phosphorus began to fume, a solution of gold in water was applied; instantly the silk was covered with a splendid coat of reduced gold. Nothing can be more striking than
MASSACHUSETTS INSTITUTI~ OF TEOHNOLOQY CAMBRIDW,MASS. March 21. 1939
ERNST A. HAUSE~R
sary equipment expansion. Restraints on transportation reduced our imports and furnished part of the inspiration which proved desirable. Idle capital was encouraged by possible profits, and technical ability was augmented by patriotism. Existing industries expanded and gaps were filled by American business initiative. If six hundred and fifty firms were reported as supplying the preponderance of equipment used in plants making chemicals and chemical products, approximately 10 per cent of these possessed the initiative to advertise the fact that they were ready to supply all the needs of industry. Quickly this figure was increased by the demand; within a year the number was more than doubled, and in another year it was doubled again. When the industry reached a point near saturation, the amount of increase gradually diminished. Later, demands for special types of equipment created new industries and brought new manufacturers.
Courtesu, Struthers- Wells
RECENT TYPEOF INCLINEDEVAPORATOR
Domestic equipment manufacturers were not encouraged to greater production. Prevailing designs were those to be found in the current textbooks, and the materials of construction were the ones most commonly availab1:-iron, steel, some nonferrous materials (less frequently alloyed than native), and, of course, wood and ceramic materials. WAR among foreign nations changed this situation. Under pressure of orders from abroad, our own peace industry was forced to augment its supplies of chemical raw materials. The necessity of producing larger quantities called for neces-
DURIRON CENTRIFUGAL PUMP MAY, 1939-Page
571
Courtesy, Baker Perkins Company, Inc.
HEAVY-DUTY VACUUM MIXERDESIGNED FOR PLASTICS, RESINOUS COMPOUNDS, PAINTS, AND INKS
To the redounding credit of the equipment manufacturers of that period the point should be made that they responded to the world’s need and produced equipment of all kinds quickly. By astute research, by trial and error, by Yankee ingenuity, and by all of the liberal methodism known as the American Way, they made equipment for every difficult type of chemical industrial service. Improvement followed improvement. Chemical engineering equipment made of ceramic materials unheard of before was brought forward to triumph over difficult applications. Plastic materials made from synthetic resins came into use as materials of construction. Suggestions were taken from history. The Sheffield plate makers provided the idea for plating over base metals high in mechanical strength with metals which were more highly resistant to corrosion. There were also innumerable side applications of plating (coating), involving rubber, plastics, glass, and ceramics. The values of impregnated lumber were rapidly discovered and applied. Reactions a t unheard of high pressures and temperatures were gradually accommodated successfully by equipment devised for a new scale of physical constants. Chemical engineering processes, such as distillation, evaporation, filtration, and drying, were advanced through improvements in corrosion-resistant materials. Known, but little used, metals and alloys became the subT H E AMERICAN WAY
