1856
I~OTES
Vol. 67
A Convenient Preparation of t-Butylamine
[Cr ena](NCS)s.&O when heated for several days a t 160 and 130°, respectively, yield cis- [Cr enzClzIC1 and trans- [Cr e n ~ ( N c S )NCS, ~ ] respecUTe wish to report a convenient method for the tively, indicating the greater stability of the chlopreparation of relatively large quantities of ride as compared with the thiocyanate. We have t-butylamine by catalytic hydrogenation of 2,2- now investigated the relative thermal stabilities dimethylethyleneimine. The imine was prepared of a number of other triethylene- and tripropyleneaccording to the method of Cairns,' 4. e., by the diamine chromic salts. sulfation of 2-amino-2-methyl- 1-propanol followed Preparation of Materials.-The amines were by alkali treatment of the 2-amino-2-methyl-l- dehydrated according to Putnam and Kobe's dipropanolsulfuric acid. It is interesting to note rections for dehydrating ethylenediamine.6 Anthat no isobutylamine was detected from the hydrous chromic sulfate, triethy!enediamine chrohydrogenation of 2,2-dimethylethy!eneimineJ a mic sulfate, and tripropylenediamine chromic product expected by cleavage of the nitrogen at sulfate were prepared by the mekho is of Rollinson the tertiary carbon. and Bailar.6 Both 2,2-dimethylethyleneimine and t-butylThe triethylene- and tripropylenediamine chroamine were obtained in a state of purity and their mic salts were for the most part prepared by metaconstants determined and recorded below. thesis between the chromammine sulfate and the PHYSICAL COXSTANTS O F &BUTYLAMINE AND 2,2-D1corresponding ammonium salt in 1 0 0 ~ oexcess, METHYLETHYLENEIMINE both in saturated aqueous solutions. The mixed 2,a-Dimethylsolution was stirred rapidly while cooled in ice. &Butylamine ethyleneimine In the cases of bromide, iodide and thiocyanate, Boililig point, "C. 45.0 70.5 crystallization occurred at once; in the,case of Refractive index, %*OD 1.3780 1.4075 the chloride, a few minutes were required. The 0.7055" 0.7902* Density, dt, nitrate and oxalate did not crystallize for several Freezing point. "C. -72.65 -47.08 hours. The yellow crystals were filtered and air a d17.6,. b d14+ dried. Experimental The triethylenediamine chromic nitrite, cyanide Hydrogenation of 2,2-Dimethylethyleneimine.-A mixture containing 710 g. of 2,2-dimethylethyleneimine and and cyanate were prepared in similar fashion using 50 g. of U. 0. P. nickel catalyst was hydrogenated in a potassium salts in place of the corresponding amrocker-type autoclave of 3-liter capacity. At a pressure of 700 lb./sq. inch, and a temperature of 130" the reaction monium compounds. These luteo salts are somewhat more soluble than any of the others, and proceeded smoothly and almost the theoretical quantity of hydrogen was consumed. After cooling, the filtered solu- crystallized only after several hours. tion was subjected to fractional distillation on a 20 theoTripropylenediamine chromic chloride was too retical-plate column. The fraction boiling from 44-46'' soluble for preparation by this method. Thereamounted to 510 g. (70%). The physical constants are fore to a solution of 8.36 g. (0.01 mole) of trirecorded above. t-Butylamine hydrochloride was prepared from the propylenediamine chromic sulfate in 50 nil. of amine and concentrated hTdrochloric acid, m. p, 290-291. water was added 7.32 g. (0.03 mole) of barium The recorded* value is 291 . chloride dihydrate dissolved in 50 ml. of water. 2,2-Dimethylethyleneimine phenylurea was prepared by treating the imine with phenyl isocyanate followed by The mixture was allowed to stand three hours at crystallization from neohexane, m. p. 88-89 '. room temperature and the barium sulfate filtereJ. Anal. Calcd. for C I I H ~ ~ O XN,~ : 14.73. Found: N, The filtrate was allowed to evaporate at room 14.62. temperature, producing yellow crystals of tri(1) T. L. Cairns, THIS J O U R N A L , 63, 871 (1941). propylenediamine chromic chloride. The salt ( 2 ) F. Rlages, G Nober, F. Kircher and M. Bock, A n n . , 54'7, 1 may also be obtained by the addition of alcohol (1941) . to the filtrate of the barium sulfate filtration. AIRCRAFT ENGIVE RESEARCH LABORATORY When produced in this manner it is not visibly NATIONALADVISORYCOMMITTEE FOR AERONAUTICS RECEIVED AUGUST 13, 1945 crystalline, but is a fine yellow powder. CLEVELAND, OHIO Thermal Decomposition:-To study the therStudies in the Chromammines. IV. Thermal mal decomposition, the loss in weight of a 1-g. sample of the ammine salt to which a small Decomposition of Luteo Salts . 2 amount of the corresponding ammonium salt had B Y THOMAS D. o ' f 3 R I E N 3 AND JOHN c. BAILAR,JR. been added was followed over a period of hours I t has been observed by Pfeiffer and others4 as described previously.* The temperatures at that the luteo salts [Cr en,]Cla.3.5H20 and which significant decomposition occurred with (1) For the preceding paper in this series see Kollinaon and Bailar, the different salts are shown in Table I. THISJ O U R N A L , 66, 641 (1944). The triethylenediamine salts, except the pre(2) Presented a t the 108th Meeting of the American Chemical viously studied thiocyanate and chloride, tleSociety, New York. N. Y.,September 12, 1944. (3) Abstracted from a portion of a thesis submitted in partial composed to a brown solid whose composition fulfilment of the requirement for the degree of Doctor of Philosophy varied apparently with the temperature and the in Chemistry a t the University of Illinois, 1940. BY JOSEPH V. KARABINOS AND USPER T.SERIJAN
(4) Pfeiffer, Koch, Lando and Trieschmann, Ber., 37, 4269, 4277 ( 1904).
( 5 ) Putnam and Kobe, T r a n s . Electrochem. Soc., 74, 610 (1938) (6) Rollinson and Bailar, THISJOURNAL, 66, 250 (1943).
NOTES
Oct., 1945
1857
TABLE I acid for growth may not be able to synthesize it DECOMPOSITION TEMPERATURES (RELATIVETHERMALfor one of several reasons. Some, such as lactic acid. bacteria, are unable to carry out the coupSTABILITY) OF CHROMIUM TRIALKYLENEDIAMINE SALTS
.
ling. They fail to grow on a mixture of &alanine and pantoyl lactone, but require the intact pantoThiocyanate 130 110 thenic acid molecule.’ In the pantothenicless Nitrite 135 ... mutant of Neurospora (5531), which has this same Nitrate 140 ... requirement, the coupling is under genetic conCyanate 150 ... troL6 Other organisms like certain yeastss and a Chloride 160 176 diphtheria bacillusI2will grow if pantothenic acid Iodide 200 ... or &alanine is supplied but cannot use the pantoyl Sulfate 210 ... moiety alone. Apparently the pantoyl moiety is Bromide 210 196 manufactured in these organisms and coupled Cyanide 230 ... with the added 8-alanine to form pantothenic Oxalate 280 ... acid. Only the synthesis of &alanine has been impaired. In still other organisms like Acetot i q e of heating so that no definite product could bacter? a strain of Proteus morganiis and a hemobe identified. The nitrite and nitrate at slightly lytic streptococcus,2 the synthesis of ,%alanine higher temperatures, namely, 135 and 140’, re- presumably is carried out, but the pantoyl moiety spectively, decomposed completely into chromium is not made. Again the capacity for coupling has oxide, not been lost since pantoyl lactone is able, even if Tripropylenediamine bromide and iodide also incompletely, to replace pantothenic acid ,as a decomposed into a dark brown substance indis- growth factor in the medium. tinguishable from the corresponding product In the course of studies on the nutrition of formed by the triethylenediamine salts. The Clostridium septuum we have observed that chloride, however, was converted completely pantoyl lactone will completely replace pantoafter five hours a t 175’ to the purple cis-dichloroacid. For these experiments a single cell propylenediamine chromic chloride. Prolonged thenic isolate (strain 59 Li A) was used. The clostridia heating or the use of higher temperatures should were grown on a chemically defined medium which be avoided because these conditions cause a pro- is a modification of that proposed by Bernheimer.g nounced darkening of the purple salt. After Growth was measured turbidometrically, the exdarkening, the salt turns black and then chars. tinction being proportional to the milligrams of Recrystallization of the purple salt is diflicult be- bacterial nitrogen as determined by a micro cause of its high solubility. Kjeldahl on washed cultures. At 37’ growth Anal. Calcd. for [Cr pn2Cl2IC1: Cr, 16.94. was complete in about twelve hours. Found: Cr, 16.75. The presence of adequate amounts of calcium Similarly the thiocyanate gave a red-orange d-pantothenate, sodium dl-pantoate or dl-pantoyl product a t 110’. The product was difficultly lactone in the medium resulted in a maximum soluble in cold water and quite soluble in hot, so yield of 16-17 mg. of bacterial nitrogen per 100 was easily crystallized. cc. (Table I). Each of these substances also supAnal. Calcd. for [Cr pnz(NCS),](NCS): Cr, ported the maximum rate of growth on this me12.88. Found: Cr, 12.98. dium. During the logarithmic growth phase one The stabilities of the tripropylenediamine salts cell generation was produced every sixty to sixtyare in the same order as, and in general appear to five minutes. However, on a molar basis calcium be slightly less than, the corresponding triethyl- d-pantothenate is the more active. The molar enediamine salts. concentration required to yield 8 mg. of bacterial nitrogen per 100 cc. was 0.2 X while ca. DEPARTMENT OF CHEMISTRY UNIVERSITY OF ILLIXOIS 4 X lo4 M d-pantoyl lactone or sodium dRECEIVED MARCH2 1 , 1945 pantoate was required for the same crop (Fig. 1). URBANA, ILLINOIS When the pantoate concentration is calculated in terms of undissociated d-pantoic acid ( P K a = The Biosynthesis of Pantothenic Acid’ 4.0),its activity per mole is still less than that of BY F. J. RYAN, R. BALLENTINE, E. STOLOW, M. E. COR- undissociated d-pantothenic acid ( p K a = 4.4) but Triethylene, temp., O C .
Salt
Tripropylene, temp., OC.
,
SON AND
L. K. SCHNEIDER
The biosynthesis of pantothenic acid has been thought to involve a coupling of &alanine with a-hydroxy-p,p-dimethyl-y-butyrolactone (pantoy1 lactone). 2.a Organisms requiring pantothenic (1) This work was supported in part by a grant from the Josiah Macy, Jr., Foundation. (2) R. J. Williams, “Advances in Enrymol.,” 8, 253 (1943). (3) H. R . Rosenberg, “Cheiistry and Physiology of the Vitamins,” Interscience Publishers, Inc., New York, N. Y..1942, p. 263.
(4) V. H. Cheldelin, E. H. Hoag and H. P. Sarett, 1.B a c f . , I S , 41 (1945). (5) E. L. Tatum and G. W. Beadle, Growth, 6, 27 (1942). (6) v. N. Nielson and V. Hartelius, Nolurwissenschaftcn, 46/46, 550 (1943); € E.ISarett . and V. H. Cheldelin, J. Bacf.,49, 31 (1945). (7) L. A. Underkofler and A. C. Banty, {bid., 46, 183 (1943). (8) G. Ivanovics, 2. physiol. Chrm., P76, 33 (1942). (9) A. W. Bernheimer, J. Ex#. Mea., 80,321 (1944). Our medium
diffen essentially from that of Bernheimer in that the casamino acids were Norite treated, 0.2% of neutralized cysteine hydrochloride replaced the thioglycolic acid and the final medium was sterilized by autoclaving.
