January, 1932
I S D U S T R I A L A N D E NG I N E E R I N G C H E M I ST R Y
Hehesus, J . Russ. Piiys. Chem. Soc., 14, 3 2 0 (158:3). Kata. Naturwissenschaften. 13.410 (1925). Katz'and Bing, Z . aniew. 'Chem., 38, 439 (1925). Gummi-Ztg.,
to the General Electric Company, Schenectady, X. Y., for making available certain equipment without which the work would have been difficult, if not impossible.
--.
.----,
39. ~ 1,554 - - (192.5). -
LITERATURE CITED (1) Bary and Fleurent, Compt. rend., 184, 947 (1927); Rev. q h , caoutchouc, 4 (31), 3 (1927). (2) Breuil, Caoutchouc &. gutta-percha (1901-5). (3) Casgari. J. Soc. Chem. Ind.. 32, 1041 (1913). (4) Chaveau, Compt. rend., 128, 388. 479 (1589). (5) Cheneveau and Heim, Ibid., 152,320 (1921). (6) Duclaux, Rev. gkn. colloide,,, 1, 3 3 (1923). (7) Fessenden. Science. 20. 4 8 (1892). (8) Feuchter. kolloidchem: Beihefte, 20, 434 (1925). April 1, 1925. (9) Freundlich and Hauser, Ko[lo?d-Z.,Spec. SO., (10) Govi, Les Nondes, 19, 640 (1869). (11) Hauser, "Latex," I). 173, Th. Steinkopff, Dresden and Leipzig, 1927. (12) Hauser, IND.EKG.CHEM..21.249-51 (1929). (13) Hauser and Mark. Kolloidchern. Beihefte. 22,63: 23, 64 (1926). (14) Hauser and Nark, Kautschuk, 3, 2 2 8 (1927).
57
(24) (25) (26) (27)
Kata and Bing, Kautschuk, 3, 17 (1927). Lunn, India Rubber J . , 64, 831 (1923); 67, 467, 303 (1925). Malock, Proc. Roy. SOC.(London),46, 233 (1889). Park, India Rubber J., 68,421 (1925). Pickles, Ibid.. 67, 69, 101 (1924). Pummerer, Kautschuk, 2, 85-8 (1926). Schwara and Kemp, Caoutchouc d! gutta-percha. 8, 329.3 11911). Thomas, Les Mondes, 20, 7 (1869). Van Rossem, Trans. Inst. RubberInd., 1, 1 3 (1923). Weber, Ber., 63,3108 (1903).
2 . 1931. T h e combined material of two papers on "An XR a y Method of Studying the Nature of Gels," and "X-Kay Evidence t h a t Rubber Is a Two-Phase System," presented before t h e Divisions of Colloid and Rubber Chemistry, reapectively, a t t h e 82nd Meeting of the American Cheniiod Soriety, Buffalo, N. Y . . August 31 t o September 4, 1981. Largely based on a thesis submitted by h f . F. Acken in partial fulfilment of t h e requirements for t h e degree of doctor of philosophy a t Pennsylvania State College. ~ E C E I V ~June D
Alkyl Amines as Solvents F. W. BERGSTROM, W. M.GILKEY,AND P. E. LUNG,Department of Chemistry, Stanford C.Tniziersit.y, Calif and redistilled. The tubes conT H E D E T E R M I N A T I O N of the solubilities taining the amines were always production has hitherto of ocer 250 organic compounds in seven of the kept tightly stoppered except s e l d o m exceeded the when solute was being added. aliphatic amines at 25" * 5" C. has permiited scale of the laboratory, have been Then a few milligrams of each the arrangement of these amines, ethyl alcohol, organic compound were introduced much less useful commercially into thecorrespondingly numdieihyl ether, liquid ammonia, and water in than the more readily available bered tube containing the amine. aromatic amines, such as aniline. the following order of decreasing solvent ability, If these first additions dissolved Nevertheless, s o m e a t t e m p t s in the course of a few moments where the parentheses include compounds of ( d u r i n g which time the tubes have recently been made to preapproximately equal average value as solvents. were gently shaken), further small pare the aliphatic amines on a portions of the organic compounds The order within the parentheses is without larger scale, and it seems evident were introduced, and this process significance: (n-buiylamine, iso-amylamine, benthat their increased availability was repeated until the saturation point was reached. This was inwill stimulate research to diszylamine, liquid ammonia at -33" C., ethyl dicated by the failure of the last cover new uses to which they alcohol, ethyl ether), (diethylamine, di-n-propylportion t o dissolve completely. may be put. It is hoped that The stoppered tubes containing amine ?), (triethylamine, di-n-butylamine), and the present paper will be of some the organic compounds were re(fri-n-butylamine, water). The primary amines weighed, and these values, subvalue in this connection, since t r a c t e d from the weights of the are thus the best solcents, and the tertiary amines t h e s o l u b i l i t i e s of over 250 same tubes before the experiment, organic compounds in seven of of high molecular weighf, the pooresi. gave the d a t a from which the the a l i p h a t i c a m i n e s have solubilities in Table I hare been calculated. been determined aualitativelv at room temperature'(4). The 2ata so obtained will allow of a Obviously, the method can give results only of a "cry comparison between the solvent properties of the anlines in rough quantitative character. It has therefore been thought and will permit the prediction of solubility best t o designate the compounds as slightly soluble, moderamines with which the authors have not worked. ately soluble, etc., these designations corresponding approxiEXPERIMENTAL METHOD matelv to the solubilitv limits indicated in the table of abbreviations* It was hoped at the beginning of this work to make fairly The solubility table prepared in this manner coiitained accurate determinations of the solubilities of purified organic a number of inconsistencies, and there were also a few results compounds in all of the lower amines, but this to be sucll a task that the greater portion the solu- that were obviously in error. A knomledge of the regularities bilities reported were out in a semi-quantitative in the solvent power of the amines generally permitted these manner a t room telllperatures (25 0 f 5 0 c.1. L~ccordingly, discrepancies to be Picked out a t a glance. As ax1 example, it was found khat triethyl- and tributylamines were poorer the experimental method adopted was rather simple. solvents than the corresponding primary or secondary amines. The organic com ounds listed in Table I, after tlrying in a Therefore, if a substance was listed as more soluble in the vacuum desiccator (?,heliquids were not so dried), were put into tertiary amine, the determination was suspected to be in individual small stoppered test tubes. These were properly labeled and numbered, weighed to 0.01 gram, and then placed on error, and Was accordingly repeated. Furthermore, the lower the lahoratorv table in front of test-tube racks in which were amines were generally distinctly better solvents than the placed the same number of tubes-mpty, stoppered, and corre- higher amines-of corresDonding -complexity. Thus, a comspondingly numbered. (It was advisable to number the stoppers pound was usually definitely iolubfe in diethyl- and on one set of test tubes to prevent mixing.) Into each of these latter tubes was introduced from a micropipet 0.50 01' 1.00 cc. of di-n-propylamines than in di-n-butylamine, although there amine that had been dried over liquid sodium potassium alloy, were cases where the solubility was not markedly different
T
HE alkyl amines, whose
,,f
more
58
INDUSTRIAL AND ENGINEERING CHEMISTRY
in the three solvents. %-Butyl-, isoamyl-, and benzylamines did not differ very greatly as solvents. With these relationships in mind, it is felt that most of the inconsistencies of the table have been eliminated. At the conclusion of the solubility experiments, there generally remained a very small amount of undissolved solute. If the amount present was too small, more substance was added and the test tube was warmed, the effect of temperature on the solubility being noted. (This was not done in all cases.) Crystals were often deposited when the warmed solutions were cooled. A few solubilities in diethylamine were determined quantitatively in the following manner:
Vol. 24, No. 1
monia a t -33' C., as given in Franklin's monograph on nitrogen compounds (6). Blank spaces (where leaders are used) in the table indicate lack of experimental data.
REACTIONS WITH AMINES Generalities concerning the solubility behavior of classes of organic compounds will be unnecessary, since this information may be obtained with a little effort from Table I. Therefore, the following remarks will be confined to a discussion of some compounds that appear to react chemically with the amines. ACIDS. Many of the listed acids react immediately with the amines a t room temperature, but the reaction is often A Pyrex tube 20 mm. in diameter and in the form of the letter H constituted the solubility cell. One leg of the H was hindered by the low solubility of the acid (succinic, malic, sealed off at the bottom and closed at the top with a small ground- maleic, and malonic acids). Monochloroacetic acid reacts glass cap. I t was through this opening that the dried amine with the amines with the liberation of heat. Primary and and solute were introduced. In the connecting limb of the H was fused a sintered Pyrex-glass filter plate. The bottom of secondary amines appear to attack the chlorine atom of the other leg of the H terminated in a male ground-glass joint the acid a t higher temperatures. which fitted a corresponding joint on a small graduated receiver CORK. Cork stoppers are slowly attacked by the vapors (a short length of Pyrex buret, closed at one end). The whole of the more readily volatile amines. The vapors of n-butylapparatus was rocked for about an hour in a thermostat (at 25.0" C.) with the empty leg above the leg containing the di- amine appear especially destructive even a t room temperaethylamine. At the end of this time the tube was rotated t o tures. allow the saturated solution t o flow through the filter into the DYES. Solutions of the dyes in the amines are not always graduated receiver. The volume of the solution was read, the the same color as the solid dyes. Thus, crystal violet forms solvent evaporated off, and the tube weighed. This weight, less the weight of the same tube when empty, gave the amount colorless or nearly colorless solutions in all of the primary of substance (or of its reaction product with diethylamine) that amines investigated. had dissolved. From this data was calculated the weight of ESTERS, ALKYLHALIDES, FATS. The esters, alkyl halides, material contained in 100 cc. of saturated solution, these figures so far as investigated, are miscible with and liquid fats, in appearing in the diethylamine column of Table I. the amines in all proportions, and usually with no apparent immediate reaction. Undoubtedly, reaction would occur The abbreviations used in Table I are as follows: in all cases with lapse of time. Benzylamine reacts fairly APPROX.SOL'Y rapidly with ethyl iodide, ethyl oxalate, and n-butyl stearate. R A N Q E PER 100 ABBREVIA cc. OF SOLVENT The fats appear to be slowly ammonolyzed by the amines, TION Grams in all probability with the formation of glycerol and a subInsoluble or extremely slightly soluble ins stituted acid amide. (0 t o 10) Slightly soluble 88 ( l o + t o 40) Moderately soluble 8 NITRO COMPOUNDS.Nearly all mononitro compounds (40+t o 70) Verv soluble VS +,t"100) (70 dissolve in the amines (that is, in the amines investigated VS (100 and above) e8 in the present work) to form colorless or light yellow miso m solutions. An exception is p-nitrophenylhydrazine, which n in hot solvent forms a reddish brown solution in n-butylamine. 2,4,6More soluble in heated amine, crystallizes X Trinitrotoluene and lJ3,5-trinitrobenzene dissolve in the on cooling More soluble in heated amine (in some cases m primary and secondary amines to form deep red or reddish because of chemical reaction) Se arates into two liquid phases brown solutions. Solutions of a similar color, but less inP Sorute reacts chemically with solvent. Re1 tense, are formed in triethylamine, but the latter may well action is rapid enough to be apparent. All acidic substances react more or less have contained traces of diethylamine (a possible test for the rapidly with amines. (The letter, r, has been omitted in these cases) purity of tertiary amines?). The solutions of these two Swells a polynitro compounds in tributylamine were colorless or light Numerals appearing in diethylamine colNumerals umn indicate number of grams of solute y ello~. (or of ita reaction product, with diethylamine) per 100 cc. of solution 2,4-Dinitrotoluene dissolves in n-butylamine with a blue color which fades to yellow or pale green on heating. The EXPLANATION OF SOLUBILITY TABLE return of the blue color on cooling indicates a reversible Since isoamylamine was available in rather limited quan- reaction whose equilibrium point depends upon the teniperatity, solubilities in this liquid were estimated qualitatively, ture. The solution of m-dinitrobenzene in n-butylamine is orange that is, without weighing the amount of added solute. The solubilities of substances forming highly colored solu- red a t room temperatures and yellow a t the boiling point tions (trinitrotoluene, trinitrobenzene, and most of the dyes) of the solvent. The color change is reversible. Picric acid, could be estimated only qualitatively because of the difficulty 3,5-dinitrobenzoic acid, 4,4'-dinitrodiphenyl, and 2,4-dinitrophenol dissolve in the amines to form yellow solutions. of determining the saturation points. The polyhydroxyphenols often appear to underPHENOLS. The solubilities of a few compounds (sugars, polyhydroxyphenols, quinones, and some acids) that appear to undergo go a slow reaction with the amines in the cold. The increased a slow reaction with the solvent may not be altogether cor- solubility of some of these compounds on heating may be ascribed in part to chemical reaction with the solvent (salt rect. For purposes of comparison there have been included the formation?). SUQARS.The slow rate of solution of glucose and sucrose solubilities in methylamine determined by Gibbs (8, 6), the solubilities in ethyl alcohol and in diethyl ether taken in n-butyl- and isoamylamines possibly points to a slow from Van Nostrand's Chemical Annual (2) and from the chemical reaction between solvent and solute. Thus, frucChemiker-Kalendar (3), and the solubilities in liquid am- tose is known to react with liquid ammonia (11). +
+
January, 1932
INDUSTRIAL AND ENGINEERING CHEMISTRY
59
TABLEI. SOLUBILITIES OF ORGANIC COMPOUXDS IN ALIPHATIC AMINES (.4t 25'
j,
5' C.)
"
a
5 g
% s
cr) r? v
2
2
R
7 8 9
10 11
12 13 14 15 16 17 18 19 20 21 22
23 24 25
Acenaphthene . . . . . . . . . . . . . . . . . . . ssx Acetaldehyde 3 Bcetamide VS Acetanilide Acetic acid Acetoacetic ester . . . . . . . . . . . . . . . . . .. 5 m Acetone m Acetophenone .. p-Acetophenylene diamine 3s p-Acetotoluide Acetylene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . s Acetylene tetrabromide VS Acetylsalicylic acid Agar-agar Alanine Aldol . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . Alizarin Allyl alcohol 1-Aminoanthraquinone p-Aminobenzoic acid m-Aminopheno! . . . . . . . . . . . . . . .. . . . . . . . . . o-Aminophenol Aminosulfonic (sulfemic) acid Ammonium benzoate Ammonium citrate .4myl alcohol (iso). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . m m n-Amyl formate m Anethole ss Anhydroformaldehydeaniline .. Aniline blue Anthracene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.8 Anthtanilic acid s Anthraquinone ss Atoxyl . . ss Azobenzene
26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 Benzene 42 Benzidine 43 B e n d 44 Benzoic acid 45 Benzoic sulfinide (Saccharin) 46 Benzoin. . . . . . 47 Benzophenone 48 Benzyl acetate 49 Benzyl alcohol 50 Borneol 51 o-Bromoacetanilide . . . . . . . . . . . . . . . . . . . . . . . 52 p-Bromoaniline 53 Bromcamphor 54 Bromocresol green 55 1-BromonaDhthalene 56 p-Bromonitrobenzene . . . . . . . . . . . . . . . . . . . . . . . . . . 57 o-Bromotoluene 58 p-Bromotoluene 59 n-Butyl alcohol 60 tert-Butyl alcohol ........................... 61 62 n-Butyl ether 63 n-Butyl formate 64 n-Butyl stearate 65 Caffeine 66 Calcium acetate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67 n-Calcium b u t j r a t e 68 Calcium formate 69 d-Camphor 70 Carbon disulfide 71 72
73 74 75
76 77
78 79
80 81 82 83 84 85 86 87 88 89 90 91 92 93
94 95
8
., .,
m
8
PS
ss
..
m m m
m
ins
..
r
s ss
. .
8
.,
vs m VSB m
ins ssx
s
vs
..
.. ..
m
sx
.. ssm
a
vs
vs
,. VF YS
..
ss 68
ins vs
es s Ts m 5s
a
8
32
..
.. ..
..
. . . .
ins vsx
.. s .. .. ins
.. Re
vs
6s
LSX
..
es
m
m
..
esx vs+x m
8
..
ss
ss
S
ssx
es
..
..
A+
s ins
..
..
s
..
.. ssx
..
65
srx
s
, .
.. es . . . . s s .. m sx
.. .
.
..
.. .. ..
..
V6
ins vs
.. S
8s
ssx ss
ss
..
..
ins
.. ssm ins
.. S 8
e8
ss 8
ssp
P
vi+
vs+x 8
.
S
..
sx ea
..
vs
+
sx
es
..
..
es vs
m
S
es
S
sx
vs
es
S S m
+
..
5s
0
..
m
S
..
vs vs+ 8sn
..
SSX
sax
ins
vs vs s
vs
+
TS
m
.
..
S
ss In
8
s
. . . .
.
S
m
.
..
ins
ins
ins ss
YS
ins
6% S
m
SS
m
..
ssx ss vs es
ssx
es
_. ..
s
SSY
. . . . . . . .
esx
ssx
s
YS
..
m
m
m
es m
m
m
.. m
..
m
c:
m
..
ins
ins ins !ns
ins
9s
vs
vs 40
m
m
VS
vsr 53
m
m
c
cc
..
8;: m
es esr ins ins es vs SX
vs
vs + ....
..
YS
ins 111s
ins ss
m
..
.. ..
SS m
insn e3 .. ins ins
ins insa
B
8
ins es
..
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V B
S
ssp
vs
ssrin
sx
VS
YP
ins !ns !ne 111s
..
,,
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SJX m
..
YS
ins
ins
ins
sx
88
ins
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.
vsf
..
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pr ins
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m
89
s
8
7.3
.. s
VS
sx
ssr ves
r vs+x
vsr
....
I
YS
insn
vsr es
....
..
..
ius
ins
vsx
..
..
s .
sr esx
..
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r
ssx
VS+S
..
es
E
es vs
.*
rss
.. \-PI
ins
..
a
..
sex
S
ssxr vs
insn ssn 8X
S
a
..
6SX
es
vsxp
X
VS
m m
X
..
..
.. 6
.. m
insn es
YS+X
m S
..
vs
. . . .
ins S S
vsr
. . . .
es r ins ins
ins
S
ss
vs
insn
m
VS
ssx
ssx
8s
..
ss
vs
..
ssx s
8
68
ins
ssx ssx
..
m
..
., ..
ss s
..
m m m
ss ins
ins Cellulose acetat,e Cellulose nitrate Cerulein Cetyl a l c o h o l , , . . . . . . . . . . . . . . . . . . . . . . . . . . S Chloroacetic acid (mono) S p-Chlorodiphenyl m Chloroform ssx Cholesterol .. Chromotropic salt . . . . . . . . . Cinchonine 88 Cinnamic acid S Coconut oil Copal Crystal violet. . . . . . . . . . . . . . . Cyclohexanol S o-Dianisidine (bianisidinej Diazoaminobenzene S 8 p-Dibromobenzene 2,3-Dibromopropyl alcohol . . . . . . . . . . . . ., .............., vs Dichloramine-T es p-Dichlorobenzene Dichlorogallein .. 9 Dicliloroh ydrin
ssn
.
9s
m
ss
ins
es
m
m
e6 m
vs
x
cc m
ins
ssm ss
ss
m
es ,.
insn
m
m
vs ,,
?sa
85
.
..
s::
85
+ vs
m
vs
..
ins
vsf ssn vsr
8
ss
s
es
S m
s
.. .. ..
vs r
m
vs
S
S
vs
.. ..
9 8
S
..
5
ssx sex
..
..
s
7'6
., .. 89 , . vs .. , .. misc ..
.. ssx
::s
..
m
m
ssx
. .. ..
ins
m
ssx
ss
.. ..
..
..
..
sx
..
m
m
m
V8
ye
8s
m
vs vs ss
..
..
ins
..
s .. vs . . . . . . .
. . . .
..
. . . .
.............................
ins S8X
,.
8s
E
ins
8s
m
. . E.
s
..
s
E
ssx
ins Psx ins
m
YP
s
!sx
..
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E
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88
8
ss
.
.. , . .,
~
S
.
m
. . . . 8
SX
, ,
..
..
ins
..
esx 11
,
m
m 9s
m 98
.
vs
8
8
15
misc vs
89
..
..
..
esx
.. ..
vs +r e8
..
85
r
..
0s S
60
I N D U S T R I A L A iK D E N G I N E E R I N G C H E M I S T R Y
Vol. 24, No. 1
TABLE 1. SOLUBILITIES OF ORGANIC COMPOUNDS I N ALIPH~TIC AMINES(Continued) tAt 25O
*
5" C.) I
I
v
96 97 98 99 100 101 102 103 104 105 106 107 108 109 110 111 112 113 114 115 116 117 118 119 120 121 122 123 124 125 126 127 128 129 130 131 132 133 134 135 136 137 138 139 140 141 142 143 144 145 146 147 148 149 150 151 152 ,153 154 155 156 157 158 159 160 161 162 163 164 165 166 167 168 169 170 171 172 173 174 175 176 177 178 179 180 181 182 183 184 186 186 187 188 189 190
2,3-Dihydroxyquinoxaline.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Dimethylaminoaaobenzene X .. p-Dimethylaminobenzaldehyde 8 8 S m Dimethylaiiiline Dimethylethylcarbinol 9 s Dimeth ylplyoxime . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . vs . vs 2.fi-T)imethvlouinoline vs YS 2;Z-Dii~aph~li~lamine 98 Z,&Diii!t roaniline 98 .. 'm-Dinitrc benzene RSX .. 3.5-Dinitrobenzoic acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . vs 38 4 4'-Dinitrodiphenyl 88 YS 2:4-Dinitro-l-naphthol-7-sulfonic acid .. .. 2,4-Dinitrophenol 88 vs 2,4-Dinitrotoluene 85 .. Diphenyl .................................. . 88 S Diphenylamine vs VS Diph en ylbenzamide .. Diphenylguanidine .. Diphenyl ketoxime .. Diphenyl sulfone (phenyl sulfone) . . . . . . . . . . . . . 86 s Diphenylurea (sym.) S 3 4,4'-Dipyridyl (hipyridine) vs Di-p-tolylselenide .. S Eosin .*
.. . . BY. . . . . .
..
.
.
m
13
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..
.. .
.. .. ..
..
..* ... .. ..
rpr
.. ..
..
..
BP
ss
SF
..
58 SX
..
41 es
VS
99 69
ins
..
ss
3s
s
..
58
.,
m m
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ss
7-95
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88
m
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vs
ss
S
3s
ss
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VS
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..
9s
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S
68
..
..
m
m
vs
vs
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2s 8s 95
vs vs
.. ..
8 S
.. ..
ins
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vs
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.. RS
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sx
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es
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m
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insn ins ins 27
98
88 .
ins ins Fx ins
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+
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S
sx
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S
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9s
ssx ssx
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.
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ss
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es
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January, 1932
INDUSTRIAL '['kBLE I.
A N D E N G I N E E R I X G CHE_\IISTHY
SOLUBILITIES OF O R G 4 I I C COWPOUNDS IN ALIPHkTIC
*
(At 250
50
61
AMINES(Conclude
c.1 . c
I v
r
c
191 192 193 194 195 196 197 198 199 200 201 202 203 204 205 206
m m o-Nitrotoluene.. . . . . . . . . . . . . . . p-Nitrotoluene 8 s vs .. 3-Nitro-4-toluidine 1-4 YS Nitrourea m m Oleic acid Olive oil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Orange I V . . . . Oxalic acid.2HsO s 94 0xanjli.de I' ss Palmitic acid 4S .. Paraffin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Paraffin oil . . . n-Pentane 2-Pente3e . . . Penacetin SP SP PP 3 Phenanthrene . . . . . . . . . . . . . . . . . . . . . . . . . . .
-
..
-Phenyl aoridii Pheriylazo-1-naphthylamine... . . . . . . . . . . . . o-Pl~enylenediamine Phenylrlucosazone Phenylhydrazine Phenylniercuric bromide 2-Phenylquinoline. ........................ Phenyl-p.toly1 sulfone Phenyl urea Phthalic acid Phthalic a i h y d r i d e Phthalimide .............................. Picric acid Potassium amide Potassium ethyl sulfate Potassium quinaldine Potassium tripbenylmethyl . . . . . . . . . . . . . . . . . Pyridine Pyrogallol Pyrrole Quinaldine Quinaldine picrate.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Quinine Quinoline Quinoline methiodide Quinoline yellow (water soluble) Quinone . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Resorcinol Rosaniline Rosin Rosolic acid Rubber, vulcaiiized. . . . . . . . . . . . . . . . . . . . . . . . Salicylic acid Selenium Shellac, white Skatole Soap . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Sodium alizarin sulfonate Sodium benzoate Sodium indigo sulfonate Sodium-p-nitrophenylantidiazotate Starch (corn) ................................... Stearic acid, tech. Strychnine Succinic acid Succinimide Sucrose . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Sulfanilic acid Sullonal Sulfur, rhombic Tallow Tannic acid. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Tartaric acid Tetraethylammonium iodide Tetraethyl iead TetrahvdronaDhthalene Tetramethyldiaminobenzophenone.. . . . . . . . . . . . . . . . . . . Tetraphenyl lead Tetraphenylmethane Thymol o-To!idine Toluene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . p-Tolueneeulfor~amide p-Toluidine Triohloropallein 2,4,6-Trinitroaniline 1,3,5-Trinjtrobenzene. .............................. 2,4.6-Trinitrotoluene Triphenylmethane Triphenylselenonium iodide Tvrosine ~" Urea .......................................... Uric acid Wax. carnauba Wax. J a p a n m-Xvlene 1,3,5-Xylenol.. Xylose (crude) Zinc stearate ~
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62
INDUSTRIAL AND E N G I N E E R I N G CHEMISTRY
SULFUR. Sulfur is crystallized, apparently unchanged, from hot solutions of the tertiary amines. Primary and secondary amines a t first dissolve sulfur, then react chemically with it, possibly in the manner that sulfur reacts with liquid ammonia (IO). Here a portion of the sulfur appears to be reduced to ammonium sulfide or polysulfide, while a corresponding amount is nitridized (“oxidized”) to sulfur nitride, NaS4. REACTIONS IN
THE
ALKYLAMINES
The numerous researches of Franklin, Kraus, and their co-workers (6, 7 ) have demonstrated the scientific value of liquid ammonia as a solvent in which chemical reactions may be carried out. With the expectation of finding in the alkylamines higher-boiling solvents in which many of the same reactions could be effected, it was shown that 2n-propylquinoline was synthesized in n-butylamine almost as readily as in liquid ammonia (1). The reaction is espressed by the following equations:
Vol. 24, No. 1
amine, isoamylamine, benzylamine, ammonia at -33 O C., ethyl alcohol, diethyl ether), (diethylamine, di-n-propylamine?), (triethylamine, di-n-butylamine), (tri-n-butylamine, water). The order of arrangement within the parentheses is without significance. The conclusion may therefore be drawn that the primary amines are the best solvents, and that the amines of lower molecular weight are usually better solvents than the higher amines of the same type. Diethyl- and di-n-propylamines would appear to be of about equal solvent ability, judging from the limited number of experiments with the latter solvent. The substitution products of water (ethyl alcohol and diethyl ether) are about equally good as solvents for the compounds examined, while the substitution products of ammonia (primary, secondary, and tertiary amines containing the same alkyl radicals) differ considerably among themselves. Franklin (6) and Hurd (9) have made comparisons of the chemical properties of these substitution products of water and of ammonia. Methylamine probably will prove to be superior to the other amines as a solvent when more experimental data are available. Tiquid ammonia a t room temperatures should prove a slightly better solvent than either n-butyl- or isoamylamine. ACKNOWLEDGMENT
N
The three butyl amines used in this work were provided by the Commercial Solvents Corporation, to whom the authors wish to express their indebtedness. Kearly all of the chemical individuals listed in Table I were high-grade preparations of the Eastman Kodak Co., Kahlbaum, or the Gesellschaft fiir Teerverwertung (Duisberg-11eiderich). The di- and triethylamines were obtained from the Eastman Kodak Co., and the isoamyl- and diisopropylamines from Kahlbaum. The benzylamine was prepared in this laboratory by Mr. Liang.
I n the first stage of the reaction, solid potassium amide is dissolved by a n-butylamine solution of quinaldine to form potassium quinaldine, which is rapidly comerted to 2-npropylquinoline (and potassium bromide) by the action of ethyl bromide. It is therefore possible to utilize the alkylamines as solvents for chemical reactions. TABLE 11. COMPARATIVE SOLVENT POWER COMPARISON OF SOLVENT POWER OF AMINES,ETHYL ALCOHOL, DIETHYLETHER,AND AMMONIA
Solvent ins, ss s vs vs+* e8 ‘ h i 1 solubilities Total determinations that a r e s , vs, vs Solvent ins, ss s v3 v s + , e s 'fad solubilities Total determinations that are s, vs, vs+, e-, 70
In view of the relatively small number of comDounds listed in Table I, and because of the qualitative nature of the solubility determinations, it is not possible to make an accurate intercomparison of the solvent power of the amines, alcohol, ether, ammonia, and water. This is additionally true because of the many gaps in the table which were not filled because it was thought that the missing solubilities could be predicted from the observed regularities in the solvent ability of the amines. Nevertheless, a rough idea of the relative value of these liquids as solvents may be gained in the following manner: The compounds listed in Table I have been divided into two classes-substances of definite solubility (s, vs, v s f , es) and substances of low solubility (ss, ins). The comparison is then made between the percentages of the compounds examined that are of definite solubility. (Liquids and mixtures, such as paraffin and lanolin, have been excluded in this comparison.) The liquids of Table I1 may be arranged in the following approximate order of decreasing solvent power: (n-butyl-
+, es, %
Hz0 CzHaOH (CzHs)zO NH3 (C1HdaNH (CzHdxN 144 68 57 46 100 96 22 86 69 67 66 30 166 154 126 113 166 126 55 59 40 24 13 56
(CdHr)*NH CrHeNHz (CIHehNH (CrHs)iN 29 04 90 115 22 108 38 21 51 172 128 136 43
63
30
CjHiiNHa CaHaCHzNHz 64 67 97 71 161 12s
15
60
56
LITERATURE CITED (1) Bergstrom, J . Am. Chem. SOC.,53, 3032 (1931). (2) Chemical Annual, p. 296, Van Nostrand. 1922. (3) Chemiker-Kalendar, Vol. 11, p. 56, Springer, 1929. (4) Elsey, H. M., J . Am. Chem. Soc., 42, 2080 (1920). (5) Franklin, Ibid., 46, 2150 (1924). (6) Franklin, A. C. S. Monograph (unpublished). (7) Franklin and Kraus, numerous articles in Am. Chem. J., J . Am. Chem. SOC.,and J . Phys. Chem.: Kraus, “Properties of Electrically Conducting Systems,” Am. Chem. SOC.Monograph, Chemical Catalog, 1922. (8) Gibbs, J . Am. Chem. SOC.,28, 1395 (1906). (9) Hurd, “Pyrolysis of Organic Compounds,” p. 290, A. C. S. Monograph, Chemical Catalog, 1929. (10) Ruff and Geisel, Ber., 38, 2659 (1905); Ruff and Hecht, 2. anorg. Chem., 70, 49 (1911). Cf. Bergstrom, J . Am. Chem. Soc., 48, 2319 (1926). (11) Strain and Smith, Ibid., 52, 5293 (1930). RECEIVED September 15, 1931.
