INDUSTRIAL AND ENGINEERING CHEMISTRY
384
grams paraffin per 100 cc. solvent and also as grams solid paraffin per mol of solvent. (Tables I1 and 111) Data for solubilities are given to two decimal places only. The relation between solubility and carbon content of the solvent is shown in Figure 1. Slight variations in the amounts of excess solid paraffin in the flask alter the solubility data. Thus the figures given may be considered as fairly close for the paraffin used. More exact data could be obtained only by the use of a solid paraffin which contained only one individual hydrocarbon. The relative solubilities for a pure paraffin in these solvents would undoubtedly be in the same order as that found in this work.
Table 11-Solubility TEMPERA-PENTURE 0
TANE
VOl. 20, No. 4
Data-Grams
Paraffin per 100 cc. Solvent HEPOcIso-
HEXANE
TANE
TANE
DECANE
2.77 3.69 4.81 6.07 8.31 16.23
1.37 2.18 3.55 5.06 7.18 14.36
0.99 1.69 2.90 4.24 5.93 11.66
0.94 1.44 2.74 4.9s 9.17
(1.
0 5 10 15 20 25
...
5.11 6.94 9.53 17.16
Table 111-Solubility
TEMPERAPENTURE
TANE
0 5 10 15 20 25
5.83 7.92 10.87 19.48
c.
... ...
...
Data-Grams Paraffin per Mol Solvent HEXHEPOCIsoANE
TANE
TANE
3.61 4.81 6.28 7.91 10.83 21.33
2.01 3.22 5.23 7.48 10.57 21.06
1.60 2.73 4.67 6.84 9.58 18.81
DECANE
...
1.84 2.84 5.40 9.80 18.03
Summary of Data
The solubility of a solid paraffin in hydrocarbons of low molecular weight increases rapidly with rise of temperature. The solubility increases from that of isodecane to that of pentane. The increase in solubility with rise of temperature is more rapid with the higher molecular-weight solvent. This can be seen by dividing the solubilities a t 10" C. into the solubility a t 25" C., the ratio being 2.3, 3.8, 4.0, 3.9, and 6.6, respectively, for pentane, hexane, heptane, octane, and isodecane; I n Table 111, except for the first three sets of data for octane and isodecane, the data run fairly constant. This indicates that the mol ratios of solvents to solute may be constant, and that we have in each case a definite number of molecules of solvent associated with a molecule of solute.
Some Azo Dyes Soluble in Non-Aqueous Solvents' Clarence E. May and Herschel Hunt INDIANA UNIVERSITY, BLOOMINOTON,IND.
IL-SOLUBLE dyes have been used for years in coloring fancy candles, oleomargarine, floor wax, shoe polish, ethyl gasoline, and plates for radio photography. One outstanding oil-soluble dye is the antiseptic oil scarlet used in medicine. This dye is used either as an ointment, a solution of the dye in paraffin, or a solution of the sulfonic acid derivative in water as an antiseptic and an aid in the promotion of granulation in wounds that do not heal readily. The authors have made and studied a number of dyes which they have been unable to find in the literature. Each new dye has been given a short name which has been selected on account of the color, the relation of the dye to some other dye, or some other point of interest. This work included the study of thirty dyes each of which was soluble in non-aqueous solvents. None of the dyes showed an appreciable solubility in water. Table I shows the dyes made, the intermediates used, and the melting points of the dyes.
0
Preparation of Dyes
ANILIXEYELLOWG(C1gH1,N8)-A solution of 10 grams of 2-naphthylamine in 20 grams of c. P. HCl and 200 cc. HzO was made, cooled and diazotized to the point where, on the addition of a dilute NaONO solution, a permanent pale blue color remained on the KI-starch paper. The diazo solution was then poured into a solution of 9 grams of dimethyl1
Received November 19, 1927.
aniline in 200 cc. HzO containing enough HCl to show a free mineral acidity in the mixture. After standing a few hours, sufficient sodium acetate was added to destroy the free mineral acidity. There resulted 11 grams of greenish yellow substance showing the following analysis: 0.2000 gram substance gave 0.5770 gram COZ and 0.0930 gram HzO Found: C = 78.68%; H = 5.48%. Theory: C = 78.54%; H = 5.18%
Azo COCCINERR(ClgHl~NzO)-Commercial xylidine (5 grams) was dissolved in 20 grams c. P. HC1 and 200 cc. HzO cooled to 15" C. This solution was diazotized in the usual way and poured into a solution of 6 grams 1-naphthol in 18 grams NaOH and 300 cc. HzO. After standing a day, 8.0 grams of dark red powder, showing the following analysis, resulted : 0.2027 gram substance gave 0.5810 gram COZand 0.1047 gram H2O Found: C = 78.16%; H = 5.81%;. Theory: C = 78.26%; H = 5.597'30
BENZIDINEBRom(C2~H20N402)-Thetetrazotization of 5 grams benzidine in 200 cc. H 2 0 and 30 grams c. P. HC1 was carried out a t 10" C. The tetrazo solution was poured into a solution of 4 grams 1-naphthol, 2.4 grams phenol, and 20 grams NaOH in 200 cc. HzO. After standing, 8 grams of black powder, showing the following analysis, were obtained: 0.2089 gram substance gave 0.5784 gram COn and 0.0851 gram Ha0
residue the mixture was allowedto stand until separated* The acetxylidid (lo grams) at l 2 O 0 was in 75 "HzS04 350 and nitrated by the cautious add i t i o n O f lo grams 1 5 0 c' in the m i x t u r e . With constant
,
andreaction 'ling for an the 'Ontinued. On addition of 400 cc. H 2 0 the nitro derivative
1
~
"*
DYE
~
~
= 5.8%. Theory: C = 74.19%; H = 5.62%
The authors have prepared about thirty new dyes of pronounced value because they were not soluble in water but showed a pronounced solubility in paraffins, aromatic hydrocarbons, linseed oil, carbon tetrachloride, etc. These dyes were all similar to oil scarlet and doubtless possessed an antiseptic value, although this was not tested. The solubilities of the dyes in two solvents, toluene and carbon tetrachloride, were determined.
I
1-Amino-2-naphthol and 4-amino-1,2-naphthoquinone have been used as couplers with diazo chlorides.
INTERMEDIATES
CONQORED A(CsaHz4Ns) -The tetrazotization of 5 grams benzidine was carried Out as before mentioned and the resulting solution was Of poured into a grams of 1-naphthylamine, 14 grams NaOH, and 200 cc. HzO. A yield of 11 grams dark red powder resulted. 0.2155 gram substance gave 0 . 6 1 6 9 gram CO2 and
MELTING POINT O
Indiana Red Xylidine Brown Scarlet H Xylidine Brown M Maroon I Maroon I1 Walnut Oil Maroon Xylidine Red N Xylidine Red Naphthol Brown Sudan VI Sudan V I 1 Sudan VI11 Oil Brown Sudan IX
3-o-Xylidine and 2-naphthol 3-c-Xylidine and 1-amino-%naphthol 4-m-Xylidine and 2-naphthol 4-m-Xylidine and 1-amino-2-naphthol 4-m-Xylidine and phenol 4-m-Xylidine and resorcinol 4-m-Xylidine and guaiacol 0-Xvlidine and 2-nanhthol b-xilidine and l-akino-Z-naphthol Aminoazo-4-m-xylene and 2-naphthol Aminoazo-4-m-xylene and 1-amino-2-naphthol Aniline and 1-naphthol Aniline and 1-amino-2-naphthol Aniline and 1-nitroso-2-naphthol o-Aminoazotoluene and salicylic acid o-Aminoazotoluene'and resorcinol
Cloth Red BB Maroon I11 Scarlet M _._.~... Naphthol Brown I1 Fast Brown 0 Aniline Yellow G Benzidine Puce A Benzidine Brown Congo Red A
o-Aminoazotoluene and I-naphthol o-Aminoazotoluene and phenol Aminoazo-$-xylene and 2-naphthol Aminoazo-p-xylene and 1-amino-2-naphthol 2-Naphthylamine and 1-naphthol 2-Naphthylamine and dimethylaniline Benzidine and 2 molecules 1-naphthol Benzidine and a molecule phenol and a molecule 1-naphthol Benzidine and 2 molecules 1-naphthylamine
Sudan X Rose Azo Coccine RR Cardinal Naphthol Black
o-Anisidine and 1-amino-2-naphthol Aminoazo-2-naphthylamine and 2-naphthol Commercial xylidine and 1-naphthol 6-Nitro-asym-m-xylidine and, 2-naphthol I-Amino-%naphthol and dimethylaniline
c.
125-30 140-45 132-36 140-44 172-74 275-80 110-12 115-20 105-6 145-50 140-50 148-50 110-15 106 125-30 Above 360 153-56 290-95 180-85 110-15 146 153-58 255-60 Above 360 Above 360 135-40 107-9 113-18 180-85 135-40
A diazotization of 4 grams 6-nitro-4-m-xylidine in 20 grams c. P. HC1 and 200 cC. &0 was carried out as Usual. The temperature was kept below 10" C. The product of
--*
-
Found: C = 80.5%; H = 4.81%. H = 4.69%
Theory:
C = 80.54%;
INDIANA R E D ( C ~ & N ~ O ) - T ~diazotization ~ of 2.5 grams 3-o-xylidine in 300 cc. HzO and 10 grams c. P. HC1 was brought about a t 18" C. and the resulting solution was poured into a solution of 3 grams 2-naphthol, 10 grams NaOH, and 200 cc. HzO. On standing, 10 grams of bright red powder separated. 0.2205 gram substance gave 0.6320 gram COa and 0,1144gram H2O Found: C = 78.13%; H = 5.81%. Theory: C = 78.26%; H = 5.78%
MAROON I(C14H14NzO)-Commercial xylidine was treated with glacial acetic acid to throw the less soluble 4-m-xylidine out of solution. After isolation the 4-m-xylidine acetate was decomposed to liberate the free base. This was identified by its 212' C. boiling point and its acetyl derivative with a 120' C. melting point. A solution of 5 grams 4-m-xylidine in 300 cc. HzO and 25 grams c. P. HC1 was diazotized a t 15" C. and the resulting diazo solution was poured into a solution of 3.85 grams phenol, 20 grams NaOH, and 200 cc. HzO. On standing, 6 grams of maroon Powder Separated. 0,2700 gram substance gave 0.03299 gram N (Dumas) Found: ru' = 12.22%. Theory: N = 12.39%
386
INDUSTRIAL AND ENGINEERING CHEMISTRY
MAROON II(C14H14Nz02)-The 4-m-xylidine (5 grams) was diazotized as before and the resulting solution was poured into a solution of 4.5 grams resorcinol 8 grams NaOH, and 250 cc. H20. On standing, 7 grams of black powder separated. 0.1930 gram substance gave 0.02216 gram N (Dumas) Found: N = 11.48%. Theory: N = 11.55%
MAROONIII(C20H18N40)-A solution of 5 grams o-aminoazotoluene in 1 liter HzO and 30 grams c. P. HC1 was cooled to 8" C. and diazotized as usual. The resulting solution was poured into a solution of 2.1 grams phenol, 20 grams NaOH, and 300 cc. HzO. A yield of 6 grams dark red powder resulted. 0.2100 gram substance gave 0.03557 gram N (Dumas) Found: N = 16.9470. Theory: N = 17.00%
NAPHTHOL BLAcK(C18H1,N40z)-The intermediate required here was 1-amino-2-naphthol made by the reduction of Orange 11. The melting point of the naphthol was not found in the literature. The authors' preparation showed no melting point. On acetylation, it melted a t 206" C., the same as shown in the literature for the acetyl derivative of l-amino2-naphthol. A solution of 5 grams 1-amino-2-naphthol in 10 grams c. P. HC1 and 400 cc. HzO was diazotized a t 15" C. and the diazo solution was then poured into a solution of 3.8 grams dimethylaniline, 10 grams c. P. HC1, and 200 cc. HzO. After standing several hours, a solution of sodium acetate was used to neutralize the excess of mineral acid. A yield of 5 grams dark green powder was obtained. This product was burned three times by the Dumas method and the nitrogen found was 17.69, 17.45, and 17.63 per cent, respectively. These data seemed to indicate that in the diazotization a nitroso group had been picked up on the nucleus. By theory, the nitrogen content was 17.44 per cent for the product with the nitroso grouping and 14.43 per cent without the secondary reaction taking place.
7 Oil Maroon Scarlet H Indiana Red Butter Yellow Maroon I Scarlet M Chrome Fast Yellow Sudan I1 Sudan VI1 Xylidine Red N Sudan I Walnut Rose Azo Coccine R R Oil Scarlet Spirit Yellow Naphthol Brown Xylidine Brown Xylidine Red Sudan VI11 Sudan I X Sudan X Naphthol Brown I1 Fast Brown 0 Scarlet R R Naphthol Black Sudan I11 Azo Turkey Red Sudan R Sudan Brown Xylidine Brown M Maroon I1 Maroon I11 Oil Brown Benzidine Puce Alizarin Scarlet Sudan VI1 Congo Red A Cloth Red BB Aniline Yellow G Cloth Red G $-Nitroaniline Red Cardinal Alizarin Yellow GG Sudan G Chrysamine G Benzidine Puce A m-Nitroaniline Orange Benzidine Brown
Vol. 20, No. 4
NAPHTHOL BROWN(C26H26N60)-Aminoazo-4-m-xylene was prepared from 4-m-xylidine and identified by its melting point of 78" C. A solution of 5 grams aminoazo-4-m-xylene in 150 cc. H 2 0 and 40 grams c. P. HC1 was diazotized a t 10" C. and the resulting solution was poured into a solution of 3.25 grams 1-amino-2-naphthol, 40 grams NaOH, and 400 CC. H,O. On standing, 4 grams chocolate-colored powder resulted. 0.1506 gram substance gave 0.02522 gram N (Dumas) Found: N = 16.75%. Theory: N = 16.55%
NAPHTHOL BROWNII(Cz~H26N,0)-A solution of 2.5 grams aminoazo-p-xylene (m. p. 150" C.) in 25 grams c. P. HC1 and 1 liter HzO was cooled to 15" C. and diazotized. The resulting diazo chloride solution was poured into a solution of 1-amino-2-naphthol, 25 grams NaOH, and 400 cc. H,O. After standing a day, 3 grams dark brown powder resulted. 0.1637 gram substance gave 0.02618 gram N (Dumas) Found: N = 16.6%. Theory: N = 16.55%
OIL M A R O O N ( C I ~ H I B N Z ~diazotization )-T~~ of 5 grams p-xylidine in 200 cc. H,O and 10 grams c. P. HCl was carried out in the usual way a t 18" C. The product was poured into a solution of 6 grams 2-naphthol, 200 CC. H20, and 10 grams NaOH. After standing, the solution yielded 8.5 grams bloodred powder. 0.2063 gram substance gave 0.5908 gram COZand 0.1086 gram H*O
F o i i d : C = 78.17,; H = 5.89%. H = 5.79%
Theory:
C = 78.26%;
OIL B R O W K ( C ~ ~ H ~ ~ N ~solution O ~ ) - A of 5 grams o-aminoazotoluene (m. p. 100" C.) in 1 liter HzO and 30 grams c. P. HCl was made, cooled to 8" C., and diazotized in the usual way. The product of diazotization was poured into a solution of 2.3 grams salicylic acid, 20 grams NaOH, and 200 cc. H20. A yield of 3 grams dark red powder resulted. 0.2100 gram substance gave 0.5186 gram COn and 0.1270 gram
HzO
Table 11-Solubility in Toluene Cc. TOLUENEREQUIREDT O DISSOLVE0.5 G R A MDYE 10 15 16 20 25 30 35
April, 1928
387
INDUSTRIAL AND ENGINEERING CHE.1.IISTRY
Found: C = 67.4%; H = 4.83%. H = 4.81%
Theory:
C = 67.387,;
R O S E ( C ~ H ~ N ~ O ) -solution A of 2-aminoazo-naphthalene (m. p. 156' C . ) (5 grams) in 200 cc. HzO and 25 grams C. P. RC1 was cooled to 10" C. and diazotized as usual. The product was poured into a solution of 2.4 grams 2-naphthol, 100 cc. HzO, and 14 grams NaOH. A yield of 5 grams pink powder resulted. 0.2100 gram substance gave 0.6140 gram COZand 0.0842 gram H.0 Found: C = 79.74%; H = 4.49%. Theory: C = 79.64%; H = 4.42%
SUDANVI(CI~H~ZN~O)-A solution of 10 grams aniline in 200 cc. HzO and 10 grams c. P. HCI was diazotized a t 8" C. and poured into a solution of 16 grams 1-naphthol, 10 grams NaOH, and 200 cc. HzO. A yield of 20 grams marooncolored powder resulted. 0.2123 gram substance gave 0.6029 gram COSand 0.0922 gram HzO Found: C = 77.45%; H = 4.86%. Theory: C = 77.42%;
H = 4.83% SUDANVII(CJ€13N,O)-A solution of aniline (3 grams) was diazotized as before and the product was poured into a solution of 5 grams 1-amino-2-naphthol, 18 grams NaOH, and 400 cc. H20. The mixture yielded 5 grams dark red powder. 0.1000 gram substance gave 0.01577 gram N (Dumas) Found: N = 15.78%. Theory: N = 16.0%
SUDAN VIII(CI&N&)-A solution of 14 grams aniline was diazotized in the usual manner and the product was poured into a solution of 25 grams 1-nitroso-2-naphthol in 30 grams NaOH and 400 cc. HzO. A yield of 14 grams marooncolored powder separated. 0.2003 gram substance gave 0.5070 gram COz an'd 0.0766 gram H10 Found: C = 69.14%; H = 4.27%. Theory: C = 69.31%; H = 4.00%
SUDANIX(CzoH18N40~)-Theproduct of diazotization of 5 grams o-aminoazotoluene was poured into a solution of 2.4 grams resorcinol, 40 grams NaOH, and 200 cc. HZO. A yield of 4 grams dark red powder resulted. 0.2280 gram substance gave 0.03711 gram N (Dumas) Found: N = 16.23%. Theory: N = 16.18%
SUDANX(C17H15N30z)-A solution of 5 grams o-anisidine in 200 cc. HzO and 10 grams c. P. HC1 was cooled to 10" C. and diazotized in the usual way. The product was poured into a solution of 6.3 grams 1-amino-2-naphthol in 10 grams NaOH and 200 cc. HzO. A yield of 7 grams dark red powder wm obtained. 0.1682 gram substance gave 0.02422 gram N (Dumas) Found: N = 14.4%. Theory: N = 14.34%
SCARLETH(CI~&&ZO)-A solution of 4-m-xylidine (5 grams) in 200 cc. HzO and 10 grams c. P. HC1 was cooled to 15' C. and diazotized. The product was poured into a solution of 6 grams 2-naphthol, 10 grams NaOH, and 200 cc. HzO. A yield of 8 grams of bright red powder resulted. 0.1875 gram substance gave 0.5382 gram COn and 0.0975 gram Hz0 Found: C = 78.28%; H = 5.81%. Theory: C = 78.267,; H = 5.807,
SCARLET1L1(C26H24N40)-A solution of 5 grams aminoazo-p-xylene in 1 liter HzO and 50 grams c. P. HCl was cooled to 18' C. and diazotized. The product was poured into a solution of 4 grams 2-naphthol in 100 cc. HzO and 25 grams KaOH. -4 yield of 8 grams dark red powder was recovered. 0.2145 gram substance gave 0.6017 gram COZand 0.1039 gram H2O Found: C = 76.54%; H = 6.04%. Theory: C = 76.47%; H = 5.S87,
T a b l e 111-Solubility
in Carbon Cc. SOLVENT 5
Sudan I Maroon I Sudan VI11 Chrome Fast Yellow Rose Sudan VI1 Scarlet H Walnut Sudan I1 Xylidine Brawn Indiana Red Oil Maroon Azo Coccine R R Xylidine Red N Xylidine Brown M Sudan I X Sudan X Naphthol Black Oil Scarlet Sudan R Fast Red A Oil Brown Spirit Yellow Sudan I11 Azo Turkey Red Cloth Red G Sudan G Maroon I1 Cloth Red BB Fast Brown 0 Maroon I11 Sudan Brown Chrysamine G Sudan VI P-Nitroaniline Red Alizarine Yellow R Aniline Yellow G Cardinal Benzidine Puce Benzidine Puce A Indoine Blue Congo Red A m-Nitroaniline Orange Alizarin Yellow GG Benzidine Brown Diazine Green Diazine Black
+++ * +t +-
t
-
8
10
--
----
-
-
_- -- - -
t _ - -- --
- - - - -
+I
+
_ - +-
_ _ _
- - -
_ _ _ _ _ _ __ __ -_
_ - - - - - - _ - _ _ _ _ _ _ - - - _ - _ _ _ -
_ - - - -
--_ _-- -_- - - - - - -
WALKUT (C15H1~Nz02)-Thediazo product from 5 grains of 4-m-xylidine was poured into a solution of 5 grams of guaiacol, 6 grams NaOH, and 300 cc. HzO. A yield of 8 grams dark red powder resulted. 0.2200 gram substance gave 0.02402 gram N (Dumas) Found: N = 10.92%. Theory: N = 10.94%
XYLIDIKE R E D ( C ~ ~ H ~ & ~ O )diazo - T ~ ~product from 5 grams aminoazo-4-m-xylene was poured into a solution of 3 grams 2-naphthol in 36 grams NaOH and 300 cc. HZO. The mixture yielded 8 grams dark red powder. 0,2242 gram substance gave 0.6280 gram COZand 0.1193 gram HzO Found: C = 76.39%; H = 5.947,. Theory: C = 76.47%; H = 5.88%
XYLIDIXE RED N(C18H17N30)-The product of diazotization of 2.5 grams p-xylidine was poured into a solution of 3.25 grams 1-amino-2-naphthol in 10 grams NaOH, and 200 cc. H20. After standing 48 hours a yield of 4 grams dark red powder was obtained. 0.1070 gram substance gave 0.0155 gram N (Dumas) Found: N = 11.44%. Theory: N = 14.437,
XYLIDINEB R O W N ( C ~ ~ H ~ ~ N ~diazo O ) - Tproduct ~~ from 2.5 grams 3-0-xylidine was poured into a solution of 3.25 grams 1-amino-2-naphthol in 10 grams NaOH and 303 cc. H20. A yield of 3 grams light brown powder resulted. 0.1213 gram substance gave 0.0175 gram N (Dumas) Found: N = 14.45%. Theory: N = 14.43%
XYLIDII-~E BROWN M(C18H17N30)-The diazo chloride from 2.5 grams 4-m-xylidine was poured into a solution of 3.25 grams 1-amino-2-naphthol in 18 grams NaOH and 233 cc. HzO. After several hours' standing a yield of 5 grams dark reddish brown powder resulted. 0.1250 gram substance gave 0.01803 gram N (DJmas) Found: N = 14.41%. Theory: N = 14.43%
Solubilities of Dyes in Toluene and Carbon Tetrachloride
Tables I1 and I11 give results of the attempt to ascertain the relative solubilities in two solvents. A 0.5-gram portion
INDUSTRIAL A N D ENGINEERING CHEMISTRY
388
of each dye was placed in separate test tubes and various quantities of the solvent were added. The tubes were stoppered and allowed to stand at room temperature. The smallest amount of solvent dissolving the 0.5-gram portion of dye was observed. The solutions were agitated from time to time. I n this work the authors tried not only the dyes they thought were new but also a variety of other dyes made in the course of the work. Reduction of Oil-Soluble Dyes The usual SnClz-HCl reduction of water-soluble azo dyes was found impossible. After trying benzaldehyde and phenylhydrazine as reducing agents in alcoholic and benzene solutions of the dyes, with unsatisfactory results, a reduction of the alcoholic solution of the dye by means of sodium amalgam gave good results. A solution of 1 gram Sudan I in 250 cc. 95 per cent alcohol was heated on a water bath with 75 grams 4 per cent amalgam for 2 hours. The pale brown solution was steam-distilled to remove the aniline and alcohol, and acidified with HC1 until the 1-amino-2-naphthol separated. This was filtered, washed, and recrystallized from alcohol and found to be the desired product. A solution of 2 grams Xylidine Brown M in 95 per cent alcohol, with 75 grams 4 per cent amalgam, was heated under a water condenser a t the boiling point for 4 hours. After the color was successfully bleached, the solution was filtered to remove the mercury and the distillate was evaporated t o a volume of 30 cc. The solution became highly colored on dilution with 200 cc. HzO and the addition of enough HCl to neutralize the NaOH formed. A dark red precipitate, readily soluble in alcohol, was obtained. 0.1070 gram substance gave 0.08719 gram N (Dumas) 0.0680 gram substance gave 0.1731 gram COZand 0.0250 gram
H20 0.200 gram substance gave 0.5091 gram COZand 0.0735 gram Hz0
Vol. 20, No. 4
Found: K = 8.15%; C = 69.42 and 69.41%; H = 4.11 and 4.10%
Theory CloHloNzO: C = 68.96%; H = 5.74%; N = 16.09% Theory ClOH7N02: C = 69.36%; H = 4.04%; N = 8.09%
The writer concluded that the reduction took place as expected but that the reduction product, a diamino naphthol, was too sensitive to oxidizing conditions to get it out in the unoxidized form. They were unable to obtain the colorless reduction product but got a quite pure oxidation product that their analytical data led them to believe was 4-amino1, 2-naphthoquinone (m. p. 136" C.). The substance was insoluble in water, strong caustic, and strong acid solutions, and gave the isocyanide test. An attempt was made to diazotize the new product and couple the diazo product with 2-naphthol. The diazotization was carried out in an alcoholic solution. From the mixture resulting on pouring the diazo product into an alkaline 2-naphthol solution, a bright red precipitate resulted. 0.0460 gram substance gave 0.00383 gram N (Dumas) 0.1100 gram substance gave 0.00956 gram N (Dumas) Found: N = 8.33% and 8.69%. Theory for Cz0H~zN208= 8.53%
Conclusion
The authors have prepared thirty new dyes that represented a monotony of color since they were all red or redbrown. Toluene and carbon tetrachloride were found to be very good solvents. Other solvents, such as gasoline and linseed oil, were useful but the degree of solubility was not determined. A method was found for the reduction of the dyes and this proved of interest on account of the products obtainable. Each dye made had some more or less antiseptic action on account of the phenolic hydroxyls present but the physiological action was not investigated.
Standardization of Ephedrine and Its Salts' Joel B. Peterson CHEMICAL LABORATORY O F AMBRICAN MEDICAL ASSOCIATION, 635 NORTRDEARBORN S T . , CHICAGO, ILL.
PHEDRIKE, the alkaloid discovered by Nagai forty years ago, was for many years an almost unknown and an almost unused drug. Owing to important discoveries of valuable therapeutic effects obtained through its use made within the last three years, ephedrine suddenly became a much talked-of and a widely sought article. When the pharmaceutical manufacturers were first asked to produce ephedrine preparations, some of them did not know, nor could they easily find out, just what would constitute a good ephedrine preparation, much less prepare it in large quantities. It is no wonder that isolated cases have been recorded in which ephedrine preparations have been prescribed, but in which ephedrine reactions have not been obtained. I n view of this situation the A. M. A. Chemical Laboratory thought it advisable to make a chemical investigation of the drug and to devise standards for it. I n devising standards this laboratory aims to secure for the medical profession the best possible product without placing undue hardship on the manufacturer. Many manufacturers are using the standards suggested by the A. M. A. Chemical Laboratory as guides for manufacture.
E
1 Received
December 3, 1927.
Relationship between Ephedrine and Epinephrine
I n examining the literature on ephedrine, the chemical similarities that exist between this drug and epinephrine become apparent, and it is not surprising to learn that, therapeutically, the two drugs have in part similar actions. These similarities can be strikingly seen by a comparative study of the structural formulas and, conversely,' the differences in action can be better appreciated by noting the chief points of difference in the molecular arrangement. H
H
It will be noted from these formulas that the side chain of ephedrine contains three consecutive carbon atoms; accordingly, the compound is named "a-hydroxy-P-methylaminopropylbenzene." The side chain in epinephrine contains Ohly two consecutive carbon atoms, and its name, therefore,
