. ~ H ~ ~ T R . ~ :C T.IKTSTUS R LIEBIG’S AXNALEN DER CHEMIE.
233
Abstracts from American and Foreign Journals. Justus Liebig’s Aiiiinlen der Chemie. Abstractor, GBO. A . PROCUAZKA, €”. D.
i V i t r o e a l i c ~ ~ f iAcids, ic uncl the Iaornerinme of t?w benzol-der6z’uticea, €3. HC‘EBNER (Ann. Chein., 195,1-55).-1n the same manner in
which, starting from metabronibei~zoicacid, the author had formerly deduced two orthohydrogen atoms in the monosubstituted benzol, he proves the’existence of two metahydrogen atoms, by a similar series of substitutions, with salicylic acid as a starting point:
, by
Orthohydroxybenzoic acid or salicylic acid, C6H4{
CO,H nitration, yields two metanitroorthohydroxybenzoic acids:
nietaiiitroorthohydroxybenzoicacid ; /3 metanitroorthohydroxybenzoic wid. The diethyl ethers of these acids on treatment with alcoholic ammonia, yield:
ti
[ GH, It
p orthoamidometanitrobenzoic acid,
orthoamidometanitrobnzoic acid ;
which by azotation yield: f m -
-
metanitrobenzoic acid.
It will be seen that the two isomeric nitrosalicylic acids furnish, in substitution of their hydroxylgroups by hydrogen, the same metanitrobenzoic acid, showing that they contain two hydrogen atoms in metaposition with reference to the carboxyl group. The different position, in the two acids, of the hydroxyl group, with reference to the nitro group, can be easily demonstrated, as the
two monoriitrosalicyIic acids, ferent ni ononitrophenolx : o
trm
1
1)
0
/AI1
011
heating with lime, yield two dif1
1
P
CaH,.OH . NO,. CO,H yields C,H,. O H . NO, Paranitrophenol
C,H, .OH . NO,. CO,H 1
1
1
0
C',H,. OH. NO,
"
0
Orthonitrophenol.
T h e derivations and derivatives thus outlined are described in detail in the paper. Two series of salicylates are mentioned. ,I
(C,H,. X . OH. CO,), 31 = semimetalsalicylates; and C',H,. X . ( C,H,. X . 0 . C ' 0 2 ( (lCH3.X . 0 . CO, 1 \ I,
r,
} = nietalsali31 11 cylaterj. C'O,. 0 .X.C6H3) Salicylic acid, on treatment with nitric acid, yields the two isomeric niononitrosalicplic acids, one dinitroszlicylic acid, di- and trinitrophenol. Methods for the preparation of the mononitrosalicylic acids. (1) 5 0 grns of nitric acid (1.5 sp. gr.) are added in small portions to a cold solation of 100 gms salicylic acid in 500 or 800 gins glacial acetic acid. T h e resulting liquid i 4 diluted with 2 or :j vol. water and cooled down very low. (2) 10 gms salicylic acid are gradually added t o a mixture of 10 gms fuming nitric and 10 or 12 gnis glacial acetic. acid ; the resulting liquid is poured in 250 cc very cold water. The precipitates obtained i n both cases are mixtures, consisting substantially of the two mononitrosalicylic acids. (:j) t i lliorionitrosalicylic acid is obtained alniost piire b y saturating a saturated Holution of salicylic acid in cold glacial acetic acid with the fumes generated in the ignition of dried plumbic nitrate. By subsequent dilution with water, a precipitate of almost pure ( r mononitrosalicylic acid is obtained. The separation'of the two nitrosalicylic acidn is effected by appropriate utilization of the difference in solubility in water of the acids and their semibarium salts. cr i t t e t w n itroorth ohydrmybenzoic-or n nitroawlicylic acid, C,H, .
ii ii l o r i\ (C,H,.X.O.CO, J
A i or
(
urn
o
1
NO,.OII.COzH (m. pt. 228') ; long known ; long colorless needles, crystallizing without water of crystallization from the fim
o
1
aqueous solution. fi uitrovulicylic acid, C,HS.NO,. OH &O,H + H,O (m. pt. 1 2 j 0 ) , seems to dissolve in water more readily than the former ;
ABSTRACT8
:
JU6TU6 LIliBII3'6 ANNALEN DER CHEMTE.
235
long colorless needles, The dehydrated acid (m.pt. 144') is hygroscopic. u monopotassium, m onoammoninm, magnesium, barium, semibarium, semistrontium, semicalcium, semizinc, semisilrernitrosalicylate, and p monopotassium, monosodium, barium, magnesium, lead, semibarium, semistrontium, semisilver, eemimercury (?) and mercurynitrosalic*ylate, are described. am
o
1
(C,H,. NO,. O H . CO,), B s + 6 H,O, small yellow needles, very soluble in water. /i' semibariumnitroa semibariumnitrosalicylate
fim
o
1
salicylate (C,H,. NO,. OH. CO,), Ba, gold colored scales or needles, very little soluble in water. a monoethylnitrosalicylat e, m. pt. 93', very long, colorless needles, readily soluble in alcohol ; p monoethylnitrosalicylate, large colorless plates, very little soluble in cold alcohol ; a sodiumethylnitrosalicylate, C,H,. NO,. O N a . CO,C!,H,, thin yellow needles, readily soluble in alcohol ; p salt, yellowish-red needle, little soluble in alcohol ; a diethylnitrosalicylate, m. pt. 98', colorless needles ; p diethylether, oily liquid, of agreeable odor. a nitrosalieylamide, m. pt. 225'; fl nitrosalicylamide (145-146') ; both long, colorless needles ; a potassium, barium, calciumnitrosaliaylamide are readily soluble i n water ; a leadnitrosalicylamide, soluble in a great deal of water ; p barium, calcium, and basic p lead nitrosalicylamide are very little soluble in water. T h e two nitrosalicylic acids were still further characterized by the preparation and examination of the following compounds : a amidosalicylic acid, u chlorohydroamidosalicylia acid, a sulphuric-amidosalicylic acid, a acetamidosalicylic acid and 0 magnesium, barium, calcium, zinc-acetarnidosalicylate, p amidosalicylic acid ; only the hydrochloric acid salt of this acid could he obtained in the same manner (evaporation of the two acids) as the corresponding lr amidosalicylic acid compound, u metnti itroorthociniirJoheiLzoic or u 9) itramidobenzoic a d ? , C,H, . am
o
NO,.",. CO,H, m. pt. 283'; long, very thin lemon-colored crystah with silver lustre ; salts described ; barium, calcium, potassium, ammonium, (copper,) lead, and the hydrochloric acid salt.--p nitrainidobenzoic acid, m. pt. 204', long yellow needles ; the salts of this acid with the just mentioned metals and acid, strontium and silver, are described.-fi ethylnitramidobenzoate, m. pt. 104', yellow scales.
(tni /hi o 1 C 6 H ~ . N 0 2 , ~ 0 2 ..CYAJI. 011
“
P
These facts demonstrate
t h e fre-
I
quently occuririg regul:wity, that negative voristituents will enter, when acting upon siib+titiitcd benmlc dcrivat,c..i, i n t o ortho and para-relation with refertirice to the most positive constitueiit, forming two isomeric coinpouiitls, which by further introductioii of the Hame negative constituent, yield the same. niore highly substitiitetl corriporintl ; in this case c~itnctaiiitroaalic~lio acid. The co!iipu-ison of the dinitrosalicylic acids ft-otn 1)oth sources, of their mono- and dipotassium, tnonoammoniiiin, nionobarium, monocalcium, monolead salts itritl their moiioetliyl ethers, establishes that there is no differenve 1)et wcwi tliern. O
P
B i1initroI)licii:)l C,H,. NO,.SO,.OH, m. pt, 6:he further action of fused potitssiiini hydrate, is finally, though very siowly, oxidized, t o triixiesic acid. Hence potassiuni mesitylene aulpliate yields all these products on fusion with potausiiun hydrate, if the reaction is coiitinueti for a sutficieiit length of time. These results would rectify the statenitant of Fittig and Hoogewerff,* and verify i i i part tlie results of i
