NOTES
Nov., 1938
FD
0.0 9.61 25.18 26.40 28.4 48.4 51.45 52.42 54.69 56.60 77.1 77.49 78.49 87.99 92.61 93.0 96.00 96.51 97.0 97.87 98.67 100
suMbfA.pY OF CWXLATED -5M x lo6HAC EXPtl.8 Calcd.
1.84
2813
TABLE 11 V S c T USING EQUATION "(6)AND OF EXPERIMENTAL DATA -KM
(1.84)
x losCalcd.
Exptl.1
6.09
X8.09)
2.66 2.36 1.94
1.36
x
-KM
EB
Exptl.'
10"-
H?Q
4.60
-KM
x
10-
Calcd.
Exptl.8"HAC
Calcd.
(2.66)
1.73
(1.73)
1.81
1.37
1.23
1.05
1.352 1 088 3.56 3.55
1.30 0.988
3.41
.756
2.61
0.895
0.827
3.18
.722
.700
0 741
0.889 2.23 .622 .608 ( .6W
2.03 .575 1.99
( ,555)
( ,555)
(1.95)
(1.95)
.657 ( ,639)
( .639)
(0.631)
( .631)
The KM values, calculated from the revised ketone (ClaHlsOa)was described. This has now equation (6),are now in very good agreement with been identified (by direct synthesis and mixed the experimental results. These are summarized melting point determination) as a-ethoxypropioin Table I1 and plotted in Figs. 1, 2, and 3. The veratrone predicted slope for chloroacetic acid is given in H~CO-~COCH(OGH~)CH~ Fig. 4; no experimental data for comparison are / available. The value oh K D for salicylic acid is OCHs extrapolated with equation (6) from the average The synthesis (after numerous unsuccessful a. d. 12%, at F D = 91.7, attempts, and using a variety of methods) was valueHM = 0.24 X a. d. accomplished as follows: and from the average KH = 0.98 X 2% determined by Korman and La Mer.' Veratrole pmpionyl chloride -+ Propioveratrone + The K D thus calculated is 0.21 X 10-3 a-Brompropioveratrone -+ Acetate of a-hydroxypropioveratrone which also has not yet been determined / \ experimentally. a-Hydroxypropioveratrone + a-Ethoxypropioveratrone The synthetic compound melted at 81-82'; It is apparent that true values of hydrogen and deuterium ion concentrations are obtainable from a mixed melting point with natural compound kinetic data when tested by means of acid dissocia- gave no depression. The melting point of the tion constants. 2,4-dinitrophenylhydrazone of the natural (6) (AC&C acid) Chitturn and La Mer, T=m JWWAL, 6% 2524 compound is 134-136'; synthetic compound, (1937). the mixed melting point also showed 134-136' ; (7) (Benzoic acid and hydroquinone) Rule and La Mer, ibid., 60, 1974 (1938). no depression.
+
( 8 ) (Chlokaeetic acid) Lewis and Sch&z, ibid., 06, 1918 (1834).
DEPARTMENT OF CERMISTRY THE CITYCOLLEGE THE COLLEGE OF T R E CITYOF NEWYORK RECEIVED AUGUST25, 1938 NEWYORK, N. Y .
The Classidcaeon of Chelating Groups
The Structure of Lignin B. C-ER, M. J. HUNTERAND HAROLDHIBBERT In a recent note1 the 3ohtjon of a new aromatic
B Y A.
(1) Cramer, Hunter and Hibbert,
TSIS J
~
~
A
DIVISIONOF INDUSTRIAL AND CELLULOSE CHEMISTRY MCGILLUNIVERSITY RECEIVED OCTOBER 18, 1938 MONTRSAL,CANADA
80,2274 L , (185s).
HgLMUT
M*HAENDLER
AND
*'
GEYER
In the course of preliminary work on organic analytical reagents which form inner complex
