COMMUNICATIONS TO THE EDITOR
Feb., 1945
point of the p-nitrophenylhydrazone was depressed by the addition of pure p-nitrophenylhydrazine, m. p. 157". Anal. Calcd. for the p-nitrophenylhydrazone, C12HlbNgOy: C. 61.78: H. 6.49. Found: C. 61.76: 11. 6.48. Calcd. for the '2,4-dinitrophenylhydrazone,Cl2H,4N404: C, 51.79; H, 5.07. Found: C, 51.82; H, 4.81. Attempts t o prepare the p-niethoxy- and p-bromophcnylhydrazones by similar methods were not successful. The authors are indebted t o Miss Joy Swan for some of the analyses.
DEPARTMENT OF CHEMISTRY INSTITUTE OF TECHNOLOGY CARNECIE PITTSIKJRGH 13, PENNSYLVANIA RECEIVED NOVEMBER 24, 1944
Condensation of Chloromaleic Anhydride with Substituted Propenylbenzenes BY MARTINE. SYNERHOLM The condensation of maleic anhydride with iso-
345
and Robinson. They similarly condensed isosafrole with ethyl acetylenedicarboxylate, obtaining the corresponding 3,4-dihydronaphthalene derivative as the acid anhydride, in. p. 178'. The latter compound has now been shown to form when chloromaleic anhydride is heated in xylene with isosafrole. Analogous compounds formed when chloromaleic anhydride was condensed wiQ isoeugenol and 2-ethoxy-4propenylphenol. Experimental.-The procedures were similar for the three cases. Thirteen grains of chloromaleic anhydride, 15 g . of the propenyl compound, and 50 ml. of xylene were refluxed for six hours. The color turned to a bright red and hydrogen chloride was eliminated during the reaction. On cooling, the products crystallized from the xylene. The yields and properties are tabulated.
DERIVATIVES OF 3-METHYL-3,4-DIHYDRONAPHTHALENE-l ,%DICARBOXYLIC ACIDANHYDRIDE Derivative
Solvent
Mo. P., C.
6,7-Methylenedioxy 6-Methoxy-7-hydroxy 6-Ethoxy-7-hydroxy
10 9 G
Benzene Xylene Toluene
176-177 225-226 192-196
-
Formula
Analyses, Calcd. CarbonFound Calcd. 'Hydrogen F o u n d
C14H1006 C1,H,,O5 C16H1406
65.1 64.7 65.7
c
Yield, P.
'
65.0 65.0 65.6
3.91 4.65 5.14
3.95 4.69 5.07
COMMUNICATIONS T O T H E E D I T O R TRIFLUOROACETIC ACID AS A CONDENSING AGENT
water. The acids were reirioved by shaking with water and the organic layer was extracted Sir: with alkali, but no phenol or p-hydroxyacetoI wish to report the use of trifluoroacetic acid phenone was found. On vacuum distillation as an agent for the condensation of acetic anhy- there were isolated 4.7 g. (31%) of anisole and 13.1 dride with anisole to produce p-methoxyaceto- g. (63%) of p-methoxyacetophenone, b. p. 134phenone. The reaction proceeds well (63Oj,, or 137 a t 15-16 mm. This material crystallized 917; if allowaiice is made for recovered anisole) and melted over the range 30-36'. The crude a t moderate teniperatures (60-70'). Trifluoro- semicarbazoiie formed in 76% yield melted a t acetic acid has several advantages over other 193-195'. 0 1 1 recrystallization it melted a t reagents coiiiiiidy einployed for such condeiisa- 195.6-197.0° cor. These facts indicate that altions : there is no demethylation of anisole or most pure para derivative was produced.' The the product; there is little if any heat of reaction mixed melting point with purified semicarbazone so that all reagents ma)- be mixed a t one time; froin coiriiriercial p-methoxyacetophenone (Eastno stirring is r e q u i r e d ; no corrosive gases are inaii Kodak Co.) was not depressed. In a similar used or formed; the tritluoroacetic acid may he espcrinicnt, except that the reaction was c:trried out a t 110-125', a inuch smaller yield of ketone recovered. Procedure.-On mixing 15 g. of anisole, 14.8 was obtained as tars were formed. I have also used trichloroacetic acid2 in a simig. of anhydrous trifluoroacetic acid, and 27 g. of acetic anhydride, heat (of mixing) was evolved and lar manncr, but it is less desirable than trifluoro(1) Wahl ;ind Silberzweig, Ball. soc. chim., 1.11 11, (19 (1912). give a pink color was produced. On warming to 6036', 197O, of 138-139' as meltiiiy points of ketone x i i d sernicarhazone '70' the color deepened into cherry red. After six and boiling poiut or ketone at 1s iuni. Iiours at 60-70' t h e mixture was pourrd into ( 2 ) l:nger, A v ? z . , 604. 269 (1933). I
COMMUNICATIONS TO THE EDITOR
346
Vol. 67
selective” membranes combine extreme ionic selectivity with great permeability for the nonrestricted ion species ; the electronegative colTHEOHIOSTATE UNIVERSITY MELVINS. NEWMAN lodion membranes are impermeable to all inorganic COLUMBUS 10, OHIO anions but permeable to the alkali cations, the RECEIVED J A N U A R Y 6, 1945 electropositive membranes being impermeable to all cations and permeable to the anions of the MEMBRARE EQUILIBRIA WHICH INVOLVE ONLY strong monobasic inorganic acids. The ionic THE IONS OF STRONG INORGANIC ELECTROLYTES screening action of the membranes in these cases .Si),: is primarily an electrical, not a mechanical (sievej, The experimental study of membrane equilibria effect. has been confined in the past to systems containThe ratios of the activity coefficients of the ing colloidal or sernicolloidal ions as “non-dif- K-1, K a t and I$Hd+ salts in the pairs of solutions fusible” ions, and systems in which the Fe(CN)6’=’= given in Table I are nearly identical. This perion acted as such in conjunction with a copper mits the use without appreciable error of the simFor lack of suitable plified original formulas of Donnan1v2which refer to ferrocyanide membrane. membranes-except for this unique case-Donnan analytical concentrations rather than to activities. The experimental study of membrane equiequilibria involving only strong inorganic eleclibria which may involve any desired combination trolytes could not be studied.
acetic acid. Further uses of trifluoroacetic acid as acid condensing agent are being explored.
l s 2
TABLE I DONNAN EQUILIBRIA ACROSS MEGAPERMSELECTIVE COLLODION MEMBRANES’ No
A
n
Solute
”,+
Original state mMoles per liter In out
30.0
K+
..
..
C1’-
30.0
Sucrose6 Vol .
30 nil.
10.0 10.0 33 30 nil.
h”&+
50.2
2.51
..
...............
Experimental tnlvloles per liter In Out
72.4 7.5 29.8
7.50 2.5 10.1
22.5 7.50 30.0 . . ..
, .
..
37.4
Calculated mMoles per liter In Out
3.79
37.5
7.50 2.50 10.0 .. ..
3.78
Ratio in/out Experimental Calcd
2.99 * 0 . 0 2 3.00 *Oo.10 2.95 1 0 . 0 2
3.00 3.00 3.00
....... .......
..
9.9 1 0 . 2
9.9
, ,
K+
2.56 12.0‘ 1.27‘ 12.7 1.29 9.5” 9.9 2.54 24.7 2.53 25.1 2.54 9.8 * 0 . 2 9.9 Sucrose’ .. 39 .. .. .. ....... .. Vol . 25 nil. 250 nil. .. .. .. ....... a The membranes are impermeable to anions, permeable to cations. * Sucrose is added in the proper concentration K+ concentration is calculated by difference. t o establish osmotic equilibrium.
czo4-
25.1
.
The use of certain recently developed collodion and protamine collodion membranes3v4 makes such investigations possible. These “niegaperm(1) F.G. Donnan, Chem. Rev.. 1, 73 (1924). (2) T. R. Bolam, “The Donnan Equilibria,” Bell and Sons, London, 1932. (3) C. W. Carr and K. Sollner, J. Gen. Physiol., 28, 119 (1944): C. W. Carr, H. P. Gregor and K. Sollner, J. Gen. Physiol., 28, 179 1944). (4) FT. 1’. (;rpgorq P1i.D. ‘I’hrsis, Minneapolis, 1415 (in pre.yAr;ition)
t
of uni-univalent, and many combinations of unipolyvalent electrolytes is of interest not only for the colloid chemist and the biologist, but also “may prove of value in the investigation of ionic activity coefficients” (Donnan). DEPARTMENT OF PrrYsroLocY THEMEDICAL SCHOOL v N I V E R S I T Y OF MINNESOTA KARLSOLLNER MIWEAPOLIS, MINNESOTA HARRYP. GRECOR RECEIVED TAVITARY 12. 194.5
