SOME CARBOXYL DERIVATIVES OF TRIMETHYLENE.
is eliminated and there is formed the a-ethoxyanilide of 4-pyrazol-carboxylic acid. HC
I1
1.517
I ,g-diphenyl-
CCONHCsH4OCzHa
NN(CsH8)
II
- CCsH6
This separated from dilute alcohol in fine needles melting a t 118'. Calc. for C U H Z ~ O ZN, N ~10.97%. : Found: 10.54%.
In the course of this investigation several compounds have been prepared, which will be briefly described, as they are not mentioned in the literature. Di-o-phenetidyl formamidine and malonic ester a t water-bath temperature gave a good yield of o-ethoxyanilido-methylene-diethyl-malonate, C2H50C8H4NHCH.C= (COOC2H5)2, long needles from 60% alcohol with a melting point of 66-7'. Calc. for C I ~ H Z ~ ON, ~ N4.54%. :
Found: 4.63%.
~-o-Tolyl-~-methyl-~-monobromo-~-pyrazolone is formed when bromine (one mol) is added to a solution of the pyrazolone in glacial acetic acid. The yellow crystals from alcohol melt a t I 16'. Calc. for CllHllONlBr: Br, 29.81%.
Found: 30.13%~29.99%.
I -0-Tolyl-g-phenyl-~-monobromo-~-pyrazolone, made in
a like manner, crystallizes from alcohol in brownish yellow needles with a melting point of I IO'. Calc. for CIBH130NZBr: Br, 24.29%. Found: 24.44%, 24.54%. LAWRENCE, KANSAS.
THE REACTIONS OF SOME CARBOXYL DERIVATIVES OF TRIMETHYLENE.' BY DOROTHY A. HAEN. Received June 3, 1916.
The principal object of this investigation was the study of the products obtained by eliminating hydrobromic acid from bromine substitution products of the esters of anisoyl-phenyl-ethyl-malonicacid. These esters are easily obtained by adding the corresponding malonic esters to phenyl-anisyl-propenone : CsH6CH = CH.COC6HdOCH3
+ CHz(C0zCHs)z + C ~ H ~ C H C H ~ C O C B H ~ O C H ~ I
CH(C0zCHa)z
They contain one hydrogen atom that is very readily replaced by bromine ; the resulting bromine substitution product may be either Part of a dissertation presented to the Faculty of the Graduate School of Yale University, 1916,in candidacy for the degree of Doctor of Philosophy. The work, suggested by Prof. Elmer P. Kohler of Harvard, was done a t Mount Holyoke College, and was accepted a t Yale upon recommendation of Prof. Treat B. Johnson.
DOROTHY A. KAHN.
1518
CeHsCHCHBrCOCeH40CH3
CsHsCH.CHzCOCsH4OCHa
I
I
or
CH.(COzCHs)z
CBr(COZCH&
(1).
(11).
By cautious treatment with bases it is possible to remove hydrobromic acid from the bromine compound without hydrolyzing much of the ester, the yield being 80 to 87y0 of bromine-free ester. The main product of this process was always a substance melting a t 86', although an isomeric substance melting a t 82 O was sometimes obtained in sufficient quantity for separation. For products obtained in this way three formulas are possible. CsHrC = CH.COCeH40CH3
CaHsC
I/
1
- CHzCOCsHdOCHa
CH (COICHB)~ C(C0zCHa)z (1). (11). CeHsCH - CHCOCeH40CH3
\/
C. (COzCHsh (111).
Between these formulas it is possible to decide by means of the following transformations : When the ester melting a t 86' is treated with alcoholates it forms a metallic derivative that on acidification gives an isomeric ester melting at 82'. This on further action of the same reagent passe.s into another metallic derivative that yields a third isomer melting at 112'. The structure of this third ester must be represented by the formula CsHbCH = C.COCsH4OCH3
I
CH.(COzCHa)p
(IV). This follows from the fact that on hydrolysis and loss of carbon dioxide, it passes into an acid that can be made synthetically by condensing benzaldehyde with ethyl-@-anisoyl-propionate, and hydrolyzing the product. CsH&!HO
+ CHzCOCeH4OCHs I
CHzCOCzHs
+
CsHaCH = C.COCeH4OCHa
I
CHzCOzCzHs
+ HzO
The structure of substances obtained by thi? reaction was established by Borsche.' From this transformation of the ester melting a t 86' into a substance with the formula represented by IV, it follows that the former must be a trimethylene compound, and that the relations between the three isomers is represented by the formulas Ber., 47,
I I I Z (1914).
SOME CARBOXYL DERIVATIVES OF TRIMETHYLENE.
1.519
C ~ H ~ C O C B H ~ O C H ~H. COCBH~OCH~ CeH6CH-CHCOCeH40CHs
v c.(CO&Hs)z
I I
H
I (86').
I t
c=c CH(C02CH3)z I1 (82').
I 1
c=c 1 1
CeHbCH(C0EHa)z I11 ( 1 1 2 0 ) .
All the properties of these three isomers support this conclusion. The substances melting at 82 and 112' readily reduce Permanganate while the ester melting a t 86' does not. They also, as would be expected] form highly colored metallic derivatives from which they are regenerated by acids, a process that is impossible with the trimethylene compound. That the esters melting a t 82 and 112" are stereoisomers is shown also by the fact that the former passes into the latter under the influence of sunlight. By using aqueous alkalies or alcoholates under special conditions it is possible to hydrolyze the trimethylene compound to the corresponding ester-acid, and then to the dibasic acid. C~H~CHCHCOCBH~OCH~ +CeHsCHCHCOCsHiOCHa 3 CBH~CHCHCOCBHIOCH~ V V COzH V C(C0zCHs)z C. (COzWz c
