R 547.538.1 : 542.958.

1
THE ACTION OF NITRIC ACID ON DERIVATIVES
OF ETHYLENE. 11. NITRATION OF SOME
STYRENE DERIVATIVES l )
BY
J. VAN DER LEE.
Introduction.
T h e first product formed by the interaction of nitric acid and a

>c=c( +HONO, -
compound containing an ethylenic linkage is a nitro-alcohol (1) :

OH NO,
\c-c(
'I . . . . (1)

In some cases this nitro-alcohol is the final product of the reaction ,)).
but generally, it is only an intermediate product, which may react
further in two directions :
a. The nitro-alcohol may be converted by nitric acid into the
corresponding nitric acid ester (11) ') :
>C-C(
I
+ HONO, SF
,+ )C--C(
I
+ H,O . . (11)
OH No, ONO, NO,
6. T h e nitro-alcohol may split up into a derivative of nitroethylene
and water (111) :

>c-c
OH H<NO,
- )c=c '
'NO,
+ HzO . . . (111)

In the action of nitric acid on the ethylenic linkage in the benzene

nucleus introduction of a nitro group takes place, a nitro-alcohol (I)
or its nitrate (11) the never having been isolated. In this case the
reaction may be represented by the final equation:

l ) The first communication on this subject appeared in 1926: The nitration of

cinnamic acid derivatives, Rec. trav. chim. 45, 674 (1926) : Dissertation Lciden 1925.
*) Examples: Llnsyrn.-diphenylethylene: H. Wieland and F. Rahn, Ber. 54, 1773
(1921). R. Anschutz and A. Hilbert. Ber. 54, 1856 (1921). Phenanthrene: H. Wieland
and F. Rahn, Ber. 54. 1774 (1921).
3 Ethylene: A. Kekule. Ber. 2. 329 (1869): H. Wieland and E. Sakellarios, Ber.
52, 898 (1919) and Ber. 53, 201 (1920).
Isopentane : H. Wieland and F. Rahn, Ber. 54. 1775 (1921). Ethyl-p-nitrocinnamate.
ethyl-m-nitrocinnamate : 1. van der Lee, Rec. trav. chim. 45, 693-703 (1926).
Unsym.-diphenylethylene : R. Anschutz and A. Hilbert, Ber. 54. 1856 (1921).
Anthracene: Meisenheimer and Conrade, Ann. 330. 158 (1903).
 -
92 1

‘C=C’
/ \H
+ HONO, > C = C<
NO2
+ H,O . . (IV)
The nitration of those ethylene derivatives in which no addition
products have been isolated may also be represented by equation IV ‘).
Finally, the nitroethylene derivative may be unstable and decom-
pose as:

>c= c\
/COOH
NO,
- >c=c<H
NO2
fCO,. . . (V)

In a previous communication ’) a study was made of the action

of absolute nitric acid o n :
O,N . C,H, . CH = CH . COOCzH5,ethyl-nitrocinnamates and
0 , N . C,H4. CH = CH . COOH, nitro-cinnamic acids.
Ethyl nitrocinnamate reacts according to equations (I) and (11) and

ethyl-x-nitro-~-hydroxy-nitrate-~[nitrophenyl]propionatewas isolated.
The nitrocinnamic acid reacts according to equations IV (or I
and 111) and V :
0 , N . C6H,. CH = CH . COOH + HNO, w-+
. COOH
~w OZN .C,H,. CH = C
+ NO, + €320

w-dinitrost yrene.

Continuing this work a study has been made of the action of

absolute nitric acid on other styrene derivatives, which contain the
following groups instead of the COOC2H5and COOH:
>C = 0, -COCH3 and -CO . C6H4.NO,
(0,N. C,H*. CH = CH),CO
4 :4’-dinitrocdibenzalacetone and 3 :3‘-dinitro-dibenzalacetone
0 , N . CBH4.CH = CH . CO . CH3
4-nitrobenzalacetone and 3-nitrobenzalacetone
OjN . C,H,. CH = CH . CO . C,H4. NO2
3 :3’-dinitrochalkone and 4 :3/-dinitrochalkone.
4, Ethyl-dimethylacrylate: L. Bouveault and A. Wahl, Compt. rend. 131,687 (1900)
and A. Wahl. ibid. 132, 693 (1901).
Nuclear substituted cinnamic acids: J. van der Lee, Rec. trav. chim. 45,687-693 (1926).
 922

Experimental.

8 1. Action of absolute nitric acid on 4 :4’-dinitro-dibenzalacetone

and 3 :3’-dinitro-dibenzalacetone.

a. Preparation of 4 : 4‘-dinitro-dibenzalacetone.
(4) 0 , N . C 6 H 4 .CH = CH . C o . CH = C H .C6H4.NO, (49,
At first this ketone was prepared according to the directions given
by P. Pretenko-Kritschenko 5, viz. by condensation of two molecules
4-nitrobenzaldehyde with one molecule acetone. Crystallised from
acetic anhydride the 4 : 4/-dinitro-dibenzalacetonemelted at 245O.
During this investigatign a second method for the preparation of
4 : 4/-dinitro-dibenzalacetonewas found viz. : from ,8[4-nitrophenyl)-
p-hydroxy-ethyl methyl ketone
H
(4) O,N .C6H4. C-CH, . C O . CH3
I
OH
(m. p. 58O) and potassium hydroxide 6).
Two grams of the p[4-nitrophenyl]-p-hydroxy-ethyl methyl ketone
were dissolved in 400 cc. of water and strong potash was added
to the boiling solution when a yellow precipitate was formed: 1
gram, m. p. 225- 230O. After crystallisation from acetic anhydride
the m. p. was 247O, a mixed m. p. with 4 : 4’-dinitro-dibenzalacetone
made by P. Petrenko Kritschenko’s method was 247O.
Analysis:
0.1064 gr. gave 7.7 cc. Nz at 1l0 and 762.2 mms.: N = 8.61 Oi0.
C,,HI,05Nz requires N = 8.92 o/o.
Hence, 4 : 4’-dinitro-dibenzalacetone is produced from ,8[4-nitro-
phenyl]-,8-hydroxy-ethyl methyl ketone and potash and not a polymer
of 4-nitrobenzalacetone (C,,H,O,N)., m. p. 254O. as has been stated
by A. Baeyer and P. Becker6).
The reaction may be represented in the following way :
Part of the ,8[4-nitropheny1]-,8-hydroxy-ethylmethyl ketone is split
up into 4-nitrobenzaldehyde and acetone (I). 4-Nitrobenzaldehyde
then reacts with the unaltered /?[4-nitrophenyl]-,8-hydroxy.ethylmethyl

H
0 , N . C,H.,. C .C H 2 . C O . CH,
OH
-
ketone and forms 4 : 4/-dinitro-dibenzalacetone(11).

w+ 0 , N . C6H4. CHO -I- H,C CO CH,. . . (I)

5, J. prakt. Chem. [2] 60, 154 (1899).
e, This ketone was prepared from 4-nitrobenzaldehyde and acetone by themethod
of A. Baeyer and P. Becker, Ber. 16. 1970-1971 (1883). See also Baeyer and Drewsen.
Ber. 15, 2857 (1882).
 923

H
OaN. CGH4. C . CH2. CO . CH, f OHC .COH4. NO, W+
OH
B-+O,N . C,H4. CH =CH . CO. CH = CH .C6H4.NO, -t2 H 2 0 . (11)

O n adding sodium hydroxide to the boiling aqueous solution of

4-nitrobenzalacetone a brown amorphous product was obtained (m. p.
about 175O) from which pure 4 : 4’-dinitro-dibenzalacetonecould not
be isolated.
b. Nitration of 4 : 4/-dinitro-dibenralacetone.
During l ’ / z hours, 1.5 gr. of 4 : 4/-dinitro-dibenzalacetone were
dissolved in 9 cc. of absolute nitric acid cooled below 0’. T h e dark
brown liquid was kept at 0’ for a n hour and then pouredintoiced
water. A yellow substance separated and carbon dioxide was evolved
(demonstrated with baryta water).
The next day the nitration product was separated from the aqueous
liquid: yield about 1 gr., m. p, 160-170’.
After being crystallised from acetone the product was obtained in
yellow needles, m. p. 196-200’. A mixed m. p. with pure w . 4-
dinitrostyrene (m. p. 200-202°) gave no depression.
Hence the reaction between 4 : 4/-dinitro-dibenzalacetoneand nitric
acid may be represented in the following way:
0 , N . CaH4.CH = C H .CO .CH =CH . C,H4. NO, -12 HNO, m
m 0 , N . C,H, .CH = C(N0,). CO .(0,N)C = CH .C,H4. NO,
0 , N . C,H4. CH = C(N0,). co . (0,N)C = CH. C,H4. NO, -k 2 H,O
2- 2 OzN . C,H4. CH = C(N0,)H 2 CO,.
+
2 H,O.

+
-
The second reaction begins after pouring the reaction mixture
into iced water.
c. Preparation of 3 : 3’-dinitro-dibenzalacetone.
.
(3) 0 2 N . C,H4. CH = CH CO . CH = CH . C,H4. NO, (3’)
At first this ketone was prepared according P. Pretenko-Kritschenko’s
method viz. by condensation of 3-nitrobenzaldehyde (2 mols.) and
acetone ( 1 mol.) in alcoholic solution by means of sodium hydroxide ’).
T h e crude product was washed twice with bo‘ling alcohol when the
m. p, was found to be 237’ as is required b&he literature.
Another method for the preparation of 3 :3/-dinitro-dibenzalacetone,
which has not been published, is as follows:
A gram of 3-nitrobenzalacetone was dissolved in 250 cc. boiling
water and a few cc. of an aqueous caustic potash solution were
added to the hot liquid. A light yellow substance separated, which,
after washing with boiling alcohol, melted at 235O and by its m. p.
was proved to be 3 : 3’-dinitro-dibenzalacetone.
-

7) J. prakt. Chem. 60, 152 (1892).

 924

d. Nitration of 3 : 3/-dinitro-dibenzalacetone.
The nitration of 3 : 3’-dinitro-dibenzalacetonewas carried out in
the same way as the nitration of 4 :4/-dibenzalacetone: carbon
dioxide was evolved after pouring the reaction-mixture into iced
water. The crude product melted at 93O. after being crystallised, at
122--123O, and was proved to be w .3-dinitrostyrene.

4 2. Action of absolute nitric acid on 4-nitrobenzalacetone and

3-nitrobenzalacetone.
a. Nitration of 4-nifrobenzalacetone
(4) OzN. C,H,. CH = CH . CO . CH,.
4-Nitrobenzalacetone was prepared from 4-nitrobenzaldehyde,
acetone and sodium hydroxide according to the method of A. Baeyer
and P. Beckera).
4-Nitrobenzalacetone (0.8 gr.) was dissolved below Oo in 2.5 cc.
absolute nitric acid, a transient red colour being produced. After the
yellow-brown liquid had been kept at Oo for an hour it was poured
on to ice. The yellow nitration product was filtered as quickly as
possible and dried on an earthenware plate. The m. p. was found
to be about 150O. The crude nitration product did not yield nitric
acid on being boiled with acetone and water and therefore did not
contain a nitric acid ester ”. After crystallisation from carbon tetra-
chloride crystals were obtained, m. p. 196O.
A second nitration showed that after a longer time the reaction
between nitric acid and 4-nitrobenzalacetonc was more complete.
Three grams of 4-nitrobenzalacetone were dissolved below Oo in
7.5 cc. absolute nitric acid and the liquid was poured into iced water
after 21/z hours (temperature OO). The m. p. of the crude product
was 175-190°, which rose to 200-202° after crystallisation from
acetone.
Analysis :
0.1338 g. gave 16.3 cc. N, at 12O and 761.4 mms.: N = 14.48O/”.
. .
0 , N . C,H, CH = CH NO, (GH,,O,N,) requires N = 14.43 o/o.
A mixed melting point with pure w.4-dinitrostyrene (m. p. 200-
202O) gave no depression.
Thus w. 4-dinitrostyrene is formed by the interaction of 4-nitro-
benzalacetone and nitric acid.
Displacement of the acetyl group by the nitro group was expected
to be accompanied by the formation of acetic acid. The latter was
proved by L. Elion’s method lo).
The crude nitration product being filtered, about two thirds of the
liquid was distilled. The distillate was neutralised with sodium
hydroxide, acidified with a few drops of dilute sulphuric acid and
Ber. 16. 1968-1971 (1883).
g, See: Nitration of ethyl nitrocinnamates. Rec. trav. chim. 45, 695 and 700 (1926).
lo) Rec. trav. chim. 42, 164 (1922).
 925

distilled again. T h e second distillate was then made alkaline with

sodium hydroxide, the water evaporated and the residue heated
with strong sulphuric acid and ethyl alcohol when the smell of ethyl
acetate was noticed. It could not be proved whether the formation
of acetic acid takes place before or after pouring the reaction mixture
into iced water. Hence we have to represent this nitration by its
final equation :

b.
-
0 2 N . C,H,. CH = C H . C O . CH3 H O N 0 2 +
0 , N . C,H4. CrI = C H . NO,
Preparation of 3-nitrobenzalacetone
+ CH3COOH.
(3)OZN . C6H4.CH = C H . CO . CH3.
3-Nitrobenzalacetone had been prepared by Vorlander ' I ) who
used Baeyer's method for the preparation of 4-nitrobenzalacetone ').
This method was modified as follows:
T w o grams 3-nitrobenzaldehyde were dissolved in a mixture of
50 cc. acetone and 10 cc, water, the liquid cooled below 0' and
12 cc. of 1 per cent.aqueous sodium hydroxide solution allowed to
drop in slowly when some of the 3-nitrobenzaldehyde separated.
O n keeping the reaction mixture at room temperature for some days,
a dark oil separated. The liquid was neutralised with dilute hydro-
chloric acid, the acetone distilled off, the remaining oil dissolved in
300 cc. of boiling water with some decolorizing carbon and filtered
hot. This liquid o n cooling deposited a fairly large quantity of white
needles of m. p. 94'.
Analysis :
0.1832 g. gave 0.4186 g. CO, and 0.0772 g. H,O: C = 62.32 and H = 4.68 O/".
0 2 N .CoH, . CH = CH . CO . CH,,
(CI0H9O3N) requires C = 62.83, H = 4.71 '/,,.
Thus both the analysis and the m. p. showed that 3-nitrobenzal-
acetone had been obtained. Boiling the crude condensation product
with acetic anhydride is unnecessary Izj.

c. Nitration of 3-nitrobenzalacetone.
Three grams of 3-nitrobenzalacetone were dissolved in 20 cc. of
absolute nitric acid cooled in an ice-salt bath (time of addition
15 minutes), after which the light brown liquid was kept at Oo for
three hours and poured on to ice. T h e light yellow nitration product
weighed 1.8 g.. m. p. 85-103O. Recrystallised twice from alcohol,
pure w .3-dinitrostyrene separated, which was identified by its m. p.
and mixed m. p. Acetic acid was proved by L. Elion's method lo).

1') Ann. 294, 293 (1897).

I*) See notes 1 1 and 8. By omitting the boiling with acetic anhydride we hoped to
isolate the unknown ~[3-nitrophenyl]-,%hydroxy-ethylmethyl ketone.
XLVII 31
 926

Q 3. Action of absolute nitric acid on 3 :3’-dinitrochalkone and

4 :3‘-dinitrochalkone 13).
a. Preparation of 3 : 3‘-dinitrochalkone :
(3) O2N . CeH,. CH = CH .CO C6H4 . NO2 (3’)- -
This chalkone derivative was prepared according to the following
equation :
+
(3) OZN . C6H4. CHO (3)CH, . CO . CeH4NOZ *
NaOH

O,N . CeH4. CH = CH . CO . COH4. NO, + H2O.

3-Nitroacetophenone was prepared according to the directions given
by Rupe and his co-workers 14) viz. by nitrating acetophenone with
a mixture of sulphuric acid and nitric acid.
For the preparation of 3 : 3’-dinitrochalkone H. Rupe and D.
Wasserzug’s method 15) was modified as follows.
A mixture of 2.7 g. mol.) 3-nitrobenzaldehyde and 3 g. mol.)
3-nitroacetophenone was dissolved in 45 cc. 96 per cent. ethyl alcohol.
About 1 cc. of a dilute alcoholic solution of sodium hydroxide was
added to this liquid at room temperature le) and about ten minutes
later, a flesh coloured precipitate separated, which was filtered ; yield
3.8 g., m. p. 175--187O. The next day an additional quantity (0.5g.,
m. p. 175-182O) was obtained from the mother liquor, which had
been treated with another cc. of sodium hydroxide solution after
being filtered. The crude 3 :3’-dinitrochalkone was purified by one
crystallisation from acetic anhydride, m. p. 206O ”).
b. Nitration of 3 : 3’-dinitrochalkone.
T h e following compound was obtained on nitrating 3 :3’-dinitro-
chalkone
/-\c
\-/
NO,
= c-c-
n \-
0
-’> NO,
.
z 3 . 3’-trinitrochalkone.

bl. Action of absolute nitric acid on 3 :3’-dinitrochalkone.

3 : 3’-Dinitrochalkone (1 gr.) was dissolved in 10 CC. absolute nitric
acid cooled in a freezing mixture, during 20 minutes.
T h e yellow brown solution was then kept at Oo during two hours

13) Chalkone : &;

3

5 6
H

4
H 0
d
II
=C - C - b + .
3’

6 5 ’
See: Beilstein. Prager. Jacobson. Organische Chemie. Vol. VII. 478 (1925).
14) H. Rupe, D. Wasserzug and K. von Zembruski, Ber. 34, 3522 (1901). The
yield was about 50 per cent of the theoretical amount.
I b ) Ber. 34, 3527 (1901).
’8) This solution was obtained by dissolving 5 gr. NaOH in a mixture of 50 cc.
ethyl alcohol and 50 cc. water.
l 7 ) Rupe and Wasserzug give the m. p. as 210°.
 927

and poured on to ice. T h e yellow nitration product after being filtered

and dried melted a t 139O Is).
b2. Action of a mixture of absolute nitric acid and acetic acid
on 3 : 3'-dinitrochalkone Is).
3 : 3'-Dinitrochalkone (0.5 gr.) was dissolved in the course of 20
minutes in 5 cc. absolute nitric acid (temperature below Oo) and after
about an hour the liquid was diluted with 10 cc. acetic acid, then
kept at Oo for an hour longer and finally poured on to ice. The
m. p. of the crude nitration product was 140O.
b,. Action of a mixture of absolute nifric acid a n d acetic anhydride
on 3 : 3'-dinitrochalkone.
A gram of 3 : 3'-dinitrochalkone was added to a mixture of 10 cc.
nitric acid and 10 cc. acetic anhydride cooled in a freezing mixture,
during 20 minutes but some time elapsed before all the crystals of
3 : 3'-dinitrochalkone were dissolved. After about two hours (temp-
erature Oo) the liquid was poured on to ice and treated as the product
mentioned above. The m. p. was about 138'.

After being crystallised from acetic acid the nitration products from
b,, b, and b3 yielded the samesubstance of m. p, 152.5--154O, which
proved to be a . 3 : 3'-trinitrochalkone.
The mixed melting points of pure a . 3 : 3'-trinitrochalkone with
the crude products from nitrations bl, b, and b3 where higher then
140° therefore, these products were almost pure a . 3 : 3'-trinitro-
chalkone.
The purified nitration product was analysed.
Analpis :
0.1555 g. gave 0 3016 g. CO, and 0.0368 g. H,O: C = 52.90, H = 2.63"/,,.
0.1038 g. gave 11.4 rc. N, at 1 5 O and 748 mms.: N = 12.60°/,.
. .
O,N C,H4 . CH = C(N0,). CO C,H, .NO,(CI,H,O;N,) requires C = 52.48.
H = 2.63 and N = 12.25 O/".

lf') Great care has t o be taken that the crude nitration product is freed fromnitric
acid by means of washing with water or a very dilute soda solution. Small quantities
of nitric acid, remaining in the crude product, cause a partial decomposition and a
lower yield of the pure x . 3 : 3'-trinitrochalkone.

- >::%
lo) The experiments b, and b, were executed in the hope of obtaining an aretyl
derivative of a nitro-alcohol in the following way:

>.= c<+ HONO,

OH NO,
\C -- C/
/I I\
+ CH,COOH w+ \C------
/I
c<
I
+ H20.
OH NO, 0-COCH, NO,
See the investigations on the nitration of anthracene with a mixture of nitric acid
and acetic acid: Meisenheimer and Conrade, Ann. 330. 158 (1903).
 928

From these figures it follows that one nitro group has been
introduced into 3 :3’-dinitrochalkone. T h e position of the third nitro
group was proved in the following way:
About 0.3 g. of the trinitrochalkone was dissolved in 25 cc. methyl
alcohol and a few cc. of a 20 per cent. methyl alcoholic potash solution
were added. O n diluting the brown liquid with 50 cc. water a clear
solution was obtained. This was treated with bromine water when
a white precipitate separated. T h e substance was filtered off, dried
(m. p. 145O) and was proved to be almost pure:
/NO2
<-%-c,
N T ;: OCH,

1, : 12-dibromo-3 : 12-dinitro-11-methoxy-l-ethylbenzene
,O), for a
mixed m. p. with this substance ,’) gave no depression. O n acidifying
the alkaline solution, m-nitrobenzoic acid was obtained. This reaction
proves the position of the third nitro group in trinitrochalkone.
T h e reactions may be represented as :
(3)0,N.C,H,. CH = C(N0,). CO C,H,. NO, (3’) . +
+ 2 KOH f CH,OH B++
0 0
H NA II
* (3)0,N.C,H,. C-C<H‘OK
I
-I- KO-C-C,H, . NO, (3).
OCH,
0
H NA
02N.C,H4. C-C4 H ‘OK + KOH + 2 Br, w+

OCH,
H /NO2
BY-, 0,N.C,H, . C-C- Br + 2 KBr + H,O.
I \Br
OCH,
a . 3 : 3’-Trinitrochalkone is very readily soluble in boiling acetic
acid, readily soluble in acetone, benzene and chloroform, slightly
soluble in carbon tetrachloride whilst it is insoluble in water and
ligroin. Recrystallisation from different solvents furnished brittle, pale
yellow crystals, m. p. 152.5 -154O.
a . 3 :3’-Trinitrochalkone is not altered by aqueous potash (1 :4)
at room temperature 22).
1’ 12
%’) ir6;\C
\ 3 2
-C Ethylbenzene. see : Beilstein, Prager, Jacobson, Organische
Chemie, Vol. V, 351 (1922).
*l) Prepared from ( , I . 3-dinitrostyrene with methyl alcohol, sodium hydroxide and
bromine water according P. Friedlander and F. Lazarus, Ann. 229, 237 (1 885) : m. p+
146-147O.
In a future publication the properties of a . 3 : 3’-trinitrochaikone and its decom-
position products will be described in detail.
 929

When crystallised from methyl or ethyl alcohol, o! . 3 : 3'-trinitro-

chalkone forms alcohol addition products, which are described below.
/3- Nitro- y-rnethoxy-a-keto-a . y-di[3-nitrophen yl]-propa ne.

( ~ > + - -I GII
No2 OCH, H 0
-'>
\-
NO,.
When pure or crude u . 3 : 3'-trinitrochalkone is recrystallised from
methyl alcohol, colourless crystals separate, m. p. 128O.5 23).
Analysis :
0.1768 g. gave 0.3308 g. CO, and 0.058 g. H,O: C = 51.02, H = 3.65O/,,.
0.1186 g. gave 11.8 cc. NP at 16O and 760 mms.: N = 11.54 "/,,.
OzN . CeH,. CH = C(N0,). CO . CBH,.NO,(C,,H,O;N,) requires C = 52.48,
H = 2.63 and N = 12.25O/".
+
C16HpO;N, CH30H(C16H1308N3) requires C = 51.2, H = 3.47 and N = 11.2
Hence one molecule of methyl added becomes attached to the
x . 3 :3'-trinitrochalkone.
The addition product is not altered by
recrystallisation from benzene or ethyl alcohol, thus methyl alcohol
of crystallisation is not present, but a real compound must have
been formed. The substance is readily soluble in various organic
solvents except ligroin and carbon tetrachloride. It is insoluble in
water. T h e constitution of the addition product was proved in the
following way :
About 0.1 g. of the finely powdered addition compound was shaken
with 4 cc. of 25 per cent. aqueous solution of caustic potash at room
temperature. The undissolved substance was filtered off, the yellow
liquid diluted with water and treated with bromine water until a
white precipitate separated. This was filtered from the alkaline
solution and proved to be
__ /NO,
c_/ ,
\E---C--Br
NO, OCH, \Br
(Identification by its m. p. and mixed m. p., see preceding page).

By the formation of this compound: l2 : 12-dibromo-3 : 12-dinitro-

1 '-methoxy-1-ethyl-benzene,the position both of the nitro groups and
the methoxy group in the methyl alcohol addition product of a . 3: 3'-
trinitrochalkone has been proved. The formula must be represented
a s mentioned 24).
*:I) This compound decomposes a few degrees above the m. p.
On heating very slowly the substance melted a few degrees below the m. p. mentioned.
2') Alcohol addition to derivatives of nitroethylene has been noticed previously :
With alkyl-z-nitro-5-[nitrophenyl]acrylates:O,N .G H , . CH = C(N0,)COOR.
P. Friedlander and L. Lazarus, Ann. 229. 210 (1885) and 234 (1885).
.
2nd. With compounds of the following type: 0 , N . C H , CH = C(NO,)Br, 8.
Flurscheim. J. prakt. Chem. 66, 16-27 (1902).
.
3rd. With z-nitrochalkone: CnH5 CH = C(N0.J . CO .C,H, (only ethyl alcohol), H.
Wieland. Ann. 328, 240-241 (1903).
 930

p- Nitro-y-ethoxy-a-keto-ay-di[3-nitrophenyl]-propane.
/-\c+-c-<-H NO,
\-/ I I I/
NO, OC,H,H o NO?.
When a sample of the crude or pure a . 3 : 3/-trinitrochalkone is
boiled with ethyl alcohol for 5 minutes, fine, colourless crystals
separate on cooling with m. p. 120.5- 121O 23).
This m. p. is not altered by recrystallisation from benzene or
methyl alcohol. The solubility of this compound agrees with that of
the corresponding methoxy derivative.
Analysis :
0.1806 g. gave 0.3466 g. CO, and 0.0644 g. HzO: C = 52.34, H = 3.96°/0.
0.1118 g . gave 10.4 cc. N, at 13O and 763.3 mms.: N = 10.99 /',.
OzN . G H , . CH = CtNO,). CO .C8H,. NO, (C15HB0,N,) requires C = 52.48.
H = 2.63 and N = 12.25 "1..
C15H907N,+~H60H(C17H160~N,) requires C = 52.44. H = 3.86 and
N = 10.80°/0.
Hence, ethyl alcohol becomes attached to a . 3 : 3/-trinitrochalkone
in the same wayas methyl alcohol. The structure of the compound
was proved in the same way as mentioned above for the corres-
ponding methoxy derivative. With caustic potash and bromine water
the following compound was obtained
/NO?
L-
-\H
NO,
C-Br
O C H ~ \Br
m. p. 97O 25).
c. Preparation of 4 : 3'-dinitrochalkone :
(4) O,N . CeH4 . CH = CH . CO . CeH4. NO2 (3').
So far 4 : 3'-dinitrochalkone has not been described in literature.
A mixture of 2.7 g. mol.)4-nitrobenzaldehyde and 3 g. mol.)
3-nitroacetophenone was dissolved in 50 cc. of 96 per cent. alcohol.
Into this liquid 1 cc. of a dilute aqueous alcoholic solution of sodium
hydroxide l e ) was added drop by drop at roomtemperature.
After 15 minutes a yellow substance separated. This was filtered
next day: yield 2.69 g., m. p. about 140O. After being twice recryst-
allised from a rather large quantity of acetic anhydride, pale yellow
needles were obtained, m. p. 205O.5. Pyridine may be used instead
of acetic anhydride. T h e pure 4 : 3'-dinitrochalkone was analysed.
Analysis :
0.1338 g. gave 10.9 cc. Ne at 17O and 771.6 mms.: N = 9.55 "0.
. . .
0 , N . C6H4 CH = CH CO .GH, NO2 (C15H1005Nz) requires N = 9.40 "0.
4 : 3'-Dinitrochalkone dissolves sparingly in the usual organic
solvents, except, acetic anhydride, pyridine and acetic acid.
*)) Identification by mixed m. p. with the same compound (m. p. 9 8 O ) prepared from
.3-dinitrostyrene, ethyl alcohol. sodium hydroxide and bromine water according
I,)

P. Friedlander and M. Lazarus, Ann. 229. 237-238 (1885).

 93 I

d. Nitration of 4 :3’-dinitrochalkone.
T h e following compound was obtained on nitrating 4 : 3’-dinitro-
chalkone
H NO,
NO,/----\C = C--C-/----
\--../ 0
II \-
NO%.
)
9. . 4 : 3/-frinitrochalkone.

A gram of 4:3‘-dinitrochalkone was dissolved in the course of

10 minutes in 10 cc. of absolute nitric acid cooled below Oo. T h e
liquid was kept a t Oo for an hour and then poured into iced water;
the white nitration product was immediately filtered, freed from
nitric acid by means of washing with water, dried between hardened
filter paper and finally in a dessiccator over sulphuric acid. T h e
crude nitration product (m. p. about 115O) was analysed after
standing a few days.
Analysis;
0.1724 g. gave 0.3332 4. CO, and 0.0500 g. H,O; C = 52.71, H = 3.22 ‘/o.
0.0828 g. gave 8.2 cc. N, at 17O and 762.2 mms.; N = 11.48 o/h
. .
0 , N . GH,. CH = C(N0,). CO C,H, NO, (CISHOOiN3)requires C = 52.48,
H = 2.63 and N = 12.25 o/io.
Hence the composition of the crude nitration product does almost
agree with that of trinitrochalkone.
On crystallising the nitration product from acetic acid, yellow
needles, m. p. 1 3 5 O , were obtained.
Analysis :
0.1306 g. gave 13.9 cc. N2 at 18O and 770.7 mms.: N = 12.41 o/o.
CISH90;N, requires N = 12.25 O i 0 .
The properties (solubility) of a . 4 :3/-trinitrochalkone agree with
those of x . 3 : 3’-trinitrochalkone.
A well crystallised addition product of a . 4 : 3/-trinitrochalkone
and methyl alcohol was isolated (see later).
O n boiling a . 4 : 3/-trinitrochalkone with ethyl alcohol, on oily
substance separated, which did not crystallise.
The position of the third nitro group in a . 4 : 3’-trinitrochalkone
was proved by the reaction of its methyl alcohol addition product
with potassium hydroxide and bromine water.

yllpropane.
~-Nitro-y-me~hoxy-~-keto-a[3-nitrophenyl]-:~-[4-ni~rophen
H NO4
-\
\-/
O,N/-\C- I 7 -
OCH,H 0
Y - L NO,.
When pure or crude c( . 4 : 3’-trinitrochalkone is crystallised from
methyl alcohol colourless crystals are obtained, m. p. 122O.5 (decom-
position) 23). The m. p. of this compound is not altered by recrystalli-
sation from benzene.
 932

Analysis :
0.1280 g. gave 12.5 cc. NP at 17O and 764.2 mms.: N = 11.33 O/O.
0 , N . GH, . CH(OCH3)C(N0,).CO . C,H, .NO, (GaHIsOsN,) requires
N = 1 1.2 “/e.
The solubility agrees with that of the corrresponding derivative
of a . 3 : 3’-trinitrochalkone.
In the same way as the corresponding derivatives of b: . 3 : 3’-
trinitrochalkone, this substance was converted into
- H /NO2
02N( ->---C-Br
\Br
OCH,
which melted a t 159-160O after being crystallised from benzene
and which was identified by its mixed m. p. with the substance
obtained from w .4-dinitrostyrene, caustic potash, methyl alcohol
and bromine water 2e).

Summary.
Continuing previous work on the reaction between absolute nitric
acid and nitrocinnamic acids and nitrocinnamates the action of an
excess of absolute nitric acid at Oo upon other styrene derivatives viz. :
a. 4 : 4’-Dinitro-dibenzalacetoneand 3 .3’-dinitro-dibenzalacetone.
b. 4-Nitrobenzalacetone and 3-nitrobenzalacetone.
c. 3 :3’-Dinitrochalkone and 4 : 3’-dinitrochalkone
has been investigated.
O n nitrating 4 : 4’-dinitrodibenzalacetone and 3 : 3’-dinitrodibenzal-
acetone nitration products were obtained, which formed carbon
dioxide and w .4-dinitrostyrene (w .3-dinitrostyrene) with water.
From 4-nitrobenzalacetone (3-nitrobenzalacetone), w .4-dinitro-
styrene (w .3-dinitrostyrene) and acetic acid were obtained by nitration.
3 : 3’-Dinitrochalkone 27) and 4 : 3’-dinitrochalkone were converted
by absolute nitric acid into b: . 3 : 3’-trinitrochalkone and a . 4 : 3’-
trinitrochalkone. On crystallisation from methyl alcohol or ethyl
alcohol b: . 3 : 3’-trinitrochalkone forms alcohol addition products, but
only the methyl alcohol addition product of a . 4 : 3-trinitrochalkone
could be isolated.
T h e structure of these alcohol addition products was proved.
In conclusion, it has been found that the action of absolutenitric
acid on the three compounds with an ethylenic linkage must be
represented by equation IV in the introduction.
This research has increased our knowledge of the phenomenon

Thiele and Haeckel, Ann. 325, 16 (1902).

--(x>
’0)

1:) <I% H H
= -f chalkone.
0
 933

of group replacement "). Summing up the facts found in this and in

the earlier publication 2Q) it may be concluded that in substances of
the tvoe

the action of an excess of nitric acid at 0' occurs in such a way

that the group R is replaced by NO, if R is represented by

If on the other hand R is a derivative of the above,

0 3')
c'C,H,. NO,
no replacement of these groups occurs, the hydrogen atom on the
x-carbon atom being replaced by NO,.
This investigation is being continued.
T h e author wishes to express his thanks to Prof. J. J. Blanksma
of Leiden for the interest showed in this research and for the
hospitality afforded him during the Easter vacation in the laboratory
for organic chemistry of the University.

This investigation was made possible by means of a grant from

the van 't Hoff Fund and the author takes this opportunity of
expressing his indebtedness to the directors of the Fund.

D e v e n t e r (Holland), College of Tropical Agriculture, Mai 1928.

( R e p le 25 mai 1928).

OR) Comprehensive literature M. P. de Lange, Dissertation Leiden. 1922 : Rec. trav.

chim. 45, 19 (1926). See also: Abderhalden, Handbuch der biologischen Arbeits-
methoden, Lief. 234 : E. Maschmann, Nitrieren (1927).
9 Rec. trav. chim. 45. 674 (1926).
3 0 ) Only one case of replacement of the acetyl group by NO, hasbeennotedwith
a benzene derivative. See L. Elion. Rec. trav. chim. 42, 164 (1923).
In this connection a most remarkable research has been carried out by H. Fischer
and W. Zerweck. Ber. 55. 1949-1955 (1922).
These investigators on nitrating pyrrol derivatives found that -COOH. -COCH3
and -C@ groups were replaced by NO?, but the C O O G H 5 group was not.
\H
31) L. Elion (Rec. trav. chim. f3, 867 (1924)) gave an example of replacement of
a benzoyl group.