Org. Synth. 1953, 33, 62
DOI: 10.15227/orgsyn.033.0062
m-NITROSTYRENE
[Styrene, m-nitro-]
Submitted by Richard H. Wiley and Newton R. Smith
1.
Checked by Richard T. Arnold, William E. Parham, and Darwin D. Davis.
1. Procedure
A. m-Nitrocinnamic acid. In a 1-l. round-bottomed flask fitted with a reflux condenser are placed 151 g. (1 mole) of m-nitrobenzaldehyde (Note 1), 115 g. (1.1 moles) of malonic acid, 250 ml. of 95% ethanol, and 25 ml. of pyridine. The mixture is heated on a steam bath under gentle reflux for 6–8 hours and cooled. The large masses of crystals are broken up with a spatula, and the reaction mixture is cooled in an ice bath. The solid is collected on a Büchner funnel, and the residue is washed with 100 ml. of cold ethanol and then with two 100-ml. portions of ether. The crude m-nitrocinnamic acid is suspended in 300 ml. of ethanol and digested on a steam plate for 2–3 hours. The mixture is cooled and filtered, and the solid is air-dried. The product, 144–155 g. (75–80%), is a light-yellow solid and melts at 200–201° (Note 2).
B. m-Nitrostyrene. In a 250-ml. two-necked flask equipped with a 250° thermometer and an air condenser are placed 30 g. (0.155 mole) of m-nitrocinnamic acid, 2 g. of copper powder, and 60 ml. of dry quinoline (Note 3). The flask is heated with a Bunsen burner to 185–195°, during which time a steady stream of carbon dioxide is evolved. After 2–3 hours (Note 4), the reaction mixture is cooled and poured into a mixture of 75 ml. of concentrated hydrochloric acid and 175 g. of ice. The m-nitrostyrene is isolated by steam distillation, approximately 1 l. of distillate being collected. The aqueous distillate is extracted with three 50-ml. portions of chloroform, which are combined and dried over anhydrous sodium sulfate. A 50-ml. Claisen flask, equipped with a dropping funnel, is heated on a steam bath, and the filtered chloroform extract is added dropwise. Heating is continued until all the solvent has been removed. The residue is then distilled at 3–5 mm. pressure. Following a small fore-run of less than 1 g. (Note 5), the m-nitrostyrene distils as a yellow liquid. The yield is 13–14 g. (56–60%), b.p. 90–96°/3.5 mm., nD20 1.5836, nD27 1.5800–1.5802 (Note 6) and (Note 7).
2. Notes
1.
The checkers used technical
m-nitrobenzaldehyde melting at
53–56°.2.
This procedure has been used by the submitters and others to prepare the following cinnamic acids from substituted benzaldehydes:
o-nitrocinnamic acid (
70%),
2 p-nitrocinnamic acid (
77%),
2 m-cyanocinnamic acid (
71%),
3 o-chlorocinnamic acid (
82%),
4 m-chlorocinnamic acid (
53%),
4 p-chlorocinnamic acid (
73%),
4 2,4-dichlorocinnamic acid (
70%),
4 3,4-dichlorocinnamic acid (
81%),
4 m-bromocinnamic acid (
31%),
4 p-methoxycinnamic acid (
60%),
4 and
3,4-dimethoxycinnamic acid (
77%).
4The method constitutes a simple preparation of ethanol-insoluble cinnamic acids, of a high degree of purity when compared with the Perkin reaction
5 or the usual procedure for the Doebner reaction
(p. 327), which uses a large excess of
pyridine. A useful modification of this reaction is to warm the reactants on a steam plate in the absence of alcohol.
6,73.
Quinoline that has been purified by steam distillation of an acid solution should be used. Crude
quinoline sometimes contains non-basic, high-boiling impurities such as
nitrobenzene, which make the purification of
m-nitrostyrene more difficult.
4.
The checkers obtained a lower yield (
9–11 g.) when a 2-hour heating period was used. The reaction must be carried out at 195° until the evolution of
carbon dioxide has practically ceased (usually 2.75 hours). The checkers used
Mallinckrodt copper powder.
5.
The checkers obtained essentially no fore-run and only trace amounts of solid residue. The refractive index of the first 200 mg. was
nD27 1.5800; of the center fractions,
nD27 1.5802; and of the last 700 mg.,
nD27 1.5800.
6.
This procedure has been used in the preparation of other nitrostyrenes in the following yields:
o-nitrostyrene (
40%),
2 p-nitrostyrene (
41%),
2 and
3-nitro-4-hydroxystyrene (
60%).
2 A better procedure for more volatile styrenes involves simultaneous decarboxylation and codistillation with
quinoline from the reaction flask. This method has been used to prepare the following styrenes:
o-chlorostyrene (
50%),
4 m-chlorostyrene (
65%),
4 p-chlorostyrene (
51%),
4 m-bromostyrene (
47%),
4 o-methoxystyrene (
40%),
4 p-methoxystyrene (
76%),
4 m-cyanostyrene (
51%),
3 and
p-formylstyrene (
52%).
87.
Larger runs usually give smaller percentage yields.
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3. Discussion
m-Nitrocinnamic acid has been prepared from
m-nitrobenzaldehyde with
sodium acetate and
acetic anhydride,
5 and by the condensation of
m-nitrobenzaldehyde with
malonic acid in the presence of bases.
7,9
m-Nitrostyrene has been prepared by boiling the
sodium salt of β-bromo-β-(m-nitrophenyl) propionic acid;
10 by the dehydration of
m-nitrophenylmethylcarbinol with
phosphorus pentoxide,
11 potassium bisulfate,
12 or
phosphoric acid13; by the decarboxylation of
m-nitrocinnamic acid;
14 and by the condensation of
m-nitrobenzaldehyde with
acetic anhydride over
bentonite at high temperatures.
15
Appendix
Chemical Abstracts Nomenclature (Collective Index Number);
(Registry Number)
bentonite
ethanol (64-17-5)
hydrochloric acid (7647-01-0)
ether (60-29-7)
acetic anhydride (108-24-7)
sodium acetate (127-09-3)
chloroform (67-66-3)
sodium sulfate (7757-82-6)
carbon dioxide (124-38-9)
potassium bisulfate (7646-93-7)
copper powder (7440-50-8)
pyridine (110-86-1)
phosphoric acid (7664-38-2)
Nitrobenzene (98-95-3)
Quinoline (91-22-5)
Malonic acid (141-82-2)
2,4-dichlorocinnamic acid
3,4-dichlorocinnamic acid
3,4-dimethoxycinnamic acid
3-nitro-4-hydroxystyrene
phosphorus pentoxide (1314-56-3)
m-Nitrobenzaldehyde (99-61-6)
m-Nitrocinnamic acid (555-68-0)
p-nitrocinnamic acid (619-89-6)
m-Chlorostyrene (2039-85-2)
o-Chlorostyrene (2039-87-4)
p-Chlorostyrene (1073-67-2)
m-Bromostyrene (2039-86-3)
o-nitrocinnamic acid
m-Nitrostyrene,
Styrene, m-nitro- (586-39-0)
m-cyanocinnamic acid
o-chlorocinnamic acid (3752-25-8)
m-chlorocinnamic acid (1866-38-2)
p-chlorocinnamic acid (1615-02-7)
m-bromocinnamic acid (32862-97-8)
p-methoxycinnamic acid
o-nitrostyrene
p-nitrostyrene (100-13-0)
o-methoxystyrene (612-15-7)
p-methoxystyrene (637-69-4)
m-cyanostyrene
p-formylstyrene (1791-26-0)
m-nitrophenylmethylcarbinol (52022-77-2)
sodium salt of β-bromo-β-(m-nitrophenyl) propionic acid
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