Org. Synth. 1955, 35, 32
DOI: 10.15227/orgsyn.035.0032
1-(p-CHLOROPHENYL)-3-PHENYL-2-PROPANONE
[2-Propanone, 1-(p-chlorophenyl)-3-phenyl-]
Submitted by Stephen B. Coan and Ernest I. Becker
1.
Checked by Charles C. Price and G. Venkat Rao.
1. Procedure
In a
250-ml. three-necked flask equipped with a stirrer and a condenser are placed
75 ml. of 60% sulfuric acid and
25 g. (0.093 mole) of α-(4-chlorophenyl)-γ-phenylacetoacetonitrile (p. 174). While being stirred, the mixture is heated at reflux until the evolution of
carbon dioxide ceases
(Note 1) and
(Note 2). The mixture is cooled, poured into 200 ml. of ice water, and extracted three times with
150-ml. portions of ether. The
ether solution is washed once with 50 ml. of water, twice with
100-ml. portions of 10% sodium hydroxide solution, and then with 50 ml. of water. After drying over
sodium sulfate and filtering, the
ether is distilled on a
steam bath, affording
15–17 g. (
66–75%) of
1-(p-chlorophenyl)-3-phenyl-2-propanone, m.p.
34.5–35.5°. Recrystallization from
160 ml. of petroleum ether (b.p.
40–60°) gives
12–13 g. (
53–57%) of product, m.p.
35.9–36.5° (Note 3).
2. Notes
1.
The hydrolysis and decarboxylation of the nitrile require from 18 to 24 hours.
2.
The evolution of
carbon dioxide is conveniently observed by passing the effluent gases through a saturated solution of
barium hydroxide.
3.
The submitters report that a similar procedure has been used in the preparation of other monosubstituted dibenzyl ketones from
α-phenyl-γ-(4-substituted phenyl)acetoacetonitriles.
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Product
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Yield, %
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M.P.
|
|
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1,3-Diphenyl-2-propanone
|
65–71
|
34.2–34.5°
|
|
1-(p-Tolyl)-3-phenyl-2-propanone
|
66
|
30.8–31.2°
|
|
1-(p-Bromophenyl)-3-phenyl-2-propanone
|
50
|
53.8–54.2°
|
|
1-(p-Fluorophenyl)-3-phenyl-2-propanone
|
50
|
36.0–36.5°
|
|
1-(p-Methylthiophenyl)-3-phenyl-2-propanone
|
40
|
43.9–44.2°
|
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1-(p-Methoxyphenyl)-3-phenyl-2-propanonea
|
19
|
46.6–47.4°
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a It is necessary to employ 5 ml. of glacial acetic acid and 5 ml. of 20% aqueous hydrochloric acid, instead of the sulfuric acid, per gram of ketonitrile as reaction solvent in order to obtain the desired product.
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3. Discussion
This method of preparation of
1-(p-chlorophenyl)-3-phenyl-2-propanone has been reported by Coan and Becker.
2 The method utilized is a modification of that described for the formation of
1,3-diphenyl-2-propanone from
α,γ-diphenylacetoacetonitrile.
3,4
Appendix
Chemical Abstracts Nomenclature (Collective Index Number);
(Registry Number)
petroleum ether
α-phenyl-γ-(4-substituted phenyl)acetoacetonitriles
sulfuric acid (7664-93-9)
hydrochloric acid (7647-01-0)
acetic acid (64-19-7)
ether (60-29-7)
sodium hydroxide (1310-73-2)
sodium sulfate (7757-82-6)
carbon dioxide (124-38-9)
barium hydroxide (17194-00-2)
1,3-Diphenyl-2-propanone (102-04-5)
α-(4-CHLOROPHENYL)-γ-PHENYLACETOACETONITRILE (35741-47-0)
α,γ-Diphenylacetoacetonitrile
1-(p-CHLOROPHENYL)-3-PHENYL-2-PROPANONE,
2-Propanone, 1-(p-chlorophenyl)-3-phenyl- (35730-03-1)
1-(p-Tolyl)-3-phenyl-2-propanone
1-(p-Bromophenyl)-3-phenyl-2-propanone
1-(p-Fluorophenyl)-3-phenyl-2-propanone
1-(p-Methylthiophenyl)-3-phenyl-2-propanone
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