[CONTRIBUTION FROM
THE
DEPARTMENT OF ORGANIC CHEMISTRY OF
THE
HEBREWUNIVERSITY J
The Synthesis of Some Esters and Amides of &p-Diarylacrylic Acids SAUL PATAI
AND
RAPHAEL IKAN
Received June
4 , 1966
The reaction of I,1-diarylethylenes with oxalyl chloride giving p,p-diarylacrylyl chlorides, has been utilized for the preparation of several aliphatic and aromatic esters of p,p-diarylacrylic acids as well as for the preparation of some N-alkyland N-aryl-p,,%diarylacrylamides.
H20 + i
Ar2C=CH2
+ (COC1)2 +Ar2C=CHCOCl-l--I1
I
This paper reports the preparation of some aliphatic and aromatic esters and N-substituted amides of @,p-diphenyl-, P,@-di-(p-tolyl)-,and p,p-di(p-anisy1)-acrylic acid. The syntheses are convenient and easy to carry out. In the standard procedure as described in the experimental section, the yields were generally not more than 50% of the theoretical (calculated on basis of the ethylene), but by using a larger excess of oxalyl chloride the yields could be improved considerably.
ROH I
R"l
+
Ar&=CHCOOH
111
ArtC=CHCOOR
IV
V
Ar2C=CHCONHR
&poi-( p-tolyZ)acrylyl chloride was obtained in the same manner from 1,l-di-( p-toly1)ethylene and oxalyl chloride but with only 45 min. heating on the water-bath; for the preparation of p,p-di-(p-anisyl)acryLyl chloride from 1,l-di(p-anisy1)ethylene and oxalyl chloride only 25 minutes of heating on the water-bath was necessary. In all three cases the yields diminished if the mixtures were heated for longer periods than stated. Preparation of p,p-diarylacrylic esters (IV). The ether solution of the p,p-diarylacrylyl chloride obtained from 0.01 mole of the corresponding ethylene, was added slowly to a solution of 0.01 mole of the alcohol or the phenol in 5-10
TABLE I ALXYLESTERS OF ~,~-DIPHENYLACRYLIC ACID ( C&)ZC=CHCOOR
R
B.P.1 OC./2 mm.
Yield, nag
%
Formula
Ethyl" Isopropyl n-Pent yl n-Heptyl n-Octyl
73-74 122 145 146-147 153
1.5973 1,5886 1,5770 1,5620 1.5466
65 54 49 43 41
C1,HI6O2 CisH~sOz CzoHzz02 C22H2602 CzrHzsOt
A4nalysis Carbon Hydrogen Calc'd Found Calc'd Found 80.9 81.2 81.6 81.9 82.1
80.6 81.6 82.4 82.3 82.6
6.4 6.8 7.5 8.1 8.4
6.1 6.7 7.0 7.8 8.3
a This compound has been prepared before by condensation of benzophenone with ethyl bromoacetate and subsequent dehydration. Rupe and Busolt, Ber., 40, 4537 (1907); Schlenk and Bergmann, Ann., 463,237 (1928).
ml. of dry ether. After about two hours the solution was refluxed on a water-bath for 15 minutes and left overnight. Preparation of p,P-diphenylacrylyl chloride. TO2 ml. (0.01 After removal of the solvent (and in the cases where phenols mole) of 1,l-diphenylethylene in a 50 ml. round-bottomed were used, after removal of the excess of the phenol by flask fitted by means of a ground-glass joint with a reflux washing with 5% sodium hydroxide solution) the products sondenser with a drying-tube, there was added 2 ml. of were purified either by distillation or by crystallization. pure oxalyl chloride. After the subsidence of the first strongly (Tables I-IV). exothermic reaction (rapid evolution of HC1) the mixture Preparation of b,p-diarylacrylyl amides. The ether solution of the p,p-diarylacrylyl chloride obtained from 0.01 mole of (1) Kharasch, Kane, and Brown, J. Am. Chem. SOC., 64, the ethylene was added dropwise with stirring in the course of 15 minutes to an ether solution of 0.02 mole of the amine 333 (1942). (2) Bergmann, Weizmann, Dimant, Patai, and Szmus- (RNH, or ArNHz) in ether, or, in the case of unsubstituted or N-methyl amides, dry ammonia or methylamine was kowicz, J. Am. Chem. Soe., 70, 1612 (1948). (3) Weizmann, Patai, Dimant, and Bergmann, J. Am. bubbled through the acrylyl chloride solution until no more Drecipitation took place. The mixtiire was refluxed for one Chem. SOC., 71, 2315 (1949). hour on a water-bath and then left overnight. After filtra(4) Micro-analyses by Drs. Weiler and Strauss, Oxford. EXPERIMENTAL4
1379
1380
VOL.
PdTAI AND IKAN
21
TABLE I1 ARYL
XI.p., Ar
“C.
ESTERS OF BJ-~IPHENYLACRYLICACID (C6Hs)2C=CHCOOAr Appearance
Yield,
Needles Rhombic plates Needles Pink need 1es Hexagonal plates Ne ed 1es
52 40
C31Hi&Z CnH1g02
83 9 84 1
84 1 84 1
5 4 5 8
53 5 7
56 57
C22H1802 C2ZHig02
84 1 84 1
83 9 83 8
5 8 58
5 7 5 5
56
CZ1H15C102 i 5 3
75 2
4 5
4 1
66
CziHi4Clp02
68.3
67.9
3.8
3.5
Grey needles
35
C21HIbNO4
73.0
73.2
4.4
4.2
Rhombic plates Yeedles Seedles
44
C27H2002
86.2
85.9
5.4
5.5
74 45
Cz~H1802 85.7 85.6 CZSHlsBrz025 9 . 1 58.8
5.2 3.2
5.2 3.1
Phenyl O-Tolyl
121 82
Ethanol Ethanol
m-Tolyl P-Tolyl
96 5 111
Ethanol Ethanol
p-Chlorophen yl
112
Ethanol
2,4Dichlorophenyl p-Nitrophenyl
146
p-Biphen ylyl
170
2-Naphthyl 1,6-Dibromo-2naphthyl
140 186
Methanol
89.5
Benzenepet. ether Benzene Ethanol Dioxanepet. ether
.ARYL
Ar
M.p., “C.
Yield,
Xeedles Needles Needles Pink needles Pink needles Needles
37 31 35 39
C23H2o02 C~~HZZOZ C23H1gC102 C23Hi8C1202
841 842 76 1 69 5
844 843 76 2 69 4
6 6 5 4
1 5 3 6
6 2 6 8 5 0 4 8
33
C2iH?OBr2OZ 60 5
60 6
38
37
31
C Z O H ~ ~ O ~8 6 1
860
6 0
6 0
Seedles
64
C27H2202
85.7
5.9
5.7
157
2-Naphthyl
135
BenzeneEthanol Benzenepet. ether Ethanol
ARYL ESTERSOF
OC.
N or Halogen Calc’d Found
C1, 10 5
11.1
N, 4 . 1
4.1
Br, 31.5
32.0
Analyses Carbon Hydrogen Halogen Calc’d Found Calc’d Found Calc’d Found
Appearance
Ethanol Afethanol Ethanol Methanol
Ar
Formula
Recryst. Solvf~nt
ST 102 98 93
.zl.p.,
5G
TABLE 111 ESTERS OF ~,@-DI-(P-TOLYL-)ACRYLIC ACID ( ~ - C H J C ~ H ~ ) ~ C = C H C O O A ~
Phenyl P-Tolyl p-Chlorophenyl 2,4-Dichlorophenyl 1,6-Dibromo2-naphthyl p-Biphenylyl
160
Analyses Carbon Hydrogen Calc’d Found Calc’d Found
Recryst. Solver1t
Recryst. Solvent
Phenyl
120
Ethanol
p-Tolvl p-Chlorophenyl
104 101
Methanol Ethanol
p-Biphenylyl
151
2-Naphthyl
154
BenzeneLigroin Ethanol
yo
Formula
85.7
29 8
29 7
TABLE IV ~,~-DI-P-ANISYLACRYLIC ACID (CH~OCGH1)2C=CHCOOAr Analyses Carbon Hydrogen Halogen Calc’d Found Calc’d Found Calc’d Found
Appearance
Yield,
Dark grey powder Needles Grey needles Needles
34
CzaH2004
76.7
76.8
5.6
5.7
34
32
Cp4HZ2O4 CzsHigC104
77.0 70 0
77.4 70.3
5.9 4.8
6.2 4.6
36
C29H2401
79.8
79.6
5.5
5.6
Needles
39
C27H2204
79.0
79.4
5.4
5.3
70
Formilla
9.0
8.7
DECEMBER
1956
ESTERS AND AMIDES OF
0, P-DIARYLACRYLICACIDS
1381
TABLE V AMIDESOF @,@-DIPHENYLACRYLIC ACID (C6H5)zC=CHCONHR M.P.,
"C.
Recryst. Solvent
H
120
Dil. ethanol
Methyl
111
Dil. ethanol
80
Dil. ethanol
R
Ethyl Phenyl O-Tolyl m-To1y 1
130 136 141
Methanol Methanol Methanol
p-Tolyl 3-Nitrophenyl 2-Methyl-4nitrophenyl 1-Naphthyl
157 187 190
Methanol Ethanol Ethanol
164
Ethanol
2-Naphthyl
136
Methanol
Appear- Yield, ance 70 Yellow needles Orange needles Orange needles Needles Needles Yellow needles Cubes Needles Grey needles Yellow needles Xeedles
Formula
Analyses Carbon Hydrogen Nitrogen Calc'd Found Calc'd Found Calc'd Found
74
C15HlaN0
80.7
80.3
5.9
5.6
50
CIBHI~NO 81.0
81.9
6.4
6.5
36
C I ~ H I ~ N O 81.3
81.6
6.8
6.8
57 47 45
CZlHI7T\rTO C22H19NO CZZHIgNO
84.3 84.4 84.4
84.3 84.3 84.5
5.7 6.1 6.1
54 41 61
C22HI9NO C21H16S203 C2zHigN203
84.4 73.3 73.7
84.3 73.1 73.6
74
CzSH19NO
85.9
49
C25H191\j0
85.9
6.3
6.1
5.6 6.1 6.2
4.7 4.5 4.5
4.6 4.6 4.7
6.1 4.7 5.1
6.3 4.7 5.1
4.5 8.1 7.8
4.7 8.2 7.9
85.9
5.5
5.7
4.0
4.0
86.0
5.5
5.4
4.0
4.2
TABLE VI AMIDES OF ~.@-DI-( p-TOLYL)ACRYLIC ACID (~-CH$~H~)ZC=CHCONHR
R
Recryst. Solvent
Rl.p., "C.
H
150
Ethanol
Methyl
185
Dil. ethanol
Phenyl m-Tolyl P-Tolyl 1-Naphthyl 2-Naphthyl
170 150 155 187 175
Ethanol Methanol Ethanol Ethanol Methanol
Analyses Carbon Hydrogen Sitrogen Calc'd Found Calc'd Found Calc'd Found
Appearance
Yield,
%
Formula
Amorph . powder Yellow powder Needles Tan plates Tan plates Red powder Red needles
48
Ci7HnNO
57
CigHiaNO
81 5
81 0
72
36 40 31 37 33
84 4 CmHziNO Cz4HzaNO 84 4 CznHzaNO 84 4 C27H23NO C27HZ3NO
83 8 84 2 84 3
6 5 6 8 6.8
5 6
5 4
7 1
5 3
5 3
6 4
4 4 4 3 3
3
4.3 4.0 4.2 3 7 3 9
6 8 6 9
I
1 7 7
TABLE VI1 AMIDESOF @,~-DI-(~-ANISYL)ACRYLIC ACID( p-CH30C6H&C=CHCONHR M p., "C.
Recryst. Solvent
H
125
Dil. ethanol
Phenyl
108
Dil. ethanol
m-Nitrophenyl
103
p-Nitrophenyl"
101
1-Naphthyl
140
Benzene-pet. ether Benzene-pet. ether Ethanol
R
Appear- Yield, ance % Orange needles Grey needles Grey needles Grey needles Scarlet rhombic plates
Formula
Analyses Carbon Hydrogen Nitrogen Calc'd Found Calc'd Found Calc'd Found
32
C17H17?JOa
72 1
72 1
6 0
6 1
4 9
4 7
44
Cz3HziSO3
76.9
76 5
5 9
5 8
3 9
4 2
54
C23HzoN206
68 3
68 6
5 0
4 8
6 9
7 3
48
CzgH26N407
64 2
63 9
4 8
4 7
10 3
10 3
30
Cz7H2aNOa 79 2
79 0
5 7
5 6
3 4
3 3
This amide precipitated as a stable compound with p-aminonitrobenzene, which remained unaffected by the standard procedure of purification.
tion, the precipitate was washed several times with dilute hydrochloric acid and with water in order to remove any unchanged amine and amine hydrochloride. The solids were
generally purified by crystallization from ethanol or mpthan01 (Tables V-VII). JERUSALEM, ISRAEL
