The Synthesis of Some Esters and Amides of β, β-Diarylacrylic Acids

The reaction of 1,1-diarylethylenes with oxalyl chloride giving 0,0-diarylacrylyl chlorides,has been utilized for the prep- aration of several aliphat...
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[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