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Condensation of phenol with propargyl alcohol
CONDENSATION
OF P H E N O L
WITH
PROPARGYL
ALCOHOL*
1~. S. I~AMETKIlq, V. D. RYA~OV and A. A. SHCHERBAKOV
I. M. Gubkin Institute of Petrochemical and Gas Industry, Moscow (Received 7 July 1971)
THE use of phenol has recently increased in petrochemical synthesis. The petrochemical industry produces a considerable number of products from it. Phenol derivatives produced by industry, such as bisphenols and triphenols are being used as oil additives and stabilizers for polymer materials [1, 2]. It is therefore of interest to examine new methods of synthesis of these products. One method of synthesizing bisphenols is based on condensation of phenols with acetylene hydrocarbons [3-5]. It may be expected that bisphenols and triphenols form during the condensation of phenol with acetylene alcohols. However, no information is available in the literature concerning the possibility of preparing bis- and triphenols by this method. It was shown in m a n y studies [6, 7] that condensation of phenol with tertiary acetylene and vinylacetylene alcohols results in formation of substituted phenols containing multiple bonds in the side chain and coumarins. There is no information in the literature about the condensation of phenols with primary acetylene alcohols. This paper describes results of investigating condensation of propargyl alcohol with phenol in the presence of several acid catalysts. Investigations show that propargyl alcohol has a very low reactivity in condensation with phenol in the presence of protonic and aprotonic acid catalysts. However, the reaction takes place readily in the presence of mixed catalysts made from an acid component and mercury sulphate. The reaction does take place but at a lower rate in the presence of mercury sulphate alone. Data of an experimental study of phenol condensation with propargyl alcohol are tabulated. Tabulated information shows that the yield of reaction products is positively influenced by an increases of reaction time and an increase of the phenol : : alcohol molar ratio. An increase in temperature increases reaction product yield in the presence of mixed catalysts and reduces this yield on using mercury sulphate only. Optimum results were obtained in the presence of catalysts containing mercury sulphate with sulphuric acid or with boron fluoride esterate. * Neftekhimiya 12, No. 5, 766-769, 1972.
194
Condensation of phenol w i t h p r o p a r g y l alcohol
195
A study of reaction products shows that instead of the propargylphenols anticipated, compounds of polyphenol type had formed. Analysis shows that 1,2-bis-(oxyphenyl)-prop-2-ene and 1,2,2-tris-(oxyphenyl)-propane are the main reaction products. 1,2-Diphenoxy-2-(oxyphenyl)- propane is also formed in the reaction mixture. C O N D E N S A T I O N OF P H E N O L W I T H P R O P A R G Y L ALCOHOL
Catalyst amount, g Type acidic
HgSO4
16
A1C13 HgSO4
--
H~SO4÷HgSO4
2
8
2 2 2 1.5 3 1.5 1.5
8
3
8 16 8
BF30(C,Hs)2 + HgSO4
11-5 10
1"5 3
Experimental temperatare, °C
Reaction time, min
50 50 50 50 90 90 50 50 50
180 15 60 180 180
50
180
180
Phenol/ /alcohol, mole
Overall yield of products,* ~/o of t h e theoretical
5:1 5:1
14:1 14:1 19:1 14:1
14:1
3.8 10"6 26'5 41.5 15-9 38-7 80'1 83.9 74-3 70"0 87"0 74"3
* Calculation was made assuming that the reaction results in the formation of triphenol compounds.
Since propargyl alcohol, unlike other acetylene alcohols, forms other reaction products, i t was of interest to observe the formation of polyphenol type products. Special experiments, in the presence of mercury sulphate--an active catalyst, in reactions with a ternary bond, indicate that reaction with propargyl alcohol takes place at higher rates, the alcohol does not undergo isomeric conversion and is completely consumed in the first stages of the reaction. On the other hand, analyses of a reaction mixture over a period of time by thin-layer chromatography show that, in the initial period of reaction, the composition of products of the reaction mixture becomes complex and the number of components then decreases. Bearing in mind the results of these experiments and the fact that 1,2-bis-(oxyphenyl)-prop-2-ene was isolated from the reaction mixture and that mixed catalysts give optimum results, the following system of formation of polyphenol type compounds may be assumed: + C6H60H
C.HsOH~HC------ C - - C H , - - 0 H
-* H s C = C - - C H z 0 H ~6H~0H
N. S. NAMETKIN eA al.
196
CHj~C--CHI--C.H,0H
~,H,0H
C6H40H CHs--~-CH~--C6H~0H
C6H4OH CHs---~-CH2--OH
+C'HsOH* I
~.H,0H ,
~ CH.=C--CH~---0--C6H6
C].H,0H O--C,H5
- - - + CH3--C~--CH~--O--C6H5
1
CJeH4OH
C6H,0H
The system proposed is not ideal, of course, but fully reflects the relations derived of the comparatively high reactivity of the ternary bond and the formation of a large number of products in the initial stages of the reaction, which are further used to form 1,2,2,-tris-(oxyphenyl)-propane and 1,2-diphenoxy-2-(oxyphenyl)-propane. I t is quite possible t h a t resins are present in reaction products owing to t h e polymerization of unsaturated compounds formed in the first stages of the reaction. EXPERIMENTAL
The reaction was carried out in a reactor provided with a stirrer, reflux condenser, dropping funnel and thermometer. While stirring vigorously, propargyl alcohol or a phenol-alcohol mixture was added dropwise at a given temperature to phenol mixed with the catalyst. The reaction was stopped by adding cold water. After washing the reaction products with water, unreacted phenol was distilled off with steam. Propargyl alcohol had the following constants: b.p. 113-114 °, d] ° = 0.963, n ~ 1.4334. Boron fluoride (b.p. 126-127 °, a~°-- 1.125; n~° 1.3480), sulphuric acid, mercury sulphate and chemically pure aluminium chloride were the catalysts. After the distillation of phenol the reaction products were dissolved in ester and repeatedly washed with a 10% solution of NaOH. The alkaline extracts were acidified with dilute HC1 and extracted with ether. The ether extracts collected were dried, ether distilled ad the residue separated into two broad fractions: 200-240°/5-6 m m and 250-300°/5-6 mmHg. 1,2-Di-(oxyphenyl)-prop-2-ene. A narrow fraction was taken from the first broad fraction (220-225°/5 m m H g ) which on standing crystallized. Yellowish crystals of m.p. 143-144 ° were obtained from this fraction by recrystallization from benzene. Found, ~: C--78.76; H--6.19; mol. wt.--232. ClsH1,Oi. Calculated, ~o: C--79.6; H--6.2; tool. wt.--226. Purified product yield was 20-25~/o stoichiometric. Intensive absorption was observed in the I R spectrum of the compound obtained in the 1250-1200 cm -I and 3400 cm -1 range, which is typical of phenol. Absorption in the region
Condensation of phenol with propargyl alcohol
197
of 826 cm -1 confirms 1,4-substitution of the benzene nucleus. Absorption in the 3100-2900 ° range (3050-2990 cm -1) is evidence of the presence of a vinyl group and conjugation of the latter with a benzene nucleus is confirmed by absorption in the 1000 and 900 cm -1 ranges. 1,2,2-Tri-(oxyphenyl)-propane. A fraction of 285-300°/5 mmHg was isolated from the second distillate which, on standing, was converted to a solid amorphous uncrystallized mass, readily soluble in ester, benzene and acetone. Product yield was 20-22% of stoichiometric Found, ~:C--78-30; H--6.20; Ott--16.7; mol.wt.--308. C:IH20Os. Calculated, ~: C--78.75; H--6-25; OH--16.0; mol.wt.--320. I R spectra of the material isolated showed the absence of absorption bands typical of double and ternary bonds. Vigorous absorption was observed in the region of 3237 and 1225 cm -1, which is typical of the phenol nucleus; absorption in the 826 cm -1 range proves the presence of 1,4-substitution in the be~lzene nucleus; the presence of a - - C H 2 group is proved bv absorption in the 1444 cm -1 range. 1,2-Diphenoxy-2-(oxyphenyl)-propane. An ether solution of reaction products insoluble in a 10°,/o alkaline solution was washed with water, dried, and after the distillation of ether, the residue was distilled in vacuum. By repeated vacuum distillation a 195-197°/3 mmHg fraction was obtained, which was a dark yellow amorphous, uncrystallized substance which is readily soluble in ether, benzene, acetone and methanol. Found, ~: C--78.46; H--6.1; Ott--5.1; mol.wt.--318. C~H20Oa. Calculated, ~: C--78.75; H--6-25; OH--5.3; mol.wt.--320. The yield of the purified product was 7 - 1 0 ~ of the stoichiometric. [ R spectrum of the compound separated showed intensive absorption in the region of 1269 and 1228 cm -~, typical of phenol ethers. Absorption in the region of 1355 cm -1 points to the presence of a phenol nucleus. Absorption in the 827 cm -~ range confirms the presence of 1,4-substitution in the benzene nucleus; absorption in the 749 cm -1 range is evidence of n/ono-substitution; finally, absorption in the range of 1444 cm -1 confirms the presence of a - - C H 2 group. The substance isolated was identified as 1,2-diphenoxy-2-(oxyphenyl)propane. SUMMARY
1. The condensation of phenol with propargyl alcohol was studied in the presence of several acid and mixed catalysts. BF30(C2Hs),~-HgS04 and H2SO4+HgSO4 are the most active catalysts, in the presence of which the yield of condensation products reaches 70-90%. 2. Condensation of phenol with propargyl alcohol ta,kes place with a triple bond in the reaction and a hydroxyl group of alcohol to form unsaturated "bisphenol" and triphenol compounds as main products.
198
N. S. NAM~.TKI~, et al.
REFERENCES 1. M. E. PRUITT and J. M. BAGGET, USA Pat. 2706189, 1955; Chem. Abstrs. 49, 9326a, 1955 2. K. K. PAPOK, S. E. KREIN, A. B. r I P P E R , B. S. ZUSEVA and M. A. LISOVSKAYA, Prisadki k maslam. Tr. I I Vsesoyuzn. nauchn.-tokhn, sovoshch. (Oil Additives. Proceedings of the I I All-Union Sciontific Toctmical Conference). Khimiya, Moscow, 1966 3. V. D. RYABOV, A. K. SOPKINA and V. S. VESOVA, Neftekhimiya 5, 335, 1965 4. A. K. SOPKINA and V. D. RYABOV, Neftekhimiya 4, 714, 1964 5. V. D. RYABOV and V. L. r A I S E R , Auth. Cert. USSR, 143812, 1962; Byull. izobrot. 1, 1962 6. L N. NAZAROV, A. I. KUZNETSOVA, Izv. AN SSSR, Otd. khim. n., 431, 1941 7. S. A. VARTANYAN, S. K. VARDAPETYAN and Sh. O. BADANYAN, Arm. kbJm. zh. 23, 85, 1970
OF P H E N O L
WITH
PROPARGYL
ALCOHOL*
1~. S. I~AMETKIlq, V. D. RYA~OV and A. A. SHCHERBAKOV
I. M. Gubkin Institute of Petrochemical and Gas Industry, Moscow (Received 7 July 1971)
THE use of phenol has recently increased in petrochemical synthesis. The petrochemical industry produces a considerable number of products from it. Phenol derivatives produced by industry, such as bisphenols and triphenols are being used as oil additives and stabilizers for polymer materials [1, 2]. It is therefore of interest to examine new methods of synthesis of these products. One method of synthesizing bisphenols is based on condensation of phenols with acetylene hydrocarbons [3-5]. It may be expected that bisphenols and triphenols form during the condensation of phenol with acetylene alcohols. However, no information is available in the literature concerning the possibility of preparing bis- and triphenols by this method. It was shown in m a n y studies [6, 7] that condensation of phenol with tertiary acetylene and vinylacetylene alcohols results in formation of substituted phenols containing multiple bonds in the side chain and coumarins. There is no information in the literature about the condensation of phenols with primary acetylene alcohols. This paper describes results of investigating condensation of propargyl alcohol with phenol in the presence of several acid catalysts. Investigations show that propargyl alcohol has a very low reactivity in condensation with phenol in the presence of protonic and aprotonic acid catalysts. However, the reaction takes place readily in the presence of mixed catalysts made from an acid component and mercury sulphate. The reaction does take place but at a lower rate in the presence of mercury sulphate alone. Data of an experimental study of phenol condensation with propargyl alcohol are tabulated. Tabulated information shows that the yield of reaction products is positively influenced by an increases of reaction time and an increase of the phenol : : alcohol molar ratio. An increase in temperature increases reaction product yield in the presence of mixed catalysts and reduces this yield on using mercury sulphate only. Optimum results were obtained in the presence of catalysts containing mercury sulphate with sulphuric acid or with boron fluoride esterate. * Neftekhimiya 12, No. 5, 766-769, 1972.
194
Condensation of phenol w i t h p r o p a r g y l alcohol
195
A study of reaction products shows that instead of the propargylphenols anticipated, compounds of polyphenol type had formed. Analysis shows that 1,2-bis-(oxyphenyl)-prop-2-ene and 1,2,2-tris-(oxyphenyl)-propane are the main reaction products. 1,2-Diphenoxy-2-(oxyphenyl)- propane is also formed in the reaction mixture. C O N D E N S A T I O N OF P H E N O L W I T H P R O P A R G Y L ALCOHOL
Catalyst amount, g Type acidic
HgSO4
16
A1C13 HgSO4
--
H~SO4÷HgSO4
2
8
2 2 2 1.5 3 1.5 1.5
8
3
8 16 8
BF30(C,Hs)2 + HgSO4
11-5 10
1"5 3
Experimental temperatare, °C
Reaction time, min
50 50 50 50 90 90 50 50 50
180 15 60 180 180
50
180
180
Phenol/ /alcohol, mole
Overall yield of products,* ~/o of t h e theoretical
5:1 5:1
14:1 14:1 19:1 14:1
14:1
3.8 10"6 26'5 41.5 15-9 38-7 80'1 83.9 74-3 70"0 87"0 74"3
* Calculation was made assuming that the reaction results in the formation of triphenol compounds.
Since propargyl alcohol, unlike other acetylene alcohols, forms other reaction products, i t was of interest to observe the formation of polyphenol type products. Special experiments, in the presence of mercury sulphate--an active catalyst, in reactions with a ternary bond, indicate that reaction with propargyl alcohol takes place at higher rates, the alcohol does not undergo isomeric conversion and is completely consumed in the first stages of the reaction. On the other hand, analyses of a reaction mixture over a period of time by thin-layer chromatography show that, in the initial period of reaction, the composition of products of the reaction mixture becomes complex and the number of components then decreases. Bearing in mind the results of these experiments and the fact that 1,2-bis-(oxyphenyl)-prop-2-ene was isolated from the reaction mixture and that mixed catalysts give optimum results, the following system of formation of polyphenol type compounds may be assumed: + C6H60H
C.HsOH~HC------ C - - C H , - - 0 H
-* H s C = C - - C H z 0 H ~6H~0H
N. S. NAMETKIN eA al.
196
CHj~C--CHI--C.H,0H
~,H,0H
C6H40H CHs--~-CH~--C6H~0H
C6H4OH CHs---~-CH2--OH
+C'HsOH* I
~.H,0H ,
~ CH.=C--CH~---0--C6H6
C].H,0H O--C,H5
- - - + CH3--C~--CH~--O--C6H5
1
CJeH4OH
C6H,0H
The system proposed is not ideal, of course, but fully reflects the relations derived of the comparatively high reactivity of the ternary bond and the formation of a large number of products in the initial stages of the reaction, which are further used to form 1,2,2,-tris-(oxyphenyl)-propane and 1,2-diphenoxy-2-(oxyphenyl)-propane. I t is quite possible t h a t resins are present in reaction products owing to t h e polymerization of unsaturated compounds formed in the first stages of the reaction. EXPERIMENTAL
The reaction was carried out in a reactor provided with a stirrer, reflux condenser, dropping funnel and thermometer. While stirring vigorously, propargyl alcohol or a phenol-alcohol mixture was added dropwise at a given temperature to phenol mixed with the catalyst. The reaction was stopped by adding cold water. After washing the reaction products with water, unreacted phenol was distilled off with steam. Propargyl alcohol had the following constants: b.p. 113-114 °, d] ° = 0.963, n ~ 1.4334. Boron fluoride (b.p. 126-127 °, a~°-- 1.125; n~° 1.3480), sulphuric acid, mercury sulphate and chemically pure aluminium chloride were the catalysts. After the distillation of phenol the reaction products were dissolved in ester and repeatedly washed with a 10% solution of NaOH. The alkaline extracts were acidified with dilute HC1 and extracted with ether. The ether extracts collected were dried, ether distilled ad the residue separated into two broad fractions: 200-240°/5-6 m m and 250-300°/5-6 mmHg. 1,2-Di-(oxyphenyl)-prop-2-ene. A narrow fraction was taken from the first broad fraction (220-225°/5 m m H g ) which on standing crystallized. Yellowish crystals of m.p. 143-144 ° were obtained from this fraction by recrystallization from benzene. Found, ~: C--78.76; H--6.19; mol. wt.--232. ClsH1,Oi. Calculated, ~o: C--79.6; H--6.2; tool. wt.--226. Purified product yield was 20-25~/o stoichiometric. Intensive absorption was observed in the I R spectrum of the compound obtained in the 1250-1200 cm -I and 3400 cm -1 range, which is typical of phenol. Absorption in the region
Condensation of phenol with propargyl alcohol
197
of 826 cm -1 confirms 1,4-substitution of the benzene nucleus. Absorption in the 3100-2900 ° range (3050-2990 cm -1) is evidence of the presence of a vinyl group and conjugation of the latter with a benzene nucleus is confirmed by absorption in the 1000 and 900 cm -1 ranges. 1,2,2-Tri-(oxyphenyl)-propane. A fraction of 285-300°/5 mmHg was isolated from the second distillate which, on standing, was converted to a solid amorphous uncrystallized mass, readily soluble in ester, benzene and acetone. Product yield was 20-22% of stoichiometric Found, ~:C--78-30; H--6.20; Ott--16.7; mol.wt.--308. C:IH20Os. Calculated, ~: C--78.75; H--6-25; OH--16.0; mol.wt.--320. I R spectra of the material isolated showed the absence of absorption bands typical of double and ternary bonds. Vigorous absorption was observed in the region of 3237 and 1225 cm -1, which is typical of the phenol nucleus; absorption in the 826 cm -1 range proves the presence of 1,4-substitution in the be~lzene nucleus; the presence of a - - C H 2 group is proved bv absorption in the 1444 cm -1 range. 1,2-Diphenoxy-2-(oxyphenyl)-propane. An ether solution of reaction products insoluble in a 10°,/o alkaline solution was washed with water, dried, and after the distillation of ether, the residue was distilled in vacuum. By repeated vacuum distillation a 195-197°/3 mmHg fraction was obtained, which was a dark yellow amorphous, uncrystallized substance which is readily soluble in ether, benzene, acetone and methanol. Found, ~: C--78.46; H--6.1; Ott--5.1; mol.wt.--318. C~H20Oa. Calculated, ~: C--78.75; H--6-25; OH--5.3; mol.wt.--320. The yield of the purified product was 7 - 1 0 ~ of the stoichiometric. [ R spectrum of the compound separated showed intensive absorption in the region of 1269 and 1228 cm -~, typical of phenol ethers. Absorption in the region of 1355 cm -1 points to the presence of a phenol nucleus. Absorption in the 827 cm -~ range confirms the presence of 1,4-substitution in the benzene nucleus; absorption in the 749 cm -1 range is evidence of n/ono-substitution; finally, absorption in the range of 1444 cm -1 confirms the presence of a - - C H 2 group. The substance isolated was identified as 1,2-diphenoxy-2-(oxyphenyl)propane. SUMMARY
1. The condensation of phenol with propargyl alcohol was studied in the presence of several acid and mixed catalysts. BF30(C2Hs),~-HgS04 and H2SO4+HgSO4 are the most active catalysts, in the presence of which the yield of condensation products reaches 70-90%. 2. Condensation of phenol with propargyl alcohol ta,kes place with a triple bond in the reaction and a hydroxyl group of alcohol to form unsaturated "bisphenol" and triphenol compounds as main products.
198
N. S. NAM~.TKI~, et al.
REFERENCES 1. M. E. PRUITT and J. M. BAGGET, USA Pat. 2706189, 1955; Chem. Abstrs. 49, 9326a, 1955 2. K. K. PAPOK, S. E. KREIN, A. B. r I P P E R , B. S. ZUSEVA and M. A. LISOVSKAYA, Prisadki k maslam. Tr. I I Vsesoyuzn. nauchn.-tokhn, sovoshch. (Oil Additives. Proceedings of the I I All-Union Sciontific Toctmical Conference). Khimiya, Moscow, 1966 3. V. D. RYABOV, A. K. SOPKINA and V. S. VESOVA, Neftekhimiya 5, 335, 1965 4. A. K. SOPKINA and V. D. RYABOV, Neftekhimiya 4, 714, 1964 5. V. D. RYABOV and V. L. r A I S E R , Auth. Cert. USSR, 143812, 1962; Byull. izobrot. 1, 1962 6. L N. NAZAROV, A. I. KUZNETSOVA, Izv. AN SSSR, Otd. khim. n., 431, 1941 7. S. A. VARTANYAN, S. K. VARDAPETYAN and Sh. O. BADANYAN, Arm. kbJm. zh. 23, 85, 1970