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Химия элементоорганических соединений
SYNTHESIS OF TRIPHENYLBISMUTH B/S(2-METHYLPROPENOATE)
V.A. Verkhovykh, Lobachevsky State University of Nizhny Novgorod, Russian Federation, gushchin@chem. unn. ru
O.S. Kalistratova, Lobachevsky State University of Nizhny Novgorod, Russian Federation, olga.kalistratova@yandex. ru
A./. Grishina, Lobachevsky State University of Nizhny Novgorod, Russian Federation, gushchin@chem. unn. ru
V.G. Artemova, Lobachevsky State University of Nizhny Novgorod, Russian Federation, decanat2005@yandex. ru
A.V. Gushchin, Lobachevsky State University of Nizhny Novgorod, Russian Federation, gushchin@chem. unn. ru
Triphenylbismuth bis(2-methylpropenoate) Ph3Bi(O2CMe=CH2)2 has been obtained by the interaction of triphenylbismuth with methacrylic acid and hydrogen peroxide in tetrahydrofuran. Its structure has been determined by IR and :H NMR spectroscopy.
Keywords: triphenylbismuth bis(2-methylpropenoate), synthesis, structure, IR spectroscopy, NMR spectroscopy.
Introduction
Organometallic compounds of bismuth are the unique reagents in the arylation reactions of amines, alcohols, phenols, and glycols in the presence of catalytic amounts of copper, as well as unsaturated compounds under the catalytic action of palladium salts. Recently, chemistry of the metal-filled polymers, including bismuth-containing ones, develops intensively. Some known copolymers of various unsaturated bismuth compounds with organic monomers are already used for the synthesis of metal-containing polymers (including organic glasses) exhibiting the fungicidal and biocidal activity, X-ray protection properties [1]. For this reason the synthesis of new organic bismuth-containing compounds and their application as methylmethacrylate comonomers are important.
Methods for obtaining organobismuth compounds Ph3Bi(O2CR)2 by the reaction of triphenylbismuth dihalides with silver, sodium and ammonium salts of carboxylic acids [2-4], triphenylbismuth carbonate with carboxylic acids [5], triphenylbismuth with carboxylic acids in the presence of benzoyl peroxide, Н2О2, t-BuOOH [6], triphenylbismuth with anhydrides of carboxylic acids in the presence of t-BuOOH [7-11], triphenylbismuth with tert-butylperacetate and carboxylic acid [1], and triphenylbismuth with peracid [3] are known.
The aim of this work has been the synthesis of triphenylbismuth bis(2-methylpropenoate) by the reaction of triphenylbismuth with methacrylic acid and hydrogen peroxide. The presence of two methacrylate groups in the molecule can provide the use of the compound as a comonomer in the synthesis of a bismuth-containing polymer.
Experimental
Purification of solvents and reagents
Benzene, diethyl ether, tetrahydrofuran (THF) were dried over CaCl2, distilled and stored over sodium. Chloroform was distilled, petroleum ether and bromobenzene were used without primary purification. Methacrylic acid was purified by sublimation.
Synthesis of triphenylbismuth
Triphenylbismuth was prepared by a modernized technique [2]. Magnesium chips (12 g, 0.5 mol), 100 mL THF and 50 mL benzene were placed in a one-liter three-necked flask equipped with a stirrer, reflux condenser and dropping funnel. Bromobenzene (52.5 mL) was added, and then the mixture was heated for 1 h in an air bath. In the end the mixture was cooled, the flask was filled with argon and left overnight. Then the mixture was heated for dissolving of Grignard reagent, the residual magnesium was
filtered through a wire filter. Solution of BiCl3 (40 g, 0.13 mol) using benzene with THF (1:2) as solvent was added to the heated Grignard reagent. Then the reaction mixture was heated for 1 h in an air bath, then it was decomposed by 25 mL H2O and 100 mL saturated NH4Cl solution while cooling in a water bath. The top organic layer was dried by Na2SO4, the solvents were removed in a rotary evaporator at reduced pressure. The resultant triphenylbismuth had MP 76 °C after purification by recrystallization from hot isopropyl alcohol, the product yield was 77 %.
Synthesis of triphenylbismuth bis(2-methylpropenoate) (1)
Methacrylic acid (1.27 mL, 15 mmol) was added to Ph3Bi solution (2.2 g, 5 mmol) in 20 mL ether, then 2.5 mL 2.03 M anhydrous H202 solution in diethyl ether was added dropwise at cooling with cold water. The mixture was left at 5 °C for 38 h. The solution attained weak yellowish color; large crystals of product 1 were formed at the bottom of the flask. The solution was decanted from the precipitate, and the crystals were washed with 4 mL of ether. The product yield was 79 %, MP: 149 °C (literature data for the product obtained by the reaction of triphenylbismuth, tert-butylperoxide and methacrylic acid were 165 °C [1]).
The product was dissolved in 10 mL of warm freshly distilled chloroform for purification by recrystallization. Hexane (40 mL) was added in portions of 5 mL to the transparent solution. Fine-crystalline white precipitate was formed. For complete precipitation the solution was left in a refrigerator for 1.5 h. The product was filtered off by means of Shott filter, washed 2 times with 4 mL hexane, and then dried in the air. The product yield of compound 1 was 60 % (1.83 g), MP: 164 °C.
After recrystallization the product did not contain impurities of methacrylic acid and triphenylbismuth, which was determined by thin-layer chromatography method (hexane:ethylacetate eluent, 4:1 by volume).
IR spectrum
The IR absorption spectra were recorded on the IR-spectrometer «IR Prestige-21» of the company Shimadzu (Japan) in a potassium bromide pellet containing 1 % of the investigated compound.
NMR spectrum
The :H, 13C-NMR spectra were recorded on the NMR-spectrometer «Ajilent DD2 400» in deuterochloroform. Decoding and modeling of spectra were performed using the program MestReNova (demo version).
Elemental analysis
Elemental analysis was carried out using the manual express gravimetric method based on pyrolytic burning of a substance in a quartz tube in oxygen flow. This method allows determination of carbon and hydrogen contents, as well as bismuth by the remainder of bismuth (III) oxide. An automatic CH-analyzer was used in parallel. We developed a titrimetric method of analysis of product 1 given in the results and discussion section.
Results and Discussion
Compound 1 has been obtained by the method of oxidative addition from triphenylbismuth, hydrogen peroxide, and excess of methacrylic acid, mixed in the 1:1:3 ratio, respectively:
Ph3Bi + 2 CH2=CMeCOOH + H202 ^ Ph3Bi(O2CMeC=CH2)2 + 2 H2O (1)
Diethyl ether was used as solvent. The reaction was carried out at room temperature. Yield of target product with m. p. 164 °C equaled 60 % after recrystallization from the mixture of chloroform and hexane.
Compound 1 is white crystalline substance, air- and moisture-stable, well soluble in chloroform, THF, methyl methacrylate, styrene, benzene, sparingly soluble in hexane and isopropyl alcohol. Good solubility in styrene and methyl methacrylate makes the product promising in order to obtain bismuth-containing polymers.
For investigation of composition and structure of compound 1, elemental analysis, :H, 13C NMR, and IR spectroscopy were used.
The elemental analysis data are in good agreement with the calculated values. Found, %: C 51.00; H 4.12; Bi 35.00 (manual apparatus for combustion); C 51.25; H 4.18 (automatic analyzer); Bi 34.23 (titrimetric bismuth determination). Calculated for C26H25O4Bi, %: C 51.13; H 4.13; Bi 34.25.
Bulletin of the South Ural State University. Ser. Chemistry.
2015, vol. 7, no. 3, pp. 61-65
Верховых В.А., Калистратова О.С., Гришина А.И. и др.
Синтез бис(2-метилпропеноата) трифенилвисмута
For titrimetric bismuth determination, which we had worked out for the first time, a sample of the analyzed compound (0.05-0.15 g) and 5 mL of concentrated H2SO4 were heated in 100 mL conical flask to appearance of white vapours. Then the solution was cooled, 5 mL of concentrated HNO3 was added and the mixture was heated to its discoloration. After cooling of the mixture, 20 mL of water was added, followed by the concentrated solution of ammonia, until slightly acidic pH was reached. Xylenol orange indicator was added into the hot solution and it was titrated by 0.1 N solution of disodium EDTA, until the colour of the solution changed from pink to lemon yellow. Content of bismuth in the sample was determined according to the formula:
rn(Bi) = 1.045 V-m^1,
V is the equivalent volume of 0.1 N solution of disodium EDTA, mL; m is the mass of the analyzed sample, g.
If addition of ammonia leads to precipitation of Bi(OH)3, it is dissolved in concentrated HNO3 and ammonia is again added, until slightly acidic pH is reached.
Triphenylbismuth dicarboxylate turns into triphenylbismuth sulfate Ph3BiSO4 at heating with concentrated H2SO4 according to equation (2); Ph3BiSO4 decomposes with decrease of Bi oxidation state according to equation (3). The phenyl derivative of Bi(III) is dephenylated to Bi2(SO4)3 and benzene by sulfuric acid according to equation (4), benzene is sulfonated to benzenesulfonic acid according to equation (5):
Ph3Bi(O2CMeC=CH2)2 + H2SO4 ^ Ph3BiSO4 + 2 CH2=CMeCOOH (2)
2 Ph3BiSO4 ^ (Ph2Bi)2SO4 + PhOSO2OPh (3)
(Ph2Bi)2SO4 + 2 H2SO4 ^ Bi2(SO4)3 + 4 PhH (4)
PhH + H2SO4 ^ PhSO3H + H2O (5)
CH2=CMeCOOH + 22 HNO3 ^ 4 CO2+22 NO2+13 H2O (6)
PhOSO2OPh + 56 HNO3 ^ 12 CO2 + 32 H2O + 34 NO2 + H2SO4 (7)
PhSO3H + 30 HNO3 ^ 6 CO2 + 17 H2O + 30 NO2 + H2SO4 (8)
Concentrated HNO3 oxidizes all organic products to CO2, H2SO4 and H2O with formation of brown NO2 in the presence of sulfuric acid according to equations (6-8).
During the titration, colour change is caused by the interaction of pink xylenol orange complex of triphenylbismuth sulfate with colourless disodium EDTA, that leads to formation of disodium xylenol orange complex with lemon yellow colour.
As the result of the chemical analysis, described above, reproducible results have been obtained. Percent of bismuth has been found to be 34.23 %; this is in good agreement with the combustion results, described above. The suggested volumetric method of bismuth content analysis of compound 1 is faster and more convenient than the known gravimetric method for bismuth determination in the BiOCl form [2].
In IR spectrum of the product, the medium absorption band, due to the stretching vibrations of Bi-C bonds, is at 679 cm-1. The band at 449 cm-1 belongs to the stretching vibration frequency of Bi-O bonds. The strong bands with maxima at 1362 cm-1 and 1559 cm-1 are related to the asymmetric and symmetric absorption vibration frequencies of СОО groups, respectively. The band with maximum at 3045 cm-1 belongs to the stretching vibration frequency of С-H bonds of phenyl groups. The wavenumbers of the noted vibrations are close to similar values for triphenylantimony dimethacrylate [12].
In 1Н NMR spectrum of compound 1 the multiplet of protons of Ph groups is observed in a weak field (5 7.4-8.2 ppm); two singlets of CH2 protons are observed in a stronger field (5.9 and 5.3 ppm); the singlet of CH3 protons is observed in a strong field (1.8 ppm). The chemical shift values of these proton groups are close to similar values for triphenylantimony dimethacrylate [12]. In 13C NMR spectrum of
compound 1 the signals of carbon atoms of phenyl groups (130.5; 130.9; 133.8; 160.4 ppm) and methacrylate groups (19.0; 122.9; 139.1; 173.5 ppm) are present.
Conclusions
1. Triphenylbismuth bis(2-methylpropenoate) has been synthesized by the reaction of triphenylbismuth with hydrogen peroxide and methacrylic acid.
2. The compound is air- and moisture-stable, well soluble in chloroform, THF, methyl methacrylate, styrene, benzene, sparingly soluble in hexane and isopropyl alcohol.
3. Composition and structure of the product have been confirmed by means of IR, !H, 13C NMR spectroscopy, and elemental analysis.
4. New technique for titrimetric bismuth content analysis of triphenylbismuth bis(2-methylpropenoate) has been suggested.
Acknowledgements
The work has been carried out with financial support of the Russian Foundation for Basic Research (assignment N 14-03-31625) and the Ministry of Education and Science of the Russian Federation (project N 2033, basic part of government contract).
References
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6. Dodonov V.A., Gushchin A.V., Brilkina T.G. [Synthesis and Some Reactions of Triphenylbismuth Diacylates]. Zhurn. Obshch. Khmii [Journal of General Chemistry], 1985, vol. 55, no. 1, pp. 73-80. (in Russ.)
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12. Gushchin A.V., Shashkin D.V., Prytkova L.K., Somov N.V., Baranov E.V., Shavyrin A.S., Rykalin V.I. Synthesis and Structure of Triphenylantinony Dimethacrylate. Russian Journal of General Chemistry, 2011, vol. 81, no. 3, pp. 493-496. DOI: 10.1134/S107036321103008X
Received 3 May 2015
Bulletin of the South Ural State University. Ser. Chemistry.
2015, vol. 7, no. 3, pp. 61-65
Верховых В.А., Калистратова О.С., Гришина А.И. и др.
Синтез бис(2-метилпропеноата) трифенилвисмута
УДК 547.1'13
СИНТЕЗ БИС(2-МЕТИЛПРОПЕНОАТА) ТРИФЕНИЛВИСМУТА
В.А. Верховых, О.С. Калистратова, А.И. Гришина, В.Г. Артемова, А.В. Гущин
Нижегородский государственный университет имени Н.И. Лобачевского, г. Нижний Новгород
Взаимодействием трифенилвисмута с метакриловой кислотой и пероксидом водорода в тетрагидрофуране получен бис(2-метилпропеноат) трифенилвисмута Р^В^02СМе=СН2)2, строение которого подтверждено данными ИК- и :Н ЯМР-спектроскопии.
Ключевые слова: бис(2-метилпропеноат) трифенилвисмута, синтез, строение, ИК-спектроскопия, ЯМР-спектроскопия.
Верховых Вадим Алексеевич - студент химического факультета, Нижегородский государственный университет им. Н.И. Лобачевского. 603950, г. Нижний Новгород, пр. им. Ю.А. Гагарина, 23. E-mail: gushchin@chem.unn.ru.
Калистратова Ольга Сергеевна - аспирант химического факультета, Нижегородский государственный университет им. Н.И. Лобачевского. 603950, г. Нижний Новгород, пр. им. Ю.А. Гагарина, 23. E-mail: olga.kalistratova@yandex.ru.
Гришина Арина Ильинична - студент химического факультета, Нижегородский государственный университет им. Н.И. Лобачевского. 603950, г. Нижний Новгород, пр. им. Ю.А. Гагарина, 23. E-mail: gushchin@chem.unn.ru.
Артемова Валентина Гавриловна - кандидат философских наук, доцент факультета социальных наук, Нижегородский государственный университет им. Н.И. Лобачевского. 603950, г. Нижний Новгород, пр. им. Ю.А. Гагарина, 23. E-mail: decanat2005@yandex.ru.
Гущин Алексей Владимирович - доктор химических наук, профессор, декан химического факультета, Нижегородский государственный университет им. Н.И. Лобачевского. 603950, г. Нижний Новгород, пр. им. Ю.А. Гагарина, 23. E-mail: gushchin@chem.unn.ru.
Поступила в редакцию 3 мая 2015 г.
ОБРАЗЕЦ ЦИТИРОВАНИЯ
FOR CITATION
Synthesis of triphenylbismuth bis(2-methylpropenoate) / VA. Verkhovykh, O.S. Kalistratova, A.I. Grishina et al. // Вестник ЮУрГУ. Серия «Химия». - 2015. - Т. 7, № 3. - С. 61-65.
Verkhovykh V.A., Kalistratova O.S., Grishina A.I., Artemova V.G., Gushchin A.V. Synthesis of Triphenylbismuth Bis(2-methylpropenoate). Bulletin of the South Ural State University. Ser. Chemistry. 2015, vol. 7, no. 3, pp. 61-65.
