Synthesis of Dithiocarbamates by Markovnikov Addition Reaction in PEG and Their Application in Amidoalkylation of Naphthols and Indoles

Azim Ziyaei Halimehjani Arefeh Dadras Meraj Ramezani Elham V. Shamiri Seyyed E. Hooshmand Mohammad M. Hashemi About the authors

Abstract

Synthesis of dithiocarbamates by the one-pot three-component Markovnikov addition reaction of an amine, carbon disulfide and an alkyl vinyl ether or N-vinylpyrrolidone is reported in polyethylene glycol (PEG) under a mild and green procedure with high yields and completely regiospecific. Also, the products were used as efficient starting materials for amidoalkylation of electron-rich arenes such as naphthols and indoles.

Keywords:
dithiocarbamate; Markovnikov addition; alkyl vinyl ether; N-vinylpyrrolidone; polyethylene glycol


Introduction

Dithiocarbamates are the analogue of carbamates in which both oxygen atoms are replaced by sulfur atoms. The dithiocarbamate group is a valuable pharmacophore that induces various biological activity when incorporated into a particular structure.1Kumar, S. T. V. S.; Kumar, L.; Sharma, V. L.; Jain, A.; Jain, R. K.; Maikhuri, J. P.; Kumar, M.; Shukla, P. K.; Gupta, G.; Eur. J. Med. Chem. 2008, 43, 2247.

Kumar, L.; Lal, N.; Kumar, V.; Sarswat, A.; Jangir, S.; Bala, V.; Kumar, L.; Kushwaha, B.; Pandey, A. K.; Siddiqi, M. I.; Shukla, P. K.; Maikhuri, J. P.; Gupta, G.; Sharma, V. L.; Eur. J. Med. Chem. 2013, 70, 68 and references therein.

Tripathi, R. P.; Khan, A. R.; Setty, B. S.; Bhaduri, A. P.; Acta Pharm. 1996, 46, 169.
-4Ates, O.; Kocabalkanli, A.; Cesur, N.; Otuk, G.; Il Farmaco 1998, 53, 541.Their biological potencies such as anti-histaminic, anti-bacterial, and anti-cancer are noteworthy.5Thorn, G. D.; Ludwig, R. A.; The Dithiocarbamates and Related Compounds; Elsevier: Amsterdam, 1962.

Aboul-Fadl, T.; El-Shorbagi, A.; Eur. J. Med. Chem. 1996, 31, 165.
-7Gerhauser, C.; You, M.; Liu, J.; Moriarty, R. T.; Hawthorne, M.; Mehta, R. G.; Moon, R. C.; Pezzuto, J. M.; Cancer Res. 1997, 57, 272.They constitute a large family of herbicides, fungicides and pesticides in agriculture and several compounds of this category such as zineb, maneb, nabam, ziram and ferbam have been commercialized. Also, their applications as sulfur vulcanization agents in rubber manufacturing,8Nieuwenhuizen, P. J.; Ehlers, A. W.; Haasnoot, J. G.; Janse, S. R.; Reedijk, J.; Baerends, E. J.; J. Am. Chem. Soc. 1999, 121, 163.and radical chain transfer agents in the reversible addition-fragmentation chain-transfer (RAFT) polymerizations are extensively investigated.9Lai, J. T.; Shea, R.; J. Polym. Sci., Part A: Polym. Chem. 2006, 44, 4298.Furthermore, they have been used as versatile synthons for the preparation of diversities of organic materials such as thioureas,1010 Ziyaei-Halimehjani, A.; Pourshojaei, Y.; Saidi, M. R.; Tetrahedron Lett. 2009, 50, 32. isothiocyanates,1111 Wong, R.; Dolman, S. J.; J. Org. Chem. 2007, 72, 3969.2-imino-1,3-dithiolanes,1212 Ziyaei-Halimehjani, A.; Maleki, H.; Saidi, M. R.; Tetrahedron Lett. 2009, 50, 2747. cyanamides,1313 Jamir, L.; Sinha, U. B.; Nath, J.; Patel, B. K.; Synth. Commun. 2012, 42, 951. heterocyclic rings,1414 Ziyaei-Halimehjani, A.; Marjani, K.; Ashouri, A.; Tetrahedron Lett. 2012, 53, 3490. the protection of aldehydes,1515 Ziyaei-Halimehjani, A.; Hajiloo Shayegan, H.; Hashemi, M. M.; Notash, B.; Org. Lett. 2012, 14, 3838. amide bond formation,1616 Ziyaei-Halimehjani, A.; Ranjbari, M. A.; Pasha Zanussi, H.; RSC Adv. 2013, 3, 22904. and protection of the amino groups in peptide synthesis.1717 Greene, T. W.; Wuts, P. G. M.; Protecting Groups in Organic Synthesis, 3rd ed.; Wiley Interscience: New York, 1999, pp. 484.Also, dithiocarbamates are important ligands in metal complexes.1818 Macias, B.; Villa, M. V.; Chicote, E.; Martin-Velasco, S.; Castineiras, A.; Borras, J.; Polyhedron 2002, 21, 1899.

The classical synthesis of dithiocarbamates involves the use of thiophosgene, a chlorothioformate and an isothiocyanate which suffer from many drawbacks such as long reaction time, harsh reaction conditions and use of an expensive and toxic reagent, base and solvent. Due to the wide applications of dithiocarbamates, several useful procedures for the synthesis of these compounds have been developed by our group and others, via the one-pot condensation of amines, carbon disulfide and electrophiles such as alkyl halides, epoxides, carbonyl compounds and α,β-unsaturated compounds.1919 Azizi, N.; Aryanasab, F.; Saidi, M. R.; Org. Lett. 2006, 8, 5275.

20 Azizi, N.; Ebrahimi, F.; Akbari, E.; Aryanasab, F.; Saidi, M. R.; Synlett 2007, 2797.

21 Azizi, N.; Aryanasab, F.; Torkiyan, L.; Ziyaei, A.; Saidi, M. R.; J. Org. Chem. 2006, 71, 3634.

22 Ziyaei-Halimehjani, A.; Marjani, K.; Ashouri, A.; Green Chem. 2010, 12, 1306.
-2323 Ziyaei-Halimehjani, A.; Pasha Zanussi, H.; Ranjbari, M. A.; Synthesis 2013, 1483. Very recently, a deep eutectic solvent (DES) was used by Azizi and Gholibeglo2424 Azizi, N.; Gholibeglo, E.; RSC Adv. 2012, 2, 7413. for synthesis of dithiocarbamates in high yields via a one-pot, three-component Michael addition of an amine and carbon disulfide to an activated olefin. Due to the aforementioned applications of dithiocarbamates, synthesis of these compounds with different substitution patterns by a convenient and safe method has become a field of increasing interest in recent years.

Solvents play a critical role in organic reactions for mixing the ingredients to allow molecular interactions. Performing organic reactions without using harmful organic solvents is now of great interest in green organic synthesis. For this purpose, attempts have been made toward the use of green mediums such as water, supercritical fluids, ionic liquids and fluorous based systems. Polyethylene glycol (PEG) has recently been considered as a novel, recyclable and eco-friendly solvent in synthetic chemistry for various organic transformations2525 Nagarapu, L.; Mallepalli, R.; Yeramanchi, L.; Bantu, R.; Tetrahedron Lett. 2011, 52, 3401.

26 Raghu, M.; Rajasekhar, M.; Reddy, B. C. O.; Reddy, C. S.; Reddy, B. V. S.; Tetrahedron Lett. 2013, 54, 3503.

27 Nagarapu, L.; Mallepalli, R.; Kumar, U. N.; Venkateswarlu, P.; Bantu, R.; Yeramanchi, L.; Tetrahedron Lett. 2012, 53, 1699.

28 Dickerson, T. J.; Reed, N. N.; Janda, K. D.; Chem. Rev. 2002, 102, 3325.
-2929 Chen, J.; Spear, S. K.; Huddleston, J. G.; Rogers, R. D.; Green Chem. 2005, 7, 64. with odd properties such as commercial availability, thermal stability, low volatility, and biodegradability and immiscibility with a number of organic solvents. Generally, PEG is an inexpensive, non-toxic, bio-compatible and completely non-halogenated solvent. The fast growth of published works about PEGs in medicinal areas reflects the importance of PEG polymers mainly related to their low toxicity.3030 Harris, J. M.; Poly(ethyleneglycol) Chemistry: Biotechnical and Biomedical Applications; Plenum Press: New York, 1992.,3131 Harris, J. M.; Zalipsky, S.; Poly(ethyleneglycol) Chemistry and Biological Applications, ACS Symposium Series 680; American Chemical Society: Washington, DC, 1997.This inspired us to concentrate on synthesis of the biologically active dithiocarbamates under catalyst-free conditions using PEG as green medium.

Results and Discussion

Previous reports by our group revealed that although high to excellent yields were obtained in the reaction of dithiocarbamates with alkyl vinyl ethers 1 in water,2222 Ziyaei-Halimehjani, A.; Marjani, K.; Ashouri, A.; Green Chem. 2010, 12, 1306. for N-vinylpyrrolidine 2, the reaction gave excellent yields under solvent-free conditions and no valuable yields were obtained in water.2323 Ziyaei-Halimehjani, A.; Pasha Zanussi, H.; Ranjbari, M. A.; Synthesis 2013, 1483.To overcome this drawback, we focused our investigation to find an efficient reaction medium to be suitable for both systems. In continuation of our research allocated to the progress of green chemistry3232 Ziyaei-Halimehjani, A.; Ebrahimi, F.; Azizi, N.; Saidi, M. R.; J. Heterocycl. Chem. 2009, 46, 347.

33 Ziyaei-Halimehjani, A.; Saidi, M. R.; Tetrahedron Lett. 2008, 49, 1244.

34 Ziyaei-Halimehjani, A.; Aryanasab, F.; Saidi, M. R.; Tetrahedron Lett. 2009, 50, 1441.

35 Ziyaei-Halimehjani, A.; Karimi, N.; Saidi, M. R.; Synth. Commun. 2013, 43, 744.
-3636 Marjani, K.; Khalesi, M.; Ashouri, A.; Jalali, A.; Ziyaei-Halimehjan, A.; Synth. Commun. 2011, 41, 451. and the chemistry of dithiocarbamates, herein we report a new and efficient protocol for synthesis of dithiocarbamates by Markovnikov addition reaction in PEG as a green and environmentally benign solvent at room temperature without using any catalyst as outlined in Scheme 1.

Scheme 1
A one-pot three-component synthesis of Markovnikov adducts

Initially, we examined the one-pot three-component reaction of pyrrolidine (5 mmol), CS2 (6 mmol), and ethyl vinyl ether (6 mmol) in liquid polyethylene glycols such as PEG-200 and PEG-400. We found that excellent yield was obtained in PEG-200 (94%) in comparison to PEG-400 (65%). Also, mixing the starting materials at room temperature for 24 h was the best condition observed for this reaction.

We then evaluated the scope and limitations of the protocol by employing a wide range of amines and electron-rich alkenes. The results are summarized in Tables 1 and 2. Various cyclic and acyclic alkyl vinyl ethers such as ethyl vinyl ether, ethyl propenyl ether and 2,3-dihydropyrane were examined with high to excellent yields (Table 1). N-Vinylpyrrolidone was also used in this transformation to afford excellent yields of products (Table 2). Primary aliphatic amines such as benzyl amine, allyl amine, cyclohexyl amine, furfuryl amine and butyl amine all gave excellent yields (entries 1-4, Table 1; and entries 1-4, Table 2). In addition, secondary amines such as pyrrolidine, piperidine, morpholine, azepane, diethyl amine, and diallyl amine reacted equally well in this protocol (entries 5-12, Table 1; entries 5-9, Table 2). Aromatic amines were not suitable starting materials for this transformation due to their low nucleophilic property toward carbon disulfide. The present method is experimentally simple and generates no byproducts. In addition, the reaction is regiospecific toward Markovnikov adducts. The PEG-200 can be simply recovered and reused in the reactions without a significant yield loss.

Having successfully synthesized Markovnikov adducts, we focused our attention on using the product 4 as suitable starting material for amidoalkylation of electron-rich arenes in the presence of AlCl3 in refluxing chloroform (Scheme 2). The results are summarized in Table 3. Electron-rich arenes such as indoles and naphthols were used in this Mannich-type amidoalkylation reaction and moderate to good yields of products were obtained. N,N-Dialkylanilines, dimethoxybenzene, catechol, 2-methoxy naphthalene, pyrrole and thiophene were also examined for this reaction without any result. The Markovnikov products of alkyl vinyl ethers were not suitable starting materials for this transformation.

Scheme 2
Mannich-type amidoalkylation of electron-rich arenes

Conclusions

In summary, the PEG-200 has been employed as a novel, mild and highly efficient solvent for the one-pot three-component synthesis of dithiocarbamates via Markovnikov addition reaction in high to excellent yields. Regiospecificity for the Markovnikov adducts, clean reaction conditions, catalyst-free, and simple experimental procedures are the main advantages of this reaction. Also, the products were applied for the Friedel-Craft (Mannich) type amidoalkylation of electron-rich arenes such as indoles and naphthols.

Experimental

All reactions were carried out in an atmosphere of air. All chemicals and solvents except water (tap water) were purchased from Merck or Fluka and used as received. All reactions were monitored by thin layer chromatography (TLC) on silica gel 60 F254 (0.25 mm), and visualization was performed with UV. The 1H and 13C nuclear magnetic resonance (NMR) spectra were recorded on a Bruker AMX 300-MHz spectrometer in CDCl3 with tetramethylsilane (TMS) as internal standard. Melting points were determined with a Branstead-Electrothermal 9200 apparatus and are uncorrected. Elemental analyses were conducted with a Perkin-Elmer 2004 (II) CHN analyzer.

General procedure for the synthesis of Markovnikov adducts 3a-l and 4a-i

To a mixture of an amine (5 mmol) and CS2 (6 mmol) in PEG (10 mL) was added an electrophile (alkyl vinyl ether or N-vinyl pyrrolidine, 6 mmol). The reaction mixture was stirred vigorously at room temperature for 24 h. After completion of the reaction, H2O (10 mL) was added and the product was extracted with EtOAc (2 × 20 mL) and combined organic layers were washed with H2O and dried over anhydrous Na2SO4. The solvent was evaporated under reduced pressure to give the corresponding product with high purity without the need of column chromatography for purification. The PEG-200 can be recovered from the aqueous phase by passing the aqueous solution through activated charcoal and evaporation of water. All compounds were characterized on the basis of their spectroscopic data (1H and 13C NMR, CHN analysis) and by comparison with those reported in the literature.2222 Ziyaei-Halimehjani, A.; Marjani, K.; Ashouri, A.; Green Chem. 2010, 12, 1306.,2323 Ziyaei-Halimehjani, A.; Pasha Zanussi, H.; Ranjbari, M. A.; Synthesis 2013, 1483.

1-Ethoxyethyl azepane-1-carbodithioate (3i)

Viscous oil; 1H NMR (300 MHz, CDCl3) Δ 1.03 (t, 3H, J 7.0 Hz, CH3), 1.42 (brs, 4H, 2CH2), 1.54 (d, 3H, J 6.3 Hz, CH3), 1.69 (brs, 4H, 2CH2), 3.45 (m, 1H, CH2O), 3.59 (m, 1H, CH2O), 3.75 (t, 2H, J6.0 Hz, CH2N), 4.01 (m, 2H, CH2N), 5.77 (q, 1H, J6.2 Hz, CH); 13C NMR (75 MHz, CDCl3) Δ 14.5, 22.9, 25.4, 25.9, 26.0, 27.2, 52.4, 54.4, 63.9, 90.1, 194.7; anal. calcd. for C11H21NOS2: C, 53.40; H, 8.55; N, 5.66; found: C, 53.75; H, 8.71; N, 5.52.

1-Ethoxypropyl pyrrolidine-1-carbodithioate (3l)

Viscous oil; 1H NMR (300 MHz, CDCl3) Δ 0.89 (t, 3H, J 7.3 Hz, CH3), 1.03 (t, 3H, J 7.0 Hz, CH3), 1.79-1.94 (m, 6H, 3CH2), 3.45-3.59 (m, 4H, CH2N and CH2O), 3.74 (t, 2H, J 6.9 Hz, CH2N), 5.70 (t, 1H, J 6.1 Hz, CH); 13C NMR (75 MHz, CDCl3) Δ 9.7, 14.4, 23.7, 26.1, 29.8, 50.2, 54.0, 64.0, 94.4, 191.6; anal. calcd. for C10H19NOS2: C, 51.46; H, 8.21; N, 6.00; found: C, 51.23; H, 8.07; N, 6.12.

General procedure for amidoalkylation of electron-rich arenes 5a-c and 6a-d

In a 25 mL round bottom flask equipped with magnetic stirrer bar, an electron-rich arene (1 mmol), a dithiocarbamate 4 (1 mmol), chloroform (5 mL) and 10 mol% of AlCl3 were added and the mixture was refluxed for 5-8 h. Progress of the reaction was monitored by TLC. After reaction completion, H2O (10 mL) and CHCl3 (10 mL) were added and the mixture was filtered to remove any undissolved materials. The filtrate was transferred to a decanter and the organic phase was separated. After treatment with Na2SO4, the solvent was evaporated to give the crude products. Purification was performed by recrystallization from ethyl acetate/petroleum.

1-(1-(2-Hydroxynaphthalen-1-yl)ethyl)pyrrolidin-2-one (5a)

Pale yellow solid; m.p. 198-200 ºC; 1H NMR (300 MHz, DMSO -d6) Δ 1.67 (d, 3H, J 7.2 Hz, CH3), 2.13-2.23 (m, 4H, 2CH2), 3.13 (m, 1H, CH2N), 3.56 (m, 1H, CH2N), 5.94 (q, 1H, J 7.2 Hz, CH), 7.14 (d, 1H, J 8.8 Hz, Ar–H), 7.25 (m, 1H, Ar–H), 7.40 (m, 1H, Ar–H), 7.68-7.76 (m, 2H, 2Ar–H), 8.10 (d, 1H, J 8.8 Hz, Ar–H), 9.8 (brs, 1H, OH); 13C NMR (75 MHz, DMSO -d6) Δ 17.3, 17.5, 30.6, 43.5, 44.4, 116.5, 119.1, 122.4, 126.5, 127.5, 128.3, 128.4, 129.2, 133.3, 154.5, 172.9; anal. calcd. for C16H17NO2: C, 75.27; H, 6.71; N, 5.49; found: C, 74.96; H, 6.71; N, 5.66.

1-(1-(1-Hydroxynaphthalen-2-yl)ethyl)pyrrolidin-2-one (5b)

Cream solid; m.p. 190-192 ºC; 1H NMR (300 MHz, DMSO -d6) Δ 1.53 (d, 3H, J 6.8 Hz, CH3), 1.58 (m, 1H, CH2), 1.60 (m, 1H, CH2), 2.16-2.39 (m, 2H, CH2), 2.44 (m, 1H, CH2N), 3.20 (m, 1H, CH2N), 5.79 (q, 1H, J 6.8 Hz, CH), 6.85 (d, 1H, J 8.1 Hz, Ar–H), 7.37-7.50 (m, 3H, 3Ar–H), 7.89 (d, 1H, J 8.1 Hz, Ar–H), 8.15 (m, 1H, Ar–H), 10.18 (brs, 1H, OH); 13C NMR (75 MHz, DMSO -d6) Δ 16.3, 17.2, 30.8, 41.6, 44.5, 106.9, 122.6, 122.8, 124.4, 124.8 (2C), 125.5, 126.6, 132.3, 153.0, 172.6; anal. calcd. for C16H17NO2: C, 75.27; H, 6.71; N, 5.49; found: C, 75.66; H, 6.76; N, 5.47.

1-(1-(2,7-Dihydroxynaphthalen-8-yl)ethyl)pyrrolidin-2-one (5c)

Cream solid; m.p. 206-208 ºC; 1H NMR (300 MHz, DMSO -d6) Δ 1.53 (d, 3H, J 7.1 Hz, CH3), 1.63-2.23 (m, 4H, 2CH2), 3.15 (m, 1H, CH2N), 3.55 (m, 1H, CH2N), 5.73 (q, 1H, J 7.1 Hz, CH), 6.82 (dd, 1H, J 8.8, 1.8 Hz, Ar–H), 6.89 (d, 1H, J 8.8 Hz, Ar–H), 7.28 (s, 1H, Ar–H), 7.51 (d, 1H, J 8.9 Hz, Ar–H), 7.55 (d, 1H, J 8.7 Hz, Ar–H), 9.58 (s, 1H, OH), 9.70 (s, 1H, OH); 13C NMR (75 MHz, DMSO -d6) Δ 17.4, 21.6, 30.7, 39.5, 44.6, 104.7, 114.7, 114.9, 115.6, 122.9, 128.9, 129.9, 135.1, 154.9, 156.0, 173.0; anal. calcd. for C16H17NO3: C, 70.83; H, 6.32; N, 5.16; found: C, 70.76; H, 6.25; N, 5.13.

1-(1-(1H-Indol-3-yl)ethyl)pyrrolidin-2-one (6a)

White solid; m.p. 164-167 ºC; 1H NMR (300 MHz, CDCl3) Δ 1.60 (d, 3H, J 7.0 Hz, CH3), 1.73-1.83 (m, 2H, CH2), 2.41-2.88 (m, 2H, CH2), 2.86 (m, 1H, CH2N), 3.26 (m, 1H, CH2N), 5.77 (q, 1H, J 7.0 Hz, CH), 7.08-7.22 (m, 3H, 2Ar–H and 1H, pyrrole), 7.36 (d, 1H, J 8.0 Hz, Ar–H), 7.62 (d, 1H, J 8.0 Hz, Ar–H), 8.31 (brs, 1H, NH); 13C NMR (75 MHz, CDCl3) Δ 16.6, 17.7, 31.3, 42.2, 42.5, 111.0, 116.2, 119.5, 119.6, 121.1, 122.0, 126.4, 136.4, 174.2; anal. calcd. for C14H16N2O: C, 73.66; H, 7.06; N, 12.27; found: C, 74.01; H, 7.21; N, 12.61.

1-(1-(2-Methyl-1H-indol-3-yl)ethyl)pyrrolidin-2-one (6b)

White solid; m.p. 176-179 ºC; 1H NMR (300 MHz, CDCl3): d 1.74 (d, 3H, J 7.3 Hz, CH3), 1.75-1.96 (m, 2H, CH2), 2.34-2.43 (m, 2H, CH2), 2.51 (s, 3H, CH3), 3.17 (m, 1H, CH2N), 3.57 (m, 1H, CH2N), 5.76 (q, 1H, J 7.3 Hz, CH), 7.07-7.16 (m, 2H, 2Ar–H), 7.29 (dd, 1H, J 7.8, 2.0 Hz, Ar–H), 7.72 (d, 1H, J 7.8 Hz, Ar–H), 8.06 (brs, 1H, NH); 13C NMR (75 MHz, CDCl3) Δ 12.6, 17.5, 17.7, 31.4, 43.4 (2C), 110.4, 110.6, 119.3, 119.5, 121.1, 127.9, 133.2, 135.0, 173.7; anal. calcd. for C15H18N2O: C, 74.35; H, 7.49; N, 11.56; found: C, 73.93; H, 7.65; N, 11.26.

1-(1-(5-Bromo-1H-indol-3-yl)ethyl)pyrrolidin-2-one (6c)

White solid; m.p. 155-157 ºC; 1H NMR (300 MHz, CDCl3) Δ 1.58 (d, 3H, J 7.0 Hz, CH3), 1.83-1.94 (m, 2H, CH2), 2.44-2.49 (m, 2H, CH2), 2.86 (m, 1H, CH2N), 3.27 (m, 1H, CH2N), 5.70 (q, 1H, J 7.0 Hz, CH), 7.15 (s, 1H, pyrrole ring), 7.24-7.31 (m, 2H, 2Ar–H), 7.74 (s, 1H, Ar­H), 8.70 (brs, 1H, NH); 13C NMR (75 MHz, CDCl3) Δ 16.6, 17.7, 31.6, 42.2, 42.4, 112.7, 113.1, 115.7, 121.8, 123.3, 125.3, 128.0, 135.1, 174.3; anal. calcd. for C14H15BrN2O: C, 54.74; H, 4.92; N, 9.12; found: C, 54.53; H, 4.83; N, 9.43.

1-(1-(1-Methyl-1H-indol-3-yl)ethyl)pyrrolidin-2-one (6d)

Yellow oil; 1H NMR (300 MHz, CDCl3) Δ 1.60 (d, 3H, J 7.0 Hz, CH3), 1.80-1.93 (m, 2H, CH2), 2.42-2.48 (m, 2H, CH2), 2.92 (m, 1H, CH2N), 3.30 (m, 1H, CH2N), 3.79 (s, 3H, CH3N), 5.78 (q, 1H, J 7.0 Hz, CH), 6.99 (s, 1H, pyrrole), 7.12 (m, 1H, Ar–H), 7.23-7.33 (m, 2H, 2Ar–H), 7.62 (dd, 1H, J 8.0, 0.7 Hz, Ar–H); 13C NMR (75 MHz, CDCl3) Δ 16.7, 17.7, 31.6, 32.7, 42.1, 42.4, 109.0, 114.6, 119.4, 119.7, 121.9, 126.6, 126.9, 137.1, 174.0; anal. calcd. for C15H18N2O: C, 74.35; H, 7.49; N, 11.56; found: C, 74.47; H, 7.65; N, 11.25.

  • Supplementary Information
    Supplementary data (copies of 1H and 13C NMR spectra for unknown compounds) are available free of charge at http://jbcs.sbq.org.br as PDF file.

Acknowledgments

We are grateful to the Research Council of Sharif University of Technology for financial support. We also thank the Faculty of Chemistry of Kharazmi University for supporting this work.

References

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Publication Dates

  • Publication in this collection
    July 2015

History

  • Received
    06 Mar 2015
  • Accepted
    12 May 2015
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