Polyaniline Supported Fecl3: an Effective Heterogeneous Catalyst for Biginelli Reaction

Supporting Information for

Polyaniline supported FeCl3: An effective heterogeneous catalyst for Biginelli reaction

Heta A. Patel,a Aishwarya M. Sawant,a Vandana J. Rao,b Arun L. Patela,* and Ashutosh V. Bedekara,*

aDepartment of Chemistry, Faculty of Science

The Maharaja Sayajirao University of Baroda, Vadodara 390 002, India

Tel. No. +91-265-2795552;Email:

bDepartment of Metallurgical and Material Engineering, Faculty of Technology and Engineering

The Maharaja Sayajirao University of Baroda, Vadodara 390 001, India

Page no.

Characterizationdata ofcatalyst

• EDX S2-S3
• TGA S3

Comparison of the catalyst S4-S5

Spectral data S6-S8

References S8

EDX:

Fig 1S: EDX of PANI

Fig 2S: EDX of PANI•Fe:

Fig 3S: EDX of PANI•Cu:

Fig 4S: EDX of PANI•Co

Fig 5S: EDX of PANI•Pd

Fig 6S: EDX of PANI•Mn

TGA:

Fig 7S:TGA Analysis of PANI•Fe

Comparison of the catalyst: We have compared our results with previously reported catalysts just to compare its efficiency. The result of coupling of 4-chlorobezaldehyde with urea and ethylaceto acetate with previously reported procedure in literature (Table 1).The catalyst showed comparable yield as compared to other catalyst. As compared to FeCl3 (Entry 9) which is homogeneous catalyst, this catalyst is giving better result.

Table 1: Catalytic performance of some catalysts for the synthesis of ethyl 4-(4-chlorophenyl)-6-methyl-2-oxo-1,2,3,4-tetrahydropyrimidine-5-carboxylate with other catalyst

Sr.No. / Catalyst / Temperature (°C) / Solvent / Time (h) / Yield (%) / Ref.
1 / D-Xylonic acid / 100 / D-Xylonic acid / 5 / 89 / Ma J, Zhong L, Peng X,Sun R (2016) Green Chem. 18: 1738.
2 / Partially Fluorinated, Water-Stable Cu(II)−MOF / 60 / Soivent free / 2 / 89 / Pal TK, De D, Senthilkumar S,Neogi S, Bharadwaj PK (2016) Inorg. Chem. 55: 7835.
3 / Fe3O4@SiO2-imid-PMAb / 80 / Solvent-free / 0.75 / 90 / Javidi J, Esmaeilpour M, Dodeji FN(2015) RSC Adv. 5: 308.
4 / Silicagel–L-pyrrolidine-2-carboxylic acid-4-hydrogen sulfate / reflux / Ethanol / 6 / 90 / Choghamarani AG, Zamani P (2013) Chin. Chem. Lett. 24: 804.
5 / PPF-SO3H(sulfonic acid functionalized
polypropylene fiber) / Reflux / Ethanol / 8 / 74 / Shi XL, Yang H, Tao M, Zhang W (2013) RSC Adv. 3: 3939.
6 / Fe3O4@mesoporous SBA-15 / 90 / Ethanol / 6 / 80 / Mondal J, Sen T, Bhaumik A (2012) Dalton Trans. 41: 6173.
7 / Imidazole-1-yl-acetic acid / 100 / Solvent free / 0.7 / 90 / Kargar M, Hekmatshoar R, Mostashari A, Hashemi Z (2011) Catal. Commun. 15: 123.
8 / 12-Tungstophosphoric acid / Reflux / AcOH / 6-7 / 70 / Heravi MM, Derikvand F, Bamoharram FF (2005) J. Mol. Catal. A 242: 173
9 / FeCl3.6H20 / Reflux / ACN / 12 / 88 / Wang ZT, Xu LW, Xia CG, Wang HQ (2004)Tetrahedron Letters. 45: 7951.
10 / Fe-PANI / Reflux / ACN / 24 / 90 / Present work

Spectral Data:

Ethyl 6-methyl-2-oxo-4-phenyl-1,2,3,4-tetrahydropyrimidine-5-carboxylate (4a)

M.p. 206C [Lit[1] 200-204C]

1H NMR (400 MHz, CDCl3): δ 1.17-1.21(t, J = 7.2Hz, 3H, -CH3),2.35(s, 3H, CH3), 4.05-4.13(m, 2H, -CH2), 5.38-5.39(d, J= 2.8Hz,1H, -CH), 6.11(br s, -NH),7.25-7.31(m, 5H, Ar-H), 8.43 (br s, -NH).

Ethyl 4-(4-fluorophenyl)-6-methyl-2-oxo-1,2,3,4-tetrahydropyrimidine-5-carboxylate (4b)

M.p. 180C [Lit[2] 180-182C]

1H NMR (400 MHz, CDCl3): δ1.16-1.20(t, J= 8Hz, 3H, -CH3), 2.36(s, 3 H, -CH3), 4.05-4.13(m, 2H, -CH2), 5.40 (d, 1H, -CH), 5.75(br s, -NH), 6.99-7.03(m, 2H, Ar-H), 7.28-7.32(m, 2H, Ar-H), 8.03(br s, -NH).

Ethyl 4-(4-chlorophenyl)-6-methyl-2-oxo-1,2,3,4-tetrahydropyrimidine-5-carboxylate(4c)

M.p. 210C-212C [Lit[1] 211-215C]

1H NMR (400 MHz, CDCl3): δ 1.16-1.20(t, J= 7.2Hz, 3 H, -CH3), 2.36(s, 3H, -CH3), 4.05-4.13(m, 2H, -CH2), 5.42-5.42(d, J= 2Hz, 1H, -CH), 5.74(br s, -NH), 7.33-7.34(m, 4H, Ar-H), 8.11(br s, -NH).

Ethyl 4-(4-bromophenyl)-6-methyl-2-oxo-1,2,3,4-tetrahydropyrimidine-5-carboxylate(4d)

M.p. 221C [Lit[3] 225-226C]

1H NMR (400 MHz, CDCl3): δ1.17-1.21(t, J= 7.2Hz, 3H, -CH3), 2.35(s, 3H, -CH3), 4.07-4.12(m, 2H, -CH2), 5.37-5.38(d, J= 2.8Hz, 1H, -CH), 5.87(br s, –NH), 7.20-7.22(m, 2H, Ar-H), 7.44-7.45 (m, 2H, Ar-H), 8.12 (br s, -NH).

Ethyl 4-(4-methoxyphenyl)-6-methyl-2-oxo-1,2,3,4-tetrahydropyrimidine-5-carboxylate (4e)

M.p. 200-202C [Lit[1] 208-211C]

1H NMR (400 MHz, CDCl3): δ 1.17-1.21(t, J= 7.2Hz, 3 H, -CH3), 2.36(s, 3 H, -CH3), 3.80(s, 3H, -CH3), 4.05-4.13(m, 2H, -CH2), 5.36-5.37(d, J= 4Hz, 1H, -CH), 5.48(br s, -NH), 6.83-6.87(m, 2H, Ar-H), 7.24-7.28(m, 2H, Ar-H), 7.47(br s, –NH).

Ethyl 6-methyl-2-oxo-4-(p-tolyl)-1,2,3,4-tetrahydropyrimidine-5-carboxylate(4f)

M.p. 208 C [Lit[4] 205-206C]

1H NMR (400 MHz, CDCl3): δ1.17-1.21(t, J=8 Hz, 3H, -CH3), 2.33-2.35(s, 6 H, -CH3), 4.06-4.11(q, J= 8Hz, 2H, -CH2), 5.37-5.38(d, J= 4Hz, 1H, -CH), 5.62(br s, -NH), 7.12-7.14(m, 2H, Ar-H), 7.21-7.23(m, 2H, Ar-H), 7.90(br s, -NH).

Ethyl 6-methyl-4-(4-nitrophenyl)-2-oxo-1,2,3,4-tetrahydropyrimidine-5-carboxylate (4g)

M.p. 206C [Lit[1] 208OC]

1H NMR (400 MHz, DMSO-d6): δ1.10-1.11(t, J= 7.2Hz, 3H, -CH3), 2.26(s, 3H, CH3), 3.95-4.00(q, J= 7.2Hz, 2H, CH2), 5.26-5.27(d, J= 3.6Hz, 1H, -CH), 7.49-7.52(m, 2H, Ar-H), 7.90-7.91(br d, J= 2Hz -NH), 8.21-8.31(m, 2H, Ar-H), 9.37(br s, -NH).

Ethyl 4-(2-chlorophenyl)-6-methyl-2-oxo-1,2,3,4-tetrahydropyrimidine-5-carboxylate (4h)

M.p. 218C [Lit[5] 216-217C]

1H NMR (400 MHz, CDCl3): δ1.06-1.09(t, J= 4Hz, 3 H, -CH3), 2.46(s, 3 H, -CH3), 4.00-4.06(q, J= 8Hz, 2H, -CH2), 5.66(br s, -NH), 5.89-5.90(q, J= 4Hz, 1H, -CH), 7.22-7.25(m, 3H, Ar-H), 7.37-7.41(m, 1H, Ar-H), 7.95(br s, –NH).

Ethyl 4-(4-cyanophenyl)-6-methyl-2-oxo-1,2,3,4-tetrahydropyrimidine-5-carboxylate (4i)

M.p. 179-182C [Lit[6] 180-182C]

1H NMR (400 MHz, CDCl3): δ1.18-1.22(t, J= 8Hz, 3H, -CH3), 2.38(s, 3 H, -CH3), 4.08-4.15(m, 2H, -CH2), 5.48-5.49(d, J= 4Hz, 1H, -CH), 5.55(br s, -NH), 7.18(br s, –NH), 7.46-7.48(m, 2H, Ar-H), 7.63-7.66(m, 2H, Ar-H).

Ethyl4-(2,4-dichlorophenyl)-6-methyl-2-oxo-1,2,3,4-tetrahydropyrimidine-5-carboxylate(4j)

M.p. 247C [Lit[7] 247-249C]

1H NMR (400 MHz, DMSO-d6): δ0.98-1.01(t, J= 8Hz, 3H, -CH3), 2.28(s, 3 H, -CH3), 3.86-3.91(q, J= 8Hz, 2H, -CH2), 5.58-5.59(d, J= 4Hz, 1H, -CH), 7.30-7.32(m, 1H, Ar-H), 7.40-7.43(m, 1H, Ar-H), 7.56-7.57(m, 1H, Ar-H), 7.77(br s, -NH), 9.33 (br s, -NH).

Ethyl 4-(2-methoxyphenyl)-6-methyl-2-oxo-1,2,3,4-tetrahydropyrimidine-5-carboxylate(4k)

M.p. 256C [Lit[8] 257-258C]

1H NMR (400 MHz, DMSO-d6): δ1.00-1.03(t, J=8 Hz, 3H, -CH3), 2.27(s, 3 H, -CH3), 3.78(s, 3H, -CH3), 3.86-3.94(m, 2H, -CH2), 5.47-5.48(d, J= 4Hz, 1H -CH), 6.85-6.88(m, 1H, Ar-H), 6.97-6.98 (m, 1H, Ar-H), 7.01-7.05(m, 1H, Ar-H), 7.20-7.25(m, 1H, Ar-H), 7.30 (br s, -NH), 9.13 (br s, -NH).

Ethyl4-(benzo[d][1,3]dioxol-5-yl)-6-methyl-2-oxo-1,2,3,4-tetrahydropyrimidine-5-carboxylate(4l)

M.p. 182C [Lit[4] 188-190C]

1H NMR(400 MHz, CDCl3): δ1.18-1.21(t, J= 8Hz, 3 H, -CH3), 2.34(s, 3 H, -CH3), 4.07-4.13(m, 2H, -CH2), 5.31-5.32(d, J =4Hz, 1H, -CH), 5.85-5.90(br t, -NH), 5.95(s, 2H, -CH2), 6.72-6.82 (m, 3H, Ar-H), 8.32 (br s, -NH).

Ethyl 4-(3-chlorophenyl)-6-methyl-2-oxo-1,2,3,4-tetrahydropyrimidine-5-carboxylate(4m)

M.p. 185-187C [Lit[5] 190-192C]

1H NMR (400 MHz, CDCl3): δ1.18-1.21 (t, J =8Hz, 3 H, -CH3), 2.37(s, 3 H, -CH3), 4.08-4.12(m, 2H, -CH2), 5.38-5.39(d, J= 4Hz, 1H, -CH), 5.88(br s, -NH), 7.22- 7.23(m, 1H, Ar-H), 7.25-7.27 (m, 2H, Ar-H), 7.28-7.31(m, 1H, Ar-H), 8.17(br s, -NH).

5-Acetyl-6-methyl-4-phenyl-3,4-dihydropyrimidin-2(1H)-one(6a)

M.p.212 C [Lit[9] 212-214C]

1H NMR (400 MHz, DMSO-d6): δ 2.10(s, 3H, -CH3), 2.28(s, 3 H, -CH3), 5.24-5.25(d, J= 4Hz, 1H -CH), 7.23-7.26(m, 3H, Ar-H), 7.30-7.34(m, 2H, Ar-H), 7.84(br s, -NH), 9.20(br s, -NH).

5-Acetyl-4-(4-fluorophenyl)-6-methyl-3,4-dihydropyrimidin-2(1H)-one(6b)

M.p.258 C [Lit[10] 260-261C]

1H NMR (400 MHz, DMSO-d6): δ 2.11(s, 3H, -CH3), 2.28(s, 3 H, -CH3), 5.24-5.25(d, J= 4Hz, 1H -CH), 7.13-7.17(m, 2H, Ar-H), 7.24-7.28(m, 2H, Ar-H), 7.86(br s, -NH), 9.24(br s, -NH).

5-Acetyl-4-(4-chlorophenyl)-6-methyl-3,4-dihydropyrimidin-2(1H)-one(6c)

M.p. 248C [Lit[11] 249-251C]

1H NMR (400 MHz, DMSO-d6): δ 2.12(s, 3H, -CH3), 2.28(s, 3 H, -CH3), 5.24-5.25(d, J= 4Hz, 1H -CH), 7.23-7.26(m, 2H, Ar-H), 7.37-7.40(m, 2H, Ar-H), 7.88(br s, -NH), 9.25 (br s, -NH).

5-Acetyl-4-(4-bromophenyl)-6-methyl-3,4-dihydropyrimidin-2(1H)-one(6d)

M.p. 233 C [Lit[11] 232-233C]

1H NMR (400 MHz, DMSO-d6): δ 2.12(s, 3 H, -CH3), 2.28(s, 3 H, -CH3), 5.23 (s, 1H -CH), 7.18-7.20(m, 2H, Ar-H), 7.51-7.53(m, 2H, Ar-H), 7.83(br s, -NH), 9.20(br s, -NH).

5-Acetyl-6-methyl-4-(p-tolyl)-3,4-dihydropyrimidin-2(1H)-one (6e)

M.p. 256 C [Lit[10] 256-257C]

1H NMR (400 MHz, DMSO-d6): δ 2.08(s, 3 H, -CH3), 2.25-2.27(two s merged, 6 H, -CH3), 5.20-5.21 (d, J= 2.8 Hz, 1H -CH), 7.12(m, 4H, Ar-H), 7.79(br s, -NH), 9.17(br s, -NH).

5-Acetyl-6-methyl-4-(4-nitrophenyl)-3,4-dihydropyrimidin-2(1H)-one (6f)

M.p. 252-254 C [Lit[12] 254-256C]

1H NMR (400 MHz, DMSO-d6): δ 2.18(s, 3 H, -CH3), 2.30(s, 3H, -CH3), 5.37-5.38 (d, J=3.6 Hz, 1H -CH), 7.48-7.52(m, 2H, Ar-H), 8.00(br s, -NH), 8.18-8.22(m, 2H, Ar-H), 9.35(br s, -NH).

References:

1. Kulkarni P (2016) Heterocyclic Letters. 6: 371.
2. Rao GBD, Acharya BN, Verma SK, Kaushik MP (2011) Tetrahedron Letters. 52: 809.
3. Pasunooti KK, Chai H, Jensen CN, Gorityala BK, Wang S,Liu XW (2011) Tetrahedron Letters. 52: 80.
4. Singh OM , Singh SJ, Devi MB, Devi LN, Singh NI, Lee SG (2008) Bioorg. Med. Chem. Lett. 18: 6462.
5. Shargh H, Jokar M (2009) Synthetic Communications 39: 958.
6. Shanmugam P, Annie G, Perumal PT (2003) J. Heterocyclic Chem. 40: 879.
7. Esfahani MN, Karami B, Montazerozohori M, Abdi. K (2008) J. Heterocyclic Chem. 45: 1183.
8. Zumpe FL, Fluß M, Schmitz K, Lender A (2007) Tetrahedron Letters. 48: 1421.
9. Zahra S, Heirati D, Shirini F, Shojaei AF (2016) RSC Adv. 6: 67072.
10. Chitra S, Pandiarajan K (2009) Tetrahedron Letters. 50: 2222.
11. Memarian HR, Farhadi A, Sabzyan H, Soleymani M (2010) Journal of Photochemistry and Photobiology A: Chemistry. 209: 95.
12. Ma J, Zhong L, Sun R (2016) Green Chem.18: 1738.

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