Molecular Iodine Catalysed Benzylic sp3 C–H Bond Amination for the Synthesis of 2-Arylquinazolines from 2-Aminobenzaldehydes, 2-Aminobenzophenones and 2-Aminobenzyl Alcohols

Dewal S. Deshmukh; Bhalchandra M. Bhanage

doi:10.1055/s-0037-1609200

Synlett, Table of Contents

Synlett 2018; 29(07): 979-985
DOI: 10.1055/s-0037-1609200

letter

Molecular Iodine Catalysed Benzylic sp³ C–H Bond Amination for the Synthesis of 2-Arylquinazolines from 2-Aminobenzaldehydes, 2-Aminobenzophenones and 2-Aminobenzyl Alcohols

Authors

Dewal S. Deshmukh

Department of Chemistry, Institute of Chemical Technology, Matunga, Mumbai-400019, India Email: bm.bhanage@ictmumbai.edu.in
Bhalchandra M. Bhanage *

Department of Chemistry, Institute of Chemical Technology, Matunga, Mumbai-400019, India Email: bm.bhanage@ictmumbai.edu.in

Abstract

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Abstract

Molecular iodine catalysed benzylic sp³ C–H bond amination has been developed for the synthesis of quinazolines from 2-aminobenzaldehydes and 2-aminobenzophenones with benzylamines. The use of oxygen as a green oxidant combined with the transition-metal-, additive- and solvent-free conditions makes the methodology economical and greener. The lack of aqueous work up also enhances the efficiency of this protocol. A series of 2-arylquinazolines was synthesised in good to excellent yields by using the developed protocol. 2-Aminobenzyl alcohols could also be employed to prepare the corresponding quinazoline derivatives.

Key words

transition-metal free - benzylic sp³ amination - 2-arylquinazoline - molecular iodine - oxygen

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References

References and Notes

1a Chen Z. Wang B. Zhang J. Yu W. Liu Z. Zhang Y. Org. Chem. Front. 2015; 2: 169
1b Gephart RT. III. Warren TH. Organometallics 2012; 31: 7728
1c Rouquet G. Chatani N. Angew. Chem. Int. Ed. 2013; 52: 11726
1d Pandey G. Laha R. Singh D. J. Org. Chem. 2016; 81: 7161
1e Truong T. Nguyen KD. Doan SH. Phan NT. S. Appl. Catal., A 2016; 510: 27
1f Tang D. Li X.-L. Guo X. Wu P. Li J.-H. Wang K. Jing H.-W. Chen B.-H. Tetrahedron 2014; 70: 4038
1g Jeffrey JL. Bartlett ES. Sarpong R. Angew. Chem. Int. Ed. 2013; 52: 2194
1h Guo S.-R. Pailla SK. Yang M. Adv. Synth. Catal. 2017; 359: 2
1i Feng J. Lv MF. Lu GP. Cai C. Org. Chem. Front. 2015; 2: 60
1j Xue D. Long Y.-Q. J. Org. Chem. 2014; 79: 4727
1k Yan Y. Zhang Y. Zha Z. Wang Z. Org. Lett. 2013; 15: 2274

2a Cenini S. Gallo E. Penoni A. Ragainia F. Tollari S. Chem. Commun. 2000; 2265
2b Lu H. Subbarayan V. Tao J. Zhang XP. Organometallics 2010; 29: 389
2c Ye Y.-H. Zhang J. Wang G. Chen S.-Y. Yu X.-Q. Tetrahedron 2011; 67: 4649

3a Powell DA. Fan H. J. Org. Chem. 2010; 75: 2726
3b Barman DN. Nicholas KM. Eur. J. Org. Chem. 2011; 908
3c Ni Z. Zhang Q. Xiong T. Zheng Y. Li Y. Zhang H. Zhang J. Liu Q. Angew. Chem. Int. Ed. 2012; 51: 1244

4a Nishioka Y. Uchida T. Katsuki T. Angew. Chem. Int. Ed. 2013; 52: 1739
4b Ichinose M. Suematsu H. Yasutomi Y. Nishioka Y. Uchida T. Katsuki T. Angew. Chem. Int. Ed. 2011; 50: 9884
4c Sun K. Sachwani R. Richert KJ. Driver TG. Org. Lett. 2009; 11: 3598

5a Intrieri D. Mariani M. Caselli A. Ragaini F. Gallo E. Chem. Eur. J. 2012; 18: 10487
5b Milczek E. Boudet N. Blakey S. Angew. Chem. Int. Ed. 2008; 47: 6825
5c Zardi P. Caselli A. Macchi P. Ferretti F. Gallo E. Organometallics 2014; 33: 2210

6 Peng H. Lin A. Zhang Y. Jiang H. Zhou J. Cheng Y. Zhu C. Hu H. ACS Catal. 2012; 2: 163
7 Zhang M. J. Chem. Res. 2013; 606

8a Liu J. Zhang H. Yi H. Liu C. Lei A. Sci. China Chem. 2015; 58: 1323
8b Yang L. Shi X. Hu B.-Q. Wang L.-X. Asian J. Org. Chem. 2016; 5: 494
8c Xue Q. Xie J. Li H. Chenga Y. Zhu C. Chem. Commun. 2013; 3700
8d Zhao D. Shen Q. Li J.-X. Adv. Synth. Catal. 2015; 357: 339
8e Liu W. Liu C. Zhang Y. Sun Y. Abdukadera A. Wang B. Li H. Ma X. Zhang Z. Org. Biomol. Chem. 2015; 13: 7154
8f Takeda Y. Hayakawa J. Yano K. Minakata S. Chem. Lett. 2012; 41: 1672
8g Fan R. Li W. Pu D. Zhang L. Org. Lett. 2009; 11: 1425

9a Zhang M. Zhang A.-Q. Peng Y. J. Organomet. Chem. 2013; 723: 224
9b Tsukano C. Chem. Pharm. Bull. 2017; 65: 409

10a Yusubova MS. Zhdankin MS. Resource-Efficient Technologies 2015; 1: 49
10b Biswas A. Selling GS. Shogren RL. Willett JL. Buchananand CM. Cheng HN. Chem. Today 2009; 27: 33
10c Yamamoto Y. Gridnev ID. Patil NT. Jin T. Chem. Commun. 2009; 5075
10d Liu D. Lei A. Chem. Asian J. 2015; 10: 806
10e Veisi H. Curr. Org. Chem. 2011; 15: 2438
10f Mphahlele MJ. Molecules 2009; 14: 5308
10g Ren Y.-M. Cai C. Yang R.-C. RSC Adv. 2013; 3: 7182
10h Mphahlele MJ. Molecules 2009; 14: 4814
10i Parvatkar PT. Parameswaran PS. Tilve SG. Chem. Eur. J. 2012; 18: 5460

11 Tekalea SU. Kauthalea SS. Dakea SA. Sardab SR. Pawar RP. Curr. Org. Chem. 2012; 16: 1485

12a Vijaychand A. Manjula SN. Bharath EN. Divya B. Int. J. Pharma Bio Sci. 2011; 2: 780
12b Ravez S. Castillo-Aguilera O. Depreux P. Goossens L. Expert Opin. Ther. Pat. 2015; 25: 1
12c Jafari E. Khajouei MR. Hassanzadeh F. Hakimelahi GH. Khodarahmi GA. Res. Pharma. Sci. 2016; 11: 1
12d Khan I. Ibrar A. Ahmed W. Saeed A. Eur. J. Med. Chem. 2015; 90: 124
12e Ajani OO. Audu OY. Aderohunmu DV. Owolabi DV. Olomieja AO. Am. J. Drug Discov. Dev. 2017; 7: 1

13a Zhang Z. Wang M. Zhang C. Zhang Z. Lua J. Wang F. Chem. Commun. 2015; 9205
13b Tiwari AR. Bhanage BM. Org. Biomol. Chem. 2016; 14: 10567
13c Li C. An S. Zhu Y. Zhang J. Kang Y. Liu P. Wang Y. Li J. RSC Adv. 2014; 4: 49888
13d Chen X. Chen T. Ji F. Zhou Y. Yin S.-F. Catal. Sci. Technol. 2015; 5: 2197
13e Ma J. Wan Y. Hong C. Li M. Hu X. Mo W. Hu B. Sun N. Jin L. Shen Z. Eur. J. Org. Chem. 2017; 3335
13f Chen X. Qi H. Wu S. Liu L. Wen J. Li W. Guo F. Bian Y. Li J. Heterocycles 2017; 94: 86

14a Sarode SA. Jadhav VG. Nagarkar JM. Tetrahedron Lett. 2017; 58: 779
14b Yao S. Zhou K. Wang J. Cao H. Yu L. Wu J. Qiu P. Xu Q. Green Chem. 2017; 19: 2945
14c Chen Z. Chen J. Liu M. Ding J. Gao W. Huang X. Wu H. J. Org. Chem. 2013; 78: 11342
14d Chen M. Zhang M. Xiong B. Tan Z. Lv W. Jiang H. Org. Lett. 2014; 16: 6028

15 Ju J. Hua R. Sua J. Tetrahedron 2012; 68: 9364

16a Omar MA. Conrad J. Beifuss U. Tetrahedron 2014; 70: 3061
16b Wang C. Li S. Liu H. Jiang Y. Fu H. J. Org. Chem. 2010; 75: 7936

17 Omar MA. Conrad J. Beifuss U. Tetrahedron 2014; 70: 5682
18 Malakar CC. Baskakova A. Conrad J. Beifuss U. Chem. Eur. J. 2012; 18: 8882
19 Wang H. Chen H. Chen Y. Deng G.-J. Org. Biomol. Chem. 2014; 12: 7792
20 Tang L. Wang P. Fan Y. Yang X. Wan C. Zha Z. ChemCatChem 2016; 8: 3565

21a Truong VL. Morrow M. Tetrahedron Lett. 2010; 51: 758
21b Xu C. Jia F.-C. Zhou Z.-W. Zheng S.-J. Li H. Wu A.-X. J. Org. Chem. 2016; 81: 3000
21c Raut AB. Tiwari AR. Bhanage BM. ChemCatChem 2017; 9: 1292
21d Yan Y. Wang Z. Chem. Commun. 2011; 9513

22 Zhang J. Zhu D. Yu C. Wan C. Wang Z. Org. Lett. 2010, 12: 2841
23 Han B. Wang C. Han R.-F. Yu W. Duan X.-Y. Fang R. Yang X.-L. Chem. Commun. 2011; 7818
24 Gopalaiah K. Saini A. Devi A. Org. Biomol. Chem. 2017; 15: 5781

25a Nale DB. Bhanage BM. Green Chem. 2015; 17: 2480
25b Wagh KV. Bhanage BM. Green Chem. 2015; 17: 4446
25c Tiwari AR. Bhanage BM. Green Chem. 2016; 18: 144
25d Yedage SL. Bhanage BM. Green Chem. 2016; 18: 5635
25e Gautam P. Dhiman P. Polshettiwar V. Bhanage BM. Green Chem. 2016; 18: 5890
25f Gautam P. Kathe P. Bhanage BM. Green Chem. 2017; 19: 823

26 General experimental procedure for the synthesis of 2-arylquinazolines (3): An oven-dried 25 mL round-bottom flask was charged with 2-aminobenzaldehyde/2-aminobenzophenone (1, 0.5 mmol) or 2-aminobenzyl alcohol (4a, 0.5 mmol) with benzylamine (2, 1.5 mmol) and molecular iodine (10 mol%). The mixture was then stirred at 130 °C for 3–15 h under an oxygen atmosphere, and the progress of the reaction was monitored by TLC. Upon completion, the mixture was cooled to room temperature and the crude product was purified by column chromatography. 6-Chloro-2-(4-methoxyphenyl)quinazoline (3b) Yellow solid (88%); mp 168–170 °C; ¹H NMR (400 MHz, CDC₃): δ = 9.32 (s, 1 H), 8.54–8.52 (m, 2 H), 7.95 (d, J = 9.0 Hz, 1 H), 7.85 (d, J = 2.1 Hz, 1 H), 7.77 (dd, J = 9.0, 2.3 Hz, 1 H), 7.02 (d, J =8.4 Hz, 2 H), 3.88 (s, 3 H); ¹³C NMR (101 MHz, CDCl₃): δ = 162.0, 161.1, 159.4, 149.3, 135.0, 132.2, 130.2, 130.1, 125.8, 123.7, 114.0, 55.4; GCMS (EI, 70 eV): m/z (%) = 270 (100), 255 (24), 227 (14), 192 (10). 2,4-Diphenylquinazoline (3q) White solid (88%); mp 117–119 °C; ¹H NMR (500 MHz, CDCl₃): δ = 8.69 (d, J = 8.1 Hz, 2 H), 8.15 (d, J = 8.4 Hz, 1 H), 8.11 (d, J = 8.4 Hz, 1 H), 7.89–7.85 (m, 3 H), 7.60–7.58 (m, 3 H), 7.54–7.47 (m, 4 H); ¹³C NMR (125 MHz, CDCl₃): δ = 168.3, 160.2, 152.0, 138.2, 137.7, 133.5, 130.5, 130.2, 129.9, 129.2, 128.7, 128.5, 127.0, 121.7; GCMS (EI, 70 eV): m/z (%) = 282 (65), 281 (100), 203 (8), 178 (8), 151 (6), 141 (7), 77 (8)

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