Room-Temperature, Base-Mediated Selective Synthesis of 2-(Arylamino)ethanols and 2-Aryloxyethanols

Rahul B. Sonawane; Swapnali R. Sonawane; Nishant K. Rasal; Sangeeta V. Jagtap

doi:10.1055/s-0039-1690334

SynOpen, Table of Contents

CC BY-ND-NC 4.0 · SynOpen 2019; 03(04): 124-137
DOI: 10.1055/s-0039-1690334

paper

Copyright with the author(s) (2019) The author(s)

Room-Temperature, Base-Mediated Selective Synthesis of 2-(Arylamino)ethanols and 2-Aryloxyethanols

Rahul B. Sonawane

,

Swapnali R. Sonawane

,

Nishant K. Rasal

,

Sangeeta V. Jagtap ∗

Department of Chemistry, Baburaoji Gholap College, Sangvi, Pune 411027, India (Affiliated to Savitribai Phule Pune University, Pune, India) Email: sangeetajagtap@rediffmail.com

› Author Affiliations

Abstract

All articles of this category

Abstract

A simple and efficient protocol for base-mediated selective synthesis of 2-(arylamino)ethanols from primary aromatic amines and 2-aryloxyethanols from phenols, promoted by K₂CO₃ has been achieved under mild conditions. Even in presence of excess alkyl halide, selective mono-N-alkylation has been achieved. Tolerance of a variety of functional groups is demonstrated by 15 examples of selective N-alkylation of aromatic amines and 19 examples of O-alkylation of phenols. The efficacy of the protocol is demonstrated by the formal synthesis of Ticlopidine^®, Vildagliptin^®, Quetiapine^®, and Gemfibrozil^®.

Key words

selective N-alkylation - 2-(arylamino)ethanols - amines - 2-aryloxyethanols - phenols - K₂CO₃ promoted - Na₂CO₃ controlled

Full Text

References

References

1a Lawrence SA. Amines: Synthesis Properties and Applications . Cambridge University Press; Cambridge: 2006
1b Patai S. Chemistry of the Amino Group. . Wiley Interscience; New York: 1968
1c Simplício AL, Clancy JM, Gilmer JF. Molecules 2008; 13: 519

2 Sheldon RA, Van Bekkum H. Fine Chemicals through Heterogeneous Catalysis . John Wiley & Sons; New York: 2008
3 Elangovan S, Neumann J, Sortais J.-B, Junge K, Darcel C, Beller M. Nat. Commun. 2016; 7: 12641
4 Harrison IR, Kozlik A, McCarthy JF, Palmer BH, Wakerley SB, Watkins TI, Weighton DM. Pestic. Sci. 1973; 4: 901
5 Wu L, Burgess K. Org. Lett. 2008; 10: 1779
6 Travis AS. The Chemistry of Anilines . Rappoport Z. John Wiley & Sons; New York: 2007: 715
7 Seayad A, Ahmed M, Klein H, Jackstell R, Gross T, Beller M. Science 2002; 297: 1676
8 Cazorla C, Pfordt É, Duclos M.-C, Métay E, Lemaire M. Green Chem. 2011; 13: 2482
9 Kan T, Fukuyama T. Chem. Commun. 2004; 4: 353
10 For a review on the direct alkylation of primary amines with alkyl halides, see: Salvatore RN, Yoon CH, Jung KW. Tetrahedron 2001; 57: 7785

11a Sorribes I, Junge K, Beller M. J. Am. Chem. Soc. 2014; 136: 14314
11b Volkov A, Tinnis F, Adolfsson H. Org. Lett. 2014; 16: 680
11c Lampland NL, Hovey M, Mukherjee D, Sadow AD. ACS Catal. 2015; 5: 4219

12a Reddy PS, Kanjilal S, Sunitha S, Prasad RB. N. Tetrahedron Lett. 2007; 48: 8807
12b Byun E, Hong B, De Castro KA, Lim M, Rhee H. J. Org. Chem. 2007; 72: 9815
12c Liao W, Chen Y, Liu Y, Duan H, Petersen JL, Shi X. Chem. Commun. 2009; 42: 6436
12d Nador F, Moglie Y, Ciolino A, Pierini A, Dorn V, Yus M, Alonso F, Radivoy G. Tetrahedron Lett. 2012; 53: 3156
12e Bogolubsky AV, Moroz YS, Mykhailiuk PK, Panov DM, Pipko SE, Konovets AI, Tolmachev A. ACS Comb. Sci. 2014; 16: 375

13a Bhat RG, Ghosh Y, Chandrasekaran S. Tetrahedron Lett. 2004; 45: 7983
13b Zhen L, Lin Y, Lianghui L, Bing W, Xuefeng F. Chem. Commun. 2013; 49: 4214

14a Surry DA, Buchwald SL. Angew. Chem. Int. Ed. 2008; 47: 6338
14b Cawley MJ, Cloke FG. N, Fitzmaurice RJ, Pearson SE, Scott JS, Caddick S. Org. Biomol. Chem. 2008; 6: 2820
14c Zhao X, Liu D, Guo H, Liu Y, Zhang W. J. Am. Chem. Soc. 2011; 133: 19354

15a Saidi O, Blacker AJ, Farah MM, Marsden SP, Williams JM. J. Angew. Chem. Int. Ed. 2009; 48: 7375; Angew. Chem. 2009, 121, 7511
15b Tsai C.-Y, Sung R, Zhuang B.-R, Sung K. Tetrahedron 2010; 66: 6869
15c Cui X, Dai X, Deng Y, Shi F. Chem. Eur. J. 2013; 19: 3665
15d Yan T, Feringa BL, Barta K. Nat. Commun. 2014; 5: 5602
15e Kolesnikov PN, Yagafarov NZ, Usanov DL, Maleev VI, Chusov D. Org. Lett. 2015; 17: 173

16a Bhattacharyya S, Pathak U, Mathur S, Vishnoi S, Jain R. RSC Adv. 2014; 4: 18229
16b Gupta M, Paul S, Gupta R. Chin. J. Catal. 2014; 35: 444
16c Hayat S, Atta-ur-Rahman, Choudhary MI, Khan KM, Schumann W, Bayer E. Tetrahedron 2001; 57: 9951
16d Gawande MB, Deshpande SS, Satam JR, Jayaram RV. Catal. Commun. 2007; 8: 576
16e Bar-Haim G, Kol M. Org. Lett. 2004; 6: 3549
16f Granchi C, Capecchi A, Del Frate G, Martinelli A, Macchia M, Minutolo F, Tuccinardi T. Molecules 2015; 20: 8772

17a Naskar S, Bhattacharjee M. Tetrahedron Lett. 2007; 48: 3367
17b Fujita K, Li Z, Ozekib N, Yamaguchi R. Tetrahedron Lett. 2003; 44: 2687
17c Kawahara R, Fujita K, Yamaguchi R. Adv. Synth. Catal. 2011; 353: 1161
17d Botta M, De Angelis F, Nicoletti R. Synthesis 1977; 722
17e Tayade KN, Mishra M, Munusamy K, Somani RS. J. Mol. Catal. A: Chem. 2014; 390: 91
17f Nagaraju N, Kuriakose G. New J. Chem. 2003; 27: 765

18 Selva M, Tundo P, Perosa A. J. Org. Chem. 2003; 68: 7374
19 Llabres-Campaner PJ, Ballesteros-Garrido R, Ballesteros R, Abarca B. Tetrahedron 2017; 73: 5552

20a Freifelder M, Stone GR. J. Org. Chem. 1961; 26: 1477
20b Azizi N, Saidi MR. Org. Lett. 2005; 7: 3649

21a Yin J, Ye G, Wang X. J. Mater. Chem. C 2013; 1: 3794
21b Ross WC. J. J. Chem. Soc. 1949; 183
21c Chen J, Peng Z, Lu M, Xiong X, Chen Z, Li Q, Cheng Z, Jiang D, Tao L, Hua G. Bioorg. Med. Chem. Lett. 2018; 28: 222
21d Campbell D, Dix LR, Rostron P. Dyes Pigm. 1995; 29: 77
21e Guo H, Zhuang Y, Cao J, Zhang G. Synth. Commun. 2014; 44: 3368
21f Rindfusz RE, Harnack VL. J. Am. Chem. Soc. 1920; 42: 1720

22 Li X.-D, Xia S.-M, Chen K.-H, Liu X.-F, Li H.-R, He L.-N. Green Chem. 2018; 20: 4853
23 Brielles C, Harnett JJ, Dorisa E. Tetrahedron Lett. 2001; 42: 8301

24a Poirot M, De Medina P, Delarue F, Perie J.-J, Klaebe A, Faye J.-C. Bioorg. Med. Chem. 2000; 8: 2007
24b Gupta PP, Sharma JN. J. Med. Chem. 1973; 16: 797
24c Srivastava SK, Chauhan PM. S, Bhaduri AP. Synth. Commun. 1999; 29: 2085

25 Singh CB, Kavala V, Samal AK, Patel BK. Eur. J. Org. Chem. 2007; 1369
26 Depreux P, Aichaoui H, Lesieur I. Heterocycles 1993; 36: 1051

27a Salvatore RN, Nagle AS, Jung KW. J. Org. Chem. 2002; 67: 674
27b Salvatore RN, Nagle AS, Schmidt SE, Jung KW. Org. Lett. 1999; 1: 1893

28a Díaz JE, Bisceglia J. Á, Mollo MC, Orelli LR. Tetrahedron Lett. 2011; 52: 1895
28b Fink DM. Synlett 2004; 2394
28c Castillo J.-C, Orrego-Hernández J, Portilla J. Eur. J. Org. Chem. 2016; 3824

29a Monopoli A, Cotugno P, Cortese M, Calvano CD, Ciminale F, Nacci A. Eur. J. Org. Chem. 2012; 3105
29b Chiappe C, Piccioli P, Pieraccini D. Green Chem. 2006; 8: 277

30 Cardullo F, Donati D, Fusillo V, Merlo G, Paio A, Salaris M, Solinas A, Taddei M. J. Comb. Chem. 2006; 8: 834
31 Landge VG, Mondal A, Kumar V, Nandakumar A, Balaraman E. Org. Biomol. Chem. 2018; 16: 8175
32 Vellakkaran M, Singh K, Banerjee D. ACS Catal. 2017; 7: 8152
33 Ogata O, Nara H, Fujiwhara M, Matsumura K, Kayaki Y. Org. Lett. 2018; 20: 3866
34 Basu B, Paul S, Nanda AK. Green Chem. 2009; 11: 1115

35a Williamson AW. J. Chem. Soc. 1852; 229
35b Fuhrmann E, Talbiersky J. Org. Process Res. Dev. 2005; 9: 206
35c Mandal S, Mandal S, Ghosh SK, Sar P, Ghosh A, Saha R, Saha B. RSC Adv. 2016; 6: 69605

36 Sueki S, Kuninobu Y. Org. Lett. 2013; 15: 1544

37a Ando T, Yamawaki J, Kawate T, Sumi S, Hanafusa T. Bull. Chem. Soc. Jpn. 1982; 55: 2504
37b Xu W, Mohan R, Morrissey MM. Tetrahedron Lett. 1997; 38: 7337
37c Huston RC, Guile RL, Chen PS, Headley WN, Warren GW, Baur LS, Mate BO. J. Am. Chem. Soc. 1933; 55: 4639
37d Johnstone RA. W, Rose ME. Tetrahedron 1979; 35: 2169
37e Keglevich G, Bálint E, Karsai É, Grün A, Bálint M, Greiner I. Tetrahedron Lett. 2008; 49: 5039
37f De Zani D, Colombo M. J. Flow Chem. 2012; 2: 5
37g Bogdal D, Pielichowski J, Boron A. Synth. Commun. 1998; 28: 3029
37h Brieger G, Hachey D, Nestrick T. J. Chem. Eng. Data 1968; 13: 581
37i Bu X, Jing H, Wang L, Chang T, Jin L, Liang Y. J. Mol. Catal. A: Chem. 2006; 259: 121

38a Cazorla C, Pfordt E, Duclos M.-C, Métay E, Lemaire M. Green Chem. 2011; 13: 2482
38b Lindstedt E, Ghosh R, Olofsson B. Org. Lett. 2013; 15: 6070
38c Samolada MC, Grigoriadou E, Kiparissides Z, Vasalos IA. J. Catal. 1995; 152: 52

39a Basak A, Nayak MK, Chakraborti AK. Tetrahedron Lett. 1998; 39: 4883
39b Perosa A, Selva M, Tundo P, Zordan F. Synlett 2000; 272

40 Trost BM, Toste FD. J. Am. Chem. Soc. 1998; 120: 815

41a Teruo Y, Shigeru I, Yoshiharu I. Bull. Chem. Soc. Jpn. 1973; 46: 553
41b Wang S, Dupin L, Noël M, Carroux CJ, Renaud L, Géhin T, Meyer A, Souteyrand E, Vasseur J.-J, Vergoten G, Chevolot Y, Morvan F, Vidal S. Chem. Eur. J. 2016; 22: 11785

42 Yamansarova ET, Kukovinets AG, Kukovinets OS, Zainullin RA, Galin FZ, Kunakova RV, Zorin VV, Tolstikov GA. Russ. J. Org. Chem. 2001; 37: 246

43a Turgut Y, Aral T, Karakaplan M, Deniz P, Hosgoren H. Synth. Commun. 2010; 40: 3365
43b Rastogi SN, Anand N, Gupta PP, Sharma JN. J. Med. Chem. 1973; 16: 797

44a Purushothaman S, Prasanna R, Niranjana P, Raghunathan R, Nagaraj S, Rengasamy R. Bioorg. Med. Chem. Lett. 2010; 20: 7288
44b Cho WS, Kim SH, Kim DJ, Mun S.-D, Kim R, Go MJ, Park MH, Kim M, Lee J, Kim Y. Polyhedron 2014; 67: 205
44c Dong M, Si YQ, Sun SY, Pu XP, Yang ZJ, Zhang LR, Zhang LH, Leung FP, Lam CM. C, Kwong AK. Y, Yue J. Org. Biomol. Chem. 2011; 9: 3246

45 Morales P, Gomez-Canas M, Navarro G, Hurst DP, Carrillo-Salinas FJ, Lagartera L, Pazos R, Goya P, Reggio PH, Guaza C, Franco R, Fernandez-Ruiz J, Jagerovic N. J. Med. Chem. 2016; 59: 6753
46 Hu Z, Zhang S, Zhou W, Ma X, Xiang G. Bioorg. Med. Chem. Lett. 2017; 27: 1854
47 Parrish JP, Sudaresan B, Jung KW. Synth. Commun. 1999; 29: 4423
48 More SV, Ardhapure SS, Naik NH, Bhusare SR, Jadhav WN, Pawar RP. Synth. Commun. 2005; 35: 3113

49a Dermer OC. Chem. Rev. 1934; 14: 385
49b Mazaleyrat J.-P, Wakselman M. J. Org. Chem. 1996; 61: 2695

50a Platonov AY, Evdokimov AN, Kurzin AV, Maiyorova HD. J. Chem. Eng. Data 2002; 47: 1175
50b Stenger VA. J. Chem. Eng. Data 1996; 41: 1111

For ticlopidine synthesis:

51a Maffrand JP, Eloy F. Eur. J. Med. Chem. 1974; 9: 483
51b Maffrand JP, Eloy F. J. Heterocycl. Chem. 1976; 13: 1347

For vildagliptin synthesis:

52a Deng Y, Wang A, Tao Z, Chen Y, Pan X, Hu X. Lett. Org. Chem. 2014; 11: 780
52b Castaldi M, Baratella M, Menegotto IG, Castaldi G, Giovenzana GB. Tetrahedron Lett. 2017; 58: 3426

53 For quetiapine synthesis: Bharathi CH, Prabahar KJ, Prasad CS, Srinivasa Rao M, Trinadhachary GN, Handa VK, Dandala R, Naidu A. Pharmazie 2008; 63: 14

For gemfibrozil synthesis:

54a Nunna R, Jayanna ND, Ramachandran D. Asian J. Chem. 2015; 27: 925
54b Madasu SB, Vekariya NA, Velladurai H, Islam A, Sanasi PD, Korupolu RB. Org. Process Res. Dev. 2013; 17: 963

55 Aillaud I, Haurena C, Gall EL, Martens T, Ricci G. Molecules 2010; 15: 8144
56 Xu X, Guo J, Su Q, Zhong X. Asian J. Chem. 2013; 25: 7557
57 Li M, Wang JJ. Org. Lett. 2018; 20: 6490
58 McManus JB, Nicewicz DA. J. Am. Chem. Soc. 2017; 139: 2880

Supplementary Material

Supporting Information