1

2-Methoxyphenylisocyanate: A chemoselective multitasking reagent for amine protection/deprotection sequence

Anand Babu Velappan,a Kogatam Subhashini,a Dhrubajyoti Datta,b Rakshantha Srithar,a Nanjappan Gunasekarana and Joy Debnatha*

aDepartment of Chemistry, SCBT, SASTRA Deemed University, Tamilnadu 613401, India. bDepartment of Chemistry, Indian Institute of Science Education and Research , Pune, Maharashtra,

411008, India.

Supporting Information II

1. 1H-NMR for 2a 4 2. 13C-NMR for 2a 4 3. 1H-NMR for 3a 5 4. 13C-NMR for 3a 5 5. 1H-NMR for 2b 6 6. 13C-NMR for 2b 6 7. 1H-NMR for 3b 7 8. 13C-NMR for 3b 7 9. 1H-NMR for 2c 8 10. 13C-NMR for 2c 8 11. 1H-NMR for 3c 9 12. 13C-NMR for 3c 9 13. 1H-NMR for 2d 10 14. 13C-NMR for 2d 10 15. 1H-NMR for 3d 11 16. 13C-NMR for 3d 11 17. 1H-NMR for 2e 12 18. 13C-NMR for 2e 12 19. 1H-NMR for 3e 13 20. 13C-NMR for 3e 13 21. 1H-NMR for 2f 14 22. 13C-NMR for 2f 14 23. 1H-NMR for 3f 15 24. 13C-NMR for 3f 15 25. 1H-NMR for 2g 16 26. 13C-NMR for 2g 16 27. 1H-NMR for 3g 17 28. 13C-NMR for 3g 17 29. 1H-NMR for 2h 18 30. 13C-NMR for 2h 18 31. 1H-NMR for 3h 19 32. 13C-NMR for 3h 19 33. 1H-NMR for 2i 20 34. 13C-NMR for 2i 20 35. 1H-NMR for 3i 21 36. 13C-NMR for 3i 21 37. 1H-NMR for 2j 22 38. 13C-NMR for 2j 22 39. 1H-NMR for 3j 23 40. 13C-NMR for 3j 23

Electronic Supplementary Material (ESI) for Organic Chemistry Frontiers.This journal is © the Partner Organisations 2019

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41. 1H-NMR for 2k 24 42. 13C-NMR for 2k 24 43. 1H-NMR for 3k 25 44. 13C-NMR for 3k 25 45. 1H-NMR for 2l 26 46. 13C-NMR for 2l 26 47. 1H-NMR for 3l 27 48. 1H-NMR for 2m 28 49. 13C-NMR for 2m 28 50. 1H-NMR for 3m 29 51. 13C-NMR for 3m 29 52. 1H-NMR for 2n 30 53. 13C-NMR for 2n 30 54. 1H-NMR for 2o 31 55. 13C-NMR for 2o 31 56. 1H-NMR for 3o 32 57. 13C-NMR for 3o 32 58. 1H-NMR for 2p 33 59. 13C-NMR for 2p 33 60. 1H-NMR for 2q 34 61. 13C-NMR for 2q 34 62. 1H-NMR for 2r 35 63. 13C-NMR for 2r 35 64. 1H-NMR for 3r 36 65. 13C-NMR for 3r 36 66. 1H-NMR for 2s 37 67. 13C-NMR for 2s 37 68. 1H-NMR for 3s 38 69. 13C-NMR for 3s 38 70. 1H-NMR for 2t 39 71. 13C-NMR for 2t 39 72. 1H-NMR for 3t 40 73. 13C-NMR for 3t 40 74. 1H-NMR for 2u 41 75. 13C-NMR for 2u 41 76. 1H-NMR for 3u 42 77. 13C-NMR for 3u 42 78. 1H-NMR for 1-(3-Methoxy-phenyl)-3-o-tolyl-urea (5) 43 79. 13C-NMR for 1-(3-Methoxy-phenyl)-3-o-tolyl-urea (5) 43 80. 1H-NMR for 1-(3-Hydroxy-phenyl)-3-o-tolyl-urea (6) 44 81. 13C-NMR for 1-(3-Hydroxy-phenyl)-3-o-tolyl-urea (6) 44 82. 1H-NMR for 1-(4-Methoxy-phenyl)-3-o-tolyl-urea (7) 45 83. 13C-NMR for 1-(4-Methoxy-phenyl)-3-o-tolyl-urea (7) 45 84. 1H-NMR for 1-(4-Hydroxy-phenyl)-3-o-tolyl-urea (8) 46 85. 13C-NMR for 1-(4-Hydroxy-phenyl)-3-o-tolyl-urea (8) 46 86. 1H-NMR for 3H-Benzooxazol-2-one (4) 47 87. 13C-NMR for 3H-Benzooxazol-2-one (4) 47 88. HRMS for 3H-Benzooxazol-2-one (4) 48 89. 1H-NMR for 9 49 90. 1H-NMR for 10 49 91. 1H-NMR for 11 50 92. 1H-NMR for 12 50 93. 1H-NMR for 13 51 94. 1H-NMR for 1-(4-Amino-phenyl)-3-(2-methoxy-phenyl)-urea 51 95. 1H-NMR for 15 52

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96. 1H-NMR for 16 52 97. 1H-NMR for 17 53 98. 1H-NMR for 18 53 99. 1H-NMR for 1-(4-Amino-phenyl)-3-(2-hydroxy-phenyl)-urea 54 100. p-phenylenediamine 54 101. 1H-NMR for Boc-aniline 55 102. 1H-NMR for Troc-aniline 55 103. 1H-NMR for Fmoc-aniline 56 104. 1H-NMR for Ac-aniline 56 105. 1H-NMR for Benzyl-aniline 57 106. 1H-NMR for Allyl-aniline 57 107. 1H-NMR for Boc-phenol 58 108. 1H-NMR for Troc- phenol 58 109. 1H-NMR for Ac- phenol 59 110. 1H-NMR for TBS- phenol 59 111. 1H-NMR for Benzyl- phenol 60 112. 1H-NMR for allyl- phenol 60 113. 1H-NMR for 20 61 114. 13C-NMR for 20 61 115. 1H-NMR for 22 62 116. 13C-NMR for 22 62 117. 1H-NMR for 24 63 118. 13C-NMR for 24 63 119. 1H-NMR for 26 64 120. 13C-NMR for 26 64

4

1H-NMR for 2a:

13C-NMR for 2a:

5

1H-NMR for 3a:

13C-NMR for 3a:

6

1H-NMR for 2b:

13C-NMR for 2b:

7

1H-NMR for 3b:

13C-NMR for 3b:

8

1H-NMR for 2c:

13C-NMR for 2c:

9

1H-NMR for 3c:

13C-NMR for 3c:

10

1H-NMR for 2d:

13C-NMR for 2d:

11

1H-NMR for 3d:

13C-NMR for 3d:

12

1H-NMR for 2e:

13C-NMR for 2e:

13

1H-NMR for 3e:

13C-NMR for 3e:

14

1H-NMR for 2f:

13C-NMR for 2f:

15

1H-NMR for 3f:

13C-NMR for 3f:

16

1H-NMR for 2g:

13C-NMR for 2g:

17

1H-NMR for 3g:

13C-NMR for 3g:

18

1H-NMR for 2h:

13C-NMR for 2h:

19

1H-NMR for 3h:

13C-NMR for 3h:

20

1H-NMR for 2i:

13C-NMR for 2i:

21

1H-NMR for 3i:

13C-NMR for 3i:

22

1H-NMR for 2j:

13C-NMR for 2j:

23

1H-NMR for 3j:

13C-NMR for 3j:

24

1H-NMR for 2k:

13C-NMR for 2k:

25

1H-NMR for 3k:

13C-NMR for 3k:

26

1H-NMR for 2l:

13C-NMR for 2l:

27

1H-NMR for 3l:

28

1H-NMR for 2m:

13C-NMR for 2m:

29

1H-NMR for 3m:

13C-NMR for 3m:

30

1H-NMR for 2n:

13C-NMR for 2n:

31

1H-NMR for 2o:

13C-NMR for 2o:

32

1H-NMR for 3o:

13C-NMR for 3o:

33

1H-NMR for 2p:

13C-NMR for 2p:

34

1H-NMR for 2q:

13C-NMR for 2q:

35

1H-NMR for 2r:

13C-NMR for 2r:

36

1H-NMR for 3r:

13C-NMR for 3r:

37

1H-NMR for 2s:

13C-NMR for 2s:

38

1H-NMR for 3s:

13C-NMR for 3s:

39

1H-NMR for 2t:

13C-NMR for 2t:

40

1H-NMR for 3t:

13C-NMR for 3t:

41

1H-NMR for 2u:

13C-NMR for 2u:

42

1H-NMR for 3u:

13C-NMR for 3u:

43

1H-NMR for 1-(3-Methoxy-phenyl)-3-o-tolyl-urea (5):

13C-NMR for 1-(3-Methoxy-phenyl)-3-o-tolyl-urea (5):

44

1H-NMR for 1-(3-Hydroxy-phenyl)-3-o-tolyl-urea (6):

13C-NMR for 1-(3-Hydroxy-phenyl)-3-o-tolyl-urea (6):

45

1H-NMR for 1-(4-Methoxy-phenyl)-3-o-tolyl-urea (7):

13C-NMR for 1-(4-Methoxy-phenyl)-3-o-tolyl-urea (7):

46

1H-NMR for 1-(4-Hydroxy-phenyl)-3-o-tolyl-urea (8):

13C-NMR for 1-(4-Hydroxy-phenyl)-3-o-tolyl-urea (8):

47

1H-NMR for 4:

13C-NMR for 4:

48

HRMS for 4:

49

1H-NMR for 9:

1H-NMR for 10:

50

1H-NMR for 11:

1H-NMR for 12:

51

1H-NMR for 13: 1H-NMR for 1-(4-Amino-phenyl)-3-(2-methoxy-phenyl)-urea:

52

1H-NMR for 15:

1H-NMR for 16:

53

1H-NMR for 17: 1H-NMR for 18:

54

1H-NMR for 1-(4-Amino-phenyl)-3-(2-hydroxy-phenyl)-urea:

p-phenylenediamine:

55

1H-NMR for Boc-aniline:

1H-NMR for Troc-aniline:

56

1H-NMR for Fmoc-aniline:

1H-NMR for Ac-aniline:

57

1H-NMR for Bn-aniline:

1H-NMR for Allyl-aniline:

58

1H-NMR for Boc-phenol:

1H-NMR for Troc-phenol:

59

1H-NMR for Ac-phenol:

1H-NMR for TBS-phenol:

60

1H-NMR for Benzyl-phenol:

1H-NMR for Allyl-phenol:

61

1H-NMR of 20:

13C-NMR of 20:

62

1H-NMR of 22:

13C-NMR of 22:

63

1H-NMR of 24:

13C-NMR of 24:

64

1H-NMR of 26:

13C-NMR of 26: