1

Supporting Information

α-Haloacrylates as acceptors in the [3+2] cycloaddition reaction with NaN3: an

expedient approach to N-unsubstituted 1,2,3-triazole-4-carboxylates

John Kallikat Augustine,* Chandrakantha Boodappa and Srinivasa Venkatachaliah

Syngene International Ltd., Biocon Park, Plot Nos. 2 & 3, Bommasandra IV Phase, Jigani

Link Road, Bangalore - 560 099, India.

john.kallikat@syngeneintl.com

Table of contents

Table of contents.………………………………………………….... 1 1H NMR, 13C NMR, HPLC and IR reports for 2a-2p…….………… 2-65 1H NMR, 13C NMR, HPLC and IR reports for 2q-2t…….………… 66-81 1H NMR, 13C NMR, HPLC and IR reports for 1e……….………..... 82-85 1H NMR, 13C NMR, HPLC and IR reports for 1k-1l……….………. 86-93 1H NMR, 13C NMR, HPLC and IR reports for 1u-1x……….………. 94-109 1H NMR, 13C NMR, HPLC and IR reports for 3a ………………… .. 110-113 1H NMR, LCMS and NOESY reports for 6a ……………................ 114-116 1H NMR, LCMS and NOESY reports for 6b ……………................ 117-119 1H NMR, 13C NMR, HPLC and IR reports for 7 ………………… .. 120-123

Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.This journal is © The Royal Society of Chemistry 2014

2

1H NMR (400 MHz) in DMSO-d6 (2a)

COOMe

NH

NN

2a

3

13C NMR (100 MHz) in CDCl3 (2a)

COOMe

NH

NN

2a

4

HPLC (2a)

COOMe

NH

NN

2a

5

IR (2a)

COOMe

NH

NN

2a

6

1H NMR (400 MHz) in DMSO-d6 (2b)

COOMe

NH

NN

Br

2b

7

13C NMR (100 MHz) in DMSO-d6 (2b)

COOMe

NH

NN

Br

2b

8

HPLC (2b)

COOMe

NH

NN

Br

2b

9

IR (2b)

COOMe

NH

NN

Br

2b

10

1H NMR (400 MHz) in CDCl3 (2c)

COOMe

NH

NN

OMe

2c

11

13C NMR (100 MHz) in CDCl3 (2c)

COOMe

NH

NN

OMe

2c

12

HPLC (2c)

COOMe

NH

NN

OMe

2c

13

IR (2c)

COOMe

NH

NN

OMe

2c

14

1H NMR (400 MHz) in DMSO-d6 (2d)

COOMe

NH

NN

O

O

2d

15

13C NMR (100 MHz) in DMSO-d6 (2d)

COOMe

NH

NN

O

O

2d

16

HPLC (2d)

COOMe

NH

NN

O

O

2d

17

IR (2d)

COOMe

NH

NN

O

O

2d

18

1H NMR (400 MHz) in DMSO-d6 (2e)

COOMe

NH

NN

NO2

2e

19

13C NMR (100 MHz) in DMSO-d6 (2e)

COOMe

NH

NN

NO2

2e

20

HPLC (2e)

COOMe

NH

NN

NO2

2e

21

IR (2e)

COOMe

NH

NN

NO2

2e

22

1H NMR (400 MHz) in DMSO-d6 (2f)

N

COOMe

NH

NN

2f

23

13C NMR (100 MHz) in DMSO-d6 + CF3COOD (2f)

N

COOMe

NH

NN

2f

24

HPLC (2f)

N

COOMe

NH

NN

2f

25

IR (2f)

N

COOMe

NH

NN

2f

26

1H NMR (400 MHz) in DMSO-d6 (2g)

COOMe

NH

NN

F

OMe

2g

27

13C NMR (100 MHz) in DMSO-d6 (2g)

COOMe

NH

NN

F

OMe

2g

28

HPLC (2g)

COOMe

NH

NN

F

OMe

2g

29

IR (2g)

COOMe

NH

NN

F

OMe

2g

30

1H NMR (400 MHz) in DMSO-d6 (2h)

Cl

COOMe

NH

NN

Cl

2h

31

13C NMR (100 MHz) in DMSO-d6 (2h)

Cl

COOMe

NH

NN

Cl

2h

32

HPLC (2h)

Cl

COOMe

NH

NN

Cl

2h

33

IR (2h)

Cl

COOMe

NH

NN

Cl

2h

34

1H NMR (400 MHz) in DMSO-d6 (2i)

COOMe

NH

NN

2i

35

13C NMR (100 MHz) in DMSO-d6 (2i)

COOMe

NH

NN

2i

36

HPLC (2i)

COOMe

NH

NN

2i

37

IR (2i)

COOMe

NH

NN

2i

38

1H NMR (400 MHz) in DMSO-d6 (2j)

COOMe

NH

NN

CN

2j

39

13C NMR (100 MHz) in DMSO-d6 (2j)

COOMe

NH

NN

CN

2j

40

HPLC (2j)

COOMe

NH

NN

CN

2j

41

IR (2j)

COOMe

NH

NN

CN

2j

42

1H NMR (400 MHz) in CDCl3 (2k)

NH

NN

O2N

F

F

FCOOMe

2k

43

13C NMR (100 MHz) in CDCl3 (2k)

NH

NN

O2N

F

F

FCOOMe

2k

44

HPLC (2k)

NH

NN

O2N

F

F

FCOOMe

2k

45

IR (2k)

NH

NN

O2N

F

F

FCOOMe

2k

46

1H NMR (400 MHz) in DMSO-d6 (2l)

NNH

NN

OMe

COOEt 2l

47

13C NMR (100 MHz) in DMSO-d6 (2l)

NNH

NN

OMe

COOEt 2l

48

HPLC (2l)

NNH

NN

OMe

COOEt 2l

49

IR (2l)

NNH

NN

OMe

COOEt 2l

50

1H NMR (400 MHz) in DMSO-d6 (2m)

NH

NN

O

COOEt 2m

51

13C NMR (100 MHz) in DMSO-d6 (2m)

NH

NN

O

COOEt 2m

52

HPLC (2m)

NH

NN

O

COOEt 2m

53

IR (2m)

NH

NN

O

COOEt 2m

54

1H NMR (400 MHz) in DMSO-d6 (2n)

COOMe

NH

NN

S Br

2n

55

13C NMR (100 MHz) in DMSO-d6 (2n)

COOMe

NH

NN

S Br

2n

56

HPLC (2n)

COOMe

NH

NN

S Br

2n

57

IR (2n)

COOMe

NH

NN

S Br

2n

58

1H NMR (400 MHz) in DMSO-d6 (2o)

COOMe

NH

NN

2o

59

13C NMR (100 MHz) in CDCl3 (2o)

COOMe

NH

NN

2o

60

HPLC (2o)

COOMe

NH

NN

2o

61

IR (2o)

COOMe

NH

NN

2o

62

1H NMR (400 MHz) in DMSO-d6 (2p)

COOMe

NH

NN

2p

63

13C NMR (100 MHz) in DMSO-d6 (2p)

COOMe

NH

NN

2p

64

HPLC (2p)

COOMe

NH

NN

2p

65

IR (2p)

COOMe

NH

NN

2p

66

1H NMR (400 MHz) in DMSO-d6 (2q)

NH

NN

CN 2q

67

13C NMR (100 MHz) in DMSO-d6 (2q)

NH

NN

CN 2q

68

HPLC (2q)

NH

NN

CN 2q

69

IR (2q)

NH

NN

CN 2q

70

1H NMR (400 MHz) in DMSO-d6 (2r)

NH

NN

O

O

CN 2r

71

13C NMR (100 MHz) in DMSO-d6 (2r)

NH

NN

O

O

CN 2r

72

HPLC (2r)

NH

NN

O

O

CN 2r

73

IR (2r)

NH

NN

O

O

CN 2r

74

1H NMR (400 MHz) in DMSO-d6 (2s)

NNH

NN

CN2s

75

13C NMR (100 MHz) in DMSO-d6 (2s)

NNH

NN

CN2s

76

HPLC (2s)

NNH

NN

CN2s

77

IR (2s)

NNH

NN

CN2s

78

1H NMR (400 MHz) in CDCl3 (2t)

NH

NN

O

CN2t

79

13C NMR (100 MHz) in DMSO-d6 (2t)

NH

NN

O

CN2t

80

HPLC (2t)

NH

NN

O

CN2t

81

IR (2t)

NH

NN

O

CN2t

82

1H NMR (400 MHz) in DMSO-d6 (1e)

Br

COOMe

1e

E

83

13C NMR (100 MHz) in DMSO-d6 (1e)

Br

COOMe

1e

E

84

HPLC (1e)

Br

COOMe

1e

E

85

IR (1e)

Br

COOMe

1e

E

86

1H NMR (400 MHz) in DMSO-d6 (1k)

Br

COOMeF

MeO1k

87

13C NMR (100 MHz) in DMSO-d6 (1k)

Br

COOMeF

MeO1k

88

HPLC (1k)

Br

COOMeF

MeO1k

89

IR (1k)

Br

COOMeF

MeO1k

90

1H NMR (400 MHz) in CDCl3 (1l)

Br

COOMeCl

Cl1l

91

13C NMR (100 MHz) in CDCl3 (1l)

Br

COOMeCl

Cl1l

92

HPLC (1l)

Br

COOMeCl

Cl1l

93

IR (1l)

Br

COOMeCl

Cl1l

94

1H NMR (400 MHz) in CDCl3 (1u)

Cl

CN

1u

95

13C NMR (100 MHz) in CDCl3 (1u)

Cl

CN

1u

96

HPLC (1u)

Cl

CN

1u

97

IR (1u)

Cl

CN

1u

98

1H NMR (400 MHz) in DMSO-d6 (1v)

Cl

O

O

CN

1v

99

13C NMR (100 MHz) in DMSO-d6 (1v)

Cl

O

O

CN

1v

100

HPLC (1v)

Cl

O

O

CN

1v

101

IR (1v)

Cl

O

O

CN

1v

102

1H NMR (400 MHz) in DMSO-d6 (1w)

NCl

CN

1w

103

13C NMR (100 MHz) in DMSO-d6 (1w)

NCl

CN

1w

104

HPLC (1w)

NCl

CN

1w

105

IR (1w)

NCl

CN

1w

106

1H NMR (400 MHz) in DMSO-d6 (1x)

Cl

O CN

1X

107

13C NMR (100 MHz) in DMSO-d6 (1x)

Cl

O CN

1X

108

HPLC (1x)

Cl

O CN

1X

109

IR (1x)

Cl

O CN

1X

110

1H NMR (400 MHz) in DMSO-d6 (3a)

O

O

N3

3a

111

13C NMR (100 MHz) in DMSO-d6 (3a)

O

O

N3

3a

112

HPLC (3a)

O

O

N3

3a

113

IR (3a)

O

O

N3

3a

114

1H NMR (400 MHz) in DMSO-d6 (6a)

1H NMR (400 MHz) in DMSO-d6 (6a)

BrNN

N

O O 6a

115

NOESY correlation (6a)

BrNN

N

O O 6a

116

LCMS (6a)

BrNN

N

O O 6a

117

1H NMR (400 MHz) in DMSO-d6 (6b)

BrNN

N

OO

6b

118

NOESY correlation (6b)

BrNN

N

OO

6b

119

LC MS (6b)

BrNN

N

OO

6b

120

1H NMR (400 MHz) in DMSO-d6 (7)

NH

NNNH

OF F

F

7

121

13C NMR (100 MHz) in DMSO-d6 (7)

NH

NNNH

OF F

F

7

122

HPLC (7)

NH

NNNH

OF F

F

7

123

IR (7)

*********************

NH

NNNH

OF F

F

7