Synthesis of substituted disulfonyl-containing polycyclic azines with the bridgehead nitrogen atom. Effects of the structure of 3-substituted pyridinium ylides on the regioselectivity of their reactions with E-1,2-di(alkylsulfonyl)-1,2-dichloroethenes

Russian Chemical Bulletin, International Edition, Vol. 66, No. 6, pp. 1030—1043, June, 2017

1030

Synthesis of substituted disulfonyl-containing polycyclic azines

with the bridgehead nitrogen atom.

Eﬀects of the structure of 3-substituted pyridinium ylides on the regioselectivity

of their reactions with E-1,2-di(alkylsulfonyl)-1,2-dichloroethenes

N. E. Dontsova and A. M. Shestopalov

N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences,

47 Leninsky prosp., 119991 Moscow, Russian Federation.

Fax: +7 (499) 135 53 28. E-mail: gsv@ioc.ac.ru

Heating the substituted pyridinium and isoquinolinium salts with E-1,2-di(alkylsulfonyl)-

1,2-dichloroethenes in either chloroform or acetone in the presence of three-fold excess of Et₃N

gave high yields of substituted 1,2-di(alkylsulfonyl)indolizines and 1,2-di(alkylsulfonyl)

pyrrolo[2,1-a]isoquinolines, respectively. Eﬀects of the structure of 3-substituted pyridinium

ylides on the regioselectivity of their reaction with E-1,2-di(alkylsulfonyl)-1,2-dichloroethenes

were revealed. It was shown that the presence of electron-releasing and electron-withdrawing

substituents in the pyridinium ylide favors the formation of 8-substituted and 6-substituted

1,2-(dialkylsulfonyl)indolizines, respectively.

Key words: azinium ylides, E-1,2-di(alkylsulfonyl)-1,2-dichloroethenes, pyridinium ylides,

isoquinolinium ylides, 1,2-di(alkylsulfonyl)indolizines, 1,2-di(alkylsulfonyl)pyrrolo[2,1-a]-

isoquinolines, regioselectivity, 3-substituted pyridinium ylides.

An indolizine moiety is a constitutive fragment of

numerous biologically active compounds.^1—9Substituted

1- and 2-sulfonylindolizines show very high antioxidant

activity^4,10,11and are widely used nowadays for treatment

of central nervous system disorders (including the

Alzheimer disease^12,13), cardiovascular system diseas-

es,^14,15asthma, and severe chronic lung diseases.¹⁶It have

recently been found that 2-sulfonylindolizines are potent

dyes for natural wool and human hair.¹⁷Moreover, the

presence of the sulfonyl group is a prerequisite for further

transformations of the compound.^13,18Substituted 1-aryl-

sulfonylindolizines are generally synthesized by the reac-

tion of substituted 2-[(arylsulfonyl)methyl]pyridines with

-halocarbonyl compounds.^{12—17,19,20}Substituted 1- and

2-sulfonylindolizines are obtained by oxidation of the

corresponding arylthioindolizines,^{16—17,19—22}which in

turn are accessible via introduction of a certain arylthio

group into indolizine. The latter is synthesized by either

the reaction of -picolines with -chalocarbonyl com-

pounds under the Chichibabin conditions^16,19or 1,3-di-

polar cycloaddition involving arylthioethenes as the di-

poles.^21,22Hu and co-workers have recently suggested

a one-pot procedure for the synthesis of polysubstituted

1-arylsulfonylindolizines form -halocarbonyl com-

pounds, pyridines, and electron deﬁcient alkenes in the

presence of potassium bichromate under base-free condi-

tions.²³Substituted 2-arylsulfonyl-3-aminoindolizines are

available via a one-pot reaction sequence involving the

Knoevenagel condensation of 2-carbonylpyridines with

arylsulfonylacetonitriles by using Hantzsch ester as a hy-

dride transfer agent.²⁴It should be emphasized that all

mentioned above methods are multistep processes giving

the target substituted 1- and 2-arylsulfonylindolizines in

low yields.

We have earlier reported on a versatile synthetic ap-

proach towards some substituted 1,2-di(alkylsulfonyl)in-

dolizines by cycloaddition of pyridinium ylides to E-1,2-

di(alkylsulfonyl)-1,2-dichloroethenes.^25,26We have found

that regiospeciﬁc reaction of pyridinium and pyrazinium

ylides with E-1,2-di(alkylsulfonyl)-1,2-dichloroethenes

upon heating in chloroform in the presence of Et₃N pro-

duces substituted 1,2-di(alkylsulfonyl)indolizines²⁵and

7,8-di(propylsulfonyl)pyrrolo[1,2-a]pyrazines²⁷in high

yields. We believe that this reaction proceeds as 1,3-dipolar

cycloaddition via hydrogenated intermediates, which

further undergo double dehydrochlorination to form

sulfonyl-substituted indolizines²⁵(Scheme 1) and pyr-

rolopyrazines.²⁷It has also been found that the solvent

nature strongly aﬀects regioselectivity of the reaction

between pyridinium ylides and E-1,2-di(alkylsulfonyl)-

1,2-dichloroethene.²⁸Thus, in aprotic solvents this reac-

tion operates as 1,3-dipolar cycloaddition to give substi-

tuted 1,2-di(alkylsulfonyl)indolizines. In a protic solvent

(EtOH), the reaction of the substituted pyridinium salts

Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1030—1043, June, 2017.

Disulfonyl-containing polycyclic azines

Russ. Chem. Bull., Int. Ed., Vol. 66, No. 6, June, 2017

1031

with E-1,2-di(alkylsulfonyl)-1,2-dichloroethenes at heat-

ing in the presence of excess Et₃N follows two pathways

simultaneously, i.e., 1,3-dipolar cycloaddition and addi-

tion-elimination (Ad_N—E_1,5) mechanisms, and results in

1,2-di(alkylsulfonyl)indolizines and 4,5-di(alkylsulfonyl)-

furans.

In continuation of our research on the synthesis of

sulfonyl-substituted polycyclic azines with bridgehead

nitrogen atom,^25—28in the present work we studied the

eﬀects of the structure of azinium ylides on the regio-

selectivity of their reactions with E-1,2-di(alkylsulfonyl)-

1,2-dichloroethenes.

We studied the reactions of E-1,2-di(alkylsulfonyl)-

1,2-dichloroethenes (1a,b) with pyridinium ylides 2a—d,

4-ethyl- (2e—g), 4-tert-butyl- (2h—k), 3,5-dimethyl-

(2l,m), 4-pyridyl- (2n—r), and 4-ethoxycarbonylpyri-

dinium ylides (2s—v), and isoquinolinium ylides (3a—e).

Ylides 2a—v and 3a—e were generated by treating salts

4a—v and 5a—e with a three-fold excess of Et₃N in either

CHCl₃or acetone followed by addition of E-1,2-di(alkyl-

sulfonyl)-1,2-dichloroethene 1a,b. After heating the reac-

tion mixture at 50 C for 40 min, substituted 1,2-di-

(alkylsulfonyl)indolizines 6a—w and 1,2-di(alkylsulfonyl)-

pyrrolo[2,1-a]isoquinolines 7a—e were isolated in good

yields (51—85%) (Scheme 1, Table 1).

All synthesized indolizines 6a—w and pyrroloiso-

quinolines 7a—e can be accessed via the general procedure

in both CHCl₃and acetone. Some 4-bipyridinium and

isoquinolinium ylides, e.g., ylides bearing R²= NH₂, are

limitedly soluble in CHCl₃. In this case, it is advisable to

carry out the reactions in acetone to achieve the highest

yields of indolizines and pyrroloisoquinolines (see Table 1).

Earlier,²⁵we observed poor regioselectivity of this

reaction involving ethene 1b and 4-ﬂuorophenacetyl-3-

picolinium ylide and formation of a mixture of isomeric

indolizines 10 and 11 (Scheme 2, Table 2).

By widening the scope of the studied 3-substituted

pyridinium ylides used in the reactions with ethenes 1a,b,

we found that the direction of annulation is determined

by the nature of the substituent in pyridinium ylide (see

Scheme 2 and Table 2).

The reaction of 3-substituted pyridinium ylides 9a—e

with ethenes 1a,b were carried out by the developed by us

procedure. Ylides 9a—e were generated by treatment of

salts 8a—e with a three-fold excess of Et₃N in CHCl₃

(acetone) with subsequent addition of E-1,2-di(alkyl-

sulfonyl)-1,2-dichloroethene 1a,b. Heating the reaction

mixture at 50 C for 40 min produces 6- and 8-substi-

tuted 1,2-di(alkylsulfonyl)indolizines 10a—o,a´,d´—g´,

and 11p—z,a´—e´, respectively (see Table 2).

Scheme 1

* Substituents R¹—R³are given in Table 1.

1032

Russ. Chem. Bull., Int. Ed., Vol. 66, No. 6, June, 2017

Dontsova and Shestopalov

Table 1. Synthesis of indolizines 6a—w and pyrroloizoquinolines 7a—e

Ylide

R¹

R²

Ethene

R³

Product

Yield (%))

2a

2b

2с

2d

2e

2f

2g

2h

2i

H

OMe

Ph

1b

1a

1b

1a

1b

1a

1b

1a

1b

1a

1b

Pr

Et

Pr

Et

Pr

Et

Pr

Et

Pr

Et

Pr

6a

6b

6c

6d

6e

6f

6g

6h

6i

74^a

62^a

H

Ph

70^a, 68^b

60^a

H

4-MeOC₆H₄

4-FC₆H₄

4-MeC₆H₄

3,4-(MeO)₂C₆H₃

4-ClC₆H₄

4-EtC₆H₄

4-MeOC₆H₄

4-FC₆H₄

2,4-Me₂C₆H₃

Ph

72^a

4-Et

64^a, 53^b

69^a

4-Et

63^a

4-Bu^t

3,5-(Me)₂

4-Py

4-COOEt

—

69^a, 67^b

62^b

6j

6k

6l

2j

2k

2l

62^a, 55^b

72^a, 66^b

67^b

6m

6n

6o

6p

6q

6r

6s

6t

6u

6v

6w

7a

7b

7c

7d

7e

2m

2n

2o

2p

2q

2r

2s

2t

2u

2v

3a

3b

3c

3d

3e

4-MeOC₆H₄

OMe

66^b

72^a, 60^b

64^a, 53^b

68^a, 51^b

74^a

NH₂

4-ClC₆H₄

4-PrⁱOC₆H₄

3,4-(MeO)₂C₆H₃

Ph

68^a

4-MeC₆H₄

4-MeOC₆H₄

3,4-(ОCH₂O)C₆H₃

OMe

NH₂

Ph

4-ClC₆H₄

2,4-(Me)₂C₆H₃

68^a

62^a

58^a

68^a

—

68^a

—

74^a

—

73^a

—

74^a

^aIn acetone.

^bIn CHCl₃.

We found that 3-picolinium ylides 9a—f react with

ethenes 1a,b to aﬀord a mixture of isomeric indolizines.

In all cases, indolizine 10 was a main component of the

mixture (see Table 2) and the ratio of isomers 10 and 11

in a compound series depends on the nature of the sub-

stituent in the benzene ring. The reactions of 3-amino-

pyridinium ylides 9g—o with ethenes 1a,b proceed in

a nearly completely selective manner with annulation at the

position 2 of pyridinium producing indolizines 10g—o in

high yields (56—84%) (see Table 2).

isomeric indolizines with high content of isomers 11p—z.

Therefore, isomers 11p—z were obtained pure by the

general procedure. Since nicotinamide salts and the cor-

responding ylides 9y—z,a´—e´ are limitedly soluble in

CHCl₃, their reactions with ethenes 1a,b were carried out

in acetone. The reaction mixtures contained mainly

indolizines 11a´—c´, which were isolated pure by the gen-

eral procedure with additional recrystallization. It is in-

teresting to note that we succeeded to isolate individual

indolizines (R¹= CONH₂) by performing the same reac-

tions in heterogeneous medium in CHCl₃(see Table 2),

however the yields of compounds 10a´,d´—g´ were poor.

3-Acetylpyridinium ylides 9p—x react with ethenes

1a,b in either CHCl₃or acetone to give the mixtures of

Scheme 2

Disulfonyl-containing polycyclic azines

Russ. Chem. Bull., Int. Ed., Vol. 66, No. 6, June, 2017

1033

Table 2. Synthesis of compounds 10a—o,a´,d´—g´ and 11c—f,p—z,d´—e´

Ylide

R¹

R²

Ethene

R³

Product

Yield (%))

9a

9b

9c

9d

9e

9f

9g

9h

9i

9j

9k

9l

9m

9n

9o

9p

9q

9r

9s

9t

9u

9v

9w

9x

9y

9z

9a´

9b´

9c´

9d´

9e´

Me

NH₂

Ph

1a

1b

1a

1b

1a

1b

1a

1b

1a

1b

Et

Pr

Et

Pr

Et

Pr

Et

Pr

Et

Pr

10a

10b

60^a

63^a, 58^b

70^b

Me

4-MeC₆H₄

4-MeOC₆H₄

3,4-(MeO)₂C₆H₃

4-BrC₆H₄

OMe

10c : 11c = 3 : 1

10d : 11d = 3 : 1

10e : 11e = 2 : 1

10f : 11f = 3 : 1

10g

Me

74^a

Me

69^b

Me

67^a

NH₂

69^a, 61^b

74^a, 68^b

74^a

NH₂

Ph

10h

10i

10j

10k

10l

10m

10n

10o

11p

11q

11r

11s

11t

11u

11v

11w

11x

NH₂

4-MeC₆H₄

2,4-Me₂C₆H₃

4-MeOC₆H₄

3,4-(MeO)₂C₆H₃

4-PrⁱOC₆H₄

3,4-(OCH₂O)C₆H₃

4-FC₆H₄

NH₂

75^a, 70^b

65^b

NH₂

59^b

NH₂

66^a

NH₂

72^a

NH₂

68^a

Ac

MeO

47^b

Ac

MeO

49^a

Ac

NH₂

53^a

Ac

Ph

42^b

Ac

52^a

Ac

4-MeC₆H₄

2,4-Me₂C₆H₃

4-MeOC₆H₄

3,4-(MeO)₂C₆H₃

4-FC₆H₄

47^b

Ac

51^b

Ac

54^b

Ac

58^b

Ac

11y

11z

49^b

Ac

4-BrC₆H₄

OMe

Ph

52^a

C(O)NH₂

10a´

11a´

11b´

11c´

10d´

11d´

10e´

11e´

10f´

10g´

37^b

54^a

47^a

2,4-Me₂C₆H₃

4-MeOC₆H₄

3,4-(MeO)₂C₆H₃

4-FC₆H₄

45^a

37^b

52^a

38^b

51^a

35^b

4-BrC₆H₄

36^b

^aIn acetone.

^bIn CHCl₃.

Thus, our ﬁndings show that the structure of 3-substi-

tuted pyridinium ylides exerts a dramatic eﬀect on the

regioselectivity of their reactions with E-1,2-dichloro-1,2-

di(alkylsulfonyl)ethenes. The electron-releasing substitu-

ent in the pyridinium ylide, e.g., the Me and NH₂groups,

favors the annulation at the C(2) pyridinium atom, while

electron-withdrawing substituent, e.g., the COMe and

CONH₂groups, directs the reaction towards annulation

at the C(6) pyridinium atom.

Spectral data for compounds 6, 7 and 10, 11 given in

Tables 3—7 are in agreement with the suggested structures.

IR spectra of compounds 6, 7, 10, and 11 contain ab-

sorptions of the stretching vibrations of the carbonyl

(1712—1688 cm^–1) and sulfonyl (1324—1308 and

1145—1140 cm^–1) groups.²²IR spectra of compounds 6p,

7b, 10a, 10g—o,a´,d´—g´, 11r, and 11a´—e´ exhibit

absorptions characteristic of the stretching and bending

vibrations of the amide and amino groups in the ranges of

3444—3168 and 1648—1636 cm^–1, respectively. Mass

spectra of all synthesized compounds revealed the mol-

ecular ion peaks ([M]⁺).

Analysis of ¹H NMR spectra allow an unambigu-

ous conclusion to be made about the regioselectivity

of the reaction and the direction of annulation. The

protons of the pyridine fragment of indolizine 10 reso-

nate as the doublets in the  6.60—7.50 (H(7)) and

 7.20—8.05 (H(5)) ranges and a triplet in the  6.40—7.05

(H(6)) range. In a comparison, ¹NMR signals of

the pyridine moiety of isomeric indolizine 11 appear as

the doublets in the  7.50—8.70 (H(7)) and 8.40—8.50

(H(8)) ranges and a singlet in the  8.45—8.60 (H(5))

range.

1034

Russ. Chem. Bull., Int. Ed., Vol. 66, No. 6, June, 2017

Dontsova and Shestopalov

Table 3. Physicochemical properties and IR and mass spectral data of compounds 6a—w and 7a—e

Com-

pound

M.p./C^a

Found

Calculated

Molecular

formula

IR,/cm^–1

MS,

m/z (I_rel(%))

(%)

С

H

N

6a

6b²⁶

6c

6d

6e

6f

109

49.78

49.60

56.41

56.28

57.96

58.17

57.16

57.00

55.68

55.86

60.78

60.61

57.84

57.56

55.73

55.69

61.09

61.32

58.38

58.64

57.38

57.60

62.98

5.55

5.46

4.80

4.72

5.21

5.35

5.48

5.44

4.87

4.91

6.22

6.15

5.76

5.99

5.30

5.28

6.34

6.38

5.89

5.95

5.39

5.46

7.00

6.81

5.87

5.90

6.05

5.95

4.55

4.62

4.61

4.54

4.00

4.09

5.75

5.67

5.25

5.30

5.24

5.38

5.59

5.63

5.44

5.46

4.99

4.95

5.51

5.30

5.64

4.60

5.29

5.21

4.16

4.11

5.74

5.71

3.68

3.62

3.31

3.45

3.23

3.05

3.02

3.07

3.10

3.18

2.94

2.44

2.69

2.79

2.82

2.85

2.86

2.81

2.85

2.88

2.92

2.48

2.71

3.00

3.03

2.91

2.85

6.30

6.42

10.09

9.97

5.33

5.42

5.02

4.93

4.82

4.91

2.98

2.77

2.73

2.70

2.59

2.61

2.80

2.55

3.13

3.20

7.14

7.10

3.02

2.90

2.91

2.86

2.77

2.74

C₁₆H₂₁NO₆S₂

C₁₉H₁₉NO₅S₂

C₂₁H₂₃NO₅S₂

C₂₂H₂₅NO₆S₂

C₂₁H₂₂FNO₅S₂

C₂₄H₂₉NO₅S₂

C₂₅H₃₁NO₇S₂

C₂₃H₂₆ClNO₅S₂

C₂₅H₃₁NO₅S₂

C₂₄H₂₉NO₆S₂

C₂₃H₂₆FNO₅S₂

C₂₇H₃₅NO₅S₂

C₂₃H₂₇NO₅S₂

C₂₄H₂₉NO₆S₂

C₁₉H₂₀N₂O₆S₂

C₁₈H₁₉N₃O₅S₂

1700 (C=O); 1322, 1141 (SO₂)

1671 (C=O); 1312, 1144 (SO₂)

1672 (C=O); 1312, 1144 (SO₂)

1652 (C=O); 1312, 1148 (SO₂)

1708 (C=O); 1322, 1140 (SO₂)

1650 (C=O); 1322, 1144 (SO₂)

1650 (C=O); 1320, 1144 (SO₂)

1648 (C=O); 1324, 1144 (SO₂)

1710 (C=O); 1316, 1145 (SO₂)

1670 (C=O); 1312, 1144 (SO₂)

1712 (C=O); 1315, 1143 (SO₂)

1652 (C=O); 1312, 1148 (SO₂)

1712 (C=O); 1316, 1152 (SO₂)

387 [М]⁺(59)

405 [М]⁺(29)

433 [М]⁺(23)

463 [М]⁺(15)

451 [М]⁺(22)

475 [М]⁺(20)

521 [М]⁺(20)

495 [М]⁺(20)

489 [М]⁺(54)

491 [М]⁺(48)

479 [М]⁺(57)

517 [М]⁺(51)

461 [М]⁺(22)

491 [М]⁺(22)

436 [М]⁺(42)

421 [М]⁺(22)

516 [М]⁺(32)

568 [М]⁺(37)

570 [М]⁺(42)

505 [М]⁺(38)

519 [М]⁺(42)

535 [М]⁺(36)

549 [М]⁺(34)

437 [М]⁺(22)

394 [М]⁺(28)

483 [М]⁺(38)

489 [М]⁺(22)

511 [М]⁺(42)

(CHCl₃)

161—162

(MeOH)

173

(MeOH)

139

(MeOH)

202

(MeOH)

162—163

(MeOH)

149—150

(CHCl₃)

178

(CHCl₃)

118

(CHCl₃)

138

(MeOH)

197—198

(MeOH)

213—214

6g

6h

6i

6j

6k

6l

(Et₂O—CHCl₃) 62.64

154—155 59.63

(Et₂O—CHCl₃) 59.85

6m

6n

6o

6p

6q

6r

190

(MeOH)

200—201^b

(MeOH)

235—2.36

(MeOH)

212

(MeOH)

175

(MeOH)

227

58.94

58.63

52.07

52.28

51.06

51.29

55.62

55.75

61.40

61.25

58.71

58.93

57.34

1696 (C=O); 1316, 1140 (SO₂);

3340, 3380, 1640 () (NH₂)

C₂₄H₂₁ClN₂O₅S₂1688 (C=O); 1320, 1148 (SO₂)

C₂₉H₃₂N₂O₆S₂

C₂₈H₃₀N₂O₇S₂

C₂₄H₂₇NO₇S₂

C₂₅H₂₉NO₇S₂

C₂₅H₂₉NO₈S₂

C₂₅H₂₇NO₉S₂

C₂₀H₂₃NO₆S₂

C₁₇H₁₈N₂O₅S₂

C₂₅H₂₅NO₅S₂

C₂₃H₂₀ClNO₅S₂

C₂₇H₂₉NO₅S₂

1656 (C=O); 1308, 1132 (SO₂)

1656 (C=O); 1318, 1148 (SO₂)

6s

6t

(Acetone)

153

1720, 1668 (C=O);

1320, 1144 (SO₂)

1712, 1660 (C=O);

1320, 1148 (SO₂)

1716, 1652 (C=O);

1328, 1144 (SO₂)

1712, 1664 (C=O);

1324, 1144 (SO₂)

(Et₂O—CHCl₃) 57.01

156 57.92

(Et₂O—CHCl₃) 57.78

162 56.19

(Et₂O—CHCl₃) 56.06

166 54.75

(Et₂O—CHCl₃) 54.63

6u

6v

6w

7a

7b

7c

7d

7e

202—204

(MeOH)

262

55.13

54.90

51.73

51.76

62.33

61.09

56.35

56.38

63.47

63.38

1724 (C=O); 1312, 1144 (SO₂)

1700 (C=O); 1312, 1144 (SO₂);

3408, 3324, 1648 () (NH₂)

1680 (C=O); 1310, 1144 (SO₂)

(Acetone)

181—182

(Acetone)

255^c

1668 (C=O); 1312, 1144 (SO₂)

1680 (C=O); 1308, 1144 (SO₂)

(Acetone)^d

204—205

(Acetone)

^aSolvent used for recrystallization is given in parenthesis. ^bDecomposition temperature. ^cSublimation temperature. ^dDecantation

from hot acetone.

Disulfonyl-containing polycyclic azines

Russ. Chem. Bull., Int. Ed., Vol. 66, No. 6, June, 2017

1035

Table 4. ¹H and ¹³C NMR spectra of compounds 6a—w and 7a—e

Com-

pound

¹H NMR,  (J/Hz)

¹³C NMR, 

6a

1.02, 1.10 (both t, 3 H each, Me, J = 7.3);

12.51 (CH₃), 12.73 (SH₃), 15.22 (CH₂), 15.91 (CH₂),

53.50 (CH₃), 57.49 (CH₂), 58.34 (CH₂), 107.88 (C),

116.18 (CH), 118.53 (CH), 121.26 (C), 126.06 (CH),

126.86 (C), 127.20 (CH), 135.63 (C), 160.18 (C)

1.38—1.90 (m, 4 H, 2 CH₂); 3.45—3.63 (m, 4 H,

2 CH₂); 4.00 (s, 3 H, OMe), 7.25 (t, 1 H, C(6)H,

J = 7.3); 7.41 (t, 1 H, C(7)H, J = 7.3); 8.28 (d, 1 H,

C(5)H, J = 7.2); 8.52 (d, 1 H, C(8)H, J = 9.2)

1.09, 1.22 (both t, 3 H each, Me, J = 7.3);

6b²⁶

6.17, 6.98, 50.64, 51.47, 105.84, 116.18, 124.89, 125.43,

126.79, 127.22, 129.15, 129.36, 134.79, 136.18, 136.61,

187.55

3.50—3.75 (m, 4 H, 2 CH₂); 7.07 (t, 1 H, C(6),

J = 7.2); 7.39—7.49 (m, 1 H, p-H, Ph); 7.57 (t, 2 H,

m-H, Ph, J = 7.7); 7.73 (t, 1 H, C(7)H, J = 7.3);

7.84 (d, 2 H, o-H, Ph, J = 7.7); 8.07 (d, 1 H, C(5)H,

J = 6.8); 8.25 (d, 1 H, C(8)H, J = 9.8)

6c

6d

6e

6f

0.87, 0.98 (both t, 3 H each, 2 Me, J = 7.3); 1.58—1.73

(m, 4 H, 2 СН₂); 3.45—3.64 (m, 4 H, 2 СН₂);

7.08 (t, 1 Н, С(6)Н, J = 6.7); 7.40—7.50 (m, 1 H,

p-Н, Ph); 7.58 (t, 2 Н, m-Н, Ph, J = 7.3);

7.73 (t, 1 Н, С(7)Н, J = 7.3); 7.82 (d, 2 Н, o-Н,

Ph, J = 7.9); 8.05 (d, 1 Н, С(5)Н, J = 6.7)

0.99, 1.09 (both t, 3 H each, 2 Me, J = 7.3);

1.72—1.93 (m, 4 H, 2 СН₂); 3.49—3.66 (m, 4 H,

2 СН₂); 3.89 (s, 3 H, ОMe); 6.84 (t, 1 H, C(6)H,

J = 7.3); 6.97 (d, 2 Н, m-H, Ph, J = 8.5);

7.26 (d, 1 Н, С(5)Н, J = 6.7); 7.71—7.82 (m, 3 H,

С(7)Н, o-Н, Ph); 8.40 (d, 1 Н, С(8)Н, J = 9.2)

0.89, 0.97 (both t, 3 H each, 2 Me, J = 7.3);

1.59, 1.72 (both q, 2 H each, 2 СН₂, J = 6.7);

3.42—3.69 (m, 4 H, 2 СН₂); 7.08 (t, 1 Н, С(6)Н,

J = 6.7); 7.33—7.55 (m, 3 H, C(7)H, m-H, Ph);

7.85—8.02 (m, 2 H, o-Н, Ph); 8.09 (d, 1 Н, С(5)Н,

J = 7.3); 8.26 (d, 1 Н, С(8)Н, J = 9.2)

0.98, 1.15, 1.30 (all t, 3 H each, 3 Me, J = 7.3); 1.70, 1.82

(both q, 2 H each, 2 СН₂, J = 7.3); 2.42 (s, 3 H, Me);

2.72 (q, 2 H, CH₂, J = 7.3); 3.43—3.57 (m, 4 H, 2 CH₂);

6.85 (d, 1 H, C(6)H, J = 7.3); 7.33 (d, 2 H, m-H, Ph,

J = 8.5); 7.65 (d, 2 H, o-H, Ph, J = 8.1); 7.78 (d, 1 H,

C(5)H, J = 7.3); 8.07 (s, 1 H, C(8)H)

0.87, 0.96, 1.21 (all t, 3 H each, 3 Me, J = 7.3);

1.53—1.80 (m, 4 H, 2 СН₂), 2.70 (q, 2 Н, СН₂, J = 7.3);

3.46—3.66 (m, 4 H, 2 СН₂); 3.86 (s, 6 H, 2 OMe); 6.97

12.55 (СН₃), 12.57 (СН₃), 15.18 (СН₂), 15.86 (СН₂),

57.63 (СН₂), 58.58 (СН₂), 106.57 (С), 116.15 (СН),

118.67 (СН), 125.41 (СН), 125.58 (С), 126.77 (СН),

126.87 (С), 128.89 (СН), 129.09 (СН), 129.29 (2 СН),

134.70 (СН), 135.91 (С), 136.73 (С), 187.57 (С)

12.40 (CH₃), 12.57 (CH₃), 15.27 (CH₂), 15.87 (CH₂),

55.72 (CH₃), 57.69 (CH₂), 58.59 (CH₂), 106.38 (C),

114.49 (2 CH), 116.02 (CH), 118.64 (CH), 124.90 (C),

125.27 (CH), 126.58 (CH), 127.44 (C), 129.62 (C),

131.94 (2 CH), 135.71 (C), 164.50 (C), 185.53 (C)

12.48 (CH₃), 15.14 (CH₂), 15.78 (CH₂), 57.66 (CH₂),

58.59 (CH₂), 106.65 (C), 116.07 (CH), 116.33 (CH),

118.64 (CH), 125.38 (CH), 125.64 (C), 126.51 (C),

126.70 (CH), 132.37 (CH), 132.49 (CH), 133.63 (C),

135.95 (C), 164.11 (C), 167.49 (C), 186.08 (C)

12.55 (2 CH₃), 13.80 (CH₃), 15.23 (CH₂), 15.89 (CH₂),

21.23 (CH₃), 27.82 (CH₂), 57.59 (CH₂), 58.57 (CH₂),

105.24 (C), 115.02 (CH), 117.58 (CH), 124.88 (CH),

125.22 (C), 126.79 (C), 129.41 (CH), 129.64 (CH),

134.31 (C), 136.18 (C), 143.13 (C), 145.57 (C), 186.91 (C)

6g

12.55 (2 CH₃), 13.80 (CH₃), 15.31 (CH₂), 15.86 (CH₂),

27.81 (CH₂), 55.53 (CH₃), 55.89 (CH₃), 57.67 (CH₂),

58.59 (CH₂), 105.00 (C), 110.03 (CH), 111.07 (CH),

(d, 1 Н, С(6)Н, J = 7.3); 7.05 (d, 1 Н, m-Н, Ph, J = 8.55); 114.96 (CH), 117.50 (CH), 124.79 (CH), 124.88 (C),

7.18 (d, 1 H, o-H, Ph, J = 8.6); 7.51 (s, 1 H, o-H, Ph);

7.91 (d, 1 H, C(5)H, J = 7.3); 8.02 (s, 1 H, C(8)H)

0.99, 1.07, 1.29 (all t, 3 H each, 3 Me, J = 7.4);

125.73 (C), 126.98 (CH), 129.67 (CH), 136.11 (CH),

143.07 (CH), 149.11 (CH), 154.59 (CH), 185.51 (C)

12.52 (CH₃), 12.57 (CH₃), 13.84 (CH₃), 15.17 (CH₂),

15.76 (CH₂), 27.82 (CH₂), 57.89 (CH₂), 58.59 (CH₂),

6h

6i

1.67—1.98 (m, 4 H, 2 СН₂); 2.61—2.81 (m, 2 H, СН₂);

3.45—3.72 (m, 4 H, 2 СН₂); 6.76 (d, 1 Н, С(6)Н, J = 6.6); 105.45 (C), 115.02 (CH), 117.68 (CH), 125.13 (CH),

7.47 (d, 2 Н, m-Н, Ph, J = 7.4); 7.64—7.81 (m, 3 H,

o-H, Ph, C(5)H); 8.18 (s, 1 H, C(8)H)

1.16 (t, 3 H, Me, J = 7.3); 1.21—1.31 (m, 6 H,

2 Me); 1.34 (s, 9 H, Bu^t); 2.74 (q, 2 H, CH₂,

J = 7.3); 3.65 (q, 4 H, 2 CH₂, J = 6.7); 7.16 (d, 1 H,

C(6)H, J = 7.3); 7.41 (d, 2 H, m-H, Ph, J = 7.9);

7.71 (d, 2 H, o-H, Ph, J = 7.9); 7.89 (d, 1 H, C(5)H,

J = 7.3); 8.16 (s, 1 H, C(8)H)

125.82 (C), 125.90 (C), 129.19 (2 CH), 131.09 (2 CH),

135.68 (C), 136.43 (C), 139.57 (C), 143.39 (C), 186.58 (C)

6.24 (CH₃), 6.92 (CH₃), 14.90 (CH₃), 28.26 (CH₂),

29.57 (3 CH₃), 34.83 (C), 50.59 (CH₂), 51.49 (CH₂),

105.02 (C), 112.47 (CH), 115.49 (CH), 124.60 (C),

124.77 (CH), 127.02 (C), 128.55 (2 CH),

129.61 (2 CH), 134.47 (C), 136.23 (C), 149.58 (C),

151.57 (C), 186.94 (C)

6.27 (CH₃), 6.91 (CH₃), 29.56 (3 CH₃), 34.80 (C),

50.61 (CH₂), 51.48 (CH₂), 55.70 (OCH₃), 104.97 (C),

112.45 (CH), 114.49 (2 CH), 115.40 (CH), 124.27 (C),

124.68 (CH), 127.25 (CH), 129.62 (CH),

6j

1.18, 1.28 (both t, 3 H each, 2 Me, J = 7.3);

1.34 (s, 9 H, Bu^t); 3.55 (m, 4 H, 2 CH₂);

3.90 (s, 3 H, OMe); 7.08 (d, 2 H, m-H, Ph, J = 8.5);

7.15 (d, 1 Н, С(6)Н, J = 8.8); 7.75 (d, 2 H, o-H, Ph,

J = 8.5); 7.87 (d, 1 H, C(5)H, J = 7.9);

131.96 (2 CH), 136.15 (C), 149.48 (C), 164.47 (C),

185.53 (C)

8.17 (s, 1 H, C(8))

(to be continued)

1036

Russ. Chem. Bull., Int. Ed., Vol. 66, No. 6, June, 2017

Dontsova and Shestopalov

Table 4 (continued)

Com-

pound

¹H NMR,  (J/Hz)

¹³C NMR, 

6k

1.12, 1.25 (both t, 3 H each, 2 Me, J = 7.3);

1.35 (s, 9 H, Bu^t); 3.56 (q, 2 H, 2 CH₂, J = 7.3);

7.18 (d, 1 H, C(6)H, J = 7.3); 7.39 (m, 2 H, m-H, Ph);

7.88 (m, 2 H, o-H, Ph); 7.98 (d, 1 H, C(5)H, J = 7.7);

8.19 (s, 1 H, C(8)H)

0.94, 1.01 (both t, 3 H each, 2 Me, J = 7.2);

1.31 (s, 9 H, Bu^t); 1.42—1.47, 1.65—1.70 (both m,

2 H each, 2 СН₂); 2.34, 2.56 (both s, 3 H each, 2 Me);

3.34—3.52 (m, 4 H, 2 CH₂); 7.07 (d, 1 H, C(6)H,

J = 7.7); 7.14—7.26 (m, 3 Н, o-H, m-Н, Ph);

8.08 (d, 1 H, C(5)H, J = 7.4); 8.14 (s, 1 H, C(8)H)

0.80—1.30 (m, 6 H, 2 Me); 1.60—2.05 (m, 4 H, 2 CН₂);

2.16, 2.78 (both s, 3 H each); 3.60 (m, 4 H, 2 СН₂);

6.95 (s, 1 H, С(7)Н); 7.46—7.55 (m, 3 H, m-H,

p-Н, Ph); 7.60 (s, 1 H, С(5)Н); 7.70—7.90 (m, 2 H,

o-Н, Ph)

0.98, 1.12 (both t, 3 H each, 2 Me, J = 7.3); 1.65—2.03

(m, 4 H, 2 СН₂); 2.15, 2.78 (both s, 3 H each, 2 Me);

3.58—3.92 (m, 4 H, 2 СН₂); 3.88 (s, 3 H, OMe);

6.95 (m, 3 H, С(7)Н, m-Н, Ph); 7.39 (s, 1 H, С(5)Н);

7.75 (d, 2 Н, o-Н, Ph, J = 8.6)

1.21, 1.34 (both t, 3 H each, 2 Me, J = 7.3); 3.40—3.85

(m, 4 H, 2 СН₂); 3.97 (s, 3 H, OMe); 7.71 (d, 1 Н,

С(6)Н, J = 7.3); 7.78 (d, 2 Н, H(3), H(5), Py, J = 6.1);

8.59 (s, 1 H, C(8)H); 8.65 (d, 1 Н, С(5)Н, J = 7.3);

8.75 (d, 2 H, H(2), H(6), Py, J = 6.1)

6.19 (CH₃), 6.91 (CH₃), 29.57 (3 CH₃), 34.84 (C),

50.61 (CH₂), 51.51 (CH₂), 105.19 (C), 112.48 (CH),

115.53 (CH), 116.12 (CH), 116.41 (CH), 124.93 (CH),

126.39 (C), 132.49 (CH), 132.62 (CH), 135.65 (C),

136.44 (C), 149.72 (C), 164.13 (C), 167.50 (C), 186.16 (C)

12.48 (CH₃), 12.52 (СН₃), 14.94 (СН₂), 15.80 (CH₂),

20.55 (CH₃), 20.94 (СН₃), 29.55 (3 CH₃), 34.80 (C),

57.40 (CH₂), 58.49 (CH₂), 105.98 (C), 112.41 (CH),

115.52 (CH), 124.83 (CH), 125.51 (C), 126.37 (CН),

127.93 (С), 131.61 (СН), 132.62 (СН), 134.26 (C),

135.87 (C), 139.82 (С), 143.70 (C), 149.70 (C), 188.29 (C)

12.78 (CH₃), 12.79 (CH₃). 15.32 (CH₂), 15.40 (CH₂),

16.95 (CH₃), 22.16 (CH₃), 58.00 (CH₂), 59.50 (CH₂),

110.33 (C), 120.58 (CH), 125.24 (C), 127.13 (C),

128.60 (C), 129.00 (C), 129.12 (3 CH), 131.86 (CH),

133.43 (C), 134.41 (CH), 136.88 (C), 187.92 (C)

12.62 (CH₃), 12.80 (CH₃), 15.41 (2 CH₂), 16.97 (CH₃),

22.19 (CH₃), 55.69 (CH₃), 58.03 (CH₂), 59.50 (CH₂),

110.17 (C), 114.39 (2 CH), 120.46 (CH), 125.10 (C),

127.19 (C), 127.67 (C), 128.57 (C), 129.78 (C),

6l

6m

6n

6o

6p

6q

131.73 (2 CH), 133.26 (C), 164.26 (C), 186.04 (C)

6.19 (CH₃), 6.88 (CH₃), 50.54 (CH₂), 50.94 (CH₂),

52.38 (СН₃), 110.53 (C), 114.14 (CH), 114.64 (C),

115.26 (CH), 120.86 (2 C), 127.96 (CH), 135.29 (С),

137.43 (C), 139,08 (C), 143.68 (C), 150.57 (2 CН),

150.63 (2 CH), 159.45 (C)

1.20—1.24 (m, 6 H, 2 Me); 3.45—3.56, 3.64—3.69

(both m, 2 H each, 2 CН₂); 7.60 (d, 1 Н, С(6)Н, J = 7.3); 106.82 (C), 114.12 (CH), 115.77 (CH), 120.91 (2 CH),

7.78 (d, 2 Н, H(3), H(5), Py, J = 5.5); 8.30 (s, 1 H, NH); 122.70 (C), 126.08 (CH), 128.30 (C), 134.54 (C),

8.37 (d, 1 Н, С(5)Н, J = 7.3); 8.43 (s, 1 H, NH); 8.54

(s, 1 H, C(8)H); 8.75 (d, 2 Н, H(2), H(6), Py, J = 6.1)

1.13, 1.29 (both t, 3 H each, 2 Me, J = 6.7);

3.53—3.68 (m, 4 H, 2 СН₂); 7.49 (d, 1 Н, С(6)Н,

J = 8.6); 7.65 (d, 2 Н, m-Н, Ph, J = 7.3);

6.04 (CH₃), 6.90 (CH₃), 50.58 (CH₂), 51.23 (CH₂),

134.64 (C), 143.97 (C), 150.59 (2 CH), 160.10 (C)

6.16 (CH₃), 6.83 (CH₃), 50.70 (CH₂), 51.48 (CH₂),

107.61 (C), 114.71 (CH), 116.07 (CH), 120.95 (2 CH),

125.90 (C), 126.32 (CH), 126.94 (C), 129.26 (2 CH),

131.08 (CH), 131.29 (CH), 135.08 (C), 135.43 (C),

135.99 (C), 139.80 (C), 143.83 (C), 150.61 (2 CH),

186.29 (C)

12.61 (2 CH₃), 15.29 (CH₂). 15.74 (CH₂), 21.54 (2 CH₃),

57.72 (CH₂), 58.56 (CH₂), 70.09 (CH), 108.07 (C),

114.58 (CH), 115.55 (2 CH), 116.10 (CH),

7.72—7.84 (m, 2 H, H(3), H(5), Py); 7.90 (d, 2 Н,

o-Н, Ph, J = 7.3); 8.27 (d, С(5)Н, J = 7.3); 8.58 (s, 1 H,

С(8)Н); 8.70—8.81 (m, 2 H, H(2), H(6), Py)

6r

6s

6t

0.90, 0.99 (both t, 3 H each, 2 Me, J = 7.3);

1.31 (d, 6 Н, 2 Me, J = 5.5); 1.62, 1.77 (both q,

2 H each, 2 СН₂, J = 7.3); 3.59—3.71 (m, 4 H, 2 СН₂);

4.73—4.85 (m, 1 H, ОСН); 7.08 (d, 2 Н, H(3), H(5),

Py, J = 8.5); 7.47 (d, 1 Н, C(6)H, J = 8.5); 7.72—7.86

(m, 4 H, Ph); 8.15 (d, 1 Н, С(5)Н, J = 7.3); 8.57 (s, 1 H,

C(8)H); 8.75 (d, 2 Н, H(2), H(6), Py, J = 5.5)

1.00, 1.09 (both t, 3 H each, 2 Me, J = 7.2);

120.90 (2 CH), 125.69 (C), 126.06 (CH), 127.81 (C),

129.14 (C), 132.14 (2 CH), 134.79 (C), 135.37 (C),

143.89 (C), 150.61 (2 CH),163.01 (C), 185.11 (C)

12.60 (2 CH₃), 15.35 (CH₂), 15.81 (CH₂), 55.58 (CH₃),

55.95 (CH₃), 57.78 (CH₂), 58.60 (CH₂), 107.98 (C),

110.13 (CH), 111.09 (CH) 114.56 (CH), 116.10 (CH),

120.90 (3 C), 125.72 (C), 126.05 (CH), 127.71 (C),

129.59 (C), 134.80 (C), 135.43 (C), 143.88 (C),

149.16 (C), 150.60 (2 CH), 154.75 (C), 185.24 (C)

1.72—1.98 (m, 4 H, 2 СН₂); 3.48—3.71 (m, 4 H,

2 СН₂); 3.95, 3.98 (both s, 3 H each, 2 OMe);

6.84 (d, 1 Н, C(6)H, J = 7.9); 7.12 (d, 2 Н, H(3), H(5),

Py, J = 7.9); 7.48—7.59 (m, 2 H, m-H, o-Н, Ph);

7.65 (s, 1 H, o-Н, Ph); 7.86 (d, 1 Н, С(5)Н, J = 7.2);

8.68—8.79 (m, 3 H, С(8)Н, H(2), H(6), Py)

0.89, 0.98, 1.34 (all t, 3 H each, 3 Me, J = 7.3);

1.6, 1.74 (both q, 2 H each, 2 СН₂, J = 7.3); 3.50—3.64

(m, 4 H, 2 СН₂); 4.39 (q, 2 Н, ОСН₂, J = 7.3); 7.37

(d, 1 Н, С(6)Н, J = 8.8); 7.52—7.63 (m, 2 Н, m-Н, Ph);

7.71—7.78 (m, 1 Н, p-Н, Ph); 7.80—7.88 (m, 2 H, o-Н,

Ph); 8.17 (d, 1 Н, С(5)Н, J = 7.3); 8.87 (s, 1 H, С(8)H)

12.52 (2 CH₃), 13.96 (CH₃), 15.12 (CH₂), 15.65 (CH₂),

57.73 (CH₂), 58.53 (CH₂), 61.67 (CH₂), 110.67 (C),

114.10 (CH), 121.35 (CH), 125.78 (CH), 126.91 (C),

128.12 (C), 129.10 (2 CH), 129.37 (2 CH), 134.43 (C),

134.89 (CH), 136.47 (C), 163.68 (C), 187.16 (C)

(to be continued)

Disulfonyl-containing polycyclic azines

Russ. Chem. Bull., Int. Ed., Vol. 66, No. 6, June, 2017

1037

Table 4 (continued)

Com-

pound

¹H NMR,  (J/Hz)

¹³C NMR, 

6u

6v

6w

0.87, 0.98 (both t, 3 H each, 2 Me, J = 7.3); 1.33 (t, 3 Н,

Me, J = 6.6); 1.58, 1.73 (both q, 2 H each, 2 СН₂,

J = 7.3); 2.41 (s, 3 H, Me); 3.47—3.67 (m, 4 H, 2 CН₂);

4.38 (q, 2 Н, 2 СН₂, J = 6.6); 7.30—7.43 (m, 3 Н, С(6)Н,

m-Н, Ph); 7.72 (d, 2 Н, o-Н, Ph, J = 8.1); 8.10 (d, 1 Н,

С(5)Н, J = 7.3); 8.87 (s, 1 H, С(8)Н)

12.54 (2 CH₃), 13.98 (CH₃), 15.18 (CH₂), 15.67 (CH₂),

21.29 (CH₃), 57.77 (CH₂), 58.53 (CH₂), 61.68 (CH₂),

110.62 (C), 114.06 (CH), 121.39 (CH), 125.70 (CH),

126.56 (C), 126.83 (C), 128.45 (C), 129.57 (CH),

129.73 (CH), 134.00 (C), 134.31 (C), 145.96 (C),

163.70 (C), 186.50 (C)

0.89, 0.98 (both t, 3 H each, 2 Me, J = 7.3); 1.34 (t, 3 Н,

12.57 (2 CH₃), 14.01 (CH₃), 15.23 (CH₂), 15.69 (CH₂),

Me, J = 6.6); 1.61, 1.74 (both q, 2 H each, 2 СН₂, J = 7.3); 55.78 (CH₃), 57.79 (CH₂), 58.53 (CH₂), 61.69 (CH₂),

3.50—3.63 (m, 4 H, 2 СН₂); 3.88 (s, 3 H, OMe); 4.39

(q, 2 H, OCH₂, J = 7.3); 7.09 (d, 2 Н, m-Н, Ph, J = 8.8);

7.37 (d, С(6)Н, J = 7.3); 7.79 (d, 2 Н, o-Н, Ph, J = 8.8);

8.09 (d, 1 Н, С(5)Н, J = 7.3); 8.87 (s, 1 H, С(8)Н)

0.89, 0.98 (both t, 3 H each, 2 Me, J = 7.3); 1.31 (t, 3 Н,

110.54 (C), 114.02 (CH), 114.55 (2 CH), 121.39 (CH),

125.70 (CH), 126.21 (C), 126.77 (C), 128.72 (C),

129.37 (C), 132.11 (2 CH), 134.22 (C), 163.73 (C),

164.69 (C), 185.10 (C)

12.57 (2 CH₃), 14.00 (CH₃), 15.21 (CH₂). 15.64 (CH₂),

Me, J = 6.6); 1.61, 1.73 (both q, 2 H each, 2 СН₂, J = 7.3); 57.81 (CH₂), 58.52 (CH₂), 61.68 (CH₂), 102.59 (CH₂),

3.48—3.64 (m, 4 H, 2 СН₂); 4.38 (q, 2 Н, СН₂, J = 6.6);

6.21 (s, 2 H, ОСН₂О); 7.04 (d, 1 Н, С(6)Н, J = 8.1);

107.73 (CH), 108.40 (CH), 110.59 (C), 113.98 (CH),

121.38 (CH), 125.70 (CH), 126.28 (C), 126.74 (C),

7.31—7.40 (m, 2 Н, m-H, o-Н, Ph); 7.43 (s, 1 H, o-Н, Ph); 127.65 (CH), 128.49 (C), 131.20 (C), 134.28 (C),

8.10 (d, 1 Н, С(5)Н, J = 7.3); 8.85 (s, 1 H, С(8)Н)

0.94—1.10 (m, 6 H, 2 Me); 1.76—2.00 (m, 4 H, OMe);

2 СН₂); 3.61—3.77 (m, 4 H, 2 СН₂); 3.98 (s, 3 H,

7.49 (d, 1 Н, С(6)Н, J = 7.6); 7.68—7.79 (m, 2 H, С(8)Н,

С(9)Н); 7.95 (d, 1 Н, С(7)Н, J = 7.6); 8.22 (d, 1 Н,

С(10)Н, J = 7.6); 9.02—9.10 (m, 1 H, С(5)Н)

148.43 (C), 153.23 (C), 163.74 (C), 184.83 (C)

12.77 (CH₃), 12.79 (CH₃), 15.16 (CH₂), 15.38 (CH₂),

53.77 (CH₃), 57.70 (CH₂), 57.86 (CH₂), 114.61 (C),

117.01 (CH), 122.16 (C), 122.35 (CH), 125.19 (C),

127.32 (C), 127.89 (CH), 127.91 (CH), 128.39 (CH),

129.78(CH), 131.58(C), 160.31(C)

7a

7b

7c

1.31, 1.48 (both t, 3 H each, 2 Me, J = 7.3); 3.54—3.79

6.15 (CH₃), 6.25 (CH₃), 50.71 (CH₂), 50.86 (CH₂),

(m, 4 H, 2 СН₂); 7.48 (d, 1 Н, С(6)Н, J = 7.6); 7.65—7.77 114.22 (C), 116.48 (CH), 122.17 (C), 122.35 (CH),

(m, 2 H, С(8)Н, С(9)Н); 7.88—7.96 (m, 1 H, С(7)Н);

8.05 (d, 1 H, С(10)Н, J = 7.6); 8.20 (s, 1 H, NH);

8.35 (s, 1 H, NH); 9.07 (d, C(5)H, J = 7.6)

124.92 (C), 127.30 (C), 127.88 (2 CH), 128.28 (CH),

129.51 (CH), 129.57 (C), 131.17 (C), 160.66 (C)

0.98, 1.11 (both t, 3 H each, 2 Me, J = 7.0); 1.53—1.74,

1.88—2.08 (both m, 2 H each, 2 СH₂); 3.56—3.80

(m, 4 H, 2 СН₂); 7.41 (d, 1 Н, С(6)Н, J = 7.6);

7.53—7.62 (m, 2 Н, m-Н, Ph); 7.69—7.87 (m, 6 Н,

С(7)Н, С(8)Н, С(9)Н, o-H, p-Н, Ph); 7.98 (d, 1 Н,

С(10)Н, J = 7.4); 9.23 (d, 1 Н, С(5)Н, J = 7.5)

1.32, 1.63 (both t, 3 H each, 2 Me, J = 7.5); 3.55—3.88

(m, 4 H, 2 СН₂); 7.08 (d, 1 Н, С(6)Н, J = 7.4);

7.38—7.53 (m, 3 H, С(7)Н, С(8)Н, С(9)Н);

7.64—7.80 (m, 5 H, o-H, m-Н, Ph, С(10)Н);

9.35 (d, 1 Н, С(5)Н, J = 7.4)

12.60 (CH₃), 12.77 (CH₃), 15.29 (CH₂), 15.47 (CH₂),

58.00 (2 CH₂), 113.79 (C), 117.08 (CH), 122.07 (CH),

122.73 (C), 126.73 (C), 127.62 (CH), 128.04 (CH),

128.57 (CH), 129.07 (2 CH), 129.31 (2 CH),

129.48 (CH), 129,65 (C), 130.03 (C), 131.66 (C),

134.62 (CH), 136.67 (C), 187.54 (C)

6.65 (CH₃), 6.77 (CH₃), 51.80 (CH₂), 51.92 (CH₂),

111.54 (C), 114.20 (C), 117.41 (CH), 121.18 (CH),

123.60 (2 C), 127.72 (C), 127.83 (C), 128.05 (CH),

128.12 (CH), 129.25 (CH), 129.59 (CH), 129.90 (CH),

130.32 (C), 130.78 (CH), 132.73 (C), 135.55 (C),

141.34 (2 C), 186.84 (C)

13.02 (CH₃), 13.25 (CH₃), 15.58 (CH₂), 15.75 (CH₂),

21.40 (CH₃), 21.64 (CH₃), 58.90 (CH₂), 59.10 (CH₂),

111.29 (C), 114.88 (C), 117.13 (CH), 121.54 (CH),

123.69 (C), 126.37 (CH), 127.93 (CH), 128.27 (CH),

129.01 (CH), 129.70 (CH), 129.81 (2 C), 131.60 (CH),

132.25 (C), 133.44 (CH), 141.48 (2 C), 144.35 (C),

188.60 (C)

7d

7e

0.91, 1.15 (both t, 3 H each, 2 Me, J = 7.4); 1.58—1.79,

2.02—2.19 (both m, 2 H each, 2 СН₂); 2.38, 2.71

(both s, 3 H each, 2 Me); 3.39—3.78 (m, 4 H, 2 СН₂);

6.98 (d, 1 Н, m-Н, Ph, J = 8.0); 7.08 (d, 1 Н, С(6)Н,

J = 7.4); 7.13 (d, 1 H, o-H, Ph, J = 8.0); 7.19 (s, 1 H,

m-H, Ph); 7.57—7.78 (m, 4 H, С(7)Н, С(8)Н, С(9)Н,

С(10)Н); 9.29 (d, С(5)Н, J = 8.1)

In summ ary, we pioneered in the synthesis of dialkyl-

sulfonyl-containing pyrroloisoquinolines. We found that

substituted 1,2-di(alkylsulfonyl)indolizines and 1,2-di-

(alkylsulfonyl)pyrrolo[2,1-a]isoquinolines can be prepared

by the general procedure via the reaction of E-1,2-

dichloro-1,2-di(alkylsulfonyl)ethenes with salts of substi-

tuted pyridinium and isoquinolinium ylides on heating

with a three-fold excess of Et₃N in either chloroform or

acetone. The best results were achieved by carrying out

the reactions in homogeneous medium, however the reac-

tions between ethenes 1a,b and 4-bipyridinium ylides with

R²= 4-BrC₆H₄, NH₂should be carried out in acetone.

Regioselectivity of the reactions of 3-substituted pyridinium

ylides with E-1,2-dichloro-1,2-di(alkylsulfonyl)ethenes

1038

Russ. Chem. Bull., Int. Ed., Vol. 66, No. 6, June, 2017

Dontsova and Shestopalov

Table 5. Physicochemical properties and IR and mass spectral data of compounds 10a—o,a´,d´—g´ and 11p—z,a´—e´

Com-

pound

M.p./C^a

Found

Calculated

Molecular

formula

IR,/cm^–1

MS,

m/z (I_rel(%))

(%)

C

H

N

10a

245

47.24 4.98

46.91 5.06 7.82

57.40 5.09 3.41

7.66

C₁₄H₁₈N₂O₅S₂

C₂₀H₂₁NO₅S₂

C₂₃H₂₇NO₅S₂

C₂₃H₂₇NO₆S₂

C₂₄H₂₉NO₇S₂

C₂₂H₂₄BrNO₅S₂

C₁₆H₂₂N₂O₆S₂

C₁₉H₂₀N₂O₅S₂

C₂₂H₂₆N₂O₅S₂

C₂₃H₂₈N₂O₅S₂

C₂₂H₂₆N₂O₆S₂

C₂₃H₂₈N₂O₇S₂

C₂₄H₃₀N₂O₆S₂

C₂₂H₂₄N₂O₇S₂

C₂₁H₂₃FN₂O₅S₂

C₁₆H₁₉NO₇S₂

C₁₈H₂₃NO₇S₂

C₁₇H₂₂N₂O₆S₂

1664 (C=O); 1320, 1144 (SO₂);

3290, 3165, 1636 () (NH₂)

1664 (C=O); 1318, 1144 (SO₂)

358 [М]⁺(22)

419 [М]⁺(20)

461 [М]⁺(22)

477 [М]⁺(18)

507 [М]⁺(20)

526 [М]⁺(18)

402 [М]⁺(34)

420 [М]⁺(20)

462 [М]⁺(24)

476 [М]⁺(22)

478 [М]⁺(28)

508 [М]⁺(26)

506 [М]⁺(20)

492 [М]⁺(18)

466 [М]⁺(28)

401 [М]⁺(24)

429 [М]⁺(22)

414 [М]⁺(28)

(EtOH)^b

169—170

10b

(Et₂O—CHCl₃) 57.26 5.05 3.34

10с+11с

10d+11d

10e+11e

10f

—

60.03 5.97 2.98

59.85 5.90 3.03

57.24 5.65 3.01

57.84 5.70 2.93

1664 (C=O); 1320, 1144 (SO₂)

1658 (C=O); 1318, 1150 (SO₂)

1650 (C=O); 1320, 1144 (SO₂)

1664 (C=O); 1312, 1144 (SO₂)

56.41

5.68 2.82

56.79 5.76 2.76

156—157

(Acetone)

112

50.01

50.19

5.51

2.70

5.59 2.66

10g

47.89 5.58

5.51

7.05

6.96

1728 (C=O); 1324, 1144 (SO₂);

3440, 3348, 1636 () (NH₂)

1712 (C=O); 1312, 1144 (SO₂);

3444, 3424, 3344, 1624 () (NH₂)

1710 (C=O); 1318, 1144 (SO₂);

3444, 3424, 3344, 1624 () (NH₂)

1670 (C=O); 1318, 1144 (SO₂);

3448, 3350, 1624 () (NH₂)

1664 (C=O); 1320, 1144 (SO₂);

3456, 3350, 1624 () (NH₂)

1664 (C=O); 1320, 1136 (SO₂);

3456, 3352, 1624 () (NH₂)

1668 (C=O); 1320, 1144 (SO₂);

3456, 3352, 1624 () (NH₂)

1668 (C=O); 1320, 1144 (SO₂)

3456, 3352, 1624 () NH₂

1668 (C=O); 1324, 1144 (SO₂);

3412, 3344, 1644 () (NH₂)

1726, 1680 (C=O);

(Et₂O—CHCl₃) 47.75

10h

173—175

(МeOH)

197—198

(МeOH)

169

(МeOH)

174

(МeOH)

146—147

(МeOH)^b

173—174

(МeOH)

189

(МeOH)

176—177

(МeOH)

186

54.43 4.85 6.43

54.27 4.79 6.66

10i

57.25 5.75

6.01

6.06

57.12

58.11

5.67

10j

5.98 5.95

57.96 5.92 5.88

10k

55.41

55.21

5.54 5.98

5.48 5.85

10l

54.09 5.49 5.59

54.32 5.55 5.51

56.83 5.92 5.68

56.90 5.97 5.53

10m

10n

53.41

53.64 4.91

53.91 4.93 5.55

4.84 5.74

5.69

10o

54.06 4.97 6.00

47.99 4.83 3.34

47.87 4.77 3.49

49.88 5.32 3.12

50.33 5.40 3.26

49.48 5.28 6.69

11p

(МeOH)

127

1318, 1148 (SO₂)

11q

1732, 1680 (C=O);

(CHCl₃)

256

1316, 1148 (SO₂)

11r

1688, 1640 (C=O);

(Acetone)^b

49.26 5.35

7.76

1324, 1136 (SO₂);

3344, 3148, 1632 () (NH₂)

1692, 1672 (C=O);

11s

11t

246—247

(МeOH)

202

(CHCl₃)

178—179

(CHCl₃)

230^c

56.12

56.36 4.73

57.85 5.18

58.09 5.30 2.95

59.00 5.61

4.68 3.19

C₂₁H₂₁NO₆S₂

C₂₃H₂₅NO₆S₂

C₂₄H₂₇NO₆S₂

C₂₃H₂₅NO₆S₂

C₂₄H₂₇NO₇S₂

C₂₅H₂₉NO₈S₂

C₂₃H₂₄FNO₆S₂

C₂₃H₂₄BrNO₆S₂

C₁₇H₂₂N₂O₇S₂

447 [М]⁺(28)

475 [М]⁺(20)

489 [М]⁺(26)

475 [М]⁺(20)

505 [М]⁺(20)

535 [М]⁺(20)

493 [М]⁺(22)

554 [М]⁺(22)

430 [М]⁺(18)

3.13

1308, 1144 (SO₂)

2.90

1692, 1672 (C=O);

1309, 1144 (SO₂)

11u

11v

11w

11x

11y

11z

10a´

2.94

1688, 1670 (C=O);

58.88 5.56 2.86

58.24 5.39 2.89

58.09 5.30 2.95

57.24 5.42 2.80

1310, 1146 (SO₂)

1689, 1666 (C=O);

(МeOH)

160

1318, 1144 (SO₂)

1690, 1666 (C=O);

(МeOH)

194—195

(CHCl₃)

148—149

(CHCl₃)

208—209

(Acetone)^b

>235

57.01

5.38 2.72

1318, 1146 (SO₂)

56.24 5.50 2.68

56.06 5.46 2.61

1688, 1660 (C=O);

1316, 1140 (SO₂)

55.75

4.86 2.79

1688, 1668 (C=O);

55.97 4.90 2.84

49.64 4.32 2.48

49.82 4.36 2.53

47.25 5.07 6.45

1316, 1148 (SO₂)

1688, 1670 (C=O);

1316, 1146 (SO₂)

1730, 1671 (C=O);

(МeOH)

47.43 5.15

6.51

1328, 1145 (SO₂);

3432, 3341, 1604 () (NH₂)

(to be continued)

Disulfonyl-containing polycyclic azines

Russ. Chem. Bull., Int. Ed., Vol. 66, No. 6, June, 2017

1039

Table 5 (continued)

Com-

pound

M.p./C^a

Found

Calculated

Molecular

formula

IR,/cm^–1

MS,

m/z (I_rel(%))

(%)

C

H

N

11a´

11b´

11с´

10d´

11d´

10e´

11e´

10f´

10g´

186

47.32 5.02 6.42

47.43 5.15 6.51

C₁₇H₂₂N₂O₇S₂

C₂₂H₂₄N₂O₆S₂

C₂₄H₂₈N₂O₆S₂

C₂₃H₂₆N₂O₇S₂

C₂₄H₂₈N₂O₈S₂

C₂₂H₂₃FN₂O₇S₂

C₂₂H₂₃BrN₂O₇S₂

1724, 1686 (C=O);

430 [М]⁺(18)

476 [М]⁺(22)

504 [М]⁺(24)

506 [М]⁺(18)

506 [М]⁺(20)

536 [М]⁺(22)

536 [М]⁺(24)

494 [М]⁺(22)

555 [М]⁺(18)

(МeOH)

1320, 1143 (SO₂);

3417, 3337, 1607 () (NH₂)

1690, 1640 (C=O);

1319, 1145 (SO₂);

3418, 3330, 1600 () (NH₂)

1693, 1644 (C=O);

1320, 1151 (SO₂);

3415, 3335, 1604 () (NH₂)

1665, 1653 (C=O);

1307, 1145 (SO₂);

3427, 3325, 1599 () (NH₂)

1693, 1663 (C=O);

1306, 1145 (SO₂);

3462, 3360, 1598 () (NH₂)

1688, 1637 (C=O);

1321, 1143 (SO₂);

3404, 3178, 1594 () (NH₂)

1695, 1647 (C=O);

1319, 1139 (SO₂);

3456, 3356, 1597 () (NH₂)

1690, 1640 (C=O);

1320, 1144 (SO₂);

3460, 3355, 1596 () (NH₂)

1683, 1621 (C=O);

158^c

(МeOH)

55.60 5.00 5.76

55.45 5.08 5.88

138—139

(МeOH)

56.94 5.50 5.39

57.12

5.59 5.55

>260

54.38 4.98 5.58

(Acetone)^b

54.53 5.17

5.53

202

(Acetone)

54.65 5.23

54.53 5.17

5.60

5.53

>250

53.58 5.18

5.29

(МeOH)^b

53.72 5.26 5.22

218

(MeOH)

53.67

5.20 5.30

53.72 5.26 5.22

>235

(МeOH)

53.54 4.74

5.71

53.43 4.69 5.66

>250

(МeOH)

47.39 4.11

47.57 4.17

5.10

5.04

1326, 1147 (SO₂);

3497, 3379, 1599 () (NH₂)

^aSolvent used for recrystallization is given in parenthesis.

^bCompound was puriﬁed by decantation from the boiling solvent.

^cSublimation temperature.

E-1,2-Di(alkylsulfonyl)ethenes (1a,b) were synthesized fol-

lowing the known procedure.²⁹Compounds 4a—v, 5a—e, and

8a—z,a´—g´ were synthesized as earlier described.³⁰

depends on the nature of the substituent in the pyridinium

ylide. In the case of pyridinium ylides bearing the electron-

releasing substituent, annulation at the C(2) pyridinium

atom predominates; while, the electron-withdrawing

substituent favors the annulation at the C(6) pyridinium atom.

Synthesis of substituted 1,2-di(alkylsulfonyl)indolizines 6a—w,

7a—e, 10a—o,a´,d´—g´, and 11p—z,a´—e´ (general procedure).

To a solution of compound 4a—v, 5a—e, 8a—z,a´—g´ (0.001 mol)

in either CHCl₃or acetone, Et₃N (0.003 mol) was added followed

by dropwise addition of a solution of sulfone 1a,b. The reaction

mixture was reﬂuxed for 40 min, diluted with CHCl₃, washed

with water, and dried with MgSO₄. The solvent was removed

in vacuo and the residue was recrystallized. The physicochemi-

cal properties of compounds 6a—w and 7a—e are given in

Tables 3 and 4 and compounds 10a—o,a´,d´—g´, and 11p—z,a´—e´,

in Tables 5—7.

This procedure was employed for the synthesis of the follow-

ing compounds: methyl 1,2-bis(propylsulfonyl)indolizine-3-

carboxylate (6a), (1,2-bis(propylsulfonyl)indolizin-3-yl)(phenyl)

methanone (6c), (1,2-bis(propylsulfonyl)indolizin-3-yl)(4-me-

thoxyphenyl)methanone (6d), (1,2-bis(propylsulfonyl)indolizin-

3-yl)(4-ﬂuorophenyl)methanone (6e), (1,2-bis(propylsulfonyl)-

7-(ethyl)indolizin-3-yl)(p-tolyl)methanone (6f), (1,2-bis(prop-

ylsulfonyl)-7-(ethyl)indolizin-3-yl)(3,4-dimethoxyphenyl)meth-

anone (6g), (1,2-bis(propylsulfonyl)-7-(ethyl)indolizin-3-yl)

Experimental

IR spectra were recorded with Perkin-Elmer-577 and Specord

M82 spectrophotometers in KBr pellets at (concentration of the

test compound of 0.01 mol L^–1) and in the CHCl₃solution

(concentration of the test compound of 0.0078 g mL^–1) applied on

the NaCl plate. ¹H NMR spectra were run on Bruker DRX-500

MP (500 MHz), Bruker WM-250 (250 MHz), and Bruker AH-300

(300 MHz) instruments for the 5—12% solutions of the test

compounds in DMSO-d₆and CDCl₃. The chemical shifts are

given in the  scale relative to Me₄Si (an internal standard).

Electron impact (70 eV) mass spectrometry was performed with

FINNIGAN MAT INCOS 50 quadrupole mass spectrometer. The

reaction course and the purity of the synthesized compounds were

monitored by TLC on the precoated Silufol UV-254 plate in hex-

ane—acetone (2 : 1). The spots were visualized with iodine vapor.

1040 Russ. Chem. Bull., Int. Ed., Vol. 66, No. 6, June, 2017

Dontsova and Shestopalov

Table 6. ¹H NMR spectra of compounds 10a—o,a´,d´—g´ and 11p—z,a´—e´

Com-

pound

¹H NMR,  (J/Hz)

10a

1.23—1.40 (m, 6 H, 2 Мe); 2.88 (s, 3 H, C(8)Мe); 3.60, 3.80 (both q, 2 H each, 2 CH₂SO₂, J = 7.9);

7.07 (t, 1 Н, С(6)Н, J = 8.0); 7.27 (d, 1 Н, С(7)Н, J = 8.0); 8.00 (s, 1 Н, NH); 8.13 (d, 1 Н, С(5)Н, J = 8.0);

8.27 (s, 1 Н, NH)

1.29, 1.54 (both t, 3 H each, 2 Мe, J = 7.3); 2.82 (s, 3 H, C(8)Мe); 3.70 (q, 4 Н, 2 CH₂SO_2,J = 7.8);

6.76 (t, 1 H, C(6)H, J = 7.9); 7.11 (d, 1 H, C(7)H, J = 8.0); 7.45—7.85 (m, 6 H, Ph, C(5)H)

0.91—1.21 (m, 6 H, 2 Мe); 1.67—2.16 (m, 4 H, 2 CH₂); 2.22 (s, C(6)Мe, 11); 2.43 (s, 3 H, C(4)Мe, Ph);

2.82 (s, C(8)Мe, 10); 3.47—3.77 (m, 4 H, 2 CH₂SO₂); 6.74 (t, C(6)H, 10, J = 6.7); 7.08—7.14 (m, C(7)H,

10; C(7)H, 11); 7.28 (d, 2 Н, m-Н, Ph, J = 7.4); 7.54 (s, C(5)H, 11); 7.61 (d, C(5)H, 10, J = 6.7);

7.67 (d, 2 Н, o-H, Ph, J = 7.4); 8.30 (d, C(8)H, 11, J= 9.4)

10b

10c+11c

10d+11d

10e+11e

0.89—1.21 (m, 6 H, 2 Мe); 1.68—2.14 (m, 2 H, 2 CH₂); 2.21 (s, CH₃, 11); 2.80 (s, CH₃, 10),

3.47—3.73 (m, 4 H, 2 CH₂SO₂); 3.87 (s, 3 H, OMe); 6.73 (t, C(6)H, 10, J = 6.6); 6.94 (d, 2 H, Ph_,J = 8.5);

7.02—7.12 (m, C(7)H, 10; C(7)H, 11); 7.51 (s, C(5)H, 11); 7.60 (d, C(5)H, 10, J = 6.6); 7.73 (d, 2 H, Ph,

J = 7.9); 8.29 (d, C(8)H, 11, J = 9.8)

0.85—1.20 (m, 6 H, 2 Me); 1.67—2.15 (m, 4 H, 2 CH₂); 2.22 (s, Me, 11); 2.80 (s, Me, 10); 3.38—3.79 (m, 4 H,

2 CH₂SO₂); 3.92 (s, 3 H, OMe, Ph); 3.96 (s, 3 H, OMe, Ph); 6.68—6.88 (m, C(6)H, 10, m-H, Ph);

7.00—7.17 (m, C(7)H, 10; C(7)H, 11; o-H, Ph); 7.50 (s, C(5)H, 11); 7.55—7.75 (m, C(5)H, 10; o-H, Ph);

8.29 (d, C(8)H, 11, J = 9.2)

10f

10g

10h

10i

10j

0.95, 1.15 (both t, 3 H each, 2 Me, J = 7.4); 1.68—2.2 (m, 4 H, 2 CH₂); 2.83 (s, 3 H, Me);

3.43—3.78 (m, 4 H, 2 CH₂SO₂); 6.75 (t, 1 H, C(6)H, J = 7.8); 7.22 (d, 1 H, C(7)H, J = 8.0);

7.45—7.72 (m, 5 H, o-H и m-H, Ph, C(5)H)

1.02, 1.15 (both t, 3 H each, 2 Me, J = 7.2); 1.78—1.95 (m, 4 Н, 2 СН₂); 3.54—3.68 (m, 4 Н, 2 CH₂SO₂);

3.95 (s, 3 Н, OMe); 6.42 (s, 2 Н, NH₂); 6.61 (d, 1 Н, С(7)Н, J = 7.4); 6.90 (t, 1 Н, С(6)Н, J = 7.4);

7.75 (d, 1 Н, С(5)Н, J = 7.4)

1.09, 1.48 (both t, 3 H each, 2 Me, J = 7.2); 3.50—3.83 (m, 4 H, 2 CH₂SO₂); 5.76 (s, 2 H, NH₂);

6.39 (d, 1 H, C(7)H, J = 7.2); 6.68 (t, 1 H, C(6)H, J = 7.2); 7.20 (d, 1 Н, С(5)Н, J = 6.6);

7.40—7.85 (m, 5 H, Ph)

0.96, 1.05 (both t, 3 H each, 2 Me, J = 7.3); 1.53—1.95 (m, 4 H, 2 CH₂); 2.45 (s, 3 H, C(4)Me, Ph);

3.40—3.73 (m, 4 H, 2 CH₂SO₂); 6.47—6.65 (m, 3 H, NH₂, C(7)H); 6.77 (t, 1 Н, С(6)Н, J = 7.3);

7.03 (d, 1 Н, С(5)Н, J = 6.8); 7.32 (d, 2 Н, m-Н, Ph, J = 7.4); 7.60 (d, 2 H, o-H, Ph, J = 7.4)

0.90, 1.08 (both t, 3 H each, 2 Me, J = 7.3); 1.50—2.05 (m, 4 H, 2 CH₂); 2.37, 2.68 (both s, 3 H each, C(3)Me и

С(4)Me, Ph); 3.30—3.74 (m, 4 H, 2 CH₂SO₂); 5.73 (s, 2 H, NH₂); 6.41 (d, 1 Н, С(7)Н, J = 7.3);

6.71 (t, 1 Н, С(6)Н, J = 6.7); 6.97 (d, 1 Н, С(5)Н, J = 7.9); 7.08 (d, 1 H, m-Н, Ph, J = 7.9); 7.17 (s, 1 H,

m-H, Ph); 7.41 (d, 1 H, p-H, Ph, J = 6.7)

10k

10l

0.89—1.21 (m, 6 H, 2 Me); 1.72—2.11 (m, 4 H, 2 CH₂); 3.40—3.72 (m, 4 H, 2 CH₂SO₂); 3.87 (s, 3 H, OMe);

5.74 (s, 2 H, NH₂); 6.38 (d, 1 H, C(7)H, J = 7.3); 6.66 (t, 1 H, C(6)H, J = 7.3); 6.95 (d, 2 H, m-H, Ph, J = 7.3);

7.20 (d, 1 H, C(5)H, J = 6.1); 7.75 (d, 2 H, o-H, Ph, J = 7.3)

0.91, 0.99 (both t, 3 H each, 2 Me, J = 7.3); 1.52—1.90 (m, 4 H, 2 CH₂); 3.44—3.80 (m, 4 H, 2 CH₂SO₂);

3.86 (s, 6 H, 2 OMe); 6.57 (d, 1 H, C(7)H, J = 7.3); 6.63 (s, 2 H, NH₂); 6.85 (t, 1 H, C(6)H, J = 7.3);

7.03 (d, 1 H, m-H, Ph, J = 8.6); 7.13 (d, 1 H, o-H, Ph, J = 8.6); 7.22 (d, 1 H, C(5)H, J = 6.7);

7.49 (s, 1 H, o-H, Ph)

10m

10n

10o

0.98, 1.03 (both t, 3 H each, 2 Me, J = 7.4); 1.20—1.35 (m, 6 H, 2 CH₃); 1.53—1.90 (m, 4 H, 2 CH₂); 3.43—3.70

(m, 4 H, 2 CH₂SO₂); 4.67—4.83 (m, 1 H, OCH); 6.50—6.68 (m, 3 H, NH₂, C(7)H); 6.86 (t, 1 H, C(6)H, J = 7.3);

7.05 (d, 2 H, m-H, Ph, J = 7.4); 7.22 (d, 1 H, C(5)H, J = 7.3); 7.68 (d, 2 H, o-H, Ph, J = 7.4)

0.91, 1.00 (both t, 3 H each, 2 Me, J = 7.3); 1.50—1.95 (m, 4 H, 2 CH₂); 3.96—3.80 (m, 4 H, 2 CH₂SO₂);

6.19 (s, 2 H, OCH₂O); 6.50—6.73 (m, 3 H, NH₂, C(7)H); 6.86 (t, 1 H, C(6)H, J = 7.3); 7.05 (d, 1 H, C(5)H,

J = 7.9); 7.18 (m, 2 H, m-H, o-H, Ph); 7.36 (s, 1 H, o-H, Ph)

1.00, 1.10 (both t, 3 H each, 2 Me, J = 7.4); 1.71—2.10 (m, 4 H, 2 CH₂); 3.52—3.75 (m, 4 H, 2 CH₂SO₂);

5.81 (s, 2 H, NH₂); 6.47 (d, 1 H, C(7)H, J = 7.4); 6.70 (t, 1 H, C(6)H, J = 7.4); 7.08—7.22 (m, 3 H, C(5)H,

m-H, Ph); 7.73—7.88 (m, 2 H, o-H, Ph)

11p

11q

1.32, 1.48 (both t, 3 H each, 2 Me, J = 7.4); 2.63 (s, 3 H, Me, Ac); 3.57—3.78 (m, 4 H, 2 CH₂SO₂);

4.05 (s, 3 H, OCH₃); 7.81 (d, 1 H, C(7)H, J = 9.8); 8.44 (d, 1 H, C(8)H, J = 9.7); 9.12 (s, 1 H, C(5)H)

0.94, 1.03 (both t, 3 H each, 2 Me, J = 7.5); 1.57—1.97 (m, 4 H, 2 CH₂); 2.63 (s, 3 H, Me, Ac); 3.40—3.68

(m, 4 H, 2 CH₂SO₂); 4.00 (s, 3 H, CH₃O); 7.87 (d, 1 H, C(7)H, J = 9.9); 8.28 (d, 1 H, C(8)H, J = 9.9);

9.09 (s, 1 H, C(5)H)

0.94, 1.05 (both t, 3 H each, 2 Me, J = 7.5); 1.55—1.88 (m, 4 H, 2 CH₂); 2.62 (s, 3 H, Me, Ac); 3.43—3.72

(m, 4 H, 2 CH₂SO₂); 7.81 (d, 1 H, C(7)H, J = 9.9); 8.25 (m, 2 H, NH, C(8)H); 8.38 (s, 1 H, NH);

8.71 (s, 1 H, C(5)H)

11r

(to be continued)

Disulfonyl-containing polycyclic azines

Russ. Chem. Bull., Int. Ed., Vol. 66, No. 6, June, 2017

1041

Table 6 (continued)

Com-

pound

¹H NMR,  (J/Hz)

11s

11t

11u

11v

11w

11x

11y

1.25, 1.39 (both t, 3 H each, 2 Me, J = 7.4); 2.47 (s, 3 H, Me, Ac); 3.55—3.73 (m, 4 H, 2 CH₂SO₂); 7.49—7.58

(m, 2 H, m-H, Ph); 7.67 (d, 1 H, C(7)H, J = 7.2); 7.78 (m, 3 H, o-H и p-H, Ph); 8.39 (d, 1 H, C(8)H, J = 7.2);

8.47 (s, 1 H, C(5)H)

0.95, 1.05 (both t, 3 H each, 2 Me, J = 7.9); 1.55—1.90 (m, 4 H, 2 CH₂); 2.48 (s, 3 H, Me, Ac); 3.48—3.62 (m, 4 H,

2 CH₂SO₂); 7.53 (t, 2 H, m-H, Ph, J = 7.9); 7.67 (d, 1 H, C(8)H, J = 7.2); 7.74—7.85 (m, 3 H, o-H и p-H, Ph);

8.39—8.48 (m, 2 H, C(5)H, C(7)H)

0.97, 1.05 (both t, 3 H each, 2 Me, J = 7.3); 1.68—1.92 (m, 4 H, 2 CH₂); 2.47, 2.49 (both s, 3 H each, 2 Me, C(4)Me,

Ph, Me, Ac); 3.40—3.70 (m, 4 H, 2 CH₂SO₂); 7.30 (d, 2 H, m-H, Ph, J = 7.9); 7.72 (d, 2 H, o-H, Ph, J = 7.9);

7.85 (d, 1 H, C(7)H, J = 9.8); 8.39 (s, 1 H, C(5)H); 8.45 (d, 1 H, C(8)H, J = 9.8)

1.15, 1.35 (both t, 3 H each, 2 Me, J = 7.5); 2.41, 2.53 (both s, 3 H each, C(2)Me, C(4)Me, Ph); 2.71 (s, 3 H, Me, Ac);

6.95 (d, 1 H, m-H, Ph, J = 7.8); 7.08 (d, 1 H, o-H, Ph, J = 7.2); 7.25 (s, 1 H, m-H, Ph); 7.78 (d, 1 H, C(7)H,

J = 9.8); 8.45 (d, 1 H, C(8)H, J = 9.8); 8.60 (s, 1 H, C(5)H)

0.85—1.21 (m, 6 H, 2 Me); 1.67—1.93 (m, 4 H, 2 CH₂); 2.17 (s, 3 H, Me, Ac); 3.40—3.73 (m, 4 H, 2 CH₂SO₂);

3.89 (s, 3 H, C(4)OMe); 6.98 (d, 2 H, m-H, Ph, J = 8.5); 7.62—7.88 (m, 3 H, o-H, Ph, C(7)H); 8.36 (s, 1 H,

C(5)H); 8.44 (d, 1 H, C(8)H, J = 9.8)

0.89—1.18 (m, 6 H, 2 Me); 1.72—1.90 (m, 4 H. 2 CH₂); 2.49 (s, 3 H, Me, Ac); 3.40—3.78 (m, 4 H, 2 CH₂SO₂);

3.95, 3.99 (both s, 3 H each, 2 MeO); 6.85 (d, 1 H, m-H, Ph, J = 7.2); 7.09 (d, 1 H, o-H, Ph, J = 7.2); 7.66 (s, 1 H,

o-H, Ph); 7.73 (d, 1 H, C(7)H, J = 9.9); 8.37 (s, 1 H, C(5)H); 8.45 (d, 1 H, C(8)H, J = 9.8)

0.95, 1.12 (both t, 3 H each, 2 Me, J = 7.7); 1.57—1.85 (m, 4 H, 2 CH₂); 2.46 (s, 3 H, Me, Ac); 3.42—3.60 (m, 4 H,

2 CH₂SO₂); 7.32 (t, 2 H, m-H, Ph, J = 8.8); 7.82 (d, 1 H, C(7)H, J = 9.9); 7.87—7.98 (m, 2 H, o-H, Ph);

8.32 (d, 1 H, C(8)H, J = 9.9); 8.57 (s, 1 H, C(5)H)

11z

0.78—1.05 (m, 6 H, 2 Me); 1.45—1.78 (m, 4 H, 2 CH₂); 2.47 (s, 3 H, Me, Ac); 3.45—3.70 (m, 4 H, 2 CH₂SO₂);

7.65—7.95 (m, 5 H, p-H, Ph, C(7)H); 8.30 (d, C(8)H, J = 8.8); 8.64 (s, 1 H, C(5)H)

10a´

1.02—1.21 (m, 6 H, 2 Me); 1.78—2.02 (m, 4 H, 2 CH₂); 3.48—3.76 (m, 4 H, 2 CH₂SO₂); 4.00 (s, 3 H, OMe);

7.18 (t, 1 H, C(6)H, J = 7.7); 7.49 (s, 1 H, NH); 7.54 (d, 1 H, C(7), J = 7.1); 8.03 (s, 1 H, NH); 8.63 (d, 1 H,

C(5)H, J = 7.1)

11a´

11b´

11s´

10d´

11d´

10e´

11e´

10f ´

10g´

0.95, 1.08 (both t, 3 H each, 2 Me, J = 7.7); 1.62—1.95 (m, 4 H, 2 CH₂); 3.40—3.65 (m, 4 H, 2 CH₂SO₂);

4.00 (s, 3 H, OMe); 7.62 (s, 1 H, NH); 7.88 (d, 1 H, C(7)H, J = 9.9); 8.15—8.28 (m, 2 H, NH, C(8)H);

9.00 (s, 1 H, C(5)H)

0.97, 1.05 (t, 6 H, 2 Me, J = 7.2); 1.40—1.95 (m, 4 H, 2 CH₂), 3.45—3.68 (m, 4 H, 2 CH₂SO₂); 6.00 (s, 2 H, NH₂);

7.43—7.50 (m, 3 H, m-H, Ph, C(8)H); 7.60—7.73 (m, 1 H, p-H, Ph); 7.80 (d, 2 H, o-H, Ph, J = 7.2); 8.39 (d, 1 H,

C(7)H, J = 9.6); 8.49 (s, 1 H, C(5)H)

0.84, 1.01 (both t, 3 H each, 2 Me, J = 7.2); 1.50—1.87 (m, 4 H, 2 CH₂); 2.36, 2.62 (both s, 3 H each, 2 Me);

3.25—3.60 (m, 4 H, 2 CH₂SO₂); 6.45 (s, 2 H, NH₂); 6.95 (d, 1 H, m-H, Ph, J = 7.9); 7.02 (d, 1 H, o-H, Ph,

J = 7.2); 7.17 (s, 1 H, m-H, Ph); 7.57 (d, 1 H, C(7)H, J = 9.9); 8.38 (d, 1 H, C(8)H, J = 9.9); 8.60 (s, 1 H, C(5)H)

0.91, 1.06 (both t, 3 H each, 2 Me, J = 7.3); 1.08—1.15 (m, 4 H, 2 CH₂); 3.50—3.78 (m, 4 H, 2 CH₂SO₂); 3.85 (s, 3 H,

OMe); 7.05 (t, 1 H, C(6)H, J = 6.7); 7.11 (d, 2 H, m-H, Ph, J = 8.6); 7.50 (d, 1 H, C(7)H, J = 6.7); 7.60 (s, 1 H,

NH); 7.72 (d, 2 H, o-H, Ph, J = 7.9); 8.01 (d, 1 H, C(5)H, J = 7.3); 8.06 (s, 1 H, NH)

0.89—1.12 (m, 6 H, 2 Me); 1.54—1.98 (m, 4 H, 2 CH₂); 3.38—3.61 (m, 4 H, 2 CH₂SO₂); 3.89 (s, 3 H, OMe);

7.04 (d, 2 H, m-H, Ph, J = 8.8); 7.42 (s, 1 H, NH); 7.76 (d, 2 H, o-H, Ph, J = 8.8); 7.79 (d, 1 H, C(7)H,

J = 10.5); 816 (s, 1 H, NH); 8.27 (d, 1 H, C(8)H, J = 9.9); 8.45 (s, 1 H, C(5)H)

1.01, 1.13 (both t, 3 H each, 2 Me, J = 7.7); 1.60—2.05 (m, 4 H, 2 CH₂); 3.41—3.80 (m, 4 H, 2 CH₂SO₂); 3.88, 3.91

(both s, 3 H each, 2 OMe); 6.98—7.23 (m, 3 H, C(6)H, o-H и m-H, Ph); 7.40 (s, 1 H, NH); 7.46 (d, 1 H, C(7)H,

J = 6.6); 7.51 (s, 1 H, o-H, Ph); 7.87 (d, 1 H, C(5)H, J = 7.5); 7.92 (s, 1 H, NH)

0.89, 0.95 (both t, 3 H each, 2 Me, J = 7.4); 1.57—1.73 (m, 4 H, 2 CH₂); 3.45—3.68 (m, 4 H, 2 CH₂SO₂);

3.87 (s, 6 H, 2 OMe); 7.04 (d, 1 H, m-H, Ph, J = 8.5); 7.27 (d, 1 H, o-H, Ph, J = 8.2); 7.54 (s, 1 H, o-H, Ph);

7.65 (s, 1 H, NH); 7.85 (d, 1 H, C(7)H, J = 9.9); 8.23—8.30 (m, 3 H, NH, C(8)H); 8.44 (s, 1 H, C(5)H)

0.98, 1.12 (both t, 3 H each, 2 Me, J = 7.2); 1.58—1.98 (m, 4 H, 2 CH₂); 3.40—3.95 (m, 4 H, 2 CH₂SO₂);

7.03 (t, 1 H, C(6)H, J = 7.2); 7.32 (t, 2 H, m-H, Ph, J = 8.8); 7.43 (s, 1 H, NH); 7.49 (d, 1 H, C(7)H, J = 7.2);

7.75—7.88 (m, 2 H, o-H, Ph); 7.94 (s, 1 H, NH); 7.98 (d, 1 H, C(5)H, J = 7.2)

0.98, 1.14 (both t, 3 H each, 2 Me, J = 7.3); 1.71—1.95 (m, 4 H, 2 CH₂); 3.45—3.85 (m, 4 H, 2 CH₂SO₂);

7.05 (t, 1 H, C(6)H, J = 7.3); 7.40 (s, 1 H, NH); 7.50 (d, 1 H, C(7)H, J = 7.3); 7.65—7.75 (m, 4 H, o-H и m-H,

Ph); 7.82 (s, 1 H, NH); 8.00 (d, 1 H, C(5)H, J = 7.3)

(to be continued)

1042 Russ. Chem. Bull., Int. Ed., Vol. 66, No. 6, June, 2017

Dontsova and Shestopalov

Table 7. ¹³C NMR spectra of compounds 10a,b,g—m,a´,d´,e´ and 11q,r,t,u,x—z,a´,d´,e´´

Com-

poune

³C NMR, 

10a

6.04 (CH₃), 6.32 (CH₃), 22.29 (CH₃), 50.66 (CH₂), 52.00 (CH₂), 109.41 (C), 115.05 (CH), 123.65 (CH),

124.64 (C), 128.45 (CH), 128.77 (C), 128.90 (C), 133.77 (C), 160.93 (C)

6.32 (CH₃), 6.36 (CH₃), 22.28 (CH₃), 50.94 (CH₂), 52.38 (CH₂), 109.98 (C), 115.58 (CH), 118.71 (CH),

123.64 (CH), 127.95 (C), 128.66 (C), 129.12 (CH), 129.17 (2 CH), 129.35 (C), 134.59 (CH), 134.71 (C),

136.52 (C), 141.45 (CH), 187.77 (C)

10b

10g

10k

12.57 (CH₃), 12.70 (CH₃), 15.36 (CH₂), 15.77 (CH₂), 53.50 (OCH₃), 57.68 (CH₂), 59.55 (CH₂), 106.25 (CH),

108.73 (C), 114.12 (CH), 117.32 (CH), 122.74 (C), 126.97 (C), 127.30 (C), 139.45 (C), 160.82 (C)

12.60 (CH₃), 12.65 (CH₃), 15.51 (CH₂), 15.81 (CH₂), 55.68 (CH₃), 58.02 (CH₂), 59.98 (CH₂), 105.42 (CH),

107.78 (C), 113.63 (CH), 114.47 (2 CH), 117.17 (CH), 126.20 (C), 127.20 (C), 128.14 (C), 129.54 (C),

131.73 (2 CH), 139.69 (C), 164.32 (C), 186.09 (C)

12.59 (CH₃), 12.64 (CH₃), 15.49 (CH₂), 15.80 (CH₂), 55.67 (2CH₃), 58.00 (CH₂), 59.96 (CH₂), 105.41 (CH),

107.76 (C), 113.63 (CH), 114.46 (2 CH), 117.16 (CH), 126.18 (C), 127.19 (C), 128.12 (C), 129.52 (C),

131.71 (CH), 136.26 (C), 139.67 (C), 164.30 (C) 186.68 (C)

10l

10m

11q

12.57 (CH₃), 12.63 (CH₃), 15.46 (CH₂), 15.78 (CH₂), 21.51 (2 CH₃), 57.98 (CH₂), 59.93 (CH₂), 69.99 (OCH),

105.39 (CH), 107.74 (C), 113.64 (CH), 115.48 (CH), 117.14 (CH), 126.14 (C), 127.14 (C), 128.16 (C),

129.08 (C), 131.76 (C), 139.65 (CH), 162.72 (CH), 185.94 (CH)

12.48 (CH₃), 12.75 (CH₃), 15.10 (CH₂), 15.84 (CH₂), 26.48 (CH₃), 53.60 (OCH₃), 57.46 (CH₂), 58.22 (CH₂),

109.45 (C), 118.42 (CH), 122.53 (C), 124.67 (CH), 125.56 (C), 129.03 (C), 129.74 (CH), 136.06 (C),

159.75 (C), 194.74 (C)

11r

11t

12.82 (2 CH₃), 15.10 (CH₂), 15.44 (CH₂), 22.37 (CH₃), 57.81 (CH₂), 59.15 (CH₂), 109.55 (C), 115.06 (CH),

123.65 (CH), 125.21 (C), 128.43 (CH), 128.59 (C), 128.79 (C), 133.61 (C), 160.92 (C), 194.56 (C)

12.55 (2 CH₃), 14.93 (CH₂), 15.80 (CH₂), 26.53 (CH₃), 57.59 (CH₂), 58.45 (CH₂), 108.24 (C), 118.65 (CH),

124.38 (CH), 125.74 (C), 127.89 (C), 128.23 (C), 128.68 (CH), 128.93 (2 CH), 129.39 (2 CH), 134.62 (CH),

136.41 (C), 137.22 (C), 187.09 (C), 194.80 (C)

11u

11x

11y

11z

12.53 (2 CH₃), 15.00 (CH₂), 15.79 (CH₂), 21.27 (CH₃), 26.53 (CH₃), 57.61 (CH₂), 58.46 (CH₂), 108.11 (C),

118.65 (CH), 124.30 (CH), 125.72 (C), 127.44 (C), 128.36 (CH), 128.55 (C), 129.56 (4 CH), 134.63 (C),

136.26 (C), 145.64 (C), 186.43 (C), 194.77 (C)

12.57 (CH₃), 12.95 (CH₃), 15.16 (CH₂), 15.89 (CH₂), 26.63 (CH₃), 55.57 (CH₃), 55.94 (CH₃), 57.72 (CH₂),

58.51 (CH₂), 107.88 (C), 110.21 (CH), 110.96 (CH), 118.69 (CH), 124.30 (CH), 125.72 (C), 125.98 (CH),

126.94 (C), 128.19 (CH), 128.81 (C), 129.97 (C), 136.24 (C), 149.08 (C), 154.73 (C), 184.99 (C), 194.86 (C)

12.55 (2 CH₃), 14.98 (CH₂), 15.79 (CH₂), 26.57 (CH₃), 57.63 (CH₂), 58.48 (CH₂), 108.25 (C), 115.94 (CH),

116.24 (CH), 118.64 (CH), 124.39 (CH), 125.78 (C), 127.96 (C), 128.81 (CH), 132.54 (CH), 132.67 (CH),

134.35 (C), 136.52 (C), 164.11 (C), 167.48 (C), 185.71 (C), 194.85 (C)

12.56 (2 CH₃), 14.97 (CH₂), 15.80 (CH₂), 26.60 (CH₃), 57.61 (CH₂), 58.47 (CH₂), 108.29 (C), 118.63 (CH),

124.47 (CH), 125.81 (C), 127.66 (C), 128.11 (C), 128.84 (C), 128.99 (2 CH), 131.27 (2 CH), 131.99 (C),

136.55 (C), 136.62 (C), 186.44 (C), 194.86 (C)

10a´

11a´

10d´

13.48 (CH₃), 13.56 (CH₃), 14.81 (CH₂), 15.45 (CH₂), 54.04 (CH₃), 55.31 (CH₂), 57.84 (CH₂), 113.10 (C),

115.60 (CH), 122.52 (C), 128.02 (CH), 128.13 (CH), 129.67 (C), 130.77 (C), 132.07 (C), 160.36 (C), 168.66 (C)

13.11 (CH₃), 13.33 (CH₃), 15.78 (CH₂), 16.44 (CH₂), 54.23 (CH₃), 58.08 (CH₂), 58.87 (CH₂), 109.94 (C),

118.70 (CH), 122.83 (C), 123.71 (C), 126.13 (CH), 127.47 (CH), 128.62 (C), 136.37 (C), 160.51 (C), 165.01 (C)

12.63 (CH₃), 12.95 (CH₃), 14.31 (CH₂), 15.19 (CH₂), 55.10 (CH₂), 55.72 (CH₃), 57.81 (CH₂), 107.32 (C),

111.23 (C), 114.55 (2 CH), 114.86 (CH), 123.42 (CH), 126.67 (CH), 127.73 (C), 128.20 (C), 129.41 (C),

131.15 (C), 131.93 (2 CH), 164.48 (C), 168.16 (C), 185.31 (C)

11d´

10e´

11e´

12.58 (CH₃), 12.97 (CH₃), 15.21 (CH₂), 15.81 (CH₂), 55.73 (CH₃), 57.69 (CH₂), 58.54 (CH₂), 107.28 (C),

114.44 (2 CH), 118.32 (CH), 122.89 (C), 124.98 (CH), 125.90 (CH), 126.08 (C), 128.47 (C), 129.45 (C),

131.96 (2 CH), 135.92 (C), 164.23 (C), 164.56 (C), 185.33 (C)

13.25 (CH₃), 13.56 (CH₃), 14.03 (CH₂), 15.80 (CH₂), 55.71 (CH₂), 56.20 (OCH₃), 56.50 (OCH₃), 58.46 (CH₂),

110.53 (CH), 111.71 (CH), 115.42 (CH), 126.56 (CH), 127.28 (CH), 127.81 (C), 128.77 (C), 130.00 (C),

132.14 (C), 149.80 (C), 155.25 (C), 168.78 (C), 185.86 (C)

12.58 (2 CH₃), 15.24 (CH₂), 15.86 (CH₂), 55.58 (CH₃), 55.94 (CH₃), 57.74 (CH₂SO₂), 58.56 (CH₂SO₂),

107.16 (C), 110.14 (CH), 111.05 (CH), 118.29 (CH), 122.87 (C), 124.95 (CH), 125.94 (CH), 126.04 (CH),

128.39 (C), 129.80 (C), 135.93 (C), 149.10 (C), 154.74 (C), 164.21 (C), 185.11 (C)

(4-chlorophenyl)methanone (6h), (7-(tert-butyl)-1,2-bis(ethyl-

sulfonyl)indolizin-3-yl)(4-ethylphenyl)methanone (6i), (7-(tert-

butyl)-1,2-bis(ethylsulfonyl)indolizin-3-yl)(4-methoxyphenyl)-

methanone (6j), (7-(tert-butyl)-1,2-bis(ethylsulfonyl)indolizin-

3-yl)(4-ﬂuorophenyl)methanone (6k), (7-(tert-butyl)-1,2-bis-

(propylsulfonyl)indolizin-3-yl)(2,4-dimethylphenyl)methanone

(6l), (6,8-dimethyl-1,2-bis(propylsulfonyl)indolizin-3-yl)(phen-

yl)methanone (6m), (6,8-dimethyl-1,2-bis(propylsulfonyl)indol-

Disulfonyl-containing polycyclic azines

Russ. Chem. Bull., Int. Ed., Vol. 66, No. 6, June, 2017

1043

izin-3-yl)(4-methoxyphenyl)methanone (6n), methyl 1,2-bis-

(ethylsulfonyl)-7-(pyridin-4-yl)indolizine-3-carboxylate (6o),

1,2-bis(ethylsulfonyl)-7-(pyridin-4-yl)indolizine-3-carboxamide

(6p), (1,2-bis(ethylsulfonyl)-7-(pyridin-4-yl)indolizin-3-yl)-

(4-chlorophenyl)methanone (6q), (1,2-bis(propylsulfonyl)-7-

(pyridin-4-yl)indolizin-3-yl)(4-isopropoxyphenyl)methanone

(6r), (1,2-bis(propylsulfonyl)-7-(pyridin-4-yl)indolizin-3-yl)-

(3,4-dimethoxyphenyl)methanone (6s), ethyl 3-benzoyl-1,2-

bis(propylsulfonyl)indolizine-7-carboxylate (6t), ethyl 3-(4-me-

thylbenzoyl)-1,2-bis(propylsulfonyl)indolizine-7-carboxylate

(6u), ethyl 3-(4-methoxybenzoyl)-1,2-bis(propylsulfonyl)indol-

izine-7-carboxylate (6v), ethyl 3-(benzo[d][1,3]dioxolane-5-

carbonyl)-1,2-bis(propylsulfonyl)indolizine-7-carboxylate (6w),

methyl 1,2-bis(propylsulfonyl)pyrrolo[2,1-a]isoquinoline-3-

carboxylate (7a), 1,2-bis(ethylsulfonyl)pyrrolo[2,1-a]isoquinol-

ine-3-carboxamide (7b), (1,2-bis(propylsulfonyl)pyrrolo[2,1-a]-

isoquinolin-3-yl)(phenyl)methanone (7c), (1,2-bis(ethylsulfonyl)-

pyrrolo[2,1-a]isoquinolin-3-yl)(4-chlorophenyl)methanone (7d),

(1,2-bis(propylsulfonyl)pyrrolo[2,1-a]isoquinolin-3-yl)(2,4-di-

methylphenyl)methanone (7e), 1,2-bis(ethylsulfonyl)-8-methyl-

indolizine-3-carboxamide (10a), (1,2-bis(ethylsulfonyl)-8-me-

thylindolizin-3-yl)(phenyl)methanol (10b), methyl 8-amino-1,2-

bis(propylsulfonyl)indolizine-3-carboxylate (10g), (8-amino-

1,2-bis(ethylsulfonyl)indolizin-3-yl)(phenyl)methanone (10h),

(8-amino-1,2-bis(propylsulfonyl)indolizin-3-yl)(p-tolyl)metha-

none (10i), (8-amino-1,2-bis(propylsulfonyl)indolizin-3-yl)-

(2,4-dimethylphenyl)methanone (10j), (8-amino-1,2-bis(prop-

ylsulfonyl)indolizin-3-yl)(4-methoxyphenyl)methanone (10k),

(8-amino-1,2-bis(propylsulfonyl)indolizin-3-yl)(3,4-dimethoxy-

phenyl)methanone (10l), (8-amino-1,2-bis(propylsulfonyl)indo-

lizin-3-yl)(4-isopropoxyphenyl)methanone (10m), (8-amino-

1,2-bis(propylsulfonyl)indolizin-3-yl)(1,3-benzo[d][1,3]dioxo-

lan-5-yl)methanone (10n), (8-amino-1,2-bis(propylsulfonyl)-

indolizin-3-yl)(4-fluorophenyl)methanone (10o), methyl

6-acetyl-1,2-bis(ethylsulfonyl)indolizine-3-carboxylate (11p), methyl

6-acetyl-1,2-bis(propylsulfonyl)indolizine-3-carboxylate (11q),

6-acetyl-1,2-bis(propylsulfonyl)indolizine-3-carboxamide (11r),

1-(3-benzoyl-1,2-bis(ethylsulfonyl)indolizin-6-yl)ethan-1-one

(11s), 1-(3-benzoyl-1,2-bis(propylsulfonyl)indolizin-6-yl)ethan-

1-one (11t), 1-(3-(4-methylbenzoyl)-1,2-bis(propylsulfonyl)-

indolizin-6-yl)ethan-1-one (11u), 1-(3-(2,4-dimethylbenzoyl)-

1,2-bis(ethylsulfonyl)indolizin-6-yl)ethan-1-one (11v),

1-(3-(4-methoxybenzoyl)-1,2-bis(propylsulfonyl)indolizin-6-yl)-

ethan-1-one (11w), 1-(3-(3,4-dimethoxybenzoyl)-1,2-bis(prop-

ylsulfonyl)indolizin-6-yl)ethan-1-one (11x), 1-(3-(4-ﬂuoro-

benzoyl)-1,2-bis(propylsulfonyl)indolizin-6-yl)ethan-1-one (11y),

1-(3-(4-bromobenzoyl)-1,2-bis(propylsulfonyl)indolizin-6-yl)-

ethan-1-one (11z), methyl 8-carbamoyl-1,2-bis(propylsulfonyl)-

indolizin-3-carboxylate (10a´), methyl 6-carbamoyl-1,2-bis-

(propylsulfonyl)indolizine-3-carboxylate (11a´), 3-benzoyl-1,2-

bis(propylsulfonyl)indolizine-6-carboxamide (11b´), 3-(2,4-di-

methylbenzoyl)-1,2-bis(propylsulfonyl)indolizine-6-carboxamide

(11c´), 3-(4-methoxybenzoyl)-1,2-bis(propylsulfonyl)indolizine-

8-carboxamide (10d´), 3-(4-methoxybenzoyl)-1,2-bis(propyl-

sulfonyl)indolizine-6-carboxamide (11d´), 3-(3,4-dimeth-

oxybenzoyl)-1,2-bis(propylsulfonyl)indolizine-8-carboxamide

(10e´), 3-(3,4-dimethoxybenzoyl)-1,2-bis(propylsulfonyl)-

indolizine-6-carboxamide (11e´), 3-(4-fluorobenzoyl)-1,2-

bis(propylsulfonyl)indolizine-8-carboxamide (10f´),

3-(4-bromobenzoyl)-1,2-bis(propylsulfonyl)indolizine-8-carbox-

amide (10g´).

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Received December 21, 2016;

in revised form March 13, 2017

Article Doi

Synthesis of substituted disulfonyl-containing polycyclic azines with the bridgehead nitrogen atom. Effects of the structure of 3-substituted pyridinium ylides on the regioselectivity of their reactions with E-1,2-di(alkylsulfonyl)-1,2-dichloroethenes

DOI: 10.1007/s11172-017-1851-3

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Full text of DOI:10.1007/s11172-017-1851-3

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