Silver iodide catalyzed the three-component reaction between terminal alkynes, carbon disulfide, and aziridines

Journal of Sulfur Chemistry

ISSN: 1741-5993 (Print) 1741-6000 (Online) Journal homepage: https://www.tandfonline.com/loi/gsrp20

Silver iodide catalyzed the three-component

reaction between terminal alkynes, carbon

disulfide, and aziridines

A. Samzadeh-Kermani

To cite this article: A. Samzadeh-Kermani (2019): Silver iodide catalyzed the three-component

reaction between terminal alkynes, carbon disulfide, and aziridines, Journal of Sulfur Chemistry,

DOI: 10.1080/17415993.2019.1631316

To link to this article: https://doi.org/10.1080/17415993.2019.1631316

Published online: 25 Jun 2019.

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JOURNAL OF SULFUR CHEMISTRY

https://doi.org/10.1080/17415993.2019.1631316

Silver iodide catalyzed the three-component reaction

between terminal alkynes, carbon disulfide, and aziridines

A. Samzadeh-Kermani

Chemistry Department, Faculty of Science, University of Zabol, Zabol, Iran

ABSTRACT

ARTICLE HISTORY

Received 16 April 2019

Accepted 7 June 2019

A novel catalytic reaction involving terminal alkynes, carbon disul-

fide, and aziridines has been described. In this transformation, silver-

acetylides react with carbon disulfide and aziridines to form 1,4-

thiomorpholine molecules in good yields. The optimum conditions

developed using silver iodide and (i-Pr)₂EtN in DMF at 70°C.

KEYWORDS

Carbon disulﬁde; aziridine;

terminal alkyne; silver salt;

multicomponent reaction

1. Introduction

Terminal alk ynes are valuable synthons in the synthesis of a wide range of organic

molecules [1–3]. Conversion of terminal alkynes to the corresponding acetylides take place

either in the presence of a strong base or using an appropriate catalyst system. The lat-

ter method takes advantage of simplicity, compatibility with a wide range of functional

groups and protic solvents. Particularly, the nucleophilic additions of metal-acetylides to

Michael acceptors serve as an eﬃcient metho d for the synthesis of highly desirable C–C

bond from the readily accessible substrates [4 –9]. In last decade, the development of cat-

alytic formations of metal-acetylides oﬀers an opportunity for the expedient synthesis of

complex molecules from such simple starting materials [10 –12]. In most of these transfor-

mations, copper salts were selected as the catalysts of choice based on the cost, tolerability

with functional groups, and eﬃciency [13 –16]. It is worth mentioning that the oxida-

tion states of copper salts have tiny eﬀect on metal-acetylides formation. For instance,

Carreira and co-workers reported the ﬁrst nucleophilic additions of copper-acetylides

into unsaturated carbonyl in aqueous reaction medium using Cu(II)/ascorbate as cata-

lyst system [17]. Particularly notable is the use of copper-acetylide as an organometallic

CONTACT A. Samzadeh-Kermani

drsamzadeh@gmail.com

2

A. SAMZADEH-KERMANI

species in such protic reaction medium. Additionally, their reports on nucleophilic a ddi-

tions of copper-acetylides to carbonyl and imine moieties were without precedent [18,19].

Recently, Garcia-Tellado reported an enantioselective route for the synthesis of chiral

propargylic amines based on the nucleophilic addition of metal-acetylides into α-imino

esters [20]. The pioneering work of Medal in use of copper-acetylides with azides has

also attracted much attentions owing to its compatibility toward synthesis of a variety of

functional groups and heterocycles [21–25 ]. To our knowledge, Ghazanfarpour reported

the ﬁrst addition of copper-acetylides to carbon disulﬁde, allowing eﬃcient access to 1,4-

oxathiane skeletons [26]. Our group have also disclosed a reaction involving terminal

alkynes, isothiocyanates, and oxiranes using silver salts as a catalyst [27 ]. Our recent report

on the reaction of copper-acetylides, isothiocyanates, and aziridines leads to the formation

of thiomorpholine derivatives in good yields [28]. Based on t he above literatures and in

continuation of our reports in synthesis of heterocycles [29 ,30], we became interested to

explore the eﬃciency of silver-acetylides in a catalytic multicomponent reaction that uses

carbon disulﬁde and aziridines.

2. Results and discussion

To develop the designed catalytic multicomponent reaction, phenyl acetylene (1a), carbon

disulﬁde (2), and aziridine 3a were chosen as reaction partners to optimize the reaction

conditions (Table 1). Initial eﬀorts using CuOTf and (i-Pr)₂EtN to implement the pro-

posed transformation were complicated by formation of compound 5 (entry 1), which

might be arising from the competing attack of the copper-acetylide to 4-methyl-N-(3-

phenylpropylidene)benzenesulfonamide derived from Meinwald rearrangement [31], of

2-benzyl-1-tosylaziridine (3a). Control experiments clearly revealed that common cop-

per (I) and (II) salts were not eﬃcient for the successful synthesis of the desired product

4 (entries 2–7). The yields of the desired product 4 and the by-product 5 could be mod-

ulated by using N-heterocyclic carbene copper(I) catalyst (IPr)CuCl (IPr = 1,3-bis(2,6-

diisopropylphenyl)imidazol-2-ylidene) (entry 8). The study also showed that Fe(OTf)₃

and In(OTf)₃were not eﬃcient in carrying out this transformation (Table 1, entries 9 and

10). Pd(OAc)₂and AuCl₃were also examined but proved unsuitable catalysts (entries 11

and 12). Various silver salts were also examined to further optimize the reaction outcome

(entries 14–18). Upon examination of silver salts, AgI has been found to be optimal (entry

14). An outcome we attributed to higher aﬃnity of silver-acetylide to sulfur atom of CS₂

in comparison of oxygen in oxirane molecule. Particularly notable was that the use of sil-

ver salts as the catalyst of choice completely inhibited the formation of undesired product

5. These results demonstrated that the insertion of carbon disulﬁde into silver-acetylide

species proceeds signiﬁcantly faster than that of aziridine to the silver-acetylide bond.

The control experiment revealed that an extremely low yield of 4a was obtained with-

out (i-Pr)₂EtN, testifying to the vital roles of base in this catalytic system (entry 19). The

reactions run with either K₂CO₃or Cs₂CO₃resulted in moderate conversions (entries 20

and 21), whereas no the desired product formation take place upon using t. BuOLi and

instead 4-benzyl-3-tosylthiazolidine-2-thione was obtained in 69% yield (entry 22). To

our surprise, polyethylene glycol (PEG) (a known solvent for activating of oxiranes and

aziridines,[32]) was not good choice here (entries 23–25), as the by-product 5 was the main

product upon using PEG as the solvent. It could be deduced that PEG activates aziridine

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Table 1. Optimization of reaction conditions^a.

Entry

Catalyst

Base

Solvent

Yield 4a (%)

Yield 5 (%)

1

2

3

4

5

6

7

8

CuOTf

Cu₂O

CuBr

CuCl

CuI

Cu(OTf)₂

Cu(OAc)₂

(IPr)CuCl

Fe(OTf)₃

In(OTf)₃

Pd(OAc)₂

AuCl₃

AgOAc

AgI

AgCl

AgNO₃

AgF

AgBF₄

AgI

(i-Pr)₂EtN

–

DMF

PEG-200

PEG-400

PEG-600

–

29

38

43

35

56

25

31

64

–

35

30

26

22

21

58

43

Traces

–

9

10

11

12

13

14

15

16

17

18

19

20

21

22

23

24

25

26

27

–

49

57

73

82

75

67

71

87

Traces

43

60

K₂CO₃

Cs₂CO₃

LiO^tBu

–

b

(i-Pr)₂EtN

–

53

70

38

–

AgI

–

Complicated

–

DMF

–

^aReaction conditions: 1a (1.2 mmol), 2 (1.0 mL), 3a (1.0 mmol), catalyst (0.1 mmol), base (1.5 mmol), ground 3 Å molecular

sieves (250 mg) in solvent (3 mL) at 70°C for 18 h.

^b4-Benzyl-3-tosylthiazolidine-2-thione was obtained in 69% yield.

and thereby the insertion of 3a into silver(I) acetylide species proceeds faster than that of

carbon disulﬁde to the silver(I) acetylide bond. The reaction conducted in neat condition

formed a complicated mixture (Table 1 , entry 26). As expected, reaction did not proceed

at all with catalyst (Table 1, entry 27).

Having determined the optimized conditions, we set out to examine the scope of this

transformation (Table 2). N-Tosyl aziridine bearing a benzyl group 3a reacted smoothly

and aﬀorded the desired product in acceptable yield (entry 1). This transformation was

sensitive to steric hindrance of substrate, as reaction conducted with 1,1-disubstituted

aziridine 3b formed only a moderate yield of 4b (entry 2). Aziridine possessing alkyl

group like n-butyl and n-hexyl were also appropriate substrates (entries 3 and 4). If a six-

membered aziridine utilized as the aziridine source, the yield increased while, the aziridine

prepared from cycloheptene gave only in moderate yield (entries 5–6). Additionally, the

desired reaction did not proceed at all with cyclopentene aziridine 3 g, most likely due

to the interference of strain energy of the product (entry 7). The diﬀerence in reactivity

was reﬂected in the case of phenyl-substituted aziridines where the internal position was

exclusively attacked by the sulfur ion (entry 8). 2,3-Diphenyl-1-tosylaziridinealso was also

successful in the preparation of thiomorpholine skeleton (Table 2, entry 9). The substrate

4

A. SAMZADEH-KERMANI

Table 2. Synthesis of functionalized thiomorpholines^a.

Entry

Alkyne

R¹

Aziridine

R²,R³, R⁴

Yield (%)

1

2

3

4

5

6

7

8

1a

1b

1c

1d

Ph

3a

3b

3c

3d

3e

3f

3g

3h

3i

Bn, H, H

n-C₃H₇, H, CH₃

n-C₄H₉, H, H

n-C₆H₁₃, H, H

–(CH₂)₄–, H

–(CH₂)₅–, H

–(CH₂)₃–, H

H, Ph, H

Ph, Ph, H

Ph, H, CH₃

Bn, H, H

4a, 82

4b, 64

4c, 86

4d, 73

4e, 89

4f, 51

–

4 g, 89^b

4 h, 92

4i, 72^b

4j, 79^c

4k, 90

4 l, 80^d

9

10

11

12

13

Ph

3j

n-Pr

2-furyl

TMS

3a

^aFor all entries except stated otherwise: 1 (1.2 mmol), 2 (1.0 mL), 3 (1.0 mmol), AgI (0.1 mmol), (i-Pr)₂EtN (1.5 mmol), ground

3 Å molecular sieves (250 mg) in DMF (3 mL) at 70°C for 18 h.

^bThe yield of benzylic- attacked product.

^cReaction mixture was stirred for 22 h.

^dReaction mixture was stirred at 90°C for 22 h.

possessing both alkyl- and phenyl- substituents 3j was also tolerated (entry 10). In this

reaction, we could not ﬁnd the other plausible regio-isomers at all. It is noteworthy that 1-

pentyne (1b), as an aliphatic alkyne, aﬀorded the targeted product in acceptable yield (entry

11). Not only phenyl- and alkyl- substituted terminal alkynes but also 2-ethynylfuran (1c)

engaged proﬁciently in this catalytic reaction to furnish compound 4k (entry 12). To our

delight, trimethylsilylacetylene (1d) could also react to form the desired thiomorpholine

motif in good yield (entry 15).

The structures of the products were conﬁrmed by spectroscopic analyses including

1

¹H-NMR, ¹³C-NMR, FT-IR, Mass spectroscopy, and elemental analysis. The H-NMR

spectrum of 4a exhibited a characteristic (AB)X spin system for the CH₂-CH H-atoms,

together with a singlet for the vinyl group. The ¹³C-NMR spectrum of 4a exhibited 25

signals and the mass spectrum of 4a displayed the molecular ion peak at m/z = 465.

Mechanistically, silver iodide coordinates with the triple bond lowering acidity of the

terminal C–H bond. The abstraction of the terminal proton easily by (i-Pr)₂EtN leads to

the formation of silver acetylide 6. Silver acetylide reacts with the carbon disulﬁde (2) to

form the corresponding ((3-phenylprop-2-ynethioyl)-λ³-sulfaneylidene)silver 7. It could

be deduced that the activation of 3a with silver cation weakened the carbon–nitrogen bond

in aziridine and produced an activated species which is attacked by anionic adduct 7. While

silver iodide system exhibited somewhat Lewis acidic character, the reaction did not pro-

ceed through the S_N1-like route as no products arising from Meinwald rearrangement are

detected by crude reaction mixture analyses.

The adduct then attacked on aziridine 3 to give 8. The N-tosyl anion of propargylic

skeleton 8 participated in the nucleophilic addition to the triple bond by intramolecular

6-exo cyclization to give 4 (Scheme 1).

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Scheme 1. Plausible mechanism for the formation of thiomorpholine derivatives.

Scheme 2. Conﬁgurational study with homonuclear NOE.

The stereochemistry of exo-cyclic double bond was determined by homonuclear NOE

experiment. This kind of experiment concerns substrates which have spatially close pro-

tons. Experiments emphasize signiﬁcant homonuclear NOE between the involved protons,

suggesting the exact Z -conﬁguration in compounds 4a (Scheme 2). When the signal

appeared at 7.68 ppm was irradiated the intensity of the vinylic hydrogens increased. This

result indicated that these two kind of protons are spatially enough close to aﬀect their

signal intensity.

3. Conclusion

In summary, we have developed a novel catalytic multicomponent reaction between in

situ generated silver-acetyilides, carbon disulﬁde, and aziridines. The study showed that

the choice of catalyst and the reaction medium had great impact in furnishing the desired

transformation with good success. Of the metal precatalysts examined, silver salts exhibited

unique reactivity and selectivity in this transformation as no product arising from the direct

attack of acetyilide on aziridine are detected in reaction mixture analysis. We found that the

eﬃciency as well as regio-selectivity of the ring opening reaction of aziridines is sensitive to

electronic and steric properties of substrates. This silver-catalyzed reaction demonstrates

good functional group tolerance and acceptable yields.

6

A. SAMZADEH-KERMANI

4. Experimental

Commercially available reagents were used without further puriﬁcation. N-Ts Aziridines

were prepared using the literature procedures [33 ]. All the solvents were purchased from

PALACHEM Chemical Industries. Solvents were dried over molecular sieves 3 Å or 4 Å

before the use. Molecular sieves were activated in vacuum oven at 200°C for 14 h and

stored under vacuum at 100 °C in the presence of P₄O₁₀. The copper (I) salts were typ-

ically weighted into smaller vials containing about 500 mg of reagent in a glovebox and

sealed. The smaller containers were transferred outside the glovebox, stored in a desiccator

while being utilized and kept for no more than 2 weeks outside the glovebox. All reactions

were carried out in Schlenk tube (25 mL) using oven-dried and/or ﬂame dried glassware

under a pure and dry argon atmosphere with magnetic stirring. All reactions were mon-

itored by TLC analyses were performed on Silica gel 60 (Merck, item number 116835).

Plates were visualized using UV light (254 nm) and/or iodine. Column chromatography

was performed on silica gel 60 (particle size 63–200 μm) (Merck, item number 7734-3) on a

glass column. Melting points (mp) were recorded with Electrothermal-9100 apparatus and

were determined in capillary tubes and are uncorrected. ¹H-NMR spectra were recorded

with Bruker DRX-500 AVANCE instrument; at 500 MHz (using TMS, as a reference), and

¹³C NMR were recorded at 125 MHz (using the CDCl₃triplet as reference) in CDCl₃as

solvent at ambient temperature. Data are reported as follows: chemical shift, integration,

multiplicity (s = singlet, d = doublet, dd = doublet of doublet, br = broad, t = triplet,

q = quartet, m = multiplet). Chemical shifts were reported as (δ) in parts per million

(ppm) and Coupling constants J values are given in Hz. Mass data were recorded with

EIMS (70 eV): Finnigan-MAT-8430 mass spectrometer, in m/z. IR spectra were recorded

with Shimadzu IR-460 FTIR spectrometer as KBr pellets or neat. Elemental analyses (C, H,

N) were performed with a Heraeus CHN-O-Rapid analyzer. The results agreed favorably

with the calculated values.

4.1. General procedure for the preparation of compounds 4

An oven-dried Schlenk tube (25 mL) equipped with a magnetic stir bar was charged with

terminal alkyne (1.2 mmol), AgI (0.1 mmol) and ground 3 Å molecular sieves (250 mg) in

DMF (3 mL). After stirring at 25°C for 30 min, carbon disulﬁde (1.0 mL) and aziridine

(1.0 mmol) were added under an Ar atmosphere. Stirring was continued at 70°C tem-

perature until the starting material was completely consumed (TLC monitoring, 16 h).

Afterwards, the mixture was quenched with sat.aq NH₄Cl (5 mL) and extracted with

EtOAc (3 × 10 mL). The combined organic layers were dried over MgSO₄, ﬁltered, and

evaporated under reduced pressure to dryness. The crude product obtained was fur-

ther puriﬁed by column chromatography (silica gel, hexane:EtOAc 3:1) to give the pure

product.

4.1.1. 5-Benzyl-3-benzylidene-4-tosylthiomorpholine-2-thione (4a, C₂₅H₂₃NO₂S₃)

Yellow powder; M.P: 113–115°C. Yield: 0.38 g (82%). IR (KBr) (ν_max, cm⁻¹): 3032, 2978,

1541, 1364, 1311, 1115. ¹H NMR (500.1 MHz, CDCl₃): δ = 2.36 (3 H, s, Me), 2.80 (1 H,

dd, ²J = 12.0 Hz, ³J = 11.8 Hz, CH), 3.01 (1 H, dd, ²J =^H12.0 Hz, ³J = 5.8 Hz, CH), 3.23

(1 H, dd, ²J = 11.9 Hz, ³J = 7.5 Hz, CH), 3.40 (1 H, dd, ²J = 11.9 Hz, ³J = 5.5 Hz, CH),

JOURNAL OF SULFUR CHEMISTRY

7

4.02–4.11 (1 H, m, CH), 5.62 (1 H, s, CH), 7.17–7.33 (6 H, m, 6 CH), 7.35–7.45 (4 H,

m, 4 CH), 7.56 (2 H, d, ³J = 6.1 Hz, 2 CH), 7.68 (2 H, d, ³J = 6.3 Hz, 2 CH). ¹³C NMR

(125.7 MHz, CDCl₃): δ = 22.8 (Me), 39.1, 43.5 (CH₂), 63.2, 111.3, 125.1, 125.8 (CH),

C

127.1 (2 CH), 128.0 (2 CH), 128.3 (2 CH), 129.1 (2 CH), 129.4 (2 CH), 130.5 (2 CH), 132.7,

135.1, 135.6, 138.6, 140.0, 226.5 (C). MS: m/z (%) = 465 (M⁺, 1), 310 (11), 155 (34), 128

(59), 91 (100), 77 (62), 54 (42). Anal. Calcd (%) for (465.64): C, 64.49, H, 4.98, N, 3.01, S,

20.66. Found: C, 64.70, H, 5.21, N, 3.26, S, 20.74.

4.1.2. 3-Benzylidene-5-methyl-5-propyl-4-tosylthiomorpholine-2-thione (4b,

C₂₂H₂₅NO₂S₃)

Yellow oil. Yield: 0.28 g (64%). IR (KBr) (ν_max, cm⁻¹): 3041, 2983, 1536, 1372, 1314, 1122.

¹H NMR (500.1 MHz, CDCl₃): δ = 0.84 (3 H, t, ³J = 6.5 Hz, Me), 1.41–1.53 (4 H, m, 2

H

CH₂), 1.55 (3 H, s, Me), 2.40 (3 H, s, Me), 3.11 (1 H, d, ²J = 10.1 Hz, CH), 3.34 (1 H, d,

²J = 10.1 Hz, CH), 5.71 (1 H, s, CH), 7.30–7.45 (5 H, m, 5 CH), 7.61 (2 H, d, ³J = 6.5 Hz,

2 CH), 7.70 (2 H, d, ³J = 6.6 Hz, 2 CH). ¹³C NMR (125.7 MHz, CDCl₃): δ = 15.8 (Me),

C

16.0 (CH₂), 22.5, 25.0 (Me), 41.8, 49.2 (CH₂), 64.9 (C), 113.0, 128.1 (CH), 127.9 (2 CH),

128.9 (2 CH), 129.9 (2 CH), 131.2 (2 CH), 132.5, 135.0, 135.8, 139.5, 225.8 (C). MS: m/z

(%) = 431 (M⁺, 1), 276 (17), 187 (25), 155 (53), 91 (42), 77 (100), 54 (63). Anal. Calcd

(%) for (431.63): C, 61.22, H, 5.84, N, 3.25, S, 22.28. Found: C, 61.45, H, 6.02, N, 3.41,

S, 22.41.

4.1.3. 3-Benzylidene-5-butyl-4-tosylthiomorpholine-2-thione (4c, C₂₂H₂₆NO₂S₃)

Yellow oil. Yield: 0.37 g (86%). IR (KBr) (ν_max, cm⁻¹): 3025, 2987, 1530, 1342, 1311, 1116.

¹H NMR (500.1 MHz, CDCl₃): δ = 0.81 (3 H, t, ³J = 6.0 Hz, Me), 1.29–1.54 (6 H, m,

H

3 CH₂), 2.40 (3 H, s, Me), 2.96 (1 H, dd, ²J = 11.2 Hz, ³J = 10.4 Hz, CH), 3.14 (1 H, dd,

²J = 11.2 Hz, ³J = 5.6 Hz, CH), 3.49–3.58 (1 H, m, CH), 5.63 (1 H, s, CH), 7.27–7.45 (5

H, m, 5 CH), 7.57 (2 H, d, ³J = 6.5 Hz, 2 CH), 7.69 (2 H, d, ³J = 6.8 Hz, 2 CH). ¹³C NMR

(125.7 MHz, CDCl₃): δ = 14.2, 22.9 (Me), 25.1, 26.2, 33.0, 41.1 (CH₂), 62.5, 113.2, 126.2

C

(CH), 127.9 (2 CH), 128.8 (2 CH), 129.4 (2 CH), 130.3 (2 CH), 132.7, 134.1, 134.6, 139.0,

224.1 (C). MS: m/z (%) = 490 (M⁺, 1), 276 (14), 187 (50), 155 (43), 77 (100), 54 (48). Anal.

Calcd (%) for (431.63): C, 61.22, H, 5.84, N, 3.25, S, 22.28. Found: C, 61.53, H, 6.05, N, 3.43,

S, 22.35.

4.1.4. 3-Benzylidene-5-hexyl-4-tosylthiomorpholine-2-thione (4d, C₂₄H₂₉NO₂S₃)

Yellow oil. Yield: 0.34 g (73%). IR (KBr) (ν_max, cm⁻¹): 3018, 2967, 1540, 1362, 1314, 1122.

¹H NMR (500.1 MHz, CDCl₃): δ = 0.79 (3 H, t, ³J = 6.2 Hz, Me), 1.23–1.38 (8 H, m, 4

H

CH₂), 1.57 (2 H, m, CH₂), 2.40 (3 H, s, Me), 2.86 (1H, dd, ²J = 12.0 Hz, ³J = 6.0 Hz, CH),

3.19 (1H, dd, ²J = 12.3 Hz, ³J = 9.1 Hz, CH), 3.57–3.67 (1 H, m, CH), 5.60 (1 H, s, CH),

7.28–7.41 (5 H, m, 5 CH), 7.58 (2 H, d, ³J = 6.2 Hz, 2 CH), 7.69 (2 H, d, ³J = 6.7 Hz, 2

CH). ¹³C NMR (125.7 MHz, CDCl₃): δ = 13.7, 23.1 (Me), 24.5, 27.8, 29.1, 33.2, 35.6, 44.1

C

(CH₂), 65.2, 113.1, 126.9 (CH), 127.9 (2 CH), 128.5 (2 CH), 129.1 (2 CH), 130.7 (2 CH),

132.5, 134.5, 135.6, 139.1, 224.1 (C). MS: m/z (%) = 459 (M⁺, 1), 304 (16), 302 (36), 155

(56), 91 (36), 77 (100), 54 (53). Anal. Calcd (%) for (459.68): C, 62.71, H, 6.36, N, 3.05, S,

20.92. Found: C, 62.90, H, 6.54, N, 3.21, S, 20.98.

8

A. SAMZADEH-KERMANI

4.1.5. 3-Benzylidene-4-tosyloctahydro-2H-benzo[b][1,4]thiazine-2-thione (4e,

C₂₂H₂₃NO₂S₃)

Yellow powder; M.P: 198–200°C. Yield: 0.38 g (89%). IR (KBr) (ν_max, cm⁻¹): 3032, 2981,

1541, 1347, 1321, 1108. ¹H NMR (500.1 MHz, CDCl₃): δ = 1.26–2.18 (8 H, m, 4 CH₂),

H

2.41 (3 H, s, Me), 2.55–2.64 (1 H, m, 1 CH), 3.01–3.11 (1 H, m, CH), 5.60 (1 H, s, CH),

7.30–7.44 (5 H, m, 5 CH), 7.59 (2 H, d, ³J = 6.2 Hz, 2 CH), 7.68 (2 H, d, ³J = 6.5 Hz, 2

CH). ¹³C NMR (125.7 MHz, CDCl₃): δ = 22.5 (Me), 25.8, 26.4, 29.1, 30.3 (CH₂), 43.5,

C

60.1, 112.1, 126.9 (CH), 127.9 (2 CH), 128.9 (2 CH), 129.6 (2 CH), 131.2 (2 CH), 132.2,

134.9, 135.1, 139.0, 226.1 (C). MS: m/z (%) = 429 (M⁺, 1), 274 (13), 185 (54), 155 (37),

91 (35), 77 (100), 54 (47). Anal. Calcd (%) for (429.61): C, 61.51, H, 5.40, N, 3.26, S, 22.39.

Found: C, 61.77, H, 5.64, N, 3.51, S, 22.51.

4.1.6. 3-Benzylidene-4-tosyloctahydrocyclohepta[b][1,4]thiazine-2(3H)-thione (4f,

C₂₃H₂₅NO₂S₃)

Yellow powder; M.P: 185–187°C; Yield: 0.23 g (51%). IR (KBr) (ν_max, cm⁻¹): 3046, 2978,

1646, 1548, 1346, 1312, 1110. ¹H NMR (500.1 MHz, CDCl₃): δ = 1.32–2.19 (10 H, m, 5

H

CH₂), 2.40 (3 H, s, Me), 2.44–2.52 (1 H, m, 1 CH), 2.91–3.02 (1 H, m, CH), 5.60 (1 H, s,

CH), 7.30–7.44 (5 H, m, 5 CH), 7.57 (2 H, d, ³J = 6.2 Hz, 2 CH), 7.68 (2 H, d, ³J = 6.5 Hz,

2 CH). ¹³C NMR (125.7 MHz, CDCl₃): δ = 23.1 (Me), 25.4, 26.9, 27.4, 30.1, 32.6 (CH₂),

C

49.1, 67.1, 113.1, 126.37 (CH), 127.9 (2 CH), 128.9 (2 CH), 129.7 (2 CH), 131.0 (2 CH),

132.9, 134.8, 136.2, 139.2, 225.7 (C). MS: m/z (%) = 443 (M⁺, 1), 288 (25), 197 (61), 155

(43), 77 (100), 54 (39). Anal. Calcd (%) for (443.64): C, 62.27, H, 5.68, N, 3.16, S, 21.68.

Found: C, 62.51, H, 5.88, N, 3.34, S, 21.82.

4.1.7. 3-Benzylidene-6-phenyl-4-tosylthiomorpholine-2-thione (4g, C₂₄H₂₁NO₂S₃)

Pale yellow powder; M.P: 137–139°C. Yield: 0.40 g (89%). IR (KBr) (ν_max, cm⁻¹): 3026,

2971, 1541, 1338, 1315, 1122. ¹H NMR (500.1 MHz, CDCl₃): δ = 2.41 (3 H, s, Me), 4.03

(1 H, dd, ³J = 11.0 Hz, ³J = 6.7 Hz, CH), 4.48 (1 H, dd, ²J = ^H12.1 Hz, ³J = 5.1 Hz, CH),

4.65 (1 H, dd, ²J = 12.1 Hz, ³J = 9.0 Hz, CH), 5.60 (1 H, s, CH), 7.17–7.26 (3 H, m, 3 CH),

7.29–7.43 (7 H, m, 7 CH), 7.58 (2 H, d, ³J = 6.1 Hz, 2 CH), 7.69 (2 H, d, ³J = 6.5 Hz, 2

CH). ¹³C NMR (125.7 MHz, CDCl₃): δ = 22.8 (Me), 51.1, 64.7, 112.7, 126.4, 126.7 (CH),

C

127.5 (2 CH), 128.2 (2 CH), 128.6 (2 CH), 129.4 (2 CH), 129.9 (2 CH), 131.2 (2 CH), 132.1,

134.1, 135.2, 138.2, 139.1, 223.7 (C). MS: m/z (%) = 451 (M⁺, 4), 296 (22), 294 (57), 155

(44), 77 (100), 54 (48). Anal. Calcd (%) for (451.62): C, 63.83, H, 4.69, N, 3.10, S, 21.30.

Found: C, 64.05, H, 4.87, N, 3.33, S, 21.52.

4.1.8. 3-Benzylidene-5,6-diphenyl-4-tosylthiomorpholine-2-thione (4h,

C₃₀H₂₅NO₂S₃)

Pale yellow powder; M.P: 188–190°C. Yield: 0.37 g (91%). IR (KBr) (ν_max, cm⁻¹): 3067,

2975, 1578, 1344, 1289, 1102. ¹H NMR (500.1 MHz, CDCl₃): δ = 2.38 (3 H, s, Me), 4.01

H

(1 H, d, ³J = 7.2 Hz, CH), 5.12 (1 H, d, ³J = 7.2 Hz, CH), 5.78 (1 H, s, CH), 7.18–7.55 (17

H, m, 17 CH), 7.6 (2 H, d, ³J = 6.9 Hz, 2 CH). ¹³C NMR (125.7 MHz, CDCl₃): δ = 23.7

C

(Me), 50.3, 69.2, 112.7, 125.2, 126.5 (CH), 127.0 (2 CH), 127.2 (2 CH), 128.1 (CH), 128.2 (2

CH), 128.6 (2 CH), 129.1 (2 CH), 129.5 (2 CH), 129.6 (2 CH), 131.3 (2 CH), 132.4, 134.3,

136.2, 138.2, 139.8, 140.2, 144.8, 222.6 (C). MS: m/z (%) = 527 (M⁺, 6), 450 (9), 373 (19),

JOURNAL OF SULFUR CHEMISTRY

9

155 (51), 131 (69), 77 (100). Anal. Calcd (%) for (527.72): C, 68.28, H, 4.78, N, 2.65, S,

18.23. Found: C, 68.41, H, 4.84, N, 2.80, S, 18.44.

4.1.9. 3-Benzylidene-6-methyl-6-phenyl-4-tosylthiomorpholine-2-thione (4i,

C₂₅H₂₃NO₂S₃)

Yellow powder; M.P: 167–169°C. Yield: 0.33 g (72%). IR (KBr) (ν_max, cm⁻¹): 3051, 2973,

1

1551, 1346, 1312, 1112. H NMR (500.1 MHz, CDCl₃): δ = 1.82 (3 H, s, Me), 2.42

H

2

(3 H, s, Me), 4.19 (1 H, d, J = 10.1 Hz, CH), 4.41 (1 H, d, J = 10.1 Hz, CH), 5.01 (1

3

H, s, CH), 7.28–7.46 (10 H, m, 10 CH), 7.60 (2 H, d, J = 6.2 Hz, 2 CH), 7.68 (2 H,

d, J = 6.5 Hz, 2 CH). ¹³C NMR (125.7 MHz, CDCl₃): δ = 23.5, 28.1 (Me), 55.9 (C),

3

C

68.1 (CH₂), 112.1, 126.3 (CH), 126.5 (2 CH), 127.1 (CH), 127.9 (2 CH), 128.4 (2 CH),

128.6 (2 CH), 129.8 (2 CH), 130.4 (2 CH), 132.1, 134.1, 136.2, 139.0, 151.2, 225.2 (C).

MS: m/z (%) = 465 (M⁺, 2), 278 (17), 192 (56), 155 (57), 91 (43), 77 (100). Anal. Calcd

(%) for (465.64): C, 64.49, H, 4.98, N, 6.87, S, 20.66. Found: C, 64.60, H, 5.22, N, 7.09,

S, 20.76.

4.1.10. 5-Benzyl-3-butylidene-4-tosylthiomorpholine-2-thione (4j, C₂₂H₂₅NO₂S₃)

Yellow powder; M.P: 83–85°C. Yield: 0.34 g (79%). IR (KBr) (ν_max, cm⁻¹): 3025, 2961,

1

3

1553, 1341, 1319, 1108. H NMR (500.1 MHz, CDCl₃): δ = 0.85 (3 H, t, J = 6.0 Hz,

H

Me), 1.48–1.60 (2 H, m, CH₂), 2.33–2.41 (2 H, m, CH₂), 2.44 (3 H, s, Me), 2.76 (1 H,

2

3

2

3

dd, J = 12.1 Hz, J = 5.7 Hz, CH), 2.91 (1 H, dd, J = 12.1 Hz, J = 8.7 Hz, CH), 3.11

2

3

2

3

(1 H, dd, J = 9.8 Hz, J = 5.8 Hz, CH), 3.31 (1 H, dd, J = 9.8 Hz, J = 8.0 Hz, CH),

3

3.76–3.85 (1 H, m, CH), 4.76 (1 H, t, J = 6.5 Hz, CH), 7.19–7.30 (5 H, m, 5 CH), 7.39

(2 H, d, J = 6.2 Hz, 2 CH), 7.68 (2 H, d, J = 6.3 Hz, 2 CH). ¹³C NMR (125.7 MHz,

3

CDCl₃): δ = 15.0, 22.1 (Me), 25.4, 28.1, 40.1, 43.7 (CH₂), 65.1, 108.2, 126.1 (CH), 127.9

C

(2 CH), 128.9 (2 CH), 129.4 (2 CH), 131.3 (2 CH), 134.1, 134.7, 139.0, 139.3, 224.1 (C).

MS: m/z (%) = 431 (M⁺, 1), 276 (18), 274 (50), 155 (43), 91 (100), 77 (55). Anal. Calcd

(%) for (431.63): C, 61.22, H, 5.84, N, 3.25, S, 22.28. Found: C, 61.46, H, 6.07, N, 3.46,

S, 22.43.

4.1.11. 5-Benzyl-3-(furan-2-ylmethylene)-4-tosylthiomorpholine-2-thione (4k,

C₂₃H₂₁NO₃S₃)

Yellow powder; M.P: 100–102°C. Yield: 0.51 g (90%). IR (KBr) (ν_max, cm⁻¹): 3035, 2978,

1647, 1548, 1341, 1308, 1111. ¹H NMR (500.1 MHz, CDCl₃): δ = 2.40 (3 H, s, Me), 2.70

(1 H, dd, ²J = 10.8 Hz, ³J = 6.0 Hz, CH), 2.88 (1 H, dd, ²J = ^H10.8 Hz, ³J = 9.0 Hz, CH),

3.11 (1 H, dd, ²J = 12.0 Hz, ³J = 4.9 Hz, CH), 3.29 (1 H, dd, ²J = 12.0 Hz, ³J = 8.5 Hz,

CH), 3.67–3.78 (1 H, m, CH), 5.67 (1 H, s, CH), 6.64 (1 H, t, ³J = 6.0 Hz, CH), 6.90 (1 H,

d, ³J = 6.0 Hz, CH), 7.17–7.34 (5 H, m, 5 CH), 7.39 (2 H, d, ³J = 6.7 Hz, 2 CH), 7.68 (2 H,

d, ³J = 6.2 Hz, 2 CH), 7.81 (1 H, d, ³J = 6.1 Hz, CH). ¹³C NMR (125.7 MHz, CDCl₃): 22.1

(Me), 40.1, 44.5 (CH₂), 65.1, 97.9, 113.4, 114.7, 125.7 (CH), 127.7 (2 CH), 128.3 (2 CH),

129.4 (2 CH), 129.7 (2 CH), 134.5, 136.7, 137.2, 138.8 (C), 145.2 (CH), 148.1, 226.7 (C).

MS: m/z (%) = 455 (M⁺, 1), 300 (19), 221 (35), 155 (52), 91 (100), 67 (51). Anal. Calcd

(%) for (455.61): C, 60.63, H, 4.65, N, 3.07, S, 21.11. Found: C, 60.82, H, 4.78, N, 3.26,

S, 21.34.

10

A. SAMZADEH-KERMANI

4.1.12. 5-Benzyl-4-tosyl-3-((trimethylsilyl)methylene)thiomorpholine-2-thione (4l,

C₂₂H₂₇NO₂S₃Si)

Yellow oil. Yield: 0.37 g (80%). IR (KBr) (ν_max, cm⁻¹): 3041, 2971, 1641, 1547, 1326, 1309,

1

1107. H NMR (500.1 MHz, CDCl₃): δ = 0.03 (9 H, s, 3 Me), 2.40 (3 H, s, Me), 2.69

H

(1 H, dd, ²J = 11.8 Hz, ³J = 6.7 Hz, CH), 2.88 (1 H, dd, ²J = 11.8 Hz, ³J = 4.5 Hz, CH),

3.11 (1 H, dd, ²J = 11.0 Hz, ³J = 7.0 Hz, CH), 3.38 (1 H, dd, ²J = 11.0 Hz, ³J = 4.7 Hz,

CH), 4.03–4.12 (1 H, m, CH), 4.63 (1 H, s, CH), 7.188–7.34 (5 H, m, 5 CH), 7.34 (2 H, d,

³J = 6.5 Hz, 2 CH), 7.68 (2 H, d, ³J = 6.2 Hz, 2 CH). ¹³C NMR (125.7 MHz, CDCl₃): 1.5

(3 Me), 23.4 (Me), 40.1, 43.5 (CH₂), 64.1, 103.2, 126.1 (CH), 128.2 (2 CH), 128.9 (2 CH),

129.1 (2 CH), 129.3 (2 CH), 134.2, 138.1, 139.2, 152.3, 224.7 (C). MS: m/z (%) = 461 (M⁺,

1), 306 (22), 221 (34), 155 (46), 91 (100), 77 (68). Anal. Calcd (%) for (461.73): C, 57.23,

H, 5.89, N, 3.03, S, 20.83, Si, 6.08. Found: C, 57.42, H, 6.05, N, 3.21, S, 20.97, Si, 6.22.

Disclosure statement

No potential conﬂict of interest was reported by the author.

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Article Doi

Silver iodide catalyzed the three-component reaction between terminal alkynes, carbon disulfide, and aziridines

DOI: 10.1080/17415993.2019.1631316

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Article abstract of DOI:10.1080/17415993.2019.1631316

Full text of DOI:10.1080/17415993.2019.1631316

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