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Synthesis of Cyclic Thiocarbonates from Thiiranes and CS with Silica-Immobilized Catalysts 2

Yasumasa Takenaka, Norihisa Fukaya, Seong Jib Choi, Goro Mori, Takahiro Kiyosu, Hiroyuki Yasuda, and Jun-Chul Choi Ind. Eng. Chem. Res., Just Accepted Manuscript • DOI: 10.1021/acs.iecr.7b04245 • Publication Date (Web): 11 Dec 2017 Downloaded from http://pubs.acs.org on December 25, 2017

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Industrial & Engineering Chemistry Research

Synthesis of Cyclic Thiocarbonates from Thiiranes and CS2 with Silica-Immobilized Catalysts Yasumasa Takenaka,*,†,‡ Norihisa Fukaya,† Seong Jib Choi,† Goro Mori,§ Takahiro Kiyosu,§ Hiroyuki Yasuda,† and Jun-Chul Choi*,†

†

National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba Central 5,

1-1-1 Higashi, Tsukuba, Ibaraki 305-8565, Japan

‡

RIKEN Center for Sustainable Resource Science (CSRS), Biomass Engineering Research

Division, Bioplastic Research Team, 2-1 Hirosawa, Wako, Saitama 351-0198, Japan

§

Wako Pure Chemical Industries, Ltd., 1633 Matoba, Kawagoe, Saitama 350-1101, Japan

RECEIVED DATE: December 06, 2017

ABSTRACT

The synthesis of cyclic thiocarbonates by the cycloaddition of carbon disulfide (CS2) to thiiranes in the presence of silica-immobilized amine catalysts was investigated. The catalytic activities of the silica-immobilized catalysts toward the synthesis of cyclic thiocarbonates were higher than the activities of their homogeneous counterparts. The silica-supported catalysts strongly accelerated the cycloaddition of CS2 to thiiranes, and the pseudo-first order rate constant of the silica-immobilized catalyst was about 430 times larger 1

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than that of the corresponding homogeneous catalyst. The coexistence of the molecular catalyst species and the neighboring surface silanols on the catalyst support was found to be key to the reaction acceleration. In addition to providing improved catalytic activity, the solid-supported catalysts were also shown to be recyclable and reusable for at least five cycles.

INTRODUCTION:

Immobilization of molecular catalysts onto a solid support not only generates recoverable and reusable catalysts, but also results in superior catalytic performance compared with traditional molecular catalysts, because of the unique surface environment of the solid support.2-5 Unfortunately, this approach generally decreases the activity and/or selectivity of the active species.6

Therefore, much attention has been focused on the study of

"cooperative catalysis" of support surfaces containing immobilized catalytic species for efficient organic synthesis.7-18 A few examples of cooperative catalysis have been reported for some carbon-carbon bond-formation reactions, including aldol condensations,11-12 Michael reaction13 and cyano-ethoxycarbonylation.15-17 We have also previously reported onium salts that were covalently bound to silica and exhibited excellent catalytic activities compared with molecular catalysts for synthesizing cyclic carbonates from epoxides and CO2.18 We concluded that the cooperative effect of the immobilized catalyst consisting of neighboring

2


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surface silanols on a silica-supported onium salt catalyst was key to the acceleration of the reaction.

Several synthetic methods have been reported for cyclic trithiocarbonates,19-23 which are used as raw materials for plastic lenses and as graft reagents for polymer composite materials.24 Taguchi et al. showed that cyclic trithiocarbonates were produced in excellent yields by the reaction of thiiranes with CS2 using organic amine catalysts under high pressure (800 MPa).25 However, the reaction of thiirane with CS2 under mild conditions, for example, at

ambient

temperature

and

atmospheric

pressure,

preferentially

formed

poly(trithiocarbonate) instead of the desired cyclic trithiocarbonate, which was obtained in less than 20% yield (Scheme 1).26 The recovery and reuse of the catalysts was also problematic in these reports, because homogeneous catalysts such as amines25,27 or a chromium complex26 were used. In this study, we report the first highly selective catalytic synthesis of cyclic trithiocarbonates from thiiranes and CS2 using a heterogeneous catalyst. We also found that the presence of silanol groups on the heterogeneous catalyst plays a pivotal role in the efficient synthesis of cyclic trithiocarbonates. (salph)CrCl S

S S

[Ph 3P=N=PPh 3]Cl +

CS 2

S

Thiirane Conversion: 60%

1.

+

25 °C, 5 h

1 equiv.

Scheme

S

The

reaction

of

S

S

TTC

Copolymer

18%

48%

n

2-methylthiirane

with

CS2

catalyzed by bis(triphenylphosphine)iminium chloride ([PPN]Cl) and (salph)CrCl complex (salph = N,N'-bis-(3,5-di-tert-butylsalicylidene)-1,2-diaminobenzene).26

3



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EXPERIMENTAL:

Materials

and

2,3-epoxypropylphenylether,

Propylene

reagents:

2,2-dimethyloxirane,

oxide,

cyclohexene

1,2-epoxydodecane, oxide,

styrene

oxide,

2,2,3,3-tetramethyloxirane, carbon disulfide (CS2), triethylamine, pyridine, acetonitrile, toluene, and dichloromethane were obtained from Wako Pure Chemical Industries and were used after distillation. [3-(iodo-N,N-dimethyl-N-ethylammonium)propyl]trimethoxysilane, [3-(N,N-dimethylamino)propyl]trimethoxysilane, [3-(N-methylamino)propyl]trimethoxysilane,

(3-aminopropyl)trimethoxysilane,

[2-(2-Pyridyl)ethyl]trimethoxysilane,

[2-(4-Pyridyl)ethyl]trimethoxysilane,

[2-(diphenylphosphino)ethyl]trimethoxysilane, and 1,3,5-trimethyl benzene were obtained from Wako Pure Chemical Industries, Gelest, Atlantic Research Chemicals, and Sigma-Aldrich, and were used without further purification. Two types of mesoporous silica with a 2D hexagonal structure (TMPS-4 was supplied by Taiyo Kagaku28,29 and SBA-15,30 abbreviated respectively as MS-1 and MS-2) were used as silica support. The specific surface area, pore volume, and average pore diameter were 1036 m2/g, 1.35 cm3/g, and 3.8 nm for MS-1 and 861 m2/g, 1.01 cm3/g, and 7.1 nm for MS-2, respectively. Amorphous silica

4


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(CARiACT Q-3 and Q-6, abbreviated as AS-1 and AS-2) was supplied by Fuji Silysia Chemical. The specific surface area of AS-1 was 603 m2/g and that of AS-2 was 543 m2/g. Argon (Taiyo Nippon Sanso, 99.9999%) was used after purification by passing through a Dryclean column (4A molecular sieve) and a Gasclean CC-XR column purchased from Nikka Seiko. Instrumentation: Powder X-ray diffraction (XRD) data were acquired on a Bruker AXS

D8-Advance

X-ray

diffractometer

using

Cu

Kα

radiation.

Nitrogen

adsorption/desorption isotherms were measured at –196 °C using a Bel Japan BELSORP-MAX analyzer after the samples were evacuated at 200 °C for 1 h. Elemental analyses of nitrogen and halogen were performed using a CE Instruments EA1110 elemental analyzer and a Dionex DX-500 ion chromatograph system equipped with a Mitsubishi AQF-100 combustion apparatus, respectively. 1H and

13

C{1H} NMR spectra were recorded

on a Jeol LA400WB spectrometer (400 MHz for 1H), a Bruker AVANCE-III spectrometer (400 MHz for 1H) and a Bruker AVANCE-III spectrometer (600 MHz for 1H). Gas chromatograph (GC) analysis was carried out on a Shimadzu GC-2014 system equipped with a flame ionization detector and a TC-1 column. Gas chromatograph mass spectrometry (GC-MS) analysis was performed on a Shimadzu GCMS-QP2010 Plus system equipped with a TC-1 column. Gel permeation chromatograph (GPC) analysis was carried out on a Shimadzu GPC system equipped with a refractive index detector RID-10A, and GPC-804c and GPC-802c columns using polystyrene standard. 5



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Preparation of thiiranes: Thiiranes were generally prepared according to the literature.31 To a solution of oxirane (20 mmol) in acetonitrile (100 mL), were added thiourea (3.0 g, 40 mmol) and montmorillonite K-10 (4.0 g) and the mixture was stirred under reflux. The reaction was monitored by GC-MS, NMR, or TLC. The reaction mixture was filtered and washed with acetonitrile. The solvent was removed under reduced pressure. Purification was achieved by distillation, recrystallization, or column chromatography. Preparation of silica-immobilized catalysts: A typical procedure for preparing the silica-immobilized 3-(N,N-dimethylamino)propyl catalytic unit (Me2N-C3H6-MS-1) catalyst is as follow: MS-1 was dried under vacuum at 150 °C for 12 h prior to use. To a suspension of MS-1

(10.0

g)

in

toluene

(300

mL)

was

added

[3-(N,N-dimethylamino)propyl]trimethoxysilane (2.34 g, 11.3 mmol) under an argon atmosphere, and the mixture was stirred while refluxing for 24 h. The resulting solid was filtered, washed with dichloromethane, and dried under vacuum at 120 °C for 3 h. The 2-(4-pyridyl)ethyl,

2-(2-pyridyl)ethyl,

3-(N-methylamino)propyl-,

3-aminopropyl-,

3-(iodo-N,N-dimethyl-N-ethylammonium)propyl-, 2-(diphenylphosphino)ethyl catalytic units were immobilized on silica in a similar manner. The Reaction of thiiranes with CS2: A typical procedure for the reaction of 2-ethyl thiirane with CS2 is as follow. Into a glass pressure vessel (10 mL) were successively placed a Teflon-coated magnetic stir bar, the catalyst (5 mol% based on nitrogen), 2-ethyl thiirane (88.2 mg, 1.0 mmol), CS2 (381.0 mg, 5.0 mmol), and 1,3,5-trimethylbenzene (6.4 mg, 0.053 6


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mmol) as an internal standard for GC analysis. The reaction mixture was stirred at 100 °C for 3 h. After cooling the reaction mixture to 0 °C, the catalyst was separated by filtration, and the filtrate was analyzed by GC, NMR, and GPC to determine the product yield and the molecular weight of the polymer, respectively. The reaction of various thiiranes or epoxides with CS2 was carried out in a similar manner. Authentic samples of cyclic trithiocarbonates were prepared according to the literature.32 The signals of cyclic trithiocarbonates for NMR were assigned according to the previous report.32,33

RESULTS AND DISCUSSION:

Characterization

of

silica-immobilized

catalysts:

Amino-

or

quaternary

ammonium-immobilized silica catalysts were prepared by reacting trialkoxysilane-type coupling reagents with mesoporous silica (MS-1 and MS-2) or amorphous silica (AS-1 and AS-2). Table 1 summarizes the compositional and textural data for the organo-immobilized silica catalysts. The organic content, quantified by nitrogen elemental analysis, was 0.53–1.03 mmol/g. The XRD patterns of the organo-immobilized mesoporous silica catalysts were similar to those of the parent mesoporous silica materials,28-30 exhibiting three peaks assigned to a 2D hexagonal structure (see Supporting Information Fig. S1). This indicated that immobilization of amines or quaternary ammonium halides preserved the mesoporous structure. The nitrogen adsorption/desorption isotherms of the organo-immobilized mesoporous silica catalysts showed type IV sorption curves that are typical of mesoporous 7



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structures (see Supporting Information Fig. S2). Introduction of the organic groups reduced the surface area by 31–59% and narrowed the average pore diameter for both MS-1 and MS-2.

Table 1. Compositional and textural data for the silica-immobilized catalysts. Organic loadinga

SBETb

Vpc

DBJHd

mmol/g

m2/g

cm3/g

nm

4-Py-C2H4-MS-1

0.97

676

0.83

3.26

4-Py-C2H4-MS-1(TMS)

0.70

515

0.59

3.12

2-Py-C2H4-MS-1

0.53

716

0.86

3.36

Me2N-C3H6-MS-1

1.01

697

0.89

3.46

MeNH-C3H6-MS-1

0.98

592

0.70

3.36

NH2-C3H6-MS-1

1.03

715

0.91

3.46

[EtMe2N]I-C3H6-MS-1

1.00

583

0.72

3.14

Ph2P-C2H4-MS-1

-

654

0.69

3.36

4-Py-C2H4-MS-2

0.74

354

0.51

6.32

4-Py-C2H4-AS-1

0.70

270

0.22

2.92

4-Py-C2H4-AS-2

0.65

393

0.55

5.22

Catalyst

a

Determined by elemental analysis of nitrogen. Brunauer-Emmett-Teller (BET) specific surface area. c Pore volume determined at a relative pressure (P/P0) of 0.99. d Average pore diameter calculated by the Barrett-Joyner-Halenda (BJH) method from the b

adsorption branch.

Reaction of 2-ethylthiirane with CS2: The reaction of 2-ethylthiirane with 5 equiv. of CS2 without solvent at 100 °C for 3 h using 5 mol% of triethylamine as a homogeneous catalyst produced a trace amount of the corresponding butylene trithiocarbonate (1) (Table 2, entry 1). The pressure of the glass reactor reached approximatey 0.2 MPa during the reaction.

8


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However, when the reaction was continued for 24 h, 1 was formed as the major product in low yield (11%) (Table 2, entry 2), which was in good agreement with the results reported by Taguchi

and

co-workers.25

The

immobilization

of

the

N,N-dimethylaminopropyl

(Me2N-C3H6-) catalytic unit onto mesoporous silica (MS-1) dramatically increased the reaction efficiency as compared to the homogeneous triethylamine catalyst (Table 2, entries 3–5). For instance, the conversion of 2-ethylthiirane with a 3 h reaction time increased from 2% to 64% (Table 2, entry 1 vs. entry 3). Additionally, the reaction of 2-ethylthiirane (1 mmol) with CS2 (1 mmol) using 2 mol% of Me2N-C3H6-MS-1 in the absence of solvent also produced 1 in high yield (81%), although the selectivity was slightly decreased (Table 2, entry 6). The remarkable acceleration of the reaction by immobilizing the molecular catalyst on mesoporous silica was also observed with pyridine as the catalyst. Whereas the reaction with pyridine as a homogeneous catalyst was very slow, the reaction using the immobilized catalyst, 4-Py-C2H4-MS-1, was much improved (Table 2, entries 7–10). It is noteworthy that the pseudo-first order rate constant of the reaction with 4-Py-C2H4-MS-1 was about 430 times larger than that of pyridine (Table 2, entry 8 vs. entry 9). A quantitative yield of 1 was produced from 2-ethylthiirane and CS2 with 4-Py-C2H4-MS-1 as the catalyst (Table 2, entry 10). However, MS-1 alone did not promote the reaction, and poly(2-ethylthiirane) was mainly produced (Table 2, entry 11). Surprisingly, the catalytic activity of pyridine was also dramatically increased by the simple addition of MS-1 (Table 2, entry 12). Therefore, it was

9



Page 10 of 23

suggested that the coexistence of pyridine and MS-1 was important for the fast and highly selective formation of cyclic trithiocarbonates (see Supporting Information Scheme S1).

Table 2. The reaction of 2-ethylthiirane with CS2.a S S

Catalyst +

S

CS 2

Et

Et

ET

Entry

Catalyst

S 1

Time

Conversionb Yield of 1b Selectivity

kc

(h)

(%)

(%)

(%)

(min−1)

1

Triethylamine

3

2

trace

-

-

2

Triethylamine

24

11

11

>99

8.14 × 10−5

3

Me2N-C3H6-MS-1

3

64

59

92

5.68 × 10−3

4

Me2N-C3H6-MS-1

6

97

92

95

-

5

Me2N-C3H6-MS-1

24

>99

98

98

-

6d

Me2N-C3H6-MS-1

3

92

81

88

1.40 × 10−2

7

Pyridine

3

trace

trace

-

-

8

Pyridine

24

3

3

>99

2.12 × 10−5

9

4-Py-C2H4-MS-1

3

81

79

98

9.23 × 10−3

4-Py-C2H4-MS-1

24

>99

>99

>99

-

f

0

-

82

1.66 × 10−2

10 11

e

12e

MS-1

3

100

0

Pyridine + MS-1

3

95

78f

a

2-Ethylthiirane: 1 mmol, CS2: 5 mmol, catalyst: 5 mol%, 100 °C. Determined by GC with 1,3,5-trimethylbenzene as an internal standard. c Pseudo-first order rate constant. d CS2: 1 mmol, catalyst: 2 mol%. e MS-1: 50 mg. f Poly(2-ethylthiirane) was observed.

b

10


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The immobilization of a variety of amines on MS-1 efficiently promoted the selective formation of 1 from 2-ethylthiirane and CS2, but the catalytic activity was dependent upon the type of amine. In general, the catalyst activity was in the order of 4-pyridylethyl > tertiary amine > secondary amine > primary amine > ammonium salt (Table 3, entries 1–5). The supported tertiary phosphine diphenylphosphinoethyl catalyst also produced 1 in moderate yield and high selectivity when reacted at 100 °C for 3 h (Table 3, entry 6). Surprisingly, the 2-pyridylethyl Table 3. Activity of the silica-immobilized catalyst for the reaction of 2-ethylthiirane with CS2.a

Entry

Catalyst

Conversionb Yield of 1b

Selectivity

(%)

(%)

(%)

1

4-Py-C2H4-MS-1

81

79

98

2

Me2N-C3H6-MS-1

64

59

92

3

MeNH-C3H6-MS-1

54

50

93

4

NH2-C3H6-MS-1

7

4

57

5

[EtMe2N]I-C3H6-MS-1

5

4

80

6

Ph2P-C2H4-MS-1

50

43

86

7

2-Py-C2H4-MS-1

9

trace

>99

8

4-Py-C2H4-MS-2

79

78

99

9

4-Py-C2H4-AS-1

90

82

91

10

4-Py-C2H4-AS-2

99

99

>99

11

4-Py-C2H4-MS-1(TMS)

6

6

>99

a b

2-Ethylthiirane: 1 mmol, CS2: 5 mmol, catalyst: 5 mol%, 100 °C, 3 h. Determined by GC with 1,3,5-trimethylbenzene as an internal standard.

11



species was less effective (Table 3, entry 7), possibly due to the interaction of the nitrogen atom with the silanol group of the mesoporous silica surface.34,35 For this reason, we investigated the apparent cooperative effect of the type of silica support. The activity of 4-Py-C2H4-MS-2, in which the 4-pyridylethyl species was immobilized on the ordered mesoporous silica SBA-15 (MS-2), was comparable to that of 4-Py-C2H4-MS-1. When two types of amorphous silica (AS-1 and AS-2) with different surface areas were used as the catalyst support, 1 was also formed in high yields (Table 3, entries 9 and 10). Therefore, the cooperative catalysis is not a phenomenon limited only to MS-1. Most interestingly, when the surface silanols of 4-Py-C2H4-MS-1 were protected by trimethylsilyl groups, the catalytic activity of the resulting 4-Py-C2H4-MS-1(TMS) dramatically decreased (Table 3, entry 11). This result implies that the key of the synergistic acceleration of the reaction is the coexistence of surface silanols with the molecular catalytic species in a heterogeneous catalyst. Reaction of 1-butene oxide with CS2: This acceleration effect was also observed in the reaction of epoxide with CS2. Whereas the reaction of epoxide with CS2 using triethylamine as a homogeneous catalyst at 100 °C for 24 h did not proceed at all, the substrate was completely converted to the corresponding cyclic trithiocarbonate (1, 18%) and cyclic dithiocarbonate (2, 80%) when catalyzed by Me2N-C3H6-MS-1 at 100 °C for 6 h (Scheme 2). The reaction was carried out under various conditions, but suitable conditions under which either 1 or 2 was selectively formed were not found. Figure 1 shows the time 12


Page 12 of 23

Page 13 of 23

course for the reaction of 1-butene oxide (BO) with CS2 using Me2N-C3H6-MS-1. 2 was formed in a 40% yield after 1 h at 100 °C, and 1 and 2-ethylthiirane (ET) were simultaneously formed at 4% and 4%, respectively. Therefore, it appears that 1 is directly formed from the epoxide and CS2 catalyzed by Me2N-C3H6-MS-1 in the initial stage of the reaction (see Supporting Information Scheme S2). S O

(A)

+

CS2

Et BO

O

(B)

5 equiv.

Et 3N (5 mol%)

BO

S

S

S O

S +

Et Conversion: 99%

S +

O +

S

S +

S

Et

O O +

Et 2 80%

S

S +

Et

S

Et 1 18%

O

Et

S

100 °C, 6 h

5 equiv.

S

Et

S

CS2

O

Et

No Reaction Me 2N-C 3H 6-MS-1 (5 mol%)

+

S S +

100 °C, 24 h

Et

S

Et

Et 3 0%

S

S +

4 trace

ET trace

98%

Scheme 2. The reaction of 1-butene oxide (BO) with CS2 catalyzed by (A) triethylemine or (B) Me2N-C3H6-MS-1.

100 Mole Fractions (%)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


2

80 60 40

1

20 BO

0 0

6 12 18 Reaction Time (h)

24

Figure 1. Time courses for the reaction of 1-butene oxide (BO) with CS2 catalyzed by Me2N-C3H6-MS-1. Butylene trithiocarbonate (1) (●), 5-ethyl-1,3-oxathiolane-2-thione (2) (■), BO (□) and ET (○).

Acceleration mechanism for the reaction of 2-ethylthiirane with CS2: A plausible reaction mechanism for the reaction of 2-ethylthiirane with CS2 using the silica-immobilized 13



Page 14 of 23

4-pyridinylethyl catalyst is shown in Scheme 3. It is well known that CS2 easily reacts with amino groups.33,36 First, the thiocarboxyl ion (-CS2-) is formed by the reaction of the pyridyl group with CS2 (Scheme 3 (A), Step A) and then attacks the three-membered ring of thiirane to promote its ring-opening This process is accelerated by the presence of the neighboring silanol, which may stabilize the reaction intermediate. Finally, the target cyclic trithiocarbonate is formed by the favorable five-membered ring closure (Scheme 3 (A), Step C). As previously mentioned, when silanol groups are unavailable on the catalyst surface, the acceleration of the thiirane ring-opening reaction does not proceed (Scheme 3 (B)).

(A)

Et

S N

Et S

C

S N

S H

C

N

S

H

Step A

O Si

S

S S

S

Si

SiO 2

N

S H

Step B

O

Si

S S H

Step C

O fast

Si

Si

SiO 2

Et

Et

C

O Si

Si SiO 2

Si SiO 2

Et

(B)

Et S

S

S

S

C N

N

S

SiMe 3

Si SiO 2

N

S

SiMe3

Step A

O Si

S

S

C

S

Si

S

Step B

O Si

N SiMe3

SiO 2

Si

S S SiMe3

Step C

O slow

Et

Et

C

O Si

Si SiO 2

Si SiO 2

Scheme 3. (A) Possible acceleration mechanism on the synergistic hybrid catalyst (4-Py-C2H4-MS-1) and (B) no acceleration mechanism on 4-Py-C2H4-MS-1 (TMS) with the surface silanol of 4-Py-C2H4-MS-1 capped by trimethylsilyl groups.

Reaction of various thiiranes with CS2: As summarized in Table 4, our synthetic method successfully produced various cyclic trithiocarbonates in excellent yields. The reactions

of

2-methylthiirane,

2-dodecylthiirane,

2-phenoxymethylthiirane,

2,2-dimethylthiirane, and cyclohexene thioepoxide with CS2 using Me2N-C3H6-MS-1 at 100

14


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°C gave the corresponding cyclic trithiocarbonates in excellent yields (Table 4, entries 1–5). In the case of styrene thioepoxide, the yield of the corresponding cyclic trithiocarbonate was low because styrene and other unknown products were simultaneously formed (Table 4, entry 6). When 4-Py-C2H4-MS-1 was used as the catalyst, the corresponding cyclic trithiocarbonate was quantitatively produced from cyclohexene thioepoxide and CS2 after 3 h (Table 4, entry 7). Although the reaction of 2,2-dimethylthiirane with CS2 using Me2N-C3H6-MS-1 at 100 °C for 16 h gave the desired cyclic trithiocarbonate in quantitative yield, the reaction using 4-Py-C2H4-MS-1 was very slow (Table 4, entry 8). 1,1,2,2-tetramethylthiirane did not react with CS2, presumably because of the large steric hindrances at the cyclic carbon atoms (Table 4, entry 9). Table 4. Reaction of various thiiranes with CS2.a

Entry

Catalyst

Thiirane

Time

Conv.b

TTC Yieldb

1

Me2N-C3H6-

R1

R2

R3

R4

(h)

(%)

(%)

CH3

H

H

H

6

>99

96

C10H21

H

H

H

24

>99

>99

CH2OC6H5

H

H

H

6

99

99

CH3

CH3

H

H

16

>99

>99

H

-CH2CH2CH2CH2-

H

6

>99

97

MS-1 2

Me2N-C3H6MS-1

3

Me2N-C3H6MS-1

4

Me2N-C3H6MS-1

5

Me2N-C3H6-

15



MS-1 6

Me2N-C3H6-

C6H5

H

24

>99

33c

-CH2CH2CH2CH2-

H

3

>99

95

CH3

H

H

60

75

70

CH3

CH3

CH3

168

trace

trace

H

H

MS-1 7

4-Py-C2H4-M H S-1

8

4-Py-C2H4-M CH3 S-1

9

4-Py-C2H4-M CH3 S-1

a

Thiirane: 1 mmol, CS2: 5 mmol, catalyst: 5 mol%, 100 °C. Determined by GC with 1,3,5-trimethylbenzene as an internal standard. c Styrene was found in 15% yield. b

Catalyst recycling experiment: Finally, we investigated the recyclability of 4-Py-C2H4-AS-2 in the reaction of 2-ethylthiirane with CS2. After each run, the catalyst was separated by filtration, washed with dichloromethane, dried under vacuum at ambient temperature for several hours, and then used in a subsequent reaction. By this process, the recovered catalyst could be recycled at least five times without notable loss in the yield of 1 (Figure 2). These results demonstrated that 4-Py-C2H4-AS-2 is a sufficiently stable heterogeneous catalyst for the reaction of 2-ethylthiirane with CS2.

100 Yield of TTC (1) (%)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

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99

98

1

2

98

99

99

99

5

6

80 60 40 20 0

3 4 Run Number

16


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Figure 2. Catalyst recycling experiments for the reaction of 2-ethylthiirane (ET) and CS2 catalyzed by 4-Py-C2H4-AS-2. Reaction conditions: ET (1 mmol), CS2 (5 mmol), catalyst (0.5 mol%), 100 ºC, 3 h.

CONCLUSIONS:

In summary, we have demonstrated that the catalytic activity for the reaction of thiiranes with CS2 dramatically increased due to the key synergistic effect of immobilized organic amines and neighboring surface silanols on a heterogeneous catalyst. The pseudo-first order rate constant of a silica-immobilized catalyst was about 430 times larger than that of the corresponding homogeneous catalyst. Furthermore, the corresponding cyclic trithiocarbonates were successfully synthesized from various thiiranes and CS2 in excellent yields. The heterogeneous amine catalysts were found to be effective even after being recycled at least five times.

ASSOCIATED CONTENT

Supporting Information The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.iecrooo.

AUTHOR INFORMATION

Corresponding Author E-mail: [email protected] (Y. Takenaka); [email protected] (J. -C. Choi)

17



ORCID J. -C. Choi: 0000-0002-7049-5032

Notes The authors declare no competing financial interest.

ACKNOWLEDGEMENT

This research was financially supported by the Project of "Development of Microspace and Nanospace Reaction Environment Technology for Functional Materials" of the New Energy and Industrial Technology Development Organization (NEDO), Japan.

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