Ionic Liquid from Vitamin B1 Analogue and Heteropolyacid: A

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Ionic Liquid from Vitamin B1 Analogue and Heteropolyacid: A Recyclable Heterogeneous Catalyst for Dehydrative Coupling in Organic Carbonate Guo-Ping Yang, Xun Wu, Bing Yu, and ChangWen Hu ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.8b06445 • Publication Date (Web): 29 Jan 2019 Downloaded from http://pubs.acs.org on January 30, 2019

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Ionic Liquid from Vitamin B1 Analogue and Heteropolyacid: A Recyclable Heterogeneous Catalyst for Dehydrative Coupling in Organic Carbonate Guo-Ping Yang,a,c Xun Wu,a Bing Yu,b* and Chang-Wen Hua* Key Laboratory of Cluster Science of Ministry of Education, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Zhongguancun South Road, No. 5, Beijing 100081, P. R. China. Email: [email protected] b. College of Chemistry and Molecular Engineering, Zhengzhou University, Kexue Road No. 100, Zhengzhou 450001, Henan Province, P. R. China. Email: [email protected] c. China Academy of Engineering Physics, China KEYWORDS: Polyoxometalate; Organic Carbonate; Dehydrative Coupling; Alcohol; Alkene. a.

ABSTRACT: The ionic liquid [HMTH]2H2[SiW12O40] was prepared from the inexpensive, non-toxic vitamin B1-like compound, i.e. 5-(2-hydroxyethyl)-4-methythiazole (HMT), and the non-corrosive heteropolyacid (H4SiW12O40). This acidic ionic liquid was found to be an efficient heterogeneous catalyst for the direct dehydrative coupling of alcohols with alcohols (or alkenes) to synthesize various polysubstituted olefins in good to excellent yields with dimethyl carbonate (DMC) as a green solvent. Furthermore, this protocol was applicable in a gram-scale reaction, and the catalyst could be used at least for 8 runs without significant loss of activity.

INTRODUCTION Polyoxometalates (POMs) are an important class of acidic/basic catalysts in organic synthesis for the past centuries.1-7 Among those, the Keggin-type heteropolyacids (HPAs) are the most well investigated structures in catalysis due to their unique stability. The application of non-corrosive, inexpensive and readily available Keggintype HPAs for organic transformations including condensation, cycloaddition, and coupling reactions has been extensively studied.8-11 However, in most of these reported systems the HPAs are generally homogeneous catalysts, rendering the recycling of the catalyst from the reaction mixture challenging. Therefore, the development of reusable heterogeneous catalytic systems based on HPAs is highly attractive from the point view of sustainable chemistry. Due to their unique advantages such as nonvolatility, high thermal stability, and good catalytic activity, ionic liquids (ILs) has drawn considerable attention in the past decades.12-20 Particularly, ionic liquids based on heteropolyanion have been applied as heterogeneous catalytic systems for organic transformations. For example, Wang’s group21-23 developed a series of HPAs contained ILs, such as [MImPS]3PW12O40, [PyPS]3PW12O40, [NMPH]3PW12O40 etc. as catalysts for esterification reactions, epoxidation of alkenes and Prins reactions. In those above-mentioned reports, the typical synthesis of relevant ionic liquids includes the use of 1-methyl imidazole (MIm), pyridine (Py), and 1-methyl-2pyrrolidinone (NMP) as precursors. From the standpoint of environmental sustainability, the development of green chemical process is of significant current synthetic

interest.24-36 Consequently, the possibility of using biomimetic precursors for ionic liquid synthesis should be considered. Scheme 1. The Precursors for HPA-based ionic liquids synthesis

As it is known that vitamins are easily available compounds with numerous functions for biologic process. Inspired by the structure of vitamin B1 (Thiamine), 37 we envisioned the analogue compound 5-(2-hydroxyethyl)-4methythiazole (HMT) could be an inexpensive, non-toxic and biomimetic precursor for the synthesis of HPAs-based ionic liquids (Scheme 1). Following our recent development of HPA-catalyzed reaction in organic carbonate,38 we herein disclosed an ionic liquid [HMTH]2H2[SiW12O40], from the vitamin B1 analogue HMT and HPA (H4SiW12O40), catalyzed dehydrative reaction of alcohols with alcohols (or alkenes) using dimethyl carbonate (DMC) as a green solvent (Scheme 2). For this atom economical dehydrative reaction, the reusable catalyst was prepared from less hazardous reagents, and a safer solvent was employed. Therefore, this work should

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ACS Sustainable Chemistry & Engineering contain some metrics from the point view of green and sustainable chemistry. Scheme 2. The biomimetic ionic liquid catalyzed dehydrative reaction in dimethyl carbonate

[PyH]2H2[SiW12O 40], were examined as catalyst, 51%, 69%, 38% yields of 3a were obtained, respectively (Table S1). A

B

80

Yield (%)

60

RESULTS AND DISCUSSION We started our study by exploring the reaction of diphenylmethanol 1a and 1-phenylethanol 2a in propylene carbonate (PC) as a green solvent at 100 oC using different Keggin-type HPAs (3 mol%), i.e., H3PW12O40, H3PMo12O40, and H4SiW12O40 as catalyst (Figure 1A). Firstly, the effect of reaction time was investigated with the catalysis of homogeneous HPAs. As shown in Figure 1B, the optimal yields of 3a were achieved around 15 min in the presence of those HPA catalysts. In the case of H4SiW12O40 as catalyst, 80% yield of 3a was obtained in 15 min. Obviously, the catalytic performance of H4SiW12O40 is better than that of H3PW12O40 and H3PMo12O40. Considering that [SiW12O40]4- possess greatest softness among those heteropolyacid anions, it is assumed that the softness of [SiW12O40]4- plays an important role in stabilizing the reaction intermediates.39-40 Although H4SiW12O40 exhibited good activity for the dehydrative reaction, it was difficult to recycle the catalyst after reaction due to its homogeneous property. Therefore, the heterogenization of H4SiW12O40 was further conducted by utilizing HMT as a precursor to synthesize HPA-based ionic liquids as catalysts.23 As a result, different ratios of HMT and HPA were applied giving the ILs [HMTH]H3[SiW12O40], [HMTH]2H2[SiW12O 40], [HMTH]3H[SiW12O40], and [HMTH]4[SiW12O40]. As delineated in Figure 1C, the catalyst such as [HMTH]4[SiW12O40], [HMTH]3H[SiW12O 40], [HMTH]2H2[SiW12O40], and [HMTH]H 3[SiW12O40] provide the product 3a in yields of 18%, 42%, 66% and 47% at 15 min. These results suggested that the protons on the [SiW12O40]4- anion are also critical for this dehydrative reaction. Subsequently, [HMTH]2H2[SiW12O40] (3 mol%) was applied as catalyst for the optimization of different green solvents41-44 including polyethylene glycols, i.e., PEG200 and PEG400, cyclopentyl methyl ether (CPME), dimethyl carbonate (DMC), ethylene carbonate (EC), propylene carbonate (PC). As can be seen in Figure 2A, only 1% and 2% yields were observed when the reaction was conducted in PEG200 and PEG400, respectively. The reaction in water delivered 3a in 13% yield. While the reactions in CPME and organic carbonates showed good yield. Notably, 3a was obtained in 76% yield when DMC was applied as solvent. Under the identical conditions (100 oC, 15 min), the congener ionic liquids from N-methyl-2pyrolidone, N-methylimidazole and pyridine, i.e., [MImH]2H2[SiW12O40], [NMPH]2H2[SiW12O 40], and

40 H3PW12O40 H3PMo12O40

20

H4SiW12O40

0 100

5

10 15 t (min)

20

H4SiW12O40

25

C

[HMTH]H3SiW12O40 [HMTH]2H2SiW12O40

80

Yield (%)

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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[HMTH]3HSiW12O40 [HMTH]4SiW12O40

60

40

20 0

3

6

t (min)

9

12

15

Figure 1. (A) The dehydrative reaction of 1a and 2a; (B) The yield/time profile for the examination of HPA catalysts; (C) The yield/time profile for the examination of HMT-HPA ionic liquids. (Yields were determined by GC using biphenyl as an internal standard.)

Further screening of reaction temperature revealed that the dehydrative reaction benefits from an elevated reaction temperature. As shown in Figure 2B, the yield of 3a can be improved to 93% by increasing the reaction temperature to 120 o C. Finally, the optimal condition for this dehydrative reaction was established by using 3 mol% of [HMTH]2H2[SiW12O40] as catalyst in DMC as solvent at 120 oC for 15 min. With the optimized conditions in hand, we further explored the substrate scope of this catalytic system. As shown in Table 1, the reaction of 1a and 2a delivered the product 3a in 90% of isolated yield (Table 1, entry 1). 1,2,3,4-Tetrahydro-1-naphthol 2b also reacted smoothly with the alcohol 1a to produce the corresponding alkene product 3b in 87% yield (Table 1, entry 2). To our delight, the aliphatic tert-butyl alcohol 2c also worked well affording the desired products 3c in yield of 71%, albeit 3 equivalents of 2c was necessary (Table 1, entry 3). Then the electron donating group (-Me) and the electronwithdrawing group (-Cl) substituted diarylmethanols 1b, 1c and 1d reacted with 2a gave the corresponding alkene products 3d, 3e and 3f in 84%, 85% and 87% yields, respectively. Additionally, when 1-phenylethanol 2a was applied as the sole reactant, the product 3g was isolated in 64% yield (Table 1, entry 7). Unfortunately, the reaction of 2a and phenyl methanol (2d) did not give the desired

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product (see the Supporting Information), indicating that primary alcohol was not suitable in this procedure. G PE

0 40

2

A

0 1 20 G E E P PM C C M D EC

43 76 37

PC

Table 2. Substrates scope of the coupling of alcohols and alkenes.

13 0

100

20

40

60

[a]

93

B

85 76

60

54 41

40

0

80

Yield (%)

80

20

seen in Table 2, the reactions of diphenylmethanol 1a and various styrene derivatives 4a-d were firstly examined. Fortunately, the corresponding coupling products 5a-d were obtained in 82-88% yields (Table 2, entries 1-4). Furthermore, the various substituted diarylmethanols 1be, bearing electron-withdrawing or electron-donating groups, were also applied as substrates for the coupling reaction with styrene 4a, affording the corresponding products 5e-g in good to excellent yields (85-92%, Table 2, entries 5-7).

66

O H2

Yield (%)

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21

40

26

29

60

34

80

o

100

120

T ( C)

Figure 2. (A) Optimization of the reaction solvents ([HMTH]2H2[SiW12O40] as catalyst, 100 oC, 15 min); (B) Investigation of the reaction temperature in DMC. (Yields were determined by GC using biphenyl as an internal standard.) Table 1. Substrates scope of the coupling of alcohols and alcohols.[a]

[a] Reaction conditions: 1 (0.6 mmol), 4 (1.2 mmol), catalyst (3 mol%), DMC (3 mL), 120 oC, 15 min. [b] Isolated yields.

Additionally, the present protocol was found to be scalable at gram-scale to synthesize substituted olefins via the direct dehydrative coupling of alcohols and alcohols (or olefins), which is significant from the standpoint of practical applications. As shown in Scheme 3, the reaction of 1c (5 mmol) and 2a (10 mmol) as substrates produced the corresponding product 3e in 82% of isolated yield using [HMTH]2H2[SiW12O40] as catalyst at 120 oC for 1 h (Scheme 3a). Similarly, the gram-scale reaction of 1a and 4d led to the product 5d in yield of 77% under identical conditions (Scheme 3b). These results indicated that this method is operationally simple, scalable, and fast under mild conditions. Scheme 3. Gram-scale synthesis of polysubstituted olefins.

[a] Reaction conditions: 1 (0.6 mmol), 2 (1.2 mmol), catalyst (3 mol%), DMC (3 mL), 120 oC, 15 min. [b] Isolated yields. [c] 2c (1.8 mmol) was applied. [d] 2a (1.2 mmol) as the sole reactant.

After demonstrating that this catalyst was suitable for the dehydrative coupling of various alcohols, we further studied the reaction of various diarylmethanols with styrene derivatives under standard conditions. As can be

To test the reusability of the catalyst, the model reaction of 1a and 2a was carried out in the presence of 6 mol% of [HMTH]2H2[SiW12O40] under the optimal reaction

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ACS Sustainable Chemistry & Engineering conditions. After each cycle, the entire reaction system was transferred to a centrifugal tube, the catalyst was then centrifuged and then washed for three times with ethyl acetate. Subsequently, the recycled catalyst was dried under vacuum for 3 h at 50 oC for next run. The results shown in Figure 3 indicate that the yields of the product 3a were almost consistent after 8 runs, indicating that the ionic liquid [HMTH]2H2[SiW12O40] was stable under the reaction conditions, and can be used at least for 8 times without significant loss of activity.

polyanion [SiW12O40]4-.39-40 Subsequently, the addition of 8 to olefin 4a afforded the carbocation intermediate 9. After deprotonation of 9, the desired product 3 was generated.

Scheme 5. The proposed mechanism

100

80

Yield (%)

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60

40

20

CONCLUSIONS 0

1

2

3

4

5

6

7

8

run

Figure 3. Recyclability of [HMTH]2H2[SiW12O40] in direct dehydrative coupling of 1a and 2a.

To gain a deeper insight into the mechanism of this reaction, the control experiments were conducted as shown in Scheme 4. Under the standard conditions, the reaction of 1a and 4a for 1 min gave the product 5a and by-product 6 in yields of 34% and 62%, respectively. While after a prolonged reaction time (15 min), the compound 6 was consumed, and only 5a was obtained in 86% yield (Scheme 4a). Additionally, the reaction of 6 and 4a under the standard conditions gave the desired product 5a in 91% yield (Scheme 4b). Based on these results, we speculated that the compound 6 might be an intermediate of this dehydrative coupling.

In conclusion, we have developed a biomimetic HMTbased acidic ionic liquid i.e., [HMTH2]H2[SiW12O40] for the dehydrative coupling of alcohols and alcohols/alkenes to synthesize various polysubstituted olefins. The dehydrative reactions proceeded in organic carbonate as a green solvent giving the product in high yields with low catalyst loadings and short reaction time. Importantly, this reaction could be scaled up and the heterogeneous catalyst was used at least for 8 times. Such findings may pave the way for the development of new green chemistry transformations.

ASSOCIATED CONTENT Supporting Information. The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acssuschemeng.xxxxxx. Experimental and spectroscopic data, copies of 1H, and 13C NMR spectra (PDF).

AUTHOR INFORMATION

Scheme 4. Control experiments.

Corresponding Author *E-mail: [email protected]. *E-mail: [email protected].

Notes The authors declare no competing financial interest.

ACKNOWLEDGMENT

Based on these experimental results and previous reports,45-56 a plausible mechanism for the dehydrative coupling was presented in Scheme 5. With the catalysis of acidic [HMTH]2H2[SiW12O 40], the carbocation species 8 could be produced from the ether 6 or directly from the alcohol 1 via a protonation-dehydration process. Similarly, olefin 4a could be generated via the dehydration of alcohol 2a under the catalysis of IL. Presumably, the carbocation species 8 and 9 were probably stabilized by the soft

We appreciate the valuable suggestions from Prof. Nicholas Gathergood. We thank the National Nature Science Foundation of China (21501010, 21671019), the 111 Project (B07012), and 973 Program (2014CB932103) for financial support.

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The ionic liquid prepared from vitamin B1 analogue and heteropolyacid was found to be an efficient heterogeneous catalyst for the direct dehydrative coupling of alcohols with alcohols (or alkenes).

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