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Highly Efficient Synthesis of Quinazoline-2,4(1H,3H) -diones from CO2 by Hydroxyl Functionalized Aprotic Ionic Liquids Guiling Shi, Kaihong Chen, Yongtao Wang, Haoran Li, and Congmin Wang ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.8b01109 • Publication Date (Web): 19 Apr 2018 Downloaded from http://pubs.acs.org on April 19, 2018

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ACS Sustainable Chemistry & Engineering

Highly

Efficient

2,4(1H,3H)

Synthesis

-diones

from

of

Quinazolineby

CO2

Hydroxyl

Functionalized Aprotic Ionic Liquids Guiling Shi, Kaihong Chen, Yongtao Wang, Haoran Li, Congmin Wang †

†

†

†

*,†,‡

†Department of Chemistry, ZJU-NHU United R&D Center, Zhejiang University, Hangzhou 310027, China. Mailing address: 148 Tianmushan Road, Xihu District, Hangzhou, Zhejiang Province ‡Key Laboratory of Biomass Chemical Engineering of Ministry of Education, Zhejiang University, Hangzhou 310027, China. Email address: [email protected]

ABSTRACT: Ionic liquids can be designed by varying a great deal of anions and cations offering efficient CO capture or CO utilization. Generally, the anion played a key role, but the cation did 2

2

not have a significant impact. Here, a strategy for rational design of functionalized ionic liquids for efficient synthesis of quinazoline-2,4(1H,3H)-diones from CO has been developed through 2

tuning the cations of aprotic ionic liquids. The basicity of cation affects its catalytic activity dramatically and the hydrogen bond from cation can promote this reaction. Then, hydroxyl functionalized ionic liquid [Ch][Im] was designed, which exhibited the best catalytic activity in this reaction. Through the combination of quantum-chemical calculations, NMR spectroscopic

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investigations, and controlled experiments, the results indicate that in situ generated [Ch][Im]-CO

2

complex is the real catalyst. Furthermore, aprotic IL [Ch][Im] exhibits good generality and reuseability. Remarkably, quinazoline-2,4(1H,3H)-dione can also be obtained under simulated flue gas system on a gram scale with excellent yield using [Ch][Im] as catalyst. As we know, this is the first time that obtains quinazoline-2,4(1H,3H)-dione in excellent yield under flue gas condition.

Keywords: Ionic liquids; CO capture and utilization; Hydrogen bond; Cation tuning; Green 2

chemistry. Introduction Ionic liquid (IL), composed of cation and anion, is a kind of novel material, which was discovered by Walden in 1914. Nowadays, because of their unique properties, ILs have garnered [1-4]

a significant amount of attention in gases absorption, such as CO , 2

[5-12]

SO , 2

[13-17]

NO, etc. The gas [18]

absorption capacity has been identified to be associated with the basicity of anion.

[7,17]

As they

showed outstanding performance in CO dissolve and absorption, ILs were also used in CO capture 2

and utilization (CCU) processes.

2

It’s always an intriguing work to reduce the energy demanding

[19-30]

in CCU by tuning the properties of ILs. Several works have revealed the advantages of anionfunctionalized ILs in these processes.

[31-35]

sensitive to the basicity of anions.

[36-37]

Recently, we have discovered that CCU reactions are

Although much is known about the role of anion, little is

known about that of cation. To design an efficient IL catalyst for CCU process, it is necessary to figure out the effects of cation. Quinazoline-2,4(1H,3H)-diones have drawn much attention because of their widespread applications in the pharmaceutical and biological industry.

[38-44]

Compared to traditional methods,


2

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constructing of quinazoline-2,4(1H,3H)-diones from 2-aminobenzonitriles and CO is a promising 2

strategy.

[45-51]

However, most of them suffer from high CO pressure, volatile organic solvents, and 2

poor reusability of catalysts. Liu et al reported that the protic IL, [HDBU][TFE], could catalyze this reaction well under mild conditions. Although many works have been devoted to develop [45]

effective ILs catalysts for this reaction, none of them can react well under flue gas conditions, and the recycling of the IL is not good. This weakness should be ascribed to the poor activity or low stability of catalysts. Herein, the synthesis of quinazoline-2,4(1H,3H)-diones from CO and 2-aminobenzonitriles was 2

chosen to investigate the effect of cations in CCU. In this work, the type of ILs and the effect of cations in this reaction were investigated systematically. The basicity of cation was found to affect the reaction dramatically while the hydrogen bond in the ILs could also promote the reaction. Considering the low stability of protic ILs, a more effective aprotic IL was designed, which exhibited excellent performance even under simulated flue gas system. To the best of our knowledge, this is the first example that obtain quinazoline-2,4(1H,3H)-diones in excellent yield under flue gas condition. Experimental Section Materials. All chemicals used in this work were purchased from commercial and used without further purification unless otherwise stated. 2-Aminobenzonitriles (1a), 4-Aminobenzonitriles, Butylamine,

2,2'-(Methylimino)diethanol(MDEA),

1-Methylimidazole(MIm),

Choline(Ch),

Imidazole (Im), Benzoimidazolide (BenIm), Benzotriazole (BenTri), Tetrazole (Tetz), 2-Amino4-methylbenzonitrile(1b),

2-Amino-5-methylbenzonitrile(1c)

and

2-Amino-5-

fluorobenzonitrile(1d) were purchased from Energy-Chemistry Co., Ltd. Benzimidazole (BenIm),


3


Page 4 of 18

1,2,4-Triazole (Triz), were purchased from Aladdin Ind. Co., Ltd. 1,8-Diazabicyclo[5.4.0]undec7-ene (DBU), 2-Amino-4-chlorobenzonitrile(1e) and 2-Dimethylaminoethanol(MDEA) were purchased from J&K Scientific Ltd. 2-Amino-4,5-dimethoxybenzonitrile (1f) was provided by Adamas-beta . CO (99.99%), CO (15%) and N (99.99%) were purchased from Hangzhou Jingong 2

2

2

Special Gas Co., Ltd. H NMR and C NMR spectra were recorded on a Bruker spectrometer (400 1

13

MHz) in DMSO-d , which was obtained from Adamas-beta, with DMSO as the standard. 6

General procedure for the synthesis of quinazoline-2,4(1H,3H)-diones. As an example, the procedure using 2-aminobenzonitrile as the substrate is described. 2- aminobenzonitrile (1 mmol, 0.118 g) and catalyst(1 mmol) was added into a Schlenk flask, connecting with a CO balloon. 2

Then reaction mixture was stirred for desired time at 80 C. After cooling to room temperature, o

10mL water was added into the reactor. The product precipitated from the mixture and was separated by centrifugation. Then, the product was washed by using ultrasonic three times with water and ether, respectively, and dried at 80 C for 24 h under vacuum. The product was further o

identified by NMR spectra. Results and Discussion

Figure 1. Structures of cations and anion used in this work.


4

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[Im], whose pKa is 18.6 in DMSO, is selected as the standard anion, and the cations used in [52]

this work are shown in Figure 1. At first, the reaction doesn’t occur without catalyst (Table 1, entry 1). When aprotic ILs [N ][Im], [N ][Im] and [N ][Im] are examined as the catalysts, they give 4444

2222

1111

2a in the yields of 76%, 78% and 78% (Entries 2, 3 and 4), respectively, which suggests that the impact of chain length is weak. Additional, a higher yield of 2a (83%) is obtained when the protic IL, [HDBU][Im], is used (Entry 5). Although it has weaker basicity, [HDBU][Im] may be a better catalyst than [N ][Im]. Considering the low stability of protic ILs, to design a better stable catalyst 4444

for this reaction, the differences between [HDBU][Im] and [N ][Im] are the key. 4444

Table 1. Effect of basic ionic liquids on the synthesis of quinazoline2,4(1H,3H)-diones. a

NH 2 + CO2

O

N

ILs

N

CN

O 2a

1a

Entry

Bases

pKa value of cation

1

-

-

0

2

[N ][Im]

-

76

3

[N ][Im]

-

78

4

[N ][Im]

-

78

5

[HDBU][Im]

11.7

83

6

[HMTBD][Im]

13.0

87

7

[HMIm][Im]

7.1

16

8

[HMDEA][Im]

8.6

27

9

[HDMEA][Im]

9.2

43

10

[Ch][Im]

-

98

b

4444

2222

1111

Yield (%)

c


5


Page 6 of 18

Reaction conditions: 1a (1 mmol), ILs (1 mmol), CO (~1 bar, balloon), 20h, 80 C. The pKa values in H O were obtained from Ref. 11. Yield of isolated product. a

2

o

b

c

2

The basicities of these ILs should be thought at first. Thus, another two cations with different basicities, [HMTBD] and [HMIm], are chosen. It was seen in Table 1 that [HMTBD][Im] with a higher basicity can improve the yield to 87% (Entry 6). However, [HMIm][Im] exhibits poor catalytic activity, maybe due to its weak basicity (Entry 7). Obviously, the cation can impact the reaction dramatically, which is different from the previous reports. Moreover, NMR spectroscopic experiments are used to compare their differences (Figure 2). The H signal of amino in 1a becomes broader when the basicity of cation is higher. Clearly, the cation with higher basicity may be helpful to activate the substrate. On the contrary, the aprotic ILs do not show better catalytic activity than protic IL (Entry 3 and 5). We believe the active H in ILs may also affect the catalytic activity besides the basicity. At this point, two protic ILs, [HDMEA][Im] and [HMDEA][Im], with one or two OH groups are synthesized and utilized as the catalyst, respectively (Entry 8 and 9). Unexpectedly, only low to mild yield of 2a are gotten in these cases, indicating that the effect of basicity is predominant. In addition, the cation with more OH groups exhibits poorer catalytic activity, because of its weak basicity. Therefore, a hydroxyl (OH) functionalized IL, [Ch][Im], is designed, which is an aprotic IL with only one OH group. More importantly, this cation is cheap and available. To our delight, the [Ch][Im] gives the yield of 2a of 98%, which is higher than that by using [N ][Im] or protic 1111

ILs (Entry 10).


6

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Obviously, the base is needed to activate the substrates, but what’s the role of OH group? At first, the role of [Im] in this reaction should be marked. As shown in previous works, the anions in ILs had two different roles in CCU process, one was a base that could activate the substrates and another was a CO absorbent. 2

[19-37]

However, [Im] is different from many other anions because it

exhibits strong interaction with CO and the desorption of CO is difficult even at a high 2

2

temperature. Herein, △G for these two processes are calculated (Figure 3). Interestingly, △G for [56]

the capture of CO is -0.2 kcal/mol, which is lower than that of the substrate activating process (8.8 2

kcal/mol). According to the calculation results, CO absorption process may be primary in the first 2

stage on this reaction.

Figure 2. H NMR spectrums of (a) 1a with (b) [HMIm][Im], (c) [HDBU][Im] or (d) 1

[HMTBD][Im].


7


Page 8 of 18

Figure 3. Energy demand of (1) CO absorption by [Ch][Im] and (2) nucleophilic attack of 1a to 2

CO . 2

Then, NMR spectroscopic experiments are also utilized to verify this hypothesis (Figure 4). In this case, in order to prevent the further reaction while obtain similar result, p-CN aniline, which shows comparable basicity with 1a, is used (the pKa values in DMSO are 25.3 and 24.3, respectively). The H signal of amino in p-CN aniline disappears after adding [Ch][Im] due to the hydrogen bond formation with [Ch][Im]. To our surprise, this signal reappears after bubbling CO , 2

suggesting that this hydrogen bond is weaken. Meanwhile, the H signals in [Im] become broader [57]

and move to downfield that is in coincident with those in [Im-CO ]. Clearly, [Ch][Im] captures 2

CO at first rather than activating the substrate. 2

To gain more information about the effect of [Im], the CO absorption experiment is conducted. 2

As shown in Figure 5, [Ch][Im] can even capture 0.93 mol CO per mol IL at 80 C because of its o

2

high basicity. Then, this [Ch][Im]-CO complex is also used to the synthesis of 2a with or without 2

CO , respectively. Only 13% yield of 2a is got, when there is no more CO introduced. It may be 2

2

ascribed to the strong interaction between [Im] and CO , and 1a is hard to acquire CO from [Im]2

2

CO . On the contrary, [Ch][Im]-CO complex can catalyze this reaction well and give 2a in 87% 2

2

yield, indicating the fact that [Ch][Im]-CO is the actual catalyst. Control experiments using 2

carboxylate based ILs as catalysts are also examined (Table S2). However, these ILs exhibited poor activity than [Ch][Im] maybe due to the weak basicity.


8

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Figure 4. H spectra of (a) p-CN aniline, (b) p-CN aniline and [Ch][Im] (c) after bubbling CO , (d) 1

2

[Ch][Im]-CO . 2

Figure 5. Controlled experiments. As evidenced by DFT calculations, NMR spectroscopic experiments and controlled experiments, [Ch][Im] is identified to capture CO at the first and [Ch][Im]-CO complex catalyze 2

2

the further reaction (Fig. S1). Therefore, the influence of the OH group in the rate-determining step (RDS) can be investigated by using DFT calculations.

[50,56,58]

As shown in Figure 6, the energy

demand for this RDS with [Ch][Im]-CO is predicted as 40.8 kcal/mol, while the demand for 2


9


Page 10 of 18

[N ][Im]-CO is 41.5 kcal/mol. Moreover, the barrier required to form 4 for [Ch][Im]-CO is much 1111

2

2

lower than that for [N ][Im]-CO (13.6 and 16.1 kcal/mol, respectively ). That is due to the 3 is 1111

2

unstable when the catalyst, [Ch][Im]-CO , with low basicity is used. The NBO charges of the O 2

atom in substrate is predicted as -0.78 for [Ch][Im]-CO ,while this charge is higher for [N ][Im]2

1111

CO . Clearly, the OH group reduces NBO charges of the O atom and the energy demand in this 2

process.

Figure 6. DFT calculation for (a) RDS with [Ch][Im]-CO (blue) or [N ][Im]-CO (red), (b) TS 2

1111

2

3-4

for [Ch][Im]-CO and (c) for [N ][Im]-CO . 2

1111

2


10

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The substrate scope and generality of this reaction are also investigated by using [Ch][Im] as catalyst. First, the catalytic activity of [Ch][Im] can maintain for five cycle and 98% yield of 2a is obtained (Table 2, entries 1). Both electron-withdrawing and -donating groups at the phenyl ring can react smoothly in this catalytic system (Entries 2-4). The positions of substituents do not affect the yields dramatically (Entries 4 and 5). When there is methoxy in R and R , [Ch][Im] can also 1

2

give 2f in excellent yield (Entry 6). Remarkably, water has little effect on this reaction, and 92% yield of 2a is got under humid condition (Entry 7).

Table 2. synthesis of various quinazoline-2,4(1H,3H)-diones.

a

Entry

Substrate

R

R

1

1a

-

-

98

2

d

1b

-

F

95

3

1c

Cl

-

90

4

1d

Me

-

87

5

1e

-

Me

92

6

1f

OMe

OMe

95

7

1a

-

-

92

8

1a

-

-

93 (13 )

9

1a

-

-

87

c,d

d,e

1

2

Yield (%)

b

f

g

h

Reaction conditions: 1 (1 mmol), [Ch][Im] (1 mmol), CO (~1 bar, balloon), 24h, 353 K. Yield of isolated product. [Ch][Im] is used for the fifth time. 20 h. CO (~1 bar, bubbling) with H O (~7%). 1 (1 g), [Ch][Im] (1 equiv.), CO (0.15 bar), 36h, 323 K. 1 a

2

b

d

c

e

2

2

f

g

2


11


Page 12 of 18

(1 g), [HDBU][TFE] (1 equiv.), CO (0.15 bar), 36h, 323 K. 1 (1 g), [Ch][Im] (1 equiv.), CO (0.15 bar), H O (~3%), 36h, 323 K. h

2

2

2

Actually, synthesis of quinazoline-2,4(1H,3H)-diones directly from flue gas is still a challenge to be addressed. Here, the reaction is also carried out under low concentration CO to 2

further evaluate its practicability. To our delight, 93% yield of 2a is obtained after bubbling CO

2

at 0.15 bar under 50 C for 36 h, even at a gram scale (Figure 7). On the contrary, [HDBU][TFE], o

an efficient catalyst under 1 bar CO , only gives 2a in 13% yield, which maybe due to the low 2

stability of protic IL . In addition, a high yield of 87% was obtained under simulated flue gas 45

system containing 15% of CO and 3% of H O. 2

2

Figure 7. Synthesis of 2a under low concentration of CO . 2

Conclusion In summary, a strategy for rational design of aprotic IL for efficient synthesis of quinazoline2,4(1H,3H)-diones has been developed. The basicity of cation is found to affect its catalytic activity dramatically and the hydrogen bond from cation can promote the reaction. Therefore, hydroxyl functionalized aprotic IL [Ch][Im] is designed, which exhibits high catalytic activity. Through a combination of quantum-chemical calculations, NMR spectroscopic investigations and controlled experiments, [Ch][Im]-CO complex is identified as the real catalyst and one OH group 2

is enough for this reaction. Notably, [Ch][Im] is reusable and this reaction can be extended to other


12

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2-aminobenzonitriles. Importantly, with [Ch][Im] as catalyst, the synthesis of quinazoline2,4(1H,3H)-dione from 2-aminobenzonitrile and CO can be carried out under simulated flue gas 2

system on a gram scale in excellent yields. We believe this strategy can be applied in other CCU processes as well as gas absorptions.

ASSOCIATED CONTENT Supporting Information. The Supporting Information is available free of charge on the ACS Publications website at DOI: Characterization data, screening of reaction conditions, effect of anions on the synthesis of quinazoline-2,4(1H,3H)-diones and the details of DFT calculation. AUTHOR INFORMATION Corresponding Author *C. Wang. E-mail: [email protected] Notes The authors declare no competing financial interest. ACKNOWLEDGMENT We acknowledge the support of the National Key Basic Research Program of China (2015CB251401), the National Natural Science Foundation of China (21776239, 21322602), the Zhejiang Provincial Natural Science Foundation of China (LZ17B060001), and the Fundamental Research Funds of the Central Universities.


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For Table of Contents Use Only

CCU under flue gas! Hydroxyl functionalized aprotic IL [Ch][Im] was used for efficient synthesis of quinazoline-2,4(1H,3H)diones from flue CO2 with excellent yields, good generality and reuseability.


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Highly Efficient Synthesis of Quinazoline-2,4(1H ... - ACS Publications

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