磺胺嘧啶银/超强碱协同催化CO<sub>2</sub>/醇耦合反应选择性制碳酸二甲酯

张福灿; 刘平; 张侃; 吉可明; 张建利; 赵亮; 宋清文

doi:10.1016/S1872-5813(22)60053-7

磺胺嘧啶银/超强碱协同催化CO₂/醇耦合反应选择性制碳酸二甲酯

doi: 10.1016/S1872-5813(22)60053-7

张福灿^{1, 2,},
刘平¹,
张侃¹,
吉可明^1, ,,
张建利³,
赵亮²,
宋清文^1, ,

1.
中国科学院山西煤炭化学研究所煤转化国家重点实验室, 山西太原 030001
2.
中国石油大学(北京) 重质油国家重点实验室, 北京 102249
3.
宁夏大学省部共建煤炭高效利用与绿色化工国家重点实验室, 宁夏银川 750021

基金项目: 山西省自然科学基金（20210302123002, 202103021223460），潞安化工集团有限公司研发基金和省部共建煤炭高效利用与绿色化工国家重点实验室开放基金（2022-K20）资助

详细信息

通讯作者:
E-mail: jikeming@sxicc.ac.cn

songqingwen@sxicc.ac.cn

中图分类号: O622.5
计量
- 文章访问数: 2148
- HTML全文浏览量: 149
- PDF下载量: 46
- 被引次数: 0
出版历程
- 收稿日期: 2022-05-19
- 修回日期: 2022-07-07
- 录用日期: 2022-07-13
- 网络出版日期: 2022-07-28
- 刊出日期: 2023-03-15

Selective synthesis of dimethyl carbonate via the coupling reaction of CO₂ and alcohols by the synergistic catalysis of silver sulfadiazine and superbase

ZHANG Fu-can^{1, 2
,},
LIU Ping¹,
ZHANG Kan¹,
JI Ke-ming^{1
, ,},
ZHANG Jian-li³,
ZHAO Liang²,
SONG Qing-wen^{1
, ,}

1.
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China
2.
State Key Laboratory of Heavy Oil Processing, Chinese University of Petroleum(Beijing), Beijing 102249, China
3.
State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering, Ningxia University, Yinchuan 750021, China

Funds: The project was supported by the Natural Science Foundation of Shanxi (20210302123002, 202103021223460), Technical research and development project from Lu'an Chemical Industry Group Co., Ltd. and the Foundation of State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering (2022-K20).

摘要

摘要: 甲醇、CO₂和炔丙醇三组分耦合反应为合成绿色化学品碳酸二甲酯（DMC）提供了一种热力学有利新路径。本工作针对该方法中存在的DMC收率低、中间产物转化速率慢的问题，研究了炔烃衍生物α-单取代炔丙醇在耦合反应中对DMC收率及选择性的影响。发展了磺胺嘧啶银与超强碱协同催化串联反应策略，进一步提升了反应效率。考察了催化剂、共催化剂、催化剂用量、溶剂、温度、原料比、压力和时间等因素的影响规律。最优的条件下，DMC选择性达89.5%，收率55.6%。研究表明，炔丙醇的结构会显著影响反应进程，同时，磺胺嘧啶银与1,8-二氮杂二环十一碳-7-烯（DBU）的协同催化作用是高收率、高选择性获得DMC的关键因素。
- 碳酸二甲酯 /
- 二氧化碳转化 /
- 耦合反应 /
- 协同催化
Abstract: The three-component coupling of methanol, CO₂ and propargyl alcohol to manufacture dimethyl carbonate (DMC) provides a new, thermodynamic favorable and green chemical synthesis route. In this work, to overcome the problems of low DMC yield and slow conversion rate of intermediates, the synergistic catalytic strategy of silver sulfadiazine and superbase is developed to improve the reaction efficiency. The effect of various parameters i.e. catalyst and cocatalyst types, catalyst loading, solvent, temperature, proportion of raw materials, pressure and time on the coupling reactions is investigated in detail. Under the optimal conditions, the selectivity of DMC is 89.5% with the yield of 55.6%. And the effect of alkyne derivative α-monosubstituted propargyl alcohol on the efficiency and selectivity of DMC are also studied. The mechanism study shows that propargyl alcohols with different structures apparently affect the reaction process, and the synergistic catalysis of silver sulfadiazine/1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) is the reason for the high yield and selectivity of DMC.
- dimethyl carbonate /
- carbon dioxide conversion /
- coupling reaction /
- synergistic catalysis

HTML全文

FIG. 2155. FIG. 2155.

下载: 全尺寸图片幻灯片

图 1 催化剂用量的影响

Figure 1 Catalyst loading investigation

Reaction condition: 1a (620 mg, 5 mmol), 2a (320 mg, 10 mmol), DBU (228 mg, 1.5 mmol), CO₂ (5 MPa), 120 ℃, 8 h, the loading of silver sulfadiazine was calculated on the basis of 1a, the results were determined by GC using biphenyl as the internal standard

下载: 全尺寸图片幻灯片

图 2 温度对反应的影响

Figure 2 Temperature effect on the reaction

Reaction condition: 1a (620 mg, 5 mmol), 2a (320 mg, 10 mmol), silver sulfadiazine (357 mg, 1 mmol), DBU (228 mg, 1.5 mmol), DMSO (1 mL), CO₂ (5 MPa), 8 h, the results were determined by GC using biphenyl as the internal standard

下载: 全尺寸图片幻灯片

图 3 原料配比对反应的影响

Figure 3 Effect of raw material ratio on reaction

Reaction condition: 1a (620 mg, 5 mmol), 2a (160−640 mg, 10− 40 mmol), silver sulfadiazine (357 mg, 1 mmol), DBU (228 mg, 1.5 mmol), DMSO (1 mL), CO₂ (5 MPa), 120 ℃, 8 h, the yield was determined by GC using biphenyl as the internal standard

下载: 全尺寸图片幻灯片

图 4 压力对三组分反应的影响

Figure 4 Pressure effect on the three-component reaction

Reaction condition: 1a (620 mg, 5 mmol), 2a (320 mg, 10 mmol), silver sulfadiazine (357 mg, 1 mmol), DBU (228 mg, 1.5 mmol), DMSO (1 mL), 120 ℃, 8 h, the results were determined by GC using biphenyl as the internal standard

下载: 全尺寸图片幻灯片

图 5 时间对反应的影响

Figure 5 Effect of the reaction time

Reaction condition: 1a (620 mg, 5 mmol), 2a (320 mg, 10 mmol), silver sulfadiazine (357 mg, 1 mmol), DBU (228 mg, 1.5 mmol), DMSO (1 mL), CO₂ (5 MPa), 120 ℃, the results were determined by GC using biphenyl as the internal standard

下载: 全尺寸图片幻灯片

图 6 炔丙醇结构与DMC收率和选择性的关系

Figure 6 Relationship between propargyl alcohol structure and the yield/selectivity of DMC

Reaction condition: propargyl alcohol (5 mmol), methanol (320 mg, 10 mmol), silver sulfadiazine (357 mg, 1 mmol), DBU (228 mg, 1.5 mmol), DMSO (1 mL), CO₂ (5 MPa), 120 ℃, 8 h, the results were determined by GC using biphenyl as the internal standard

下载: 全尺寸图片幻灯片

图 7 磺胺嘧啶银/DBU催化炔丙醇、甲醇和CO₂三组分耦合反应机理示意图（修改：炔丙醇底物红色标记的氧原子漏了一个氢原子，氢原子和带负电荷N原子发生相互作用，实现羟基活化；中间体A中DBU, 修改为DBUH⁺，DBUH⁺ 与碳酸酯中带负电荷的蓝色标记的氧原子作用，稳定过渡态）

Figure 7 Cascade reaction mechanism of propargyl alcohol, methanol and CO₂ catalyzed by silver sulfadiazine/DBU

下载: 全尺寸图片幻灯片

表 1 催化剂性能

Table 1 Catalysts investigation


Entry	Catalyst	1a conv./%	2a conv./%	DMC yield/%	4a yield/%	DMC sel./%	4a sel./%
1^a	−	0	0	0	0	−	−
2	−	62.9	50.0	15.6	25.2	31.2	50.4
3	CoCO₃	14.1	10.2	3.7	5.6	36.3	54.9
4	NiBr₂	33.7	32.3	3.3	8.0	10.2	24.8
5	CuBr	96.5	48.6	35.4	36.3	72.9	74.7
6	ZnCl₂	99.9	80.3	29.6	34.7	36.9	43.2
7	ZnBr₂	98.7	77.5	33.1	39.0	42.7	54.6
8	ZnI₂	98.3	40.6	17.8	27.1	43.8	42.5
9	Zn(OAc)₂	99.2	58.6	30.4	41.6	51.9	71.1
10	AgCl	98.1	39.2	30.5	35.1	77.7	89.6
11	AgI	99.5	38.1	16.7	23.7	43.8	62.1
12	AgOAc	99.0	44.0	34.8	41.5	79.1	94.2
13	Ag₂SO₄	99.3	64.9	26.2	35.9	40.5	55.4
14	Ag₃PO₄	96.3	41.9	27.7	36.9	66.2	88.1
15	AgVO₃	53.6	35.8	20.0	27.7	56.1	77.5
16	CF₃SO₃Ag	95.7	62.8	10.1	23.1	16.0	36.9
17	C₇H₅AgO₂	97.2	38.9	25.2	29.7	64.8	76.3
18	Ag₂CO₃	76.8	61.9	12.2	46.9	19.7	75.9
19	Ag₂O	98.8	53.8	40.4	46.3	75.1	86.1
20	silver sulfadiazine	99.9	53.1	41.8	42.6	78.7	80.4
Reaction condition: 1a (620 mg, 5 mmol), 2a (320 mg, 10 mmol), catalyst (1 mmol), DBU (228 mg, 1.5 mmol), CO₂ (5 MPa), 120 ℃, 8 h, ^a: In the absence of any catalyst and cocatalyst, the results were determined by GC using biphenyl as the internal standard, conversion (conv.), selectivity (sel.)

下载: 导出CSV

表 2 共催化剂性能

Table 2 Co-catalyst investigation

Entry	Co-catalyst	1a conv./%	2a conv./%	DMC yield/%	4a yield/%	DMC sel./%	4a sel./%
1^a	−	87.6	42.3	2.2	4.4	5.2	10.4
2	DBU	99.9	53.1	41.8	42.6	78.7	80.2
3	DBN	98.5	72.7	21.9	34.8	30.1	47.9
4	TMG	99.7	65.0	17.5	18.5	26.9	28.5
5	TBD	98.7	72.6	2.2	3.5	3.0	4.8
6	TBAB	100.0	88.2	3.2	3.4	3.6	3.9
7	TEAC	99.5	78.7	4.7	7.2	6.0	9.1
8	TBAB/DBU	99.7	73.6	22.8	35.5	31.0	48.2
9	PPh₃/DBU	100.0	49.2	2.8	6.4	5.7	13.0
Reaction condition: 1a (620 mg, 5 mmol), 2a (320 mg, 10 mmol), silver sulfadiazine (1 mmol), cocatalyst (1.5 mmol), CO₂ (5 MPa), 120 ℃, 8 h, ^a: only silver sulfadiazine was used, the results were determined by GC using biphenyl as the internal standard

下载: 导出CSV

表 3 溶剂对反应的影响

Table 3 Solvent effect on the reaction

Entry	Solvent	1a conv./%	2a conv./%	DMC yield/%	4a yield/%	DMC sel./%	4a sel./%
1	Blank	99.9	53.1	41.8	42.6	78.7	80.4
2	DMSO	99.6	62.1	55.6	59.4	89.5	95.7
3	DMF	99.5	53.9	35.7	39.0	66.3	72.4
4	CH₃CN	99.5	58.2	34.4	37.8	59.1	65.0
5	EtOAc	99.4	48.7	24.4	33.3	50.0	68.4
6	PhCH₃	98.0	51.3	37.3	41.7	72.8	81.3
7	tetrahydrofuran	99.6	49.2	29.2	35.2	59.3	71.5
Reaction condition: 1a (620 mg, 5 mmol), 2a (320 mg, 10 mmol), silver sulfadiazine (357 mg, 1 mmol), DBU (228 mg, 1.5 mmol), solvent (1 mL), CO₂ (5 MPa), 120 ℃, 8 h, the results were determined by GC using biphenyl as the internal standard

下载: 导出CSV

参考文献(24)

[1]	SONG Q W, ZHOU Z H, HE L N. Efficient, selective and sustainable catalysis of carbon dioxide[J]. Green Chem,2017,19(16):3707−3728. doi: 10.1039/C7GC00199A
[2]	LU M, ZHANG M, LIU J, CHEN Y, LIAO J P, YANG M Y, CAI Y P, LI S L, LAN Y Q. Covalent organic framework based functional materials: important catalysts for efficient CO₂ utilization[J]. Angew Chem Int Ed,2022,61(15):e202200003.
[3]	HE X, QIU L Q, WANG W J, CHEN K H, HE L N. Photocarboxylation with CO₂: an appealing and sustainable strategy for CO₂ fixation[J]. Green Chem,2020,22(21):7301−7320. doi: 10.1039/D0GC02743J
[4]	AOMCHAD V, CRISTOFOL A, DELLA F, LIMBURG B, DELIA V, KLEIJ A W. Recent progress in the catalytic transformation of carbon dioxide into biosourced organic carbonates[J]. Green Chem,2021,23(3):1077−1113. doi: 10.1039/D0GC03824E
[5]	BURKART M D, HAZARI N, TWAY C L, ZEITLER E L. Opportunities and challenges for catalysis in carbon dioxide utilization[J]. ACS Catal,2019,9(9):7937−7956. doi: 10.1021/acscatal.9b02113
[6]	TAN H Z, WANG Z Q, XU Z N, SUN J, XU Y P, CHEN Q S, CHEN Y, GUO G C. Review on the synthesis of dimethyl carbonate[J]. Catal Today,2018,316:2−12. doi: 10.1016/j.cattod.2018.02.021
[7]	KUMAR P, SRIVASTAVA V C, STANGAR U L, MUSIC B, MISHRA I M, MENG Y. Recent progress in dimethyl carbonate synthesis using different feedstock and techniques in the presence of heterogeneous catalysts[J]. Catal Rev,2019,63(3):363−421.
[8]	TAMBOLI A H, CHAUGULE A A, KIM H. Catalytic developments in the direct dimethyl carbonate synthesis from carbon dioxide and methanol[J]. Chem Eng J,2017,323:530−544. doi: 10.1016/j.cej.2017.04.112
[9]	BALLIVET D, JERPHAGNON T, LIGABUE R, PLASSERAUD L, POINSOT D. The role of distannoxanes in the synthesis of dimethyl carbonate from carbon dioxide[J]. Appl Catal A: Gen,2003,255(1):93−99. doi: 10.1016/S0926-860X(03)00647-1
[10]	HONDA M, TAMURA M, NAKAGAWA Y, SONEHARA S, SUZUKI K, FUJIMOTO K, TOMISHIGE K. Ceria-catalyzed conversion of carbon dioxide into dimethyl carbonate with 2-cyanopyridine[J]. ChemSusChem,2013,6(8):1341−1346. doi: 10.1002/cssc.201300229
[11]	HE H, QI C, HU X, GUAN Y, JIANG H. Efficient synthesis of tertiary α-hydroxy ketones through CO₂-promoted region-selective hydration of propargylic alcohols[J]. Green Chem,2014,16(8):3729−3733. doi: 10.1039/C4GC00522H
[12]	ZHAO Y, YANG Z, YU B, ZHANG H, XU H, HAO L, HAN B, LIU Z. Task-specific ionic liquid and CO₂-cocatalysed efficient hydration of propargylic alcohols to α-hydroxy ketones[J]. Chem Sci,2015,6(4):2297−2301. doi: 10.1039/C5SC00040H
[13]	ZHOU Z H, SONG Q W, HE L N. Silver(I)-promoted cascade reaction of propargylic alcohols, carbon dioxide, and vicinal diols: thermodynamically favorable route to cyclic carbonates[J]. ACS Omega,2017,2(1):337−345. doi: 10.1021/acsomega.6b00407
[14]	ZHOU H, ZHANG H, MU S, ZHANG W Z, REN W M, LU X B. Highly regio and stereoselective synthesis of cyclic carbonates from biomass-derived polyols via organocatalytic cascade reaction[J]. Green Chem,2019,21(23):6335−6341. doi: 10.1039/C9GC03013A
[15]	HU J, MA J, LU L, QIAN Q, ZHANG Z, XIE C, HAN B. Synthesis of asymmetrical organic carbonates using CO₂ as a feedstock in AgCl/ionic liquid system at ambient conditions[J]. ChemSusChem,2017,10(6):1292−1297. doi: 10.1002/cssc.201601773
[16]	张乾霞, 刘平, 张侃, 韩丽华, 宋清文. 多组分串联策略固定CO₂制碳酸二甲酯和α-羟基酮[J]. 科学通报,2020,65(31):3429−3437. doi: 10.1360/TB-2020-0351 ZHANG Qian-xia, LIU Ping, ZHANG Kan, HAN Li-hua, SONG Qing-wen. Multicomponent cascade strategy of CO₂ fixation for synthesis of dimethyl carbonate and α-hydroxy ketone[J]. Chin Sci Bull,2020,65(31):3429−3437. doi: 10.1360/TB-2020-0351
[17]	SONG Q W, CHEN W Q, MA R, YU A, LI Q Y, CHANG Y, HE L N. Bifunctional silver(I) complex-catalyzed CO₂ conversion at ambient conditions: synthesis of α-methylene cyclic carbonates and derivatives[J]. ChemSusChem,2015,8(5):821−827. doi: 10.1002/cssc.201402921
[18]	YUAN Y, XIE Y, ZENG C, SONG D, CHAEMCHUEN S, CHEN C, VERPOORT F. A simple and robust AgI/KOAc catalytic system for the carboxylative assembly of propargyl alcohols and carbon dioxide at atmospheric pressure[J]. Catal Sci Technol,2017,7(14):2935−2939. doi: 10.1039/C7CY00696A
[19]	LI J Y, HAN L H, XU Q C, SONG Q W, LIU P, ZHANG K. Cascade strategy for atmospheric pressure CO₂ fixation to cyclic carbonates via silver sulfadiazine and Et₄NBr synergistic catalysis[J]. ACS Sustainable Chem Eng,2019,7(3):3378−3388. doi: 10.1021/acssuschemeng.8b05579
[20]	CERVANTES R A, SAXL T, STEIN P M, RUDOLPH M, ROMINGER F, ASIRI A M, HASHMI A S. Expanded ring NHC silver carboxylate complexes as efficient and reusable catalysts for the carboxylative cyclization of unsubstituted propargylic derivatives[J]. ChemSusChem,2021,14(11):2367−2374. doi: 10.1002/cssc.202002822
[21]	MCCORMACK A C, OFERRALL R A, ODONOGHU A C, RAO S N. Protonated benzofuran, anthracene, naphthalene, benzene, ethene, and ethyne: measurements and estimates of pK_a and pK_R[J]. J Am Chem Soc,2002,124(29):8575−8583. doi: 10.1021/ja012613x
[22]	CA N D, GABRIELE B, RUFFOLO G, VELTRI L, ZANETTA T, COSTA M. Effective Guanidine-catalyzed synthesis of carbonate and carbamate derivatives from propargyl alcohols in supercritical carbon dioxide[J]. Adv Synth Catal,2011,353(1):133−146. doi: 10.1002/adsc.201000607
[23]	ZHOU Z H, SONG Q W, XIE J N, MA R, HE L N. Silver(I)-catalyzed three-component reaction of propargylic alcohols, carbon dioxide and monohydric alcohols: Thermodynamically feasible access to β-oxopropyl carbonates[J]. Chem-Asian J,2016,11(14):2065−2071.
[24]	SEKINE K, YAMADA T. Silver-catalyzed carboxylation[J]. Chem Soc Rev,2016,45(16):4524−4532. doi: 10.1039/C5CS00895F