CN113996339A - 一种用于制备环状碳酸酯的催化剂及其环状碳酸酯的制备方法 - Google Patents
一种用于制备环状碳酸酯的催化剂及其环状碳酸酯的制备方法 Download PDFInfo
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- CN113996339A CN113996339A CN202111186131.XA CN202111186131A CN113996339A CN 113996339 A CN113996339 A CN 113996339A CN 202111186131 A CN202111186131 A CN 202111186131A CN 113996339 A CN113996339 A CN 113996339A
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- cyclic carbonate
- carbon dioxide
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- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- SBYHFKPVCBCYGV-UHFFFAOYSA-N quinuclidine Chemical compound C1CC2CCN1CC2 SBYHFKPVCBCYGV-UHFFFAOYSA-N 0.000 description 1
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- 238000007142 ring opening reaction Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0271—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds also containing elements or functional groups covered by B01J31/0201 - B01J31/0231
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
- C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
- C07D317/50—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to atoms of the carbocyclic ring
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
Abstract
本发明提供了一种用于制备环状碳酸酯的催化剂及其环状碳酸酯的制备方法,属于有机催化技术领域。本发明提出一种用于合成环状碳酸酯的催化剂,环氧化物和二氧化碳在糖精盐有机催化体系下,合成得到环状碳酸酯。该方法所用催化剂可以一步法即可制备,产率可达90%以上,且原料商业可得,便宜,其中糖精一种天然绿色产物。同时,该类催化剂不含金属,不含卤素,可以在相对温和的条件下,合成环状碳酸酯。
Description
技术领域
本发明属于有机催化技术领域,具体涉及一种环氧化物固定二氧化碳合成环状碳酸酯的催化剂及其方法。
背景技术
二氧化碳(CO2)的化学固定化将有助于找到降低大气中CO2浓度的方法。自工业革命以来,大气中的二氧化碳含量从280ppm上升到419ppm。将CO2固定在高附加值化学品中,特别是将CO2环加成环氧化物(CCE)反应,因其高原子经济性而受到广泛关注。其产品环碳酸酯广泛应用于聚氨酯合成、绿色电解质电池、精细化工、医药中间体等领域。由于CO2的热力学和动力学稳定性,如果没有催化剂系统,环加成反应很难进行。
到目前为止,已经有许多催化剂被证明可以用于二氧化碳和环氧化物的反应。金属催化剂通常用于催化CCE反应,并有着很高的活性和选择性,但是,金属催化剂在催化反应中有金属残留,产品中容易残留毒素。氢键作为一种重要的非共价催化剂,在CCE反应中也得到了广泛的关注和应用。在氢键催化过程中,大多通过氢键活化环氧化物,然后卤素离子进攻开环环氧化物,与二氧化碳加成后,卤素离子离去形成碳酸酯。但是,卤素离子参与的催化反应,对一般的金属材质有腐蚀性,对环境有不利影响。而无金属,无卤素体系的催化剂报道较少,本专利旨在开发一种廉价易得的无金属,无卤素催化剂催化二氧化碳和环氧化物的反应。
目前,无卤素催化CCE反应的例子有不少,但是至今为止很难找到一种可以替代卤素离子,在具有亲核性的同时,也有很好的离去性可以将产物环状碳酸酯释放出来。我们上一篇工作吡啶类糖精催化剂(202110052677.X),可以将糖精阴离子作为亲核试剂进攻环氧化物使其开环,但是由于有副反应的生成,导致之前的选择性很低。在此基础上,我们选择了离去能力更好的三乙烯二胺类的阳离子,降低副反应的生成,大大提高选择性。
发明内容
为了解决上述问题,本发明提供了一种将二氧化碳和环氧化物制备环状碳酸酯的方法,该方法所用催化剂可以一步法即可制备,产率可达90%以上,且原料商业可得,便宜,其中糖精一种天然绿色产物。同时,该类催化剂不含金属,不含卤素,可以在相对温和的条件下,合成环状碳酸酯。
本发明提出一种用于合成环状碳酸酯的催化剂,环氧化物和二氧化碳在糖精盐有机催化体系下,合成得到环状碳酸酯,所述的糖精盐为以下结构:
所述的环氧化物选自式I的结构:
其中,R1、R2选自H、具有1-4个碳原子的支链或直链烷基、烯丁基、苯基、卤素或烷基取代的苯基、氯或溴取代的烷基、R3-O-CH2-,所述的R3选自苯基、被1~3个碳原子的烷基取代的苯基、烯丙基或1~4个碳原子的支链或直链的烷基或者R1和R2是连接成六元环、五元环。
所述的环氧化物,R1、R2选自H、正丁基、苯基、卤代苯基、R3-O-CH2-,所述R3选自苯基、甲苯基、烯丙基,叔丁基或甲基。
所述的环氧化物选自如下结构:
得到的环状碳酸酯的结构如下:
所述制备方法的初始压力为0.1-2MPa,反应温度为25-120℃,催化剂的负载量为1mol%-10mol%。
优选初始压力为0.1MPa,的反应温度为60℃,催化剂的负载量为10mol%。
所述的环状碳酸酯合成方法
为向反应容器中加入催化剂和环氧化物,用二氧化碳置换反应容器中的空气3次,充入二氧化碳至0.1-2MPa,在无溶剂条件下升温至25-120℃,反应6~24h,冷却,反应液通过柱层析得到产物碳酸酯。
所述的催化剂的制备方法:将糖精的有机溶剂在搅拌的情况下缓慢加入有机碱的有机溶剂,加入完毕后,25-60℃下反应1-24h,得到沉淀物。
所述的糖精的有机溶液中的溶剂为二氯甲烷、四氢呋喃或甲苯,所述的有机碱的有机溶液中的溶剂为二氯甲烷、四氢呋喃或甲苯。
一种环状碳酸酯的制备方法,采用环氧化物和二氧化碳在上述所述的糖精盐有机催化体系下合成得到环状碳酸酯。
有益效果:
(1)本发明通过上述催化体系,将环氧化物和二氧化碳合成环状碳酸酯可以在温和的条件(60℃,1atm CO2压力)下。
(2)该方法所用催化剂不含金属,在对有严格毒素残留的生物医药,精细化学品等领域有巨大的商业价值。
(3)本发明所用的催化体系不含卤素,对铝,铁制品金属容器没有腐蚀性,在生产过程中对环境保护有着极大地优势。
(4)合成催化剂的原料糖精和三乙烯二胺,原料简单商业可得,价格低廉天然绿色,一步法即可获得很高的产率(>90%)。
综上所述,本发明相比于现有的其他催化体系具有温和、高效、催化剂易制备、不含金属、不含卤素、不需要溶剂等明显优势。
附图说明
图1:实施例1所得催化剂1的氢谱图
图2:实施例2所得催化剂2的氢谱图
图3:实施例1所得环状碳酸酯产物的氢谱图
图4:实施例11所得环状碳酸酯产物的氢谱图
图5:实施例12所得环状碳酸酯产物的氢谱图
图6:实施例15所得环状碳酸酯产物的氢谱图
图7:实施例19所得环状碳酸酯产物的氢谱图
图8:实施例14所得环状碳酸酯产物的氢谱图
图9:实施例17所得环状碳酸酯产物的氢谱图
图10:实施例20所得环状碳酸酯产物的氢谱图
具体实施方式
通过下列实施例可以进一步说明本发明,实施例是为了说明而非限制本发明的。本领域的任何普通技术人员都能够理解这些实施例不以任何方式限制本发明,可以对其做适当的修改和数据变换而不违背发明的实质和偏离本发明的范围。
实施例中所涉及的核磁共振氢谱采用布鲁克公司(Bruker)的Bruker Ascend TM-400型核磁共振氢谱仪测定,所使用氘代试剂为氘代氯仿(CDCl3)。
实施例1:
催化剂1的制备,对反应瓶进行除水除氧操作,在通入惰性气体氩气保护下,加入454mg(4.09mmol)奎宁环和749mg(4.09mmol)糖精,加入20ml四氢呋喃作为溶剂,在60℃温度下反应12小时,产生白色沉淀。反应结束后,冷却,用真空法除去四氢呋喃溶剂,得到粗产物。粗产物加入甲醇形成饱和溶液,加入正己烷(10ml)。溶剂在室温下扩散一段时间内产生白色针状结晶的结晶,干燥后得到1.17g的催化剂1。产率(纯化)97.3%。
对反应瓶进行除水除氧操作,在通入惰性气体氩气保护下,加入0.294g(1mmol)催化剂1和0.93g(10mmol)环氧氯丙烷(化合物14)。用二氧化碳置换反应瓶内的惰性气氩气体3次,然后在反应瓶上扎上充有二氧化碳的气球,放入60℃的油浴锅中,反应24小时。反应结束后,冷却,色柱分离(石油醚:乙酸乙酯=2:1)后,产物干燥,得到淡黄色液体化合物27,转化率:68%。1H NMR(400MHz,Chloroform-d)δ5.10–4.89(m,1H),4.59(t,J=8.6Hz,1H),4.40(dd,J=8.9,5.7Hz,1H),3.75(qd,J=12.1,4.7Hz,2H).13C NMR(101MHz,Chloroform-d)δ154.12,74.21,66.93,43.59.
实施例2:
催化剂2的制备,对反应瓶进行除水除氧操作,在通入惰性气体氩气保护下,加入458mg(4.09mmol)三乙烯二胺和749mg(4.09mmol)糖精,加入20ml四氢呋喃作为溶剂,在60℃温度下反应12小时,产生白色沉淀。反应结束后,冷却,用真空法除去四氢呋喃溶剂,得到粗产物。粗产物加入甲醇形成饱和溶液,加入正己烷(10ml)。溶剂在室温下扩散一段时间内产生白色针状结晶的结晶,干燥后得到1.10g的催化剂2。产率(纯化)91.1%。
对反应瓶进行除水除氧操作,在通入惰性气体氩气保护下,加入0.295g(1mmol)催化剂2和0.93g(10mmol)环氧氯丙烷(化合物14)。用二氧化碳置换反应瓶内的惰性气氩气体3次,然后在反应瓶上扎上充有二氧化碳的气球,放入60℃的油浴锅中,反应24小时。反应结束后,冷却,色柱分离(石油醚:乙酸乙酯=2:1)后,产物干燥,得到淡黄色液体化合物27,转化率:96%。1H NMR(400MHz,CDCl3).δ5.10–4.89(m,1H),4.59(t,J=8.6Hz,1H),4.40(dd,J=8.9,5.7Hz,1H),3.75(qd,J=12.1,4.7Hz,2H).13C NMR(101MHz,Chloroform-d)δ154.12,74.21,66.93,43.59.
实施例3:
催化剂3的制备,对反应瓶进行除水除氧操作,在通入惰性气体氩气保护下,加入519mg(4.09mmol)奎宁环-3-醇和749mg(4.09mmol)糖精,加入20ml四氢呋喃作为溶剂,在60℃温度下反应12小时,产生白色沉淀。反应结束后,冷却,用真空法除去四氢呋喃溶剂,得到粗产物。粗产物加入甲醇形成饱和溶液,加入正己烷(10ml)。溶剂在室温下扩散一段时间内产生白色针状结晶的结晶,干燥后得到1.16g的催化剂3。产率(纯化)91.5%。
对反应瓶进行除水除氧操作,在通入惰性气体氩气保护下,加入0.310g(1mmol)催化剂3和0.93g(10mmol)环氧氯丙烷(化合物14)。用二氧化碳置换反应瓶内的惰性气氩气体3次,然后在反应瓶上扎上充有二氧化碳的气球,放入60℃的油浴锅中,反应24小时。反应结束后,冷却,色柱分离(石油醚:乙酸乙酯=2:1)后,产物干燥,得到淡黄色液体化合物27,转化率:78%。1H NMR(400MHz,CDCl3).δ5.10–4.89(m,1H),4.59(t,J=8.6Hz,1H),4.40(dd,J=8.9,5.7Hz,1H),3.75(qd,J=12.1,4.7Hz,2H).13C NMR(101MHz,Chloroform-d)δ154.12,74.21,66.93,43.59.
实施例4:
对反应瓶进行除水除氧操作,在通入惰性气体氩气保护下,加入0.295g(1mmol)催化剂2和0.93g(10mmol)环氧氯丙烷(化合物14)。用二氧化碳置换反应瓶内的惰性气氩气体3次,然后在反应瓶上扎上充有二氧化碳的气球,放入25℃的油浴锅中,反应24小时。反应结束后,冷却,色柱分离(石油醚:乙酸乙酯=2:1)后,产物干燥,得到淡黄色液体化合物27,转化率:8%。1H NMR(400MHz,CDCl3).δ5.10–4.89(m,1H),4.59(t,J=8.6Hz,1H),4.40(dd,J=8.9,5.7Hz,1H),3.75(qd,J=12.1,4.7Hz,2H).13C NMR(101MHz,Chloroform-d)δ154.12,74.21,66.93,43.59.
实施例5:
对反应瓶进行除水除氧操作,在通入惰性气体氩气保护下,加入0.295g(1mmol)催化剂2和0.93g(10mmol)环氧氯丙烷(化合物14)。用二氧化碳置换反应瓶内的惰性气氩气体3次,然后在反应瓶上扎上充有二氧化碳的气球,放入40℃的油浴锅中,反应24小时。反应结束后,冷却,色柱分离(石油醚:乙酸乙酯=2:1)后,产物干燥,得到淡黄色液体化合物27,转化率:87%。1H NMR(400MHz,CDCl3).δ5.10–4.89(m,1H),4.59(t,J=8.6Hz,1H),4.40(dd,J=8.9,5.7Hz,1H),3.75(qd,J=12.1,4.7Hz,2H).13C NMR(101MHz,Chloroform-d)δ154.12,74.21,66.93,43.59.
实施例6:
对反应瓶进行除水除氧操作,在通入惰性气体氩气保护下,加入0.295g(1mmol)催化剂2和0.93g(10mmol)环氧氯丙烷(化合物14)。用二氧化碳置换反应瓶内的惰性气氩气体3次,然后在反应瓶上扎上充有二氧化碳的气球,放入120℃的油浴锅中,反应24小时。反应结束后,冷却,色柱分离(石油醚:乙酸乙酯=2:1)后,产物干燥,得到淡黄色液体化合物27,转化率:95%。1H NMR(400MHz,CDCl3).δ5.10–4.89(m,1H),4.59(t,J=8.6Hz,1H),4.40(dd,J=8.9,5.7Hz,1H),3.75(qd,J=12.1,4.7Hz,2H).13C NMR(101MHz,Chloroform-d)δ154.12,74.21,66.93,43.59.
实施例7:
对反应瓶进行除水除氧操作,在通入惰性气体氩气保护下,加入0.030g(1mmol)催化剂2和0.93g(10mmol)环氧氯丙烷(化合物14)。用二氧化碳置换反应瓶内的惰性气氩气体3次,然后在反应瓶上扎上充有二氧化碳的气球,放入60℃的油浴锅中,反应24小时。反应结束后,冷却,色柱分离(石油醚:乙酸乙酯=2:1)后,产物干燥,得到淡黄色液体化合物27,转化率:45%。1H NMR(400MHz,CDCl3).δ5.10–4.89(m,1H),4.59(t,J=8.6Hz,1H),4.40(dd,J=8.9,5.7Hz,1H),3.75(qd,J=12.1,4.7Hz,2H).13C NMR(101MHz,Chloroform-d)δ154.12,74.21,66.93,43.59.
实施例8:
对反应瓶进行除水除氧操作,在通入惰性气体氩气保护下,加入0.148g(1mmol)催化剂2和0.93g(10mmol)环氧氯丙烷(化合物14)。用二氧化碳置换反应瓶内的惰性气氩气体3次,然后在反应瓶上扎上充有二氧化碳的气球,放入60℃的油浴锅中,反应24小时。反应结束后,冷却,色柱分离(石油醚:乙酸乙酯=2:1)后,产物干燥,得到淡黄色液体化合物27,转化率:78%。1H NMR(400MHz,CDCl3).δ5.10–4.89(m,1H),4.59(t,J=8.6Hz,1H),4.40(dd,J=8.9,5.7Hz,1H),3.75(qd,J=12.1,4.7Hz,2H).13C NMR(101MHz,Chloroform-d)δ154.12,74.21,66.93,43.59.
实施例9:
对高压反应釜进行除水除氧操作,加入0.295g(1mmol)催化剂2和0.93g(10mmol)环氧氯丙烷(化合物14)。用二氧化碳置换高压反应釜内空气3次,然后冲入1MPa的二氧化碳气体,放入60℃的油浴锅中,反应24小时。反应结束后,冷却,色柱分离(石油醚:乙酸乙酯=2:1)后,产物干燥,得到淡黄色液体化合物27,转化率:77%。1H NMR(400MHz,CDCl3).δ5.10–4.89(m,1H),4.59(t,J=8.6Hz,1H),4.40(dd,J=8.9,5.7Hz,1H),3.75(qd,J=12.1,4.7Hz,2H).13C NMR(101MHz,Chloroform-d)δ154.12,74.21,66.93,43.59.
实施例10:
对高压反应釜进行除水除氧操作,加入0.295g(1mmol)催化剂2和0.93g(10mmol)环氧氯丙烷(化合物14)。用二氧化碳置换高压反应釜内空气3次,然后冲入2MPa的二氧化碳气体,放入60℃的油浴锅中,反应24小时。反应结束后,冷却,色柱分离(石油醚:乙酸乙酯=2:1)后,产物干燥,得到淡黄色液体化合物27,转化率:35%。1H NMR(400MHz,CDCl3).δ5.10–4.89(m,1H),4.59(t,J=8.6Hz,1H),4.40(dd,J=8.9,5.7Hz,1H),3.75(qd,J=12.1,4.7Hz,2H).13C NMR(101MHz,Chloroform-d)δ154.12,74.21,66.93,43.59.
实施例11:
对反应瓶进行除水除氧操作,在通入惰性气体氩气保护下,加入0.295g(1mmol)催化剂2和1.2g(10mmol)2-苯基环氧乙烷(化合物4)。用二氧化碳置换反应瓶惰性气体氩气3次,然后在反应瓶上扎上充有二氧化碳的气球,放入120℃的油浴锅中,反应24小时。反应结束后,冷却,色柱分离(石油醚:乙酸乙酯=2:1)后,产物干燥,得到淡黄色固体化合物17,转化率:72%。1H NMR(400MHz,Chloroform-d)δ7.48–7.34(m,5H),5.68(t,J=8.0Hz,1H),4.80(t,J=8.4Hz,1H),4.34(dd,J=8.6,7.9Hz,1H).
实施例12:
对反应瓶进行除水除氧操作,在通入惰性气体氩气保护下,加入0.295g(1mmol)催化剂2和1.0g(10mmol)丁基环氧乙烷(化合物5)。用二氧化碳置换反应瓶惰性气体氩气3次,然后在反应瓶上扎上充有二氧化碳的气球,放入120℃的油浴锅中,反应24小时。反应结束后,冷却,色柱分离(石油醚:乙酸乙酯=2:1)后,产物干燥,得到淡黄色液体化合物18,转化率:83%。1H NMR(400MHz,Chloroform-d)δ4.69(td,J=7.5,5.4Hz,1H),4.52(t,J=8.1Hz,1H),4.06(dd,J=8.4,7.2Hz,1H),1.88–1.74(m,1H),1.73–1.64(m,1H),1.53–1.21(m,4H),0.92(t,J=7.0Hz,3H).
实施例13:
化合物19的制备方法:对反应瓶进行除水除氧操作,在通入惰性气体保护氩气下,加入0.295g(1mmol)催化剂2和1.3g(10mmol)2-(叔丁氧基甲基)环氧乙烷(化合物6)。用二氧化碳置换反应瓶惰性气体氩气3次,然后在反应瓶上扎上充有二氧化碳的气球,放入120℃的油浴锅中,反应12小时。反应结束后,冷却,采用以均三甲苯为内标,核磁定量法测定反应液中环氧化物的转化率,得到转化率89%。1H NMR 1H NMR(400MHz,Chloroform-d)δ4.75(ddt,J=8.0,5.8,3.9Hz,1H),4.44(t,J=8.3Hz,1H),4.34(dd,J=8.3,5.8Hz,1H),3.58(dd,J=10.5,4.2Hz,1H),3.48(dd,J=10.5,3.5Hz,1H),1.15(s,9H).
实施例14:
化合物20的制备方法:对反应瓶进行除水除氧操作,在通入惰性气体氩气保护下,加入0.295g(1mmol)催化剂2和1.0g(10mmol)2-(甲氧基甲基)环氧乙烷(化合物7)。用二氧化碳置换反应瓶惰性气体氩气3次,然后在反应瓶上扎上充有二氧化碳的气球,放入120℃的油浴锅中,反应24小时。反应结束后,冷却,采用以均三甲苯为内标,核磁定量法测定反应液中环氧化物的转化率,得到转化率99%。1H NMR(400MHz,Chloroform-d)δ4.78(ddt,J=8.5,6.1,3.6Hz,1H),4.45(t,J=8.4Hz,1H),4.31(dd,J=8.4,6.1Hz,1H),3.60(dd,J=11.1,3.5Hz,1H),3.50(dd,J=11.1,3.8Hz,1H),3.36(s,3H).
实施例15:
化合物21的制备方法:对反应瓶进行除水除氧操作,在通入惰性气体保护氩气下,加入0.295g(1mmol)催化剂2和1.14g(10mmol)2-((烯丙氧基)甲基)环氧乙烷(化合物8)。用二氧化碳置换反应瓶惰性气体氩气3次,然后在反应瓶上扎上充有二氧化碳的气球,放入120℃的油浴锅中,反应24小时。反应结束后,冷却,色柱分离(石油醚:乙酸乙酯=2:1)后,产物干燥,得到淡黄色液体,转化率:82%。1H NMR(400MHz,Chloroform-d)δ5.85(ddt,J=17.3,10.8,5.6Hz,1H),5.32–5.16(m,2H),4.82(ddt,J=7.9,6.0,3.8Hz,1H),4.49(t,J=8.4Hz,1H),4.38(dd,J=8.4,6.0Hz,1H),4.11–3.97(m,2H),3.68(dd,J=11.0,3.9Hz,1H),3.60(dd,J=11.0,3.8Hz,1H).
实施例16:
化合物22的制备方法:对反应瓶进行除水除氧操作,在通入惰性气体氩气保护下,加入0.295g(1mmol)催化剂2和1.54g(10mmol)2-(4-氯苯基)环氧乙烷(化合物9)。用二氧化碳置换反应瓶惰性气体氩气3次,然后在反应瓶上扎上充有二氧化碳的气球,放入120℃的油浴锅中,反应24小时。反应结束后,冷却,采用以均三甲苯为内标,核磁定量法测定反应液中环氧化物的转化率,得到转化率85%。
实施例17:
化合物23的制备方法:对反应瓶进行除水除氧操作,在通入惰性气体氩气保护下,加入0.295g(1mmol)催化剂2和1.5g(10mmol)2-(苯氧基甲基)环氧乙烷(化合物10)。用二氧化碳置换反应瓶惰性气体氩气3次,然后在反应瓶上扎上充有二氧化碳的气球,放入120℃的油浴锅中,反应24小时。反应结束后,冷却,采用以均三甲苯为内标,核磁定量法测定反应液中环氧化物的转化率,得到转化率88%。1H NMR(400MHz,Chloroform-d)δ7.37–7.27(m,2H),7.06–6.97(m,1H),6.96–6.87(m,2H),5.03(ddt,J=8.1,6.0,3.9Hz,1H),4.61(t,J=8.4Hz,1H),4.53(dd,J=8.5,5.9Hz,1H),4.24(dd,J=10.6,4.2Hz,1H),4.14(dd,J=10.6,3.6Hz,1H).
实施例18:
化合物24的制备方法:对反应瓶进行除水除氧操作,在通入惰性气体氩气保护下,加入0.295g(1mmol)催化剂2和0.98g(10mmol)2-(3-丁烯基)环氧乙烷(化合物11)。用二氧化碳置换反应瓶惰性气体氩气3次,然后在反应瓶上扎上充有二氧化碳的气球,放入120℃的油浴锅中,反应24小时。反应结束后,冷却,采用以均三甲苯为内标,核磁定量法测定反应液中环氧化物的转化率,得到转化率93%。1H NMR(400MHz,Chloroform-d)δ5.76(ddt,J=17.0,10.2,6.7Hz,1H),5.13–4.96(m,2H),4.70(td,J=7.6,5.1Hz,1H),4.51(t,J=8.2Hz,1H),4.06(dd,J=8.5,7.2Hz,1H),2.28–2.13(m,2H),1.90(dtd,J=14.0,8.1,5.9Hz,1H),1.75(dddd,J=14.0,8.7,7.0,5.1Hz,1H).
实施例19:
化合物25的制备方法:对反应瓶进行除水除氧操作,在通入惰性气体氩气保护下,加入0.295g(1mmol)催化剂2和1.37g(10mmol)环氧溴丙烷(化合物12)。用二氧化碳置换反应瓶惰性气体氩气3次,然后在反应瓶上扎上充有二氧化碳的气球,放入120℃的油浴锅中,反应24小时。反应结束后,冷却,色柱分离(石油醚:乙酸乙酯=2:1)后,产物干燥,得到淡黄色液体,转化率:94%。1H NMR(400MHz,Chloroform-d)δ4.94(dtd,J=8.1,6.0,4.6Hz,1H),4.59(dd,J=8.9,8.1Hz,1H),4.35(dd,J=8.9,5.9Hz,1H),3.57(dd,J=5.3,1.4Hz,2H).
实施例20:
化合物26的制备方法:对反应瓶进行除水除氧操作,在通入惰性气体氩气保护下,加入0.295g(1mmol)催化剂2和0.98g(10mmol)2-((邻甲苯氧基)甲基)环氧乙烷(化合物13)。用二氧化碳置换反应瓶惰性气体氩气3次,然后在反应瓶上扎上充有二氧化碳的气球,放入120℃的油浴锅中,反应24小时。反应结束后,冷却,采用以均三甲苯为内标,核磁定量法测定反应液中环氧化物的转化率,得到转化率86%。1H NMR(400MHz,Chloroform-d)δ7.16(ddt,J=6.5,5.2,2.0Hz,2H),6.93(td,J=7.5,1.1Hz,1H),6.86–6.72(m,1H),5.05(ddt,J=8.6,5.6,3.3Hz,1H),4.68–4.52(m,2H),4.26(dd,J=10.6,3.6Hz,1H),4.13(dd,J=10.6,3.1Hz,1H),2.22(s,3H).
Claims (9)
2.根据权利要求1所述的催化剂,其特征在于:所述的环氧化物,R1、R2选自H、正丁基、苯基、卤代苯基、R3-O-CH2-,所述R3选自苯基、甲苯基、烯丙基,叔丁基或甲基。
4.权利要求1所述的催化剂,其特征在于:所述环状碳酸酯的制备方法的初始压力为0.1-2Mpa,反应温度为25-120℃,催化剂的负载量为1mol%-10mol%。
5.根据权利要求1所述的催化剂,其特征在于:所述环状碳酸酯的制备方法的初始压力为0.1MPa,反应温度为60℃,催化剂的负载量为10mol%。
6.根据权利要求1所述的催化剂,其特征在于:所述环状碳酸酯的制备方法为向反应容器中加入催化剂和环氧化物,用二氧化碳置换反应容器中的空气3次,充入二氧化碳至0.1-2MPa,在无溶剂条件下升温至25-120℃,反应6~24h,冷却,反应液通过柱层析得到产物碳酸酯。
7.根据权利要求2~6任一项所述的催化剂,其特征在于,所述的催化剂的制备方法:将糖精的有机溶剂在搅拌的情况下缓慢加入有机碱的有机溶剂,加入完毕后,25-60℃下反应1-24h,得到沉淀物。
8.根据权利要求7所述的催化剂,其特征在于,所述的糖精的有机溶液中的溶剂为二氯甲烷、四氢呋喃或甲苯,所述的有机碱的有机溶液中的溶剂为二氯甲烷、四氢呋喃或甲苯。
9.一种环状碳酸酯的制备方法,其特征在于:采用环氧化物和二氧化碳在如权利要求1-8任意一项所述的糖精盐有机催化体系下合成得到环状碳酸酯。
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