CN116751182B - 一种碳酸亚乙烯酯及其衍生物的制备方法 - Google Patents
一种碳酸亚乙烯酯及其衍生物的制备方法 Download PDFInfo
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- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims abstract description 74
- 238000006243 chemical reaction Methods 0.000 claims abstract description 57
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 48
- 229910052757 nitrogen Inorganic materials 0.000 claims description 24
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 13
- 238000002425 crystallisation Methods 0.000 claims description 12
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- 238000004817 gas chromatography Methods 0.000 claims description 12
- 238000010813 internal standard method Methods 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
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- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 238000005070 sampling Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- ZONYXWQDUYMKFB-UHFFFAOYSA-N flavanone Chemical compound O1C2=CC=CC=C2C(=O)CC1C1=CC=CC=C1 ZONYXWQDUYMKFB-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims 1
- -1 aldehyde compounds Chemical class 0.000 abstract description 22
- 239000002994 raw material Substances 0.000 abstract description 13
- 239000003054 catalyst Substances 0.000 abstract description 9
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 abstract description 7
- 238000001308 synthesis method Methods 0.000 abstract description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052744 lithium Inorganic materials 0.000 abstract description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 4
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- 231100000086 high toxicity Toxicity 0.000 abstract description 2
- SROHGOJDCAODGI-UHFFFAOYSA-N 4,5-diphenyl-1,3-dioxol-2-one Chemical compound O1C(=O)OC(C=2C=CC=CC=2)=C1C1=CC=CC=C1 SROHGOJDCAODGI-UHFFFAOYSA-N 0.000 description 15
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- RCXAAIAVHBOPRN-UHFFFAOYSA-M 2-phenyl-6,7-dihydro-5h-pyrrolo[2,1-c][1,2,4]triazol-4-ium;chloride Chemical compound [Cl-].C1=[N+]2CCCC2=NN1C1=CC=CC=C1 RCXAAIAVHBOPRN-UHFFFAOYSA-M 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 7
- QYIOFABFKUOIBV-UHFFFAOYSA-N 4,5-dimethyl-1,3-dioxol-2-one Chemical compound CC=1OC(=O)OC=1C QYIOFABFKUOIBV-UHFFFAOYSA-N 0.000 description 5
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 4
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- 239000012011 nucleophilic catalyst Substances 0.000 description 4
- DTUQWGWMVIHBKE-UHFFFAOYSA-N phenylacetaldehyde Chemical compound O=CCC1=CC=CC=C1 DTUQWGWMVIHBKE-UHFFFAOYSA-N 0.000 description 4
- ADLVDYMTBOSDFE-UHFFFAOYSA-N 5-chloro-6-nitroisoindole-1,3-dione Chemical compound C1=C(Cl)C([N+](=O)[O-])=CC2=C1C(=O)NC2=O ADLVDYMTBOSDFE-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical group O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000005676 cyclic carbonates Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- KKBONGWVMVUYPA-UHFFFAOYSA-M 2-(2,4,6-trimethylphenyl)-6,7-dihydro-5h-pyrrolo[2,1-c][1,2,4]triazol-4-ium;chloride Chemical compound [Cl-].CC1=CC(C)=CC(C)=C1N1N=C2CCC[N+]2=C1 KKBONGWVMVUYPA-UHFFFAOYSA-M 0.000 description 2
- FRPZAASMSPGXLF-UHFFFAOYSA-N 2-phenyl-3,5,6,7-tetrahydro-1h-pyrrolo[2,1-c][1,2,4]triazol-4-ium;chloride Chemical compound [Cl-].C1CCC(N2)=[N+]1CN2C1=CC=CC=C1 FRPZAASMSPGXLF-UHFFFAOYSA-N 0.000 description 2
- BUPLCMMXKFWTTA-UHFFFAOYSA-N 4-methylidene-1,3-dioxetan-2-one Chemical compound C=C1OC(=O)O1 BUPLCMMXKFWTTA-UHFFFAOYSA-N 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 150000003934 aromatic aldehydes Chemical class 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000006352 cycloaddition reaction Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920002866 paraformaldehyde Polymers 0.000 description 2
- 229940100595 phenylacetaldehyde Drugs 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
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- 238000010146 3D printing Methods 0.000 description 1
- 239000005485 Azilsartan Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000002000 Electrolyte additive Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
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- 125000000217 alkyl group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- KGSXMPPBFPAXLY-UHFFFAOYSA-N azilsartan Chemical compound CCOC1=NC2=CC=CC(C(O)=O)=C2N1CC(C=C1)=CC=C1C1=CC=CC=C1C1=NOC(=O)N1 KGSXMPPBFPAXLY-UHFFFAOYSA-N 0.000 description 1
- 229960002731 azilsartan Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- HUMNYLRZRPPJDN-KWCOIAHCSA-N benzaldehyde Chemical group O=[11CH]C1=CC=CC=C1 HUMNYLRZRPPJDN-KWCOIAHCSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 1
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- QPMJENKZJUFOON-PLNGDYQASA-N ethyl (z)-3-chloro-2-cyano-4,4,4-trifluorobut-2-enoate Chemical compound CCOC(=O)C(\C#N)=C(/Cl)C(F)(F)F QPMJENKZJUFOON-PLNGDYQASA-N 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- 238000005935 nucleophilic addition reaction Methods 0.000 description 1
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- VTRAEEWXHOVJFV-UHFFFAOYSA-N olmesartan Chemical compound CCCC1=NC(C(C)(C)O)=C(C(O)=O)N1CC1=CC=C(C=2C(=CC=CC=2)C=2NN=NN=2)C=C1 VTRAEEWXHOVJFV-UHFFFAOYSA-N 0.000 description 1
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- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
- C07D317/10—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
- C07D317/40—Vinylene carbonate; Substituted vinylene carbonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J2231/341—1,2-additions, e.g. aldol or Knoevenagel condensations
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
- B01J2231/4288—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues using O nucleophiles, e.g. alcohols, carboxylates, esters
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
本发明涉及锂电池技术领域,本发明提供了一种碳酸亚乙烯酯及其衍生物的制备方法,制备方法包括:以碳酸二苯酯和醛类化合物为原料,以吡咯并三唑盐类化合物和4‑二甲基氨基吡啶作为催化剂进行反应得到碳酸亚乙烯酯或其衍生物。本发明提供了碳酸亚乙烯酯或其衍生物的通用合成方法,最高收率可达99%。吡咯并三唑盐类化合物和4‑二甲基氨基吡啶作为组合催化剂,提高了反应的选择性和收率,操作简单,通用性强,适合于工业化应用。另外,制备方法所用的原料绿色环保,避免了传统方法使用毒性较大的光气和固体光气等原料,副产物苯酚可通过再生处理得到碳酸二苯酯,可多次循环利用,节约成本。
Description
技术领域
本发明涉及锂电池技术领域,具体涉及一种碳酸亚乙烯酯及其衍生物的制备方法。
背景技术
有机碳酸酯是一类环境友好和可持续的化合物,其合成方法是目前很多科研院所深入研究的课题,此类化合物可以作为锂电池中的添加剂,也可以作为有机溶剂,并用于生产聚碳酸酯和聚氨酯。其中有机环状碳酸酯的化学性质得到了广泛的发展,因为它们可以通过环氧化合物与二氧化碳环加成来制备,从而得到饱和环状碳酸酯。相反,不饱和环状碳酸酯由于其合成方法受限,影响其工业化应用,在所有的碳酸亚乙烯酯衍生物中,碳酸亚乙烯酯是目前应用最广泛的化合物,它可以作为锂电池中的电解质添加剂,或作为制备聚碳酸乙烯酯的单体,也可用于3D打印原料的前体,在有机化学中,它主要用作DA反应中的二烯亲和试剂。最近,碳酸亚乙烯酯的化学性质在环化反应中显著发展,它作为乙炔、乙醛、乙酰乙基或乙基的替代物。带取代基的碳酸亚乙烯酯衍生物也是提供补充应用的有用化合物。例如,4,5-二甲基碳酸亚乙烯酯是一个带可切割基团的关键前体,该化合物可用于原料药合成,如奥美沙坦美索米和阿齐沙坦美索米。最近,也有研究表明,部分功能化碳酸亚乙烯酯衍生物可以用于制备优良的聚合物添加剂,以制备高密度锂离子电池,同时含有一些特殊官能团的结构,其在锂电池应用方面有待于开发。
4,5-二甲基-1,3-二氧杂环戊烯-2-酮,4,5-二苄基-1,3-二氧杂环戊烯-2-酮、4,5-二苯基-1,3-二氧杂环戊烯-2-酮,都是碳酸亚乙烯酯的衍生物。
文献中报道的关于含取代基的碳酸亚乙烯酯合成的方法很少,且收率不高,制备方法通用性不强。有文献报到,银催化的丙炔醇与二氧化碳环加成得到偏乙烯碳酸酯中间体,该中间体进行重排后得到偏甲基碳酸亚乙烯酯,然而,该反应过程中只有部分结构可以异构化为偏碳酸酯,因此限制了应用范围。专利公开号为CN113149953A的专利公开了一种4,5-二甲基-1,3-二氧杂环戊烯-2-酮合成方法,以碳酸二苯酯作为羰基源制备4,5-二甲基-1,3-二氧杂环戊烯-2-酮的方法,以2,3-丁二醇、碳酸二苯酯为原料,加入到有机溶剂中,在催化剂作用下,保温搅拌反应,所得反应液经过减压蒸馏去除溶剂进一步重结晶得到高纯度的4,5-二甲基-1,3-二氧杂环戊烯-2-酮,但是该方法原料成本较高。也有采用固体光气为酰化试剂,溶剂法脱出氯化氢制备4,5-二甲基-1,3-二氧杂环戊烯-2-酮,如印度专利2013CH00686, 胡来月等人在文章《4 ,5-二甲基-1 ,3-二氧杂环戊烯-2-酮的合成》中,采用二甲基乙酰胺或甲苯作为溶剂,90-110℃下,脱出氯化氢。该法避免无溶剂高温脱出氯化氢导致的产品碳化分解,但反应过程生成氯化氢对设备腐蚀性强,同时固体光气在反应中分解出的剧毒的光气。无法进一步大规模生产利用。因此,现有技术有待于进一步发展。
发明内容
在本发明的目的在于克服上述技术不足,提供一种碳酸亚乙烯酯及其衍生物的制备方法,以解决相关技术中的收率较低的技术问题。
为达到上述技术目的,本发明采取了以下技术方案:提供了一种碳酸亚乙烯酯及其衍生物的制备方法,制备方法包括:以碳酸二苯酯和醛类化合物为原料,以吡咯并三唑盐类化合物和4-二甲基氨基吡啶作为催化剂进行反应得到碳酸亚乙烯酯或其衍生物。
进一步的,碳酸二苯酯和醛类化合物摩尔比为(1.0 -1.5):2。
进一步的,以碳酸二苯酯的摩尔用量为基准参照物,加入0.01 mol%-0.1 mol%的吡咯并三唑盐类化合物,加入0.06 mol%-0.1 mol%的4-二甲基氨基吡啶。
进一步的,以碳酸二苯酯的摩尔用量为基准参照物,加入0.01 mol%的吡咯并三唑盐类化合物,加入0.1 mol%的4-二甲基氨基吡啶。
进一步的,反应温度为60-90℃,反应时间为8-16h。
进一步的,吡咯并三唑盐类化合物为2-苯基-2,5,6,7-四氢吡咯并[2,1-C][1,2,4]三唑-4-鎓氯化物、2-均三甲苯基-2,5,6,7-四氢吡咯并[2,1-C][1,2,4]三唑-4-鎓氯化物或6,7-二氢-2-苯基-5H-吡咯并[2,1-c]-1,2,4-三唑氯化物。
进一步的,醛类化合物为烷基醛或芳香醛。
进一步的,烷基醛为甲醛或乙醛。
进一步的,芳香醛为苯甲醛或苯乙醛。
进一步的,反应结束后还进行后处理,所述后处理包括精馏、结晶。
有益效果:
1、本发明提供了碳酸亚乙烯酯或其衍生物的通用合成方法,最高收率可达99%。
2、本发明的碳酸亚乙烯酯或其衍生物的制备方法中吡咯并三唑盐类化合物和4-二甲基氨基吡啶作为组合催化剂,提高了反应的选择性和收率,操作简单,通用性强,适合于工业化应用。
3、本发明首次将碳酸二苯酯作为制备碳酸亚乙烯酯或其衍生物的羰基源,碳酸二苯酯环保易得,并且有利于碳酸亚乙烯酯或其衍生物的合成反应的进行。
4、本发明的制备方法所用的原料绿色环保,避免了传统方法使用毒性较大的光气和固体光气等原料,副产物苯酚可通过再生处理得到碳酸二苯酯,可多次循环利用,节约成本。
附图说明
图1是本发明的2-苯基-2,5,6,7-四氢吡咯并[2,1-C][1,2,4]三唑-4-鎓氯化物和4-二甲基氨基吡啶的反应机理示意图。
具体实施方式
为了使本技术领域的人员更好地理解本申请方案,下面将结合本申请实施例中的附图,对本申请实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本申请一部分的实施例,而不是全部的实施例。基于本申请中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都应当属于本申请保护的范围。
根据本发明实施例,提供了一种碳酸亚乙烯酯及其衍生物的制备方法,制备方法包括:以碳酸二苯酯和醛类化合物为原料,以吡咯并三唑盐类化合物和4-二甲基氨基吡啶作为催化剂进行反应得到碳酸亚乙烯酯或其衍生物。本发明提供了碳酸亚乙烯酯或其衍生物的通用合成方法,最高收率可达99%。另外,吡咯并三唑盐类化合物和4-二甲基氨基吡啶作为组合催化剂,提高了反应的选择性和收率,操作简单,通用性强,适合于工业化应用。碳酸亚乙烯酯或其衍生物的制备方法的化学反应方程式如下,其中R可以为-H,-CH3,-CH2CH3,-Ph,-CH2Ph,当然也可以为其他的烷基或者芳烃基。
如图1所示,苯基取代三唑盐化合物和DMAP(4-二甲基氨基吡啶)的组合催化剂是该反应中必不可少的,根据反应现象和亲电芳香取代机制,反应机理如下:DMAP同时作为碱和亲核催化剂,第一步反应中,吡咯并三唑盐类化合物被DMAP去质子化得到N-杂环卡宾(NHC)化合物,NHC对第一个醛的亲核加成得到化合物I,然后经过1,2质子迁移得到中间体II。在第二个醛上继续亲核得到中间体III,通过1,4质子迁移转化为中间体IV,最后释放游离卡宾后得到安息香V。在第二步中,碳酸二苯酯被亲核催化剂DMAP激活,得到中间体VI。用安息香将VI中亲核试剂取代可以得到中间体VII并释放第一个苯酚分子。该中间态继续生成中间体VIII,并释放亲核催化剂DMAP。在最后一步,在亲核催化剂的存在下,VIII将产生中间体IX,产生烯酸盐中间体X并释放第二个苯酚分子。最后烯酸酯X在活性碳基上通过环化形成目标产物。
反应过程严格控制反应温度,温度过低会导致反应不充分,原料剩余较多,产品含量不合格。温度过高导致副反应较多,收率低。同时在反应过程中避免空气的混入,过多的氧气混入会导致原料的氧化。
实施例1:碳酸亚乙烯酯制备
准备带有搅拌和氮气保护的四口瓶,分别向四口瓶内加入60.06g多聚甲醛(2mol)和218.5g碳酸二苯酯(1.02 mol),氮气保护条件下升温至83℃,待多聚甲醛完全溶解后再继续加入0.022g 2-苯基-2,5,6,7-四氢吡咯并[2,1-C][1,2,4]三唑-4-鎓氯化物(0.0001mol)和0.12g DMAP(4-二甲基氨基吡啶)(0.001mol),继续反应10h,取样进行气相色谱内标法检测碳酸亚乙烯酯含量不变后降温停止反应,物料进行后处理精馏、结晶。碳酸亚乙烯酯含量26.61%,反应液质量278.6g,收率86.2%。
实施例2:4,5-二苯基-1,3-二氧杂环戊烯-2-酮制备
准备带有搅拌和氮气保护的四口瓶,分别向四口瓶内加入212.2g苯甲醛(2 mol)和218.5g碳酸二苯酯(1.02 mol),氮气保护条件下升温至90℃,待反应底物完全溶解后再继续加入0.044g 2-苯基-2,5,6,7-四氢吡咯并[2,1-C][1,2,4]三唑-4-鎓氯化物(0.0002mol)和0.12g DMAP(4-二甲基氨基吡啶)(0.001mol),继续反应16h,取样进行气相色谱内标法检测产物含量不变后降温停止反应,物料进行后处理精馏、结晶。4,5-二苯基-1,3-二氧杂环戊烯-2-酮含量54.76%,反应液质量430.62g,收率99.0%。
实施例3:4,5-二甲基-1,3-二氧杂环戊烯-2-酮制备
准备带有搅拌和氮气保护的四口瓶,分别向四口瓶内加入88.0g乙醛(2 mol)和218.5g碳酸二苯酯(1.02 mol),氮气保护条件下升温至70℃,待反应底物完全溶解后再继续加入0.044g 2-苯基-2,5,6,7-四氢吡咯并[2,1-C][1,2,4]三唑-4-鎓氯化物(0.0002mol)和0.12g DMAP(4-二甲基氨基吡啶)(0.001mol),继续反应9h,取样进行气相色谱内标法检测产物含量不变后降温停止反应,物料进行后处理精馏、结晶。4,5-二甲基-1,3-二氧杂环戊烯-2-酮含量29.97%,反应液质量306.60g,4,5-二甲基碳酸亚乙烯酯收率80.6%。
实施例4:4,5-二苄基-1,3-二氧杂环戊烯-2-酮制备
准备带有搅拌和氮气保护的四口瓶,分别向四口瓶内加入240.3g苯乙醛(2 mol)和218.5g碳酸二苯酯(1.02 mol),氮气保护条件下升温至65℃,待反应底物完全溶解后再继续加入0.044g 2-苯基-2,5,6,7-四氢吡咯并[2,1-C][1,2,4]三唑-4-鎓氯化物(0.0002mol)和0.12g DMAP(4-二甲基氨基吡啶)(0.001mol),继续反应13h,取样进行气相色谱内标法检测产物含量不变后降温停止反应,物料进行后处理精馏、结晶。4,5-二苄基-1,3-二氧杂环戊烯-2-酮含量53.72%,反应液质量458.90g,收率92.6%。
实施例5:4,5-二苯基-1,3-二氧杂环戊烯-2-酮制备
准备带有搅拌和氮气保护的四口瓶,分别向四口瓶内加入212.2g苯甲醛(2 mol)和218.5g碳酸二苯酯(1.02 mol),氮气保护条件下升温至90℃,待反应底物完全溶解后再继续加入0.22g 2-苯基-2,5,6,7-四氢吡咯并[2,1-C][1,2,4]三唑-4-鎓氯化物(0.001mol)和0.12g DMAP(4-二甲基氨基吡啶)(0.001mol),继续反应8h,取样进行气相色谱内标法检测产物含量不变后降温停止反应,物料进行后处理精馏、结晶。4,5-二苯基-1,3-二氧杂环戊烯-2-酮含量54.04%,反应液质量430.21g,4,5-二苯基碳酸亚乙烯酯收率97.6%。
实施例6:4,5-二苯基-1,3-二氧杂环戊烯-2-酮制备
准备带有搅拌和氮气保护的四口瓶,分别向四口瓶内加入212.2g苯甲醛(2 mol)和214.2g碳酸二苯酯(1mol),氮气保护条件下升温至60℃,待反应底物完全溶解后再继续加入0.22g 2-苯基-2,5,6,7-四氢吡咯并[2,1-C][1,2,4]三唑-4-鎓氯化物(0.001mol)和0.07g DMAP(4-二甲基氨基吡啶)(0.0006mol),继续反应11h,取样进行气相色谱内标法检测产物含量不变后降温停止反应,物料进行后处理精馏、结晶。4,5-二苯基-1,3-二氧杂环戊烯-2-酮含量53.72%,反应液质量426.5g,4,5-二苯基碳酸亚乙烯酯收率96.2%。
实施例8:4,5-二苯基-1,3-二氧杂环戊烯-2-酮制备
准备带有搅拌和氮气保护的四口瓶,分别向四口瓶内加入212.2g苯甲醛(2 mol)和321.3g碳酸二苯酯(1.5mol),氮气保护条件下升温至60℃,待反应底物完全溶解后再继续加入0.22g 2-苯基-2,5,6,7-四氢吡咯并[2,1-C][1,2,4]三唑-4-鎓氯化物(0.001mol)和0.07g DMAP(4-二甲基氨基吡啶)(0.0006mol),继续反应11h,取样进行气相色谱内标法检测产物含量不变后降温停止反应,物料进行后处理精馏、结晶。4,5-二苯基-1,3-二氧杂环戊烯-2-酮含量43.25%,反应液质量533.6g,4,5-二苯基碳酸亚乙烯酯收率96.9%。
实施例9:4,5-二苯基-1,3-二氧杂环戊烯-2-酮制备
准备带有搅拌和氮气保护的四口瓶,分别向四口瓶内加入212.2g苯甲醛(2 mol)和321.3g碳酸二苯酯(1.5mol),氮气保护条件下升温至60℃,待反应底物完全溶解后再继续加入0.27g 2-均三甲苯基-2,5,6,7-四氢吡咯并[2,1-C][1,2,4]三唑-4-鎓氯化物(0.001mol)和0.07g DMAP(4-二甲基氨基吡啶)(0.0006mol),继续反应11h,取样进行气相色谱内标法检测产物含量不变后降温停止反应,物料进行后处理精馏、结晶。4,5-二苯基-1,3-二氧杂环戊烯-2-酮含量32.60%,反应液质量533.4g,4,5-二苯基碳酸亚乙烯酯收率73.0%。
实施例10:4,5-二苯基-1,3-二氧杂环戊烯-2-酮制备
准备带有搅拌和氮气保护的四口瓶,分别向四口瓶内加入212.2g苯甲醛(2 mol)和321.3g碳酸二苯酯(1.5mol),氮气保护条件下升温至60℃,待反应底物完全溶解后再继续加入0.22g 6,7-二氢-2-苯基-5H-吡咯并[2,1-c]-1,2,4-三唑氯化物三唑-4-鎓氯化物(0.001mol)和0.07g DMAP(4-二甲基氨基吡啶)(0.0006mol),继续反应11h,取样进行气相色谱内标法检测产物含量不变后降温停止反应,物料进行后处理精馏、结晶。4,5-二苯基-1,3-二氧杂环戊烯-2-酮含量39.28%,反应液质量533.5g,4,5-二苯基碳酸亚乙烯酯收率88.0%。
对比例1:
准备带有搅拌和氮气保护的四口瓶,分别向四口瓶内加入212.2g苯甲醛(2 mol)和218.5g碳酸二苯酯(1.02 mol),氮气保护条件下升温至90℃,待反应底物完全溶解后再继续加入0.044g 2-苯基-2,5,6,7-四氢吡咯并[2,1-C][1,2,4]三唑-4-鎓氯化物(0.0002mol),继续反应16h,取样进行气相色谱内标法检测产物含量不变后降温停止反应,物料进行后处理精馏、结晶。4,5-二苯基-1,3-二氧杂环戊烯-2-酮含量17.21%,反应液质量430.4g,收率31.1%。
对比例2:
准备带有搅拌和氮气保护的四口瓶,分别向四口瓶内加入212.2g苯甲醛(2 mol)和218.5g碳酸二苯酯(1.02 mol),氮气保护条件下升温至90℃,待反应底物完全溶解后再继续加入0.12g DMAP(4-二甲基氨基吡啶)(0.001mol),继续反应16h,取样进行气相色谱内标法检测产物含量不变后降温停止反应,物料进行后处理精馏、结晶4,5-二苯基-1,3-二氧杂环戊烯-2-酮含量9.51%,反应液质量430.5g,收率17.2%。
由上述实施例1-10和对比例1-2可以看出,本发明提供了一种碳酸亚乙烯酯或其衍生物的通用合成方法,收率最高可达99%,其中吡咯并三唑盐类化合物和4-二甲基氨基吡啶为组合催化剂,只有同时加入两者,才能提高反应的选择性和收率。
此外,应当理解,虽然本说明书按照实施方式加以描述,但并非每个实施方式仅包含一个独立的技术方案,说明书的这种叙述方式仅仅是为清楚起见,本领域技术人员应当将说明书作为一个整体,各实施例中的技术方案也可以经适当组合,形成本领域技术人员可以理解的其他实施方式。
Claims (1)
1. 一种碳酸亚乙烯酯及其衍生物的制备方法,其特征在于,制备方法包括:准备带有搅拌和氮气保护的四口瓶,分别向四口瓶内加入212.2g苯甲醛和218.5g碳酸二苯酯,氮气保护条件下升温至90℃,待反应底物完全溶解后再继续加入0.044g 2-苯基-2,5,6,7-四氢吡咯并[2,1-C][1,2,4]三唑-4-鎓氯化物和0.12g 4-二甲基氨基吡啶,继续反应16h,取样进行气相色谱内标法检测产物含量不变后降温停止反应,物料进行后处理精馏、结晶。
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