CN115028583A - 一种超交联氮杂环卡宾咪唑鎓盐配体、其制备方法及应用 - Google Patents
一种超交联氮杂环卡宾咪唑鎓盐配体、其制备方法及应用 Download PDFInfo
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- CN115028583A CN115028583A CN202210812023.7A CN202210812023A CN115028583A CN 115028583 A CN115028583 A CN 115028583A CN 202210812023 A CN202210812023 A CN 202210812023A CN 115028583 A CN115028583 A CN 115028583A
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- imidazolium salt
- carbene
- substituted
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- -1 N-heterocyclic carbene imidazolium salt Chemical class 0.000 title claims abstract description 77
- 239000003446 ligand Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 99
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 62
- 238000006243 chemical reaction Methods 0.000 claims abstract description 61
- 239000003054 catalyst Substances 0.000 claims abstract description 38
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 20
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 16
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000011065 in-situ storage Methods 0.000 claims abstract description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 32
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 16
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 15
- 125000003118 aryl group Chemical group 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 12
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 12
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 12
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 claims description 12
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 claims description 12
- 229910000071 diazene Inorganic materials 0.000 claims description 12
- 125000005842 heteroatom Chemical group 0.000 claims description 12
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 claims description 12
- 150000001491 aromatic compounds Chemical class 0.000 claims description 11
- 230000035484 reaction time Effects 0.000 claims description 11
- UFFBMTHBGFGIHF-UHFFFAOYSA-N 2,6-dimethylaniline Chemical group CC1=CC=CC(C)=C1N UFFBMTHBGFGIHF-UHFFFAOYSA-N 0.000 claims description 10
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 10
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 10
- 239000012038 nucleophile Substances 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 8
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 8
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 8
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 8
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 229920002866 paraformaldehyde Polymers 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- NGDCLPXRKSWRPY-UHFFFAOYSA-N Triptycene Chemical compound C12=CC=CC=C2C2C3=CC=CC=C3C1C1=CC=CC=C12 NGDCLPXRKSWRPY-UHFFFAOYSA-N 0.000 claims description 6
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 6
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- YNHJECZULSZAQK-UHFFFAOYSA-N tetraphenylporphyrin Chemical compound C1=CC(C(=C2C=CC(N2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3N2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 YNHJECZULSZAQK-UHFFFAOYSA-N 0.000 claims description 6
- 229930192474 thiophene Natural products 0.000 claims description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical group COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 5
- 150000004982 aromatic amines Chemical class 0.000 claims description 5
- 239000004305 biphenyl Substances 0.000 claims description 5
- 235000010290 biphenyl Nutrition 0.000 claims description 5
- 239000012295 chemical reaction liquid Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 235000019253 formic acid Nutrition 0.000 claims description 5
- 229940015043 glyoxal Drugs 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical group [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 5
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 4
- SXWIAEOZZQADEY-UHFFFAOYSA-N 1,3,5-triphenylbenzene Chemical compound C1=CC=CC=C1C1=CC(C=2C=CC=CC=2)=CC(C=2C=CC=CC=2)=C1 SXWIAEOZZQADEY-UHFFFAOYSA-N 0.000 claims description 4
- 239000005711 Benzoic acid Substances 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 235000010233 benzoic acid Nutrition 0.000 claims description 4
- 239000007810 chemical reaction solvent Substances 0.000 claims description 4
- 239000012065 filter cake Substances 0.000 claims description 4
- 125000001072 heteroaryl group Chemical group 0.000 claims description 4
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 229920005862 polyol Polymers 0.000 claims description 4
- 150000003077 polyols Chemical class 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 125000004076 pyridyl group Chemical group 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 150000005846 sugar alcohols Polymers 0.000 claims description 4
- PEQHIRFAKIASBK-UHFFFAOYSA-N tetraphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 PEQHIRFAKIASBK-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
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- 150000002989 phenols Chemical class 0.000 claims description 3
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- WKBALTUBRZPIPZ-UHFFFAOYSA-N 2,6-di(propan-2-yl)aniline Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N WKBALTUBRZPIPZ-UHFFFAOYSA-N 0.000 claims description 2
- FOYHNROGBXVLLX-UHFFFAOYSA-N 2,6-diethylaniline Chemical compound CCC1=CC=CC(CC)=C1N FOYHNROGBXVLLX-UHFFFAOYSA-N 0.000 claims description 2
- WFGHUOGOUOTVBO-UHFFFAOYSA-N 2,6-dipropylaniline Chemical compound CCCC1=CC=CC(CCC)=C1N WFGHUOGOUOTVBO-UHFFFAOYSA-N 0.000 claims description 2
- RZSUJIUTUGMZPG-UHFFFAOYSA-N 2,6-ditert-butylaniline Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1N RZSUJIUTUGMZPG-UHFFFAOYSA-N 0.000 claims description 2
- 125000001313 C5-C10 heteroaryl group Chemical group 0.000 claims description 2
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- 150000002596 lactones Chemical class 0.000 claims description 2
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- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
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- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 2
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- 239000007858 starting material Substances 0.000 claims description 2
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- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
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- 125000004202 aminomethyl group Chemical group [H]N([H])C([H])([H])* 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 125000002619 bicyclic group Chemical group 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
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- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 125000006413 ring segment Chemical group 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
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- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- FNQJDLTXOVEEFB-UHFFFAOYSA-N 1,2,3-benzothiadiazole Chemical compound C1=CC=C2SN=NC2=C1 FNQJDLTXOVEEFB-UHFFFAOYSA-N 0.000 description 1
- CSNIZNHTOVFARY-UHFFFAOYSA-N 1,2-benzothiazole Chemical compound C1=CC=C2C=NSC2=C1 CSNIZNHTOVFARY-UHFFFAOYSA-N 0.000 description 1
- KTZQTRPPVKQPFO-UHFFFAOYSA-N 1,2-benzoxazole Chemical compound C1=CC=C2C=NOC2=C1 KTZQTRPPVKQPFO-UHFFFAOYSA-N 0.000 description 1
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种超交联氮杂环卡宾咪唑鎓盐配体、其制备方法及应用,所述方法是一种新的合成思路和路线,主要包括以下步骤:先制备氮杂环卡宾咪唑鎓盐单体,再通过Scholl反应,合成了超交联氮杂环卡宾咪唑鎓盐配体,该方法工艺简单、操作方便、原料廉价易得。所述超交联氮杂环卡宾咪唑鎓盐配体可与钯催化剂原位生成超交联卡宾钯催化剂,成功将均相催化剂转化为非均相,在保证具有均相催化剂催化效果的前提下,还便于贵金属催化剂的回收循环利用,并进一步提高了催化剂的稳定性。更加重要的是,该催化剂在丁二烯与甲醇的调聚反应中展现出优异的1‑MOD选择性和L/B值。
Description
技术领域
本发明属于有机合成及多相催化技术领域,具体涉及一种超交联氮杂环卡宾咪唑鎓盐配体、其制备方法及其在丁二烯调聚反应中的应用。
背景技术
丁二烯调聚反应已被广泛用于丁二烯与一系列亲核试剂(水、甲醇、乙醇、多元醇、苯酚、淀粉、胺、二氧化碳等)发生调聚反应制备高附加值化合物。目前,丁二烯调聚反应的催化体系普遍由均相贵金属Pd催化剂和均相膦配体(PR3)或者卡宾配体组成。其中,氮杂环卡宾(NHC)结构是一类性能极其优异的功能配体,在Pd催化丁二烯调聚反应中展现出惊人的催化反应活性和优异的目标产物选择性(包括区域选择性)。尽管均相氮杂环卡宾配体在丁二烯调聚反应中取得了不错的进展,但仍面临昂贵催化体系分离回收利用难及稳定性差的问题。
为了解决该类问题,多种非均相催化剂制备策略被开发出来,并在一定程度上解决了催化剂分离和回收困难的问题,但是催化性能与均相催化剂相差仍较大,活性和选择性低,且催化剂的稳定性不理想。
发明内容
针对上述的不足,本发明的第一个目的是提供一种超交联氮杂环卡宾咪唑鎓盐配体。
本发明的第二个目的是提供上述超交联氮杂环卡宾咪唑鎓盐配体的制备方法。
本发明的第三个目的是提供该超交联氮杂环卡宾咪唑鎓盐配体在1,3-丁二烯的调聚反应中的应用。
本发明的第四个目的是提供应用上述超交联氮杂环卡宾咪唑鎓盐配体由1,3-丁二烯的调聚反应生成1-取代的2,7-辛二烯的方法。
基于上述目的,本发明的第一个方面,提供一种超交联氮杂环卡宾咪唑鎓盐配体,其结构如下所示:
其中,Ar选自取代或未取代的C6-20芳基、取代或未取代的含有1-4个选自N、O、S中的杂原子的5-20元杂芳基、取代或未取代的卟啉基,所述取代是指含有1-4个选自C1-4烷基、羟基、甲氧基、氰基、羧基、氨基、氨基C1-4烷基、苯基、吡啶基、三苯甲基、二苯膦基的取代基。
优选地,Ar选自取代或未取代的C6-14芳基、取代或未取代的含有1-3个选自N、O、S中的杂原子的5-10元杂芳基、取代或未取代的卟啉基,所述取代的是指含有1-3个选自C1-4烷基、羟基、甲氧基、氰基、羧基、氨基、氨基C1-4烷基、苯基、吡啶基、三苯甲基、二苯膦基的取代基;
更优选地,Ar选自苯、联苯、萘、三苯基苯、四苯基甲烷、三苯基膦、苯甲醚、苯酚、苯甲腈、苯甲酸、苄胺、邻苯二胺、三蝶烯、芘、四苯基卟啉、联吡啶、邻菲罗啉、吡咯、呋喃、噻吩去除芳环上的两个或多个氢形成的取代基中的一种或者多种。
本发明的第二个方面,提供上述超交联氮杂环卡宾咪唑鎓盐配体的制备方法,所述制备方法路线如下:
具体方法步骤包括:
S1:以2,6-二取代的苯胺为起始原料,在醇中与乙二醛水溶液反应,生成二亚胺中间体;
S2:将S1所得二亚胺中间体溶于有机溶剂,在一定温度下与加入的多聚甲醛和三甲基氯硅烷(TMSCl)溶液反应,搅拌至完全反应,将反应液冷却,分离得到氮杂环卡宾咪唑鎓盐;
S3:将S2所得氮杂环卡宾咪唑鎓盐和芳香化合物溶于氯仿中,慢慢加入无水三氯化铝,在0℃充分混合搅拌,然后升温至40~60℃,在该温度下搅拌形成初始网络结构,然后加热至70~90℃直至反应完全,分离得到超交联氮杂环卡宾咪唑鎓盐配体。
根据上述超交联氮杂环卡宾咪唑鎓盐配体的制备方法,步骤S1中,
所述2,6-二取代的苯胺选自2,6-二甲基苯胺、2,6-二乙基苯胺、2,6-二丙基苯胺、2,6-二异丙基苯胺、2,6-二叔丁基苯胺;优选为2,6-二甲基苯胺;
优选地,所述反应中,2,6-二取代的苯胺与乙二醛的物质的量比为:1~3:1,优选为2:1;
优选地,所述反应在氮气保护下进行;所述反应在催化剂催化下进行,所述催化剂选自甲酸、醋酸,优选为甲酸;所述2,6-二取代的苯胺与催化剂的物质的量比为:3~7:1;优选为5:1;
优选地,所述醇选自甲醇、乙醇、丙醇、异丙醇,优选为甲醇;
优选地,所述反应温度为室温;反应时间为5~20h,优选为10~15h,更优选为11h;
优选地,所述反应结束后还包括纯化步骤,所述纯化步骤为:将反应产物过滤,用冷醇洗涤2-5次得到纯化的二亚胺中间体,优选洗涤3次。
根据上述超交联氮杂环卡宾咪唑鎓盐配体的制备方法,步骤S2中,
所述二亚胺中间体与多聚甲醛、TMSCl的物质的量比为:1~2:1~2:1~1.5;优选为1:1:1.2;
优选地,溶解二亚胺中间的有机溶剂选自乙酸乙酯、二甲亚砜、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、四氢呋喃;优选为乙酸乙酯;
优选地,所述TMSCl溶液的溶剂选自乙酸乙酯、二甲亚砜、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、四氢呋喃;优选为乙酸乙酯;
优选地,所述加入多聚甲醛和TMSCl溶液,在一定温度下反应中,所述反应的温度为60~80℃,优选为70℃;所述反应的时间为1-48h;优选为2h;
优选地,所述分离步骤包括:将冷却的反应液过滤,用冷的有机溶剂洗涤滤饼,得到氮杂环卡宾咪唑鎓盐固体;优选地,所述冷却温度为-20℃;所述有机溶剂可选自乙酸乙酯、乙醚、丙酮;优选地,所述洗涤步骤为使用冷的乙酸乙酯和乙醚分别洗涤滤饼。
根据上述超交联氮杂环卡宾咪唑鎓盐配体的制备方法,步骤S3中,
所述芳香化合物选自苯、联苯、萘、三苯基苯、四苯基甲烷、三苯基膦、苯甲醚、苯酚、苯甲腈、苯甲酸、苄胺、邻苯二胺、三蝶烯、芘、四苯基卟啉、联吡啶、邻菲罗啉、吡咯、呋喃、噻吩的一种或者多种,优选为苯;
优选地,氮杂环卡宾咪唑鎓盐、芳香化合物与无水三氯化铝的物质的量的比为:1~2:10~20:70~100;优选为1:10:80;
优选地,在0℃搅拌反应的时间为0.5~2h,优选为1h;
优选地,在40~60℃下搅拌反应的时间为0.5~4h,优选为2h;所述搅拌反应的优选温度为50℃;
优选地,在70~90℃反应的时间为20~80h,优选为40~50h;
优选地,所述分离步骤包括:将反应完全后得到的固体产物分别用甲醇、10%稀盐酸和去离子水洗涤,然后在索氏提取器中用甲醇洗涤后,真空干燥得到纯化的超交联氮杂环卡宾咪唑鎓盐配体;优选地,索氏提取器的时间为24~72h,更优选为48h。
本发明的第三个方面,提供上述超交联氮杂环卡宾咪唑鎓盐配体在1,3-丁二烯的调聚反应中的应用,所述调聚反应包括:1,3-丁二烯与亲核试剂反应生成1-取代的2,7-辛二烯(1-MOD)、1,3-丁二烯与CO2反应生成δ-环内脂;
优选地,所述亲核试剂选自水、甲醇、乙醇、丙醇、多元醇、苯酚、芳香胺、脂肪胺。
本发明的第四个方面,提供应用上述超交联氮杂环卡宾咪唑鎓盐配体由1,3-丁二烯的调聚反应生成1-取代的2,7-辛二烯的方法,所述方法包括以下步骤:
钯催化剂和超交联氮杂环卡宾咪唑鎓盐配体在碱性条件下原位生成非均相的超交联卡宾钯催化剂,在催化剂作用下,1,3-丁二烯与亲核试剂在预定温度下发生调聚反应,生成1-取代的-2,7-辛二烯。
优选地,所述亲核试剂选自水、甲醇、乙醇、丙醇、多元醇、苯酚、芳香胺、脂肪胺;所述调聚反应的反应溶剂选自甲醇、乙醇、丙醇、丁醇、多元醇、水;更优选地,所述调聚反应的亲核试剂和反应溶剂均为甲醇;
优选地,所述钯催化剂选自醋酸钯、乙酰丙酮钯、氯化钯;优选为醋酸钯;
优选地,所述超交联氮杂环卡宾咪唑鎓盐配体与钯催化剂的质量比:5~50:1:优选为10~20:1,更优选为10:1;
优选地,所述1,3-丁二烯与亲核试剂在-50℃下的体积比为:1:1~10,优选为1:2;
优选地,通过加入碱添加剂获得碱性环境,所述碱添加剂选自甲醇钠、甲醇钾、碳酸钠、碳酸钾、甲酸钠;优选为甲醇钠;
优选地,所述调聚反应的温度为50~80℃,优选为60℃;所述调聚反应的时间为8~24h,优选为16h。
根据应用上述超交联氮杂环卡宾咪唑鎓盐配体由1,3-丁二烯的调聚反应生成1-取代的2,7-辛二烯的方法,所述方法还包括回收超交联卡宾钯催化剂的步骤,所述回收步骤包括:将超交联卡宾钯催化剂分离,并用甲醇清洗,烘干,继续用于下次反应;
优选地,所述分离方法为离心分离;
优选地,用甲醇清洗三次;
优选地,所述烘干温度为50~80℃,优选为60℃。
有益效果
1、本发明提供的超交联氮杂环卡宾咪唑鎓盐配体的制备方法,是一种新的合成思路与路线,通过Scholl反应利用不同氮杂环卡宾咪唑鎓盐单体与芳香化合物制备了一类新型超交联氮杂环卡宾咪唑鎓盐配体,合成方法具有制备方法简单、操作方便、原料廉价易得的优点。
2、本发明提供的超交联氮杂环卡宾咪唑鎓盐配体,可以在碱性环境下先生成卡宾,而后卡宾与钯催化剂直接形成C-Pd键,即原位生成非均相的超交联卡宾钯催化剂。本发明通过将氮杂环卡宾咪唑鎓盐与芳香化合物发生Scholl反应,两者芳香环脱氢连接获得超交联网络结构,赋予配体一定的物理形态,成功将均相Pd催化剂和均相卡宾配体转化为非均相,在保证具有均相催化剂催化效果的前提下,还便于贵金属催化剂的回收循环利用,并进一步提高了催化剂的稳定性。
3、本发明通过对于卡宾配体上取代基的空间位阻和电子效应的调控,实现在1,3-丁二烯调聚反应中,线性产物1-MOD的选择性达到93%以上,同时L/B达到49:1以上,达到高化学和区域选择性的催化效果。
附图说明
图1为实施例1制备得到的HCP-NHC-HCl-Ph的红外谱图;
图2为实施例1制备得到的HCP-NHC-HCl-Ph的固体核磁碳谱图;
图3为实施例1制备得到的HCP-NHC-HCl-Ph的SEM图。
具体实施方式
术语:
“芳香化合物”是指具有芳环结构的化合物,包括环上不含有杂原子的苯环化合物或环上含有一个或多个选自氮、氧和硫环杂原子的杂芳环化合物,芳环结构可以为单环、多环或稠环,实例如苯、取代苯、联苯、多苯代脂烃、多苯代磷、萘、菲、蒽、芘、三蝶烯、吡咯、呋喃、噻吩、四苯基卟啉联吡啶、邻菲罗啉等。
“C6-20芳基”是指具有6-20个环原子,且环上不含有杂原子的单环、多环(例如,双环或三环)或稠环的芳环结构的化合物去除芳环上的两个或多个氢形成的取代基,实例如由苯,C1-4烷基、羟基、甲氧基、氰基、羧基、氨基、氨C1-4烷基、苯基、三苯甲基、二苯膦基等取代基取代的苯,萘,菲,蒽,芘,三蝶烯等去除芳环上的两个或多个氢形成的取代基。
“C1-4烷基”是指具有1-4个碳原子的直链或支链烷基,包括甲基、乙基、正丙基、异丙基、丁基、异丁基、叔丁基,其中甲基较优。
“5-20元杂芳基”:具有5-20个环原子,且环上包括选自氮、氧和硫的1-4个环杂原子的单环或多环(例如,双环或三环)芳族环,实例如由吡咯,呋喃,噻吩,咪唑,吡唑,噁唑,异噁唑,噻唑,异噻唑,三唑,噁二唑,噻二唑,吡啶,哒嗪,嘧啶,吡嗪,吲哚,异吲哚,吲唑,苯并三唑,苯并噻吩,异苯并噻吩,苯并呋喃,苯并异呋喃,苯并咪唑,苯并噁唑,苯并异噁唑,苯并噻唑,苯并异噻唑,苯并噻二唑,吲哚嗪,嘌呤,咪唑并吡啶,咪唑并嘧啶,咪唑并吡嗪,咪唑并哒嗪,咪唑并三嗪,吡唑并吡啶,吡唑并嘧啶,吡唑并吡嗪,吡唑并吡嗪,吡唑并三嗪,吡咯并吡啶,吡咯并嘧啶,吡咯并哒嗪,吡咯并吡嗪和吡咯并三嗪、四苯卟啉联吡啶、邻菲罗啉去除芳环上的两个或多个氢形成的取代基。
“氨基C1-4烷基”是指被氨基取代的C1-4烷基,实例如氨甲基、氨乙基、氨丙基等,其中氨甲基较优。
“多元醇”是指分子中含有二个或二个以上羟基的醇类,包括乙二醇、丙二醇、丁二醇、戊二醇、己二醇、二缩二乙二醇、一缩二丙二醇、甘油、三羟基甲基丙烷等。
“芳香胺”是指具有一个或多个芳香性取代基的胺,包括苯胺、N-甲基苯胺、β-萘胺与联苯胺等。
“脂肪胺”是指碳链长度在C8-22范围内的一类有机胺化合物,包括甲胺、乙胺、甲乙胺、己胺、十二胺、十四胺、十六胺等。
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅用以解释本发明,并不用于限定本发明,即所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。
因此,以下对提供的本发明的实施例的详细描述并非旨在限制要求保护的本发明的范围,而是仅仅表示本发明的选定实施例。基于本发明的实施例,本领域技术人员在没有做出创造性劳动的前提下所获得的所有其他实施例,都属于本发明保护的范围。
下面结合实施例对本发明作进一步的详细描述。
实施例1超交联氮杂环卡宾咪唑鎓盐配体HCP-NHC-HCl-Ph的制备方法
包括以下步骤:
S1:在氮气保护下,100mL三口瓶中放入磁子,将2,6-二甲基苯胺(25mmol)和50mL甲醇加入三口瓶中,室温下加入乙二醛水溶液(12.5mmol)和催化量的甲酸(5mmol),室温反应11h,反应结束后过滤,用冷的甲醇洗涤3次得到二亚胺为亮黄色固体(1.85g)直接用于下步反应;
S2:将S1所得二亚胺(1.85g)溶于30mL乙酸乙酯中,然后加入多聚甲醛(7.0mmol)在70℃反应,然后滴入TMSCl(8.5mmol)的乙酸乙酯(5.0mL)溶液,搅拌反应约2h至完全反应后,将反应液冷却至-20℃,过滤,用冷的乙酸乙酯和乙醚分别洗涤3次,得到氮杂环卡宾鎓盐为黄色固体(1.5g);
1H NMR(400MHz,CDCl3)δ10.95(s,1H),7.68(d,J=1.3Hz,2H),7.36–7.29(m,2H),7.19(d,J=7.6Hz,4H),2.20(s,12H);
13C NMR(101MHz,CDCl3)δ139.43,134.52,133.10,131.12,129.28,124.49,17.76.
S3:往氮杂环卡宾咪唑鎓盐(2.0mmol)和苯(20mmol)的氯仿溶液中慢慢加入无水三氯化铝(160mmol),在0℃充分混合搅拌1h,然后50℃下搅拌2h,然后加热至80℃反应40h直至反应完全,得到的固体产物分别用甲醇、10%稀盐酸和去离子水洗涤3次,然后在索氏提取器中用甲醇洗涤24h,最后于60℃真空干燥得到超交联氮杂环卡宾咪唑鎓盐配体为深棕色固体粉末(HCP-NHC-HCl-Ph,2.7g)。
制备得到的HCP-NHC-HCl-Ph红外谱图如图1,在1600-1450cm-1和900-650cm-1范围内有强振动吸收峰,归结于苯环骨架振动和苯环C-H面外弯曲振动特征峰,说明该超交联骨架由芳香化合物构建;另外,在1650-1600cm-1范围内有-C=N-的伸缩振动峰,说明氮杂环咪唑鎓盐成功交联于聚合物中。
固体核磁碳谱图如图2,在135ppm处的峰是卡宾碳,123ppm处的峰是苯环上的碳,也证实了氮杂环咪唑鎓盐与苯环成功形成超交联网络。
HCP-NHC-HCl-Ph的SEM图如图3所示,出现明显的形状和大小不规则的团聚颗粒,为典型的无晶型块状形貌,也证明了超交联聚合物的成功制备。
实施例2基于超交联氮杂环卡宾咪唑鎓盐配体在1,3-丁二烯调聚反应中的应用
具体过程如下:将配有搅拌子的25mL Schlenk反应管在真空下加热干燥好后,准确称入20mg超交联氮杂环卡宾咪唑鎓盐配体,1mg Pd(OAc)2和20mg甲醇钠,然后加入2.5mL甲醇,封管后置于-50℃冷却液中,在Ar气双排管下抽置换气三次,每次5分钟,抽置换完毕后,在-50℃下,于Ar气流下加入2.5mL 1,3-丁二烯和2.5mL甲醇;加完后封管置于油浴中,在60℃下搅拌16h,反应结束后,用GC定量分析。
实施例3基于超交联氮杂环卡宾咪唑鎓盐配体在1,3-丁二烯调聚反应中的应用
具体过程如下:将配有搅拌子的25mL Schlenk反应管在真空下加热干燥好后,准确称入20mg超交联氮杂环卡宾咪唑鎓盐配体,2mg Pd(OAc)2和20mg甲醇钠,然后加入2.5mL甲醇,封管后置于-50℃冷却液中,在Ar气双排管下抽置换气三次,每次5分钟,抽置换完毕后,于Ar气流下加入2.5mL 1,3-丁二烯;加完后封管置于油浴中,在60℃下搅拌16h,反应结束后,用GC定量分析。
实施例4催化剂循环实验:
具体过程如下:将配有搅拌子的25mL Schlenk反应管在真空下加热干燥好后,准确称入20mg超交联氮杂环卡宾咪唑鎓盐配体,2mg Pd(OAc)2和20mg甲醇钠,然后加入2.5mL甲醇,封管后置于-50℃冷却液中,在Ar气双排管下抽置换气三次,每次5分钟,抽置换完毕后,于Ar气流下加入2.5mL 1,3-丁二烯;加完后封管置于油浴中,在60℃下搅拌16h,反应结束后,取上层液用GC定量分析。将所有反应液进行离心,用甲醇洗三次,60℃烘干后得到的催化剂继续用于下一次反应,反应完后继续取上层液用GC定量分析。按照此操作,循环三次,催化剂活性没有明显变化。
具体结果如下:
注:L/B为直链产物1-MOD与支链产物3-MOD的产率之比。
本发明所述超交联氮杂环卡宾咪唑鎓盐配体,将其作为配体与醋酸钯组成催化体系应用于1,3-丁二烯与甲醇的调聚反应,在反应时间为16h,催化量甲醇钠为添加剂,溶剂为甲醇的条件下,实现了线性产物1-MOD的选择性达到93%以上,L/B可达到49:1,且催化剂在循环使用三次后仍保持优秀的活性和选择性。
虽然结合实施例对本发明的具体实施方式进行了详细地描述,但不应理解为对本专利的保护范围的限定。在权利要求书所描述的范围内,本领域技术人员不经创造性劳动即可作出的各种修改和变形仍属本专利的保护范围。
Claims (10)
2.根据权利要求1所述的超交联氮杂环卡宾咪唑鎓盐配体,其特征在于,Ar选自取代或未取代的C6-14芳基、取代或未取代的含有1-3个选自N、O、S中的杂原子的5-10元杂芳基、取代或未取代的卟啉基,所述取代的是指含有1-3个选自C1-4烷基、羟基、甲氧基、氰基、羧基、氨基、氨基C1-4烷基、苯基、吡啶基、三苯甲基、二苯膦基的取代基;
优选地,Ar选自苯、联苯、萘、三苯基苯、四苯基甲烷、三苯基膦、苯甲醚、苯酚、苯甲腈、苯甲酸、苄胺、邻苯二胺、三蝶烯、芘、四苯基卟啉、、联吡啶、邻菲罗啉、吡咯、呋喃、噻吩去除芳环上的两个或多个氢形成的取代基中的一种或者多种。
4.根据权利要求3所述的超交联氮杂环卡宾咪唑鎓盐配体的制备方法,其特征在于,步骤S1中,
所述2,6-二取代的苯胺选自2,6-二甲基苯胺、2,6-二乙基苯胺、2,6-二丙基苯胺、2,6-二异丙基苯胺、2,6-二叔丁基苯胺;优选为2,6-二甲基苯胺;
优选地,所述反应中,2,6-二取代的苯胺与乙二醛的物质的量比为:1~3:1,优选为2:1;
优选地,所述反应在氮气保护下进行;所述反应在催化剂催化下进行,所述催化剂选自甲酸、醋酸,优选为甲酸;所述2,6-二取代的苯胺与催化剂的物质的量比为:3~7:1;优选为5:1;
优选地,所述醇选自甲醇、乙醇、丙醇、异丙醇,优选为甲醇;
优选地,所述反应温度为室温;反应时间为5~20h,优选为10~15h,更优选为11h;
优选地,所述反应结束后还包括纯化步骤,所述纯化步骤为:将反应产物过滤,用冷醇洗涤2-5次得到纯化的二亚胺中间体,优选洗涤3次。
5.根据权利要求3所述的超交联氮杂环卡宾咪唑鎓盐配体的制备方法,其特征在于,步骤S2中,
所述二亚胺中间体与多聚甲醛、TMSCl的物质的量比为:1~2:1~2:1~1.5;优选为1:1:1.2;
优选地,溶解二亚胺中间的有机溶剂选自乙酸乙酯、二甲亚砜、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、四氢呋喃;优选为乙酸乙酯;
优选地,所述TMSCl溶液的溶剂选自乙酸乙酯、二甲亚砜、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、四氢呋喃;优选为乙酸乙酯;
优选地,所述加入多聚甲醛和TMSCl溶液,在一定温度下反应中,所述反应的温度为60~80℃,优选为70℃;所述反应的时间为1-48h;优选为2h;
优选地,所述分离步骤包括:将冷却的反应液过滤,用冷的有机溶剂洗涤滤饼,得到氮杂环卡宾咪唑鎓盐固体;优选地,所述冷却温度为-20℃;所述有机溶剂可选自乙酸乙酯、乙醚、丙酮;优选地,所述洗涤步骤为使用冷的乙酸乙酯和乙醚分别洗涤滤饼。
6.根据权利要求3所述的超交联氮杂环卡宾咪唑鎓盐配体的制备方法,其特征在于,步骤S3中,
所述芳香化合物选自苯、联苯、萘、三苯基苯、四苯基甲烷、三苯基膦、苯甲醚、苯酚、苯甲腈、苯甲酸、苄胺、邻苯二胺、三蝶烯、芘、四苯基卟啉、联吡啶、邻菲罗啉、吡咯、呋喃、噻吩的一种或者多种,优选为苯;
优选地,氮杂环卡宾咪唑鎓盐、芳香化合物与无水三氯化铝的物质的量的比为:1~2:10~20:70~100;优选为1:10:80;
优选地,在0℃搅拌反应的时间为0.5~2h,优选为1h;
优选地,在40~60℃下搅拌反应的时间为0.5~4h,优选为2h;所述搅拌反应的优选温度为50℃;
优选地,在70~90℃反应的时间为20~80h,优选为40~50h;
优选地,所述分离步骤包括:将反应完全后得到的固体产物分别用甲醇、10%稀盐酸和去离子水洗涤,然后在索氏提取器中用甲醇洗涤后,真空干燥得到纯化的超交联氮杂环卡宾咪唑鎓盐配体;优选地,索氏提取器的时间为24~72h,更优选为48h。
7.权利要求1所述的超交联氮杂环卡宾咪唑鎓盐配体在1,3-丁二烯的调聚反应中的应用,其特征在于,所述调聚反应包括:1,3-丁二烯与亲核试剂反应生成1-取代的2,7-辛二烯(1-MOD)、1,3-丁二烯与CO2反应生成δ-环内脂;
优选地,所述亲核试剂选自水、甲醇、乙醇、丙醇、多元醇、苯酚、芳香胺、脂肪胺。
8.权利要求1所述的超交联氮杂环卡宾咪唑鎓盐配体由1,3-丁二烯的调聚反应生成1-取代的2,7-辛二烯的方法,其特征在于,所述方法包括以下步骤:
钯催化剂和超交联氮杂环卡宾咪唑鎓盐配体在碱性条件下原位生成非均相的超交联卡宾钯催化剂,在催化剂作用下,1,3-丁二烯与亲核试剂在预定温度下发生调聚反应,生成1-取代的-2,7-辛二烯。
9.根据权利要求8所述的超交联氮杂环卡宾咪唑鎓盐配体由1,3-丁二烯的调聚反应生成1-取代的2,7-辛二烯的方法,其特征在于,
所述亲核试剂选自水、甲醇、乙醇、丙醇、多元醇、苯酚、芳香胺、脂肪胺;所述调聚反应的反应溶剂选自甲醇、乙醇、丙醇、丁醇、多元醇、水;更优选地,所述调聚反应的亲核试剂和反应溶剂均为甲醇;
优选地,所述钯催化剂选自醋酸钯、乙酰丙酮钯、氯化钯;优选为醋酸钯;
优选地,所述超交联氮杂环卡宾咪唑鎓盐配体与钯催化剂的质量比:5~50:1:优选为10~20:1,更优选为10:1;
优选地,所述1,3-丁二烯与亲核试剂在-50℃下的体积比为:1:1~10,优选为1:2;
优选地,通过加入碱添加剂获得碱性环境,所述碱添加剂选自甲醇钠、甲醇钾、碳酸钠、碳酸钾、甲酸钠;优选为甲醇钠;
优选地,所述调聚反应的温度为50~80℃,优选为60℃;所述调聚反应的时间为8~24h,优选为16h。
10.根据权利要求9所述的超交联氮杂环卡宾咪唑鎓盐配体由1,3-丁二烯的调聚反应生成1-取代的2,7-辛二烯的方法,其特征在于,所述方法还包括回收超交联卡宾钯催化剂的步骤,所述回收步骤包括:将超交联卡宾钯催化剂分离,并用甲醇清洗,烘干,继续用于下次反应;
优选地,所述分离方法为离心分离;
优选地,用甲醇清洗三次;
优选地,所述烘干温度为50~80℃,优选为60℃。
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