CN117362162A - 一种羰基类化合物的制备方法 - Google Patents
一种羰基类化合物的制备方法 Download PDFInfo
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- CN117362162A CN117362162A CN202311108009.XA CN202311108009A CN117362162A CN 117362162 A CN117362162 A CN 117362162A CN 202311108009 A CN202311108009 A CN 202311108009A CN 117362162 A CN117362162 A CN 117362162A
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- Prior art keywords
- benzaldehyde
- formula
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- preparation
- acid
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- 238000002360 preparation method Methods 0.000 title claims abstract description 48
- 150000001728 carbonyl compounds Chemical class 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 104
- 239000002904 solvent Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 20
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 19
- 229930195733 hydrocarbon Chemical class 0.000 claims abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000001301 oxygen Substances 0.000 claims abstract description 17
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 17
- 239000004215 Carbon black (E152) Chemical class 0.000 claims abstract description 16
- 239000002253 acid Chemical class 0.000 claims abstract description 15
- 150000001298 alcohols Chemical class 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 66
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 41
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 38
- -1 4-chlorobenzophenone 4, 4-dicyanobenzophenone Chemical compound 0.000 claims description 21
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- 150000007513 acids Chemical class 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 8
- UOQXIWFBQSVDPP-UHFFFAOYSA-N 4-fluorobenzaldehyde Chemical compound FC1=CC=C(C=O)C=C1 UOQXIWFBQSVDPP-UHFFFAOYSA-N 0.000 claims description 7
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 7
- OPHQOIGEOHXOGX-UHFFFAOYSA-N 3,4,5-trimethoxybenzaldehyde Chemical compound COC1=CC(C=O)=CC(OC)=C1OC OPHQOIGEOHXOGX-UHFFFAOYSA-N 0.000 claims description 6
- GOUHYARYYWKXHS-UHFFFAOYSA-N 4-formylbenzoic acid Chemical compound OC(=O)C1=CC=C(C=O)C=C1 GOUHYARYYWKXHS-UHFFFAOYSA-N 0.000 claims description 6
- ISDBWOPVZKNQDW-UHFFFAOYSA-N 4-phenylbenzaldehyde Chemical compound C1=CC(C=O)=CC=C1C1=CC=CC=C1 ISDBWOPVZKNQDW-UHFFFAOYSA-N 0.000 claims description 6
- 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
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 6
- JARKCYVAAOWBJS-UHFFFAOYSA-N hexanal Chemical compound CCCCCC=O JARKCYVAAOWBJS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 5
- 239000012965 benzophenone Substances 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 125000003107 substituted aryl group Chemical group 0.000 claims description 5
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 4
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims description 4
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- QJXCFMJTJYCLFG-UHFFFAOYSA-N 2,3,4,5,6-pentafluorobenzaldehyde Chemical compound FC1=C(F)C(F)=C(C=O)C(F)=C1F QJXCFMJTJYCLFG-UHFFFAOYSA-N 0.000 claims description 3
- NDOPHXWIAZIXPR-UHFFFAOYSA-N 2-bromobenzaldehyde Chemical compound BrC1=CC=CC=C1C=O NDOPHXWIAZIXPR-UHFFFAOYSA-N 0.000 claims description 3
- YCTNWTBGSOCMRO-UHFFFAOYSA-N 3,5-dinitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC(C=O)=CC([N+]([O-])=O)=C1 YCTNWTBGSOCMRO-UHFFFAOYSA-N 0.000 claims description 3
- HGZJJKZPPMFIBU-UHFFFAOYSA-N 3-formylbenzonitrile Chemical compound O=CC1=CC=CC(C#N)=C1 HGZJJKZPPMFIBU-UHFFFAOYSA-N 0.000 claims description 3
- BEOBZEOPTQQELP-UHFFFAOYSA-N 4-(trifluoromethyl)benzaldehyde Chemical compound FC(F)(F)C1=CC=C(C=O)C=C1 BEOBZEOPTQQELP-UHFFFAOYSA-N 0.000 claims description 3
- ZRYZBQLXDKPBDU-UHFFFAOYSA-N 4-bromobenzaldehyde Chemical compound BrC1=CC=C(C=O)C=C1 ZRYZBQLXDKPBDU-UHFFFAOYSA-N 0.000 claims description 3
- AVPYQKSLYISFPO-UHFFFAOYSA-N 4-chlorobenzaldehyde Chemical compound ClC1=CC=C(C=O)C=C1 AVPYQKSLYISFPO-UHFFFAOYSA-N 0.000 claims description 3
- NIEBHDXUIJSHSL-UHFFFAOYSA-N 4-iodobenzaldehyde Chemical compound IC1=CC=C(C=O)C=C1 NIEBHDXUIJSHSL-UHFFFAOYSA-N 0.000 claims description 3
- BXRFQSNOROATLV-UHFFFAOYSA-N 4-nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=C(C=O)C=C1 BXRFQSNOROATLV-UHFFFAOYSA-N 0.000 claims description 3
- OTXINXDGSUFPNU-UHFFFAOYSA-N 4-tert-butylbenzaldehyde Chemical compound CC(C)(C)C1=CC=C(C=O)C=C1 OTXINXDGSUFPNU-UHFFFAOYSA-N 0.000 claims description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
- IIRFCWANHMSDCG-UHFFFAOYSA-N cyclooctanone Chemical compound O=C1CCCCCCC1 IIRFCWANHMSDCG-UHFFFAOYSA-N 0.000 claims description 3
- OHUWRYQKKWKGKG-UHFFFAOYSA-N formaldehyde;pyrene Chemical compound O=C.C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 OHUWRYQKKWKGKG-UHFFFAOYSA-N 0.000 claims description 3
- 150000004002 naphthaldehydes Chemical class 0.000 claims description 3
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 2
- 125000001072 heteroaryl group Chemical group 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- 229940071870 hydroiodic acid Drugs 0.000 claims description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 abstract description 2
- 150000003624 transition metals Chemical class 0.000 abstract description 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 150
- 235000019445 benzyl alcohol Nutrition 0.000 description 50
- 239000000047 product Substances 0.000 description 42
- 239000000758 substrate Substances 0.000 description 40
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 38
- 150000001299 aldehydes Chemical class 0.000 description 15
- 230000000694 effects Effects 0.000 description 14
- NGDMLQSGYUCLDC-UHFFFAOYSA-N pyren-1-ylmethanol Chemical compound C1=C2C(CO)=CC=C(C=C3)C2=C2C3=CC=CC2=C1 NGDMLQSGYUCLDC-UHFFFAOYSA-N 0.000 description 9
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- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 8
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Abstract
本申请公开了一种羰基类化合物的制备方法,所述制备方法包括:在含氧气氛下,将含有醇类或碳氢化合物、酸性化合物、溶剂的混合物,采用光照射,反应,得到所述羰基类化合物。该方法具有收率高,原子经济性高、绿色环保、无过渡金属参与,反应条件温和,后处理简单便捷等优点。
Description
技术领域
本申请涉及一种羰基类化合物的制备方法,属于有机合成技术领域。
背景技术
醛/酮类化合物,特别是醛类,在香精、药物合成,天然产物合成以及新材料制备等领域有广泛的应用。通过光驱动活化C-H键绿色温和的合成醛/酮类化合物更是备受青睐。
全球苯甲醛市场规模增长趋势。我国对苯甲醛的需求量比较大,年消费以7%的速率增长,特别是对高品质的无氯苯甲醛的需求量大为增加,占总需求量的47%。
传统苯甲醛类化合物生产路线是将甲苯侧链氯化后水解或甲苯液相氧化法生产,反应步骤多、条件苛刻、原子利用率低、附加试剂及副产物多,不符合可持续绿色化学工业发展的需求。近年来,光催化氧化甲苯等碳氢化合物或醇类制备醛/酮开辟了一条绿色可持续的路线,已引起研究者的高度关注。2014年报道负载钌Ru的TiO2光催化选择性氧化甲苯,展现出较高的苯甲醛选择性达到89%(Angew Chem,2014,126:12813-12816),但需要使用贵金属钌。Cao等通过光致变色复合光催化剂Bi2WO6-x/BiOCl选择性氧化甲苯,甲苯的转化率接近100%,但苯甲醛的选择性仅为30%(Nat Catal,2018,1:704-710)。2022年报道了利用碱金属改性氮化碳光催化剂选择性氧化4-甲基联苯制备4-甲醛联苯的方法(CN115353446A)。因此,发展光催化直接活化C-H键同时高选择性和高转化率的制备醛类化合物的新方法,依然是该领域的研究热点。
发明内容
本发明的目的在于为了解决以上现有技术的缺点和不足之处,提供了一种利用光(可见光)作为反应的驱动力,通过原位生成高活性的自由基中间体实现C-H键的直接活化,以氧气为氧化剂,高活性、高选择性的合成醛/酮类化合物的方法。
根据本申请的一个方面,提供了一种羰基类化合物的制备方法,所述制备方法包括:
在含氧气氛下,将含有醇类或碳氢化合物、酸性化合物、溶剂的混合物,采用光照射,反应,得到所述羰基类化合物;
其中,所述醇类或碳氢化合物、酸性化合物、溶剂和含氧气氛自发形成反应催化剂;
所述醇类或碳氢化合物选自式I-1、式I-2、式I-3中的一种;
所述羰基类化合物选自式II-1、式II-2、式II-3中的一种;
式I-1、式II-1中,R1、R2独立地选自氢、卤素、硝基、氰基、三氟甲基、C1~C10的烷基、C1~C10的取代烷基、C6~C10的芳基、C4~C10的杂芳基中的一种;
式I-2、式II-2中,R3、R4独立地选自氢、C1~C10的烷基、C1~C10的取代烷基中的一种;
其中,所述取代烷基的取代基选自C6~C10的芳基中的一种;
式I-3、式II-3中,R5独立地选自C1~C10的烷基、C6~C10的芳基、C6~C10的取代芳基中的一种;
其中,所述取代芳基中的取代基选自卤素、硝基、氰基中的一种。
可选地,所述羰基类化合物选自苯甲醛、4-氟-苯甲醛、2-溴-苯甲醛、4-碘-苯甲醛、4-硝基-苯甲醛、4-三氟甲基-苯甲醛、3-氰基-苯甲醛、4-氰基-苯甲醛、4-羧基-苯甲醛、4-羧酸甲酯-苯甲醛、4-叔丁基-苯甲醛、4-苯基-苯甲醛、3,5-二硝基-苯甲醛、3,4,5-三甲氧基-苯甲醛、五氟-苯甲醛、萘甲醛、芘甲醛、呋喃甲醛、苯并呋喃2-甲醛、苯并噻唑2-甲醛、对二苯甲醛、二苯甲酮、4-氯二苯甲酮、4,4-二氰基二苯甲酮、2,2-二苯二酮、苯乙酮、环己酮、环辛酮、对甲基苯甲醛、对氟苯甲醛、对氯苯甲醛、对溴苯甲醛、正己醛或2a、2b、2c、2d、2e、2f、2g、2h、2i、2j、2k、2l、2m、2n、2o、2p、2q、2r、2s、2t、2u、2v、2w、2x、2y、2z、2aa、2ab、2ac、2ad、2ae、2af、2ag、2ah、2ai、2aj、2ak、2al、2am、2an、2ao、2ap、2aq、2ar、2as所示结构中的一种;
可选地,所述酸性化合物、醇类或碳氢化合物、溶剂的摩尔比为1:(1~10):(1~10000)。
可选地,所述酸性化合物、醇类或碳氢化合物、溶剂的摩尔比选自1:(1~10):(1~10000)、1:(2~10):(200~10000)、1:(3~10):(500~10000)、1:(4~10):(1000~10000)、1:(5~10):(5000~10000)、1:(6~10):(6000~10000)、1:(7~10):(7000~10000)、1:(4~7):(5000~7000)中的任意值或上述任意两者之间的范围值。
可选地,所述酸性化合物、醇类或碳氢化合物、溶剂的摩尔比为1:(4~7):(5000~7000)。
可选地,所述酸性化合物选自盐酸、硫酸、氢溴酸、磷酸、醋酸、氢碘酸中的至少一种。
可选地,所述溶剂选自环己烷、二氯甲烷、乙酸乙酯、丙酮、乙腈、四氢呋喃、水、甲苯、苯甲醚、1,4-二氧六环、二丁醚、二苯醚中的至少一种。
可选地,所述含氧气氛中氧气的体积分数为20~100%。
可选地,所述含氧气氛中氧气的体积分数选自20%、30%、50%、70%、90%、100%中的任意值或上述任意两者之间的范围值。
可选地,所述反应的温度为20~50℃。
可选地,所述反应的温度选自20℃、25℃、30℃、35℃、40℃、50℃中的任意值或上述任意两者之间的范围值。
可选地,所述反应的时间为0.15~8h。
可选地,所述反应的时间选自0.15h、1h、2h、3h、5h、7h、8h中的任意值或上述任意两者之间的范围值。
本申请通过下述技术方案实现:
一种光催化制备醛/酮类化合物的方法,包括以下步骤:
(1)将酸、溶剂、氧气和反应物混合,在搅拌下形成一种复合物,即反应催化剂。此复合物形成的条件是酸、溶剂和反应物之间存在氢键或者静电引力等分子间相互作用,这是也是提高反应产物选择性的关键。
(2)在光驱动下有氧环境下进行反应,通过薄层色谱法跟踪检测反应;
(3)待反应完成以后,经过用有机溶剂旋蒸,除去有机溶剂后分离得到目标产物。
一种光驱动选择性的氧化醇类化合物或者二甲苯等碳氢化合物制备醛/酮的方法。将酸、溶剂、氧气和反应物混合,在搅拌下自发形成一种复合物,即反应催化剂。在光(可见光)驱动下,该复合物可以将二甲苯等碳氢化合物或者醇类化合物选择性的氧化到醛/酮。
在本申请中,通过光驱动原位形成的复合物产生溴自由基和超氧自由基负离子,溴自由基夺取C-H键的氢原子形成碳中心的自由基,然后超氧自由基负离子与碳中心的自由基结合形成过氧化物中间件,最后再脱除一份子水形成目标产物醛/酮。该方法具有收率高,原子经济性高、绿色环保、无过渡金属参与,反应条件温和,后处理简单便捷等优点。
在本申请中,C1~C10、C6~C10等均是指基团中所包含的碳原子数。
在本申请中,术语“烷基”是指由烷烃化合物分子上失去任意一个氢原子所形成的基团。
在本申请中,术语“芳基”是指由芳香族化合物分子上失去芳环上的一个氢原子所形成的基团;例如甲苯失去苯环上甲基对位的氢原子所形成的对甲苯基。
在本申请中,“取代烷基”、“取代芳基”等,分别指任意基团取代的烷基、任意基团取代的芳香基。
本申请能产生的有益效果包括:
1)本申请所提供的合成方法避免了化学计量的氧化剂或者贵重金属的使用,在光驱动下,仅在室温条件下就能实现醇或者碳氢化合物的氧气制备目标产物醛/酮,此方法简单易行,条件温和,操作安全。
2)本申请所提供的方法,具有绿色环保、原子经济性高、后处理简单便捷以及适合可规模生产的优点,能够使得合成醛/酮类化合物的更为绿色,降低合成成本。
附图说明
图1为本申请筛选例1和2中苯甲醇在不同种类酸、酸的用量的筛选(a图为在乙酸乙酯(EA)中不同卤素酸反应性能;b图为反应性能与EA中HBr浓度的关系)。
图2为本申请筛选例3和4中苯甲醇在不同种类溶剂的筛选(a图为在各种溶剂中的反应性能;b图为不同酯溶剂中的反应性能(EA:乙酸乙酯,MP:丙酸甲酯;EP:丙酸乙酯))。
图3为本申请中1-芘基甲醇的丁达尔(Tyndall)效应实验和复合物的可能的结构示意图(a图为Tyndall效应实验;b图为微乳粒子和自组装复合物的结构示意图(PM:1-芘基甲醇;EA:乙酸乙酯))。
具体实施方式
下面结合实施例详述本申请,但本申请并不局限于这些实施例。
如无特别说明,本申请的实施例中的原料均通过商业途径购买。
在本申请实施例中,采用美国瓦里安公司的VarianI NOVA 400MHz型核磁共振仪对产物进行定性分析。
本申请中的目标产物的收率采用以下方法计算得到:
目标产物的收率=实际得到的目标产物质量/理论得到目标产物的质量×100%。
筛选例1:不同种类的氢卤酸对羰基类化合物的影响
如图1中a所示,选用苯甲醇1a作为模板底物,首先对不同种类的氢卤酸进行考察(图1a)。通过实验研究发现,在20mol%盐酸(HCl)存在的情况下,光氧化苯甲醇(BA)产生的苯甲醛(BAL)量可以忽略不计;有趣的是,当使用HBr或HI时,对BAL的选择性超过97%,并且在20mol%HBr存在的情况下,BA的转化率达到93%远高于使用20mol%HI获得的18%转化率在EA溶剂中。这些实验结果表明,BA的光氧化活性取决于所采用的卤素酸,而HBr在三种实验的氢卤酸中呈现出最优的反应性能。
筛选例2:氢溴酸的用量对羰基类化合物的影响
如图1中b所示,筛选HBr的量对苯甲醇反应性能的影响,随着HBr的浓度从20mol%到5mol%的降低,BA的转化率从93%下降到42%,而对BAL的选择性从97%提高到99%。当HBr的浓度从20mol%增加到40mol%时,BA的转化率仍然保持很高(约95%),但对BAL的选择性却下降到36%(图1b)。这些结果表明,反应性能也受到HBr浓度的影响。
筛选例3:不同种类的溶剂对羰基类化合物的影响
如图2中a所示,筛选溶剂对该光氧化醇反应的影响,通过采用CH3CN、EA、CH3COCH3、CH2Cl2和H2O作为溶剂。图2a显示,当使用乙酸乙酯(EA)作为溶剂时,可以获得高转化率(93%)和选择性(97%)。以CH3CN为溶剂,苯甲醇(BA)的转化率下降到26%,但对苯甲醛(BAL)的选择性却保持高达98%。在其他相同的条件下,用CH3COCH3、CH2Cl2和H2O作为溶剂时,BA的光氧化过程基本不能发生。该实验结果表明:溶剂对光氧化醇反应过程具有很大的影响。
筛选例4:不同种类的酯溶剂对羰基类化合物的影响
如图2中b所示,从筛选例3中可知,乙酸乙酯溶剂是对光氧化醇反应过程有利,并对其他类似的酯溶剂进行了筛选。图2b显示,当使用丙酸甲酯(MP)和丙酸乙酯(EP)作为溶剂时,BA的转化率为93%-99%,对BAL具有高选择性(92%-97%),这表明低碳酯类溶剂对BA的光氧化反应性能是有利的。
实施例1制备苯甲醛
在一个带有橡胶塞子和磁性搅拌棒的透明石英瓶中,将反应底物苯甲醇(0.2mmol)、20mol%的氢溴酸加入到12mL反应溶剂中,在光照射下,反应混合液在环境温度下氧气氛围中搅拌。在反应过程中,通过GC或TLC监测反应进度。在室温下反应0.15h完成后,抽真空或萃取除去溶剂,残余物经石油醚/乙醇在柱层析上的柱纯化,得到所需产品苯甲醛。目标产物的收率,90%。
实施例2制备苯甲醛
同实施例1中的反应条件,只改变反应溶剂,将反应溶剂更换为乙腈,目标产物的收率,25%。
实施例3制备苯甲醛
同实施例1中的反应条件,只改变反应溶剂,将反应溶剂更换为二氯甲烷,目标产物的收率:0%。
实施例4制备4-氟-苯甲醛
同实施例1中的反应条件,将反应底物苯甲醇替换为4-氟-苯甲醇,目标产物的收率:92%。
实施例5制备2-溴-苯甲醛
同实施例1中的反应条件,将反应底物苯甲醇替换为2-溴-苯甲醇,目标产物的收率:86%。
实施例6制备4-碘-苯甲醛
同实施例1中的反应条件,将反应底物苯甲醇替换为4-碘-苯甲醇,目标产物的收率:90%。
实施例7制备4-硝基-苯甲醛
同实施例1中的反应条件,将反应底物苯甲醇替换为4-硝基-苯甲醇,目标产物的收率:90%。
实施例8制备4-三氟甲基-苯甲醛
同实施例1中的反应条件,将反应底物苯甲醇替换为4-三氟甲基-苯甲醇,目标产物的收率:92%。
实施例9制备3-氰基-苯甲醛
同实施例1中的反应条件,将反应底物苯甲醇替换为3-氰基-苯甲醇,目标产物的收率:88%。
实施例10制备4-氰基-苯甲醛
同实施例1中的反应条件,将反应底物苯甲醇替换为4-氰基-苯甲醇,目标产物的收率:93%。
实施例11制备4-羧基-苯甲醛
同实施例1中的反应条件,将反应底物苯甲醇替换为4-羧基-苯甲醇,目标产物的收率:87%。
实施例12制备4-羧酸甲酯-苯甲醛
同实施例1中的反应条件,将反应底物苯甲醇替换为4-羧酸甲酯-苯甲醇,目标产物的收率:87%。
实施例13制备4-叔丁基-苯甲醛
同实施例1中的反应条件,将反应底物苯甲醇替换为4-叔丁基-苯甲醇,目标产物的收率:81%。
实施例14制备4-苯基-苯甲醛
同实施例1中的反应条件,将反应底物苯甲醇替换为4-苯基-苯甲醇,目标产物的收率:81%。
实施例15制备3,5-二硝基-苯甲醛
同实施例1中的反应条件,将反应底物苯甲醇替换为3,5-二硝基-苯甲醇,目标产物的收率:73%。
实施例16制备3,4,5-三甲氧基-苯甲醛
同实施例1中的反应条件,将反应底物苯甲醇替换为3,4,5-三甲氧基-苯甲醇,目标产物的收率:63%。
实施例17制备五氟-苯甲醛
同实施例1中的反应条件,将反应底物苯甲醇替换为五氟-苯甲醇,目标产物的收率:76%。
实施例18制备萘甲醛
同实施例1中的反应条件,将反应底物苯甲醇替换为萘甲醇,目标产物的收率:86%。
实施例19制备芘甲醛
同实施例1中的反应条件,将反应底物苯甲醇替换为芘甲醇,目标产物的收率:82%。
实施例20制备呋喃甲醛
同实施例1中的反应条件,将反应底物苯甲醇替换为呋喃甲醇,目标产物的收率:56%。
实施例21制备苯并呋喃2-甲醛
同实施例1中的反应条件,将反应底物苯甲醇替换为苯并呋喃2-甲醇,目标产物的收率:82%。
实施例22制备苯并噻唑2-甲醛
同实施例1中的反应条件,将反应底物苯甲醇替换为苯并噻唑2-甲醇,目标产物的收率:77%。
实施例23制备苯并噻唑2-甲醛
同实施例1中的反应条件,将反应底物苯甲醇替换为苯并噻唑2-甲醇,目标产物的收率:77%。
实施例24制备对二苯甲醛
同实施例1中的反应条件,将反应底物苯甲醇替换为对二苯甲醇,目标产物的收率:72%。
实施例25制备均三苯甲醛
同实施例1中的反应条件,将反应底物苯甲醇替换为均三苯甲醇,目标产物的收率:62%。
实施例26制备二苯甲酮
同实施例1中的反应条件,将反应底物苯甲醇替换为二苯甲醇,目标产物的收率:96%。
实施例27制备4-氯二苯甲酮
同实施例1中的反应条件,将反应底物苯甲醇替换为4-氯二苯甲醇,目标产物的收率:95%。
实施例28制备4,4-二氰基二苯甲酮
同实施例1中的反应条件,将反应底物苯甲醇替换为4,4-二氰基二苯甲醇,目标产物的收率:95%。
实施例29制备2,2-二苯二酮
同实施例1中的反应条件,将反应底物苯甲醇替换为2,2-二苯二醇,目标产物的收率:93%。
实施例30制备苯乙酮
同实施例1中的反应条件,将反应底物苯甲醇替换为苯乙醇,目标产物的收率:65%。
实施例31制备环己酮
同实施例1中的反应条件,将反应底物苯甲醇替换为环己醇,目标产物的收率:51%。
实施例31制备环辛酮
同实施例1中的反应条件,将反应底物苯甲醇替换为环辛醇,目标产物的收率:56%。
实施例32制备苯甲醛
在一个带有橡胶塞子和磁性搅拌棒的透明石英瓶中,将反应底物甲苯(10mmol)、0.25mol%的氢溴酸加入到12mL反应溶剂中,在光照射下,反应混合液在环境温度下氧气氛围中搅拌。在反应过程中,通过GC或TLC监测反应进度。在环境温度下反应1h完,通过GC分析反应液,计算目标产物的量。苯甲醛的量为349800μmol·gHBr -1,选择性为95%。
实施例33制备对甲基苯甲醛
同实施例32,将反应底物甲苯替换为对二甲苯,对甲基苯甲醛的量为327600μmol·gHBr -1,选择性为92%。
实施例34制备对氟苯甲醛
同实施例32,将反应底物甲苯替换为对氟甲苯,对氟苯甲醛的量为318200μmol·gHBr -1,选择性为94%。
实施例35制备对氯苯甲醛
同实施例32,将反应底物甲苯替换为对氯甲苯,对氯苯甲醛的量为341300μmol·gHBr -1,选择性为94%。
实施例36制备对溴苯甲醛
同实施例32,将反应底物甲苯替换为对溴甲苯,对溴苯甲醛的量为320800μmol·gHBr -1,选择性为93%。
实施例37制备正己醛
同实施例32,将反应底物甲苯替换为正己烷,正己醛的量为112400μmol·gHBr -1,选择性为81%。
以醇类化合物为反应物时,反应方程式如下:
光诱导选择性氧化醇至醛/酮反应底物的拓展结构式如下:
以碳氢化合物为反应物时,反应方程式如下:
光诱导选择性氧化碳氢化合物生成醛的反应底物拓展结构式如下:
光诱导选择性氧化碳氢化合物生成醛的反应底物扩展如下表1:
表1
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对光驱动选择性制备羰基类化合物的丁达尔现象进行实验:
如图3中a所示,当BA溶解在EA的溶液,没有观察到Tyndall现象,而当HBr被添加到BA的EA溶液中时,可以观察到Tyndall效应,但该现象并不明显,这可能是由于BA分子的尺寸太小。因此,具有较大分子尺寸的1-芘基甲醇(PM)被用于Tyndall效应实验。同样地,PM的EA溶液也没有丁达尔效应。令人惊讶的是,当HBr被添加到PM的EA溶液中时,出现了明显的Tyndall现象(图3a)。另外,在同时含有PM和HBr的CH2Cl2溶液中没有观察到Tyndall现象,但在CH2Cl2溶液中加入EA,Tyndall现象出现了,这证实了溶剂EA在分子聚集自组装形成微乳复合物中的独特作用。Tyndall实验的结果表明,微乳是由反应体系中的分子之间的自发聚集形成的。
图3中b所示,经推测,反应系统中形成的微乳是可能由复合物通过再离子分子间的非共价作用自组装聚集而成的。物种[EA…(BAH)+Br-]是通过HBr对BA的质子化形成的,氢键的相互作用引起了BA、HBr和EA分子的预组织。因此,该复合系统被认为可能是光诱导有氧氧化醇的高选择性和高活性的来源。
以上所述,仅是本申请的几个实施例,并非对本申请做任何形式的限制,虽然本申请以较佳实施例揭示如上,然而并非用以限制本申请,任何熟悉本专业的技术人员,在不脱离本申请技术方案的范围内,利用上述揭示的技术内容做出些许的变动或修饰均等同于等效实施案例,均属于技术方案范围内。
Claims (9)
1.一种羰基类化合物的制备方法,其特征在于,所述制备方法包括:
在含氧气氛下,将含有醇类或碳氢化合物、酸性化合物、溶剂的混合物,采用光照射,反应,得到所述羰基类化合物;
其中,所述醇类或碳氢化合物、酸性化合物、溶剂和含氧气氛自发形成反应催化剂;
所述醇类或碳氢化合物选自式I-1、式I-2、式I-3中的一种;
所述羰基类化合物选自式II-1、式II-2、式II-3中的一种;
式I-1、式II-1中,R1、R2独立地选自氢、卤素、硝基、氰基、三氟甲基、C1~C10的烷基、C1~C10的取代烷基、C6~C10的芳基、C4~C10的杂芳基中的一种;
式I-2、式II-2中,R3、R4独立地选自氢、C1~C10的烷基、C1~C10的取代烷基中的一种;
其中,所述取代烷基的取代基选自C6~C10的芳基中的一种;
式I-3、式II-3中,R5独立地选自C1~C10的烷基、C6~C10的芳基、C6~C10的取代芳基中的一种;
其中,所述取代芳基中的取代基选自卤素、硝基、氰基中的一种。
2.根据权利要求1所述的制备方法,其特征在于,所述羰基类化合物选自苯甲醛、4-氟-苯甲醛、2-溴-苯甲醛、4-碘-苯甲醛、4-硝基-苯甲醛、4-三氟甲基-苯甲醛、3-氰基-苯甲醛、4-氰基-苯甲醛、4-羧基-苯甲醛、4-羧酸甲酯-苯甲醛、4-叔丁基-苯甲醛、4-苯基-苯甲醛、3,5-二硝基-苯甲醛、3,4,5-三甲氧基-苯甲醛、五氟-苯甲醛、萘甲醛、芘甲醛、呋喃甲醛、苯并呋喃2-甲醛、苯并噻唑2-甲醛、对二苯甲醛、二苯甲酮、4-氯二苯甲酮、4,4-二氰基二苯甲酮、2,2-二苯二酮、苯乙酮、环己酮、环辛酮、对甲基苯甲醛、对氟苯甲醛、对氯苯甲醛、对溴苯甲醛、正己醛或2a、2b、2c、2d、2e、2f、2g、2h、2i、2j、2k、2l、2m、2n、2o、2p、2q、2r、2s、2t、2u、2v、2w、2x、2y、2z、2aa、2ab、2ac、2ad、2ae、2af、2ag、2ah、2ai、2aj、2ak、2al、2am、2an、2ao、2ap、2aq、2ar、2as所示结构中的一种;
3.根据权利要求1所述的制备方法,其特征在于,所述酸性化合物、醇类或碳氢化合物、溶剂的摩尔比为1:(1~10):(1~10000)。
4.根据权利要求1所述的制备方法,其特征在于,所述酸性化合物、醇类或碳氢化合物、溶剂的摩尔比为1:(4~7):(5000~7000)。
5.根据权利要求1所述的制备方法,其特征在于,所述酸性化合物选自盐酸、硫酸、氢溴酸、磷酸、醋酸、氢碘酸中的至少一种。
6.根据权利要求1所述的制备方法,其特征在于,所述溶剂选自环己烷、二氯甲烷、乙酸乙酯、丙酮、乙腈、四氢呋喃、水、甲苯、苯甲醚、1,4-二氧六环、二丁醚、二苯醚中的至少一种。
7.根据权利要求1所述的制备方法,其特征在于,所述含氧气氛中氧气的体积分数为20~100%。
8.根据权利要求1所述的制备方法,其特征在于,所述反应的温度为20~50℃。
9.根据权利要求1所述的制备方法,其特征在于,所述反应的时间为0.15~8h。
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