CN110483585A - 一种可调节的高效选择性催化还原硝基苯甲醛的金属有机笼状化合物的制备方法及其应用 - Google Patents
一种可调节的高效选择性催化还原硝基苯甲醛的金属有机笼状化合物的制备方法及其应用 Download PDFInfo
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- CN110483585A CN110483585A CN201910682424.3A CN201910682424A CN110483585A CN 110483585 A CN110483585 A CN 110483585A CN 201910682424 A CN201910682424 A CN 201910682424A CN 110483585 A CN110483585 A CN 110483585A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
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- 238000010531 catalytic reduction reaction Methods 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 239000003446 ligand Substances 0.000 claims abstract description 18
- BXRFQSNOROATLV-UHFFFAOYSA-N 4-nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=C(C=O)C=C1 BXRFQSNOROATLV-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 13
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- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 claims abstract description 7
- DERZBLKQOCDDDZ-JLHYYAGUSA-N cinnarizine Chemical compound C1CN(C(C=2C=CC=CC=2)C=2C=CC=CC=2)CCN1C\C=C\C1=CC=CC=C1 DERZBLKQOCDDDZ-JLHYYAGUSA-N 0.000 claims abstract description 6
- 229960000876 cinnarizine Drugs 0.000 claims abstract description 6
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 claims abstract description 5
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 claims abstract description 5
- 229930016911 cinnamic acid Natural products 0.000 claims abstract description 5
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- 238000001308 synthesis method Methods 0.000 claims abstract description 4
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- CSDSSGBPEUDDEE-UHFFFAOYSA-N 2-formylpyridine Chemical compound O=CC1=CC=CC=N1 CSDSSGBPEUDDEE-UHFFFAOYSA-N 0.000 claims description 3
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- IMAKHNTVDGLIRY-UHFFFAOYSA-N methyl prop-2-ynoate Chemical class COC(=O)C#C IMAKHNTVDGLIRY-UHFFFAOYSA-N 0.000 claims description 3
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
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- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 8
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
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- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
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- 229910052700 potassium Inorganic materials 0.000 description 2
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- HYHCSLBZRBJJCH-UHFFFAOYSA-N sodium polysulfide Chemical compound [Na+].S HYHCSLBZRBJJCH-UHFFFAOYSA-N 0.000 description 2
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- IEDVJHCEMCRBQM-UHFFFAOYSA-N trimethoprim Chemical compound COC1=C(OC)C(OC)=CC(CC=2C(=NC(N)=NC=2)N)=C1 IEDVJHCEMCRBQM-UHFFFAOYSA-N 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
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- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- BAWFJGJZGIEFAR-NNYOXOHSSA-N NAD zwitterion Chemical group NC(=O)C1=CC=C[N+]([C@H]2[C@@H]([C@H](O)[C@@H](COP([O-])(=O)OP(O)(=O)OC[C@@H]3[C@H]([C@@H](O)[C@@H](O3)N3C4=NC=NC(N)=C4N=C3)O)O2)O)=C1 BAWFJGJZGIEFAR-NNYOXOHSSA-N 0.000 description 1
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- WKDDRNSBRWANNC-UHFFFAOYSA-N Thienamycin Natural products C1C(SCCN)=C(C(O)=O)N2C(=O)C(C(O)C)C21 WKDDRNSBRWANNC-UHFFFAOYSA-N 0.000 description 1
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- 239000011668 ascorbic acid Substances 0.000 description 1
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- YZBQHRLRFGPBSL-RXMQYKEDSA-N carbapenem Chemical compound C1C=CN2C(=O)C[C@H]21 YZBQHRLRFGPBSL-RXMQYKEDSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 description 1
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- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
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- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- SMANXXCATUTDDT-QPJJXVBHSA-N flunarizine Chemical compound C1=CC(F)=CC=C1C(C=1C=CC(F)=CC=1)N1CCN(C\C=C\C=2C=CC=CC=2)CC1 SMANXXCATUTDDT-QPJJXVBHSA-N 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- OZGNYLLQHRPOBR-DHZHZOJOSA-N naftifine Chemical compound C=1C=CC2=CC=CC=C2C=1CN(C)C\C=C\C1=CC=CC=C1 OZGNYLLQHRPOBR-DHZHZOJOSA-N 0.000 description 1
- 229960004313 naftifine Drugs 0.000 description 1
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 1
- 229950011346 panipenem Drugs 0.000 description 1
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- 238000004064 recycling Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C221/00—Preparation of compounds containing amino groups and doubly-bound oxygen atoms bound to the same carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/023—Preparation; Separation; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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Abstract
本发明属于精细化工技术领域,一种可调节的高效选择性催化还原硝基苯甲醛的金属有机笼状化合物的制备方法及其应用,其中制备法是以过渡金属盐中的M2+作为节点,以L作为配体反应制得金属有机笼状化合物,其合成路线如下:M2++L→M‑L;所述配体L选自H2FPB;所述过渡金属盐选自高氯酸亚铁、四氟硼酸钴、高氯酸镍或四氟硼酸锌中的一种;采用该方法制备金属有机笼状化合物原料价格低廉,产率高,得到的化合物化学性质稳定,易于投入实际应用中。作为目标化合物M‑FPB,在还原对硝基苯甲醛制对硝基苯甲醇,还原催化肉桂醛一步法合成桂利嗪及还原对硝基苯甲醛制对氨基苯甲醛方面中的应用,选择性可达99%。
Description
技术领域
本发明涉及一种可调节的高效选择性催化还原硝基苯甲醛的金属有机笼状化合物的制备方法及其应用,属于精细化工技术领域。
背景技术
精细化学品如药物分子、食用香料以及调味剂等因其合成的复杂性和困难度,往往具有更高的附加值。而这类化合物的具有多种官能团,需要在合成过程中高选择性的催化化合物官能团的转化。例如,对硝基苯甲醇是一种重要的医药合成中间体,其可以用于合成亚胺培南,帕尼培南等碳青霉素烯类抗生素,需要选择性通过还原硝基苯甲醛的羰基获得;α,β-不饱和醇是香料和制药工业的重要中间体,其可以用于合成氟桂利嗪、桂利嗪以及萘替芬等,其需要通过选择性的氢化α,β-不饱和醛的碳氧双键基团来生产它们。氨基苯甲醛在医药工业中用于合成磺胺类抗菌增效剂甲氧苄胺嘧啶(TMP),也用作大茴香醛、香兰素等香料的中间体以及用作农药对氯苯甲醛的合成原料。
在工业反应中选择性的还原羰基,以制备肉桂醇为例,以乙醇或甲醇作为溶剂,在碱性介质(pH=12-14)中加入硼氢化钾,完全溶解后,在12~30℃以下滴加肉桂醛,肉桂醛滴加完毕后继续反应至反应完全,加丙酮分解过量的硼氢化钾,用盐酸或稀硫酸调PH值到7,升温常压回收乙醇或甲醇,完毕降温到40~50℃静置分层,分掉下层废水得肉桂醇粗品,将肉桂醇粗品减压蒸馏得肉桂醇成品。此方法工艺简单,生产成本低,无污染,产品质量稳定可靠,生产肉桂醇的收率可高达90%。但是需要使用大量的硼氢类还原剂存在危险,又需要加入过量的丙酮中和,存在大量的浪费。同时,工业上合成对氨基苯甲醛以对硝基苯甲醛为原料,用多硫化钠或硫酸亚铁等还原剂还原而得,工艺简单,生产成本低,但会产生大量的废水,需要大量还原剂投入。第二种方法是对硝基甲苯经氧化,还原而得,将硫化钠及氢氧化钠溶于水,过滤,滤液加热至68℃加入硫黄粉,于98℃反应18min得到多硫化钠溶液。加入65%乙醇及对硝基甲苯,于80-86℃反应1.5h,回收乙醇,水蒸气蒸馏,除去副产物对氨基甲苯。反应液用苯提取,经水蒸汽蒸馏,冷却、过滤、干燥而得成品。此方法工艺相对简单,生产成本低,但选择性有待提高,另外会对环境产生一定的污染。
发明内容
针对现有技术中存在的不足,本发明目的是提供一种可调节的高效选择性催化还原硝基苯甲醛的金属有机笼状化合物的制备方法及其应用。采用该种方法制备的金属有机笼状化合物包含有二氢吡啶结构单元,此结构是生物分子烟酰胺腺嘌呤二核苷酸的模拟结构,具有良好的递氢能力,且可以促进氢负转移反应,以可再生的甲酸、三乙胺作为氢源,利用光能作为清洁能源,通过简单的浓度调节可以实现高选择性的还原反应。
为了实现上述发明目的,解决己有技术中存在的问题,本发明采取的技术方案是:一种可调节的高效选择性催化还原硝基苯甲醛的金属有机笼状化合物的制备方法,以过渡金属盐中的M2+作为节点,以L作为配体反应制得金属有机笼状化合物,其合成路线如下:
M2++L→M-L;
所述配体L选自H2FPB;
所述过渡金属盐选自高氯酸亚铁、四氟硼酸钴、高氯酸镍或四氟硼酸锌中的一种;
所述配体H2FPB具有如下(A)分子结构式,
式中:R1为氢,R2为苯基,X为氧;
所述一种可调节的高效选择性催化还原硝基苯甲醛的金属有机笼状化合物的制备方法,包括以下步骤:
步骤1、将炔丙酸甲酯、苯甲醛与2-呋喃甲胺按1:0.5~0.55:0.5~0.55的摩尔比加入到2.0~2.5毫升的冰醋酸中,在75~85℃的条件下搅拌15~25小时,反应溶液冷却并加入20~40毫升的乙醇,超声至固体粉末化,抽滤并用乙醇洗涤抽滤所得滤饼,真空干燥洗涤后的滤饼,得到淡黄色固体;
步骤2、将步骤1反应所得到的淡黄色固体与水合肼按1:30~50的摩尔比混合,在90~100℃温度下回流搅拌10~15小时,反应结束后抽滤并用乙醇洗涤抽滤所得滤饼,真空干燥洗涤后的滤饼,得到白色粉末;
步骤3、将步骤2反应所得到的白色粉末与2-吡啶甲醛按照1:2.2~2.5的摩尔比加入到40~60毫升乙醇中混合,再加入5~6滴冰醋酸,将混合溶液在80~90℃温度下回流10~15小时,反应停止后抽滤,用甲醇洗涤所得滤饼,真空干燥洗涤后的滤饼得到黄色粉末,即配体H2FPB;
步骤4、将步骤3得到的配体H2FPB与过渡金属盐按照1:1.0~1.5的摩尔比加入到25~35毫升二氯甲烷与乙腈的混合溶剂中,室温下搅拌4~7小时,搅拌过滤后,将乙醚向滤液中扩散,室温下2周后溶液中析出固体,制得目标化合物M-FPB,所述二氯甲烷与乙腈的体积比为1:3~10。
所述制备方法制备的目标化合物M-FPB,在还原对硝基苯甲醛制对硝基苯甲醇,还原催化肉桂醛一步法合成桂利嗪及还原对硝基苯甲醛制对氨基苯甲醛方面中的应用。
本发明有益效果是:一种可调节的高效选择性催化还原硝基苯甲醛的金属有机笼状化合物的制备方法,以过渡金属盐中的M2+作为节点,以L作为配体反应制得金属有机笼状化合物,其合成路线如下:M2++L→M-L;所述配体L选自H2FPB;所述过渡金属盐选自高氯酸亚铁、四氟硼酸钴、高氯酸镍或四氟硼酸锌中的一种;与已有技术相比,采用该方法制备金属有机笼状化合物原料价格低廉,产率高,得到的化合物化学性质稳定,易于投入实际应用中。作为目标化合物M-FPB,在还原对硝基苯甲醛制对硝基苯甲醇,还原催化肉桂醛一步法合成桂利嗪及还原对硝基苯甲醛制对氨基苯甲醛方面中的应用,选择性可达99%
附图说明
图1是化合物Fe-FPB的结构晶体图。
图2是化合物Fe-FPB的溶液ESI-MS高分辨质谱图。
图3是化合物Co-FPB的结构晶体图。
图4是化合物Co-FPB的溶液ESI-MS高分辨质谱图。
图5是化合物Ni-FPB的结构晶体图。
图6是化合物Ni-FPB的溶液ESI-MS高分辨质谱图。
图7是化合物Zn-FPB的结构晶体图。
图8是化合物Zn-FPB的溶液ESI-MS高分辨质谱图。
图9是化合物Ni-FPB还原对硝基苯甲醛制对硝基苯甲醇的反应产率随时间的变化图。
具体实施方式
下面结合实施例对本发明作进一步说明。
实施例1化合物Fe-FPB的制备
将炔丙酸甲酯(1.68g,20mmol)、苯甲醛(1.06g,10mmol)与2-呋喃甲胺(1.13g,10mmol)加入到2.0毫升的冰醋酸中,在80℃的条件下搅拌20小时。反应溶液冷却并加入25毫升的乙醇,超声至固体粉末化,抽滤并用乙醇洗涤抽滤所得滤饼,真空干燥洗涤后的滤饼,得到淡黄色固体1.78g,产率51.8%。1H NMR(400MHz,CDCl3,ppm):δ7.51(s,2H),7.46(s,1H),7.18(m,3H),7.10(m,2H),6.49(s,1H),6.43(s,1H),4.82(s,2H),4.70(s,1H),3.53(s,6H).13C NMR(101MHz,CDCl3,ppm)δ167.3,149.3,146.3,143.6,137.4,128.2,128.1,126.6,110.8,109.3,109.2,51.4,51.1,37.3.ESI-MS calcd for C20H19NO5 353.1263,found354.1337[M+H]+,376.1150[M+Na]+.将淡黄色固体(1.76g,5mmol)与210mmol水合肼混合后,在95℃下回流搅拌12小时。反应结束后抽滤并用乙醇洗涤滤饼,真空干燥所得滤饼,得到白色粉末1.52g,产率86.3%。1H NMR(400MHz,DMSO-d6,ppm):δ8.65(s,2H),7.69(s,2H),7.44(s,1H),7.17(m,3H),7.09(m,2H),6.47(s,1H),6.44(s,1H),4.94(s,1H),4.60(s,2H),4.15(s,4H).13C NMR(101MHz,DMSO-d6,ppm)δ166.4,150.1,146.3,143.4,133.5,127.9,127.5,126.1,110.6,108.9,108.6,49.6,35.3.ESI-MS calcd for C18H19N5O3 353.1482,found354.1561[M+H]+,376.1388[M+Na]+.将白色粉末(1.41g,4mmol)、2-吡啶甲醛(1.07g,10mmol)加入到50ml乙醇中混合,加入5滴冰醋酸后,将混合溶液在90℃下回流搅拌12小时。反应结束后进行抽滤并用甲醇洗涤滤饼,真空干燥滤饼后得到黄色粉末1.62g,产率79%,即配体H2FPB。1H NMR(400MHz,DMSO-d6,ppm):δ11.38(s,2H),8.57(d,2H),8.24(s,2H),7.84(m,4H),7.75(s,1H),7.47(s,2H),7.37(m,2H),7.24(m,4H),7.11(t,1H),6.52(s,2H),5.33(s,1H),4.76(s,2H).13C NMR(101MHz,DMSO-d6,ppm)δ163.9,153.5,150.6,149.4,146.4,145.3,143.5,136.7,135.2,128.1,127.6,126.2,124.0,119.6,110.7,109.3,108.8,50.1,36.1.ESI-MS calcd for C30H25N7O3 531.2019,found 532.2088[M+H]+,554.1927[M+Na]+.将Fe(ClO4)2·6H2O(36.3mg,0.10mmol),配体H2FPB(53.2mg,0.10mmol)溶于30ml二氯甲烷和乙腈体积比为1:5的混合溶剂中,室温下搅拌4小时,搅拌过滤后,将乙醚向滤液中扩散,室温下2周后溶液中析出固体,即可制得目标化合物Fe-FPB 32.0mg,产率42%。ESI-MS:m/z:785.5038[H3Fe4(FPB)4]3+,1171.7513[H2Fe4(FPB)4]2+。化合物Fe-FPB的结构晶体图,如图1所示,化合物Fe-FPB的溶液ESI-MS高分辨质谱图,如图2所示。
实施例2化合物Co-FPB的制备
将Co(BF4)2·6H2O(34.0mg,0.10mmol)与实施例1制备的配体H2FPB(53.2mg,0.10mmol)溶于30毫升二氯甲烷和乙腈体积比为1:4的混合溶剂中,室温下搅拌4小时,搅拌过滤后,将乙醚向滤液中扩散,室温下2周后溶液中析出固体,即可制得目标化合物Co-FPB27.4mg,产率36%。ESI-MS:m/z:785.4830[H3Co4(FPB)4]3+,1177.6599[H2Co4(FPB)4]2+,1231.2565[H3Co4(FPB)4·BF4]2+。化合物Co-FPB的结构晶体图,如图3所示,化合物Co-FPB的溶液ESI-MS高分辨质谱图,如图4所示。
实施例3化合物Ni-FPB的制备
将Ni(ClO4)2·6H2O(36.5mg,0.10mmol)与实施例1制备的配体H2FPB(53.2mg,0.10mmol)溶于30毫升二氯甲烷和乙腈体积比为1:7的混合溶剂中,室温下搅拌4小时,搅拌过滤后,将乙醚向滤液中扩散,室温下2周后溶液中析出固体,即可制得目标化合物Ni-FPB42.7mg,产率56%。ESI-MS:m/z:785.1693[H3Ni4(FPB)4]3+,1177.2492[H2Ni4(FPB)4]2+。化合物Ni-FPB的结构晶体图,如图5所示,化合物Ni-FPB的溶液ESI-MS高分辨质谱图,如图6所示。
实施例4化合物Zn-FPB的制备
将Zn(BF4)2·6H2O(34.7mg,0.10mmol)与实施例1制备的配体H2FPB(53.2mg,0.10mmol)溶于30毫升二氯甲烷和乙腈体积比为1:8的混合溶剂中,室温下搅拌4小时,搅拌过滤后,将乙醚向滤液中扩散,室温下2周后溶液中析出固体,即可制得目标化合物Zn-FPB27.4mg,产率36%。1H NMR(400MHz,DMSO-d6,ppm):δ12.00(s,2H),8.53(s,2H),8.33(s,2H),7.93(m,4H),7.76(s,1H),7.61(s,2H),7.51(s,2H),7.22(m,4H),7.12(m,1H),6.53(s,2H),5.29(s,1H),4.84(s,2H).ESI-MS:m/z:793.8252[H3Zn4(FPB)4]3+,1190.2319[H2Zn4(FPB)4]2+。化合物Zn-FPB的结构晶体图,如图7所示,化合物Zn-FPB的溶液ESI-MS高分辨质谱图,如图8所示。
实施例5利用Ni-FPB还原对硝基苯甲醛制对硝基苯甲醇
在光反应管中加入5毫升乙腈与水体积比为1:1的混合溶液,然后依次加入0.5微摩尔的Ni-FPB,0.5毫摩尔的甲酸以及0.25毫摩尔的三乙胺,采用硫酸和氢氧化钠溶液调节pH值至8.5。再依次加入5.0微摩尔的氰基硼氢化钠及25.0微摩尔的对硝基苯甲醛。最后将光反应管置于氩气氛围中,利用100W的420nm的LED灯光照6h,对硝基苯甲醛可转化为对硝基苯甲醇,产率可达到82%,选择性为99%,化合物Ni-FPB还原对硝基苯甲醛制对硝基苯甲醇的反应产率随时间的变化图,如图9所示。
实施例6利用Ni-FPB还原催化肉桂醛一步法合成桂利嗪
在光反应管中加入5毫升乙腈与水体积比为1:1的混合溶液,然后依次加入0.5微摩尔的Ni-FPB,0.5毫摩尔的甲酸以及0.25毫摩尔三乙胺,采用硫酸和氢氧化钠溶液调节pH值至8.5。再依次加入5.0微摩尔的氰基硼氢化钠,20.0微摩尔的肉桂醛及60微摩尔的1-苯甲酰哌嗪。最后将光反应管置于氩气氛围中,利用100W的420nm的LED灯光照12h,可得到桂利嗪,产率可达到72%,选择性为99%。
实施例7利用Ni-FPB还原对硝基苯甲醛制对氨基苯甲醛
在光反应管中加入5毫升乙腈与水体积比为1:1的混合溶液,然后依次加入0.5微摩尔的Ni-FPB,5.0微摩尔的Ir(ppy)2(phen)(PF6),0.5毫摩尔的甲酸以及0.25毫摩尔三乙胺,采用硫酸和氢氧化钠溶液调节pH值至8.5。再依次加入5.0微摩尔的氰基硼氢化钠,25.0微摩尔的对硝基苯甲醛及50.0微摩尔的抗坏血酸。最后将光反应管置于氩气氛围中,利用100W的420nm的LED灯光照6h,对硝基苯甲醛可转化为对氨基苯甲醛,产率可达到72%,选择性为78%。
Claims (2)
1.一种可调节的高效选择性催化还原硝基苯甲醛的金属有机笼状化合物的制备方法,其特征在于:以过渡金属盐中的M2+作为节点,以L作为配体反应制得金属有机笼状化合物,其合成路线如下:
M2++L→M-L;
所述配体L选自H2FPB;
所述过渡金属盐选自高氯酸亚铁、四氟硼酸钴、高氯酸镍或四氟硼酸锌中的一种;
所述配体H2FPB具有如下(A)分子结构式,
式中:R1为氢,R2为苯基,X为氧;
所述一种可调节的高效选择性催化还原硝基苯甲醛的金属有机笼状化合物的制备方法,包括以下步骤:
步骤1、将炔丙酸甲酯、苯甲醛与2-呋喃甲胺按1:0.5~0.55:0.5~0.55的摩尔比加入到2.0~2.5毫升的冰醋酸中,在75~85℃的条件下搅拌15~25小时,反应溶液冷却并加入20~40毫升的乙醇,超声至固体粉末化,抽滤并用乙醇洗涤抽滤所得滤饼,真空干燥洗涤后的滤饼,得到淡黄色固体;
步骤2、将步骤1反应所得到的淡黄色固体与水合肼按1:30~50摩尔比混合,在90~100℃温度下回流搅拌10~15小时,反应结束后抽滤并用乙醇洗涤抽滤所得滤饼,真空干燥洗涤后的滤饼,得到白色粉末;
步骤3、将步骤2反应所得到的白色粉末与2-吡啶甲醛按照1:2.2~2.5的摩尔比加入到40~60毫升乙醇中混合,再加入5~6滴冰醋酸,将混合溶液在80~90℃温度下回流10~15小时,反应停止后抽滤,用甲醇洗涤所得滤饼,真空干燥洗涤后的滤饼得到黄色粉末,即配体H2FPB;
步骤4、将步骤3得到的配体H2FPB与过渡金属盐按照1:1.0~1.5的摩尔比加入到25~35毫升二氯甲烷与乙腈的混合溶剂中,室温下搅拌4~7小时,搅拌过滤后,将乙醚向滤液中扩散,室温下2周后溶液中析出固体,制得目标化合物M-FPB,所述二氯甲烷与乙腈的体积比为1:3~10。
2.根据权利要求1所述制备方法制备的目标化合物M-FPB,在还原对硝基苯甲醛制对硝基苯甲醇,还原催化肉桂醛一步法合成桂利嗪及还原对硝基苯甲醛制对氨基苯甲醛方面中的应用。
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