CN111662169A - 一种采用多金属氧酸盐催化氧化苯甲醇制备苯甲醛的方法 - Google Patents
一种采用多金属氧酸盐催化氧化苯甲醇制备苯甲醛的方法 Download PDFInfo
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- CN111662169A CN111662169A CN202010594573.7A CN202010594573A CN111662169A CN 111662169 A CN111662169 A CN 111662169A CN 202010594573 A CN202010594573 A CN 202010594573A CN 111662169 A CN111662169 A CN 111662169A
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- polyoxometallate
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- benzaldehyde
- benzyl alcohol
- preparing benzaldehyde
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- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 title claims abstract description 100
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 title claims abstract description 50
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 25
- 235000019445 benzyl alcohol Nutrition 0.000 title claims abstract description 14
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 12
- 230000003647 oxidation Effects 0.000 title claims abstract description 11
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 73
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000007810 chemical reaction solvent Substances 0.000 claims description 6
- 229910000510 noble metal Inorganic materials 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 239000002798 polar solvent Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract 2
- 239000000047 product Substances 0.000 description 33
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 14
- 230000005311 nuclear magnetism Effects 0.000 description 14
- 239000000758 substrate Substances 0.000 description 14
- 238000000746 purification Methods 0.000 description 13
- 238000000926 separation method Methods 0.000 description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical class OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 10
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 8
- 238000005070 sampling Methods 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000013460 polyoxometalate Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical class C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- -1 aliphatic aldehyde Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 2
- 229940073608 benzyl chloride Drugs 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000012790 confirmation Methods 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 239000011964 heteropoly acid Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- ZETIVVHRRQLWFW-UHFFFAOYSA-N 3-nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=CC(C=O)=C1 ZETIVVHRRQLWFW-UHFFFAOYSA-N 0.000 description 1
- CAHQGWAXKLQREW-UHFFFAOYSA-N Benzal chloride Chemical compound ClC(Cl)C1=CC=CC=C1 CAHQGWAXKLQREW-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007336 electrophilic substitution reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002192 fatty aldehydes Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
- C07C45/38—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a primary hydroxyl group
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Abstract
本发明涉及一种采用多金属氧酸盐催化氧化苯甲醇制备苯甲醛的方法,以多金属氧酸盐为催化剂,往反应溶剂中加入原料苯甲醇,在氧气气氛下,搅拌反应,即制得苯甲醛。与现有技术相比,本发明的催化剂可回收再利用,对环境友好,提高了反应的清洁性,降低了生产制造成本并且易于控制和工业化生产。
Description
技术领域
本发明属于苯甲醛制备技术领域,涉及一种采用多金属氧酸盐催化氧化苯甲醇制备苯甲醛的方法。
背景技术
苯甲醛是一种重要的化工原料,其化学性质与脂肪醛类似,但也有不同。苯甲醛不能还原斐林试剂;用还原脂肪醛时所用的试剂还原苯甲醛时,除主要产物苯甲醇外,还产生一些四取代邻二醇类化合物和均二苯基乙二醇。在氰化钾存在下,两分子苯甲醛通过授受氢原子生成安息香。苯甲醛还可进行芳核上的亲电取代反应,主要生成间位取代产物,例如硝化时主要产物为间硝基苯甲醛。苯甲醛在空气中极易被氧化,生成白色苯甲酸。苯甲醛还可与酰胺类物质反应,生产医药中间体。由于其应用广泛使得苯甲醛的合成和应用研究得到人们的广泛关注。
苯甲醛在工业中主要由甲苯在催化剂(五氧化二钒、三氧化钨或三氧化钼)作用下以空气或氧进行气相氧化;或者在光照下将甲苯氯化成氯化苄,然后再水解、氧化;也可氯化成二氯甲基苯再水解。工业中也有以苯为原料,在加压和三氯化铝作用下与一氧化碳和氯化氢反应制取。实验室中是用催化还原苯甲酰氯的方法制备苯甲醛。这些制备方法步骤繁琐且产率不高,所需催化剂氧化性极强,极具不安全因素,不仅对反应设备要求高,而且反应过程及副产物对环境不友好。
多金属氧酸盐(多酸)催化剂是一种新型高效的绿色催化剂,不但具有优良的氧化还原催化性能,而具有高稳定性和高活性,是一类很有前景的绿色环保型催化剂。自1927年,以多酸为催化剂催化丙烯水合制取异丙醇反应在日本实现工业化以后,越来越多的科研工作者投入到多酸催化领域的研究工作中.研究比较多的主要为Dawson结构(2:18系列)、Keggin结构(1:12A系列)等。而Anderson结构(1:6系列)是一种结构比较简单的多酸,近些年,关于Anderson型多金属氧酸盐的报道多集中于多酸修饰以及其结构的优化。至今,Anderson型多酸应用于催化领域的研究没有文献正式报道。
发明内容
本发明的目的就是为了提供一种采用多金属氧酸盐催化氧化苯甲醇制备苯甲醛的方法,以简化工艺流程,提高产品收率与环保性能等。
本发明的目的可以通过以下技术方案来实现:
一种采用多金属氧酸盐催化氧化苯甲醇制备苯甲醛的方法,以多金属氧酸盐为催化剂,往反应溶剂中加入原料苯甲醇,在氧气气氛下,搅拌反应,即制得苯甲醛。
进一步的,所述的多金属氧酸盐的构型为Anderson型。
进一步的,所述的多金属氧酸盐为以非贵族金属为中心金属的Anderson型多金属氧酸盐。
更进一步的,所述的非贵族金属为Fe、Cu、Ni或Cr。
进一步的,多金属氧酸盐的加入量为0.1mol%~5mol%。
进一步的,多金属氧酸盐的加入量为1mol%。
进一步的,搅拌反应的温度为0~80℃,反应时间为6h~24h。
进一步的,搅拌反应的温度为60℃,反应时间为12h。
进一步的,所述的反应溶剂为非质子极性溶剂,其选自DMF、DMSO、无水乙腈或甲苯中的任一种。
进一步的,反应结束后,还往反应体系中加入有机溶剂回收催化剂循环使用,所述有机溶剂为乙醚、乙醇或甲醇。
本发明中涉及到的多金属氧酸盐催化氧化苯甲醇制备苯甲醛的反应通式表示为:
与现有技术相比,本发明具有以下优点:
(1)原料单一、制备过程简单、产物收率高、无三废。
(2)所用催化剂为新型的催化剂多金属氧酸盐(杂多酸),中心金属都为常见的非贵金属Al,Fe,Cu,Ni,Cr,廉价易得且经简单处理后还可以循环使用多次,这十分有利于工业化生产,因此该发明具有潜在的应用前景。
附图说明
图1是以Anderson型为主的多金属氧酸盐红外和Tris衍生物修饰的Anderson型多酸红外(以铁是金属中心为例);
图2是Tris衍生物修饰的Anderson型多酸核磁(以铁是金属中心为例);
图3是Anderson型多金属氧酸盐SEM图(以铁是金属中心为例);
图4是Tris衍生物修饰的Anderson型多酸SEM图(以铁是金属中心为例);
图5是Anderson型多酸(以铁是金属中心为例)催化氧化苯甲醇制备的苯甲醛的1HNMR图。
具体实施方式
下面结合附图和具体实施例对本发明进行详细说明。本实施例以本发明技术方案为前提进行实施,给出了详细的实施方式和具体的操作过程,但本发明的保护范围不限于下述的实施例。
以下各实施例中,所用Anderson型多金属氧酸盐催化剂均可从北京环宇浩森生物科技有限公司直接购买,其余如无特别说明的原料或处理技术,则表明均为本领域的常规市售原料产品或常规处理技术。
实施例1:
在25mL洁净的反应管中加入0.0240g(0.02mmol)以镍为中心的多金属氧酸盐[NH4]4[NiMo6O18(OH)6]·7H2O(NiMo6)、6mL乙腈、2mmol苯甲醇,最后在反应管上方套上装有氧气的气球,在60℃下反应12h;反应结束后,取样测GC-MS,得知反应底物转化率大于93%,产物选择性为90%,分离提纯后经核磁确认是产物苯甲醛。
实施例2:
在25mL洁净的反应管中加入0.0240g(0.02mmol)以铁为中心的多金属氧酸盐[NH4]3[FeMo6O18(OH)6]·7H2O(FeMo6)、6mL乙腈、2mmol苯甲醇,最后在反应管上方套上装有氧气的气球,在60℃下反应12h;反应结束后,取样测GC-MS,得知反应底物转化率大于94%,产物选择性为92%,分离提纯后经核磁确认是产物苯甲醛。
本实施例所用[NH4]3[FeMo6O18(OH)6]·7H2O(FeMo6)红外光谱图与SEM图分别参考如图1和图3所示,从图1可知,根据图中出峰位置与标准图谱对照可以确定本催化剂结构为Anderson型,同时,结合图3可知,其为Fe-Anderson型杂多酸。
图5是[NH4]3[FeMo6O18(OH)6]·7H2O(FeMo6)催化氧化苯甲醇制备的苯甲醛的1HNMR图,可知,该催化反应产率较高,催化选择性也比较好。
实施例3:
在25mL洁净的反应管中加入0.0240g(0.02mmol)以铜为中心的多金属氧酸盐[NH4]4[CuMo6O18(OH)6]·7H2O(CuMo6)、6mL乙腈、2mmol苯甲醇,最后在反应管上方套上装有氧气的气球,在60℃下反应12h;反应结束后,取样测GC-MS,得知反应底物转化率大于95%,产物选择性为90%,分离提纯后经核磁确认是产物苯甲醛。
实施例4:
在25mL洁净的反应管中加入0.0240g(0.02mmol)以铬为中心的多金属氧酸盐[NH4]3[CrMo6O18(OH)6]·7H2O(CrMo6)、6mL乙腈、2mmol苯甲醇,最后在反应管上方套上装有氧气的气球,在60℃下反应12h;反应结束后,取样测GC-MS,得知反应底物转化率大于96%,产物选择性为92%,分离提纯后经核磁确认是产物苯甲醛。
实施例5:
在25mL洁净的反应管中加入0.0407g(0.02mmol)以Tris衍生物单侧修饰的以镍为中心的多金属氧酸盐[[N(C4H9)4]4[NiMo6O18(OH)3{(OCH2)3CCH2OH}]·13H2O(CH2OH-NiMo6)、6mL乙腈、2mmol苯甲醇,最后在反应管上方套上装有氧气的气球,在60℃下反应12h;反应结束后,取样测GC-MS,得知反应底物转化率大于95%,产物选择性为91%,分离提纯后经核磁确认是产物苯甲醛。
实施例6:
在25mL洁净的反应管中加入0.0407g(0.02mmol)以Tris衍生物单侧修饰的以铁为中心的多金属氧酸盐[[N(C4H9)4]3[FeMo6O18(OH)3{(OCH2)3CCH2OH}]·13H2O(CH2OH-FeMo6)、6mL乙腈、2mmol苯甲醇,最后在反应管上方套上装有氧气的气球,在60℃下反应12h;反应结束后,取样测GC-MS,得知反应底物转化率大于95%,产物选择性为90%,分离提纯后经核磁确认是产物苯甲醛。
本实施例所用Tris衍生物修饰的[NH4]3[FeMo6O18(OH)6]·7H2O(FeMo6)的核磁与SEM图分别如图2和图4所示,从图2中可以看出,该催化剂结构为Tris衍生物配体修饰的铁Anderson型多金属氧酸盐,结合图4可知,其为Tris衍生物修饰的Fe-Anderson型多酸。
实施例7:
在25mL洁净的反应管中加入0.0407g(0.02mmol)以Tris衍生物单侧修饰的以铜为中心的多金属氧酸盐[[N(C4H9)4]4[CuMo6O18(OH)3{(OCH2)3CCH2OH}]·13H2O(CH2OH-CuMo6)、6mL乙腈、2mmol苯甲醇,最后在反应管上方套上装有氧气的气球,在60℃下反应12h;反应结束后,取样测GC-MS,得知反应底物转化率大于92%,产物选择性为89%,分离提纯后经核磁确认是产物苯甲醛。
实施例8:
在25mL洁净的反应管中加入0.0407g(0.02mmol)以Tris衍生物单侧修饰的以铬为中心的多金属氧酸盐[[N(C4H9)4]3[CrMo6O18(OH)3{(OCH2)3CCH2OH}]·13H2O(CH2OH-CrMo6)、6mL乙腈、2mmol苯甲醇,最后在反应管上方套上装有氧气的气球,在60℃下反应12h;反应结束后,取样测GC-MS,得知反应底物转化率大于91%,产物选择性为91%,分离提纯后经核磁确认是产物苯甲醛。
实施例9:
反应步骤同实施例6,与实施例2不同之处在于,所用催化剂为回收后第1次使用,GC-MS分析得知反应底物转化率大于91%,选择性约为89%,分离提纯得到产物,核磁确认为苯甲醛。
实施例10:
反应步骤同实施例6,与实施例2不同之处在于,所用催化剂为回收后第2次使用,GC-MS分析得知反应底物转化率大于90%,选择性约为88%,分离提纯得到产物,核磁确认为苯甲醛。
实施例11:
反应步骤同实施例6,与实施例2不同之处在于,所用催化剂为回收后第3次使用,GC-MS分析得知反应底物转化率为88%,选择性约为88%,分离提纯得到产物,核磁确认为苯甲醛。
实施例12:
反应步骤同实施例6,与实施例2不同之处在于,所用催化剂为回收后第4次使用,GC-MS分析得知反应底物转化率为88%,选择性约为86%,分离提纯得到产物,核磁确认为苯甲醛。
实施例13:
反应步骤同实施例6,与实施例2不同之处在于,所用催化剂为回收后第5次使用,GC-MS分析得知反应底物转化率为87%,选择性约为85%,分离提纯得到产物,核磁确认为苯甲醛。
实施例14:
反应步骤同实施例6,与实施例2不同之处在于,所用催化剂为回收后第6次使用,GC-MS分析得知反应底物转化率为83%,选择性约为84%,分离提纯得到产物,核磁确认为苯甲醛。
以上各实施例中,各原料的添加量、反应溶剂的种类等工艺条件均可以根据实际需要在以下限定范围内任意调整:所用的多金属氧酸盐的加入量可以调整为0.1mol%~5mol%中的端值或任意中间点值;搅拌反应的温度为0~80℃,反应时间为6h~24h(反应温度与时间也可以调整为前面限定范围的任一端值或任意中间点值);反应溶剂也可以替换为DMF、DMSO或甲苯等非质子极性溶剂中的任一种。
所有上述的首要实施方式,并没有设定实施这种新产品和/或新方法的其他形式。本领域技术人员将利用这一重要信息,上述内容修改,以实现类似的执行情况。但是,所有基于本发明的修改或改造属于本发明保留的权利。
上述的对实施例的描述是为便于该技术领域的普通技术人员能理解和使用发明。熟悉本领域技术的人员显然可以容易地对这些实施例做出各种修改,并把在此说明的一般原理应用到其他实施例中而不必经过创造性的劳动。因此,本发明不限于上述实施例,本领域技术人员根据本发明的揭示,不脱离本发明范畴所做出的改进和修改都应该在本发明的保护范围之内。
Claims (10)
1.一种采用多金属氧酸盐催化氧化苯甲醇制备苯甲醛的方法,其特征在于,以多金属氧酸盐为催化剂,往反应溶剂中加入原料苯甲醇,在氧气气氛下,搅拌反应,即制得苯甲醛。
2.根据权利要求1所述的一种采用多金属氧酸盐催化氧化苯甲醇制备苯甲醛的方法,其特征在于,所述的多金属氧酸盐的构型为Anderson型。
3.根据权利要求1或2所述的一种采用多金属氧酸盐催化氧化苯甲醇制备苯甲醛的方法,其特征在于,所述的多金属氧酸盐为以非贵族金属为中心金属的Anderson型多金属氧酸盐。
4.根据权利要求3所述的一种采用多金属氧酸盐催化氧化苯甲醇制备苯甲醛的方法,其特征在于,所述的非贵族金属为Fe、Cu、Ni或Cr。
5.根据权利要求1所述的一种采用多金属氧酸盐催化氧化苯甲醇制备苯甲醛的方法,其特征在于,多金属氧酸盐的加入量为0.1mol%~5mol%。
6.根据权利要求1或5所述的一种采用多金属氧酸盐催化氧化苯甲醇制备苯甲醛的方法,其特征在于,多金属氧酸盐的加入量为1mol%。
7.根据权利要求1所述的一种采用多金属氧酸盐催化氧化苯甲醇制备苯甲醛的方法,其特征在于,搅拌反应的温度为0~80℃,反应时间为6h~24h。
8.根据权利要求1或7所述的一种采用多金属氧酸盐催化氧化苯甲醇制备苯甲醛的方法,其特征在于,搅拌反应的温度为60℃,反应时间为12h。
9.根据权利要求1所述的一种采用多金属氧酸盐催化氧化苯甲醇制备苯甲醛的方法,其特征在于,所述的反应溶剂为非质子极性溶剂,其选自DMF、DMSO、无水乙腈或甲苯中的任一种。
10.根据权利要求1所述的一种采用多金属氧酸盐催化氧化苯甲醇制备苯甲醛的方法,其特征在于,反应结束后,还往反应体系中加入有机溶剂回收催化剂循环使用,所述有机溶剂为乙醚、乙醇或甲醇。
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