CN110627619A - A kind of preparation method of pinacol - Google Patents
A kind of preparation method of pinacol Download PDFInfo
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- CN110627619A CN110627619A CN201910938415.6A CN201910938415A CN110627619A CN 110627619 A CN110627619 A CN 110627619A CN 201910938415 A CN201910938415 A CN 201910938415A CN 110627619 A CN110627619 A CN 110627619A
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- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 title claims abstract description 139
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 79
- 238000006243 chemical reaction Methods 0.000 claims abstract description 68
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 64
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 36
- HHAVHBDPWSUKHZ-UHFFFAOYSA-N propan-2-ol;propan-2-one Chemical compound CC(C)O.CC(C)=O HHAVHBDPWSUKHZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000007789 gas Substances 0.000 claims abstract description 32
- 239000000047 product Substances 0.000 claims abstract description 26
- 229910052786 argon Inorganic materials 0.000 claims abstract description 18
- 238000003760 magnetic stirring Methods 0.000 claims abstract description 18
- 230000035484 reaction time Effects 0.000 claims abstract description 18
- 239000000706 filtrate Substances 0.000 claims abstract description 16
- 238000002425 crystallisation Methods 0.000 claims description 15
- 230000008025 crystallization Effects 0.000 claims description 15
- 230000003068 static effect Effects 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 1
- 238000005859 coupling reaction Methods 0.000 abstract description 17
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 17
- 238000000034 method Methods 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 4
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 abstract description 3
- 239000012295 chemical reaction liquid Substances 0.000 abstract description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 39
- 229910052753 mercury Inorganic materials 0.000 description 16
- 230000001699 photocatalysis Effects 0.000 description 16
- 238000004817 gas chromatography Methods 0.000 description 15
- 239000007791 liquid phase Substances 0.000 description 15
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 15
- 238000004587 chromatography analysis Methods 0.000 description 13
- 238000006356 dehydrogenation reaction Methods 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 10
- 238000013032 photocatalytic reaction Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000006519 Mcmurry reaction Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001728 carbonyl compounds Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 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
- 229910007565 Zn—Cu Inorganic materials 0.000 description 1
- PUZCUNCKTTTWOS-UHFFFAOYSA-N [Sn].CC(=O)C Chemical compound [Sn].CC(=O)C PUZCUNCKTTTWOS-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- CCLUHSUSTSVOPJ-UHFFFAOYSA-N propan-2-ol;tin Chemical compound [Sn].CC(C)O CCLUHSUSTSVOPJ-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000006578 reductive coupling reaction Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
- C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Hydrogenated Pyridines (AREA)
Abstract
本发明公开了一种频哪醇的制备方法，该方法是将四氯化锡源溶液加入丙酮‑异丙醇反应液中，磁力搅拌下通入氩气10分钟，开启紫外灯源，开始光催化异丙醇脱氢‑丙酮加氢耦合反应制备频哪醇；控制反应温度20‑50℃，反应时间5‑36小时；低温静置，频哪醇晶体析出，过滤，得到产物频哪醇，滤液继续循环利用。本发明具有过程简单、选择性高、活性高、产率高、成本低廉和环境友好等优点，频哪醇纯度达98％。
The invention discloses a preparation method of pinacol. The method comprises adding a tin tetrachloride source solution into an acetone-isopropanol reaction liquid, feeding argon gas for 10 minutes under magnetic stirring, turning on an ultraviolet light source, and starting to light Catalyze the coupling reaction of isopropanol dehydrogenation-acetone hydrogenation to prepare pinacol; control the reaction temperature at 20-50°C, and the reaction time is 5-36 hours; stand at low temperature, pinacol crystals are precipitated, and filtered to obtain the product pinacol, The filtrate continues to be recycled. The invention has the advantages of simple process, high selectivity, high activity, high yield, low cost, environmental friendliness and the like, and the pinacol has a purity of 98%.
Description
技术领域technical field
本发明涉及频哪醇(四甲基乙二醇)的合成，具体地说是一种光照条件下使用原位制备的锡-异丙醇或锡-丙酮配合物为光催化剂催化异丙醇脱氢-丙酮加氢耦合制备频哪醇的方法。The present invention relates to the synthesis of pinacol (tetramethylethylene glycol), specifically a tin-isopropanol or tin-acetone complex prepared in situ under light conditions as a photocatalyst to catalyze the removal of isopropanol. A method for preparing pinacol by hydrogen-acetone hydrogenation coupling.
技术背景technical background
频哪醇广泛应用于高分子聚合物、农药、医药等精细化工产品的合成，具有广泛的应用前景。频哪醇通常由羰基化合物在金属试剂或金属络合物作用下还原偶联得到，如McMurry反应(参考文献：J.E.McMurry,Chem.Rev.1989,89,1513；A.Fiirstner,B.Bogdanovic,Angew Chem.Int.Ed.1996,35,2442)。McMurry反应通常由原位反应得到的具有强烈还原性的低价态钛还原耦合羰基化合物(化学计量比的钛与酮)，生成烯烃过程中首先形成金属-频哪醇中间体，低温条件下生成频哪醇，高温条件下进一步反应生成烯烃(参考文献：K.G.Pierce,M.A.Barteau,J.Org.Chem.1995,60,2405；M.Stahl,U.Pidun,G.Frenking,Angew.Chem.Int.Ed.1997,36,2234；R.Dams,M.Malinowski,I.Westdorp,H.J.Geise,J.Org.Chem.1981,46,2407；T.A.Lipski,M.A.Hilfiker,S.G.Nelson,J.Org.Chem.,1997,62,4566)。关于McMurry反应的研究主要集中在催化剂的调制和改进以及应用范围的拓展，例如NbCl5/NaAlH4、Mg-Hg、Zn-Cu等催化剂均被用于McMurry反应。最近，文献报道SnCl4-Zn体系为催化剂可以顺利进行McMurry反应，被Zn原位还原得到的Sn(II)具有强还原性(G.K.Pathe,N.K.Konduru,I.Parveen,N.Ahmed，RSC Adv.,2015,5,83512–83521)。目前工业上频哪醇由丙酮还原制得，反应过程用到Mg屑、HgCl2和苯，环境不友好。Pinacol is widely used in the synthesis of high molecular polymers, pesticides, pharmaceuticals and other fine chemical products, and has broad application prospects. Pinacol is usually obtained by reductive coupling of carbonyl compounds under the action of metal reagents or metal complexes, such as McMurry reaction (references: JEMcMurry, Chem.Rev.1989,89,1513; A.Fiirstner, B.Bogdanovic, Angew Chem. Int. Ed. 1996, 35, 2442). The McMurry reaction is usually obtained by the in situ reaction with a strongly reducing low-valent titanium reduction coupling carbonyl compound (stoichiometric ratio of titanium and ketone), and the metal-pinacol intermediate is first formed during the formation of olefins, which is generated under low temperature conditions Pinacol, further reacts to generate olefins under high temperature conditions (references: KGPierce, MABarteau, J.Org.Chem.1995,60,2405; M.Stahl, U.Pidun, G.Frenking, Angew.Chem.Int.Ed .1997,36,2234; R.Dams, M.Malinowski, I.Westdorp, HJGeise, J.Org.Chem.1981,46, 2407; TALipski, MAHilfiker, SGNelson, J.Org.Chem., 1997,62, 4566). The research on McMurry reaction mainly focuses on the modulation and improvement of catalysts and the expansion of application range. For example, NbCl 5 /NaAlH 4 , Mg-Hg, Zn-Cu and other catalysts have been used in McMurry reaction. Recently, it has been reported that the SnCl 4 -Zn system can successfully carry out the McMurry reaction as a catalyst, and the Sn(II) obtained by in-situ reduction of Zn has strong reducibility (GKPathe, NKKonduru, I.Parveen, N.Ahmed, RSC Adv., 2015 ,5,83512–83521). At present, pinacol is produced industrially by reduction of acetone. The reaction process uses Mg chips, HgCl 2 and benzene, which is not environmentally friendly.
光催化反应通常在常温常压下进行，条件温和，操作简单，不会产生二次污染，是一种绿色合成技术。目前关于光催化有机合成的报道很多，但由于光催化反应的自由基特性致使反应选择性较低，因此光催化有机合成并没有得到广泛的实际应用。2014年山西煤炭化学研究所报道，以钽酸钠为催化剂，在异丙醇和丙酮水溶液中实现了异丙醇脱氢-丙酮加氢的偶联，得到产物频哪醇(B.Y.Cao,J.Zhang,J.H.Zhao,Z.J.Wang,P.J.Yang,H.X.Zhang,L.Li,Z.P.Zhu,ChemCatChem 2014,6,1673–1678)，获得发明专利(专利号：ZL201210497768.5)，为频哪醇的高效绿色合成提供了一条可行途径。但催化剂结构和反应体系有待进一步优化，反应效率有待进一步提升。Photocatalytic reactions are usually carried out at normal temperature and pressure, with mild conditions, simple operation, and no secondary pollution. It is a green synthesis technology. At present, there are many reports on photocatalytic organic synthesis, but the photocatalytic organic synthesis has not been widely used in practice due to the low reaction selectivity due to the free radical characteristics of photocatalytic reactions. In 2014, Shanxi Institute of Coal Chemistry reported that using sodium tantalate as a catalyst, the coupling of isopropanol dehydrogenation-acetone hydrogenation was realized in isopropanol and acetone aqueous solution, and the product pinacol was obtained (B.Y.Cao, J.Zhang ,J.H.Zhao,Z.J.Wang,P.J.Yang,H.X.Zhang,L.Li,Z.P.Zhu,ChemCatChem 2014,6,1673–1678), obtained an invention patent (patent number: ZL201210497768.5), for the efficient green synthesis of pinacol A feasible way is provided. However, the catalyst structure and reaction system need to be further optimized, and the reaction efficiency needs to be further improved.
发明内容Contents of the invention
本发明的目的在于提供一种高收率、高纯度、低成本、无环境污染、工艺简单的光催化异丙醇脱氢-丙酮加氢耦合制备频哪醇的方法。The object of the present invention is to provide a high yield, high purity, low cost, no environmental pollution, simple process photocatalytic isopropanol dehydrogenation-acetone hydrogenation coupled method for preparing pinacol.
本发明提供的一种频哪醇的制备方法，利用SnCl4为催化剂，异丙醇和丙酮为原料，Sn4+与异丙醇或丙酮形成具有光响应的配合物，并在紫外光照射下原位还原四价锡为低价锡，同时催化异丙醇脱氢-丙酮加氢耦合制备频哪醇。本发明工艺方法简单，催化剂成本低廉，产物选择性最高可达98.2％；异丙醇和丙酮均为反应原料，无需溶剂，易于分离，产品纯度可达98％；反应液可循环利用，环保节能，是一种高效绿色合成频哪醇的方法。反应过程如下所示：A kind of preparation method of pinacol provided by the invention, utilize SnCl 4 as catalyst, isopropanol and acetone are raw material, Sn 4+ and isopropanol or acetone form the complex with photoresponse, and under ultraviolet light irradiation Si-site reduction of tetravalent tin to low-valent tin, while catalyzing the coupling of isopropanol dehydrogenation-acetone hydrogenation to prepare pinacol. The process method of the present invention is simple, the cost of the catalyst is low, and the product selectivity can reach up to 98.2%. Both isopropanol and acetone are reaction raw materials, no solvent is needed, the product is easy to separate, and the product purity can reach 98%. The reaction liquid can be recycled, environmentally friendly and energy-saving. It is an efficient and green method for synthesizing pinacol. The reaction process is as follows:
本发明的技术方案：Technical scheme of the present invention:
按体积比100:0.05-0.15将SnCl4源溶液加入丙酮-异丙醇反应液，磁力搅拌下通入氩气10分钟，除去体系中的氧气后，开启紫外灯，控制反应温度20-50℃，反应5-36小时，静止结晶法析出频哪醇，过滤得到产物，滤液继续循环使用。Add the SnCl 4 source solution to the acetone-isopropanol reaction solution according to the volume ratio of 100:0.05-0.15, and pass in argon gas for 10 minutes under magnetic stirring. After removing the oxygen in the system, turn on the ultraviolet lamp and control the reaction temperature at 20-50°C , react for 5-36 hours, pinacol is precipitated by static crystallization, the product is obtained by filtration, and the filtrate is continuously recycled.
所述的丙酮-异丙醇反应液为丙酮和异丙醇体积比100:0-0:100的反应液，优选40:60-60:40，更优选50:50。The acetone-isopropanol reaction solution is a reaction solution with a volume ratio of acetone and isopropanol of 100:0-0:100, preferably 40:60-60:40, more preferably 50:50.
所述的SnCl4源溶液是浓度为100mg/ml的SnCl4异丙醇或丙酮溶液，优选SnCl4丙酮溶液。The SnCl 4 source solution is a SnCl 4 isopropanol or acetone solution with a concentration of 100 mg/ml, preferably a SnCl 4 acetone solution.
所述的紫外灯功率为200-500W。The power of the ultraviolet lamp is 200-500W.
反应温度优选20-30℃；反应时间优选9-20小时。The reaction temperature is preferably 20-30°C; the reaction time is preferably 9-20 hours.
与现有技术相比本发明具有如下优点：1、采用SnCl4为催化剂，Sn4+与异丙醇或丙酮形成具有光响应的配合物并在光照下原位还原为低价锡进行进一步的光催化反应，催化剂价格低廉。2、采用异丙醇和丙酮为原料，无污染，操作方便，原料可重复利用。3、工艺过程简单，催化剂具有性能稳定、活性高、价格低廉、环境友好等优点。4、反应无需溶剂，产物频哪醇与异丙醇-丙酮反应液的分离简单，产物选择性高，纯度高达98％以上。Compared with the prior art, the present invention has the following advantages: 1. Using SnCl4 as a catalyst, Sn4 + forms a complex with photoresponse with isopropanol or acetone and is reduced to low-valent tin in situ under light to carry out further Photocatalytic reaction, the catalyst is cheap. 2. Using isopropanol and acetone as raw materials, no pollution, easy to operate, and the raw materials can be reused. 3. The process is simple, and the catalyst has the advantages of stable performance, high activity, low price, and environmental friendliness. 4. No solvent is needed for the reaction, the product pinacol is easy to separate from the isopropanol-acetone reaction solution, the product has high selectivity, and the purity is as high as 98%.
附图说明：Description of drawings:
图1实施例1异丙醇-丙酮光催化反应液的气相色谱图The gas chromatogram of Fig. 1 embodiment 1 isopropanol-acetone photocatalytic reaction liquid
图2为产物频哪醇的电子轰击质谱图Fig. 2 is the electron bombardment mass spectrogram of product pinacol
具体实施方式Detailed ways
下面通过实施例对本发明做进一步说明，其目的仅在于更好地理解本发明的内容，而非限制本发明的保护范围。The present invention will be further described below by way of examples, the purpose of which is only to better understand the contents of the present invention, rather than limiting the protection scope of the present invention.
实施例中所用的SnCl4源溶液是浓度为100mg/ml的SnCl4异丙醇或丙酮溶液。The SnCl4 source solution used in the examples is a SnCl4isopropanol or acetone solution with a concentration of 100mg/ml.
实施例1Example 1
将0.2ml SnCl4丙酮源溶液加入到200ml异丙醇-丙酮溶液(体积比为50:50)中，磁力搅拌下通入氩气10分钟，开启300W高压汞灯进行光催化异丙醇脱氢-丙酮加氢耦联反应，控制反应温度20℃，反应时间9h。反应结束后，通过静置结晶法析出频哪醇，滤液继续循环使用。气相色谱分析表明，液相产物中频哪醇选择性为98.2％，异丙醇-丙酮总转化率为29％。气相色谱检测频哪醇纯度可达98％。Add 0.2ml SnCl 4 acetone source solution to 200ml isopropanol-acetone solution (volume ratio 50:50), pass argon gas under magnetic stirring for 10 minutes, turn on a 300W high-pressure mercury lamp for photocatalytic isopropanol dehydrogenation - Acetone hydrogenation coupling reaction, the reaction temperature is controlled at 20° C., and the reaction time is 9 hours. After the reaction finishes, pinacol is separated out by static crystallization, and the filtrate continues to be recycled. Gas chromatographic analysis showed that the selectivity of pinacol in the liquid phase product was 98.2%, and the total conversion rate of isopropanol-acetone was 29%. The purity of pinacol can reach 98% as detected by gas chromatography.
实施例2Example 2
将0.2ml SnCl4丙酮源溶液加入到200ml异丙醇-丙酮溶液(体积比为90:10)中，磁力搅拌下通入氩气10分钟，开启300W高压汞灯进行光催化异丙醇脱氢-丙酮加氢耦联反应，控制反应温度20℃，反应时间9h。反应结束后，通过静置结晶法析出频哪醇，滤液继续循环使用。气相色谱分析表明，液相产物中频哪醇选择性为98％，异丙醇-丙酮总转化率为13％。气相色谱检测频哪醇纯度可达98％。Add 0.2ml SnCl 4 acetone source solution to 200ml isopropanol-acetone solution (volume ratio 90:10), pass argon gas under magnetic stirring for 10 minutes, turn on a 300W high-pressure mercury lamp for photocatalytic isopropanol dehydrogenation - Acetone hydrogenation coupling reaction, the reaction temperature is controlled at 20° C., and the reaction time is 9 hours. After the reaction finishes, pinacol is separated out by static crystallization, and the filtrate continues to be recycled. Gas chromatographic analysis showed that the selectivity of pinacol in the liquid phase product was 98%, and the total conversion rate of isopropanol-acetone was 13%. The purity of pinacol can reach 98% as detected by gas chromatography.
实施例3Example 3
将0.2ml SnCl4丙酮源溶液加入到200ml异丙醇-丙酮溶液(体积比为80:20)中，磁力搅拌下通入氩气10分钟，开启300W高压汞灯进行光催化异丙醇脱氢-丙酮加氢耦联反应，控制反应温度20℃，反应时间9h。反应结束后，通过静置结晶法析出频哪醇，滤液继续循环使用。气相色谱分析表明，液相产物中频哪醇选择性为97.5％，异丙醇-丙酮总转化率为13.6％。气相色谱检测频哪醇纯度可达98％。Add 0.2ml SnCl 4 acetone source solution to 200ml isopropanol-acetone solution (volume ratio 80:20), pass argon gas under magnetic stirring for 10 minutes, turn on a 300W high-pressure mercury lamp for photocatalytic isopropanol dehydrogenation - Acetone hydrogenation coupling reaction, the reaction temperature is controlled at 20° C., and the reaction time is 9 hours. After the reaction finishes, pinacol is separated out by static crystallization, and the filtrate continues to be recycled. Gas chromatography analysis showed that the selectivity of pinacol in the liquid phase product was 97.5%, and the total conversion rate of isopropanol-acetone was 13.6%. The purity of pinacol can reach 98% as detected by gas chromatography.
实施例4Example 4
将0.2ml SnCl4丙酮源溶液加入到200ml异丙醇中，磁力搅拌下通入氩气10分钟，开启300W高压汞灯进行光催化反应，控制反应温度20℃，反应时间9h。反应结束后，气相色谱分析表明，液相产物中频哪醇选择性为15％，异丙醇转化率为0.8％。Add 0.2ml of SnCl 4 acetone source solution to 200ml of isopropanol, pass in argon gas for 10 minutes under magnetic stirring, turn on a 300W high-pressure mercury lamp for photocatalytic reaction, control the reaction temperature at 20°C, and the reaction time for 9h. After the reaction, gas chromatographic analysis showed that the pinacol selectivity in the liquid phase product was 15%, and the conversion rate of isopropanol was 0.8%.
实施例5Example 5
将0.2ml SnCl4丙酮源溶液加入到200ml异丙醇-丙酮溶液(体积比为20:80)中，磁力搅拌下通入氩气10分钟，开启300W高压汞灯进行光催化异丙醇脱氢-丙酮加氢耦联反应，控制反应温度20℃，反应时间9h。反应结束后，通过静置结晶法析出频哪醇，滤液继续循环使用。气相色谱分析表明，液相产物中频哪醇选择性为66％，异丙醇-丙酮总转化率为29％。气相色谱检测频哪醇纯度可达98％。Add 0.2ml SnCl 4 acetone source solution to 200ml isopropanol-acetone solution (volume ratio 20:80), pass argon gas under magnetic stirring for 10 minutes, turn on 300W high-pressure mercury lamp for photocatalytic isopropanol dehydrogenation - Acetone hydrogenation coupling reaction, the reaction temperature is controlled at 20° C., and the reaction time is 9 hours. After the reaction finishes, pinacol is separated out by static crystallization, and the filtrate continues to be recycled. Gas chromatographic analysis showed that the selectivity of pinacol in the liquid phase product was 66%, and the total conversion rate of isopropanol-acetone was 29%. The purity of pinacol can reach 98% as detected by gas chromatography.
实施例6Example 6
将0.2ml SnCl4丙酮源溶液加入到200ml异丙醇-丙酮溶液(体积比为10:90)中，磁力搅拌下通入氩气10分钟，开启300W高压汞灯进行光催化异丙醇脱氢-丙酮加氢耦联反应，控制反应温度20℃，反应时间9h。反应结束后，通过静置结晶法析出频哪醇，滤液继续循环使用。气相色谱分析表明，液相产物中频哪醇选择性为55％，异丙醇-丙酮总转化率为29％。气相色谱检测频哪醇纯度可达98％。Add 0.2ml SnCl 4 acetone source solution to 200ml isopropanol-acetone solution (volume ratio 10:90), pass argon gas under magnetic stirring for 10 minutes, turn on a 300W high-pressure mercury lamp for photocatalytic isopropanol dehydrogenation - Acetone hydrogenation coupling reaction, the reaction temperature is controlled at 20° C., and the reaction time is 9 hours. After the reaction finishes, pinacol is separated out by static crystallization, and the filtrate continues to be recycled. Gas chromatographic analysis showed that the selectivity of pinacol in the liquid phase product was 55%, and the total conversion rate of isopropanol-acetone was 29%. The purity of pinacol can reach 98% as detected by gas chromatography.
实施例7Example 7
将0.2ml SnCl4丙酮源溶液加入到200ml丙酮溶液中，磁力搅拌下通入氩气10分钟，开启300W高压汞灯进行光催化反应，控制反应温度20℃，反应时间9h。反应结束后，气相色谱分析表明，液相产物中频哪醇选择性为5.6％，丙酮转化率为0.9％。Add 0.2ml of SnCl 4 acetone source solution to 200ml of acetone solution, pass in argon gas for 10 minutes under magnetic stirring, turn on a 300W high-pressure mercury lamp for photocatalytic reaction, control the reaction temperature at 20°C, and the reaction time for 9h. After the reaction, gas chromatography analysis showed that the pinacol selectivity in the liquid phase product was 5.6%, and the conversion rate of acetone was 0.9%.
实施例8Example 8
将0.5ml SnCl4丙酮源溶液加入到500ml异丙醇-丙酮溶液(体积比为50:50)中，磁力搅拌下通入氩气10分钟，开启300W高压汞灯进行光催化异丙醇脱氢-丙酮加氢耦联反应，控制反应温度20℃，反应时间9h。反应结束后，通过静置结晶法析出频哪醇，滤液继续循环使用。气相色谱分析表明，液相产物中频哪醇选择性为97.5％，异丙醇-丙酮总转化率为29％。气相色谱检测频哪醇纯度可达98％。Add 0.5ml SnCl 4 acetone source solution to 500ml isopropanol-acetone solution (volume ratio 50:50), pass argon gas under magnetic stirring for 10 minutes, turn on a 300W high-pressure mercury lamp for photocatalytic isopropanol dehydrogenation - Acetone hydrogenation coupling reaction, the reaction temperature is controlled at 20° C., and the reaction time is 9 hours. After the reaction finishes, pinacol is separated out by static crystallization, and the filtrate continues to be recycled. Gas chromatographic analysis showed that the selectivity of pinacol in the liquid phase product was 97.5%, and the total conversion rate of isopropanol-acetone was 29%. The purity of pinacol can reach 98% as detected by gas chromatography.
实施例9Example 9
将0.2ml SnCl4丙酮源溶液加入到200ml异丙醇-丙酮溶液(体积比为50:50)中，磁力搅拌下通入氩气10分钟，开启500W高压汞灯进行光催化异丙醇脱氢-丙酮加氢耦联反应，控制反应温度20℃，反应时间9h。反应结束后，通过静置结晶法析出频哪醇，滤液继续循环使用。气相色谱分析表明，液相产物中频哪醇选择性为98％，异丙醇-丙酮总转化率为36％。气相色谱检测频哪醇纯度可达98％。Add 0.2ml SnCl 4 acetone source solution to 200ml isopropanol-acetone solution (volume ratio 50:50), pass argon gas under magnetic stirring for 10 minutes, turn on a 500W high-pressure mercury lamp for photocatalytic isopropanol dehydrogenation - Acetone hydrogenation coupling reaction, the reaction temperature is controlled at 20° C., and the reaction time is 9 hours. After the reaction finishes, pinacol is separated out by static crystallization, and the filtrate continues to be recycled. Gas chromatographic analysis showed that the selectivity of pinacol in the liquid phase product was 98%, and the total conversion rate of isopropanol-acetone was 36%. The purity of pinacol can reach 98% as detected by gas chromatography.
实施例10Example 10
将0.2ml SnCl4丙酮源溶液加入到200ml异丙醇-丙酮溶液(体积比为50:50)中，磁力搅拌下通入氩气10分钟，开启200W高压汞灯进行光催化异丙醇脱氢-丙酮加氢耦联反应，控制反应温度20℃，反应时间9h。反应结束后，通过静置结晶法析出频哪醇，滤液继续循环使用。气相色谱分析表明，液相产物中频哪醇选择性为98％，异丙醇-丙酮总转化率为22％。气相色谱检测频哪醇纯度可达98％。Add 0.2ml SnCl 4 acetone source solution to 200ml isopropanol-acetone solution (volume ratio 50:50), pass argon gas under magnetic stirring for 10 minutes, turn on 200W high-pressure mercury lamp for photocatalytic isopropanol dehydrogenation - Acetone hydrogenation coupling reaction, the reaction temperature is controlled at 20° C., and the reaction time is 9 hours. After the reaction finishes, pinacol is separated out by static crystallization, and the filtrate continues to be recycled. Gas chromatographic analysis showed that the selectivity of pinacol in the liquid phase product was 98%, and the total conversion rate of isopropanol-acetone was 22%. The purity of pinacol can reach 98% as detected by gas chromatography.
实施例11Example 11
将0.2ml SnCl4丙酮源溶液加入到200ml异丙醇-丙酮溶液(体积比为50:50)中，磁力搅拌下通入氩气10分钟，开启300W高压汞灯进行光催化异丙醇脱氢-丙酮加氢耦联反应，控制反应温度50℃，反应时间9h。反应结束后，通过静置结晶法析出频哪醇，滤液继续循环使用。气相色谱分析表明，液相产物中频哪醇选择性为86％，异丙醇-丙酮总转化率为33％。气相色谱检测频哪醇纯度可达98％。Add 0.2ml SnCl 4 acetone source solution to 200ml isopropanol-acetone solution (volume ratio 50:50), pass argon gas under magnetic stirring for 10 minutes, turn on a 300W high-pressure mercury lamp for photocatalytic isopropanol dehydrogenation - Acetone hydrogenation coupling reaction, the reaction temperature is controlled at 50° C., and the reaction time is 9 hours. After the reaction finishes, pinacol is separated out by static crystallization, and the filtrate continues to be recycled. Gas chromatographic analysis showed that the selectivity of pinacol in the liquid phase product was 86%, and the total conversion rate of isopropanol-acetone was 33%. The purity of pinacol can reach 98% as detected by gas chromatography.
实施例12Example 12
将0.2ml SnCl4丙酮源溶液加入到200ml异丙醇-丙酮溶液(体积比为50:50)中，磁力搅拌下通入氩气10分钟，开启300W高压汞灯进行光催化异丙醇脱氢-丙酮加氢耦联反应，控制反应温度30℃，反应时间9h。反应结束后，通过静置结晶法析出频哪醇，滤液继续循环使用。气相色谱分析表明，液相产物中频哪醇选择性为89％，异丙醇-丙酮总转化率为32％。气相色谱检测频哪醇纯度可达98％。Add 0.2ml SnCl 4 acetone source solution to 200ml isopropanol-acetone solution (volume ratio 50:50), pass argon gas under magnetic stirring for 10 minutes, turn on a 300W high-pressure mercury lamp for photocatalytic isopropanol dehydrogenation - Acetone hydrogenation coupling reaction, the reaction temperature is controlled at 30° C., and the reaction time is 9 hours. After the reaction finishes, pinacol is separated out by static crystallization, and the filtrate continues to be recycled. Gas chromatographic analysis showed that the selectivity of pinacol in the liquid phase product was 89%, and the total conversion rate of isopropanol-acetone was 32%. The purity of pinacol can reach 98% as detected by gas chromatography.
实施例13Example 13
将0.2ml SnCl4丙酮源溶液加入到200ml异丙醇-丙酮溶液(体积比为50:50)中，磁力搅拌下通入氩气10分钟，开启300W高压汞灯进行光催化异丙醇脱氢-丙酮加氢耦联反应，控制反应温度20℃，反应时间5h。反应结束后，通过静置结晶法析出频哪醇，滤液继续循环使用。气相色谱分析表明，液相产物中频哪醇选择性为98％，异丙醇-丙酮总转化率为18％。气相色谱检测频哪醇纯度可达98％。Add 0.2ml SnCl 4 acetone source solution to 200ml isopropanol-acetone solution (volume ratio 50:50), pass argon gas under magnetic stirring for 10 minutes, turn on a 300W high-pressure mercury lamp for photocatalytic isopropanol dehydrogenation - Acetone hydrogenation coupling reaction, the reaction temperature is controlled at 20°C, and the reaction time is 5h. After the reaction finishes, pinacol is separated out by static crystallization, and the filtrate continues to be recycled. Gas chromatographic analysis showed that the selectivity of pinacol in the liquid phase product was 98%, and the total conversion rate of isopropanol-acetone was 18%. The purity of pinacol can reach 98% as detected by gas chromatography.
实施例14Example 14
将0.2ml SnCl4丙酮源溶液加入到200ml异丙醇-丙酮溶液(体积比为50:50)中，磁力搅拌下通入氩气10分钟，开启300W高压汞灯进行光催化异丙醇脱氢-丙酮加氢耦联反应，控制反应温度20℃，反应时间20h。反应结束后，通过静置结晶法析出频哪醇，滤液继续循环使用。气相色谱分析表明，液相产物中频哪醇选择性为98％，异丙醇-丙酮总转化率为30％。气相色谱检测频哪醇纯度可达98％。Add 0.2ml SnCl 4 acetone source solution to 200ml isopropanol-acetone solution (volume ratio 50:50), pass argon gas under magnetic stirring for 10 minutes, turn on a 300W high-pressure mercury lamp for photocatalytic isopropanol dehydrogenation -Acetone hydrocoupling reaction, the reaction temperature is controlled at 20°C, and the reaction time is 20h. After the reaction finishes, pinacol is separated out by static crystallization, and the filtrate continues to be recycled. Gas chromatographic analysis showed that the selectivity of pinacol in the liquid phase product was 98%, and the total conversion rate of isopropanol-acetone was 30%. The purity of pinacol can reach 98% as detected by gas chromatography.
实施例15Example 15
将0.2ml SnCl4异丙醇源溶液加入到200ml异丙醇-丙酮溶液(体积比为50:50)中，磁力搅拌下通入氩气10分钟，开启300W高压汞灯进行光催化异丙醇脱氢-丙酮加氢耦联反应，控制反应温度20℃，反应时间9h。反应结束后，通过静置结晶法析出频哪醇，滤液继续循环使用。气相色谱分析表明，液相产物中频哪醇选择性为98％，异丙醇-丙酮总转化率为16％。气相色谱检测频哪醇纯度可达98％。Add 0.2ml SnCl 4 isopropanol source solution to 200ml isopropanol-acetone solution (volume ratio 50:50), pass argon gas under magnetic stirring for 10 minutes, turn on a 300W high-pressure mercury lamp for photocatalytic isopropanol Dehydrogenation-acetone hydrogenation coupling reaction, the reaction temperature is controlled at 20°C, and the reaction time is 9h. After the reaction finishes, pinacol is separated out by static crystallization, and the filtrate continues to be recycled. Gas chromatographic analysis showed that the selectivity of pinacol in the liquid phase product was 98%, and the total conversion rate of isopropanol-acetone was 16%. The purity of pinacol can reach 98% as detected by gas chromatography.
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