CN105481671B - It is a kind of can catalyzed alkene allylic oxidation in aqueous method - Google Patents

It is a kind of can catalyzed alkene allylic oxidation in aqueous method Download PDF

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CN105481671B
CN105481671B CN201610036342.8A CN201610036342A CN105481671B CN 105481671 B CN105481671 B CN 105481671B CN 201610036342 A CN201610036342 A CN 201610036342A CN 105481671 B CN105481671 B CN 105481671B
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catalyst
metal ion
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CN105481671A (en
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唐瑞仁
周银
颜瑞
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Central South University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/28—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of CHx-moieties
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    • B01J31/22—Organic complexes
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    • B01J31/2208—Oxygen, e.g. acetylacetonates
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    • B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
    • B01J2531/22—Magnesium
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    • B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
    • B01J2531/72—Manganese
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    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
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    • B01J2531/842—Iron
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/847—Nickel
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    • B01J2531/90—Catalytic systems characterized by the solvent or solvent system used
    • B01J2531/96—Water

Abstract

It is a kind of can catalyzed alkene allylic oxidation in aqueous method, the present invention relates to one kind using various alkene as substrate, metal ion is cooperateed with as catalyst using soluble small molecule organic ligand and is catalyzed the method that allylic oxidation prepares corresponding carbonyls in aqueous.This method is using deionized water as solvent, soluble small moleculeN,O‑It is that catalyst, cetyl trimethylammonium bromide and the like is phase transfer catalyst that part, which assists metal ion, and the carbonyls of high selectivity is obtained by oxidizer catalytic oxyalkylene of tert-Butanol peroxide.The reaction is carried out in aqueous, and reaction temperature is 30 110 DEG C, and the reaction time is 3 30 h, and reaction condition is gentle, and high catalytic efficiency, catalyst system and catalyzing is practical, and use range is wide and easy cycling and reutilization.

Description

It is a kind of can catalyzed alkene allylic oxidation in aqueous method
Technical field
The present invention is organic synthesis field, more particularly to a kind of soluble small moleculeN,O-Part assists metal ion to make For catalyst, the preparation of efficient catalytic alkene allylic oxidation is corresponding in aqueousα,β-The side of beta-unsaturated carbonyl compounds Method.
Background technology
Alkene is obtained corresponding by allylic oxidationα,β-The conversion process of beta-unsaturated carbonyl compounds is all the time One of focus in catalysis oxidation field, the carbonylation product generated after reaction have the work do not replaced in different fields With particularly they can be widely used in the synthesis of food additives, spices, agricultural product, medicine and chemicals.For example, The allylic oxidation product cyclonene of cyclohexene is intermediate important in organic synthesis, the raw material of a variety of medicines and perfume, It is also a kind of important herbicide simultaneously；α-Isophorone (α-IP carbonylation product 4- ketoisophorones (KIP)) are to close Into carotenoid and the intermediate of vitamin E, added at the same time as natural perfume material in cigarette and play perfuming；β-Violet The oxidation product 4- oxos of ketone-β-Irisone is the key intermediate during carotenogenesis；Cholesterol acetate alkene 7- ketone-cholesterol that third oxidation obtains is then synthesis of vitamin d3Important source material.Traditional allylic oxidation method will be through Halogenation, hydrolysis and oxidation are gone through, synthesis step is cumbersome, and the side reaction of each reactions steps is more.And direct allylic oxidation Step is simple, less energy consumption, can effectively avoid these problems, have very big research and application value.Direct allylic oxidation The conventional catalyst system and catalyzing of reaction is concentrated mainly on transition metal, but because the hydrogen activity on the allylic carbon of alkene is not high, It is difficult to be oxidized, it usually needs using the catalyst of difficult recovery or complicated difficult synthesis and in expensive, inflammable and explosive and toxicity Reaction could obtain higher yield in larger organic solvent.Therefore, a kind of simple, efficient, environment-friendly, reaction bar is sought The allylic of gentle, using water as solvent the catalyst system and catalyzing Direct Catalytic Oxidation alkene of part prepares correspondingα,β-Unsaturated carbonyl The method of compound is still a greatly challenge.
The content of the invention
The purpose of the present invention aim to provide cost it is cheap, it is simple it is efficient, environment-friendly, reaction condition is gentle, with deionization Water is prepared as solvent catalysis oxyalkyleneα,β-The method of carbonyls, method of the invention use soluble small moleculeN, O-Part assists metal ion to be used as solvent using deionized water as catalyst.Catalyst is cheap, high catalytic efficiency, instead Short between seasonable, reaction condition is gentle, and energy consumption is low, and after selectivity of product is high, and reaction terminates, stratification is easily isolated, catalysis System is recyclable to be recycled, and operating process is simple and the reaction effect of recycling is suitable with the effect of former catalyst system and catalyzing.
The technical scheme is that：Using alkene as substrate, in aqueous, soluble small molecule is usedN,O-Part is assisted Aided metal ion is as catalyst, and CTMAB and other quaternary ammonium salts are phase transfer catalyst, and TBHP is oxidizer catalytic allylic olefin Third oxidation prepares correspondingα,β-Beta-unsaturated carbonyl compounds；
Soluble small molecule of the present inventionN,O-It is Cu that part, which assists the metal cation of metal ion catalyst,2+, Cu+, Co3+, Co2+, Mn2+, Mg2+, Fe3+, Fe2+, Ni2+, Cr3+, Mo2+Any of, the catalyst metal salts Anion be Br-、Cl-、SO4 2-、NO3 -、CH3COO-Any of, preferably CuCl2、CuSO4、Cu(OAc)2、Co (OAc)2；
The soluble small moleculeN,O-Part assist metal ion catalyst part beL-Proline,L-Phenylpropyl alcohol ammonia Acid,L-Histidine,L-Valine,L-Any of threonine, 2- pyridine carboxylic acids, preferablyL-Proline,L-Phenylalanine, 2- Pyridine carboxylic acid；
The phase transfer catalyst is cetyl trimethylammonium bromide, hexadecyltrimethylammonium chloride, tetrabutyl bromine Change ammonium, tetrabutyl ammonium hexafluorophosphate, tetrabutylammonium chloride, benzyltriethylammoinium chloride, DTAC, three pungent Any of methyl ammonium, preferably cetyl trimethylammonium bromide, TBAB, tetrabutylammonium chloride, ten Six alkyl trimethyl ammonium chlorides；
The olefin substrate and the mol ratio of catalyst are 50:1~5:1, preferably 30:1~5:1；
The soluble small moleculeN,O-The mol ratio of part and metal ion is 4:1~1:2, preferably 2:1~1:2；
The olefin substrate and the mol ratio of phase transfer catalyst are 500:1~50:1, preferably 400:1~100:1；
The olefin substrate and TBHP mol ratio are 1:2~1:5, preferably 1:3~1:5；
The reaction temperature is 30~110 DEG C, preferably 60 ~ 90 DEG C；
The reaction time is 3~30 h, preferably 5 ~ 15 h；
The olefin substrate is：α-Isophorone, cyclohexene,β-Irisone, ethylo benzene, tetrahydrochysene tetralin, indane, hexichol One kind of the derivative of methylmethane and these substrates；
It is described that the corresponding of synthesis is reacted by allylic carbonylationα,β-Beta-unsaturated ketone is 4- ketoisophorones, 2- rings Hexene -1- ketone, 4- oxos -β-Irisone, acetophenone, tetralone, indone, benzophenone and these carbonyls One kind of derivative.
A kind of soluble small molecule of the present inventionN,O-Part assists metal ion catalyst catalyzed alkene alkene in aqueous The method of third oxidation reaction, specific technical scheme are as follows：
Add what is necessarily matched into the round-bottomed flask with return ductN,O-Part and metal salt, deionized water is as molten Agent, it is allowed to be completely dissolved under magnetic agitation effect, quaternary ammonium salt phase transfer catalyst is added into bottle, sequentially adds alkene bottom Thing and TBHP, after heating a period of time at a certain temperature, stand, reaction solution is divided into two layers and is directly separated（Product be solid then Directly filter and be further purified）.Aqueous phase reclaims after being extracted with ethyl acetate 3 times, can direct circulation recycling；Organic phase Merge, respectively with saturation NaHSO3Washed with saturation NaCl solution, anhydrous Na2SO4Dry, be evaporated under reduced pressure recovery ethyl acetate, slightly Product is through further isolating and purifying accordinglyα,β- beta-unsaturated ketone.
Prepared with traditional alkeneα,βThe method of-beta-unsaturated ketone is compared, and the present invention has advantages below：
1st, reaction condition is gentle, and the reaction time is short, and reaction efficiency is high, and olefin conversion can reach about more than 60%（Up to 97%）, the selectivity of carbonylation product can reach about more than 70%（Up to 96%）；
2nd, catalyst cost is cheap, simple efficient, soluble in water, is easy to the separation of catalyst system and catalyzing using water as solvent with following Ring recycles, while can avoid organic solvent pollution on the environment.
Embodiment
The invention will be further described for following specific embodiment, but is not limitation of the invention further.
Embodiment 1 synthesizes 4- ketoisophorones
0.115 g (1 mmol) is sequentially added into the round-bottomed flask with return ductL-Proline and 0.170 g (1 mmol) CuCl2, add 5 mL deionized waters and be used as solvent, stir 5 min in the case where magnetic agitation acts on and be allowed to be completely dissolved, to 0.018 g (0.05 mmol) CTMAB is added in bottle, sequentially adds 1.38 g (10 mmol)α-Isophorone and 5.14 G (40 mmol) 70% tert-Butanol peroxide, the h of heating response 12 at 80 DEG C.Stop reaction, stand, reaction solution is divided into two Layer, is directly separated.Aqueous phase reclaims after being extracted with ethyl acetate 3 times, can direct circulation recycling；Organic phase merges, respectively with full And NaHSO3Washed with saturation NaCl solution, anhydrous Na2SO4Dry, be spin-dried for solvent.It is measured with gas-chromatography, is returned with area One change method is calculated, and is measuredα-The conversion ratio of isophorone is that the selectivity of 75.6%, 4- KIPs is 80.2%.
Embodiment 2-3
Similar to embodiment 1, conversionN,O-Part, react and 12 h are reacted at 80 DEG C, its result is as shown in Table 1：
Table oneN,O-Part pairα-The influence of isophorone oxidation reaction
。
Embodiment 4-6
Similar to embodiment 1, metal salt is converted, reacts and 12 h is reacted at 80 DEG C, its result is as shown in Table 2：
The metal salt pair of table twoα-The influence of isophorone oxidation reaction
。
Embodiment 7-9
Similar to embodiment 1, phase transfer catalyst is converted, reacts and 12 h is reacted at 80 DEG C, its result such as institute of table three Show：
Table triphase-transfer catalyst pairα-The influence of isophorone oxidation reaction
。
Embodiment 10-16
Similar to embodiment 1, conversionL-Proline and CuCl2The dosage of mol ratio and CTMAB, react at 80 DEG C 12 h are reacted, its result is as shown in Table 4：
Table fourL-Proline and CuCl2Mole when CTMAB dosages pairα-The influence of isophorone oxidation reaction
。
Embodiment 17-18
Similar to embodiment 1, TBHP dosage is converted, reacts and 12 h is reacted at 80 DEG C, its result is as shown in Table 5：
The TBHP dosages pair of table fiveα-The influence of isophorone oxidation reaction
。
Embodiment 19-23
Similar to embodiment 1, transformationreation time and reaction temperature, its result is as shown in Table 6：
The differential responses condition pair of table sixα-The influence of isophorone oxidation reaction
。
Embodiment 24
The blue aqueous phase (5 mL) reclaimed after embodiment 1-23 is reacted is added in reaction bulb, sequentially adds 1.38 g (10 mmol) α-The tert-Butanol peroxide of isophorone and 5.14 g (40 mmol) 70%, the h of heating response 12 at 80 DEG C. Stop reaction, stand, reaction solution is divided into two layers, is directly separated.Aqueous phase reclaims after being extracted with ethyl acetate 3 times, can direct circulation Recycle；Organic phase merges, respectively with saturation NaHSO3Washed with saturation NaCl solution, anhydrous Na2SO4Dry, be spin-dried for solvent. It is measured with gas-chromatography, is calculated with area normalization method, is measuredα-IP conversion ratio is 72.5%, KIP selectivity For 78.6%.
Embodiment 25
Similar to embodiment 24, it is transformed into the blue aqueous phase reclaimed after embodiment 23 is reacted and is added in reaction bulb, measureα-The selectivity that IP conversion ratio is 70.3%, KIP is 78.1%.
Embodiment 26
The product being spin-dried for after embodiment 1-25 reaction is summed up, vacuum distillation obtains colourless 4- KIPs cut （Bp.94-96 DEG C, 12 mmHg）.1H-NMR: δ 1.26 (s, 6H), δ 2.01 (s, 3H), δ 2.72 (s, 2H),δ 6.58 (s, 1H) 。
Embodiment 27 synthesizes 2- cyclohexene -1- ketone
0.115 g (1 mmol) is added into reaction bulbL-Proline and 0.170 g (1 mmol) CuCl2, add 5 ML deionized waters, 5 min of stirring make to be completely dissolved, and sequentially add 0.018 g (0.05 mmol) CTMAB, 0.82 g (10 Mmol) cyclohexene and 5.14 g (40 mmol) 70% tert-Butanol peroxide, the heating response at 60 DEG C.After 3 h, gas phase is used Chromatogram is measured, and is calculated with area normalization method, and the conversion ratio for measuring cyclohexene is 97.5%, 2- cyclohexene -1- ketone Selectivity is 96.8%.
The synthesis 4- of embodiment 28 oxos-β-Irisone
0.115 g (1 mmol) is added into reaction bulbL-Proline and 0.170 g (1 mmol) CuCl2, add 5 ML water, 5 min of stirring make to be completely dissolved, and sequentially add 0.018 g (0.05 mmol) CTMAB, 1.92 g (10 mmol)βThe tert-Butanol peroxide of-irisone and 5.14 g (40 mmol) 70%, the h of heating response 8 at 80 DEG C.Stop reaction, it is quiet Put, reaction solution is divided into two layers, is directly separated.Aqueous phase reclaims after being extracted with ethyl acetate 3 times, can direct circulation recycling；It is organic Mutually merge, respectively with saturation NaHSO3Washed with saturation NaCl solution, anhydrous Na2SO4Dry, be spin-dried for solvent.Use petroleum ether：Second Acetoacetic ester=8：1 is used as eluant, eluent, column chromatography carry out the isolated light yellow 4- oxos of 1.36 g (66.0%)-β-Irisone Liquid,1H-NMR: δ 1.15 (s, 6H), δ 1.69 (s, 3H), δ 1.82 (m, 2H), δ 2.31 (s, 3H),δ 2.48 (m, 2H), δ 6.12 (m, 1H), δ 7.26 (m, 1H) 。
Embodiment 29 synthesizes acetophenone
0.115 g (1 mmol) is added into reaction bulbL-Proline and 0.170 g (1 mmol) CuCl2, add 5 ML deionized waters, 5 min of stirring make to be completely dissolved, sequentially add 0.018 g (0.05 mmol) CTMAB, sequentially add The tert-Butanol peroxide of 1.06 g (10 mmol) ethylo benzenes and 5.14 g (40 mmol) 70%, the heating response at 60 DEG C, gas Phase chromatogram tracking reacts, and the conversion ratio that ethylo benzene is measured after 5h is 93.2%, and the selectivity of acetophenone is 96.8%.Stop reaction, Stand, reaction solution is divided into two layers, is directly separated.Aqueous phase reclaims after being extracted with ethyl acetate 3 times, can direct circulation recycling；Have Machine mutually merges, respectively with saturation NaHSO3Washed with saturation NaCl solution, anhydrous Na2SO4Dry, be spin-dried for solvent.Use petroleum ether： Ethyl acetate=8：1 is used as eluant, eluent, and column chromatography carries out the isolated colourless acetophenone liquid of 1.03 g (85.8%),1H-NMR:δ 2.69 (s, 3H), δ 7.48 (m, 2H), δ 7.61 (m, 1H), δ 2.32 (s, 3H), δ 7.96 (dd,J 1 =7.6, J 2 =6.2, 1H) 。
The synthesizing tetralone of embodiment 30
0.115 g (1 mmol) is added into reaction bulb L-Proline and 0.170 g (1 mmol) CuCl2, add 5 ML deionized waters, 5 min of stirring make to be completely dissolved, and sequentially add 0.018 g (0.05 mmol) CTMAB, 1.38 g (10 Mmol) tetrahydrochysene tetralin and 5.14 g (40 mmol) 70% tert-Butanol peroxide, the heating response at 60 DEG C, gas-chromatography tracking React, after 5 h, the conversion ratio for measuring tetrahydrochysene tetralin is 95.0%, and the selectivity of tetralone is 69.2%.
Embodiment 31 synthesizes indone
0.115 g (1 mmol) is added into reaction bulb L-Proline and 0.170 g (1 mmol) CuCl2, add 5 ML deionized waters, 5 min of stirring make to be completely dissolved, and sequentially add 0.018 g (0.05 mmol) CTMAB, 1.18 g (10 Mmol) indane and 5.14 g (40 mmol) 70% tert-Butanol peroxide, the h of heating response 12 at 80 DEG C.Stop reaction, it is quiet Put to room temperature, there is crystal precipitation.Directly filter, disposing mother liquor is recyclable to be recycled, and product is dried after being washed with water 3 times, uses stone Oily ether：Ethyl acetate=8：1 is used as eluant, eluent, and column chromatography progress is isolated to obtain the light yellow g of flat crystal 0.93 (70.5%) ,1H-NMR: δ 2.70 (m, 2H), δ 3.16 (m, 2H), δ 7.38 (t, J=7.4, 1H), δ 7.49 (m, 1H), δ 7.59 (dd, J 1 =10.6, J 2 =4.2, 1H), δ 7.77 (d, J=7.7, 1H) 。
Embodiment 32 synthesizes benzophenone
0.115 g (1 mmol) is added into reaction bulb L-Proline and 0.170 g (1 mmol) CuCl2, add 5mL deionized waters, 5 min of stirring make to be completely dissolved, and sequentially add 0.018 g (0.05 mmol) CTMAB, add successively again Enter 1.68 g (10 mmol) diphenyl methanes and 5.14 g (40 mmol) 70% tert-Butanol peroxide, heated at 80 DEG C React 8 h.Stop reaction, stand to room temperature, there is solid precipitation.Directly filter, disposing mother liquor is recyclable to be recycled, product water After washing 3 times, recrystallized with methanol and water, obtain the g of yellow solid 1.49 (81.9%),1H-NMR: δ 7.83 (m, 4H), δ 7.62 (m, 2H), δ 7.62 (dd, J 1 =10.5, J 2 =4.7, 4H)。

Claims (3)

1. it is a kind of can catalyzed alkene allylic oxidation in aqueous method, it is characterised in that with various alkene orα-Different Fo Er Ketone is substrate, using deionized water as solvent, soluble small moleculeN,O-It is catalyst that part, which assists metal ion, hexadecane Base trimethylammonium bromide, i.e. CTMAB, are phase transfer catalyst, tert-Butanol peroxide, i.e. TBHP, are the alkene of oxidizer catalytic alkene Third oxidation prepares various correspondingα,β-Beta-unsaturated carbonyl compounds；
The soluble small moleculeN,O-It is Cu that part, which assists the metal ion of metal ion catalyst,2+,Co2+In one kind；
The soluble small moleculeN,O-Part assist metal ion catalyst part beL-Proline, in 2- pyridine carboxylic acids One kind；
The phase transfer catalyst is cetyl trimethylammonium bromide；
The olefin substrate and the mol ratio of catalyst are 50:1~5:1；
It is describedN,O-The mol ratio of part and metal ion is 4:1~1:2；
The olefin substrate and the mol ratio of phase transfer catalyst are 500:1~50:1；
The olefin substrate and TBHP mol ratio are 1:2~1:5；
The reaction temperature is 30~110 DEG C, and the reaction time is 3~30 h.
2. according to claim 1 it is a kind of can catalyzed alkene allylic oxidation in aqueous method, it is characterised in that institute Stateα-Isophorone, in aqueous, using described catalyst, TBHP is oxidant, and it is different that catalysis oxidation obtains 4- oxos Phorone；It is describedα-Isophorone and soluble small moleculeN,O-It is 10 that part, which assists the mol ratio of metal ion catalyst,:1, It is describedN,O-The mol ratio of part and metal ion is 1:1；It is describedα-Isophorone and the mol ratio of phase transfer catalyst are 200:1；It is describedα-Isophorone and TBHP mol ratio are 1:4, reaction temperature is 80 DEG C, and the reaction time is 12 h.
3. according to claim 1 it is a kind of can catalyzed alkene allylic oxidation in aqueous method, it is characterised in that institute The olefin substrate stated is cyclohexene.
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