CN101565361A - Method for preparing carbonyl compound by oxygen catalysis and alcohol oxidation - Google Patents

Method for preparing carbonyl compound by oxygen catalysis and alcohol oxidation Download PDF

Info

Publication number
CN101565361A
CN101565361A CNA2008100111901A CN200810011190A CN101565361A CN 101565361 A CN101565361 A CN 101565361A CN A2008100111901 A CNA2008100111901 A CN A2008100111901A CN 200810011190 A CN200810011190 A CN 200810011190A CN 101565361 A CN101565361 A CN 101565361A
Authority
CN
China
Prior art keywords
alcohol
carbonyl compound
nitrite
compound according
oxygen
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CNA2008100111901A
Other languages
Chinese (zh)
Other versions
CN101565361B (en
Inventor
梁鑫淼
王心亮
刘仁华
徐青
薛兴亚
章飞芳
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dalian Institute of Chemical Physics of CAS
Original Assignee
Dalian Institute of Chemical Physics of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dalian Institute of Chemical Physics of CAS filed Critical Dalian Institute of Chemical Physics of CAS
Priority to CN2008100111901A priority Critical patent/CN101565361B/en
Publication of CN101565361A publication Critical patent/CN101565361A/en
Application granted granted Critical
Publication of CN101565361B publication Critical patent/CN101565361B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Abstract

The invention provides a method for preparing a carbonyl compound by oxygen catalysis and alcohol oxidation. The method takes the nitrite or the nitrite ester and the hydrobromate as the catalysts, the 0.1-0.8 MPa oxygen or the air is taken as the oxidant, the reaction is carried out for 1-48 h at the temperature of 0-80 DEG C, and a series of alcohols can be oxidized into carbonyl compound with high selectivity. The invention has the advantages of high yield, relatively mild reaction conditions, easily controlled operation, low cost, security, entire environmental-friendly process, no pollution, and the like.

Description

A kind of method of preparing carbonyl compound by oxygen catalysis and alcohol oxidation
Technical field
The present invention relates to the preparation of carbonyl compound, specifically by the chemical reaction process of oxygen catalytic oxidation alcohol, specifically a kind of nitrite (or nitrous acid ester) and Hydrogen bromide of utilizing made the corresponding method that is equipped with aldehyde, ketone or symmetric fatty acid ester fatty alcohol mixture as the dioxygen oxidation alcohol of catalyzer.
Background technology
It is to be one of most important unit process in the organic synthesis that alcohol is oxidized to carbonyl compound, this reaction is widely used in [document 1.Hudlicky in synthesizing of fine chemicals and organic intermediate, M.Oxidations in Organic Chemistry.Washington, DC:ACS, 1990].Stoichiometric oxygenant, for example chromic oxide [document 2.Muzart, J.Chem.Rev., 1992,92,113-140.], manganese oxide [document 3.Regen, S.L. are adopted in this class reaction traditionally; Koteel, C.J.Am.Chem.Soc., 1977,99,3837-3838.], ruthenium oxide [document 4.Griffith, W.P.Chem.Soc.Rev., 1992,21,179-185], Dess-Martin reagent [document 5.Dess, D.B.; Martin, J.C.J.Org.Chem., 1983,48,4155-4156] etc. oxygenant.Traditional method needs to use plurality of heavy metal reagent on the one hand, has increased raw materials cost; On the other hand, a large amount of waste severe contaminations of producing of reaction process environment.Therefore no matter from the angle of economy,, press for the dioxygen oxidation method of the green of development high-efficiency cleaning still from the viewpoint of protection environment and Sustainable development.
2004, Minisci etc. developed the Br that adopts catalytic amount 2/ HNO 3The catalyst system of oxygen catalytic oxidation alcohol, in ethylene dichloride/water (5: 1, volume ratio) in the mixed solvent, active substituted benzyl alcohol and primary aliphatic alcohols high-selectivity oxidation have been realized, generate corresponding substituted benzaldehyde and symmetric fatty acid ester fatty alcohol compound respectively, but this system is to catalytic activity very low [document 6.Minisci, the F. of secondary alcohol; Porta, O.; Recupero, F.; Punta, C.; Gambarotti, C.; Pierini, M.; Galimberti, L.Synlett, 2004,2203-2205].
Summary of the invention
The method that the purpose of this invention is to provide a kind of dioxygen oxidation alcohol system carbonyl compound; It has the productive rate height, and reaction conditions is gentle relatively, and operation is easy to control, and cost is low, safety, and whole process is environmentally friendly, does not have characteristics such as pollution.
For achieving the above object, the technical solution used in the present invention is:
The invention provides the method that a kind of dioxygen oxidation alcohol prepare carbonyl compound, in organic solvent, with oxygen or air oxidant, is catalyzer with nitrite or nitrous acid ester, Hydrogen bromide, oxidation alcohol generation carbonyl compound;
Wherein, the ratio of alcohol, nitrite or nitrous acid ester, hydrobromic amount of substance is 100: 1-25: 5-50;
Oxygen or air pressure are 0.1-0.8MPa; Temperature of reaction is 0-100 ℃; Reaction times is 1-48h.
This described nitrite is Sodium Nitrite or potassium nitrite, and nitrous acid ester is an alkyl nitrite; Described oxygen or air pressure are generally 0.1-0.4MPa; Described temperature of reaction is generally 10-80 ℃.
Dioxygen oxidation alcohol provided by the invention prepares the method for carbonyl compound, described organic solvent is benzene, toluene, chlorobenzene, fluorobenzene, trifluoromethylbenzene, methylene dichloride, ethylene dichloride, chloroform, tetracol phenixin, acetonitrile, acetate, ethyl acetate, α, α, the mixed solvent of one or more in α-trifluoroethanol.
Dioxygen oxidation alcohol provided by the invention prepares the method for carbonyl compound, and described alcohol has following structure:
Figure A20081001119000041
Wherein: R 1Be heterocycle or non-heterocyclic aromatic base or the C1-20 fatty group that contains various substituted radicals; R 2Be hydrogen or C1-20 alkyl.
The present invention can be oxidized to a series of alcohol carbonyl compound such as aldehyde, ketone or symmetric fatty acid ester fatty alcohol by highly selective.
The present invention is applicable to that the high-selectivity oxidation of reactive alcohols becomes aldehydes or ketones; Be applicable to that fat or alicyclic ring secondary alcohol high-selectivity oxidation become ketone; Be applicable to primary aliphatic alcohols is oxidized to symmetric fatty acid ester fatty alcohol.
The present invention is applicable to fine chemicals and the productions of the aldehydes or ketones compounds of chemical substantially such as medicine intermediate, agrochemicals, spices.
The present invention has following advantage:
1. adopt cheap, abundant air or oxygen instead of chemical oxygenant, effectively reduce raw materials cost.
2. the reaction conditions gentleness operates being easy to control.Be reflected in the organic solvent and carry out, temperature of reaction is controlled at 10～80 ℃, and at room temperature, reaction just can be carried out smoothly.Oxygen pressure is low, and under 0.1MPa oxygen or air pressure, reaction can be carried out smoothly.
3. aftertreatment is simple, the product yield height.
4. whole process is environmentally friendly, does not have pollution.Because used oxygenant is an oxygen in the reaction process, by product is a water, so whole process almost can not cause any pollution to environment, is a kind of green chemical synthesis method.
Embodiment
Give further instruction below by embodiment to the present invention, certainly, the present invention is not limited only to following embodiment.
Embodiment 1
Oxidizing reaction is carried out in the long-neck single necked round bottom flask (50mL) of magneton is housed.Earlier with 5.0mmol sec-n-octyl alcohol and 0.40mmol NaNO 2Join in the round-bottomed flask, add the 10mL ethylene dichloride again and make reaction solvent, and then add 0.80mmol concentrated hydrobromic acid (HBr), the flask top is airtight, communicates with the oxygen ball of a band cock.Stirring reaction under the room temperature, the transformation efficiency and the selectivity of gas-chromatography trace analysis reaction carried out in sampling, and specimen is without any purifying.After stirring certain hour, react completely and stop stirring.Reaction liquid is transferred in the separating funnel, carefully used the washed with dichloromethane flask then, merge organic solution.Use saturated Na successively 2S 2O 3The aqueous solution and NaHCO 3The solution washing organic phase, the organic layer anhydrous sodium sulfate drying, rotary evaporation is removed organic solvent and can be obtained pure product then, is benchmark counting yield yield with 5.0mmol.The content of product and optionally measure to adopt Agilent 6890N gas chromatography system, the HP-5 post (30mm * 0.25mm), hydrogen flame detector, the temperature of detector is 250 ℃, the temperature of sampler is 250 ℃, furnace temperature adopts temperature programming: earlier at 50 ℃ of constant temperature 5min, be warming up to 250 ℃ with 10 ℃/min then, and at 250 ℃ of constant temperature 3min.The contrast and the gas chromatography retention time of n-compound, GC-MS and 1H NMR, 13C NMR proves conclusively product, the results are shown in Table 1.
Embodiment 2
Test methods and procedures is used 0.40mmol HNO with embodiment 1 3Substitute NaNO 2, the results are shown in Table 1.
Embodiment 3
Test methods and procedures substitutes NaNO with embodiment 1 with the 0.40mmol nitrite tert-butyl 2, the results are shown in Table 1.
Embodiment 4
Test methods and procedures is used 0.40mmol Br with embodiment 1 2Substitute HBr, the results are shown in Table 1.
Embodiment 5
Test methods and procedures is used 0.40mmol Br with embodiment 2 2Substitute HBr, the results are shown in Table 1.
Embodiment 6
Test methods and procedures is used 0.40mmol Br with embodiment 3 2Substitute HBr, the results are shown in Table 1.
Embodiment 7
Test methods and procedures is with embodiment 1, but the flask open-top, direct and environmental communication, uncovered stirring reaction certain hour, transformation efficiency and selectivity with GC analyzes sec-n-octyl alcohol the results are shown in Table 1.
Embodiment 8
Test methods and procedures is with embodiment 3, but the flask open-top, direct and environmental communication, uncovered stirring reaction certain hour, transformation efficiency and selectivity with GC analyzes sec-n-octyl alcohol the results are shown in Table 1.
Table 1
Embodiment Time (hour) Transformation efficiency (%) Selectivity (%)
1 24 99.8 96.5
2 24 1.5 86.7
3 24 94.0 93.8
4 24 3.4 20.6
5 24 0.8 100
6 16 99.4 95.4
7 48 97.2 93.0
8 48 96.8 97.1
As can be seen from Table 1, HNO 3/ HBr, HNO 3/ Br 2, NaNO 2/ Br 2Deng not being the effective catalyst of catalyzed oxidation sec-n-octyl alcohol all, and has only NaNO 2/ HBr, t-BuONO/HBr and t-BuONO/Br 2Be only effective catalyst.In addition, adopt concentrated hydrobromic acid HBr and NaNO cheap and easy to get 2The catalyst system of forming, easy to operate, reaction effect is good.
Embodiment 9-23
Test methods and procedures is with embodiment 1, but in the different organic solvent of 10mL the stirring reaction certain hour, transformation efficiency and selectivity with GC analyzes sec-n-octyl alcohol the results are shown in Table 2.
Table 2
Embodiment Organic solvent Time (hour) Transformation efficiency (%) Selectivity (%)
1 ClCH 2CH 2Cl 24 99.8 96.5
9 CH 2Cl 2 24 97.3 98.7
10 CHCl 3 24 91.4 97.0
11 CCl 4 24 78.7 94.2
12 CF 3CH 2OH 24 95.0 94.9
13 t-BuOH 24 93.4 93.9
14 PhF 24 76.1 90.5
15 PhCl 24 70.0 86.0
16 PhMe 24 80.8 99.6
17 PhCF 3 24 3.1 45.2
18 HOAc 24 50.7 87.0
19 EtOAc 24 24.7 87.9
20 MeCN 24 1.6 87.5
21 THF 24 63.5 89.8
22 DMSO 24 51.7 81.6
23 n-heptane 24 62.5 91.2
As seen from Table 2, adopt oxygen catalytic oxidation system and ethylene dichloride cheap and easy to get to make reaction solvent, the transformation efficiency of reaction and selectivity are all preferable, and be simple to operate, and convenient product separation.
Embodiment 24-39
Test methods and procedures is with embodiment 1, and as reaction substrate, stirring reaction certain hour in the oxygen atmosphere in the 10mL ethylene dichloride is taken a sample and analyzed the transformation efficiency and the selectivity of substrate with GC with different alcohol (5.0mmol).React completely and stop stirring, reaction liquid is transferred in the separating funnel, carefully use the washed with dichloromethane flask then, merge organic solution.Use saturated Na successively 2S 2O 3The aqueous solution and NaHCO 3The solution washing organic phase, the organic layer anhydrous sodium sulfate drying, rotary evaporation is removed organic solvent and can be obtained pure product then, is benchmark counting yield yield with 5.0mmol.Concrete outcome sees Table 3.
Table 3
[a] method A:NaNO 2(8mol%), HBr (16mol%); Method B:NaNO 2(10mol%), HBr (20mol%); Method C:NaNO 2(15mol%), HBr (30mol%); Method D:NaNO 2(20mol%), HBr (40mol%).[b] is 60 ℃ of reactions down.
As shown in table 3, HBr/NaNO under the room temperature 2Catalyst system will need just can react completely at 60 ℃ of employing method C much smaller than secondary alcohol for the activity of active substituted benzyl alcohol and primary aliphatic alcohols, generates corresponding substituted benzaldehyde and symmetric fatty acid ester fatty alcohol (embodiment 24-30) respectively.For fragrant secondary alcohol, the employing method A generation arone that just can react completely, product selectivity also very high (embodiment 31-33); And employing method B also successfully oxidation of fat secondary alcohol (sec-n-octyl alcohol) become corresponding ketone (embodiment 34-36) with alicyclic ring secondary alcohol (hexalin, 1-fenchol).Possibility is owing to sterically hindered too big, and is slower such as the speed of response of alicyclic ring secondary alcohol such as 2-baras camphor and menthol, even extend to 48h, can not transform fully, and be attended by the product generation (embodiment 37-38) of small amounts bromo.
But it should be noted that HBr/NaNO 2But catalyst system chemo-selective oxidation 2-ethyl-1, the secondary hydroxyl in the 3-hexylene glycol and oxidation of primary hydroxyl (embodiment 39) not.
Show by above-mentioned example, dioxygen oxidation alcohol provided by the present invention prepares the method for carbonyl compound, can be at room temperature the effective ketone that becomes of oxygen catalytic oxidation secondary alcohol, obtain corresponding ketone with high yield, for sterically hindered big alicyclic ring secondary alcohol catalytic activity is preferably arranged also, and can chemo-selective oxidation secondary hydroxyl.Catalytic activity to primary alconol is lower, but after improving catalyst levels and temperature of reaction, active substituted benzyl alcohol of oxidation and primary aliphatic alcohols generate corresponding substituted benzaldehyde and symmetric fatty acid ester fatty alcohol equally smoothly.This method has the productive rate height, and reaction conditions is gentle relatively, and operation is easy to control, and cost is low, safety, and whole process is environmentally friendly, does not have characteristics such as pollution.

Claims (8)

1. the method for a preparing carbonyl compound by oxygen catalysis and alcohol oxidation, it is characterized in that: in organic solvent, with oxygen or air oxidant, with the amount that is equivalent to alcohol matter nitrite or nitrous acid ester, Hydrogen bromide be catalyzer, oxidation alcohol generates carbonyl compound;
Wherein, the ratio of alcohol, nitrite or nitrous acid ester, hydrobromic amount of substance is 100: 1-25: 5-50;
Oxygen or air pressure are 0.1-0.8MPa; Temperature of reaction is 0-100 ℃; Reaction times is 1-48h.
2. prepare the method for carbonyl compound according to the described dioxygen oxidation alcohol of claim 1, it is characterized in that: described carbonyl compound is aldehyde, ketone or symmetric fatty acid ester fatty alcohol compound.
3. prepare the method for carbonyl compound according to the described dioxygen oxidation alcohol of claim 1, it is characterized in that: described nitrite is Sodium Nitrite or potassium nitrite.
4. prepare the method for carbonyl compound according to the described dioxygen oxidation alcohol of claim 1, it is characterized in that: described nitrous acid ester is an alkyl nitrite.
5. prepare the method for carbonyl compound according to the described dioxygen oxidation alcohol of claim 1, it is characterized in that: described oxygen or air pressure are 0.1-0.4MPa.
6. prepare the method for carbonyl compound according to the described dioxygen oxidation alcohol of claim 1, it is characterized in that: described temperature of reaction is 10-80 ℃.
7. make the method for carbonyl compound according to the described dioxygen oxidation alcohol of claim 1, it is characterized in that: described organic solvent is benzene, toluene, chlorobenzene, fluorobenzene, trifluoromethylbenzene, methylene dichloride, ethylene dichloride, chloroform, tetracol phenixin, acetonitrile, acetate, ethyl acetate, α, α, the mixed solvent of one or more in α-trifluoroethanol, described organic solvent and pure weight ratio 5-30: 1.
8. prepare the method for carbonyl compound according to the described dioxygen oxidation alcohol of claim 1, it is characterized in that: described alcohol has following structure:
Figure A2008100111900002C1
Wherein: R 1Be heterocycle or non-heterocyclic aromatic base or the C1-20 fatty group that contains various substituted radicals; R 2Be hydrogen or C1-20 alkyl.
CN2008100111901A 2008-04-25 2008-04-25 Method for preparing carbonyl compound by oxygen catalysis and alcohol oxidation Expired - Fee Related CN101565361B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2008100111901A CN101565361B (en) 2008-04-25 2008-04-25 Method for preparing carbonyl compound by oxygen catalysis and alcohol oxidation

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2008100111901A CN101565361B (en) 2008-04-25 2008-04-25 Method for preparing carbonyl compound by oxygen catalysis and alcohol oxidation

Publications (2)

Publication Number Publication Date
CN101565361A true CN101565361A (en) 2009-10-28
CN101565361B CN101565361B (en) 2012-05-23

Family

ID=41281756

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2008100111901A Expired - Fee Related CN101565361B (en) 2008-04-25 2008-04-25 Method for preparing carbonyl compound by oxygen catalysis and alcohol oxidation

Country Status (1)

Country Link
CN (1) CN101565361B (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102653504A (en) * 2011-03-01 2012-09-05 华东理工大学 Method for preparing carbonyl compounds by alcohol catalytic oxidation through oxygen without transition metal
CN102826979A (en) * 2012-07-04 2012-12-19 华东师范大学 Method for selectively oxidizing benzyl alcohols into benzaldehyde and methyl benzoate compounds through using 1,3-dibromo-5,5-dimethylhydantoin (DBDMH)
CN110963947A (en) * 2019-12-23 2020-04-07 张家港格瑞特化学有限公司 Preparation method of surfactant
WO2022006690A1 (en) * 2020-06-23 2022-01-13 惠州学院 Method for preparing carbonyl derivative by oxidation of alcohol by nitrogen-containing catalyst

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100348565C (en) * 2004-12-16 2007-11-14 中国科学院大连化学物理研究所 Method for preparing aromatic aldehyde ketone by utilizing air as oxidant in hydro solvent system
CN101024602A (en) * 2006-02-17 2007-08-29 德古萨公司 Method for making alcohol to generate aerobe oxidation with transistion metal catalyst using stable nitroxyl free radical under moderate condition

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102653504A (en) * 2011-03-01 2012-09-05 华东理工大学 Method for preparing carbonyl compounds by alcohol catalytic oxidation through oxygen without transition metal
CN102826979A (en) * 2012-07-04 2012-12-19 华东师范大学 Method for selectively oxidizing benzyl alcohols into benzaldehyde and methyl benzoate compounds through using 1,3-dibromo-5,5-dimethylhydantoin (DBDMH)
CN102826979B (en) * 2012-07-04 2014-12-24 华东师范大学 Method for selectively oxidizing benzyl alcohols into benzaldehyde and methyl benzoate compounds through using 1,3-dibromo-5,5-dimethylhydantoin (DBDMH)
CN110963947A (en) * 2019-12-23 2020-04-07 张家港格瑞特化学有限公司 Preparation method of surfactant
WO2022006690A1 (en) * 2020-06-23 2022-01-13 惠州学院 Method for preparing carbonyl derivative by oxidation of alcohol by nitrogen-containing catalyst

Also Published As

Publication number Publication date
CN101565361B (en) 2012-05-23

Similar Documents

Publication Publication Date Title
CN101544548B (en) Method for preparing aldehydes or ketones by oxidizing alcohols with oxygen
CN101148400A (en) Method for preparing aldehydes and ketones by using oxygen gas to oxidize alcohols
CN101565344B (en) Method for preparing aldehyde or alkone by oxygen catalysis and alcohol oxidation under mild condition
CN101486621A (en) Method for preparing aldehyde or ketone by catalyzing air and oxidizing alcohol
CN100467432C (en) Synthesis method of substituted cyclohexanone and/or substituted cyclohexanol
CN101274922A (en) Preparation for epoxypropane
CN101903366B (en) Method for producing cis-rose oxide
CN101565361B (en) Method for preparing carbonyl compound by oxygen catalysis and alcohol oxidation
CN108707076A (en) A kind of preparation method of 4- acetoxyl-2-methyl-2-butylenoic aldehydes
JP2020512319A (en) Process for producing α, β unsaturated aldehyde by oxidation of alcohol in the presence of liquid phase
CN101580462B (en) Method for preparing ethyl methyl ketone by dehydrating 2,3-butanediol efficiently
CN106554281A (en) A kind of method that methyl benzoate hydrogenation reaction produces cyclohexanecarboxylic acid methyl esters
CN1962602A (en) Process for preparing dimethyl carbonate by reacting methanol, carbon monoxide and oxygen
CN103864549B (en) Method for preparing diphenyl ketone compound
CN102786499A (en) Method for preparing cyclohexene oxide
CN107398264B (en) Mg-Zr-Zn composite metal oxide catalyst and preparation method and application thereof
CN109622031B (en) Preparation method of 2-hydroxy phosphono zirconium acetate and application thereof in furfuryl alcohol synthesis
Zhenying et al. An efficient and stable ionic liquid system for synthesis of ethylene glycol via hydrolysis of ethylene carbonate
CN101830783B (en) Method for preparing aldehyde by oxidizing alcohol with oxygen in presence of Schiff-base complex catalyst
CN102452918B (en) Method for preparing corresponding dicarboxylic acid by catalytic oxidation of hydroxy acid
CN103537301A (en) Catalyst for coproduction of methylal and methyl formate from methanol through oxidization as well as preparation method and application of catalyst
CN102653504A (en) Method for preparing carbonyl compounds by alcohol catalytic oxidation through oxygen without transition metal
CN102173977A (en) Cu/Al2O3 catalyst and preparation method thereof as well as method for catalyzing hydrolysis of glycerol
CN103084192B (en) Cobalt phosphide catalyst for preparing 3-pentanone and propanal from hydrogen, carbon monoxide and ethylene
CN113651786A (en) Method for synthesizing 6-hydroxy-2-ethyl-2H-pyrone- [3] by catalyzing alpha-furylpropanol oxidation and product

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20120523

Termination date: 20150425

EXPY Termination of patent right or utility model