CN102653504A - Method for preparing carbonyl compounds by alcohol catalytic oxidation through oxygen without transition metal - Google Patents

Method for preparing carbonyl compounds by alcohol catalytic oxidation through oxygen without transition metal Download PDF

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CN102653504A
CN102653504A CN2011100479915A CN201110047991A CN102653504A CN 102653504 A CN102653504 A CN 102653504A CN 2011100479915 A CN2011100479915 A CN 2011100479915A CN 201110047991 A CN201110047991 A CN 201110047991A CN 102653504 A CN102653504 A CN 102653504A
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transition metal
carbonyl compound
contain
alcohol
oxygen
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梁鑫淼
王心亮
柯燕雄
何学冬
方成斌
张志光
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East China University of Science and Technology
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East China University of Science and Technology
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Abstract

The invention relates to a method for preparing carbonyl compounds by alcohol catalytic oxidation through oxygen without transition metal, wherein N-bromosuccinimide (NBS) or other halogen compounds, and nitrite esters are used as catalysts, oxygen at a pressure of 0.1-0.8 MPa is used as an oxidant, the reaction is carried out at 0-100 DEG C for 1-72 hours, and a series of alcohol can be oxidized into carbonyl compounds with high selectivity. The invention has the characteristics of high yield, relatively mild reaction conditions, easy operation control, low cost, safety, environment-friendly process, no pollution, and the like.

Description

A kind of pure method for preparing carbonyl compound of transition metal-catalyzed dioxygen oxidation that do not contain
[technical field]
The present invention relates to the carbonyl compound preparing technical field, specifically, is a kind of method that does not contain the preparing carbonyl compound by oxygen catalysis and alcohol oxidation of transition metal.
[background technology]
It is one of most important unit process in the organic synthesis that alcohol is oxidized to carbonyl compound, and this reaction is widely used in [document 1.Hudicky, M in synthesizing of fine chemicals and organic intermediate; Oxidations inOrganic Chemistry.Washington, DC:ACS, 1990].Stoichiometric oxygenant is adopted in this type reaction traditionally, for example chromic oxide [document 2.Muzart, J.Chem.Rev.1992,92,113-140], manganese oxide [document 3.Regen, S.L.; Koteel, C.J.Am.Chem.Soc., 1977,99,3837-383], 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., 1983,48,4159-4156] etc. oxygenant.Traditional method, one side need to use plurality of heavy metal reagent, have increased raw materials cost; On the other hand, a large amount of waste severe contaminations that produce in the reaction process environment.Therefore, no matter,, press for the dioxygen oxidation method of the green that develops high-efficiency cleaning still from the viewpoint of protection environment and Sustainable development from the angle of economy.
2004, Minisci etc. developed the Br that adopts catalytic amount 2/ HNO 3The catalystsystem of oxygen catalytic oxidation alcohol; In ethylene dichloride/water (5: 1; Volume ratio) in the mixed solvent, realizes active substituted benzyl alcohol and primary aliphatic alcohols high-selectivity oxidation, generated 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.; Gambaroti, C.; Pierini, M.; Galimberti, L.Synlett, 2004,2203-2205].
[summary of the invention]
The objective of the invention is to overcome the deficiency of prior art, a kind of method that transition metal-catalyzed dioxygen oxidation alcohol prepares carbonyl compound that do not contain is provided.
The objective of the invention is to realize through following technical scheme:
A kind of pure method for preparing carbonyl compound of transition metal-catalyzed dioxygen oxidation that do not contain; In organic solvent; Make oxygenant with oxygen, as catalyzer, oxidation alcohol generates carbonyl compound with halogen compounds, nitrous acid ester; Wherein, the ratio of the amount of substance of alcohol, halogen compounds, nitrous acid ester is 100: 5～8: 5～8; Carbonyl compound is aldehyde, ketone or symmetric fatty acid ester fatty alcohol compound;
Described organic solvent is an ETHYLE ACETATE, 1, one or several in 2-ethylene dichloride, methylene dichloride, chlorobenzene, trichloromethane, tetracol phenixin, toluene, THF, acetonitrile, the normal heptane;
Described halogen compounds is N-bromo-succinimide (NBS), liquid bromine (Br 2), a kind of in the Hydrogen bromide (HBr); Be preferably N-bromo-succinimide (NBS);
Described nitrous acid ester is nitrite tert-butyl (TBN);
Described oxygen, its oxygen pressure are 0.1～0.8MPa, and temperature of reaction is 0～100 ℃, and the reaction times is 1～72h; Pressure is preferably 0.1～0.4MPa, and temperature is preferably 10～80 ℃;
Described alcohol has following structure:
Figure BDA0000048342940000021
Wherein: R 1Heterocycle or non-heterocyclic aromatic base or C1～20 fatty group for various substituted radicals; R 2A kind of in hydrogen, C1～20 alkyls or the aromatic base;
Described organic solvent is 5～30: 1 with the mass ratio of alcohol;
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 active alcohol becomes aldehydes or ketones; Be applicable to that fragrance, fat or cycloaliphatic ring secondary alcohol high-selectivity oxidation become ketone; Be applicable to that various substituted benzylalcohols are oxidized to aldehyde; Be applicable to that various primary aliphatic alcohols are 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 basically such as medicine intermediate, agrochemicals, spices.
Compared with prior art, positively effect of the present invention is:
(1) the present invention adopt cheaply, abundant oxygen instead of chemical oxygenant, effectively reduce raw materials cost;
(2) reaction conditions of the present invention is gentle, and operation is easy to control; Be reflected in the organic solvent and carry out, temperature of reaction is controlled at 10～80 ℃, and reaction at room temperature can be carried out smoothly; Oxygen pressure is low, and under 0.1～0.4MPa oxygen pressure, reaction can be carried out smoothly;
(3) aftertreatment of the present invention is simple, and the productive rate yield is high;
(4) whole process of the present invention is environmentally friendly, does not have pollution, because used oxygenant is an oxygen in the reaction process, by product is a water, and whole process can produce any pollution to environment hardly, is a kind of green chemical synthesis method.
[embodiment]
The present invention below is provided a kind of pure embodiment for preparing the method for carbonyl compound of transition metal-catalyzed dioxygen oxidation that do not contain.
Embodiment 1
Oxidizing reaction is carried out in the 25mL single port eggplant-shape bottle of stirrer is housed.In eggplant-shape bottle, add 5.0mmol 1-phenylethyl alcohol, 0.25mmol N-bromo-succinimide (NBS), 0.25mmol nitrite tert-butyl (TBN), 5mL ETHYLE ACETATE (EtOAc) successively, balloon airtight and that make flask top and be full of oxygen directly communicates.Heated and stirred under 25 ℃ of water-baths, the transformation efficiency and the selectivity of gc trace analysis reaction carried out in sampling, and specimen is without any purifying.After reaction finishes, stop to stir.Reaction liquid is transferred in the separating funnel, carefully washed eggplant-shape bottle then, merge organic liquor with EtOAc.Use saturated Na successively 2S 2O 3The aqueous solution and NaHCO 3The solution washing organic phase is removed NBS and TBN.Organic layer is used anhydrous sodium sulfate drying, and rotary evaporation is removed organic solvent and can be obtained pure 1-phenylethyl alcohol then, is benchmark counting yield yield with 5.0mmol.The content of product and optionally measure to adopt Agilent 7890N gas chromatograph; (30mm * 0.25mm), fid detector, detector temperature are 300 ℃ to the HP-5 gas chromatographic column; Injector temperature is 300 ℃; Furnace temperature adopts temperature programming: furnace temperature keeps 5min at 80 ℃ earlier, is warming up to 300 ℃ with 10 ℃/min then, and at 250 ℃ of constant temperature 2min.The gas chromatography retention time of contrast and n-compound, GC-MS, 1HNMR with 13CNMR confirms product, and the result sees table 1.
Embodiment 2
Test methods and procedures is with embodiment 1, with 0.125mmol liquid bromine (Br 2) substituting NBS, the result sees table 1.
Embodiment 3
Test methods and procedures substitutes NBS with embodiment 1 with 0.25mmol Hydrogen bromide (HBr), and the result sees table 1.
Embodiment 4
Test methods and procedures substitutes NBS, 0.25mmolNaNO with embodiment 1 with 0.50mmol HBr 2Substitute TBN, the result sees table 1.
Embodiment 5
Test methods and procedures is with embodiment 1, with 0.25mmol concentrated nitric acid (HNO 3) substituting TBN, the result sees table 1.
Embodiment 6
Test methods and procedures is used 0.125mmol Br with embodiment 1 2Substitute NBS, 0.25mmolNaNO 2Substitute TBN, the result sees table 1.
Embodiment 7
Test methods and procedures is used 0.125mmol Br with embodiment 1 2Substitute NBS, 0.25mmol HNO 3Substitute TBN, the result sees table 1.
Embodiment 8
Test methods and procedures substitutes NBS, 0.25mmol HNO with embodiment 1 with 0.25mmol HBr 3Substitute TBN, the result sees table 1.
Table 1
Embodiment Time (hour) Transformation efficiency (%) Selectivity (%)
1 24 100.0 98.9
2 24 97.2 98.9
3 24 89.1 98.7
4 24 23.7 93.2
5 24 17.5 2.5
6 24 0.0 -
7 24 0.0 -
8 24 0.0 -
Can be found out by table 1, be solvent with EtOAc, and in the presence of TBN, catalyst n BS, Br 2, HBr all can obtain effect (embodiment 1～3) preferably.But with respect to NBS, HBr and Br 2All the severe toxicity and have very strong volatility, very high to equipment requirements, limited their practical application.
With ETHYLE ACETATE is solvent, HBr/NaNO 2The transformation efficiency of catalystsystem significantly reduces (embodiment 4); NBS/HNO 3Catalystsystem gets transformation efficiency and also is low to moderate 17.5%, selectivity also very poor (embodiment 5); And Br 2/ NaNO 2, Br 2/ HNO 3And HBr/HNO 3Catalystsystem does not then have catalytic activity (embodiment 6～8) to oxidation 1-phenylethyl alcohol.
Embodiment 9～19
Test methods and procedures is with embodiment 1, but in the 5mL different organic solvents stirring reaction certain hour, analyze the transformation efficiency and the selectivity of 1-phenylethyl alcohol with GC, the result sees table 2.
Table 2
Embodiment Organic solvent Time (hour) Transformation efficiency (%) Selectivity (%)
1 ClCH 2CH 2Cl 24 100.0 100.0
9 CH 2Cl 2 24 99.8 100.0
10 EtOAc 24 99.7 100.0
11 PhCl 24 99.6 97.4
12 CHCl 3 24 96.6 100.0
13 CF 3CH 2OH 24 95.6 46.5
14 CCl 4 24 91.4 99.1
15 PhMe 24 83.8 98.5
16 THF 24 79.1 100.0
17 MeCN 24 75.6 86.8
18 n-heptane 24 65.9 97.6
19 HOAc 24 55.4 95.5
Can find out that by table 2 adopt catalytic oxygen system and ETHYLE ACETATE cheap and easy to get to make reaction solvent, reaction conversion ratio and selectivity are all preferable, and be simple to operate, and convenient product separation.
Embodiment 20～39
Test methods and procedures is with embodiment 1; With different alcohol (5.0mmol) as reaction substrate; Stirring reaction certain hour in the oxygen atmosphere in 5mL EtOAc, the transformation efficiency and the selectivity of gc trace analysis reaction carried out in sampling, and specimen is without any purifying.After reaction finishes, stop to stir.Reaction liquid is transferred in the separating funnel, carefully washed eggplant-shape bottle then, merge organic liquor with EtOAc.Use saturated Na successively 2S 2O 3The aqueous solution and NaHCO 3The solution washing organic phase is removed NBS and TBN.Organic layer is used anhydrous sodium sulfate drying, and rotary evaporation is removed organic solvent and can be obtained pure article then, is benchmark counting yield yield with 5.0mmol.Concrete outcome is seen table 3.
Table 3
Figure BDA0000048342940000071
Figure BDA0000048342940000081
[a] method A:NBS (5mol%), TBN (5mol%), 25 ℃ of temperature of reaction; Method B:NBS (8mol%), TBN (8mol%), 70 ℃ of temperature of reaction.
As shown in table 3, the benzylalcohol compounds can obtain very high transformation efficiency and selectivity under N-bromo-succinimide (NBS)/nitrite tert-butyl (TBN) catalystsystem.And the substituent electronics property on the substituted benzyl alcohol no matter be electron-donating group (embodiment 21) or electron-withdrawing group (embodiment 22), can both be converted into corresponding aldehyde to the not obviously influence of this system fully.
For the primary aliphatic alcohols compounds, this system has reasonable catalytic effect, can be oxidized to symmetric fatty acid ester fatty alcohol compounds to primary aliphatic alcohols, and selectivity is also than higher (embodiment 23～25).
And fragrant secondary alcohol compounds can be converted into ketone smoothly, and is sterically hindered to the influence of this system very big (embodiment 26～27).The 1-phenylethyl alcohol can be oxidized to methyl phenyl ketone under the room temperature in 24h, and benzhydrol will extend to 72h, just can be oxidized to corresponding UVNUL MS-40.
For fatty secondary alcohol compounds, the borneol that sec-n-octyl alcohol and steric hindrance are very big all can be oxidized to corresponding ketone (embodiment 28～29) very easily.
In a word, N-bromo-succinimide (NBS)/nitrite tert-butyl (TBN) catalystsystem ability various alcohols of oxygen catalytic oxidation (benzylalcohol class, various primary alconol and secondary alcohol) is to obtain corresponding product than higher selectivity; It is a kind of relatively more green, cheap, nontoxic pure organic catalytic system of oxidation.
The above only is a preferred implementation of the present invention; Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the present invention's design; Can also make some improvement and retouching, these improvement and retouching also should be regarded as in protection scope of the present invention.

Claims (10)

1. one kind does not contain the method that transition metal-catalyzed dioxygen oxidation alcohol prepares carbonyl compound; It is characterized in that; In organic solvent, make oxygenant with oxygen, with halogen compounds, nitrous acid ester as catalyzer; Oxidation alcohol generates carbonyl compound, and carbonyl compound is aldehyde, ketone or symmetric fatty acid ester fatty alcohol compound.
2. a kind of method that transition metal-catalyzed dioxygen oxidation alcohol prepares carbonyl compound that do not contain as claimed in claim 1 is characterized in that the ratio of the amount of substance of described alcohol, halogen compounds, nitrous acid ester is 100: 5～8: 5～8.
3. a kind of method that transition metal-catalyzed dioxygen oxidation alcohol prepares carbonyl compound that do not contain as claimed in claim 1; It is characterized in that; Described organic solvent is an ETHYLE ACETATE, 1, one or several in 2-ethylene dichloride, methylene dichloride, chlorobenzene, trichloromethane, tetracol phenixin, toluene, THF, acetonitrile, the normal heptane.
4. a kind of method that transition metal-catalyzed dioxygen oxidation alcohol prepares carbonyl compound that do not contain as claimed in claim 1 is characterized in that described halogen compounds is N-bromo-succinimide (NBS), liquid bromine (Br 2), a kind of in the Hydrogen bromide (HBr).
5. a kind of method that transition metal-catalyzed dioxygen oxidation alcohol prepares carbonyl compound that do not contain as claimed in claim 4 is characterized in that described halogen compounds is N-bromo-succinimide (NBS).
6. a kind of method that transition metal-catalyzed dioxygen oxidation alcohol prepares carbonyl compound that do not contain as claimed in claim 1 is characterized in that described nitrous acid ester is nitrite tert-butyl (TBN).
7. a kind of method that transition metal-catalyzed dioxygen oxidation alcohol prepares carbonyl compound that do not contain as claimed in claim 1 is characterized in that described oxygen, its oxygen pressure are 0.1～0.8MPa, and temperature of reaction is 0～100 ℃, and the reaction times is 1～72h.
8. a kind of method that transition metal-catalyzed dioxygen oxidation alcohol prepares carbonyl compound that do not contain as claimed in claim 7 is characterized in that described oxygen, its oxygen pressure are 0.1～0.4MPa, and temperature of reaction is 10～80 ℃.
9. a kind of method that transition metal-catalyzed dioxygen oxidation alcohol prepares carbonyl compound that do not contain as claimed in claim 1 is characterized in that described alcohol has following structure:
Figure FDA0000048342930000021
Wherein: R 1Heterocycle or non-heterocyclic aromatic base or C1～20 fatty group for various substituted radicals; R 2A kind of in hydrogen, C1～20 alkyls or the aromatic base.
10. a kind of method that transition metal-catalyzed dioxygen oxidation alcohol prepares carbonyl compound that do not contain as claimed in claim 1 is characterized in that described organic solvent is 5～30: 1 with the mass ratio of alcohol.
CN2011100479915A 2011-03-01 2011-03-01 Method for preparing carbonyl compounds by alcohol catalytic oxidation through oxygen without transition metal Pending CN102653504A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103539646A (en) * 2013-10-14 2014-01-29 天津理工大学 Method for preparing aldehyde or ketone by catalyzing oxygen to oxidize organic alcohol
CN103880617A (en) * 2012-12-20 2014-06-25 中国科学院大连化学物理研究所 Method for preparing acetylenic ketone through oxidizing propargyl alcohol

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CN101434538A (en) * 2007-11-14 2009-05-20 中国科学院大连化学物理研究所 Method for converting fatty into ester by direct catalytic oxidation
CN101565361A (en) * 2008-04-25 2009-10-28 中国科学院大连化学物理研究所 Method for preparing carbonyl compound by oxygen catalysis and alcohol oxidation

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CN101565361A (en) * 2008-04-25 2009-10-28 中国科学院大连化学物理研究所 Method for preparing carbonyl compound by oxygen catalysis and alcohol oxidation

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Title
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103880617A (en) * 2012-12-20 2014-06-25 中国科学院大连化学物理研究所 Method for preparing acetylenic ketone through oxidizing propargyl alcohol
CN103880617B (en) * 2012-12-20 2016-06-15 中国科学院大连化学物理研究所 A kind of propargyl alcohol aoxidizes the method for acetylenic ketone processed
CN103539646A (en) * 2013-10-14 2014-01-29 天津理工大学 Method for preparing aldehyde or ketone by catalyzing oxygen to oxidize organic alcohol

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Application publication date: 20120905