CN105152829B - Method for synthesizing ketones from methyl tertiary alcohol - Google Patents
Method for synthesizing ketones from methyl tertiary alcohol Download PDFInfo
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- CN105152829B CN105152829B CN201510580441.8A CN201510580441A CN105152829B CN 105152829 B CN105152829 B CN 105152829B CN 201510580441 A CN201510580441 A CN 201510580441A CN 105152829 B CN105152829 B CN 105152829B
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- methyl tertiary
- tertiary alcohol
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Abstract
The invention provides a simple synthesis method of ketones. According to the method, in the presence of a solvent and a dehydrating agent, an oxygen agent is utilized to oxidize alpha-methyl tertiary alcohol by using ammonium ceric nitrate as a catalyst, thereby generating the carbonyl compounds. Compared with the traditional method, the method is simple, economical, green and environment-friendly, has the advantages of high yield, mild reaction conditions, no use of any ligand, low catalyst consumption and wide application range of the substrate, and is a simple synthesis method for synthesizing the compounds.
Description
Technical field
The present invention relates to the synthesis technical field of carbonyl compound.
Background technology
In organic synthesiss, the dehydrated in situ of the Alpha-Methyl tertiary alcohol generates alkene, and and then oxicracking is a kind of important
Functional group's transition regime, the always focal issue of academia and industrial quarters research.It can rupture and C-C keys introduce oxygen-containing
Functional group, generates carbonyl compound.
However, at present, the report for directly generating carbonyl compound by the Alpha-Methyl tertiary alcohol does not almost have.Although passing through alkene
The method of oxidation scission synthesizing carbonyl compound has many reports, but these methods are primarily present following some drawback：（1）Make
With enzyme catalysiss, response time for growing very much and special experimental assembly is needed；（2）Ozonolysiss, in addition to safety problem, are also present
The problems such as preparing ozone and need to consume the substantial amounts of energy and need special reaction unit；（3）Using the chemical oxygen of metering
Agent, needs high cost and brings substantial amounts of solid refuse；（4）Using cleaning oxidizer, such as TBHP or H2O2,
But these methods generally require the part of complexity and the metallic catalyst of high capacity；（5）Some have been used recently without metal
Organic catalyst, these methods are avoided and use transition-metal catalyst, it appears that in pharmaceutical synthesis, have very big application front
Scape, but these methods often there are problems that needing the organic catalyst and catalyst of high capacity cannot.These
The all more or less extensive application for limiting the method for shortcoming.
On the other hand, cerium compound low price, aboundresources, be readily available, and ammonium ceric nitrate（CAN）The list of participation
Electron transfer reaction（SET）, have huge application in organic synthesiss.
The content of the invention
It is an object of the invention to provide a kind of simplicity of the class carbonyl compound that can overcome above prior art defect
Synthetic method.
The technical scheme is that：Under conditions of solvent and dehydrant are present, with ammonium ceric nitrate as catalyst, using oxygen
Gas agent aoxidizes the Alpha-Methyl tertiary alcohol, generates carbonyl compound.
It is substrate and reaction initial feed that the present invention directly uses the Alpha-Methyl tertiary alcohol, with simple economy, environmental protection, product
Rate is high, reaction condition is gentle, do not use that any part, catalyst amount be low, substrate applied range, is that synthesis is this kind of with life
The simple synthesis of thing activity important compound.
The present invention has simple economy, environmental protection, yield is high, reaction condition is gentle, do not use any part, catalyst
Consumption is low, substrate applied range, is this kind of simple synthesis with biological activity important compound of synthesis.
In the present invention, solvent can be Isosorbide-5-Nitrae-dioxane, DMF, acetonitrile, dimethyl sulfoxide, second
One kind in alcohol, water, cyclohexyl, tetrahydrofuran, wherein preferred Isosorbide-5-Nitrae-dioxane.The synthetic ratio of reaction can be effectively improved.
In the present invention, reaction temperature wherein preferably 80 DEG C, can also effectively improve reaction between 30 DEG C～100 DEG C
Synthetic ratio.
In the present invention, the ammonium ceric nitrate is 0.1 %～10 with the molar ratio of the Alpha-Methyl tertiary alcohol: 100, preferably 5:
100, equally, can also effectively improve the synthetic ratio of reaction.
In the present invention, dehydrant can be trifluoroacetic acid（TFA）Or acetic acid, wherein preferably TFA, also react beneficial to improving
Synthetic ratio.
In the present invention, the consumption of dehydrant TFA can be the 13.4 mol%～134mol% of reactant, wherein preferably
Dehydrant TFA consumptions are optimum amount for 26.9 mol% of reactant, are greatly improved the synthetic ratio of reaction.
Specific embodiment
The following examples are illustrated in more detail to the present invention, rather than limitation of the invention further.
Embodiment 1
Under the pure oxygen of 1 atm, 1, the 1- benzoins of 0.5 mmol are added in 10 mL test tubes, 1,1- bis- is accounted for
The CAN of phenethanol mole 5%（Ammonium ceric nitrate）With 26.9 mol% TFA, the Isosorbide-5-Nitrae-dioxane solvent of 2 mL, 80 are heated to
DEG C, reacted with thin layer chromatography monitoring（Developing solvent: petrol ether/ethyl acetate 10: 1）.Terminate after reaction 24h, reactant liquor pours 10 into
In mL saturated aqueous ammonium chlorides, extracted with ether（10 mL, 3 times）.Merge organic layer, with anhydrous sodium sulfate drying, boil off molten
Agent, residue are used column chromatography（Eluent: petrol ether/ethyl acetate 10: 1）.Product benzophenone is obtained, yield is 90.8%.
Embodiment 2
Other conditions check the reaction under different solvents with embodiment 1, and experimental result is as shown in table 1.
The inspection of 1 different solvents of table
From the above results, when reaction dissolvent is Isosorbide-5-Nitrae-dioxane（Embodiment 1）When, the benzophenone yield of acquirement
Apparently higher than other solvents, therefore, the present invention preferably Isosorbide-5-Nitrae-dioxane is reaction dissolvent.
Embodiment 3
Other conditions check the reaction under different temperatures with embodiment 1, and experimental result is as shown in table 2.
The inspection of 2 differential responses temperature of table
From the above results, when the reaction temperature of oxidation reaction is 80 DEG C（Embodiment 1）, the benzophenone yield of acquirement
Apparently higher than other temperature, therefore, currently preferred reaction temperature is 80 DEG C.
Embodiment 4
, with embodiment 1, the reaction of catalyst testing consumption, experimental result are as shown in table 3 for other conditions.
The inspection of 3 catalyst amount effect of table
From the above results, when the consumption of CAN is 5 mol%（Based on reactant 1,1- benzoins）（Embodiment
1）When, the benzophenone yield of acquirement apparently higher than other consumptions, therefore, the consumption of currently preferred CAN is 5 mol%（Base
In reactant 1,1- benzoins）.
Embodiment 5
, with embodiment 1, the reaction of the different acid of inspection, experimental result are as shown in table 4 for other conditions.
The inspection of 4 different acid effects of table
From the above results, when reaction is trifluoroacetic acid using dehydrant（TFA）（Embodiment 1）When, the hexichol of acquirement
Ketone yield apparently higher than acetic acid, therefore, the present invention preferably trifluoroacetic acid（TFA）As dehydrant.
Embodiment 6
Other conditions check the reaction of TFA consumptions with embodiment 1, and experimental result is as shown in table 5.
The inspection of 5 TFA consumption effects of table
From the above results, when the dehydrant that reaction is used is trifluoroacetic acid（TFA）Consumption be 26.9 mol%（It is real
Apply example 1）When, the benzophenone yield of acquirement apparently higher than other consumptions, therefore, the present invention preferably trifluoroacetic acid（TFA）Use
Measure as 26.9 mol%.
Embodiment 7
With embodiment 1, the range of application of the different Alpha-Methyl tertiary alcohols of inspection, experimental result are shown in Table 6 to other conditions.
Table 6 checks the range of application of the different Alpha-Methyl tertiary alcohols
As seen from the above table, this method has a wide range of applications scope.
Claims (8)
1. a kind of method for synthesizing ketone by the methyl tertiary alcohol, under conditions of solvent and dehydrant are present, with ammonium ceric nitrate as catalysis
Agent, aoxidizes the Alpha-Methyl tertiary alcohol using oxygen agent, generates carbonyl compound；It is characterized in that：The solvent is 1,4- dioxane.
2. method according to claim 1, it is characterised in that：The reaction temperature during oxidation is 30 DEG C～100 DEG C.
3. method according to claim 2, it is characterised in that：The reaction temperature during oxidation is 80 DEG C.
4. method according to claim 1, it is characterised in that：The ammonium ceric nitrate with the molar ratio of the Alpha-Methyl tertiary alcohol is
0.1 %～10: 100.
5. method according to claim 4, it is characterised in that：The ammonium ceric nitrate with the molar ratio of the Alpha-Methyl tertiary alcohol is
5∶100。
6. method according to claim 1, it is characterised in that：The dehydrant is trifluoroacetic acid or acetic acid.
7. method according to claim 6, it is characterised in that：The dehydrant is trifluoroacetic acid.
8. according to claim 1 or 6 or 7 methods describeds, it is characterised in that：The inventory of the trifluoroacetic acid accounts for reactant and always rubs
The 13.4%～134% of that amount.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510580441.8A CN105152829B (en) | 2015-09-14 | 2015-09-14 | Method for synthesizing ketones from methyl tertiary alcohol |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510580441.8A CN105152829B (en) | 2015-09-14 | 2015-09-14 | Method for synthesizing ketones from methyl tertiary alcohol |
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| Publication Number | Publication Date |
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| CN105152829A CN105152829A (en) | 2015-12-16 |
| CN105152829B true CN105152829B (en) | 2017-03-22 |
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| CN108164402B (en) * | 2018-02-12 | 2020-11-03 | 南京林业大学 | Method for preparing ketone by oxidizing tertiary alcohol in water phase |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101906027A (en) * | 2009-06-05 | 2010-12-08 | 复旦大学 | Method for preparing aldehydes or ketones by alcohol oxidation reaction |
| CN104024201A (en) * | 2011-12-26 | 2014-09-03 | 公益财团法人相模中央化学研究所 | Method for producing farnesal using vanadium complex |
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2015
- 2015-09-14 CN CN201510580441.8A patent/CN105152829B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101906027A (en) * | 2009-06-05 | 2010-12-08 | 复旦大学 | Method for preparing aldehydes or ketones by alcohol oxidation reaction |
| CN104024201A (en) * | 2011-12-26 | 2014-09-03 | 公益财团法人相模中央化学研究所 | Method for producing farnesal using vanadium complex |
Non-Patent Citations (2)
| Title |
|---|
| CERIC AMMONIUM NITRATE CATALYZED OXIDATION OF ALDEHYDES AND ALCOHOLS;GOWDA,RAVIKUMAR R.;《CHINESE JOURNAL OF CHEMISTRY》;20111231(第29期);2380页，表1，2382页，图2，表4 * |
| EFFICIENT AEROBIC OXIDATION OF ALCOHOLS TO CARBONYL COMPOUNDS WITH NHPI/CAN CATALYTIC SYSTEM;sung soo Kim;《SYNTHETIC COMMUNICATIONS》;20041231;第34卷(第12期);2239页 * |
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