CN104276938B - Method for preparing gamma-carbonyl carboxylic acid, amino acid, amino acid ester and amide compounds - Google Patents
Method for preparing gamma-carbonyl carboxylic acid, amino acid, amino acid ester and amide compounds Download PDFInfo
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- CN104276938B CN104276938B CN201310273287.0A CN201310273287A CN104276938B CN 104276938 B CN104276938 B CN 104276938B CN 201310273287 A CN201310273287 A CN 201310273287A CN 104276938 B CN104276938 B CN 104276938B
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- 0 CC(c(cc1)ccc1C(CCC(O)=O)=O)=* Chemical compound CC(c(cc1)ccc1C(CCC(O)=O)=O)=* 0.000 description 1
- OLYYRBJHDBLBAB-ACGXKRRESA-N CCC(C)[C@@H](C(OC)=O)N(C(c1ccccc11)=O)C1=O Chemical compound CCC(C)[C@@H](C(OC)=O)N(C(c1ccccc11)=O)C1=O OLYYRBJHDBLBAB-ACGXKRRESA-N 0.000 description 1
- QZPUBZPFCZHUMI-UHFFFAOYSA-N CCCCNC(c1ccccn1)=O Chemical compound CCCCNC(c1ccccn1)=O QZPUBZPFCZHUMI-UHFFFAOYSA-N 0.000 description 1
- WEGIIJLHGPBEKL-UFBFGSQYSA-N C[C@H]([C@@H](C(OC)=O)N(C(c1ccccc11)=O)C1=O)C(C)=O Chemical compound C[C@H]([C@@H](C(OC)=O)N(C(c1ccccc11)=O)C1=O)C(C)=O WEGIIJLHGPBEKL-UFBFGSQYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/373—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of functional groups containing oxygen only in doubly bound form
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/185—Saturated compounds having only one carboxyl group and containing keto groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/40—Unsaturated compounds
- C07C59/76—Unsaturated compounds containing keto groups
- C07C59/84—Unsaturated compounds containing keto groups containing six membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/44—Iso-indoles; Hydrogenated iso-indoles
- C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/81—Amides; Imides
Abstract
The invention discloses a method for preparing gamma-carbonyl carboxylic acid, amino acid, amino acid ester and amide compounds. The method comprises the following steps: uniformly mixing a methylene-containing compound, an oxidizing agent and water to perform selective methylene carbon-hydrogen bond oxidation, so as to obtain at least one of gamma-carbonyl carboxylic acid, gamma-carbonyl amino acid and gamma-carbonyl amide compounds after the reaction is finished. The method is a methylene selective oxidation reaction which does not need a catalyst for catalysis and employs a persulfate as an oxidizing agent, and the reaction is successfully applied to oxidation of methylene carbon-hydrogen bonds of carboxylic acids, amino acids and amide compounds, excellent selectivity is obtained, and the method has important application value.
Description
Technical field
The present invention relates to a kind of method preparing gamma-carbonyl group carboxylic acid, amino acid, amino-acid ester and amides compound.
Background technology
Methylene is widely present in all kinds of organic compound molecules.Because methylene is not sent out with most chemical reagent
Give birth to reaction and in an organic molecule, there is the methylene of multiple chemistry non-equivalences, therefore for a long time, methylene is carried out
Selective oxidation is always and synthesizes the significant challenge that chemistry is faced.At present, still dependence sky main to methylene oxidation
So enzyme compound such as Cytochrome P450 (Nature.2004,432,829), bionical non-enzyme iron catalyst
(Science.2007,318,783；Science.2007,327,566；Angew.Chem.Int.Ed.2009,48,5720；
Angew.Chem.Int.Ed.2012,51,3448.), and the metal cluster class composition catalyst of complexity
(Nat.Chem.2010,2,478) to be realized with oxidant collective effect.However, expensive due to employing in the reaction,
The homogeneous catalyst being not easily recycled and recycling, limits its application in compound probability.
Content of the invention
It is an object of the invention to provide the methylene carbon-hydrogen link selective oxidation of carboxylic acid, amino acid and amides compound
Reaction.
The method preparing gamma-carbonyl group carboxylic acid that the present invention provides, is designated as method one, comprises the steps：
By HOOC-R1-CH2-R2Shown compound containing methylene, oxidant and water mix and carry out selective methylene
Carbon-hydrogen link oxidation reaction, reaction finishes and obtains described gamma-carbonyl group carboxylic acid；
Described R1Alkyl for C1-C3, R2For methyl or phenyl；
A kind of method preparing gamma-carbonyl group amino acid, is designated as method two, comprises the steps：
WillShown compound containing methylene, oxidant and water mix and carry out selective methylene
Carbon-hydrogen link oxidation reaction, reaction finishes and obtains described gamma-carbonyl group amino acid；
Described R3Alkyl for C1-C2；
A kind of method preparing gamma-carbonyl group amino-acid ester, is designated as method three, comprises the steps：
WillShown compound containing methylene, oxidant and water mix and carry out selective methylene
Carbon-hydrogen link oxidation reaction, reaction finishes and obtains described gamma-carbonyl group amino-acid ester；
Described R4Alkyl for C1-C2；
A kind of method preparing gamma-carbonyl group amides compound, is designated as method four, comprises the steps：
By EWG- (CH2)n-CH2-CH3Shown compound containing methylene, oxidant and water mix and carry out selective Asia
Methyl carbon-hydrogen link oxidation reaction, reaction finishes and obtains described gamma-carbonyl group amides compound；
Described EWG be phthaloyl imino (- NPhth, namely) or pyridine -2- formoxyl (-
NHPA, namely)；N is the integer of 1-2.
Specifically, in methods described one, HOOC-R1-CH2-CH3The shown compound containing methylene is in following compound
Any one：
In methods described two,The shown compound containing methylene isOr
In methods described three,The shown compound containing methylene isOr
In methods described four, EWG- (CH2)n-CH2-CH3The shown compound containing methylene is
Or
Described oxidant is persulfate.Described persulfate is selected from potassium peroxydisulfate, sodium peroxydisulfate and ammonium persulfate
At least one.
The amount ratio of described compound, oxidant and water containing methylene is 1mmol: 2mmol: 5-10mL.
Specifically, in methods described one, gamma-carbonyl group carboxylic acid is
In methods described two, gamma-carbonyl group amino acid is
In methods described three, gamma-carbonyl group amino-acid ester is
In methods described four, gamma-carbonyl group amides compound is
In described selective methylene carbon-hydrogen link oxidation step, temperature is 70-120 DEG C, specially 100 DEG C；When
Between be 4-12 hour, specially 4,6,8,12,4-8,6-8,6-12 or 8-12 hour.
This reaction can use thin-layer chromatography to be monitored, different according to substrate structure, available uviol lamp, bromophenol blue, and CAM etc. shows
Color method develops the color.
Methods described also comprises the steps：After described selective methylene carbon-hydrogen link oxidation step, will
Reaction system ethyl acetate or ether extraction, collect organic phase and are dried.
The present invention have devised no catalyst first, and the methylene selective oxidation with persulfate as oxidant is anti-
Should, and successfully use it for aoxidizing carboxylic acid, amino acid, the methylene carbon-hydrogen link in amides compound, obtain excellent area
Field selectivity, has important using value.
Specific embodiment
With reference to specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Institute
Method of stating is conventional method if no special instructions.Described raw material all can obtain from open commercial sources if no special instructions.
In the present invention, refer in particular to as non-, all of amount, percentage are mol ratio.
Embodiment 1, the preparation (method one) of compound 1
Reaction equation is as follows：
The positive valeric acid (102mg) of 1mmol is placed in the reaction vessel with polytetrafluoroethylene (PTFE) cock of 25mL, adds 2 times
The oxidant potassium peroxydisulfate K of amount2S2O8(2mmol, 540mg), distills water dissolves with 5mL, heats 4 hours at 100 DEG C.Reaction
After end, reaction system is cooled to room temperature, adds ethyl acetate to extract three times (10mL × 3 time), organic phase is through anhydrous Na2SO4
It is spin-dried for after drying, column chromatography purifies (dichloromethane: the volume ratio of methyl alcohol is 15: 1).Reaction thin-layer chromatography is monitored, and uses
Bromophenol blue or CAM colour developing.
The structure confirmation data of this product is as follows：
1H NMR (400MHz, CDCl3)：δ (ppm) 2.20 (s, 3H), 2.26 (t, J=6.4Hz, 2H), 2.76 (t, J=
6.4Hz, 2H).
This product structure is correct as from the foregoing, is target product.
Embodiment 2, the preparation (method one) of compound 2
Reaction equation is as follows：
The positive valeric acid of the 2- methyl (116mg) of 1mmol is placed in the reaction vessel with polytetrafluoroethylene (PTFE) cock of 25mL, plus
Enter the oxidant potassium peroxydisulfate K of 2 times amount2S2O8(2mmol, 540mg), with the distillation water dissolves of 10mL, at 100 DEG C, heating 6 is little
When.After reaction terminates, reaction system is cooled to room temperature, adds ethyl acetate to extract three times (10mL × 3 time), organic phase is through no
Water Na2SO4It is spin-dried for after drying, column chromatography purifies (dichloromethane: the volume ratio of methyl alcohol is 15: 1).Reaction is carried out with thin-layer chromatography
Monitoring, with bromophenol blue or CAM colour developing.
The structure confirmation data of this product is as follows：
1H NMR (400MHz, CDCl3)：δ (ppm) 1.23 (d, J=6.8Hz, 3H), 2.18 (s, 3H), 2.44-2.55 (m,
1H), 2.89-3.01 (m, 2H).
This product structure is correct as from the foregoing, is target product.
Embodiment 3, the preparation (method one) of compound 3
Reaction equation is as follows：
The positive valeric acid of the 3- methyl (116mg) of 1mmol is placed in the reaction vessel with polytetrafluoroethylene (PTFE) cock of 25mL, plus
Enter the oxidant potassium peroxydisulfate K of 2 times amount2S2O8(2mmol, 540mg), with the distillation water dissolves of 10mL, heats 12 at 100 DEG C
Hour.After reaction terminates, reaction system is cooled to room temperature, adds ethyl acetate to extract three times (10mL × 3 time), organic phase warp
Anhydrous Na2SO4It is spin-dried for after drying, column chromatography purifies (dichloromethane: the volume ratio of methyl alcohol is 15: 1).Reaction thin-layer chromatography enters
Row monitoring, with bromophenol blue or CAM colour developing.
The structure confirmation data of this product is as follows：
1H NMR (400MHz, CDCl3)：δ (ppm) 1.18 (d, J=7.2Hz, 3H), 2.23 (s, 3H), 2.31-2.39 (m,
1H), 2.79-2.86 (m, 1H), 2.92-3.05 (m, 1H).
This product structure is correct as from the foregoing, is target product.
Embodiment 4, the preparation (method one) of compound 4
Reaction equation is as follows：
4- phenyl n-butyric acie (164mg) of 1mmol is placed in the reaction vessel with polytetrafluoroethylene (PTFE) cock of 25mL, plus
Enter the oxidant potassium peroxydisulfate K of 2 times amount2S2O8(2mmol, 540mg), with the distillation water dissolves of 10mL, at 100 DEG C, heating 6 is little
When.After reaction terminates, reaction system is cooled to room temperature, adds ethyl acetate to extract three times (10mL × 3 time), organic phase is through no
Water Na2SO4It is spin-dried for after drying, column chromatography purifies (petroleum ether: the volume ratio of ethyl acetate is 1: 1).Reaction is carried out with thin-layer chromatography
Monitoring, is developed the color with uviol lamp.
The structure confirmation data of this product is as follows：
1H NMR (400MHz, CDCl3)：δ (ppm) 2.82 (d, J=6.4Hz, 2H), 3.32 (d, J=6.4Hz, 2H),
7.47 (t, J=7.2Hz, 2H), 7.58 (t, J=7.2Hz, 1H), 7.98 (d, J=8.4Hz, 2H).
This product structure is correct as from the foregoing, is target product.
Embodiment 5, the preparation (method two) of compound 5
Reaction equation is as follows：
By N- phthalyl -2- aminovaleric acid (247mg) of 1mmol be placed in 25mL with polytetrafluoroethylene (PTFE) cock
In reaction vessel, add the oxidant potassium peroxydisulfate K of 2 times amount2S2O8(2mmol, 540mg), with the distillation water dissolves of 10mL,
Heat 8 hours at 100 DEG C.After reaction terminates, reaction system is cooled to room temperature, adds ether to extract three times (10mL × 3 time),
Organic phase is through anhydrous Na2SO4It is spin-dried for after drying, column chromatography purifies (petroleum ether: the volume ratio of ethyl acetate is 2: 1).Reaction is with thin
Layer chromatography is monitored, and is developed the color with uviol lamp.
The structure confirmation data of this product is as follows：
1H NMR (400MHz, CD3OD)：δ (ppm) 2.19 (s, 3H), 3.17 (dd, J=7.2,17.6Hz, 1H), 3.58
(dd, J=7.2,17.6Hz, 1H), 5.37 (t, J=7.2Hz, 1H), 7.81-7.83 (m, 2H), 7.86-7.88 (m, 2H).
This product structure is correct as from the foregoing, is target product.
Embodiment 6, the preparation (method two) of compound 6
Reaction equation is as follows：
N-- phthalyl isoleucine (261mg) of 1mmol is placed in the anti-with polytetrafluoroethylene (PTFE) cock of 25mL
Answer in container, add the oxidant potassium peroxydisulfate K of 2 times amount2S2O8(2mmol, 540mg), with the distillation water dissolves of 10mL, 100
Heat 8 hours at DEG C.After reaction terminates, reaction system is cooled to room temperature, adds ether to extract three times (10mL × 3 time), have
Machine is through anhydrous Na2SO4It is spin-dried for after drying, column chromatography purifies (petroleum ether: the volume ratio of ethyl acetate is 2: 1).Reaction thin layer
Chromatogram is monitored, and is developed the color with uviol lamp.
The structure confirmation data of this product is as follows：
1H NMR (300MHz, CD3OD)：δ (ppm) 2.19 (s, 3H), 3.17 (dd, J=7.2,17.6Hz, 1H), 3.58
(dd, J=7.2,17.6Hz, 1H), 5.37 (t, J=7.2Hz, 1H), 7.81-7.83 (m, 2H), 7.86-7.88 (m, 2H).
This product structure is correct as from the foregoing, is target product.
Embodiment 7, the preparation (method three) of compound 7
Reaction equation is as follows：
By N- phthalyl -2- aminovaleric acid (261mg) of 1mmol be placed in 25mL with polytetrafluoroethylene (PTFE) cock
In reaction vessel, add the oxidant potassium peroxydisulfate K of 2 times amount2S2O8(2mmol, 540mg), with the distillation water dissolves of 10mL,
Heat 8 hours at 100 DEG C.After reaction terminates, reaction system is cooled to room temperature, adds ether to extract three times (10mL × 3 time),
Organic phase is through anhydrous Na2SO4It is spin-dried for after drying, column chromatography purifies (petroleum ether: the volume ratio of ethyl acetate is 2: 1).Reaction is with thin
Layer chromatography is monitored, and is developed the color with uviol lamp.
The structure confirmation data of this product is as follows：
1H NMR (300MHz, CDCl3)：δ (ppm) 2.23 (s, 3H), 3.19 (dd, J=10.5,18.0Hz, 1H), 3.56
(dd, J=10.5,18.0Hz, 1H), 3.73 (s, 3H), 5.49 (t, J=10.5Hz, 1H), 7.74-7.78 (m, 2H), 7.86-
7.88 (m, 2H).
This product structure is correct as from the foregoing, is target product.
Embodiment 8, the preparation (method three) of compound 8
Reaction equation is as follows：
N-- phthalyl isoleucine (275mg) of 1mmol is placed in the anti-with polytetrafluoroethylene (PTFE) cock of 25mL
Answer in container, add the oxidant potassium peroxydisulfate K of 2 times amount2S2O8(2mmol, 540mg), with the distillation water dissolves of 10mL, 100
Heat 8 hours at DEG C.After reaction terminates, reaction system is cooled to room temperature, adds ether to extract three times (10mL × 3 time), have
Machine is through anhydrous Na2SO4It is spin-dried for after drying, column chromatography purifies (petroleum ether: the volume ratio of ethyl acetate is 2: 1).Reaction thin layer
Chromatogram is monitored, and is developed the color with uviol lamp.
The structure confirmation data of this product is as follows：
1H NMR (300MHz, CDCl3)：δ (ppm) 1.39 (d, J=7.2Hz, 2H), 2.22 (s, 3H), 3.74 (s, 3H),
3.68-3.72 (m, 1H), 5.08 (d, J=8.7Hz, 1H), 7.72-7.79 (m, 2H), 7.84-7.89 (m, 2H).
This product structure is correct as from the foregoing, is target product.
Embodiment 9, the preparation (method four) of compound 9
Reaction equation is as follows：
The N- butyl phthalimide (203mg) of 1mmol is placed in the reaction with polytetrafluoroethylene (PTFE) cock of 25mL
In container, add the oxidant potassium peroxydisulfate K of 2 times amount2S2O8(2mmol, 540mg), with the distillation water dissolves of 10mL, at 100 DEG C
Lower heating 8 hours.After reaction terminates, reaction system is cooled to room temperature, adds ether to extract three times (10mL × 3 time), organic
Through anhydrous Na2SO4It is spin-dried for after drying, column chromatography purifies (petroleum ether: the volume ratio of ethyl acetate is 4: 1).Thin layer color is used in reaction
Spectrum is monitored, and is developed the color with uviol lamp.
The structure confirmation data of this product is as follows：
1H NMR (300MHz, CDCl3)：δ (ppm) 2.19 (s, 3H), 2.89 (t, J=7.6Hz, 2H), 3.96 (t, J=
7.6Hz, 2H), 7.71-7.78 (m, 2H), 7.82-7.93 (m, 2H).
This product structure is correct as from the foregoing, is target product.
Embodiment 10, the preparation (method four) of compound 10
Reaction equation is as follows：
The reaction with polytetrafluoroethylene (PTFE) cock that N- butyl-pyridinium -2- formamide (178mg) of 1mmol is placed in 25mL is held
In device, add the oxidant potassium peroxydisulfate K of 2 times amount2S2O8(2mmol, 540mg), with the distillation water dissolves of 10mL, at 100 DEG C
Heating 8 hours.After reaction terminates, reaction system is cooled to room temperature, adds ether to extract three times (10mL × 3 time), organic phase
Through anhydrous Na2SO4It is spin-dried for after drying, column chromatography purifies (dichloromethane: the volume ratio of methyl alcohol is 15: 1).Reaction thin-layer chromatography
It is monitored, developed the color with uviol lamp.
The structure confirmation data of this product is as follows：
1H NMR (300MHz, CDCl3)：δ (ppm) 2.18 (s, 3H), 2.80 (t, J=9.0Hz, 2H), 3.71 (t, J=
9.0Hz, 2H), 7.40-7.46 (m, 1H), 7.81-7.90 (m, 1H), 8.22 (d, J=7.8Hz, 1H), 8.58 (d, J=
4.8Hz, 1H).
This product structure is correct as from the foregoing, is target product.
Claims (8)
1. a kind of method preparing gamma-carbonyl group carboxylic acid, is designated as method one, comprises the steps：
By HOOC-R1-CH2-R2Shown compound containing methylene, oxidant and water mix and carry out selective mesomethylene carbon-hydrogen
Key oxidation reaction, reaction finishes and obtains described gamma-carbonyl group carboxylic acid；
Described R1Alkyl for C1-C3, R2For methyl or phenyl；
A kind of method preparing gamma-carbonyl group amino acid, is designated as method two, comprises the steps：
WillShown compound containing methylene, oxidant and water mix and carry out selective mesomethylene carbon-hydrogen
Key oxidation reaction, reaction finishes and obtains described gamma-carbonyl group amino acid；
Described R3Alkyl for C1-C2；
A kind of method preparing gamma-carbonyl group amino-acid ester, is designated as method three, comprises the steps：
WillShown compound containing methylene, oxidant and water mix and carry out selective mesomethylene carbon-hydrogen
Key oxidation reaction, reaction finishes and obtains described gamma-carbonyl group amino-acid ester；
Described R4Alkyl for C1-C2；
A kind of method preparing gamma-carbonyl group amides compound, is designated as method four, comprises the steps：
By EWG- (CH2)n-CH2-CH3Shown compound containing methylene, oxidant and water mix and carry out selective methylene
Carbon-hydrogen link oxidation reaction, reaction finishes and obtains described gamma-carbonyl group amides compound；
Described EWG is phthaloyl imino or pyridine -2- formoxyl；N is the integer of 1-2；
In methods described one to four, oxidant is persulfate.
2. method according to claim 1 it is characterised in that：In methods described one, HOOC-R1-CH2-R2Shown containing methylene
The compound of base is any one in following compound：
In methods described two,The shown compound containing methylene is
In methods described three,The shown compound containing methylene is
In methods described four, EWG- (CH2)n-CH2-CH3The shown compound containing methylene is
3. method according to claim 1 it is characterised in that：
In methods described one to four, persulfate is selected from least one in potassium peroxydisulfate, sodium peroxydisulfate and ammonium persulfate.
4. method according to claim 1 it is characterised in that：In methods described one to four, the compound containing methylene, oxygen
The amount ratio of agent and water is 1mmol：2mmol：5-10mL.
5. method according to claim 1 it is characterised in that：In methods described one, gamma-carbonyl group carboxylic acid is
In methods described two, gamma-carbonyl group amino acid is
In methods described three, gamma-carbonyl group amino-acid ester is
In methods described four, gamma-carbonyl group amides compound is
6. method according to claim 1 it is characterised in that：The selective methylene carbon-hydrogen link of methods described one to four
In oxidation step, temperature is 70-120 DEG C；
Time is 4-12 hour.
7. method according to claim 6 it is characterised in that：The selective methylene carbon-hydrogen link of methods described one to four
In oxidation step, temperature is 100 DEG C.
8. according to the arbitrary described method of claim 1-7 it is characterised in that：Methods described one to four all also includes walking as follows
Suddenly：After described selective methylene carbon-hydrogen link oxidation step, by reaction system ethyl acetate or ether extraction
Take, collect organic phase and be dried.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5874633A (en) * | 1981-10-30 | 1983-05-06 | Teijin Ltd | Preparation of carboxylic acid |
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|---|---|---|---|---|
| EP0990634A1 (en) * | 1998-02-13 | 2000-04-05 | Daicel Chemical Industries, Ltd. | Acylating agents, acylation method with the use of the same and adamantane derivatives |
| JP5874633B2 (en) * | 2010-05-28 | 2016-03-02 | 住友ベークライト株式会社 | Manufacturing method of epoxy resin composition for semiconductor encapsulation and manufacturing method of semiconductor device using the same |
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| DIRECT REMOTE OXIDATION OF ALIPHATIC KETONES TO γ- AND δ-DIKETONES;Gennady I. Nikishin等;《Tetrahedron Letters》;19841231;第25卷(第43期);第4987-4988页 * |
| H Oxidation with Sodium Periodate As the Terminal Oxidant.《Organometallics》.2013,第32卷第957-965页. * |
| Meng Zhou等.Cp* Iridium Precatalysts for Selective C− * |
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