CN105348060B - A kind of preparation method of 1,2 derovatives - Google Patents
A kind of preparation method of 1,2 derovatives Download PDFInfo
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- CN105348060B CN105348060B CN201510927525.4A CN201510927525A CN105348060B CN 105348060 B CN105348060 B CN 105348060B CN 201510927525 A CN201510927525 A CN 201510927525A CN 105348060 B CN105348060 B CN 105348060B
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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
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/673—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by change of size of the carbon skeleton
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
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- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
- C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D207/33—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with substituted hydrocarbon radicals, directly attached to ring carbon atoms
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Abstract
The invention discloses the method that one kind prepares 1,2 derovatives, and the derovatives of raw material 1,3 and the tetramethyl piperidine nitrogen oxides of industrial goods 2,2,6,6 cheap and easy to get are reacted under copper catalysis and produce the derovatives of product 1,2.The present invention is starting material using 1,3 derovatives, and raw material is easy to get, species is a lot；The product types obtained using the inventive method are various, not only can directly using but also can be used for other and further react；In addition, reagent dosage is few in reaction, reduces pollution, reduce production cost；And reaction condition is gentle, operation and last handling process are simple, the reaction time is short, yield is high, is suitable for industrialized production.
Description
Technical field
The invention belongs to the preparing technical field of organic compound, and in particular to the preparation side of one kind 1,2- derovatives
Method.
Background technology
1,2- Sesamin-group Lignans derivative is also known as benzil derivatives, is a kind of widely used fine chemicals, it
It is widely used in the synthesis of organic synthesis, medicine, agricultural chemicals and functional material.1,2- diphenylthanediones can be used for synthetic drug
Dilantin (popular name Phenyltoin) and its derivative（Referring to：Istvan, Timeea, Modra, Dorina, Annals
of West University of Timisoara, Series of Chemistry, 2013, 22(2), 67-76）.Should
Medicine can be used for the treatment disease such as trigeminal neuralgia and sciatica, hypotensive, anti-epileptic and anti-arrhythmia.Its structure and
Synthetic route is as follows：
In above route, the Cymag of severe toxicity is needed to use when synthesizing 1,2- diphenylthanediones.
1,2- diphenylthanedione derivative can easily be converted into benzoin dimethylether derivative, such compound tool
There is the features such as light-initiated efficiency high, dark stable storage and be used as sensitising agent；1,2- diphenylthanediones derivative is in alkaline bar
It can occur to reset generation benzoin acid derivative under part；Benzoin acid derivative can continue to generate hexichol second with acid reaction
Alkyd borate complex, the complex can be used as the charge adjusting agent of Toner in electronic photography, electrostatic image processing；1,2- bis-
The reaction of benzil derivative and O-phenylene diamine derivatives can synthesizing quinoxaline derivant, it is a kind of important compound,
It is widely used as medicine and agricultural chemicals, is widely used in materials synthesis；In addition, 1,2- diphenylthanedione derivative and cyclohexanone
Through three-step reaction can synthesis of chiral 1,2- diphenyl -1,2- ethylene diamine derivatives, the derivative contains C2Symmetry axis, as hand
Property part is widely used in asymmetric syntheses.
The synthetic technology of existing 1,2- Sesamin-group Lignans derivative can be broadly divided into following three class：1）By styrax through oxygen
Change and prepare.Various oxidants are needed to use in this method, such as nitric acid and various metal onidiges.The defects of this method is production peace
Breath perfume needs to use the Cymag of severe toxicity, and nitric acid and various metal onidiges environmental pollutions are larger；2）By tolans or two
The oxidized preparation of styrene.The defects of this method is that raw materials used talan or tolans are expensive, it is strong to need to use
Oxidant, environmental pollution are larger；3）By the oxidized preparation of phenylbenzyl ethanone derivatives.The defects of this method is that raw material is not easy
Obtain, need to use strong oxidizer, environmental pollution is larger；Can be by 1,3- in ferric trichloride/nitrite tert-butyl system
Derovatives are converted into 1,2- derovatives, are to need to use large excess of nitrite tert-butyl the defects of this method,
The product price is expensive, sees light, is heated or is easily decomposed when being impacted.
The deficiencies of severe reaction conditions, yield be not high, pollution is big, expensive reagents be present in existing method；Therefore find a kind of
Raw material sources are simple, meet Green Chemistry requirement, the method for preparing 1,2- derovatives that reaction condition is gentle, universality is good
It is critically important.
The content of the invention
It is an object of the invention to provide the preparation method that one kind prepares 1,2- derovatives, and it has raw material sources simple
It is single, in high yield, the advantages of reaction condition is gentle, universality is good.
To achieve the above object of the invention, the technical solution adopted by the present invention is：A kind of preparation side of 1,2- derovatives
Method, comprise the following steps：1,3- derovatives, 2,2,6,6- tetramethyl piperidines nitrogen oxides, copper catalyst and solvent are added
Enter in reactor, in 70~120 DEG C of reactions, obtain 1,2- derovatives；
The 1,3- derovatives are as shown in following chemical structure of general formula：
Wherein R1It is selected from：One kind in alkyl, aryl or heteroaryl；R2It is selected from：One kind in alkyl, aryl or heteroaryl；
The chemical formula of the copper catalyst is CuXn, wherein X is selected from：One kind in Cl, Br, I or trifluoromethanesulfonic acid base；
N is 1 or 2；
The solvent is selected from：One kind in ethanol, acetonitrile, acetic acid, propionic acid, toluene, dimethylformamide；
The 1,2- derovatives are as shown in following chemical structure of general formula：
。
In above-mentioned technical proposal, 1, the 3- Dicarbonyl derivatives are selected from 1,3- diphenyl -1,3- propanedione, 1- (4- first
Base phenyl) -3- diphenylpropane-1,3-dione (DPPO)s, 1- (4- methoxyphenyls) -3- diphenylpropane-1,3-dione (DPPO)s, 1- (4- chlorphenyls) -2-
Diphenylpropane-1,3-dione (DPPO), 1- (4- bromophenyls) -3- diphenylpropane-1,3-dione (DPPO)s, 1- (4- nitrobenzophenones) -3- phenyl -1,3- the third two
Ketone, 1,3- bis- (4- aminomethyl phenyls) -1,3- propanedione, 1,3- bis- (4- methoxyphenyls) -1,3- propanedione, (4- of 1,3- bis-
Bromophenyl) -1,3- propanedione, 1- (4- bromophenyls) -3- (4- methoxyphenyls) -1,3- propanedione, (the 2- bromobenzenes of 1,3- bis-
Base) -1,3- propanedione, 1,3- bis- (2- methoxyphenyls) -1,3- propanedione, 1,3- bis- (2- aminomethyl phenyls) -1,3- propanedione,
1- phenyl -1,3- pentanediones, heptadione -3,5,5,5- dimedones -1,3,1- (2- aminomethyl phenyls) -3- phenyl -1,
3- propanedione, 1- (2- furyls) -3- diphenylpropane-1,3-dione (DPPO)s, 1- (2- thienyls) -3- diphenylpropane-1,3-dione (DPPO)s, 1- (2-
Pyrrole radicals) -3- diphenylpropane-1,3-dione (DPPO)s, one kind in 1,3- bis- (2- furyls) -1,3- propanedione.
In above-mentioned technical proposal, thin-layer chromatography is utilized（TLC）Tracking reaction is until be fully completed.
In above-mentioned technical proposal, in molar ratio, 1,3- derovatives: 2,2,6,6- tetramethyl piperidine nitrogen oxides: copper
Catalyst is 1:（1~3）: (0.05~0.2）；Preferably 1: 2: 0.1.
In above-mentioned technical proposal, the reaction is carried out in atmosphere.Operation is simple and safe.
In preferable technical scheme, reaction carries out column chromatography for separation purification processes after terminating to product；Column chromatography for separation carries
Using petrol ether/ethyl acetate as eluant, eluent during pure processing, preferably the volume ratio of petroleum ether and ethyl acetate is 40: 1.
Preparation method disclosed by the invention is simple, and universality is good, therefore the invention also discloses according to above-mentioned preparation method
The 1,2- derovatives of preparation.
The course of reaction of above-mentioned technical proposal is represented by：
Due to the utilization of above-mentioned technical proposal, the present invention has following advantages compared with prior art:
1. the present invention is first using 1,3- derovatives and industrial goods 2,2,6,6- tetramethyl piperidine nitrogens cheap and easy to get
Oxide is starting material, only in the presence of copper catalyst, in air, efficiently prepares 1,2- derovatives；Raw material is easy to get, species
More, the product being prepared can be used directly, and intermediate can also be used as to be used for other further reactions.
2. the present invention is simple using raw material, without a variety of reagents of prior art requirement, reagent dosage is few, cost
It is low, wastage of material is avoided, and the application of existing toxic compounds is avoided, reduce pollution environment；Only need a small amount of catalyst
Product can be efficiently obtained, not only simplify the purification process of product, reduces the generation of discarded object, and have for commercial Application
There is positive realistic meaning.
3. preparation method reaction condition disclosed by the invention is simple, without the complicated atmosphere of prior art, in air
Reaction can efficiently obtain product, post-process very simple, column chromatography, avoid existing for existing course of reaction it is dangerous because
Element, be advantageous to chemical synthesis safety in production, ensure the security of the lives and property.
4. in method disclosed by the invention, reaction is carried out in atmosphere, and reaction condition is gentle, pollution is small, the reaction time is short,
Especially suitable for a variety of 1,3- derovatives, the high income of target product, operation and last handling process are simple, suitable for work
Industry metaplasia is produced.
Embodiment
With reference to embodiment, the invention will be further described：
Embodiment one：The synthesis of 1,2- diphenylthanediones
It is as follows as raw material, its reactions steps with 1,3- diphenyl -1,3- propanedione：
1,3- diphenyl -1,3- propanedione is added in reaction bulb（0.224 g, 1 mmol）, 2,2,6,6- tetramethyls
Piperidines nitrogen oxides（0.31 g, 2 mmol）, stannous chloride（0.010 g, 0.1 mmol）And ethanol（2 milliliters）, 70 DEG C of reactions；
TLC tracking reactions are until be fully completed；
The crude by column chromatography separation that reaction obtains after terminating (petroleum ether: ethyl acetate=40: 1), obtains target production
Thing（Yield 81%）.The analyze data of product is as follows：1H NMR (400 MHz, CDCl3): δ 7.97 (d, J = 7.5 Hz,
4H), 7.65 (t, J = 7.4 Hz, 2H), 7.50 (t, J = 7.7 Hz, 4H)。
Embodiment two：The synthesis of 1- (4- aminomethyl phenyls) -2- benzils
It is as follows as raw material, its reactions steps with 1- (4- aminomethyl phenyls) -3- phenyl -1,3- propanedione：
1- (4- aminomethyl phenyls) -3- diphenylpropane-1,3-dione (DPPO)s are added in reaction bulb（0.24 g, 1 mmol）、2,2,
6,6- tetramethyl piperidine nitrogen oxides（0.31 g, 2 mmol）, copper chloride（0.013 g, 0.1 mmol）And acetonitrile（2 milliliters）,
80 DEG C of reactions；
TLC tracking reactions are until be fully completed；
The crude by column chromatography separation that reaction obtains after terminating (petroleum ether: ethyl acetate=40: 1), obtains target production
Thing（Yield 80%）.The analyze data of product is as follows：1H NMR (400 MHz, CDCl3): δ 8.01 – 7.93 (m, 2H),
7.87 (d, J = 8.2 Hz, 2H), 7.69 – 7.58 (m, 1H), 7.50 (t, J = 7.7 Hz, 2H), 7.30
(d, J = 8.0 Hz, 2H), 2.43 (s, 3H)。
Embodiment three：The synthesis of 1- (4- methoxyphenyls) -2- benzils
It is as follows as raw material, its reactions steps with 1- (4- methoxyphenyls) -3- phenyl -1,3- propanedione：
1- (4- methoxyphenyls) -3- diphenylpropane-1,3-dione (DPPO)s are added in reaction bulb（0.25 g, 1 mmol）、2,
2,6,6- tetramethyl piperidine nitrogen oxides（0.31 g, 2 mmol）, copper bromide（0.022 g, 0.1 mmol）And acetic acid（2 millis
Rise）, 90 DEG C of reactions；
TLC tracking reactions are until be fully completed；
The crude by column chromatography separation that reaction obtains after terminating (petroleum ether: ethyl acetate=40: 1), obtains target production
Thing（Yield 88%）.The analyze data of product is as follows：1H NMR (400 MHz, CDCl3): δ 8.11 – 7.76 (m, 4H),
7.77 – 7.56 (m, 1H), 7.58 – 7.40 (m, 2H), 7.12 – 6.78 (m, 2H), 3.87 (s, 3H)。
Example IV：The synthesis of 1- (4- chlorphenyls) -2- benzils
It is as follows as raw material, its reactions steps with 1- (4- chlorphenyls) -2- phenyl -1,3- propanedione：
1- (4- chlorphenyls) -2- diphenylpropane-1,3-dione (DPPO)s are added in reaction bulb（0.26 g, 1 mmol）、2,2,6,
6- tetramethyl piperidine nitrogen oxides（0.31 g, 2 mmol）, cuprous bromide (0.014 g, 0.1 mmol) and propionic acid（2 millis
Rise）, 100 DEG C of reactions；
TLC tracking reactions are until be fully completed；
The crude by column chromatography separation that reaction obtains after terminating (petroleum ether: ethyl acetate=40: 1), obtains target production
Thing（Yield 82%）.The analyze data of product is as follows：1H NMR (400 MHz, CDCl3): δ 8.11 – 7.86 (m, 4H),
7.69 (t, J = 7.4 Hz, 1H), 7.60 – 7.45 (m, 4H)。
Embodiment five：The synthesis of 1- (4- bromophenyls) -2- benzils
It is as follows as raw material, its reactions steps with 1- (4- bromophenyls) -3- phenyl -1,3- propanedione：
1- (4- bromophenyls) -3- diphenylpropane-1,3-dione (DPPO)s are added in reaction bulb（0.30 g, 1 mmol）、2,2,6,
6- tetramethyl piperidine nitrogen oxides（0.31 g, 2 mmol）, cuprous iodide（0.020 g, 0.1 mmol）And toluene（2 milliliters）,
110 DEG C of reactions；
TLC tracking reactions are until be fully completed；
The crude by column chromatography separation that reaction obtains after terminating (petroleum ether: ethyl acetate=40: 1), obtains target production
Thing（Yield 80%）.The analyze data of product is as follows：1H NMR (400 MHz, CDCl3): δ 7.96 (d, J = 7.4 Hz,
2H), 7.84 (d, J = 8.5 Hz, 2H), 7.66 (d, J = 8.4 Hz, 3H), 7.52 (t, J = 7.7 Hz,
2H)。
Embodiment six：The synthesis of 1- (4- nitrobenzophenones) -2- benzils
It is as follows as raw material, its reactions steps with 1- (4- nitrobenzophenones) -3- phenyl -1,3- propanedione：
1- (4- nitrobenzophenones) -3- diphenylpropane-1,3-dione (DPPO)s are added in reaction bulb（0.27 g, 1 mmol）、2,2,
6,6- tetramethyl piperidine nitrogen oxides（0.31 g, 2 mmol）, cupric iodide（0.064 g, 0.2 mmol）And toluene（2 milliliters）,
120 DEG C of reactions；
TLC tracking reactions are until be fully completed；
The crude by column chromatography separation that reaction obtains after terminating (petroleum ether: ethyl acetate=40: 1), obtains target production
Thing（Yield 74%）.The analyze data of product is as follows：1H NMR (400 MHz, CDCl3): δ 8.36 (d, J = 8.1 Hz,
2H), 8.17 (d, J = 8.1 Hz, 2H), 7.99 (d, J = 7.3 Hz, 2H), 7.70 (d, J = 6.9 Hz,
1H), 7.55 (t, J = 7.1 Hz, 2H)。
Embodiment seven：The synthesis of 1,2- bis- (4- aminomethyl phenyls) second diketone
It is as follows as raw material, its reactions steps with 1,3- bis- (4- aminomethyl phenyls) -1,3- propanedione：
1,3- bis- (4- aminomethyl phenyls) -1,3- propanedione is added in reaction bulb（0.25 g, 1 mmol）、2,2,6,
6- tetramethyl piperidine nitrogen oxides（0.16 g, 1 mmol）, trifluoromethanesulfonic acid it is cuprous（0.021 g, 0.1 mmol）And dimethyl
Formamide（2 milliliters）, 120 DEG C of reactions；
TLC tracking reactions are until be fully completed；
The crude by column chromatography separation that reaction obtains after terminating (petroleum ether: ethyl acetate=40: 1), obtains target production
Thing（Yield 60%）.The analyze data of product is as follows：1H NMR (400 MHz, CDCl3): δ7.75 (d, J = 8.0 Hz,
4H), 7.18 (d, J = 8.0 Hz, 4H), 2.31 (s, 6H)。
Embodiment eight：The synthesis of 1,2- bis- (4- methoxyphenyls) second diketone
It is as follows as raw material, its reactions steps with 1,3- bis- (4- methoxyphenyls) -1,3- propanedione：
1,3- bis- (4- methoxyphenyls) -1,3- propanedione is added in reaction bulb（0.28 g, 1 mmol）、2,2,6,
6- tetramethyl piperidine nitrogen oxides（0.31 g, 2 mmol）, copper trifluoromethanesulfcomposite（0.036 g, 0.1 mmol）And dimethyl methyl
Acid amides（2 milliliters）, 120 DEG C of reactions；
TLC tracking reactions are until be fully completed；
The crude by column chromatography separation that reaction obtains after terminating (petroleum ether: ethyl acetate=40: 1), obtains target production
Thing（Yield 85%）.The analyze data of product is as follows：1H NMR (400 MHz, CDCl3): δ 7.94 (d, J = 9.0 Hz,
4H), 6.96 (d, J = 9.0 Hz, 4H), 3.88 (s, 6H)。
Embodiment nine：The synthesis of 1,2- bis- (4- bromophenyls) second diketone
It is as follows as raw material, its reactions steps with 1,3- bis- (4- bromophenyls) -1,3- propanedione：
1,3- bis- (4- bromophenyls) -1,3- propanedione is added in reaction bulb（0.38 g, 1 mmol）, 2,2,6,6- tetra-
Methyl piperidine nitrogen oxides（0.48 g, 3 mmol）, cuprous bromide (0.014 g, 0.1 mmol) and dimethylformamide（2
Milliliter）, 120 DEG C of reactions；
TLC tracking reactions are until be fully completed；
The crude by column chromatography separation that reaction obtains after terminating (petroleum ether: ethyl acetate=40: 1), obtains target production
Thing（Yield 78%）.The analyze data of product is as follows：1H NMR (400 MHz, CDCl3): δ 7.83 (d, J = 8.2 Hz,
4H), 7.67 (d, J = 8.2 Hz, 4H)。
Embodiment ten：The synthesis of 1- (4- bromophenyls) -2- (4- methoxyphenyls) second diketone
It is as follows as raw material, its reactions steps with 1- (4- bromophenyls) -3- (4- methoxyphenyls) -1,3- propanedione：
1- (4- bromophenyls) -3- (4- methoxyphenyls) -1,3- propanedione is added in reaction bulb（0.33 g, 1
mmol）, 2,2,6,6- tetramethyl piperidine nitrogen oxides（0.31 g, 2 mmol）, cuprous bromide (0.007 g, 0.05 mmol)
And dimethylformamide（2 milliliters）, 120 DEG C of reactions；
TLC tracking reactions are until be fully completed；
The crude by column chromatography separation that reaction obtains after terminating (petroleum ether: ethyl acetate=40: 1), obtains target production
Thing（Yield 61%）.The analyze data of product is as follows：1H NMR (400 MHz, CDCl3): δ 7.94 (d, J = 9.0 Hz,
2H), 7.84 (d, J = 8.7 Hz, 2H), 7.65 (d, J = 8.7 Hz, 2H), 6.98 (d, J = 9.0 Hz,
2H), 3.89 (s, 3H)。
Embodiment 11：The synthesis of 1,2- bis- (2- bromophenyls) second diketone
It is as follows as raw material, its reactions steps with 1,3- bis- (2- bromophenyls) -1,3- propanedione：
1,3- bis- (2- bromophenyls) -1,3- propanedione is added in reaction bulb（0.38 g, 1 mmol）, 2,2,6,6- tetra-
Methyl piperidine nitrogen oxides（0.31 g, 2 mmol）, cuprous bromide (0.014 g, 0.1 mmol) and dimethylformamide（2
Milliliter）, 120 DEG C of reactions；
TLC tracking reactions are until be fully completed；
The crude by column chromatography separation that reaction obtains after terminating (petroleum ether: ethyl acetate=40: 1), obtains target production
Thing（Yield 75%）.The analyze data of product is as follows：1H NMR (400 MHz, CDCl3): δ 8.09 – 7.92 (m, 2H),
7.69 (dd, J = 7.5, 1.5 Hz, 2H), 7.56 – 7.40 (m, 4H)。
Embodiment 12：The synthesis of 1,2- bis- (2- methoxyphenyls) second diketone
It is as follows as raw material, its reactions steps with 1,3- bis- (2- methoxyphenyls) -1,3- propanedione：
1,3- bis- (2- methoxyphenyls) -1,3- propanedione is added in reaction bulb（0.28 g, 1 mmol）、2,2,6,
6- tetramethyl piperidine nitrogen oxides（0.31 g, 2 mmol）, stannous chloride（0.010 g, 0.1 mmol）And dimethylformamide
（2 milliliters）, 120 DEG C of reactions；
TLC tracking reactions are until be fully completed；
The crude by column chromatography separation that reaction obtains after terminating (petroleum ether: ethyl acetate=40: 1), obtains target production
Thing（Yield 73%）.The analyze data of product is as follows：1H NMR (400 MHz, CDCl3): δ 8.07 (dd, J = 7.8,
1.7 Hz, 2H), 7.63 – 7.49 (m, 2H), 7.16 – 7.06 (m, 2H), 6.94 (d, J = 8.4 Hz,
2H), 3.57 (s, 6H)。
Embodiment 13：The synthesis of 1,2- bis- (2- aminomethyl phenyls) second diketone
It is as follows as raw material, its reactions steps with 1,3- bis- (2- aminomethyl phenyls) -1,3- propanedione：
1,3- bis- (2- aminomethyl phenyls) -1,3- propanedione is added in reaction bulb（0.25 g, 1 mmol）、2,2,6,6-
Tetramethyl piperidine nitrogen oxides（0.31 g, 2 mmol）, stannous chloride（0.010 g, 0.1 mmol）And dimethylformamide（2
Milliliter）, 120 DEG C of reactions；
TLC tracking reactions are until be fully completed；
The crude by column chromatography separation that reaction obtains after terminating (petroleum ether: ethyl acetate=40: 1), obtains target production
Thing（Yield 75%）.The analyze data of product is as follows：1H NMR (400 MHz, CDCl3): δ 7.57 (dd, J = 7.8,
1.1 Hz, 2H), 7.38 (td, J = 7.5, 1.3 Hz, 2H), 7.24 (d, J = 7.7 Hz, 2H), 7.18
(dd, J = 11.2, 3.9 Hz, 2H), 2.61 (s, 6H)。
Embodiment 14：The synthesis of 1- phenyl -1,2- diacetyl
It is as follows as raw material, its reactions steps with 1- phenyl -1,3- pentanedione：
1- phenyl -1,3- pentanediones are added in reaction bulb（0.18 g, 1 mmol）, 2,2,6,6- tetramethyl piperidine nitrogens
Oxide（0.31 g, 2 mmol）, cuprous bromide (0.014 g, 0.1 mmol) and dimethylformamide（2 milliliters）, 120 DEG C
Reaction；
TLC tracking reactions are until be fully completed；
The crude by column chromatography separation that reaction obtains after terminating (petroleum ether: ethyl acetate=40: 1), obtains target production
Thing（Yield 64%）.The analyze data of product is as follows：1H NMR (400 MHz, CDCl3): δ7.97 (d, J = 7.5 Hz,
2H), 7.65 (t, J = 7.4 Hz, 1H), 7.50 (t, J = 7.7 Hz, 2H), 2.70 (q, J = 8.6,
2H), 1.23 (t, J = 8.6, 3H)。
Embodiment 15：The synthesis of acetyl butyryl -3,4
Raw material is used as with heptadione -3,5, its reactions steps is as follows：
Heptadione -3,5 is added in reaction bulb（0.13 g, 1 mmol）, 2,2,6,6- tetramethyl piperidine nitrogen oxides
（0.31 g, 2 mmol）, cuprous bromide (0.014 g, 0.1 mmol) and acetic acid（2 milliliters）, 100 DEG C of reactions；
TLC tracking reactions are until be fully completed；
The crude by column chromatography separation that reaction obtains after terminating (petroleum ether: ethyl acetate=40: 1), obtains target production
Thing（Yield 63%）.The analyze data of product is as follows：1H NMR (400 MHz, CDCl3): δ2.70 (q, J = 8.6,
4H), 1.23 (t, J = 8.6, 6H)。
Embodiment 16：The synthesis of 4,4- dimethyl cyclopentanedione -1,2
Raw material is used as with 5,5- dimedones -1,3, its reactions steps is as follows：
5,5- dimedones -1,3 are added in reaction bulb（0.140 g, 1 mmol）, 2,2,6,6- tetramethyls
Piperidines nitrogen oxides（0.31 g, 2 mmol）, cuprous bromide (0.014 g, 0.1 mmol) and acetic acid（2 milliliters）, 100 DEG C anti-
Should；
TLC tracking reactions are until be fully completed；
The crude by column chromatography separation that reaction obtains after terminating (petroleum ether: ethyl acetate=40: 1), obtains target production
Thing（Yield 69%）.The analyze data of product is as follows：1H NMR (400 MHz, CDCl3):δ 2.83 (s, 4H), 1.31
(s, 6H)。
Embodiment 17：The synthesis of 1- (2- aminomethyl phenyls) -2- benzils
It is as follows as raw material, its reactions steps with 1- (2- aminomethyl phenyls) -3- phenyl -1,3- propanedione：
1- (2- aminomethyl phenyls) -3- diphenylpropane-1,3-dione (DPPO)s are added in reaction bulb（0.24 g, 1 mmol）、2,2,
6,6- tetramethyl piperidine nitrogen oxides（0.31 g, 2 mmol）, cuprous bromide (0.014 g, 0.1 mmol) and acetic acid（2 millis
Rise）, 100 DEG C of reactions；
TLC tracking reactions are until be fully completed；
The crude by column chromatography separation that reaction obtains after terminating (petroleum ether: ethyl acetate=40: 1), obtains target production
Thing（Yield 85%）.The analyze data of product is as follows：1H NMR (400 MHz, CDCl3): δ 7.99 (dd, J = 8.4,
1.3 Hz, 2H), 7.67 (tt, J = 6.8, 1.2 Hz, 2H), 7.61 – 7.45 (m, 3H), 7.36 (d, J
= 7.7 Hz, 1H), 7.33 – 7.23 (m, 1H), 2.73 (s, 3H)。
Embodiment 18：The synthesis of 1- (2- furyls) -2- benzils
It is as follows as raw material, its reactions steps with 1- (2- furyls) -3- phenyl -1,3- propanedione：
1- (2- furyls) -3- diphenylpropane-1,3-dione (DPPO)s are added in reaction bulb（0.21 g, 1 mmol）、2,2,6,
6- tetramethyl piperidine nitrogen oxides（0.31 g, 2 mmol）, cuprous bromide (0.014 g, 0.1 mmol) and acetic acid（2 millis
Rise）, 100 DEG C of reactions；
TLC tracking reactions are until be fully completed；
The crude by column chromatography separation that reaction obtains after terminating (petroleum ether: ethyl acetate=40: 1), obtains target production
Thing（Yield 78%）.The analyze data of product is as follows：1H NMR (400 MHz, CDCl3): δ8.85–8.50 (m, 2H),
7.88 –7.50 (m, 5H), 7.33 –7.30 (m, 1H).
Embodiment 19：The synthesis of 1- (2- thienyls) -2- benzils
It is as follows as raw material, its reactions steps with 1- (2- thienyls) -3- phenyl -1,3- propanedione：
1- (2- thienyls) -3- diphenylpropane-1,3-dione (DPPO)s are added in reaction bulb（0.23 g, 1 mmol）、2,2,6,
6- tetramethyl piperidine nitrogen oxides（0.31 g, 2 mmol）, cuprous bromide (0.014 g, 0.1mmol) and acetic acid（2 milliliters）,
100 DEG C of reactions；
TLC tracking reactions are until be fully completed；
The crude by column chromatography separation that reaction obtains after terminating (petroleum ether: ethyl acetate=40: 1), obtains target production
Thing（Yield 74%）.The analyze data of product is as follows：1H NMR (400 MHz, CDCl3): δ8.03 (m, 2H), 7.90 –
7.40 (m, 5H), 7.30 –7.10 (m, 1H)。
Embodiment 20：The synthesis of 1- (2- pyrrole radicals) -2- benzils
It is as follows as raw material, its reactions steps with 1- (2- pyrrole radicals) -3- phenyl -1,3- propanedione：
1- (2- pyrrole radicals) -3- diphenylpropane-1,3-dione (DPPO)s are added in reaction bulb（0.21 g, 1 mmol）、2,2,6,
6- tetramethyl piperidine nitrogen oxides（0.31 g, 2 mmol）, cuprous bromide (0.028 g, 0.2 mmol) and acetic acid（2 millis
Rise）, 100 DEG C of reactions；
TLC tracking reactions are until be fully completed；
The crude by column chromatography separation that reaction obtains after terminating (petroleum ether: ethyl acetate=40: 1), obtains target production
Thing（Yield 70%）.The analyze data of product is as follows：1H NMR (400 MHz, CDCl3): δ10.80 (s, 1H), 8.21–
8.00 (m, 3H), 7.74 –7.48 (m, 3H), 7.35–7.00 (m, 2H)。
Embodiment 21：The synthesis of 1,2- bis- (2- furyls) second diketone
It is as follows as raw material, its reactions steps with 1,3- bis- (2- furyls) -1,3- propanedione：
1,3- bis- (2- furyls) -1,3- propanedione is added in reaction bulb（0.20 g, 1 mmol）, 2,2,6,6- tetra-
Methyl piperidine nitrogen oxides（0.31 g, 2 mmol）, cuprous bromide (0.014 g, 0.1 mmol) and acetic acid（2 milliliters）, 100
DEG C reaction；
TLC tracking reactions are until be fully completed；
The crude by column chromatography separation that reaction obtains after terminating (petroleum ether: ethyl acetate=40: 1), obtains target production
Thing（Yield 81%）.The analyze data of product is as follows：1H NMR (400 MHz, CDCl3): δ8.75–8.60 (m, 2H),
8.10–7.80 (m, 4H)。
Claims (3)
1. one kind 1, the preparation method of 2- derovatives, it is characterised in that including one kind in following technical scheme：
（1）1 mmol 1,3- bis- (4- bromophenyls) -1,3- propanedione, 3 mmol 2,2,6,6- tetramethyls are added in reaction bulb
Piperidines nitrogen oxides, 0.1 mmol cuprous bromides and 2 milliliters of dimethylformamides, 120 DEG C of reactions；TLC tracking reactions are until complete
Terminate entirely；The crude by column chromatography separation that reaction obtains after terminating, obtains target product；
（2）1 mmol 1,3- bis- (2- bromophenyls) -1,3- propanedione, 2 mmol 2,2,6,6- tetramethyls are added in reaction bulb
Piperidines nitrogen oxides, 0.1 mmol cuprous bromides and 2 milliliters of dimethylformamides, 120 DEG C of reactions；TLC tracking reactions are until complete
Terminate entirely；The crude by column chromatography separation that reaction obtains after terminating, obtains target product；
（3）1 mmol 1,3- bis- (2- methoxyphenyls) -1,3- propanedione, 2 mmol 2,2,6,6- tetra- are added in reaction bulb
Methyl piperidine nitrogen oxides, 0.1 mmol stannous chlorides and 2 milliliters of dimethylformamides, 120 DEG C of reactions；TLC tracking reactions are straight
To being fully completed；The crude by column chromatography separation that reaction obtains after terminating, obtains target product.
2. the preparation method of 1,2- derovatives according to claim 1, it is characterised in that：The column chromatography for separation purification
Using petrol ether/ethyl acetate as eluant, eluent during processing.
3. the preparation method of 1,2- derovatives according to claim 2, it is characterised in that：The petroleum ether and acetic acid second
The volume ratio of ester is 40: 1.
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| Catalytic α-hydroxylation of ketones under CuBr2 or HBr/DMSO systems;Hong-Liang Li et al.;《Tetrahedron》;20150402;第71卷;3247-3252,第3249页Scheme 1. * |
| Iron-Promoted C-C Bond Cleavage of 1,3-Diketones: A Route to 1,2-Diketones under Mild Reaction Conditions;Lehao Huang et al.;《The Journal of Organic Chemistry》;20110601;第76卷;5732-5737 * |
| Oxone-Mediated Oxidative Cleavage of β‑Keto Esters and 1,3-Diketones to α‑Keto Esters and 1,2-Diketones in Aqueous Medium;Anastasios Stergiou et al.;《The Journal of Organic Chemistry》;20130619;第78卷;7268-7273 * |
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