CN105461496B - A kind of preparation method of the Dicarbonyl derivatives of 2 halo 1,3 - Google Patents
A kind of preparation method of the Dicarbonyl derivatives of 2 halo 1,3 Download PDFInfo
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- 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
- C07C45/63—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 introduction of halogen; by substitution of halogen atoms by other halogen atoms
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- 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
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- 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 the Dicarbonyl derivatives of 2 halo 1,3, and suitable for extensive 1,3 Dicarbonyl derivatives, such raw material is easy to get, species is a lot；The product types that profit is obtained by the present invention are various, not only can directly using but also can be used for other and further react；The inventive method reaction condition is gentle, operation and last handling process are simple, and the reaction time is short, yield is high, pollution is few, is suitable for industrialized production.
Description
Technical field
The invention belongs to the preparing technical field of organic compound, and in particular to a kind of 2- halos -1,3- dicarbapentaborane derives
The preparation method of thing.
Background technology
Bromo- 1, the 3- Dicarbonyl derivatives of 2- have active anticancer, and the compound 1-4 being shown below has to 1A9 cell lines
There is obvious inhibitory action.Particularly compound 3 is to many cell lines（Including HOS（Bone cancer cell line）And 1A9（Breast cancer is thin
Born of the same parents system））All there is very strong inhibitory action.
In addition, bromo- 1, the 3- Dicarbonyl derivatives of 2- are also important intermediate, it is widely used in bioactivity and again
In the synthesis for wanting purposes compound.Shen Xinghai discloses one kind using the bromo- 1,3- Dicarbonyl derivatives of 2- and acrylic acid or methyl
The method of propylene acid reaction prepare compound 5.The compound is aggregated can to synthesize uranyl ion imprinted polymer, and this trace gathers
Compound can be used for adsorbing and extracting in seawater from complicated component, that uranium concentration is low to have radioactive uranium, and its technology path is as follows：
Miyosh discloses 2-（1H- pyrazol-1-yl）The synthetic method of-thiazole, wherein compound 6 is to PGE2's
Acceptor EP1It is as follows with good inhibiting effect, its synthetic route：
Yu is disclosed a kind of reacted using the bromo- 1,3- Dicarbonyl derivatives of 2- with phenylacetylene derivatives and prepares polysubstituted naphthols
The method of derivative and furan derivatives, polysubstituted naphthol derivative are the key intermediates for synthesizing many medicines, and cyclohexanone is simultaneously
Furan derivatives can be used for the compound of synthesis treatment tropical disease（Referring to Shekarchi, M.; Ellahiyan, F.;
Akbarzadeh, T.; Shafiee, A. J. Heterocyclic Chem., 2003, 40, 427-433）.
Iodo- 1, the 3- Dicarbonyl derivatives of 2- are a kind of important organic synthesis intermediates, are widely used in natural products, life
In thing bioactive molecule, the synthesis of medicine and the modification of graphene.Xie Jianwu discloses one kind and utilizes salicylide and 2- iodos -1,3-
The method that Dicarbonyl derivatives prepare 3- hydroxyl -2,3- dihydro-benzofuran derivatives 3a.Experiment shows that compound 3a is to white
Candida albicans, staphylococcus aureus and Escherichia coli all have good inhibitory activity.Its synthetic route is as follows：
Can be without metallic green synthesizing benzoic acids derivative and pyrimido quinoline from the iodo- 1,3- Dicarbonyl derivatives of 2-
Promise ketone derivatives 7, its technology path are as follows：
Benzoic acid derivative has antibiotic and sterilizing effect, as antimicrobial, corrosion-proof and sterilization medicine and widely use（Referring to：
Arnold, L. D.; Drover, J. C. D.; Vederas, J. C. J. Am. Chem. Soc. 1987, 109,
4649–4659）；Pyrimido quinolones oxygen biology there are multiple biological activities, be widely used in antiallergy, anti-hypertension,
The fields such as anti-inflammatory, calmness, anti HIV-1 virus, anti-malarial, anticancer and antithrombotic（Referring to：Althuis, T. H.; Moore, P.
F.; Hess, H. J. J. Med. Chem. 1979, 22, 44）.
Muller discloses the reaction of iodo- 1, the 3- Dicarbonyl derivatives of 2- and fullerene, realizes the official of fullerene surface
Energyization, its technology path are as follows：
Fullerene is a kind of conductive and excellent thermal conductivity novel nano-material, can substantially be changed by the modification on its surface
It is apt to its performance（Referring to：Hirsch, A.; Brettreich, M. Fullerenes: Chemistry and Reactions,
Wiley-VCH, Weinheim, 2005）.
The synthetic method of the published bromo- 1,3- Dicarbonyl derivatives of 2- mainly has following several：
Stavber et al. discloses one kind with N-bromosuccinimide（NBS）For brominated reagent, 2- bromo- 1,3- is prepared
The method of Dicarbonyl derivatives, this method exist operation inconvenience, be difficult to amplify, can not industrialized deficiency；Khan discloses one
Kind is with bromination dimethyl bromination sulfonium（BDMS）For brominated reagent, the method for preparing bromo- 1, the 3- Dicarbonyl derivatives of 2-, this method institute
Brominated reagent is costly（TCI：5g/934 members, 25g/3270 members）, reaction be difficult to amplify, and the bromine used in this method
For in the synthesis of reagent, lower boiling raw material and solvent are used, therefore loss of material is big；The liquid of severe corrosive is used simultaneously
Bromine；Whole course of reaction pollution is big, is not suitable for large-scale production.
Prior art is also disclosed in the presence of OXOne, the method that grinding prepares bromo- 1, the 3- Dicarbonyl derivatives of 2-, should
Method is only applicable to the preparation of bromo- 1, the 3- Dicarbonyl derivatives of 3 2-, substrate narrow application range, unhandy defect be present.
Nama discloses one kind with OXOne/NH4Br is brominated reagent, the method for preparing bromo- 1, the 3- Dicarbonyl derivatives of 2-, this method
The defects of 1,3- dicarbapentaborane substrates narrow application range, peroxide explosive be present.
The preparation method of the published iodo- 1,3- Dicarbonyl derivatives of 2- mainly has following several：
Beaudry discloses one kind with 2- iodoxybenzoic acids（IBX）For iodo reagent, iodo- 1, the 3- diketone derivatives of 2- are prepared
Substrate narrow application range, severe reaction conditions be present in the method for thing, this method（Part substrate is needed in -78 DEG C of reactions）Deng not
Foot.Khalilzadeh discloses one kind with HIO4/Al2O3For iodo reagent, the method for preparing iodo- 1, the 3- derovatives of 2-,
The shortcomings of bad substrate narrow application range, selectivity, low yield be present in this method.
Lee et al. discloses one kind with HTIB/I2Or HTIB/ICH3For iodo reagent, iodo- 1, the 3- diketone derivatives of 2- are prepared
The shortcomings of substrate narrow application range, pollution is big be present in the method for thing, this method.Goswami discloses one kind with Oxone/I2For
Iodo reagent, by grinding the method for preparing iodo- 1, the 3- derovatives of 2-, there is substrate narrow application range, peroxide in this method
Compound easily explodes, is not easy the shortcomings of scale.
Krasnokutskaya discloses one kind using ICl as iodo reagent, and the side of iodo- 1, the 3- diketone of 2- is prepared by grinding
Corrosive gas, difficulty is produced and there is unstable easily decompose of substrate narrow application range, agents useful for same price, reagent in method, this method
The defects of to accomplish scale production.
One halo technology of published 1,3- Dicarbonyl derivatives exist substrate narrow application range, halogenating agent it is expensive,
Severe reaction conditions, selective bad, low yield, production cost is high, pollution is big, operation is inconvenient, reaction scale is difficult to amplify
Deficiency.Therefore, find it is a kind of meet Green Chemistry requirement, reaction condition is gentle, universality is good, is suitable for the side of large-scale production
Method is critically important.
The content of the invention
It is an object of the invention to provide the method that one kind prepares 2- halo -1,3- Dicarbonyl derivatives, it has raw material
Source is simple, 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 halogen of 1,3- Dicarbonyl derivatives
For method, comprise the following steps：1,3- Dicarbonyl derivatives, sodium halide, manganese acetate and copper catalyst are added in solvent, in 20
Reacted at~80 DEG C, obtain 2- halo -1,3- Dicarbonyl derivatives；
The 1,3- Dicarbonyl derivatives are as shown in following chemical structure of general formula：
Wherein R1It is selected from：One kind in alkyl, aryl, heteroaryl or alkoxy；R2It is selected from：Alkyl, aryl, heteroaryl or
One kind in alkoxy；
The sodium halide is sodium bromide or sodium iodide；
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 methanol, ethanol, ethylene glycol, acetonitrile, acetic acid, propionic acid.
2- halos -1,3- the Dicarbonyl derivatives are as shown in following chemical structure of general formula：
Or。
In above-mentioned technical proposal, 1, the 3- Dicarbonyl derivatives be selected from ethyl benzoylacetate,（4- toluyls）
Ethyl acetate,（4- methoxybenzoyls）Ethyl acetate,（2- toluyls）Ethyl acetate,（2- methoxybenzoyls）Acetic acid
Ethyl ester, naphthalene formyl acetic acid ethyl ester,（4- chlorobenzoyls）Ethyl acetate,（4- Bromophenacyls）Ethyl acetate,（4- nitrobenzene formyls）
Ethyl acetate,（3- Bromophenacyls）Ethyl acetate, 1,3- diphenyl -1,3- propanedione, 1- (2- furyls) -3- phenyl -1,3-
Propanedione, 1- (2- thienyls) -3- diphenylpropane-1,3-dione (DPPO)s, 1- (2- pyrrole radicals) -3- diphenylpropane-1,3-dione (DPPO)s, 1-（4- first
Base phenyl）- 3- diphenylpropane-1,3-dione (DPPO)s, 1-（4- methoxyphenyls）- 3- diphenylpropane-1,3-dione (DPPO)s, 1-（2- aminomethyl phenyls）-
3- diphenylpropane-1,3-dione (DPPO)s, 1,3- bis-（2- methoxyphenyls）- 1,3- propanedione, 1- phenyl -1,3- pentanediones, 3,5- heptan two
Ketone, diethyl malonate, 1-（4- chlorphenyls）- 3- diphenylpropane-1,3-dione (DPPO)s, 1-（4- bromophenyls）- 3- diphenylpropane-1,3-dione (DPPO)s
In one kind.
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- Dicarbonyl derivatives: sodium halide: manganese acetate: copper catalyst 1:（1
~3）∶（1~5）∶（0.05~0.2）；Preferably 1: 2: 3: 0.1.
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 20: 1.
Preferably, reaction temperature of the invention is 40~60 DEG C.Reaction is gentle, product yield high, avoids energy waste.
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 starting material using 1,3- Dicarbonyl derivatives, sodium halide, only in manganese acetate and copper catalysis
In the presence of agent, in air, 2- halo -1,3- Dicarbonyl derivatives are efficiently prepared；Raw material is easy to get, species is more, the production being prepared
Thing 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, selection
Property it is good, cost is low, and avoids the application of existing toxic compounds, reduce pollution environment；Only need a small amount of catalyst high
Effect obtains product, not only simplify the purification process of product, reduces the generation of discarded object, and manganese acetate and copper catalyst can
Recycle, avoid wastage of material, there is positive realistic meaning for commercial Application.
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- Dicarbonyl derivatives, the high income of target product, operation and last handling process are simple, are suitable to
Industrialized production.
Embodiment
With reference to embodiment, the invention will be further described：
Embodiment one：The synthesis of 2- Bromophenacyl ethyl acetate
It is as follows using ethyl benzoylacetate, sodium bromide as raw material, its reactions steps：
Ethyl benzoylacetate is added in reaction bulb（0.192 g, 1 mmol）, sodium bromide（0.103 g, 1
mmol）, stannous chloride（0.010 g, 0.1 mmol）, manganese acetate（0.27 g, 1 mmol）And methanol（10 milliliters）, 20 DEG C anti-
Should；
TLC tracking reactions are until be fully completed；
Crude by column chromatography separation (the ethyl acetate that reaction obtains after terminating：Petroleum ether=1:20) target, is obtained
Product（Yield 53%）.The analyze data of product is as follows：1HNMR (400 MHz, CDCl3): δ 8.04 – 7.94 (m,
2H), 7.66 – 7.58 (m, 1H), 7.54 – 7.44 (m, 2H), 5.66 (s, 1H), 4.28 (q, J = 7.1
Hz, 2H), 1.24 (t, J = 7.1 Hz, 3H)。
Embodiment two：The synthesis of 2- iodine ethyl benzoylacetates
It is as follows using ethyl benzoylacetate, sodium iodide as raw material, its reactions steps：
Ethyl benzoylacetate is added in reaction bulb（0.192 g, 1 mmol）, sodium iodide（0.300g, 2 mmol）、
Cuprous iodide（0.020 g, 0.1 mmol）, manganese acetate（0.81 g, 3 mmol）And ethanol（10 milliliters）, 30 DEG C of reactions；
TLC tracking reactions are until be fully completed；
Crude by column chromatography separation (the ethyl acetate that reaction obtains after terminating：Petroleum ether=1:20) target, is obtained
Product（Yield 68%）.The analyze data of product is as follows：1HNMR (400 MHz, CDCl3): δ 8.04 – 7.94 (m,
2H), 7.66 – 7.58 (m, 1H), 7.54 – 7.44 (m, 2H), 5.84 (s, 1H), 4.28 (q, J = 7.1
Hz, 2H), 1.24 (t, J = 7.1 Hz, 3H)。
Embodiment three：2- bromines（4- toluyls）The synthesis of ethyl acetate
With（4- toluyls）Ethyl acetate, sodium bromide are as follows as raw material, its reactions steps：
Added in reaction bulb（4- toluyls）Ethyl acetate（0.206 g, 1 mmol）, sodium bromide（0.206g,
2 mmol）, cuprous bromide（0.014 g, 0.1 mmol）, manganese acetate（0.54 g, 2 mmol）And ethylene glycol（10 milliliters）, 40 DEG C
Reaction；
TLC tracking reactions are until be fully completed；
Crude by column chromatography separation (the ethyl acetate that reaction obtains after terminating：Petroleum ether=1:20) target, is obtained
Product（Yield 70%）.The analyze data of product is as follows：1H NMR (400 MHz, CDCl3):δ 7.89 (d, J = 8.3
Hz, 2H), 7.29 (d, J = 8.1 Hz, 2H), 5.64 (s, 1H), 4.28 (q, J= 7.1 Hz, 2H),
2.43 (s, 3H), 1.25 (t, J = 7.1 Hz, 3H)。
Example IV：2- bromines（4- methoxybenzoyls）The synthesis of ethyl acetate
With（4- methoxybenzoyls）Ethyl acetate, sodium bromide are as follows as raw material, its reactions steps：
Added in reaction bulb（4- methoxybenzoyls）Ethyl acetate（0.222 g, 1 mmol）, sodium bromide
（0.309g, 3 mmol）, copper chloride（0.013 g, 0.1 mmol）, manganese acetate（0.81 g, 3 mmol）And acetonitrile（10 milliliters）,
50 DEG C of reactions；
TLC tracking reactions are until be fully completed；
Crude by column chromatography separation (the ethyl acetate that reaction obtains after terminating：Petroleum ether=1:20) target, is obtained
Product（Yield 80%）.The analyze data of product is as follows：1H NMR (400 MHz, CDCl3):δ 8.03 – 7.93 (m,
2H), 7.00 – 6.90 (m, 2H), 5.62 (s, 1H), 4.28 (q, J = 7.1 Hz, 2H), 3.89 (s,
3H), 1.25 (t, J = 7.1 Hz, 3H)。
Embodiment five：2- iodine（4- methoxybenzoyls）The synthesis of ethyl acetate
With（4- methoxybenzoyls）Ethyl acetate, sodium iodide are as follows as raw material, its reactions steps：
Added in reaction bulb（4- methoxybenzoyls）Ethyl acetate（0.222 g, 1 mmol）, sodium iodide
（0.300g, 2 mmol）, cuprous iodide（0.020 g, 0.1 mmol）, manganese acetate（0.81 g, 3 mmol）And acetic acid（10 millis
Rise）, 60 DEG C of reactions；
TLC tracking reactions are until be fully completed；
Crude by column chromatography separation (the ethyl acetate that reaction obtains after terminating：Petroleum ether=1:20) target, is obtained
Product（Yield 74%）.The analyze data of product is as follows：1H NMR (400 MHz, CDCl3): δ 8.03 – 7.93 (m,
2H), 7.00 – 6.90 (m, 2H), 5.81 (s, 1H), 4.28 (q, J = 7.1 Hz, 2H), 3.89 (s,
3H), 1.25 (t, J = 7.1 Hz, 3H)。
Embodiment six：2- bromines（2- toluyls）The synthesis of ethyl acetate
With（2- toluyls）Ethyl acetate, sodium bromide are as follows as raw material, its reactions steps：
Added in reaction bulb（2- toluyls）Ethyl acetate（0.206 g, 1 mmol）, sodium bromide（0.206g,
2 mmol）, copper bromide（0.022 g, 0.1 mmol）, manganese acetate（1.08 g, 4 mmol）And propionic acid（10 milliliters）, 70 DEG C anti-
Should；
TLC tracking reactions are until be fully completed；
Crude by column chromatography separation (the ethyl acetate that reaction obtains after terminating：Petroleum ether=1:20) target, is obtained
Product（Yield 78%）.The analyze data of product is as follows：1H NMR (400 MHz, CDCl3): δ 7.66 (d, J = 7.8
Hz, 1H), 7.47 – 7.40 (m, 1H), 7.29 (t, J = 8.4 Hz, 2H), 5.63 (s, 1H), 4.26
(q, J = 7.1 Hz, 2H), 2.52 (s, 3H), 1.23 (t, J = 7.1 Hz, 3H)。
Embodiment seven：2- bromines（2- methoxybenzoyls）The synthesis of ethyl acetate
With（2- methoxybenzoyls）Ethyl acetate, sodium bromide are as follows as raw material, its reactions steps：
Added in reaction bulb（2- methoxybenzoyls）Ethyl acetate（0.222 g, 1 mmol）, sodium bromide
（0.206g, 2 mmol）, cupric iodide（0.064 g, 0.2 mmol）, manganese acetate（1.35 g, 5 mmol）And acetonitrile（10 milliliters）,
80 DEG C of reactions；
TLC tracking reactions are until be fully completed；
Crude by column chromatography separation (the ethyl acetate that reaction obtains after terminating：Petroleum ether=1:20) target, is obtained
Product（Yield 76%）.The analyze data of product is as follows：1H NMR (400 MHz, CDCl3): δ 7.92 (dd, J = 7.8,
1.8 Hz, 1H), 7.57 – 7.51 (m, 1H), 7.09 – 7.04 (m, 1H), 6.98 (d, J = 8.4 Hz,
1H), 5.81 (s, 1H), 4.29 – 4.20 (m, 2H), 3.91 (s, 3H), 1.24 (t, J = 7.1 Hz,
3H)。
Embodiment eight：The synthesis of 2- bromonaphthalene formyl acetic acid ethyl esters
It is as follows using naphthalene formyl acetic acid ethyl ester, sodium bromide as raw material, its reactions steps：
Naphthalene formyl acetic acid ethyl ester is added in reaction bulb（0.242 g, 1 mmol）, sodium bromide（0.206g, 2 mmol）、
Trifluoromethanesulfonic acid is cuprous（0.021 g, 0.1 mmol）, manganese acetate（0.81 g, 3 mmol）And acetic acid（10 milliliters）, 60 DEG C anti-
Should；
TLC tracking reactions are until be fully completed；
Crude by column chromatography separation (the ethyl acetate that reaction obtains after terminating：Petroleum ether=1:20) target, is obtained
Product（Yield 71%）.The analyze data of product is as follows：1H NMR (400 MHz, CDCl3): δ 8.55 (d, J = 8.6
Hz, 1H), 8.06 (d, J = 8.2 Hz, 1H), 7.93 (d, J = 7.2 Hz, 1H), 7.90 (d, J = 8.1
Hz, 1H), 7.67 – 7.62 (m, 1H), 7.60 – 7.55 (m, 1H), 7.52 (t, J = 7.8 Hz, 1H),
5.82 (s, 1H), 4.28 – 4.20 (m, 2H), 1.18 (t, J = 7.1 Hz, 3H)。
Embodiment nine：2- bromines（4- chlorobenzoyls）The synthesis of ethyl acetate
With（4- chlorobenzoyls）Ethyl acetate, sodium bromide are as follows as raw material, its reactions steps：
Added in reaction bulb（4- chlorobenzoyls）Ethyl acetate（0.226 g, 1 mmol）, sodium bromide（0.206g, 2
mmol）, cuprous bromide（0.007 g, 0.05 mmol）, manganese acetate（0.81 g, 3 mmol）And acetic acid（10 milliliters）, 60 DEG C anti-
Should；
TLC tracking reactions are until be fully completed；
Crude by column chromatography separation (the ethyl acetate that reaction obtains after terminating：Petroleum ether=1:20) target, is obtained
Product（Yield 70%）.The analyze data of product is as follows：1H NMR (400 MHz, CDCl3): δ 7.94 (d, J = 8.6
Hz, 2H), 7.47 (d, J = 8.6 Hz, 2H), 5.59 (s, 1H), 4.29 (q, J = 7.1 Hz, 2H),
1.26 (t, J = 7.1 Hz, 3H)。
Embodiment ten：2- bromines（4- Bromophenacyls）The synthesis of ethyl acetate
With（4- Bromophenacyls）Ethyl acetate, sodium bromide are as follows as raw material, its reactions steps：
Added in reaction bulb（4- Bromophenacyls）Ethyl acetate（0.269 g, 1 mmol）, sodium bromide（0.206g, 2
mmol）, cuprous bromide（0.014 g, 0.1 mmol）, manganese acetate（0.81 g, 3 mmol）And acetic acid（10 milliliters）, 60 DEG C anti-
Should；
TLC tracking reactions are until be fully completed；
Crude by column chromatography separation (the ethyl acetate that reaction obtains after terminating：Petroleum ether=1:20) target, is obtained
Product（Yield 61%）.The analyze data of product is as follows：1H NMR (400 MHz, CDCl3): δ 7.86 (d, J = 8.6
Hz, 2H), 7.65 (d, J = 8.6 Hz, 2H), 5.58 (s, 1H), 4.29 (q, J = 7.1 Hz, 2H),
1.26 (t, J = 7.1 Hz, 3H)。
Embodiment 11：2- bromines（4- nitrobenzene formyls）The synthesis of ethyl acetate
With（4- nitrobenzene formyls）Ethyl acetate, sodium bromide are as follows as raw material, its reactions steps：
Added in reaction bulb（4- nitrobenzene formyls）Ethyl acetate（0.237 g, 1 mmol）, sodium bromide（0.206g,
2 mmol）, cuprous bromide（0.028 g, 0.2 mmol）, manganese acetate（0.81 g, 3 mmol）And acetonitrile（10 milliliters）, 50 DEG C anti-
Should；
TLC tracking reactions are until be fully completed；
Crude by column chromatography separation (the ethyl acetate that reaction obtains after terminating：Petroleum ether=1:20) target, is obtained
Product（Yield 67%）.The analyze data of product is as follows：1HNMR (400 MHz, CDCl3): δ 8.40 – 8.31 (m,
2H), 8.20 – 8.10 (m, 2H), 5.61 (s, 1H), 4.31 (q, J = 7.1Hz, 2H), 1.27 (t, J =
7.1 Hz, 3H)。
Embodiment 12：2- bromines（3- Bromophenacyls）The synthesis of ethyl acetate
With（3- Bromophenacyls）Ethyl acetate, sodium bromide are as follows as raw material, its reactions steps：
Added in reaction bulb（3- Bromophenacyls）Ethyl acetate（0.269 g, 1 mmol）, sodium bromide（0.206g, 2
mmol）, cuprous bromide（0.042 g, 0.3 mmol）, manganese acetate（0.81 g, 3 mmol）And acetonitrile（10 milliliters）, 50 DEG C anti-
Should；
TLC tracking reactions are until be fully completed；
Crude by column chromatography separation (the ethyl acetate that reaction obtains after terminating：Petroleum ether=1:20) target, is obtained
Product（Yield 61%）.The analyze data of product is as follows：1H NMR (400 MHz, CDCl3): δ 8.13 (t, J = 1.7
Hz, 1H), 7.91 (d, J = 7.8 Hz, 1H), 7.75 (d, J = 8.0 Hz, 1H), 7.39 (t, J = 7.9
Hz, 1H), 5.59 (s, 1H), 4.30 (q, J =7.1 Hz, 2H), 1.27 (t, J = 7.1 Hz, 3H)。
Embodiment 13：The synthesis of the bromo- 1,3- diphenyl -1,3- propanedione of 2-
It is as follows as raw material, its reactions steps with 1,3- diphenyl -1,3- propanedione, sodium bromide：
1,3- diphenyl -1,3- propanedione is added in reaction bulb（0.224 g, 1 mmol）, sodium bromide（0.206g, 2
mmol）, cuprous bromide（0.014 g, 0.1 mmol）, manganese acetate（0.81 g, 3 mmol）And acetonitrile（10 milliliters）, 50 DEG C anti-
Should；
TLC tracking reactions are until be fully completed；
Crude by column chromatography separation (the ethyl acetate that reaction obtains after terminating：Petroleum ether=1:20) target, is obtained
Product（Yield 78%）.The analyze data of product is as follows：1H NMR (400 MHz, CDCl3): δ 8.07 – 7.89 (m,
4H), 7.61 (t, J = 7.4 Hz, 2H), 7.47 (t, J = 7.8 Hz, 4H), 6.55 (s, 1H)。
Embodiment 14：The synthesis of the iodo- 1,3- diphenyl -1,3- propanedione of 2-
It is as follows as raw material, its reactions steps with 1,3- diphenyl -1,3- propanedione, sodium iodide：
1,3- diphenyl -1,3- propanedione is added in reaction bulb（0.224 g, 1 mmol）, sodium iodide（0.300g, 2
mmol）, cuprous bromide（0.014 g, 0.1 mmol）, manganese acetate（0.81 g, 3 mmol）And acetic acid（10 milliliters）, 60 DEG C anti-
Should；
TLC tracking reactions are until be fully completed；
Crude by column chromatography separation (the ethyl acetate that reaction obtains after terminating：Petroleum ether=1:20) target, is obtained
Product（Yield 77%）.The analyze data of product is as follows：1H NMR (400 MHz, CDCl3): δ 8.07 – 7.89 (m,
4H), 7.61 (t, J = 7.4 Hz, 2H), 7.47 (t, J = 7.8 Hz, 4H), 6.68 (s, 1H)。
Embodiment 15：The synthesis of the bromo- 3- diphenylpropane-1,3-dione (DPPO)s of 1- (2- furyls) -2-
It is as follows as raw material, its reactions steps with 1- (2- furyls) -3- phenyl -1,3- propanedione, sodium bromide：
1- (2- furyls) -3- diphenylpropane-1,3-dione (DPPO)s are added in reaction bulb（0.214 g, 1 mmol）, sodium bromide
（0.206g, 2 mmol）, cuprous bromide（0.014 g, 0.1 mmol）, manganese acetate（0.81 g, 3 mmol）And acetic acid（10 millis
Rise）, 60 DEG C of reactions；
TLC tracking reactions are until be fully completed；
Crude by column chromatography separation (the ethyl acetate that reaction obtains after terminating：Petroleum ether=1:20) target, is obtained
Product（Yield 81%）.The analyze data of product is as follows：1H NMR (400 MHz, CDCl3): δ 8.85–8.50 (m, 2H),
7.88 –7.50 (m, 5H), 7.33 –7.30 (m, 1H), 6.75 (s, 1H)。
Embodiment 16：The synthesis of the bromo- 3- diphenylpropane-1,3-dione (DPPO)s of 1- (2- thienyls) -2-
It is as follows as raw material, its reactions steps with 1- (2- thienyls) -3- phenyl -1,3- propanedione, sodium bromide：
1- (2- thienyls) -3- diphenylpropane-1,3-dione (DPPO)s are added in reaction bulb（0.230 g, 1 mmol）, sodium bromide
（0.206g, 2 mmol）, cuprous bromide（0.014 g, 0.1 mmol）, manganese acetate（0.81 g, 3 mmol）And ethanol（10 millis
Rise）, 60 DEG C of reactions；
TLC tracking reactions are until be fully completed；
Crude by column chromatography separation (the ethyl acetate that reaction obtains after terminating：Petroleum ether=1:20) target, is obtained
Product（Yield 75%）.The analyze data of product is as follows：1H NMR (400 MHz, CDCl3): δ 8.15–7.90 (m, 4H),
7.88 –7.50 (m, 3H), 7.33 –7.20 (m, 1H), 6.63 (s, 1H)。
Embodiment 17：The synthesis of the iodo- 3- diphenylpropane-1,3-dione (DPPO)s of 1- (2- thienyls) -2-
It is as follows as raw material, its reactions steps with 1- (2- thienyls) -3- phenyl -1,3- propanedione, sodium iodide：
1- (2- thienyls) -3- diphenylpropane-1,3-dione (DPPO)s are added in reaction bulb（0.230 g, 1 mmol）, sodium iodide
（0.300g, 2 mmol）, cuprous iodide（0.020 g, 0.1 mmol）, manganese acetate（0.81 g, 3 mmol）And ethanol（10 millis
Rise）, 60 DEG C of reactions；
TLC tracking reactions are until be fully completed；
Crude by column chromatography separation (the ethyl acetate that reaction obtains after terminating：Petroleum ether=1:20) target, is obtained
Product（Yield 77%）.The analyze data of product is as follows：1H NMR (400 MHz, CDCl3): δ 8.15–7.90 (m, 4H),
7.88 –7.50 (m, 3H), 7.33 –7.20 (m, 1H), 6.76 (s, 1H)。
Embodiment 18：The synthesis of the bromo- 3- diphenylpropane-1,3-dione (DPPO)s of 1- (2- pyrrole radicals) -2-
It is as follows as raw material, its reactions steps with 1- (2- pyrrole radicals) -3- phenyl -1,3- propanedione, sodium bromide：
1- (2- pyrrole radicals) -3- diphenylpropane-1,3-dione (DPPO)s are added in reaction bulb（0.213 g, 1 mmol）, sodium bromide
（0.206g, 2 mmol）, cuprous bromide（0.014 g, 0.1 mmol）, manganese acetate（0.81 g, 3 mmol）And ethanol（10 millis
Rise）, 60 DEG C of reactions；
TLC tracking reactions are until be fully completed；
Crude by column chromatography separation (the ethyl acetate that reaction obtains after terminating：Petroleum ether=1:20) target, is obtained
Product（Yield 69%）.The analyze data of product is as follows：1H NMR (400 MHz, CDCl3): δ 10.80 (s, 1H),
8.21–8.00 (m, 3H), 7.74 –7.48 (m, 3H), 7.35–7.00 (m, 2H), 6.63 (s, 1H)。
Embodiment 19：The bromo- 1- of 2-（4- aminomethyl phenyls）The synthesis of -3- diphenylpropane-1,3-dione (DPPO)s
With 1-（4- aminomethyl phenyls）- 3- phenyl -1,3- propanedione, sodium bromide are as follows as raw material, its reactions steps：
1- is added in reaction bulb（4- aminomethyl phenyls）- 3- diphenylpropane-1,3-dione (DPPO)s（0.238 g, 1 mmol）, bromination
Sodium（0.206g, 2 mmol）, cuprous bromide（0.014 g, 0.1 mmol）, manganese acetate（0.81 g, 3 mmol）And acetic acid（10 millis
Rise）, 60 DEG C of reactions；
TLC tracking reactions are until be fully completed；
Crude by column chromatography separation (the ethyl acetate that reaction obtains after terminating：Petroleum ether=1:20) target, is obtained
Product（Yield 70%）.The analyze data of product is as follows：1H NMR (400 MHz, CDCl3): δ 8.00 – 7.97 (m,
2H), 7.90 (d, J = 8.3 Hz, 2H), 7.62 – 7.57 (m, 1H), 7.49 – 7.44 (m, 2H), 7.27
(d, J = 8.0 Hz, 2H), 6.53 (s, 1H), 2.41 (s, 3H)。
Embodiment 20：The bromo- 1- of 2-（4- methoxyphenyls）The synthesis of -3- diphenylpropane-1,3-dione (DPPO)s
With 1-（4- methoxyphenyls）- 3- phenyl -1,3- propanedione, sodium bromide are as follows as raw material, its reactions steps：
1- is added in reaction bulb（4- methoxyphenyls）- 3- diphenylpropane-1,3-dione (DPPO)s（0.254 g, 1 mmol）, bromine
Change sodium（0.206g, 2 mmol）, cuprous bromide（0.014 g, 0.1 mmol）, manganese acetate（0.81 g, 3 mmol）And acetic acid（10
Milliliter）, 60 DEG C of reactions；
TLC tracking reactions are until be fully completed；
Crude by column chromatography separation (the ethyl acetate that reaction obtains after terminating：Petroleum ether=1:20) target, is obtained
Product（Yield 77%）.The analyze data of product is as follows：1H NMR (400 MHz, CDCl3): δ 8.00 – 7.96 (m,
2H), 7.60 – 7.54 (m, 1H), 7.45 (t, J = 7.8 Hz, 2H), 6.95 – 6.89 (m, 2H), 6.50
(s, 1H), 3.86 (s, 3H)。
Embodiment 21：The bromo- 1- of 2-（2- aminomethyl phenyls）The synthesis of -3- diphenylpropane-1,3-dione (DPPO)s
With 1-（2- aminomethyl phenyls）- 3- phenyl -1,3- propanedione, sodium bromide are as follows as raw material, its reactions steps：
1- is added in reaction bulb（2- aminomethyl phenyls）- 3- diphenylpropane-1,3-dione (DPPO)s（0.238 g, 1 mmol）, bromination
Sodium（0.206g, 2 mmol）, cuprous bromide（0.014 g, 0.1 mmol）, manganese acetate（0.81 g, 3 mmol）And acetic acid（10 millis
Rise）, 60 DEG C of reactions；
TLC tracking reactions are until be fully completed；
Crude by column chromatography separation (the ethyl acetate that reaction obtains after terminating：Petroleum ether=1:20) target, is obtained
Product（Yield 81%）.The analyze data of product is as follows：1H NMR (400 MHz, CDCl3): δ 7.98 – 7.93 (m,
2H), 7.70 (d, J = 7.7 Hz, 1H), 7.59 (t, J = 7.4 Hz, 1H), 7.46 (t, J = 7.8 Hz,
2H), 7.40 (t, J = 7.6 Hz, 1H), 7.26 (t, J = 7.6 Hz, 2H), 6.54 (s, 1H), 2.49
(s, 3H)。
Embodiment 22：The bromo- 1,3- bis- of 2-（2- methoxyphenyls）The synthesis of -1,3- propanedione
With 1,3- bis-（2- methoxyphenyls）- 1,3- propanedione, sodium bromide are as follows as raw material, its reactions steps：
1,3- bis- is added in reaction bulb（2- methoxyphenyls）- 1,3- propanedione（0.284 g, 1 mmol）, bromination
Sodium（0.206g, 2 mmol）, cuprous bromide（0.014 g, 0.1 mmol）, manganese acetate（0.81 g, 3 mmol）And acetic acid（10 millis
Rise）, 60 DEG C of reactions；
TLC tracking reactions are until be fully completed；
Crude by column chromatography separation (the ethyl acetate that reaction obtains after terminating：Petroleum ether=1:20) target, is obtained
Product（Yield 70%）.The analyze data of product is as follows：1H NMR (400 MHz, CDCl3): δ 8.03 (dd, J = 7.9,
1.8 Hz, 2H), 7.57 – 7.49 (m, 2H), 7.14 (s, 1H), 7.10 – 7.03 (m, 2H), 6.97 (d,J = 8.3 Hz, 2H), 3.78 (s, 6H)。
Embodiment 23：The synthesis of the bromo- 1- phenyl -1,3- pentanediones of 2-
It is as follows as raw material, its reactions steps with 1- phenyl -1,3- pentanedione, sodium bromide：
1- phenyl -1,3- pentanediones are added in reaction bulb（0.176 g, 1 mmol）, sodium bromide（0.206g, 2
mmol）, cuprous bromide（0.014 g, 0.1 mmol）, manganese acetate（0.81 g, 3 mmol）And acetic acid（10 milliliters）, 60 DEG C anti-
Should；
TLC tracking reactions are until be fully completed；
Crude by column chromatography separation (the ethyl acetate that reaction obtains after terminating：Petroleum ether=1:20) target, is obtained
Product（Yield 72%）.The analyze data of product is as follows：1H NMR (400 MHz, CDCl3): δ 8.02 – 7.91 (m,
2H), 7.66 – 7.60 (m, 1H), 7.54 – 7.47 (m, 2H), 5.66 (s, 1H), 2.92 – 2.83 (m,
1H), 2.76 – 2.64 (m, 1H), 1.11 (t, J = 7.2 Hz, 3H)。
Embodiment 24：The synthesis of the bromo- 3,5- heptadione of 4-
It is as follows as raw material, its reactions steps with 3,5- heptadione, sodium bromide：
3,5- heptadione is added in reaction bulb（0.128 g, 1 mmol）, sodium bromide（0.206g, 2 mmol）, bromination
It is cuprous（0.014 g, 0.1 mmol）, manganese acetate（0.81 g, 3 mmol）And acetic acid（10 milliliters）, 50 DEG C of reactions；
TLC tracking reactions are until be fully completed；
Crude by column chromatography separation (the ethyl acetate that reaction obtains after terminating：Petroleum ether=1:20) target, is obtained
Product（Yield 70%）.The analyze data of product is as follows：1H NMR (400 MHz, CDCl3): δ 5.80 (s, 1H), 2.75
(q, J = 7.2 Hz, 4H), 1.23 (t, J = 7.2 Hz, 6H)。
Embodiment 25：The synthesis of the iodo- 3,5- heptadione of 4-
It is as follows as raw material, its reactions steps with 3,5- heptadione, sodium iodide：
3,5- heptadione is added in reaction bulb（0.128 g, 1 mmol）, sodium iodide（0.300g, 2 mmol）, iodate
It is cuprous（0.020 g, 0.1 mmol）, manganese acetate（0.81 g, 3 mmol）And acetic acid（10 milliliters）, 50 DEG C of reactions；
TLC tracking reactions are until be fully completed；
Crude by column chromatography separation (the ethyl acetate that reaction obtains after terminating：Petroleum ether=1:20) target, is obtained
Product（Yield 65%）.The analyze data of product is as follows：1H NMR (400 MHz, CDCl3): δ 5.93 (s, 1H), 2.75
(q, J = 7.2 Hz, 4H), 1.23 (t, J = 7.2 Hz, 6H)。
Embodiment 26：The synthesis of 2- diethyl bromomalonates
It is as follows using diethyl malonate, sodium bromide as raw material, its reactions steps：
Diethyl malonate is added in reaction bulb（0.160 g, 1 mmol）, sodium bromide（0.206g, 2 mmol）, bromine
Change cuprous（0.014 g, 0.1 mmol）, manganese acetate（0.81 g, 3 mmol）And acetic acid（10 milliliters）, 50 DEG C of reactions；
TLC tracking reactions are until be fully completed；
Crude by column chromatography separation (the ethyl acetate that reaction obtains after terminating：Petroleum ether=1:20) target, is obtained
Product（Yield 74%）.The analyze data of product is as follows：1H NMR (400 MHz, CDCl3): δ 5.91 (s, 1H), 4.75
(q, J = 7.3 Hz, 4H), 1.63 (t, J = 7.3 Hz, 6H)。
Embodiment 27：The bromo- 1- of 2-（4- chlorphenyls）The synthesis of -3- diphenylpropane-1,3-dione (DPPO)s
With 1-（4- chlorphenyls）- 3- phenyl -1,3- propanedione, sodium bromide are as follows as raw material, its reactions steps：
1- is added in reaction bulb（4- chlorphenyls）- 3- diphenylpropane-1,3-dione (DPPO)s（0.256 g, 1 mmol）, sodium bromide
（0.206g, 2 mmol）, cuprous bromide（0.014 g, 0.1 mmol）, manganese acetate（0.81 g, 3 mmol）And acetic acid（10 millis
Rise）, 40 DEG C of reactions；
TLC tracking reactions are until be fully completed；
Crude by column chromatography separation (the ethyl acetate that reaction obtains after terminating：Petroleum ether=1:20) target, is obtained
Product（Yield 65%）.The analyze data of product is as follows：1H NMR (400 MHz, CDCl3): δ 8.02 – 7.96 (m,
4H), 7.96 – 7.91 (m, 3.6H), 7.62 (t, J = 7.4 Hz, 1.9H), 7.48 (t, J = 7.7 Hz,
4H), 7.44 (d, J = 8.6 Hz, 3.6H), 6.47 (s, 1H), 6.34 (s, 1H)。
Embodiment 28：The bromo- 1- of 2-（4- bromophenyls）The synthesis of -3- diphenylpropane-1,3-dione (DPPO)s
With 1-（4- bromophenyls）- 3- phenyl -1,3- propanedione, sodium bromide are as follows as raw material, its reactions steps：
1- is added in reaction bulb（4- bromophenyls）- 3- diphenylpropane-1,3-dione (DPPO)s（0.301 g, 1 mmol）, sodium bromide
（0.206g, 2 mmol）, cuprous bromide（0.014 g, 0.1 mmol）, manganese acetate（0.81 g, 3 mmol）And acetic acid（10 millis
Rise）, 40 DEG C of reactions；
TLC tracking reactions are until be fully completed；
Crude by column chromatography separation (the ethyl acetate that reaction obtains after terminating：Petroleum ether=1:20) target, is obtained
Product（Yield 70%）.The analyze data of product is as follows：1H NMR (400 MHz, CDCl3): δ 8.02 – 7.98 (m,
2H), 7.90 – 7.85 (m, 2H), 7.67 – 7.60 (m,3H), 7.50 (t, J = 7.8 Hz, 2H), 6.48
(s, 1H)。
Claims (1)
1. a kind of preparation method of 2- halos -1,3- Dicarbonyl derivatives, it is characterised in that comprise the following steps：In reaction bulb
Middle addition 1,3- diphenyl -1,3- propanedione 1mmol, sodium iodide 2mmol, cuprous bromide 0.1mmol, manganese acetate 3mmol and second
10 milliliters of acid, 60 DEG C of reactions；TLC tracking reactions are until be fully completed；The crude by column chromatography separation that reaction obtains after terminating,
Obtain target product；During the column chromatography for separation using volume ratio as 20: 1 petroleum ether, ethyl acetate is eluant, eluent.
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