CN105461496A - Preparation method for 2-halogenated-1,3-dicarbonyl derivative - Google Patents
Preparation method for 2-halogenated-1,3-dicarbonyl derivative Download PDFInfo
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- 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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- 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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- C07C67/307—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of halogen; by substitution of halogen atoms by other halogen atoms
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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 a preparation method for a 2-halogenated-1,3-dicarbonyl derivative. The preparation method is suitable for wide 1,3-dicarbonyl derivatives. The raw materials are easy to obtain, and multiple varieties are achieved. The product obtained through the method is diversified in type, and can be directly used and used for other further reactions. According to the method, reaction conditions are gentle, the reaction operation and after-treatment process is simple, reaction time is short, the yield is high, pollution is low, and the preparation method is suitable for industrial production.
Description
Technical field
The invention belongs to the preparing technical field of organic compound, be specifically related to a kind of preparation method of 2-halo-1,3-Dicarbonyl derivatives.
Background technology
Bromo-1, the 3-Dicarbonyl derivatives of 2-has antitumour activity, and the compound 1-4 be shown below has obvious restraining effect to 1A9 clone.Particularly compound 3 is to much clone (comprising HOS(bone cancer cell line) and 1A9(breast cancer cell line)) all there is very strong restraining effect.
In addition, bromo-1, the 3-Dicarbonyl derivatives of 2-is also important intermediate, is widely used in having in the synthesis of biological activity and important use compound.Shen Xinghai discloses one and utilizes bromo-1, the 3-Dicarbonyl derivatives of 2-and acrylic or methacrylic acid-respons to prepare the method for compound 5.This compound can synthesize uranyl ion imprinted polymer through polymerization, this imprinted polymer can be used for from complicated component, seawater that uranium concentration is low, adsorbing and extracting has radioactive uranium, its technological line is as follows:
Miyosh discloses 2-(1H-pyrazol-1-yl) synthetic method of-thiazole derivative, wherein compound 6 couples of PGE
2acceptor EP
1have good restraining effect, its synthetic route is as follows:
Yu discloses one and utilizes 2-bromo-1; 3-Dicarbonyl derivatives and phenylacetylene derivatives react the method preparing polysubstituted naphthol derivative and furan derivatives; polysubstituted naphthol derivative is the key intermediate synthesizing many medicines; pimelinketone benzofuran derivs can be used for the compound of synthesis treatment tropical disease (see Shekarchi, M.; Ellahiyan, F.; Akbarzadeh, T.; Shafiee, A.J.HeterocyclicChem., 2003,40,427-433).
Iodo-1, the 3-Dicarbonyl derivatives of 2-is the important organic synthesis intermediate of a class, is widely used in natural product, bioactive molecules, the synthesis of medicine and the modification of Graphene.Xie Jianwu discloses one and utilizes salicylic aldehyde and 2-iodo-1,3-Dicarbonyl derivatives to prepare the method for 3-hydroxyl-2,3-dihydro-benzofuran derivative 3a.Experiment shows, compound 3a has good inhibit activities to Candida albicans, streptococcus aureus and intestinal bacteria.Its synthetic route is as follows:
Setting out from iodo-1, the 3-Dicarbonyl derivatives of 2-can without metallic green synthesizing benzoic acids derivative and Kui Linpyrimido quinoline Carbostyril derivative 7, and its technological line is as follows:
benzoic acid derivative has antibiotic and sterilizing effect, as antimicrobial drug, corrosion-proof and sterilization medicine and widely use (see Arnold, L.D.; Drover, J.C.D.; Vederas, J.C.J.Am.Chem.Soc.1987,109,4649 – 4659); Kui Linpyrimido quinoline quinolones oxygen biology has multiple biological activity, and the fields such as antianaphylaxis, hypertension, anti-inflammatory, calmness, anti HIV-1 virus, anti-malarial, anticancer and antithrombotic of being widely used in are (see 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 soccerballene, and achieve the functionalized of fullerene surface, its technological line is as follows:
Soccerballene is conduction and a kind of novel nano-material of excellent thermal conductivity, obviously can improve its performance (see Hirsch, A. by the modification on its surface; Brettreich, M.Fullerenes:ChemistryandReactions, Wiley-VCH, Weinheim, 2005).
The synthetic method of bromo-1, the 3-Dicarbonyl derivatives of published 2-mainly contains following several:
The people such as Stavber disclose a kind of with N-bromosuccinimide (NBS) for brominated reagent, the method for bromo-1, the 3-Dicarbonyl derivatives of preparation 2-, there is operation inconvenience in the method, be difficult to amplify, cannot industrialized deficiency; Khan discloses one with bromination dimethyl bromination sulfonium (BDMS) for brominated reagent, preparation 2-bromo-1, the method of 3-Dicarbonyl derivatives, brominated reagent costly (the TCI:5g/934 unit that the method is used, 25g/3270 unit), reaction be difficult to amplify, and in the synthesis of the method brominated reagent used, lower boiling raw material and solvent be used, therefore loss of material is large; The bromine of severe corrosive will be used simultaneously; Whole reaction process is polluted large, is not suitable for large-scale production.
Prior art also discloses under OXOne exists, and the method for bromo-1, the 3-Dicarbonyl derivatives of grinding preparation 2-, the method is only applicable to the preparation of 3 bromo-1,3-Dicarbonyl derivatives of 2-, there is substrate narrow application range, unhandy defect.Nama discloses a kind of with OXOne/NH
4br is brominated reagent, the method for bromo-1, the 3-Dicarbonyl derivatives of preparation 2-, and the method exists the defects such as 1,3-dicarbapentaborane substrate narrow application range, superoxide explosive.
The preparation method of iodo-1, the 3-Dicarbonyl derivatives of published 2-mainly contains following several:
Beaudry discloses one with 2-iodoxybenzoic acid (IBX) for iodo reagent, the method for iodo-1, the 3-derovatives of preparation 2-, and the method exists the deficiency such as substrate narrow application range, severe reaction conditions (part substrate needs-78 DEG C of reactions).Khalilzadeh discloses a kind of with HIO
4/ Al
2o
3for iodo reagent, the method for iodo-1, the 3-derovatives of preparation 2-, there is the shortcomings such as substrate narrow application range, selectivity is bad, productive rate is low in the method.
The people such as Lee disclose a kind of with HTIB/I
2or HTIB/ICH
3for iodo reagent, the method for iodo-1, the 3-derovatives of preparation 2-, there is substrate narrow application range, pollutes the shortcomings such as large in the method.Goswami discloses a kind of with Oxone/I
2for iodo reagent, by the method for grinding preparation 2-iodo-1,3-derovatives, there is substrate narrow application range in the method, superoxide easily explodes, the not easily shortcoming such as mass-producing.
It is iodo reagent with ICl that Krasnokutskaya discloses a kind of; by grinding preparation 2-iodo-1; the method of 3-diketone, there is substrate narrow application range, agents useful for same price, reagent unstable easily decomposition generation corrosive gases, is difficult to defects such as accomplishing scale production in the method.
Published 1,3-Dicarbonyl derivatives there is substrate narrow application range, halogenating agent costliness, severe reaction conditions in a halo technology, selectivity is bad, productive rate is low, production cost is high, pollution is large, operation is inconvenient, reaction scale is difficult to the deficiencies such as amplification.Therefore, find and a kind ofly meet that Green Chemistry requires, reaction conditions is gentle, universality method that is good, that be suitable for large-scale production is very important.
Summary of the invention
The object of this invention is to provide the method that one prepares 2-halo-1,3-Dicarbonyl derivatives, it has simple, the high yield of raw material sources, reaction conditions is gentle, universality is good advantage.
To achieve the above object of the invention, the technical solution used in the present invention is: a kind of 1, one halo method of 3-Dicarbonyl derivatives, comprise the following steps: by 1,3-Dicarbonyl derivatives, sodium halide, manganese acetate and copper catalyst add in solvent, react at 20 ~ 80 DEG C, obtain 2-halo-1,3-Dicarbonyl derivatives;
Described 1,3-Dicarbonyl derivatives is as shown in following chemical structure of general formula:
Wherein R
1be selected from: the one in alkyl, aryl, heteroaryl or alkoxyl group; R
2be selected from: the one in alkyl, aryl, heteroaryl or alkoxyl group;
Described sodium halide is Sodium Bromide or sodium iodide;
The chemical formula of described copper catalyst is CuX
n, wherein X is selected from: the one in Cl, Br, I or trifluoromethanesulfonic acid base; N is 1 or 2;
Described solvent is selected from: the one in methyl alcohol, ethanol, ethylene glycol, acetonitrile, acetic acid, propionic acid.
Described 2-halo-1,3-Dicarbonyl derivatives is as shown in following chemical structure of general formula:
or
.
In technique scheme, described 1,3-Dicarbonyl derivatives is selected from ethyl benzoylacetate, (4-toluyl) ethyl acetate, (4-methoxybenzoyl) ethyl acetate, (2-toluyl) ethyl acetate, (2-methoxybenzoyl) ethyl acetate, naphthoyl ethyl acetate, (4-chlorobenzoyl) ethyl acetate, (4-Bromophenacyl) ethyl acetate, (4-oil of mirbane formyl) ethyl acetate, (3-Bromophenacyl) ethyl acetate, 1,3-diphenylpropane-1，3-dione, 1-(2-furyl)-3-phenyl-1,3-propanedione, 1-(2-thienyl)-3-phenyl-1,3-propanedione, 1-(2-pyrryl)-3-phenyl-1,3-propanedione, 1-(4-aminomethyl phenyl)-3-phenyl-1,3-propanedione, 1-(4-p-methoxy-phenyl)-3-phenyl-1,3-propanedione, 1-(2-aminomethyl phenyl)-3-phenyl-1,3-propanedione, 1,3-bis-(2-p-methoxy-phenyl)-1,3-propanedione, 1-phenyl-1,3-diacetylmethane, 3,5-heptadione, diethyl malonate, 1-(4-chloro-phenyl-)-3-phenyl-1,3-propanedione, 1-(4-bromophenyl) one in-3-phenyl-1,3-propanedione.
In technique scheme, thin-layer chromatography (TLC) is utilized to follow the tracks of reaction until terminate completely.
In technique scheme, in molar ratio, 1,3-Dicarbonyl derivatives: sodium halide: manganese acetate: copper catalyst is 1: (1 ~ 3): (1 ~ 5): (0.05 ~ 0.2); Be preferably 1: 2: 3: 0.1.
In preferred technical scheme, reaction terminates to carry out column chromatography for separation purification processes to product afterwards; Be eluent with petrol ether/ethyl acetate during column chromatography for separation purification processes, the volume ratio of preferred sherwood oil and ethyl acetate is 20: 1.
Preferably, temperature of reaction of the present invention is 40 ~ 60 DEG C.Reaction temperature and, product yield is high, avoids energy dissipation.
The reaction process of technique scheme can be expressed as:
Due to the utilization of technique scheme, the present invention compared with prior art has following advantages:
1. the present invention uses 1,3-Dicarbonyl derivatives, sodium halide to be initiator first, only under manganese acetate and copper catalyst exist, in air, and efficient preparation 2-halo-1,3-Dicarbonyl derivatives; Raw material is easy to get, kind is many, and the product prepared can directly use, and can also be used for other further react as intermediate.
2. the present invention uses raw material simple, and without the need to the multiple reagents that prior art requires, reagent dosage is few, and selectivity is good, and cost is low, and avoids the application of existing toxic compounds, decreasing pollution environment; Only need a small amount of catalyzer efficiently can obtain product, not only simplify the purification process of product, reduce the generation of waste, and manganese acetate and copper catalyst reusable edible, avoid wastage of material, for industrial application, there is positive realistic meaning.
3. preparation method's reaction conditions disclosed by the invention is simple, without the need to the complicated atmosphere of prior art, in air, reaction efficiently can obtain product, aftertreatment is very simple, column chromatography, avoid the Hazard Factor that existing reaction process exists, be conducive to chemosynthesis 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 conditions is gentle, pollute little, the reaction times is short, is specially adapted to multiple 1,3-Dicarbonyl derivatives, the yield of target product is high, and operation and last handling process simply, are suitable for suitability for industrialized production.
Embodiment
Below in conjunction with embodiment, the invention will be further described:
The synthesis of embodiment one: 2-Bromophenacyl ethyl acetate
Using ethyl benzoylacetate, Sodium Bromide as raw material, its reactions steps is as follows:
ethyl benzoylacetate (0.192g, 1mmol), Sodium Bromide (0.103g, 1mmol), cuprous chloride (0.010g, 0.1mmol), manganese acetate (0.27g, 1mmol) and methyl alcohol (10 milliliters) is added, 20 DEG C of reactions in reaction flask;
tLC follows the tracks of reaction until terminate completely;
the crude by column chromatography obtained after reaction terminates is separated (ethyl acetate: sherwood oil=1:20), obtains target product (productive rate 53%).The analytical data of product is as follows:
1hNMR (400MHz, CDCl
3): 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=7.1Hz, 2H), 1.24 (t, J=7.1Hz, 3H).
The synthesis of embodiment two: 2-iodine ethyl benzoylacetate
Using ethyl benzoylacetate, sodium iodide as raw material, its reactions steps is as follows:
ethyl benzoylacetate (0.192g, 1mmol), sodium iodide (0.300g, 2mmol), cuprous iodide (0.020g, 0.1mmol), manganese acetate (0.81g, 3mmol) and ethanol (10 milliliters) is added, 30 DEG C of reactions in reaction flask;
tLC follows the tracks of reaction until terminate completely;
the crude by column chromatography obtained after reaction terminates is separated (ethyl acetate: sherwood oil=1:20), obtains target product (productive rate 68%).The analytical data of product is as follows:
1hNMR (400MHz, CDCl
3): 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=7.1Hz, 2H), 1.24 (t, J=7.1Hz, 3H).
The synthesis of embodiment three: 2-bromine (4-toluyl) ethyl acetate
Using (4-toluyl) ethyl acetate, Sodium Bromide as raw material, its reactions steps is as follows:
(4-toluyl) ethyl acetate (0.206g, 1mmol), Sodium Bromide (0.206g, 2mmol), cuprous bromide (0.014g, 0.1mmol), manganese acetate (0.54g, 2mmol) and ethylene glycol (10 milliliters) is added, 40 DEG C of reactions in reaction flask;
tLC follows the tracks of reaction until terminate completely;
the crude by column chromatography obtained after reaction terminates is separated (ethyl acetate: sherwood oil=1:20), obtains target product (productive rate 70%).The analytical data of product is as follows:
1hNMR (400MHz, CDCl
3): δ 7.89 (d, J=8.3Hz, 2H), 7.29 (d, J=8.1Hz, 2H), 5.64 (s, 1H), 4.28 (q, J=7.1Hz, 2H), 2.43 (s, 3H), 1.25 (t, J=7.1Hz, 3H).
The synthesis of embodiment four: 2-bromine (4-methoxybenzoyl) ethyl acetate
Using (4-methoxybenzoyl) ethyl acetate, Sodium Bromide as raw material, its reactions steps is as follows:
(4-methoxybenzoyl) ethyl acetate (0.222g, 1mmol), Sodium Bromide (0.309g, 3mmol), cupric chloride (0.013g, 0.1mmol), manganese acetate (0.81g, 3mmol) and acetonitrile (10 milliliters) is added, 50 DEG C of reactions in reaction flask;
tLC follows the tracks of reaction until terminate completely;
the crude by column chromatography obtained after reaction terminates is separated (ethyl acetate: sherwood oil=1:20), obtains target product (productive rate 80%).The analytical data of product is as follows:
1hNMR (400MHz, CDCl
3): δ 8.03 – 7.93 (m, 2H), 7.00 – 6.90 (m, 2H), 5.62 (s, 1H), 4.28 (q, J=7.1Hz, 2H), 3.89 (s, 3H), 1.25 (t, J=7.1Hz, 3H).
The synthesis of embodiment five: 2-iodine (4-methoxybenzoyl) ethyl acetate
Using (4-methoxybenzoyl) ethyl acetate, sodium iodide as raw material, its reactions steps is as follows:
(4-methoxybenzoyl) ethyl acetate (0.222g, 1mmol), sodium iodide (0.300g, 2mmol), cuprous iodide (0.020g, 0.1mmol), manganese acetate (0.81g, 3mmol) and acetic acid (10 milliliters) is added, 60 DEG C of reactions in reaction flask;
tLC follows the tracks of reaction until terminate completely;
the crude by column chromatography obtained after reaction terminates is separated (ethyl acetate: sherwood oil=1:20), obtains target product (productive rate 74%).The analytical data of product is as follows:
1hNMR (400MHz, CDCl
3): δ 8.03 – 7.93 (m, 2H), 7.00 – 6.90 (m, 2H), 5.81 (s, 1H), 4.28 (q, J=7.1Hz, 2H), 3.89 (s, 3H), 1.25 (t, J=7.1Hz, 3H).
The synthesis of embodiment six: 2-bromine (2-toluyl) ethyl acetate
Using (2-toluyl) ethyl acetate, Sodium Bromide as raw material, its reactions steps is as follows:
(2-toluyl) ethyl acetate (0.206g, 1mmol), Sodium Bromide (0.206g, 2mmol), cupric bromide (0.022g, 0.1mmol), manganese acetate (1.08g, 4mmol) and propionic acid (10 milliliters) is added, 70 DEG C of reactions in reaction flask;
tLC follows the tracks of reaction until terminate completely;
the crude by column chromatography obtained after reaction terminates is separated (ethyl acetate: sherwood oil=1:20), obtains target product (productive rate 78%).The analytical data of product is as follows:
1hNMR (400MHz, CDCl
3): δ 7.66 (d, J=7.8Hz, 1H), 7.47 – 7.40 (m, 1H), 7.29 (t, J=8.4Hz, 2H), 5.63 (s, 1H), 4.26 (q, J=7.1Hz, 2H), 2.52 (s, 3H), 1.23 (t, J=7.1Hz, 3H).
The synthesis of embodiment seven: 2-bromine (2-methoxybenzoyl) ethyl acetate
Using (2-methoxybenzoyl) ethyl acetate, Sodium Bromide as raw material, its reactions steps is as follows:
(2-methoxybenzoyl) ethyl acetate (0.222g, 1mmol), Sodium Bromide (0.206g, 2mmol), cupric iodide (0.064g, 0.2mmol), manganese acetate (1.35g, 5mmol) and acetonitrile (10 milliliters) is added, 80 DEG C of reactions in reaction flask;
tLC follows the tracks of reaction until terminate completely;
the crude by column chromatography obtained after reaction terminates is separated (ethyl acetate: sherwood oil=1:20), obtains target product (productive rate 76%).The analytical data of product is as follows:
1hNMR (400MHz, CDCl
3): δ 7.92 (dd, J=7.8,1.8Hz, 1H), 7.57 – 7.51 (m, 1H), 7.09 – 7.04 (m, 1H), 6.98 (d, J=8.4Hz, 1H), 5.81 (s, 1H), 4.29 – 4.20 (m, 2H), 3.91 (s, 3H), 1.24 (t, J=7.1Hz, 3H).
The synthesis of embodiment eight: 2-bromonaphthalene malonaldehydic acid ethyl ester
Using naphthoyl ethyl acetate, Sodium Bromide as raw material, its reactions steps is as follows:
naphthoyl ethyl acetate (0.242g, 1mmol), Sodium Bromide (0.206g, 2mmol), trifluoromethanesulfonic acid cuprous (0.021g, 0.1mmol), manganese acetate (0.81g, 3mmol) and acetic acid (10 milliliters) is added, 60 DEG C of reactions in reaction flask;
tLC follows the tracks of reaction until terminate completely;
the crude by column chromatography obtained after reaction terminates is separated (ethyl acetate: sherwood oil=1:20), obtains target product (productive rate 71%).The analytical data of product is as follows:
1hNMR (400MHz, CDCl
3): δ 8.55 (d, J=8.6Hz, 1H), 8.06 (d, J=8.2Hz, 1H), 7.93 (d, J=7.2Hz, 1H), 7.90 (d, J=8.1Hz, 1H), 7.67 – 7.62 (m, 1H), 7.60 – 7.55 (m, 1H), 7.52 (t, J=7.8Hz, 1H), 5.82 (s, 1H), 4.28 – 4.20 (m, 2H), 1.18 (t, J=7.1Hz, 3H).
The synthesis of embodiment nine: 2-bromine (4-chlorobenzoyl) ethyl acetate
Using (4-chlorobenzoyl) ethyl acetate, Sodium Bromide as raw material, its reactions steps is as follows:
(4-chlorobenzoyl) ethyl acetate (0.226g, 1mmol), Sodium Bromide (0.206g, 2mmol), cuprous bromide (0.007g, 0.05mmol), manganese acetate (0.81g, 3mmol) and acetic acid (10 milliliters) is added, 60 DEG C of reactions in reaction flask;
tLC follows the tracks of reaction until terminate completely;
the crude by column chromatography obtained after reaction terminates is separated (ethyl acetate: sherwood oil=1:20), obtains target product (productive rate 70%).The analytical data of product is as follows:
1hNMR (400MHz, CDCl
3): δ 7.94 (d, J=8.6Hz, 2H), 7.47 (d, J=8.6Hz, 2H), 5.59 (s, 1H), 4.29 (q, J=7.1Hz, 2H), 1.26 (t, J=7.1Hz, 3H).
The synthesis of embodiment ten: 2-bromine (4-Bromophenacyl) ethyl acetate
Using (4-Bromophenacyl) ethyl acetate, Sodium Bromide as raw material, its reactions steps is as follows:
(4-Bromophenacyl) ethyl acetate (0.269g, 1mmol), Sodium Bromide (0.206g, 2mmol), cuprous bromide (0.014g, 0.1mmol), manganese acetate (0.81g, 3mmol) and acetic acid (10 milliliters) is added, 60 DEG C of reactions in reaction flask;
tLC follows the tracks of reaction until terminate completely;
the crude by column chromatography obtained after reaction terminates is separated (ethyl acetate: sherwood oil=1:20), obtains target product (productive rate 61%).The analytical data of product is as follows:
1hNMR (400MHz, CDCl
3): δ 7.86 (d, J=8.6Hz, 2H), 7.65 (d, J=8.6Hz, 2H), 5.58 (s, 1H), 4.29 (q, J=7.1Hz, 2H), 1.26 (t, J=7.1Hz, 3H).
The synthesis of embodiment 11: 2-bromine (4-oil of mirbane formyl) ethyl acetate
Using (4-oil of mirbane formyl) ethyl acetate, Sodium Bromide as raw material, its reactions steps is as follows:
(4-oil of mirbane formyl) ethyl acetate (0.237g, 1mmol), Sodium Bromide (0.206g, 2mmol), cuprous bromide (0.028g, 0.2mmol), manganese acetate (0.81g, 3mmol) and acetonitrile (10 milliliters) is added, 50 DEG C of reactions in reaction flask;
tLC follows the tracks of reaction until terminate completely;
the crude by column chromatography obtained after reaction terminates is separated (ethyl acetate: sherwood oil=1:20), obtains target product (productive rate 67%).The analytical data of product is as follows:
1hNMR (400MHz, CDCl
3): 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=7.1Hz, 3H).
The synthesis of embodiment 12: 2-bromine (3-Bromophenacyl) ethyl acetate
Using (3-Bromophenacyl) ethyl acetate, Sodium Bromide as raw material, its reactions steps is as follows:
(3-Bromophenacyl) ethyl acetate (0.269g, 1mmol), Sodium Bromide (0.206g, 2mmol), cuprous bromide (0.042g, 0.3mmol), manganese acetate (0.81g, 3mmol) and acetonitrile (10 milliliters) is added, 50 DEG C of reactions in reaction flask;
tLC follows the tracks of reaction until terminate completely;
the crude by column chromatography obtained after reaction terminates is separated (ethyl acetate: sherwood oil=1:20), obtains target product (productive rate 61%).The analytical data of product is as follows:
1hNMR (400MHz, CDCl
3): δ 8.13 (t, J=1.7Hz, 1H), 7.91 (d, J=7.8Hz, 1H), 7.75 (d, J=8.0Hz, 1H), 7.39 (t, J=7.9Hz, 1H), 5.59 (s, 1H), 4.30 (q, J=7.1Hz, 2H), 1.27 (t, J=7.1Hz, 3H).
The synthesis of bromo-1, the 3-diphenylpropane-1，3-dione of embodiment 13: 2-
With 1,3-diphenylpropane-1，3-dione, Sodium Bromide as raw material, its reactions steps is as follows:
1,3-diphenylpropane-1，3-dione (0.224g, 1mmol), Sodium Bromide (0.206g, 2mmol), cuprous bromide (0.014g, 0.1mmol), manganese acetate (0.81g, 3mmol) and acetonitrile (10 milliliters) is added, 50 DEG C of reactions in reaction flask;
tLC follows the tracks of reaction until terminate completely;
the crude by column chromatography obtained after reaction terminates is separated (ethyl acetate: sherwood oil=1:20), obtains target product (productive rate 78%).The analytical data of product is as follows:
1hNMR (400MHz, CDCl
3): δ 8.07 – 7.89 (m, 4H), 7.61 (t, J=7.4Hz, 2H), 7.47 (t, J=7.8Hz, 4H), 6.55 (s, 1H).
The synthesis of iodo-1, the 3-diphenylpropane-1，3-dione of embodiment 14: 2-
With 1,3-diphenylpropane-1，3-dione, sodium iodide as raw material, its reactions steps is as follows:
1,3-diphenylpropane-1，3-dione (0.224g, 1mmol), sodium iodide (0.300g, 2mmol), cuprous bromide (0.014g, 0.1mmol), manganese acetate (0.81g, 3mmol) and acetic acid (10 milliliters) is added, 60 DEG C of reactions in reaction flask;
tLC follows the tracks of reaction until terminate completely;
the crude by column chromatography obtained after reaction terminates is separated (ethyl acetate: sherwood oil=1:20), obtains target product (productive rate 77%).The analytical data of product is as follows:
1hNMR (400MHz, CDCl
3): δ 8.07 – 7.89 (m, 4H), 7.61 (t, J=7.4Hz, 2H), 7.47 (t, J=7.8Hz, 4H), 6.68 (s, 1H).
The synthesis of embodiment 15: 1-(2-furyl)-2-bromo-3-phenyl-1,3-propanedione
With 1-(2-furyl)-3-phenyl-1,3-propanedione, Sodium Bromide as raw material, its reactions steps is as follows:
1-(2-furyl)-3-phenyl-1,3-propanedione (0.214g, 1mmol), Sodium Bromide (0.206g is added in reaction flask, 2mmol), cuprous bromide (0.014g, 0.1mmol), manganese acetate (0.81g, 3mmol) and acetic acid (10 milliliters), 60 DEG C of reactions;
tLC follows the tracks of reaction until terminate completely;
the crude by column chromatography obtained after reaction terminates is separated (ethyl acetate: sherwood oil=1:20), obtains target product (productive rate 81%).The analytical data of product is as follows:
1hNMR (400MHz, CDCl
3): δ 8.85 – 8.50 (m, 2H), 7.88 – 7.50 (m, 5H), 7.33 – 7.30 (m, 1H), 6.75 (s, 1H).
The synthesis of embodiment 16: 1-(2-thienyl)-2-bromo-3-phenyl-1,3-propanedione
With 1-(2-thienyl)-3-phenyl-1,3-propanedione, Sodium Bromide as raw material, its reactions steps is as follows:
1-(2-thienyl)-3-phenyl-1,3-propanedione (0.230g, 1mmol), Sodium Bromide (0.206g is added in reaction flask, 2mmol), cuprous bromide (0.014g, 0.1mmol), manganese acetate (0.81g, 3mmol) and ethanol (10 milliliters), 60 DEG C of reactions;
tLC follows the tracks of reaction until terminate completely;
the crude by column chromatography obtained after reaction terminates is separated (ethyl acetate: sherwood oil=1:20), obtains target product (productive rate 75%).The analytical data of product is as follows:
1hNMR (400MHz, CDCl
3): δ 8.15 – 7.90 (m, 4H), 7.88 – 7.50 (m, 3H), 7.33 – 7.20 (m, 1H), 6.63 (s, 1H).
The synthesis of embodiment 17: 1-(2-thienyl)-2-iodo-3-phenyl-1,3-propanedione
With 1-(2-thienyl)-3-phenyl-1,3-propanedione, sodium iodide as raw material, its reactions steps is as follows:
1-(2-thienyl)-3-phenyl-1,3-propanedione (0.230g, 1mmol), sodium iodide (0.300g is added in reaction flask, 2mmol), cuprous iodide (0.020g, 0.1mmol), manganese acetate (0.81g, 3mmol) and ethanol (10 milliliters), 60 DEG C of reactions;
tLC follows the tracks of reaction until terminate completely;
the crude by column chromatography obtained after reaction terminates is separated (ethyl acetate: sherwood oil=1:20), obtains target product (productive rate 77%).The analytical data of product is as follows:
1hNMR (400MHz, CDCl
3): δ 8.15 – 7.90 (m, 4H), 7.88 – 7.50 (m, 3H), 7.33 – 7.20 (m, 1H), 6.76 (s, 1H).
The synthesis of embodiment 18: 1-(2-pyrryl)-2-bromo-3-phenyl-1,3-propanedione
With 1-(2-pyrryl)-3-phenyl-1,3-propanedione, Sodium Bromide as raw material, its reactions steps is as follows:
1-(2-pyrryl)-3-phenyl-1,3-propanedione (0.213g, 1mmol), Sodium Bromide (0.206g is added in reaction flask, 2mmol), cuprous bromide (0.014g, 0.1mmol), manganese acetate (0.81g, 3mmol) and ethanol (10 milliliters), 60 DEG C of reactions;
tLC follows the tracks of reaction until terminate completely;
the crude by column chromatography obtained after reaction terminates is separated (ethyl acetate: sherwood oil=1:20), obtains target product (productive rate 69%).The analytical data of product is as follows:
1hNMR (400MHz, CDCl
3): 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).
The bromo-1-(4-aminomethyl phenyl of embodiment 19: 2-) synthesis of-3-phenyl-1,3-propanedione
With 1-(4-aminomethyl phenyl)-3-phenyl-1,3-propanedione, Sodium Bromide as raw material, its reactions steps is as follows:
in reaction flask, add 1-(4-aminomethyl phenyl)-3-phenyl-1,3-propanedione (0.238g, 1mmol), Sodium Bromide (0.206g, 2mmol), cuprous bromide (0.014g, 0.1mmol), manganese acetate (0.81g, 3mmol) and acetic acid (10 milliliters), 60 DEG C of reactions;
tLC follows the tracks of reaction until terminate completely;
the crude by column chromatography obtained after reaction terminates is separated (ethyl acetate: sherwood oil=1:20), obtains target product (productive rate 70%).The analytical data of product is as follows:
1hNMR (400MHz, CDCl
3): δ 8.00 – 7.97 (m, 2H), 7.90 (d, J=8.3Hz, 2H), 7.62 – 7.57 (m, 1H), 7.49 – 7.44 (m, 2H), 7.27 (d, J=8.0Hz, 2H), 6.53 (s, 1H), 2.41 (s, 3H).
The bromo-1-(4-p-methoxy-phenyl of embodiment 20: 2-) synthesis of-3-phenyl-1,3-propanedione
With 1-(4-p-methoxy-phenyl)-3-phenyl-1,3-propanedione, Sodium Bromide as raw material, its reactions steps is as follows:
in reaction flask, add 1-(4-p-methoxy-phenyl)-3-phenyl-1,3-propanedione (0.254g, 1mmol), Sodium Bromide (0.206g, 2mmol), cuprous bromide (0.014g, 0.1mmol), manganese acetate (0.81g, 3mmol) and acetic acid (10 milliliters), 60 DEG C of reactions;
tLC follows the tracks of reaction until terminate completely;
the crude by column chromatography obtained after reaction terminates is separated (ethyl acetate: sherwood oil=1:20), obtains target product (productive rate 77%).The analytical data of product is as follows:
1hNMR (400MHz, CDCl
3): δ 8.00 – 7.96 (m, 2H), 7.60 – 7.54 (m, 1H), 7.45 (t, J=7.8Hz, 2H), 6.95 – 6.89 (m, 2H), 6.50 (s, 1H), 3.86 (s, 3H).
The bromo-1-(2-aminomethyl phenyl of embodiment 21: 2-) synthesis of-3-phenyl-1,3-propanedione
With 1-(2-aminomethyl phenyl)-3-phenyl-1,3-propanedione, Sodium Bromide as raw material, its reactions steps is as follows:
in reaction flask, add 1-(2-aminomethyl phenyl)-3-phenyl-1,3-propanedione (0.238g, 1mmol), Sodium Bromide (0.206g, 2mmol), cuprous bromide (0.014g, 0.1mmol), manganese acetate (0.81g, 3mmol) and acetic acid (10 milliliters), 60 DEG C of reactions;
tLC follows the tracks of reaction until terminate completely;
the crude by column chromatography obtained after reaction terminates is separated (ethyl acetate: sherwood oil=1:20), obtains target product (productive rate 81%).The analytical data of product is as follows:
1hNMR (400MHz, CDCl
3): δ 7.98 – 7.93 (m, 2H), 7.70 (d, J=7.7Hz, 1H), 7.59 (t, J=7.4Hz, 1H), 7.46 (t, J=7.8Hz, 2H), 7.40 (t, J=7.6Hz, 1H), 7.26 (t, J=7.6Hz, 2H), 6.54 (s, 1H), 2.49 (s, 3H).
The synthesis of embodiment 22: 2-bromo-1,3-bis-(2-p-methoxy-phenyl)-1,3-propanedione
With 1,3-bis-(2-p-methoxy-phenyl)-1,3-propanedione, Sodium Bromide as raw material, its reactions steps is as follows:
1,3-bis-(2-p-methoxy-phenyl)-1,3-propanedione (0.284g is added in reaction flask, 1mmol), Sodium Bromide (0.206g, 2mmol), cuprous bromide (0.014g, 0.1mmol), manganese acetate (0.81g, 3mmol) with acetic acid (10 milliliters), 60 DEG C of reactions;
tLC follows the tracks of reaction until terminate completely;
the crude by column chromatography obtained after reaction terminates is separated (ethyl acetate: sherwood oil=1:20), obtains target product (productive rate 70%).The analytical data of product is as follows:
1hNMR (400MHz, CDCl
3): δ 8.03 (dd, J=7.9,1.8Hz, 2H), 7.57 – 7.49 (m, 2H), 7.14 (s, 1H), 7.10 – 7.03 (m, 2H), 6.97 (d, J=8.3Hz, 2H), 3.78 (s, 6H).
The synthesis of embodiment 23: 2-bromo-1-phenyl-1,3-diacetylmethane
With 1-phenyl-1,3-diacetylmethane, Sodium Bromide as raw material, its reactions steps is as follows:
1-phenyl-1,3-diacetylmethane (0.176g, 1mmol), Sodium Bromide (0.206g, 2mmol), cuprous bromide (0.014g, 0.1mmol), manganese acetate (0.81g, 3mmol) and acetic acid (10 milliliters) is added, 60 DEG C of reactions in reaction flask;
tLC follows the tracks of reaction until terminate completely;
the crude by column chromatography obtained after reaction terminates is separated (ethyl acetate: sherwood oil=1:20), obtains target product (productive rate 72%).The analytical data of product is as follows:
1hNMR (400MHz, CDCl
3): 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=7.2Hz, 3H).
The synthesis of bromo-3, the 5-heptadione of embodiment 24: 4-
With 3,5-heptadione, Sodium Bromide as raw material, its reactions steps is as follows:
3,5-heptadione (0.128g, 1mmol), Sodium Bromide (0.206g, 2mmol), cuprous bromide (0.014g, 0.1mmol), manganese acetate (0.81g, 3mmol) and acetic acid (10 milliliters) is added, 50 DEG C of reactions in reaction flask;
tLC follows the tracks of reaction until terminate completely;
the crude by column chromatography obtained after reaction terminates is separated (ethyl acetate: sherwood oil=1:20), obtains target product (productive rate 70%).The analytical data of product is as follows:
1hNMR (400MHz, CDCl
3): δ 5.80 (s, 1H), 2.75 (q, J=7.2Hz, 4H), 1.23 (t, J=7.2Hz, 6H).
The synthesis of iodo-3, the 5-heptadione of embodiment 25: 4-
With 3,5-heptadione, sodium iodide as raw material, its reactions steps is as follows:
3,5-heptadione (0.128g, 1mmol), sodium iodide (0.300g, 2mmol), cuprous iodide (0.020g, 0.1mmol), manganese acetate (0.81g, 3mmol) and acetic acid (10 milliliters) is added, 50 DEG C of reactions in reaction flask;
tLC follows the tracks of reaction until terminate completely;
the crude by column chromatography obtained after reaction terminates is separated (ethyl acetate: sherwood oil=1:20), obtains target product (productive rate 65%).The analytical data of product is as follows:
1hNMR (400MHz, CDCl
3): δ 5.93 (s, 1H), 2.75 (q, J=7.2Hz, 4H), 1.23 (t, J=7.2Hz, 6H).
The synthesis of embodiment 26: 2-diethyl bromomalonate
Using diethyl malonate, Sodium Bromide as raw material, its reactions steps is as follows:
diethyl malonate (0.160g, 1mmol), Sodium Bromide (0.206g, 2mmol), cuprous bromide (0.014g, 0.1mmol), manganese acetate (0.81g, 3mmol) and acetic acid (10 milliliters) is added, 50 DEG C of reactions in reaction flask;
tLC follows the tracks of reaction until terminate completely;
the crude by column chromatography obtained after reaction terminates is separated (ethyl acetate: sherwood oil=1:20), obtains target product (productive rate 74%).The analytical data of product is as follows:
1hNMR (400MHz, CDCl
3): δ 5.91 (s, 1H), 4.75 (q, J=7.3Hz, 4H), 1.63 (t, J=7.3Hz, 6H).
The bromo-1-(4-chloro-phenyl-of embodiment 27: 2-) synthesis of-3-phenyl-1,3-propanedione
With 1-(4-chloro-phenyl-)-3-phenyl-1,3-propanedione, Sodium Bromide as raw material, its reactions steps is as follows:
in reaction flask, add 1-(4-chloro-phenyl-)-3-phenyl-1,3-propanedione (0.256g, 1mmol), Sodium Bromide (0.206g, 2mmol), cuprous bromide (0.014g, 0.1mmol), manganese acetate (0.81g, 3mmol) and acetic acid (10 milliliters), 40 DEG C of reactions;
tLC follows the tracks of reaction until terminate completely;
the crude by column chromatography obtained after reaction terminates is separated (ethyl acetate: sherwood oil=1:20), obtains target product (productive rate 65%).The analytical data of product is as follows:
1hNMR (400MHz, CDCl
3): δ 8.02 – 7.96 (m, 4H), 7.96 – 7.91 (m, 3.6H), 7.62 (t, J=7.4Hz, 1.9H), 7.48 (t, J=7.7Hz, 4H), 7.44 (d, J=8.6Hz, 3.6H), 6.47 (s, 1H), 6.34 (s, 1H).
The bromo-1-(4-bromophenyl of embodiment 28: 2-) synthesis of-3-phenyl-1,3-propanedione
With 1-(4-bromophenyl)-3-phenyl-1,3-propanedione, Sodium Bromide as raw material, its reactions steps is as follows:
in reaction flask, add 1-(4-bromophenyl)-3-phenyl-1,3-propanedione (0.301g, 1mmol), Sodium Bromide (0.206g, 2mmol), cuprous bromide (0.014g, 0.1mmol), manganese acetate (0.81g, 3mmol) and acetic acid (10 milliliters), 40 DEG C of reactions;
tLC follows the tracks of reaction until terminate completely;
the crude by column chromatography obtained after reaction terminates is separated (ethyl acetate: sherwood oil=1:20), obtains target product (productive rate 70%).The analytical data of product is as follows:
1hNMR (400MHz, CDCl
3): δ 8.02 – 7.98 (m, 2H), 7.90 – 7.85 (m, 2H), 7.67 – 7.60 (m, 3H), 7.50 (t, J=7.8Hz, 2H), 6.48 (s, 1H).
Claims (10)
1. the preparation method of 2-halo-1, a 3-Dicarbonyl derivatives, is characterized in that, comprise the following steps: 1,3-Dicarbonyl derivatives, sodium halide, manganese acetate and copper catalyst are added in solvent, react at 20 ~ 80 DEG C, obtain 2-halo-1,3-Dicarbonyl derivatives;
Described 1,3-Dicarbonyl derivatives is as shown in following chemical structure of general formula:
Wherein R
1be selected from: the one in alkyl, aryl, heteroaryl or alkoxyl group; R
2be selected from: the one in alkyl, aryl, heteroaryl or alkoxyl group;
Described sodium halide is Sodium Bromide or sodium iodide;
The chemical formula of described copper catalyst is CuX
n, wherein X is selected from: the one in Cl, Br, I or trifluoromethanesulfonic acid base; N is 1 or 2;
Described solvent is selected from: the one in methyl alcohol, ethanol, ethylene glycol, acetonitrile, acetic acid, propionic acid;
Described 2-halo-1,3-Dicarbonyl derivatives is as shown in following chemical structure of general formula:
or
.
2. the preparation method of 2-halo-1,3-Dicarbonyl derivatives according to claim 1, is characterized in that: described 1,3-Dicarbonyl derivatives is selected from ethyl benzoylacetate, (4-toluyl) ethyl acetate, (4-methoxybenzoyl) ethyl acetate, (2-toluyl) ethyl acetate, (2-methoxybenzoyl) ethyl acetate, naphthoyl ethyl acetate, (4-chlorobenzoyl) ethyl acetate, (4-Bromophenacyl) ethyl acetate, (4-oil of mirbane formyl) ethyl acetate, (3-Bromophenacyl) ethyl acetate, 1,3-diphenylpropane-1，3-dione, 1-(2-furyl)-3-phenyl-1,3-propanedione, 1-(2-thienyl)-3-phenyl-1,3-propanedione, 1-(2-pyrryl)-3-phenyl-1,3-propanedione, 1-(4-aminomethyl phenyl)-3-phenyl-1,3-propanedione, 1-(4-p-methoxy-phenyl)-3-phenyl-1,3-propanedione, 1-(2-aminomethyl phenyl)-3-phenyl-1,3-propanedione, 1,3-bis-(2-p-methoxy-phenyl)-1,3-propanedione, 1-phenyl-1,3-diacetylmethane, 3,5-heptadione, diethyl malonate, 1-(4-chloro-phenyl-)-3-phenyl-1,3-propanedione, 1-(4-bromophenyl) one in-3-phenyl-1,3-propanedione.
3. the preparation method of 2-halo-1,3-Dicarbonyl derivatives according to claim 1, is characterized in that: described reaction is carried out in atmosphere.
4. the preparation method of 2-halo-1,3-Dicarbonyl derivatives according to claim 1, is characterized in that: in molar ratio, 1,3-Dicarbonyl derivatives: sodium halide: manganese acetate: copper catalyst is 1: (1 ~ 3): (1 ~ 5): (0.05 ~ 0.2).
5. the preparation method of 2-halo-1,3-Dicarbonyl derivatives according to claim 4, is characterized in that: in molar ratio, 1,3-Dicarbonyl derivatives: sodium halide: manganese acetate: copper catalyst is 1: 2: 3: 0.1.
6. the preparation method of 2-halo-1,3-Dicarbonyl derivatives according to claim 1, is characterized in that: utilize thin-layer chromatography to follow the tracks of reaction until terminate completely.
7. the preparation method of 2-halo-1,3-Dicarbonyl derivatives according to claim 1, is characterized in that: reaction terminates to carry out column chromatography for separation purification processes to product afterwards.
8. the preparation method of 2-halo-1,3-Dicarbonyl derivatives according to claim 7, is characterized in that: be eluent with petrol ether/ethyl acetate during described column chromatography for separation purification processes.
9. the preparation method of 2-halo-1,3-Dicarbonyl derivatives according to claim 8, is characterized in that: the volume ratio of described sherwood oil and ethyl acetate is 20: 1.
10. the preparation method of 2-halo-1,3-Dicarbonyl derivatives according to claim 1, is characterized in that: described temperature of reaction is 40 ~ 60 DEG C.
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