CN105777510A - Synthesizing method for diketone compound - Google Patents
Synthesizing method for diketone compound Download PDFInfo
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- CN105777510A CN105777510A CN201610086073.6A CN201610086073A CN105777510A CN 105777510 A CN105777510 A CN 105777510A CN 201610086073 A CN201610086073 A CN 201610086073A CN 105777510 A CN105777510 A CN 105777510A
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- 0 **C(CC1)=CC=C1Cl Chemical compound **C(CC1)=CC=C1Cl 0.000 description 1
- CGRCLWNQGJQSLH-NSCUHMNNSA-N C/C=C/CCC(CC(C1C=CC=CC1)O)C(CC1)=CC=C1Cl Chemical compound C/C=C/CCC(CC(C1C=CC=CC1)O)C(CC1)=CC=C1Cl CGRCLWNQGJQSLH-NSCUHMNNSA-N 0.000 description 1
Classifications
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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
- C07C45/68—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 increase in the number of carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
- C07C49/782—Ketones containing a keto group bound to a six-membered aromatic ring polycyclic
- C07C49/784—Ketones containing a keto group bound to a six-membered aromatic ring polycyclic with all keto groups bound to a non-condensed ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
- C07C49/80—Ketones containing a keto group bound to a six-membered aromatic ring containing halogen
- C07C49/813—Ketones containing a keto group bound to a six-membered aromatic ring containing halogen polycyclic
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
- C07C49/84—Ketones containing a keto group bound to a six-membered aromatic ring containing ether groups, groups, groups, or groups
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a synthesizing method for a diketone compound shown in the formula (III).The method comprises the steps that under a nitrogen atmosphere with a catalyst, an assistant and alkali, a compound shown in the formula (I) and a compound shown in the formula (II) are added into an organic solvent for a reaction, posttreatment is carried out after the reaction is finished, and thus the compound shown in the formula (III) is obtained, wherein R1 is selected from H or C1-C6 alkyl or C1-C6 alkoxy or halogen, R2 is selected from H or C1-C6 alkyl or C1-C6 alkoxy, and X is halogen.According to the method, the composite reaction system composed of a unique reaction substrate, the catalyst, the assistant, alkali and the organic solvent is adopted, the reaction among the materials is effectively promoted through the synthetic action of the system, convention of the materials to the product is promoted, the target product can be obtained at a high yield, and wide market prospects are achieved.
Description
Technical field
The present invention relates to the synthetic method of a kind of carbonyl compound, relate more particularly to a kind of two
The synthetic method of ketone compounds, belongs to organic chemical synthesis field.
Background technology
Cyclohexadione compounds is the compound that a class is important, its important frequently as in organic synthesis
Synthesis unit is to build other medicines compound or functional material.Therefore, research diones chemical combination
The synthetic method of thing is also a thing the most significant, and it is to chemical industry, medicine synthesis field
The most necessary.
The synthetic method of cyclohexadione compounds often relates to the Michael of alpha, beta-unsaturated carbonyl compound
Additive reaction, and deepening continuously recently as research, occur in that the most successively many other
Synthetic method, such as:
(" the One-pot Synthesis of 1,5-diketones catalyzed such as Akira Yanagisawa
By barium isopropoxide ", Tetrahedron, 2007,63,8581-8585) report one
The benzaldehyde using titanate catalyst catalysis reacts preparation 1,5-diketone chemical combination with acetophenone compounds
The method of thing, its reaction equation is as follows:
Andreas Marx etc. (" Aluminum Bis (trifluoromethylsulfonyl) amides:
New Highly Efficient and Remarkably Versatile Catalysts for C-C Bond
Formation Reactions ", Angew.Chem.Int.Ed., 2000,39,178-181) report
A kind of alpha, beta-unsaturated carbonyl compound prepares dione compounds with silylenolethers compounds reaction
Method, its reaction equation is as follows:
As it has been described above, prior art discloses the multiple method of synthesis cyclohexadione compounds, but
These methods still suffer from certain defect, such as substrate still need to be expanded, reaction yield too low etc..
Therefore, for developing the novel method for synthesizing of cyclohexadione compounds, still suffer from continuing research
Necessity, this power place that present invention is accomplished the most just and basis leaned on.
Summary of the invention
In order to overcome many defects as indicated above and seek the novel of cyclohexadione compounds
Synthetic method, present inventor has performed in-depth study and exploration, is paying enough creation
Property work after, thus complete the present invention.
Specifically, technical scheme and content relate to diketone shown in formula (III) under one
The synthetic method of compounds, described method includes: under nitrogen atmosphere, in catalyst, helps
In the presence of agent and alkali, under adding in organic solvent, (I) compound and lower formula (II) compound are carried out instead
Should, react after terminating through post processing, thus obtain described formula (III) compound,
Wherein, R1Selected from H, C1-C6Alkyl, C1-C6Alkoxy or halogen；
R2Selected from H, C1-C6Alkyl or C1-C6Alkoxyl；
X is halogen.
In the described synthetic method of the present invention, described C1-C6The implication of alkyl refers to have 1-6
The straight or branched alkyl of individual carbon atom, can be the most such as methyl, ethyl, positive third
Base, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl or
N-hexyl etc..
In the described synthetic method of the present invention, described C1-C6The implication of alkoxyl refers to have
The C of above-mentioned implication1-C6The group that alkyl obtains after being connected with oxygen atom.
In the described synthetic method of the present invention, described halogen is halogen, can be such as F,
Cl, Br or I.
In the described synthetic method of the present invention, described catalyst is [1,1 '-bis-(diphenylphosphines) two
Cyclopentadienyl ferrum] Nickel Chloride, trifluoromethanesulfonic acid nickel, double (diphenylphosphine propane) Nickel Chloride of 1,3-
((DPPP)NiCl2) or double (diphenylphosphine) ethane chlorination nickel ((DPPE) NiCl of 1,2-2Any in)
One, double (diphenylphosphine propane) Nickel Chloride ((DPPP) NiCl of most preferably 1,3-2)。
In the described synthetic method of the present invention, described auxiliary agent is zirconium acetate.
In the described synthetic method of the present invention, described alkali is NaOH, sodium carbonate, cesium carbonate,
Sodium phosphate, potassium acetate, potassium tert-butoxide, Sodium ethylate, 1,4-diazabicylo [2.2.2] octane
(DABCO) any one or in diethanolamine, most preferably cesium carbonate.
In the described synthetic method of the present invention, described organic solvent is DMF (N, N-dimethyl
Methanamide), DMSO (dimethyl sulfoxide), benzene, acetonitrile, N-Methyl pyrrolidone (NMP) or
Any one or the most multiple mixture, most preferably volume ratio 1:3 in Isosorbide-5-Nitrae-dioxane
The mixture of DMF (N,N-dimethylformamide) and acetonitrile.
Wherein, the consumption of described organic solvent does not has strict restriction, those skilled in the art
Can suitably select according to practical situation and determine, such as its consumption size is to facilitate reaction
Carry out and post processing, be no longer described in detail at this.
In the described synthetic method of the present invention, described formula (I) compound rubs with formula (II) compound
That ratio is 1:1.5-2.5, such as, can be 1:1.5,1:2 or 1:2.5.
In the described synthetic method of the present invention, described formula (I) compound and the mol ratio of catalyst
For 1:0.1-0.16, such as, can be 1:0.1,1:0.13 or 1:0.16.
In the described synthetic method of the present invention, described formula (I) compound with the mol ratio of auxiliary agent is
1:0.05-0.1, such as, can be 1:0.5,1:0.07,1:0.09 or 1:0.1.
In the described synthetic method of the present invention, described formula (I) compound with the mol ratio of alkali is
1:2-3, such as, can be 1:2,1:2.5 or 1:3.
In the described synthetic method of the present invention, reaction temperature is 80-100 DEG C, such as, can be
80 DEG C, 90 DEG C or 100 DEG C.
In the described synthetic method of the present invention, the response time is 6-9 hour, such as, can be 6
Hour, 7 hours, 8 hours or 9 hours.
In the described synthetic method of the present invention, the post processing after reaction terminates can be specific as follows:
After reaction terminates, reacting liquor while hot being filtered, the pH value of regulation filtrate, to neutral, is then used
Saturated aqueous common salt fully washs, and adds ether and extracts 2-3 time, merges organic facies, anhydrous
Magnesium sulfate is dried, concentrating under reduced pressure, and gained residue crosses 300-400 mesh silica gel column chromatography, with
The acetone of equal-volume ratio and the mixed liquor of petroleum ether carry out drip washing, thus obtain described formula (III)
Compound.
In sum, the invention provides the synthetic method of a kind of cyclohexadione compounds, the party
Method uses by being combined that unique reaction substrate, catalyst, auxiliary agent, alkali and organic solvent form
Reaction system, thus the reaction of storeroom has been effectively facilitated by the comprehensive function of this kind of system,
Promote the material conversion to product, purpose product can have been obtained with high yield, have widely
Market prospect.
Detailed description of the invention
Below by specific embodiment, the present invention is described in detail, but these are exemplary
The purposes of embodiment and purpose are only used for enumerating the present invention, the not actual guarantor to the present invention
Scope of protecting constitutes any type of any restriction, more non-protection scope of the present invention is confined to
This.
Embodiment 1
Under room temperature and nitrogen atmosphere, the appropriate organic solvent in reactor is (for volume ratio 1:3
The mixture of DMF (DMF) and acetonitrile) in, add 100mmol above formula
(I) compound, 150mmol upper formula (II) compound, the double (diphenyl of 16mmol catalyst 1,3-
Phosphine propane) Nickel Chloride ((DPPP) NiCl2), 7mmol auxiliary agent zirconium acetate and 250mmol alkali
Cesium carbonate, then heats to 80 DEG C, and is sufficiently stirred at such a temperature reacting 9 hours；
After reaction terminates, reacting liquor while hot being filtered, the pH value of regulation filtrate is to neutral, so
Fully wash with saturated aqueous common salt afterwards, add ether and extract 2-3 time, merge organic facies, nothing
Water magnesium sulfate is dried, concentrating under reduced pressure, and gained residue crosses 300-400 mesh silica gel column chromatography, with
The acetone of equal-volume ratio and the mixed liquor of petroleum ether carry out drip washing, thus obtain upper formula (III) chemical combination
Thing, productivity is 96.9%.
1H NMR(CDCl3, 400MHz): δ 7.96 (d, J=7.2Hz, 4H), 7.51-7.55
(m,2H),7.42-7.46(m,4H),7.21-7.23(m,4H),4.04-4.08(m,1H),3.47
(dd, J=5.6,16.8Hz, 2H), 3.34 (dd, J=6.0,16.0Hz, 2H).
Embodiment 2
Under room temperature and nitrogen atmosphere, the appropriate organic solvent in reactor is (for volume ratio 1:3
The mixture of DMF (DMF) and acetonitrile) in, add 100mmol above formula
(I) compound, 200mmol upper formula (II) compound, the double (diphenyl of 10mmol catalyst 1,3-
Phosphine propane) Nickel Chloride ((DPPP) NiCl2), 5mmol auxiliary agent zirconium acetate and 200mmol alkali
Cesium carbonate, then heats to 90 DEG C, and is sufficiently stirred at such a temperature reacting 7 hours；
After reaction terminates, reacting liquor while hot being filtered, the pH value of regulation filtrate is to neutral, so
Fully wash with saturated aqueous common salt afterwards, add ether and extract 2-3 time, merge organic facies, nothing
Water magnesium sulfate is dried, concentrating under reduced pressure, and gained residue crosses 300-400 mesh silica gel column chromatography, with
The acetone of equal-volume ratio and the mixed liquor of petroleum ether carry out drip washing, thus obtain upper formula (III) chemical combination
Thing, productivity is 97.1%.
1H NMR(CDCl3, 400MHz): δ 7.88 (d, J=6.0Hz, 4H), 7.17-7.26
(m, 9H), 4.02-4.06 (m, 1H), 3.45 (dd, J=6.8,16.4Hz, 2H), 3.32 (dd, J
=4.8,14.4Hz, 2H), 2.37 (m, 6H).
Embodiment 3
Under room temperature and nitrogen atmosphere, the appropriate organic solvent in reactor is (for volume ratio 1:3
The mixture of DMF (DMF) and acetonitrile) in, add 100mmol above formula
(I) compound, 250mmol upper formula (II) compound, the double (diphenyl of 13mmol catalyst 1,3-
Phosphine propane) Nickel Chloride ((DPPP) NiCl2), 10mmol auxiliary agent zirconium acetate and 230mmol
Alkali cesium carbonate, then heats to 100 DEG C, and is sufficiently stirred at such a temperature reacting 6 hours；
After reaction terminates, reacting liquor while hot being filtered, the pH value of regulation filtrate is to neutral, so
Fully wash with saturated aqueous common salt afterwards, add ether and extract 2-3 time, merge organic facies, nothing
Water magnesium sulfate is dried, concentrating under reduced pressure, and gained residue crosses 300-400 mesh silica gel column chromatography, with
The acetone of equal-volume ratio and the mixed liquor of petroleum ether carry out drip washing, thus obtain upper formula (III) chemical combination
Thing, productivity is 97.2%.
1H NMR(CDCl3, 400MHz): δ 7.96 (d, J=7.6Hz, 4H), 7.15 (d, J
=6.8Hz, 2H), 7.09 (d, J=7.2Hz, 2H), 6.92 (d, J=7.2Hz, 4H),
3.98-4.00 (m, 1H), 3.85 (s, 6H), 3.41 (dd, J=6.8,16.0Hz, 2H), 3.25 (dd,
J=6.4,16.0Hz, 2H), 2.29 (s, 3H).
Embodiment 4
Under room temperature and nitrogen atmosphere, the appropriate organic solvent in reactor is (for volume ratio 1:3
The mixture of DMF (DMF) and acetonitrile) in, add 100mmol above formula
(I) compound, 200mmol upper formula (II) compound, the double (diphenyl of 15mmol catalyst 1,3-
Phosphine propane) Nickel Chloride ((DPPP) NiCl2), 8mmol auxiliary agent zirconium acetate and 300mmol alkali
Cesium carbonate, then heats to 85 DEG C, and is sufficiently stirred at such a temperature reacting 8 hours；
After reaction terminates, reacting liquor while hot being filtered, the pH value of regulation filtrate is to neutral, so
Fully wash with saturated aqueous common salt afterwards, add ether and extract 2-3 time, merge organic facies, nothing
Water magnesium sulfate is dried, concentrating under reduced pressure, and gained residue crosses 300-400 mesh silica gel column chromatography, with
The acetone of equal-volume ratio and the mixed liquor of petroleum ether carry out drip washing, thus obtain upper formula (III) chemical combination
Thing, productivity is 57.3%.
1H NMR(CDCl3, 400MHz): δ 7.98 (d, J=7.2Hz, 4H)；7.52-7.55
(m,2H)；7.42-7.46(m,4H)；7.15-7.31(m,2H)；6.82-6.88(m,2H)；
4.33-4.35(m,1H)；3.76(s,3H)；3.41-3.52(m,4H).
It was unexpectedly determined that when the product prepared in embodiment 4, relative to embodiment 1-3,
Products collection efficiency has a reduction drastically, and the most only 57.3%, this is possibly due to formula (II) chemical combination
Ortho position-OCH in thing3Existence, reduce and put on-CHBr2On and phenyl ring self
Cloud density, and then result in the passivation of this reaction site reactivity, thus create
Significantly reduced productivity.
For this situation, inventor is further studied, and finds when to reaction system
In when further adding activator, the productivity of this product can be significantly improved, these are studied into
Fruit is disclosed in the another piece patent application applied on the same day, is no longer described in detail at this,
Its content can be incorporated by reference into into.
Below, inventor is investigated for each technical characteristic, thus has investigated each
Key element is for the impact of final result, owing to the productivity of embodiment 4 is relatively low, the most right
Embodiment 1-3 has carried out repeating experiment, specific as follows:
Embodiment 5-13
Embodiment 5-7: except by catalyst (DPPP) NiCl2Replace with [1,1 '-bis-(diphenylphosphines)
Ferrocene] outside Nickel Chloride, other operation is the most constant, thus repeats to implement embodiment 1-3,
Sequentially obtain embodiment 5-7.
Embodiment 8-10: except by catalyst (DPPP) NiCl2Replace with outside trifluoromethanesulfonic acid nickel,
Other operation is the most constant, thus repeats to implement embodiment 1-3, sequentially obtains embodiment 8-10.
Embodiment 11-13: except by catalyst (DPPP) NiCl2Replace with 1,2-double (diphenylphosphine)
Ethane chlorination nickel ((DPPE) NiCl2) outward, other operation is the most constant, thus repeats to implement enforcement
Example 1-3, sequentially obtains embodiment 11-13.
Result see table 1.
Table 1
As can be seen here, in all of catalyst, 1,3-double (diphenylphosphine propane) Nickel Chlorides
((DPPP)NiCl2) there is best catalytic effect, even if similar with it 1,2-double (two
Phenylphosphine) ethane chlorination nickel ((DPPE) NiCl2) (differ only by-a CH2-), productivity also has
Significantly reducing, other catalyst then reduces the most notable.
Embodiment 14-16
In addition to being omitted by auxiliary agent zirconium acetate, other operation is the most constant, thus repeats to implement
Embodiment 1-3, sequentially obtains embodiment 14-16.It was found that the product of embodiment 14-16
Productivity is 90.5-91.3%, has significantly reduction compared with embodiment 1-3.This proves acetic acid
The existence of zirconium, it is possible to significantly improve reaction effect, improves products collection efficiency.
Embodiment 17-40
Embodiment 17-19: be in addition to NaOH except alkali cesium carbonate being replaced with consumption, other operation
The most constant, thus repeat to implement embodiment 1-3, sequentially obtain embodiment 17-19.
Embodiment 20-22: be in addition to sodium carbonate except alkali cesium carbonate being replaced with consumption, other operation
The most constant, thus repeat to implement embodiment 1-3, sequentially obtain embodiment 20-22.
Embodiment 23-25: be in addition to sodium phosphate except alkali cesium carbonate being replaced with consumption, other operation
The most constant, thus repeat to implement embodiment 1-3, sequentially obtain embodiment 23-25.
Embodiment 26-28: be in addition to potassium acetate except alkali cesium carbonate being replaced with consumption, other operation
The most constant, thus repeat to implement embodiment 1-3, sequentially obtain embodiment 26-28.
Embodiment 29-31: be in addition to potassium tert-butoxide except alkali cesium carbonate being replaced with consumption, other behaviour
Make the most constant, thus repeat to implement embodiment 1-3, sequentially obtain embodiment 29-31.
Embodiment 32-34: be in addition to Sodium ethylate except alkali cesium carbonate being replaced with consumption, other operation
The most constant, thus repeat to implement embodiment 1-3, sequentially obtain embodiment 32-34.
Embodiment 35-37: be in addition to DABCO except alkali cesium carbonate being replaced with consumption, other behaviour
Make the most constant, thus repeat to implement embodiment 1-3, sequentially obtain embodiment 35-37.
Embodiment 38-40: be in addition to diethanolamine except alkali cesium carbonate being replaced with consumption, other behaviour
Make the most constant, thus repeat to implement embodiment 1-3, sequentially obtain embodiment 38-40.
Result see table 2.
Table 2
As can be seen here, in all of alkali, cesium carbonate has best effects, even if non-with it
Similar sodium carbonate, its productivity also has significantly reduction, and diethanolamine also can obtain height
In the good yield of 90%.
Embodiment 41-58
Embodiment 41-43: in addition to organic solvent is replaced with single solvent component DMF, its
Its operation is the most constant, thus repeats to implement embodiment 1-3, sequentially obtains embodiment 41-43.
Embodiment 44-46: in addition to organic solvent is replaced with single solvent component DMSO, its
Its operation is the most constant, thus repeats to implement embodiment 1-3, sequentially obtains embodiment 44-46.
Embodiment 47-49: in addition to organic solvent is replaced with single solvent component benzene, other behaviour
Make the most constant, thus repeat to implement embodiment 1-3, sequentially obtain embodiment 47-49.
Embodiment 50-52: in addition to organic solvent is replaced with single solvent component acetonitrile, other
Operate the most constant, thus repeat to implement embodiment 1-3, sequentially obtain embodiment 50-52.
Embodiment 53-55: in addition to organic solvent is replaced with single solvent component NMP, its
Its operation is the most constant, thus repeats to implement embodiment 1-3, sequentially obtains embodiment 53-55.
Embodiment 56-58: except organic solvent being replaced with single solvent component 1,4-dioxane
Outward, other operation is the most constant, thus repeats to implement embodiment 1-3, sequentially obtains embodiment
56-58。
Result see table 3.
Table 3
As can be seen here, when using any single solvent, productivity all has significantly reduction,
Such as when being used alone DMF or acetonitrile, only obtain 86.6-87.3% and 83.4-84.1%
Productivity.But it was unexpectedly determined that when the mixture of volume ratio 1:3 both using, but
The excellent productivity (see embodiment 1-3) of up to about 97% can be obtained, thus demonstrate use this two
Person's mixture can obtain beyond thought technique effect.
Embodiment 59-66
In addition to using following solvent combination, other operation is the most constant, thus repeats to implement reality
Execute example 1-3.The solvent combination, embodiment corresponding relation and the products collection efficiency that are used see table 4,
Wherein organic solvent is defined as component A and the mixture of component B that volume ratio is 1:3.
Table 4
As can be seen here, in all of solvent, only DMF just can take with the mixture of acetonitrile
Obtaining best technique effect, the component two-by-two of other solvent all can not obtain the most excellent product
Productivity.
In sum, the invention provides the synthetic method of a kind of cyclohexadione compounds, the party
Method uses by being combined that unique reaction substrate, catalyst, auxiliary agent, alkali and organic solvent form
Reaction system, thus the reaction of storeroom has been effectively facilitated by the comprehensive function of this kind of system,
Promote the material conversion to product, purpose product can have been obtained with high yield, have widely
Market prospect.
Should be appreciated that the purposes of these embodiments is merely to illustrate the present invention and is not intended to limit this
The protection domain of invention.Additionally, it will also be appreciated that after the technology contents having read the present invention,
The present invention can be made various change, amendment and/or modification by those skilled in the art, all of this
Within a little equivalent form of values fall within the protection domain that the application appended claims is limited equally.
Claims (10)
1. a synthetic method for cyclohexadione compounds shown in lower formula (III), described method includes:
Under nitrogen atmosphere, in the presence of catalyst, auxiliary agent and alkali, under adding in organic solvent (I)
Compound and lower formula (II) compound react, and react after terminating through post processing, thus obtain institute
State formula (III) compound,
Wherein, R1Selected from H, C1-C6Alkyl, C1-C6Alkoxy or halogen；
R2Selected from H, C1-C6Alkyl or C1-C6Alkoxyl；
X is halogen.
2. synthetic method as claimed in claim 1, it is characterised in that: described catalyst is
Double (the diphenyl of [1,1 '-bis-(diphenylphosphine) ferrocene] Nickel Chloride, trifluoromethanesulfonic acid nickel, 1,3-
Phosphine propane) Nickel Chloride ((DPPP) NiCl2) or double (diphenylphosphine) the ethane chlorination nickel of 1,2-
((DPPE)NiCl2Any one in), double (diphenylphosphine propane) dichloride of most preferably 1,3-
Nickel ((DPPP) NiCl2)。
3. synthetic method as claimed in claim 1 or 2, it is characterised in that: described auxiliary agent
For zirconium acetate.
4. the synthetic method as described in any one of claim 1-3, it is characterised in that: described
Alkali is NaOH, sodium carbonate, cesium carbonate, sodium phosphate, potassium acetate, potassium tert-butoxide, ethanol
Any one in sodium, Isosorbide-5-Nitrae-diazabicylo [2.2.2] octane (DABCO) or diethanolamine,
Most preferably cesium carbonate.
5. the synthetic method as described in any one of claim 1-4, it is characterised in that have described in:
Machine solvent is DMF (N,N-dimethylformamide), DMSO (dimethyl sulfoxide), benzene, acetonitrile,
In N-Methyl pyrrolidone (NMP) or 1,4-dioxane any one or the most multiple mixed
The DMF (DMF) of compound, most preferably volume ratio 1:3 and the mixing of acetonitrile
Thing.
6. the synthetic method as described in any one of claim 1-5, it is characterised in that: described formula
(I) compound is 1:1.5-2.5 with the mol ratio of formula (II) compound.
7. the synthetic method as described in any one of claim 1-6, it is characterised in that: described formula
(I) compound is 1:0.1-0.16 with the mol ratio of catalyst.
8. the synthetic method as described in any one of claim 1-7, it is characterised in that: described formula
(I) compound is 1:0.05-0.1 with the mol ratio of auxiliary agent.
9. the synthetic method as described in any one of claim 1-8, it is characterised in that: described formula
(I) compound is 1:2-3 with the mol ratio of alkali.
10. the synthetic method as described in any one of claim 1-9, it is characterised in that: reaction
Temperature is 80-100 DEG C；Response time is 6-9 hour.
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| US20020065192A1 (en) * | 2000-02-18 | 2002-05-30 | Mackenzie Peter Borden | Productivity catalysts and microstructure control |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020065192A1 (en) * | 2000-02-18 | 2002-05-30 | Mackenzie Peter Borden | Productivity catalysts and microstructure control |
Non-Patent Citations (3)
| Title |
|---|
| T.V.MOSKOVKINA等: "Transformations of Stereoisomeric 2-Chloro-3-R-pentane-1,5-diones in Reaction with Phenylhydrazine", 《RUSSIAN JOURNAL OF ORGANIC CHEMISTRY》 * |
| WANG CAN等: "One-pot Synthesis of 3-Aryl-1,5-bis(2-hydroxyaryl)pentane-1,5-diones", 《CHINESE JOURNAL OF CHEMISTRY》 * |
| ZHENG LI等: "Copper-catalyzed synthesis of 1,3,5- triarylpentane-1,5-diones from a,b-unsaturated ketones", 《RSC ADV》 * |
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