CN106117265A - A kind of synthetic method of diphenylphosphoric acid ester compounds - Google Patents
A kind of synthetic method of diphenylphosphoric acid ester compounds Download PDFInfo
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- CN106117265A CN106117265A CN201610442194.XA CN201610442194A CN106117265A CN 106117265 A CN106117265 A CN 106117265A CN 201610442194 A CN201610442194 A CN 201610442194A CN 106117265 A CN106117265 A CN 106117265A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids R2P(=O)(OH); Thiophosphinic acids, i.e. R2P(=X)(XH) (X = S, Se)
- C07F9/32—Esters thereof
- C07F9/3258—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/3288—Esters with arylalkanols
Abstract
The present invention relates to the synthetic method of diphenylphosphoric acid ester compounds shown in a kind of lower formula (IV),Described method includes: in organic solvent, in the presence of catalyst, oxidant, alkali and activator, lower formula (I) compound, (II) compound and (III) compound react 8 12 hours at 70 90 DEG C, react after terminating through post processing, thus obtain described formula (IV) compoundWherein, R1Selected from H, C1‑C6Alkyl, C1‑C6Alkoxy or halogen；R2Selected from C1‑C6Alkyl, most preferably methyl；X is bromine.Described method passes through the combined selection of suitable reactions substrate, catalyst, oxidant, alkali and activator and organic solvent with collaborative, such that it is able to high yield obtains purpose product, thus have a good application prospect and wide industrial production potential in medicine intermediate synthesis technical field.
Description
Technical field
The present invention relates to the synthetic method of a kind of ester type compound, relate more particularly to a kind of diphenylphosphoric acid ester compounds
Synthetic method, belong to medicine intermediate synthesis field.
Background technology
Phosphate ester is the key structural elements forming multiple biological tissue, and such as DNA, ATP, cell membrane etc., it sets at medicine
Meter is extremely important with in the preparation of agricultural chemicals, is alternatively arranged as sugar analogue, is also for synthetic fat plastid, the key of oligopeptide
Intermediate, thus by the common concern of research worker.
Up to now, prior art only reports the synthetic method of a limited number of kind of phosphate compounds, such as:
(" the Regiospecific Conversion of Termknalalkynesto ketol such as Gerald F.Koser
Phosphates with an Iodine(iii)-phosphate Rreagent”,Tetrahedron Letters,1993,
34,779-782) reporting a kind of technique using iodine (III) reagent catalysis to prepare phosphate compounds, its reaction equation is such as
Under:
(" the Reactivities of Novel [Hydroxy (tosyloxy) io do] such as Takahiro Nabana
arenes and[Hydroxy(phosphoryloxy)iodo]arenes forα-Tosyloxyla tion andα-
Phosphoryloxylation of Ketones ", J.Org.Chem., 2002,67,4362-4365) report a kind of ketone
The method that phosphate compounds is prepared in compound and iodine reagent reaction, its reaction equation is as follows:
As it has been described above, prior art discloses the synthetic method of multiple phosphate compounds, but, these existing skills
Art still suffers from that some defects, such as reacting precursor need activation, Atom economy is poor, need to use the mistake fraud such as peroxygen oxidising agent of danger
End.
For the problems referred to above, the invention provides the synthetic method of a kind of diphenylphosphoric acid ester compounds, the method uses
By specific combined reaction system, such that it is able to high yield obtains diphenylphosphoric acid ester compounds, show the technology of excellence
Effect, possesses market application foreground widely.
Summary of the invention
In order to overcome many defects as indicated above, present inventor has performed in-depth study and exploration, paying
After enough creative works, thus complete the present invention.
Specifically, technical scheme and content relate to diphenylphosphoric acid ester compounds shown in formula (IV) under one
Synthetic method,
Described method includes: in organic solvent, in the presence of catalyst, oxidant, alkali and activator, and lower formula (I)
Compound, (II) compound and (III) compound react 8-12 hour at 70-90 DEG C, react after terminating through post processing, thus
To described formula (IV) compound,
Wherein, R1Selected from H, C1-C6Alkyl, C1-C6Alkoxy or halogen；
R2Selected from C1-C6Alkyl, most preferably methyl；
X is bromine.
In the described synthetic method of the present invention, described C1-C6The implication of alkyl refers to the straight chain with 1-6 carbon atom
Or branched alkyl, can be the most such as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, uncle
Butyl, n-pentyl, isopentyl or n-hexyl etc..
In the described synthetic method of the present invention, described C1-C6The implication of alkoxyl refers to the C with above-mentioned implication1-C6
The group that alkyl obtains after being connected with oxygen atom.
In the described synthetic method of the present invention, described halogen is halogen, such as, can be F, Cl, Br or I.
In the described synthetic method of the present invention, described catalyst is 1-(1-ferrocenyl the ethyl)-3-of mol ratio 1:4
Isopropyl-1-iodonium imidazolide salts and the mixture of Nickel dichloride..
In the described synthetic method of the present invention, described oxidant is 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone
(DDQ), iodobenzene diacetate (PhI (OAc)2), dibenzoyl peroxide, tert-butyl hydroperoxide (TBHP) or Cupric chromate(III).
(Cr2Cu2O5Any one in), most preferably Cupric chromate(III). (Cr2Cu2O5)。
In the described synthetic method of the present invention, described alkali is potassium tert-butoxide, dimethylamino naphthyridine (DMPA), Isosorbide-5-Nitrae-phenodiazine
Miscellaneous bicyclo-[2.2.2] octane (DABCO), 1,8-diazabicylo 11 carbon-7-alkene (DBU), tetramethylethylenediamine (TMEDA),
Triethylamine, N, any one in N-dimethylethanolamine (DMEA) or NaOH, preferably dimethylamino naphthyridine (DMPA), Isosorbide-5-Nitrae-
Diazabicylo [2.2.2] octane (DABCO) or N, N-dimethylethanolamine (DMEA), most preferably N, N-dimethylethanolamine
(DMEA)。
In the described synthetic method of the present invention, described activator is any one in following formula L1-L3:
Described activator is most preferably L1.
In the described synthetic method of the present invention, described organic solvent is component A and the polyethylene glycol 200 of volume ratio 4:1
(PEG-200) mixture, wherein said component A is DMF (DMF), dimethyl sulfoxide (DMSO), benzene, second
Any one in alcohol, acetonitrile or Isosorbide-5-Nitrae-dioxane, most preferably Isosorbide-5-Nitrae-dioxane.
Wherein, the consumption of described organic solvent does not has strict restriction, and those skilled in the art can be according to practical situation
Suitably selecting and determine, such as its consumption size, to facilitate reaction to carry out and post processing, is no longer carried out at this in detail
Thin description.
In the described synthetic method of the present invention, described formula (I) compound is 1 with the mol ratio of formula (II) compound:
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 is 1:1-with the mol ratio of formula (III) compound
1.4, can be such as 1:1,1:1.1,1:1.2,1:1.3 or 1:1.4.
In the described synthetic method of the present invention, described formula (I) compound is 1:0.1-0.2 with the mol ratio of catalyst,
The mole dosage of the most described formula (I) compound and 1-(1-ferrocenyl the ethyl)-3-isopropyl-1-miaow constituting described catalyst
Azoles iodine salt is 1:0.1-0.2 with the ratio of total mole dosage of Nickel dichloride., such as, can be 1:0.1,1:0.15 or 1:0.2.
In the described synthetic method of the present invention, described formula (I) compound is 1:1.4-2 with the mol ratio of oxidant, example
As being 1:1.4,1:1.6,1:1.8 or 1:2.
In the described synthetic method of the present invention, described formula (I) compound is 1:1.2-1.8 with the mol ratio of alkali, such as
Can be 1:1.2,1:1.4,1:1.6 or 1:1.8.
In the described synthetic method of the present invention, described formula (I) compound is 1:0.1-0.2 with the mol ratio of activator,
Can be such as 1:0.1,1:0.15 or 1:0.2.
In the described synthetic method of the present invention, the post processing that reaction terminates can be specific as follows: after reaction terminates, and Bu Shi leaks
Bucket sucking filtration, by the regulation of filtrate pH value to neutral, then washs with saturated aqueous sodium carbonate, adds acetone extract 2-3 time, be associated with
Machine phase, concentrating under reduced pressure, residue crosses 300-400 mesh silica gel column chromatography, with ethyl acetate and the mixing of petroleum ether of volume ratio 1:2
Thing carries out eluting, thus obtains described formula (IV) compound.
As it has been described above, the invention provides the synthesis side of a kind of diphenylphosphoric acid ester compounds that can be used as medicine intermediate
Method, described method by suitable reactions substrate, catalyst, oxidant, alkali and activator and organic solvent combined selection with
Collaborative, such that it is able to high yield obtains purpose product, thus before medicine intermediate synthesis technical field has good application
Scape and wide industrial production potential.
Detailed description of the invention
Below by specific embodiment, the present invention is described in detail, but the purposes of these exemplary embodiments and
Purpose is only used for enumerating the present invention, and not the real protection scope to the present invention constitutes any type of any restriction, more non-general
Protection scope of the present invention is confined to this.
Embodiment 1
Under room temperature, at appropriate organic solvent (Isosorbide-5-Nitrae-dioxane of volume ratio 4:1 and polyethylene glycol 200 (PEG-200)
Mixture) in, add formula (I) compound, 200mmol upper formula (II) compound, the upper formula (III) of 120mmol on 100mmol
Compound, 15mmol catalyst are (for 3mmol 1-(1-ferrocenyl ethyl)-3-isopropyl-1-iodonium imidazolide salts and 12mmol chlorination
The mixture of nickel), 170mmol oxidant Cupric chromate(III). (Cr2Cu2O5), 150mmol alkali N, N-dimethylethanolamine (DMEA) and
15mmol activator L1, then heats to 80 DEG C, and stirring reaction 10 hours at such a temperature；
After reaction terminates, buchner funnel sucking filtration, by the regulation of filtrate pH value to neutral, then wash with saturated aqueous sodium carbonate
Washing, add acetone extract 2-3 time, merge organic facies, concentrating under reduced pressure, residue is crossed 300-400 mesh silica gel column chromatography, is used volume ratio
The ethyl acetate of 1:2 and the mixture of petroleum ether carry out eluting, thus obtain upper formula (IV) compound, and productivity is 89.9%.
1H NMR(CDCl3,400MHz):δ7.94-7.85(m,4H),7.78-7.73(m,2H),7.58-7.53(m,2H),
7.51-7.45 (m, 2H), 7.44-7.41 (m, 3H), 7.38-7.33 (m, 2H), 5.91-5.85 (m, 1H), 1.61 (d, J=
6.8Hz,3H)。
Embodiment 2
Reaction equation is with embodiment 1, and concrete operations are as follows:
Under room temperature, at appropriate organic solvent (Isosorbide-5-Nitrae-dioxane of volume ratio 4:1 and polyethylene glycol 200 (PEG-200)
Mixture) in, add formula described in formula (II) compound, 140mmol described in formula (I) compound, 150mmol described in 100mmol
(III) compound, 10mmol catalyst (for 2mmol 1-(1-ferrocenyl ethyl)-3-isopropyl-1-iodonium imidazolide salts with
The mixture of 8mmol Nickel dichloride .), 200mmol oxidant Cupric chromate(III). (Cr2Cu2O5), 120mmol alkali N, N-dimethylethanolamine
And 20mmol activator L1 (DMEA), 70 DEG C are then heated to, and stirring reaction 12 hours at such a temperature；
After reaction terminates, buchner funnel sucking filtration, by the regulation of filtrate pH value to neutral, then wash with saturated aqueous sodium carbonate
Washing, add acetone extract 2-3 time, merge organic facies, concentrating under reduced pressure, residue is crossed 300-400 mesh silica gel column chromatography, is used volume ratio
The ethyl acetate of 1:2 and the mixture of petroleum ether carry out eluting, thus obtain upper formula (IV) compound, and productivity is 89.6%.
Characterize data consistent with Example 1.
Embodiment 3
Reaction equation is with embodiment 1, and concrete operations are as follows:
Under room temperature, at appropriate organic solvent (Isosorbide-5-Nitrae-dioxane of volume ratio 4:1 and polyethylene glycol 200 (PEG-200)
Mixture) in, add formula described in formula (II) compound, 100mmol described in formula (I) compound, 250mmol described in 100mmol
(III) compound, 20mmol catalyst (for 4mmol 1-(1-ferrocenyl ethyl)-3-isopropyl-1-iodonium imidazolide salts with
The mixture of 16mmol Nickel dichloride .), 140mmol oxidant Cupric chromate(III). (Cr2Cu2O5), 180mmol alkali N, N-dimethyl ethanol
Amine (DMEA) and 10mmol activator L1, then heat to 90 DEG C, and stirring reaction 8 hours at such a temperature；
After reaction terminates, buchner funnel sucking filtration, by the regulation of filtrate pH value to neutral, then wash with saturated aqueous sodium carbonate
Washing, add acetone extract 2-3 time, merge organic facies, concentrating under reduced pressure, residue is crossed 300-400 mesh silica gel column chromatography, is used volume ratio
The ethyl acetate of 1:2 and the mixture of petroleum ether carry out eluting, thus obtain upper formula (IV) compound, and productivity is 90.0%.
Characterize data consistent with Example 1.
By above-described embodiment 1-3 it can be seen that when using the synthetic method of the present invention, purpose can be obtained with high yield
Product, thus have a good application prospect and industrial production potential at medicine intermediate and organic chemical synthesis field.
Below, carry out experiment is repeated several times to embodiment 1-3, to investigate the impact for reaction result of each factor.
Embodiment 4-9
Embodiment 4-6: except catalyst being replaced with the one-component 1-(1-that consumption is original two kinds of component total consumption sums
Ferrocenyl ethyl) outside-3-isopropyl-1-iodonium imidazolide salts, other operation is the most constant, thus repeats to implement embodiment 1-3, suitable
Secondary obtain embodiment 4-6.
Embodiment 7-9: except catalyst being replaced with the one-component chlorination that consumption is original two kinds of component total consumption sums
Outside nickel, other operation is the most constant, thus repeats to implement embodiment 1-3, sequentially obtains embodiment 7-9.
Reaction result see table 1.
Table 1
As can be seen here, when using any one-component as catalyst, products collection efficiency is all caused to have significantly fall
Low, when especially simply using 1-(1-ferrocenyl ethyl)-3-isopropyl-1-iodonium imidazolide salts, productivity drastically reduces, and has lost
Meaning and the possibility of any actual production are gone.This proves only to use both mixture as catalyst, Cai Nengfa simultaneously
Wave beyond thought collaborative facilitation effect, thus achieve the excellent productivity of embodiment 1-3.
Embodiment 10-21
Embodiment 10-12: except oxidant Cupric chromate(III). being replaced with 2,3-bis-chloro-5,6-dicyano-1,4-benzoquinone (DDQ)
Outward, other operation is the most constant, thus repeats to implement embodiment 1-3, sequentially obtains embodiment 10-12.
Embodiment 13-15: except oxidant Cupric chromate(III). being replaced with iodobenzene diacetate (PhI (OAc)2) outward, other operation
The most constant, thus repeat to implement embodiment 1-3, sequentially obtain embodiment 13-15.
Embodiment 16-18: in addition to oxidant Cupric chromate(III). is replaced with dibenzoyl peroxide, other operation is the most constant,
Thus repeat to implement embodiment 1-3, sequentially obtain embodiment 16-18.
Embodiment 19-21: in addition to oxidant Cupric chromate(III). is replaced with tert-butyl hydroperoxide (TBHP), other operation is all
Constant, thus repeat to implement embodiment 1-3, sequentially obtain embodiment 19-21.
Result see table 2.
Table 2
As can be seen here, in all of oxidant, the effect of Cupric chromate(III). to be significantly better than other oxidants, and this is to make us
Beyond thought.
Embodiment 22-42
Embodiment 22-24: except replacing with outside potassium tert-butoxide by alkali N, N-dimethylethanolamine (DMEA), other operation is the most not
Become, thus repeat to implement embodiment 1-3, sequentially obtain embodiment 22-24.
Embodiment 25-27: except alkali N, N-dimethylethanolamine (DMEA) are replaced with dimethylamino naphthyridine (DMPA) outward, its
Its operation is the most constant, thus repeats to implement embodiment 1-3, sequentially obtains embodiment 25-27.
Embodiment 28-30: pungent except alkali N, N-dimethylethanolamine (DMEA) are replaced with 1,4-diazabicylo [2.2.2]
Outward, other operation is the most constant, thus repeats to implement embodiment 1-3, sequentially obtains embodiment 28-30 for alkane (DABCO).
Embodiment 31-33: except alkali N, N-dimethylethanolamine (DMEA) are replaced with 1,8-diazabicylo 11 carbon-7-
Outward, other operation is the most constant, thus repeats to implement embodiment 1-3, sequentially obtains embodiment 31-33 for alkene (DBU).
Embodiment 34-36: except alkali N, N-dimethylethanolamine (DMEA) are replaced with tetramethylethylenediamine (TMEDA) outward,
Other operation is the most constant, thus repeats to implement embodiment 1-3, sequentially obtains embodiment 34-36.
Embodiment 37-39: except replacing with outside triethylamine by alkali N, N-dimethylethanolamine (DMEA), other operation is the most not
Become, thus repeat to implement embodiment 1-3, sequentially obtain embodiment 37-39.
Embodiment 40-42: except replacing with outside NaOH by alkali N, N-dimethylethanolamine (DMEA), other operation is the most constant,
Thus repeat to implement embodiment 1-3, sequentially obtain embodiment 40-42.
Result see table 3.
Table 3
As can be seen here, in all of alkali, N, N-dimethylethanolamine (DMEA) has best effect, and other alkali is equal
Cause productivity decrease to some degree, be the most significantly greatly lowered, such as NaOH.
Embodiment 43-48
Embodiment 43-45: in addition to organic solvent is replaced with one-component Isosorbide-5-Nitrae-dioxane, other operation is the most constant,
Thus repeat to implement embodiment 1-3, sequentially obtain embodiment 43-45.
Embodiment 46-48: in addition to organic solvent is replaced with one-component polyethylene glycol 200 (PEG-200), other operation
The most constant, thus repeat to implement embodiment 1-3, sequentially obtain embodiment 46-48.
Result see table 4.
Table 4
As can be seen here, when using single solvent component, productivity has reduction in various degree, especially simply uses
During PEG-200, it is reduced to 72.6-73.4%, reduces 16-17 percentage point than embodiment 1-3.
Embodiment 49-63
Embodiment 49-51: except component A1,4-dioxane in organic solvent is replaced with N,N-dimethylformamide DMF
Outward, other operation is the most constant, thus repeats to implement embodiment 1-3, sequentially obtains embodiment 49-51.
Embodiment 52-54: except by component A1 in organic solvent, 4-dioxane replaces with dimethyl sulfoxide (DMSO) outward,
Other operation is the most constant, thus repeats to implement embodiment 1-3, sequentially obtains embodiment 52-54.
Embodiment 55-57: except by component A1 in organic solvent, 4-dioxane replaces with outside benzene, and other operation is the most constant,
Thus repeat to implement embodiment 1-3, sequentially obtain embodiment 55-57.
Embodiment 58-60: except by component A1 in organic solvent, 4-dioxane replaces with outside ethanol, other operation is the most not
Become, thus repeat to implement embodiment 1-3, sequentially obtain embodiment 58-60.
Embodiment 61-63: except by component A1 in organic solvent, 4-dioxane replaces with outside acetonitrile, other operation is the most not
Become, thus repeat to implement embodiment 1-3, sequentially obtain embodiment 61-63.
Result see table 5.
Table 5
As can be seen here, in the selection of all of solvent composition A, only the combination of Isosorbide-5-Nitrae-dioxane and PEG-200 is
Best technique effect can be produced, and other component all causes productivity to have significantly reduction.
Below, the impact caused is selected to be investigated the kind that whether there is activator and activator.
Embodiment 64-72
Embodiment 64-66: in addition to activator L1 is replaced with L2, other operation is the most constant, thus repeats to implement enforcement
Example 1-3, sequentially obtains embodiment 64-66.
Embodiment 67-69: in addition to activator L1 is replaced with L3, other operation is the most constant, thus repeats to implement enforcement
Example 1-3, sequentially obtains embodiment 64-66.
Embodiment 70-72: in addition to being omitted by activator L1, other operation is the most constant, thus repeats to implement enforcement
Example 1-3, sequentially obtains embodiment 70-72.
Result see table 6.
Table 6
Wherein, there is not activator in "--" expression；The product of the embodiment 70 (its repetition is embodiment 1) in " * " produces
Rate is 61.4%.
As can be seen here, when activator L1 is replaced with L2 or L3, products collection efficiency is significantly reduced, although this proves
L1-L3 structure is similar, but L1 has technique effect the most excellent.It can also be seen that when not using any activator,
Productivity drastically reduces to 60.8-61.6%, and this proves that L1-L3 can produce excellent steric effect and improve effect, and this is to make us
Beyond thought.
As it has been described above, the invention provides the synthesis side of a kind of diphenylphosphoric acid ester compounds that can be used as medicine intermediate
Method, described method by suitable reactions substrate, catalyst, oxidant, alkali and activator and organic solvent combined selection with
Collaborative, such that it is able to high yield obtains purpose product, thus before medicine intermediate synthesis technical field has good application
Scape and wide industrial production potential.
Should be appreciated that the purposes of these embodiments is merely to illustrate the present invention and is not intended to limit the protection model of the present invention
Enclose.Additionally, it will also be appreciated that after the technology contents having read the present invention, the present invention can be made respectively by those skilled in the art
Planting change, amendment and/or modification, all these equivalent form of value falls within the guarantor that the application appended claims is limited equally
Within the scope of protecting.
Claims (10)
1. a synthetic method for diphenylphosphoric acid ester compounds shown in lower formula (IV),
Described method includes: in organic solvent, in the presence of catalyst, oxidant, alkali and activator, lower formula (I) compound,
(II) compound and (III) compound react 8-12 hour at 70-90 DEG C, react after terminating through post processing, thus obtain institute
State formula (IV) compound,
Wherein, R1Selected from H, C1-C6Alkyl, C1-C6Alkoxy or halogen；
R2Selected from C1-C6Alkyl, most preferably methyl；
X is bromine.
2. synthetic method as claimed in claim 1, it is characterised in that: described catalyst is 1-(the 1-ferrocene of mol ratio 1:4
Base ethyl) mixture of-3-isopropyl-1-iodonium imidazolide salts and Nickel dichloride..
3. synthetic method as claimed in claim 1 or 2, it is characterised in that: described oxidant is 2,3-bis-chloro-5,6-dicyan
Base-1,4-benzoquinone (DDQ), iodobenzene diacetate (PhI (OAc)2), dibenzoyl peroxide, tert-butyl hydroperoxide (TBHP) or
Cupric chromate(III). (Cr2Cu2O5Any one in), most preferably Cupric chromate(III). (Cr2Cu2O5)。
4. the synthetic method as described in any one of claim 1-3, it is characterised in that: described alkali is potassium tert-butoxide, dimethylamino
Pyridine (DMPA), 1,4-diazabicylo [2.2.2] octane (DABCO), 1,8-diazabicylo 11 carbon-7-alkene (DBU), four
Any one in methyl ethylenediamine (TMEDA), triethylamine, N, N-dimethylethanolamine (DMEA) or NaOH, preferably diformazan
Aminopyridine (DMPA), Isosorbide-5-Nitrae-diazabicylo [2.2.2] octane (DABCO) or N, N-dimethylethanolamine (DMEA), optimum
Elect N, N-dimethylethanolamine (DMEA) as.
5. the synthetic method as described in any one of claim 1-4, it is characterised in that: described activator is in following formula L1-L3
Any one:
Described activator is most preferably L1.
6. the synthetic method as described in any one of claim 1-5, it is characterised in that: described formula (I) compound is changed with formula (II)
The mol ratio of compound is 1:1.5-2.5.
7. the synthetic method as described in any one of claim 1-6, it is characterised in that: described formula (I) compound is changed with formula (III)
The mol ratio of compound is 1:1-1.4.
8. the synthetic method as described in any one of claim 1-7, it is characterised in that: described formula (I) compound and catalyst
Mol ratio is 1:0.1-0.2.
9. the synthetic method as described in any one of claim 1-8, it is characterised in that: described formula (I) compound and oxidant
Mol ratio is 1:1.4-2.
10. the synthetic method as described in any one of claim 1-9, it is characterised in that: described formula (I) compound and alkali mole
Ratio is 1:1.2-1.8.
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