CN105536873A - Compound catalyst and application thereof - Google Patents
Compound catalyst and application thereof Download PDFInfo
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- CN105536873A CN105536873A CN201610082654.2A CN201610082654A CN105536873A CN 105536873 A CN105536873 A CN 105536873A CN 201610082654 A CN201610082654 A CN 201610082654A CN 105536873 A CN105536873 A CN 105536873A
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- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
- B01J31/1835—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline comprising aliphatic or saturated rings
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- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
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- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
- B01J2231/4288—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues using O nucleophiles, e.g. alcohols, carboxylates, esters
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- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
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- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
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- B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
- B01J2531/72—Manganese
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Abstract
The invention relates to a novel compound catalyst which is formed by compounding a compound A or/and salt thereof and a metal compound W, wherein the compound A has a structure as shown in a general formula I in the specification, in the general formula I, R1, R3, R5 and R6 are respectively hydrogen, halogen, C1-C10 oxygen or oxygen-free aliphatic hydrocarbon group, aryl, or ester group; and R2 and R4 are respectively hydrogen, halogen, or C1-C10 oxygen or oxygen-free aliphatic hydrocarbon group or aryl. The compound catalyst can be used for efficiently catalyzing the synthesis reaction of asymmetric 4,6-diaryloxy pyrimidine derivative, is stable in performance, can be recycled by a simple method, is reduced in catalyst consumption, avoids environment pollution, and is suitable for large-scale industrial production.
Description
Technical field
The present invention relates to catalyst field, be specifically related to a kind of novel composite catalyst and the application in asymmetric 4, the 6-bis aryloxy pyrimidine derivatives of synthesis thereof.
Background technology
Asymmetric 4,6-bis aryloxy pyrimidine derivatives, especially Fluoxastrobin and fluoxastrobin, the bactericide of, broad spectrum type efficient as a class, is widely used in the prevention and therapy of plurality of plant diseases.
Prior art discloses a kind of with the method for the halide of copper for catalyst preparing Fluoxastrobin; The method is by (E)-2-[2-(6-chlorine pyrimidine-4-yl oxygen base] phenyl]-3-methoxy-methyl acrylate and salicylonitrile, potash with the halide of copper for catalyst, at polar solvent particularly N, etherification reaction is there is in dinethylformamide, reaction terminates rear filtration desalination and washs with DMF, and filtrate and cleaning solution merge decompression distillation and obtain thick product except after desolventizing, thick product methanol crystallization, drying obtains product.In the method, copper salt catalyst catalytic efficiency is low.
Patent document WO0172719 discloses asymmetric 4, the 6-bis aryloxy pyrimidine derivatives of preparation under Isosorbide-5-Nitrae-diazabicylo [2.2.2] octane (DABCO) of 2-40mol% exists as catalyst, the especially method of fluoxastrobin.The method is by (E)-5,6-dihydro-1,4,2-dioxazines-3-base-(2-hydroxyphenyl) ketone 0-methyloxime adds in the mixture of methylisobutylketone and water with potash and DABCO, under 80oC, 6-chloro-with 4-(2-chlorophenoxy)-5-FU mixes etherification reaction occurs, and obtains product through conventional post processing.
In addition, patent document WO2008043978 discloses, under Isosorbide-5-Nitrae-diazabicylo [2.2.2] octane (DABCO) of 0.1-2mol% exists as catalyst, substrate (E)-2-[2-(6-chlorine pyrimidine-4 base oxygen base) phenyl]-3-methoxy-methyl acrylate and salicylonitrile or its salt generation etherification reaction is obtained product Fluoxastrobin.
Patent WO0172719 and WO2008043978 disclosed in above-mentioned two sections is the improvement to the synthetic method being catalyst with the halide of copper in aforementioned prior art.But, do not relate to the recovery to catalyst in the technical scheme that these patents provide, be unfavorable for realizing production that is efficient, environmental protection.
Prior art also discloses when preparing Fluoxastrobin and uses Isosorbide-5-Nitrae-diazabicylo [2.2.2] octane to be fixedly connected on Silica Surface by derivatization reaction, reaches catalyst etherifying reaction and reclaims the object of catalyst.Silica gel is suspended in toluene by the preparation method of this catalyst, 3-r-chloropropyl trimethoxyl silane is added under adding hot reflux, backflow, cooling, filter, washing, dry, the solid obtained again with 2-methylol-1, 4-diazabicylo [2.2.2] octane and sodium hydride, heating reflux reaction in oxolane, cooling, filter, washing, drying just obtains the catalyst preparing Fluoxastrobin etherification reaction, the preparation process of this callable catalyst is quite complicated and harsh, and cost of material is very high, thus this catalyst is unfavorable for the application of suitability for industrialized production.
Summary of the invention
The present invention overcomes the defect of prior art, provides a kind of environmental protection, is easy to the catalyst that reclaims, can the synthetic reaction of effective asymmetric 4,6-bis aryloxy pyrimidine derivatives of catalysis.
Specifically, the invention provides a kind of composite catalyst, by compd A or/and its salt metallizing thing W is composited; Described compd A has structure shown in general formula I:
In described general formula I, R
1, R
3, R
5, R
6represent independently of one another hydrogen, halogen, C1 ~ C10 containing oxygen or oxygen-free aliphatic group, aryl or ester group; R
2, R
4represent independently of one another hydrogen, halogen, C1 ~ C10 containing oxygen or oxygen-free aliphatic group or aryl.
Compd A of the present invention is or/and its salt can be compd A monomer, the salt of compd A or the mixture of described monomer and salt.The salt of described compd A be preferably in the acid salt of compd A, alkyl quaternary ammonium salts, aryl quaternary ammonium salt one or more.
Described compd A can be preferably Isosorbide-5-Nitrae-diazabicylo [2,2,2] octane or/and 2-methyl isophthalic acid, 4-diazabicylo [2.2.2] octane.
Compd A of the present invention is or/and its salt metallizing thing W is with A
mw
nform be composited.Owing to containing multiple nitrogen-atoms in compd A, can combine with multiple mol ratio metallizing thing W.Therefore, in preparation process, the composite catalyst AW that the present invention obtains can be composited with single molar ratio by compd A metallizing thing W, also can be the mixture that compd A metallizing thing W is composited with multiple molar ratio; Or the mixture that the multiple mixture of the multiple mixture metallizing thing W of compd A is composited with multiple molar ratio.The present invention, by great many of experiments, carries out preferably, to improve catalytic reaction efficiency to the proportioning of described compd A and metallic compound W.Wherein, the mol ratio m:n of A and W can be 1 ~ 2:1, also can be 1:1 ~ 2, is preferably 1:1, i.e. mole compound such as compd A metallizing thing W.
Described metallic compound W is one or more in metal halide, acid metal, basic metal, metal alkyl or metal aryl and hydrate thereof; Be preferably metal halide.Wherein, described metal is copper, manganese, cobalt, nickel, palladium, iron, aluminium or zinc; Be preferably copper or manganese.
As preferred version of the present invention, described metallic compound W is copper chloride, cupric iodide, stannous chloride, cuprous iodide or manganese chloride, more preferably stannous chloride, copper chloride or manganese chloride, most preferably is copper chloride or manganese chloride.The present invention is found by great many of experiments, and when metallic compound selects copper chloride or manganese chloride, gained composite catalyst not only catalytic activity is high, and performance is more stable, after participating in catalytic reaction recovery, still has good catalytic activity.Specifically, composite catalyst of the present invention is prepared from by the method comprised the following steps: get metallic compound W, joins in diluent, add the dilution of compd A while stirring, after abundant reaction, filtration, washing, drying, obtain composite catalyst AW;
Or adjustment charging sequence: get compd A, join in diluent, add the dilution of metallic compound W while stirring, fully after reaction, filtration, washing, drying, obtain composite catalyst AW.
Described diluent and to prepare described dilution solvent used be one or more in water, ethers, lipid, ketone, the fragrant same clan, amide-type, sulfone class or halogenated hydrocarbons; Be preferably DMF or acetonitrile or butyl acetate or methyl iso-butyl ketone (MIBK); More preferably acetonitrile.Described dilution refers to the solution, suspension or the mixed form of the two that adopt described diluent formulated.The present invention is found by great many of experiments, in numerous organic solvents, adopt acetonitrile as diluent, the composite catalyst yield for preparing can be made higher, when being applied to the catalytic reaction of synthesizing asymmetric 4,6-bis aryloxy pyrimidine derivatives, there is higher catalytic activity and stability.
Described preparation process is preferably carried out under normal temperature, normal pressure.
As a preferred embodiment of the present invention, described composite catalyst adopts following steps to be prepared from: the dilution in acetonitrile liquid of preparation copper chloride, add the dilution in acetonitrile liquid of Isosorbide-5-Nitrae-diazabicylo [2.2.2] octane under normal temperature and pressure while stirring, be added to described 1, the mol ratio of 4-diazabicylo [2.2.2] octane and copper chloride is after 1:1, continue reaction 1h, filter, with acetonitrile wash, drying, to obtain final product.
As a preferred embodiment of the present invention, described composite catalyst adopts following steps to be prepared from: the dilution in acetonitrile liquid of preparation stannous chloride, add the dilution in acetonitrile liquid of Isosorbide-5-Nitrae-diazabicylo [2.2.2] octane under normal temperature and pressure while stirring, be added to described 1, the mol ratio of 4-diazabicylo [2.2.2] octane and stannous chloride is after 1:1, continue reaction 1h, filter, with acetonitrile wash, drying, to obtain final product.
As a preferred embodiment of the present invention, described composite catalyst adopts following steps to be prepared from: the dilution in acetonitrile liquid of preparation copper chloride, add 2-methyl isophthalic acid while stirring under normal temperature and pressure, the dilution in acetonitrile liquid of 4-diazabicylo [2.2.2] octane, be added to described 2-methyl isophthalic acid, the mol ratio of 4-diazabicylo [2.2.2] octane and copper chloride is after 1:1, continue reaction 1h, filter, with acetonitrile wash, drying, to obtain final product.
As a preferred embodiment of the present invention, described composite catalyst adopts following steps to be prepared from: the dilution in acetonitrile liquid of preparation stannous chloride, add 2-methyl isophthalic acid while stirring under normal temperature and pressure, the dilution in acetonitrile liquid of 4-diazabicylo [2.2.2] octane, be added to described 2-methyl isophthalic acid, the mol ratio of 4-diazabicylo [2.2.2] octane and stannous chloride is after 1:1, continue reaction 1h, filter, with acetonitrile wash, drying, to obtain final product.
As a preferred embodiment of the present invention, described composite catalyst adopts following steps to be prepared from: the dilution in acetonitrile liquid of preparation manganese chloride, add the dilution in acetonitrile liquid of Isosorbide-5-Nitrae-diazabicylo [2.2.2] octane under normal temperature and pressure while stirring, be added to described 2-methyl isophthalic acid, the mol ratio of 4-diazabicylo [2.2.2] octane and stannous chloride is after 1:1, continue reaction 1h, filter, with acetonitrile wash, drying, to obtain final product.
As a preferred embodiment of the present invention, described composite catalyst adopts following steps to be prepared from: the dilution in acetonitrile liquid of preparation manganese chloride, add 2-methyl isophthalic acid while stirring under normal temperature and pressure, the dilution in acetonitrile liquid of 4-diazabicylo [2.2.2] octane, be added to described 2-methyl isophthalic acid, the mol ratio of 4-diazabicylo [2.2.2] octane and stannous chloride is after 1:1, continue reaction 1h, filter, with acetonitrile wash, drying, to obtain final product.
The present invention finds the excellence application of composite catalyst AW in asymmetric 4, the 6-bis aryloxy pyrimidine derivatives of synthesis simultaneously.Described asymmetric 4,6-bis aryloxy pyrimidine derivatives are preferably structure as shown in general formula I I:
In described general formula I I, G
1represent hydrogen or halogen; G
3represent halogen or cyano group; G
2representative
(wherein, asterisk represents the position that substituting group is combined with parent nucleus), i.e. G
2representative (E)-5,6-dihydros-Isosorbide-5-Nitrae, 2-dioxazines-3-base-ketone-0-methyloxime, (E)-2-(3-methoxyl group) methyl acrylate or 2-(3,3-dimethoxy) methyl propionate.
Described asymmetric 4,6-bis aryloxy pyrimidine derivatives more preferably Fluoxastrobin or/and fluoxastrobin.
Described composite catalyst AW by compd A or/and its salt metallizing thing W is composited; Described compd A has structure shown in general formula I:
In described general formula I, R
1, R
3, R
5, R
6represent independently of one another hydrogen, halogen, C1 ~ C10 containing oxygen or oxygen-free aliphatic group, aryl or ester group; R
2, R
4represent independently of one another hydrogen, halogen, C1 ~ C10 containing oxygen or oxygen-free aliphatic group or aryl; Described compd A is or/and its salt can be compd A monomer, the salt of compd A or the mixture of described monomer and salt.The salt of described compd A be preferably in the acid salt of compd A, alkyl quaternary ammonium salts, aryl quaternary ammonium salt one or more.
Described metallic compound W is one or more in metal halide, acid metal, basic metal, metal alkyl or metal aryl and hydrate thereof, and wherein, described metal is copper, manganese, cobalt, nickel, palladium, iron, aluminium or zinc.
Described compd A is or/and its salt metallizing thing W is with A
mw
nform be composited, wherein, the mol ratio m:n of A and W is 1 ~ 2:1 or 1:1 ~ 2, be preferably 1:1.
Be applied to catalyze and synthesize asymmetric 4,6-bis aryloxy pyrimidine derivatives time, the preferred version of described composite catalyst AW is identical with the preferred version of composite catalyst product of the present invention.In order to improve Fluoxastrobin or/and the catalytic synthesis efficiency of fluoxastrobin, catalyst in described catalytic reaction process is most preferably by 1,4-diazabicylo [2.2.2] octane or 2-methyl isophthalic acid, 4-diazabicylo [2.2.2] octane and copper chloride or manganese chloride are composited with mol ratio 1:1.
As a kind of concrete scheme of the present invention, the synthetic route of described asymmetric 4,6-bis aryloxy pyrimidine derivatives is:
Wherein, described G
1, G
2, G
3representative group is identical with referring to of general formula I I of the present invention;
Specifically comprise the following steps:
(1) with the alkali metal salt of compound 1 and compound 2 or compound 2 for raw material, under composite catalyst AW existence condition, carry out etherification reaction, obtain compound 3; In this step, the consumption of composite catalyst AW is 0.1 ~ 50mol% of compound 1;
(2) alkali metal salt of described compound 3 and compound 4 or compound 4 is raw material, under composite catalyst AW existence condition, carries out etherification reaction, obtains compound 5; In this step, the consumption of composite catalyst AW is 0.1 ~ 50mol% of compound 3.
More than reaction can be carried out step by step, and one kettle way also can be adopted to carry out.The solvent of described reaction is one or more in ethers, lipid, ketone, the fragrant same clan, amide-type, sulfone class or halogenated hydrocarbons, be preferably N, dinethylformamide or acetonitrile or butyl acetate or methyl iso-butyl ketone (MIBK), more preferably acetonitrile, in numerous organic solvents, adopt acetonitrile can make efficient, stable the playing a role of composite catalyst as solvent, in the reaction system of acetonitrile, composite catalyst still can keep higher catalytic efficiency after reclaiming.Described reaction temperature is 10 ~ 180 DEG C, is preferably 30 ~ 120 DEG C, more preferably 60 ~ 80 DEG C; Reaction is preferably carried out at ambient pressure.
As a kind of concrete scheme of the present invention, the synthetic route of described asymmetric 4,6-bis aryloxy pyrimidine derivatives is:
Wherein, described G
1, G
2, G
3representative group is identical with referring to of general formula I I of the present invention;
Specifically comprise the following steps:
(1) with the alkali metal salt of compound 1 and compound 4 or compound 4 for raw material, under composite catalyst AW existence condition, carry out etherification reaction, obtain compound 6; In this step, the consumption of composite catalyst AW is 0.1 ~ 50mol% of compound 1;
(2) alkali metal salt of described compound 6 and compound 2 or compound 2 is raw material, under composite catalyst AW existence condition, carries out etherification reaction, obtains compound 5; In this step, the consumption of composite catalyst AW is 0.1 ~ 50mol% of compound 6.
More than reaction can be carried out step by step, and one kettle way also can be adopted to carry out.The solvent of described reaction is one or more in ethers, lipid, ketone, the fragrant same clan, amide-type, sulfone class or halogenated hydrocarbons, be preferably N, dinethylformamide or acetonitrile or butyl acetate or methyl iso-butyl ketone (MIBK), more preferably acetonitrile, in numerous organic solvents, adopt acetonitrile can make efficient, stable the playing a role of composite catalyst as solvent, in the reaction system of acetonitrile, composite catalyst still can keep higher catalytic efficiency after reclaiming.Described reaction temperature is 10 ~ 180 DEG C, is preferably 30 ~ 120 DEG C, more preferably 60 ~ 80 DEG C; Reaction is preferably carried out at ambient pressure.
Described composite catalyst AW is catalyzing and synthesizing asymmetric 4, after 6-bis aryloxy pyrimidine derivatives, following methods can be adopted to reclaim: after reaction terminating, through precipitation, acidifying and extraction, isolate water layer, regulate water layer pH value to 4 ~ 8, preferable ph is 6, separates out solid, filters, drying, the catalyst be recycled.
Composite catalyst provided by the invention can efficient catalytic asymmetric 4, the synthetic reaction of 6-bis aryloxy pyrimidine derivatives, and can be reused by simple method recovery, decrease the consumption of catalyst, avoid environmental pollution, adapt to large-scale industrial production.
Detailed description of the invention
Following examples for illustration of the present invention, but are not used for limiting the scope of the invention.
Embodiment 1: the preparation of composite catalyst AW1
Present embodiments provide the preparation method of a kind of composite catalyst AW, be specially: in 100ml there-necked flask, add stannous chloride 10g (99%, 0.101mol), DMF 30ml, 1 is added under stirring at room temperature, 4-diazabicylo [2,2,2] octane 11.3g (98%, N 0.101mol), dinethylformamide solution 30mL, continues reaction 1h, filters after adding, with 40mlN, dinethylformamide washing solid twice, solid drying, obtains bronzing product 19.2g, i.e. composite catalyst AW1, yield 90%.
Embodiment 2: the preparation of composite catalyst AW2
Compared with embodiment 1, difference is only: stannous chloride is replaced with cuprous iodide 19.23g (99.5%, 0.101mol), by 1,4-diazabicylo [2,2,2] octane replaces with equimolar 1,4-diazabicylo [2,2,2] octane hydrochloride, obtains 27.8g light green solid, i.e. composite catalyst AW2, yield 90%.
Embodiment 3: the preparation of composite catalyst AW3
Compared with embodiment 1, difference is only: the manganese chloride (can the select four chloride hydrate manganese) molal quantity such as stannous chloride being replaced with, obtains 27.8g dark brown solid product, i.e. composite catalyst AW3, yield 89%.
Embodiment 4: the preparation of composite catalyst AW4
Compared with embodiment 1, difference is only: stannous chloride is replaced with copper chloride 13.5g (98%, 0.101mol), and DMF is replaced with acetonitrile, obtain 23.1g red brown solid product, i.e. composite catalyst AW4, yield 93%.
Embodiment 5: the preparation of the acetonitrile suspension of composite catalyst AW4
Copper chloride 0.109g (99% is added in 100ml there-necked flask, 0.8mmol), acetonitrile 10ml, Isosorbide-5-Nitrae-diazabicylo [2,2 is added under stirring at room temperature, 2] octane 0.091g (98%, acetonitrile solution 10mL 0.8mmol), continues reaction 1h, obtains the acetonitrile suspension 20ml containing 0.2g composite catalyst AW4 in theory after adding.
Embodiment 6: the preparation of composite catalyst AW5
Compared with embodiment 1, difference is only: by 1,4-diazabicylo [2,2,2] octane to replace with etc. molal quantity 2 ?Jia Ji ?1,4 ?diazabicylo [2.2.2] octane, and DMF is replaced with acetonitrile, obtain 20.67g greenish yellow solid product, i.e. composite catalyst AW5, yield 91%.
Embodiment 7: the preparation of composite catalyst AW6
Compared with embodiment 1, difference is only: the copper chloride molal quantity such as stannous chloride being replaced with, by Isosorbide-5-Nitrae-diazabicylo [2,2,2] octane to replace with etc. molal quantity 2 ?Jia Ji ?1,4 ?diazabicylo [2.2.2] octane, and by N, dinethylformamide replaces with acetonitrile, obtain 24.74g red brown solid product, i.e. composite catalyst AW6, yield 94%.
Embodiment 8: the synthesis of Fluoxastrobin
20mlN is added in 100ml there-necked flask, dinethylformamide, potash 5.60g (98%, 40.53mmol), salicylonitrile 4.17g (98%, 34.30mmol), be warming up to 60 DEG C and stir 10min, add embodiment 1 gained composite catalyst AW10.2g (0.95mmol), continue at this temperature to stir and to add (E)-2-[2-(6-pyrimidine-4-yl oxygen] phenyl after 10min]-3-methoxy-methyl acrylate 10g (95%, 31.18mmol), be warming up to 80 DEG C of reactions, HPLC monitoring display (E)-2-after 2h [2-(6-pyrimidine-4-yl oxygen] phenyl]-3-methoxy-methyl acrylate content <0.1%, N is reclaimed in decompression distillation, dinethylformamide, 30ml toluene joins in bottoms, add 40ml subsequently, the aqueous hydrochloric acid solution of 5mol/L, and mixture is stirred 1h at 80 DEG C, layering, 20ml toluene aqueous phase extracted, merge organic phase 51.54g altogether, this toluene solution is analyzed, containing Fluoxastrobin (24.2%w/w), for 99.1% of theoretical value.
Embodiment 9: the synthesis of Fluoxastrobin
Compared with embodiment 8, difference is only: replace AW1 with the composite catalyst AW2 of embodiment 2 gained, obtaining toluene solution 53.52g, containing Fluoxastrobin (23.2%w/w), is 98.9% of theoretical value.
Embodiment 10: the synthesis of Fluoxastrobin
Compared with embodiment 8, difference is only: replace AW1 with the composite catalyst AW3 of embodiment 3 gained, obtaining toluene solution 51.35g, containing Fluoxastrobin (24.3%w/w), is 99.3% of theoretical value.
Embodiment 11: the synthesis of Fluoxastrobin
Compared with embodiment 8, difference is only: replace AW1 with the composite catalyst AW4 of embodiment 4 gained, and by reaction dissolvent N, dinethylformamide replaces with acetonitrile, obtaining toluene solution 52.38g, containing Fluoxastrobin (23.9%w/w), is 99.5% of theoretical value.
Embodiment 12: the synthesis of Fluoxastrobin
Compared with embodiment 11, difference is only: not adding potash and salicylonitrile, add the sylvite (4.89g, 31.18mmol) of salicylonitrile, obtain toluene solution 50.25g, containing Fluoxastrobin (24.7%w/w), is 99.1% of theoretical value.
Embodiment 13: the synthesis of Fluoxastrobin
Compared with embodiment 8, difference is only: replace AW1 with the composite catalyst AW5 of embodiment 6 gained, and by reaction dissolvent N, dinethylformamide replaces with acetonitrile, obtaining toluene solution 52.14g, containing Fluoxastrobin (24.1%w/w), is 99.9% of theoretical value.
Embodiment 14: the synthesis of Fluoxastrobin
Compared with embodiment 12, difference is only: replace AW1 with the composite catalyst AW6 of embodiment 7 gained, obtaining toluene solution 53.0g, containing Fluoxastrobin (23.7%w/w), is 100% of theoretical value.
Embodiment 15:2-{2-[6-(2-cyano-benzene oxygen) pyrimidine-4-yl oxygen base] phenyl } synthesis of-3,3-dimethoxy methyl propionates
20ml methyl iso-butyl ketone (MIBK) is added in 100ml there-necked flask, potash 5.09g (98%, 36.85mmol), salicylonitrile 3.79g (98%, 31.18mmol), be warming up to 60 DEG C and stir 10min, add embodiment 4 gained composite catalyst AW40.2g (0.81mmol), 2-{2-[6-chlorine pyrimidine-4-yl oxygen base] phenyl is added after continuing to stir 10min at this temperature }-3, 3-dimethoxy methyl propionate 10.53g (95%, 28.35mmol), be warming up to 80 DEG C of reactions, HPLC monitoring display 2-{2-[6-chlorine pyrimidine-4-yl oxygen base] phenyl after 2h }-3, 3-dimethoxy methyl propionate content <0.1%, methyl iso-butyl ketone (MIBK) is reclaimed in decompression distillation, 30ml toluene joins in bottoms, add 40ml subsequently, the aqueous hydrochloric acid solution of 5mol/L, and mixture is stirred 1h at 80 DEG C, layering, 20ml toluene aqueous phase extracted, merge organic phase 51.8g altogether, this toluene solution is analyzed, display 2-{2-[6-(2-cyano-benzene oxygen) pyrimidine-4-yl oxygen base] phenyl }-3, 3-dimethoxy methyl propionate (68.8%) and Fluoxastrobin (29.2%).
Embodiment 16:2-{2-[6-(2-cyano-benzene oxygen) pyrimidine-4-yl oxygen base] phenyl } synthesis of-3,3-dimethoxy methyl propionates
20ml butyl acetate is added in 100ml there-necked flask, potash 7.76g (98%, 56.12mmol), 2-(2-hydroxy phenyl)-3, 3-dimethoxy methyl propionate 11.41g (98%, 47.49mmol), be warming up to 60 DEG C and stir 10min, add embodiment 4 gained composite catalyst AW40.2g (0.81mmol), the chloro-6-of 4-(2-cyano-benzene oxygen) pyrimidine 10.31g (97% is added after continuing to stir 10min at this temperature, 43.17mmol), be warming up to 80 DEG C of reactions, the chloro-6-of HPLC monitoring display 4-(2-cyano-benzene oxygen) pyrimidine content <0.1% after 2h, butyl acetate is reclaimed in decompression distillation, 30ml toluene joins in bottoms, add 40ml subsequently, the aqueous hydrochloric acid solution of 5mol/L, and mixture is stirred 1h at 80 DEG C, layering, 20ml toluene aqueous phase extracted, merge organic phase 51.3g altogether, this toluene solution is analyzed, display 2-{2-[6-(2-cyano-benzene oxygen) pyrimidine-4-yl oxygen base] phenyl }-3, 3-dimethoxy methyl propionate (60.5%) and Fluoxastrobin (38.0%).
Embodiment 17: the synthesis of fluoxastrobin
(E)-5 is added in 100ml there-necked flask, 6-dihydro-1, 4, 2-dioxazine-3-base-(2-hydroxyphenyl) ketone O-methyloxime 13.0g (98%, 50.5mmol), potash 9.0g (98%, 65mmol), acetonitrile 60ml, be warming up to 60 DEG C and stir 10min, add embodiment 4 gained composite catalyst AW40.2g (0.81mmol), after stirring 10min again, add the chloro-6-of 4-(2-chlorophenoxy)-5-FU 12.9g (98%, 49.8mmol), be warming up to 80 DEG C of stirring reactions, the chloro-6-of HPLC monitoring display 4-(2-chlorophenoxy)-5-FU content <0.05% after 2h, acetonitrile is reclaimed in decompression distillation, 50ml toluene joins in bottoms, add 40ml subsequently, the aqueous hydrochloric acid solution of 5mol/L, and mixture is stirred 1h at 80 DEG C, layering, 20ml toluene aqueous phase extracted, merge organic phase 75.3g altogether, this toluene solution is analyzed, containing fluoxastrobin (28.9%w/w), for 99.3% of theoretical value.
Embodiment 18:
React according to described in embodiment 14, after adding the extraction of 20ml toluene, by isolated water layer adjust ph to 6, the solid of precipitation, filters, and drying obtains the catalyst A W6 ' that 0.15g reclaims.
Embodiment 19:
React according to described in embodiment 14, replace catalyst A W6 with the catalyst A W6 ' that embodiment 18 reclaims, and after reaction 3.5h, obtain toluene solution 50.28g, containing Fluoxastrobin (23.6%w/w), 95.3% of theoretical value.
Embodiment 20:
React according to described in embodiment 12, the sylvite of salicylonitrile is added unlike the composite catalyst AW4 not adding embodiment 4 gained in acetonitrile suspension directly to the composite catalyst AW4 described in embodiment 5, subsequent operation is consistent, obtain toluene solution 52.34g, containing Fluoxastrobin (23.9%w/w), it is 99.5% of theoretical value.
Comparative example 1
Compared with embodiment 14, difference is only: will add catalyst A W6 and change into and do not add catalyst in course of reaction, HPLC monitoring display (E)-2-after reaction 6h [2-(6-pyrimidine-4-yl oxygen] phenyl]-3-methoxy-methyl acrylate remains 15%.Obtain 47.32g toluene solution through identical post processing, this toluene solution is analyzed, containing Fluoxastrobin (17.3%w/w), 65.1% of theoretical value.
Comparative example 2
Compared with embodiment 14, difference is only: in course of reaction, change copper chloride into unlike by catalyst A W6, HPLC monitoring display (E)-2-[2-(6-pyrimidine-4-yl oxygen] phenyl after reaction 6h]-3-methoxy-methyl acrylate residue 10%.Obtaining 49.58g toluene solution through identical post processing, analyze this toluene solution, containing Fluoxastrobin (19.2%w/w), is 75.6% of theoretical value.
Comparative example 3
Compared with embodiment 14, difference is only: in course of reaction, add copper chloride and 2-methyl isophthalic acid respectively, 4-diazabicylo [2.2.2] octane replaces described catalyst A W6 as catalyst, and the mol ratio of the two is 1:1, and total amount is 0.2g; Obtaining toluene solution 55.47g, containing Fluoxastrobin (22.1%w/w), is 97.5% of theoretical value.
Although above with general explanation, detailed description of the invention and test, the present invention is described in detail, and on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, all belong to the scope of protection of present invention.
Claims (10)
1. a composite catalyst, is characterized in that, by compd A or/and its salt metallizing thing W is composited; Described compd A has structure shown in general formula I:
In described general formula I, R
1, R
3, R
5, R
6represent independently of one another hydrogen, halogen, C1 ~ C10 containing oxygen or oxygen-free aliphatic group, aryl or ester group; R
2, R
4represent independently of one another hydrogen, halogen, C1 ~ C10 containing oxygen or oxygen-free aliphatic group or aryl;
Described metallic compound W is one or more in metal halide, acid metal, basic metal, metal alkyl or metal aryl and hydrate thereof, and wherein, described metal is copper, manganese, cobalt, nickel, palladium, iron, aluminium or zinc.
2. composite catalyst according to claim 1, is characterized in that, described compd A is or/and its salt metallizing thing W is with A
mw
nform be composited;
Wherein, the mol ratio m:n of A and W is 1 ~ 2:1 or 1:1 ~ 2, is preferably 1:1.
3. composite catalyst according to claim 1 and 2, is characterized in that, described compd A is Isosorbide-5-Nitrae-diazabicylo [2.2.2] octane, 2-methyl isophthalic acid, one or both in 4-diazabicylo [2.2.2] octane;
Described metallic compound W is stannous chloride CuCl, copper chloride CuCl
2, manganese chloride MnCl
2in one or more.
4. the composite catalyst according to claims 1 to 3 any one, it is characterized in that, be prepared from by the method comprised the following steps: get metallic compound W, join in diluent, add compd A while stirring or/and the dilution of its salt, after abundant reaction, filtration, washing, drying, obtain composite catalyst AW;
Or get compd A or/and its salt, join in diluent, add the dilution of metallic compound W while stirring, fully after reaction, filtration, washing, drying, obtain composite catalyst AW;
Described diluent is one or more in water, ethers, lipid, ketone, the fragrant same clan, amide-type, sulfone class or halogenated hydrocarbons; Be preferably DMF, acetonitrile or butyl acetate or methyl iso-butyl ketone (MIBK); More preferably acetonitrile.
5. composite catalyst according to claim 1, it is characterized in that, be prepared from by the method comprised the following steps: the dilution in acetonitrile liquid of preparation stannous chloride, copper chloride or manganese chloride, adds 1 under normal temperature and pressure while stirring, 4-diazabicylo [2.2.2] octane or 2-methyl isophthalic acid, the dilution in acetonitrile liquid of 4-diazabicylo [2.2.2] octane, the mol ratio being added to the two is after 1:1, continues to react completely, filter, with acetonitrile wash, dry, to obtain final product.
6. composite catalyst AW is catalyzing and synthesizing the application in asymmetric 4,6-bis aryloxy pyrimidine derivatives, it is characterized in that, described composite catalyst by compd A or/and its salt metallizing thing W is composited; Described compd A has structure shown in general formula I:
In described general formula I, R
1, R
3, R
5, R
6represent independently of one another hydrogen, halogen, C1 ~ C10 containing oxygen or oxygen-free aliphatic group, aryl or ester group; R
2, R
4represent independently of one another hydrogen, halogen, C1 ~ C10 containing oxygen or oxygen-free aliphatic group or aryl;
Described metallic compound W is one or more in metal halide, acid metal, basic metal, metal alkyl or metal aryl and hydrate thereof, and wherein, described metal is copper, manganese, cobalt, nickel, palladium, iron, aluminium or zinc;
Described compd A is or/and its salt metallizing thing W is with A
mw
nform be composited, wherein, the mol ratio m:n of A and W is 1 ~ 2:1 or 1:1 ~ 2;
Described asymmetric 4,6-bis aryloxy pyrimidine derivatives are preferably the structure as shown in general formula I I:
In described general formula I I, G
1represent hydrogen or halogen, G
3represent halogen or cyano group, G
2representative
Described asymmetric 4,6-bis aryloxy pyrimidine derivatives are more preferably Fluoxastrobin and fluoxastrobin.
7. application according to claim 6, is characterized in that, the synthetic route of described asymmetric 4,6-bis aryloxy pyrimidine derivatives is:
Wherein, described G
1represent hydrogen or halogen; Described G
3represent halogen or cyano group; Described G
2representative
Specifically comprise the following steps:
(1) with the alkali metal salt of compound 1 and compound 2 or compound 2 for raw material, under composite catalyst AW existence condition, carry out etherification reaction, obtain compound 3; In this step, the consumption of composite catalyst AW is 0.1 ~ 50mol% of compound 1;
(2) alkali metal salt of described compound 3 and compound 4 or compound 4 is raw material, under composite catalyst AW existence condition, carries out etherification reaction, obtains compound 5; In this step, the consumption of composite catalyst AW is 0.1 ~ 50mol% of compound 3.
8. application according to claim 6, is characterized in that, the synthetic route of described asymmetric 4,6-bis aryloxy pyrimidine derivatives is:
Wherein, described G
1represent hydrogen or halogen; Described G
3represent halogen or cyano group; Described G
2representative
Specifically comprise the following steps:
(1) with the alkali metal salt of compound 1 and compound 4 or compound 4 for raw material, under composite catalyst AW existence condition, carry out etherification reaction, obtain compound 6; In this step, the consumption of composite catalyst AW is 0.1 ~ 50mol% of compound 1;
(2) alkali metal salt of described compound 6 and compound 2 or compound 2 is raw material, under composite catalyst AW existence condition, carries out etherification reaction, obtains compound 5; In this step, the consumption of composite catalyst AW is 0.1 ~ 50mol% of compound 6.
9. the application according to claim 7 or 8, it is characterized in that, described two step etherification reactions for carrying out step by step, or first carry out a wherein step etherification reaction in same reactor, then then carry out another step etherification reaction, or carry out two step etherification reactions simultaneously in same reactor;
Reaction dissolvent is one or more in ethers, lipid, ketone, the fragrant same clan, amide-type, sulfone class or halogenated hydrocarbons; Be preferably DMF or acetonitrile or butyl acetate or methyl iso-butyl ketone (MIBK); More preferably acetonitrile;
Reaction temperature is: 10 ~ 180 DEG C; Be preferably 30 ~ 120 DEG C; More preferably 60 ~ 80 DEG C.
10. the application according to claim 6 ~ 9 any one, is characterized in that, described composite catalyst AW, after catalyzing and synthesizing asymmetric 4,6-bis aryloxy pyrimidine derivatives, adopts following methods to reclaim:
After reaction terminating, through precipitation, acidifying and extraction, isolate water layer, regulate water layer pH value to 4 ~ 8, separate out solid, filter, dry, the catalyst be recycled.
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