CN105061322B - The preparation method of the 3- hydroxypyrazoles compounds of N- substitutions - Google Patents
The preparation method of the 3- hydroxypyrazoles compounds of N- substitutions Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two 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, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D233/70—One oxygen atom
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Abstract
The present invention relates to organic synthesis fields, disclose a kind of preparation method of 3 hydroxypyrazoles compounds of N substitutions.This method includes that formula (II) compound represented is carried out oxidation reaction in the presence of oxidant, and the oxidant is hydrogen peroxide or hypochlorite, and when the oxidant is hydrogen peroxide, the oxidation reaction carries out under alkaline condition；When the oxidant is hypochlorite, the oxidation reaction carries out in acid condition.The preparation method of 3 hydroxypyrazoles compounds of N substitutions provided by the invention does not generate a large amount of three wastes, reaction is simple and efficient, and can obtain very high feed stock conversion and selectivity of product without using the catalyst for needing to detach from product.
Description
Technical field
The present invention relates to organic synthesis fields, and in particular, to a kind of preparation of the 3- hydroxypyrazoles compounds of N- substitutions
Method.
Background technology
The 3- hydroxypyrazoles compounds of N- substitutions are a kind of important intermediates, due to wide spectrum biological activity,
Pesticide and field of medicaments have a wide range of applications.
The method of the existing 3- hydroxypyrazoles compounds for preparing N- substitutions has very much, however these methods use sulphur mostly
Element or halogens are aoxidized as oxidant, to lead to the generation of a large amount of three wastes, and the selection of these methods
Property is not high, is unfavorable for industrialized production.
WO9703969 is disclosed using molysite or mantoquita as catalyst, basic in pH using air oxygen as oxidant
The upper method to be reacted to prepare the 3- hydroxypyrazoles compounds that N- replaces in neutral medium, this method can be in high yield
Obtain N- substitution 3- hydroxypyrazoles compounds.But the problems such as this method has post-processing complexity, and catalyst is difficult to remove.
WO9827062, which is disclosed, does not add catalyst, using pure oxygen as oxidant, or uses molysite, mantoquita or cobalt
Salt is reacted as catalyst using air oxygen as oxidant in water in the presence of a base, and the 3- of N- substitutions is prepared
The method of hydroxypyrazoles compound.But this method can cause selectivity of product poor, yield is inclined due to the presence of a large amount of water
It is low, also it is unfavorable for industrialized production.
Invention content
In order to which the method for solving the existing 3- hydroxypyrazoles compounds for preparing N- substitutions is easy to generate a large amount of three wastes, product
Poor selectivity, yield is relatively low, the problem of being unfavorable for industrialized production, and the present invention proposes a kind of 3- hydroxypyrazoles of N- substitutions
Close the preparation method of object.
The present inventor is after research it was unexpectedly observed that by formula (II) compound represented in the presence of oxidant
Carrying out oxidation reaction, wherein the oxidant is hydrogen peroxide or hypochlorite, when the oxidant is hydrogen peroxide, institute
Oxidation reaction is stated to carry out under alkaline condition；When the oxidant is hypochlorite, the oxidation reaction is in acid condition
It carries out, formula (II) compound represented efficient can be converted to the 3- hydroxypyrazoles compounds that N- replaces, while raw material
High conversion rate, selectivity of product are high, so as to complete the present invention.
The present invention provides a kind of preparation methods of the 3- hydroxypyrazoles compounds of N- substitutions, and this method includes by formula (II)
Compound represented carries out oxidation reaction in the presence of oxidant, and the oxidant is hydrogen peroxide or hypochlorite, works as institute
State oxidant be hydrogen peroxide when, the oxidation reaction carries out under alkaline condition；When the oxidant is hypochlorite, institute
Oxidation reaction is stated to carry out in acid condition；
In Formulas I and Formula II,
R1For the alkyl of substituted or unsubstituted 1-6 carbon atom, substituted or unsubstituted aryl and substitution or unsubstituted
Heteroaryl in any one；
R2And R3Separately be hydrogen, cyano, halogen, substituted or unsubstituted 1-4 carbon atom alkyl, replace or
Any one in unsubstituted aryl and substituted or unsubstituted heteroaryl.
The preparation method of the 3- hydroxypyrazoles compounds of N- substitutions provided by the invention is detached without using needs from product
Catalyst, do not generate a large amount of three wastes, reaction is simple and efficient, and can obtain very high feed stock conversion and selectivity of product.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific implementation mode
The specific implementation mode of the present invention is described in detail below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides the preparation method of the 3- hydroxypyrazoles compounds replaced of N- shown in a kind of formula (I), this method
Including formula (II) compound represented is carried out oxidation reaction in the presence of oxidant, wherein the oxidant is peroxidating
Hydrogen or hypochlorite, when the oxidant is hydrogen peroxide, the oxidation reaction carries out under alkaline condition；When the oxidation
When agent is hypochlorite, the oxidation reaction carries out in acid condition；
In Formulas I and Formula II,
R1For the alkyl of substituted or unsubstituted 1-6 carbon atom, substituted or unsubstituted aryl and substitution or unsubstituted
Heteroaryl in any one.
R2And R3Separately be hydrogen, cyano, halogen, substituted or unsubstituted 1-6 carbon atom alkyl, replace or
Any one in unsubstituted aryl and substituted or unsubstituted heteroaryl.
Wherein, the alkyl of the 1-6 carbon atom is preferably the alkyl of 1-4 carbon atom.The alkane of the 1-6 carbon atom
Base for example can be methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tertiary butyl, n-pentyl, isoamyl
Any one in base, neopentyl, sec-amyl, tertiary pentyl, n-hexyl, isohesyl, new hexyl, Sec-Hexyl and tertiary hexyl.
The aryl for example can be any one in phenyl, naphthalene, anthryl, phenanthryl and pyrenyl.
The heteroaryl for example can be any one in thienyl, furyl, pyrrole radicals and pyridyl group.
Substituent group in the alkyl of the 1-6 substituted carbon atom can be any one in halogen, nitro and cyano
Kind.The halogen can be any one in F, Cl, Br and I.Preferably, the halogen is Cl or Br.
Preferably, the substituent group in the alkyl of the 1-6 substituted carbon atom is in F, Cl, Br, I, nitro and cyano
Any one.
Preferably, the alkyl of the 1-6 substituted carbon atom is chloromethyl, 2- chloroethyls, bromomethyl and 2- bromoethyls
In any one.
Substituent group in the substituted aryl and substituted heteroaryl can be alkyl, the nitre of halogen, 1-6 carbon atom
Any one in base and cyano.
The halogen is same as described above.
The alkyl of the 1-6 carbon atom is same as described above.
Preferably, the substituted aryl be p-methylphenyl, adjacent ethylbenzene, p-bromophenyl, chlorphenyl, rubigan,
P-nitrophenyl and to any one in cyano-phenyl.
Preferably, the substituted heteroaryl is In any one.
The hydrogen peroxide can be aqueous hydrogen peroxide solution.The mass fraction of the aqueous hydrogen peroxide solution can be
5%-30%, preferably 10%-20%.
The alkaline condition can be pH7.1-14, preferably 7.5-9.
The alkaline condition can be realized using organic base or inorganic base.The organic bases such as can be triethylamine
And/or pyridine.The inorganic base can be in the hydroxide of alkali or alkaline earth metal, carbonate and bicarbonate at least
It is a kind of.The inorganic basis such as can be NaOH, KOH, Ca (OH)2、Na2CO3、K2CO3、NaHCO3And KHCO3In at least one
Kind.
The hypochlorite can be the aqueous solution of hypochlorite.The mass fraction of the aqueous hypochlorite solution can be
5%-15%, preferably 10%.
The hypochlorite can be at least one of calcium hypochlorite, sodium hypochlorite and postassium hypochlorite.
The acid condition can be pH1-6.9, preferably 3-5.
The acid condition can be realized using organic acid or inorganic acid.The organic acids such as can be formic acid, second
At least one of acid, benzoic acid and phenylacetic acid.The inorganic acid for example can be nitric acid, hydrochloric acid, sulfuric acid and phosphoric acid in extremely
Few one kind.
In method provided by the invention, the molar ratio of formula (II) compound represented and hydrogen peroxide or hypochlorite can
Think 1：(1-5), preferably 1：(1-3).
The condition of the contact can also include that reaction temperature is 0-100 DEG C, and preferably 20-80 DEG C, the reaction time can be
3-10 hours, preferably 5-8 hours.
The oxidation reaction can also include carrying out in a solvent.The solvent can be water, aromatic hydrocarbons, 1-6 carbon atom
Halogenated hydrocarbons, the alcohol of 1-4 carbon atom, the ether of 2-6 carbon atom, 2-6 carbon atom ester, N-Methyl pyrrolidone, diformazan
At least one of base formamide, dimethylacetylamide and dimethyl sulfoxide.
The aromatic hydrocarbons for example can be at least one of benzene, toluene and dimethylbenzene.
The halogenated hydrocarbons of the 1-6 carbon atom such as can be dichloromethane, 1,2- dichloroethanes, chloroform and chlorobenzene
At least one of.
The alcohol of the 1-4 carbon atom for example can be at least one of methanol, ethyl alcohol, isopropanol and butanol.
The ether of the 2-6 carbon atom for example can be ether, methyl tertiary butyl ether(MTBE), tetrahydrofuran and glycol dimethyl ether
At least one of.
The ester of the 2-6 carbon atom for example can be at least one in ethyl acetate, butyl acetate and isopropyl acetate
Kind.
It below will the present invention will be described in detail by specific embodiment.
In following embodiment and comparative example：
The concentration of hydrogen peroxide and hypochlorite is mass fraction.
The testing conditions of liquid chromatogram are：Chromatographic column：XDB-C8,4.6*150mm, Detection wavelength：275nm, mobile phase：
Acetonitrile：Water=90:10 (volume ratios), flow velocity：1.2mL/min.
The conversion ratio of raw material is：The area normalization content of 1- raw materials.
The selectivity of 3- hydroxypyrazoles compounds of N- substitutions is：The area normalization of the 3- hydroxypyrazoles compounds of N- substitutions
Content/feed stock conversion.
Note：Area normalization content is the percentage that each peak area accounts for total peak area.
Embodiment 1
The present embodiment is illustrating 3- hydroxypyrazoles compound (1- (4- chlorphenyls) -3- of N- provided by the invention substitution
Hydroxypyrazoles) preparation method.
In the four-hole bottle equipped with mechanical agitation, thermometer and condenser pipe, 1- (4- chlorphenyls) pyrazoles of 0.1mol is added
20% sodium hydrate aqueous solution (matter of alkane -3- ketone (being synthesized according to the method in WO 9703969), 100mL tetrahydrofurans and 5g
Measure score), then into four-hole bottle be added dropwise 13.6g the 30% hydrogen peroxide (H containing 0.12mol2O2), reaction 8 is small under the conditions of 30 DEG C
When, obtain 1- (4- chlorphenyls) -3- hydroxypyrazoles.
Through liquid chromatographic detection, the conversion ratio of 1- (4- chlorphenyls) pyrazolidine -3- ketone is 99.5% (1- (4- chlorphenyls) pyrrole
The conversion ratio of oxazolidine -3- ketone is 1- [the area normalization content of 1- (4- chlorphenyls) pyrazolidine -3- ketone]).1- (4- chlorphenyls) -3-
The selectivity of hydroxypyrazoles is that 90% (selectivity of 1- (4- chlorphenyls) -3- hydroxypyrazoles is 1- (4- chlorphenyls) -3- hydroxyl pyrroles
The conversion ratio of area normalization content/1- (4- chlorphenyls) pyrazolidine -3- ketone of azoles；Wherein, 1- (4- chlorphenyls) -3- hydroxypyrazoles
Area normalization content be 89.5%).
Embodiment 2
The present embodiment is illustrating 3- hydroxypyrazoles compound (1- (the 3,4- dichloro-benzenes of N- provided by the invention substitution
Base) -3- hydroxypyrazoles) preparation method.
In the four-hole bottle equipped with mechanical agitation, thermometer and condenser pipe, the 1- (3,4- dichlorophenyl) of 0.1mol is added
Pyrazolidine -3- ketone (synthesizes) 1.5g triethylamines and 100mL chlorobenzenes according to the method in WO 9703969, then is added dropwise into four-hole bottle
30% hydrogen peroxide (the H containing 0.15mol of 17.0g2O2), it reacts 5 hours under the conditions of 50 DEG C, obtains 1- (3,4- dichlorophenyl)-
3- hydroxypyrazoles.
Through liquid chromatographic detection, the conversion ratio of 1- (3,4- dichlorophenyl) pyrazolidine -3- ketone is 99.5% (1- (3,4- bis-
Chlorphenyl) pyrazolidine -3- ketone conversion ratio be 1- [the area normalization content of 1- (3,4- dichlorophenyls) pyrazolidine -3- ketone]).1-
The selectivity of (3,4- dichlorophenyls) -3- hydroxypyrazoles is that 85% (selectivity of 1- (3,4- dichlorophenyls) -3- hydroxypyrazoles is
The conversion ratio of area normalization content/1- (4- chlorphenyls) pyrazolidine -3- ketone of 1- (3,4- dichlorophenyls) -3- hydroxypyrazoles；Its
In, 84.6%) the area normalization content of 1- (3,4- dichlorophenyl) -3- hydroxypyrazoles is.
Embodiment 3
The present embodiment is illustrating the 3- hydroxypyrazoles compound (1- (4- aminomethyl phenyls)-of N- provided by the invention substitution
3- hydroxypyrazoles) preparation method.
In the four-hole bottle equipped with mechanical agitation, thermometer and condenser pipe, 1- (4- aminomethyl phenyls) pyrrole of 0.1mol is added
Oxazolidine -3- ketone (synthesizes) DMF of 1.5g hydrochloric acid (31%) and 100mL according to the method in WO 9703969, then into four-hole bottle
10% liquor natrii hypochloritis (sodium hypochlorite containing 0.2mol) of 148.9g is added dropwise, is reacted 9 hours under the conditions of 80 DEG C, obtains 1-
(4- aminomethyl phenyls) -3- hydroxypyrazoles.
Through liquid chromatographic detection, the conversion ratio of 1- (4- aminomethyl phenyls) pyrazolidine -3- ketone is 99.5% (1- (4- methylbenzenes
Base) pyrazolidine -3- ketone conversion ratio be 1- [the area normalization content of 1- (4- aminomethyl phenyls) pyrazolidine -3- ketone]).1- (4- first
Base phenyl) selectivity of -3- hydroxypyrazoles is that 80% (selectivity of 1- (4- aminomethyl phenyls) -3- hydroxypyrazoles is 1- (4- methyl
Phenyl) -3- hydroxypyrazoles area normalization content/1- (4- aminomethyl phenyls) pyrazolidine -3- ketone conversion ratio；Wherein, 1- (4- first
Base phenyl) -3- hydroxypyrazoles area normalization content be 79.6%).
Embodiment 4
The present embodiment is illustrating 3- hydroxypyrazoles compound (1- (4- chlorphenyls) -3- of N- provided by the invention substitution
Hydroxypyrazoles) preparation method.
In the four-hole bottle equipped with mechanical agitation, thermometer and condenser pipe, 1- (4- chlorphenyls) pyrazoles of 0.1mol is added
5% potassium hydroxide aqueous solution of alkane -3- ketone (being synthesized according to the method in WO9703969), 135g, then be added dropwise into four-hole bottle
30% hydrogen peroxide (the H containing 0.12mol of 13.6g2O2), it reacts 6 hours under the conditions of 30 DEG C, obtains 1- (4- chlorphenyls) -3- hydroxyls
Base pyrazoles.
Through liquid chromatographic detection, the conversion ratio of 1- (4- chlorphenyls) pyrazolidine -3- ketone is 99.5% (1- (4- chlorphenyls) pyrrole
The conversion ratio of oxazolidine -3- ketone is 1- [the area normalization content of 1- (4- chlorphenyls) pyrazolidine -3- ketone]).1- (4- chlorphenyls) -3-
The selectivity of hydroxypyrazoles is that 85% (selectivity of 1- (4- chlorphenyls) -3- hydroxypyrazoles is 1- (4- chlorphenyls) -3- hydroxyl pyrroles
The conversion ratio of area normalization content/1- (4- chlorphenyls) pyrazolidine -3- ketone of azoles；Wherein, 1- (4- chlorphenyls) -3- hydroxypyrazoles
Area normalization content be 84.6%).
Comparative example 1
1- (4- chlorphenyls) -3- hydroxypyrazoles are prepared according to the method for embodiment 1, the difference is that being added without hydroxide
Sodium water solution.
Through liquid chromatographic detection, the conversion ratio of 1- (4- chlorphenyls) pyrazolidine -3- ketone is 40% (1- (4- chlorphenyls) pyrazoles
The conversion ratio of alkane -3- ketone is 1- [the area normalization content of 1- (4- chlorphenyls) pyrazolidine -3- ketone]).1- (4- chlorphenyls) -3- hydroxyls
The selectivity of base pyrazoles is that 85% (selectivity of 1- (4- chlorphenyls) -3- hydroxypyrazoles is 1- (4- chlorphenyls) -3- hydroxypyrazoles
Area normalization content/1- (4- chlorphenyls) pyrazolidine -3- ketone conversion ratio；Wherein, 1- (4- chlorphenyls) -3- hydroxypyrazoles
89.5%) area normalization content is.
Comparative example 2
1- (3,4- dichlorophenyl) -3- hydroxypyrazoles are prepared according to the method for embodiment 2, the difference is that being added without double
Oxygen water aqueous solution.
Through liquid chromatographic detection, the conversion ratio of 1- (3,4- dichlorophenyl) pyrazolidine -3- ketone is 0.5% (1- (3,4- dichloros
Phenyl) pyrazolidine -3- ketone conversion ratio be 1- [the area normalization content of 1- (3,4- dichlorophenyls) pyrazolidine -3- ketone]).
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail can carry out a variety of simple variants to technical scheme of the present invention within the scope of the technical concept of the present invention, this
A little simple variants all belong to the scope of protection of the present invention.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (4)
1. a kind of preparation method of the 3- hydroxypyrazoles compounds of N- substitution, the method includes by formula (II) compound represented
The 3- hydroxypyrazoles compounds that oxidation reaction prepares N- substitutions shown in formula (I), the oxidation are carried out in the presence of oxidant
Agent is hydrogen peroxide or hypochlorite, and when the oxidant is hydrogen peroxide, the oxidation reaction carries out under alkaline condition；
When the oxidant is hypochlorite, the oxidation reaction carries out in acid condition；
In Formulas I and Formula II,
R1For phenyl；
R2And R3For hydrogen；
The hydrogen peroxide is aqueous hydrogen peroxide solution, and the mass fraction of the aqueous hydrogen peroxide solution is 5%-30%；
The alkaline condition is pH7.5-9；
The hypochlorite is the aqueous solution of hypochlorite, and the mass fraction of the aqueous hypochlorite solution is 5%-15%；
The acid condition is pH3-5；
The hypochlorite is at least one of calcium hypochlorite, sodium hypochlorite and postassium hypochlorite；
Formula (II) compound represented and the molar ratio of oxidant are 1：1-3.
2. a kind of preparation method of the 3- hydroxypyrazoles compounds of N- substitutions according to claim 1, which is characterized in that institute
The mass fraction for stating aqueous hydrogen peroxide solution is 10%-20%.
3. a kind of preparation method of the 3- hydroxypyrazoles compounds of N- substitutions according to claim 1, which is characterized in that institute
The condition for stating contact further includes that reaction temperature is 20-80 DEG C, and the reaction time is 5-8 hours.
4. a kind of preparation method of the 3- hydroxypyrazoles compounds of N- substitutions according to claim 1, which is characterized in that institute
Oxidation reaction is stated to carry out in a solvent；The solvent be water, aromatic hydrocarbons, the halogenated hydrocarbons of 1-6 carbon atom, 1-4 carbon atom alcohol,
Ester, N-Methyl pyrrolidone, dimethylformamide, the dimethylacetylamide and two of the ether of 2-6 carbon atom, 2-6 carbon atom
At least one of first sulfoxide.
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| CN114181151B (en) * | 2021-12-16 | 2024-03-29 | 湖南化工研究院有限公司 | Oxidation method of 1- (4-chlorophenyl) -3-pyrazolol |
| CN114195717A (en) * | 2021-12-31 | 2022-03-18 | 江苏七洲绿色科技研究院有限公司 | Preparation method of 1- (4-chlorphenyl) -2H-pyrazoline-3-ketone |
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