CN105061322A - Preparation method of N-substituted 3-hydroxypyrazole compound - Google Patents

Preparation method of N-substituted 3-hydroxypyrazole compound Download PDF

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CN105061322A
CN105061322A CN201510446250.2A CN201510446250A CN105061322A CN 105061322 A CN105061322 A CN 105061322A CN 201510446250 A CN201510446250 A CN 201510446250A CN 105061322 A CN105061322 A CN 105061322A
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hypochlorite
substituted
hydrogen peroxide
carbon atom
hydroxypyrazoles
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CN105061322B (en
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吴坤
谭徐林
王磊
倪肖元
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Suzhou jingzida Testing Service Co., Ltd
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Beijing Nutrichem Co Ltd
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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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  • Organic Chemistry (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

The invention relates to the field of organic synthesis, and discloses a preparation method of a N-substituted 3-hydroxypyrazole compound. The method is characterized in that an oxidation reaction of the compound shown in a formula (II) is carried out under existence of an oxidizing agent, the oxidizing agent is hydrogen peroxide or hypochlorite, when the oxidizing agent is hydrogen peroxide, the oxidation reaction is carried out under alkaline condition; and when the oxidizing agent is hypochlorite, the oxidation reaction is carried out under acidic condition. The preparation method does not require a catalyst separated from the products, a lot of three wastes can not be generated, the reaction has the advantages of simpleness and high efficiency, and high raw material conversion rate and products selectivity can be obtained.

Description

The preparation method of the 3-hydroxypyrazoles compound that N-replaces
Technical field
The present invention relates to organic synthesis field, particularly, relate to the preparation method of the 3-hydroxypyrazoles compound that a kind of N-replaces.
Background technology
The 3-hydroxypyrazoles compound that N-replaces is a kind of important intermediate, owing to having the biological activity of wide spectrum, has a wide range of applications at agricultural chemicals and field of medicaments.
The method of the 3-hydroxypyrazoles compound that existing preparation N-replaces has a lot, but these methods use element sulphur or halogens to be oxidized as oxygenant mostly, thus can cause the generation of a large amount of three wastes, and the selectivity of these methods is not high, is unfavorable for suitability for industrialized production.
WO9703969 discloses and uses molysite or mantoquita as catalyzer, use atmospheric oxygen as oxygenant, in the medium that pH is essentially neutral, carry out reacting the method preparing the 3-hydroxypyrazoles compound that N-replaces, the method can high yield obtain the 3-hydroxypyrazoles compound that N-replaces.But the method exists aftertreatment complexity, catalyzer is difficult to the problems such as removing.
WO9827062 discloses and does not add catalyzer, use pure oxygen as oxygenant, or use molysite, mantoquita or cobalt salt as catalyzer, use atmospheric oxygen as oxygenant, react in water in the presence of a base, prepare the method for the 3-hydroxypyrazoles compound that N-replaces.But the method is due to the existence of large water gaging, selectivity of product can be caused poor, and yield is on the low side, is also unfavorable for suitability for industrialized production.
Summary of the invention
In order to the method solving the 3-hydroxypyrazoles compound that existing preparation N-replaces is easy to produce a large amount of three wastes, selectivity of product is poor, yield is on the low side, is unfavorable for the problem of suitability for industrialized production, the present invention proposes the preparation method of the 3-hydroxypyrazoles compound that a kind of N-replaces.
The present inventor is surprised to find that after deliberation afterwards, compound shown in formula (II) is carried out oxidizing reaction under the existence of oxygenant, wherein, described oxygenant is hydrogen peroxide or hypochlorite, when described oxygenant is hydrogen peroxide, described oxidizing reaction is carried out in the basic conditions; When described oxygenant is hypochlorite, described oxidizing reaction is carried out in acid condition, can the high efficiency 3-hydroxypyrazoles compound becoming N-to replace the converting compounds shown in formula (II), feed stock conversion is high simultaneously, selectivity of product is high, thus completes the present invention.
The invention provides the preparation method of the 3-hydroxypyrazoles compound that a kind of N-replaces, the method comprises carries out oxidizing reaction by the compound shown in formula (II) under the existence of oxygenant, described oxygenant is hydrogen peroxide or hypochlorite, when described oxygenant is hydrogen peroxide, described oxidizing reaction is carried out in the basic conditions; When described oxygenant is hypochlorite, described oxidizing reaction is carried out in acid condition;
In formula I and formula II,
R 1for the alkyl of a substituted or unsubstituted 1-6 carbon atom, any one in substituted or unsubstituted aryl and substituted or unsubstituted heteroaryl;
R 2and R 3be separately the alkyl of hydrogen, cyano group, halogen, a substituted or unsubstituted 1-4 carbon atom, any one in substituted or unsubstituted aryl and substituted or unsubstituted heteroaryl.
The preparation method of the 3-hydroxypyrazoles compound that N-provided by the invention replaces does not use the catalyzer needing to be separated from product, does not produce a large amount of three wastes, and reaction is simple efficient, can obtain very high feed stock conversion and selectivity of product.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides the preparation method of the 3-hydroxypyrazoles compound that the N-shown in a kind of formula (I) replaces, the method comprises carries out oxidizing reaction by the compound shown in formula (II) under the existence of oxygenant, wherein, described oxygenant is hydrogen peroxide or hypochlorite, when described oxygenant is hydrogen peroxide, described oxidizing reaction is carried out in the basic conditions; When described oxygenant is hypochlorite, described oxidizing reaction is carried out in acid condition;
In formula I and formula II,
R 1for the alkyl of a substituted or unsubstituted 1-6 carbon atom, any one in substituted or unsubstituted aryl and substituted or unsubstituted heteroaryl.
R 2and R 3be separately the alkyl of hydrogen, cyano group, halogen, a substituted or unsubstituted 1-6 carbon atom, any one in substituted or unsubstituted aryl and substituted or unsubstituted heteroaryl.
Wherein, the alkyl of a described 1-6 carbon atom is preferably the alkyl of 1-4 carbon atom.The alkyl of a described 1-6 carbon atom can be such as any one in methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, isopentyl, neo-pentyl, sec.-amyl sec-pentyl secondary amyl, tert-pentyl, n-hexyl, isohexyl, new hexyl, Sec-Hexyl and tertiary hexyl.
Described aryl can be such as any one in phenyl, naphthyl, anthryl, phenanthryl and pyrenyl.
Described heteroaryl can be such as any one in thienyl, furyl, pyrryl and pyridyl.
Substituting group in the alkyl of 1-6 carbon atom of described replacement can be any one in halogen, nitro and cyano group.Described halogen can be any one in F, Cl, Br and I.Preferably, described halogen is Cl or Br.
Preferably, the substituting group in the alkyl of 1-6 carbon atom of described replacement is any one in F, Cl, Br, I, nitro and cyano group.
Preferably, the alkyl of 1-6 carbon atom of described replacement is any one in chloromethyl, 2-chloroethyl, brooethyl and 2-bromotrifluoromethane.
Substituting group in the aryl of described replacement and the heteroaryl of replacement can be any one in halogen, the alkyl of a 1-6 carbon atom, nitro and cyano group.
Described halogen is same as described above.
The alkyl of a described 1-6 carbon atom is same as described above.
Preferably, the aryl of described replacement be p-methylphenyl, adjacent ethylbenzene, to bromophenyl, a chloro-phenyl-, rubigan, p-nitrophenyl and to any one in cyano-phenyl.
Preferably, the heteroaryl of described replacement is in any one.
Described hydrogen peroxide can be aqueous hydrogen peroxide solution.The massfraction of described aqueous hydrogen peroxide solution can be 5%-30%, preferred 10%-20%.
Described alkaline condition can be pH7.1-14, preferred 7.5-9.
Organic bases or mineral alkali can be used to realize described alkaline condition.Described organic bases is as being triethylamine and/or pyridine.Described mineral alkali can be at least one in the oxyhydroxide of basic metal or alkaline-earth metal, carbonate and supercarbonate.Described inorganic basis is as being NaOH, KOH, Ca (OH) 2, Na 2cO 3, K 2cO 3, NaHCO 3and KHCO 3in at least one.
Described hypochlorite can be the aqueous solution of hypochlorite.The massfraction of described aqueous hypochlorite solution can be 5%-15%, preferably 10%.
Described hypochlorite can be at least one in Losantin, clorox and potassium hypochlorite.
Described acidic conditions can be pH1-6.9, preferred 3-5.
Organic acid or mineral acid can be used to realize described acidic conditions.Described organic acids is as being at least one in formic acid, acetic acid, phenylformic acid and toluylic acid.Described mineral acid can be such as at least one in nitric acid, hydrochloric acid, sulfuric acid and phosphoric acid.
In method provided by the invention, the mol ratio of the compound shown in formula (II) and hydrogen peroxide or hypochlorite can be 1:(1-5), be preferably 1:(1-3).
It is 0-100 DEG C that the condition of described contact can also comprise temperature of reaction, preferred 20-80 DEG C, and the reaction times can be 3-10 hour, preferred 5-8 hour.
Described oxidizing reaction can also comprise carries out in a solvent.Described solvent can be at least one in water, aromatic hydrocarbons, the halohydrocarbon of a 1-6 carbon atom, the alcohol of a 1-4 carbon atom, the ether of a 2-6 carbon atom, the ester of a 2-6 carbon atom, N-Methyl pyrrolidone, dimethyl formamide, N,N-DIMETHYLACETAMIDE and methyl-sulphoxide.
Described aromatic hydrocarbons can be such as at least one in benzene, toluene and dimethylbenzene.
The halogenated hydrocarbons of a described 1-6 carbon atom is as being at least one in methylene dichloride, 1,2-ethylene dichloride, trichloromethane and chlorobenzene.
The alcohol of a described 1-4 carbon atom can be such as at least one in methyl alcohol, ethanol, Virahol and butanols.
The ether of a described 2-6 carbon atom can be such as at least one in ether, methyl tertiary butyl ether, tetrahydrofuran (THF) and glycol dimethyl ether.
The ester of a described 2-6 carbon atom can be such as at least one in ethyl acetate, butylacetate and isopropyl acetate.
Below will be described the present invention by specific embodiment.
In following examples and comparative example:
The concentration of hydrogen peroxide and hypochlorite is massfraction.
The testing conditions of liquid chromatography is: chromatographic column: XDB-C8,4.6*150mm, determined wavelength: 275nm, moving phase: acetonitrile: water=90:10 (volume ratio), flow velocity: 1.2mL/min.
The transformation efficiency of raw material is: the area normalization content of 1-raw material.
The selectivity of the 3-hydroxypyrazoles compound that N-replaces is: the area normalization content/feed stock conversion of the 3-hydroxypyrazoles compound that N-replaces.
Note: area normalization content is the percentage that each peak area accounts for total peak area.
Embodiment 1
The preparation method of 3-hydroxypyrazoles compound (1-(4-chloro-phenyl-)-3-hydroxypyrazoles) of the present embodiment in order to N-provided by the invention to be described to replace.
In the four-hole bottle that mechanical stirring, thermometer and prolong are housed, add 1-(4-chloro-phenyl-) pyrazolidine-3-ketone (the method synthesis according in WO9703969) of 0.1mol, 20% aqueous sodium hydroxide solution (massfraction) of 100mL tetrahydrofuran (THF) and 5g, then drip in four-hole bottle 13.6g 30% hydrogen peroxide (containing the H of 0.12mol 2o 2), react 8 hours under 30 DEG C of conditions, obtain 1-(4-chloro-phenyl-)-3-hydroxypyrazoles.
Through liquid chromatographic detection, the transformation efficiency of 1-(4-chloro-phenyl-) pyrazolidine-3-ketone is 99.5% (transformation efficiency of 1-(4-chloro-phenyl-) pyrazolidine-3-ketone is 1-[the area normalization content of 1-(4-chloro-phenyl-) pyrazolidine-3-ketone]).The selectivity of 1-(4-chloro-phenyl-)-3-hydroxypyrazoles is that 90% (selectivity of 1-(4-chloro-phenyl-)-3-hydroxypyrazoles is the transformation efficiency of area normalization content/1-(4-chloro-phenyl-) pyrazolidine-3-ketone of 1-(4-chloro-phenyl-)-3-hydroxypyrazoles; Wherein, the area normalization content of 1-(4-chloro-phenyl-)-3-hydroxypyrazoles is 89.5%).
Embodiment 2
The preparation method of 3-hydroxypyrazoles compound (1-(3,4-dichlorophenyl)-3-hydroxypyrazoles) of the present embodiment in order to N-provided by the invention to be described to replace.
In the four-hole bottle that mechanical stirring, thermometer and prolong are housed, add the 1-(3 of 0.1mol, 4-dichlorophenyl) pyrazolidine-3-ketone (the method synthesis according in WO9703969) 1.5g triethylamine and 100mL chlorobenzene, then drip in four-hole bottle 17.0g 30% hydrogen peroxide (containing the H of 0.15mol 2o 2), react 5 hours under 50 DEG C of conditions, obtain 1-(3,4-dichlorophenyl)-3-hydroxypyrazoles.
Through liquid chromatographic detection, 1-(3,4-dichlorophenyl) transformation efficiency of pyrazolidine-3-ketone is 99.5% (1-(3,4-dichlorophenyl) transformation efficiency of pyrazolidine-3-ketone is 1-[the area normalization content of 1-(3,4-dichlorophenyl) pyrazolidine-3-ketone]).1-(3,4-dichlorophenyl) selectivity of-3-hydroxypyrazoles is 85% (1-(3,4-dichlorophenyl) selectivity of-3-hydroxypyrazoles is the transformation efficiency of area normalization content/1-(4-chloro-phenyl-) pyrazolidine-3-ketone of 1-(3,4-dichlorophenyl)-3-hydroxypyrazoles; Wherein, the area normalization content of 1-(3,4-dichlorophenyl)-3-hydroxypyrazoles is 84.6%).
Embodiment 3
The preparation method of 3-hydroxypyrazoles compound (1-(4-aminomethyl phenyl)-3-hydroxypyrazoles) of the present embodiment in order to N-provided by the invention to be described to replace.
In the four-hole bottle that mechanical stirring, thermometer and prolong are housed, add 1-(4-aminomethyl phenyl) pyrazolidine-3-ketone (the method synthesis according in WO9703969) the 1.5g hydrochloric acid (31%) of 0.1mol and the DMF of 100mL, chlorine bleach liquor's (clorox containing 0.2mol) of 10% of 148.9g is dripped again in four-hole bottle, react 9 hours under 80 DEG C of conditions, obtain 1-(4-aminomethyl phenyl)-3-hydroxypyrazoles.
Through liquid chromatographic detection, the transformation efficiency of 1-(4-aminomethyl phenyl) pyrazolidine-3-ketone is 99.5% (transformation efficiency of 1-(4-aminomethyl phenyl) pyrazolidine-3-ketone is 1-[the area normalization content of 1-(4-aminomethyl phenyl) pyrazolidine-3-ketone]).The selectivity of 1-(4-aminomethyl phenyl)-3-hydroxypyrazoles is that 80% (selectivity of 1-(4-aminomethyl phenyl)-3-hydroxypyrazoles is the transformation efficiency of area normalization content/1-(4-aminomethyl phenyl) pyrazolidine-3-ketone of 1-(4-aminomethyl phenyl)-3-hydroxypyrazoles; Wherein, the area normalization content of 1-(4-aminomethyl phenyl)-3-hydroxypyrazoles is 79.6%).
Embodiment 4
The preparation method of 3-hydroxypyrazoles compound (1-(4-chloro-phenyl-)-3-hydroxypyrazoles) of the present embodiment in order to N-provided by the invention to be described to replace.
In the four-hole bottle that mechanical stirring, thermometer and prolong are housed, add 1-(4-chloro-phenyl-) pyrazolidine-3-ketone (the method synthesis according in WO9703969), 5% potassium hydroxide aqueous solution of 135g of 0.1mol, then drip in four-hole bottle 13.6g 30% hydrogen peroxide (containing the H of 0.12mol 2o 2), react 6 hours under 30 DEG C of conditions, obtain 1-(4-chloro-phenyl-)-3-hydroxypyrazoles.
Through liquid chromatographic detection, the transformation efficiency of 1-(4-chloro-phenyl-) pyrazolidine-3-ketone is 99.5% (transformation efficiency of 1-(4-chloro-phenyl-) pyrazolidine-3-ketone is 1-[the area normalization content of 1-(4-chloro-phenyl-) pyrazolidine-3-ketone]).The selectivity of 1-(4-chloro-phenyl-)-3-hydroxypyrazoles is that 85% (selectivity of 1-(4-chloro-phenyl-)-3-hydroxypyrazoles is the transformation efficiency of area normalization content/1-(4-chloro-phenyl-) pyrazolidine-3-ketone of 1-(4-chloro-phenyl-)-3-hydroxypyrazoles; Wherein, the area normalization content of 1-(4-chloro-phenyl-)-3-hydroxypyrazoles is 84.6%).
Comparative example 1
Prepare 1-(4-chloro-phenyl-)-3-hydroxypyrazoles according to the method for embodiment 1, difference is, does not add aqueous sodium hydroxide solution.
Through liquid chromatographic detection, the transformation efficiency of 1-(4-chloro-phenyl-) pyrazolidine-3-ketone is 40% (transformation efficiency of 1-(4-chloro-phenyl-) pyrazolidine-3-ketone is 1-[the area normalization content of 1-(4-chloro-phenyl-) pyrazolidine-3-ketone]).The selectivity of 1-(4-chloro-phenyl-)-3-hydroxypyrazoles is that 85% (selectivity of 1-(4-chloro-phenyl-)-3-hydroxypyrazoles is the transformation efficiency of area normalization content/1-(4-chloro-phenyl-) pyrazolidine-3-ketone of 1-(4-chloro-phenyl-)-3-hydroxypyrazoles; Wherein, the area normalization content of 1-(4-chloro-phenyl-)-3-hydroxypyrazoles is 89.5%).
Comparative example 2
Prepare 1-(3,4-dichlorophenyl)-3-hydroxypyrazoles according to the method for embodiment 2, difference is, does not add aqueous hydrogen peroxide solution.
Through liquid chromatographic detection, 1-(3,4-dichlorophenyl) transformation efficiency of pyrazolidine-3-ketone is 0.5% (1-(3,4-dichlorophenyl) transformation efficiency of pyrazolidine-3-ketone is 1-[the area normalization content of 1-(3,4-dichlorophenyl) pyrazolidine-3-ketone]).
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.

Claims (10)

1. the preparation method of the 3-hydroxypyrazoles compound that the N-shown in a formula (I) replaces, the method comprises carries out oxidizing reaction by the compound shown in formula (II) under the existence of oxygenant, it is characterized in that, described oxygenant is hydrogen peroxide or hypochlorite, when described oxygenant is hydrogen peroxide, described oxidizing reaction is carried out in the basic conditions; When described oxygenant is hypochlorite, described oxidizing reaction is carried out in acid condition;
In formula I and formula II,
R 1for the alkyl of a substituted or unsubstituted 1-6 carbon atom, any one in substituted or unsubstituted aryl and substituted or unsubstituted heteroaryl;
R 2and R 3be separately the alkyl of hydrogen, cyano group, halogen, a substituted or unsubstituted 1-6 carbon atom, any one in substituted or unsubstituted aryl and substituted or unsubstituted heteroaryl.
2. method according to claim 1, wherein, described hydrogen peroxide is aqueous hydrogen peroxide solution, and the massfraction of described aqueous hydrogen peroxide solution is 5%-30%.
3. method according to claim 2, wherein, the massfraction of described aqueous hydrogen peroxide solution is 10%-20%.
4. the method according to any one of claim 1-3, wherein, described alkaline condition is pH7.1-14, preferred 7.5-9.
5. method according to claim 1, wherein, described hypochlorite is the aqueous solution of hypochlorite, and the massfraction of described aqueous hypochlorite solution is 5%-15%.
6. method according to claim 1 or 5, wherein, described acidic conditions is pH1-6.9, preferred 3-5.
7. method according to claim 6, wherein, described hypochlorite is at least one in Losantin, clorox and potassium hypochlorite.
8. method according to claim 1, wherein, the mol ratio of the compound shown in formula (II) and oxygenant is 1:(1-5), preferred 1:(1-3).
9. method according to claim 1, wherein, it is 0-100 DEG C that the condition of described contact also comprises temperature of reaction, and preferred 20-80 DEG C, the reaction times is 3-10 hour, preferred 5-8 hour.
10. method according to claim 1, wherein, described oxidizing reaction is carried out in a solvent; Described solvent is at least one in water, aromatic hydrocarbons, the halohydrocarbon of a 1-6 carbon atom, the alcohol of a 1-4 carbon atom, the ether of a 2-6 carbon atom, the ester of a 2-6 carbon atom, N-Methyl pyrrolidone, dimethyl formamide, N,N-DIMETHYLACETAMIDE and methyl-sulphoxide.
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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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