CN104557464A - Tertiary alcohol compound and preparation method thereof - Google Patents
Tertiary alcohol compound and preparation method thereof Download PDFInfo
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- CN104557464A CN104557464A CN201310481955.9A CN201310481955A CN104557464A CN 104557464 A CN104557464 A CN 104557464A CN 201310481955 A CN201310481955 A CN 201310481955A CN 104557464 A CN104557464 A CN 104557464A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
- C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
- C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D207/33—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D207/333—Radicals substituted by oxygen or sulfur atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/04—1,2,3-Triazoles; Hydrogenated 1,2,3-triazoles
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- C07—ORGANIC CHEMISTRY
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- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/42—Singly bound oxygen atoms
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Abstract
The invention provides a tertiary alcohol compound and a preparation method thereof. The tertiary alcohol compound can be a compound shown in the structural formula (1) in the specification, or salt acceptable in agricultural chemicals and medical science, and is prepared through nucleophilic addition reaction of an aromatic (heterocyclic) ring benzyl Grignard reagent shown in the structural formula (III) in the specification and phenyl ethyl ketone shown in the structural formula (II) in the specification. The reactivity is excellent, the reaction can be performed at a room temperature, the reaction completion time is short, short aldol condensation by-products and reduction by-products are reduced greatly, an additive for the nucleophilic addition reaction is not needed, the reaction yield is high, the purification is easy, the tertiary alcohol compound with the purity about 95 percent can be obtained through simple extraction and concentration, and the obtained tertiary alcohol compound has wide application values in the organic synthetic methodology, agricultural chemicals, medicine and the like.
Description
Technical field
The present invention relates to a kind of alcohol compound, particularly relate to a kind of tertiary alcohols compound and preparation method thereof.
Background technology
The tertiary alcohol is that hydroxyl position has three substituently not have
αthe alcohol of-H.The nucleophilic addition formula of Grignard reagent to ketone prepare tertiary alcohols compound the most important, use one of method the most widely.This method not only raw material be easy to get, simple to operate, the carbochain of reactant can also be increased, therefore can be used for preparing the various tertiary alcohol.But traditional Grignard reagent to the shortcoming that the nucleophilic addition of ketone exists is: in nucleophilic addition process, usually along with the aldol condensation by product of substrate itself and the generation of reduzate, the yield of principal product is caused greatly to reduce.In order to stop the generation of these side reactions; people use excessive additive; especially inorganic metal salt additive, such as Imamoto group reports and uses excessive anhydrous chlorides of rase caesium as additive to promote that Grignard reagent is to reaction system (Imamoto, the T. of the efficient addition of ketone; Sugiura, Y.; Takiyama, N. Tetrahedron Lett. 1984,25,4233-4236), and for example Knochel group reports and uses LnCl
32LiCl facilitates the addition of Grignard reagent to ketone well, especially adds the LnCl of 30mol%
32LiCl is very effective to this reaction as additive.But, use anhydrous metal salt as additive, carry out activated carbonyl or form active higher transition state intermediate, reach and reduce the object that side reaction improves productive rate, there is defect: 1, additive is expensive, the easier moisture absorption, will weigh, be not suitable for suitability for industrialized production in glove box; 2, with metal-salt as additive, aftertreatment trouble is complicated, and easy remaining metal ions in product after aftertreatment, and it is unfriendly to environment that final metal ion remains in agricultural chemicals, or remains in medicine and reduce drug effect and have a great impact human health.
Tertiary alcohols compound is with a wide range of applications in methodology of organic synthesis and the product such as agricultural chemicals, medicine.Such as CN102976891A discloses a kind of asymmetric tertiary alcohol, has non-aromatic ring or the aromatic ring of monocycle or many rings, can be used as the raw material of the precision chemical such as functional high-polymer or the pharmaceuticals product such as photoresist etc.Because tertiary alcohols compound has very high using value, all there is active effect to the exploitation of all kinds of relevant agricultural chemicals and pharmaceutical prod, therefore, need the more tertiary alcohols compound of exploitation further to meet research and Production requirement.
Summary of the invention
The object of the invention is to overcome above-mentioned deficiency, provide a kind of novel tertiary alcohols compound, and the preparation method of this tertiary alcohols compound is simple, reaction conditions is gentle, product purity is high, yield is high, and environmentally friendly.
First aspect of the present invention is to provide a kind of tertiary alcohols compound, it is characterized in that, described tertiary alcohols compound is compound shown in structure formula I or the medically acceptable salt of its agricultural chemicals:
（Ⅰ）
Preferably, described tertiary alcohols compound comprises the cis-trans-isomer of compound shown in the optical isomer of compound shown in structure formula I or the medically acceptable salt of its agricultural chemicals or structure formula I or the medically acceptable salt of its agricultural chemicals.
In a kind of preferred embodiment of the tertiary alcohols compound described in the present invention first, Ar is the one in aromatic base, substituted aromatic base.
Wherein, aromatic base can be that also can contain one or more heteroatoms, described heteroatoms can be O, S, N, P, Si etc. not containing heteroatoms, is preferably O, S, N.
Further preferably, Ar is not containing substituting group or containing the one in one or more substituent phenyl, triazol radical, pyridyl, naphthyl, thiazolyl, pyrimidyl, furyl, thienyl, oxazolyl, quinolyl.
Still more preferably, Ar is the one in phenyl, triazol radical, pyridyl, thiazolyl, pyrimidyl, tetrahydrofuran base or its halides.
Preferably, the substituting group in described substituted aromatic base is 1-8, is more preferably 1-6, is more preferably 1-4, is more preferably 1-3, such as 2.
Substituting group in described substituted aromatic base be selected from halogen, itrile group, nitro, hydroxyl, methylamino-, dimethylamino, alkyl, alkoxyl group or haloalkyl one or more.
Alkyl is preferably C
1-20alkyl, is more preferably C
1-10alkyl, is more preferably C
1-8alkyl, be more preferably C
1-6alkyl, be more preferably C
1-4alkyl, such as methyl, ethyl, propyl group, sec.-propyl, butyl, the tertiary butyl etc.
Alkoxyl group is preferably C
1-20alkoxyl group, is more preferably C
1-10alkoxyl group, is more preferably C
1-8alkoxyl group, be more preferably C
1-6alkoxyl group, be more preferably C
1-4alkoxyl group, such as methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy, tert.-butoxy etc.
Haloalkyl is preferably C
1-20haloalkyl, is more preferably C
1-10haloalkyl, is more preferably C
1-8haloalkyl, be more preferably C
1-6haloalkyl, be more preferably C
1-4haloalkyl, such as halogenated methyl, halogenated ethyl, halopropyl, haloisopropyl, halogenated butyl, the halo tertiary butyl etc.
Haloalkyl can be part haloalkyl (such as unitary halo, binary halo or ternary halo etc.) or whole haloalkyl.Halo group can be I, Br, Cl, F etc.
In a kind of preferred embodiment of the tertiary alcohols compound described in the present invention first, R
1for H, halogen (such as I, Br, Cl, F etc.), itrile group, nitro, hydroxyl, methylamino-, dimethylamino, alkyl, alkoxyl group or haloalkyl, be more preferably halogen, alkoxyl group, alkyl or nitro.
Alkyl is preferably C
1-20alkyl, is more preferably C
1-10alkyl, is more preferably C
1-8alkyl, be more preferably C
1-6alkyl, be more preferably C
1-4alkyl, such as methyl, ethyl, propyl group, sec.-propyl, butyl, the tertiary butyl etc.
Alkoxyl group is preferably C
1-20alkoxyl group, is more preferably C
1-10alkoxyl group, is more preferably C
1-8alkoxyl group, be more preferably C
1-6alkoxyl group, be more preferably C
1-4alkoxyl group, such as methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy, tert.-butoxy etc.
Haloalkyl is preferably C
1-20haloalkyl, is more preferably C
1-10haloalkyl, is more preferably C
1-8haloalkyl, be more preferably C
1-6haloalkyl, be more preferably C
1-4haloalkyl, such as halogenated methyl, halogenated ethyl, halopropyl, haloisopropyl, halogenated butyl, the halo tertiary butyl etc.
Haloalkyl can be part haloalkyl (such as unitary halo, binary halo or ternary halo etc.) or whole haloalkyl.Halo group can be I, Br, Cl, F etc.
In a kind of preferred embodiment of the tertiary alcohols compound described in the present invention first, R
2for C
1-6alkyl (is more preferably C
1-4alkyl, such as methyl, ethyl, propyl group, sec.-propyl, butyl, the tertiary butyl etc.), allyl group, benzyl, C
1-4alkoxy-C
1-4alkyl (such as first alkoxy methyl, second alkoxyl group propyl group, the first alkoxyl group tertiary butyl etc.) or Ar, be more preferably C
1-6alkyl (is more preferably C
1-4alkyl, such as methyl, ethyl, propyl group, sec.-propyl, butyl, the tertiary butyl etc.) or C
1-4alkoxy-C
1-4alkyl (such as first alkoxy methyl, second alkoxyl group propyl group, the first alkoxyl group tertiary butyl etc.).
In a particularly preferred embodiment, in tertiary alcohols compound shown in structure formula I, Ar is triazol radical, R
1for halogen (such as I, Br, Cl, F etc.) or methoxyl group, R
2for the tertiary butyl or methyl.
Second aspect of the present invention is to provide a kind of preparation method of above-mentioned tertiary alcohols compound, and react tertiary alcohols compound shown in obtained structure formula I by Grignard reagent shown in carbonyl compound and structure formula III shown in structure formula II, reaction formula is as follows:
（Ⅱ） （Ⅲ） （Ⅰ）
Wherein, the X in structure formula III is Cl or Br.
Wherein, after shown in structure formula II, shown in carbonyl compound and structure formula III, Grignard reagent has reacted, hydrolysis, extraction, namely concentrated extract obtains tertiary alcohols compound shown in structure formula I.
Wherein, Grignard reagent shown in structure formula III is obtained by halogenide shown in structure formula IV and reactive magnesium:
（Ⅳ）。
The solvent that halogenide shown in structure formula IV and reactive magnesium use can be one or more in tetrahydrofuran (THF), ether, toluene.
Preferably, the concentration of described Grignard reagent is 0.1-10 mol/L, is more preferably 0.2-8 mol/L, is more preferably 0.5-6 mol/L, is more preferably 1-4 mol/L, is more preferably 1.5-3 mol/L.
Preferably, shown in structure formula II, shown in carbonyl compound and structure formula III, Grignard reagent temperature of reaction is 0-70 DEG C, is more preferably 10-60 DEG C, is more preferably 15-50 DEG C, is more preferably 20-40 DEG C, is more preferably 25-35 DEG C.
Preferably, shown in structure formula II, shown in carbonyl compound and structure formula III, the Grignard reagent reaction times is 1-4h, is more preferably 1.5-3.5h, is more preferably 2-3h.
The above-mentioned all respects of the present invention and each preferred embodiment can unrestricted arbitrary combination.
The present invention adopts virtue (mixing) ring benzyl position Grignard reagent (shown in structure formula III) to carry out nucleophilic addition with Propiophenone (shown in structure formula II), reactive behavior is good, at room temperature can react, the reaction deadline, short aldol condensation by product and reduction by product greatly reduce, without the need to adding additive to promote nucleophilic addition, reaction yield is high, and easy purifying, only need concentrate through simple extraction and can obtain the tertiary alcohols compound that purity is about 95%, gained tertiary alcohols compound is in methodology of organic synthesis, and agricultural chemicals, be with a wide range of applications in the products such as medicine.
Through biological activity test, the inhibit activities of tertiary alcohols structure provided by the present invention to wheat hypochnus and alternaria leaf spot of apple is more remarkable.
Embodiment
Referring to specific embodiment, the present invention is further described, to understand the present invention better.
embodiment 12-methyl isophthalic acid, the synthesis of 4-phenylbenzene-2-butanols
In 25ml tetrahydrofuran (THF), add 4-Phenyl 2 butanone (2 mmol), then add benzyl bromine Grignard reagent (2 mmol/ml, 1 ml), stir and reacted for 2 hours, add aqueous acetic acid, continue stirring 1 hour, add methylene dichloride and water extraction, merge organic phase, dry concentrating obtains product, yield 82%, purity 97%, 2-methyl isophthalic acid is accredited as, 4-phenylbenzene-2-butanols through infrared and nuclear-magnetism.
embodiment 2the synthesis of 4-(4-chloro-phenyl-)-1-(furans-2-base)-2-methyl 2-butanols
4-rubigan-2-butanone (2 mmol) is added in 25ml tetrahydrofuran (THF), add the Grignard reagent (2 mmol/ml, 1 ml) of brooethyl furans again, stir and reacted for 3 hours, add aqueous acetic acid, continue stirring 1 hour, add methylene dichloride and water extraction, merge organic phase, dry concentrating obtains product, yield 75%, purity 96%, is accredited as 4-(4-chloro-phenyl-)-1-(furans-2-base)-2-methyl 2-butanols through infrared and nuclear-magnetism.
embodiment 3the synthesis of 3-(2-p-methoxy-phenyl)-1-phenyl-1-(1H-pyrroles-2-base)-1-propyl alcohol:
3-(2-p-methoxy-phenyl)-1-phenyl-1-acetone (2 mmol) is added in 25ml tetrahydrofuran (THF), add Grignard reagent (2 mmol/ml of brooethyl pyrroles again, 1 ml), stir and reacted for 2 hours, add aqueous acetic acid, continue stirring 1 hour, add methylene dichloride and water extraction, merge organic phase, dry concentrating obtains product, yield 71%, purity 94%, is accredited as 3-(2-p-methoxy-phenyl)-1-phenyl-1-(1H-pyrroles-2-base)-1-propyl alcohol through infrared and nuclear-magnetism.
embodiment 4the synthesis of 4,4-dimethyl-1-(p-methylphenyl)-3-(1H-1,2,3-triazol-1-yl)-3-amylalcohol:
In 25ml tetrahydrofuran (THF), add 4,4-dimethyl-1-(p-methylphenyl)-propione (2.0 mmol), then add Grignard reagent (2.0 mmol/ml of brooethyl triazole, 1.0 ml), stir and reacted for 2 hours, add aqueous acetic acid, continue stirring 1 hour, add methylene dichloride and water extraction, merge organic phase, dry concentrating obtains product, yield 74%, purity 95%, is accredited as 4,4-dimethyl-1-(p-methylphenyl)-3-(1 through infrared and nuclear-magnetism
h-1,2,3-triazoles-1-base)-3-amylalcohol.
embodiment 5above-mentioned Grignard reagent and reactive ketone, the synthetic method of synthesis tertiary alcohols structural compounds is equally applicable to synthesis (the 3-((1H-1 of tebuconazole, 2,4-triazole-1-base) methyl)-1-(4-chloro-phenyl-)-4,4-dimethyl-3-amylalcohol)
In 25ml tetrahydrofuran (THF), add 1-(4-chloro-phenyl-)-4,4-dimethyl-propione (2.0 mmol), then add
nthe Grignard reagent (2.0 mmol/ml, 1.0 ml) of-brooethyl triazole, stirs and has reacted for 2 hours, add aqueous acetic acid, continue stirring 1 hour, add methylene dichloride and water extraction, merge organic phase, dry concentrating obtains product, yield 78%, purity 96%, 3-((1H-1 is accredited as through infrared and nuclear-magnetism, 2,4-triazole-1-base) methyl)-1-(4-chloro-phenyl-)-4,4-dimethyl-3-amylalcohol.
Prepare compound as described in Table 1 according to the method similar with embodiment 1-5, and confirm structure through infrared and nuclear-magnetism qualification.
（Ⅱ） （Ⅲ） （Ⅰ）
Table 1, compound structure and biological activity table look-up
R in table 1
1numeral before group in is corresponding with the location label in structure formula I, such as R
1for 2-Cl, corresponding tertiary alcohols compound is:
。
Be described in detail specific embodiments of the invention above, but it is just as example, the present invention is not restricted to specific embodiment described above.To those skilled in the art, any equivalent modifications that the present invention is carried out and substituting also all among category of the present invention.Therefore, equalization conversion done without departing from the spirit and scope of the invention and amendment, all should contain within the scope of the invention.
Claims (10)
1. a tertiary alcohols compound, is characterized in that, described tertiary alcohols compound is compound shown in structure formula I or the medically acceptable salt of its agricultural chemicals:
（Ⅰ）
Wherein, Ar group is the one in aromatic base, substituted aromatic base; Substituting group in described substituted aromatic base be selected from halogen, itrile group, nitro, hydroxyl, methylamino-, dimethylamino, alkyl, alkoxyl group or haloalkyl one or more;
R
1for H, halogen, itrile group, nitro, hydroxyl, methylamino-, dimethylamino, alkyl, alkoxyl group or haloalkyl;
R
2for C
1-6alkyl, allyl group, benzyl, C
1-4alkoxy-C
1-4alkyl or Ar group.
2. tertiary alcohols compound according to claim 1, is characterized in that, described tertiary alcohols compound comprises the optical isomer of compound shown in structure formula I or the medically acceptable salt of its agricultural chemicals.
3. tertiary alcohols compound according to claim 1 and 2, is characterized in that, described tertiary alcohols compound comprises the cis-trans-isomer of compound shown in structure formula I or the medically acceptable salt of its agricultural chemicals.
4. tertiary alcohols compound according to claim 1, it is characterized in that, described Ar is not containing substituting group or containing the one in one or more substituent phenyl, triazol radical, pyridyl, naphthyl, thiazolyl, pyrimidyl, furyl, thienyl, oxazolyl, quinolyl.
5. tertiary alcohols compound according to claim 2, is characterized in that, described Ar is the one in phenyl, triazol radical, pyridyl, thiazolyl, pyrimidyl, tetrahydrofuran base or its halides.
6. tertiary alcohols compound according to claim 1, is characterized in that, R
1for halogen, alkoxyl group, alkyl or nitro.
7. tertiary alcohols compound according to claim 1, is characterized in that, R
2for C
1-6alkyl or C
1-4alkoxy-C
1-4alkyl.
8. the preparation method of a tertiary alcohols compound according to claim 1, it is characterized in that, reacted by Grignard reagent shown in carbonyl compound and structure formula III shown in structure formula II, be hydrolyzed tertiary alcohols compound shown in obtained structure formula I, reaction formula is as follows:
（Ⅱ） （Ⅲ） （Ⅰ）
Wherein, the X in structure formula III is Cl or Br.
9. preparation method according to claim 8, is characterized in that, the concentration of described Grignard reagent is 0.1-10mol/L.
10. preparation method according to claim 8, is characterized in that, shown in structure formula II, Grignard reagent temperature of reaction shown in carbonyl compound and structure formula III is 0-70 DEG C.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106117009A (en) * | 2016-06-13 | 2016-11-16 | 湖北华世通生物医药科技有限公司 | The preparation method of tertiary alcohols compound |
| CN106588791A (en) * | 2016-11-01 | 2017-04-26 | 盐城辉煌化工有限公司 | Novel technology for synthesizing bactericide tebuconazole without solvent |
| CN114409600A (en) * | 2022-01-19 | 2022-04-29 | 武汉回盛生物科技股份有限公司 | Synthetic method of enilconazole |
| CN117924197A (en) * | 2024-03-21 | 2024-04-26 | 山东百农思达生物科技有限公司 | High-purity synthesis method of tebuconazole |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106117009A (en) * | 2016-06-13 | 2016-11-16 | 湖北华世通生物医药科技有限公司 | The preparation method of tertiary alcohols compound |
| CN106588791A (en) * | 2016-11-01 | 2017-04-26 | 盐城辉煌化工有限公司 | Novel technology for synthesizing bactericide tebuconazole without solvent |
| CN114409600A (en) * | 2022-01-19 | 2022-04-29 | 武汉回盛生物科技股份有限公司 | Synthetic method of enilconazole |
| CN117924197A (en) * | 2024-03-21 | 2024-04-26 | 山东百农思达生物科技有限公司 | High-purity synthesis method of tebuconazole |
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| CN104557464B (en) | 2019-05-07 |
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