CN102452978A - 2-chloro-substituted or unsubstituted aliphatic hydrocarbyl-oxy pyridine and preparation method thereof - Google Patents
2-chloro-substituted or unsubstituted aliphatic hydrocarbyl-oxy pyridine and preparation method thereof Download PDFInfo
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- CN102452978A CN102452978A CN2010105262604A CN201010526260A CN102452978A CN 102452978 A CN102452978 A CN 102452978A CN 2010105262604 A CN2010105262604 A CN 2010105262604A CN 201010526260 A CN201010526260 A CN 201010526260A CN 102452978 A CN102452978 A CN 102452978A
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- 0 *Oc1cccc(Cl)n1 Chemical compound *Oc1cccc(Cl)n1 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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
- C07D213/62—Oxygen or sulfur atoms
- C07D213/63—One oxygen atom
- C07D213/64—One oxygen atom attached in position 2 or 6
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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
- C07D213/62—Oxygen or sulfur atoms
- C07D213/63—One oxygen atom
- C07D213/64—One oxygen atom attached in position 2 or 6
- C07D213/643—2-Phenoxypyridines; Derivatives thereof
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Abstract
The invention relates to a 2-chloro-substituted or unsubstituted aliphatic hydrocarbyl-oxy pyridine compound shown as a formula I and a preparation method thereof, wherein R is an unsubstituted or substituted aliphatic hydrocarbyl, preferably, an unsubstituted or substituted low-grade alkyl or an unsubstituted or substituted phenyl. The preparation method provided by the invention comprises that substitution reaction is carried out between 2,6-dichloropyridine and [RO<->]aM<a+> to generate a compound shown as the formula I, wherein M is an alkali metal or an alkaline earth metal, and a is 1 or 2.
Description
Technical field
The present invention relates to the 2-chloro-and replace or do not replace aliphatic hydrocrbon oxygen yl pyridines and preparation method thereof.
Background technology
3,5,6-trichloropyridine-2-phenol (or 3,5,6-trichloropyridine-2-alcohol) and 3,5,6-trichloropyridine-2-phenates (or 3,5,6-trichloropyridine-2-alkoxide) be the key intermediate of synthetic pesticide Chlorpyrifos 94 and Multiple Pesticides.3,5,6-trichloropyridine-2-phenol or 3,5, the synthesis method of 6-trichloropyridine-2-phenates is divided into two big types: cyclization method and pyridine method.In the pyridine method, mainly comprise the pyridine chlorination hydrolysis:
Pyridine chlorination hydrolysis route
In the method for pyridine chlorination hydrolysis chlorination hydrolysis, the gas phase chlorination of pyridine need be carried out under 340 ℃ high temperature, and high for the requirement of equipment and operation, difficulty is big.
In order to overcome existing pyridine route synthetic 3; 5; 6-trichloropyridine-2-phenol and 3,5,6-trichloropyridine-2-phenates cost is high, to shortcomings such as equipment requirements height, feature of environmental protection differences; The contriver is surprised to find that through the replacement of 2-chloro-or does not replace aliphatic hydrocrbon oxygen yl pyridines through research and synthesizes 3; 5,6-trichloropyridine-2-phenol and 3,5; 6-trichloropyridine-2-phenates has overcome above-mentioned all deficiencies of prior art.
Summary of the invention
First aspect of the present invention provides the 2-chloro-that new usefulness formula I representes and replaces or do not replace aliphatic hydrocrbon oxygen yl pyridines compound,
Formula I
Wherein R is not substituted or substituted aliphatic hydrocarbyl, and preferred R is not for being substituted or substituted low alkyl group, not being substituted or substituted phenyl.
The present invention is a lower alkyl group is unsubstituted C1-C8 alkyl, such as methyl, ethyl, propyl, isopropyl
1 - butyl
2 - butyl
2 - methyl-1 - propyl
tert-butyl
1 - amyl
2 - pentyl
3 - amyl
2 - methyl-1 - butyl
3 - methyl-1 - butyl
2 - methyl-2 - butyl
3 - methyl - D base
2,2 - dimethyl-1 - propyl
1 - hexyl
2 - hexyl
3 - hexyl
2 - methyl-1 - amyl
2 - methyl-2 - pentyl
2 - methyl-3 - amyl
4 - methyl-2 - pentyl
4 - methyl-1 - amyl
3 - methyl-1 - amyl
3 - methyl-2 - pentyl
3 - methyl-3 - amyl
2,3 - dimethyl -1 - butyl
2,3 - dimethyl-2 - butyl
2,2 - dimethyl-1 - butyl
and so on.
The alkyl of the preferred C3-C6 of unsubstituted low alkyl group according to the invention; For example; Propyl group; Sec.-propyl; The 1-butyl; The 2-butyl; 2-methyl isophthalic acid-propyl group; The tertiary butyl; The 1-amyl group; The 2-amyl group; The 3-amyl group; The 2-methyl-1-butene base; 3-methyl isophthalic acid-butyl; 2-methyl-2-butyl; 3-methyl-2-butyl; 2,2-dimethyl-1-propyl group; The 1-hexyl; The 2-hexyl; The 3-hexyl; 2-methyl-1-pentene base; 2-methyl-2-amyl group; 2-methyl-3-amyl group; 4-methyl-2-amyl group; 4-methyl-1-pentene base; 3-methyl-1-pentene base; 3-methyl-2-amyl group; 3-methyl-3-amyl group.
Substituted low alkyl group according to the invention is substituted C1-C8 alkyl; Preferably by the alkyl of halogen atom, alkoxyl group, carboxyl or the substituted C2-C6 of nitro; Further preferably by chlorine atom, the substituted C2-C6 alkyl of methoxyl group, wherein the chlorine atom can be one or more, for example; Chloromethyl, dichloromethyl, chloroethyl, 1; 1-Dichloroethyl, 1,2-Dichloroethyl, chloropropyl, 1,2-two chloropropyls, 1; 1,1-three chloropropyls, methoxyl group etc.
Substituted phenyl according to the invention is by halogen atom, alkoxyl group, carboxyl or nitro substituted-phenyl, and preferably by chlorine atom or methoxyl group substituted-phenyl, wherein the chlorine atom can be one or more, for example, and 4-chloro-phenyl-, 4-p-methoxy-phenyl.
Second aspect of the present invention provides the synthesis method (synthetic route one) that 2-chloro-that new usefulness formula I representes replaces or do not replace aliphatic hydrocrbon oxygen yl pyridines compound,
Formula I
Wherein the R group definition as above,
Said method comprises:
2,6-dichloropyridine and [RO
-]
aM
A+Substitution reaction production I compound takes place, and wherein said R group definition as above; M is basic metal or alkaline-earth metal, preferred Na, K, Mg or Ca, further preferred Na or K, first-selected Na.Wherein a is 1 or 2.2,6-dichloropyridine and [RO
-]
aM
A+Mol ratio smaller or equal to 1, be preferably 1: 1 to 1: 10, more preferably 1: 1 to 1: 5.
Said [RO
-]
aM
A+Be to be prepared from ROH and basic metal, alkalimetal hydride or alkaline earth metal hydride.Preferred Na of said basic metal or K, first-selected Na; The preferred NaH of said alkalimetal hydride or alkaline earth metal hydride, KH or CaH2, first-selected NaH.Wherein the mol ratio of ROH and basic metal, alkalimetal hydride or alkaline earth metal hydride is looked [RO
-]
aM
A+Consumption and reaction solvent demand and decide, basic metal, alkalimetal hydride or alkaline earth metal hydride and 2, the mol ratio of 6-dichloropyridine is generally more than or equal to 1.
Said [RO
-]
aM
A+Also can generate by ROH and the reaction of other organic basess, for example, metal alkylide lithium compound, amido lithium compound or hexamethyldisilazane lithium, preferred butyllithium, phenyl lithium, lithium diisopropyl amido (LDA), LiHMDS.Wherein the mol ratio of ROH and said organic bases is looked [RO
-]
aM
A+Consumption and reaction solvent demand and decide, said organic bases and 2, the mol ratio of 6-dichloropyridine is generally more than or equal to 1.
Also can be by 2,6-dichloropyridine and basic metal, alkalimetal hydride, alkaline earth metal hydride or organic bases material and alcohol roh adopt " one kettle way " preparation formula I compound of the present invention, and wherein the R group definition is as above.In this synthesis method, 2, the mol ratio of 6-dichloropyridine, said alkali and ROH is selected identical with stepwise reaction.
Can with an organic solvent for example, be selected from single solvent or mixed solvent among Fatty Alcohol(C12-C14 and C12-C18), alkane, halogenated alkane, aromatic hydrocarbons, halogenated aryl hydrocarbon, ether, ester, DMSO, the DMF in the synthetic method of formula I compound of the present invention.Be preferably selected from methyl alcohol; Ethanol; Propyl alcohol; Virahol; The 1-butanols; The 2-butanols; 2-methyl isophthalic acid-propyl alcohol; The trimethyl carbinol; The 1-amylalcohol; The 2-amylalcohol; The 3-amylalcohol; 2-methyl isophthalic acid-butanols; 3-methyl isophthalic acid-butanols; 2-methyl-2-butanols; 3-methyl-2-butanols; 2,2-dimethyl-1-propyl alcohol; The 1-hexanol; The 2-hexanol; The 3-hexanol; 2-methyl-1-pentene alcohol; 2-methyl-2-amylalcohol; 2-methyl-3-amylalcohol; 4-methyl-2-amylalcohol; 4-methyl-1-pentene alcohol; 3-methyl-1-pentene alcohol; 3-methyl-2-amylalcohol; 3-methyl-3-amyl group; Normal hexane; Trichloromethane; Tetracol phenixin; Sherwood oil; Ethyl acetate; Benzene; Toluene; DMSO; Single solvent among the DMF or mixed solvent.More preferably 1-butanols, 2-butanols, 2-methyl isophthalic acid-propyl alcohol, the trimethyl carbinol, 1-amylalcohol, 2-amylalcohol, 3-amylalcohol, 2-methyl-1-butene alcohol, 3-methyl isophthalic acid-butanols, 2-methyl-2-butanols, 3-methyl-2-butanols, 2, single solvent or mixed solvent in 2-dimethyl-1-propyl alcohol, 1-hexanol, 2-hexanol, 3-hexanol, 2-methyl-1-pentene alcohol, 2-methyl-2-amylalcohol, 2-methyl-3-amylalcohol, 4-methyl-2-amylalcohol, 4-methyl-1-pentene alcohol, 3-methyl-1-pentene alcohol, 3-methyl-2-amylalcohol, the toluene.First-selected through strengthening the amount of above-mentioned alcohol, as organic solvent, without other organic solvents, wherein the R group definition as above with alcohol roh.
The present invention is by 2,6-dichloropyridine and [RO
-]
aM
A+Temperature of reaction in the synthetic compound of formula i method is 0-150 ℃, preferred 20-80 ℃, and first-selected 40-80 ℃.
Formula I compound of the present invention can also prepare through following synthesis method two:
2, the 6-dichloropyridine with under alkaline matter with ROH generation condensation reaction production I compound, wherein the R group definition is as above.Used alkaline matter is selected from one or more in oxyhydroxide, carbonate, supercarbonate, ammoniacal liquor and the organic amine of basic metal or alkaline-earth metal in this reaction; Preferred said alkaline matter is selected from and is in NaOH, KOH, yellow soda ash and the sodium hydrogencarbonate one or more, first-selected NaOH.
Reaction raw materials ratio in the synthetic method two of formula I compound of the present invention: 2, the mol ratio of 6-dichloropyridine and said alkaline matter is 1: 20, wherein preferred 1: 1-10, first-selected 1: 1-5; 2, the mol ratio of 6-dichloropyridine and ROH can be selected according to the amount of the required solvent of reaction by those skilled in the art, generally is at least 1: 1.
Solvent is selected from organic solvent in the synthetic method two of formula I compound of the present invention.For example, be selected from single solvent or mixed solvent among Fatty Alcohol(C12-C14 and C12-C18), alkane, halogenated alkane, aromatic hydrocarbons, halogenated aryl hydrocarbon, ether, ester, DMSO, the DMF.Be preferably selected from methyl alcohol; Ethanol; Propyl alcohol; Virahol; The 1-butanols; The 2-butanols; 2-methyl isophthalic acid-propyl alcohol; The trimethyl carbinol; The 1-amylalcohol; The 2-amylalcohol; The 3-amylalcohol; 2-methyl-1-butene alcohol; 3-methyl isophthalic acid-butanols; 2-methyl-2-butanols; 3-methyl-2-butanols; 2,2-dimethyl-1-propyl alcohol; The 1-hexanol; The 2-hexanol; The 3-hexanol; 2-methyl-1-pentene alcohol; 2-methyl-2-amylalcohol; 2-methyl-3-amylalcohol; 4-methyl-2-amylalcohol; 4-methyl-1-pentene alcohol; 3-methyl-1-pentene alcohol; 3-methyl-2-amylalcohol; 3-methyl-3-amyl group; Normal hexane; Trichloromethane; Tetracol phenixin; Sherwood oil; Ethyl acetate; Benzene; Toluene; DMSO; Single solvent among the DMF or mixed solvent.More preferably 1-butanols, 2-butanols, 2-methyl isophthalic acid-propyl alcohol, the trimethyl carbinol, 1-amylalcohol, 2-amylalcohol, 3-amylalcohol, 2-methyl-1-butene alcohol, 3-methyl isophthalic acid-butanols, 2-methyl-2-butanols, 3-methyl-2-butanols, 2, single solvent or mixed solvent in 2-dimethyl-1-propyl alcohol, 1-hexanol, 2-hexanol, 3-hexanol, 2-methyl-1-pentene alcohol, 2-methyl-2-amylalcohol, 2-methyl-3-amylalcohol, 4-methyl-2-amylalcohol, 4-methyl-1-pentene alcohol, 3-methyl-1-pentene alcohol, 3-methyl-2-amylalcohol, the toluene.First-selected through strengthening the amount of above-mentioned alcohol, as organic solvent, without other organic solvents, wherein the R group definition as above with alcohol roh.
The temperature of reaction of the synthetic method two of formula I compound of the present invention is 0-150 ℃, preferred 40-120 ℃, and first-selected 50-80 ℃.Be two kinds of synthetic routes of formula I of the present invention as follows:
A third aspect of the present invention provides the compound 3,5 of following formula I, 6-trichloropyridine-2-phenates or 3,5, and the purposes in 6-trichloropyridine-2-phenol,
Formula I
Wherein the R group definition as above.
A fourth aspect of the present invention provides preparation 3,5,6-trichloropyridine-2-phenates or 3,5, the method for 6-trichloropyridine-2-phenol.
According to the invention synthetic 3,5,6-trichloropyridine-2-phenates or 3,5, the synthetic route of 6-trichloropyridine-2-phenol is:
In the said synthesis route 3,5,6-trichloropyridine-2-phenates can change 3,5 into according to this area ordinary method as required, 6-trichloropyridine-2-phenol.
Said method reactions step comprises:
(1) by pyridine or 2-chloro-pyridine according to US Patent No. 5,696,269 or US5468864 in method preparation 2, the 6-dichloropyridine;
(2) by 2 of preparation in the step (1), the 6-dichloropyridine prepares the compound of formula I of the present invention;
(3) obtain 6-chloropyridine-2-phenol by gained formula I compound in the step (2) through acid treatment;
(4) obtain 6-chloropyridine-2-phenates of formula II through alkaline purification by gained 6-chloropyridine in the step (3)-2-phenol;
(5) the 6-chloropyridine-2-phenates by gained formula II in the step (4) obtains 3,5,6-trichloropyridine-2-phenates through the chlorination reagent processing.
In the wherein above-mentioned reactions step (1) 2, the 6-dichloropyridine also can be purchased.
In the above-mentioned reactions step (2), formula I compound of the present invention prepares according to method described in the second aspect present invention.
Acid comprises organic acid or mineral acid described in the above-mentioned reactions step (3), for example, and sulfuric acid, nitric acid, hydrochloric acid, wherein preferred hydrochloric acid.Those skilled in the art can adjust the concentration and the consumption of said acid as required, if in reaching with the purpose of pH value.The preferred 0.1N-12N of concentration of acid, more preferably 1N-10N.Reacting solution pH value is adjusted between the 0-5, wherein preferred 1-4.
Described in the above-mentioned reactions step (4) in this reaction of alkali used alkaline matter comprise oxyhydroxide, carbonate, supercarbonate, ammoniacal liquor, the organic amine of basic metal or alkaline-earth metal; Preferred said alkaline matter is NaOH, KOH, yellow soda ash, sodium hydrogencarbonate, first-selected NaOH.The concentration of said alkali is 1-90% (weightmeasurement ratio), preferred 10-50% (weightmeasurement ratio).Reacting solution pH value is adjusted to 8-12, preferred 9-10.Temperature of reaction is 0-150 ℃, preferred 15-80 ℃, and more preferably 25-50 ℃.
In the above-mentioned reactions step (5); Said chlorination reagent comprises the material that can produce Cl positive ion, Cl radical or chlorine; For example; Be selected from chlorine, N-chloro-succinimide, 1; 3-two chloro-5; In 5-dimethyl beta-lactam, trichloroisocyanuric acid, hypochlorite, oxymuriate, chlorite, the perchlorate one or more, preferred clorox or potassium hypochlorite, preferred especially Javelle water.
In the above-mentioned reactions step (5), 2, the mol ratio of 6-dichloropyridine chlorine element in chlorination reagent was at least 1: 2, and preferred 1: 2-100, preferred especially 1: 2-5.
In the step of the present invention (5), temperature of reaction is 0-150 ℃, preferred 20-100 ℃, and preferred 25-50 ℃ especially.
It is in order to strengthen chlorating reactive behavior and control chlorating position on the pyridine ring that formation 6-chloropyridine-2-phenates carries out the chlorating purpose again.Wherein the 6-chloropyridine-the 2-phenates can be that metal-salt is suc as formula the II compound in the step (5).
Wherein, M is basic metal, alkaline-earth metal, preferred Na, K, Mg or Ca, further preferred Na or K, first-selected Na.Wherein a is 1 or 2.M can be metals such as M=Na, K, Li, Ca, Mg, Cs, Fe, Cu also, and a is the valence mumber of metal ion.
In the above-mentioned reactions step (5), M also can be organic ammonium ion or an ammonium ion in the following formula.Wherein R1, R2, R3 are respectively H, alkyl or aromatic base etc.For example, R1=R2=R3=H, R1=R2=R3=Et.
The present invention 3; 5; Solvent is any solvent of reacting of not participating in 6-trichloropyridine-2-phenates synthesis method; Be selected from alcohol, DMSO, DMF, the water isopolarity solvent one or more; In particular methanol, ethanol, Virahol, butanols, amylalcohol, hexanol, the water one or more, special preferably water is as solvent.
Said synthetic 3,5,6-trichloropyridine-2-phenates or 3,5, the synthetic of the intermediate formula II of 6-trichloropyridine-2-phenol or II-a can carry out according to this area usual way.By 6-chloropyridine-2-phenol and alkali reaction production II compound.
Wherein, M is basic metal, alkaline-earth metal, preferred Na, K, Mg or Ca, further preferred Na or K, first-selected Na.Wherein a is 1 or 2.M also can be organic ammonium ion or ammonium ion metal.Alkali described in this reaction comprises oxyhydroxide, carbonate, supercarbonate, ammoniacal liquor, the organic amine of basic metal or alkaline-earth metal, and preferred said alkaline matter is NaOH, KOH, yellow soda ash, sodium hydrogencarbonate, ammonia, triethylamine or aniline, preferred especially NaOH.
In addition; Alkali described in this reaction can also be alkalimetal hydride, alkaline earth metal hydride, metal alkylide lithium compound, amido lithium compound or six alkyl, two silicon amido lithiums; Preferred NaH, KH, CaH2, butyllithium, phenyl lithium, lithium diisopropyl amido (LDA), LiHMDSNaH, preferred especially NaH.
This route also can be accomplished through one kettle way, and promptly from 2, the 6-dichloropyridine begins via formula I compound, 6-chloropyridine-2-phenol, formula II compound directly to be synthesized to 3,5,6-trichloropyridine-2-phenates without separation.Reaction conditions is identical with the method for fractional steps.
A fifth aspect of the present invention provides the purposes of the compound agricultural chemicals Chlorpyrifos 94 of formula I of the present invention.
With concrete embodiment all respects of the present invention are described below.But those skilled in the art are to be understood that the present invention is not limited to the technical scheme of these specific embodiments.
Embodiment
Embodiment 1
2,6-dichloropyridine synthetic
According to US Patent No. 5,696, instance 1,4 or 5 method are raw material by pyridine, tetracol phenixin, chlorine in 269, with (trichloromethyl) sulfone as initiator, at 250 ℃ of Synthetic 2s at room temperature, 6-dichloropyridine.
Embodiment 2
2,6-chloropyridine synthetic
According to the method for embodiment 4 in the US Patent No. 5468864, be raw material with 2-chloropyridine, chlorine, add the trapping agent of lime carbonate as hydrogenchloride, under UV-irradiation, under 98-120 ℃, react, obtain 2, the 6-chloropyridine.
Embodiment 3
Synthetic (the method A) of 2-chloro-6-methoxypyridine
Under nitrogen environment, the methyl alcohol that drops into 130mmol in the there-necked flask of 150ml exsiccant toluene is housed to one, add the sodium Metal 99.5 of 130mmol then, reaction solution slowly heats until backflow then.Reflux after 24 hours, be cooled to room temperature, add 2 of 100mmol, the 6-dichloropyridine in batches.Then, be warmed up to backflow, and refluxed 24 hours.Reduce to room temperature, add 120ml water behind the evaporate to dryness, extract (60mlx3) with ethyl acetate/petroleum ether (1: 1), then extraction liquid is merged, use the saturated common salt water washing, drying is filtered, and filtrating gets product through column chromatography for separation after concentrating.Yield 63%.m/z：143。
Embodiment 4
Synthetic (the method B) of 2-chloro-6-methoxypyridine
Under nitrogen environment, to be equipped with in the 150ml exsiccant methyl alcohol there-necked flask to one and to drop into the 150mmol sodium Metal 99.5, oil bath is elevated to 100 ℃ gradually, after 16 hours, is cooled to room temperature.Add 2 of 100mmol, the 6-dichloropyridine in batches.Then, oil bath is elevated to 100 ℃ gradually, reacts after 18 hours.Reduce to room temperature, add 120ml water behind the evaporate to dryness, extract (60mlx3) with ethyl acetate/petroleum ether (1: 1), then extraction liquid is merged, use the saturated common salt water washing, drying is filtered, and filtrating gets product through column chromatography for separation after concentrating.Yield 65%.m/z：143。
Embodiment 5
Synthetic (the method C) of 2-chloro-6-methoxypyridine
150ml exsiccant methyl alcohol and 100mmol 2 are housed to one, drop into Na 120mmol in the there-necked flask of 6-dichloropyridine, fully stir, temperature remains on about 50 ℃, reacts 8 hours.Then, oil bath is being warming up to 100 ℃, was reacting 20 hours.Reduce to room temperature, add 120ml water behind the evaporate to dryness, extract (60mlx3) with ethyl acetate/petroleum ether (1: 1), then extraction liquid is merged, use the saturated common salt water washing, drying is filtered, and filtrating gets product through column chromatography for separation after concentrating.Yield 58%.m/z：143。
Embodiment 6
Synthetic (the method D) of 2-chloro-6-methoxypyridine
, the round-bottomed flask of reflux adds 2 of 100mmol in being housed, the 6-dichloropyridine, and the NaOH of 450mmol and 200ml anhydrous methanol, the heated and stirred reaction was cooled off after 16 hours.Add 120ml water behind the evaporate to dryness, extract (60mlx3) with ethyl acetate/petroleum ether (1: 1), then extraction liquid is merged, use the saturated common salt water washing, drying is filtered, and filtrating gets product through column chromatography for separation after concentrating.Yield 66%.
m/z：143。
Embodiment 7
Synthetic (the method E) of 2-chloro-6-methoxypyridine
, the round-bottomed flask of reflux adds 2 of 100mmol in being housed, the 6-dichloropyridine, and the NaOH of 450mmol, 150ml anhydrous methanol and 50ml tetrahydrofuran (THF), the heated and stirred reaction was cooled off after 19 hours.Add 120ml water behind the evaporate to dryness, extract (60mlx3) with ethyl acetate/petroleum ether (1: 1), then extraction liquid is merged, use the saturated common salt water washing, drying is filtered, and filtrating gets product through column chromatography for separation after concentrating.Yield 67%.。Yield: 58%; M/z:143.
Embodiment 8
Synthesizing of 2-chloro-6-ethoxy pyridine
Method with embodiment 3, embodiment 4, embodiment 5, embodiment 6 or embodiment 7 adopts similar reaction conditions, and wherein methyl alcohol is replaced with the ethanol with the methyl alcohol equimolar amount.Yield: 67%; M/z:157.
Embodiment 9
Synthesizing of 2-chloro-6-(1-propoxy-) pyridine
Method with embodiment 3, embodiment 4, embodiment 5, embodiment 6 or embodiment 7 adopts similar reaction conditions, and wherein methyl alcohol is replaced with the 1-propyl alcohol with the methyl alcohol equimolar amount.Yield: 67%; M/z:171.
Embodiment 10
Synthesizing of 2-chloro-6-isopropoxy pyridine
Method with embodiment 3, embodiment 4, embodiment 5, embodiment 6 or embodiment 7 adopts similar reaction conditions, and wherein methyl alcohol is replaced with the Virahol with the methyl alcohol equimolar amount.Yield: 55%.m/z：171；1H?NMR(300MHz，CDCl3) 1.35[d，J(H，H)＝6.1Hz，6H]，5.32[m，J(H，H)＝6.1，1H]，6.57[d，J＝7.8Hz，1H]，6.88[d，J(H，H)＝7.5Hz，1H]，7.51[dd，J(H，H)＝7.8Hz，7.5Hz，1H]ppm。
Embodiment 11
Synthesizing of 2-chloro-6-(1-butoxy) pyridine
Method with embodiment 3, embodiment 4, embodiment 5, embodiment 6 or embodiment 7 adopts similar reaction conditions, and wherein methyl alcohol is replaced with the 1-butanols with the methyl alcohol equimolar amount.Yield: 67%; M/z:185.
Embodiment 12
Synthesizing of 2-chloro-6-(2-butoxy) pyridine
Method with embodiment 3, embodiment 4, embodiment 5, embodiment 6 or embodiment 7 adopts similar reaction conditions, and wherein methyl alcohol is replaced with the 2-butanols with the methyl alcohol equimolar amount.Yield: 72%; M/z:185.
Embodiment 13
Synthesizing of 2-chloro-6-(2-methyl isophthalic acid-propoxy-) pyridine
Method with embodiment 3, embodiment 4, embodiment 5, embodiment 6 or embodiment 7 adopts similar reaction conditions, and wherein methyl alcohol is replaced with the 2-methyl isophthalic acid-propyl alcohol with the methyl alcohol equimolar amount.Yield: 55%; M/z:185.
Embodiment 14
Synthesizing of 2-chloro-6-tert.-butoxy pyridine
Method with embodiment 3, embodiment 4, embodiment 5, embodiment 6 or embodiment 7 adopts similar reaction conditions, and wherein methyl alcohol is replaced with the 2-chloro-6-trimethyl carbinol with the methyl alcohol equimolar amount.Yield: 66%; M/z:185.
Embodiment 15
Synthesizing of 2-chloro-6-(1-pentyloxy) pyridine
Method with embodiment 3, embodiment 4, embodiment 5, embodiment 6 or embodiment 7 adopts similar reaction conditions, and wherein methyl alcohol is replaced with the 1-amylalcohol with the methyl alcohol equimolar amount.Yield: 72%; M/z:199.
Embodiment 16
Synthesizing of 2-chloro-6-(2-pentyloxy) pyridine
Method with embodiment 3, embodiment 4, embodiment 5, embodiment 6 or embodiment 7 adopts similar reaction conditions, and wherein methyl alcohol is replaced with the 2-amylalcohol with the methyl alcohol equimolar amount.Yield: 73%; M/z:199.
Embodiment 17
Synthesizing of 2-chloro-6-(3-pentyloxy) pyridine
Method with embodiment 3, embodiment 4, embodiment 5, embodiment 6 or embodiment 7 adopts similar reaction conditions, and wherein methyl alcohol is replaced with the 3-amylalcohol with the methyl alcohol equimolar amount.Yield: 66%; M/z:199.
Embodiment 18
Synthesizing of 2-chloro-6-(2-methyl-1-butene oxygen base) pyridine
Method with embodiment 3, embodiment 4, embodiment 5, embodiment 6 or embodiment 7 adopts similar reaction conditions, and wherein methyl alcohol is replaced with the 2-methyl-1-butene alcohol with the methyl alcohol equimolar amount.Yield: 63%; M/z:199.
Embodiment 19
Synthesizing of 2-chloro-6-(3-methyl isophthalic acid-butoxy) pyridine
Method with embodiment 3, embodiment 4, embodiment 5, embodiment 6 or embodiment 7 adopts similar reaction conditions, and wherein methyl alcohol is replaced with the 3-methyl isophthalic acid-butanols with the methyl alcohol equimolar amount.Yield: 65%; M/z:199.
Embodiment 20
Synthesizing of 2-chloro-6-(2-methyl-2-butoxy) pyridine
Method with embodiment 3, embodiment 4, embodiment 5, embodiment 6 or embodiment 7 adopts similar reaction conditions, and wherein methyl alcohol is replaced with the 2-methyl-2-butanols with the methyl alcohol equimolar amount.Yield: 67%; M/z:199.
Embodiment 21
Synthesizing of 2-chloro-6-(3-methyl-2-butoxy) pyridine
Method with embodiment 3, embodiment 4, embodiment 5, embodiment 6 or embodiment 7 adopts similar reaction conditions, and wherein methyl alcohol is replaced with the 3-methyl-2-butanols with the methyl alcohol equimolar amount.Yield: 62%; M/z:199.
Embodiment 22
Synthesizing of 2-chloro-6-(2,2-dimethyl-1-propoxy-) pyridine
Method with embodiment 3, embodiment 4, embodiment 5, embodiment 6 or embodiment 7 adopts similar reaction conditions, and wherein methyl alcohol is replaced with and 2 of methyl alcohol equimolar amount 2-dimethyl-1-propyl alcohol.Yield: 64%; M/z:199.
Embodiment 23
Synthesizing of 2-chloro-6-(1-hexyloxy) pyridine
Method with embodiment 3, embodiment 4, embodiment 5, embodiment 6 or embodiment 7 adopts similar reaction conditions, and wherein methyl alcohol is replaced with the 1-hexanol with the methyl alcohol equimolar amount.Yield: 67%; M/z:213.
Embodiment 24
Synthesizing of 2-chloro-6-(2-hexyloxy) pyridine
Method with embodiment 3, embodiment 4, embodiment 5, embodiment 6 or embodiment 7 adopts similar reaction conditions, and wherein methyl alcohol is replaced with the 2-hexanol with the methyl alcohol equimolar amount.Yield: 66%; M/z:213.
Embodiment 25
Synthesizing of 2-chloro-6-(3-hexyloxy) pyridine
Method with embodiment 3, embodiment 4, embodiment 5, embodiment 6 or embodiment 7 adopts similar reaction conditions, and wherein methyl alcohol is replaced with the 3-hexanol with the methyl alcohol equimolar amount.Yield: 68%; M/z:213.
Embodiment 26
Synthesizing of 2-chloro-6-(2-methyl-1-pentene oxygen base) pyridine
Method with embodiment 3, embodiment 4, embodiment 5, embodiment 6 or embodiment 7 adopts similar reaction conditions, and wherein methyl alcohol is replaced with the 2-methyl-1-pentene alcohol with the methyl alcohol equimolar amount.Yield: 65%; M/z:213.
Embodiment 27
Synthesizing of 2-chloro-6-(2-methyl-2-pentyloxy) pyridine
Method with embodiment 3, embodiment 4, embodiment 5, embodiment 6 or embodiment 7 adopts similar reaction conditions, and wherein methyl alcohol is replaced with the 2-methyl-2-amylalcohol with the methyl alcohol equimolar amount.Yield: 58%; M/z:213.
Embodiment 28
Synthesizing of 2-chloro-6-(2-methyl-3-pentyloxy) pyridine
Method with embodiment 3, embodiment 4, embodiment 5, embodiment 6 or embodiment 7 adopts similar reaction conditions, and wherein methyl alcohol is replaced with the 2-methyl-3-amylalcohol with the methyl alcohol equimolar amount.Yield: 55%; M/z:213.
Embodiment 29
Synthesizing of 2-chloro-6-(4-methyl-2-pentyloxy) pyridine
Method with embodiment 3, embodiment 4, embodiment 5, embodiment 6 or embodiment 7 adopts similar reaction conditions, and wherein methyl alcohol is replaced with the 4-methyl-2-amylalcohol with the methyl alcohol equimolar amount.Yield: 64%; M/z:213.
Embodiment 30
Synthesizing of 2-chloro-6-(4-methyl-1-pentene oxygen base) pyridine
Method with embodiment 3, embodiment 4, embodiment 5, embodiment 6 or embodiment 7 adopts similar reaction conditions, and wherein methyl alcohol is replaced with the 4-methyl-1-pentene alcohol with the methyl alcohol equimolar amount.Yield: 67%; M/z:213.
Embodiment 31
Synthesizing of 2-chloro-6-(3-methyl-2-pentyloxy) pyridine
Method with embodiment 3, embodiment 4, embodiment 5, embodiment 6 or embodiment 7 adopts similar reaction conditions, and wherein methyl alcohol is replaced with the 3-methyl-2-amylalcohol with the methyl alcohol equimolar amount.Yield: 59%; M/z:213.
Embodiment 32
Synthesizing of 2-chloro-6-(3-methyl-3-pentyloxy) pyridine
Method with embodiment 3, embodiment 4, embodiment 5, embodiment 6 or embodiment 7 adopts similar reaction conditions, and wherein methyl alcohol is replaced with the 3-methyl-3-amylalcohol with the methyl alcohol equimolar amount.Yield: 69%; M/z:213.
Embodiment 33
Synthesizing of 2-chloro-6-(2,3-dimethyl-1-butoxy) pyridine
Method with embodiment 3, embodiment 4, embodiment 5, embodiment 6 or embodiment 7 adopts similar reaction conditions, and wherein methyl alcohol is replaced with and 2 of methyl alcohol equimolar amount 3-dimethyl-1-butanols.Yield: 53%; M/z:213.
Embodiment 34
Synthesizing of 2-chloro-6-(2,3-dimethyl-2-butoxy) pyridine
Method with embodiment 3, embodiment 4, embodiment 5, embodiment 6 or embodiment 7 adopts similar reaction conditions, and wherein methyl alcohol is replaced with and 2 of methyl alcohol equimolar amount 3-dimethyl-2-butanols.Yield: 60%; M/z:213.
Embodiment 35
Synthesizing of 2-chloro-6-(2,2-dimethyl-1-butoxy) pyridine
Method with embodiment 3, embodiment 4, embodiment 5, embodiment 6 or embodiment 7 adopts similar reaction conditions, and wherein methyl alcohol is replaced with and 2 of methyl alcohol equimolar amount 2-dimethyl-1-butanols.Yield: 55%; M/z:213.
Embodiment 36
3,5,6-trichloropyridine-2-phenol sodium synthetic
The 2-chloro-6-methoxypyridine of 100mmol is put into the tetrahydrofuran (THF) of 150ml and the mixed solvent of water (1: 1), adds 6N HCl, transfers to pH=2-3, stirs after 3 hours, and the solution evaporate to dryness adds entry 50ml again.Transfer to about pH=11 with 2N NaOH.10% the aqueous sodium hypochlorite solution that adds 500ml.Be heated to 50-80 ℃ of stirring, 16h.Product is separated out, yield 85%.
Product is converted into 3,5, and 6-trichloropyridine-2-phenol is white solid, identifies, its NMR data are (DMSO-d
6): 8.23 (1H), 11.8 (1H); (DMSO-d
6): 156.9,141.5,140.5,117.9,114.9.
Embodiment 37
3,5,6-trichloropyridine-2-phenol sodium synthetic
With the method for embodiment 36, adopt similar reaction conditions, wherein 2-chloro-6-methoxypyridine is replaced with the equimolar 2-chloro-of 2-chloro-6-methoxypyridine 6-ethoxy pyridine, yield 87%.
Product is converted into 3,5, and 6-trichloropyridine-2-phenol is white solid, identifies, its NMR data are (DMSO-d
6): 8.23 (1H), 11.7 (1H); (DMSO-d
6): 156.9,141.8,140.6,117.8,114.9.
Embodiment 38
3,5,6-trichloropyridine-2-phenol sodium synthetic
With the method for embodiment 36, adopt similar reaction conditions, wherein 2-chloro-6-methoxypyridine is replaced with the equimolar 2-chloro-of 2-chloro-6-methoxypyridine 6-(1-propoxy-) pyridine, yield 89%.
Product is converted into 3,5, and 6-trichloropyridine-2-phenol is white solid, identifies, its NMR data are (DMSO-d
6): 8.23 (1H), 11.7 (1H); (DMSO-d
6): 156.9,141.6,140.5,117.8,114.9.
Embodiment 39
3,5,6-trichloropyridine-2-phenol sodium synthetic
With the method for embodiment 36, adopt similar reaction conditions, wherein 2-chloro-6-methoxypyridine is replaced with the equimolar 2-chloro-of 2-chloro-6-methoxypyridine 6-(2-propoxy-) pyridine, yield 88%.
Product is converted into 3,5, and 6-trichloropyridine-2-phenol is white solid, identifies, its NMR data are (DMSO-d
6): 8.23 (1H), 11.8 (1H); (DMSO-d
6): 156.9,141.8,140.5,117.8,114.9.
Embodiment 40
3,5,6-trichloropyridine-2-phenol sodium synthetic
With the method for embodiment 36, adopt similar reaction conditions, wherein 2-chloro-6-methoxypyridine is replaced with the equimolar 2-chloro-of 2-chloro-6-methoxypyridine 6-(1-butoxy) pyridine, yield 81%.
Product is converted into 3,5, and 6-trichloropyridine-2-phenol is white solid, identifies, its NMR data are (DMSO-d
6): 8.25 (1H), 11.6 (1H); (DMSO-d
6): 156.9,141.7,140.5,117.8,114.9.
Embodiment 41
3,5,6-trichloropyridine-2-phenol sodium synthetic
With the method for embodiment 36, adopt similar reaction conditions, wherein 2-chloro-6-methoxypyridine is replaced with the equimolar 2-chloro-of 2-chloro-6-methoxypyridine 6-(2-butoxy) pyridine, yield 79%.
Product is converted into 3,5, and 6-trichloropyridine-2-phenol is white solid, identifies, its NMR data are (DMSO-d
6): 8.26 (1H), 11.6 (1H); (DMSO-d
6): 156.8,141.5,140.5,117.8,114.9.
Embodiment 42
3,5,6-trichloropyridine-2-phenol sodium synthetic
With the method for embodiment 36, adopt similar reaction conditions, wherein 2-chloro-6-methoxypyridine is replaced with the equimolar 2-chloro-of 2-chloro-6-methoxypyridine 6-(2-methyl isophthalic acid-propoxy-) pyridine, yield 73%.
Product is converted into 3,5, and 6-trichloropyridine-2-phenol is white solid, identifies, its NMR data are (DMSO-d
6): 8.26 (1H), 11.6 (1H); (DMSO-d
6): 157.0,141.4,140.5,117.8,114.9.
Embodiment 43
3,5,6-trichloropyridine-2-phenol sodium synthetic
With the method for embodiment 36, adopt similar reaction conditions, wherein 2-chloro-6-methoxypyridine is replaced with the equimolar 2-chloro-of 2-chloro-6-methoxypyridine 6-tert.-butoxy pyridine, yield 79%.
Product is converted into 3,5, and 6-trichloropyridine-2-phenol is white solid, identifies, its NMR data are (DMSO-d
6): 8.23 (1H), 11.9 (1H); (DMSO-d
6): 156.9,141.4,140.7,117.8,114.9.
Embodiment 44
3,5,6-trichloropyridine-2-phenol sodium synthetic
With the method for embodiment 36, adopt similar reaction conditions, wherein 2-chloro-6-methoxypyridine is replaced with the equimolar 2-chloro-of 2-chloro-6-methoxypyridine 6-(1-pentyloxy) pyridine, yield 88%.
Product is converted into 3,5, and 6-trichloropyridine-2-phenol is white solid, identifies, its NMR data are (DMSO-d
6): 8.23 (1H), 11.8 (1H); (DMSO-d
6): 156.9,141.4,140.1,117.8,114.9.
Embodiment 45
3,5,6-trichloropyridine-2-phenol sodium synthetic
With the method for embodiment 36, adopt similar reaction conditions, wherein 2-chloro-6-methoxypyridine is replaced with the equimolar 2-chloro-of 2-chloro-6-methoxypyridine 6-(2-pentyloxy) pyridine, yield 85%.
Product is converted into 3,5, and 6-trichloropyridine-2-phenol is white solid, identifies, its NMR data are (DMSO-d
6): 8.23 (1H), 11.7 (1H); (DMSO-d
6): 156.9,141.9,140.5,117.8,114.9.
Embodiment 46
3,5,6-trichloropyridine-2-phenol sodium synthetic
With the method for embodiment 36, adopt similar reaction conditions, wherein 2-chloro-6-methoxypyridine is replaced with the equimolar 2-chloro-of 2-chloro-6-methoxypyridine 6-(3-pentyloxy) pyridine, yield 82%.
Product is converted into 3,5, and 6-trichloropyridine-2-phenol is white solid, identifies, its NMR data are (DMSO-d
6): 8.23 (1H), 12.1 (1H); (DMSO-d
6): 156.9,141.4,140.8,117.8,114.9.
Embodiment 47
3,5,6-trichloropyridine-2-phenol sodium synthetic
With the method for embodiment 36, adopt similar reaction conditions, wherein 2-chloro-6-methoxypyridine is replaced with the equimolar 2-chloro-of 2-chloro-6-methoxypyridine 6-(2-methyl-1-butene oxygen base) pyridine, yield 76%.
Product is converted into 3,5, and 6-trichloropyridine-2-phenol is white solid, identifies, its NMR data are (DMSO-d
6): 8.27 (1H), 11.6 (1H); (DMSO-d
6): 156.9,141.4,140.7,117.8,114.9.
Embodiment 48
3,5,6-trichloropyridine-2-phenol sodium synthetic
With the method for embodiment 36, adopt similar reaction conditions, wherein 2-chloro-6-methoxypyridine is replaced with the equimolar 2-chloro-of 2-chloro-6-methoxypyridine 6-(3-methyl isophthalic acid-butoxy) pyridine, yield 81%.
Product is converted into 3,5, and 6-trichloropyridine-2-phenol is white solid, identifies, its NMR data are (DMSO-d
6): 8.26 (1H), 12.0 (1H); (DMSO-d
6): 156.9,141.4,140.5,117.8,114.9.
Embodiment 49
3,5,6-trichloropyridine-2-phenol sodium synthetic
With the method for embodiment 36, adopt similar reaction conditions, wherein 2-chloro-6-methoxypyridine is replaced with the equimolar 2-chloro-of 2-chloro-6-methoxypyridine 6-(2-methyl-2-butoxy) pyridine, yield 86%.
Product is converted into 3,5, and 6-trichloropyridine-2-phenol is white solid, identifies, its NMR data are (DMSO-d
6): 8.23 (1H), 12.1 (1H); (DMSO-d
6): 156.9,141.4,140.5,118.1,114.9.
Embodiment 50
3,5,6-trichloropyridine-2-phenol sodium synthetic
With the method for embodiment 36, adopt similar reaction conditions, wherein 2-chloro-6-methoxypyridine is replaced with the equimolar 2-chloro-of 2-chloro-6-methoxypyridine 6-(3-methyl-2-butoxy) pyridine, yield 82%.
Product is converted into 3,5, and 6-trichloropyridine-2-phenol is white solid, identifies, its NMR data are (DMSO-d
6): 8.27 (1H), 11.6 (1H); (DMSO-d
6): 156.9,141.4,141.0,117.8,114.9.
Embodiment 51
3,5,6-trichloropyridine-2-phenol sodium synthetic
With the method for embodiment 36, adopt similar reaction conditions, wherein 2-chloro-6-methoxypyridine is replaced with the equimolar 2-chloro-of 2-chloro-6-methoxypyridine 6-(2,2-dimethyl-1-propoxy-) pyridine, yield 89%.
Product is converted into 3,5, and 6-trichloropyridine-2-phenol is white solid, identifies, its NMR data are (DMSO-d
6): 8.25 (1H), 11.6 (1H); (DMSO-d
6): 156.9,141.6,140.5,117.8,114.9.
Embodiment 52
3,5,6-trichloropyridine-2-phenol sodium synthetic
With the method for embodiment 36, adopt similar reaction conditions, wherein 2-chloro-6-methoxypyridine is replaced with the equimolar 2-chloro-of 2-chloro-6-methoxypyridine 6-(1-hexyloxy) pyridine, yield 76%.
Product is converted into 3,5, and 6-trichloropyridine-2-phenol is white solid, identifies, its NMR data are (DMSO-d
6): 8.27 (1H), 11.8 (1H); (DMSO-d
6): 156.9,141.6,140.5,117.8,114.9.
Embodiment 53
3,5,6-trichloropyridine-2-phenol sodium synthetic
With the method for embodiment 36, adopt similar reaction conditions, wherein 2-chloro-6-methoxypyridine is replaced with the equimolar 2-chloro-of 2-chloro-6-methoxypyridine 6-(2-hexyloxy) pyridine, yield 67%.
Product is converted into 3,5, and 6-trichloropyridine-2-phenol is white solid, identifies, its NMR data are (DMSO-d
6): 8.30 (1H), 11.9 (1H); (DMSO-d
6): 156.9,141.4,140.5,117.8,114.9.
Embodiment 54
3,5,6-trichloropyridine-2-phenol sodium synthetic
With the method for embodiment 36, adopt similar reaction conditions, wherein 2-chloro-6-methoxypyridine is replaced with the equimolar 2-chloro-of 2-chloro-6-methoxypyridine 6-(3-hexyloxy) pyridine, yield 78%.
Product is converted into 3,5, and 6-trichloropyridine-2-phenol is white solid, identifies, its NMR data are (DMSO-d
6): 8.27 (1H), 12.0 (1H); (DMSO-d
6): 156.9,141.4,140.5,117.8,114.9.
Embodiment 55
3,5,6-trichloropyridine-2-phenol sodium synthetic
With the method for embodiment 36, adopt similar reaction conditions, wherein 2-chloro-6-methoxypyridine is replaced with the equimolar 2-chloro-of 2-chloro-6-methoxypyridine 6-(2-methyl-1-pentene oxygen base) pyridine, yield 85%.
Product is converted into 3,5, and 6-trichloropyridine-2-phenol is white solid, identifies, its NMR data are (DMSO-d
6): 8.27 (1H), 12.1 (1H); (DMSO-d
6): 156.9,141.4,140.5,117.8,114.9.
Embodiment 56
3,5,6-trichloropyridine-2-phenol sodium synthetic
With the method for embodiment 36, adopt similar reaction conditions, wherein 2-chloro-6-methoxypyridine is replaced with the equimolar 2-chloro-of 2-chloro-6-methoxypyridine 6-(2-methyl-2-pentyloxy) pyridine, yield 86%.
Product is converted into 3,5, and 6-trichloropyridine-2-phenol is white solid, identifies, its NMR data are (DMSO-d
6): 8.50 (1H), 12.6 (1H); (DMSO-d
6): 156.9,141.4,140.5,117.8,114.9.
Embodiment 57
3,5,6-trichloropyridine-2-phenol sodium synthetic
With the method for embodiment 36, adopt similar reaction conditions, wherein 2-chloro-6-methoxypyridine is replaced with the equimolar 2-chloro-of 2-chloro-6-methoxypyridine 6-(2-methyl-3-pentyloxy) pyridine, yield 87%.
Product is converted into 3,5, and 6-trichloropyridine-2-phenol is white solid, identifies, its NMR data are (DMSO-d
6): 8.30 (1H), 11.6 (1H); (DMSO-d
6): 156.8,141.4,140.5,117.8,114.9.
Embodiment 58
3,5,6-trichloropyridine-2-phenol sodium synthetic
With the method for embodiment 36, adopt similar reaction conditions, wherein 2-chloro-6-methoxypyridine is replaced with the equimolar 2-chloro-of 2-chloro-6-methoxypyridine 6-(4-methyl-2-pentyloxy) pyridine, yield 85%.
Product is converted into 3,5, and 6-trichloropyridine-2-phenol is white solid, identifies, its NMR data are (DMSO-d
6): 8.26 (1H), 11.69 (1H); (DMSO-d
6): 156.7,141.4,140.5,117.8,114.9.
Embodiment 59
3,5,6-trichloropyridine-2-phenol sodium synthetic
With the method for embodiment 36, adopt similar reaction conditions, wherein 2-chloro-6-methoxypyridine is replaced with the equimolar 2-chloro-of 2-chloro-6-methoxypyridine 6-(4-methyl-1-pentene oxygen base) pyridine, yield 79%.
Product is converted into 3,5, and 6-trichloropyridine-2-phenol is white solid, identifies, its NMR data are (DMSO-d
6): 8.29 (1H), 11.6 (1H); (DMSO-d
6): 156.9,141.4,140.5,117.9,114.9.
Embodiment 60
3,5,6-trichloropyridine-2-phenol sodium synthetic
With the method for embodiment 36, adopt similar reaction conditions, wherein 2-chloro-6-methoxypyridine is replaced with the equimolar 2-chloro-of 2-chloro-6-methoxypyridine 6-(3-methyl-2-pentyloxy) pyridine, yield 81%.
Product is converted into 3,5, and 6-trichloropyridine-2-phenol is white solid, identifies, its NMR data are (DMSO-d
6): 8.23 (1H), 11.6 (1H); (DMSO-d
6): 156.9,141.4,140.5,118.1,114.9.
Embodiment 61
3,5,6-trichloropyridine-2-phenol sodium synthetic
With the method for embodiment 36, adopt similar reaction conditions, wherein 2-chloro-6-methoxypyridine is replaced with the equimolar 2-chloro-of 2-chloro-6-methoxypyridine 6-(3-methyl-3-pentyloxy) pyridine, yield 78%.
Product is converted into 3,5, and 6-trichloropyridine-2-phenol is white solid, identifies, its NMR data are (DMSO-d
6): 8.26 (1H), 11.6 (1H); (DMSO-d
6): 156.9,141.8,140.5,117.8,114.9.
Embodiment 62
3,5,6-trichloropyridine-2-phenol sodium synthetic
With the method for embodiment 36, adopt similar reaction conditions, wherein 2-chloro-6-methoxypyridine is replaced with the equimolar 2-chloro-of 2-chloro-6-methoxypyridine 6-(2,3-dimethyl-1-butoxy) pyridine, yield 79%.
Product is converted into 3,5, and 6-trichloropyridine-2-phenol is white solid, identifies, its NMR data are (DMSO-d
6): 8.29 (1H), 11.6 (1H); (DMSO-d
6): 156.9,141.7,140.5,117.8,114.9.
Embodiment 63
3,5,6-trichloropyridine-2-phenol sodium synthetic
With the method for embodiment 36, adopt similar reaction conditions, wherein 2-chloro-6-methoxypyridine is replaced with the equimolar 2-chloro-of 2-chloro-6-methoxypyridine 6-(2,3-dimethyl-2-butoxy) pyridine, yield 77%.
Product is converted into 3,5, and 6-trichloropyridine-2-phenol is white solid, identifies, its NMR data are (DMSO-d
6): 8.23 (1H), 11.9 (1H); (DMSO-d
6): 156.9,142.0,140.5,117.8,114.9.
Embodiment 64
3,5,6-trichloropyridine-2-phenol sodium synthetic
With the method for embodiment 36, adopt similar reaction conditions, wherein 2-chloro-6-methoxypyridine is replaced with the equimolar 2-chloro-of 2-chloro-6-methoxypyridine 6-(2,2-dimethyl-1-butoxy) pyridine, yield 87%.
Product is converted into 3,5, and 6-trichloropyridine-2-phenol is white solid, identifies, its NMR data are (DMSO-d
6): 8.23 (1H), 11.8 (1H); (DMSO-d
6): 156.9,141.7,140.5,117.8,114.9.
Embodiment 65
3,5,6-trichloropyridine-2-phenol sodium synthetic
, the round-bottomed flask of reflux adds 2 of 100mmol in being housed, the 6-dichloropyridine, and the NaOH of 600mmol, the 1.5L anhydrous methanol, room temperature is reduced in heated and stirred reaction one day, adds 2N HCl, transfers to pH=2-3.Methyl alcohol in the retort solution.In reactor, add 6N NaOH again and transfer to pH=11.10% aqueous sodium hypochlorite solution that adds 500ml.Be heated to 80 ℃, reacted 12 hours.Product is separated out.Yield: 56%.
Product is converted into 3,5, and 6-trichloropyridine-2-phenol is white solid, identifies, its NMR data are (DMSO-d
6): 8.26 (1H), 11.6 (1H); (DMSO-d
6): 156.9,141.7,140.5,117.8,114.9.
Embodiment 66
3,5,6-trichloropyridine-2-phenol sodium synthetic
With the method for embodiment 65, adopt similar reaction conditions, wherein methyl alcohol is replaced with and the equimolar ethanol of methyl alcohol, yield 54%.
Product is converted into 3,5, and 6-trichloropyridine-2-phenol is white solid, identifies, its NMR data are (DMSO-d
6): 8.23 (1H), 11.9 (1H); (DMSO-d
6): 157.1,141.4,140.5,117.8,114.9.
Embodiment 67
3,5,6-trichloropyridine-2-phenol sodium synthetic
With the method for embodiment 65, adopt similar reaction conditions, wherein methyl alcohol is replaced with and the equimolar 1-propyl alcohol of methyl alcohol, yield 55%.
Product is converted into 3,5, and 6-trichloropyridine-2-phenol is white solid, identifies, its NMR data are (DMSO-d
6): 8.23 (1H), 11.7 (1H); (DMSO-d
6): 156.8,141.4,140.5,117.8,114.9.
Embodiment 68
3,5,6-trichloropyridine-2-phenol sodium synthetic
With the method for embodiment 65, adopt similar reaction conditions, wherein methyl alcohol is replaced with and the equimolar 2-propyl alcohol of methyl alcohol, yield 53%.
Product is converted into 3,5, and 6-trichloropyridine-2-phenol is white solid, identifies, its NMR data are (DMSO-d
6): 8.23 (1H), 11.9 (1H); (DMSO-d
6): 157.3,141.4,140.5,117.8,114.9.
Embodiment 69
3,5,6-trichloropyridine-2-phenol sodium synthetic
With the method for embodiment 65, adopt similar reaction conditions, wherein methyl alcohol is replaced with and the equimolar 1-butanols of methyl alcohol, yield 53%.
Product is converted into 3,5, and 6-trichloropyridine-2-phenol is white solid, identifies, its NMR data are (DMSO-d
6): 8.23 (1H), 11.7 (1H); (DMSO-d
6): 156.9,141.8,140.5,117.8,114.9.
Embodiment 70
3,5,6-trichloropyridine-2-phenol sodium synthetic
With the method for embodiment 65, adopt similar reaction conditions, wherein methyl alcohol is replaced with and the equimolar 2-butanols of methyl alcohol, yield 57%.
Product is converted into 3,5, and 6-trichloropyridine-2-phenol is white solid, identifies, its NMR data are (DMSO-d
6): 8.23 (1H), 11.69 (1H); (DMSO-d
6): 156.9,141.3,140.5,117.8,114.9.
Embodiment 71
3,5,6-trichloropyridine-2-phenol sodium synthetic
With the method for embodiment 65, adopt similar reaction conditions, wherein methyl alcohol is replaced with and the equimolar 2-methyl isophthalic acid-propyl alcohol of methyl alcohol, yield 54%.
Product is converted into 3,5, and 6-trichloropyridine-2-phenol is white solid, identifies, its NMR data are (DMSO-d
6): 8.23 (1H), 11.67 (1H); (DMSO-d
6): 156.9,141.9,140.5,117.8,114.9.
Embodiment 72
3,5,6-trichloropyridine-2-phenol sodium synthetic
With the method for embodiment 65, adopt similar reaction conditions, wherein methyl alcohol is replaced with the trimethyl carbinol with the equimolar 2-chloro-of methyl alcohol 6-, yield 56%.
Product is converted into 3,5, and 6-trichloropyridine-2-phenol is white solid, identifies, its NMR data are (DMSO-d
6): 8.25 (1H), 11.6 (1H); (DMSO-d
6): 156.9,141.8,140.5,117.8,114.9.
Embodiment 73
3,5,6-trichloropyridine-2-phenol sodium synthetic
With the method for embodiment 65, adopt similar reaction conditions, wherein methyl alcohol is replaced with and the equimolar 1-amylalcohol of methyl alcohol, yield 58%.
Product is converted into 3,5, and 6-trichloropyridine-2-phenol is white solid, identifies, its NMR data are (DMSO-d
6): 8.26 (1H), 11.6 (1H); (DMSO-d
6): 156.9,141.4,140.7,118.1,114.9.
Embodiment 74
3,5,6-trichloropyridine-2-phenol sodium synthetic
With the method for embodiment 65, adopt similar reaction conditions, wherein methyl alcohol is replaced with and the equimolar 2-amylalcohol of methyl alcohol, yield 55%.
Product is converted into 3,5, and 6-trichloropyridine-2-phenol is white solid, identifies, its NMR data are (DMSO-d
6): 8.23 (1H), 11.9 (1H); (DMSO-d
6): 156.9,141.6,140.5,117.8,114.9.
Embodiment 75
3,5,6-trichloropyridine-2-phenol sodium synthetic
With the method for embodiment 65, adopt similar reaction conditions, wherein methyl alcohol is replaced with and the equimolar 3-amylalcohol of methyl alcohol, yield 57%.
Product is converted into 3,5, and 6-trichloropyridine-2-phenol is white solid, identifies, its NMR data are (DMSO-d
6): 8.23 (1H), 11.7 (1H); (DMSO-d
6): 156.9,141.8,140.5,117.8,114.9.
Embodiment 76
3,5,6-trichloropyridine-2-phenol sodium synthetic
With the method for embodiment 65, adopt similar reaction conditions, wherein methyl alcohol is replaced with and the equimolar 2-methyl-1-butene alcohol of methyl alcohol yield 54%.
Product is converted into 3,5, and 6-trichloropyridine-2-phenol is white solid, identifies, its NMR data are (DMSO-d
6): 8.25 (1H), 11.6 (1H); (DMSO-d
6): 156.9,141.6,140.5,117.8,114.9.
Embodiment 77
3,5,6-trichloropyridine-2-phenol sodium synthetic
With the method for embodiment 65, adopt similar reaction conditions, wherein methyl alcohol is replaced with and the equimolar 3-methyl isophthalic acid-butanols of methyl alcohol, yield 51%.
Product is converted into 3,5, and 6-trichloropyridine-2-phenol is white solid, identifies, its NMR data are (DMSO-d
6): 8.23 (1H), 11.9 (1H); (DMSO-d
6): 157.2,141.4,140.5,117.8,114.9.
Embodiment 78
3,5,6-trichloropyridine-2-phenol sodium synthetic
With the method for embodiment 65, adopt similar reaction conditions, wherein methyl alcohol is replaced with and the equimolar 2-methyl of methyl alcohol-2-butanols, yield 52%.
Product is converted into 3,5, and 6-trichloropyridine-2-phenol is white solid, identifies, its NMR data are (DMSO-d
6): 8.23 (1H), 11.6 (1H); (DMSO-d
6): 157.1,141.4,140.5,117.8,114.9.
Embodiment 79
3,5,6-trichloropyridine-2-phenol sodium synthetic
With the method for embodiment 65, adopt similar reaction conditions, wherein methyl alcohol is replaced with and the equimolar 3-methyl of methyl alcohol-2-butanols, yield 53%.
Product is converted into 3,5, and 6-trichloropyridine-2-phenol is white solid, identifies, its NMR data are (DMSO-d
6): 8.234 (1H), 11.6 (1H); (DMSO-d
6): 157.0,141.4,140.5,117.8,114.9.
Embodiment 80
3,5,6-trichloropyridine-2-phenol sodium synthetic
With the method for embodiment 65, adopt similar reaction conditions, wherein methyl alcohol is replaced with methyl alcohol equimolar 2,2-dimethyl-1-propyl alcohol, yield 56%.
Product is converted into 3,5, and 6-trichloropyridine-2-phenol is white solid, identifies, its NMR data are (DMSO-d
6): 8.23 (1H), 11.8 (1H); (DMSO-d
6): 156.9,141.4,140.3,117.8,114.9.
Embodiment 81
3,5,6-trichloropyridine-2-phenol sodium synthetic
With the method for embodiment 65, adopt similar reaction conditions, wherein methyl alcohol is replaced with and the equimolar 2-hexanol of methyl alcohol, yield 50%.
Product is converted into 3,5, and 6-trichloropyridine-2-phenol is white solid, identifies, its NMR data are (DMSO-d
6): 8.23 (1H), 11.6 (1H); (DMSO-d
6): 156.9,141.4,140.6,117.9,114.9.
Embodiment 82
3,5,6-trichloropyridine-2-phenol sodium synthetic
With the method for embodiment 65, adopt similar reaction conditions, wherein methyl alcohol is replaced with and the equimolar 3-hexanol of methyl alcohol, yield 59%.
Product is converted into 3,5, and 6-trichloropyridine-2-phenol is white solid, identifies, its NMR data are (DMSO-d
6): 8.23 (1H), 11.6 (1H); (DMSO-d
6): 156.9,142.0,140.5,117.8,114.9.
Embodiment 83
3,5,6-trichloropyridine-2-phenol sodium synthetic
With the method for embodiment 65, adopt similar reaction conditions, wherein methyl alcohol is replaced with and the equimolar 2-methyl-1-pentene alcohol of methyl alcohol yield 55%.
Product is converted into 3,5, and 6-trichloropyridine-2-phenol is white solid, identifies, its NMR data are (DMSO-d
6): 8.27 (1H), 11.6 (1H); (DMSO-d
6): 156.9,141.4,140.5,117.8,114.9.
Embodiment 84
3,5,6-trichloropyridine-2-phenol sodium synthetic
With the method for embodiment 65, adopt similar reaction conditions, wherein methyl alcohol is replaced with and the equimolar 2-methyl of methyl alcohol-2-amylalcohol, yield 57%.
Product is converted into 3,5, and 6-trichloropyridine-2-phenol is white solid, identifies, its NMR data are (DMSO-d
6): 8.23 (1H), 11.6 (1H); (DMSO-d
6): 156.9,141.5,140.5,117.8,114.9.
Embodiment 85
3,5,6-trichloropyridine-2-phenol sodium synthetic
With the method for embodiment 65, adopt similar reaction conditions, wherein methyl alcohol is replaced with and the equimolar 2-methyl of methyl alcohol-3-amylalcohol, yield 58%.
Product is converted into 3,5, and 6-trichloropyridine-2-phenol is white solid, identifies, its NMR data are (DMSO-d
6): 8.23 (1H), 11.6 (1H); (DMSO-d
6): 157.0,141.4,140.5,117.8,114.9.
Embodiment 86
3,5,6-trichloropyridine-2-phenol sodium synthetic
With the method for embodiment 65, adopt similar reaction conditions, wherein methyl alcohol is replaced with and the equimolar 4-methyl of methyl alcohol-2-amylalcohol, yield 60%.
Product is converted into 3,5, and 6-trichloropyridine-2-phenol is white solid, identifies, its NMR data are (DMSO-d
6): 8.23 (1H), 12.0 (1H); (DMSO-d
6): 156.9,141.4,140.5,117.8,114.9.
Embodiment 87
3,5,6-trichloropyridine-2-phenol sodium synthetic
With the method for embodiment 65, adopt similar reaction conditions, wherein methyl alcohol is replaced with and the equimolar 4-methyl-1-pentene alcohol of methyl alcohol yield 57%.
Product is converted into 3,5, and 6-trichloropyridine-2-phenol is white solid, identifies, its NMR data are (DMSO-d
6): 8.23 (1H), 11.9 (1H); (DMSO-d
6): 156.9,141.4,140.5,117.6,114.9.
Embodiment 88
3,5,6-trichloropyridine-2-phenol sodium synthetic
With the method for embodiment 65, adopt similar reaction conditions, wherein methyl alcohol is replaced with and the equimolar 3-methyl of methyl alcohol-2-amylalcohol, yield 61%.
Product is converted into 3,5, and 6-trichloropyridine-2-phenol is white solid, identifies, its NMR data are (DMSO-d
6): 8.23 (1H), 11.6 (1H); (DMSO-d
6): 156.9,141.4,140.5,118.1,114.9.
Embodiment 89
3,5,6-trichloropyridine-2-phenol sodium synthetic
With the method for embodiment 65, adopt similar reaction conditions, wherein methyl alcohol is replaced with and the equimolar 3-methyl of methyl alcohol-3-amylalcohol, yield 54%.
Product is converted into 3,5, and 6-trichloropyridine-2-phenol is white solid, identifies, its NMR data are (DMSO-d
6): 8.23 (1H), 11.6 (1H); (DMSO-d
6): 156.9,141.4,140.5,117.8,115.0.
Embodiment 90
3,5,6-trichloropyridine-2-phenol sodium synthetic
With the method for embodiment 65, adopt similar reaction conditions, wherein methyl alcohol is replaced with methyl alcohol equimolar 2,3-dimethyl-1-butanols, yield 56%.
Product is converted into 3,5, and 6-trichloropyridine-2-phenol is white solid, identifies, its NMR data are (DMSO-d
6): 8.23 (1H), 11.69 (1H); (DMSO-d
6): 156.9,141.4,140.6,117.8,114.9.
Embodiment 91
3,5,6-trichloropyridine-2-phenol sodium synthetic
With the method for embodiment 65, adopt similar reaction conditions, wherein methyl alcohol is replaced with methyl alcohol equimolar 2,3-dimethyl-2-butanols, yield 58%.
Product is converted into 3,5, and 6-trichloropyridine-2-phenol is white solid, identifies, its NMR data are (DMSO-d
6): 8.21 (1H), 11.5 (1H); (DMSO-d
6): 156.9,141.3,140.5,117.8,114.9.
Embodiment 92
3,5,6-trichloropyridine-2-phenol sodium synthetic
With the method for embodiment 65, adopt similar reaction conditions, wherein methyl alcohol is replaced with methyl alcohol equimolar 2,2-dimethyl-1-butanols, yield 59%.
Product is converted into 3,5, and 6-trichloropyridine-2-phenol is white solid, identifies, its NMR data are (DMSO-d
6): 8.24 (1H), 11.6 (1H); (DMSO-d
6): 156.7,141.4,140.5,117.8,114.9.
Claims (10)
1. the 2-chloro-represented of formula I replaces or does not replace aliphatic hydrocrbon oxygen yl pyridines compound,
Formula I
Wherein R is not substituted or substituted aliphatic hydrocarbyl.
2. the described compound of claim 1, wherein R is not for being substituted or substituted low alkyl group, not being substituted or substituted phenyl.
3. the described compound of claim 2, wherein said unsubstituted low alkyl group is the alkyl of C1-C8.
4. the described compound of claim 3; The alkyl of wherein said C1-C8 is a methyl; Ethyl; Propyl group; Sec.-propyl; The 1-butyl; The 2-butyl; 2-methyl isophthalic acid-propyl group; The tertiary butyl; The 1-amyl group; The 2-amyl group; The 3-amyl group; The 2-methyl-1-butene base; 3-methyl isophthalic acid-butyl; 2-methyl-2-butyl; 3-methyl-2-butyl; 2; 2-dimethyl-1-propyl group; The 1-hexyl; The 2-hexyl; The 3-hexyl; 2-methyl-1-pentene base; 2-methyl-2-amyl group; 2-methyl-3-amyl group; 4-methyl-2-amyl group; 4-methyl-1-pentene base; 3-methyl-1-pentene base; 3-methyl-2-amyl group; 3-methyl-3-amyl group; 2; 3-dimethyl-1-butyl; 2; 3-dimethyl-2-butyl or 2,2-dimethyl-1-butyl.
5. the described compound of claim 2, wherein said substituted low alkyl group is by the alkyl of halogen atom, alkoxyl group, carboxyl or the substituted C2-C6 of nitro.
6. the described compound of claim 2, wherein said substituted phenyl is by halogen atom, alkoxyl group, carboxyl or nitro substituted-phenyl.
7. the method for preparing each said formula I compound of claim 1 to 6,
Formula I
Wherein the R group definition is like claim 1 to 5 as described in each,
Said method comprises:
2,6-dichloropyridine and [RO
-]
aM
A+Substitution reaction production I compound takes place; Wherein M is basic metal or alkaline-earth metal, and wherein a is 1 or 2,2,6-dichloropyridine and [RO
-]
aM
A+Mol ratio smaller or equal to 1.
8. the said preparation method of claim 7, wherein M is Na, K, Mg or Ca.
9. the said preparation method of claim 8, wherein M is Na or K.
10. the method for preparing each said formula I compound of claim 1 to 6,
Formula I
Wherein the R group definition is like claim 1 to 5 as described in each,
Said method comprises:
2; The 6-dichloropyridine with under alkaline matter with ROH generation condensation reaction production I compound, wherein used alkaline matter is selected from one or more of oxyhydroxide, carbonate, supercarbonate, ammoniacal liquor or organic amine of basic metal or alkaline-earth metal in this reaction.
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| PCT/CN2011/081471 WO2012059024A1 (en) | 2010-11-01 | 2011-10-28 | 2-chloro-substituted or unsubstituted aliphatic hydrocarbyloxy-pyridine and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104478794A (en) * | 2014-11-20 | 2015-04-01 | 盐城恒盛化工有限公司 | Synthesis method of 2,6-dichloropyridine |
| CN106905229A (en) * | 2017-03-07 | 2017-06-30 | 怀化金鑫新材料有限公司 | The novel synthesis of ortho alkoxy substituted pyridines |
| CN107935922A (en) * | 2017-12-07 | 2018-04-20 | 山东昆达生物科技有限公司 | A kind of synthetic method and aftertreatment technology of 6 chlorine, 2 oxyl pyridine |
| CN107954928A (en) * | 2017-12-07 | 2018-04-24 | 山东昆达生物科技有限公司 | A kind of preparation method of 6- Chloro-2-Pyridyles phenol sodium and 6- Chloro-2-Pyridyle ketone |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2459240A1 (en) * | 1979-06-21 | 1981-01-09 | Cm Ind | ANOREXIGENOUS AMINOPIPERIDINES, PROCESS FOR THEIR PREPARATION, INTERMEDIATES IN SAID METHOD AND MEDICAMENTS CONTAINING SAME |
| US4393213A (en) * | 1981-01-14 | 1983-07-12 | Nissan Chemical Industries, Ltd. | Process for producing 6-phenoxypicolinic aldehydes |
| JPS58206565A (en) * | 1982-05-27 | 1983-12-01 | Toyo Soda Mfg Co Ltd | Preparation of 2-alkoxy-6-chloropyridine |
| JPH07300474A (en) * | 1994-05-02 | 1995-11-14 | Asahi Chem Ind Co Ltd | Tetrahydroquinoxaline derivative and use thereof |
| DE102004014474A1 (en) * | 2003-03-25 | 2004-10-21 | Basf Ag | Preparation of phosphinopyridone derivatives, useful e.g. as ligands for metal catalysts, by reacting phosphine and pyridine derivative containing leaving group and protected hydroxy, then deprotection |
| EP2253618A1 (en) * | 2008-02-27 | 2010-11-24 | Takeda Pharmaceutical Company Limited | Compound having 6-membered aromatic ring |
-
2010
- 2010-11-01 CN CN2010105262604A patent/CN102452978A/en active Pending
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104478794A (en) * | 2014-11-20 | 2015-04-01 | 盐城恒盛化工有限公司 | Synthesis method of 2,6-dichloropyridine |
| CN106905229A (en) * | 2017-03-07 | 2017-06-30 | 怀化金鑫新材料有限公司 | The novel synthesis of ortho alkoxy substituted pyridines |
| CN107935922A (en) * | 2017-12-07 | 2018-04-20 | 山东昆达生物科技有限公司 | A kind of synthetic method and aftertreatment technology of 6 chlorine, 2 oxyl pyridine |
| CN107954928A (en) * | 2017-12-07 | 2018-04-24 | 山东昆达生物科技有限公司 | A kind of preparation method of 6- Chloro-2-Pyridyles phenol sodium and 6- Chloro-2-Pyridyle ketone |
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