CN102807505B - Method for producing phenylhydrazine - Google Patents
Method for producing phenylhydrazine Download PDFInfo
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- CN102807505B CN102807505B CN201210171842.4A CN201210171842A CN102807505B CN 102807505 B CN102807505 B CN 102807505B CN 201210171842 A CN201210171842 A CN 201210171842A CN 102807505 B CN102807505 B CN 102807505B
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Abstract
The invention provides a method for producing phenylhydrazine (II), and the method has excellent yields. More specifically, the invention provides a method for producing phenylhydrazine which comprises the following steps: diazonium salt (I) is reacted with at least one substance selected from sulfite and hydrosulphite in the presence of water; and a reaction mixture obtained is mixed with hydrogen chloride at a temperature of 0 to 10 DEG C, and the mixture is subsequently maintained in the range of 10 to 30 DEG C. The maintaining is preferably implemented at a temperature higher than the temperature when the reaction mixture is mixed with the hydrogen chloride.
Description
Technical field
The present invention relates to the method for the compound of a kind of production represented by formula (II):
(wherein, R
1represent hydrogen atom, alkyl, cycloalkyl, alkenyl, aralkyl, alkoxyl group or carboxyalkyl) [hereinafter may be referred to as phenylhydrazine (II)].Phenylhydrazine (II) is as the production intermediate of medicine and agrochemicals and photograph coupler.
Background technology
As the method for producing phenylhydrazine (II), such as, JP-A2005-336103 describes the method utilizing Reduction with Stannous Chloride aromatic diazonium salt.
Summary of the invention
But, the method for above-mentioned routine can not be inevitable satisfactory in the yield of phenylhydrazine (II).
Therefore, the object of the invention is to, the method for the production phenylhydrazine (II) providing a kind of yield outstanding.
Through the present inventor's further investigation, reach above-mentioned purpose, thus completed the present invention.That is, the present invention includes following aspect:
(1) a kind of method of producing the compound represented by formula (II):
(wherein, R
1represent hydrogen atom, alkyl, cycloalkyl, alkenyl, aralkyl, alkoxyl group or carboxyalkyl), described method comprises:
Diazonium salt by formula (I) represents:
(wherein R
1represent the implication identical with above-mentioned definition, and X-representing negatively charged ion) material that is selected from sulphite and hydrosulphite with at least one reacts in the presence of water; And the reaction mixture of gained is mixed with hydrogenchloride at 0 to 10 DEG C, subsequently described mixture is remained on 10 to 30 DEG C.
(2) according to the method for above-mentioned (1), wherein, the temperature of the temperature when mixing with hydrogenchloride higher than described reaction mixture implements described maintenance.
(3) method according to above-mentioned (1) or (2), wherein, after described reaction mixture and hydrogenchloride being mixed at 0 to 10 DEG C, remains on 10 to 30 DEG C by reaction mixture, keeps its pH not higher than 3 simultaneously.
(4) method according to any one of above-mentioned (1) to (3), wherein, the R in formula (I) and (II)
1it is alkoxyl group.
(5) method according to any one of above-mentioned (1) to (3), wherein, the R in formula (I) and (II)
1it is methoxyl group.
(6) method according to any one of above-mentioned (1) to (5), wherein, the X in formula (I)
-cl
-.
(7) according to the method described in above-mentioned (6), wherein, the compound by formula (III) is represented:
(wherein R
1represent the implication identical with above-mentioned definition) react under the existence of hydrogenchloride with nitrite, obtain the described diazonium salt represented by formula (I).
According to the present invention, can with outstanding produced in yields phenylhydrazine (II).
Specific embodiments
In the present invention, by the described diazonium salt represented by formula (I):
(wherein, R
1represent hydrogen atom, alkyl, cycloalkyl, alkenyl, aralkyl, alkoxyl group or carboxyalkyl, and X-representing negatively charged ion) material that is selected from sulphite and hydrosulphite of [hereinafter may be referred to as diazonium salt (I)] and at least one reacts in the presence of water.
In formula (I), as alkyl, preferably have the alkyl of 1 to 6 carbon atom, the example comprises methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, 2-methyl butyl, 3-methyl butyl, hexyl, 2-methyl amyl and 3-methyl amyl.As cycloalkyl, preferably have the cycloalkyl of 3 to 6 carbon atoms, the example comprises cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.As alkenyl, preferably there is the alkenyl of 2 to 6 carbon atoms, the example comprises vinyl, allyl group, 2-methacrylic, pseudoallyl, 1-propenyl, 1-butylene base, crotyl, 3-butenyl, 1-methyl-1-propylene base, 1-methyl-2-propenyl, 2-methyl-1-propylene base, 2-methyl-2-propenyl, 1-pentenyl, pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl isophthalic acid-butenyl, 2-methyl-1-butene thiazolinyl, 3-methyl-1-butene base, 1-methyl-2-butene base, 2-methyl-2-butene base, 3-methyl-2-butene base, 2-methyl-3-butenyl, 2-methyl-pentenyl and 3-methyl-pentenyl.The example of aralkyl comprises phenmethyl, styroyl, 3-hydrocinnamyl, diphenyl-methyl, trityl, three styroyls, (1-naphthyl) methyl and (2-naphthyl) methyl.As alkoxyl group, preferably have the alkoxyl group of 1 to 6 carbon atom, the example comprises methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert.-butoxy, pentyloxy and hexyloxy.The example of carboxyalkyl comprises carboxymethyl, 1-carboxy ethyl and 2-carboxy ethyl.As diazonium salt (I), preferably use wherein R
1it is the diazonium salt of alkoxyl group.In these diazonium salts, preferably use wherein R
1it is the diazonium salt of methoxyl group.
In formula (I), the example of negatively charged ion comprises Cl
-, 1/2SO
4 2-, 1/3PO
4 3-and NO
3 -.As diazonium salt (I), preferably use wherein X
-cl
-or 1/2SO
4 2-diazonium salt, more preferably use wherein X
-cl
-diazonium salt.
In the example of above-mentioned diazonium salt (I), when containing the o-methoxyl group diazobenzene of chlorination as raw material time, adopt method of the present invention to be favourable.
Diazonium salt of the present invention (I) is by such as obtaining the compound diazotization that formula (III) represents:
(wherein R
1represent the implication identical with above-mentioned definition) [hereafter may be referred to as the aniline (III) of ortho position-replacement].Diazo reagent for diazotization reaction comprises nitrogen oxide, as nitrous acid, nitrogen protoxide, nitrogen peroxide etc.; Nitrite is as Sodium Nitrite, potassium nitrite etc.; And nitrous acid ester is as nitrous acid straight butyl, isobutyl nitrite, n-amyl nitrite, Isopentyl nitrite etc.In these reagent, in easy process, preferred nitrite.When using nitrite, nitrite can use with solid-state or aqueous solution form, and preferably uses as an aqueous solution.The amount ranges of nitrite is in the scope of 1.0 to 1.2 moles at the aniline (III) of every mole of ortho position-replacement usually.
For described diazotization reaction, usually acid and diazo reagent are together used.By carrying out diazotization reaction in the presence of acid, obtain having the counter anion of acid used as X
-diazonium salt (I).As described acid, preferably mineral acid, and the example comprises hydrogenchloride, sulfuric acid, phosphoric acid and nitric acid.In described mineral acid, preferred hydrogenchloride and sulfuric acid.Particularly, when using nitrogen oxide as diazo reagent, with regard to the yield of the diazonium salt (I) of acquisition, preferably use sulfuric acid as described acid.When using nitrite as diazo reagent, with regard to the yield of the diazonium salt (I) of acquisition, preferably use hydrogenchloride as described acid.Described acid preferably uses as an aqueous solution.The amount ranges of described acid is normally: be 1.0 to 10mol relative to the aniline (III) of every mole of ortho position-replacement, is preferably 1.5 to 5mol, and is more preferably 2.0 to 4.0mol.
Usually water-containing solvent is used for diazotization reaction.As water-containing solvent, can be used alone water, also can use the mixed solvent of water and organic solvent, preferably be used alone water.The example of organic solvent comprises alcohol, as methyl alcohol, ethanol, propyl alcohol, Virahol, propyl carbinol, n-hexyl alcohol, 2-Ethylhexyl Alcohol, n-dodecane alcohol etc.; Aliphatic hydrocrbon, as pentane, hexane, sherwood oil, raw gasline etc.; Aromatic hydrocarbon, as benzene,toluene,xylene etc.; And halohydrocarbon, as methylene dichloride, chloroform, 1,2-ethylene dichloride, 1，1，1-trichloroethane, 1,1,2-trieline, 1,1,2,2-zellon, chlorobenzene, o-dichlorobenzene etc.In these, if need to use two or more organic solvents.
The consumption of described water-containing solvent is generally 1 to 20 times of aniline (III) weight of ortho position-replacement, is preferably 1 to 10 times.
In diazotization reaction, add the aniline (III) of ortho position-replacement, diazo reagent, acid and water-containing solvent order be not particularly limited, preferably diazo reagent is added in the mixture of the aniline (III) of ortho position-replacement, acid and water-containing solvent.When using above-mentioned nitrogen oxide as diazo reagent, preferably above-mentioned nitrogen oxide is blown in the mixture of the aniline (III) of ortho position-replacements, sour and water-containing solvent.The scope of the temperature of reaction of diazotization reaction is in-20 to 20 DEG C usually, is preferably-10 to 10 DEG C, is more preferably the scope of-5 to 5 DEG C.The reaction times of diazotization reaction depends on that reaction conditions changes, normally 1 to 20 hour as temperature of reaction etc.Diazotization reaction is carried out usually at about atmospheric pressure, and if there are needs also can carry out at an elevated pressure.As the reaction pattern of diazotization reaction, any one in continuous mode, semi-batch pattern and batch mode can be used.
As for the material be selected from for described at least one of the present invention in sulphite and hydrosulphite, the example of sulphite comprises sulfurous acid, ammonium sulphite, S-WAT and potassium sulfite.The example of hydrosulphite comprises ammonium bisulfite, sodium bisulfite and Potassium hydrogen sulfite.It is 2mol that the described at least one amount of substance be selected from sulphite and hydrosulphite is no less than every moles diazonium salt (I) usually, preferably in the scope of 2.0 to 3.0mol, is more preferably 2.1 to 2.8mol.When combinationally using sulphite and hydrosulphite, as long as their total amount is in above-mentioned scope.The material that described at least one is selected from sulphite and hydrosulphite can use with solid-state or the aqueous solution, preferably uses with the aqueous solution.As the aqueous solution comprising described at least one and be selected from the material in sulphite and hydrosulphite, preferred adjustment in use crosses the aqueous solution of pH value, and its pH value is preferably 5.0 to 8.0, more preferably 5.5 to 7.5 scope.The acid of such as hydrogenchloride, sulfuric acid etc. and so on and the alkali of such as sodium hydroxide, potassium hydroxide, ammoniacal liquor etc. and so on all can be used for regulating described pH value.
Suitably select for mixing diazonium salt (I), described at least one is selected from material in sulphite and hydrosulphite and the method for water, and the example comprises: diazonium salt (I) is added to the method for the aqueous solution being selected from the material in sulphite and hydrosulphite containing described at least one by (A); (B) aqueous solution of the material be selected from sulphite and hydrosulphite containing described at least one is added to the method for diazonium salt (I); (C) the described at least one material be selected from sulphite and hydrosulphite is added to the method in the mixture of diazonium salt (I) and water; (D) by diazonium salt (I) and the method being fed to reactive system containing the aqueous solution that described at least one is selected from the material in sulphite and hydrosulphite simultaneously; (E) mixture of diazonium salt (I) and water and the described at least one material be selected from sulphite and hydrosulphite are fed to simultaneously the method for reactive system; (F) diazonium salt (I), described at least one are selected from the method that material in sulphite and hydrosulphite and water are fed to reactive system simultaneously.Preferred use aforesaid method (A).In aforesaid method (A), (B) and (D), diazonium salt (I) can be the mixture formed with water.
Be selected from the temperature normally 20 to 100 DEG C in the reaction of the material in sulphite and hydrosulphite in diazonium salt (I) and described at least one, be preferably 30 to 85 DEG C.With regard to can improving phenylhydrazine (II) yield of final acquisition, react preferably by following process: diazonium salt (I), described at least one are selected from material in sulphite and hydrosulphite and water 45 to 100 DEG C of mixing, preferably 50 to 80 DEG C of mixing, thus by gained mixture 45 to 100 DEG C of thermal treatments, preferably 55 to 85 DEG C of thermal treatments.In this case, just can improve with regard to final phenylhydrazine (II) yield obtained, pH during mixing preferably 5.5 to 7.5, more preferably 6.0 to 7.0 scope.Above-mentioned acid or alkali all can be used for regulating pH.
Be selected from the substance reaction in sulphite and hydrosulphite in described diazonium salt (I) and described at least one, the consumption of water is generally 1 to 20 times that described at least one is selected from the weight of the material in sulphite and hydrosulphite, is preferably 1 to 10 times.When combinationally using sulphite and hydrosulphite, corresponding to the total amount of used sulphite and hydrosulphite, as long as the consumption of water is in above-mentioned scope.
Be selected from the reaction of the material in sulphite and hydrosulphite in diazonium salt (I) and described at least one, can be with an organic solvent.The example of described organic solvent comprises alcohol, as methyl alcohol, ethanol, propyl alcohol, Virahol, propyl carbinol, n-hexyl alcohol, 2-Ethylhexyl Alcohol, n-dodecane alcohol etc.; Aliphatic hydrocrbon is as pentane, hexane, sherwood oil, raw gasline etc.; Aromatic hydrocarbon is as benzene,toluene,xylene etc.; And halohydrocarbon is as methylene dichloride, chloroform, 1,2-ethylene dichloride, 1，1，1-trichloroethane, 1,1,2-trieline, 1,1,2,2-zellon, chlorobenzene, o-dichlorobenzene etc.In these, if need to use two or more organic solvents.
The reaction that diazonium salt (I) and described at least one are selected from the material in sulphite and hydrosulphite is carried out usually at about atmospheric pressure, and also can carry out at an elevated pressure if necessary.As the reaction pattern of described reaction, any one in continuous mode, semi-batch pattern and batch mode can be used.
The reaction mixture that diazonium salt (I) and described at least one obtain after being selected from the substance reaction in sulphite and hydrosulphite mixes at 0 to 10 DEG C with hydrogenchloride subsequently.The example of blending means comprises method hydrogenchloride being added into above-mentioned reaction mixture, above-mentioned reaction mixture is added into the method for hydrogenchloride, and above-mentioned reaction mixture and hydrogenchloride are fed to the method for reactive system simultaneously.With regard to can improving phenylhydrazine (II) yield of final acquisition, preferably hydrogenchloride is added into the method for above-mentioned reaction mixture.As hydrogenchloride, hydrogen chloride gas or hydrochloric acid can be used, preferably use hydrochloric acid.In hydrochloric acid, the concentration of hydrogenchloride is generally 10 to 40 % by weight, is preferably 25 to 37 % by weight.The consumption of hydrogenchloride is generally 1.0 to 10mol relative to every moles diazonium salt (I), is preferably 2.0 to 8.0mol, is preferably 3.0 to 7.0mol.In addition, the pH of the mixture after mixing with hydrogenchloride preferably more than 3, more preferably no more than 1.By being set to be no more than 3 by the pH of the mixture after mixing with hydrogenchloride, the yield of the final phenylhydrazine (II) obtained can be improved.The pH of the mixture after mixing with hydrogenchloride can be regulated by the consumption of hydrogenchloride.Temperature when mixing with hydrogenchloride is generally 0 to 10 DEG C, is preferably 2 to 7 DEG C.By temperature when mixing with muriate is set to 0 to 10 DEG C, the yield of the final phenylhydrazine (II) obtained can be improved.Usually implement at about atmospheric pressure with mixing of hydrogenchloride, if necessary, can implement at an elevated pressure.
When above-mentioned reaction mixture mixes with hydrogenchloride, solvent can be added in addition.The example of described solvent comprises alcohol, as methyl alcohol, ethanol, propyl alcohol, Virahol, propyl carbinol, n-hexyl alcohol, 2-Ethylhexyl Alcohol, n-dodecane alcohol etc.; Aliphatic hydrocrbon, as pentane, hexane, sherwood oil, raw gasline etc.; Aromatic hydrocarbon is as benzene,toluene,xylene etc.; Halohydrocarbon, as methylene dichloride, chloroform, 1,2-ethylene dichloride, 1，1，1-trichloroethane, 1,1,2-trieline, 1,1,2,2-zellon, chlorobenzene, o-dichlorobenzene etc.; And water.In these, if need to use two or more solvents.
The reaction product obtained be selected from the substance reaction in sulphite and hydrosulphite in diazonium salt (I) and described at least one after mixes at 0 to 10 DEG C with hydrogenchloride, and remains on 10 to 30 DEG C subsequently.Maintenance temperature after mixing with hydrogenchloride is preferably 10 to 25 DEG C.By maintenance temperature is set to 10 to 30 DEG C, the yield of the final phenylhydrazine (II) obtained can be improved.Described maintenance temperature is preferably higher than temperature when mixing with hydrogenchloride.Hold-time is depended on and such as keeps the condition of temperature etc. and so on and change, and is preferably 0.5 to 3 hour.Pressure during maintenance is typically about normal atmosphere, if necessary, can be in the pressure of rising.
In above-mentioned maintenance, solvent can be used.The example of described solvent comprises alcohol, as methyl alcohol, ethanol, propyl alcohol, Virahol, propyl carbinol, n-hexyl alcohol, 2-Ethylhexyl Alcohol, n-dodecane alcohol etc.; Aliphatic hydrocrbon, as pentane, hexane, sherwood oil, raw gasline etc.; Aromatic hydrocarbon is as benzene,toluene,xylene etc.; Halohydrocarbon, as methylene dichloride, chloroform, 1,2-ethylene dichloride, 1，1，1-trichloroethane, 1,1,2-trieline, 1,1,2,2-zellon, chlorobenzene, o-dichlorobenzene etc.; And water.In these, if need to use two or more solvents.
Above-mentioned with hydrogenchloride mix and maintenance upon mixing can be implemented with batch mode in same reactor, or described mixing and keep to implement in a continuous mode in the container separated, that is, continuously by the reactor of material by multiple series connection.As above-mentioned reactor, usually use Agitation and mixing type reactor.When adding hydrogenchloride by batch mode in above-mentioned reaction mixture, the time of adding hydrogenchloride being suitably set by consumption etc. usually, being preferably 0.5 to 5 hour.
Like this, the reaction mixture containing the compound represented by formula (II) can be obtained:
(wherein R
1represent the implication identical with above-mentioned definition) [phenylhydrazine (II)].The post-processing operation of suitable selection after above-mentioned maintenance, such as, by after above-mentioned maintenance, can concentrate the reaction mixture of gained and is separated phenylhydrazine (II); The pH of the reaction mixture of gained after above-mentioned maintenance can be regulated, then by organic solvent extraction by phenylhydrazine (II) with organic solvent solution isolated in form out; And, when the reaction mixture of gained is the slurries of phenylhydrazine (II) after above-mentioned maintenance, phenylhydrazine (II) can be separated by filtering.In above-mentioned extraction, usually by pH regulator in the scope of 8 to 12, and can to regulate by adding alkali such as sodium hydroxide, potassium hydroxide, ammoniacal liquor etc.Organic solvent for extracting can be can by the solvent be separated from water, and the example comprises the fatty alcohol with 4 to 12 carbon atoms, such as propyl carbinol, n-hexyl alcohol, 2-Ethylhexyl Alcohol, n-dodecane alcohol etc.; Aliphatic hydrocrbon, as pentane, hexane, sherwood oil, raw gasline etc.; Aromatic hydrocarbon, as benzene,toluene,xylene etc.; And halohydrocarbon, as methylene dichloride, chloroform, 1,2-ethylene dichloride, 1，1，1-trichloroethane, 1,1,2-trieline, 1,1,2,2-zellon, chlorobenzene, o-dichlorobenzene etc.In these, if need also can use two or more organic solvents.When diazonium salt (I) is selected from the substance reaction in sulphite and hydrosulphite with described at least one, when above-mentioned mixing with hydrogenchloride, or during maintenance after above-mentioned mixing with hydrogenchloride, can use the organic solvent that can be separated from water, this organic solvent is also used as extraction solvent.If needed, phenylhydrazine (II) to be separated can be purified by operations such as such as recrystallization, distillation, chromatographies.
Embodiment
Hereafter embodiments of the invention are described.But, it should be noted that and the invention is not restricted to these embodiments.In an embodiment, by high-efficient liquid phase chromatogram technique analysis and calculating o-methoxyaniline [compound of formula (III), wherein R
1methoxyl group] content, the o-methoxyl group diazobenzene of chlorination [compound of formula (I), wherein R
1be methoxyl group and X
-cl
-] yield and content and o-methoxyl group phenylhydrazine [compound of formula (II), wherein R
1methoxyl group] yield and content.
Reference example 1
The hydrochloric acid of 20.14g (0.16mol) o-methoxyaniline, 25.12g water and 60.77g (0.33mol) 20 % by weight is placed in the flask of 300ml, and by these contents in stirring at room temperature, thus generate solution.Described solution is cooled to 0 DEG C while stirring, and while keeping the temperature of mixing solutions to be 0 DEG C, in 1 hour, dropwise add the sodium nitrite in aqueous solution of 28.49g (0.17mol) 40 % by weight wherein, thus obtain the mixing solutions (i) that 134.52g contains the o-methoxyl group diazobenzene of chlorination.When by this mixing solutions (i) of high-efficient liquid phase chromatogram technique analysis, the content of the o-methoxyl group diazobenzene of the chlorination in this mixing solutions (i) is 20.76 % by weight, and the o-methoxyl group diazobenzene of chlorination is 100% relative to the yield of o-methoxyaniline.
Embodiment 1
The aqueous solution of sodium bisulfite of 107.89g (0.36mol) 35 % by weight, 34.65g (0.59mol) sodium-chlor and 83.40g water are placed in the flask of 1L, and by these contents in stirring at room temperature, thus generate solution.Along with stirring, in this solution, add the aqueous solution of the ammonia of 25 % by weight, with by pH regulator to 6.0, obtain mixing solutions (A).The mixing solutions (A) produced is heated to 60 DEG C while stirring, and adds the aqueous solution of the ammonia of 25 % by weight wherein in 60 DEG C.Keep pH to be 6.0, in 0.5 hour, in the mixture of gained, add the mixing solutions (i) of the whole amount obtained by reference to method described in example 1.Then the mixture of gained is heated to 75 DEG C, and stirs 1 hour in 75 DEG C, be cooled to 5 DEG C subsequently, obtain reaction mixture (A).The reaction mixture (A) of gained is solution, and its pH is 9.1.Make it remain in while 5 DEG C at stirred reaction mixture (A), in 2 hours, dropwise add the hydrochloric acid of 83.60g (0.80mol) 35 % by weight wherein.After dropwise adding, the pH of mixture is-0.14.After being added dropwise to complete, content is heated to 25 DEG C, stirs 1 hour at 25 DEG C, obtain reaction mixture (B).The pH of the reaction mixture (B) of gained is-0.85.In the reaction mixture (B) of gained, add the aqueous sodium hydroxide solution of 48 % by weight, with by pH regulator to 9.6, add 142.76g toluene subsequently, and by contents stirred 0.5 hour.After stirring, make Oil-water separation by the mixture 0.2 hour of standing gained, obtain the toluene solution of 161.22g as the o-methoxyl group phenylhydrazine of organic phase.When by this solution of high-efficient liquid phase chromatogram technique analysis, in solution, the content of o-methoxyl group phenylhydrazine is 11.67 % by weight, and o-methoxyl group phenylhydrazine is 83.3% relative to the yield of the o-methoxyl group diazobenzene of chlorination.
Embodiment 2
Carry out the operation identical with embodiment 1, obtain reaction mixture (A).Reaction mixture (A) is remained on 10 DEG C while stirring, and in 2 hours, drips the hydrochloric acid of 86.12g (0.83mol) 35 % by weight.The pH being added dropwise to complete rear mixture is-0.50.After being added dropwise to complete, content is heated to 25 DEG C, stirs 1 hour at 25 DEG C, obtain reaction mixture (C).The pH of the reaction mixture (C) of gained is-0.87.In the reaction mixture (C) of gained, add the aqueous sodium hydroxide solution of 48 % by weight, with by pH regulator to 9.6, add 142.90g toluene subsequently, and by contents stirred 0.5 hour.After stirring, make Oil-water separation by the mixture 0.2 hour of standing gained, obtain the toluene solution of 161.17g as the o-methoxyl group phenylhydrazine of organic phase.When by this solution of high-efficient liquid phase chromatogram technique analysis, in solution, the content of o-methoxyl group phenylhydrazine is 11.41 % by weight, and o-methoxyl group phenylhydrazine is 81.4% relative to the yield of the o-methoxyl group diazobenzene of chlorination.
Embodiment 3
Carry out the operation identical with embodiment 1, obtain reaction mixture (A).Reaction mixture (A) is remained on 5 DEG C while stirring, and in 2 hours, drips the hydrochloric acid of 92.28g (0.89mol) 35 % by weight.The pH being added dropwise to complete rear mixture is-0.11.After being added dropwise to complete, content is heated to 10 DEG C, stirs 2.5 hours at 10 DEG C, obtain reaction mixture (D).The pH of the reaction mixture (D) of gained is-0.55.In the reaction mixture (D) of gained, add the aqueous sodium hydroxide solution of 48 % by weight, with by pH regulator to 9.6, add 143.22g toluene subsequently, and by contents stirred 0.5 hour.After stirring, make Oil-water separation by the mixture 0.2 hour of standing gained, obtain the toluene solution of 160.49g as the o-methoxyl group phenylhydrazine of organic phase.When by this solution of high-efficient liquid phase chromatogram technique analysis, in solution, the content of o-methoxyl group phenylhydrazine is 11.36 % by weight, and o-methoxyl group phenylhydrazine is 80.7% relative to the yield of the o-methoxyl group diazobenzene of chlorination.
Embodiment 4
Carry out the operation identical with embodiment 1, obtain reaction mixture (A).Reaction mixture (A) is remained on 5 DEG C while stirring, and in 2 hours, drips the hydrochloric acid of 84.39g (0.81mol) 35 % by weight.The pH being added dropwise to complete rear mixture is-0.13.After being added dropwise to complete, content is heated to 15 DEG C, stirs 3 hours at 15 DEG C, obtain reaction mixture (E).The pH of the reaction mixture (E) of gained is-0.59.In the reaction mixture (E) of gained, add the aqueous sodium hydroxide solution of 48 % by weight, with by pH regulator to 9.6, add 142.48g toluene subsequently, and by contents stirred 0.5 hour.After stirring, implement Oil-water separation by the mixture 0.2 hour of standing gained, obtain the toluene solution of 160.45g as the o-methoxyl group phenylhydrazine of organic phase.When by this solution of high-efficient liquid phase chromatogram technique analysis, in solution, the content of o-methoxyl group phenylhydrazine is 11.63 % by weight, and o-methoxyl group phenylhydrazine is 82.6% relative to the yield of the o-methoxyl group diazobenzene of chlorination.
Embodiment 5
Carry out the operation identical with embodiment 1, obtain reaction mixture (A).Reaction mixture (A) is remained on 5 DEG C while stirring, and in 2 hours, drips the hydrochloric acid of 84.45g (0.81mol) 35 % by weight.The pH being added dropwise to complete rear mixture is-0.17.After being added dropwise to complete, content is heated to 20 DEG C, stirs 1.5 hours at 20 DEG C, obtain reaction mixture (F).The pH of the reaction mixture (F) of gained is-0.80.In the reaction mixture (F) of gained, add the aqueous sodium hydroxide solution of 48 % by weight, with by pH regulator to 9.6, add 143.66g toluene subsequently, and by contents stirred 0.5 hour.After stirring, the mixture of standing gained 0.2 hour, to make Oil-water separation, obtains the toluene solution of 161.39g as the o-methoxyl group phenylhydrazine of organic phase.When by this solution of high-efficient liquid phase chromatogram technique analysis, in solution, the content of o-methoxyl group phenylhydrazine is 11.40 % by weight, and o-methoxyl group phenylhydrazine is 81.4% relative to the yield of the o-methoxyl group diazobenzene of chlorination.
Comparative example 1
Carry out the operation identical with embodiment 1, obtain reaction mixture (A).Reaction mixture (A) is remained on 15 DEG C while stirring, and in 2 hours, drips the hydrochloric acid of 85.77g (0.82mol) 35 % by weight.The pH being added dropwise to complete rear mixture is-0.61.After being added dropwise to complete, content is heated to 25 DEG C, stirs 1 hour at 25 DEG C, obtain reaction mixture (G).The pH of the reaction mixture (G) of gained is-0.81.In the reaction mixture (G) of gained, add the aqueous sodium hydroxide solution of 48 % by weight, with by pH regulator to 9.6, add 142.78g toluene subsequently, and by contents stirred 0.5 hour.After stirring, the mixture of standing gained 0.2 hour, to make Oil-water separation, obtains the toluene solution of 159.34g as the o-methoxyl group phenylhydrazine of organic phase.When by this solution of high-efficient liquid phase chromatogram technique analysis, in solution, the content of o-methoxyl group phenylhydrazine is 9.58 % by weight, and o-methoxyl group phenylhydrazine is 67.6% relative to the yield of the o-methoxyl group diazobenzene of chlorination.
Comparative example 2
Carry out the operation identical with embodiment 1, obtain reaction mixture (A).Reaction mixture (A) is remained on 25 DEG C while stirring, and in 2 hours, drips the hydrochloric acid of 86.61g (0.83mol) 35 % by weight.The pH being added dropwise to complete rear mixture is-0.82.After being added dropwise to complete, content being stirred 1 hour at 25 DEG C, obtains reaction mixture (H).The pH of the reaction mixture (H) of gained is-0.76.In the reaction mixture (H) of gained, add the aqueous sodium hydroxide solution of 48 % by weight, with by pH regulator to 9.6, add 143.22g toluene subsequently, and by contents stirred 0.5 hour.After stirring, the mixture of standing gained 0.2 hour, to make Oil-water separation, obtains the toluene solution of 160.94g as the o-methoxyl group phenylhydrazine of organic phase.When by this solution of high-efficient liquid phase chromatogram technique analysis, in solution, the content of o-methoxyl group phenylhydrazine is 9.47 % by weight, and o-methoxyl group phenylhydrazine is 67.4% relative to the yield of the o-methoxyl group diazobenzene of chlorination.
Comparative example 3
Carry out the operation identical with embodiment 1, obtain reaction mixture (A).Reaction mixture (A) is remained on 5 DEG C while stirring, and in 2 hours, drips the hydrochloric acid of 84.97g (0.82mol) 35 % by weight.The pH being added dropwise to complete rear mixture is-0.16.After being added dropwise to complete, content being stirred 4 hours at 5 DEG C, obtains reaction mixture (I).The pH of the reaction mixture (I) of gained is-0.10.In the reaction mixture (I) of gained, add the aqueous sodium hydroxide solution of 48 % by weight, with by pH regulator to 9.6, add 142.69g toluene subsequently, and by contents stirred 0.5 hour.After stirring, the mixture of standing gained 0.2 hour, to make Oil-water separation, obtains the toluene solution of 157.95g as the o-methoxyl group phenylhydrazine of organic phase.When by this solution of high-efficient liquid phase chromatogram technique analysis, in solution, the content of o-methoxyl group phenylhydrazine is 9.64 % by weight, and o-methoxyl group phenylhydrazine is 67.4% relative to the yield of the o-methoxyl group diazobenzene of chlorination.
Claims (7)
1. produce the method for the compound represented by formula (II) for one kind:
Wherein, R
1represent hydrogen atom, alkyl, cycloalkyl, alkenyl, aralkyl, alkoxyl group or carboxyalkyl,
Described method comprises:
Diazonium salt by formula (I) represents:
Wherein R
1represent the implication identical with above-mentioned definition, and X
-represent negatively charged ion,
The material be selected from sulphite and hydrosulphite with at least one reacts in presence of water; And
The reaction mixture of gained is mixed at 0 to 10 DEG C with hydrogenchloride, subsequently mixture is remained on 10 to 30 DEG C.
2. method according to claim 1, wherein, described in remain on the high temperature of temperature when mixing with hydrogenchloride than described reaction mixture and implement.
3. method according to claim 1 and 2, wherein, remains on 10 to 30 DEG C by described reaction mixture, keeps its pH not higher than 3 simultaneously after described reaction mixture and hydrogenchloride being mixed at 0 to 10 DEG C.
4. method according to claim 1, wherein, the R in formula (I) and (II)
1it is alkoxyl group.
5. method according to claim 1, wherein, the R in formula (I) and (II)
1it is methoxyl group.
6. method according to claim 1, wherein, the X in formula (I)
-cl
-.
7. according to the method described in claim 6, wherein, the compound of the described diazonium salt represented by formula (I) by formula (III) is represented:
Wherein R
1represent the implication identical with above-mentioned definition,
React under the existence of hydrogenchloride with nitrite and obtain.
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