CN100546972C - The method for preparing the 4-amino-diphenyl-amine - Google Patents
The method for preparing the 4-amino-diphenyl-amine Download PDFInfo
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- CN100546972C CN100546972C CNB028164474A CN02816447A CN100546972C CN 100546972 C CN100546972 C CN 100546972C CN B028164474 A CNB028164474 A CN B028164474A CN 02816447 A CN02816447 A CN 02816447A CN 100546972 C CN100546972 C CN 100546972C
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
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Abstract
The present invention relates to the method for a kind of 4-of production amino-diphenyl-amine or its substitutive derivative, comprise the steps: to make aniline or anils and nitrobenzene derivative to carry out reactivity and contact; Aniline and oil of mirbane are being comprised under suitable time and the temperature in the zone that limits in the presence of the mixture of highly basic, suitable phase-transfer catalyst and oxygenant react, obtain 4-amino-diphenyl-amine intermediate product.In addition, this mixture can comprise cationic inorganic salt or metal organic salt, oxygenant and the organic bases that has for the suitable cation of strong inorganic base, but this mixture does not comprise the reaction product of trimethyl-glycine and strong inorganic base.With this amino-diphenyl-amine intermediate product reduction, produce 4-amino-diphenyl-amine or its substitutive derivative.
Description
Technical field
The present invention relates to a kind of method of the 4-of preparation amino-diphenyl-amine intermediate.
Background technology
The 4-amino-diphenyl-amine is widely used as intermediate in the alkyl derivative of producing as antiozonidate and antioxidant, be used as the stablizer of monomer and polymkeric substance and be used for various special applications.For example, 4-amino-diphenyl-amine (4-ADPA) obtains N-(1, the 3-dimethylbutyl)-N '-phenyl-Ursol D with the standard reductive alkylation of methyl iso-butyl ketone (MIBK), and the latter is the useful antiozonidate that is used to protect various rubber products.
4-amino-diphenyl-amine derivative can prepare in every way.Interesting synthetic method is optional aniline that replaces and the optional reaction of oil of mirbane in the presence of alkali that replaces, for example at U.S.5, and 608,111 (authorizing people such as Stern) and U.S.5, open in 739,403 (the authorizing people such as Reinartz).
U.S.5,608,111 have described a kind of method for preparing the optional 4-ADPA that replaces, and wherein make optional aniline that replaces and the optional oil of mirbane that replaces react (coupling) in the first step in the presence of alkali.In an embodiment, make the reaction in the presence of as the Tetramethylammonium hydroxide of alkali of aniline and oil of mirbane, and in coupling reaction process azeotropic removal of water and aniline.
International publication WO 00/35853 discloses a kind of by making aniline and oil of mirbane react the method for the intermediate for preparing the 4-amino-diphenyl-amine in liquid medium, and wherein reaction system is by the solution composition of the salt of true zwitter-ion and oxyhydroxide.Exemplified the combination of potassium hydroxide and hydration trimethyl-glycine.This reaction can be carried out in the presence of oxygen free gas.
EP announce 566 783 described a kind of by make oil of mirbane and aniline in the medium of polar aprotic solvent in the strong basicity reaction system reaction prepare the method for 4-nitro diphenylamine.Use phase-transfer catalyst such as 4-butyl ammonium hydrogen sulfate.The document requires to be reflected under the oxygen-free atmosphere to carry out, with the undesirable side reaction that prevents to cause because of oxidation.
US patent 5,117,063 and international publication WO 01/14312 disclose the method for using mineral alkali and crown ether, phase-transfer catalyst to prepare 4-nitro diphenylamine and 4-nitroso-group diphenylamine.
US patent 5,453,541 have instructed and can outside siccative such as anhydrous sodium sulphate be used to absorb excessive water in the anaerobism or the aerobic method that are used for producing one or more 4-ADPA intermediates, make substituted aniline derivative and oil of mirbane carry out reactivity in described method and contact.
The purpose of this invention is to provide a kind of by making aniline and oil of mirbane react the excellent process of producing one or more 4-ADPA intermediates in the presence of highly basic and the phase-transfer catalyst or in the presence of organic bases and inorganic salt or metal organic salt.
Summary of the invention
In brief, the present invention provides the method for a kind of 4-of production amino-diphenyl-amine or its substitutive derivative in one embodiment, comprises the steps:
(a) making aniline or anils carry out reactivity with oil of mirbane or nitrobenzene derivative contacts;
(b) obtain 4-amino-diphenyl-amine intermediate product by aniline or anils and oil of mirbane or nitrobenzene derivative are reacted in the zone that limits in the presence of the mixture that is comprising highly basic, oxygenant and phase-transfer catalyst under suitable time, the pressure and temperature, described phase-transfer catalyst is selected from the defined compound of formula I:
R wherein
1, R
2, R
3Identical or different and be selected from any straight chain or branching C
1-C
20Alkyl, (R
4)
eWhen e=0 hydrogen, at e=1 or 2 o'clock R
4Be R
1R
2R
3N
+Y is alkyl, aryl, alkaryl or benzyl and substitutive derivative thereof, Z is for being selected from hydroxyl, halogen and other heteroatomic substituting group, X is the anionicsite of the form of mixtures of fluorochemical, muriate, oxyhydroxide, vitriol, hydrosulfate, acetate, formate, nitrate, phosphoric acid salt, hydrophosphate, dihydrogen phosphate, oxalate, carbonate, borate, tartrate, Citrate trianion, malonate and described compound, wherein a is the valence mumber (1,2 or 3) of anionicsite, and b and c are that 1,2 or 3 integer and d are the integer of 0-4; With
(c) with the 4-amino-diphenyl-amine intermediate product reduction of step (b), produce 4-amino-diphenyl-amine or its substitutive derivative.
In second embodiment, the invention provides the method for a kind of 4-of production amino-diphenyl-amine or its substitutive derivative, comprise the steps:
(a) making aniline or anils carry out reactivity with oil of mirbane or nitrobenzene derivative contacts;
(b) by making aniline or anils and oil of mirbane or nitrobenzene derivative comprise oxygenant under suitable time, the pressure and temperature in the zone that limits and also obtaining 4-amino-diphenyl-amine intermediate product as reaction in the presence of the alkaline mixture of phase-transfer catalyst, described highly basic is selected from the defined compound of formula II:
R wherein
1, R
2, R
3Identical or different and be selected from any straight chain or branching C
1-C
20Alkyl, (R
4)
eWhen e=0 hydrogen, at e=1 or 2 o'clock R
4Be R
1R
2R
3N
+, Y is alkyl, aryl, alkaryl or benzyl and substitutive derivative thereof, and Z is for being selected from hydroxyl, halogen and other heteroatomic substituting group, and b and c are that 1,2 or 3 integer and d are the integer of 0-4; With
(c) with the 4-amino-diphenyl-amine intermediate product reduction of step (b), produce 4-amino-diphenyl-amine or its substitutive derivative.
In the 3rd embodiment, the invention provides the method for a kind of 4-of production amino-diphenyl-amine or its substitutive derivative, comprise the steps:
(a) making aniline or anils carry out reactivity with oil of mirbane or nitrobenzene derivative contacts;
(b) obtain 4-amino-diphenyl-amine intermediate product by aniline or anils and oil of mirbane or nitrobenzene derivative being comprised under suitable time, the pressure and temperature have to react in the presence of the mixture for the cationic inorganic salt of the suitable cation of strong inorganic base or metal organic salt or its mixture, oxygenant and one or more organic basess in the zone that limits, described organic bases is selected from the defined compound of formula III:
R wherein
1, R
2, R
3Identical or different and be selected from any 1 straight chain or branched-alkyl to about 20 carbon atoms that contain, e is 0,1,2 or 3 integer, (R
4)
eWhen e=0 hydrogen, at e=1,2 or 3 o'clock R
4Be R
1R
2R
3N
+X is for capturing the negatively charged ion of proton from the nitrogen of aniline or anils, Y is alkyl, aryl, alkaryl or benzyl and substitutive derivative thereof, Z is for being selected from hydroxyl, halogen and other heteroatomic substituting group, wherein a is the valence mumber of anionicsite and is 1,2,3 or 4 integer, b and c are that 1,2,3 or 4 integer and d are 0,1,2,3 or 4 integer, and described mixture does not comprise the reaction product of trimethyl-glycine and strong inorganic base; With
(c) with the 4-amino-diphenyl-amine intermediate product reduction of step (b), produce 4-amino-diphenyl-amine or its substitutive derivative.
Other embodiment of the present invention comprises relevant reaction mixture and each components in proportions, specific phase transfer catalyst and specific alkaline details, and all these details are disclosed in the following discussion to each side of the present invention hereinafter.
Detailed Description Of The Invention
The present invention relates to the method for the intermediate of a kind of aforesaid preparation 4-ADPA, this method has excellent productive rate and selectivity to these intermediates.These intermediates comprise 4-nitroso-group-and/or 4-nitro diphenylamine (being respectively p-NDPA and 4-NDPA) and salt thereof.Intermediate hydrogenation can be produced the 4-amino-diphenyl-amine then.
The replacement that conforms to above-mentioned formula I and the example of multifunctional phase-transfer catalyst be (2S, 3S)-two (trimethyl ammonium)-1,4-butyleneglycol dichloride.Except shown in the following example those, other effective phase-transfer catalyst that meets formula I can be from document such as C.M.Starks and C.Liotta, PhaseTransfer C atalysis, Principles and Techniques (phase-transfer catalysis, principle and technology), Academic Press, 1978 and W.E.Keller, Fluka-Compendium, 1st, 2,3 volumes, Georg Thieme Verlag, New York, 1986, embodiment in 1987,1992.
The replacement that conforms to III with above-mentioned formula II and the example of multifunctional organic bases be (2S, 3S)-two (trimethyl ammonium)-1,4-butyleneglycol dihydroxide.Except shown in the following example those, other effective organic bases that meets formula II and III can be derived from above-mentioned phase-transfer catalyst, and wherein negatively charged ion is replaced by hydroxide radical or other suitable anionic form.
Known or it is believed that in the methods of the invention especially effectively phase-transfer catalyst comprises tetramethyl ammonium chloride, Methanaminium, N,N,N-trimethyl-, fluoride, Tetramethylammonium hydroxide, carbonic acid two (tetramethyl-ammonium), tetramethyl-ammonium formiate and tetramethyl ammonium acetate; 4-butyl ammonium hydrogen sulfate and tetrabutyl ammonium sulfate; Methyltributylammonichloride chloride; And benzyltrimethylammonium hydroxide (Triton B), tri-n-octyl methyl ammonium chloride (Aliquat 336), tetrabutylammonium chloride, tetramethyl-ammonium nitrate, palmityl trimethyl ammonium chloride and bursine.
Phase-transfer catalyst of the present invention is compared with crown ether such as 18-hat-6 has several advantages, and it is effective that described crown ether is described to alkali metal hydroxide in the document such as above-mentioned US patent 5,117,063 and international publication WO 01/14312.The distinct disadvantage of crown ether is very high initial cost and high toxicity.In addition, most of crown ethers poorly soluble in water, thereby they can not the recirculation with aqueous bases materials flow recovery.In addition, the boiling point of crown ether is high to having under the situation of extra distilation steps by the distillation recovery.Even also like this for that class crown ether that in water, has good solubility, their solvabilities in organic solvent also are good, thereby produce high loss in the organic product materials flow.At last, crown ether is known sequestrant, thereby the possibility height of expensive hydrogenation catalyst metal because of unacceptably losing with the crown ether complexing.
In the methods of the invention, the mol ratio of phase-transfer catalyst and oil of mirbane reactant is preferably about 0.05: 1 to about 1.2: 1.
The inventive method can also begin with the organic bases in top the 3rd embodiment and inorganic salt or metal organic salt.Organic bases is defined by the formula III in the described embodiment.
Known or it is believed that to the second and the 3rd embodiment especially effectively organic bases comprise and be selected from but be not limited to following quaternary ammonium hydroxide: Tetramethylammonium hydroxide, TBAH, methyl tributyl ammonium hydroxide, benzyltrimethylammonium hydroxide (Triton B), the trioctylphosphine ammonium hydroxide, cetyltrimethylammonium hydroxide and bursine and quaternary ammonium alkoxide of equal value, acetate, carbonate, supercarbonate, prussiate, phenates, phosphoric acid salt, hydrophosphate, hypochlorite, borate, the boric acid hydrogen salt, the boric acid dihydric salt, sulfide, silicate, the silicic acid hydrogen salt, silicic acid dihydric salt and silicic acid three hydrogen salts.
The term " inorganic strong alkali " of use with regard to the cationic implication of inorganic salt or metal organic salt means the alkali that can capture proton from the nitrogen of aniline or anils, and it can comprise any pK
bBe lower than about 9.4 alkali, this value is the pK of aniline
bVarious anilss can have different pK
bValue, but about 9.4 pK
bAs general standard.The pK that this alkali preferably has
bBe lower than about 7.4.
The term that is used for the negatively charged ion " X " of formula III " can be captured proton from the nitrogen of aniline or anils " and mean the pK that above also having inorganic strong alkali is discussed
bThe negatively charged ion of value.
Except hydroxide radical, the possible negatively charged ion of " X " in the formula III comprises alkoxy radical (pK
b＜1), acetate moiety (pK
b=9.25), carbonate (pK
b=3.75), bicarbonate radical (pK
b=7.6), cyanate radical (pK
b=4.7), phenol root (pK
b=4.1), phosphate radical (pK
b=1.3), hydrogen phosphate (pK
b=6.8), hypochlorite (pK
b=6.5), borate (pK
b＜1), boric acid hydrogen root (pK
b＜1), boric acid dihydro root (pK
b=4.7), sulfonium ion (pK
b=1.1), silicate (pK
b=2), silicic acid hydrogen root (pK
b=2), silicic acid dihydro root (pK
b=2.2) and silicic acid three hydrogen root (pK
b=4.1).
Although aniline most effectively with the oil of mirbane coupling, some anils that comprises acid amides such as formanilide, phenylurea, carbanilide and thiocarbanilide can substitute and be used for producing the 4-ADPA intermediate.
Although the reactant of the inventive method be called " aniline " and " oil of mirbane " and when to be produced when being 4-ADPA these reactants in fact be aniline and oil of mirbane, be understood that these reactants also can comprise the aniline of replacement and the oil of mirbane of replacement.The representative instance that can be used for the substituted aniline of the inventive method includes but not limited to 2-anisidine, 4-anisidine, 4-chloroaniline, to monomethylaniline, 4-N-methyl-p-nitroaniline, 3-bromaniline, 3-bromo-4-phenylmethylamine, para-amino benzoic acid, 2,4-diaminotoluene, 2,5-dichlorphenamide bulk powder, 1,4-phenylenediamine, 4,4 '-methylene dianiline (MDA), 1,3,5-triaminobenzene and composition thereof.The representative instance that can be used for the substituted-nitrobenzene of the inventive method includes but not limited to ortho-methylnitrobenzene, meta-methylnitrobenzene, adjacent ethyl-nitrobenzene, an ethyl-nitrobenzene, O-methoxy oil of mirbane, meta-methoxy oil of mirbane and composition thereof.
The inventive method comprises wherein and will use hydrogenation catalyst to carry out the step of hydrogenation from 4-ADPA intermediate or its substitutive derivative of step (b).The details of the others of relevant catalyzer selection and hydrogenation can find in the US patent in being incorporated herein as a reference 6,140,538.
Other does not relate to direct use hydrogen and the known method of reducing of those skilled in the art also be can be used for 4-ADPA intermediate or its substitutive derivative are reduced into 4-ADPA or its substitutive derivative.
The invention further relates to a kind of method of alkyl derivative of the 4-of preparation amino-diphenyl-amine; especially the method for preparing the alkyl derivative of 4-ADPA itself; these derivatives can be used to protect rubber product; make the optional aniline that replaces with the optional oil of mirbane coupling that replaces and subsequently according to the inventive method reduction in the method, the 4-amino-diphenyl-amine standard reductive alkylation that will so obtain according to the known method of these those skilled in the art becomes the alkyl derivative of 4-amino-diphenyl-amine then.Be typically, carry at hydrogen with as the carbon of catalyzer and make 4-ADPA and suitable ketone or aldehyde reaction in the presence of the platinum.Suitable ketone comprises methyl iso-butyl ketone (MIBK), acetone, methyl isoamyl ketone and methyln-hexyl ketone.For example referring to U.S.4,463,191 and people such as Banerjee,
J.Chem.Soc.Chem.Comm.(chemistry meeting will, chemical communication), 18,1275-1276 (1988).Appropriate catalyst can be with top described those be identical in order to obtain 4-ADPA, but are not limited to these.
In a preferred embodiment of the invention, reduction is carried out in the presence of water, for example water is added in the reaction mixture.When the appropriate base of using when at aniline or substituted aniline derivative and oil of mirbane or substituted-nitrobenzene derivatives reaction was water-soluble alkali, the use of water was particularly advantageous.When this alkali was water-soluble alkali, the add-on of water preferably was at least the required amount of this alkali of extraction from organic phase.Similarly, if this alkylation is carried out in the presence of for water miscible appropriate base, then the adding of water also is preferred to standard reductive alkylation.
The mol ratio of aniline and oil of mirbane particularly important not in the methods of the invention because this method any is excessive all effective down therein.
Especially effectively highly basic comprises potassium hydroxide, sodium hydroxide, cesium hydroxide, rubidium hydroxide and potassium tert.-butoxide in first embodiment of the inventive method.The mol ratio of preferred highly basic and oil of mirbane was greater than about 1: 1.The mol ratio of preferred especially highly basic and oil of mirbane is about 2: 1 to about 6: 1.
The positively charged ion that inorganic salt that can be used in combination in the 3rd embodiment of the inventive method with organic bases and metal organic salt have is the suitable cation of inorganic strong alkali.These inorganic salt and metal organic salt are selected from but are not limited to fluorochemical, muriate, bromide, vitriol, hydrosulfate, nitrate, phosphoric acid salt, dihydrogen phosphate, formate, acetate, oxalate, malonate, Citrate trianion, tartrate, maleate, oxymuriate, perchlorate, chromic salt, rhenate and the carbonate of caesium, rubidium, potassium and sodium.In the methods of the invention, inorganic salt or metal organic salt can be use in about 0.05: 1 to about 6.5: 1 with the mol ratio of oil of mirbane.
Known or it is believed that in the 3rd embodiment of the inventive method especially effectively inorganic salt and metal organic salt be in reaction medium for inorganic salt or metal organic salt-organic bases combination provide acceptable deliquescent those, comprise fluorochemical, muriate, bromide, vitriol, hydrosulfate, nitrate, phosphoric acid salt, formate, acetate and carbonate of caesium, rubidium, potassium and sodium and composition thereof.Preferably the mol ratio of organic bases that uses with inorganic salt or metal organic salt and oil of mirbane was more than or equal to about 1: 1.The mol ratio of also preferred inorganic salt or metal organic salt and organic bases was more than or equal to about 1: 1.The particularly preferred mol ratio of organic bases and oil of mirbane is about 1.1: 1 to about 6: 1.
If the used equipment of present method is had corrosive nature one of in inorganic salt and the metal organic salt but be effective to the inventive method, then maybe advantageously use the combination of combination, two or more inorganic salt and/or two or more metal organic salts of inorganic salt and metal organic salt in others.Compare with using a kind of salt, this combination also can provide better result.
The use of also believing inorganic salt and metal organic salt and organic bases has reduced undesirable alkali decomposition.
In the method for third embodiment of the invention, it should be noted that organic bases forms some mineral alkali of equal value and phase-transfer catalysts with inorganic salt or metal organic salt with putting up with, wherein for the phase-transfer catalyst of formation like this, the negatively charged ion among the formula I is the negatively charged ion from this salt.For example, Tetramethylammonium hydroxide adds Potassium Bromide and will produce some KOH and add 4 bromide.Therefore, the present invention will comprise mineral alkali and any phase-transfer catalyst that can form on the spot such as the direct use of 4 bromide, to replace Tetramethylammonium hydroxide and the bromide salt as separate constituent.
Particularly preferred highly basic and phase-transfer catalyst be combined as potassium hydroxide and quaternary alkylammonium halides.Preferred halogenide is muriate.The combination of particularly preferred organic bases and inorganic salt be tetra-alkyl ammonium hydroxide and wherein negatively charged ion be halogen ionic salt such as potassium halide.Preferred halide anions is a chlorion.Above-mentioned reaction is undertaken by the aniline of continuous still battery in the aqueous solution-water azeotrope.
Reactivity contact according to the method for first embodiment of the invention is carried out in the presence of oxygenant.This oxygenant can be oxygen free gas, or comprises oxidising agent such as superoxide, especially hydrogen peroxide.Oil of mirbane also can be used as oxidising agent.
In the methods of the invention, oxygenant only maybe advantageously needs to exist in the part-time that aniline and oil of mirbane react.This partial oxygen voltinism condition is effective especially to improving selectivity.A kind of in these situations is when the inorganic salt that have fluoride anion are used for the reaction mixture of the 3rd embodiment under partial oxygen voltinism condition.It is believed that negatively charged ion when this salt is sulfate radical, carbonate or nitrate radical and also can obtains better result, transformation efficiency and selectivity under partial oxygen voltinism condition when providing low optionally other negatively charged ion.Another kind of situation is when TMAH being used as also can play the highly basic of phase-transfer catalyst effect to second embodiment time.In addition, although first embodiment of the inventive method is not proved as yet, it is believed that partial oxygen voltinism condition is also effective to the combination that provides low optionally mineral alkali and phase-transfer catalyst.
The oxygenant that in the present invention second and the 3rd embodiment, uses can with first embodiment in the same.
Reactive contact can be carried out to about 150 ℃ temperature at about 20 ℃.Other condition of reactive contact comprises about 20 millibars of gauge pressure pressure to about 20 crust.Reaction times is less than about 3.5 hours usually.Stirred reaction mixture in entire reaction course advantageously.
The reaction of the step (b) of the inventive method first, second and the 3rd embodiment can be not more than about 10: 1 times in the mol ratio of water and oil of mirbane and carry out.The amount of water do not comprise with reactant and/or with the water of the compound hydration that forms in the method.When comprising highly basic and phase-transfer catalyst or comprising organic bases and the mixture of inorganic salt or metal organic salt when being the aqueous solution, this reaction can be undertaken by continuous still battery aniline-water azeotrope.
First embodiment of the present invention can use the 4 bromide as phase-transfer catalyst to carry out with the highly basic that comprises one or more mineral alkalis.
Water can utilize to form new reaction mixture again.Add fresh alkali and phase-transfer catalyst or organic bases and inorganic salt or metal organic salt to replenish because of decomposition, by product formation and the deliquescent loss in isolating organic phase.Can will merge and recirculation by mixture of reaction products excessive aniline that reclaims and the fresh aniline that replenishes, thereby form new reaction mixture by distillation.The recovery of excessive oil of mirbane was preferably undertaken by independent step before hydrogenation 4-ADPA intermediate, and can and be used for this method with oil of mirbane that reclaims and the fresh oil of mirbane merging that replenishes, or was hydrogenated to aniline.
The present invention is used to prepare the method for 4-amino-diphenyl-amine intermediate and can uses the well-known method and apparatus of those skilled in the art to carry out or carry out continuously with batch process.
The inventive method first, second with the 3rd embodiment in step (a) in reactivity contact and can in proper solvent system, take place.Proper solvent system comprises polar aprotic solvent.This polar aprotic solvent can be selected from but be not limited to methyl-sulphoxide, dibenzyl ether, 1-Methyl-2-Pyrrolidone and N, dinethylformamide.
In second embodiment of the present invention, the present invention also can be in the method that does not have to carry out in the presence of the alkali metal hydroxide as phase-transfer catalyst and reaction for a kind of wherein highly basic.In this case, highly basic/phase-transfer catalyst is defined by following formula II.
The present invention is illustrated by the following example.
Test conditions is described in detail in each embodiment.In embodiment 1-10, feeding in raw material of reactor carried out in the air that opens wide, and this causes having some oxygen free gas in reaction process, even also is like this when this reactor is plugged, but is used to contrast except the test of purpose.In embodiment 1-10, do not attempt from reaction mixture, removing anhydrating.
In embodiment 11-16, feed in raw material, be heated at reactant in the whole of temperature of reaction, nitrobenzene feed and maintenance or the part process, airflow is infeeded the reactor head space, this causes existing oxygen free gas in reaction process, except as otherwise noted.Anhydrate by from reaction mixture, removing with the aniline component distillation.Yet this reaction also may be effective when not azeotropic removal of water and aniline.Analyze
The productive rate of each component is measured by external perimysium reference HPLC.About 0.6g material to be analyzed accurately is weighed in the 50ml volumetric flask also with the buffered soln dilution that contains 39 volume % water, 36 volume % acetonitriles, 24 volume % methyl alcohol and 1 volume %pH, 7 buffer reagents.This solution is expelled to the anti-phase Zorbax ODS HPLC post (on 250 * 4.6mm) that uses binary gradient pumping system and following gradient by 10 μ l loops with the constant flow rate of 1.5ml/min.
Eluent A is 75 volume % water, 15 volume % acetonitriles and 10 volume % methyl alcohol.Eluent B is 60 volume % acetonitriles and 40 volume % methyl alcohol.Use the UV of 250nm to detect.
The transformation efficiency of embodiment 1-10 calculates by the adduction of known component and any unknown peak of analyzing (setting a molal weight value 216 arbitrarily, aniline+oil of mirbane).In some cases, total conversion rate is because of only forming derivative greater than 100% by aniline.
The transformation efficiency of embodiment 11-16 calculates based on the amount that remains in the unreacted oil of mirbane in the final linked reaction thing.If do not detect oil of mirbane, suppose that then transformation efficiency is 100%.
Selectivity is defined by following formula: (p-NDPA productive rate+4-NDPA productive rate)/(overall yield).4-NDPA is a 4-nitro diphenylamine, and p-NDPA is a 4-nitroso-group diphenylamine.Overall yield is the productive rate sum of all known and unknown peaks (setting a molal weight value 216 arbitrarily, aniline+oil of mirbane).
In table, " An Recr " refers to therefrom can easily reclaim out the compound of aniline and is the summation of trans nitrogen benzide and zinin; " other " is the coupling by product of aniline and oil of mirbane, as azophenlyene, N-oxygen base azophenlyene, 2-NDPA, 4-phenylazo--diphenylamine (4-phenazo-diphenylamine) and any unknown materials.
Test
Test conditions describes in detail in each embodiment.
Embodiment 1
Embodiment 1 explanation 4-ADPA intermediate can (tetramethyl ammonium chloride TMACl) exists and time is forming than under the mild conditions in solvent-free system at mineral alkali (potassium hydroxide) and phase-transfer catalyst by aniline and oil of mirbane.The productive rate of required product depends on the add-on of phase-transfer catalyst.
With aniline (99%, 22.58g, 240mmol), oil of mirbane (99%, 4.97g, 40mmol), potassium hydroxide (86% fine grinding powder, 7.83g, 120mmol) and the following the amount of Table 1 of tetramethyl ammonium chloride add and be equipped with in the 50ml round-bottomed flask of magnetic stirring apparatus.Make to be reflected in the flask that clogs and under 60 ℃, carried out 1 hour.Analyze to the content sampling and by HPLC then.
Table 1
Productive rate, %
When reacting under the condition that changes a little as shown in table 2 below (equimolar An/NB, higher temperature of reaction, add entry etc. at long cycling time), obtain similar result.
With aniline (99%, 2.33g, 24.8mmol), oil of mirbane (99%, 3.08g, 24.8mmol), potassium hydroxide (86% fine grinding powder, 9.77g, 150mmol), the adding of tetramethyl ammonium chloride (97%, see Table 2) and water (table 2) is equipped with in the 50ml round-bottomed flask of magnetic stirring apparatus.The amount of water be total reactor reinforced 20%, suppose 14 weight %H
2O is from KOH.Make to be reflected in the unlimited flask and under 80 ℃, carried out 2 hours.Analyze to the content sampling and by HPLC then.
Table 2
Productive rate, %
The productive rate of 4-ADPA intermediate when not using tetramethyl ammonium chloride＜1% be increased to adding with respect to oil of mirbane almost 77% the during phase-transfer catalyst of equimolar amount almost.
In both cases, along with the increase of tetramethyl ammonium chloride add-on, produce more p-NDPA with respect to 4-NDPA.In addition, in the presence of excessive aniline, form more p-NDPA (seeing embodiment 7).
Embodiment 2
In several phase-transfer catalysts of embodiment 2 explanations any all can use cause aniline and oil of mirbane to produce p-NDPA and 4-NDPA with KOH.The series arrangement that the result reduces with productive rate.
In the 50ml round-bottomed flask that magnetic stirring apparatus is housed, add aniline (99%, 22.58g, 240mmol), oil of mirbane (99%, 4.97g, 40mmol), potassium hydroxide (86% fine grinding powder, 7.83g 120mmol) with phase-transfer catalyst shown in the following table 3, wherein the amount of phase-transfer catalyst equals to limit the reagent feed amount.(annotate: some test 20 or the 30mmol scale under move.) make to be reflected in the flask that clogs and under 60 ℃, carried out 1 hour.Analyze to the content sampling and by HPLC then.
Result in the table 3 shows that the adding of phase-transfer catalyst has improved the productive rate of required product in all cases.As with mineral alkali bonded phase-transfer catalyst, tetramethyl ammonium chloride, Methanaminium, N,N,N-trimethyl-, fluoride, Tetramethylammonium hydroxide, tetramethyl-volatile salt, tetramethyl-ammonium formiate and tetramethyl ammonium acetate; 4-butyl ammonium hydrogen sulfate and tetrabutyl ammonium sulfate; Methyltributylammonichloride chloride; And benzyltrimethylammonium hydroxide (Triton B) is the most effective.Other is medium effective as tri-n-octyl methyl ammonium chloride (Aliquat 336), tetrabutylammonium chloride, tetramethyl-ammonium nitrate and bursine.Bromide and iodide salt and zwitterionic betaines are also improper.Tetramethyl ammonium is observed periodically trend, because productive rate, transformation efficiency and selectivity all reduce when the sequence from the fluorochemical to iodide descends.
Table 3
Productive rate, %
*30mmol scale (16.93g aniline, 3.73g oil of mirbane, 5.87g KOH and listed PTC)
^20mmol (TMA)
2CO
3(TBA)
2SO
4(0.5-1 to NB, identical equivalents)
Embodiment 3
Embodiment 3 shows that oil of mirbane can produce the 4-ADPA intermediate with various anils couplings.
Following table 4 listed reactants with stoichiometric quantity: oil of mirbane (99%, 3.08g, 24.8mmol), potassium hydroxide (86% fine grinding powder, 9.77g, 150mmol), tetramethyl ammonium chloride (97%, 2.74g, 24.3mmol) and water (2.84g) add and to be equipped with in the 50ml round-bottomed flask of magnetic stirring apparatus.Make to be reflected in the unlimited flask and under 80 ℃, carried out 2 hours.Analyze to the content sampling and by HPLC then.
Table 4
Productive rate, %
Although the coupling in the KOH-TMACl system of aniline and oil of mirbane is the most effective, can uses to substitute and produce the 4-ADPA intermediate such as the acid amides of formanilide, phenylurea and carbanilide and thiocarbanilide.
Embodiment 4
The various alkali of embodiment 4 explanation uses combine with tetramethyl ammonium chloride aniline and oil of mirbane are reacted and production 4-ADPA intermediate.
With aniline (99%, 22.58g, 240mmol), oil of mirbane (99%, 4.97g, 40mmol), (97%, 4.52g 40mmol) adds and is equipped with in the 50ml round-bottomed flask of magnetic stirring apparatus for following table 5 alkali of giving of appropriate amount and tetramethyl ammonium chloride.Make to be reflected in the flask that clogs and under 60 ℃, carried out 1 hour.Analyze to the content sampling and by HPLC then.
Table 5
Productive rate, %
*The 30mmol scale (16.93g aniline, 3.73g oil of mirbane, 3.39g TMACl and shown in alkali)
^ only uses Tetramethylammonium hydroxide.Do not add TMACl.
Lithium hydroxide and calcium hydroxide are got rid of in screening, because these two kinds of alkali are not observed reaction.
Potassium hydroxide is preferred alkali, but sodium hydroxide, cesium hydroxide, potassium tert.-butoxide and Tetramethylammonium hydroxide also are suitable alkali, and any in them all can be used in combination with tetramethyl ammonium chloride and obtain acceptable transformation efficiency.
Embodiment 5
The reinforced influence to aniline under others constant reaction conditions-oil of mirbane link coupled product of embodiment 5 explanations increasing potassium hydroxide wherein uses tetramethyl ammonium chloride as phase-transfer catalyst.
With aniline (99%, 22.58g, 240mmol), oil of mirbane (99%, 4.97g, 40mmol), (97%, 4.52g 40mm0l) adds and is equipped with in the 50ml round-bottomed flask of magnetic stirring apparatus for the potassium hydroxide of following table 6 amounts of giving and tetramethyl ammonium chloride.Make to be reflected in the flask that clogs and under 60 ℃, carried out 1 hour.Analyze to the content sampling and by HPLC then.
Table 6
Productive rate, %
Alkali excessive higher causes the poorer and by product of reaction preference to form more.When under the reaction conditions of following table 7 described relative milders, moving, observe identical trend.Similarly, transformation efficiency is the function of alkali consumption.
With aniline (99%, 32.60g, 346.5mmol), oil of mirbane (99%, 6.16g, 49.5mmol), the potassium hydroxide of following table 7 amounts of giving (86% fine grinding powder, 16.31g, 250mmol) and tetramethyl ammonium chloride (97%, 5.48g 48.5mmol) adding is equipped with in the 100ml round-bottomed flask of Teflon blade agitator.Make and be reflected in the flask that clogs under the situation that does not apply external heat (KOH dissolves and produces some heat) carried out 1 hour in reaction water.Analyze to the content sampling and by HPLC then.
Table 7
Productive rate, %
Embodiment 6
Embodiment 6 has shown introduced oxygenant changes into p-NDPA, 4-NDPA and by product to aniline and oil of mirbane influence when utilizing potassium hydroxide/tetramethyl ammonium chloride alkali-PTC system.
With aniline (99%, 2.33g, 24.8mmol), oil of mirbane (99%, 3.08g, 24.8mmol), potassium hydroxide (86% fine grinding powder, 9.77g, 150mmol), tetramethyl ammonium chloride (97%, 0.69g, 6.1mmol) and water (2.32g) add and to be equipped with in the 50ml round-bottomed flask of magnetic stirring apparatus.Make to be reflected under the following atmospheric condition and under 80 ℃, carried out 2 hours.Analyze to the content sampling and by HPLC then.
The definition of closed system is the flask that clogs.Unlimited system is not plugged and atmosphere is opened wide.For the gas purging test, single neck flask is substituted with three-necked flask, the latter is the system that gas inlet and outlet line are housed, and is hanging down under the flow velocity with suitable gas purging reaction mass.
Table 8
Productive rate, %
When this reaction pair excess air was opened wide, selectivity was significantly improved, and this is with wherein the restricted test of oxidant content is opposite.Being formed under one situation of back of nitrogen benzide increases greatly.
The improvement of reaction preference is strengthened by the test in the table 9, and the influence of hydrogen peroxide is added in these test explanations in reaction mixture.
With aniline (99%, 22.58g, 240mmol), oil of mirbane (99%, 4.97g, 40mmol), hydrogen peroxide (50% aqueous solution, following the amount of Table 9), water (the extra water and the total amount of superoxide are constant to be 2.16g), potassium hydroxide (86% fine grinding powder, 7.83g, 120mmol) and tetramethyl ammonium chloride (97%, 4.52g 40mmol) adds and to be equipped with in the 50ml round-bottomed flask of magnetic stirring apparatus.Superoxide is added in the reaction mixture, add KOH and TMACl then and flask is clogged fast, make then to react on and carried out under 60 ℃ 1 hour.Analyze to the content sampling and by HPLC then.
Table 9
Productive rate, %
To superoxide also observe with to reaction content is opened wide viewed same trend to air, promptly be exposed to and improved selectivity in the oxygenant.This observations is by wherein excessive oil of mirbane being strengthened (seeing embodiment 7) as the test of oxygenant.
Embodiment 7
How the ratio of embodiment 7 explanation 4-ADPA intermediates can be controlled by regulating the aniline amount that adds in the reaction.
With aniline (99%, table 10 amount of giving), oil of mirbane (99%, 4.97g, 40mmol), potassium hydroxide (86% fine grinding powder, 7.83g, 120mmol) and tetramethyl ammonium chloride (97%, 4.52g 40mmol) adds and is equipped with in the 50ml round-bottomed flask of magnetic stirring apparatus.Make to be reflected in the flask that clogs and under 60 ℃, carried out 1 hour.Analyze to the content sampling and by HPLC then.
Table 10
Productive rate, %
*25mmol scale (35.28g aniline, 3.11g oil of mirbane, 4.89g KOH and 2.82g TMACl)
^30mmol scale (36.69g aniline, 3.73g oil of mirbane, 5,87g KOH and 3.39g TMACl)
#35mmol scale (36.22g aniline, 4.35g oil of mirbane, 6.85g KOH and 3.95g TMACl)
Along with more aniline adds in the reaction, form more p-NDPA with respect to 4-NDPA.Under the differential responses condition shown in the following table 11, observe identical trend.
With aniline (99%, table 11 amount of giving), oil of mirbane (99%, 3.08g, 24.8mmol), potassium hydroxide (86% fine grinding powder, 9.77g, 150mmol), tetramethyl ammonium chloride (97%, 0.69g, 6.1mmol) and water (table 11,20 weight %) add and to be equipped with in the 50ml round-bottomed flask of magnetic stirring apparatus.Make to be reflected in the unlimited flask and reacted 2 hours down in 80 ℃.Analyze to the content sampling and by HPLC then.
Table 11
Productive rate, %
The productive rate of 4-ADPA intermediate (p-NDPA+4-NDPA) does not still become when aniline excessive (about 20%) uses relatively, but significantly improves (being 73.8% under 0.25-1An/NB) when aniline becomes restricted reagent, and is as shown in table 11.Also have, when the excessive use of oil of mirbane and total water more after a little while, selectivity be improved (being 96.1% under 0.25-1An/NB).Shown in embodiment 9, less water reduces the selectivity in the mineral alkali system usually.The excessive oil of mirbane here is as oxygenant, and it improves selectivity shown in the embodiment 6 that uses air and superoxide.
Embodiment 8
When using potassium hydroxide to combine with tetramethyl ammonium chloride as alkali, being reflected between embodiment 8 explanation aniline and the oil of mirbane can under the temperature of wide region, carry out.
With aniline (99%, 2.33g, 24.8mmol), oil of mirbane (99%, 3.08g, 24.8mmol), potassium hydroxide (86% fine grinding powder, 9.77g, 150mmol), tetramethyl ammonium chloride (97%, 0.69g, 6.1mmol) and water (2.32g, 20 weight %) add and to be equipped with in the 50ml round-bottomed flask of magnetic stirring apparatus.Make and be reflected in the unlimited flask in to carrying out under the fixed temperature 2 hours.Analyze to the content sampling and by HPLC then.
Table 12
Productive rate, %
Improve temperature of reaction and cause productive rate and transformation efficiency to be improved, but the loss reaction preference.P-NDPA increases with the temperature rising with respect to the amount of 4-NDPA.
Table 13
Embodiment 9
The influence of water in aniline and oil of mirbane reaction formation 4-ADPA intermediate when KOH-TMACl alkali/phase transfer system are used in embodiment 9 explanation.
With aniline (99%, 22.58g, 240mmol), oil of mirbane (99%, 4.97g, 40mmol), potassium hydroxide (86% fine grinding powder, 7.83g, 120mmol), tetramethyl ammonium chloride (97%, 4.52g, 40mmol) be equipped with in the 50ml round-bottomed flask of magnetic stirring apparatus with table 14 and 15 listed water addings.Make to be reflected in the flask that clogs and under 60 ℃, carried out 1 hour.Analyze to the content sampling and by HPLC then.
Table 14
Productive rate, %
Table 15
Along with the amount of water increases, selectivity totally is improved and p-NDPA becomes obvious with respect to the higher level of 4-NDPA.
Also can be observed the influence of too many water by embodiment 2 and table 3, wherein show validity as 60% tetramethyl-ammonium carbonate solution of phase-transfer catalyst.The data presentation that does not report the front that is obtained by 25% dilute solution does not have to transform substantially.
Embodiment 10
Embodiment 10 shows that reaction can carry out in several solvents.
With aniline (99%, 11.29g, 120mmol), oil of mirbane (99%, 2.49g, 20mmol), potassium hydroxide (86% fine grinding powder, 3.91g, 60mmol), tetramethyl ammonium chloride (97%, 2.26g, 20mmol) be equipped with in the 50ml round-bottomed flask of magnetic stirring apparatus with the suitable solvent adding shown in the 20ml table 16.Make to be reflected in the flask that clogs and under 60 ℃, carried out 1 hour.Analyze to the content sampling and by HPLC then.
Table 16
Productive rate, %
When saving phase-transfer catalyst, that productive rate significantly reduces is about 2/3rds (71.8% when 26.7% during by no TMACl in DMSO is increased to TMACl).
Selectivity still relatively becomes (～70%) in polar solvent, but significantly reduces when selection non-polar hydrocarbon such as p-Xylol or toluene, because the nitrogen benzide productive rate is all above 40% in each of this two kinds of solvents.
Embodiment 11
Embodiment 11 explanation aniline and oil of mirbane combine the reaction by continuous still battery aniline-water azeotrope with the potassium hydroxide and the tetramethyl ammonium chloride aqueous solution.
With 111.8g aniline (99%, 1.19mol), 31.2g potassium hydroxide aqueous solution (45%, 0.250mol) (55%, 0.25mol) be equipped with in the 500ml flask of Teflon blade agitator, thermopair, nitrobenzene feed pipe and needle valve with the 50.0g tetramethyl ammonium chloride aqueous solution by adding.This mixture is evacuated to 120mm Hg, regulates pressure in the reactor by air is put into.Begin to heat and when the desired reaction temperature that reaches 80 ℃, start the oil of mirbane materials flow (24.6g, 99%, 0.20mol).Temperature is controlled by increasing vacuum tightness, to finish the NB charging under the resulting pressure of 60mm Hg in about 1 hour.Under 60mm Hg, kept 45 minutes, and reacted completely guaranteeing.With 40ml water quick cooling mixture.HPLC analyzes: 32.1% aniline, 0%NB, 20.3%p-NDPA, 7.6%4-NDPA, 0.50%t-nitrogen benzide and 0.05% azophenlyene.Productive rate based on the 100%NB transformation efficiency: 72.6%p-NDPA, 25.3%4-NDPA, 1.9%t-nitrogen benzide, 0.2% azophenlyene.
As shown in table 17 below, the identical reaction of operation causes low 12% (97.9% pair 85.5%) of productive rate and nitrogen benzide content to increase to its 7 times in the presence of no air.The overview of other reaction in this series also is shown in the following table 17.
Table 17
Productive rate, %
*6: 1 aniline/NB, 80 ℃, the NB feed time is 49 minutes, 1.25mol KOH is to NB, air atmosphere
Embodiment 12
This embodiment illustrate aniline and oil of mirbane with tetramethylammonium hydroxide aqueous solution and various inorganic salt bonded oxygenant in the presence of reaction by continuous still battery aniline-water azeotrope.The representative of TMAH/ salt binding is from the ion mixture of the latent alkali recycle stream of technology, and it comprises mineral alkali and the phase-transfer catalyst after the linked reaction material is reduced into 4-ADPA.
In the 500ml round-bottomed flask that Teflon blade agitator, thermopair, nitrobenzene feed pipe and air inlet valve are housed, add 139.7g aniline (99%, 1.49mol), 73.9g tetramethylammonium hydroxide aqueous solution (35.5%, 0.29mol) and the following table 18 listed salt (with respect to alkali, based on the excessive 15 moles of % of oil of mirbane) of equivalent amount.This mixture was heated 30 minutes under 120mm Hg, begin then to add nitrobenzene feed (30.8g, 99%, 0.25mol).By regulating the air inlet valve and regulation system pressure, to keep 80 ℃ temperature required and to make the NB charging in about 75 minutes, finishing under the resulting pressure of 72mmHg in entire reaction cycle period.This mixture was kept 30 minutes under 70mm Hg, react completely guaranteeing, use the 25ml water quick cooling subsequently.Adding reactant, be heated to temperature of reaction, adding oil of mirbane and remain in the full cycle that reacts completely and air introduced the reactor head space.Is that salt/NB=1.15 is reinforced with salt with the molar equivalent with oil of mirbane.For example, salt of wormwood and sodium sulfate have two normal inorganic cations, so mol ratio is 0.575.
With the low slightly situation of the mol ratio of oil of mirbane under use the result of KCl in full accord with the result who obtains by use highly basic and phase-transfer catalyst (KOH+TMACl), continuous still battery aniline-water azeotrope wherein.This shows that using inorganic salt and organic bases to be equivalent to uses highly basic and phase-transfer catalyst.It should be noted that concerning finishing reaction sodium does not have potassium effective like that.Nitrate and bromide also are not too effective negatively charged ion concerning finish reaction under the condition of this embodiment.Yet for these salt, it should be possible increasing transformation efficiency by the change reaction conditions as the raising temperature of reaction.The most significant is the positive influence that adds the salt pair reaction preference.The contrast of the second and the 3rd test shows in the following table 18, only adds KCl and can make nitrogen benzide reduce almost 2/3rds and form more a spot of " other " compound such as 4-phenylazo--diphenylamine.The operation of " only using TMAH " also is feature with the Trimethylamine 99 of the compound of high-load compound such as methylphenylamine and band stink, and these two shows alkaline degradation has taken place.
Table 18
Embodiment 13
This embodiment illustrates the influence of the mol ratio of inorganic salt and oil of mirbane.Reaction conditions and embodiment's 12 is suitable, and different is the mol ratio that changes KCl and oil of mirbane.Result in the table 19 shows that only adding small amounts of inorganic salt just makes selectivity increase.Therefore, need therein to pay close attention under the corrosive situation that causes because of high salt concentration, can obtain moderate at least selectivity and improve.
Table 19
Embodiment 14
This embodiment illustrates and adds the influence of non-salt compound to the transformation efficiency of selectivity and oil of mirbane.Reaction conditions and embodiment's 12 is suitable.Trimethyl-glycine, i.e. (ethanoyl) trimethylammonium hydroxide inner salt, the salt that forms for tetra-allkylammonium group by acetate moiety and positively charged.Although therefore title is like this, in fact this compound does not have and tetra-allkylammonium group bonded hydroxide radical.Yet when adding highly basic, trimethyl-glycine changes into the compound that contains acetate group and tetra-alkyl ammonium hydroxide group.Therefore, use TMAH trimethyl-glycine to be changed into compound with tetramethyl ammonium acetate group and (ethanoyl) trimethylammonium hydroxide group.If use KOH, then this compound has potassium acetate group and (ethanoyl) trimethylammonium hydroxide group.Under the KOH situation, metal organic salt and the organic bases of this compounds represented in a molecule.Trimethyl-glycine is known as phase transition compound or PTC (Starks and Liotta, ibid) in the literature, because it is brought inorganic or organic bases in the organic phase into.
Result in the table 20 shows that trimethyl-glycine only has moderate influence to selectivity or the transformation efficiency that uses TMAH.Wherein the result of trimethyl-glycine/NB=1.15 only is equivalent to the result of KCl/NB=0.25.In addition, the negatively charged ion (ammonium acetate) with inorganic cation is not invalid substantially in adding.Therefore, using inorganic salt or metal organic salt is the key that obtains best result.
Table 20
Embodiment 15
This embodiment shows the selectivity of using partial oxygen voltinism condition can provide remarkable increase.Unless otherwise, otherwise reaction conditions and embodiment 12 quite.The results are shown in the table 21.The conditionally complete of reaction 1 and embodiment's 12 is suitable.For reacting 2, air introduce only in the nitrobenzene feed process, use and finish 75% charging after stop.For reacting 3, the nitrobenzene feed time is shortened to 45 minutes and will be increased to 60 minutes the hold-time, only in the nitrobenzene feed process, use air to introduce simultaneously.Expection also obtains higher selectivity for vitriol, carbonate and nitrate by using partial oxygen voltinism condition.
Table 21
Embodiment 16
This embodiment shows that the highly basic that uses oxygenant and also be used as phase-transfer catalyst can increase selectivity.Be reflected under azeotropic removal of water and the aniline and carry out.
For operation 1-3, and adding 145.28g aniline (1.56mol) and 87.36g tetramethylammonium hydroxide aqueous solution in the 500ml round-bottomed flask that Teflon blade agitator, thermopair, nitrobenzene feed pipe and air inlet valve are housed (36.0%, 0.345mol).Mixture was heated 30 minutes under 120mm Hg, start then nitrobenzene feed (36.93g, 0.30mol).During entire reaction, system pressure is held constant at 70mm Hg.Temperature rises to about 80 ℃ by about 66 ℃ between this reaction period.Oil of mirbane was added in about 80 minutes, then this batch of material was kept 40 minutes under 70mm Hg, react completely guaranteeing, use the 25ml water quick cooling then.Hydrogen peroxide is added simultaneously with 20.40g (0.03mol) the 5 weight % aqueous solution and oil of mirbane.Because therefore water also may use 20.40g also to control with the water that oil of mirbane infeeds simultaneously by protection TMAH in case its degraded and change molecular balance influence selectivity.The condition of operation 4-7 is slightly different.Main difference is to begin with 25 weight %TMAH, and removes water and some aniline in the reactor before nitrobenzene feed.In whole nitrobenzene feed process or a half of its feed time add air.
Result in the table 22 shows that with independent use water ratio, hydrogen peroxide provides bigger selectivity and improves, and this shows that it may be favourable using oxygenant.These results also are presented at the last air that adds of whole reactor circulation and as oxygenant selectivity are had disadvantageous effect.Yet, only limiting to the partial reaction circulation time in the air adding and obtained the selectivity improvement, this shows that partial oxygen voltinism condition may be favourable.These reactions compare with the situation of 100% air in the table 18 under wet slightly condition and move, and this has explained that the selectivity in the table 18 why is lower.Operation 4 and 5 shows that reaction has excellent reproducibility, thereby selectivity increase 1-2% is significant.
Table 22
Claims (51)
1. a method of producing 4-amino-diphenyl-amine or its substitutive derivative comprises the steps:
(a) making aniline or anils carry out reactivity with oil of mirbane or nitrobenzene derivative contacts, wherein anils is selected from formanilide, phenylurea, carbanilide and thiocarbanilide, perhaps anils is selected from the 2-anisidine, the 4-anisidine, the 4-chloroaniline, to monomethylaniline, the 4-N-methyl-p-nitroaniline, the 3-bromaniline, 3-bromo-4-phenylmethylamine, para-amino benzoic acid, 2, the 4-diaminotoluene, 2, the 5-dichlorphenamide bulk powder, 1, the 4-phenylenediamine, 4,4 '-methylene dianiline (MDA), 1,3,5-triaminobenzene and composition thereof, and nitrobenzene derivative is selected from ortho-methylnitrobenzene, meta-methylnitrobenzene, adjacent ethyl-nitrobenzene, between ethyl-nitrobenzene, O-methoxy oil of mirbane, meta-methoxy oil of mirbane and composition thereof;
(b) by being reacted, aniline or anils and oil of mirbane or nitrobenzene derivative obtain 4-amino-diphenyl-amine intermediate product in the zone that limits in the presence of the mixture that is comprising highly basic, superoxide and phase-transfer catalyst under suitable time, the pressure and temperature, perhaps the reaction of aniline and oil of mirbane is only carried out in the presence of the mixture that comprises highly basic, air and phase-transfer catalyst during the part, and described phase-transfer catalyst is selected from the defined compound of formula I:
R wherein
1, R
2, R
3Identical or different and be selected from any straight chain or branching C
1-C
20Alkyl, (R
4)
eWhen e=0 hydrogen, at e=1 or 2 o'clock R
4Be R
1R
2R
3N
+Y is an alkyl, aryl, alkaryl or benzyl, Z is the substituting group that is selected from hydroxyl and halogen, X is a fluorochemical, muriate, oxyhydroxide, vitriol, hydrosulfate, acetate, formate, nitrate, phosphoric acid salt, hydrophosphate, dihydrogen phosphate, oxalate, carbonate, borate, tartrate, Citrate trianion, the anionicsite of the form of mixtures of malonate and described compound, wherein a is the valence mumber of anionicsite, b and c are 1,2 or 3 integer and d are the integer of 0-4, and wherein highly basic and phase-transfer catalyst are identical or different; With
(c) with the 4-amino-diphenyl-amine intermediate product reduction of step (b), produce 4-amino-diphenyl-amine or its substitutive derivative; With
(d) randomly, the alkyl derivative that 4-amino-diphenyl-amine or its substitutive derivative reductive alkylation of step (c) become 4-amino-diphenyl-amine or its substitutive derivative.
2. according to the process of claim 1 wherein that described phase-transfer catalyst is selected from tetramethyl ammonium chloride, Methanaminium, N,N,N-trimethyl-, fluoride, Tetramethylammonium hydroxide, carbonic acid two (tetramethyl-ammonium), tetramethyl-ammonium formiate and tetramethyl ammonium acetate; 4-butyl ammonium hydrogen sulfate and tetrabutyl ammonium sulfate; Methyltributylammonichloride chloride; And benzyltrimethylammonium hydroxide, tri-n-octyl methyl ammonium chloride, tetrabutylammonium chloride, tetramethyl-ammonium nitrate, palmityl trimethyl ammonium chloride and bursine.
3. according to the process of claim 1 wherein that the mol ratio of phase-transfer catalyst and oil of mirbane is 0.05: 1 to 1.2: 1.
4. according to the process of claim 1 wherein that described highly basic is selected from potassium hydroxide, sodium hydroxide, cesium hydroxide, rubidium hydroxide and potassium tert.-butoxide.
5. according to the process of claim 1 wherein that the mol ratio of highly basic and oil of mirbane was greater than 1: 1.
6. according to the process of claim 1 wherein that the mol ratio of highly basic and oil of mirbane is 2: 1 to 6: 1.
7. according to the process of claim 1 wherein that described superoxide is a hydrogen peroxide.
8. according to the process of claim 1 wherein that described superoxide only exists in the part-time that aniline and oil of mirbane react.
9. according to the process of claim 1 wherein that the temperature of described reactive contact at 20 ℃ to 150 ℃, 20 millibars are to the gauge pressure pressure of 20 crust be less than under reaction times of 3.5 hours and carry out.
10. according to the process of claim 1 wherein that mol ratio that being reflected at of step (b) got rid of water beyond the water of hydration and oil of mirbane is not more than 10: 1 times and carries out.
11. according to the process of claim 1 wherein that the described mixture that comprises highly basic and phase-transfer catalyst is the aqueous solution and reaction is undertaken by continuous still battery aniline-water azeotrope.
12. according to the process of claim 1 wherein that described phase-transfer catalyst is a tetramethyl ammonium chloride.
13. according to the process of claim 1 wherein that described reactive contact takes place in solvent system.
14. according to the method for claim 13, wherein said solvent system comprises polar aprotic solvent.
15. according to the method for claim 14, wherein said polar aprotic solvent is selected from methyl-sulphoxide, dibenzyl ether, 1-Methyl-2-Pyrrolidone and N, dinethylformamide.
16. according to the process of claim 1 wherein the alkyl derivative that the 4-amino-diphenyl-amine reductive alkylation of being produced is become the 4-amino-diphenyl-amine.
17. according to the process of claim 1 wherein that described highly basic is identical with described phase-transfer catalyst, and described highly basic is selected from the defined compound of formula II:
R wherein
1, R
2, R
3Identical or different and be selected from any straight chain or branching C
1-C
20Alkyl, (R
4)
eWhen e=0 hydrogen, at e=1 or 2 o'clock R
4Be R
1R
2R
3N
+, Y is alkyl, aryl, alkaryl or benzyl, and Z is the substituting group that is selected from hydroxyl and halogen, and b and c are that 1,2 or 3 integer and d are the integer of 0-4.
18. according to the method for claim 17, the wherein said highly basic that also is used as phase-transfer catalyst comprises Tetramethylammonium hydroxide and/or benzyltrimethylammonium hydroxide.
19. according to the method for claim 17, wherein the mol ratio of highly basic and oil of mirbane was greater than 1: 1.
20. according to the method for claim 17, wherein the mol ratio of highly basic and oil of mirbane is 2: 1 to 6: 1.
21. according to the method for claim 17, wherein said superoxide is a hydrogen peroxide.
22. according to the method for claim 17, wherein said superoxide only exists in the part-time that aniline and oil of mirbane react.
23. according to the method for claim 17, exist oxygen free gas wherein said comprising in highly basic and the AIR MIXTURES.
24. according to the method for claim 17, wherein said reactive contact 20 ℃ to 150 ℃ temperature, 20 millibars to the gauge pressure pressure of 20 crust be less than under reaction times of 3.5 hours and carry out.
25. according to the method for claim 17, wherein the mol ratio that is reflected at the water got rid of beyond the water of hydration and oil of mirbane of step (b) is not more than 10: 1 times and carries out.
26. according to the method for claim 17, wherein said reactive contact takes place in solvent system.
27. according to the method for claim 26, wherein said solvent system comprises polar aprotic solvent.
28. according to the method for claim 27, wherein said polar aprotic solvent is selected from methyl-sulphoxide, dibenzyl ether, 1-Methyl-2-Pyrrolidone and N, dinethylformamide.
29., wherein the 4-amino-diphenyl-amine reductive alkylation of being produced is become the alkyl derivative of 4-amino-diphenyl-amine according to the method for claim 17.
30. a method of producing 4-amino-diphenyl-amine or its substitutive derivative comprises the steps:
(a) making aniline or anils carry out reactivity with oil of mirbane or nitrobenzene derivative contacts, wherein anils is selected from formanilide, phenylurea, carbanilide and thiocarbanilide, perhaps anils is selected from the 2-anisidine, the 4-anisidine, the 4-chloroaniline, to monomethylaniline, the 4-N-methyl-p-nitroaniline, the 3-bromaniline, 3-bromo-4-phenylmethylamine, para-amino benzoic acid, 2, the 4-diaminotoluene, 2, the 5-dichlorphenamide bulk powder, 1, the 4-phenylenediamine, 4,4 '-methylene dianiline (MDA), 1,3,5-triaminobenzene and composition thereof, and nitrobenzene derivative is selected from ortho-methylnitrobenzene, meta-methylnitrobenzene, adjacent ethyl-nitrobenzene, between ethyl-nitrobenzene, O-methoxy oil of mirbane, meta-methoxy oil of mirbane and composition thereof;
(b) obtain 4-amino-diphenyl-amine intermediate product by aniline or anils and oil of mirbane or nitrobenzene derivative being comprised under suitable time, the pressure and temperature have to react in the presence of the mixture for the cationic inorganic salt of strong inorganic base or metal organic salt or its mixture, superoxide and one or more organic basess in the zone that limits, perhaps the reaction of aniline and oil of mirbane is only carried out in the presence of the mixture that comprises highly basic, air and organic bases during the part, and described organic bases is selected from the defined compound of formula III:
R wherein
1, R
2, R
3Identical or different and be selected from any straight chain or branched-alkyl that contains 1 to 20 carbon atom, e is 0,1,2 or 3 integer, (R
4)
eWhen e=0 hydrogen, at e=1,2 or 3 o'clock R
4Be R
1R
2R
3N
+X is for capturing the negatively charged ion of proton from the nitrogen of aniline or anils, Y is alkyl, aryl, alkaryl or benzyl, Z is the substituting group that is selected from hydroxyl and halogen, wherein a is the valence mumber of anionicsite and is 1,2,3 or 4 integer, b and c are that 1,2,3 or 4 integer and d are 0,1,2,3 or 4 integer, and described mixture does not comprise the reaction product of trimethyl-glycine and strong inorganic base;
(c) with the 4-amino-diphenyl-amine intermediate product reduction of step (b), produce 4-amino-diphenyl-amine or its substitutive derivative; With
(d) randomly, the alkyl derivative that 4-amino-diphenyl-amine or its substitutive derivative reductive alkylation of step (c) become 4-amino-diphenyl-amine or its substitutive derivative.
31. according to the method for claim 30, wherein said organic bases is for being selected from Tetramethylammonium hydroxide, TBAH, methyl tributyl ammonium hydroxide, benzyltrimethylammonium hydroxide, the trioctylphosphine ammonium hydroxide, cetyltrimethylammonium hydroxide and bursine and corresponding quaternary ammonium alkoxide, acetate, carbonate, supercarbonate, prussiate, phenates, phosphoric acid salt, hydrophosphate, hypochlorite, borate, the boric acid hydrogen salt, the boric acid dihydric salt, sulfide, silicate, the silicic acid hydrogen salt, the quaternary ammonium hydroxide of silicic acid dihydric salt and silicic acid three hydrogen salts.
32. according to the method for claim 30, wherein the mol ratio of organic bases that uses with inorganic salt or metal organic salt and oil of mirbane was more than or equal to 1: 1.
33. according to the method for claim 30, wherein the mol ratio of organic bases and oil of mirbane is 1.1: 1 to 6: 1.
34. according to the method for claim 30, wherein the mol ratio of inorganic salt or metal organic salt and oil of mirbane is 0.05: 1 to 6.5: 1.
35. according to the method for claim 30, wherein the mol ratio of inorganic salt or metal organic salt and organic bases was more than or equal to 1: 1.
36. according to the method for claim 30, wherein said inorganic salt that are used in combination with organic bases or metal organic salt are selected from fluorochemical, muriate, bromide, vitriol, hydrosulfate, nitrate, phosphoric acid salt, formate, acetate and carbonate of caesium, rubidium, potassium and sodium and composition thereof.
37., have oxygen free gas in the wherein said mixture that comprises highly basic, air and organic bases according to the method for claim 30.
38. according to the method for claim 30, wherein the described mixture that contains superoxide that is reflected at of step (b) carries out under existing.
39. according to the method for claim 30, wherein said superoxide is a hydrogen peroxide.
40. according to the method for claim 30, wherein said superoxide only exists in the part-time that aniline and oil of mirbane react.
41. according to the method for claim 30, wherein said reactive contact 20 ℃ to 150 ℃ temperature, 20 millibars to the gauge pressure pressure of 20 crust be less than under reaction times of 3.5 hours and carry out.
42. according to the method for claim 30, wherein the mol ratio that is reflected at the water got rid of beyond the water of hydration and oil of mirbane of step (b) is not more than 10: 1 times and carries out.
43. according to the method for claim 30, the wherein said mixture that comprises organic bases and inorganic salt or metal organic salt is the aqueous solution and reaction is undertaken by continuous still battery aniline-water azeotrope.
44. according to the method for claim 30, wherein said reactive contact takes place in solvent system.
45. according to the method for claim 44, wherein said solvent system comprises polar aprotic solvent.
46. according to the method for claim 45, wherein said polar aprotic solvent is selected from methyl-sulphoxide, dibenzyl ether, 1-Methyl-2-Pyrrolidone and N, dinethylformamide.
47., wherein the 4-amino-diphenyl-amine reductive alkylation of being produced is become the alkyl derivative of 4-amino-diphenyl-amine according to the method for claim 30.
48. according to the method for claim 30, wherein the X of formula III is selected from the negatively charged ion of oxyhydroxide, alkoxide, acetate, carbonate, supercarbonate, prussiate, phenates, phosphoric acid salt, hydrophosphate, hypochlorite, borate, boric acid hydrogen salt, boric acid dihydric salt, sulfide, silicate, silicic acid hydrogen salt, silicic acid dihydric salt and silicic acid three hydrogen salts.
49. according to the method for claim 30, wherein said organic bases is a Tetramethylammonium hydroxide, described inorganic salt comprise halide anions and react and undertaken by the aniline of continuous still battery in the aqueous solution-water azeotrope.
50. according to the method for claim 49, wherein said halide anions is a chlorion.
51. a method of producing 4-amino-diphenyl-amine or its substitutive derivative comprises the steps:
(a) making aniline or anils carry out reactivity with oil of mirbane or nitrobenzene derivative contacts, wherein anils is selected from formanilide, phenylurea, carbanilide and thiocarbanilide, perhaps anils is selected from the 2-anisidine, the 4-anisidine, the 4-chloroaniline, to monomethylaniline, the 4-N-methyl-p-nitroaniline, the 3-bromaniline, 3-bromo-4-phenylmethylamine, para-amino benzoic acid, 2, the 4-diaminotoluene, 2, the 5-dichlorphenamide bulk powder, 1, the 4-phenylenediamine, 4,4 '-methylene dianiline (MDA), 1,3,5-triaminobenzene and composition thereof, and nitrobenzene derivative is selected from ortho-methylnitrobenzene, meta-methylnitrobenzene, adjacent ethyl-nitrobenzene, between ethyl-nitrobenzene, O-methoxy oil of mirbane, meta-methoxy oil of mirbane and composition thereof;
(b) by make aniline or anils and oil of mirbane or nitrobenzene derivative in the zone that limits in the suitable time, comprising the highly basic that comprises one or more mineral alkalis under the pressure and temperature, superoxide and have reaction down and obtain 4-amino-diphenyl-amine intermediate product as the mixture of the 4 bromide of phase-transfer catalyst, perhaps the reaction of aniline and oil of mirbane is only comprising the highly basic that comprises one or more mineral alkalis during the part, air and exist down as the mixture of the 4 bromide of phase-transfer catalyst carries out, and the wherein said mixture that comprises highly basic and phase-transfer catalyst is the aqueous solution and reacts and undertaken by continuous still battery aniline-water azeotrope; With
(c) with the 4-amino-diphenyl-amine intermediate product reduction of step (b), produce 4-amino-diphenyl-amine or its substitutive derivative; With
(d) randomly, the alkyl derivative that 4-amino-diphenyl-amine or its substitutive derivative reductive alkylation of step (c) become 4-amino-diphenyl-amine or its substitutive derivative.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/911,058 | 2001-07-23 | ||
| US09/911,058 US6395933B1 (en) | 2001-07-23 | 2001-07-23 | Process for preparing 4-aminodiphenylamine intermediates |
| US10/143,478 | 2002-05-10 | ||
| US10/143,478 US6583320B2 (en) | 2001-07-23 | 2002-05-10 | Process for preparing 4-aminodiphenylamine intermediates |
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| CN200910167072.4A Division CN101665437B (en) | 2001-07-23 | 2002-07-09 | Process for preparing 4-aminodiphenylamine |
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| CN100546972C true CN100546972C (en) | 2009-10-07 |
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| EP (1) | EP1414782A1 (en) |
| JP (1) | JP4603260B2 (en) |
| CN (1) | CN100546972C (en) |
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| CA (1) | CA2454603A1 (en) |
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| PL (1) | PL206080B1 (en) |
| RS (1) | RS3904A (en) |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108558675A (en) * | 2018-04-25 | 2018-09-21 | 南通理工学院 | A kind of synthetic method of 4-ADPA |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US6395933B1 (en) * | 2001-07-23 | 2002-05-28 | Flexsys America, L.P. | Process for preparing 4-aminodiphenylamine intermediates |
| US7183439B2 (en) * | 2002-12-10 | 2007-02-27 | Flexsys America L.P. | Process for preparing 4-aminodiphenylamine intermediates |
| US8486223B2 (en) | 2003-07-04 | 2013-07-16 | Jiangsu Sinorgchem Technology Co., Ltd. | Falling film evaporator |
| JP4546958B2 (en) * | 2003-07-04 | 2010-09-22 | チアンス・シノケム・テクノロジー・カンパニー・リミテッド | Method for producing 4-aminodiphenylamine |
| US8686188B2 (en) | 2003-07-04 | 2014-04-01 | Jiangsu Sinorgchem Technology Co., Ltd. | Process for preparing 4-aminodiphenylamine |
| KR100612922B1 (en) | 2003-07-04 | 2006-08-14 | 농유 왕 | A process for producing 4-aminodiphenylamine |
| KR100621310B1 (en) * | 2005-05-16 | 2006-09-06 | 금호석유화학 주식회사 | Method for preparing 4-aminodiphenylamine |
| JP4876707B2 (en) * | 2006-05-10 | 2012-02-15 | 住友化学株式会社 | Method for producing 4-nitrosodiphenylamine and 4-nitrodiphenylamine |
| KR100932208B1 (en) * | 2009-05-21 | 2009-12-16 | 엘아이지넥스원 주식회사 | Sdr apparatus based on sca and method for executing waveform in the apparatus |
| CN101717339A (en) * | 2009-12-08 | 2010-06-02 | 江苏扬农化工集团有限公司 | Double quaternary ammonium base compound and preparation method as well as application thereof |
| CN101830811B (en) * | 2010-02-23 | 2013-04-03 | 江苏扬农化工集团有限公司 | Preparation method of 4-aminodiphenylamine |
| WO2011148976A1 (en) * | 2010-05-26 | 2011-12-01 | 住友化学株式会社 | Method for producing 4-nitrodiphenylamine |
| CN102372640A (en) * | 2010-08-20 | 2012-03-14 | 中国石油化工集团公司 | Method for preparing 4-nitrodiphenylamine and 4-nitrosodiphenylamine |
| CN102344376B (en) * | 2011-08-17 | 2014-04-02 | 中国石油化工股份有限公司 | Method for preparing p-aminodiphenylamine |
| RU2553984C2 (en) * | 2013-02-28 | 2015-06-20 | Олег Александрович ГОДЗОЕВ | Method of obtaining 4-aminodiphenylamine and its alkylated derivatives |
| CN103819346B (en) * | 2014-03-17 | 2015-11-04 | 山东尚舜化工有限公司 | A kind of production unit of precursor of 4-ADPA and production technique |
| CN111689866A (en) * | 2019-03-15 | 2020-09-22 | 中石化南京化工研究院有限公司 | Preparation method of tower reaction RT base |
| RU2706682C1 (en) * | 2019-07-24 | 2019-11-20 | Вахтанг Нодарович Лемонджава | Apparatus for monitoring and regulating the process of defrosting plasma and blood cells |
| CN113527111B (en) * | 2020-04-10 | 2023-09-15 | 中国石油化工股份有限公司 | Method for preparing RT (reverse transcription) sauce by normal pressure condensation |
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| US4463191A (en) * | 1983-09-26 | 1984-07-31 | The Goodyear Tire & Rubber Company | Process for the reductive alkylation of aromatic nitro-containing compounds with ketones or aldehydes |
| DE3620639A1 (en) * | 1986-06-20 | 1987-12-23 | Bayer Ag | Process for the preparation of 4-nitrodiphenylamines |
| US5117063A (en) * | 1991-06-21 | 1992-05-26 | Monsanto Company | Method of preparing 4-aminodiphenylamine |
| EP0566783A1 (en) * | 1992-04-21 | 1993-10-27 | Akzo N.V. | Process for the production of nitrodiarylamines |
| JPH07149695A (en) * | 1993-09-30 | 1995-06-13 | Seiko Kagaku Kk | Production of 4-aminodiphenylamine |
| DE4427249A1 (en) * | 1994-08-02 | 1996-02-08 | Bayer Ag | Process for the preparation of nitro-substituted arylamines |
| DE19600722A1 (en) * | 1996-01-11 | 1997-07-17 | Bayer Ag | Process for the preparation of optionally substituted 4-aminodiphenylamines |
| US5977411A (en) * | 1997-06-10 | 1999-11-02 | Flexsys America L.P. | Catalytic hydrogeneration of nitrobenzene to 4-aminodiphenylamine in the presence of a hydroxyl compound and a solvent |
| SK283209B6 (en) * | 1998-12-11 | 2003-03-04 | Duslo, A. S. | Preparation method for 4-aminodiphenylamine |
| KR100298572B1 (en) * | 1999-08-19 | 2001-09-22 | 박찬구 | The method for preparing 4-nitrodiphenylamine and 4-nitrosodiphenylamine from carbanilide |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108558675A (en) * | 2018-04-25 | 2018-09-21 | 南通理工学院 | A kind of synthetic method of 4-ADPA |
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| JP4603260B2 (en) | 2010-12-22 |
| JP2005515163A (en) | 2005-05-26 |
| NO20040292L (en) | 2004-03-19 |
| CN1545497A (en) | 2004-11-10 |
| PL374267A1 (en) | 2005-10-03 |
| BR0211391A (en) | 2006-05-23 |
| BR0211391B1 (en) | 2013-05-14 |
| RU2004105163A (en) | 2005-08-10 |
| CA2454603A1 (en) | 2003-02-06 |
| WO2003010126A1 (en) | 2003-02-06 |
| IL159994A0 (en) | 2004-06-20 |
| AU2002315530B2 (en) | 2008-05-22 |
| RS3904A (en) | 2006-12-15 |
| EP1414782A1 (en) | 2004-05-06 |
| TWI265919B (en) | 2006-11-11 |
| MXPA04000665A (en) | 2004-04-05 |
| PL206080B1 (en) | 2010-06-30 |
| HUP0501066A2 (en) | 2006-09-28 |
| RU2280640C2 (en) | 2006-07-27 |
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