CA2063817A1 - Method for the preparation of nitroanilines - Google Patents
Method for the preparation of nitroanilinesInfo
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- CA2063817A1 CA2063817A1 CA 2063817 CA2063817A CA2063817A1 CA 2063817 A1 CA2063817 A1 CA 2063817A1 CA 2063817 CA2063817 CA 2063817 CA 2063817 A CA2063817 A CA 2063817A CA 2063817 A1 CA2063817 A1 CA 2063817A1
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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
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
- C07C209/10—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of amino groups bound to carbon atoms of six-membered aromatic rings or from amines having nitrogen atoms bound to carbon atoms of six-membered aromatic rings
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Abstract
Abstract of the disclosure:
Process for the preparation of nitroanilines A process for the preparation of nitroanilines of the formula (I) (I) in which R1, R2 are a hydrogen atom or a (C1-C4)alkyl group and R is a hydrogen atom or a nitro group, by reacting 1 mol of a nitrochlorobenzene of the formula (II) (II) in which R has the meaning mentioned, with about 200 to about 4000 mol-% of a compound of the formula III
Process for the preparation of nitroanilines A process for the preparation of nitroanilines of the formula (I) (I) in which R1, R2 are a hydrogen atom or a (C1-C4)alkyl group and R is a hydrogen atom or a nitro group, by reacting 1 mol of a nitrochlorobenzene of the formula (II) (II) in which R has the meaning mentioned, with about 200 to about 4000 mol-% of a compound of the formula III
Description
HOECHST ARTIENGESELLSCHAFT HOE 8g~ 8 ~ 7 Dr.MU/PP
De~cription Proce~s for the preparation of nitroanilines The invention relates to an Lmproved process for the preparation of mononitro- or dinitroanilines in very good yields and high purity by reaction of mononitro- or dinitrochlorobenzenes with ammonia or amines in the pre~ence of surface-active compounds.
The nitroanilines mentioned below are important inter-mediates in the preparation of dyes and pigments and for the preparation of pharmaceuticals and plant protection agents. They are, for example, the compounds N-methyl-4-nitroaniline, N,N-dimethyl-4-nitroaniline, N-methyl-2-nitroaniline, N,N-dimethyl-2-nitroaniline, 2,4-dinitro-aniline, 2,4-dinitro-N-methylaniline and 2,4-dinitro-N,N-dimethylaniline.
De~cription Proce~s for the preparation of nitroanilines The invention relates to an Lmproved process for the preparation of mononitro- or dinitroanilines in very good yields and high purity by reaction of mononitro- or dinitrochlorobenzenes with ammonia or amines in the pre~ence of surface-active compounds.
The nitroanilines mentioned below are important inter-mediates in the preparation of dyes and pigments and for the preparation of pharmaceuticals and plant protection agents. They are, for example, the compounds N-methyl-4-nitroaniline, N,N-dimethyl-4-nitroaniline, N-methyl-2-nitroaniline, N,N-dimethyl-2-nitroaniline, 2,4-dinitro-aniline, 2,4-dinitro-N-methylaniline and 2,4-dinitro-N,N-dimethylaniline.
2,4-dinitroaniline is prepared, for example, by rearrangement of N,4-dinitroacetanilide, which is ther-mally labile, in acetic acid at 0 to 70~C and subsoquent hydroly~is in 200 to 3800 mol-% sulfuric acid of the resulting 2,4-dinitroacetanilide to give the desired product (PL 131,799 of 30.04.87). In this procedure, ~
concentrated ncid-polluted wa~te water containing ~trong organic contamination is obtained, which has to be 2S disposed of in a very complicated manner. The safety aspecta of the rearrangement of the thermally labile dinitro ~tarting compound are ~n sdditional problem of this procedure.
2,4~dinitroaniline is also prepared by reaction of a melt of 2,4-dinitrochlorobenzene with ~mmonia at 180C in 71%
yield (CN 86,100,379 of 19.01.86). This renction variant invol~es the difficult problem, certainly for industrial production, of the homogeneous mixing of the two reaction components ammonia and 2,4-dinitrochlorobenzene. In addition, there i8 the necessity to wssh out totally the ammonium chloride formed in the reaction from the 2,4-dinitroaniline after dischar~ing the excess ammonia.
2~3817 Owing to the high melting point of the final product, the reaction must be conducted at a hazardously high tempera-ture level (180C) at which an explosive decomposition cannot be excluded during the relatively long reaction time.
A further preparation possibility for 2,4-dinitroaniline described by Gitis et al. (US 3,398,194) is preparation by reaction of 2,2'-4,4'-tetranitrodiphenyl ether in dimethylformamide while passing ammonia through at room temperature. The very labile and extremely reactive - starting material for this reaction - the 2,2~-4,4'-tetranitrodiphenyl ether - i8 prepared by reaction of 2,4-dinitrophenol with 2,4-dinitrochlorobenzene by means of base catalysis, extremely thermally labile 2,4-dinitrophenolate being formed as an intermediate. It ensues that, through the preparation of the diphenyl ether, a process step is added to the normal preparation of 2,4-dinitroaniline from 2,4-dinitrochlorobenzene, which prohibits pr~paration by this reaction route for economical reasons. Other nitroanilines described by way of example above are also prepared by reaction of the corresponding alkylamlne with 2,2'-4,4'-tetranitro-diphenyl ether, where this procedure principally drives up the costs of industrial production owing to its two-step nature and can therefore be re~ected for ecological and economic reason~, but al~o owing to the rel~tively high chemical expenditure and the purification process necessary in each ~tep.
DE-OS 2,725,957 of 22.12.77 de~cribe~ the prepar~tion of 2,4-dinitro-N-methylaniline a8 followss 203.5 parts of 2,4-dinitrochlorobenzene are ~u~pended in 390 parts by weight of water by stirring nt room temperature. This suspension is brought to 85C, after which the addition of 120 part~ by volume of 41.5% strength methylamine solution is begun. The temper~ture increases to 88C
during this exothermic reaction. The description text then reads: ~the emulsion solidifies slowly and forms a
concentrated ncid-polluted wa~te water containing ~trong organic contamination is obtained, which has to be 2S disposed of in a very complicated manner. The safety aspecta of the rearrangement of the thermally labile dinitro ~tarting compound are ~n sdditional problem of this procedure.
2,4~dinitroaniline is also prepared by reaction of a melt of 2,4-dinitrochlorobenzene with ~mmonia at 180C in 71%
yield (CN 86,100,379 of 19.01.86). This renction variant invol~es the difficult problem, certainly for industrial production, of the homogeneous mixing of the two reaction components ammonia and 2,4-dinitrochlorobenzene. In addition, there i8 the necessity to wssh out totally the ammonium chloride formed in the reaction from the 2,4-dinitroaniline after dischar~ing the excess ammonia.
2~3817 Owing to the high melting point of the final product, the reaction must be conducted at a hazardously high tempera-ture level (180C) at which an explosive decomposition cannot be excluded during the relatively long reaction time.
A further preparation possibility for 2,4-dinitroaniline described by Gitis et al. (US 3,398,194) is preparation by reaction of 2,2'-4,4'-tetranitrodiphenyl ether in dimethylformamide while passing ammonia through at room temperature. The very labile and extremely reactive - starting material for this reaction - the 2,2~-4,4'-tetranitrodiphenyl ether - i8 prepared by reaction of 2,4-dinitrophenol with 2,4-dinitrochlorobenzene by means of base catalysis, extremely thermally labile 2,4-dinitrophenolate being formed as an intermediate. It ensues that, through the preparation of the diphenyl ether, a process step is added to the normal preparation of 2,4-dinitroaniline from 2,4-dinitrochlorobenzene, which prohibits pr~paration by this reaction route for economical reasons. Other nitroanilines described by way of example above are also prepared by reaction of the corresponding alkylamlne with 2,2'-4,4'-tetranitro-diphenyl ether, where this procedure principally drives up the costs of industrial production owing to its two-step nature and can therefore be re~ected for ecological and economic reason~, but al~o owing to the rel~tively high chemical expenditure and the purification process necessary in each ~tep.
DE-OS 2,725,957 of 22.12.77 de~cribe~ the prepar~tion of 2,4-dinitro-N-methylaniline a8 followss 203.5 parts of 2,4-dinitrochlorobenzene are ~u~pended in 390 parts by weight of water by stirring nt room temperature. This suspension is brought to 85C, after which the addition of 120 part~ by volume of 41.5% strength methylamine solution is begun. The temper~ture increases to 88C
during this exothermic reaction. The description text then reads: ~the emulsion solidifies slowly and forms a
- 3 - 20~17 thick yellow cru~t on the wall of the flask." Dissolu-tion of the crust, combined with a reduction in the reaction temperature, is achieved by addition of 103 parts by volume of 30~ strength sodium hydroxide solu-tion. Using the procedure described, a yield of 97.8% oftheory of 2,4-dinitro-N-methylaniline i8 obtained, relative to 2,4-dinitrochlorobenzene.
The difficulties of the procedure described can already be seen from the description text (DE-OS 2,725,957):
0 1. Strongly exothermic reaction, with high heat of reaction and temperature increase in the reaction mixture, i.e. during industrial production with substantially impaired surface/volume ratios, uncon-trollable dQcomposition can occur as a result of the heat of reaction.
2. Crust formation on the wall of the flask, i.e. reac-tion reRidues which can possibly no longer be removed accumulate in the industrial reaction app~ratu~ and have to be removad with great mechanical expen~e.
Many users attempted to counter the disadvantage of this reaction procedure by the use of solvents such as forma-mide (DD 229,017) or dimethylformamide. However, the process using solvent has to be conducted at temperaturQs around 100C and has a poorer yield (914) than that described above.
The reaction of 2,4-dinitrophenol alkyl ethers (JP 50/126,625) or 2,4-dinitrophenol (JP 49~14,431) h~s been de~cribed a~ an alternative to the preparation proce~s of, for ex~mple, 2,4-dinitroaniline shown further above. In this process, for example, 2,4-dinitroanisole is treated with ~mmonia at high pressure in a non-water-mi~cible solvent for 6 hours. No statements were made therein about yiolds and purity.
In another example, 100 part~ of 2,4-dinitrophenol in 420 _ 4 _ 2 ~ S 3 8 ~ 7 parts of water are reacted in an autoclave at 165 to 170DC for 10 hours with 180 parts of ammonium sulfate and 120 parts of liquid ammonia. g5 parts of 2,4-dinitro-aniline are obtained in this reaction, corresponding to a yield of 94.5% of theory, relative to 2,4-dinitro-phenol.
A disadvantage of the described preparation variant from 2,4-dinitrophenol - as well as from the 2,4-dinitrophenol alkyl ethers - is on the one hand the accumulation of concentrated salt-polluted waste water - the mother liquor of the reaction - but on the other hand, much more seriously, the fact that the 2,4-dinitrophenol and the 2,4-dinitrophenol alkyl ethers are prepared from 2,4-dinitrochlorobenzene by nucleophilic exchange, i.e. a further process step with chemical and apparatu~ co~ts and purification procedures is added to the route from ~,4-dinitro-chlorobenzene to 2,4-dinitroaniline.
There was therefore a need for an improved and industrial preparation process for nitroanilines, of which some have been mentioned by way of example further above, which leads in one process step, starting from nitrochloro-;~ benzene derivatives, if possible at low temperature, if possible without using solvents necessary ~sic] distilla-tion or other separations, and in good yield and high purity to products which Lf possible c~n be separated off by ~imple filtration.
It has now ~urprisingly been found that nitroanilines of the general formula (I) R R
1 ~ ~ 2 ~ ~2 (I) in which Rl, R2 are a hydrogen atom or a (Cl-C,)alkyl group 2~3~7 and R is a hydrogen atom or a nitro group, can be pre-pared in very good yields and high purity in one process step, by reacting 1 mol of a nitrochlorobenzene of the general formula (II) ~ NO~
~ (II) R
in which R has the abovementioned meaning, with about 200 to 4000 mol-%, preferably about 200 to about 1200 mol-%, particularly preferably about 200 to about 600 mol-%, of a compound of the general formula (III) ~Rl ~ - ~ ~ (III) in which R1 and R2 have the abovementioned meanings, at temperatures of about 40C to ~bout 120C, preferably about 50C to about 90C, particularly preferably about 55C to about 80C in the presence of ~t lea~t one ionic or non-ionic surface-active compound.
After the completion of the reaction, the resulting nitroaniline~ are sepnrated off by filtration and washed.
The yields are very good (> 98~ of theory), and also the purities of the products (degreo of purity (HPLC) > 99%).
~aking-on and inclu~ions also do not take place in the cour~e of the reaction, i.e. product resldues remaining in the reaction vessel do not hnve to be taken into account with the process according to the invention.
There is also the great advantage that, owing to the "homogenisation" of the reaction mixture achieved by the addition of surface-active compounds, the reaction temperature can be reduced to a very low value which allows the non-corrosive, but al30 expensive apparatus .
.
6 2~3~
materials customarily employed in uch media, such as, for example, Ha~elloy C, to be dispen~ed with in favour of steel, which secures a high economic adYantage for the process accordin~ to the invention.
S The surface-active compounds include both ionic (anionic and cationic) and non-ionic ~urface-active compounds.
The ionic auxiliaries include anionic surface-active compounds, such a~, for example, the alkali metal salts of (Cl4-Cl~)alkylsulfonic acids, (Cl2-Cl,)aralkylsulfonic acids, for example ~odium dodecylbenzoylsulfonate tsic], or of (~3-Cs)alkylnaphthalenesulfonic acids, for example sodium l-isopropylnapthalQne-2-sulfonate, or the alkali metal Ralts of saturated or unsaturated higher fatty acids (C11-C18), for example sodium laurate, sodium myristatQ, sodium palmitate, sodium ~tearate ox sodium oleate, and furthermore the alkali metal salts of (C12-C3,)alkyl sulfates, i.e. of sulfuric acid esters of higher fatty alcohols, such as, for example, lauryl sulfate, tridecyl ~ulfate, myri~tyl sulfate, pentadecyl sulfate, cetyl ~ulfate, octadecyl sulfate, or oleyl sulfste, or of phosphoric acid esters of higher fatty alcohols or of phenol~
~he ionic auxiliaries also include cationic surface active compound~, such ~8~ for example, primary, secondary or tertiary amine salts, quaternnry ammonium salts or pyridinium salts, preferably the chlorides, sulfates or methylsufates ~ic], and al~o amphoteric surface-active compounds, for example those of the nmino salt type, for example ~odium ~minoethanesulfonate or sodium N-methylaminoethylsulfonate, or of the betaine type.
Non-ionic ~urface-act~ve compounds are those of the polyethylene glycol or polyhydroxyalcohol type. Examples of these are the alkyl polyglycol ether~, alkylphenyl polyglycol ethers, alkylnaphthyl polyglycol e~hers, fatty acid polyglycol ethers, fatty acid amide polyglycol _ 7 - 2~ g 3 ~l ethers and fatty amine polyglycol ethers.
Typical examples of these surface-active compounds are found, for example, in "Surface Active Agents and Deter-gents", Volume I, by A. M. Schwarz and J. W. Perry, or in "Catalysis in Micellar and Macromolecular Systems" by J. H. Fendler and E.J. Fendler, Academic Press N.Y. 1975.
Some surface-active compounds which are preferably used according to the invention are indicated below.
Compound 1: 30% strength aqueous solution of (Cl2-Cl~)-alkyldimethylbetaine.
Compound 2: 30% strength aqueous solution of a disul-fonated phenol-formaldehyde conden~ation product.
Compound 3: Di~ulfonated cresol-formaldehyde condensa-tion product.
Compound 4s Sulfated cresol-phenol condensation product as a 35~ strength aqueous solution.
Compound 5s Novolak derivative of the formula C~ C~H ~ ~H~9 ~ ~ ~, co~ c~;co To~l n~ ~6-20 x I
~ I ~ O ~
R n ~ ~ ~ ~
Compound 5a~ Novolak derivative of the above general formula R ~ -C0-CH2-CH (S03Na)-COONa .: -. . .
'' .
.
- 8 - 2 0 ~ 3 ~ ~ 7 R = -C0-Ph Total n = 100-110 x = 5 Compo~nd 6: Dimethylnaphthalene-sulfonated-formaldehyde condensate of the formula H3 C~31 ~R3 C ~ C~ ~ ~3 ~031ia 503~3 S~3~a Compound 7: Sulfomethylated cresol-phenol-formaldehyde conden~ate A greater molar excefis than 4000 mol-% of a compound of the general formula III can also be used. However, since in this connection a greater positive effect i8 not achieved, the use of larger amounts of this type only mean~ a reduction in the efficiency of the process.
The proces~ according to the invention can be carried out both at normal pressure and ~t elevated pressure and nlso batchwise or continuously.
The process ~ccording to the invention will be illus-trated in more detail by the ex~mples below. However, it may be empha~ised that the invention is limited neither to the use of the n$troanil$nes mentioned therein nor ; exclusively to the surfsce-active compounds mentioned in these examples and further above.
9 2~3~ ~
~sample 1 (2,4-dinitro-N-methylaniline) 340 ml of water, 270 g (1.33 mol) of 2,4-dinitrochloro-benzene and 10 g (3.7% by weight) of the compound 5a are initially introduced into a 1 1 4-neck flask fitted with a stirrer, dropping funnel, internal contact thermometer and heating bath, and the mixture is heated to 50C with stirring. A mixture of 130 ml of 40% strength mono-methyl2mine ~olution (1.67 mol), 110 ml of 35~ strength NaO~ (0.96 mol) and 160 ml of water is added dropwise at 50C in the course of 2 hours to the resulting well-distributed suspension. The mixture is subsequently stirred at 50-55C for 11 hours and the product suspen-sion is filtered off from the mother liquor with suction after stirring until it has cooled to room temperature.
After filtering off with suction and washing with 500 ml of water, 2a8 g of a 10% water-moist pale yellow finely cry~talline product hsving a melting point of 179 to 182C are obtained, corresponding to a yield of 98.9~ of theory and with a purity of 98.5% according to HPLC
(HPLC - High Performance Liquid Chromatography).
E~ample 2 (2-nitro-N,N-dimethylaniline) 451 g of 40% ~trength dimethylamine solution (4.02 mol) and 10 g of the compound 6 are initially introduced into a 2 1 4-neck flask fitted with a stirrer, internal thermometer, heatable dropping funnel and heatlng bath and the mixture 18 heated to 55 to 60C with stirring.
288 g (1.83 mol) of 2-nitrochlorobenzene are added dropwise by means of the heatable dropping funnel in the course of 4 hours. After the completion of the addition, the mixture is subsequently stirred at 60 to 70-C for 8 hours and then cooled to 30C with stirring. 150 g of 35% ~trength sodium hydroxide solution (1.3 mol) are allowed to run in with stirring. The lower phase is then separated off in a separating funnel and the upper pha~e is worked up in order to recover dimethylamine. The lo ~3~ ~
lower phase - the crude product - is washed twice with 200 ml of water each tLme, separated off and isolated.
It is briefly sub~ected to incipient distillation in vacuo in order to dry it. 283 g of 2-nitro-N,N-dimethyl-aniline are obtained as an oily yellow-brown liquid in a purity of 98.8~ according to HPLC, corresponding to a yield of 93.23 of theory.
~sample 3 (3,4-dinitroaniline) 1000 ml of 16% ~trength aqueous ammonia (9.4 mol) and 8 g (2% ~y weight) of the compound 6 are initially introduced into a 2 1 4-necked flask fitted with a stirrer, internal thermometer and heatable dropping funnel, and the mixture is heated to 55~C with stirring. The addition of 406 g (2 mol) of 2,4-dinitrochlorobenzene a~ a melt (the dropping funnel ha~ a ~acket temperature of 60C) is then ~tarted, and takes place within four hours. After this time, the mixture is subsequently stirred at 55C for 20 hours and the 2,4-dinitroaniline obtained i8 filtered off with suction through a G-3 glass frit. It is washed with 500 ml of water and sucked dry for 30 min. 412 g of 2,4-dinitroaniline which is 16% water-moist are obtained.
This corre~ponds to a yield of 94.5% of theory. The product has a melting point of 179 to 180C and a purity of 97.8% according to HPLC.
~he applicability of the compounds 1 to 7 mentioned further above a8 surfnce-active ndditives for the prep-aration of nitronniline~ was checked in sever~l experi-ments nnalogously to this exnmple. In all cases, very good yields and purities of very finely dlvided 2,4-dinitroaniline were obtained.
~s~mple 4 (2,4-dinitroaniline) 350 ml of water, 240 ml of 25% strength ammonia (3.52 mol) and 1.9 g of the compound 6 are initially introduced into a 1 1 glas~ autoclave fitted with a ~tirrer and 11 2~8~ 7 heated feed pump and, after flushing with nitrogen and closing the autoclave, heated to 55C. 187 g (0.92 mol) of 2l4-dinitrochlorobenzene are then pumped in at this temperature with ~tirring in the course of four hours.
After completion of the addition, the mixture i8 heated to 80C and subsequently ~tirred again for 16 hours. At the end of this period, the mixture is stirred until it has cooled to room temperature and the autoclave is firs~
depressurised and then emptied. 182 g of 2,4-dinitro-aniline having a residual moisture of 9% are obtained byfiltering off with suction, corresponding to a yield of 99.1% of theory. The dried product has a melting point of 179.5 to 181C and a purity of 98.7~ according to HPLC.
All surface-active compounds mentioned further above were again employed analogously to the reaction procedure and batch size in this example, good results being obtained here both in terms of the yield and the purity of the resulting 2,4-dinitroaniline.
The difficulties of the procedure described can already be seen from the description text (DE-OS 2,725,957):
0 1. Strongly exothermic reaction, with high heat of reaction and temperature increase in the reaction mixture, i.e. during industrial production with substantially impaired surface/volume ratios, uncon-trollable dQcomposition can occur as a result of the heat of reaction.
2. Crust formation on the wall of the flask, i.e. reac-tion reRidues which can possibly no longer be removed accumulate in the industrial reaction app~ratu~ and have to be removad with great mechanical expen~e.
Many users attempted to counter the disadvantage of this reaction procedure by the use of solvents such as forma-mide (DD 229,017) or dimethylformamide. However, the process using solvent has to be conducted at temperaturQs around 100C and has a poorer yield (914) than that described above.
The reaction of 2,4-dinitrophenol alkyl ethers (JP 50/126,625) or 2,4-dinitrophenol (JP 49~14,431) h~s been de~cribed a~ an alternative to the preparation proce~s of, for ex~mple, 2,4-dinitroaniline shown further above. In this process, for example, 2,4-dinitroanisole is treated with ~mmonia at high pressure in a non-water-mi~cible solvent for 6 hours. No statements were made therein about yiolds and purity.
In another example, 100 part~ of 2,4-dinitrophenol in 420 _ 4 _ 2 ~ S 3 8 ~ 7 parts of water are reacted in an autoclave at 165 to 170DC for 10 hours with 180 parts of ammonium sulfate and 120 parts of liquid ammonia. g5 parts of 2,4-dinitro-aniline are obtained in this reaction, corresponding to a yield of 94.5% of theory, relative to 2,4-dinitro-phenol.
A disadvantage of the described preparation variant from 2,4-dinitrophenol - as well as from the 2,4-dinitrophenol alkyl ethers - is on the one hand the accumulation of concentrated salt-polluted waste water - the mother liquor of the reaction - but on the other hand, much more seriously, the fact that the 2,4-dinitrophenol and the 2,4-dinitrophenol alkyl ethers are prepared from 2,4-dinitrochlorobenzene by nucleophilic exchange, i.e. a further process step with chemical and apparatu~ co~ts and purification procedures is added to the route from ~,4-dinitro-chlorobenzene to 2,4-dinitroaniline.
There was therefore a need for an improved and industrial preparation process for nitroanilines, of which some have been mentioned by way of example further above, which leads in one process step, starting from nitrochloro-;~ benzene derivatives, if possible at low temperature, if possible without using solvents necessary ~sic] distilla-tion or other separations, and in good yield and high purity to products which Lf possible c~n be separated off by ~imple filtration.
It has now ~urprisingly been found that nitroanilines of the general formula (I) R R
1 ~ ~ 2 ~ ~2 (I) in which Rl, R2 are a hydrogen atom or a (Cl-C,)alkyl group 2~3~7 and R is a hydrogen atom or a nitro group, can be pre-pared in very good yields and high purity in one process step, by reacting 1 mol of a nitrochlorobenzene of the general formula (II) ~ NO~
~ (II) R
in which R has the abovementioned meaning, with about 200 to 4000 mol-%, preferably about 200 to about 1200 mol-%, particularly preferably about 200 to about 600 mol-%, of a compound of the general formula (III) ~Rl ~ - ~ ~ (III) in which R1 and R2 have the abovementioned meanings, at temperatures of about 40C to ~bout 120C, preferably about 50C to about 90C, particularly preferably about 55C to about 80C in the presence of ~t lea~t one ionic or non-ionic surface-active compound.
After the completion of the reaction, the resulting nitroaniline~ are sepnrated off by filtration and washed.
The yields are very good (> 98~ of theory), and also the purities of the products (degreo of purity (HPLC) > 99%).
~aking-on and inclu~ions also do not take place in the cour~e of the reaction, i.e. product resldues remaining in the reaction vessel do not hnve to be taken into account with the process according to the invention.
There is also the great advantage that, owing to the "homogenisation" of the reaction mixture achieved by the addition of surface-active compounds, the reaction temperature can be reduced to a very low value which allows the non-corrosive, but al30 expensive apparatus .
.
6 2~3~
materials customarily employed in uch media, such as, for example, Ha~elloy C, to be dispen~ed with in favour of steel, which secures a high economic adYantage for the process accordin~ to the invention.
S The surface-active compounds include both ionic (anionic and cationic) and non-ionic ~urface-active compounds.
The ionic auxiliaries include anionic surface-active compounds, such a~, for example, the alkali metal salts of (Cl4-Cl~)alkylsulfonic acids, (Cl2-Cl,)aralkylsulfonic acids, for example ~odium dodecylbenzoylsulfonate tsic], or of (~3-Cs)alkylnaphthalenesulfonic acids, for example sodium l-isopropylnapthalQne-2-sulfonate, or the alkali metal Ralts of saturated or unsaturated higher fatty acids (C11-C18), for example sodium laurate, sodium myristatQ, sodium palmitate, sodium ~tearate ox sodium oleate, and furthermore the alkali metal salts of (C12-C3,)alkyl sulfates, i.e. of sulfuric acid esters of higher fatty alcohols, such as, for example, lauryl sulfate, tridecyl ~ulfate, myri~tyl sulfate, pentadecyl sulfate, cetyl ~ulfate, octadecyl sulfate, or oleyl sulfste, or of phosphoric acid esters of higher fatty alcohols or of phenol~
~he ionic auxiliaries also include cationic surface active compound~, such ~8~ for example, primary, secondary or tertiary amine salts, quaternnry ammonium salts or pyridinium salts, preferably the chlorides, sulfates or methylsufates ~ic], and al~o amphoteric surface-active compounds, for example those of the nmino salt type, for example ~odium ~minoethanesulfonate or sodium N-methylaminoethylsulfonate, or of the betaine type.
Non-ionic ~urface-act~ve compounds are those of the polyethylene glycol or polyhydroxyalcohol type. Examples of these are the alkyl polyglycol ether~, alkylphenyl polyglycol ethers, alkylnaphthyl polyglycol e~hers, fatty acid polyglycol ethers, fatty acid amide polyglycol _ 7 - 2~ g 3 ~l ethers and fatty amine polyglycol ethers.
Typical examples of these surface-active compounds are found, for example, in "Surface Active Agents and Deter-gents", Volume I, by A. M. Schwarz and J. W. Perry, or in "Catalysis in Micellar and Macromolecular Systems" by J. H. Fendler and E.J. Fendler, Academic Press N.Y. 1975.
Some surface-active compounds which are preferably used according to the invention are indicated below.
Compound 1: 30% strength aqueous solution of (Cl2-Cl~)-alkyldimethylbetaine.
Compound 2: 30% strength aqueous solution of a disul-fonated phenol-formaldehyde conden~ation product.
Compound 3: Di~ulfonated cresol-formaldehyde condensa-tion product.
Compound 4s Sulfated cresol-phenol condensation product as a 35~ strength aqueous solution.
Compound 5s Novolak derivative of the formula C~ C~H ~ ~H~9 ~ ~ ~, co~ c~;co To~l n~ ~6-20 x I
~ I ~ O ~
R n ~ ~ ~ ~
Compound 5a~ Novolak derivative of the above general formula R ~ -C0-CH2-CH (S03Na)-COONa .: -. . .
'' .
.
- 8 - 2 0 ~ 3 ~ ~ 7 R = -C0-Ph Total n = 100-110 x = 5 Compo~nd 6: Dimethylnaphthalene-sulfonated-formaldehyde condensate of the formula H3 C~31 ~R3 C ~ C~ ~ ~3 ~031ia 503~3 S~3~a Compound 7: Sulfomethylated cresol-phenol-formaldehyde conden~ate A greater molar excefis than 4000 mol-% of a compound of the general formula III can also be used. However, since in this connection a greater positive effect i8 not achieved, the use of larger amounts of this type only mean~ a reduction in the efficiency of the process.
The proces~ according to the invention can be carried out both at normal pressure and ~t elevated pressure and nlso batchwise or continuously.
The process ~ccording to the invention will be illus-trated in more detail by the ex~mples below. However, it may be empha~ised that the invention is limited neither to the use of the n$troanil$nes mentioned therein nor ; exclusively to the surfsce-active compounds mentioned in these examples and further above.
9 2~3~ ~
~sample 1 (2,4-dinitro-N-methylaniline) 340 ml of water, 270 g (1.33 mol) of 2,4-dinitrochloro-benzene and 10 g (3.7% by weight) of the compound 5a are initially introduced into a 1 1 4-neck flask fitted with a stirrer, dropping funnel, internal contact thermometer and heating bath, and the mixture is heated to 50C with stirring. A mixture of 130 ml of 40% strength mono-methyl2mine ~olution (1.67 mol), 110 ml of 35~ strength NaO~ (0.96 mol) and 160 ml of water is added dropwise at 50C in the course of 2 hours to the resulting well-distributed suspension. The mixture is subsequently stirred at 50-55C for 11 hours and the product suspen-sion is filtered off from the mother liquor with suction after stirring until it has cooled to room temperature.
After filtering off with suction and washing with 500 ml of water, 2a8 g of a 10% water-moist pale yellow finely cry~talline product hsving a melting point of 179 to 182C are obtained, corresponding to a yield of 98.9~ of theory and with a purity of 98.5% according to HPLC
(HPLC - High Performance Liquid Chromatography).
E~ample 2 (2-nitro-N,N-dimethylaniline) 451 g of 40% ~trength dimethylamine solution (4.02 mol) and 10 g of the compound 6 are initially introduced into a 2 1 4-neck flask fitted with a stirrer, internal thermometer, heatable dropping funnel and heatlng bath and the mixture 18 heated to 55 to 60C with stirring.
288 g (1.83 mol) of 2-nitrochlorobenzene are added dropwise by means of the heatable dropping funnel in the course of 4 hours. After the completion of the addition, the mixture is subsequently stirred at 60 to 70-C for 8 hours and then cooled to 30C with stirring. 150 g of 35% ~trength sodium hydroxide solution (1.3 mol) are allowed to run in with stirring. The lower phase is then separated off in a separating funnel and the upper pha~e is worked up in order to recover dimethylamine. The lo ~3~ ~
lower phase - the crude product - is washed twice with 200 ml of water each tLme, separated off and isolated.
It is briefly sub~ected to incipient distillation in vacuo in order to dry it. 283 g of 2-nitro-N,N-dimethyl-aniline are obtained as an oily yellow-brown liquid in a purity of 98.8~ according to HPLC, corresponding to a yield of 93.23 of theory.
~sample 3 (3,4-dinitroaniline) 1000 ml of 16% ~trength aqueous ammonia (9.4 mol) and 8 g (2% ~y weight) of the compound 6 are initially introduced into a 2 1 4-necked flask fitted with a stirrer, internal thermometer and heatable dropping funnel, and the mixture is heated to 55~C with stirring. The addition of 406 g (2 mol) of 2,4-dinitrochlorobenzene a~ a melt (the dropping funnel ha~ a ~acket temperature of 60C) is then ~tarted, and takes place within four hours. After this time, the mixture is subsequently stirred at 55C for 20 hours and the 2,4-dinitroaniline obtained i8 filtered off with suction through a G-3 glass frit. It is washed with 500 ml of water and sucked dry for 30 min. 412 g of 2,4-dinitroaniline which is 16% water-moist are obtained.
This corre~ponds to a yield of 94.5% of theory. The product has a melting point of 179 to 180C and a purity of 97.8% according to HPLC.
~he applicability of the compounds 1 to 7 mentioned further above a8 surfnce-active ndditives for the prep-aration of nitronniline~ was checked in sever~l experi-ments nnalogously to this exnmple. In all cases, very good yields and purities of very finely dlvided 2,4-dinitroaniline were obtained.
~s~mple 4 (2,4-dinitroaniline) 350 ml of water, 240 ml of 25% strength ammonia (3.52 mol) and 1.9 g of the compound 6 are initially introduced into a 1 1 glas~ autoclave fitted with a ~tirrer and 11 2~8~ 7 heated feed pump and, after flushing with nitrogen and closing the autoclave, heated to 55C. 187 g (0.92 mol) of 2l4-dinitrochlorobenzene are then pumped in at this temperature with ~tirring in the course of four hours.
After completion of the addition, the mixture i8 heated to 80C and subsequently ~tirred again for 16 hours. At the end of this period, the mixture is stirred until it has cooled to room temperature and the autoclave is firs~
depressurised and then emptied. 182 g of 2,4-dinitro-aniline having a residual moisture of 9% are obtained byfiltering off with suction, corresponding to a yield of 99.1% of theory. The dried product has a melting point of 179.5 to 181C and a purity of 98.7~ according to HPLC.
All surface-active compounds mentioned further above were again employed analogously to the reaction procedure and batch size in this example, good results being obtained here both in terms of the yield and the purity of the resulting 2,4-dinitroaniline.
Claims (15)
1. A process for the preparation of nitroanilines of the formula (I) (I) in which R1, R2 are a hydrogen atom or a (C1-C4)alkyl group and R is a hydrogen atom or a nitro group, which com-prises reacting 1 mol of a nitrochlorobenzene of the formula (II) (II) in which R has the abovementioned meaning, with about 200 to about 4000 mol-% of a compound of the formula III
(III) in which R1 and R2 have the abovementioned meanings, at temperatures of about 40°C to about 120°C in the presence of at least one ionic or non-ionic surface-active com-pound.
(III) in which R1 and R2 have the abovementioned meanings, at temperatures of about 40°C to about 120°C in the presence of at least one ionic or non-ionic surface-active com-pound.
2. The process as claimed in claim 1, wherein the reaction is carried out at temperatures of about 50°C to about 90°C.
3. The process as claimed in at least one of claims 1 and 2, wherein the reaction is carried out at tempera-tures of about 55°C to about 80°C.
4. The process as claimed in at least 1 of claims 1 to 3, wherein the reaction is carried out in the presence of alkali metal salts of alkylsulfonic acids, or aralkyl-sulfonic acids, saturated or unsaturated higher fatty acids, alkyl sulfates or phosphoric acid esters of higher fatty alcohols or phenol as anionic surface-active compounds.
5. The process as claimed in at least one of claims 1 to 3, wherein the reaction is carried out in the presence of amphoteric surface-active compounds of the amino salt type or betaine type as ionic surface-active compounds.
6. The process as claimed in at least one of claims 1 to 3, wherein the reaction is carried out in the presence of compounds of the polyethylene glycol or polyhydroxy-alcohol type as non-ionic surface-active compounds.
7. The process as claimed in at least one of claims 1 to 3, wherein the reaction is carried out in the presence of (C12-C14)alkyldimethylbetaine in the form of a 30%
strength aqueous solution, a sulfonated formaldehyde condensation product in the form of a 30% strength aqueous solution, a sulfonated cresol-formaldehyde condensation product, a sulfonated cresol-phenol condensa-tion product in the form of a 35% aqueous solution, a sulfomethylated cresol-phenol-formaldehyde condensate, a dimethylnaphthalene-sulfonated formaldehyde condensate or a novolak derivative as a surface-active compound.
strength aqueous solution, a sulfonated formaldehyde condensation product in the form of a 30% strength aqueous solution, a sulfonated cresol-formaldehyde condensation product, a sulfonated cresol-phenol condensa-tion product in the form of a 35% aqueous solution, a sulfomethylated cresol-phenol-formaldehyde condensate, a dimethylnaphthalene-sulfonated formaldehyde condensate or a novolak derivative as a surface-active compound.
8. The process as xlIMWS in at least one of claims 1 to 3, wherein the reaction is carried out in the presence of salts of primary, secondary or tertiary amines, quaternary ammonium salts or pyridinium salts as cationic surface-active compounds.
9. The process as claimed in at least one of claims 1 to 8, wherein the reaction is carried out with about 200 to 1200 mol-% of the compound of the formula III.
10. The process as claimed in at least one of claims 1 to 9, wherein the reaction is carried out with about 200 to about 600 mol-% of the compound of the formula III.
11. The process as claimed in at least one of claims 1 to 10, wherein the reaction is carried out in the presence of about 0.1 to about 10 % by weight of surface-active compound, relative to the starting compound of the formula II.
12. The process as claimed in at least one of claims 1 to 11, wherein the reaction is carried out in the presence of about 0.2 to about 5 % by weight of surface-active compound, relative to the starting compound of the formula II.
13. The process as claimed in at least one of claims 1 to 12, wherein the reaction is carried out in the presence of about 0.5 to about 3 % by weight of surface-active compound, relative to the starting compound of the formula II.
14. The process as claimed in at least one of claims 1 to 13, wherein the reaction is carried out at normal pressure or elevated pressure.
15. The process as claimed in at least one of claims 1 to 14, wherein the reaction is carried out batchwise or continuously.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19893924092 DE3924092C1 (en) | 1989-07-20 | 1989-07-20 | |
| DEP3924092.4 | 1989-07-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2063817A1 true CA2063817A1 (en) | 1991-01-21 |
Family
ID=6385493
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2063817 Abandoned CA2063817A1 (en) | 1989-07-20 | 1990-07-19 | Method for the preparation of nitroanilines |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0483241A1 (en) |
| JP (1) | JPH04506805A (en) |
| CA (1) | CA2063817A1 (en) |
| DE (1) | DE3924092C1 (en) |
| WO (1) | WO1991001292A1 (en) |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE375793C (en) * | 1919-04-03 | 1923-05-17 | O Matter Dipl Ing | Process for the preparation of nitrated aromatic amines and their halogen substitution products |
| DE2536454C3 (en) * | 1975-08-16 | 1985-05-30 | Hoechst Ag, 6230 Frankfurt | Process for the preparation of 2,4-dinitroaniline |
| ES453556A1 (en) * | 1975-11-28 | 1977-11-16 | Hoechst Ag | Process for the preparation of n-phenyl-5-chloro-2-nitroaniline |
| CH622009A5 (en) * | 1976-06-11 | 1981-03-13 | Ciba Geigy Ag | |
| US4155936A (en) * | 1978-03-08 | 1979-05-22 | The Goodyear Tire & Rubber Company | Para-nitrodiphenylamines synthesis using Polyethers and macrocyclic esters as solubilizing agents |
| DE2814860A1 (en) * | 1978-04-06 | 1979-10-11 | Bayer Ag | PROCESS FOR PRODUCING AROMATIC AMINES |
| DE3200308A1 (en) * | 1982-01-08 | 1983-07-21 | Hoechst Ag, 6230 Frankfurt | METHOD FOR PRODUCING 5-NITRO-2-AMINOTOLUOL |
| US4481371A (en) * | 1983-07-26 | 1984-11-06 | The United States Of America As Represented By The United States Department Of Energy | Method of making fine-grained triaminotrinitrobenzene |
-
1989
- 1989-07-20 DE DE19893924092 patent/DE3924092C1/de not_active Expired - Fee Related
-
1990
- 1990-07-19 EP EP19900911416 patent/EP0483241A1/en not_active Withdrawn
- 1990-07-19 CA CA 2063817 patent/CA2063817A1/en not_active Abandoned
- 1990-07-19 JP JP51084690A patent/JPH04506805A/en active Pending
- 1990-07-19 WO PCT/EP1990/001180 patent/WO1991001292A1/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| DE3924092C1 (en) | 1990-11-29 |
| WO1991001292A1 (en) | 1991-02-07 |
| JPH04506805A (en) | 1992-11-26 |
| EP0483241A1 (en) | 1992-05-06 |
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