GB2236535A - Process for the preparation of N1-substituted nitro-p-phenylenediamines - Google Patents
Process for the preparation of N1-substituted nitro-p-phenylenediamines Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/34—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups
- C07C233/42—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a six-membered aromatic ring
- C07C233/43—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a six-membered aromatic ring having the carbon atom of the carboxamide group bound to a hydrogen atom or to a carbon atom of a saturated carbon skeleton
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
- C07C215/02—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C215/04—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated
- C07C215/06—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic
- C07C215/16—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic the nitrogen atom of the amino group being further bound to carbon atoms of six-membered aromatic rings
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/06—Esters of carbamic acids
- C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
- C07C271/26—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring
- C07C271/28—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring to a carbon atom of a non-condensed six-membered aromatic ring
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
- C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D263/16—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D263/18—Oxygen atoms
- C07D263/20—Oxygen atoms attached in position 2
- C07D263/22—Oxygen atoms attached in position 2 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to other ring carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
- C07D265/04—1,3-Oxazines; Hydrogenated 1,3-oxazines
- C07D265/06—1,3-Oxazines; Hydrogenated 1,3-oxazines not condensed with other rings
- C07D265/08—1,3-Oxazines; Hydrogenated 1,3-oxazines not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D265/10—1,3-Oxazines; Hydrogenated 1,3-oxazines not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with oxygen atoms directly attached to ring carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D269/00—Heterocyclic compounds containing rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms according to more than one of groups C07D261/00 - C07D267/00
- C07D269/02—Heterocyclic compounds containing rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms according to more than one of groups C07D261/00 - C07D267/00 having the hetero atoms in positions 1 and 3
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Abstract
Compounds of formula (I), useful as direct hair dyes, are synthesised from 4-acetylamino-2-nitroaniline (V) via novel intermediates of formulae (II), (III) or (IV). Reaction of (V) with chloroalkyl chloroformate yields (II), successive base and acid treatments of which yield (I) either directly or via (III) or (IV). <IMAGE> R is 2-hydroxyethyl, or 2- or 3-hydroxypropyl; Z is H or Me; n is I or 2; CH(X)-CH2Y is 2-chloroethyl, 1-methyl-2-chloroethyl, or 3-chloropropyl; CH2-CH(A)-B is the same as R. ir
Description
Process for the pnRana-t-úOn Of Nl-Bubstiltut nitro-R-Rhg-ny-leneaeE' The
invention relates to a process for the preparation of N1substituted nitro-p-phenylenediamines and to new intermediate products for the preparation thereof.
Nitro dyestuffs play an important role In hair dyeing. These dyestuffs, which are employed both in direct dyeing and in oxidation dyeing, must produce the desired colour of adequate intensity during dyeing. The colours achieved should have a good fastness to light and acid and should not tend towards shifts in the original shade of the colour under wearing conditions. They should moreover be toxicologically and dermatologically acceptable.
These requirements cannot always be reconciled. This becomes particularly clear In the field of the so-called red direct dyestuffs. The compound nitro-p-phenylenediamine.is an the one hand almost completely satisfactory from the technological point of view but an the other hand is)roblematic from the toxicological point of view.
Red direct dyestuffs which meet all the above-mentioned requirements are compounds of general formula I.
NHR N02 NH2 (1) 2 Compounds wherein R represents a 2-hydroxyethyl, 3hydroxypropyl or 2- hydroxypropyl group are known as hair dyestuffs from GB Patent No. 1,206, 491.
We have now found it possible to provide a technically advanced process for the preparation of these known compounds as red direct dyestuffs which a) are completely satisfactory from the point of view of dyeing, b) are toxicologically acceptable and c) are distinguished by a high purity.
Various processes have been described for the preparation of these compounds. It is thus reported, for example (GB 955.743 and US 3F168j442)i that compounds of the general formula I wherein R represents a 2-hydroxyethyl or a 3-hydroxypropyl group are accessible by partial reduction of the corresponding dinitro compounds. In generali howeveri two isomers are formed in this process. Even when one isomer predominates,, the resolution is difficult and troublesome. Furthermore, in some cases the completely reduced triamino product Is also often formed. depending on the reducing agent and the reaction conditions r which means that it becomes even more expensive to separate off the desired compound.
E.S. Lazer. i.S. Andersonj J.E. Kijek and X.C. Brown [Synthetic Communications,, 12 (9)r 691-694 (1982)] describe a process for the preparation of 1-(2hydroxyethyl)amino-2-nitro-4-aminobenzene by partial reduction of the corresponding dinitro compound. However, the yield is only between 45 % and 55 % and the product contains the starting compounds and the Isomeric compounds as an impurity.
A process for the preparation of compounds of the general formula I wherein R is 2-hydroxyethyl, 3-hydroxypropyl or 2-hydroxypropyl 3 is furthermore known, In which 2-nitro-4 -aminofluorobenzene is reacted with the corresponding aminoalcohols [GB 1.206.491; and A.T. Peters. J. appl.Chem. Biotechnol. 1976. 26r 131-134]. Howevert the compounds of the formula I thus prepared do not have a high purity. Reaction of 2nitro-4-aminofluorobenzene with ethanolamine by this process results in the formation of a bY-PrOducto, which Is clearly recognizable In a thin layer chromatogram. in addition to 2-[(4-amino-2nitrophenyl) amino]ethanol. The content of dyestuff in the product thus obtained compared with that in a purified sample in only 82 % (content assay by spectrapho-ometry, In this context see also Comparison Example below. The products obtained by reactions of 2-nitro-4;-aninofluorobenzene with 1azinopropan-3-ol and 1-aminopropan-2-ol likewise contain the abovementioned by-product.
According to one aspect of the present invention there is provided a process for the preparation of an N 1_ substituted nitro-pphenylenediamine of general formula I NHR N02 NH2 (I) wherein R represents a 2-hydroxyethyll 3-hydroxypropyl or 2- hydrc)xypropyl group, which comprises a) reacting 4-acetylamino-2- nitroaniline with a chloroformic acid alkyl ester of general formula Cl- COO-CH(X)-CH2-Y (wherein X=Ht Y=Cl; X=CH3P Y=Cl; or X=HI Y=CH2C1, to give a carbarnate of general formula II 4 - NH-COO-CH(x)-CH2"Y NO2 NH-CO-CH3 (II) b) converting the carbamate of general formula II into a compound of general formula III R-CH2-CH(A)-8 N02 KH-CO-CH3 (III) wherein A=H, B=OH; A=CH3, B=OH or A=H, B=CH20H, by treatment with a base; and c) deacylating the compound of general formula III with a inorganic acid to give a compound of general formula I wherein R represents a 2-hydroxyethyl, 3-hydroxypropyl or 2-hydroxypropyl group.
Preferably, the carbarnates of general formula II is converted into a compound of general formula 1, in a one-pot process first by treatment with a base and then by treatment with an inorganic acid.
According to another aspect of the present invention there is provided a process for the preparation of a compound of general formula I as defined in claim 1, which comprises a) converting a carbarnate of general formula II as defined in claim 1, into an oxazolidone of general formula IV (wherein Z represents a hydrogen atom or a CH3 group and n is 1 or 2) by treatment with a base and then by treatment with an inorganic acid; and z - 0 (CH2) n 0 IV) b) converting oxazolidone into a compound of general formula I by treatment with about twice the molar amount of a base.
These processes allow the compounds of general formula I to be prepared in high yields and in a high purity.
Various preferred features and embodiments of the invention will now be described by way of non-limiting example.
The reaction of 4-acetylamino-2-nitroanj-ll;-ne witzl a chlorof ormic acid alkyl ester is ca=ied out in accordance with the method of known selective hydroxyalkylation of an amine with a chloroformic acid chloroalkyl ester with subsequent treatment of the chloroalkyl carbamates with a base [compare Otto, J. Prak. Chem.. 2 j 44 j page 15 (1890); R. Adams and J.B. Segur,, J. Am. Chem. Soc. 45, page 785 (1923)]. TO form the compounds of the general formula II, the 4-acetylaminO-2-nitroaniline is initially introduced into an inert solvent (for example dioxane, monoethylene glycol dimethyl ether, chlorobenzene, toluene or methylethyl ketone). A chloroformic acid alkyl ester of the general formula Cl-COO-CH(X)-CH,-Y, wherein X=Hr Y-Clo, X- CH3, Y=Cl or X=Hr Y-CH2C1, in metred Into this mixture In an equimolar amount or in a slight excess at a temperature between room temperature and the reflux temperature. preferably between 70C and the reflux temperature. If appropriate, the solvents can be combined with water. Possible acid-binding agents are bases. such as alkaline earth metal hydroxides,, bicarbonates and carbonatest alkaline earth metal oxidesr hydroxides. bicarbonates and carbonates and tertiary organic amines. The reaction is complete after about 2-8 hours. For working up, it is possible either to add water and to stir the mixture until-cold, or to filter off the inorganic salts and to distill off some or all of the solvent.
To form the compounds of the general formula Ill wherein A and B have the meanings already given, the carbamates of the general formula II are treated with strong bases (alkali metal hydroxides or alkaline earth metal hydroxides), preferably with 10-50 % strength sodium hydroxide solution or potassium hydroxide solution. The carbamate of the formula II is Initially introduced Into water or an organic solvent, such as, for example, a (C,-CJ -alcohol,, a water-miscible ether or mixtures thereof, and approximately 3 mol of hydroxide solution per mol of carbonate are then metred in at too= temperature. It is similarly possible for the hydroxide solutiont which can be diluted with the solvents mentioned. to be initially introduced Into the reaction vessel and for the carbamate to be metred into this in pure form or as a solution in one of the organic solvents mentioned. The mixture is then subsequently sti=ed to 7 - bring the reaction to completionf and it can be heated up to the reflux temperature if necessary. The duration of the reaction is about 2 to 10 hours. For working up, the reaction solution. which has a pH of about 1214,, is buf f ered to a pH of about 7 to 10 with an organic or inorganic acid. Water is then added, if appropriate the solvents are distilled off and the product in Isolated.
The compounds of the general formula III can he deacetylated by heating to about 60 to WC with a strong inorganic acid (for example hydrochloric acid, sulphuric acid or phosphoric acid) in an aqueous medium in the course of about 1 to 3 hours. The compound of the general formula I wherein R has the meanings givenj which has a content of 93-95 %1 is thus obtained.
The compounds of the general formula I can likewise be prepared in a onepot reaction starting from the carbamates of the general formula II, without isolation of the compounds of the general formula III. In this reactiont a carbamate of the formula II is initially introduced Into water and a strong base (alkali metal hydroxides or alkaline earth mrtal hydroxides), pref erab1Y 10-50 % strength sodium hydroxide solution or potas- sium hydroxide solution, is metred In at a temperature of about 30 to WC. When the reaction is complete. the pH of the reaction solution is brought to about 7 with an organic or inorganic acid. A further amount of a strong inorganic acid (for example hydrochloric acid or sulphuric acid) Is then added and deacetylation Is carried out at a temperature of about 60 to WC. The pH in then brought to about 7 again with a base (sodium hydroxide solution, potassium hydroxide solution or ammonia) and the product is isolated.
In the above procedure,, the reaction time is shortened considerably by addition of about 25 to 30 % by weight of a water-miscible solvent[ (ClC3)-alcohol or monoethylene glycol dimethyl ether] to the aqueous reaction mixture, the inorganic salts still remaining dissolved in the reaction medium.
The carbamates of the general formula II can be converted into the oxazolldones of the formula (IV) using an equimolar amount of base (alkali metal hydroxides or alkaline earth metal hydroxides)r preferably using 1050 % strength sodium hydroxide solution or potassium hydroxide solution.
A carbamate of the formula II- is initially introduced into water or an organic solvent, such as, for example, a (Cl-C,)-alcoholf a watermiscible ether or mixtures thereof. Approximately 1 mol of hydroxide solution per mol of carbamate Is metred in at a temperature of 30-85C. The mixture is then subsequently stirred to bring the reaction to completion. it being possible to heat the mixture to the reflux temperature if appropriate. The reaction time is about one hour. A strong inorganic acid (for example hydrochloric acid or sulphuric acid). is then added to the reaction solution and the mixture is subsequently stirred at a temperature of about W-95C. The subsequent stirring time is about 3 hours. When the reaction has ended, the pE of the reaction solution is brought to about pH 7 with a base, salts are filtered off if appropriate. the solvents are distilled off and the product Is isolated.
The compounds of the formula IV are then initially introduced into water or an organic solvent. such as. for example, a (C,-Cj -alcohol j, a watermiscible ether or mixtures thereof. Approximately 2 mol of hydroxide solution per mol of starting substance are metred in at a temperature of 45-WC. When the pH of the reaction solution has been brought to pH 7-8,, salts have been filtered off if appropriate and solvents have been distilled off, the product is Isolated. The compounds of the formula I thus obtained have a high degree of purity. No by-product is detectable on the thin layer chromatogram. The purity according to spectrophotometric content assay is about 97 %.
9 The preparation processes are illustrated by the following non-limiting examples and accompanying drawings which show the infrared absorption spectra of the following compounds as Figures 1 to 10:
Figure 1 p-chloroethyl N-(4-acetylamino-2- nitrophenyl)carbainate Figure 2 2-[(4-acetylamino-2-nitrophenyl)amino]ethanol Figure 3 2-[(4amino-2-nitrophenyl)amino]ethanol Figure 4 N-[(4-amino-2-nitro)phenyl]oxazolid-2-one Figure 5 -y-chloropropyl H-(4-acetylamino-2- nitrophenyl)carbxmnte Figure 6 3-[(4-acetylamino-2-nitrophenyl)amino]propan- 1-01 Figure 7 3-[(4-amino-2-nitrophenyl)amino]propan-l-ol Figure 8 N-[(4-amino-2-nitro)phenyll-tetrahydro-1,3- oxazin-2-one Figure 9 (2-chloro-i-methyl)ethyl N-(4-acetylamino-2- nitrophenyl)carbamate Figure 10 3-[(4-amino-2-nitrophenyl)amino]propan-2- ol Example 1 PreVaration of 2-r(4-amino-2-nitroi)hepyl)aminolethancl Process: A I. Preparation of p-chloroethyl N-(4-acetylamino- 2nitrophenyl)carbamate:
g (1 mol) of 4-acetylamino-2-nitroaniline are intially Introduced into 650 ml of moncethylene glycol dimethyl ether and 75 M1 of water together with 50 g of calcium carbonate. The reaction mixture is heated to abOut GO&C and 150 g of p-chloroethyl chloroformate are then added. in the course of about 5 hours, so that the reaction mixture is under gentle reflux. Stirring is then continued under reflux for 2 hours, the mixture in subsequently cooled to 65%, water is added and the product which has precipitated is Isolatedr washed with water and dried in a vacuum drying cabinet.
Yield: 271.5 g (90 % of the theoretical value) melting point: 1596c IR spectrum: see Figure 1 II. Preparation of 2-[(4-acetylamino-2-nitrophenyl)amino]ethanol:
90.5 g (0.3 mol) of the carbam^te prepared above under I are heated to about 75C with 450 M1 of water and 108 9 of 50 % strength potassium hydroxide solution are added in the course of 45 minutes. The mixture is subsequently stirred at 80C for 2 hours. the pH is then brought to 7 with glacial acetic acid and the mixture Is cooled to loC. The product which has precipitated is filtered off with suction, washed with water and dried.
Yield: 63.2 g (88 % of the theoretical value) Melting point: 170C IR spectrum: see Figure 2 III. Preparation of 2o-[ (4-amino-2-nitrophenyl) amino]ethanol:
49 g (0.2 mol) of the product prepared above under II. are introduced into 200 g of 25 % strength sulphuric acid at about WC in the course of 30 minutes. The mixture is subsequently stirred at about WC for one hour and the pH is then brought to 8 with aqueous ammonia. The mixture is then cooled to 10C in the course of 3 hours and the product which has precipitated is filtered off with suction. washed with water and dried.
Yield: 33.5 g (85 % of the theoretical value) Melting point: 123C IR spectrum: see Figure 3 Content: 94 % (Content assay by spectrophotometry against purified sample) Process: B I. Preparation of 2-[(4-amino-2-nitrophenyl) amino]ethanol 90.5 g (0.3 mol) of the carbamate prepared under process A.I are heated to 75C with 325 ml of water and 30 g of 50 % strength potassium hydroxide solution. A further 79 g of 50 % strength potassium hydroxide solution are added dropwise in the course of 11 hours. The mixture is subsequently stirred at 80C for one hour and the pH is brought to 7 with hydrochloric acid. 50 ml of hydrochloric acid are now added to the reaction mixture and the mixture Is heated under reflux for two hours. The PH is brought to 8 again with Ammonia and the mixture is slowly cooled. The product which has precipitated is filtered off with suction, washed with water and dried.
Yield: 50.8 g (86 % of the theoretical value) Melting point: 122'C Content: 93 % (Content assay by spectrophotometry against purified samples) Process: C I. Preparation of N- [ (4 -amino -2 -nitro) phenyl] oxazolid2one 90.5 g (0.3 mol) of the carbamate prepared under process A. I are heated to about 90 C together with 325 ml of water and 34 g of 50 % strength potassium hydroxide solution. The mixture is subsequently stirred for a further hour at the same temperature and the pH is brought to 7 with hydrochloric acid. 45 ml of concentrated hydrochloric acid are now added to the reaction mixture and the mixture is heated under reflux for 3 hours. The pH Is then brought to 7 again with aqueous ammonia. The mixture is cooled slowly and the product which has precipitated is filtered off with suction, washed with water and dried in a vacuum drying cabinet.
Yield: 61.5 g (92 % of the theoretical value) Melting point: 195-196C IR spectrum: see Figure 4 11. Preparation of 2-[(4-amúno-2-nitrophenyl)amlno]- ethanol 44. 5 g of the oxazolidone prepared above under I. are initially Introduced into 175 M1 of water and the reaction mixture is heated to 80C. 45 g of 50 % strength potassium hydroxide solution are added dropwise In the course Of 50 minutes. The mixture is subsequently stirred at 80C for 1 hour and the pH is brought to 8 with glacial acetic acid. The mixture is cooled to 10C in the course Of one hour and the product which has precipitated is filtered off with suction, washed with water and dried.
Yield: 32.7 g (83 % of the theoretical value) Melting point: 124-C COntent: 97 (Content assay by spectrophotometry against purified sample) Examole 2- Prevanag-tion of 3-ri4-amLino-2-nitrophen3ELLazlinol-p-roDan1-01 Process: A 1. Preparation of y-chloropropyl N-(4-acetylamino-2nitrophenyl)carbamate 97.5 g (0.5 mol) of 4-acetylamino-2-nitroaniline and 26.5 g of calcium carbonate are reacted with 83.5 g 1 of 7-chloropropyl chloroformate in 425 ml of a monoethylene glycol dimethyl etherlwater mixture (9:1) under the conditions mentioned in Example 1 - A.I. and the mixture is worked up correspondingly.
Yield: 153 g (97 % of the theoretical value) Melting point: 112C IR sPectrumt see Figure 5 II. Preparation of 3-[(4-acetylamino-2-nitrophenyl)- aminolpropan-l-ol 63 g (0.2 mol) of the 7-chloropropyl N-(4-acetylamino- 2 -nitrophenyl) carbaTnate prepared above under I. are reacted with 72 g of 50 % strength aqueous potassium hydroxide solution in 200 ml of water and 50 ml of ethanol under the conditions mentioned in Example 1 A.II. After adjustment of the pH,, the mixture is cooled to 15C and the product is filtered off with suction, washed with water and dried.
Yield: 42 g (83 % of the theoretical value) Melting point: 1290C IR spectrum: see Figure 6 III. Preparation of 3-[(4-amino-2-nitrophenyl)amino]propan-l-ol 50.5 g (0.2 mol) of the product prepared above under Il. are initially introduced into 180 M1 of water and 50 mi of ethanol and the mixture Is heated to about 7S&C. 40 mI of concentrated hydrochloric acid are metred into this mixture in the course of about 30 minutes. the mixture is subsequently stirred at the reflux temperature for two hours,, the pH is brought to 7.5 with aqueous sodium hydroxide solution and the mixture is cooled to 1CC. The-product which has precipitated Is filtered off with suction, washed with water and dried.
Yield: 33.8 g (8o % of the theoretical value) Melting point: 102-C IR spectr=: see Figure 7 Process: B I. Preparation of 3-[(4amino-2-nitrophenyl)amino]propan-l-ol 31.5 g (0.1 mol) of the 7-chloropropyl N-(4acetylamino-2- nitrophenyl)carbamate prepared under process A.I. are reacted with 36.5 g of 50 % strength aqueous potassium hydroxide solution and then with 16 mI of concentrated hydrochloric acid under the conditions mentioned in Example 1 - B.I. and the mixture is worked up correspondingly.
Yield: 18.4 g (87 % of the theoretical value) Melting point: 1OVC Process: C I. Preparation of N- [ (4 -amino -2 -nitro) phenyl] -tetrahYdro-1,3oxazin-2-one 31.5 g (o.l mol) of the carbamate prepared under process A.I. are reacted with 11.2 g of 50 % strength aqueous potassium hydroxide solution In 100 ml of water and with 15 ml of concentrated hydrochloric acid under the conditions mentioned in Example 1 - C.I. and the mixture is deacetylated and worked up.
Yield: 19.5 g (82 % of the theoretical value) Melting point: 181C IR spectrum: see Figure 8 Il. Preparation of 3-[(4-amino-3-nitrophenyl)amino]Propan-l-ol 19 g (0.08 mol) of the oxazine prepared above under I. are initially introduced into 80 ml of water and 20 M1 of ethanol and the mixture is heated to about 75C. 20 g of 50 % strength aqueous potassium hydroxide solution are-added dropwise in the course of 45 minutes. The mixture is subsequently stirred at 75C for a further hour and the pH is brought to 9 with glacial acetic acid. The mixture is cooled to 10C in the course of 45 minutes and the product which has precipitated is filtered off with suction. washed with water and dried.
Yield: 15.7 g (92.7 % of the theoretical value) melting point: 102C Examole 3 Pre12aration of 3-r ( 4-amino-2-nitrol3henyll amino lvro;)an-201 I. Preparationof (2 -chloro- 1-methyl) ethyl -N- (4 -acetyl amino-2nitrophenyl)carbamate 19.5 g (0.1 mol) of 4-acetylamino-2-nitroaniline and 5. 2 g of calcium carbonate are reacted with 15. 7 g of (2-chloro-i-methyl)ethyl chloroformate in 75 ml of monoethylene glycol dimethyl ether under the conditions mentioned in Example 1 - A.I. and the mixture is worked up correspondingly.
Yield: 26.8 g (85 % of the theoretical value) Melting point: 134-135C IR spectrum: see Figure 9 Il. Preparation of 3-[(4-amino-2-nitrophenyl)amino]propan-2-ol 15.8 g (0. 05 mol) of the carbamate prepared above under I. are reacted with 17 g of 50 % strength aqueous potassium hydroxide solution and then with 8 ml of concentrated hydrochloric acid under the conditions mentioned In Example 1 - B.I. and the mixture is worked up correspondingly.
Yield: 8.5 g (80 % of the theoretical value) Melting point: 153 - 154C IR spectrum: see Figure 10 Conison Exa=le 1 Preparation of 2-r(4-amino-2-nitrolDhenvl)aminolethano1 (analogously to Example 21 GB 1f206f491) 15. 6 g of 4-fluoro-3-nitroaniline, 13.5 g of monoethanolamine and 5.3 g of sodium carbonate are Initially introduced into 100 ml of water and the mixture is heated under reflux for 5 liours. It is then cooled to room temperature and the solid product which has precipitated Is filtered off with suctiont washed with water and dried.
Yield: 14.4 g (73 % of the theoretical value) Melting point: 118C (theoretical 121-123C) Content: 82 % (Content assay by spectrophotometry against purified sample) In the thin-layer chromatogram. (mobile phase: toluene/2-butanol in the ratio 713)r a secondary spot is clearly recognizable at a k value of 0.36.
16
Claims (10)
1. A process for the preparation of an N1-substituted nitro-pphenylenedia mine of gerWal formula r NHR NO2 NH2 (I) wherein R represents a 2-hydroxyethyl, 3-hydroxypropyl or 2-hydroxypropyl group, which comprises a) reacting 4-acetylamino-2-nitroan Rine with a chloroformic acid alkyl ester of general formula Cl-COO-CH(X)-CH2-Y wherein X=H, Y=Cl; X=CH3, Y=Cl; or X=H, Y=CH2C1, to give a carbamate of general formula II RH-COO-CH(X)-CH2-Y H02 NH-CO-CH3 b) converting the carbamate of general formula II into a compound of general formula III 17 NH-CH2-CH(A)-8 NO2 NH-CO-CH3 (III) wherein A=H, B=OH; A=CH3, B=OH or A=H, B=CH20H, by treatment with a base; and c) deacylating the compound of general formula III with art inorganic acid to give a compound of general formula I wherein R represents a 2- hydroxyethyl, 3-hydroxypropyl or 2-hydroxypropyl group.
2. A process according to claim 1 wherein 4-acetylamino-2nitroaniline is reacted with an approximately equimalar amount of the chloroformic acid alkyl ester.
3. A process according to either or claims 1 and 2 in which the carbarnate of general formula II is converted into a compound of general formula I, in a one-pot pr:ocess first by treatment with a base and then by treatment with an inorganic acid.
4. A process for the preparation of a compound of general formula 1 as defined in claim 1, which comprises a) converting a carbarnate of general formula II as defined in claim 1, into an oxazolidone of general formula IV (wherein Z represents a hydrogen atom or a CH3 group and n is 1 or 2) by treatment with a base and then by treatment with an inorganic acid; and 18 z 0 H2)n 0 NO2 NH2 (M b) converting oxazolidone into a compound of general formula 1 by treatment with about twice the molar amount of a base.
5. A process according to claim 4 wherein the carbamate of general formula II is treated with an equimalar amount of base.
6. A compound of general formula II YH.coo-CH(X)-CH,-y 902 NH-CO-CH3 wherein X and Y are as defined in claim 1.
- 19
7. A compound of general formula III NE-C82" CH(A)-B 902 R-CO-CR3 wherein A and B are as defined in claim 1.
8. A compound of general formula IV z -0 (CH2)a 0 M02 wherein Z and n are as defined in claim 4.
9. A process substantially as hereinbefore described with reference to the examples.
10. A compound as def ined in any one of claims 6 to 8 as herein specifically disclosed.
Published 1991 at Ile Patent Office. State House, 66171 High HoWorn. Londo"WC I R 4TP. Further copies may be obtained from Sales Branch. Unit 6. Nine mile Point. Cwrnfelinfach, Cross Keys. Newport, NPI 7HZ. Printed bY MulUplex techniques ltd. St Mary Cray. Kent.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19893931836 DE3931836C1 (en) | 1989-09-23 | 1989-09-23 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB9020642D0 GB9020642D0 (en) | 1990-10-31 |
| GB2236535A true GB2236535A (en) | 1991-04-10 |
| GB2236535B GB2236535B (en) | 1992-06-17 |
Family
ID=6390065
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB9020642A Expired - Fee Related GB2236535B (en) | 1989-09-23 | 1990-09-21 | Process for the preparation of nu-substituted nitro-p-phenylenediamines |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPH03122169A (en) |
| DE (1) | DE3931836C1 (en) |
| FR (1) | FR2652350A1 (en) |
| GB (1) | GB2236535B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5387716A (en) * | 1991-12-20 | 1995-02-07 | Cassella Aktiengesellschaft | N4-substituted 1-alkoxy-2-acylamino-4-aminobenzenes, process for their preparation and their use |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4141369A1 (en) * | 1991-12-14 | 1993-06-17 | Cassella Ag | METHOD FOR PRODUCING N-SUBSTITUTED NITRO-P-PHENYLENEDIAMINES |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1104970A (en) * | 1964-11-19 | 1968-03-06 | Oreal | New hair dye and methods of making it |
| GB1206491A (en) * | 1967-11-02 | 1970-09-23 | Clairol Inc | PROCESS FOR PREPARING NITRO-p-PHENYLENEDIAMINES |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB955743A (en) * | 1960-09-12 | 1964-04-22 | Bristol Myers Co | N-substituted nitrophenylene diamines, their preparation and use in hair-dyeing compoitions |
| USRE30798E (en) * | 1967-11-02 | 1981-11-17 | Clairol Incorporated | Process for preparing nitro-p-phenylenediamines |
| US3742048A (en) * | 1968-05-13 | 1973-06-26 | Oreal | Keratin fiber dye compounds |
| LU74807A1 (en) * | 1976-04-21 | 1977-12-02 | ||
| LU82860A1 (en) * | 1980-10-16 | 1982-05-10 | Oreal | TINCTORIAL COMPOSITIONS BASED ON PRECURSORS OF OXIDATION DYES AND NITER BENZENIC DYES STABLE IN AN ALKALINE REDUCING MEDIUM AND THEIR USE FOR DYEING KERATIN FIBERS |
| LU83900A1 (en) * | 1982-01-26 | 1983-09-02 | Oreal | NOVEL COMPOUNDS FOR HAIR DYEING, PROCESS FOR THEIR PREPARATION, DYEING COMPOSITION CONTAINING THEM, AND CORRESPONDING HAIR DYEING METHOD |
| DE3430513A1 (en) * | 1984-08-18 | 1986-02-27 | Wella Ag, 6100 Darmstadt | HAIR DYE WITH DIAMINO-TETRAFLUORETHOXYBENZENE AND NEW DIAMINO-TETRAFLUORETHOXYBENZENE |
| FR2571364B1 (en) * | 1984-10-09 | 1987-07-17 | Oreal | NEW PROCESS FOR THE PREPARATION OF N, NON-DISUBSTITUTED NITROPARAPHENYLENEDIAMINES N, NEW OXAZOLIDONES USED IN THIS PROCESS, NEW NITROPARAPHENYLENEDIAMINES N, N'-DISUBSTITUEES OBTAINED BY THIS PROCESS AND COMPOSITIONS TINCTUTINE |
-
1989
- 1989-09-23 DE DE19893931836 patent/DE3931836C1/de not_active Expired - Fee Related
-
1990
- 1990-09-21 GB GB9020642A patent/GB2236535B/en not_active Expired - Fee Related
- 1990-09-21 FR FR9011664A patent/FR2652350A1/en active Pending
- 1990-09-25 JP JP25203690A patent/JPH03122169A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1104970A (en) * | 1964-11-19 | 1968-03-06 | Oreal | New hair dye and methods of making it |
| GB1206491A (en) * | 1967-11-02 | 1970-09-23 | Clairol Inc | PROCESS FOR PREPARING NITRO-p-PHENYLENEDIAMINES |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5387716A (en) * | 1991-12-20 | 1995-02-07 | Cassella Aktiengesellschaft | N4-substituted 1-alkoxy-2-acylamino-4-aminobenzenes, process for their preparation and their use |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03122169A (en) | 1991-05-24 |
| FR2652350A1 (en) | 1991-03-29 |
| GB2236535B (en) | 1992-06-17 |
| DE3931836C1 (en) | 1991-04-18 |
| GB9020642D0 (en) | 1990-10-31 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19940921 |