Classifications

• • 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

Definitions

• the invention relates to an improved process for the preparation of mononitro- or dinitro-anilines in very good yields and high purity by reacting mononitro- or dinitro-chlorobenzenes with ammonia or amines in the presence of surface-active compounds.
• nitro-anilines mentioned below are important intermediates in the manufacture of dyes and pigments as well as in the manufacture of pharmaceuticals and plant protection products. These are, for example, the compounds N-methyl-4-nitro-aniline, N, N-dimethyl-nitro-aniline, N-methyl-2-nitro-aniline, N, N-dimethyl-2-nitro-aniline , 2,4-dinitro-aniline, 2,4-dinitro-N-methyl-aniline and 2,4-dinitro-N, N-dimethyl-aniline.
• 2,4-Dinitro-aniline is prepared, for example, by rearrangement of N, 4-dinitro-acetanilide, which is thermally labile, in acetic acid at 0 to 70 ° C. with subsequent hydrolysis in 200 to 3800 mol%
• 2,4-Dinitro-aniline is also prepared by reacting a melt of 2,4-dinitro-chlorobenzene with ammonia at 180 ° C in 71% yield (CN 86100379 from 1/19/86).
• This reaction variant harbors the task of homogeneous mixing of the two reactants ammonia and 2,4-dinitro-chlorobenzene, which is certainly difficult for industrial production.
• the ammonium chloride formed in the reaction is completely washed out of the 2,4-dinitro-aniline. Because of the high melting point of the end product, the reaction must be carried out up to an alarmingly high temperature level (180 ° C), at which an explosive decomposition cannot be ruled out with a longer reaction time.
• 2,4-dinitro-phenolate is formed.
• the preparation of the diphenyl ether adds a process step for the normal preparation of the 2, -dinitro-aniline from 2,4-dinitro-chlorobenzene, which prohibits the production by this reaction route for economic reasons.
• nitronilines described by way of example above are also prepared by reacting the corresponding alkylamine with 2,2'-4.4 l -tetranitro-diphenyl ether, this procedure, because of its two stages, is principally the case Costs for technical production are soaring and therefore, but also because of the higher chemical costs and the cleaning processes required at every stage, must be rejected for ecological and economic reasons.
• 2,4-dinitro-aniline As an alternative to the production processes of 2,4-dinitro-aniline shown above, the reaction of 2,4-dinitro-phenol alkyl ethers (JP 50/126625) or 2,4-dinitro-phenol (JP 49/14431) described.
• 2,4-dinitro-ani ⁇ ol is treated with ammonia in a non-water-miscible solvent for 6 hours at high pressure. No information was given there about yield and purity.
• a disadvantage of the described production variant from 2,4-dinitro-phenol - also from the 2,4-dinitro-phenol alkyl ethers - is on the one hand the accumulation of a highly salt-contaminated wastewater - the mother liquor of the reaction - but on the other hand, much more serious, that
• the fact that the 2,4-dinitro-phenol and the 2,4-dinitro-phenol alkyl ethers are prepared from 2,4-dinitro-chlorobenzene by nucleophilic exchange, that is to say on the way from 2,4-dinitro-chlorobenzene to the second , 4-Dinitro-aniline, a further process step with chemical and apparatus costs and cleaning procedures is added.
• R- ⁇ , R2 represents a hydrogen atom or a
• Alky1 (C - ⁇ - C ⁇ ) group and R is a hydrogen atom or a
• Purity can be produced in one process step by using 1 mole of a nitro-chlorobenzene of the general type
• R has the meaning given above, with about 200 to about 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)
• the surface-active compounds include both ionic (anionic and cationic) and nonionic surface-active compounds.
• the ionic auxiliaries include anionic surface-active compounds, such as, for example, the alkali metal salts of alkyl (C 14 -C 18 ) sulfonic acids, aralkyl (C 12 -C 14 ) sulfonic acids, for example sodium dodecylbenzoyl sulfonate, or of alkyl (C 3 - ⁇ ) -naphthalenesulfonic acids, for example l-isopropyl-naphthalene-2-sulfonic acid sodium, or the alkali metal salts of saturated or unsaturated higher fatty acids (Ci ⁇ -C ⁇ ), for example sodium laurate, Sodium myristate, sodium palmitate, sodium stearate or sodium oleate, furthermore the alkali metal salts of alkyl (C 12 -C 35 ) sulf
• the ionic auxiliaries also include cationic surface-active compounds, such as, for example, primary, secondary or tertiary amine salts, guaternary ammonium salts or pyridinium salts, preferably the chlorides, sulfates or methyl sulfates, and amphoteric surface-active compounds, for example those of the amino salt type sodium or amino amino acid type, for example amino amino acid type sulfon, for example amino amino acid type sulfon Methylamino-ethyl ⁇ ulfonic acid sodium, or of the betaine type.
• cationic surface-active compounds such as, for example, primary, secondary or tertiary amine salts, guaternary ammonium salts or pyridinium salts, preferably the chlorides, sulfates or methyl sulfates, and amphoteric surface-active compounds, for example those of the amino salt type sodium or amino amino acid type, for example amino amino acid type sulfon,
• Non-ionic surface-active compounds are those of the polyethylene glycol or polyhydroxy alcohol type. Examples include the alkyl polyglycol ethers, alkyl phenyl polyglycol ethers,
• Typical examples of these surface-active compounds can be found, for example, in "Surface Active Agents and Detergents", Volume I, by A.M. Schwarz and J.W. Perry, or in “Cataly ⁇ i ⁇ in Micellar and Macromolecular Systems” by J.H. Fendler and E.J. Fendler, Academic Press N.Y. 1975.
• Compound 1 30% aqueous solution of alkyl (C 12 -C 14 ) dimethyl betaine.
• Compound 2 30% aqueous solution of a diolsulfonic acid phenol-formaldehyde condensation product.
• Compound 3 disulfonic acid creole-formaldehyde condensation product.
• Compound 4 sulfated creole-phenol condensation product as 35% aqueous solution.
• the process according to the invention can be carried out either at normal pressure or at elevated pressure, as well as discontinuously or continuously.
• 2,4-Dinitro-chlorobenzene pumped in.
• the mixture is heated to 80 ° C. and stirred for a further 16 hours. After this period of time is cold stirred to room temperature 'and the autoclave is first expanded and then deflated.
• the dried product has a melting point of 179.5 to 181 ° C and a purity of 98.7% by HPLC.
• all the surface-active compounds listed above were again used, and very good results were obtained both from the yield and from the purity of the 2,4-dinitro-aniline obtained.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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• 1989
  • 1989-07-20 DE DE19893924092 patent/DE3924092C1/de not_active Expired - Fee Related
• 1990
  • 1990-07-19 EP EP19900911416 patent/EP0483241A1/de not_active Withdrawn
  • 1990-07-19 CA CA 2063817 patent/CA2063817A1/en not_active Abandoned
  • 1990-07-19 JP JP51084690A patent/JPH04506805A/ja active Pending
  • 1990-07-19 WO PCT/EP1990/001180 patent/WO1991001292A1/de not_active Application Discontinuation

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