WO1999012886A1 - Procede de production d'un melange d'isomeres de dinitronaphtalene a proportion elevee en 1,5-dinitronaphtalene - Google Patents

Procede de production d'un melange d'isomeres de dinitronaphtalene a proportion elevee en 1,5-dinitronaphtalene Download PDF

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Publication number
WO1999012886A1
WO1999012886A1 PCT/EP1998/005409 EP9805409W WO9912886A1 WO 1999012886 A1 WO1999012886 A1 WO 1999012886A1 EP 9805409 W EP9805409 W EP 9805409W WO 9912886 A1 WO9912886 A1 WO 9912886A1
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WO
WIPO (PCT)
Prior art keywords
nitronaphthalene
dinitronaphthalene
nitric acid
mixture
solvent
Prior art date
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PCT/EP1998/005409
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German (de)
English (en)
Inventor
Christian Steinlein
Gerhard Wegener
Original Assignee
Bayer Aktiengesellschaft
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by Bayer Aktiengesellschaft filed Critical Bayer Aktiengesellschaft
Priority to AU96226/98A priority Critical patent/AU9622698A/en
Publication of WO1999012886A1 publication Critical patent/WO1999012886A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06—Preparation of nitro compounds
    • C07C201/08—Preparation of nitro compounds by substitution of hydrogen atoms by nitro groups

Definitions

  • the invention relates to the production of a dinitronaphthalene isomer mixture with an increased proportion of 1,5-dinitronaphthalene (hereinafter called 1,5-DNN g ' ) by the nitration of pure 1-nitronaphthalene or a raw nitronaphthalene mixture.
  • 1,5-dinitronaphthalene is a key compound for the production of 1,5-diaminonaphthalene (hereinafter referred to as 1,5-NDA). This is, among other things, the starting compound for the production of 1,5-diisocyanatonaphthalene (1,5- NDI, trade name
  • Desmodur 15 ® Desmodur 15 ® ).
  • the 1,5-NDI is used as an isocyanate component in polyurethanes.
  • nitrated aromatics has long been known (G.A. Olah et al., Nitration: Methods and Mechanism, NCH, New York, 1989).
  • Corresponding nitroaromatics have been produced industrially by nitration with a mixture of sulfuric and nitric acid (so-called mixed or nitrating acid) for decades.
  • mixed or nitrating acid a mixture of sulfuric and nitric acid
  • naphthalene Houben-Weyl; Methods of Organic Chemistry, 1971, Vol. 10, pages 492-495
  • the nitration of the isomerically pure 1-nitronaphthalene with a mixture of sulfuric and nitric acid produces a mixture of 1,5- and 1,8-dinitronaphthalene in a ratio of about 1: 2 in addition to about 5% of the other isomers (e.g. 1, 6- and 1.7-DNN).
  • the unfavorable selectivity of the reaction preferably leads to a high and undesirable proportion of 1,8-DNN in the production of the 1,5-DNN.
  • WO 94/19310 describes nitrations of nitroaromatics on aluminum silicates, sometimes known as clay cops, doped with heavy metals, so-called clay cops, which provide high yields of dinitrated products with small amounts of trititroaromatics. Nitrations of 1 -nitronaphthalene carried out using this process, however, provide isomer ratios as in the case of classic nitriding oranges with mixed acid.
  • Nitrations with nitric acid in organic solvents e.g. Dichloroethane and azeotropic removal of the water of reaction are described in DE-A 24 53 529. They provide dinitronaphthalene in high yields without affecting the isomer ratio.
  • the object was therefore to find a process for the preparation of a dinitronaphthalene isomer mixture with a high proportion of 1,5-dinitronaphthalene by nitrating 1-nitronaphthalene.
  • the invention thus relates to a process for the preparation of a dinitronaphthalene isomer mixture by nitration of nitronaphthalene, in which nitronaphthalene, if appropriate in the presence of an acidic ion exchanger, with 1 to 20 times the amount, based on the amount of nitronaphthalene, in a solvent of the following formula
  • X represents nitrogen or sulfur, n being zero if X is nitrogen and n being 1 if X is sulfur,
  • Rj and R 2 independently of one another are a C ⁇ to C alkyl group or
  • R ] ⁇ and R 2 together represent a C 4 or C 5 alkylene chain
  • the 1-20 times equivalent corresponds to e.g. 65% nitric acid 33-92
  • nitric acid based on the mixture nitric acid / nitronaphthalene, in the case of 100% nitric acid 26-88% by weight nitric acid in the mixture nitric acid / nitronaphthalene.
  • the DNN isomer mixtures produced according to the invention contain a surprisingly high proportion of the 1,5-DNN isomer.
  • the selectivity of the nitration to the 1,5-DNN is usually over 30% by weight, in particular between 34 and 50% by weight. Pure 1 -nitronaphthalene or a crude nitronaphthalene mixture, as obtained as a crude product in the nitration of naphthalene, can be used as the starting product.
  • an acidic ion exchanger catalyzes the conversion to the 1,5-dinitronaphthalene-enriched end product.
  • a solid perfluorinated strongly acidic ion exchanger is preferably used.
  • Such perfluorinated strongly acidic ion exchangers are known in the art and, for example, under the trade name Nafion ® com- shoutally available.
  • An ion exchange resin is preferably used under the name Nafion ® NR50 Superacid Catalyst (Fa. Dupont).
  • the ion exchanger which may be used is chemically inert and can easily be obtained from the reaction mixture, e.g. by filtration.
  • the concentration of nitric acid is between 50% and 100%, preferably between 60% and 100%.
  • the amount of nitric acid added is between 1 equivalent and 20 equivalents based on the amount of nitronaphthalene used. In the case of 65% nitric acid, this corresponds to 33-92% by weight 65% nitric acid based on the mixture of nitric acid and nitronaphthalene. To be favoured
  • Amounts of nitric acid between 3 equivalents (for 65% nitric acid: 62.7% by weight) and 12 equivalents (corresponding to 87.0% by weight 65% nitric acid) are used.
  • the process is usually carried out at temperatures between 20 ° C. and 100 ° C., preferably 80 ° C.
  • the reaction is carried out with thorough mixing of the reaction, for example by vigorous stirring, for a reaction time between 20 minutes and 8 hours, for example 3 hours.
  • the 1,5-selectivity is surprisingly increased by the inert solvent of the formula given.
  • solvents are sulfolane or nitroalkanes such as nitromethane.
  • the process according to the invention is preferably carried out in sulfolane or nitromethane, particularly preferably in sulfolane.
  • the amount of organic solvent added is between 0.1 and 20
  • Parts based on the amount of nitronaphthalene used preferably between 0.5 and 3 parts.
  • the concentration of the nitric acid is adjusted to the amount of solvent added and is between 50% and 100%, preferably 60-80%.
  • the dinitronaphthalene isomer mixture can be prepared in a known manner, e.g. can be separated into the isomeric dinitronaphthalenes by fractional crystallization.
  • Such isomer separations e.g. with dimethylformamide or dichloroethane as solvent have already been described (cf. Houben-Weyl; Methods of Organic Chemistry, 1971, Vol. 10, page 494).
  • the invention further relates to isomer mixtures containing 1,5- and 1,8-dinitronaphthalene and containing 1,5-dinitronaphthalene in excess of 30% by weight, in particular between 34 and 50% by weight.
  • dinitronaphthalene isomer mixtures are preferably obtainable by the process according to the invention described above.
  • the 1,5-DNN can be separated off from the isomer mixture according to the invention in a known manner and used to prepare 1,5-NDA and 1,5-NDI.
  • Catalyst (DuPont) is only briefly named Nafion in the following examples.
  • the isomer composition of the residue was determined by gas chromatography (HP 5890, column: 25 m SE30, injector: 300 ° C, detector (FLD): 320 ° C, temperature program: start: 100 ° C, heating rate: 10 ° C / min, final temperature: 320 ° C, sample quantity: 2% in dioxane, injection quantity: 1 ⁇ l).
  • Table 1 shows the experimentally determined isomer compositions. When the solvent is added, higher ratios (1.5) / (1.8) -DNN result. This corresponds to a corresponding increase in the 1.5 selectivity
  • the proportion of 1 -nitronaphthalene (1-MNN), 1,5 -dinitronaphthalene (1,5-DNN), 1,8 -dinitronaphthalene (1,8-DNN) and the sum of the proportions of other DNN isomers and trinitronaphthalenes are given (DNN + TNN) and the ratio of the formed products 1,5-DNN and 1,8-DNN
  • the work-up can also be carried out simply by filtering off the catalyst directly from the hot reaction mixture.
  • Table 2 shows the experimentally determined isomer compositions.
  • sulfolane / sulfuric acid instead of sulfuric acid as solvent
  • higher ratios (1.5) / (1.8) -DNN result.
  • the best ratio (1,5) / (1,8) -DNN is achieved when using Nafion as a catalyst and Sulfolan as a solvent.
  • Lower sales of the Nafion Sulfolan system are not a hindrance, since the unreacted l-nitronaphthalene can be returned to the process.
  • Another advantage of this system is compared to that
  • Nitrations with a heterogeneous catalyst e.g. in Table 1, the homogeneity during the reaction so that work-up and catalyst recovery, e.g. by simply filtering off the heterogeneous catalyst.
  • a heterogeneous catalyst e.g. Sulfuric acid
  • the elaborate and costly work-up of the catalyst is eliminated when using a heterogeneous catalyst.
  • Table 2 Composition of the product mixture for the nitration of l-nitronaphthalene with nitric acid as the nitrating agent and sulfuric acid or Nafion as the catalyst (Examples 2.1 to 2.3); the equivalents of nitrating agent, the concentration of the nitric acid used and the reaction temperature are indicated.

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

Abstract

L'invention concerne un procédé de production d'un mélange d'isomères de dinitronaphtalène par nitration de nitronaphtalène. Le procédé selon l'invention est caractérisé en ceci que l'on fait réagir du nitronaphtalène, éventuellement en présence d'un échangeur d'ions acide, avec 1 à 20 fois la quantité - par rapport à la quantité de nitronaphtalène - d'un solvant de formule (I). Dans la formule (I), X représente azote ou soufre, n étant égal à zéro si X représente azote et étant égal à 1 si X représente soufre; R1 et R2 représentent indépendamment l'un de l'autre un groupe alkyle C1 à C4 ou bien représentent ensemble une chaîne alkylène C4 ou C5.
PCT/EP1998/005409 1997-09-08 1998-08-26 Procede de production d'un melange d'isomeres de dinitronaphtalene a proportion elevee en 1,5-dinitronaphtalene WO1999012886A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU96226/98A AU9622698A (en) 1997-09-08 1998-08-26 Method for producing a dinitronaphthalene-isomer mixture with a high proportion of 1,5-dinitronaphthalene

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1997139201 DE19739201C1 (de) 1997-09-08 1997-09-08 Verfahren zur Herstellung eines Dinitronaphthalin-Isomerengemisches mit hohem Anteil an 1,5-Dinitronaphthalin
DE19739201.6 1997-09-08

Publications (1)

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WO1999012886A1 true WO1999012886A1 (fr) 1999-03-18

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DE (1) DE19739201C1 (fr)
WO (1) WO1999012886A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6737554B2 (en) 2002-03-05 2004-05-18 Bayer Aktiengesellschaft Process for the production of a dinitronaphthalene isomer mixture with a high proportion of 1,5-dinitronaphthalene

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1248426A (fr) * 1958-02-11 1960-12-16 Pittsburg Coke & Chemical Comp Procédé de nitration de composés aromatiques présentant au moins un noyau aromatique dépourvu de groupement en position méta
DE2349753A1 (de) * 1972-10-05 1974-04-11 Ciba Geigy Ag Verfahren zur nitrierung von aromatischen verbindungen
US3976704A (en) * 1975-01-06 1976-08-24 Varen Technology Nitration process
JPS59122442A (ja) * 1982-06-05 1984-07-14 Oosakashi 高純度α−ニトロナフタレンの製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1248426A (fr) * 1958-02-11 1960-12-16 Pittsburg Coke & Chemical Comp Procédé de nitration de composés aromatiques présentant au moins un noyau aromatique dépourvu de groupement en position méta
DE2349753A1 (de) * 1972-10-05 1974-04-11 Ciba Geigy Ag Verfahren zur nitrierung von aromatischen verbindungen
US3976704A (en) * 1975-01-06 1976-08-24 Varen Technology Nitration process
JPS59122442A (ja) * 1982-06-05 1984-07-14 Oosakashi 高純度α−ニトロナフタレンの製造方法

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 96, no. 4, 25 January 1982, Columbus, Ohio, US; abstract no. 26286e, ACHORD, J. M. ET AL.: "Electrochemical nitration of aromatic hydrocarbons in a aprotic media" page 415; column 2; XP002090376 *
JOURNAL OF THE ELECTROCHEMICAL SOCIETY., vol. 128, no. 12, 1981, MANCHESTER, NEW HAMPSHIRE US, pages 2556 - 2561 *
PATENT ABSTRACTS OF JAPAN vol. 008, no. 241 (C - 250) 6 November 1984 (1984-11-06) *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6737554B2 (en) 2002-03-05 2004-05-18 Bayer Aktiengesellschaft Process for the production of a dinitronaphthalene isomer mixture with a high proportion of 1,5-dinitronaphthalene

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AU9622698A (en) 1999-03-29
DE19739201C1 (de) 1999-03-25

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