EP0610236B1 - Procede de fabrication de pieces moulees nickelees - Google Patents

Procede de fabrication de pieces moulees nickelees Download PDF

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EP0610236B1
EP0610236B1 EP92919740A EP92919740A EP0610236B1 EP 0610236 B1 EP0610236 B1 EP 0610236B1 EP 92919740 A EP92919740 A EP 92919740A EP 92919740 A EP92919740 A EP 92919740A EP 0610236 B1 EP0610236 B1 EP 0610236B1
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Prior art keywords
alkyl
ammonium compounds
general formula
cyclic ammonium
brighteners
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EP0610236A1 (fr
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Alfred Oftring
Bernd Burkhart
Volker Schwendemann
Klaus Glaser
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
    • C25D3/14—Electroplating: Baths therefor from solutions of nickel or cobalt from baths containing acetylenic or heterocyclic compounds
    • C25D3/18—Heterocyclic compounds

Definitions

  • the present invention relates to an improved process for the production of nickel-plated moldings by electrodeposition of nickel from aqueous acid baths which contain, as essential components, one or more nickel salts, one or more inorganic acids and one or more brighteners.
  • Such brighteners which are generally divided into primary brighteners (“brighteners”) and secondary brighteners (“brighteners”), are usually used as a combination of several of these agents in order to increase the effect.
  • DE-B 11 91 652 (2) describes mono- or polynuclear heterocyclic nitrogen bases of the aromatic type in quaternized form such as pyridinium salts, e.g. 2-pyridinium-1-sulfatoethane, as a leveling agent, i.e. Brightener, described for acidic galvanic nickel baths. These agents are used together with conventional basic gloss agents such as benzene-m-disulfonic acid, diaryl disulfimides or sulfonamides.
  • pyridinium salts e.g. 2-pyridinium-1-sulfatoethane
  • Brightener i.e. Brightener
  • DD 81 548 (3) and DD 108 777 (4) describe pyridinium acetic acid derivatives of the general formula II in which R9 is hydrogen, alkyl or alkenyl, described as a brightener for the electrodeposition of nickel layers.
  • cyclic ammonium compounds of the general formula III in which R10 represents hydrogen, methyl, ethyl, propyl, iso-propyl, carboxyl or aliphatic carboxyl ester, R11 denotes hydrogen, methyl, carboxyl or aliphatic carboxyl ester, R12 denotes the residue of an aliphatic alcohol, q denotes the number 0, 1 or 2 and Y ⁇ stands for hydroxide or halide, described as a brightener in galvanic baths for the deposition of nickel.
  • alkenyl sulfonic acids such as sodium vinyl sulfonate or sodium allylsulfonate are usually used as brighteners in combination with other brighteners such as propargyl alcohol, 2-butyne-1,4-diol, propyne sulfonic acid or 3-pyridinium propyl sulfonate.
  • a disadvantage of the agents known from the prior art is the generally relatively high use concentration in the nickel electrolyte baths used.
  • the invention was therefore an improved process for the production of nickel-plated moldings using brighteners which, with better or at least the same gloss formation as, for example, 2-pyridinium-1-sulfatoethane, 3-pyridinium-propylsulfonate or compounds of the general formulas II or III in a lower concentration need to be used as a task.
  • C1 to C4 alkyl radicals for R1 and R2 and for possible substituents on the heterocyclic ring system and on the phenyl nucleus are n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl and especially Consider methyl and ethyl.
  • alkyl-substituted heterocyclic ring systems for I are: 2-, 3- or 4-methylpyridinium, 2-, 3- or 4-ethylpyridinium, 3- or 4-n-propylpyridinium, 3- or 4-iso-propylpyridinium, 3- or 4-n-butylpyridinium, 4-tert-butylpyridinium, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dimethylpyridinium, 3-methyl-4-isopropylpyridinium, 4-tert-butyl-3-methylpyridinium, 2-, 3-, 4-, 5-, 6-, 7- or 8-methylquinolinium and 1-, 3-, 4-, 5-, 6-, 7- or 8-methylisoquinolinium.
  • Unsubstituted pyridinium is preferred.
  • C1 to C12 alkyl radicals for R3 for example, in addition to the C1 to C4 alkyl radicals mentioned above, n-amyl, iso-amyl, sec.-amyl, tert.-amyl, neopentyl, n-hexyl, n- Heptyl, n-octyl, 2-ethylhexyl, n-nonyl, iso-nonyl, n-decyl, n-undecyl and n-dodecyl.
  • C1 to C4 alkyl radicals are preferred.
  • Suitable C5- to C8-cycloalkyl radicals for R3 are in particular cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl and ethylcyclohexyl. Of these, cyclopentyl and cyclohexyl are preferred.
  • Suitable C7- to C12-phenylalkyl groups for R3 are, for example, 1-phenylethyl, 2-phenylethyl, 1-phenylpropyl, 2-phenylpropyl, 3-phenylpropyl, 2-phenylprop-2-yl, 4-phenylbutyl, 2,2-dimethyl- 2-phenylethyl, 5-phenylamyl, 6-phenylhexyl and especially benzyl.
  • the substitution scheme is ortho, meta or preferably para, in the case of disubstituted phenyl radicals the substituents are mainly in the 2,4-position, for example in the case of 2,4-xylyl.
  • a degree of substitution of 1 is preferred in the presence of substituents.
  • unsubstituted phenyl is particularly preferred.
  • C1 to C4 alkoxy radicals here are in particular methoxy and ethoxy, but also n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy and tert-butoxy.
  • C1 to C4 alkoxycarbonyl groups for example, n-propoxycarbonyl, iso-propoxycarbonyl, n-butoxycarbonyl, iso-butoxycarbonyl, sec.-butoxycarbonyl, tert.-butoxycarbonyl, but especially ethoxycarbonyl and methoxycarbonyl.
  • halogen atom here includes fluorine, iodine, but especially bromine and especially chlorine.
  • the radical R1 is preferably hydrogen, methyl or ethyl, the radical R2 is preferably hydrogen.
  • m preferably represents a number from 0 to 8, in particular 0 to 5.
  • Suitable n-valent anions X are the customary inorganic or organic anions which normally promote water solubility, in particular chloride, bromide, fluoride, sulfate, hydrogen sulfate, methanesulfonate, trifluoromethanesulfonate, 2-hydroxyethanesulfoant, p-toluenesulfonate, nitrate, tetrafluoroborate, Perchlorate, 1-hydroxyethane-1,1-diphosphonate, dihydrogen phosphate, hydrogen phosphate, phosphate, formate, acetate, oxalate and tartrate.
  • cyclic ammonium compounds of the general formula Ib in which the variables m, n and X ⁇ have the meanings given above and R5 denotes C7- to C12-phenylalkyl or phenyl, which can be substituted by one or two C1- to C4-alkyl radicals.
  • cyclic ammonium compounds of the general formula If in which the variables R1, R2, R3, m, n and X ⁇ have the meanings given above.
  • cyclic ammonium compounds I used according to the invention can advantageously be implemented by reacting the corresponding precursor of the general formula IV in which Z represents a nucleofugic leaving group, preferably chlorine or bromine, with a heterocycle of the general formula V. and, if desired, then exchange the anion Z ⁇ for X ⁇ .
  • Z represents a nucleofugic leaving group, preferably chlorine or bromine
  • reaction of components IV and V is advantageously carried out in an inert organic solvent such as toluene, xylene, petroleum ether, ligroin, cyclohexane, acetone, tetrahydrofuran, dioxane, methanol, ethanol, isopropanol, ethyl acetate or methyl benzoate or in a mixture thereof.
  • an inert organic solvent such as toluene, xylene, petroleum ether, ligroin, cyclohexane, acetone, tetrahydrofuran, dioxane, methanol, ethanol, isopropanol, ethyl acetate or methyl benzoate or in a mixture thereof.
  • the reaction can also be carried out in water or in a single-phase or two-phase mixture of water and one or more organic solvents, preferably polar organic solvents.
  • a customary phase transfer catalyst can be used. It is usually carried
  • the cyclic ammonium compounds I have the effect character of secondary brighteners, they are preferably used in combination with further, normally primary brighteners, if appropriate also with one or more further secondary brighteners.
  • the primary brighteners are, for example, vinylsulfonic acid or allylsulfonic acid sodium salts
  • the secondary brighteners are, for example, 2-butyne-1,4-diol or propargyl alcohol.
  • aqueous acidic nickel electrolyte baths used one or usually more nickel salts, e.g. nickel sulfate and nickel chloride, one or more inorganic acids, preferably boric acid and sulfuric acid, the compounds I alone or preferably in combination with other customary gloss agents as well as optionally other customary auxiliaries and additives in the concentrations customary for this purpose, e.g. Wetting agents and pore prevention agents.
  • nickel salts e.g. nickel sulfate and nickel chloride
  • inorganic acids preferably boric acid and sulfuric acid
  • Common aqueous acidic nickel electrolytes (“Watts electrolytes”) have the following basic composition: 200 to 350 g / l NiSO4 ⁇ 7 H2O 30 to 150 g / l NiCl2 ⁇ 6 H2O 30 to 50 g / l H3BO3.
  • the pH of the electrolyte baths is usually between 3 and 6, preferably between 4 and 5.
  • a strong mineral acid preferably sulfuric acid, is expediently used to set this pH.
  • the compounds I are present in the electrolyte baths in low concentrations, generally between 0.04 and 0.5 g / l, preferably between 0.1 and 0.3 g / l.
  • concentrations of other customary brighteners are normally in the range from 0.1 to 10 g / l, in particular 0.1 to 2.0 g / l.
  • the nickel electrolyte baths described above can be used to produce nickel coatings on molded parts made of steel, but also on molded parts made of other materials, for example brass, which have been pretreated as usual. This is usually done at temperatures of 30 to 80 ° C, preferably 40 to 60 ° C.
  • the compounds I used according to the invention are distinguished by an extraordinarily high level of gloss. As a rule, they achieve a stronger shine than with the usual brighteners at a significantly lower dosage in the nickel electrolyte baths.
  • the title compound was prepared analogously to Example 1 from pyridine and 2-bromoethyl acetate in a yield of 81%.
  • the title compound was prepared analogously to Example 1 from pyridine and 2-bromobutyric acid methyl ester in a yield of 85%.
  • the title compound was prepared analogously to Example 1 from pyridine and pentyl 2-bromopropionate in a yield of 79%.
  • the title compound was prepared analogously to Example 1 from pyridine and 4-bromo-crotonic acid ethyl ester in a yield of 70%.
  • the title compound was prepared analogously to Example 1 from pyridine and 4-bromocrotonic acid methyl ester in a yield of 71%.
  • the title compound was prepared analogously to Example 1 from pyridine and benzyl bromoacetate in a yield of 80%.
  • the title compound was prepared analogously to Example 1 from pyridine and 3-chloropropionate in a yield of 86%.
  • the title compound was prepared analogously to Example 1 from pyridine and isopropyl 4-chloroacetoacetate in a yield of 71%.
  • the title compound was prepared analogously to Example 1 from pyridine and 4-chloroacetoacetic acid tert-butyl ester in a yield of 73%.
  • the title compound was prepared analogously to Example 1 from pyridine and 4-chloroacetoacetic acid methyl ester in a yield of 74%.
  • the title compound was prepared analogously to Example 1 from pyridine and 4-chloroacetoacetic acid ethyl ester in a yield of 70%.
  • the title compound was prepared analogously to Example 1 from pyridine and 2-bromoethyl methyl ether in a yield of 69%.
  • the aqueous nickel electrolyte used had the following composition: 300 g / l NiSO47 H2O 60 g / l NiCl2 ⁇ 6 H2O 45 g / l H3BO3 2 g / l saccharin 0.8 g / l vinyl sulfonic acid sodium salt xg / l brightener according to table 0.5 g / l of a fatty alcohol derivative of the formula C12H25 / C14H29-O- (CH2CH2O) 2-SO3Na as a wetting agent The pH of the electrolyte was adjusted to 4.2 with sulfuric acid.
  • Brass sheets were used, which were degreased cathodically in an alkaline electrolyte by the usual methods before the coating with nickel.
  • the nickel was deposited in a 250 ml Hull cell at 55 ° C. and a current of 2A over a period of 10 minutes.
  • the sheets were then rinsed with water and dried with compressed air.
  • comparison compounds C and D are known from (3) and (4) and the comparison compound E is known from (5).

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Pyridine Compounds (AREA)
  • Electroplating Methods And Accessories (AREA)

Abstract

Fabrication de pièces moulées nickelées par dépôt galvanique de nickel à partir de bains aqueux et acides contenant comme principaux composants un ou plusieurs sels du nickel, un ou plusieurs acides inorganiques et un ou plusieurs brillanteurs, fabrication pour laquelle on utilise comme brillanteurs des composés cycliques de l'ammonium de formule (I) dans laquelle l'atome de N est un constituant d'un système cyclique de la pyridine, de la quinoline ou de l'isoquinoline qui peut comporter en outre un ou deux substituants alkyle C1 à C4, R1 et R2 désignent l'hydrogène ou un alkyle C¿1? à C4, A désigne un groupement de formule CO-R?3¿, -CO-O-R3, -CO-CH¿2?-CO-O-R?3¿, O-CO-R3, ou -O-R3, dans lequel R3 désigne un alkyle C¿1? à C12, un cycloalkyle C5 à C8, un phénylalkyle C7 à C12 ou un phényle pouvant être substitué par un ou deux restes alkyle C1 à C4, par des restes alcoxy C1 à C4, des atomes d'halogènes, des groupes hydroxyle, des restes phényle ou des groupes alcoxycarbonyle C1 à C4, m désigne un nombre de 0 à 10, n désigne un nombre de 1 à 4 et p vaut 0 ou 1 et X?-¿ désigne un anion inorganique ou organique de valeur n qui stimule la solubilité dans l'eau, à la condition que pour p = 0 et A = -CO-O-alkyle C¿1?-C12, m ne puisse pas prendre les valeurs 1, 2 ou 3 et que R?1¿, dans le même cas, ne désigne pas l'hydrogène, si m prend la valeur 0.

Claims (11)

  1. Procédé de fabrication d'articles moulés nickelés par la déposition ou le dépôt galvanique de nickel à partir de bains aqueux-acides, qui contiennent, à titre de constituants essentiels, un ou plusieurs sels de nickel, un ou plusieurs acides organiques et un ou plusieurs agents de brillantage, caractérisé en ce que l'on utilise, à titre d'agents de brillantage, des composés d'ammonium cycliques de la formule générale I
    Figure imgb0036
     dans laquelle l'atome d'azote fait partie d'un système cyclique pyridinique, quinoléinique, ou isoquinoléinique, qui peuvent complémentairement porter un ou deux substituants alkyle en C₁ à C₄,
    R¹ et R² représentent des atomes d'hydrogène ou des radicaux alkyle en C₁ à C₄,
    A représente un groupement de la formule -CO-O-R³, -CO-CH₂-CO-O-R³, -O-CO-R³ ou -O-R³, où
    R³ représente un radical alkyle en C₁ à C₁₂, cycloalkyle en C₅ à C₈, phénylalkyle en C₇ à C₁₂, ou phényle, qui peut être substitué par un ou deux radicaux alkyle en C₁ à C₄, radicaux alcoxy en C₁ à C₄, atomes d'halogènes, radicaux hydroxyle, radicaux phényle, ou radicaux alcoxycarbonyle en C₁ à C₄,
    m représente un nombre dont la valeur varie de 0 à 10,
    n représente un nombre dont la valeur varie de 1 à 4 et
    p est égal à 0 ou à 1 et
    X⊖ représente un anion inorganique ou organique, n-valant, qui confère de l'hydrosolubilité, avec la condition que, dans le cas où p = O et A = -CO-O-alkyle en C₁ à C₁₂, m ne soit ni 1, ni 2, ni 3 et R¹, dans le même cas, diffère de l'hydrogène dans le cas où m est égal à 0.
  2. Procédé de fabrication d'articles moulés nickelés suivant la revendication 1, caractérisé en ce que l'on utilise, à titre d'agents de brillantage, des composés d'ammonium cycliques répondant à la formule générale Ia
    Figure imgb0037
     dans laquelle les variables R¹, n et X⊖ possèdent les valeurs qui leur ont été précédemment attribuées, R⁴ représente un radical alkyle en C₁ à C₁₂ ou cycloalkyle en C₅ à C₈ et k est égal à 0 ou représente un nombre dont la valeur varie de 4 à 10, avec la condition que R¹ diffère de l'hydrogène dans le cas où k est égal à 0.
  3. Procédé de fabrication d'articles moulés nickelés suivant la revendication 1, caractérisé en ce que l'on utilise, à titre d'agents de brillantage, des composés d'ammonium cycliques répondant à la formule générale Ib
    Figure imgb0038
     dans laquelle les variables m, n et X⊖ possèdent les significations qui leur ont été précédemment attribuées et R⁵ représente un radical phénylalkyle en C₇ à C₁₂, ou un radical phényle, qui peut être substitué par un ou deux radicaux alkyle en C₁ à C₄.
  4. Procédé de fabrication d'articles moulés nickelés suivant la revendication 1, caractérisé en ce que l'on utilise, à titre d'agents de brillantage, des composés d'ammonium cycliques répondant à la formule générale Ic
    Figure imgb0039
     dans laquelle les variables R¹, R², R³, m, n et X⊖ possèdent les significations qui leur ont été précédemment attribuées.
  5. Procédé de fabrication d'articles moulés nickelés suivant la revendication 1, caractérisé en ce que l'on utilise, à titre d'agents de brillantage, des composés d'ammonium cycliques répondant à la formule générale Id
    Figure imgb0040
     dans laquelle les variables R¹, R³, n et X⊖ possèdent les significations qui leur ont été précédemment attribuées.
  6. Procédé de fabrication d'articles moulés nickelés suivant la revendication 1, caractérisé en ce que l'on utilise, à titre d'agents de brillantage, des composés d'ammonium cycliques répondant à la formule générale Ie
    Figure imgb0041
     dans laquelle les variables R¹, R³, n et X⊖ possèdent les significations que leur ont été précédemment attribuées.
  7. Procédé de fabrication d'articles moulés nickelés suivant la revendication 1, caractérisé en ce que l'on utilise, à titre d'agents de brillantage, des composés d'ammonium cycliques répondant à la formule générale If
    Figure imgb0042
     dans laquelle les variables R¹, R², R³, m, n et X⊖ possèdent les significations qui leur ont été précédemment attribuées.
  8. Procédé de fabrication d'articles moulés nickelés suivant l'une quelconque des revendications 1 à 7, caractérisé en ce que l'on utilise, outre les composés d'ammonium cycliques I, au moins un agent de brillantage supplémentaire.
  9. Composés d'ammonium cycliques répondant à la formule générale Ig
    Figure imgb0043
     dans laquelle
    R⁴   représente un radical alkyle en C₁ à C₁₂ ou cycloalkyle en C₅ à C₈,
    k   est égal à 0 ou représente un nombre dont la valeur varie de 4 à 10,
    n   représente un nombre dont la valeur varie de 1 à 4,
    X⊖   représente un anion inorganique ou organique, n-valant, qui favorise l'hydrosolubilité et
    R⁶   représente un radical alkyle en C₂ à C₄.
  10. Composés d'ammonium cycliques répondant à la formule générale Ih
    Figure imgb0044
     dans laquelle
    m   représente un nombre dont la valeur varie de 0 à 10,
    n   représente un nombre dont la valeur varie de 1 à 4,
    X⊖   représente un anion inorganique ou organique, n-valant, qui favorise l'hydrosolubilité et
    R⁷   représente un radical phénylalkyle en C₇ à C₁₂.
  11. Composés d'ammonium cycliques répondant à la formule générale Ij
    Figure imgb0045
     dans laquelle
    R¹   représente un atome d'hydrogène ou un radical alkyle en C₁ à C₄,
    n   représente un nombre dont la valeur varie de 1 à 4 et
    X⊖   représente un anion inorganique ou organique, n-valant, qui favorise l'hydrosolubilité et
    R⁸   représente un radical alkyle en C₃ à C₁₂, cycloalkyle en C₅ à C₈, phénylalkyle en C₇ à C₁₂, ou phényle, qui peut être substitué par un ou deux radicaux alkyle en C₁ à C₄, radicaux alcoxy en C₁ à C₄, atomes d'halogènes, radicaux hydroxyle, radicaux phényle, ou radicaux alcoxycarbonyle en C₁ à C₄.
EP92919740A 1991-10-30 1992-09-21 Procede de fabrication de pieces moulees nickelees Expired - Lifetime EP0610236B1 (fr)

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DE4135710 1991-10-30
DE4135710A DE4135710A1 (de) 1991-10-30 1991-10-30 Cyclische ammoniumverbindungen und ihre verwendung als glanzmittel fuer waessrig-saure galvanische nickelbaeder
PCT/EP1992/002180 WO1993009275A1 (fr) 1991-10-30 1992-09-21 Procede de fabrication de pieces moulees nickelees

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WO2004072320A2 (fr) * 2003-02-07 2004-08-26 Pavco, Inc. Utilisation d'amines a substitution n-allyle et leurs sels utilises en tant qu'agents d'avivage dans des bains de nickelage
AU2007328210B2 (en) * 2006-12-06 2012-11-22 Cornell Research Foundation, Inc. Intermediate duration neuromuscular blocking agents and antagonists thereof
US8592451B2 (en) 2009-03-17 2013-11-26 Cornell University Reversible nondepolarizing neuromuscular blockade agents and methods for their use
US9220700B2 (en) 2009-08-19 2015-12-29 Cornell University Cysteine for physiological injection
GB202214330D0 (en) * 2022-09-30 2022-11-16 Mahriche Sami Akram Automated platform universally useable for automating storage, handling and transport of goods

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DE1191652B (de) * 1963-05-15 1965-04-22 Dehydag Gmbh Saures galvanisches Nickelbad
US3206383A (en) * 1964-03-26 1965-09-14 Kappel Mario Electrolyte for use in the galvanic deposition of bright leveling nickel coatings
DE1496833A1 (de) * 1966-12-05 1969-07-17 Henkel & Cie Gmbh Saures galvanisches Nickelbad
FR2292057A1 (fr) * 1974-11-20 1976-06-18 Popescu Francine Bain galvanique pour nickelage brillant
US4457934A (en) * 1982-05-01 1984-07-03 Stauffer Chemical Company Insect repellent compounds
JPH03161486A (ja) * 1989-11-17 1991-07-11 Teijin Ltd 酵素阻害剤

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Chemical Abstracts, Band 115, 1991, Banks, Roland Eric et al: "Fluorcarbon derivates of nitrogen. Part 19. Synthesis and mass spectometric analysis of some pyridnium (tetrafluoro-4-pyridy) methylides" Zusammenfassung 158920c, & J. Fluorine Chem., 53(1), 127-142 *

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DE59203781D1 (de) 1995-10-26
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EP0610236A1 (fr) 1994-08-17
US5438140A (en) 1995-08-01
JPH07500634A (ja) 1995-01-19

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