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WO2000026189A1 - Procede de production de composes nitroxyle d'amines secondaires - Google Patents

Procede de production de composes nitroxyle d'amines secondaires Download PDF

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Publication number
WO2000026189A1
WO2000026189A1 PCT/EP1999/008170 EP9908170W WO0026189A1 WO 2000026189 A1 WO2000026189 A1 WO 2000026189A1 EP 9908170 W EP9908170 W EP 9908170W WO 0026189 A1 WO0026189 A1 WO 0026189A1
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Prior art keywords
alkyl
hydrogen
acidic
oxidation
hydrogen peroxide
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PCT/EP1999/008170
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German (de)
English (en)
Inventor
Heinz Friedrich Sutoris
Gerhard Bertlein
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BASF SE
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BASF SE
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Priority to AU11561/00A priority Critical patent/AU1156100A/en
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Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/22—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with hetero atoms directly attached to ring nitrogen atoms
    • C07D295/24—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods
    • C07B61/02—Generation of organic free radicals; Organic free radicals per se
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C291/00—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00
    • C07C291/02—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00 containing nitrogen-oxide bonds
    • C07C291/04—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00 containing nitrogen-oxide bonds containing amino-oxide bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/92—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with a hetero atom directly attached to the ring nitrogen atom
    • C07D211/94—Oxygen atom, e.g. piperidine N-oxide

Definitions

  • the present invention relates to a process for the preparation of nitroxyl compounds of secondary amines which do not have any hydrogen atoms on the ⁇ -carbon atoms by oxidation of such amines with hydrogen peroxide, the oxidation being carried out in the presence of an acidic substance.
  • 4-Substituted 2, 2, 6, 6-tetramethylpiperidine-N-oxylene is prepared starting from the corresponding amine in accordance with US Pat. No. 4,665,185 by oxidation with t-butyl hydroperoxide using transition metal catalysts.
  • European patent application 0 574 667 describes a process for the preparation of 2, 2, 6, 6-tetramethylpiperidine-N-oxyl and its derivatives substituted in the 4-position by oxidation of the corresponding amines with hydrogen peroxide with catalysis of divalent metal salts, alkaline earth metal -, In particular magnesium and zinc salts are preferably used.
  • nitroxyl compounds are obtained by oxidation of secondary amines with potassium peroxomonosulfate in buffered aqueous solutions.
  • a disadvantage of most of the preparations mentioned is that they usually only yield yields of the desired nitroxyl compound in the range of 73-85% and partly take place under heavy metal catalysis, which is economical and / or ecological, especially with regard to the large-scale production of Nitroxyl compounds is unsatisfactory.
  • the object was therefore to provide a process for the preparation of nitroxyl compounds which does not have these disadvantages of the prior art.
  • At least one substance selected from the group consisting of inorganic acids, organic acids, inorganic acidic solids and organic acidic solids is preferably used as the acidic substance.
  • the acidic substance usually you will only use an acidic substance, but in individual cases you can also use a mixture of acids from one or from different of the classes mentioned.
  • inorganic acids sulfuric acid and phosphoric acid should be mentioned in particular.
  • peroxomono- or disulfuric acid optionally in a mixture with sulfuric acid, can also be used. Accordingly, a reduction in the amount of hydrogen peroxide required for the oxidation of the secondary amine is possible.
  • Organic acids include formic acid and acetic acid. Of course, you can also use the corresponding peroxyacids in individual cases, ie peroxo-formic or peroxoacetic acid, optionally in a mixture with formic or acetic acid, with a corresponding reduction in the amount of hydrogen peroxide required.
  • mixed oxides containing acidic centers or inorganic solids which contain such mixed oxides as an essential constituent consisting of a combination of (a) oxides of titanium, zirconium, hafnium, tin, iron or Cr (III) on the one hand with (b ) Oxides of vanadium, chromium (VI), molybdenum, tungsten or scandium on the other hand, or the mixed oxides are sulfated or phosphated oxides of group (a) and the mixed oxides have been calcined after their combination at temperatures of 450 to 800 ° C.
  • the compounds of group A) to be used according to the invention as acidic substances are above all aluminum silicates. They belong to the clay minerals and are made up of Si0 tetrahedron and Al 2 ⁇ 3 octahedron layers, part of the silicon in the tetrahedron layer being formed by trivalent cations, preferably aluminum and / or part of the aluminum in the octahedral layer being preferably by divalent cations Magnesium is replaced, so that negative stratified charges arise.
  • Layered silicates with negative charges occur naturally in the form of montmorillonites, vermiculites or hectorites or can also be synthesized.
  • the exchangeable cations contained in the natural or synthetic layer silicates are exchanged for protons. This is done in a manner known per se, e.g. by treatment with sulfuric acid or hydrochloric acid.
  • pillared clays in which the layers are supported against one another, can also be used as acidic substances.
  • the production of such "pillared clays” is in Figuras, Catal. Rev. Be. Closely. 30 (1988) 457 and Jones, Catal. Today (2 (1988) 357. The information given there is hereby incorporated by reference and is intended to be incorporated here.
  • layered silicates with negative layer charges which are saturated by protons, are: montmorillonite, vermiculite and hectorite.
  • zeolites come in the acid H form of the structure types MFI, MEL, BOG, BEA, EMT, MOR, FAU, MTW, LTL, NES, CON or MCM-22 according to the structure classification from WM Meier, DH Olson, Ch.Baerlocher, Atlas of Zeolithe Structure Types, Elsevier, 4 th ed., 1996.
  • the acid H form of 12-ring zeolites of the BETA, Y, EMT and mordenite structure type, and 10-ring zeolites of the Pentasil type are preferred.
  • the zeolites can also contain boron, gallium, iron or titanium in the framework. They can also be partially exchanged with elements of the IB, IIB, IIIB, IIIA or VIIIB group, as well as with the elements of the lanthanides.
  • the zeolites ZBM-20, Fe-H-ZSM5, Sn-beta zeolite, beta zeolite, Zr-beta zeolite, H-beta zeolite, H-mordenite, USY, Ce-V zeolite, HY zeolite, Ti / B beta zeolite, B beta zeolite or ZB-10 are considered as acidic substances.
  • Acidic substances of group C) include, in particular, so-called superacid mixed oxides, which have been described several times in the literature.
  • so-called superacid mixed oxides which have been described several times in the literature.
  • Suitable sulfated or phosphated metal oxides (a) of group C) are, in particular, phosphated or sulfated zirconium oxide or titanium oxide, which may also contain further elements, such as iron, cobalt or manganese.
  • Sulfated or phosphated compounds as acidic substances are in particular:
  • Fe / Mn / Zr0 2 S0 4 (S content 0.5 to 4 mol%; Fe / Mn content 0.1 to 5 mol%)
  • Superacid mixed metal oxides (a) and (b) of group C) are in particular those which contain zirconium, titanium, iron, tin or chromium on the one hand and tungsten or molybdenum on the other hand.
  • Ti0 2 W0 3 , Fe 2 0 3 W0 3 , Zr0 2 Mo0 3 , Zr0 2 W0 3 , Cr 2 0 3 W0 3 , W0 3 Ti0, Ti0 2 W0 3 or Sn0 2 W0 3 Si0 2 should be mentioned, wherein the molar ratio of the oxides of group (a) to group (b) is usually 70 to 30 to 90 to 10.
  • these are phenol / formaldehyde resins and polymers of styrene and copolymers of styrene and divinylbenzene, each of which contains sulfonyl and / or carboxyl groups as acidic groups.
  • One approach (a) to carry out the method according to the invention is e.g. in that the total amount of the amine and the acidic substance, if appropriate in a suspending, emulsifying or solvent (hereinafter such a suspending, emulsifying or solvent is also referred to as SEL agent), the desired Setting the temperature and adding the hydrogen peroxide in portions or continuously.
  • a suspending, emulsifying or solvent hereinafter such a suspending, emulsifying or solvent is also referred to as SEL agent
  • a further procedure (b) for carrying out the process according to the invention consists, for example, in that part of the amine and the total amount of the acidic substance, if appropriate in a SEL agent, are initially introduced, the desired temperature is set and the remaining part of the amine and the hydrogen peroxide are added in portions or continuously admits that the addition of the remaining amine and the hydrogen peroxide is completed at about the same time.
  • a further procedure (c) for carrying out the process according to the invention consists, for example, in that a portion of the amine and the acidic substance, if appropriate in a SEL agent, is initially introduced, the desired temperature is set and the remaining portion of the amine and the remaining portion of the acidic Substance as a mixture and the hydrogen peroxide are added in portions or continuously in such a way that the addition of the remaining amine (and the remaining acidic substance) and the hydrogen peroxide has ended approximately at the same time.
  • a further procedure (d) for carrying out the process according to the invention consists, for example, in that part of the amine and the acidic substance, if appropriate in a SEL agent, The desired temperature is set and the remaining part of the amine and the hydrogen peroxide and the remaining part of the acidic substance are added in portions or continuously in such a way that the addition of the remaining amine and the hydrogen peroxide (and the remaining acidic substance) approximately simultaneously is finished.
  • a further procedure (e) for carrying out the process according to the invention consists, for example, in that the acidic substance or part of the acidic substance, if appropriate in a SEL agent, is initially introduced, the desired temperature is set and the amine, if appropriate in a mixture with the remaining portion of the acidic substance, and the hydrogen peroxide, optionally in a mixture with the remaining part of the acidic substance, added in portions or continuously such that the addition of the amine (and optionally the remaining acidic substance) and the hydrogen peroxide (and optionally the remaining acidic substance ) has ended at about the same time.
  • the mixture of the remaining part of the amine and the remaining part of the acidic substance is preferably and if possible as a solution, otherwise as a suspension or emulsion.
  • Suitable acidic substances are inorganic or organic acids which are soluble in the SEL agent used or are miscible with the SEL agent used.
  • the ammonium compound formed or formed (from the starting amine and the acidic substance) should also be soluble in this SEL agent in order to ensure the most defined dosage possible.
  • the remaining part of the amine if it is liquid, can also be added as a pure substance, if possible in the form of a solution, or else as a suspension or emulsion.
  • a SEL agent is advantageously used.
  • the acidic substance preference is given to inorganic or organic acids which are soluble in hydrogen peroxide or with hydrogen peroxide are miscible, the term "hydrogen peroxide" being understood here and elsewhere as meaning its aqueous solution.
  • procedures (b) to (d) apply analogously and depending on whether part of the acidic substance should be added to the starting amine or the hydrogen peroxide.
  • a SEL agent can be dispensed with.
  • water is inevitably added or water is additionally formed, which can be regarded as a SEL agent.
  • this amine or adduct is preferably mixed with a SEL agent.
  • the oxidation is carried out in the presence of a SEL agent which consists of water, an organic liquid which is at least partially miscible with water or a mixture of water and such an organic liquid.
  • a SEL agent which consists of water, an organic liquid which is at least partially miscible with water or a mixture of water and such an organic liquid.
  • Organic liquids which are at least partially miscible with water are, for example, C 1 -C 4 -alcohols, such as methanol, ethanol, n- or i-propanol, n-, i-, sec- or tert-butanol, C 2 -C 6 -Diols, such as ethylene glycol, propylene glycol, 1,4-butanediol, 1, 6-hexanediol, oligomeric and polymeric ethylene and propylene glycols (polyethylene glycols or polypropylene glycols) and their C ⁇ -C-alkyl, especially their methyl ethers , cyclic
  • Ethers such as Tetrahydrofuran or 1,4-dioxane, ketones, e.g. Acetone, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone or methyl tert-butyl ketone, and also C 1 -C 8 -carboxylic acid C 1 -C 4 -alkyl esters, such as e.g. the methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl or tert-butyl ester of formic, acetic, propionic or butyric acid.
  • ketones e.g. Acetone, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone or methyl tert-butyl ketone
  • organic liquids can also be mixed with one another or such a mixture of organic liquids in a mixture with water can also be used as the SEL agent.
  • Preferred organic liquids are C 1 -C 4 -alcohols, such as, for example, methanol, ethanol, n- or i-propanol, n-, i-, sec- or tert-butanol.
  • Methanol, ethanol, n- or i-propanol are particularly preferably used as organic liquids.
  • Water, methanol, ethanol, n- or i-propanol or mixtures of these liquids with one another are preferably used as SEL agents.
  • Oxidation of the amine is usually accomplished in the absence of a SEL agent (apart from the amount of water that results from the addition of the aqueous solution of hydrogen peroxide and the reduction of the hydrogen peroxide to water)
  • the oxidation of the amine is usually carried out analogously to what has been said at temperatures from 50 ° C. to the boiling point of the lowest-boiling component of the SEL agent.
  • the oxidation is usually carried out in the temperature range from about 20 ° C. below the boiling temperature (the lowest-boiling component) of the SEL agent to the boiling temperature (the lowest-boiling component) of the SEL agent.
  • the temperatures mentioned are understood as those temperatures which are set in the template.
  • the hydrogen peroxide (optionally mixed with acidic substance, see procedure (d)) is usually not preheated.
  • the remaining amine see procedure (b), optionally mixed with acidic substance, see procedure (c)) or its solution, suspension or emulsion can be preheated if desired, but this is usually not used.
  • the reaction is advantageously carried out in such a way that a pH of the suspension or solution of about 8.3 (at the temperature of the reaction measured) is not exceeded or, if this value is exceeded for a short time, the pH is adjusted to the mentioned range again by adding acidic substance.
  • the process according to the invention is preferably used to prepare nitroxyl compounds, which are secondary amines of the formulas Ia
  • R 1 and R 2 independently of one another, are each C 1 -C 4 -alkyl, phenyl or, together with the C atom to which they are attached, a 5- or 6-membered saturated hydrocarbon ring,
  • R 3 is hydrogen, hydroxy, amino, S0 3 H, S0 3 M, P0 3 H 2 , PO 3 HM, P0 3 M 2 , organosilicon radicals or an m-valent organic or silicon-organic radical bonded via oxygen or nitrogen , where M stands for an alkali metal,
  • R 4 is hydrogen, -CC 2 -alkyl, C ⁇ -C 12 alkoxy or together with
  • R 3 is oxygen or, together with R 3 and the carbon atom to which they are attached, the following ring structures
  • R 5 is hydrogen, -CC 2 -alkyl or - (CH 2 ) z -COOR 6 ,
  • R 6 are the same or different C ⁇ -C ⁇ g alkyl
  • z and p each independently represent an integer from 1 to 12 and
  • n is an integer from 1 to 100 and
  • R is the same or different C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl, C 7 -C ⁇ o aralkyl or C 6 -C aryl
  • R 1 and R 2 are methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl or tert-butyl or R 1 and R 2 form together a tetra or pentamethylene bridge.
  • R 1 and R 2 are preferably the same.
  • R 1 and R 2 are particularly preferred methyl groups.
  • C ⁇ ⁇ C für 2 alkyl for R 4 come in addition to the aforementioned C ⁇ -C alkyl groups also pentyl, sec-pentyl, tert-pentyl, neopentyl, 2, 3-dimethyl-but-2-yl, n-hexyl, 2-methylpentyl, n-heptyl, 2-methylhexyl, 2-ethylhexyl, n-octyl, isooctyl, 2-ethylhexyl, nonyl, 2-methylnonyl, isononyl, 2-methyloctyl, n-decyl, isodecyl, 2- Methylnonyl, n-undecyl, isoundecyl, n-dodecyl and isododecyl, (the designations isooctyl, isononyl and isodecyl are trivial designations and
  • the C 1 -C 2 alkoxy radicals which are suitable for R 4 can be derived accordingly from the C 1 -C 4 alkyl radicals.
  • p is preferably an integer from 6 to 12, particularly preferably 9.
  • z is preferably an integer from 1 to 4, particularly preferably 2.
  • R 5 includes, for example, the C 1 -C 2 -alkyl radicals mentioned above.
  • R 5 preferably represents hydrogen, C ⁇ -C-alkyl, which has already been mentioned above by way of example, or (CH 2 ) z -COO (-CC 16 alkyl), where -CC 6 alkyl, for example under C ⁇ -C ⁇ s-alkyl is listed below.
  • the radicals -CH 2 -CH -COO (CH 2 ) 11 -CH 3 and -CH 2 -CH 2 -COO (CH 2 ) 13 -CH 3 are particularly preferred.
  • C 1 -C 8 alkyl for R 6 is, for example, one of the above-mentioned C 2 alkyl groups, n-tridecyl, isotridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl or n-octadecyl .
  • N-Dodecyl and n-Hexadecyl are preferred.
  • Preferred monovalent radicals R 3 are hydrogen, the C ⁇ -C-alkyl groups already mentioned above and organosilicon radicals of the formula
  • groups T may be the same or different from one another and denote C Ci-Ci 2 alkyl or phenyl.
  • C ⁇ -C ⁇ 2 alkyl radicals have already been mentioned as examples under radical R 4 .
  • Li, Na and K are preferably used as alkali metals M in the groups -SO 3 M, -PO 3 HM and -P ⁇ 3 2 .
  • R 3 are hydroxy, a group of the formula
  • R 7 C ⁇ -C alkyl are, that is C ⁇ -C alkoxy, such as methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, sec-butoxy and tert-butoxy.
  • R 3 are also the oxygen-bonded siloxane residues derived from the above organosilicon residues.
  • Preferred m-valent radicals R 3 are, for example, the following radicals
  • R 8 is C ⁇ -C 12 alkyl or - (CH 2 ) z -C00R 6
  • R 9 is hydrogen or C ⁇ -C ⁇ s-alkyl
  • x is an integer from 1 to 12
  • z and R 6 have the meaning already given above.
  • C ⁇ -C und 2 alkyl and the group - (CH 2 ) z -C00R 6 for R 8 have already been listed for R 5 .
  • C ⁇ -C fürs-alkyl for R 9 has already been mentioned above for R 6 .
  • R 9 preferably represents hydrogen.
  • m-valent radicals R 3 are, for example, the following
  • U is hydrogen or an organic residue
  • x is an integer from 1 to 12 and
  • n is an even number m.
  • R 3 is one of these radicals, R 4 is preferably hydrogen, m can mean an integer from 1 to 100.
  • M is preferably 1, 2, 3, 4 or an integer from 10 to 50, with mixtures (with a corresponding molecular weight distribution) usually being used, particularly in the case of the oligomeric or polymeric radicals R 3 , so that, owing to such statistical distributions, as a rule fractional values for m result.
  • Suitable amines as starting materials for the production of N-oxylene according to the invention are also oligomeric or polymeric compounds which have a polysiloxane as the main polymer chain and in the side chain with 2, 2, 6, 6-tetraalkylpiperidine, preferably with 2, 2, 6, 6 tetramethyl piperidine rings are substituted.
  • Examples of amino compounds which can serve as corresponding starting materials in the process according to the invention can be found e.g. in the document WO 96/17002.
  • Preferred secondary amines as starting material for the production of nitroxyl compounds according to the invention are
  • TAA-ol 2, 2, 6, 6-tetramethylpiperidin-4-ol (from Hüls; hereinafter referred to as TAA-ol), 30 ml of 85% phosphoric acid (0.439 mol) and 150 ml of distilled Water was heated to 90 ° C. and then 302 ml of 30% hydrogen peroxide solution (2.96 mol hydrogen peroxide) were metered in over the course of 4 h. The temperature rose in the meantime to 99 ° C. After the addition of the hydrogen peroxide solution had ended, stirring was continued at 91 ° C. for 1.5 h. The conversion of TAA-ol to the corresponding nitroxyl compound was 94% of the theoretically expected conversion (determined by gas chromatography). 5

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

Abstract

L'invention concerne un procédé de production de composés nitroxyle d'amines secondaires, qui ne comportent aucun atome d'hydrogène au niveau des atomes d' alpha -carbone, par oxydation de ces amines avec du peroxyde d'hydrogène en présence d'une substance acide.
PCT/EP1999/008170 1998-11-03 1999-10-28 Procede de production de composes nitroxyle d'amines secondaires Ceased WO2000026189A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU11561/00A AU1156100A (en) 1998-11-03 1999-10-28 Method for producing nitroxyl compounds of secondary amines

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1998150625 DE19850625A1 (de) 1998-11-03 1998-11-03 Verfahren zur Herstellung von Nitroxylverbindugen sekundärer Amine
DE19850625.2 1998-11-03

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WO2000026189A1 true WO2000026189A1 (fr) 2000-05-11

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DE (1) DE19850625A1 (fr)
WO (1) WO2000026189A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004023640A1 (de) * 2004-05-10 2005-12-08 Degussa Ag Verfahren zur Herstellung von 4-substituierten 2,2,6,6-Tetramethyl-piperidin-N-oxy- und 2,2,6,6-Tetramethyl-piperidin-N-hydroxy-verbindungen

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06247932A (ja) * 1993-02-25 1994-09-06 Asahi Denka Kogyo Kk Ｎ−オキシル化合物の製造方法
WO1996029311A1 (fr) * 1995-03-21 1996-09-26 Basf Aktiengesellschaft 4-acylaminopiperidin-n-oxyles

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06247932A (ja) * 1993-02-25 1994-09-06 Asahi Denka Kogyo Kk Ｎ−オキシル化合物の製造方法
WO1996029311A1 (fr) * 1995-03-21 1996-09-26 Basf Aktiengesellschaft 4-acylaminopiperidin-n-oxyles

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 122, no. 21, 22 May 1995, Columbus, Ohio, US; abstract no. 265260d, NAKAHARA Y ET AL: "METHOD FOR PRODUCING 2,2,6,6-TETRAMETHYLPIPERIDINE N-OXYL COMPOUNDS" page 1093; column 1; XP002129763 *
SOSNOVSKY G ET AL: "PREPARATION OF 4-HYDROXY-2,2,6,6-TETRAMETHYLPIPERIDINE-1-OXYL A REINVESTIGATION OF METHODS USING HYDROGEN PEROXIDE IN THE PRESENCE OF CATALYSTS", ZEITSCHRIFT FUER NATURFORSCHUNG, TEIL B: ANORGANISCHE CHEMIE, ORGANISCHE CHEMIE, vol. 31B, no. 10, 1 October 1976 (1976-10-01), pages 1376 - 1378, XP000564266 *
SUNAMOTO J ET AL, BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, vol. 65, no. 4, 1992, pages 1041 - 1046, XP002129762, ISSN: 0009-2673 *

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DE19850625A1 (de) 2000-05-04

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