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WO2011113926A1 - Procédé de préparation d'alcoxydes d'étain - Google Patents

Procédé de préparation d'alcoxydes d'étain Download PDF

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Publication number
WO2011113926A1
WO2011113926A1 PCT/EP2011/054108 EP2011054108W WO2011113926A1 WO 2011113926 A1 WO2011113926 A1 WO 2011113926A1 EP 2011054108 W EP2011054108 W EP 2011054108W WO 2011113926 A1 WO2011113926 A1 WO 2011113926A1
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WO
WIPO (PCT)
Prior art keywords
tin
alcohol
general formula
elemental
heated
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/EP2011/054108
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German (de)
English (en)
Inventor
Klaus Jurkschat
Ljuba Lovkova-Berends
Thomas Zöller
Markus SCHÜRMANN
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Technische Universitaet Dortmund
Original Assignee
Technische Universitaet Dortmund
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.)
Filing date
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Application filed by Technische Universitaet Dortmund filed Critical Technische Universitaet Dortmund
Publication of WO2011113926A1 publication Critical patent/WO2011113926A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/68—Preparation of metal alcoholates
    • C07C29/70—Preparation of metal alcoholates by converting hydroxy groups to O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/08—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups

Definitions

  • the present invention relates to a process for the preparation of tin alkoxides.
  • Tin (II) - and tin (IV) alkoxides find a variety of applications, for example in the sol-gel chemistry for the preparation of mixed elemental oxides.
  • DE 10 2008 021 980 A1 describes these compounds or their derivatives as efficient la
  • Polyurethanes are compounds of great industrial importance, which are used in a variety of applications. Its annual production is eight million tons worldwide. Industrial polyurethanes are nowadays predominantly by polyaddition of alcohols with isocyanates. However, a catalyst is necessary for this reaction. In many cases, organopolymers are still widely used as catalysts.
  • UD 40292 / SAM @ X01uAFe @
  • mercuric compounds include phenylmercuric neo-decaonate PhHgOCOCH 2 CMe 2 CH 2 CMe 2 CH3.
  • such compounds are very hazardous because of their toxicity to the environment. Consequently, a search is made for a suitable replacement. As such a substitution, the tin alkoxides described above have proven.
  • the elemental tin is refluxed with the alcohol.
  • the alcohol is heated to boiling.
  • the ascending vapors are condensed via appropriate facilities, such as reflux condensers and fed back into the reaction mixture.
  • the elemental tin is heated with the alcohol under anaerobic, anhydrous conditions to obtain a tin alkoxide of the general formula Sn (OR) 2 .
  • the elemental tin is heated to obtain a tin alkoxide of the general formula Sn (OR) 4 in the presence of at least oxygen and / or water with the alcohol.
  • R alkyl, aryl, functionalized radicals
  • R alkyl, aryl, functionalized radicals
  • tin (II) alkoxides In order to provide anaerobic and anhydrous conditions for reacting tin with alcohols to give corresponding tin (II) alkoxides, it may be provided according to the invention to carry out the reaction in a protective gas atmosphere.
  • Preferred shielding gases are nitrogen, argon or helium.
  • tin (IV) alkoxides it may be provided according to the invention to add water to the reaction mixture in a targeted manner in order to establish suitable reaction conditions.
  • the added amount of water may be between> 0.01% by weight and ⁇ 10% by weight.
  • excess alcohol is thermally separated to obtain a corresponding tin alkoxide, preferably distilled off. It may be inventively provided to separate the excess alcohol and reduced pressure, for example by means of a vacuum distillation.
  • the tin is presented in the form of tin powder and / or granules.
  • This offers the advantage that the tin thus presented offers a high reactive surface area.
  • the tin is used as a powder, this is presented or added with a mean particle size ⁇ 0.1 mm.
  • these preferably have a mean grain size between> 0.1 mm and ⁇ 30 mm.
  • the tin is brought into contact with the corresponding alcohol as a solid solid, for example as a plate or cube.
  • the elemental tin is heated with the alcohol for a period of> 4 hours, preferably> 8 hours, more preferably> 60 hours and particularly preferably> 120 hours. It has been found that, depending on the selected alcohol and the associated boiling temperature, a substantially quantitative reaction can be achieved within the stated period, so that the desired Zinnalkoxide can be obtained in outstanding yield free of by-products.
  • the reaction of the corresponding alcohol or alcohols to form tin alkoxides was carried out continuously.
  • a partial stream of the product-alcohol mixture present in a reaction space is removed and the excess of alcohol contained in this partial stream is separated off and recycled back into the reaction space, with reacted tin and alcohol being continuously metered in.
  • the reaction takes place as the heating, under elevated pressure, preferably at a pressure between> 1013mbar and ⁇ 10000mbar, more preferably between> 1013mbar and ⁇ 5000mbar. Due to the increased pressure, the boiling point of the alcohol used increases, causing the Reaction mixture can be heated higher. As a result, a faster conversion of the alcohol is achieved to the corresponding Zinnalkoxid.
  • the added solvent has to be substantially inert to the alcohol used and the tin used and preferably to have a higher boiling point than the alcohol used.
  • the solvent is preferably selected from the group consisting of toluene, xylene, butyl acetate, benzonitrile, aniline, anisole and triglyme.
  • R 1 , R 2 , R 3 , R 4 , R 5 are independently saturated or unsaturated, aromatic or non-aromatic, cyclic or acyclic, branched or unbranched, substituted or unsubstituted, optionally interrupted by heteroatoms or terminated hydrocarbon radicals or R 3 , R 4 , R 5 are independently hydrogen or OR 2 are used. In this case, R 3 and R 4 or R 3 and R 2 or R 4 and R 2 or R 5 and R 2 or R 5 and R 3 may form a ring.
  • the process according to the invention will be further explained below with reference to examples.
  • Elemental tin powder (1. 8 13 g, 15.28 mmol) was heated at reflux under a protective gas atmosphere with an excess of n-butanol for 5 d. After distilling off excess n-butanol, di- /? -Butoxy-tin (II) (4.05 g, 15.28 mmol, quant.) was obtained as a colorless, amorphous solid.
  • Elemental tin powder (1.57 g, 13.19 mmol) was heated to 210 ° C under an inert gas atmosphere (argon) with an excess of N-methyldiethanolamine for 5 days.
  • the 119 Sn NMR spectrum in MeN (CH 2 CH 2 OH) 2 / C 6 D 6 of the reaction solution for the preparation of the Sn (II) alkoxide shows a signal at -328 ppm.
  • Elemental tin powder (1.49 g, 12.55 mmol) was heated to 210 ° C under an inert gas atmosphere (argon) with an excess of N-methyldiethanolamine for 5 days. Then a little water was added dropwise and stirred at 140 ° C for 5 hours. After this Distillation of the excess N-methyldiethanolamine gave Sn [(OCH 2 CH 2 ) 2 NMe] 2 (4.43 g, 12.55 mmol, quant.) As a colorless amorphous solid.
  • the residue was recrystallized from THF to afford the spiro compound as a colorless, crystalline solid.
  • the compound crystallizes monoclinically in the space group P2i / c with eight formal units in the unit cell and two independent tin atoms in the asymmetric unit.
  • the tin atoms in both molecules are surrounded as shown in Fig. 1 distorted octahedral and each carry two molecules of N-methyldiethanolamine as ligands.
  • the molecular structure shown in FIG. 1 was determined by diffraction of X-rays on a single crystal of the spiro compound on a device SMART CCD BrukerAXS with Mo -IQ radiation (0.71073 A) at 173 (1) K.
  • SHELXS97, [11] and subsequent successive Differenzfouriersynthese was used.
  • SHELXL97 [12] was used for refinement. Nuclear scattering factors for neutral atoms and real and imaginary parts of the dispersion were taken from the International Tables for X-Ray Crystallography [13] .
  • the images were created with the program SHELXTL [14] .
  • Table 1 shows an example of a list of different reaction conditions for the preparation of tin alkoxides.
  • Table 2 shows selected bond lengths of the compound shown in FIG.
  • Table 2 Selected bond lengths of the compound according to FIG. 1
  • Table 3 shows a list of the crystallographic data of the compound shown in FIG.
  • Table 3 List of crystallographic data of the compound formula Sn [(OCH 2 CH 2 ) 2NMe] 2 shown in FIG. 1.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)

Abstract

L'invention concerne un procédé de préparation d'alcoxydes d'étain. En particulier, l'invention concerne un procédé de synthèse directe d'alcoxydes d'étain de formule générale Sn(OR)n, dans laquelle n est égal 2 ou 4, à partir d'étain élémentaire par mise en réaction avec des alcools correspondants. Selon l'invention, de l'étain élémentaire est chauffé avec une quantité molaire au moins n fois supérieure d'un alcool de formule générale ROH, en particulier avec recirculation, et de séparer l'alcool en excès pour obtenir l'alcoxyde d'étain correspondant.
PCT/EP2011/054108 2010-03-19 2011-03-18 Procédé de préparation d'alcoxydes d'étain Ceased WO2011113926A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102010012237.8 2010-03-19
DE201010012237 DE102010012237A1 (de) 2010-03-19 2010-03-19 Direktsynthese von Zinn(II)- und Zinn(IV)-Alkoxiden aus elementarem Zinn und Alkoholen

Publications (1)

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WO2011113926A1 true WO2011113926A1 (fr) 2011-09-22

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DE (1) DE102010012237A1 (fr)
WO (1) WO2011113926A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014048879A1 (fr) 2012-09-25 2014-04-03 Bayer Materialscience Ag Produits de polyaddition de polyisocyanate
WO2014048854A1 (fr) 2012-09-25 2014-04-03 Bayer Materialscience Ag Produits de polyaddition de polyisocyanate
EP2772496A1 (fr) * 2013-02-28 2014-09-03 Bayer MaterialScience AG Synthèse directe d'alcoxydes d'étain (II) et (IV) à partir d'étain élémentaire et alcools en présence de réactifs d'activation
EP2990381A1 (fr) 2014-08-29 2016-03-02 Covestro Deutschland AG Procédé de fabrication de composés d'étain
KR102696546B1 (ko) * 2023-03-13 2024-08-21 한국화학연구원 아미노알코올 리간드를 포함한 주석 전구체, 이의 제조방법 및 이를 이용한 박막 형성 방법

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3922636A1 (fr) 2020-06-08 2021-12-15 Covestro Deutschland AG Procédé de fabrication pour aminoalcools
EP4234602A1 (fr) 2022-02-28 2023-08-30 Covestro Deutschland AG Utilisation de catalyseurs spéciaux pour la fabrication de revêtements polyuréthane

Citations (1)

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Publication number Priority date Publication date Assignee Title
DE102008021980A1 (de) 2008-05-02 2009-11-05 Bayer Materialscience Ag Neue Katalysatoren und deren Einsatz bei der Herstellung von Polyurethanen

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008021980A1 (de) 2008-05-02 2009-11-05 Bayer Materialscience Ag Neue Katalysatoren und deren Einsatz bei der Herstellung von Polyurethanen

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"International TablesforX-Ray Crystallography", 1992, KLUWER ACADEMIC PUBLISHERS
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HOLLEMANN A. F., WIBERG E.: "Lehrbuch der Anorganischen Chemie", 1 January 1995, LEHRBUCH DER ANORGANISCHEN CHEMIE, WALTER DE GRUYTER, BERLIN/NEW YORK, ISBN: 978-3-11-012641-9, pages: 794, XP002639461 *
J. CIROBE; N. VOULGARAKIS, ZEITSCHRIFT FÜR NATURFORSCHUNG B, vol. 38B, 1983, pages 269
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M. GUGLIELMI; M. CARTURAN, J. NON-CRYST. SO//C, vol. 103, 1988, pages 16
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THOMAS ZÖLLER, DR. LJUBA IOVKOVA-BERENDS, CHRISTINA DIETZ, DR. THORSTEN BERENDS, PROF. DR. KLAUS JURKSCHAT: "On the Reaction of Elemental Tin with Alcohols: A Straightforward Approach to Tin(II) and Tin(IV) Alkoxides and Related Tinoxo Clusters", CHEMISTRY - A EUROPEAN JOURNAL, vol. 17, no. 8, 20 January 2011 (2011-01-20), pages 2361 - 2364, XP002639460 *
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014048879A1 (fr) 2012-09-25 2014-04-03 Bayer Materialscience Ag Produits de polyaddition de polyisocyanate
WO2014048854A1 (fr) 2012-09-25 2014-04-03 Bayer Materialscience Ag Produits de polyaddition de polyisocyanate
EP2772496A1 (fr) * 2013-02-28 2014-09-03 Bayer MaterialScience AG Synthèse directe d'alcoxydes d'étain (II) et (IV) à partir d'étain élémentaire et alcools en présence de réactifs d'activation
WO2014131750A1 (fr) * 2013-02-28 2014-09-04 Bayer Materialscience Ag Synthèse directe d'alcoxydes d'étain (ii) et (iv) à partir d'étain élémentaire et d'alcools en présence de réactifs d'activation
EP2990381A1 (fr) 2014-08-29 2016-03-02 Covestro Deutschland AG Procédé de fabrication de composés d'étain
KR102696546B1 (ko) * 2023-03-13 2024-08-21 한국화학연구원 아미노알코올 리간드를 포함한 주석 전구체, 이의 제조방법 및 이를 이용한 박막 형성 방법

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DE102010012237A1 (de) 2011-09-22

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