WO2003102002A1 - Polyazides de silicium et procede pour les produire - Google Patents

Polyazides de silicium et procede pour les produire Download PDF

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Publication number
WO2003102002A1
WO2003102002A1 PCT/EP2003/005589 EP0305589W WO03102002A1 WO 2003102002 A1 WO2003102002 A1 WO 2003102002A1 EP 0305589 W EP0305589 W EP 0305589W WO 03102002 A1 WO03102002 A1 WO 03102002A1
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WIPO (PCT)
Prior art keywords
silicon
iso
alkyl groups
general formula
polyazide
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/EP2003/005589
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German (de)
English (en)
Inventor
Constantin Alexander Filippou
Peter Portius
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.)
Humboldt Universitaet zu Berlin
Original Assignee
Humboldt Universitaet zu Berlin
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
Publication date
Application filed by Humboldt Universitaet zu Berlin filed Critical Humboldt Universitaet zu Berlin
Priority to AU2003237700A priority Critical patent/AU2003237700A1/en
Publication of WO2003102002A1 publication Critical patent/WO2003102002A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/54—Quaternary phosphonium compounds
    • C07F9/5463—Compounds of the type "quasi-phosphonium", e.g. (C)a-P-(Y)b wherein a+b=4, b>=1 and Y=heteroatom, generally N or O
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/025—Silicon compounds without C-silicon linkages

Definitions

  • the invention relates to silicon polyazides of the general formula (I) (K + ) n [L 2 - n Si (N 3 ) 4 + n ] (n) " where n assumes the values 0 or 2, L for N-heterocycles, K for Alkali metals, NH 4 or ER 4 , where EN, P, As or Sb and
  • R represent n- or iso-alkyl groups or phenyl groups, and processes for their preparation.
  • Silicon tetraazide is known. It is produced by reacting silicon tetrachloride with, for example, sodium azide. Here, the reaction takes place in an anhydrous organic solvent such as. B. benzing instead.
  • the result of the implementation is a hydrolysis-sensitive, highly explosive product.
  • the total nitrogen content of these compounds is lower than in silicon tetraazide and they also contain Si-C bonds, so that these compounds do not appear to be suitable for further economic use, for example for the low-temperature synthesis of silicon nitride or silicon and for the release of large, hot amounts of gas.
  • the invention is therefore based on the object of specifying silicon polyazides and processes for their preparation, to reduce or eliminate the thermal instability and the shock sensitivity of chemical compounds from the class of silicon polyazides with high nitrogen contents, in order to enable economical production and use of these compounds ,
  • n takes the values 0 or 2
  • K represents alkali metals, NH 4 or ER 4 ,
  • R represent n- or iso-alkyl groups or phenyl groups.
  • a process for the preparation of the compound having the general formula (I) is characterized in that silicon tetrachloride in the presence of a solvent initially with a compound of the general formula
  • K ' is a cation, in particular an alkali metal ion, ammonium ion, a substituted ammonium or phosphonium ion, is reacted and then monodentate or polydentate, neutral or basic anionic ligands L are added, L being N- Heterocycles (such as pyridines, 2, 2'-bipyridines,
  • R represent n- or iso-alkyl groups or phenyl groups and the alkyl groups have 1 to 5 carbon atoms.
  • pyridines, 2, 2'-bipyridines and 2,2'-bipyrimidines are provided as N-heterocycles.
  • the pyridines have n- or iso-alkyl groups or phenyl groups in the 2-, 3- or 4-position.
  • the 2,2'-bipyridines have alkyl groups in 4,4'- or 5, 5 '-position and the 2, 2'-bipyrimidines in 4,4'- or 5,5'- or 6, 6 'position n- or iso-alkyl groups or phenyl groups.
  • ethylenediamines or N- (n- or iso-) alkylated ethylenediamines are provided as diamines.
  • All alkyl groups have 1 to 5 carbon atoms.
  • alkyl-substituted ammonium ions are used for the substituted ammonium ions provided as K ', carbon contents of Ci to C 4 being provided.
  • methyl- or phenyl-substituted phosphonium ions are advantageously used for the substituted phosphonium ions.
  • pyridines, 2,2′-bipyridines and 2,2′-bipyrimidines are used for the N-heterocycles provided as ligand L.
  • Pyridines which have n- or iso-alkyl groups or phenyl groups in the 2-, 3- or 4-position have proven to be very advantageous for the course of the reaction.
  • the diamines are ethylenediamines or N- (n- or iso-) alkylated ethylenediamines, while 1,2-dimethoxyethane is used in particular as the polyether.
  • alkyl-substituted N-heterocycles used are those which have alkyl groups with 1 to 5 C atoms.
  • the reactions are carried out at temperatures between -30 ° C and + 40 ° C.
  • the reactions are carried out in an aprotic polar solvent, these being carried out in an aprotic polar inorganic solvent, such as SO 2 at normal pressure below -10 ° C. and CO 2 at 35 bar below -20 ° C., or in an aprotic polar organic solvent such as acetonitrile, propionitrile, diethyl ether, benzene, toluene.
  • an aprotic polar inorganic solvent such as SO 2 at normal pressure below -10 ° C. and CO 2 at 35 bar below -20 ° C.
  • an aprotic polar organic solvent such as acetonitrile, propionitrile, diethyl ether, benzene, toluene.
  • the compound of general formula (I) is used as a source for the release of silicon tetraazide.
  • the silicon tetraazide can be released again by heating the compound (I) and thus serve to form large amounts of hot gas.
  • the compound (I) must be heated to 200 to 400 ° C at normal pressure or in a vacuum.
  • Test conditions The starting materials and solvents used during the synthesis must be absolutely free of water and oxygen. In the case of liquids, this is achieved by means of standard procedures that have been introduced and also by means of recondensation and pump-evacuation cycles. All synthesis operations are carried out with the help of a protective gas (argon or nitrogen), heated Pyrex glass vessels and a spatula with a Teflon coating. It is filtered through glass fiber filters.
  • a protective gas argon or nitrogen
  • heated Pyrex glass vessels and a spatula with a Teflon coating It is filtered through glass fiber filters.
  • the silicon polyazide (N (PPh 3 ) 2 ) 2 [Si (N 3 ) 6 ] is placed in a high vacuum apparatus made of glass and stainless steel and after application of a high vacuum (p ⁇ 1-10 -3 mbar) at 30 K / min the decomposition temperature of 320 ° C warmed.
  • the crystals of 2, 2 '-bipyridine gradually dissolve to give an abso-
  • the solution is clear and colorless, and cloudiness occurs for the first time from approx. -10 ° C. It quickly increases until the ambient temperature is reached.
  • the precipitated substance is filtered off (257 mg) and the clear colorless filtrate is concentrated to approx 0.5 ml, where crystallization occurs
  • the isolated substance is first recrystallized in tetrahydrofuran and then in acetonitrile by cooling Cooling of solutions saturated at room temperature.
  • the yield after recrystallization from tetrahydrofuran is 81% and after recrystallization from acetonitrile it is 60%.
  • the information relates to SiCl 4 .
  • 453 mg of colorless, air-sensitive small single crystals of [(2,2'-bipy) Si (N 3 ) 4 ] appearing in a thick layer slightly rose.
  • the compound was identified by IR and NMR spectroscopy, elemental analysis, mass spectrometry, thermal analysis and X-ray single crystal structure analysis.
  • the compound melts at 211-212 ° C with sublimation and without decomposition, as was proven by comparison of IR and NMR spectra with an authentic sample. Heating the material to an even higher temperature leads to detonation.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)

Abstract

La présente invention concerne des polyazides de silicium de formule générale (I) (K<+>)n[L2-nSi(N3) 4+n] <(n)-> dans laquelle n représente 0 ou 2, L représente des N-hétérocycles, K représente des métaux alcalins, NH4 ou ER4, avec E représentant N, P, As ou Sb et R représentant des groupes n- ou isoalkyle ou des groupes phényle, ainsi que des procédés pour les produire. Les procédés pour les produire consistent à mettre en réaction du tétrachlorure de silicium, en présence d'un solvant, d'abord avec un composé de formule générale (II) K'(N3) dans laquelle K' représente un cation, notamment un ion de métal alcalin, un ion d'ammonium ou un ion d'ammonium ou de phosphonium substitué, puis est mélangé avec un ligand L neutre ou basique anionique, monodentelé ou polydentelé, avec L représentant des N-hétérocycles, des diamines ou des polyesters, ou consistent à mettre en réaction du tétrachlorure de silicium avec des composés de formule générale (III) (ER4)<+>(N3)<-> afin de le transformer directement en (I), avec E représentant N, P, As ou Sb et R représentant des groupes n- ou isoalkyle ou des groupes phényle, les groupes alkyle présentant de 1 à 5 atomes de C. Les nouveaux polyazides de silicium et les procédés pour les produire selon cette invention permettent de réduire ou de supprimer l'instabilité thermique et la sensibilité aux chocs de composés chimiques de la classe des polyazides de silicium présentant de hautes teneurs en azote et d'obtenir ainsi une production et une utilisation économiques de ces composés.
PCT/EP2003/005589 2002-05-31 2003-05-27 Polyazides de silicium et procede pour les produire Ceased WO2003102002A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003237700A AU2003237700A1 (en) 2002-05-31 2003-05-27 Silicon polyazides and a method for their production

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10225175 2002-05-31
DE10225175.4 2002-05-31

Publications (1)

Publication Number Publication Date
WO2003102002A1 true WO2003102002A1 (fr) 2003-12-11

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PCT/EP2003/005589 Ceased WO2003102002A1 (fr) 2002-05-31 2003-05-27 Polyazides de silicium et procede pour les produire

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AU (1) AU2003237700A1 (fr)
WO (1) WO2003102002A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010034317A1 (fr) 2008-09-26 2010-04-01 As Sivex International Procédé et système pour vérifier et gérer une file de véhicules au passage de frontière
US8809566B2 (en) 2008-11-11 2014-08-19 Merck Patent Gmbh Materials for organic electroluminescence devices

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3232958A (en) * 1961-11-03 1966-02-01 American Potash & Chem Corp Metalloid azides and process for preparing the same
JPH01143878A (ja) * 1987-12-01 1989-06-06 Nippon Tokushu Kagaku Kogyo Kk ケイ素アジド化合物の製造方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3232958A (en) * 1961-11-03 1966-02-01 American Potash & Chem Corp Metalloid azides and process for preparing the same
JPH01143878A (ja) * 1987-12-01 1989-06-06 Nippon Tokushu Kagaku Kogyo Kk ケイ素アジド化合物の製造方法

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
DATABASE CA [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; WIBERG, EGON ET AL: "Silicon tetraazide, Si(N3)4", XP002251601, retrieved from STN Database accession no. 49:3965 *
FILIPPOU, ALEXANDER C. ET AL: "The Hexaazidosilicate(IV) Ion: Synthesis, Properties, and Molecular Structure", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2002), 124(42), 12396-12397, XP002251600 *
PATENT ABSTRACTS OF JAPAN vol. 013, no. 402 (C - 633) 6 September 1989 (1989-09-06) *
ZEITSCHRIFT FUER NATURFORSCHUNG (1954), 9B, 500 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010034317A1 (fr) 2008-09-26 2010-04-01 As Sivex International Procédé et système pour vérifier et gérer une file de véhicules au passage de frontière
US8809566B2 (en) 2008-11-11 2014-08-19 Merck Patent Gmbh Materials for organic electroluminescence devices

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Publication number Publication date
AU2003237700A1 (en) 2003-12-19

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