DE1055511B - Process for the production of hydrogen compounds of the elements of main group IV of the Periodic Table with atomic numbers 14 to 50 - Google Patents
Process for the production of hydrogen compounds of the elements of main group IV of the Periodic Table with atomic numbers 14 to 50Info
- Publication number
- DE1055511B DE1055511B DEK30589A DEK0030589A DE1055511B DE 1055511 B DE1055511 B DE 1055511B DE K30589 A DEK30589 A DE K30589A DE K0030589 A DEK0030589 A DE K0030589A DE 1055511 B DE1055511 B DE 1055511B
- Authority
- DE
- Germany
- Prior art keywords
- weight
- parts
- sodium hydride
- elements
- mineral oil
- Prior art date
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- 238000000034 method Methods 0.000 title claims description 7
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 230000000737 periodic effect Effects 0.000 title claims description 5
- 150000002483 hydrogen compounds Chemical class 0.000 title claims description 4
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 17
- 239000012312 sodium hydride Substances 0.000 claims description 17
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 150000004678 hydrides Chemical class 0.000 claims description 6
- 239000012190 activator Substances 0.000 claims description 5
- -1 aluminum alkyls activated sodium hydride Chemical class 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 150000004820 halides Chemical class 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 150000008282 halocarbons Chemical class 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000000375 suspending agent Substances 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims 1
- 150000002366 halogen compounds Chemical class 0.000 claims 1
- 239000002480 mineral oil Substances 0.000 description 22
- 235000010446 mineral oil Nutrition 0.000 description 22
- 238000009835 boiling Methods 0.000 description 11
- 239000000725 suspension Substances 0.000 description 8
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical group CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 description 6
- UCXUKTLCVSGCNR-UHFFFAOYSA-N diethylsilane Chemical compound CC[SiH2]CC UCXUKTLCVSGCNR-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- BYLOHCRAPOSXLY-UHFFFAOYSA-N dichloro(diethyl)silane Chemical compound CC[Si](Cl)(Cl)CC BYLOHCRAPOSXLY-UHFFFAOYSA-N 0.000 description 4
- 229910052732 germanium Inorganic materials 0.000 description 4
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- OJBGGLLCYJYHPG-UHFFFAOYSA-N diethyl(difluoro)silane Chemical compound CC[Si](F)(F)CC OJBGGLLCYJYHPG-UHFFFAOYSA-N 0.000 description 2
- KCWYOFZQRFCIIE-UHFFFAOYSA-N ethylsilane Chemical compound CC[SiH3] KCWYOFZQRFCIIE-UHFFFAOYSA-N 0.000 description 2
- SIAPCJWMELPYOE-UHFFFAOYSA-N lithium hydride Chemical compound [LiH] SIAPCJWMELPYOE-UHFFFAOYSA-N 0.000 description 2
- 229910000103 lithium hydride Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- AQRLNPVMDITEJU-UHFFFAOYSA-N triethylsilane Chemical compound CC[SiH](CC)CC AQRLNPVMDITEJU-UHFFFAOYSA-N 0.000 description 2
- GEAOJWKXHMGANA-UHFFFAOYSA-N $l^{1}-stannane Chemical class [SnH] GEAOJWKXHMGANA-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001343 alkyl silanes Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- PIMYDFDXAUVLON-UHFFFAOYSA-M chloro(triethyl)stannane Chemical compound CC[Sn](Cl)(CC)CC PIMYDFDXAUVLON-UHFFFAOYSA-M 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 description 1
- VDCSGNNYCFPWFK-UHFFFAOYSA-N diphenylsilane Chemical compound C=1C=CC=CC=1[SiH2]C1=CC=CC=C1 VDCSGNNYCFPWFK-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- NHOREJPMXSLGGR-UHFFFAOYSA-N ethyl(trifluoro)silane Chemical compound CC[Si](F)(F)F NHOREJPMXSLGGR-UHFFFAOYSA-N 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- UBGXLEFOIVWVRP-UHFFFAOYSA-N fluoro(triphenyl)silane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(F)C1=CC=CC=C1 UBGXLEFOIVWVRP-UHFFFAOYSA-N 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- QUZPNFFHZPRKJD-UHFFFAOYSA-N germane Chemical compound [GeH4] QUZPNFFHZPRKJD-UHFFFAOYSA-N 0.000 description 1
- 229910052986 germanium hydride Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 210000002837 heart atrium Anatomy 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- MLSKXPOBNQFGHW-UHFFFAOYSA-N methoxy(dioxido)borane Chemical compound COB([O-])[O-] MLSKXPOBNQFGHW-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- ZOYFEXPFPVDYIS-UHFFFAOYSA-N trichloro(ethyl)silane Chemical compound CC[Si](Cl)(Cl)Cl ZOYFEXPFPVDYIS-UHFFFAOYSA-N 0.000 description 1
- QVMRVWAOMIXFFW-UHFFFAOYSA-N triethyl(fluoro)silane Chemical compound CC[Si](F)(CC)CC QVMRVWAOMIXFFW-UHFFFAOYSA-N 0.000 description 1
- JLZWQNRGNMXIJY-UHFFFAOYSA-N triethylstannane Chemical compound CC[SnH](CC)CC JLZWQNRGNMXIJY-UHFFFAOYSA-N 0.000 description 1
- AKQNYQDSIDKVJZ-UHFFFAOYSA-N triphenylsilane Chemical compound C1=CC=CC=C1[SiH](C=1C=CC=CC=1)C1=CC=CC=C1 AKQNYQDSIDKVJZ-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C07F7/30—Germanium compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/04—Hydrides of silicon
- C01B33/043—Monosilane
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B6/00—Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
-
- 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
-
- 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
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0896—Compounds with a Si-H linkage
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
Description
Verfahren zur Herstellung von Wasserstoffverbindungen der Elemente der IV. Hauptgruppe des Periodischen Systems mit den Ordnungszahlen 14 bis 50 Gegenstand der Erfindung ist ein Verfahren zur Herstellung von verschiedenen Hydriden des Siliciums, Germaniums und Zinns, welches durch die Umsetzung der Halogenide bzw. Organohalogenide dieser Elemente der IV. Hauptgruppe des Periodischen Systems mit durch sogenannte Aktivatoren in den reaktionsfähigen Zustand versetztem Natriumhydrid gekennzeichnet ist.Process for the production of hydrogen compounds of the elements of the IV. main group of the periodic system with the ordinal numbers 14 to 50 subject the invention is a process for the preparation of various hydrides of silicon, Germanium and tin, which is produced by the conversion of the halides or organohalides these elements of the IV. main group of the periodic table with so-called Activators marked with sodium hydride which has been rendered reactive is.
Natriurnhydrid ist in den gebräuchlichen Lösungsmittel praktisch unlöslich und daher für Hydrierungen wenig geeignet. Versuche. mit Natriumhydrid Alkylsiliciumhalogenverbindungen zu den entsprechenden Alkylsilanen zu reduzieren, verliefen negativ. Dagegen erwiesen sich Lithiumhydrid, besonders aber Lithiumaluminiumhydrid, als durchaus brauchbare Hydrierungsmittel für derartige Verbindungen. Einer Verwendung im größeren Umfange steht jedoch der relativ hohe Preis dieser Hydride entgegen, zumal Lithiumhydrid meist nur in drei- bis vierfachem Überschuß angewendet zu befriedigenden Ergebnissen führt. Für die Herstellung von Germanium- oder Zinnwasserstoffverbindungen hingegen eignet sich Lithiumh_vdrid nicht.Sodium hydride is practically insoluble in common solvents and therefore not very suitable for hydrogenation. Try. with sodium hydride alkyl silicon halogen compounds to reduce to the corresponding alkylsilanes, were negative. Proved against it Lithium hydride, but especially lithium aluminum hydride, prove to be quite useful Hydrogenating agents for such compounds. A use on a larger scale however, this is offset by the relatively high price of these hydrides, especially lithium hydride usually only used in a three to four-fold excess to give satisfactory results leads. For the production of germanium or hydrogen tin compounds, however Lithiumh_vdrid is not suitable.
Es wurde nun gefunden, daß sich vorteilhaft das preiswerte und einfach herzustellende Natriumhydrid zur Herstellung von Wasserstoffverbindungen verschiedener Elemente der IV. Hauptgruppe des Periodischen Systems verwenden läßt, wenn sogenannte Aktivatoren zugegeben werden. Unter einem Aktivator werden Verbindungen verstanden, welche das Natriumhydrid in den aktiven, d. h. unmittelbar vor der Reaktion reaktionsfähigen gelösten Zustand versetzen. Zu diesen Verbindungen zählen Boralkyle, Borsäureester und Aluminiumalkyle, welche in Mengen von vorzugsweise 0,1 bis 30°/0, bezogen auf das Natriumhydrid, eingesetzt werden.It has now been found that the inexpensive and simple Sodium hydride to be produced for the production of hydrogen compounds of various Elements of main group IV of the periodic table can be used if so-called Activators are added. An activator is understood to mean compounds which the sodium hydride in the active, d. H. reactive immediately before the reaction move the dissolved state. These compounds include boron alkyls and boric acid esters and aluminum alkyls, which in amounts of preferably 0.1 to 30 ° / 0, based on the sodium hydride, can be used.
Als reduzierbare Verbindungen gelten die Halogenide bzw. Organohalogenide von Silicium, Germanium und Zinn. Unter Halogeniden werden die Fluoride, Bromide und Jodide, vorzugsweise aber die Chloride, verstanden. Auch Halogene neben einem, zwei oder drei organischen Resten am Atom lassen sich nach dem erfindungsgemäßen Verfahren gegen Wasserstoff austauschen, wobei die organischen Reste Alkyle, Aryle oder ungesättigte Radikale darstellen.The halides or organohalides are considered reducible compounds of silicon, germanium and tin. Under halides are the fluorides, bromides and iodides, but preferably the chlorides, understood. Also halogens next to one, two or three organic radicals on the atom can be according to the invention Replacing the process for hydrogen, the organic radicals being alkyls, aryls or represent unsaturated radicals.
Die Umsetzung wird in Gegenwart eines Lösungs-oder Suspensionsmittels durchgeführt, welches sich besonders in Form von hochsiedendem Mineralöl ausgezeichnet bewährt hat. Die angewendeten Temperaturen betragen bis zu 2001 C, meist zwischen 80 und 150° C.The reaction is carried out in the presence of a solvent or suspending agent carried out, which is particularly excellent in the form of high-boiling mineral oil has proven itself. The temperatures used are up to 2001 C, mostly between 80 and 150 ° C.
Die hergestellten Hydride sind gute Reduktionsmittel und finden auch als Katalysatoren bei Polymerisationsvorgängen oft Verwendung. Ferner werden sie als Treib- und Brennstoffe, eventuell als Zusätze, benutzt. Reine Hydride, wie beispielsweise Si H4, dienen auch als Ausgangssubstanz für die Herstellung reinster Elemente. Beispiel 1 94 Gewichtsteile einer 37,8°/oigen Suspension von Natriumhydrid in hochsiedendem Mineralöl, welche mit weiteren 120 Gewichtsteilen des Mineralöls verdünnt worden waren, wurden mit 5 Gewichtsteilen Aluminiumtriäthyl versetzt. Nach Erwärmung des Gemisches auf 110° C wurde eine Lösung von 102 Gewichtsteilen Diäthyldichlorsilan in 50 Gewichtsteilen Mineralöl unter Rühren zugetropft. Während der sofort einsetzenden Reaktion wurde gekühlt, wobei die Reaktionstemperatur nach 0,5stündiger Reaktionszeit 90° C betrug. Es wurden 54,2 Gewichtsteile reines, chloridfreies Diäthylsilan erhalten, entsprechend 94,6 °/o der Theorie.The hydrides produced are and find good reducing agents too often used as catalysts in polymerization processes. Furthermore, they will used as propellants and fuels, possibly as additives. Pure hydrides such as Si H4, also serve as the starting substance for the production of the purest elements. example 194 parts by weight of a 37.8% suspension of sodium hydride in high-boiling Mineral oil, which has been diluted with a further 120 parts by weight of the mineral oil 5 parts by weight of aluminum triethyl were added. After the Mixture at 110 ° C was a solution of 102 parts by weight of diethyldichlorosilane in 50 parts by weight of mineral oil was added dropwise with stirring. During the immediately starting The reaction was cooled, the reaction temperature being reached after a reaction time of 0.5 hours Was 90 ° C. 54.2 parts by weight of pure, chloride-free diethylsilane were obtained, corresponding to 94.6% of theory.
Beispiel2 Zu 80,5 Gewichtsteilen einer 37,8°/oigen Suspension von Natriumhydrid in hochsiedendem Mineralöl wurden 100 Gewichtsteile weiteres Mineralöl und 5 Gewichtsteile Bortriäthyl zugesetzt. Daraufhin wurden bei 80 bis 90° C 62 Gewichtsteile Äthyltrichlorsilan zugegeben. Erhalten wurden 19,5 Gewichtsteile = 85,5% der Theorie an reinem, chloridfreiem Äthylsilan.Example 2 To 80.5 parts by weight of a 37.8% suspension of Sodium hydride in high-boiling mineral oil became 100 parts by weight of additional mineral oil and 5 parts by weight of boron triethyl added. Then at 80 to 90 ° C 62 Parts by weight of ethyltrichlorosilane added. 19.5 parts by weight were obtained = 85.5% of theory of pure, chloride-free ethylsilane.
Beispiel 3 Es wurde analog Beispiel 1 an Stelle von Diäthyldichlorsilan Siliciumtetrachlorid eingesetzt, wobei Monosilan in 95%iger Ausbeute erhalten wurde.Example 3 Example 1 was used instead of diethyldichlorosilane Silicon tetrachloride used, monosilane being obtained in 95% yield.
Beispiel 4 Eine Suspension von 20 Gewichtsteilen Natriumhydrid in 80 Gewichtsteilen hochsiedendem Mineralöl wurde unter Rühren mit 4 Gewichtsteilen Bortriäthyl vermischt und auf 140° C erhitzt. Daraufhin wurde eine Lösung von 40 Gewichtsteilen Diäthyldifluorsilan in 30 Gewichtsteilen Mineralöl innerhalb von 1,5 Stunden zugetropft. Durch Destillation wurden 26,4 Gewichtsteile = 92,5% der Theorie an reinem, fluoridfreiem Diäthylsilan erhalten.Example 4 A suspension of 20 parts by weight of sodium hydride in 80 parts by weight of high-boiling mineral oil was added with stirring at 4 parts by weight Boron triethyl mixed and heated to 140 ° C. A solution of 40 Parts by weight of diethyl difluorosilane in 30 parts by weight of mineral oil within Added dropwise for 1.5 hours. By distillation, 26.4 parts by weight = 92.5% of the Theory obtained on pure, fluoride-free diethylsilane.
Gleich gute Ausbeuten an Diäthylsilan wurden erhalten, wenn Natriumhydrid mit 5 Gewichtsteilen Bortributyl aktiviert wurde.Equally good yields of diethylsilane were obtained when using sodium hydride was activated with 5 parts by weight of boron tributyl.
Wurde an Stelle von Diäthyldifluorsilan Triäthylfluorsilan oder Triphenylfluorsilan eingesetzt, so erhielt man Triäthyl- bzw. Triphenylsilan in über 95%iger Ausbeute.Triethylfluorosilane or triphenylfluorosilane was used instead of diethyl difluorosilane used, triethylsilane or triphenylsilane was obtained in a yield of over 95%.
Beispiel s In eine gut gerührte Suspension von 75 Gewichtsteilen N atriumhydrid in 220 Gewichtsteilen hochsiedendem Mineralöl wurden 9 Gewichtsteile Bortriäthyl eingetragen. Nach Erwärmung des Reaktionsgemisches auf 120 bis 140°C wurden innerhalb von 3 Stunden 77 Gewichtsteile gasförmiges Äthyltrifluorsilan eingeleitet. Es wurden 39 Gewichtsteile fluoridfreies Äthylsilan erhalten, welches einer Ausbeute von 96,3% der Theorie entsprach.Example s In a well-stirred suspension of 75 parts by weight of N. atrium hydride in 220 parts by weight of high-boiling mineral oil became 9 parts by weight Boron triethyl registered. After heating the reaction mixture to 120 to 140 ° C 77 parts by weight of gaseous ethyltrifluorosilane were introduced within 3 hours. 39 parts by weight of fluoride-free ethylsilane were obtained, which is a yield of 96.3% corresponded to theory.
Beispiel 6 42 Gewichtsteile Diäthyldichlarsilan in 30 Gewichtsteilen hochsiedendem Mineralöl wurden zu einer auf 150° C erwärmten und gut gerührten Suspension von 20 Gewichtsteilen Natriumhydrid in 70 Gewichtsteilen Mineralöl, welcher zuvor 6 Gewichtsteile Borsäuremethylester zugesetzt worden waren, innerhalb von einer Stunde zugetropft. Erhalten wurden 21,6 Gewichtsteile chloridfreies Diäthylsilan.Example 6 42 parts by weight of diethyldichlarsilane in 30 parts by weight high-boiling mineral oil became a suspension heated to 150 ° C. and stirred well of 20 parts by weight of sodium hydride in 70 parts by weight of mineral oil, which previously 6 parts by weight of methyl borate had been added within one Added dropwise for an hour. 21.6 parts by weight of chloride-free diethylsilane were obtained.
Beispiel 7 40 Gewichtsteile einer 50%igen Suspension von Natriumhydrid in hochsiedendem Mineralöl wurden mit weiteren 45 Gewichtsteilen Mineralöl verdünnt. Als Aktivator wurden 4 Gewichtsteile Bortriäthyl zugefügt. Bei einer Temperatur von 70° C wurden unter Rühren 86,4 Gewichtsteile Triäthylchlorstannan, welches mit 45 Gewichtsteilen Mineralöl verdünnt war, allmählich eingetragen. Durch Vakuumdestillation wurden 63,2 Gewichtsteile = 95°/o der Theorie reines chloridfreies Triäthylstannan vom Kp.21 = 46 bis 48° C erhalten.Example 7 40 parts by weight of a 50% strength suspension of sodium hydride in high-boiling mineral oil were diluted with a further 45 parts by weight of mineral oil. 4 parts by weight of boron triethyl were added as an activator. At one temperature of 70 ° C were with stirring 86.4 parts by weight of triethylchlorostannane, which with 45 parts by weight of mineral oil was diluted, gradually added. By vacuum distillation 63.2 parts by weight = 95% of theory were pure chloride-free triethylstannane obtained from b.p. 21 = 46 to 48 ° C.
Beispiel 8 Eine Suspension von 36,2 Gewichtsteilen Natriumhvdrid in 210 Gewichtsteilen hochsiedendem Mineralöl wurde bei einer Temperatur von 110° C mit 7 Gewichtsteilen Bortriäthyl versetzt. Daraufhin wurden zwischen 85 und 95° C innerhalb von 2 Stunden 72 Gewichtsteile technisches Vinyltrichlorsilan eingeleitet. In einer angeschlossenen Kühlfalle wurden 21 Gewichtsteile Vinylsilan = 84'% der Theorie erhalten.Example 8 A suspension of 36.2 parts by weight of sodium hydride in 210 parts by weight of high-boiling mineral oil was at a temperature of 110 ° C mixed with 7 parts by weight of boron triethyl. Thereupon were between 85 and 95 ° C initiated 72 parts by weight of technical grade vinyltrichlorosilane within 2 hours. In an attached cold trap, 21 parts by weight of vinylsilane = 84% of the Theory received.
Beispiel 9 12,1 Gewichtsteile Natriumhydrid, suspendiert in 140 Gewichtsteilen hochsiedendem Mineralöl wurden bei einer Temperatur von 110° C mit 7 Gewichtsteilen Bortriäthyl versetzt, woraufhin innerhalb von 1,5 Stunden eine Lösung von 56 Gewichtsteilen Diphenyldichlorsilan in 40 Gewichtsteilen Mineralöl zugetropft wurde. Es wurden 33,5 Gewichtsteile = 84'% der Theorie Diphenylsilan erhalten.Example 9 12.1 parts by weight of sodium hydride suspended in 140 parts by weight high-boiling mineral oil were at a temperature of 110 ° C with 7 parts by weight Boron triethyl added, whereupon a solution of 56 parts by weight within 1.5 hours Diphenyldichlorosilane in 40 parts by weight of mineral oil was added dropwise. There were 33.5 parts by weight = 84% of theory of diphenylsilane.
Beispiel 10 Zu 35 Gewichtsteilen feindispersem Natriumhydrid in 175 Gewichtsteilen hochsiedendem Mineralöl wurden 8 Gewichtsteile Aluminiumtriäthyl zugegeben. Nach einer 0,5stündigen Vorwärmung des Reaktionsgemisches auf 110° C wurden unter Rühren 102 Gewichtsteile Diäthyldichlorsilan; welche mit 50 Gewichtsteilen Mineralöl verdünnt worden waren, zugetropft. Die Reaktionstemperatur sank während der 0,5-stündigen Eintropfdauer infolge zunehmenden Rückflusses des entstandenen Silans auf 90 bis 95° C. Nach weiterer halbstündiger Nachreaktion wurde bei einem Kp. 702 = 57 bis 59° C das Diäthylsilan in einer Menge von 54,2 g destilliert, entsprechend einer Ausbeute von 94,6% der Theorie.Example 10 To 35 parts by weight of finely divided sodium hydride in 175 Parts by weight of high-boiling mineral oil became 8 parts by weight of aluminum triethyl admitted. After preheating the reaction mixture to 110 ° C. for 0.5 hour 102 parts by weight of diethyldichlorosilane; which with 50 parts by weight Mineral oil had been diluted, added dropwise. The reaction temperature decreased during the 0.5 hour dripping time due to increasing reflux of the resulting Silane to 90 to 95 ° C. After a further half-hour post-reaction was at a Bp. 702 = 57 to 59 ° C, the diethylsilane distilled in an amount of 54.2 g, accordingly a yield of 94.6% of theory.
Beispiel 11 9,2 Gewichtsteile einer 48%igen Suspension von Na H in einem hochsiedenden Mineralöl wurden mit 13 Gewichtsteilen Bortriäthvl in 27 Gewichtsteilen des gleichen Mineralöls versetzt. Nach dem Abkühlen dieser Mischung auf 0° C wurden 6,1 Gewichtsteile Germaniumtetrachlorid in 14 Gewichtsteilen Mineralöl zugesetzt, woraufhin unter Abscheidung von Na Cl die sofortige Reaktion eintrat. Zur Ermittlung der Aus-, beute wurde das in einer Kühlvorrichtung erhaltene GeH4 destilliert und durch ein auf etwa 800° C erhitztes Quarzrohr geleitet. Es wurden 1,3 Gewichtsteile reines Germanium erhalten.Example 11 9.2 parts by weight of a 48% strength suspension of Na H in a high-boiling mineral oil with 13 parts by weight of Bortriäthvl in 27 parts by weight the same mineral oil added. After cooling this mixture to 0 ° C were 6.1 parts by weight of germanium tetrachloride added in 14 parts by weight of mineral oil, whereupon the immediate reaction occurred with the separation of Na Cl. For investigation the yield, the GeH4 obtained in a cooling device was distilled and passed through a quartz tube heated to around 800 ° C. It became 1.3 parts by weight get pure germanium.
Claims (3)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEK30589A DE1055511B (en) | 1956-12-15 | 1956-12-15 | Process for the production of hydrogen compounds of the elements of main group IV of the Periodic Table with atomic numbers 14 to 50 |
| DEK35787A DE1085505B (en) | 1956-12-15 | 1958-09-19 | Process for the production of hydrogen compounds of the elements of main group IV of the Periodic Table with atomic numbers 14 to 50 |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEK30589A DE1055511B (en) | 1956-12-15 | 1956-12-15 | Process for the production of hydrogen compounds of the elements of main group IV of the Periodic Table with atomic numbers 14 to 50 |
| DEK35787A DE1085505B (en) | 1956-12-15 | 1958-09-19 | Process for the production of hydrogen compounds of the elements of main group IV of the Periodic Table with atomic numbers 14 to 50 |
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| DE1055511B true DE1055511B (en) | 1959-04-23 |
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| DEK30589A Pending DE1055511B (en) | 1956-12-15 | 1956-12-15 | Process for the production of hydrogen compounds of the elements of main group IV of the Periodic Table with atomic numbers 14 to 50 |
| DEK35787A Pending DE1085505B (en) | 1956-12-15 | 1958-09-19 | Process for the production of hydrogen compounds of the elements of main group IV of the Periodic Table with atomic numbers 14 to 50 |
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| DEK35787A Pending DE1085505B (en) | 1956-12-15 | 1958-09-19 | Process for the production of hydrogen compounds of the elements of main group IV of the Periodic Table with atomic numbers 14 to 50 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1170914B (en) * | 1959-07-15 | 1964-05-27 | Du Pont | Process for the production of silicon-hydrogen compounds |
| DE102009056731A1 (en) | 2009-12-04 | 2011-06-09 | Rev Renewable Energy Ventures, Inc. | Halogenated polysilanes and polygermanes |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE949943C (en) * | 1951-09-26 | 1956-09-27 | Dr Oskar Glemser | Process to replace the halogen atoms of volatile halides of the elements of the 3rd, 4th and 5th group of the Periodic Table in whole or in part with hydrogen and / or organic radicals |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1037428B (en) * | 1955-11-21 | 1958-08-28 | Degussa | Process for the production of sodium borohydride |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE949943C (en) * | 1951-09-26 | 1956-09-27 | Dr Oskar Glemser | Process to replace the halogen atoms of volatile halides of the elements of the 3rd, 4th and 5th group of the Periodic Table in whole or in part with hydrogen and / or organic radicals |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1170914B (en) * | 1959-07-15 | 1964-05-27 | Du Pont | Process for the production of silicon-hydrogen compounds |
| DE102009056731A1 (en) | 2009-12-04 | 2011-06-09 | Rev Renewable Energy Ventures, Inc. | Halogenated polysilanes and polygermanes |
| US9040009B2 (en) | 2009-12-04 | 2015-05-26 | Spawnt Private S.à.r.1. | Kinetically stable chlorinated polysilanes and production thereof |
| US9139702B2 (en) | 2009-12-04 | 2015-09-22 | Spawnt Private S.A.R.L. | Method for producing halogenated polysilanes |
| US9458294B2 (en) | 2009-12-04 | 2016-10-04 | Spawnt Private S.À.R.L. | Method for removing impurities from silicon |
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| DE1085505B (en) | 1960-07-21 |
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