DE1117090B - Process for the production of hydrogen compounds of the elements of the 4th main group of the periodic table with atomic numbers 14 to 50 - Google Patents
Process for the production of hydrogen compounds of the elements of the 4th main group of the periodic table with atomic numbers 14 to 50Info
- Publication number
- DE1117090B DE1117090B DEK36959A DEK0036959A DE1117090B DE 1117090 B DE1117090 B DE 1117090B DE K36959 A DEK36959 A DE K36959A DE K0036959 A DEK0036959 A DE K0036959A DE 1117090 B DE1117090 B DE 1117090B
- Authority
- DE
- Germany
- Prior art keywords
- elements
- sodium hydride
- production
- main group
- periodic table
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims description 6
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 230000000737 periodic effect Effects 0.000 title claims description 4
- 150000002483 hydrogen compounds Chemical class 0.000 title claims description 3
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 14
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 13
- 239000012312 sodium hydride Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000012190 activator Substances 0.000 claims description 6
- 150000004820 halides Chemical class 0.000 claims description 6
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- -1 activated sodium hydride Chemical class 0.000 claims description 3
- 150000004678 hydrides Chemical class 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims 1
- 150000008282 halocarbons Chemical class 0.000 claims 1
- 150000002366 halogen compounds Chemical class 0.000 claims 1
- 239000005662 Paraffin oil Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 229910052732 germanium Inorganic materials 0.000 description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- HJXBDPDUCXORKZ-UHFFFAOYSA-N diethylalumane Chemical compound CC[AlH]CC HJXBDPDUCXORKZ-UHFFFAOYSA-N 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
Description
Verfahren zur Herstellung von Wasserstoffverbindungen der Elemente der 4. Hauptgruppe des Periodischen Systems mit den Ordnungszahlen 14 bis 50 Gegenstand des Hauptpatents 1055 511 ist ein Verfahren zur Herstellung von Hydriden des Siliciums, Germaniums und Zinns, das durch Umsetzung der Halogenide, auch der zum Teil organisch substituierten Halogenide, dieser Elemente der 4. 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 4th main group of the periodic system with the ordinal numbers 14 to 50. The subject of the main patent 1 055 511 is a process for the production of hydrides of silicon, germanium and tin organically substituted halides, of these elements of the 4th main group of the periodic system, is characterized by sodium hydride which has been brought into the reactive state by so-called activators.
Unter dem Begriff »Aktivatoren« werden Verbindungen verstanden, die das in den gebräuchlichen Lösungsmitteln praktisch unlösliche und daher für Hydrierungen wenig geeignete Natriumhydrid in den aktiven, d. h. unmittelbar vor der Reaktion reaktionsfähigen, gelösten Zustand versetzen. »Gelöst« bedeutet, daß der Aktivator geeignet ist, mit Natriumhydrid eine Komplexverbindung zu bilden, die in dem angewendeten Suspensions- bzw. Lösungsmittel gelöst ist. Nach der Reaktion des Natriumhydrids mit dem Halogenid eines der obengenannten Elemente wird der Aktivator unverändert wieder freigesetzt und ist in der Lage, sofort neues Natriumhydrid zu aktivieren. Es genügt daher, solche als Aktivatoren bezeichnete Verbindungen, zu denen Boralkyle, Borsäureester und Aluminiumalkyle gemäß dem Hauptpatent 1055 511 gerechnet werden, in nur geringen Mengen einzusetzen. Vorzugsweise werden je nach Art der Ausgangsstoffe 0,1 bis 30 Molprozent, bezogen auf das Natriumhydrid, verwendet, die eine glatte und nahezu quantitative Reaktion gewährleisten.The term “activators” is understood to mean compounds which convert sodium hydride, which is practically insoluble in common solvents and therefore not very suitable for hydrogenation, into the active, ie reactive, dissolved state immediately before the reaction. "Dissolved" means that the activator is capable of forming a complex compound with sodium hydride, which is dissolved in the suspension or solvent used. After the reaction of the sodium hydride with the halide of one of the abovementioned elements, the activator is released again unchanged and is able to activate new sodium hydride immediately. It is therefore sufficient, such as activators described compounds, including, boric acid esters and aluminum alkyls are calculated according to the main patent 1,055,511 alkylborons to use in only small amounts. Depending on the nature of the starting materials, 0.1 to 30 mol percent, based on the sodium hydride, are preferably used, which ensure a smooth and almost quantitative reaction.
Es wurde nun gefunden, daß außer den bereits genannten Bor- und Aluminiumalkylen sowie Borsäureester auch Alkylaluminiumverbindungen, insbesondere Alkylaluminiumhydride, das Natriumhydrid in geeigneter Weise aktivieren. Bezüglich der Menge, die, bezogen auf das Natriumhydrid, zugesetzt werden müssen, gilt das gleiche wie bei den erstgenannten Verbindungen. Eine Zugabe von 0,1 bis 30 Molprozent genügt, damit das Natriumhydrid glatt reagieren kann.It has now been found that, in addition to the boron and aluminum alkyls already mentioned as well as boric acid esters also alkyl aluminum compounds, in particular alkyl aluminum hydrides, activate the sodium hydride in a suitable manner. Regarding the amount that, related to the sodium hydride must be added, the same applies as for the former Links. An addition of 0.1 to 30 mol percent is sufficient for the sodium hydride can react smoothly.
Zum Unterschied gegenüber den Bor- und Aluminiumalkylen, sowie Borsäureestern, können die Alkylaluminiumhydride auch erst in dem Reaktionsgemisch hergestellt werden. So werden die Alkylaluminiumhalogenide durch das Natriumhydrid in die entsprechenden Hydride übergeführt, bevor die eigentliche Reduktion der Halogenide des Siliciums, Germaniums und Zinns einsetzt.In contrast to the boron and aluminum alkyls, as well as boric acid esters, the alkylaluminum hydrides can also only be prepared in the reaction mixture. Thus, the sodium hydride converts the alkylaluminum halides into the corresponding ones Hydrides transferred before the actual reduction of the halides of silicon, Germanium and tin are used.
Als reduzierbare Verbindungen gelten außer den Tetrahalogeniden auch die teilweise organisch substituierten Halogenide von Silicium, Germanium und Zinn. Die organischen Reste neben 1, 2 oder 3 Halogenatomen sind Alkyle, Aryle oder auch ungesättigte Radikale. Unter Halogeniden werden Fluoride, Bromide und Jodide, vorzugsweise aber die Chloride, verstanden.In addition to the tetrahalides, reducible compounds are also considered the partially organically substituted halides of silicon, germanium and tin. The organic radicals besides 1, 2 or 3 halogen atoms are alkyls, aryls or else unsaturated radicals. Among halides, fluorides, bromides and iodides are preferred but the chlorides, understood.
Die Umsetzung findet in einem Suspensions- bzw. Lösungsmittel statt. Als solches eignet sich besonders hochsiedendes Mineral- oder Paraffinöl. Die Temperaturen, bei denen die Reaktionen durchgeführt werden, betragen bis zu 200°C, meist zwischen 80 und 150° C. Beispiel 1 51,5 Gewichtsteile Natriumhydrid, suspendiert in 350 Gewichtsteilen Paraffinöl, wurden mit 33 Gewichtsteilen Diäthylaluminiumchlorid (Chlorgehalt 33°/0) bei 120°C aktiviert: Zwischen 100 und 120°C wurden daraufhin 90,6 Gewichtsteile SiC14, gelöst in 50 Gewichtsteilen Paraffinöl, zugetropft. Das entstandene S' H4 wurde zur Ausbeutebestimmung durch ein auf 800°C erhitztes Quarzrohr geleitet, wobei durch thermische Zersetzung des SiH4 reinstes Si entstand. Erhalten wurden 14,3 Gewichtsteile Si = 96°/o der Theorie.The reaction takes place in a suspension or solvent. High-boiling mineral or paraffin oil is particularly suitable as such. The temperatures, in which the reactions are carried out, are up to 200 ° C, usually between 80 and 150 ° C. Example 1 51.5 parts by weight of sodium hydride, suspended in 350 parts by weight Paraffin oil, 33 parts by weight of diethyl aluminum chloride (chlorine content 33 ° / 0) activated at 120 ° C: between 100 and 120 ° C were then 90.6 parts by weight SiC14, dissolved in 50 parts by weight of paraffin oil, was added dropwise. The resulting S 'H4 was passed through a heated to 800 ° C quartz tube to determine the yield, wherein pure Si was created by thermal decomposition of SiH4. 14.3 were obtained Parts by weight Si = 96% of theory.
Beispiel 2 Vier hintereinandergeschaltete Reaktionsgefäße, beschickt mit je 55 Gewichtsteilen NaH (suspendiert in 400 Gewichtsteilen Paraffinöl), wurden mit je 20 Gewichtsteilen Diäthylaluminiumhydrid aktiviert. In die -ersten drei Reaktionsgefäße wurden nacheinander je 80 Gewichtsteile SiC14 (gelöst in 50 Gewichtsteilen Paraffinöl) bei einer Reaktionstemperatur von 85°C zugetropft. Das entstandene Si H4 wurde zur Ausbeutebestimmung gemäß Beispiel 1 thermisch zersetzt. Erhalten wurden 37 Gewichtsteile reinstes Si = 93,50/, der Theorie.Example 2 Four reaction vessels connected in series, each charged with 55 parts by weight of NaH (suspended in 400 parts by weight of paraffin oil), were activated with 20 parts by weight of diethylaluminum hydride each. 80 parts by weight of SiC14 (dissolved in 50 parts by weight of paraffin oil) were added dropwise to each of the first three reaction vessels at a reaction temperature of 85.degree. The Si H4 formed was thermally decomposed according to Example 1 to determine the yield. 37 parts by weight of the purest Si = 93.50 /, theoretical.
Beispiel 3 Es wurde gemäß Beispiel 1 gearbeitet. An Stelle von 33 Gewichtsteilen Diäthylaluminiumchlorid wurden jedoch 122 Gewichtsteile zugegeben. Durch Eintropfen von 82 Gewichtsteilen Si C14 verdünnt mit 50 Gewichtsteilen Paraffinöl, entstand sofort SiH4, welches in über 95 °%ger Ausbeute erhalten werden konnte. Die Reaktionstemperatur betrug 80 °C.Example 3 Example 1 was followed. Instead of 33 parts by weight of diethylaluminum chloride, however, 122 parts by weight were added. The dropwise addition of 82 parts by weight of SiC14 diluted with 50 parts by weight of paraffin oil resulted immediately in SiH4, which could be obtained in a yield of over 95%. The reaction temperature was 80 ° C.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEK36959A DE1117090B (en) | 1958-10-30 | 1958-10-30 | Process for the production of hydrogen compounds of the elements of the 4th main group of the periodic table with atomic numbers 14 to 50 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEK36959A DE1117090B (en) | 1958-10-30 | 1958-10-30 | Process for the production of hydrogen compounds of the elements of the 4th main group of the periodic table with atomic numbers 14 to 50 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1117090B true DE1117090B (en) | 1961-11-16 |
Family
ID=7220862
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEK36959A Pending DE1117090B (en) | 1958-10-30 | 1958-10-30 | Process for the production of hydrogen compounds of the elements of the 4th main group of the periodic table with atomic numbers 14 to 50 |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1117090B (en) |
-
1958
- 1958-10-30 DE DEK36959A patent/DE1117090B/en active Pending
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