DE1167345B - Process for stabilizing organotin hydrides - Google Patents
Process for stabilizing organotin hydridesInfo
- Publication number
- DE1167345B DE1167345B DEST17092A DEST017092A DE1167345B DE 1167345 B DE1167345 B DE 1167345B DE ST17092 A DEST17092 A DE ST17092A DE ST017092 A DEST017092 A DE ST017092A DE 1167345 B DE1167345 B DE 1167345B
- Authority
- DE
- Germany
- Prior art keywords
- ecm
- hydride
- water
- aluminum
- tin
- 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
- 150000004678 hydrides Chemical class 0.000 title claims description 14
- 238000000034 method Methods 0.000 title claims description 5
- 230000000087 stabilizing effect Effects 0.000 title claims description 4
- -1 aluminum halogen compounds Chemical class 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- CPRPKIMXLHBUGA-UHFFFAOYSA-N triethyltin Chemical compound CC[Sn](CC)CC CPRPKIMXLHBUGA-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- HJXBDPDUCXORKZ-UHFFFAOYSA-N diethylalumane Chemical compound CC[AlH]CC HJXBDPDUCXORKZ-UHFFFAOYSA-N 0.000 claims description 2
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims 2
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims 1
- PIMYDFDXAUVLON-UHFFFAOYSA-M chloro(triethyl)stannane Chemical compound CC[Sn](Cl)(CC)CC PIMYDFDXAUVLON-UHFFFAOYSA-M 0.000 claims 1
- ISXUHJXWYNONDI-UHFFFAOYSA-L dichloro(diphenyl)stannane Chemical compound C=1C=CC=CC=1[Sn](Cl)(Cl)C1=CC=CC=C1 ISXUHJXWYNONDI-UHFFFAOYSA-L 0.000 claims 1
- WCOXDAZXJKCQGG-UHFFFAOYSA-N diethylstannane Chemical compound CC[SnH2]CC WCOXDAZXJKCQGG-UHFFFAOYSA-N 0.000 claims 1
- OLGIDLDDXHSYFE-UHFFFAOYSA-N dihydridotin Chemical compound [SnH2] OLGIDLDDXHSYFE-UHFFFAOYSA-N 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- 239000012074 organic phase Substances 0.000 claims 1
- 229920006395 saturated elastomer Polymers 0.000 claims 1
- 229910000029 sodium carbonate Inorganic materials 0.000 claims 1
- 229910052938 sodium sulfate Inorganic materials 0.000 claims 1
- 235000011152 sodium sulphate Nutrition 0.000 claims 1
- 230000006641 stabilisation Effects 0.000 claims 1
- 238000011105 stabilization Methods 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- 150000004820 halides Chemical class 0.000 description 3
- 229910000104 sodium hydride Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 239000012280 lithium aluminium hydride Substances 0.000 description 2
- 239000012312 sodium hydride Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- YFAXVVMIXZAKSR-UHFFFAOYSA-L dichloro(diethyl)stannane Chemical compound CC[Sn](Cl)(Cl)CC YFAXVVMIXZAKSR-UHFFFAOYSA-L 0.000 description 1
- 208000001848 dysentery Diseases 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 150000002483 hydrogen compounds Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010626 work up procedure Methods 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
- C07F7/22—Tin compounds
- C07F7/2208—Compounds having tin linked only to carbon, hydrogen and/or halogen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Description
DEUTSCHESGERMAN
PATENTAMTPATENT OFFICE
AUSLEGESCHRIFTEDITORIAL
Internat. Kl.: C07fBoarding school Class: C07f
Deutsche Kl.: 12 ο-26/03 German class: 12 ο -26/03
Nummer:
Aktenzeichen:
Anmeldetag:
Auslegetag:Number:
File number:
Registration date:
Display day:
St 17092 IVb/12 οSt 17092 IVb / 12 ο
8. November 1960November 8, 1960
9. April 1964April 9, 1964
Zur Herstellung von Organozinnhydriden der allgemeinen Formeln R3SnH, R2SnH2 und RSnH3 (R = Alkyl oder Aryl) sind bisher mehrere Verfahren bekanntgeworden. So wurden Metallverbindungen, ζ. Β. (CH3)3SnNa oder (C6H5)3SnLi, mit NH4Cl bzw. NH4Br zu den entsprechenden Wasserstoffverbindungen umgesetzt. Die Durchführung dieser Reaktionen ist jedoch kompliziert. Die Ausbeuten erreichen dabei höchstens 33 % der Theorie, meist jedoch liegen sie noch weit niedriger. Erfolgreicher verliefen die Versuche, Organozinnhydride aus den entsprechenden Halogeniden in ätherischer Lösung durch Reduktion mit Lithiumaluminiumhydrid zu gewinnen. Eine Reihe von Stoffen der allgemeinen Formel R«SnH4_re (n = 1, 2, 3) wurde so im Laboratoriumsmaßstab mit befriedigenden Ausbeuten hergestellt. Einer Durchführung dieser Reaktion in größerem Umfang steht jedoch die erforderliche umständliche Aufarbeitung im Wege, deren Nebenprodukte zudem sämtlich wertlos sind, sowie der hohe Preis des Lithiumaluminiumhydride. Einsatz der billigeren Alkali- oder Erdalkalihydride führte, wenn überhaupt, nur unter Anwendung von Druck und höheren Temperaturen zum Umsatz. Bei solchen Bedingungen sind aber die gesuchten Reaktionsprodukte zersetzlich.For the preparation of organotin hydrides of the general formulas R 3 SnH, R 2 SnH 2 and RSnH 3 (R = alkyl or aryl), several processes have become known to date. Metal compounds, ζ. Β. (CH 3 ) 3 SnNa or (C 6 H 5 ) 3 SnLi, reacted with NH 4 Cl or NH 4 Br to give the corresponding hydrogen compounds. However, these reactions are complicated to carry out. The yields reach a maximum of 33% of theory, but they are usually much lower. The attempts to obtain organotin hydrides from the corresponding halides in ethereal solution by reduction with lithium aluminum hydride were more successful. A number of substances of the general formula R «SnH 4 - re (n = 1, 2, 3) were produced in this way on a laboratory scale with satisfactory yields. Carrying out this reaction on a larger scale, however, stands in the way of the laborious work-up required, all of the by-products of which are also worthless, and the high price of the lithium aluminum hydride. Use of the cheaper alkali or alkaline earth metal hydrides led, if at all, to conversion only under the application of pressure and higher temperatures. Under such conditions, however, the desired reaction products are decomposable.
In neuester Zeit wurde vorgeschlagen, zur Darstellung von Alkylzinnhydriden die entsprechenden Halogenide mit Hilfe von komplex gebundenem und damit besser löslich gemachtem Natriumhydrid zu reduzieren.Recently it has been proposed to prepare alkyltin hydrides using the corresponding Halides with the help of complexly bound and thus made more soluble sodium hydride to reduce.
Weiterhin war vorgeschlagen worden, Natriumhydrid zur Reduktion von Alkylzinnhalogeniden zu
verwenden und als Katalysator eine kleine Menge Boroder Aluminiumalkylverbindung zuzusetzen. Ein in
diesem Sinne mit NaH (handelsübliches Produkt), Bortriäthyl und Triäthylzinnchlorid bei 65 bis 700C
in hochsiedendem Mineralöl durchgeführter Ansatz lieferte nach Destillation bei 33 Torr aber nur 37°/0
der Theorie an Triäthylzinnhydrid, daneben wieder Zinntetraäthyl und einen dunkelgefärbten Destillationsrückstand.
(In diesem und dem vorstehenden Fall zerfiel das gebildete Hydrid mindestens teilweise
unter den Reaktionsbedingungen.) In neuester Zeit wurde es möglich, Organozinnhydride durch Reduktion
von Organozinnhalogeniden mit Dialkylaluminiumhydriden unter schonenden Bedingungen herzustellen.
Die hergestellten Organozinnhydride können in üblicher Weise der Aufarbeitung nach Hydrolyse
der aluminiumorganischen Verbindung isoliert werden, jedoch ist es häufig vorteilhaft, sie direkt aus dem
Reaktionsgemisch abzudestillieren. Auch derart hergestellte Organozinnhydride. sind oft unbeständig und
Verfahren zur Stabilisierung von
OrganozinnhydridenIt has also been proposed to use sodium hydride to reduce alkyl tin halides and to add a small amount of boron or aluminum alkyl compound as a catalyst. With this in mind with NaH (commercially available product), Bortriäthyl and triethyltin at 65 to 70 0 C carried out in a high boiling mineral oil mixture gave, after distillation at 33 torr but only 37 ° / 0 of theory of Triäthylzinnhydrid, deviated again Zinntetraäthyl and a dark-colored distillation residue. (In this and the above case, the hydride formed at least partially decomposed under the reaction conditions.) Recently, it has become possible to prepare organotin hydrides by reducing organotin halides with dialkylaluminum hydrides under mild conditions. The organotin hydrides produced can be isolated in the usual way of working up after hydrolysis of the organoaluminum compound, but it is often advantageous to distill them off directly from the reaction mixture. Also organotin hydrides produced in this way. are often fickle and methods of stabilizing
Organotin hydrides
Anmelder:Applicant:
Studiengesellschaft Kohle m. b. H.,Study Society Coal m. B. H.,
Mülheim/Ruhr, Kaiser-Wilhelm-Platz 2Mülheim / Ruhr, Kaiser-Wilhelm-Platz 2
Als ErfirMer benannt:Named as the inventor:
Dr. Wilhelm Paul Neumann, Gießen,Dr. Wilhelm Paul Neumann, Giessen,
Dipl.-Chem. Dr. Horst Niermann,Dipl.-Chem. Dr. Horst Niermann,
Köln-StammheimCologne-Stammheim
zersetzen sich selbst bei 00C im Verlauf einiger Tage unter Zinnabscheidung und Wasserstoffentwicklung.decompose even at 0 0 C over the course of several days under tin deposition and hydrogen.
Es wurde jetzt festgestellt, daß Spuren von Aluminiumhalogenverbindungen, die beim Destillieren im Dampf mitgerissen worden sind, diese Zersetzung sehr beschleunigen. Befreit man die Organozinnhydride von den Aluminiumverbindungen durch Ausschütteln mit wenig Wasser oder besser Natriumbicarbonatlösung, so nimmt ihre Beständigkeit beträchtlich zu, so daß man sie im allgemeinen wochenlang (unter Luftausschluß) aufbewahren kann.It has now been found that traces of aluminum halogen compounds, which have been entrained in the steam during distillation, greatly accelerate this decomposition. Free the organotin hydrides from the aluminum compounds by shaking them out with a little water or better sodium bicarbonate solution, so their persistence increases considerably, so that they are generally kept for weeks (under Exclusion of air).
Gegenstand der Erfindung ist ein Verfahren zur Stabilisierung von Organozinnhydriden, das dadurch gekennzeichnet ist, daß man zur Entfernung der die Instabilität bewirkenden Aluminiumhalogenverbindungen diese in an sich bekannter Weise durch Behandlung mit wenig Wasser oder vorzugsweise Natriumbicarbonatlösungen entfernt.The invention relates to a method for stabilizing organotin hydrides, which thereby is characterized in that to remove the instability causing aluminum halogen compounds this in a manner known per se by treatment with a little water or preferably sodium bicarbonate solutions removed.
B ei s piel 1Example 1
Ein abdestilliertes Triäthylzinnhydrid, das geringe Mengen von mitgerissenem Diäthylaluminiumchlorid enthält, wird nach Destillation tropfenweise mit wenig Wasser oder besser NaHCO3-Lösung versetzt, von der entstandenen Trübung (Aluminiumhydroxyd) filtriert, getrocknet und nochmals destilliert. Kp.12 = 470C. Der Zinngehalt beträgt dann 57,4% (berechnet für C6H16Sn: 57,4%), die Ausbeute 51,5 g = 83 % der Theorie.A distilled triethyltin hydride containing small amounts of entrained diethylaluminum chloride is, after distillation, added dropwise with a little water or, better, NaHCO 3 solution, the resulting turbidity (aluminum hydroxide) is filtered off, dried and distilled again. Bp 12 = 47 ° C. The tin content is then 57.4% (calculated for C 6 H 16 Sn: 57.4%), the yield 51.5 g = 83% of theory.
In 34,5 g (0,4 Mol) Diäthylaluminiumhydrid wird bei 0°C gepulvertes Diäthylzinndichlorid (49,6 g = 0,2 Mol) im Argonstrom in kleinen Anteilen zugegeben. Die Mischung klärt sich bald völlig beimIn 34.5 g (0.4 mol) of diethyl aluminum hydride, powdered diethyl tin dichloride (49.6 g = 0.2 mol) was added in small portions in a stream of argon. The mixture soon becomes completely clear
409 558/461409 558/461
Claims (1)
zersetzt mitgerissene Spuren von Diäthylaluminium-the resulting diethyltin dihydride in vacuo, R SnC] + R A1H ^ R SnH + R A1C ,
decomposes entrained traces of diethylaluminum
Dibutyläther. Das völlig klare Reaktionsgemisch wird 1517.5 g (0.2MoI) diethyl aluminum hydride in 50 ecm claim "
Dibutyl ether. The completely clear reaction mixture is 15
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEST17092A DE1167345B (en) | 1960-11-08 | 1960-11-08 | Process for stabilizing organotin hydrides |
GB39837/61A GB951150A (en) | 1960-11-08 | 1961-11-07 | Manufacture of organo-tin hydrides |
DE19621468709 DE1468709A1 (en) | 1960-11-08 | 1962-10-19 | Process for stabilizing organotin hydrides |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEST17092A DE1167345B (en) | 1960-11-08 | 1960-11-08 | Process for stabilizing organotin hydrides |
Publications (1)
Publication Number | Publication Date |
---|---|
DE1167345B true DE1167345B (en) | 1964-04-09 |
Family
ID=7457339
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DEST17092A Pending DE1167345B (en) | 1960-11-08 | 1960-11-08 | Process for stabilizing organotin hydrides |
Country Status (2)
Country | Link |
---|---|
DE (1) | DE1167345B (en) |
GB (1) | GB951150A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5288886A (en) * | 1992-07-17 | 1994-02-22 | Witco Gmbh | Method of preparing trialkyl-tin hydrides |
-
1960
- 1960-11-08 DE DEST17092A patent/DE1167345B/en active Pending
-
1961
- 1961-11-07 GB GB39837/61A patent/GB951150A/en not_active Expired
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5288886A (en) * | 1992-07-17 | 1994-02-22 | Witco Gmbh | Method of preparing trialkyl-tin hydrides |
Also Published As
Publication number | Publication date |
---|---|
GB951150A (en) | 1964-03-04 |
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