DE1003731B - Process for the stabilization of organosodium compounds - Google Patents
Process for the stabilization of organosodium compoundsInfo
- Publication number
- DE1003731B DE1003731B DEB36854A DEB0036854A DE1003731B DE 1003731 B DE1003731 B DE 1003731B DE B36854 A DEB36854 A DE B36854A DE B0036854 A DEB0036854 A DE B0036854A DE 1003731 B DE1003731 B DE 1003731B
- Authority
- DE
- Germany
- Prior art keywords
- stabilization
- benzophenone
- sodium
- compounds
- lithium bromide
- 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
- 150000001875 compounds Chemical class 0.000 title claims description 6
- 238000000034 method Methods 0.000 title claims description 5
- 230000006641 stabilisation Effects 0.000 title claims description 5
- 238000011105 stabilization Methods 0.000 title claims description 5
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Inorganic materials [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 15
- 150000002900 organolithium compounds Chemical class 0.000 claims description 4
- -1 organolithium compounds Lithium bromide Chemical class 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 9
- 239000012965 benzophenone Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 5
- KSMWLICLECSXMI-UHFFFAOYSA-N sodium;benzene Chemical compound [Na+].C1=CC=[C-]C=C1 KSMWLICLECSXMI-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- LZTRCELOJRDYMQ-UHFFFAOYSA-N triphenylmethanol Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(O)C1=CC=CC=C1 LZTRCELOJRDYMQ-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- BWIQYVHBCNLPQJ-UHFFFAOYSA-N CC1=CC=C([Na])C=C1 Chemical compound CC1=CC=C([Na])C=C1 BWIQYVHBCNLPQJ-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- NPDACUSDTOMAMK-UHFFFAOYSA-N 4-Chlorotoluene Chemical compound CC1=CC=C(Cl)C=C1 NPDACUSDTOMAMK-UHFFFAOYSA-N 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 150000003388 sodium compounds Chemical class 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000010414 supernatant solution Substances 0.000 description 1
- 238000010792 warming 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
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/04—Sodium compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Stabilisierung von natriumorganischen Verbindungen Gegenstand des Patents 955 596 ist ein Verfahren zur Stabilisierung von natriumorganischen Verbindungen, bei dem man diesen als Stabilisierungsmittel lithiumorganische Verbindungen zusetzt.Process for the stabilization of organosodium compounds subject of patent 955 596 is a method for stabilizing organosodium Compounds in which these stabilizers are organolithium compounds clogs.
Es wurde nun gefunden, daß man an Stelle fertiger lithiumorganischer Verbindungen auch Lithiumbromid verwenden kann. Dessen Wirkung beruht t-ermutlich darauf, daß es mit den natriumorganischen Verbindungen in doppelter Umsetzung die entsprechende Menge einer lithiumorganischen Verbindung bildet, die dann ihrerseits die noch vorhandene natriumorganische Verbindung durch Komplexbildung stabilisiert.It has now been found that in place of finished organolithium Compounds can also use lithium bromide. Its effect is based on t-probable ensure that it reacts twice with the organosodium compounds corresponding amount of an organolithium compound forms, which then in turn the remaining organic sodium compound is stabilized by complex formation.
Die erfolgte Stabilisierung kann wie beim Verfahren des Hauptpatents durch die bei der Umsetzung mit Benzophenon erhaltenen Ausbeuten an Carbinolen nachgewiesen «-erden.The stabilization that has taken place can be carried out in the same way as in the process of the main patent demonstrated by the yields of carbinols obtained in the reaction with benzophenone "-earth.
Beispiel 1 Man stellt nach den Angaben von K. Ziegler (Angew. Chemie, 19 [1936], 455) und H. G i l m an (j. Amer. chem. Soc., 62,[19401, 1514) aus 11,3 g Chlorbenzol (0,1 1Mol), 6 g Natriumpulver (0,26Mol) und 100 ccm absolutem Benzol unter Stickstoff eine benzolische Suspension von Phenylnatrium her. Sie enthält zufolge der Umsetzung mit Benzophenon zu Triphenylcarbinol 0,08 Mol Phenylnatrium. Zu dieser schwarzen Suspension gibt man nach Abgießen des Benzols eine Lösung von 1,7 g Lithiumbromid (0,02 Mol) in etwa 100 ccm absolutem Äther. Dabei erfolgt keine Erwärmung und Gasentwicklung; der Niederschlag nimmt eine graugrüne Farbe an, während die überstehende Lösung sich tiefbraunrot färbt. Es bildet sich dabei durch doppelte Umsetzung zwischen dem Lithiumbromid und der entsprechenden Menge Phenylnatrium zum Teil die Komplexverbindung Diphenyllithiumnatrium. Nach 2stündigem Rühren bildet sich bei der Umsetzung mit Benzophenon noch 72,5% der Theorie Triphenylcarbinol, während man bei Zugabe von absolutem Äther ohne Lithiumbromid allmähliche Zersetzung des Phenylnatriums unter Selbsterwärmung und Gasentwicklung beobachtet und nach 3 Stunden mit Benzophenon kein Triphenylcarbinol mehr erhält.Example 1 According to the information provided by K. Ziegler (Angew. Chemie, 19 [1936], 455) and H. G i l m an (j. Amer. Chem. Soc., 62, [19401, 1514) from 11.3 g chlorobenzene (0.1 mol), 6 g sodium powder (0.26 mol) and 100 cc absolute benzene a benzene suspension of phenyl sodium under nitrogen. It contains according to the reaction with benzophenone to triphenylcarbinol 0.08 mol of phenyl sodium. After the benzene has been poured off, a solution of is added to this black suspension 1.7 g lithium bromide (0.02 mol) in about 100 cc of absolute ether. There is none Warming and gas evolution; the precipitate turns a gray-green color while the supernatant solution turns deep brown-red. It is formed by double Conversion between the lithium bromide and the corresponding amount of phenyl sodium partly the complex compound diphenyllithium sodium. Forms after stirring for 2 hours in the reaction with benzophenone still 72.5% of the theory triphenylcarbinol, while the addition of absolute ether without lithium bromide results in gradual decomposition of phenyl sodium observed with self-heating and evolution of gas and after No more triphenylcarbinol received for 3 hours with benzophenone.
lne ähnliche Stabilisierung des Phenylnatriums erzielt man auch, wenn man nur 0,67g Lithiumbromid (7,7 m-Mol), in 100 ccm absolutem Äther gelöst, hinzugibt. Die Ausbeute an Triphenylcarbinol beträgt nach 2 Stunden noch 71% der Theorie.A similar stabilization of the phenyl sodium is also achieved if only 0.67 g of lithium bromide (7.7 m-mol), dissolved in 100 cc of absolute ether, is added. The yield of triphenylcarbinol is still 71% of theory after 2 hours.
Beispiel 2 Man stellt durch Umsetzen von 12,7g p-Chlortoluol mit 5,5g Natriumsand in 75 ccm thiophenfreiem trockenem Benzol unter Stickstoff im Schlenkrohr bei 35 bis 40° eine Suspension von p-Tolylnatrium her. Sie liefert bei der Umsetzung mit Benzophenon 65 bis 700/0 der Theorie an p-Methyltriphenylcarbinol. Fügt man vor der Zugabe des Benzophenons 150 ccm absoluten Äther hinzu, so erfolgt lebhafte Gasentwicklung und Erwärmung; bei nachfolgender Zugabe von Benzophenon bilden sich keine nachweisbaren Mengen p - Methyltriphenylcarbinol.Example 2 By reacting 12.7 g of p-chlorotoluene with 5.5 g Sodium sand in 75 cc of thiophene-free dry benzene under nitrogen in a Schlenk tube a suspension of p-tolyl sodium at 35 to 40 °. She delivers in the implementation with benzophenone 65 to 700/0 of theory on p-methyltriphenylcarbinol. One adds before the addition of the benzophenone, 150 cc of absolute ether is added Gas evolution and heating; with the subsequent addition of benzophenone are formed no detectable amounts of p-methyltriphenylcarbinol.
Fügt man jedoch zu der benzolischen Suspension des p-Tolylnatriums nach Abdekantieren der Hauptmenge des Benzols 54 ccm einer 3 g trockenes Lithiumbromid enthaltenden Ätherlösung unter Rühren hinzu, so erfolgt auch bei weiterem Verdünnen mit absolutem Äther keine Gasentwicklung. Bei der Umsetzung des Gemisches mit Benzophenon erhält man 68% der Theorie p-Methyltriphenylcarbinol.However, one adds to the benzene suspension of the p-tolyl sodium after decanting off most of the benzene, 54 cc of 3 g of dry lithium bromide containing ether solution is added with stirring, the same is done with further dilution no gas development with absolute ether. When implementing the mixture with benzophenone 68% of theory of p-methyltriphenylcarbinol are obtained.
Verwendet man nur 10,5 ccm einer 0,59 g Lithiumbromid enthaltenden ätherischen Lösung als Stabilisiermittel, so erhält man beim Verdünnen mit Äther ebenfalls keine Gasentwicklung und bei der Umsetzung mit Benzophenon 63,5% der Theorie an p-Methyltriphenylcarbinol.If only 10.5 ccm of a 0.59 g lithium bromide is used ethereal solution as a stabilizing agent is obtained by diluting it with ether likewise no evolution of gas and 63.5% of theory when reacted with benzophenone of p-methyltriphenylcarbinol.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEB36854A DE1003731B (en) | 1955-02-25 | 1955-02-25 | Process for the stabilization of organosodium compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEB36854A DE1003731B (en) | 1955-02-25 | 1955-02-25 | Process for the stabilization of organosodium compounds |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1003731B true DE1003731B (en) | 1957-03-07 |
Family
ID=6965036
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEB36854A Pending DE1003731B (en) | 1955-02-25 | 1955-02-25 | Process for the stabilization of organosodium compounds |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1003731B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1158067B (en) | 1956-04-25 | 1963-11-28 | Phil Oliver Wallis Burke Jun D | Process for the production of organolithium compounds |
-
1955
- 1955-02-25 DE DEB36854A patent/DE1003731B/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1158067B (en) | 1956-04-25 | 1963-11-28 | Phil Oliver Wallis Burke Jun D | Process for the production of organolithium compounds |
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