DE1119268B - Process for the production of o-phenylene-bis- (diaethylphosphine) - Google Patents
Process for the production of o-phenylene-bis- (diaethylphosphine)Info
- Publication number
- DE1119268B DE1119268B DEI16112A DEI0016112A DE1119268B DE 1119268 B DE1119268 B DE 1119268B DE I16112 A DEI16112 A DE I16112A DE I0016112 A DEI0016112 A DE I0016112A DE 1119268 B DE1119268 B DE 1119268B
- Authority
- DE
- Germany
- Prior art keywords
- phenylene
- bis
- production
- diethylphosphine
- diaethylphosphine
- 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 7
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- WWXFZLVLAJUATK-UHFFFAOYSA-N (2-diethylphosphanylphenyl)-diethylphosphane Chemical compound CCP(CC)C1=CC=CC=C1P(CC)CC WWXFZLVLAJUATK-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- UVTLTCJBYXBVBA-UHFFFAOYSA-N diethylphosphanyl(diethyl)phosphane Chemical compound CCP(CC)P(CC)CC UVTLTCJBYXBVBA-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 description 4
- KLYCPFXDDDMZNQ-UHFFFAOYSA-N Benzyne Chemical compound C1=CC#CC=C1 KLYCPFXDDDMZNQ-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- QBELEDRHMPMKHP-UHFFFAOYSA-N 1-bromo-2-chlorobenzene Chemical compound ClC1=CC=CC=C1Br QBELEDRHMPMKHP-UHFFFAOYSA-N 0.000 description 2
- OIRHKGBNGGSCGS-UHFFFAOYSA-N 1-bromo-2-iodobenzene Chemical compound BrC1=CC=CC=C1I OIRHKGBNGGSCGS-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000007818 Grignard reagent Substances 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 150000003003 phosphines Chemical group 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- ZHCOAYADQQGAHV-UHFFFAOYSA-N (2-diethylphosphanyl-4-methylphenyl)-diethylphosphane Chemical compound CC1=CC(=C(C=C1)P(CC)CC)P(CC)CC ZHCOAYADQQGAHV-UHFFFAOYSA-N 0.000 description 1
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 description 1
- PLAKKSAFIZVHJP-UHFFFAOYSA-N 2-bromo-1-iodo-4-methylbenzene Chemical compound CC1=CC=C(I)C(Br)=C1 PLAKKSAFIZVHJP-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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
- 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
- C07F9/50—Organo-phosphines
- C07F9/5027—Polyphosphines
-
- 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
- C07F9/50—Organo-phosphines
- C07F9/505—Preparation; Separation; Purification; Stabilisation
Landscapes
- 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)
Description
Verfahren zur Herstellung von o-Phenylen-bis-(diäthylphosphin) Die Erfindung betrifft ein Verfahren zur Herstellung von o-Phenylen-bis-(diäthylphosphin). Process for the preparation of o-phenylene-bis- (diethylphosphine) Die The invention relates to a process for the production of o-phenylene-bis (diethylphosphine).
Ditertiäre Phosphine, in denen die Phosphoratome an verschiedene Kohlenstoffatome eines aromatischen Ringes, der noch andere Substituenten trägt, gebunden sind, wie 4-Methyl-o-phenylen-bis-(diäthylphosphin), sind bekannte Verbindungen. Jedoch sind die nichtsubstituierten o-phenylen-ditertiären Phosphine bisher nicht hergestellt worden. Ditertiary phosphines, in which the phosphorus atoms are attached to different Carbon atoms of an aromatic ring that has other substituents, Are bound, such as 4-methyl-o-phenylene-bis- (diethylphosphine), are known compounds. However, the unsubstituted o-phenylene-ditertiary phosphines are not yet has been manufactured.
In Analogie zur Herstellung von 4-Methyl-o-phenylen-bis-(diäthylphosphin) aus 3-Brom-4-jodtoluol und Magnesium unter Bildung des Di-Grignardreagenzes und weiteres Umsetzen des letzteren mit Chloräthyldiphosphin konnte man annehmen, daß es möglich sein würde, in derselben Weise vom 3-Brom-4-jod benzol ausgehend zu o-Phenylen-bis-(dialkylenphosphinen) zu gelangen. Eine derartige analoge Arbeitsweise ist jedoch nicht brauchbar, da die Reaktion von Magnesium mit 3-Brom-4-jodbenzol keine befriedigende Ausbeute am Di-Grignardreagenz gibt. In analogy to the production of 4-methyl-o-phenylene-bis- (diethylphosphine) from 3-bromo-4-iodotoluene and magnesium to form the di-Grignard reagent and further reaction of the latter with chloroethyldiphosphine one could assume that it would be possible to proceed in the same way from 3-bromo-4-iodobenzene to o-phenylenebis (dialkylenephosphines) to get. However, such an analogous procedure is not useful because the reaction of magnesium with 3-bromo-4-iodobenzene does not yield a satisfactory result Di-Grignard reagent there.
Es wurde nun gefunden, daß man o-Phenylen-bis-(diäthylphosphin) der Formel dadurch herstellen kann, daß man o-Halogenlithiumbenzol mit Tetraäthyldiphosphin in Gegenwart von Äthern als Lösungsmittel und einem inerten Gas bei einer tiefen Temperatur von etwa -120"C mischt und danach das Gemisch allmählich auf Raumtemperatur erwärmt.It has now been found that o-phenylene-bis- (diethylphosphine) of the formula can be prepared by mixing o-halyllithium benzene with tetraethyldiphosphine in the presence of ethers as a solvent and an inert gas at a low temperature of about -120 "C and then gradually warming the mixture to room temperature.
Der Chemismus der Umsetzung ist bisher nicht geklärt. Es ist möglich, daß beim Erwärmen des o-Halogenlithiumbenzols von etwa -120 auf etwa -50"C unbeständiges Dehydrobenzol als Zwischenprodukt gebildet wird, das sich mit dem Tetraäthyldiphosphin umsetzt. Wird dieses Zwischenprodukt in Abwesenheit einer anderen reaktionsfähigen Substanz gebildet, so kondensiert es mit sich selbst und ergibt das Diphenylen. Zur Durchführung des erfindungsgemäßen Verfahrens ist es daher erforderlich, daß das Tetraäthyldiphosphin im Reaktionsgemisch bereits vorhanden ist, wenn das Zwischenprodukt gebildet wird. Die Möglichkeit der Bildung von Dehydrobenzol als Zwischenprodukt wurde zuerst von Wittig in den Naturwissenschaften, Bd. 30, 1942, S. 696, erörtert; folgende Strukturformel wird angenommen: (vgl. auch Wittig und Pohmer, Angewandte Chemie, Bd. 67, 1955, S. 348, und Gilman und Gorsich, Journal of the American Chemical Society, Bd. 78, 1956, S. 2217).The chemistry of the implementation has not yet been clarified. It is possible that when the o-halolithiumbenzene is heated from about -120 to about -50 "C, unstable dehydrobenzene is formed as an intermediate, which reacts with the tetraethyldiphosphine. If this intermediate is formed in the absence of another reactive substance, it condenses with it It is therefore necessary to carry out the process according to the invention that the tetraethyldiphosphine is already present in the reaction mixture when the intermediate is formed. The possibility of the formation of dehydrobenzene as an intermediate was first discussed by Wittig in den Naturwissenschaften, Vol. 30, 1942, p. 696; the following structural formula is assumed: (See also Wittig and Pohmer, Angewandte Chemie, Vol. 67, 1955, p. 348, and Gilman and Gorsich, Journal of the American Chemical Society, Vol. 78, 1956, p. 2217).
Zur Herstellung der Ausgangsstoffe wird beispielsweise o-Chlorbrombenzol bei -120"C mit Butyllithium zu o-Chlorlithiumbenzol und Butylbromid umgesetzt: Von dem erfindungsgemäßen Verfahren kann angenommen werden, daß es in zwei Reaktionsstufen verläuft, beispielsweise wird zur Herstellung von o-Phenylen-bis-(diäthylphosphin) -Chlorlithiumbenzol zunächst durch Erwärmen von - 120 auf -60"C in Dehydrobenzol und Lithiumchlorid übergeführt: das dann Tetraäthyldiphosphin addiert: o-Phenylen-bis-(diäthylphosphin) hat die Eigenschaft, mit Metallen, wie Kobalt, Palladium oder Palladiummohr, Komplexverbindungen zu bilden, aus denen das Metall in feinem Zustand durch Erwärmen abgeschieden werden kann. Es ist so möglich, aus diesen Komplexverbindungen, die in dünner Schicht auf inertes Material, wie Glas, Porzellan, Silikate oder Tonerde, aufgebracht worden sind, Metallspiegel herzustellen.To produce the starting materials, for example, o-chlorobromobenzene is reacted with butyllithium at -120 "C to form o-chlorolithiumbenzene and butyl bromide: It can be assumed from the process according to the invention that it proceeds in two reaction stages, for example, for the production of o-phenylene-bis- (diethylphosphine) -chlorlithiumbenzene, it is first converted into dehydrobenzene and lithium chloride by heating from -120 to -60 "C: which then adds tetraethyldiphosphine: o-Phenylen-bis- (diethylphosphine) has the property of forming complex compounds with metals such as cobalt, palladium or palladium black, from which the metal can be deposited in a fine state by heating. It is thus possible to produce metal mirrors from these complex compounds, which have been applied in a thin layer to inert material such as glass, porcelain, silicates or alumina.
Beispiel Die Umsetzung wurde in einer Stickstoffatmosphäre durchgeführt. Eine Lösung von 39,3 g o-Bromchlorbenzol in 200 ccm Äther wurde in einen 1,5-1-Kolben gegeben, der mit einem Rührer, einer Vorrichtung zum Durchleiten von Stickstoff und einem Thermometer ausgestattet war, und die Lösung auf -120"C gekühlt. Zu dieser Lösung wurde unter Rühren innerhalb von 20 Minuten eine auf -120"C gekühlte Lösung von 1 Mol n-Butyllithium in 438 ccm Petroläther (Kp. = 40 bis 60"C) und 400 ccm Äther gegeben. Nach weiteren 15 Minuten Rühren bei - l200C wurde zu der Lösung unter Rühren bei - l200C innerhalb von 10 Minuten eine Lösung von 1 Mol (36,6 g) Tetraäthyldiphosphin in 100 ccm Äther gegeben. Danach ließ man die Lösung innerhalb etwa 30 Minuten auf Raumtemperatur erwärmen. Während dieser Zeit wurde die ursprünglich nahezu farblose Lösung dunkelrot. Nach dem Ausschütteln der Lösung mit kaltem Wasser wurde die organische Schicht abgetrennt und destilliert. Man erhielt 10,7 g rohes Diphosphin mit einem Kr.0,2 = 90 bis l100C, woraus durch fraktionierte Destillation hiervon 7,7 g reines Diphosphin, Kr.0,13 = 103"C, erhalten wurden. Die Ausbeute betrug 15 O/o. Example The reaction was carried out in a nitrogen atmosphere. A solution of 39.3 g of o-bromochlorobenzene in 200 cc of ether was placed in a 1.5 l flask given, with a stirrer, a device for passing nitrogen through and a thermometer, and the solution was cooled to -120 "C. To this Solution was stirring a solution cooled to -120 ° C. within 20 minutes of 1 mole of n-butyllithium in 438 cc of petroleum ether (b.p. = 40 to 60 "C) and 400 cc Ether given. After stirring for a further 15 minutes at -1200C, the solution under Stir a solution of 1 mol (36.6 g) of tetraethyldiphosphine at -1200C for 10 minutes given in 100 cc of ether. The solution was then allowed to dissolve within about 30 minutes Warm up to room temperature. During this time the originally almost colorless Solution dark red. After shaking the solution with cold water, the organic Layer separated and distilled. 10.7 g of crude diphosphine were obtained with a Kr 0.2 = 90 to 1100C, from which 7.7 g of pure by fractional distillation Diphosphine, Kr 0.13 = 103 "C, were obtained. The yield was 15%.
Für die Herstellung der Ausgangsstoffe wird ein Schutz nicht beansprucht. No protection is claimed for the manufacture of the starting materials.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB1119268X | 1958-03-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1119268B true DE1119268B (en) | 1961-12-14 |
Family
ID=10875489
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEI16112A Pending DE1119268B (en) | 1958-03-14 | 1959-03-05 | Process for the production of o-phenylene-bis- (diaethylphosphine) |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1119268B (en) |
-
1959
- 1959-03-05 DE DEI16112A patent/DE1119268B/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| None * |
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