DE817909C - Process for the production of complex phosphines, arsines and stibines - Google Patents
Process for the production of complex phosphines, arsines and stibinesInfo
- Publication number
- DE817909C DE817909C DEP11828D DEP0011828D DE817909C DE 817909 C DE817909 C DE 817909C DE P11828 D DEP11828 D DE P11828D DE P0011828 D DEP0011828 D DE P0011828D DE 817909 C DE817909 C DE 817909C
- Authority
- DE
- Germany
- Prior art keywords
- complex
- phosphines
- stibines
- arsines
- parts
- 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.)
- Expired
Links
- 150000003003 phosphines Chemical class 0.000 title claims description 8
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical class [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 title claims description 7
- OUULRIDHGPHMNQ-UHFFFAOYSA-N stibane Chemical class [SbH3] OUULRIDHGPHMNQ-UHFFFAOYSA-N 0.000 title claims description 7
- 238000000034 method Methods 0.000 title claims description 4
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 15
- 150000002896 organic halogen compounds Chemical class 0.000 claims description 4
- 229910001385 heavy metal Chemical class 0.000 claims description 3
- 150000002736 metal compounds Chemical class 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 8
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 8
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 description 7
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- -1 B. (C6H5) 3PO Chemical compound 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- WQONPSCCEXUXTQ-UHFFFAOYSA-N 1,2-dibromobenzene Chemical compound BrC1=CC=CC=C1Br WQONPSCCEXUXTQ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical class OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- VEUUMBGHMNQHGO-UHFFFAOYSA-N ethyl chloroacetate Chemical compound CCOC(=O)CCl VEUUMBGHMNQHGO-UHFFFAOYSA-N 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 150000003977 halocarboxylic acids Chemical class 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 125000002577 pseudohalo group Chemical group 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- NBRKLOOSMBRFMH-UHFFFAOYSA-N tert-butyl chloride Chemical compound CC(C)(C)Cl NBRKLOOSMBRFMH-UHFFFAOYSA-N 0.000 description 1
- MDDUHVRJJAFRAU-YZNNVMRBSA-N tert-butyl-[(1r,3s,5z)-3-[tert-butyl(dimethyl)silyl]oxy-5-(2-diphenylphosphorylethylidene)-4-methylidenecyclohexyl]oxy-dimethylsilane Chemical compound C1[C@@H](O[Si](C)(C)C(C)(C)C)C[C@H](O[Si](C)(C)C(C)(C)C)C(=C)\C1=C/CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MDDUHVRJJAFRAU-YZNNVMRBSA-N 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/04—Nickel compounds
- C07F15/045—Nickel compounds without a metal-carbon linkage
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
-
- 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
- C07F9/66—Arsenic compounds
- C07F9/70—Organo-arsenic compounds
-
- 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
- C07F9/90—Antimony compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1895—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing arsenic or antimony
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Description
Verfahren zur Herstellung von komplexen Phosphinen, Arsinen und Stibinen Es wurde gefunden, daß man komplexe Phosphine, Arsine und Stibine erhält, wenn man organische Halogenverbindungen auf Komplexverbindungen aus Phosphinen, Arsinen oder Stibinen und Schwermetallverbindungen einwirken läßt.Process for the production of complex phosphines, arsines and stibines It it has been found that complex phosphines, arsines and stibines are obtained if organic halogen compounds on complex compounds of phosphines, arsines or Lets stibines and heavy metal compounds act.
Geeignete Ausgangsstoffe für das Verfahren sind z. B. durch Umsetzen von primären, sekundären oder tertiären Phosphinen, Oxyphosphinen oder entsprechenden Arsinen oder Stibinen mit Metallhalogeniden, Metallpseudohalogeniden oder halogencarbonsauren Metallsalzen in Gegenwart von Lösungsmitteln oder im Schmelzfluß leicht zugänglich. Auch die durch Einwirkung von Metallcarbonylen auf Phosphine usw. sowie die durch Umsetzen derMetallsalz-Phosphin-Komplexverbindungen mit Metallcarbonylen erhältlichen substituierten Metallcarbonyle sind geeignet. Suitable starting materials for the process are, for. B. by implementing of primary, secondary or tertiary phosphines, oxyphosphines or the like Arsines or stibines with metal halides, metal pseudohalides or halocarboxylic acids Metal salts easily accessible in the presence of solvents or in the melt flow. Also by the action of metal carbonyls on phosphines, etc. as well as by Reacting the metal salt-phosphine complex compounds with metal carbonyls available substituted metal carbonyls are suitable.
Die Reaktion dieser Komplexverbindungen mit Halogenkohlenwasserstoffen verläuft, am Beispiel von Brombenzol und komplexen Nickelverbindungen erläutert, nach folgenden Gleichungen: In den obigen Gleichungen kann das Triarylphosphin beispielsweise auch durch ein primäres Phosphin, z. B.The reaction of these complex compounds with halogenated hydrocarbons proceeds, explained using the example of bromobenzene and complex nickel compounds, according to the following equations: In the above equations, the triarylphosphine can, for example, also be replaced by a primary phosphine, e.g. B.
Cd H5PCl2, durch ein Phosphinoxyd, z. B. (C6H5)3PO, das Nickelbromid durch ein anderes komplexbildendes Schwermetallsalz ersetzt sein.Cd H5PCl2, by a phosphine oxide, e.g. B. (C6H5) 3PO, the nickel bromide be replaced by another complex-forming heavy metal salt.
Im Falle der Gleichung (I) wird unter Austritt von Kohlenoxyd eine Phosphin-Nickelbromid-Brombenzol-Komplexverbindung gebildet, während Gleichung (II) die Bildung der gleichen Komplexverbindung durch Zusammenlagern der drei Komponenten wiedergibt. In the case of equation (I), a Phosphine-nickel bromide-bromobenzene complex compound formed while equation (II) the formation of the same complex compound by assembling the three components reproduces.
Statt Phosphor können die Komplexverbindungen Arsen oder Antimon enthalten, und das Brombenzol kann durch andere organische Halogenverbindungen, z. B. Dibrombenzol, Butylbromid, tertiäres Butylchlorid, Chloressigsäureäthylester oder chloressigsaure Salze, ersetzt werden.Instead of phosphorus, the complex compounds can contain arsenic or antimony, and the bromobenzene can be replaced by other organic halogen compounds, e.g. B. Dibromobenzene, Butyl bromide, tertiary butyl chloride, ethyl chloroacetate or chloroacetic acid Salts, to be replaced.
Die Bildung der Komplexverbindungen vollzieht sich, insbesondere im Falle der durch die Gleichung (II) dargestellten Ausführungsform der Erfindung, meist mit großer Leichtigkeit. Es genügt, die Komponenten, zweckmäßig in einem inerten Lösungsmittel oder unter Verwendung eines Überschusses der organischen Halogenverbindung, zusammenzubringen und einige Zeit, erforderlichenfalls unter Druck, zu erhitzen. The formation of the complex compounds takes place, in particular in the case of the embodiment of the invention represented by equation (II), mostly with great ease. It is sufficient to use the components in an inert Solvent or using an excess of the organic halogen compound, bring together and heat for some time, if necessary under pressure.
Die nach der Erfindung hergestellten Komplexverbindungen sind meist intensiv gefärbte stabile Körper von wohldefinierten Eigenschaften. Sie können als Katalysatoren für chemische Umsetzungen verwendet werden. The complex compounds prepared according to the invention are mostly intensely colored stable bodies of well-defined properties. You can as Catalysts are used for chemical reactions.
Die in den nachstehenden Beispielen angegebenen Teile sind Gewichtsteile. The parts given in the examples below are parts by weight.
Beispiel I 32 Teile der durch Verschmelzen von Nickelbromid mit Triphenylphosphin bei 2409 hergestellten Komplexverbindung der Formel [(CH5)3P]2 NiBr2 erhitzt man mit 10 Teilen Butylbromid und I30 Teilen Butanol 5 Stunden lang in einem geschlossenen Gefäß aus Edelstahl auf 1500. Nach dem Erkalten destilliert man das Butanol und das nicht umgesetzte Butylbromid ab und erhält so 37 Teile einer tief dunkelgrüngefärbten Komplexverbindung der Formel {(C6H5)3P2 NiBr2 [C4H9Br], die bei I77 bis 1780 schmilzt. Die Verbindung ist schon in der Kälte in Alkohol leicht löslich. Example I 32 parts of the obtained by fusing nickel bromide with triphenylphosphine complex compound of the formula [(CH5) 3P] 2 NiBr2 prepared in 2409 is heated with 10 parts of butyl bromide and 130 parts of butanol for 5 hours in a closed Stainless steel vessel to 1500. After cooling, the butanol is distilled and the unreacted butyl bromide and thus 37 parts of a deep dark green colored Complex compound of the formula {(C6H5) 3P2 NiBr2 [C4H9Br], which melts at 1777-1780. The compound is easily soluble in alcohol even in the cold.
Beispiel 2 In einem Druckgefäß aus Edelstahl erhitzt man 32 Teile der Verbindung Ni (C 0)2 [(C6H5)3P]2 mit I6 Teilen Brombenzol in Gegenwart von I30 Teilen Butanol 4 Stunden lang auf 1900. Beim Aufarbeiten in der im Beispiel I angegebenen Weise erhält man 40 Teile einer kristallisierten Verbindung, die bei 269 bis 270° schmilzt und schon in der Kälte in Alkoholen löslich, in Äther jedoch fast unlöslich ist. Example 2 32 parts are heated in a stainless steel pressure vessel of the compound Ni (C 0) 2 [(C6H5) 3P] 2 with 16 parts of bromobenzene in the presence of I30 Parts of butanol to 1900 for 4 hours. When working up in that given in Example I. Way, 40 parts of a crystallized compound are obtained, which at 269 to 270 ° melts and already soluble in alcohol in the cold, but almost insoluble in ether is.
Sie hat folgende Zusammensetzung: {(C6Hi)3P]2 NiBr2 KH5Br] H20.It has the following composition: {(C6Hi) 3P] 2 NiBr2 KH5Br] H20.
Beim Trocknen bis 1000 verliert sie Kristallwasser und färbt sich dabei tiefblau. When drying up to 1000, it loses crystal water and changes color thereby deep blue.
Die gleiche Verbindung vom Sp. 269 bis 270° erhält man, wenn man 32 Teile der durch Verschmelzen von Nickelbromid mit Triphenylphosphin bei 240° hergestellten Komplexverbindung der Formel {(C6H5).P}2 NiBr2 mit I2 Teilen Brombenzol und 130 Teilen Butanol 4 Stunden lang bei I70 bis I80° unter Druck erhitzt. The same connection from Sp. 269 to 270 ° is obtained if one 32 parts by fusing nickel bromide with triphenylphosphine at 240 ° Complex compound of the formula {(C6H5) .P} 2 NiBr2 with I2 parts of bromobenzene and 130 parts of butanol heated under pressure at 170 to 180 ° for 4 hours.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR817909X | 1946-04-01 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE817909C true DE817909C (en) | 1951-10-22 |
Family
ID=9268581
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEP11828D Expired DE817909C (en) | 1946-04-01 | 1948-10-02 | Process for the production of complex phosphines, arsines and stibines |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE817909C (en) |
-
1948
- 1948-10-02 DE DEP11828D patent/DE817909C/en not_active Expired
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