DE4039449A1 - Copper (I) formamidine complexes prepn. useful as oxidn. catalysts etc. - by reacting aniline with formanilide in presence of copper(I) halide in an organic solvent - Google Patents
Copper (I) formamidine complexes prepn. useful as oxidn. catalysts etc. - by reacting aniline with formanilide in presence of copper(I) halide in an organic solventInfo
- Publication number
- DE4039449A1 DE4039449A1 DE19904039449 DE4039449A DE4039449A1 DE 4039449 A1 DE4039449 A1 DE 4039449A1 DE 19904039449 DE19904039449 DE 19904039449 DE 4039449 A DE4039449 A DE 4039449A DE 4039449 A1 DE4039449 A1 DE 4039449A1
- Authority
- DE
- Germany
- Prior art keywords
- copper
- halide
- formanilide
- formamidine
- organic solvent
- 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.)
- Withdrawn
Links
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 title claims abstract description 22
- DYDNPESBYVVLBO-UHFFFAOYSA-N formanilide Chemical compound O=CNC1=CC=CC=C1 DYDNPESBYVVLBO-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 239000003960 organic solvent Substances 0.000 title claims abstract description 6
- -1 copper(I) halide Chemical class 0.000 title claims 2
- 239000003054 catalyst Substances 0.000 title abstract description 4
- SRRWFIKBVDPTBC-UHFFFAOYSA-N C(=N)N.[Cu+] Chemical class C(=N)N.[Cu+] SRRWFIKBVDPTBC-UHFFFAOYSA-N 0.000 title 1
- 238000000034 method Methods 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N formamide Substances NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims 1
- 230000001376 precipitating effect Effects 0.000 claims 1
- 239000011541 reaction mixture Substances 0.000 claims 1
- 239000010949 copper Substances 0.000 abstract description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052802 copper Inorganic materials 0.000 abstract description 6
- 239000004952 Polyamide Substances 0.000 abstract description 2
- 239000000417 fungicide Substances 0.000 abstract description 2
- 150000004820 halides Chemical class 0.000 abstract description 2
- 229920002647 polyamide Polymers 0.000 abstract description 2
- 239000003381 stabilizer Substances 0.000 abstract description 2
- 241000196324 Embryophyta Species 0.000 abstract 1
- PNKUSGQVOMIXLU-UHFFFAOYSA-N Formamidine Chemical class NC=N PNKUSGQVOMIXLU-UHFFFAOYSA-N 0.000 abstract 1
- 244000043261 Hevea brasiliensis Species 0.000 abstract 1
- 239000002917 insecticide Substances 0.000 abstract 1
- 229920003052 natural elastomer Polymers 0.000 abstract 1
- 229920001194 natural rubber Polymers 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 241000238631 Hexapoda Species 0.000 description 1
- 241000158147 Sator Species 0.000 description 1
- CMGCAQOUARLVKY-UHFFFAOYSA-N [Cu].C(=N)N Chemical compound [Cu].C(=N)N CMGCAQOUARLVKY-UHFFFAOYSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001055 chewing effect Effects 0.000 description 1
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 1
- BSXLQMJXFJCSCC-UHFFFAOYSA-N copper;formamide Chemical compound [Cu].NC=O BSXLQMJXFJCSCC-UHFFFAOYSA-N 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 244000144980 herd Species 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- ZQUVDXMUKIVNOW-UHFFFAOYSA-N n,n'-diphenylmethanimidamide Chemical compound C=1C=CC=CC=1NC=NC1=CC=CC=C1 ZQUVDXMUKIVNOW-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- RCIBIGQXGCBBCT-UHFFFAOYSA-N phenyl isocyanide Chemical compound [C-]#[N+]C1=CC=CC=C1 RCIBIGQXGCBBCT-UHFFFAOYSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C257/00—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines
- C07C257/10—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines
- C07C257/12—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines having carbon atoms of amidino groups bound to hydrogen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Die Erfindung betrifft ein Verfahren zur Herstellung eines Kupfer-I-Formamidin-Komplexes durch Umsetzung von Anilin mit Formanilid in Gegenwart von Kupfer-I-halo genid.The invention relates to a method for manufacturing of a copper-I-formamidine complex by reacting Aniline with formanilide in the presence of copper I halo genid.
Aus Recl. Trav. Chim. Pays-Bas 1974, 93(12) 314-16 ist ein Verfahren zur Herstellung eines Kupfer-I-Formamidin- Komplexes bekannt. Der dort beschriebene Kupfer-Formami din-Komplex wird hergestellt durch Umsetzung von Phenyl isocyanid mit Ethanol in Gegenwart von Cu(PhNC)4BF4 und Natriumhydroxid oder durch Reaktion von N,N′-Diphenyl formamidin in Gegenwart von Cu(CH3CN)4BF4. Das in der genannten Veröffentlichung beschriebene Verfahren zur Herstellung des Kupfer-Formamidin-Komplexes ist aus wirtschaftlichen Gründen von geringem Interesse, da der dort benutzte Katalysator und die Einsatzprodukte teuer bzw. umständlich herzustellen sind und deshalb für einen großtechnischen Einsatz nicht in Frage kommen. From Recl. Trav. Chim. Pays-Bas 1974, 93 (12) 314-16, a process for the preparation of a copper-I-formamidine complex is known. The copper-formamide complex described there is prepared by reacting phenyl isocyanide with ethanol in the presence of Cu (PhNC) 4 BF 4 and sodium hydroxide or by reacting N, N′-diphenyl formamidine in the presence of Cu (CH 3 CN) 4 BF 4. The process for the preparation of the copper-formamidine complex described in the publication mentioned is of little interest for economic reasons, since the catalyst used there and the feed products are expensive or cumbersome to manufacture and are therefore out of the question for large-scale use come.
Es wurde nun ein Verfahren zur Herstellung eines Kupfer- I-Formamidin-Komplexes der FormelA method for producing a copper I-formamidine complex of the formula
worin
Ph für Phenyl steht,
gefunden, das dadurch gekennzeichnet ist, daß man Anilin
mit Formanilid in Gegenwart von Kupfer-I-halogenid in
einem organischen Lösungsmittel bei Temperaturen von 170
bis 210°C umsetzt.wherein
Ph represents phenyl,
found, which is characterized in that aniline is reacted with formanilide in the presence of copper-I-halide in an organic solvent at temperatures of 170 to 210 ° C.
Bevorzugt wird die Umsetzung bei Temperaturen von 180 bis 200°C durchgeführt.The reaction at temperatures of 180 is preferred up to 200 ° C.
Nach dem erfindungsgemäßen Verfahren werden pro 2 Mol Kupfer-I-halogenid 2-2,3 Mol Anilin sowie 2-2,3 Mol Formanilid eingesetzt. Bevorzugt werden pro 2 Mol Kupfer-I-halogenid 2 Mol Anilin und 2 Mol Formanilid eingesetzt. According to the process of the invention, 2 mol Copper-I-halide 2-2.3 mol aniline and 2-2.3 mol Formanilide used. Per 2 moles are preferred Copper I halide 2 moles of aniline and 2 moles of formanilide used.
Als Kupfer-I-halogenide können in das erfindungsgemäße Verfahren Kupfer-I-chlorid, Kupfer-I-bromid und/oder Kupfer-I-iodid, bevorzugt Kupfer-I-chlorid eingesetzt herden.As copper-I-halides in the invention Process copper-I-chloride, copper-I-bromide and / or Copper I-iodide, preferably copper I-chloride used herds.
Als organische Lösungsmittel kommen für das erfindungs gemäße Verfahren aromatische, cycloaliphatische und aliphatische Kohlenwasserstoffe in Frage, die mit Wasser nicht mischbar sind bzw. ein azeotropes Gemisch bilden. Genannt werden z. B. Toluol, Xylol, Octan, bevorzugt Xylol. Die Menge an einzusetzendem organischen Lösungs mittel kann leicht durch Vorversuche bestimmt werden. Üblicherweise werden pro Mol Kupfer-I-halogenid 0,2 bis 0,5 Mol, bevorzugt 0,3 bis 0,4 Mol, bezogen auf Aus gangsprodukt an organischen Lösungsmitteln eingesetzt. Die Lösungsmittel können sowohl einzeln als auch ge mischt untereinander eingesetzt werden.As organic solvents come for the Invention according to aromatic, cycloaliphatic and aliphatic hydrocarbons in question with water are not miscible or form an azeotropic mixture. Are called z. B. toluene, xylene, octane, preferred Xylene. The amount of organic solution to be used medium can easily be determined by preliminary tests. Usually 0.2 to 1 mole of copper I-halide 0.5 mol, preferably 0.3 to 0.4 mol, based on Aus gear product used in organic solvents. The solvents can be used both individually and ge mixes with each other.
Gemäß einer Ausführungsform des erfindungsgemäßen Ver fahrens werden Anilin, Formanilid und Kupfer-I-chlorid bei Temperaturen von etwa 200°C in Gegenwart von Xylol so lange am Rückfluß gekocht bis kein Reaktionswasser mehr gebildet wird. Zur Aufarbeitung des Reaktionsge misches wird dieses mit wäßrigem Alkali (beispielsweise Kaliumcarbonat und/oder Natriumhydroxid) so lange am Rückfluß gekocht bis kein Anilin mehr übergeht. Das an fallende Reaktionsprodukt wird dann neutral gewaschen und unter Vakuum in der Wärme getrocknet. According to an embodiment of the Ver Aniline, formanilide and copper-I-chloride are used at temperatures of about 200 ° C in the presence of xylene boiled at reflux until no water of reaction more is formed. To work up the reaction This is mixed with aqueous alkali (for example Potassium carbonate and / or sodium hydroxide) as long as Boiled reflux until no more aniline passes. That on falling reaction product is then washed neutral and heat dried under vacuum.
Der erfindungsgemäße Kupfer-I-Komplex kann als Oxida tions-Katalysator verwendet werden, ferner als Stabili sator für Polyamide, als Mastiziermittel für Naturkau tschuk sowie im Pflanzenschutz als Fungizid und Insekti zid.The copper-I complex according to the invention can be used as an oxide tion catalyst can also be used as a stabilizer sator for polyamides, as a masticating agent for natural chewing Tschuk and in plant protection as a fungicide and insect zid.
In einem 500 ml 4-Halskolben, ausgestattet mit Rührer, Thermometer, Heizpilz, Kondensator-Abscheider, werden 93,12 g (1 Mol) Anilin, 121,13 g (1 Mol) Formanilid, 49 50 g (0,5 Mol) Cu(I)-Cl rein und 15,00 ml Xylol vor gelegt und unter Rückfluß gekocht. Durch Zugabe von Xylol wird die Reaktionstemperatur auf 195°C gestellt und gehalten. ln dem Abscheider angesammeltes Reaktions wasser wird in Zeitabständen abgenommen und notiert. Nach ca. 3 h spaltet kein Wasser mehr ab; die Reaktion ist dann beendet. Der Ansatz wird abgekühlt und in einem mit Kondensator-Abscheider versehenen Kolben überführt. Hierzu werden 70,0 g Kaliumcarbonat oder 20 g NaOH und 500 ml Wasser zugegeben und der Ansatz so lange unter Rückfluß gekocht, bis kein Anilin mehr überdestilliert. Das Produkt wird sodann auf einer Nutsche neutral gewa schen und unter Vakuum bei 70°C getrocknet. Man erhält ca. 130 g (100% d.Th. bez. auf Cu(I)Cl) graues, pul veriges Produkt mit einem Schmelzpunkt von ca. 330°C. Erforderlichenfalls kann ein reineres Produkt durch Umkristallisation in einem geeigneten Lösungsmittel, z. B. o- Dichlorbenzol, erhalten werden.In a 500 ml 4-necked flask equipped with a stirrer, Thermometer, patio heater, condenser separator 93.12 g (1 mol) aniline, 121.13 g (1 mol) formanilide, 49 50 g (0.5 mol) of Cu (I) -Cl pure and 15.00 ml of xylene laid and boiled under reflux. By adding Xylene, the reaction temperature is set to 195 ° C. and held. Reaction accumulated in the separator Water is drawn off and noted at regular intervals. After about 3 hours, no more water is released; the reaction is then ended. The batch is cooled and in one pistons equipped with a condenser separator. 70.0 g of potassium carbonate or 20 g of NaOH and 500 ml of water are added and the mixture is so long Boiled reflux until no more aniline distilled over. The product is then washed neutral on a suction filter and dried under vacuum at 70 ° C. You get approx. 130 g (100% of theory based on Cu (I) Cl) gray, pul verige product with a melting point of approx. 330 ° C. If necessary, a purer product can pass through Recrystallization in a suitable solvent, e.g. B. o-dichlorobenzene can be obtained.
Claims (2)
Ph für Phenyl steht,
dadurch gekennzeichnet, daß man Anilin mit Formani lid in Gegenwart von Kupfer-I-halogenid in einem organischen Lösungsmittel bei Temperaturen von 170 bis 210°C umsetzt.1. Process for the preparation of a copper-I-formamide complex of the formula wherein
Ph represents phenyl,
characterized in that aniline is reacted with formani lid in the presence of copper (I) halide in an organic solvent at temperatures of 170 to 210 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19904039449 DE4039449A1 (en) | 1990-12-11 | 1990-12-11 | Copper (I) formamidine complexes prepn. useful as oxidn. catalysts etc. - by reacting aniline with formanilide in presence of copper(I) halide in an organic solvent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19904039449 DE4039449A1 (en) | 1990-12-11 | 1990-12-11 | Copper (I) formamidine complexes prepn. useful as oxidn. catalysts etc. - by reacting aniline with formanilide in presence of copper(I) halide in an organic solvent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE4039449A1 true DE4039449A1 (en) | 1992-06-17 |
Family
ID=6420023
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19904039449 Withdrawn DE4039449A1 (en) | 1990-12-11 | 1990-12-11 | Copper (I) formamidine complexes prepn. useful as oxidn. catalysts etc. - by reacting aniline with formanilide in presence of copper(I) halide in an organic solvent |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE4039449A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006009590A1 (en) * | 2004-06-16 | 2006-01-26 | Advanced Technology Materials, Inc. | Copper (i) compounds useful as deposition precursors of copper thin films |
| JP2009132708A (en) * | 2007-11-16 | 2009-06-18 | Air Products & Chemicals Inc | Organometallic precursor complex |
| US7557229B2 (en) | 2002-11-15 | 2009-07-07 | President And Fellows Of Harvard College | Atomic layer deposition using metal amidinates |
| US7750173B2 (en) | 2007-01-18 | 2010-07-06 | Advanced Technology Materials, Inc. | Tantalum amido-complexes with chelate ligands useful for CVD and ALD of TaN and Ta205 thin films |
| US9029189B2 (en) | 2003-11-14 | 2015-05-12 | President And Fellows Of Harvard College | Bicyclic guanidines, metal complexes thereof and their use in vapor deposition |
-
1990
- 1990-12-11 DE DE19904039449 patent/DE4039449A1/en not_active Withdrawn
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8455672B2 (en) | 2002-11-15 | 2013-06-04 | President And Fellows Of Harvard | Atomic layer deposition using metal amidinates |
| US7557229B2 (en) | 2002-11-15 | 2009-07-07 | President And Fellows Of Harvard College | Atomic layer deposition using metal amidinates |
| US7737290B2 (en) | 2002-11-15 | 2010-06-15 | President And Fellows Of Harvard University | Atomic layer deposition using metal amidinates |
| US9029189B2 (en) | 2003-11-14 | 2015-05-12 | President And Fellows Of Harvard College | Bicyclic guanidines, metal complexes thereof and their use in vapor deposition |
| US7166732B2 (en) | 2004-06-16 | 2007-01-23 | Advanced Technology Materials, Inc. | Copper (I) compounds useful as deposition precursors of copper thin films |
| US7241912B2 (en) | 2004-06-16 | 2007-07-10 | Advanced Technology Materials, Inc. | Copper (I) compounds useful as deposition precursors of copper thin films |
| JP2008502680A (en) * | 2004-06-16 | 2008-01-31 | アドバンスド テクノロジー マテリアルズ，インコーポレイテッド | Copper(I) Compounds Useful as Precursors for the Deposition of Thin Copper Films - Patent application |
| US7371880B2 (en) | 2004-06-16 | 2008-05-13 | Advanced Technology Materials, Inc. | Copper (I) compounds useful as deposition precursors of copper thin films |
| US7531031B2 (en) | 2004-06-16 | 2009-05-12 | Advanced Technology Materials, Inc. | Copper (I) compounds useful as deposition precursors of copper thin films |
| WO2006009590A1 (en) * | 2004-06-16 | 2006-01-26 | Advanced Technology Materials, Inc. | Copper (i) compounds useful as deposition precursors of copper thin films |
| US7750173B2 (en) | 2007-01-18 | 2010-07-06 | Advanced Technology Materials, Inc. | Tantalum amido-complexes with chelate ligands useful for CVD and ALD of TaN and Ta205 thin films |
| US7858816B2 (en) | 2007-01-18 | 2010-12-28 | Advanced Technology Materials, Inc. | Tantalum amido-complexes with chelate ligands useful for CVD and ALD of TaN and Ta205 thin films |
| JP2009132708A (en) * | 2007-11-16 | 2009-06-18 | Air Products & Chemicals Inc | Organometallic precursor complex |
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