CS216417B1 - Process for preparing aldehydes from primary aliphatic alcohols - Google Patents

Process for preparing aldehydes from primary aliphatic alcohols Download PDF

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CS216417B1
CS216417B1 CS548680A CS548680A CS216417B1 CS 216417 B1 CS216417 B1 CS 216417B1 CS 548680 A CS548680 A CS 548680A CS 548680 A CS548680 A CS 548680A CS 216417 B1 CS216417 B1 CS 216417B1
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acetonitrile
solution
weight
parts
alcohol
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CS548680A
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Czech (cs)
Slovak (sk)
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Jan Sykora
Maria Jakubcova
Eduard Horvath
Jan Gazo
Zuzana Cvengrosova
Jan Ilavsky
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Jan Sykora
Maria Jakubcova
Eduard Horvath
Jan Gazo
Zuzana Cvengrosova
Jan Ilavsky
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Priority to CS548680A priority Critical patent/CS216417B1/en
Publication of CS216417B1 publication Critical patent/CS216417B1/en

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Abstract

Vynález rieši spósob přípravy aldehydov z primárných alifatických alkoholov s počtom uhlíkov 1 až 4 fotoasistovanou reakciou chloromedhatých komplexov. Postupuje sa tým spósobom, že sa připraví roztok z 10 hmotnostných dielov roztoku chloridu měďnatého v acetonitrile o koncentrácii Cu(II) 1 . 10~2mol. dm-3, z 2 až 25 dielov hmotnostných primárného alifatického alkoholu s počtom uhlíkov 1 až 4 doplněný do 100 hmotnostných dielov acetonitrilom a tento sa ožaruje žiarením o λ ožiarenia < 500 nm v čase nad 30 minút.The invention solves a method of preparing aldehydes from primary aliphatic alcohols with the number of carbons 1 to 4 by photoassisted reaction of chlorocopper complexes. The procedure is to prepare a solution of 10 parts by weight of a solution of copper chloride in acetonitrile with a concentration of Cu(II) 1. 10~2mol. dm-3, from 2 to 25 parts by weight of a primary aliphatic alcohol with a number of carbons of 1 to 4 supplemented to 100 parts by weight of acetonitrile and this is irradiated with radiation of λ radiation < 500 nm for a time of more than 30 minutes.

Description

Vynález rieši spósob přípravy aldehydov z primárných alifatických alkoholov s počtom uhlíkov 1 až 4 fotoasistovanou reakciou chloromedhatých komplexov. Postupuje sa tým spósobom, že sa připraví roztok z 10 hmotnostných dielov roztoku chloridu medhatého v acetonitrile o koncentrácii Cu(II) 1 . 10~2mol. dm-3, z 2 až 25 dielov hmotnostných primárného alifatického alkoholu s počtom uhlíkov 1 až 4 doplněný do 100 hmotnostných dielov acetonitrilom a tento sa ozařuje žiarením o λ ožiarenia < 500 nm v čase nad 30 minut. 216417 3The present invention provides a process for the preparation of aldehydes from primary aliphatic alcohols having carbon numbers of 1 to 4 by a photo-assisted reaction of chloro-rich complexes. In this way, a solution of 10 parts by weight of copper (II) chloride solution in Cu (II) 1 acetonitrile is prepared. 10 ~ 2mol. dm-3, from 2 to 25 parts by weight of primary aliphatic alcohol having carbon numbers 1-4, supplemented to 100 parts by weight with acetonitrile and irradiated with λ irradiation <500 nm over 30 minutes. 216417 3

Vynález sa týká spósobu přípravy aldehydov z primárných alifatických alkoholov s počtom uhlíkov 1 až 4 fotoasistovanou reakciou chloromednatých komplexov v acetonitrile.The present invention relates to a process for the preparation of aldehydes from primary aliphatic alcohols having a carbon number of 1 to 4 by a photo-assisted reaction of chlorinated complexes in acetonitrile.

Za katalytického pósobenia médi možno dehydrogenovať primárné alkoholy na aldehydy v plynnej fáze pri 250 až 320 °C (D. Weismann, S. F. Garrard, J. Chem. Soc., 117, 328, 1920) a sekundárné alkoholy na ketony (Amer. patent 1,497817 1918). Dehydrogenáciu je možné tiež uskutočniť v prúde nosného plynu hélia v plynnéj fáze pri 250 až 300 °C za přítomnosti kysličníka meďného (M. Y. Sheikh, F. Eadon, Tetrahedron Letters, 1972 257).Under medium catalytic action, primary alcohols can be dehydrogenated to gas phase aldehydes at 250 to 320 ° C (D. Weismann, SF Garrard, J. Chem. Soc., 117, 328, 1920) and secondary alcohols to ketones (Amer. , 497817, 1918). Dehydrogenation can also be carried out in a helium gas stream in the gaseous phase at 250-300 ° C in the presence of cuprous oxide (M. Y. Sheikh, F. Eadon, Tetrahedron Letters, 1972 257).

Dehydrogenácia primárných alifatických alkoholov na aldehydy prebieha pri vaření alkoholu v chinolíne za přítomnosti kysličníka meďnatého a nitro- alebo dinitrobenzénu (F. Zetsche, P. Žale, Helv. 9, 288 [1926]). V parách pri 150 až 165 °C na médi za přítomnosti nitrobenzénu, chinolínu, xylénu a vzduchu sa připravili z etylalkoholu, propylalkoholu, 2-metylpropylalkoholu a furfuralu příslušné aldehydy (F. Zetsche, B, 54, 2033 [1921]). Dehydrogenáciu etylalkoholu, 1-propylalkoholu, 2-propylalkoholu a 1-butylalkoholu na příslušné aldehydy na redukované j médi za účinku polychromatického UV žiarenia pri 250 °C v parách popisujú další autoři (S. Nakamura, K. Kawamoto, Bull. Chem. Soc. Japan, 44, 1072 [1972]). Popísané je ožarovanie sústavy Cu(II) - Cl(_)-metylalkohol polychromatickým UV-žiarením za vzniku metanalu (J. K. Kochi, J. Am. Chem. Soc., 84, 2121, [1962]).Dehydrogenation of primary aliphatic alcohols to aldehydes takes place in the cooking of alcohol in quinoline in the presence of copper oxide and nitro- or dinitrobenzene (F. Zetsche, P. Zale, Helv. 9, 288 [1926]). Appropriate aldehydes were prepared from ethyl alcohol, propyl alcohol, 2-methylpropyl alcohol and furfural in vapors at 150-165 ° C in medium in the presence of nitrobenzene, quinoline, xylene and air (F. Zetsche, B, 54, 2033 [1921]). Other dehydrogenation of ethyl alcohol, 1-propanol, 2-propanol and 1-butyl alcohol to the corresponding aldehydes on the reduced medium under the action of polychromatic UV radiation at 250 ° C (S. Nakamura, K. Kawamoto, Bull. Chem. Soc. Japan, 44, 1072 [1972]. Disclosed is the irradiation of a Cu (II) - Cl () - methyl alcohol system by polychromatic UV irradiation to form methanal (J. K. Kochi, J. Am. Chem. Soc., 84, 2121, [1962]).

Nedostatky týchto spósobov přípravy sú odstránené u spósobu přípravy aldehydov z primárných alifatických alkoholov s počtom uhlíkov 1 až 4 fotoasistovanou reakciou chloromeďnatých komplexov, ktorého podstatou je, že roztok připravený z 10 hmotnostných dielov chloridu meďnatého v acetonitrile o koncentrácii Cu(II) 1.10“2 mol.dm“3 a 2 až 25 hmotnostných dielov primárného alifatického alkoholu doplněný do 100 hmotnostných dielov acetonitrilom sa pri 16 ažThe drawbacks of these methods of preparation are eliminated in the process of preparing aldehydes from primary aliphatic alcohols having carbon numbers of 1 to 4 by a photo-assisted reaction of chlorinated complexes, the principle being that a solution prepared from 10 parts by weight of copper (II) chloride in acetonitrile having a Cu (II) 1.10 - 2 mol concentration 3 and 2 to 25 parts by weight of primary aliphatic alcohol added to 100 parts by weight of acetonitrile at 16 to

Claims (4)

PREDMETSUBJECT Spósob přípravy aldehydov z primárných alifatických alkoholov s počtom uhlíkov 1 až 4 fotoasistovanou reakciou chloromeďnatých komplexov vyznačujúci sa tým, že roztok připravený z 10 hmotnostných dielov roztoku chloridu meďnatého v acetonitrile o koncentrácii Cu(II)Process for the preparation of aldehydes from primary aliphatic alcohols having a carbon number of 1 to 4 by a photo-assisted reaction of copper (II) complexes, characterized in that a solution prepared from 10 parts by weight of a Cu (II) solution of copper (II) chloride in acetonitrile 25 °C ožaruje žiarením o λ ožiarenia < 50Ónm v čase nad 30 minút.25 ° C is irradiated with λ irradiation of <50 nm over 30 minutes. Výhody sposobu přípravy aldehydov spočívajú v porovnaní s publikovanými postupmi predovšetkým v nižšej energetickej náročnosti, v miernych podmienkach reakcie a jednoduchosti prevedenia. Pre fotoaktívne žiarenie o λ < 500 nm nie je potřebné používať zdroje UV žiarenia, možné je pracovat’ i so zdrojmi světla viditelnej oblasti.The advantages of the process for the preparation of aldehydes are, in comparison with the published procedures, mainly in lower energy intensity, mild reaction conditions and ease of implementation. For photoactive radiation of λ <500 nm it is not necessary to use UV light sources, it is possible to work with light sources of visible area. Predmet vynálezu je opísaný v príkladoch prevedenia bez toho, aby sa iba na tieto vztahoval.The subject matter of the invention is described in the examples without being limited thereto. PřikladlEXAMPLE Roztok na bžarovanie sa připravil zmiešaním 15 cm3 zásobného roztoku chloridu mednatého v acetonitrile o koncentrácii CCu(II) = 1.10“2.dm“3, 15 cm3 metylalkoholu a doplněním do 150 cm3 čištěným a sušeným acetonitrilom. Tento roztok sa ozařoval svetlom výbojky Tesla RVKW vo vodou temperovanom reaktore pri teplote 18 °C ± 1 °C·, . ktorého skleněný plášť prepúšťa len žiarenie o λ > 350 nm. Plynovou chromatografiou bol dokázaný vznik formaldehydu po 50 minútach ožarovania v 1,5 %-nom výtažku vzMadom na počiatočné množstvo metylalkoholu.The braking solution was prepared by mixing 15 cm 3 of a stock solution of Cu (II) acetonitrile = 1.10 " 2 .dm" 3 , 15 cm 3 of methanol and making up to 150 cm 3 with purified and dried acetonitrile. This solution was irradiated with a Tesla RVKW lamp in a water-tempered reactor at 18 ° C ± 1 ° C ·. whose glass sheath only transmits radiation of λ> 350 nm. Gas chromatography showed the formation of formaldehyde after 50 minutes of irradiation in 1.5% yield based on the initial amount of methanol. Příklad 2Example 2 Postupovalo sa ako v příklade 1 s tým rozdielom, že namiesto metylalkoholu sa použilo 20 cm3 etylalkoholu. Dokázaný bol vznik acetaldehydu v 1,3 %-nom výtažků.The procedure was as in Example 1 except that 20 cm 3 of ethyl alcohol was used instead of methanol. Acetaldehyde formation in 1.3% yields was shown. Příklad 3 ‘Example 3 ‘ Postupovalo sa ako v příklade 1, s tým rozdier lom, že namiesto metylalkoholu sa použil n-propylalkohol a vznikol n-propylaldehyd v 1,7 %-nom výtažku.The procedure was as in Example 1, except that n-propyl alcohol was used instead of methyl alcohol to give n-propylaldehyde in 1.7% yield. Příklad 4Example 4 Postupovalo sa ako v příklade 1 s tým rozdielom, že namiesío metylalkoholu sa použilo 30 cm3 n-butylalkohol a vznikol n-butyraldehyd v 1,8 %-nom výtažku.The procedure was as in Example 1 except that 30 cm 3 of n-butyl alcohol was used in place of methyl alcohol to give n-butyraldehyde in a 1.8% yield. VYNÁLEZUINVENTION 1.10“2 mol.dm“3 a 2 až 25 dielov hmotnostných primárného alifatického alkoholu s počtom uhlíkov 1 až 4 doplněný do 100 hmotnostných dielov acetonitrilom sa pri 16 až 25 °C ožaruje žiarením o λ ožiarenia < 500 nm v čase nad 30 minút.1.10 " 2 mol.dm" 3 and 2 to 25 parts by weight of a primary aliphatic alcohol having a carbon number of 1 to 4, supplemented to 100 parts by weight with acetonitrile, are irradiated at 16 to 25 ° C with radiation of λ irradiation <500 nm for more than 30 minutes.
CS548680A 1980-08-08 1980-08-08 Process for preparing aldehydes from primary aliphatic alcohols CS216417B1 (en)

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