CS245091B1 - C- (4-azidophenyl) -N-phenylnitrone and its preparation - Google Patents

C- (4-azidophenyl) -N-phenylnitrone and its preparation Download PDF

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CS245091B1
CS245091B1 CS852406A CS240685A CS245091B1 CS 245091 B1 CS245091 B1 CS 245091B1 CS 852406 A CS852406 A CS 852406A CS 240685 A CS240685 A CS 240685A CS 245091 B1 CS245091 B1 CS 245091B1
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Prior art keywords
azidophenyl
phenylnitrone
preparation
phenylhydroxylamine
temperature
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CS852406A
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Czech (cs)
Slovak (sk)
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CS240685A1 (en
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Gabriel Cik
Iva Srokova
Milan Zuffa
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Gabriel Cik
Iva Srokova
Milan Zuffa
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Priority to CS852406A priority Critical patent/CS245091B1/en
Publication of CS240685A1 publication Critical patent/CS240685A1/en
Publication of CS245091B1 publication Critical patent/CS245091B1/en

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Abstract

Predmetom vynálezu je C-(4-azidofenyl)- -N-fenylnitrón. Připravuje sa z N-fenylhydroxylamínu působením 4-azidobenzaldehydu v rozpúšťadle pri teplote 10 až 60 °C. Aromatické nitróny s azidovou skupinou sa vyznačujú spektrálnou citlivosťou v blízkej ultrafialovej oblasti. Možno ich použit na záznam optickej informácie do tenkých polymérnych vrstiev.The subject of the invention is C-(4-azidophenyl)- -N-phenylnitrone. It is prepared from N-phenylhydroxylamine by the action of 4-azidobenzaldehyde in a solvent at a temperature of 10 to 60 °C. Aromatic nitrones with an azide group are characterized by spectral sensitivity in the near ultraviolet region. They can be used for recording optical information in thin polymer layers.

Description

245091

Vynález sa týká C-(4-azidofenyl)-N-fenyl-nitrónu a sposobu jeho přípraVy.·^ ‘ V literatuře sú popísané rožne nitróny asposoby ich přípravy. Možno ich pripráVfí: — oxidáciou Ν,Ν-disubstituovaných hydro-xylamínov, — reakciou N-substituovaných hydroxyl-amínov s aldehydmi, — alkyláciou oxímov, — reakciou aromatických nitrózozlúče-nín a zlúčenín s aktívnou metylovou alebometylénovo>u skupinou.

Spektrálná citlivost takto připravenýchnitrónov bez azidoskupiny je priemerná.

Ns-^-CHO + (ζ^-NHOH- C-(4-azidofenyl)-N-fenylnitrón nie je v li-teratuře doteraz popísaný.

Jento nedostatok v podstatnej miere od-straňuje vynález, týkajúci sa C-( 4-azidof e-nyl j-N-fenylnitrónu a sposobu jeho přípra-vy.

Podstatou sposobu přípravy C-(4-azido-fenyl j-N-fenylnitrónu je, že na 4-azidobenz-aldehyd sa posobí N-fenylhydroxylamínemv rozpúšťadle, ako je metanol, etanol, pro-panol alebo ich zmesi, pri teplote 10 až 60°Celsia.

Reaikcia prebieha podlá všeobecnej sché-my:

V ďalšom je předmětný vynález objasněnýpríkladmi bez toho, že by sa na tieto vý-lučné vztahoval. Příklad 1 0,01 molu (1,09 g) N-fenylhydroxylamínučerstvo připraveného sa rozpustí v 10 mlmetanolu a přidá sa k němu po kvapkácha za miešania 0,01 molu (1,56 g) 4-azido-benzaldehydu. Po niekotkých minútach za-čne vypadávat kondenzačný produkt vo for-mě žitých kryštálov. Reakčná zmes sa po-nechá ešte stát pri teplote miestnosti nie-kofko hodin. Potom sa produkt odsaje, pre-myje metanolem alebo n-hexánom. V pří-pade potřeby sa prekryštalizuje. Výtažek je95 %-ný. Příklad 2 0,01 molu (1,09 gj čerstvo připravenéhoN-fenylhydroxylamínu sa rozpustí za teplav 10 ml etanolu. Potom sa k němu dávkuje0,01 molu (1,56 gj 4-azidobenzaldehydu roz-puštěného v 5 ml etanolu za miešania, pri-čom sa reakčná teplota udržuje pri 45 °C.Takmer okamžité začne sa z reakčnej zme-si vylučovat' žitý C-(4-azidof enyl)-N-f enyl-nitrón. Reakčná zmes sa mieša ešte 0,5 ho-diny pri teplote 20 °C a potom sa produktodsaje, premyje etanolem a vysuší. Výťažokje 98,5 %-ný. C-(4-azidofenyl)-N-f enylnitrometán podlávynálezu je látka sumárneho vzorca

C131H10N4O s molekulovou hmotnosťou 238,08 a teplotoutopenia 149 až 152 °C.

Jeho štruktúra bola dokázaná IČ, UV ahmotnostnou spektrometriou. IC spektrum bolo namerané na přístrojiSpecord IR 71 (Zeiss Jena) v CHCI3. Vykazu-je tieto charakteristiciké pásy (v cm-1): esa 2 100 (vn3), 1 505 (vc=n), 1210 (7n _ o). UV spektrum bolo namerané na přístrojiSpecord UV VIS (Zeiss Jena) v dioxáne priUV. Látka vykazuje dva pásy: pri λ = 268 nm (log ε = 3,90) a priλ = 348 nm (loge = 4,41).

Hmotnostně spektrum boto namerané na přístroji MS 902 S (AEI, Manchester). C-(4--azidofenyl)-N-fenylnitrón nedává v hmot-nostnom spekťre molekulový ión M+ 238, alelen fragment m/e 198 s relativnou intenzi-tou 25 %.

Analýza: vypočítané: 23,52 % N, 65,52 '% C, 4,23 % H, ZÍSt61161 23,30 % N, 65,04 % C, 4,19 % H. Výhodou látok podfa vynálezu je, že aro-matické nitróny obsahujúce azidovú skupinusa vyznačujú požadovanou spektrálnou cit-livosťou v blízkej ultrafialovej oblasti spek-tra. C-(4-azidofenyl)-N-fenylnitrón je svetlo- citlivá látka a možno· ju využiť na záznam optickej informácie do tenkých polymérnych vrstiev.

245091

The present invention relates to C- (4-azidophenyl) -N-phenyl-nitron and to its preparation. In the literature, nitrons and their preparation are described. They may be prepared by: - oxidation of Ν, Ν-disubstituted hydroxylamines, - reaction of N-substituted hydroxyl amines with aldehydes, - alkylation of oximes, - reaction of aromatic nitroso compounds and compounds with active methyl and methylene groups.

The spectral sensitivity of thus prepared azrone-free nitrons is average.

N5-N-CHO + (N-NHOH-C- (4-azidophenyl) -N-phenylnitrone has not been described in the literature until now.

This drawback substantially relieves the invention of C- (4-azidophenyl) N-phenylnitrone and its preparation.

The principle of the preparation of C- (4-azido-phenyl-N-phenylnitrone is that the 4-azidobenzaldehyde is treated with N-phenylhydroxylamine in a solvent such as methanol, ethanol, propanol or mixtures thereof at a temperature of 10 to 60 ° C) .

Reaction takes place according to the general scheme:

In the following, the present invention will be elucidated by the Examples without being bound by them. Example 1 0.01 mol (1.09 g) N-phenylhydroxylamine was prepared in 10 ml of methanol and treated dropwise with 0.01 mol (1.56 g) of 4-azido-benzaldehyde. After a few minutes, the condensation product began to precipitate in the form of the crystals. The reaction mixture was allowed to stand at room temperature for several hours. The product is then filtered off with suction, washed with methanol or n-hexane. If necessary, it is recrystallized. The yield is 95%. EXAMPLE 2 0.01 mol (1.09 g of freshly prepared N-phenylhydroxylamine was dissolved in 10 ml of ethanol under stirring, then 0.01 mol (1.56 g of 4-azidobenzaldehyde dissolved in 5 ml of ethanol was added with stirring while stirring) While the reaction temperature is maintained at 45 ° C. C- (4-azidophenyl) -N-phenyl-nitron is immediately precipitated from the reaction mixture, and the reaction mixture is stirred for a further 0.5 hours at room temperature. The product is washed with ethanol and dried to yield 98.5% of C- (4-azidophenyl) -N-phenylnitromethane.

C131H10N4O having a molecular weight of 238.08 and a temperature of 149 to 152 ° C.

Its structure was proved by IR, UV and mass spectrometry. The IC spectrum was measured on a Spec IR IR 71 (Zeiss Jena) instrument in CHCl 3. It shows the following characteristic bands (in cm-1): aces 2 100 (vn3), 1 505 (vc = n), 1210 (7n o). The UV spectrum was measured on a Specord UV VIS (Zeiss Jena) instrument in dioxane. The substance shows two bands: at λ = 268 nm (log ε = 3.90) and at λ = 348 nm (loge = 4.41).

Mass spectrum boto measured on MS 902 S (AEI, Manchester). C- (4-azidophenyl) -N-phenylnitrone does not give an M + 238 molecular ion, the m / e 198 allele, with a relative intensity of 25% in the mass spectra.

Analysis: Calculated: 23.52% N, 65.52% C, 4.23% H, 64661 23.30% N, 65.04% C, 4.19% H. The advantage of the compounds of the invention is that aro the azide-containing nitrons possess the desired spectral sensitivity in the near ultraviolet region of the spectrum. C- (4-azidophenyl) -N-phenylnitron is a light-sensitive substance and can be used to record optical information in thin polymer layers.

Claims (2)

1. C-(4-azidofenyl j-N-fenylnitrón vzorca:1. C- (4-Azidophenyl) -N-phenylnitrone of the formula: Nq-^Q^-C H=IM ~^Q^>Nq- ^ Q ^ -H = IM ~ ^ Q ^> OABOUT VYNÁLEZUINVENTION 2. Sposob přípravy C-(4-azidofenyl)-N-fenylnitrónu podfa bodu 1 vyznačujúci sa tým, že sa na N-fenylhydroxylamín působí 4-azidobenzaldehydom v rozpúšťadle, ako je metanol, etanol, propanol alebo ich zmesi, pri teplote od 10 do 60 °C.2. A process for the preparation of C- (4-azidophenyl) -N-phenylnitrone according to claim 1, wherein the N-phenylhydroxylamine is treated with 4-azidobenzaldehyde in a solvent such as methanol, ethanol, propanol or mixtures thereof at a temperature of from 10 to 60 ° C.
CS852406A 1985-04-02 1985-04-02 C- (4-azidophenyl) -N-phenylnitrone and its preparation CS245091B1 (en)

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