Due occhi per non vedere e Utente:Grasso Luigi/sanbox1/Riordinamento Fries: differenze tra le pagine

Versione delle 01:16, 21 lug 2015

Versione delle 19:35, 21 set 2018

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{{S|film commedia}}

{{Film

|titoloitaliano= Due occhi per non vedere

|immagine=

|didascalia=

|titolooriginale=

|linguaoriginale= italiano

|paese= [[Italia]]

|titoloalfabetico=

|annouscita= [[1939]]

|durata= 75 min

|tipocolore= B/N

|tipoaudio= sonoro

|ratio= 1,37 : 1

|genere= commedia

|regista= [[Gennaro Righelli]]

|soggetto= [[Pietro Solari (scrittore)|Pietro Solari]]

|sceneggiatore= [[Gennaro Righelli]], [[Pietro Solari (scrittore)|Pietro Solari]]

|produttore= [[Giorgio Carini]]

|produttoreesecutivo=

|casaproduzione= Mediterranea Film

|distribuzioneitalia= CINF

|attori= *[[Renato Cialente]]: avv. Vito Normanni

*[[Loretta Vinci]]: Benedetta, sua moglie

*[[Giuseppe Porelli]]: avv. Demetrio Sansoni

*[[Alma Klaric]]: baronessa Vania Pljevja

*[[Romolo Costa]]: Marco

*[[Armando Migliari]]: prof. Santoro

|fotografo= [[Domenico Scala]]

|montatore= [[Gennaro Righelli]]

|effettispeciali=

|musicista= [[Renzo Rossellini]]

|musicale=

|scenografo= [[Alfredo Montori]]

|costumista=

|truccatore=

|sfondo=

|premi=

}}

'''''Due occhi per non vedere''''' è un [[film]] del [[1939]] diretto da [[Gennaro Righelli]].

==Trama==

Benedetta e Vito sono sposati ma lei sospetta che il marito la tradisca. Finge quindi di aver perso la vita per metterlo poi alla prova ma l'uomo scopre il trucco. Dopo una serie di piccoli liti tra i due torna la pace.

Il '''riarrangiamento di Fries''' o '''reazione di Fries''', che prende il nome dal chimico tedesco [[Karl Theophil Fries]], è una [[reazione di riarrangiamento]] di un estere fenolico a un [[idrossile|idrossi]] [[arile]] [[chetone]] tramite [[catalisi]] di un [[acido di Lewis]].<ref>{{cite journal | title = Über Homologe des Cumaranons und ihre Abkömmlinge | author = [[Karl Theophil Fries|Fries, K.]] ; Finck, G. | journal = [[Chemische Berichte]] | volume = 41 | issue = 3 | pages = 4271–4284 | year = 1908 | url = | doi = 10.1002/cber.190804103146}}</ref><ref>{{cite journal | title = Über ein Kondensationsprodukt des Cumaranons und seine Umwandlung in Oxindirubin |author1=Fries, K. |author2=Pfaffendorf, W. | journal = [[Chemische Berichte]] | volume = 43 | issue = 1 | pages = 212–219 | year = 1910 | url = | doi = 10.1002/cber.19100430131}}</ref><ref>March, J. ''Advanced Organic Chemistry'', 3rd Ed.; John Wiley & Sons: Chichester, 1985; S. 499ff.</ref><ref>Blatt, A. H. [[Organic Reactions|''Org. React.'']] '''1942''', ''1''.</ref>

==Bibliografia==

*R. Chiti, E. Lancia - ''Dizionario del cinema italiano. I film'', vol. 1 - Roma, Gremese, 2005, ISBN 8884403510.

*F. Savio - ''Ma l'amore no: realismo, formalismo, propaganda e telefoni bianchi nel cinema italiano di regime (1930-1943)'' - Milano, Sonzogno, 1975.

==Collegamenti esterni==

*{{Imdb}}

[[Image:Fries-Umlagerung 1.svg|600px|center|Riarrangiamento di Fries]]

{{Portale|cinema}}

Implica la migrazione di un gruppo [[acile]] di un estere [[fenolo|fenolico]] nell'anello [[arile]]. La reazione è [[Pattern di sostituzione in idrocarburi aromatici|orto e para selettiva]] e uno dei due prodotti si ottiene cambiando le condizioni di reazione, come la [[temperatura]] e il [[solvente]].

[[Categoria:Film commedia]]

== Meccanismo della reazione ==

Despite many efforts, a definitive [[reaction mechanism]] for the Fries rearrangement has not been determined. Evidence for inter- and [[intramolecular]] mechanisms have been obtained by [[Crossover experiment (chemistry)|crossover experiments]] with mixed reactants.

The Reaction progress is not dependent on [[solvent]] or [[Substrate (chemistry)|substrate]]. A widely accepted mechanism involves a [[carbocation]] intermediate.

In the first reaction step a [[Lewis acid]] for instance [[aluminium chloride]] {{chem|AlCl|3}} co-ordinates to the [[carbonyl]] oxygen atom of the [[acyl]] group. This oxygen atom is more [[electron]] rich than the [[phenol]]ic oxygen atom and is the preferred [[Lewis base]]. This interaction [[Chemical polarity|polarizes]] the [[covalent bond|bond]] between the acyl residue and the phenolic oxygen atom and the aluminium chloride group rearranges to the phenolic oxygen atom. This generates a free [[acylium]] [[carbocation]] which reacts in a classical [[electrophilic aromatic substitution]] with the aromatic ring. The abstracted proton is released as [[hydrochloric acid]] where the chlorine is derived from aluminium chloride. The orientation of the substitution reaction is temperature dependent.

[[image:Fries-Umlagerung 2a.svg|600px|center|Riarrangiamento di Fries parte prima]]

A low reaction temperature favors [[Arene substitution patterns|para substitution]] and with high temperatures the [[Arene substitution patterns|ortho]] product prevails, this can be rationalised as exhibiting classic [[Thermodynamic versus kinetic reaction control]] as the ortho product can form a more stable bidentate complex with the Aluminium.<ref>{{cite book |title= Aromatic Chemistry (Oxford Chemistry Primers)|last= Sainsbury|first= Malcolm|year= 1992|publisher= Oxford University Press|isbn=0198556748 |page= 65}}</ref> Formation of the ortho product is also favoured in non-polar solvents; as the solvent polarity increases, the ratio of the para product also increases.<ref>{{cite book |title= Strategic Applications of Named Reactions in Organic Synthesis: Background and Detailed Mechanisms|last= Kürti|first= László|last2= Czakó|first2= Barbara|year= 2005|publisher= Elsevier Academic Press|isbn= 0123694833|page= 181}}</ref>

Sostituzione ''para'':

[[image:Fries-Umlagerung 3.svg|600px|center|Riarrangiamento di Fries parte prima]]

Sostituzione ''orto'':

[[image:Fries-Umlagerung 4.svg|400px|center|Riarrangiamento di Fries parte prima]]

==Applicazioni==

[[Phenol]]s react to form [[ester]]s instead of hydroxyarylketones when reacted with [[acyl halide]]s under [[Friedel-Crafts acylation]] conditions. Therefore, this reaction is of industrial importance for the synthesis of hydroxyarylketones, which are important intermediates for several pharmaceuticals. As an alternative to [[aluminium chloride]], other [[Lewis acid]]s such as [[boron trifluoride]] and [[bismuth]] [[triflate]] or strong protic acids such as [[hydrogen fluoride]] and [[methanesulfonic acid]] can also be used. In order to avoid the use of these corrosive and environmentally unfriendly [[catalyst]]s altogether research into alternative

[[heterogeneous catalysis|heterogeneous]] catalysts is actively pursued.

== Limiti==

In all instances only [[ester]]s can be used with stable acyl components that can withstand the harsh conditions of the Fries rearrangement. If the aromatic or the acyl component is heavily substituted then the [[chemical yield]] will drop due to [[steric hindrance|steric]] constraints. Deactivating meta-directing groups on the benzene group will also have an adverse effect as can be expected for a [[Friedel-Crafts reaction|Friedel–Crafts acylation]].

== Riarrangiamento foto-Fries ==

In addition to the ordinary thermal phenyl ester reaction a so-called [[photochemistry|photochemical]] '''photo-Fries rearrangement''' exists<ref>Bellus, D. ''Advances in Photochemistry''; John Wiley & Sons: Chichester, 1971; Vol. 8, 109–159.</ref> that involves a [[radical (chemistry)|radical]] [[reaction mechanism]]. This reaction is also possible with deactivating [[substituent]]s on the aromatic group. Because the yields are low this procedure is not used in commercial production. However, photo-Fries rearrangement may occur naturally, for example when a plastic bottle made of polycarbonate (PC) is exposed to the sun, particularly to UV light at a wavelength of about 310&nbsp;nm, if the plastic has been heated to 40° Celsius or above (as might occur in a car with windows closed on a hot summer day). In this case, photolysis of the ester groups would lead to leaching of phthalate from the plastic.<ref>Norma Searle, "Environmental effects on polymeric materials," pp. 313–358, in ''Plastics and the Environment'', edited by Anthony Andrade, Wiley, 2003.</ref>

[[Image:Fries rearrangement (photo).svg|center|600px|Photo Fries rearrangement]]

== Riarrangiamento di Fries anionico ==

In addition to Lewis acid and photo-catalysed Fries rearrangements, there also exists an anionic Fries rearrangement. In this reaction, the aryl ester undergoes ortho-metalation with a strong base, which then rearranges in a nucleophilic attack mechanism.

== Voci correlate ==

*Reazione del tipo [[Reazione di Friedel-Crafts|alchilazione di Friedel–Crafts]]:

**[[Riarrangiamento di Hofmann-Martius]]

** Riarrangiamento di Fries

**[[Riarrangiamento di Fischer-Hepp]]

* [[Reazione di Duff]]

== Note ==

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{{portale|chimica}}