Saturated ketones exhibit four main bands in their ultraviolet absorption spectra. These bands are centered on 280, 195, 170 and 155 nm. The most important band is at 280 nm for the Photochemistry of carbonyl group. This band corresponds to the n —» m* transition. The photochemical reactions of carbonyl group is initiated by n — n* transition. Promotion of an electron will lead to either a singlet state or a triplet state. Photochemical reactions given by carbonyl group takes place either by singlet state or by triplet state or by both states. Dem According to the Kasha’s rule, only the lowest excited states will be involved in the Primary photochemical or photophysical processes of organic molecules in solution Carbonyl compounds give four type of reactions, These reactions include: (i) o-Cleavage. (ii) B-Cleavage. (ii) Intramolecular and intermolecular hydrogen abstraction by carbonyl oxygen. (iv) Addition of carbonyl oxygen atom to a carbon-carbon multiple bond. ; In many cases the four Processes are competitive and the major process followed is sensitive to structural variations in the ketones and the choice of the solvents. 71 G- CLEAVAGE OR NORRISH TYPET PROCESS nl Norrish type I process is given by three type of ketones (i) Saturated acyclic ketones. wy rom — >é-0- (ii) Saturated cyclic ketones, (iii) B, y-Unsaturated ketones. 7.1.1 Norrish Type | Process Given by Acyclic Sat. Saturated carbonyl compounds undergo photoind process was first observed by R.G.W. Norrish an lurated Ketones luced decarbonylation in the gas phase: ™* d is known as Norrish Type I or a-cleava#® 184 aereaction of this type is uncommon, Primary Processes Norrish Type I process is characterised by initial cleavage of the carbonyl carbon and alpha carbon bond to give an acyl and an alkyl radical. This process is known as primary photochemical process)(Scheme 1). 1 Ce ea mae R’ [> I. R—CH,—C’ + fH —CH,—R” R’ ‘Scheme 1: Primary process The initially formed acyl radical and alkyl radical is stabilised by one of the secondary processes [(a) — (c)] shown in the Scheme 2, Similarly the alkyl radical can be stabilised by recombination or disproportionation (Scheme 2). Secondary Processes (a) Decarbonylation of acyl radical to give carbon monoxide and an alkyl radical. This alkyl radical can recombine to give an alkane or can undergo intermolecular hydrogen abstraction to form an alkane and an alkene [Scheme 2(a)]. I Decarbonyation R-CH,—C* —————» R—CH, + CO R—GH,+ R —CH, ——> R-CH,—CH,-R (Recombination) R—CH,+ (H—CH,—R + RCH, +’—CH#—= CHR” nt Intermolecular hydrogen abstraction ‘Scheme 2 (a)© Photchomiy and Peteyete Ramotons (b) Intermolecular hydrogen abstraction by the acyl radical from the alkyl radica an aldehyde and an alkene (Scheme 2(6)]. ll ; R-CH,—C: +R_—CH—CH, —R” s B ll R—CH,—C—H +R'—CH=CH—R’” ‘Scheme 2 (b) This process can only be possible if alkyl radical has atleast one f-hydrogen. (©) Intermolecular hydrogen abstraction by the alkyl radical from the a-carbon of the acyl radical to form a ketene and an alkane [Scheme 2 ©). i R-CH,—C- + R_CH—CH, —R” | | R—CH=C=0+ R’—CH,—CH,—R” Scheme 2 (c) ‘The main secondary reaction of saturated acyclic ketones is decarbonpaton) A cals ca 1 secondary process. Formation of acyl and alkyl radicels Fon amen teabring of these radicals by the use of suitable trapping at 23 2,4, 4 Tetramethylpiperidne-1-oxy radical was used for the trapping and the "4 ements produced by the fission of 1, 3-diphenyl ster am ether (Scheme 3). ip! ylacetone were trapped as anll C,H,—CH,—C—CH,—C,H, hy ° Ct —CH, + C,H,—CH, ——> C,H,—CH,—CH,—C,H, + CO co Gk + N’ b-c_cH,—caH, H,—C,H, ster) 6 Ether Scheme 3 Formation of ether and ester confirms that there should be the formation of acyl and alkyl mixture of ketones (A) and (B) which give products from mixed radical combination. ° The formation of radical intermediates is also readily demonstrated by photolysis of a I I Ph,—CH—C—CHPh, + Ph—CH,—C—CH,—Ph (a) B®) |» Ph,—CH—CH—Ph, + Ph—CH,—CH,—Ph + Ph,—CH—CH,—Ph + CO (Cross product) . (93%) “his cross over experiment also confirmed the two steps radical mechanism. ny qh2ttish Type I process occurs from both the excited singlet and the triplet states of from oe tion. Photolysis of ditertbutylketone results in high yield of carbon monoxide (90%) the excited singlet and triplet states. This clearly shows that the Norrish Type I ste an om — from both the excited states. The lifetime of the singlet state is 4.5 — 5.6 x 10° from both ten with 0.11 x 10-° sec for the excited triplet state. Since the reaction occurs “ Singlet and triplet excited states, the Type I process must occur about 100 times 1, Seyelon Tiplet than from singlet excited state. Studies with triplet quenchers, such as And sing entadiene, have also shown that Norrish Type I processes occurs from both triplet ct excited states. age ee | try and Perioyole Reactions we Norrish Type I cleavage is given mostly by those ketones whose nn stay lowest erat ete Ln mmostat the cages, the n>" state is the lowest excited state. Ho” Tonoa and diaryi ketones is less efficient because n -» x* exci aE sae Uae aoeas cacied Sate In this case, there is a large barrier on the reaction coordina, eee 8, (n,m) 100 kcal/mole —— 81 (rm) 76 kcal/mole So Fig. 7.1 Energy of diphenyl ketone (CH,COC,Hs) In Norrish Type I reactions there is a preference for the formation of most stable ally radical in case of unsymmetrical ketones. CH, 0 CH,—G,—C—-CH,—CH,—CH, CH, CH, ° CH,—C: + ca,—cx,—cr,_& cn, | CH, O cn,o_bs CH,—CH,—CH cn, In the above case, only a-bond undergoes cleavage. If both alkyl substituents ar® s** then there is little selectivity of bond cleavage. I CH,—CH,—CH,—C_CH, cH, |o 0 | . I CH,—CH,—CH,—C- + CH,—CH, + CH,—CH,—CH, + CHy—CHs"ke Photochemistry of Carbony! Compounds 499 The Norrish Type I process is mostly favoured by photolysis in the vapour phase and is Joss pronounced for photolysis in the inert solvents. In inert solvent formation of solvent cage place. Formation of solvent cage facilitates recombination of the initially generated radical pair. Thus low quantum yield of products is obtained in inert solvents, Norrish Type I process is efficient in liquid phase only if a stable radical is formed. The stable radical includes allylic, benzylic, tert alkyl and acyl radicale, I C.H,;—CH,—C_CH,—C,H, |». Liquid phase I] ' (C.H,—CH,—C- + C,H,—CH,] C,H,;—CH,—CH,—C,H, + CO "Problem 1: Complete the following Norrish Type 1 reaction: q CcHhy—GR—C—CH_O, =e CoH, CH; | Solution: Compound is saturated acyclic ketone. It will give Norrish Type I process in ‘€ases as well as in solution phase. f Process: CHC: + feos Cit PCat k ent encit a ca cies e i i—C CH , Beet "Sea +co CoHs Den + eC ogi, --orCa 5 SCoHs oH, CoH (200% yield)[iige_Provccnemsty and Percyte Reactions q 7.1.2 Norrish Type I Reaction of Saturated Cyclic Ketones Cyclic ketones, in contrast to the acyclic ketones, show a greater tendoncy to undergo ceclonyy to furnish acybalky! biradicals Norrish Type [ cloavage of acyclic ketones take place by sin as well as by triplet excited state, In cyclic ketones, the reaction takes place exclusively bY the triplet state. It is possible, however, that inter system crossing in cyclic ketones is so rap that reaction from the singlet state would not be observed. The triplet state is at least 100 times more reactive than the excited singlet state. Available information indicates that the excited triplet state for Norrish Type I Processes is n + n* triplet state, This was demonstrated first for the irradiation of cyclopentanone jg. both gases and in solution phases. Under both conditions, the product is 4-pentenal, Formation of 4-pentenal takes place at 313 nm and 254 nm, The formation of the aldehyde can be quenched by 1, 3-cyclopentadiene. This quenching experiment confirms the formation of the triplet state, Norrish Type I process involves the initial cleavage of a carbonyl carbon-alpha carbon bond. Subsequent secondary processes [(a) to (c)] correspond to those observed for acyclic ketones. (a) Decarbonylation of acyl-alkyl diradical to give carbon monoxide and a dialkyl radical The dialkyl radical can recombine to give a cycloalkane or it undergoes intramolecular hydrogen abstraction to form an alkene. [Scheme 4 (a)]. CHy (CH), c=0 CH,—CHy hw §, 1, 7, 7a (CHD, CH;—CH, Acyl-alkyl diradical | Pecesbonyition CHy (CH), CH;—CH, Radical Fecocabicetion Intramole- Pa tiiecon (CHa), CH, CHs cy” (CH), Cycloalkane CH=CH: Alkene Scheme 4 (a)) Intramolecular hydrogen abstraction by the acyl radical from the B-carbon of the alkyl sedical to give an unsaturated aldehyde [Scheme 4 ()]. ou (CH), CH,—CH, (eo aH, tt (CH,), CH=CH, Unsaturated aldehyde ‘Scheme 4 (b) (© Intramolecular B-hydrogen abstraction from the acyl radical by the alkyl radical to produce a ketene [Scheme 4 (c)]. B 7H (CH,), CH,—CH, | CH=C=0 (CH), CH,—CH, Ketene ‘Scheme 4 (c) [ang (0) vi. can undergo one of the two hydrogen transfer processes on 32 cyclic transition state in which a hydrogen atom is transferred to one radical = atom adjacent to other radical centre. hydrogen ab, Jsis of cyclic ketones in gas phase gives decarbonylation as well as intramolecular stra ion. Intramolec n abstraction mai: i icti¢ ular hy droge! stractic ‘inly leads to the formation of “rated aldehyde (Scheme 5). : The biradical of cyclic ketones a a182 Photochemistry and Perloyolc Reactions a Oe Decarbonylation Intramolecular Unsaturated aldehyde C+ ‘Scheme 5 In solution phase biradical pair is not usually stabilised by decarbonylation. In this as, biradical is mainly stabilised by intramolecular hydrogen atom transfer. This intramolenkr hydrogen atom transfer leads to the formation of either unsaturated aldehyde or a ketene both (Scheme 6). C=? -atier Cho a C0 phase ° Intramolecular Intramolecular hydrogen abstraction by hydrogen abstraction carbonyl carbon radical C+ ( =o H Ketene ‘Scheme 6 a When photolysis is carried out in the presence of polar protic solvent then the species formed is ketene. This ketene then undergoes solvent addition to give carboxy (with water) or its derivative (ester with alcohol) as the only product. hy Opnente Om One OR EsterPhotochemistry of Carbonyl Compounds 193 SS ee ee with UV light in the presence of MeO) ‘Solution: In In the presence of polar protic solvent, cyclic ketone forms only ketene. Me CH, ay anes OE 0) ‘CH,OH Carvone camphor | CH, CH, CH, CH H eo CH,OH = ‘OCH, le alkyl radical ul In case of unsymmetrical ketones, the o-bond that produces more stabl cleaves preferentially. - Problem 3: Complete the following reaction: E 9 Ay ‘Liquid phase hv a "Solution: The a-bond that produces the more stable alkyl radical cleaves preferentially "in unsymmetrical ketone. The vapour phase photolysis gives decarbonylation and intramolecular hydrogen abstraction. R= = COG i: In the liquid phase, the main reaction is intramolecular hydrogen ebetraction which to the formation of unsaturated aldehydes.. ; - ata According to the biradical mechanism, reaction to reform the starting material. i i hy CO ‘Recombination =, aaa, Use of suitably a-substituted cyclic ketones show that recombination reaction resulted in epimerisation at the a-carbon if a-carbon is a chiral. H.C O fa 9 CoO = CO = “@ Epimer of (A) Experimently it has been found that photolysis product formation via route ((a) -() is faster than the photochemical interconversion of the epimers. Since there is the formation of epimeric mixtures, each epimer affords the same mixture of products. HC. cH, HO. § cH, hy LY _—_ Av 3 cH, CH, CH, + + HC. 9 HC. 9? CH, 7 I + |Photochemistry of Carbonyl Compounds 195_ P rds the same mixture of products. This clearly indicates that the Each epimer affor i tional integrity of the a-carbon is lost during the course of the reaction. This loss of commgaty is due to the free rotation about C,—C, bond in the diradical. ° 9 HC, 1 CH, . CH, a Ls “A oe — 3 3 Rotation about C;—C, single bond ° ° scH, H,C, 1 as a Recombination * = ‘The recombination process is important even when hydrogen transfer reactions occur, but loss of carbon monoxide in solution phase photochemistry is a major reaction pathway only when the alkyl radical centres are stabilised by inductive effect, by B, y-unsaturation or by cyclopropyl conjugation. This reflects an increase in the rate of loss of carbon monoxide from the acyl-alkyl biradical in these systems. 2, 6-Dimethyl-cyclohexanone gives carbon monoxide on photolysis in solution at room temperature. 2, 2, 6, 6-tetramethyleyclohexanone gives carbon monoxide in a yield greater than 70%, 7, 7, 9, 9-tetramethylbicyclo [4, 3, 0] non- 1, 6-en-8-one gives 100% yield of carbon monoxide and hydrocarbon products. TF — US Highly stable) |Fission to ethylene is much more efficient in comparison to cyclobutane formation (Sehem*Photochemistry of Carbonyl Compounds 197 2 atx je LI Oo H,=CH, + CH,=CH, ‘Scheme 7 In solution the loss of carbon monoxide from a cyclopentanone is a major path only ne the radical centres formed are stabilised by alkyl substitution, double bond or cyclopropyl ox -at- ce (Highly stable) Cyclopropyl |» conjugation {> ste fe ZF — Minor product (Both radicals are conjugated ict (13%) Maj oduct (80%) i (is product) eo. by cyclopropyl ring)198 Photochemistry and Pericyclic Reactions Problem 5: Give the mechanism of the following transformation: CE 70% Yield Solution: (Stabilished by cyclopropyl ring) -Cleavage is not given only by eyclic ketones. Other cyclic compounds such as lactones lactams and cyclic anhydrides undergo a-cleavage to give a biradical species on photolysis n gas or solution phase. 9 9 9 L H ° hy . ‘0 0 Li we \ ~—\ } (Unsaturated i Fa q 9 6 Intramolecular H Lh hydrogen o H abstraction (Wialdehyde) 7.1.4 a-Cleavage Given by Cyclobutanones a Cyclobutanone also gives a-cleavage reaction. The efficiency of a-cleavage reastio cyclobutanone is ten times more than the cyclopentanone due to the angle strain. Angle *# ; and steric strain increase the efficiency of a-cleavage. The photochemistry of arcleavat cyclobutanone differs significantly from the photochemistry of o-cleavage of other evel Ke"Fo ccc eee Photochemistry of Carbonyl Compounds 199 & Unlike other ketones, cleavage occurs from S, (n—>n*) and leads to the formation of a 1, 4-acyl- ikyl diradical. There are three following different pathways for stabilisation of the diradical: ae (Loss of carbon monoxide and formation of 1, 3-diradical that undergoes either recombination to cyclopropane or an hydrogen abstraction to form propene. CHAPTER 7 — 0 a hy 3, —> 1, Aeyhalcyl diradical [-co ATL K (ii) By a subsequent B-cleavage and formation of ethylene and ketene. K —— CH,=C=0 + CH,=CH, . | 2+21—Cycloaddition (iii) 1, 4-Acyl-alkyl biradical can undergo ring expansion by rebonding to oxygen to give oxacarbene. This carbene can be trapped by polar protic nucleophile solvents. The over all Teaction is a ring expansion. Ring 0. 0. H expansion K Y ROH < Ker Oxacarbene Acetal re Formation of 1, 4-acyl-alkyl radical can be proved by trapping experiment. 1, 4-acyl- ten liradical can be trapped by 1, 3-butadiene at low temperature (-78°C) because low ature suppress the decarbonylation and | 2 +2 |—cycloaddition reaction. Photolysis of Cyclobutanone hexanone® ** ~78°C in the presence of trapping agent, 1, 3-butadiene gives 3-vinyleyclo-NS “NS 3-Vinyleyclohexanone Scheme 8: Trapping of 1,4-acyl-alky! diradical by 1,3-butadiene 9 p (nstable alkyl radical) (Stable alkyl radical) 0, H, gor Re HH i Co : CS “ S; . : 28 Photolysis of eyclobutanone is also stereospecific reaction, Stereochemistty # Gis retained during the rearrangement to the oxacarbene. Ring expansion reaction always © retention of configuration in methanol,Photochemistry of Carbonyl Compounds 201 0 0. OMe Pa : Pou, Av/MeOH. Pha “a SN” - : ’ “H - C HC : H,C Ph mw, CH, HC ih “Problem 6: Identify (A) and (B) in thia reaction: ° H,C, CH, > Oe Pi Ph CH, | 2 | HAC ‘ Ph (ui Hy HAC h [avon H,C, _20Me HC. 7° ‘OMe Phi HOt Phy “NH (CH, mat CH, H, h HC h ® w Problem 7: Give mechanism of the given reaction: Et, Et » > a MeO! | vio MeO Et, 0. H Meo"Photochemistry of Carbonyl Compounds 208 Some class of compounds have relatively weak C,—C, bonds which ean undergo cleavage asa py result of electronic excitation of the carbonyl group. Cyclopropyl ketones are one such class, and evidence for interaction between the carbonyl and cyclopropyl groups, which provides a mechanism by which energy may be transferred from the carbonyl group to the bond which is broken, is found in the UV spectrum. ‘The mechanism of the reaction has been shown to involve the formation of a 1,3-biradical intermediate. Photolysis of acetyleyclopropane leads to the cleavage of the cyclopropane ring, and this is followed by a 1,2-hydrogen shift or alkyl shift. H Oo fo) (a) {I Cone mcance CH =CH—CH, ton a Minor) * . Ina similar way, bicyclo [4, 2 Ina similar way cyclo (4, 1, 0] heptane-2-ones undergo cleavage of one of the cyclopropyl 9 ° o @ 5 wy, SH 1, 2-Hydrogen shift cH, Ei 1, 3-Diradical 0 ‘CH,1, 2-Hydrogen shift @ In some cases the o-cleavage and B-cleavage are often in competition as shown below: ° ° t H—C. Q @ In the above case, product (1) is formed due to the B-cleavage and product (2) is formed due to the a-cleavage. a, B-Epoxy ketones have also a relatively weak C,—C, bond which can be cleaved in the excited state. Epoxy ketone reacts by way of B-cleavage and alkyl migration on photolysis Mechanistically this reaction arises from a singlet nn* state and result is the fission of t C—O bond. The migratory aptitudes shown within such compounds is best explained via th? involvement of a biradical species formed by C—O bond fission. Some examples are: en) Ph ? Pa aD) @ 1H, ‘CHs ee Me [: ‘2-Methy! shift 7 fl peaega emcee CHs— = Photochemistry of Carbonyl Compounds. 207 +) excited carbonyl compounds having an accessible hydrogen atom in the y-position 1,3(" * “naracteristic 1, 5-hydrogen atom transfer by an intramolecular cyclic process with ws fe _ medion of Ketyl like 1, 4-diradica, E : H z H. oO OH 6 Es § PS siort —> = J, Hie sen RY R R~ Cyclic transition state 1,4-Diradical Depending on the conformation of the initially formed 1, 4-diradical, two different pathways to stabilisation are possible: (i) only the sp-orbitals of the radical centres can overlap, a cyclobutanol is the product. (i) If the sp-orbitals of the radical centres are parallel to the B-bond, they participate in formation of two double bonds (one in the enol and one in the alkene), a result of the cleavage of the B-bonds. OH . = 4 R sp-Orbital sp-Orbital H Cyclisation HH '—CH, | Cleavage of B-bond t | 0ae 208 Photochemistry and Pericyclic Reactions The second process of this reaction is known 48 Norrish Type II process which lead, the formation of alkene and alkenol. Although the reaction occurs from both the singlet and the triplet states of tansy the quantum yield from the singlet state is generally lower than iplet state, j, case of aryl-alkyl ketones, the reaction occurs only with the eierat th bese aroma, ketones can undergo rapid intersystem crossing. Solvents also af f if e ciency of reaction. The singlet state reactions are unaltered in the presence O° poldr. solvents, P solvents such as alcohol, on the other hand, enhance the reaction from the triplet state ‘The quantum yield of the reaction is poor since radiationless deactivation from the § and T, states and reversal of the hydrogen transfer can compete with reactions Proceeding , products. The reversal process is confirmed by using the optical active ketone (1) having chiral y-carbon, Ketone (1) undergoes racemisation. Racemisation reaction confirmed that th reaction intermediate is 1, 4-diradical. This also confirmed the back transfer of hydroge, atom. CH, CoHs PH, . on + on 4 . | Ay Le = I Qa Back transfer of hydrogen atom i.e., photoracemisation can be quenched by the addition of 1, 3-cyclopentadiene. This quenching experiment confirmed the formation of triplet stat Participation of a 1, 4-diradical intermediate in the Norrish Type II reaction has bea confirmed by trapping experiments and spectroscopic techniques. Formation of 1, 4-diradi has also been proven chemically. Photoracemisation of a ketone with a y-chiral carbon sles and loss of the chirality in the product was observed. Hf AS Ry hy [na an) Rs Reversal of Ry R, on «AR, on «Aap, angen og HLA, on =) J transfer SS +a+@t! Ry RR R; Ry Ph HO R, as OH R, wn we 7 “ ®) © o, Photochemistry of Carbonyl Compounds 209 The y-hydrogen transfer to the oxygen atom has been shown to be intramolecular. The transfer involves @ SiX membered cyclic transition state. 5, 5-Dideuterohexan-2-one on agradiation gives 2-deuteropropene and 1-deuteroacetone. Formation of thee Products confirms that the transfer of hydrogen takes place from y-carbon and Process is intramolecular CH3 D. OD OH 0 iy ° CH _hv | DH i As oJ D = cH;—C=cH, + i + Ph—-C=CH, | + Ph He CH,—cH=cH, ll CH;—C—CH,D When a molecule has two y-carbons both having hydrogens, transfer of hydrogen in the Norrish Type II process is marked by a preference of cleavage of the weaker carbon-hydrogen bond as in case of ketone (2). h aS g by ts ‘CH—CH;—C—CH,; —“~ > HCC ® CH; Weaker C—H bond ous ? CHa=CH—CHC = + CHs~C=CH—CH, + CHp—C_CH, ‘CH Hy (Minor) (Major) Intramolecular hydrogen abstraction is not possible if y-carbon has no hydrogen. For alkylaryl ketones the electron donating groups such as p-methyl and p-methoxy substituents decreases the rate and quantum yield for Norrish Type II cleavage. Following this tend p-hydroxy, p-amino and p-phenyl substituents inhibit the reaction completely. This isbecause in such cases energy for m— n* excitation is less than that for the n —> n* excitation. ._, Therate of radical recombination to give cyclobutanols compared with a, B-bond cleavage soften dependent on a-substitution, ‘ RZto be studied was the formation of oxetanes from own as the Paterno-Biich) yield of an oxetane. One of the first photocyclonddition reactions to be A was to alkenes. This reaction is kn addition of carbony! compounds : : 4 reaction. For example, benzophenone ‘with isobutene gives a high oO C,Hs—C=0 + cH,=¢—-CHh a | én, H,Ce CH, Hs CH, CH; 90% Yield Paterno-Biichi reaction can be studied under two categories and the categories depend on the nature“of alkenes. 7.7.1 Addition to Electron-Rich Alkenes Mechanistic studies have shown that the reaction pathway varies according to the type of carbonyl compound and alkenes involved. ‘Addition of simple aliphatic or aromatic ketones i electron rich alkenes involves attack on ground state alkene by the n >7* triplet state of the carbonyl compound in a non-concerted manner, giving rise to all possible isomers of the oxetane, ‘The reaction is non-concerted because the reactive excited state is a triplet state. The initial adduct of this reaction is a triplet 1, 4-diradical, which must undergo spin inversion before Jete, Stereospecificity is lost if the intermediate 1, 4-diradical product formation is comp! Prefergoes bond rotation faster than ring closure (Scheme 8). Il Cols —C—Colts > 8, $5 tt CoHs—C—O CoH Excited state triplet CHa\ cHy c= CHe CcHs Cells H;Cs—C—O HyCs—C—O 4 + 4 H3C\ L Hoo CHa—F Hs CHs Spin Spin inversion inversionColts Geils Call HsCs—-——9 er CcHs—C—0 i | + rt | a mest ou, CH.~C_CH, Cc H,C~ I ae CH; CoHs HsCs—4——-0. CH, CH, 10% ‘Scheme 9 Although the reaction is not stereospecific, there is a preference for one orientation of addition, which can be rationalised in terms of initial attack on the alkene by the oxygen atom of the excited carbonyl group to give a biradical intermediate. The existance of biradicals has been confirmed by picosecond spectroscopy. The more energetically stable of the two possible biradicals is formed more readily. Thus reaction is regioselective reaction. The consideration of biradical stability is certainly applicable to the prediction of the major product of the cycloaddition (see Scheme 9). ‘Two important rules for the successful synthesis of oxetanes have been put forward. ‘These rules are as follows: ( Only carbonyl compounds with a low-lying n — n* state will form oxetanes. (ii) The energy of the carbonyl excited state must be less than that of the alkene to prevent energy transfer from the carbonyl excited state to the alkene. As far as the addition of aromatic carbonyl compounds is concerned only the triplet State is reactive (because inter system crossing is very efficient in case of aromatic ketones) and consequently a triplet biradical intermediate is produced. The reaction of alkyl ketones can be complicated by the less efficient inter system crossing shogt tmitting reaction of both the singlet and the triplet state. Both singlet and triplet state ee reactivity for the reaction. The singlet state reaction is obtained at ne eae of the alkene. On the other hand, triplet state reaction is obtained at low ‘ation of the alkene, 772 Addit, ation to Electron Deficient Alkenes “eloaddition of aliphatic ketones to electron-deficient alkenes, particularly dicyano- * Involves addition of singlet state (n > m*) excited ketone to ground state alkene. The i i i i roduct, Oetang ” *t@te08pecific and the stereochemistry of the alkene is retained in the p CHAPTER 7Photochemistry and Pericyclic Reactions - aS HC a NY H,C c=0 + a 5 7 713 nm cH, Is CN 7 CN CH ON we ° ’Nceo + [ —w_, He CH. 4 313 nm 3 NC nce CN ‘The course of the photocycloaddition of electron-deficient alkenes to ketones falloy certain rules. While oxetanes are formed only from S,(n, ™*) state, the Ty(n, m4) stat stereospecifically sensitises the cis-trans isomerisation of electron-deficient alkenes and does not lead to oxetanes. t cH,—C—CH, Tina) C CN ‘CN J cN cH, CN So=0 + S CHa CH De=0 + [| NC cH, cc Stereospecificity of the oxetane formation with electron-deficient alkenes can be explaitel as follows: It is suggested that in case of electron-deficient alkenes, oxetane formation ‘takes pit via formation of exciplex. Exciplex formation takes place between the singlet excited stat ketone and ground state of alkene. Exciplex is stabilised by charge transfer as well as ete! transfer between the constituent molecules. \Z 4 Nao ¥ mw Ne o>? Lwit* 2 UN aN Exciplex _ 7 , elo yt (2) Formation of an exciplex between a carbonyl excited state and an olefin ground (6) Charge transfer interaction in the formation of the carbony-oleie Photochemistry of Carbonyl Compounds 224 The excipler (6, excited state cyclic complex) has “afe formation of the products is accounted reously in the complex, or if the second is formed Me of bond rotation. There is again a preference for the rate © o that expected on the basis of the most stable bi i considerable charge-transfer and the for if both new bonds are formed after the first at a rate faster than one orientation of addition, but this iradical intermediate. The preference fects the preferred orientation in the exciplex which is governed by charge densities se iijustrated 5 & co oN Gen XA ee ya S| n—>K Exciplex 7.13 Oxetane Formation with Dienes and Alkynes (A) With Dienes Addition of carbonyl compounds to conjugated dienes is also feasible. The E, of dienes is usually Jess than that of carbonyl compounds. However, the formation of oxetanes competes successfully with excitation energy transfer because dienes quench the 7, (n — n*) state. Thus formation of oxetanes occurs from the S, (n — n*) state of the carbonyl compounds. Therefore, dienes give stereospecific reactions with dienes. Examples are as follows: 0: Yc=0 + O _w_, OC H H ail “i Yc=0 ae i) _hv, 0. 2 H H . 0. 0. Ss Mi 00+ ZY. f + J Z The third reaction takes place as follows: Ab Af Natt cncen : 3 | oO i —JI- i CH—CH=CH, CHAPTER 7 s223°" Prenochemistry and Perioyctc Reactions 6 CH-CH=CH, o—cH—-CH=CH, AC ba, A St (B) With Alicynes Carbony! compounds undergo photochemical cyeload hich are usually not isolated but isomerises (0 subsequent thermal reaction. dition reaction to alkynes to give oxetey Pareetureted carbonyl compuumas a a ° i C,H,—CH + CH,—C=C—CH, ay 78°C O%—C—CH, cgi en e—cH, Oxetene I, 1 CqH,—CH=C—C—CH, CH, a. B-Unsaturated carbonyl compound 9 cat & + CH,C=C—OCH, Hs mle Q—C_OCH, 1 ol CoH,—C—C—CH, CoH \ i CHC = 6 it ¢-<-ocH, C,H, CH,Photochemistry of Carbonyl Compounds 223 aterno-Biichi reaction is mainly given : ground c=C group. This combination of substrates allows the arte ee egioisomer- Thus yields are high and there is usually no byproduct(s). This reaction lt ‘ oe mad versatile method for the synthesis of a variety of compound that are d is highly possible to be prepared by other methods. are difficult or Some Pana the examples are as follows: (© CH,=CH—CH,—CH,—C—CH, |» Te, CH, cH,—C—O H I | |, ~t CH,—CH=CH, CH,—CH—CH, CH, OAC EAR. — 3 S 7 qF ms Photochemistry and Pericycic Reactions One of the most important reaction of this class is the preparation of azulene as follows: OOO won Perhaps the most useful reaction of a, B-unsatur reaction with alkenes which affords cyclobutane below: ‘Alkene + Enone <= [Enone]* sc (Enone)” |ateene Biradical <—————_ [Exciplex|" | Product ‘The biradical can be formed by bondin; the an be g at the a-carbon or the B-carbon 0 § the alkene. The reaction is stereoselective at the fused junction. Cis-fused 45, systems are common and are much more stabl a i 5/6 ca A le than their trans isomers. trans. 6/6 can be cis or trans but prefers trans. reat’ aOo a-Bond ° Biradical oH OH *C | H H 65% 26% + 9 14% Bive he Oo | hv ‘OMe Electron rich alkene Photochemistry of Carbonyl Compounds 225 Lx 9 OH H + 9 Cp ow. The reaction is regioselective with respect to unsymmetrical alkenes. Electron rich alkenes ‘ead to tail adduct whereas electron-deficient alkenes form head to head adduct. OH ‘OMe Head to tail adduct ? c258 Photochemistry and Pericyclic Reactions X \t Photo-Fries Rearrangement pyre most extensively investigated photo rearrangement is Photo-Fries rearrangement v o-t-R OH g OH OH OQ hy ot a + oO = Phenol ester ortho acyl phenol ¢=o R p-Acyl phenol This rearrangement is an intramolecular rearrangement. In this rearrangement: substrate undergoes dissociation into phenoxy and acyl radicals which combine within the solvent cagetn give intermediates which on aromatisation (or enolisation) give the product. The phend ix produced by phenoxy radicals which escape from the solvent cage. in 9 I hy [ II ] [ I | Ph—-O—C_R ——> |Ph—O—C-—R} —> [PhOC-R Excited state Solvent cage oO oO 0 HH a + + H fe oO ono on on CR Oo t R: When this reaction is carried out in gaseous phase. only phoned is chtained 7 the formation of solvent cage. Jar rearrangements are also obtained from the following ompomunds Simi e o-SO.R OH - . FA S0.R Cy Ss UO 'o) ay ae GHAPTER 8 GLossary Photo-Fries Reaction: The Phenol ester in solution. Dix Methane Rearrangement: M ‘systems bonded to a single sp° ca! fansformation to vinyley: Oxa-Di-n. ketone is ‘methane rearrangement: Di-x-methane rearrange™ known as oxa-di-n-methane rearrangement C: Jniversity Press. Londen. © SM. Coron and B. Halton. Organic Photochemistry, Cambridge Unt y 1974. New : % Vol. 3 Academic Press} ® P. de Mayo, od Rearrangements in Ground and Excited States, Vol. 3 Ac York, 1980, a. " , El a. hensive Treatment. W. Horspoot and D Arester, Organic Photochemistry. A Comprehensive “i. Horwood/Prentice Hall, 1992. ICH, Weinhim, Germany, 1982. s ) Kopecky, Organic Photochemistry, A Viewal Appeal. 1: ae? Organic, Photochemistry, Principles and Applications a