Photochemische Reaktionen. 104. Mitteilung [1]. Zur Photospaltung der C,C-Oxiranbindung konjugierter γ, δ-Epoxy-enone: Photolyse von 4-Methyliden-5,6-epoxy-5,6-dihydro-β-jonon

The photoinduced cleavage of the C,C-oxirane bond of γ, δ-epoxy-enones: UV.-irradiation of 4-methylidene-5,6-epoxy-5,6-dihydro-β-ionone On ¹n, π*-excitation (λ ≥ 347 nm, pentane) 5 gives the isomeric bicyclic ether 10 in 75% yield (s. Scheme 2). In methanol the photoconversion of 5 to 10 is strongly reduced (12%) in favour of the formation of the methanol adduct 11 (43%). On photolysis in aqueous acetonitrile 5 is converted to the bicyclic ether 10 (9%), the dihydrofurane 12 (18%) as well as to the triketones 13A and 13B (7%), and 14 (23%). On ¹π, π*-excitation (λ = 254 nm) in pentane no 10 is formed, but 5 isomerizes to the tricyclic cyclopropyl compound 16 (59%), the allenic product 17 (10%), and the cyclopropene compound 18 (12%; s. Scheme 3). Photolysis in methanol furnishes 11 (63%), and 18 (4%), but no tricyclic cyclopropyl compound 16 . In a secondary photoreaction (λ = 254 nm) the dihydrofurane 12 is isomerized to the bicyclic cyclopropyl compound 20 . Evidence is given that the products 11 and 13 are formed by solvent addition to an intermediate ketonium ylide b (s. Scheme 12). The presence of b is further proven by the formation of 12 , a product of an electrocyclization of b . On photofragmentation of b carbenoids d and e are presumably formed (s. Scheme 14). 1,2-Hydrogen shift in d yields the allene derivative 17 , and cyclization of d gives the cyclopropene compound 18 . On the other hand, e cyclizes to the non isolated cyclopropene compound 69 which is transformed to 16 by an intramolecular [4 + 2]-cycloaddition. The present investigation shows that the photochemistry of 5 is determined by photoinduced C,C-bond cleavage of the oxirane ring. This is in sharp contrast to the photochemistry of conjugated γ, δ-epoxy-enones without the additional double bond in ε, ζ-position, where selective photocleavage of the C(λ), O-bond is observed.     

Photochemical reactions. 144th Communication. Photochemistry of 5,6-epoxy-1,3-dienes in the ionone series: Influence of a methoxy group in position 7

On triplet excitation (λ > 280 nm, acetone), the epoxydiene (E)- 5 undergoes initial cleavage of the C(5)? O bond of the oxirane and subsequent cleavage of the C(6)? C(7) bond leading to the diradical intermediate e which reacts by recombination furnishing the cyclic compounds (E/Z)- 6 , (E/Z)- 7,8 , and 9 . Alternatively, a H -shift leads to the aliphatic methyl-enol ether 10 which undergoes a photochemical [2+2]-cycloaddition to compounds 12 and 13 , the main products on triplet excitation of (E)- 5 . On singlet excitation (λ = 254 nm, MeCN), (E)- 5 undergoes cleavage to the carbene intermediates f and g . The vinyl carbene f reacts with the adjacent double bond furnishing the cyclopropene 14 as the main product. From the carbene intermediate g , the methyl-enol ether 15 arises by carbene insertion into the neighboring C? H bond. Furthermore, the diastereomer of the starting material, the epoxydiene (E)- 16 , and compounds 17A+B are formed via the ylide intermediate h . Finally, the cyclobutene 18 is the product of an electrocyclic reaction of the diene side chain.     

Photochemical Reactions. 129th Communication. Photochemistry of a conjugated diepoxydiene: Product formation via carbonyl ylide and carbene intermediates with participation of neighbouring epoxy functions

On singlet excitation (λ=254 nm, acetonitrile) the diepoxydiene (E)- 7 undergoes photocleavage to the carbonyl ylide VII and the carbenes X and XI . The carbonyl ylide VII rearranges to the thermally labile dioxabicyclo [3.2.1]octene 20 or fragments via VIII to the aldehyde 9 and propyne. The carbene X , showing behaviour typical of vinyl carbenes, undergoes addition to the adjacent double bond furnishing the cyclopropene 11 . The carbene XI , however, undergoes an insertion reaction into the neighbouring oxirane C,C-bond leading to the oxetene (E)- 21 which can be isolated at ?78°, but at room temperature is rapidly transformed to the aldehyde 10 . On triplet excitation (acetone, λ>280 nm), however, (E)- 7 shows the typical behaviour of epoxydienes, undergoing C, O-cleavage of the oxirane and isomerization to 22, 23 and (E/Z)- 24 .     

Photochemical reactions. 143rd communication. Photochemistry of 5,6-epoxy-1,3-dienes in the ionone series. Influence of a hydroxy group in the 7-position

The synthesis and photolyses of the epoxydiene (E)- 5 are described. On triplet excitation (λ > 280 nm, acetone), (E)- 5 undergoes initial cleavage of the C(5) O bond leading to the intermediate c. Presumably an H-shift ( c → e ) followed by the fragmentation of the 1,4-diradical e leads (via the enol 37 ) to the diketones (E)- 6 and (Z)- 12 . Alternatively cleavage of the C(6) C(7) bond of c furnishes the diradical intermediate d which reacts by recombination leading to (E)- 13A + B, 16 , and 17A + B , or by an H-shift to the enol intermediate 38 . The latter undergoes an aldol-type reaction to (E/Z)- 14A + B and (E/Z)- 15A + B , as well as a photochemical [2 + 2]-cycloaddition to 18 . On singlet excitation (λ = 254 nm, MeCN), (E)- 5 undergoes photocleavage to the carbene intermediates f and g . The vinyl carbene f reacts with the adjacent double bond furnishing the cyclopropene 22 as the main product. From the carbene intermediate g , compounds 23, 24 , and 25 arise by carbene insertion into the neighboring C C or C H bond. Furthermore, the diastereomer of the starting material, the epoxydiene (E)- 20 , is formed via the ylide intermediate h .     

Photochemical reactions. 146th communication. Photochemistry of conjugated methano-epoxydienes: Participation of the neighboring cyclopropane ring in product formation via carbonyl ylide and carbene intermediates

On singlet excitation (λ = 254 nm, THF, pentane or hexane), the diastereoisomeric methano-epoxydienes (E)- 6 and (E)- 7 undergo interconversion and yield the products 8 – 11 . The main process is the cleavage of the oxirane ring to the vinyl carbene intermediate e which undergoes addition to the adjacent double bond furnishing the cyclopropene 8 . The alternative carbene intermediate f is evidenced by the formation of the cyclobutene 10 . For the fragmentation leading to 11 , the carbene f as well as the dipolar species h are considered as possible intermediates. On triplet sensitization (acetone, λ > 280 nm), (E)- 7 shows behavior typical of epoxydienes, undergoing fission of the C? O bond of the oxirane ring and isomerization to the compounds 13 , 14 and (E/Z)- 15 .     

Photochemische Reaktionen 130. Mitteilung. Zur Photochemie von 5,6-Epoxy-1,3-dienen: Der Einfluss eines 7-Hydroxysubstituenten auf die Carbenbildung

Photochemistry of 5,6-Epoxy-1,3-dienes: Influence of a 7-Hydroxy Substituent on the Carbene Formation On singlet excitation (λ=254 nm) in MeCN the hydroxy-epoxydiene (E)- 4 undergoes photocleavage to the carbene intermediates d and e as main processes. The carbene d , showing behaviour typical of vinyl carbenes, undergoes addition to the adjacent double bond furnishing the cyclopropenes 5A + B. The carbene e , however, undergoes an insertion reaction into the neighbouring carbinol C,H-bond leading to the enol intermediate 21 , which gives rise to the compounds 6A + B and 7A + B. To a lesser extent the products 8A + B are formed via another enol intermediate (32). On photolysis of (E)- 4 in MeOH instead of MeCN the enol intermediates 21 and 32 undergo rapid tautomerisation to the ketones 9A + B (main products) and 11.     

Photochemical reactions, 136th communication. Photochemistry of conjugated epoxyenones and dienes of the ionone series: Influence of a neighboring spiro-oxirane function

The preparation and photolyses of the diepoxyenones (E)- 8 and (E)- 9 as well as the diepoxydiene (E)- 10 are described. On ¹π,π^*-excitation (λ = 254 nm), the diastereoisomeric diepoxyenones (E)- 8 and (E)- 9 undergo isomerization via the ylide intermediate f and the carbene intermediate g leading to the primary photoproducts 17A and 18–21 (Scheme 8). On ¹n, π^*-excitation (λ > 347 nm), (E)- 8 shows behaviour typical of epoxyenones undergoing C(γ), O-bond cleavage of the oxirane and isomerization to compounds 22 , (E/Z)- 23 and (E)- 24 (Scheme 10). On singlet excitation, the diepoxydiene (E)- 10 , is cleaved to the carbonyl ylide j and the carbenes 1 and m (Scheme 11). The carbonyl ylide j fragments via the dipolar intermediate k to the acetylenic dienone (E)- 31 . The carbene 1 , showing behaviour typical of vinyl carbenes, furnishes the cyclopropene 30 . The alternative carbene m , however, undergoes an insertion reaction into the neighboring oxirane C,C-bond leading to the proposed but not isolated oxetene 43 , which is further transformed to the products 33A _ B by an intramolecular cycloaddition.     

Photochemische Reaktionen. 90. Mitteilung. Die UV.-Bestrahlung von (E)-5-Isopropyl-6-methyl-5,6-epoxy-hept-3-en-2-on

Photolysis of (E)-5-Isopropyl-6-methyl-5,6-epoxy-hept-3-en-2-on. This paper continues the series of investigations of the photochemistry of α, β-unsaturated γ, δ-epoxy-ketones, by examinating the photochemical behaviour of the aliphatic vinylogous epoxy-ketone 1 , the chromophore of which is structurally similar to that of γ, δ-epoxy-(E),β-ionone ( 44 ). On π, π*-excitation (λ = 254 nm) 1 isomerizes mainly to the enol-ether 2 and gives as minor products the isomeric dihydrofurane 3 , the 1,5-diketones 4 and 5 and the 1,3-diketone 6 . To a smaller extent, 1 also undergoes photofragmentation to the furane 7 , the allenyl-ketone 8 and the cyclopropenyl-ketone 9 . On n,π*-excitation (λ ≥ = 347 nm) 1 yields the photoisomers 3 , 4 , 5 and in traces the hydroxyallenyl-ketone 14 , but no fragmentation products. It is shown that on irradiation at λ ≥ = 254 nm the 1,5-diketone 4 isomerizes to 5 , 6 and 15 and photodecarbonylates to the β, γ-unsaturated ketone 16 . The isomers 3 , 4 and 5 , obtained both from n, π*- and π,π*-excitation, represent products of cleavage of the C(γ)? O-bond in 1 . The enolether 2 , on the other hand, formed only by π,π*-excitation, results from cleavage of the C(γ)? C(δ)-bond. Finally, the fragmentation products 7 , 8 and 9 , which could be detected only on π,π*-excitation, may arise from a common intermediate g ? h .     

Photochemische Reaktionen 122. Mitteilung [1]. Zur vinylogen β-spaltung von epoxy-enonen: Photoisomerisierung des 3,4:5,6-diepoxy-5,6-dihydro-β-jonons

Vinylogous β-Cleavage of Epoxy-enones: Photoisomerization of 3,4: 5,6-Diepoxy-5,6-dihydro-β-ionone On ¹n,π*-excitation (λ>347 nm), 3,4:5,6-diepoxy-5,6-dihydro-β-ionone ((E)- 3 ) shows the typical behaviour of α,β-unsaturated γ,δ-epoxy ketones furnishing the (Z)-enone 3 and by C(γ),O cleavage of the oxirane the dihydrofuryl ketone 10 and the cyclohexanones (E/Z)- 11 . However, on ¹π,π*-excitation an unexpected type of transformation is observed: (E)- 3 is isomerized to the four aliphatic triketones 5 – 8 as the main products. To a smaller extent the allene diketone 9 is formed by a known type of isomerization as well as (Z)- 3 . As the starting material for the preparation of (E)- 3 , the known epidioxy-enone (E)- 4 was used. In addition to (E)- 3 , (E)- 4 gives the aliphatic triketone 6 and the hydroxyenone 15 by thermal or catalytic isomerization.     

Photochemical reactions. 132nd communication. Photochemistry of 5,6-epoxy-5,6-dihydro-7-methyl-β-ionine: Influence of a methyl group at the enone side chain on the oxirane cleavage

¹n, π*-Excitation of the γ,δ-epoxy-enone (E)- 3 leads exclusively to the conformers (Z)- 3A + B . On ¹π, π*-excitation of (E)- 3 , in addition to (Z)- 3A + B , products 6–9 arising from a carbene intermediate e are formed. However, products of an isomerization via C(γ), O-bond cleavage of the oxirane were not formed on either mode of excitation. On thermolysis, at 80° the conformer (Z)- 3A is transformed into (Z)- 3B , which on photolysis returns to (Z)- 3A and (E) -3 . At 160°, however, (Z) -3B rearranges to the isomers 6, 10 and 11 .     

Photochemical reactions. 142nd communication. Photochemistry of a 6,7-epoxy-1,3-diene of the ionone series

On singlet excitation (λ = 254 nm), the epoxydiene (E)- 3 underwent (E)/(Z)-isomerization, electrocyclic ring closure of the diene side chain leading to the cyclobutenes 4A + B , and rearrangement to the cyclohexanones 5A + B . Compounds 5A + B were presumably formed in a series of processes including a 1,3-acyl shift of the homoconjugated ketone 8 , arising from (Z)- 3 by a 1,5-H-shift accompanied by cleavage of the C,O-bond of the oxirane.     

Photochemische Reaktionen 94. Mitteilung. Vinyloge β-Spaltung bei Epoxy-enonen der Jonon-Reihe

Photoinduced Vinylogous β-Cleavage of Epoxy-enones of the Ionone Series The photochemistry of the α,β-unsaturated γ,δ-epoxy-enones 1–3 is determined by: (i) C(γ)-O-scission of the epoxide (vinylogous β-cleavage of Type A); (ii) C(γ)-C(δ)-cleavage of the oxirane (vinylogous β-cleavage of Type B); (iii) (E/Z)-isomerization of the enone chromophore. In contrast, 4 with tertiary C(β) shows no Type B cleavage. Type A cleavage is induced both by n,π*- and π,π*-excitation and arises probably from the T₁-state, but Type B cleavage is observed only on π,π*-excitation and represents presumably a S₂-reaction. On Type A cleavage 1–4 undergo 1,2-alkyl-shifts to 1,5-dicarbonyl compounds ( 15–18, 25–28, 34 and 35 ) or rearrange to dihydrofuranes ( 7 and 30 ). The isomerization 1→7 proceeds by a stereoselective [1,3]-sigmatropic shift. On Type B cleavage 1–3 isomerize to a bicyclic enol-ether ( 8, 29 ) or to a monocyclic enol-ether ( 9 ; product of a homosigmatropic [1,5]-shift) or undergo fragmentation to isomers such as allenes 10, 22 and 31 or cyclopropenes 11 and 21 . The non-isolated, unstable (Z)-epoxy-enones 14, 19, 24 and 38 isomerize by fragmentation to the furanes 12, 23, 33 and 39 respectively, on contact with traces of acid or by heating. However, for 19 and 4 , Type B cleavage may lead to the furanes 23 and 39 . On UV. irradiation of the epoxy-enone 4 the initially formed (E/Z)-isomers 34 and 35 yield on π,π*-excitation the enones 37 and 40 by a vinylogous β-fragmentation. In addition, on n,π*-excitation 34 isomerizes to 35 , which decarbonylates exclusively to the enone 37 . The reactions of 1–4 with BF₃ · O(C₂H₅)₂ were also studied (see appendix). The epoxy-enones 1 and 2 isomerize by an 1,2-alkyl shift in good yield to the 1,4-dicarbonyl compounds 79 and 81 , whereas 3 gives the 1,4-diketone 83 , and in small amounts the 1,5-diketone 84 . On the other hand, 4 is converted to the fluorohydroxy-enone 85 and to the 1,5-dicarbonyl product 34 , the only isomer in this series which is identical with one of the photoproducts.     

Photochemische Reaktionen. 109. Mitteilung [1]. Zur Photochemie konjugierter δ-Keto-enone und β,γ,δ,ϵ-ungesättigter Ketone

Photochemistry of Conjugated δ-Keto-enones and β,γ,δ,?-Unsaturated Ketones On ¹π,π*-excitation the δ-keto-enones 5–8 are isomerized to compounds B ( 18 , 22 , 26 , 28 ) via 1,3-acyl shift and to compounds C ( 19 , 23 , 27 , 29 ) via 1,2-acyl shift, whereas the β,γ,δ,?-unsaturated ketone 9 gives the isomers 32 and 33 by 1,2-and 1,5-acyl shift, respectively. Furthermore, isomerization of 6 to 24 , dimerization of 8 to 30 and addition of methanol to 8 ( 8 → 31 ) is observed. Unlike 7 and 8 the acyclic ketones 5 , 6 and 9 undergo photodecarbonylation on ¹π,π*-excitation ( 5 → 20 , 21 ; 6 → 20 , 25 ; (E)- 9 → 35–38 ). Evidence is given, that the conversion to B as well as the photodecarbonylation of 5,6 and 9 arise from an excited singulet state, but the conversion to C as well as the dimerization of 8 from the T₁-state.     

Photochemische Reaktionen 111. Mitteilung [1] Zur Photochemie α, β-ungesättigter γ, δ-Epoxyester I: Singulett- versus Triplettreaktivität

On triplet excitation (E)- 2 isomerizes to (Z)- 2 and reacts by cleavage of the C(γ), O-bond to isomeric δ-ketoester compounds ( 3 and 4 ) and 2,5-dihydrofuran compounds ( 5 and 19 , s. Scheme 1). - On singulet excitation (E)- 2 gives mainly isomers formed by cleavage of the C(γ), C(δ)-bond ( 6–14 , s. Scheme 1). However, the products 3–5 of the triplet induced cleavage of the C(γ), O-bond are obtained in small amounts, too. The conversion of (E)- 2 to an intermediate ketonium-ylide b (s. Scheme 5) is proven by the isolation of its cyclization product 13 and of the acetals 16 and 17 , the products of solvent addition to b . - Excitation (λ = 254 nm) of the enol ether (E/Z)- 6 yields the isomeric α, β-unsaturated ε-ketoesters (E/Z)- 8 and 9 , which undergo photodeconjugation to give the isomeric γ, δ-unsaturated ε-ketoesters (E/Z)- 10 . - On treatment with BF₃O(C₂H₅)₂ (E)- 2 isomerizes by cleavage of the C(δ), O-bond to the γ-ketoester (E)- 20 (s. Scheme 2). Conversion of (Z)- 2 with FeCl₃ gives the isomeric furan compound 21 exclusively.     

Photochemische Reaktionen. 116. Mitteilung [1]. Notiz zur 1γ, δ*-induzierten Photospaltung von γ, δ-Epoxy-eucarvon

π, π*-Induced Photocleavage of γ, δ-Epoxy-eucarvone . On ¹π, π*-excitation 1 undergoes cleavage of the C, C-oxirane bond ( 1 → c ) and isomerizes to the bicyclic dihydrofurane compound 5 . In addition, 1 shows photocleavage of the C (γ), O-oxirane bond ( 1 → d ) and gives the isomers 2, 3, 6, 7 and 8. Furthermore, the cyclohexenone 9 and the cyclohexene-1, 4-dione 10 are formed presumably via an intermediate 13 , which could also arise from d. Besides these products the compounds 11 and 12 are obtained, which are photoproducts of 2 .     

Photochemische Reaktionen. 93. Mitteilung. Zur Photochemie konjugierter Epoxy-inone: Die UV.-Bestrahlung von 5,6-Epoxy-5-isopropyl-6-methyl-hept-3-in-2-on

The Photochemistry of Conjugated Epoxy-Inones: Photolysis of 5,6-Epoxy-5-isopropyl-6-methyl-hept-3-in-2-on This paper continues the series of investigations of the photochemistry of α,β-unsaturated γ,δ-epoxyketones by examining the hitherto unknown photochemical behaviour of α,β-acetylenic-γ,δ-epoxy-ketones. As model compound, the aliphatic epoxy-ynone 7 (thermally stable at 180°) was synthesized (Scheme 1). It can be converted with BF₃O (C₂H₅)₂ in good yields to the 1,5-diketone 8 , the yne-1,4-diketone 49 and in small amounts to the fluorhydrine 50 (Scheme 1). On n,π*- or π, π*-excitation, 7 shows mainly cleavage of the C (γ)-O-bond to give a diradical a (Scheme 11), whose ultimate fate is strongly solvent dependent. In acetonitrile a mainly rearranges to the 1,5-diketone 8 and, to a smaller extent, shows fragmentation to acetone and formation of polymers. Except for small amounts of the dimeric products 9A,9B and biphenyl, the same compounds are obtained in benzene. In cyclopentane, however, a gives only little of 8 , and mainly a plethora of compounds formed by a radical process like H-abstraction from solvent, incorporation of cyclopentylradicals, dimerization and fragmentation reactions (9A, 9B, 11–20) (Scheme 3). Irradiation of 7 in propan-2-ol or in dioxane yields products of analogous radical processes as well of photoreduction (Scheme 4). However, the analogous epoxyenone 32 gives mainly products of photoisomerizations without interference by the solvent [6]. On photochemical excitation in acetonitrile, the 1,5-diketone 8 shows unspecific decomposition, but in cyclopentane it yields the reduction products 12, 26A, 26B, 27, 28 plus cyclopentylcyclopentane (15) (Scheme 6).     

Ironcarbonyl Complexes of 5,6-Dimethylidene-7-oxabicyclo[2.2.1]hept-2-ene Derivatives. Synthesis of Substituted Tricarbonyl(ortho-quinodimethane)iron Complexes and 2-Indanones

The l-dimethoxymethyl-5,6-dimethyldene-7-oxabicyclo[2.2.1]hept-2-ene ( 9 ) has been prepared. On treatment with Fe₂(CO)₉, the endocyclic double bond C(2)?C(3) was coordinated first giving the corresponding exo-Fe(CO)₄ complex 10 . The latter reacted with Fe₂(CO)₉ and afforded cis-heptacarbonyl-μ-[1RS,2SR,3RS,4SR,5RS,6SR-2,3-η: C5,6,C-η-(1-(dimethoxymethyl)-5,6-dimethylidene-7-oxabicyclo[2.2.1]hept-2-ene)]diiron ( 11 ) as a major product. On heating, 11 underwent deoxygenation of the 7-oxabicyclo[2.2.1]heptene moiety yielding tricarbonyl[C,5,6,C-η-(1-(dimethoxymethyl)-5,6-dimethylidenecyclohexa-1,3-diene)]iron ( 13 ). In MeOH, a concurrent, regioselective methoxycarbonylation was observed giving tricarbonyl[C,3,4,C-η-(methyl 5-(dimethoxymethyl)-3,4-dimethylidenecyclohexa-1,5-diene-1-carboxylate)]iron ( 14 ). Oxidative removal of the Fe(CO)₃ moiety in 13 and 14 did not afford the expected ortho-quinodimethane derivatives but led to CO insertions giving 2,3-dihydro-2-oxo-1Hindene-4-carbaldehyde ( 20 ) and methyl 7-formyl-2-3-dihydro-2-oxo-lH-indene-5-carboxylate ( 21 ), respectively.     

Photochemische Reaktionen. 88. Mitteilung [1]. Zur Photochemie des Iso-methyl-β,(E)-jonon-epoxids

Photolysis of iso-methyl-β,(E)-ionone-epoxide On n, π*-excitation (λ ≥ 347 nm) the title compound 7 isomerizes to the (Z)-enone-epoxide 8 , which yields the bicyclic alkohol 9 in a second photochemical step. The photoisomerization 8 → 9 is a further example for the influence of a methyl substituent at C(α) of an enone-chromophore on the nature of the photochemical processes. On UV. irradiation in the presence of traces of hydrochloric acid 7 gives quantitatively the furane 10 .     

Acid-Catalyzed Rearrangements of 5,6-exo-Epoxy-7-oxabicyclo[2.2.1]hept-2-yl Derivatives. Migratory Aptitudes of Acyl vs. Alkyl Groups in Wagner-Meerwein Transpositions

In the presence of HSO₃F/Ac₂O in CH₂CL₂, 2-exo- and 2-endo-cyano-5,6-exo-epoxy-7-oxabicyclo[2.2.1]hept-2-yl acetates ( 6a , b ) gave products derived from the epoxide-ring opening and a 1,2-shift of the unsubstituted alkyl group (σ bond C(3)–C(4)). In contrast, under similar conditions, the 5,6-exo-epoxy-7-oxabicyclo[2.2.1]heptan-2-one ( 6c ) gave 5-oxo-2-oxabicyclo[2.2.1]heptane-3,7-diyl diacetates 20 and 21 arising from the 1,2-shift of the acyl group. Acid treatment of 5,6-exo-epoxy-2,2-dimethoxy-7-oxabicyclo[2.2.1]heptane ( 6d ) and of 5,6-exo-epoxy-2,2-bis(benzyloxy)-7-oxabicyclo[2.2.1]heptane ( 6e ) gave minor products arising from epoxide-ring opening and the 1,2-shift of σ bond C(3)–C(4) and major products ( 25 , 29 ) arising from the 1,3-shift of a methoxy and benzyloxy group, respectively. Under similar conditions, 5,6-exo-epoxy-2,2-ethylenedioxy-7-oxabicyclo[2.2.1]heptane ( 6f ) gave 1,1-(ethylenedioxy)-2-(2-furyl)ethyl acetate ( 32 , major) and a minor product 33 , arising from the 1,2-shift of σ bond C(3)–C(4). The following order of migratory aptitudes for 1,2-shifts toward electron-deficient centers has been established: acyl > alkyl > alkyl α-substituted with inductive electron-withdrawing groups. This order is valid for competitive Wagner-Meerwein rearrangements involving equilibria between carbocation intermediates with similar exothermicities.     

Photochemische Reaktionen. 85. Mitteilung [1]. Zur Photochemie von α, β-Epoxy-eucarvon

Photochemistry of α,β-epoxy-eucarvone . On π,π^*-excitation (λ = 254 nm) 4 isomerizes to the bicyclic ketoaldehyde 5 ; on n,π^*-excitation (λ ? 280 nm) 4 gives 5 , the β,γ-unsaturated ketone 6 , the enone 7 and the cyclobutanone 8 . Scission of the (C—C)-bond of the oxirane 4 would give the dihydrofurane e , which could isomerize to the ketoaldehyde 5 . On the other hand, 4 is assumed to isomerize to the β,γ-unsaturated aldehyde c , which could yield 6 and 7 by photodecarbonylation. The cyclo-butanone 8 is shown to be a photoisomer of the ketone 6 . Furthermore, eucarvol ( 18 ) rearranges by a thermal [1,5]-H-shift to dihydro-eucarvone ( 20 ); on UV.-irradiation 18 gives the bicyclic isomers 27 and 28 .