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 .     

Spezifisch π→π*-induzierte Reaktionen von γ-Dimethoxymethylcyclohexen-2-onen: 1,3-Umlagerung und Wasserstoffabstraktion durch das α-Kohlenstoffatom

When α,β-unsaturated γ-dimethoxymethyl cyclohexenones are excited to the S₂(π,π*) state, certain unimolecular reactions can be observed to compete with S₂ → S₁ internal conversion. These reactions do not occur from the S₁(n,π*) or the lowest T(π,π* and n,π*) states. They comprise the radical elimination of the formylacetal substituent (cf. 8 , 9 → 32 + 33 ), γ → α formylacetal migration (cf. 6 → 27 , 8 → 30 , 9 → 34 , 12 → 37 ), and a cyclization process involving the transfer of a methoxyl hydrogen to the α carbon and ring closure at the β position (cf. 6 → 28 , 8 → 31 , 12 → 38 , 20 → 40 + 41 ). The quantum yield of the ring closure 20a → 40a + 41a is 0.016 at ≤ 0.05M concentration. It is independent of the excitation wavelength within the π→π* absorption band (238–254 nm), but Φ ( 40a + 41a ) decreases at higher concentrations. According to the experimental data the reactive species of these specifically π→π*-induced transformations is placed energetically higher than the S₁(n,π*) state, and it is either identical with the thermally equilibrated S₂(n,π*) state, or reached via this latter state. The linear dienone 14 undergoes a similar π→π*-induced cyclization (→ 42 ) whereas the benzohomologue 26 proved unreactive, and the dienone 22 at both n → π and π→π* excitation only gives rise to rearrangements generally characteristic of cross-conjugated cyclohexadienones.     

Photochemische Reaktionen 49. Mitteilung [1] Spezifisch π → π*-induzierte Keton-Photoreaktionen: Die Doppelbindungsverschiebung von O-Acetyl-10α-testosteron Protonisierung der Doppelbindung seines δ5-Isomeren

The α,β-unsatured ketone 10α-testosterone has been reported previously [6] to photoisomerize in t-butanol solution to the β,γ-unsaturated ketone. The irradiation had been carried out using a high-pressure mercury lamp in a quartz vessel. For structural reasons this double bond shift cannot proceed through a photoenolization mechanism involving an intramolecular hydrogen transfer from the γ-position to the enone oxygen as has been suggested to operate in several formally analogous cases of aliphatic enone isomerizations. In the present reinvestigation, O-acetyl 10α-testosterone ( 1 ) was used, employing selectively either excitation of its n → π* (with wavelengths > 300 nm) or its π → π* absorption band (with 253,7 nm). In t-butanol solution the doublebond shift 1 → 2 could be effected with π→* excitation only. Experiments in deuterated solvent (t-BuOD) resulted in deuterium in corporation in both the δ5-ketone in the C(4)-position, cf.( 3 ) and in the conjugated ketone. These results indicate that the reactions is initiated either in the, S_π,π* state or in a high vibrational mode of the S₀ or t_ππ*state. n→ π* Excitation of 1 in t-butanol gave essentially no over-all chemical change, while in benzene solution it resulted again in a double bond isomerization ( 1 → 2 ). In analogy to results with similar enones [28] under identical conditions the deconjugation in benzene may be the consequence of an intermolecular hydrogen abstraction of the T_n,π* excited state of the enone. Another specifically π →π* induced photoreaction was observed on irradiation of the β, γ-unsaturated ketone 2 in t-BuOD with 253,7 nm. The olefinic hydrogen at C-6 of 2 was exchanged with deuterium and, to a small extent, isomerization to the conjugated ketone 1 with concomitant deuterium incorporation occurred. It is concluded that from the higher excited state of the β, γ-unsaturated ketone, but not from its S_n,π* state, an activation mode of the double bond is accessible to effect D+ addition at C-6 followed by deprotonation to 4 and to deuterated 1 , respectively.     

Photochemische Reaktionen. 106. Mitteilung. Zur Photochemie tetraalkylsubstituierter γ-Keto-olefine

The Photochemistry of Tetraalkyl Substituted γ-Keto-olefines The photochemistry of 7,8-dihydro-β-ionone ( 1 ) in solution is shown to depend on temperature, polarity and viscosity of the solvent. UV. irradiation (λ ≥ 245 nm) in pentane at +25° converts 1 to the isomeric ethers 3 (16%), 5A (48%) and 5B (22%), whereas at ?65° 7,8-dihydro-γ-ionone ( 26 ) is obtained in 12% yield together with 13% of 3 , 12% of 5A and 9% of 5B . The ¹n,π*-excitation of 1 in acetonitrile gives similar results. In the more viscous 1,2,3-triacetoxypropane the photoisomerization 1 → 26 takes place even at + 60° (10% yield, cf. 40% at ?15°). In alcoholic solvents, however, no formation of 26 is detected, but the hitherto unknown [2+2]-photocycloaddition 1 → 11 can be observed (4% at ?7°, 15% at ?65S° in 2-propanol). An intermediate e may be involved (Scheme 14). In addition to the photoreactions 1 → 3, 5A, 5B and 11 the isomerization of 1 to the novel spirocyclic ketone 28 takes place in alcoholic solvents only. Photoisomerization 1 → 3 is presumably a photo-ene process involving a stereoselective intramolecular H-transfer. This type of photoisomerization is restricted to cyclic γ-keto-olefines. The tetraalkylated acyclic γ-keto-olefines 14 and 15 photoisomerize exclusively by [2+2]-cycloaddition, independent of the solvent. On ¹n,π*-excitation the δ,?-unsaturated bicyclic ketone 44 undergoes Norrish-Type-II photofragmentation to the diene 45 or isomerizes to the γ, ?-unsaturated ketone 17 . Competition between these two reactions is strongly temperature dependent: photolysis in pentane at ?72° yields quantitatively 45 , whereas at + 35° only 30% of 45 and 68% of 17 are obtained. UV. irradiation of the novel spirocyclic ketone 28 gives as primary photoproduct the isomeric aldehyde 29 , and in a secondary photoreaction the isomeric oxetanes 30A and 30B . Experiments with deuteriated substrates show that the isomerization of type 28 → 29 is stereocontrolled.     

Photochemische Reaktionen. 103. Mitteilung [1]. Zur Photochemie konjugierter Epoxy-en-carbonylverbindungen der Jonon-Reihe: UV.-Bestrahlung α,β-ungesättigter ε-Oxo-γ, δ-epoxy-carbonylverbindungen und Untersuchung des Mechanismus der Epoxy-enon/Furan-Isomerisierung

The Photochemistry of Conjugated γ,δ-Epoxy-ene-carbonyl Compounds of the Ionone Series: UV.-Irradiation of α,β-Unsaturated ε-Oxo-γ,δ-epoxy Compounds and Investigation of the Mechanism of the Isomerization of Epoxy-enones to Furanes On ¹n, π*-excitation (λ ≥ 347 nm; pentane) of the enonechromophore of 3 , three different reactions are induced: (E/Z)-isomerization to give 13 (7%), isomerization by cleavage of the C(γ)–C(δ) bond to yield the bicyclic ether 14 (36%) and isomerization by cleavage of the C(γ)? O bond to give the cyclopentanones 15 (13%) and 16 (11%; s. Scheme 2). On ¹π, π*-excitation (λ = 254 nm; acetonitrile) 13 (14%), 15 (6%), and 16 (6%) are formed, but no 14 is detected. In contrast, isomerization by cleavage of the C(δ)? O bond to give the cyclopentanone 17 (23%) is observed. The reaction 3 → 17 appears to be the consequence of an energy transfer from the excited enone chromophore to the cyclohexanone chromophore, which then undergoes β-cleavage. Irradiation of 4 with light of λ = 254 nm (pentane) yields the analogous products 20 (18%), 21 (9%), 22 (7%), and 24 (7%; s. Scheme 2). Selective ¹n, π*-excitation (λ ≥ 280 nm) of the cyclohexanone chromophore of 4 induces isomerization by cleavage of the C(δ)? O bond to give the cyclopentanones 23 (9%) and 24 (44%). Triplet-sensitization of 4 by excited acetophenone induces (E/Z)-isomerization to provide 20 (12%) and isomerization by cleavage of the C(δ)? O bond to yield 21 (26%) and 22 (20%), but no isomerization via cleavage of the C(δ)? O bond. It has been shown, that the presence of the ε;-keto group facilitates C(γ)? C(δ) bond cleavage to give a bicyclic ether 14 , but hinders the epoxy-en-carbonyl compounds 3 and 4 from undergoing cycloeliminations. The activation parameters of the valence isomerization 13 → 18 , a thermal process, have been determined in polar and non-polar solvents by analysing the ¹H-NMR. signal intensities. The rearrangement proceeds faster in polar solvents, where the entropy of activation is about ?20 e.u. Opening of the epoxide ring and formation fo the furan ring are probably concerted.     

Specifically π→π* Induced Photoreactions of α,β-Unsaturated Ketones: Hydrogen Abstraction by the α-carbon. (Preliminary Communication)

Irradiations at 254 nm of the α,β-unsaturated γ-dimethoxy-methyl ketone 7 in iso-octane and t-butyl alcohol afforded in a specifically π→π*induced process and in high chemical yield the epimeric products 9 and 10 . These products were not formed on n→π* excitation of 7 at > 340 nm, but triplet energy transfer to 1,3-cyclohexadiene could be observed. Photolyses of the hexadeuterio analog 7-d₆ at 254 nm led to the fully deuteriated products (cf. 9-d₆ ) in both solvents, with stereospecific incorporation of a deuterium atom in position C(1α). The structures of 9 and 10 were determined by an X-ray diffraction analysis of 9 and chemical correlations of the two products. The structural constraints in 7 demand a hitherto unprecedented direct transfer of a methoxyl hydrogen to the α-carbon of the excited enone and formation of intermediate 8 .     

Photochemical reactions. 141st communication. Photochemistry of α,β-unsaturated δ,ϵ-epoxyketones of the ionone series

On n,π*- as well as on π,π*-excitation, the 4,5-epoxy-α-ionones (E)- 1 , (E)- 2 , and (E)- 3 undergo (E)/(Z)-isomerization and subsequent γ-H-abstraction leading to the corresponding 4-hydroxy-β-ionones (E/Z)- 9 , (E/Z)- 13 , and (E/Z)- 17 as primary photoproducts. On photolysis of (E)- 3 , as an additional primary photoproduct, the β,γ-unsaturated σ,?-epoxy ketone 18 was obtained. The other isolated compounds, namely the 2H-pyrans 10A + B and 14A + B as well as the retro γ-ionones 11 and 15A + B , represent known types of products, which are derived from the 4-hydroxy-β-ionones (E/Z)- 9 and (E/Z)- 13 , respectively.     

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.     

The electronic structure and optical activity of conjugated dienes: 1,3-Butadiene and α- and β-phellandrene

The optical activity of conjugated dienes is investigated by means of ab initio SCF–CI calculations. The computed electronic spectrum of trans-1,3-butadiene is shown to be in good agreement with the results of more rigorous calculations of the valence transitions and in satisfactory agreement with experiment. The optical rotatory strengths of the lower electronic transitions of twisted 1,3-butadiene as a function of dihedral angle are presented and simulated CD spectra are produced. The N → V₁ (π₂ → π₃*) transition is predicted to have a positive rotational strength for all dihedral angles that correspond to a right-handed twist of the chromophore, in accord with the empirically deduced “diene rule” although for a twist angle of 60°, the rotatory strength is calculated to be almost zero. The role of the orientation of allylic bonds is investigated in the model system 1-butene in which the rotational strength of the π → π* transition as a function of rotation about the 2,3 bond is determined. The effect of allylic bond disposition in dienes on the optical activity of the long-wavelength π₂ → π₃* transition is simulated by use of the exciton coupling model of Harada and Nakanishi in which two 1-butene molecules with suitable geometries are coupled via interactions of the electric dipole transition moments of their π → π* transitions. The model systems 1,3-butadiene and 1-butene are used to rationalize the apparently anomalous optical activity of (?)-α-phellandrene and (?)-β-phellandrene, both of which should have a diene chromophore with a right-handed twist in their most stable conformers and so should be dextrorotatory. The experimental CD spectrum of α-phellandrene is determined at several temperatures down to ?180°C. The observed variation of the apparent rotational strength of the N → V₁ transition is in good agreement with that predicted by use of the exciton coupling model.     

Photochemische Reaktionen. 65.(vorläufige) Mitteilung. Spezifisch π → π*-induzierte Photoisomerisierungen von 10-Dimethoxymethyl-Δ1,9-octal-2-on. Ein photochemischer Zugang zu [4.4.3]-12-Oxapropellan-Derivaten

Selective n → π* excitation of the α,β-unsaturated enone 1 in hydrocarbon solvents resulted in a deconjugation reaction to 3 , reminiscent of results previously reported for similar systems [2], whereas the photoreactivity of 1 in alcohol solvents at wavelengths >3400 Å was so small that only product 4 has been identified as yet. Excitation of the π → π* transition of compound 1 at 2537 Å initiated additional phototransformations which could not be effected by irradiation in the first absorption band. The [4.4.3]-12-oxapropellane derivative 2 was identified as one of the two new major photo-isomers. A 6:8 mixture of products 2 and 3 , plus about 1 part of an isomer of still unknown structure (see however, the Addendum), were readily formed in hydrocarbon solvents, and a 1:10 ratio of 2 and the unknown product was obtained in methanol. Abstraction of a methoxyl hydrogen by the ketone oxygen is proposed to account for the primary photochemical step in the cyclization to 2 . A hydrogen-deuterium isotope effect of 2.7 was observed in a competitive experiment using 1 and 1-d _6. 34% of one deuterium atom were exchanged for hydrogen when 1-d ₆ was photolyzed to 2-d ₆ in t-butyl alcohol, which suggests an intermediate of type a in the pathway 1 → 2 possessing a readily exchangeable proton. Steric considerations would require a strongly distorted, non-planar excited-state geometry of the enone group of 1 for the oxygen to approach a methoxyl hydrogen. The transformation 1 → 2 represents a novel reaction type in photochemical processes of conjugated enones which are specifically induced by π → π* excitation only.     

Photochemische Reaktionen. 110. Mitteilung [1]. Zur Photochemie γ,δ-Methano-α-enone

Photochemistry of γ,δ-Methano-α-enones Direct excitation (λ = 254 or ≥ 347 nm) converts the γ,δ-methano-α-enone (E)- 10 into the isomeric ether 23 and the isomeric diene-ketone 24 . Furthermore, on ¹π,π*-excitation (λ = 254 nm) (E)- 10 undergoes an 1,3-homosigmatropic rearrangement yielding the enone (E)- 25 . In addition (E → Z)-isomerization of (E)- 10 and conversion of 10 to the isomeric furan 28 is observed. The isomerization (E)- 10 → 23 , 24 and (E)- 25 proceeds by photocleavage of the C(γ), C(δ)-bond, whereas the formation of 28 occurs by photocleavage the C(γ), C(δ)-bond together with that of the C(γ), C(δ′)-bond of 10 . On direct excitation the bicyclic diene-ether 23 yields the methano-enone 10 , the dieneketone 24 and the tricyclic ether 29 . Evidence is given, that the conversion 23 → 10 is a singulet process. On the other hand, the isomerization 23 → 24 and the intramolecular [2 + 2]-photocycloaddition 23 → 29 are shown to be triplet reactions. Irradiation (λ = 254 nm) of the homoconjugated ketone 24 yields the isomeric ketone 27 by an 1,3-acyl shift. The excitation of the (E)-enone 25 induces (E → Z)-isomerization and photoenolization to give the homoconjugated ketone 26 .     

Photochemische Reaktionen. 112. Mitteilung [1] Zur Photochemie α, β-ungesättigter γ, δ-Epoxyester. III. Ergänzende Untersuchungen zur Triplettreaktivität

On triplet sensitization (E)- 5 gives (Z)- 5 and isomerizes via C(δ), O-bond cleavage to the cyclobutanone 6 and the conjugated γ-ketoester 7 . - On singulet excitation 6 undergoes decarbonylation and yields the bicyclo [4.1.0]heptane 8 . However, on triplet sensitization 6 is converted to the isomeric tricyclononane 9 by a stereospecific oxa-di-π-methane rearrangement. The structure of 9 is determined by X-ray analysis of the p-nitrobenzoate 15: a = 10.573, b = 14.707, c = 13.494 Å, β = 112.40°, P2₁/n, Z, = 4.     

Photochemische Reaktionen 119. Mitteilung [1] Zur Photospaltung konjugierter γ,δ-Epoxyenone. UV.-Bestrahlung von 3-(1′,2′-Epoxy-2′-methyl-prop-1′-yl)-5,5-dimethyl-2-cyclohexen-1-on

Photocleavage of Conjugated π,π-Epoxyenones. UV.-Irradiation of 3-(1′,2′-Epoxy-2′-methyl-prop-1′-yl)-5,5-dimethyl-2-cyclohexene-1-one On ¹π,π*-excitation (δ = 254 nm) 9 undergoes cleavage of the C(δ), C(δ)-bond yielding 17 and a , which gives 18 by photofragmentation. In presence of maleinic ester the photolysis of 9 yields 20 , in presence of methanol 21 and 22 are obtained. By photocleavage of the C(δ), O-bond 9 is converted into b giving 14 . Photolysis of 14 yields 15 ( A + B ) and 16 . On ¹n,π*-excitation (δ λ? 347 nm) of 9 cleavage of the C(δ), O-bond ( 9 → b ) seems to be the preferred reaction, whereas products of a are formed in traces, only.     

Selective Population of the n, π* and π, π* Triplet States of 1-Indanones

The two components of the dual phosphorescence of 1-indanone ( 1 ) and six related ketones ( 2–7 ) possess different excitation spectra exhibiting the vibrational progression characteristic of the S₀ → S₁ (n, π*) transition (shorter-lived emission) and two bands of the S₀ → S_{2 and 3} (π,π*) 0–0 transitions, respectively. The most favorable intersystem crossing routes are S₁ (n, π*) → T (n, π*) and S_2,3 (π*) → T (π, π*). Internal conversion to S₁ competes more effectively with S (π, π*) → T (π, π*) intersystem crossing only from higher vibrational levels of the S₂ and S₃ states.     

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. 121. Mitteilung. Zur Photochemie von ε,ζ-Methano-α,γ-dienonen und 7,8-Methano-1,3,5-trienen

Photochemistry of ε,ζ-Methano-α,γ-dienones and 7,8-Methano-1,3,5-trienes Irradiation of the δ-cyclopropyl-dienone (E)- 6 (λ ≥ 347 nm) gives (Z)- 6, 10 (1,5-sigmatropic H-shift), (E/Z)- 9 (electrocyclic process involving C(ε), C(ζ)-cleavage) and 11 (ring opening). The corresponding 6-cyclopropyl-triene (E)- 7 gives on singlet excitation (δ > 280 nm) 14 (1,5-sigmatropic H-shift) and, to a smaller extent, the bicyclo [3.2.0] heptenyl-dienes (E/Z)- 13 . However, on triplet excitation (λ ≥ 347 nm, benzophenone) (E)- 7 gives (E/Z)- 13 as the main products. On both ¹π,π*- and ³π,π*-excitation, (Z)- 7 and 15 are formed in small amounts.     

Photochemische Reaktionen 115. Mitteilung [1]. Zur Photochemie konjugierter γ,δ-Epoxyenone: Der Einfluss eines Hydroxylsubstituenten in ϵ-Stellung

Photochemistry of Conjugated γ,δ-Epoxyenones: The Influence of a Hydroxy Substituent in ?-Position On ¹n, π*- or ¹π,π*-excitation (λ ≥ 347 or λ=254 nm), the ?-hydroxy-γ;,δ-epoxyenone 8 undergoes fission of the C(γ)? O bond followed by the cleavage of the C(δ)-C(?) bond. This hitherto unknown sequence of reactions is evidenced by the structure determination of the new type products 10–17 and 25 , including a synthetic proof for 12 and the X-ray analysis of 11 (X-ray data: triclinic P1; a=7,386(2), b=8,904(4), c=9,684(5)Å; α=82,29(4)°, β=74,46(3)°, γ=82,29(3)°; Z=2). The selective ¹π,π*-excitation also induces competitive C(γ)-C(δ) bond cleavage to yield the bicyclic acetal 18 and a ketonium-ylide intermediate a , which photochemically forms a carbene b giving the allene 19 and the cyclopropene 20 . On ¹n,π*-excitation of the acetate 9 the initial C(γ)-O bond fission is, in contrast to the behaviour of the corresponding alcohol 8 , followed by a 1,2-methyl shift affording (E/Z)- 28 or by a cyclization-autoxidation process yielding the lactone 29 .     

Photochemische Reaktionen. 52. Mitteilung [1]. Zur Photochemie von α,β-ungesättigten cyclischen Ketonen: Spezifische Reaktionen der n,π*- und π,π*-Triplettzustände von O-Acetyl-testosteron und 10-Methyl-Δ1,9-octalon-(2)

The photochemistry of the conjugated cyclohexenones O-acetyl testosterone ( 1 ) and 10-methyl-Δ^1,9-octalone-(2) ( 24 ) has been investigated in detail. The choice of reaction paths of both ketones depends strongly on the solvent used. In t-butanol, a photostationary equilibrium 1 ? 3 is reached which is depleted solely by the parallel rearrangement 1 → 5 (Chart 1; for earlier results on these reactions see [2a] [6] [7]). In benzene, double bond shift 1 → 16 (Chart 3) occurs instead, which is due to hydrogen abstraction from a ground-state ketone by the oxygen of an excited ketone as the primary photochemical process. In toluene, the major reaction is solvent incorporation ( 1 → 17 , Chart 4) through hydrogen addition to the β-carbon of the enone, accompanied by double bond shift and formation of saturated dihydroketone as the minor reactions. Contrary in part to an earlier report [19], the photochemical transformation of the bicyclic enoné 24 exhibit a similar solvent dependence. The corresponding products 25 – 29 are summarized in Chart 5 and Table 1. Sensitization and quenching experiments established the triplet nature of the above reactions of 1 and 24 . Based on STERN -VOLMER analyses of the quenching data (cf. Figures 2, 4–8, and Table 3), rearrangement, double bond reduction and toluene addition are attributed to one triplet state of the enones which is assigned tentatively as ³(π, π*) state, and the double bond shift is attributed to another triplet assigned as ³(n, π*) state (cf. Figure 9). The stereospecific rearrangement of the 1α-deuterated ketone 2 to the 4β-deuterio isomer 4 shows the reaction to proceed with retention at C-1 and inversion at C-10. The 4-substituted testosterone derivatives 33 – 36 (Chart 8) were found to be much less reactive in general than 1 . In particular, 4-methyl ketone 33 remains essentially unchanged on irradiation in t-butanol, benzene and toluene.     

Photochemische Reaktionen. 97 Mitteilung [1]. Zur Photochemie konjugierter Epoxy-diene II. Versuche mit (E)-β-Jonyliden-epoxiden

Photolysis of Conjugated Epoxy-dienes Direct and sensitized excitation of the (E)-β-ionylidene-epoxides 1 and 4 leads to different types of isomerizations. Thus photocycloelimination to the cyclopropene-ketones 2 and 6 is only achieved by ¹(π, π*)-excitation (λ=254 nm), whereas ³(π, π*)-excitation (λ > 280 nm, acetone) gives selective C(1′), O-cleavage of the oxirane ( 1 → 7 – 10 and 4 → 11 – 13 ). In contrast to 1 the twofold methylsubstituted epoxy-diene 4 shows mainly (E/Z)-isomerization ( 4 → 5 ) on both ¹(π, π*)- and ³(π, π*)-excitation while the isomerizations 4 → 6 and 4 → 11 – 13 are minor processes, only.     

Photochemische Reaktionen. 44. Mitteilung [1]. Zur Photochemie von gesättigten β-Ketosulfiden

Ultraviolet irradiation of the saturated β-ketosulfides 6 and 7 (direct n → π* excitation) in benzene and methanol solutions resulted mainly in the selective α-cleavage of the bond between C?O and C_α-S, producing ketenes by the well known hydrogen transfer as secondary reactions. Depending upon the availability of internal and/or external nucleophiles, the compounds 8 , 9 , 10 and 11 were formed as major products. The high yields in some of these light-induced transformations open an attractive synthetic approach to new heterocompounds.