Photochemische Reaktionen. 117. Mitteilung [1] Zur Photochemie von 5,6-Epoxydienen und konjugierten 5,6-Epoxytrienen

Photochemistry of 5,6-Epoxydienes and of Conjugated 5,6-Epoxytrienes On singulet excitation (δ = 254 nm) the 5,6-epoxydiene 6 and the conjugated 5,6-epoxytrienes 7 and 8 exclusively give products arising from cleavage of the C, C-bond of the oxirane (cf. 6 → 9 , 10 , 11 ; 7 → (E)- 15 , 16 , 17 ; 8 → 18 (A+B) , 19 (A+B) , 20 , 21 ). The dihydrofuran compounds 11 and (E/Z)- 15 are formed by cyclization of a ketonium-ylide a and d , respectively. Photolysis of a gives the carbene b which yields the cyclopropene 9 , whereas d forms photochemically the carbenes f and g which yield the methano compounds 16 and 17 . The isomeric cyclopropene derivatives 20 and 21 are products of the intermediates h and i , respectively, which are formed by photolysis of the ylide e . The cyclopropene 21 isomerizes by intramolecular cycloadditions to 18 (A+B) and 19 (A+B) . - On triplet excitation (λ?LD nm; 280 nm; acetone) 6 undergoes cleavage of the C(5), O-bond and isomerizes to 12 and 14 . However, 7 is converted by cleavage of the C, C-bond of the oxirane to yield 15 . On treatment with BF₃O(C₂H₅)₂ 6 gives 14 , whereas 7 yields 22 , and 8 forms 23 and 24 .     

Photochemische Reaktionen. 95. Mitteilung. Zur Photochemie konjugierter Epoxy-enone: Die UV.-Bestrahlung von 9-Isopropyl-6-methyl-9, 10-epoxybicyclo [4.4.0] dec-1-en-3-on

The Photochemistry of Conjugated Epoxy-enones: Photolysis of 9-Isopropyl-6-methyl-9,10-epoxybicyclo [4.4.0]dec-l-en-3-on The title compound 1 undergoes on π, π*-excitation vinylogous β-cleavage of the C(γ), O-bond and isomerizes to the unsaturated 1, 5-diketone 8 (58%) and the tricyclic diketone 9 (14%). On n, π*-excitation, however, 1 undergoes only desoxygenation to the dienone 7 (ca. 15%) besides polymerization. UV.-irradiation of 1 (λ ≥ 347 nm) in the presence of tributyl-stannane gives 7 in 85% yield; in the presence of tributylstannane-d₁ 1 yields 13 , the deuterated analogon of 7 (85% yield; d₁ ca. 50%); 7 has been proven to be stable on π, π* - as well as on n, π*-excitation.     

Photochemische Reaktionen. 53. Mitteilung [1]. Photochemische Addition von Alkylaromaten an Aryl-Carbonylverbindungen

In the preceding paper [1] a novel primary photochemical process of triplet excited α,β-conjugated cycloalkenones in toluene solution has been reported: the abstraction of a benzylic hydrogen from the solvent by the β-carbon (cf. 1 → 2 + 3 + 4 ). The reaction has been attributed to the π,π* triplet. Aromatic aldehydes and ketones ( 5–11a ), the triplet state reactivity of which is known to be mostly π,π* in nature, have now been examined under the same irradiation conditions. However, a reaction similar to that of cycloalkenones — expected to result in the addition of hydrogen to the ortho and para positions of the aryl moiety and the formation of benzylcyclohexa-1,3-and 1,4-diene derivatives — could not been found. Compounds 5 – 10 remained essentially unchanged. 4-Methoxyacetophenone ( 11a ) reacted slowly to form the same type of products [tert-carbinol 12a , pinacol 13a and dibenzyl ( 4 )] as the aromatic carbonyl compounds 11b-d , benzophenone and cyclopropylphenylketone, which exhibit typical n,π* triplet reactivity (hydrogen abstraction by the carbonyl oxygen).     

Substituierte 9-Oxabicyclo[4.2.1]- und 9-Oxabicyclo[3.3.1]nonane III. neue ergiebige synthese von 2, 7-dioxatwistan und endo-2-hydroxy-9-oxabicyclo[3.3.1]nonen-(6)

Iodine cleavage of the [3.3.1]-iodomercuri compound 4 , easily prepared from cis, cis-cyclooctadiene-(1,5) by oxymercuration of the monoepoxide 1 (→ 3 ) followed by treatment with potassium iodide, leads to three isomeric iodides 6, 7 , and 8 , the [3.3.1]-exo-iodo isomer 8 being the predominant product. Intramolecular substitution in 8 opens an attractive new route to unsubstituted 2,7-dioxatwistane ( 19 ) [2], whereas dehydrohalogenation of 7 and 8 yields the unsaturated alcohol 17 [2], a suitable starting material for the preparation of substituted 2,7-dioxatwistanes [2], 2,7-dioxaisotwistanes ( e ) [2], and 2,8-dioxa-homotwistbrendanes ( f ).     

Substituted 9-Oxabicyclo[4.2.1]- and 9-Oxabicyclo[3.3.1]nonanes (Part II)

The preparation, isolation, structure determination, and some reactions of the two stereoisomers of 2-iodo-9-oxabicyclo[4.2.1]nonane ( 9 and 10 ) and of 2-iodo-9-oxabicyclo[3.3.1]-nonane ( 11 and 12 ), respectively, are described. Iodine cleavage of the [4.2.1]-iodomercuri compound 3 yielded the iodides 9, 10 , and 11 , and iododemercuration of the [3.3.1]-iodomercuri compound 6 afforded the iodo compounds 9, 11 , and 12 , respectively. Direct treatment of 4-cycloocten-1-ol ( 1 ) with iodine in chloroform resulted in the exclusive formation of the two endo-iodides 9 and 11 . Raney nickel treatment as well as lithium aluminium hydride reduction of each índividual iodo compound 9, 10, 11 , and 12 gave the corresponding unsubstituted 9-oxabicyclononane ( 4 or 8 , respectively) with the unaltered skeleton. No rearrangement products could be observed. An oxonium ion is involved as an intermediate in the reaction of the endo-iodides 9 and 11 with silver acetate leading to an identical mixture of the two acetates 15 and 16 as well as in the isomerization of 9 to 11 .     

Photochemische Reaktionen. 62. Mitteilung [1]. Die Photofragmentierung von O-acetyljervin

On ultraviolet irradiation O-acetyljervine ( 1 ) is subjected to several parallel fragmentations. From the complex reaction mixtures obtained in a variety of solvents (dioxan, tetrahydrofuran, acetonitrile, iso-octane, benzene) the major alicyclic products 6 – 8 and the heterocyclic compounds 12 – 16 have been isolated. Products 6 – 8 undergo further photochemical changes, e.g., decarbonylation of 7 to 9 and hydrolytic cleavage of 8 to 10 . These photofragmentations are initiated almost specifically upon selective π → π* excitation at 2537 Å with a quantum yield of Φ²⁵³⁷ = 0.145 for conversion of starting material. Reaction upon irradiation in the long-wavelength n → π* absorption band is very much less efficient (Φ³⁶⁶⁰ = 0.611 · 10^?3, both determinations for O-trimethylsilyl-jervine ( 2 ) in tetrahydrofuran). A high degree of photostability is observed also at 2537 Å on N-protonation of O-acetyljervine ( 1 ) in acetic acid. Furthermore, reactivity is greatly reduced for the N-methyl ( 3 ) and N-acetyl ( 4 ) derivatives in neutral solvents at 2537 Å. N-Chloro-O-acetyljervine ( 5 ) in dioxan at 2537 Å gave preferentially O-acetyljervine hydrochloride.     

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).     

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.     

Photochemische Reaktionen. 39. Mitteilung. Photochemische Umwandlungen von endo-Tricyclo[4.3.12,5.0]-decadien-(3,8)-dion-(7,10) und cis-8, 9-Dihydroindenon

In boiling xylene the cyclopentadienedione 1 is thermally decarbonylated to cis-8,9-dihydroindenone ( 8 ). This method avoids secondary reactions and allows the preparation of 8 in high yield.     

Synthesis of N-arylmethyl-3-azabicyclo[3.3.1]nonan-9-ones

Russian Journal of Organic Chemistry -     

Photochemische Reaktionen. 43. Mitteilung [1]. UV.-Bestrahlung von N-Phenylurethan und N-Phenylthiourethan

Ultraviolet irradiation of N-phenylurethane (I) solutions with wavelength 253,7 nm resulted in the formation o polymeric material, the characteristic pattern of monomeric products associated with Photo-FRIES -type rearrangements [→ ethyl anthranilate (II), ethyl p-aminobenzoate (III)], and accompanying dissociation products [→ aniline (IV)]. N-Phenylthiourethance (V) showed no tendency to undergo Photo-FRIES -type rearrangements. Formation of polymeric material and aniline (IV), and in the presence of molecular oxygen, cyclodehydrogenation to the 2-ethoxy-benzthiazol (VI) as well as a ready exchange of the sulfure atom in V by oxygen occurred instead.     

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 .     

Structure elucidation with lanthanide induced shifts. 9. bicyclo[3.3.1]nonan-9-one

Lanthanide shift reagents have been used for the conformational analysis of bicyclo[3.3.1]-nonan-9-one. Comparison of predicted shifts and experimental values obtained with Eu(fod)₃ indicate that the boat-chair conformation constitutes 22% of the mixture of conformers.     

Photochemische Reaktionen. 48. Mitteilung [1]. Photolytische Substitutionen von Aromaten mit α-Sulfonyloxyketonen. Vorläufige Mitteilung

Photo-excited arenes have been found to initiate a substitution reaction in which the sulfonyloxy group of α-sulfonyloxyketones is displaced, and the corresponding β-arylketones are formed. Evidence is presented that the electronically excited arene need not be involved directly in the substitution step. It would seem to be more likely that upon interaction with the sulfonyloxyketone a reactive species derived from the latter is produced which is capable of aromatic substitution.     

Photochemische Reaktionen. 118. Mitteilung [1] Zur vinylogen β-Spaltung von Enonen. UV.-Bestrahlung von 4-(3',7',7'-Trimethyl-2'-oxabicyclo [3.2.0]hept-3'-en-1'-yl)but-3-en-2-on

Vinylogous β-Cleavage of Enones: UV.-irradiation of 4-(3′,7′,7′-trimethyl-2′-oxabicyclo[3.2.0]hept-3′-ene-1′-yl)but-3-ene-2-on On ¹π,π*-excitation (λ = 254 nm) in acetonitrile (E/Z)- 2 is converted into the isomers 4–9 and undergoes fragmentation yielding 10 ; in methanol (E/Z)- 2 gives 7–10 and is transformed into 11 by incorporation of the solvent. On ¹π,π*-excitation (λ λ?347 nm; benzene-d₆) (E)- 2 is isomerized into (Z)- 2 , which is converted into the isomers 3 and 4 by further irradiation. ¹π,π*-Excitation (λ = 254 nm; acetonitrile) of 4 gives 6 and (E)- 9 , whereas UV.-irradiation (λ = 254 nm; acetonitrile-d₃) of 5 yields (E)- 7 and 8 . On ¹π,π*-excitation (λ = 254 nm; acetonitrile) of (E/Z)- 12 the compounds (E)- 14 and (E)- 15 are obtained.     

Thermische Umlagerung von 2-Oxa-bicyclo [3.3.1]-non-7-en-3-on; eine neuartige Lactonumlagerung. Vorläufige Mitteilung

Thermal Rearrangement of 2-Oxa-bicyclo [3.3.1]-non-7-en-3-ones; a Novel Lactone Rearrangement Lactone (+)- 2 was prepared by iodolactonisation and subsequent elimination in 51% yield from the known acid (+)- 1 (Scheme 1). Alkylation of (+)- 2 furnished (+)- 3a , (+)- 3b and (+)- 3c , respectively (Scheme 2). Heating of (+)- 3a in boiling DMF racemized the compound ((+)- 3a ? (?)- 4a ). Heating of (+)- 3b and (+)- 3c , respectively, equilibrated them with (?)- 4b and (?)- 4c , respectively. This results are interpreted as a [3.3]-sigmatropic rearrangement with a transition state as depicted in a .     

Photochemische Reaktionen 114. Mitteilung [1]. Zur Photochemie cyclischer Acetale vom 1,3-Dioxa-4,6-cycloheptadien-Typus

Photochemistry of Cyclic Acetals of the 1,3-Dioxa-4,6-cycloheptadiene Type UV.-irradiation (λ=254 nm) of 3 gives the isomers (E)- 5 (4%), (Z)- 5 (60%) and 6 (3%). On triplet sensitization (acetone; λ ≥ 280 nm) 3 is converted to (E)- 5 (3%), (Z)- 5 (7%) and 7 (9%). ? The ¹π,π*-excitation (λ=254 nm) of 4 yields the isomers 2 (9%), 8 (10%), 9 (34%), 10 (20%) and 11 (3%). On thermolysis (200°) 4 gives 10 (87%) by a Claisen-rearrangement.