Photosensitized oxygenation of alkyl-substituted furans

Foote, Christopher S.; Wuesthoff, Michael T.; Wexler, S.; Burstain, I.G.; Denny, Robert W.; Schenck, Günther O.; Schulte‐Elte, K. H.

doi:10.1016/0040-4020(67)85123-8

Cited by 181 publications

(53 citation statements)

References 24 publications

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“…And these NMR data of 10 completely agreed with those of the synthetic sample previously reported. 19 ) Consequently the absolute configuration of 10 was demonstrated to be (6R, 7aR)-3, 6-dimethyl-5, 6, 7, 7a-tetrahydro-2 (4H)-benzofuranone.…”

Section: Resultsmentioning

confidence: 99%

“…The other was through the improved sensitized photooxidation of Foote et al 19 ,20) Photooxidation of 13 in methanol in the presence of Rose Bengal as a photosensitizer gave 9-hydroperoxy-3-methoxy-3,9-dihydromenthofuran (16), 19) which was further converted to 3,9-dimethoxy-3 9-dihydromenthofuran (17),20) 3, 6-dimethyl-7a-methoxy-5, 6, 7, 7a-tetrahydro-2(4H)-benzofuranone (18) and mintlactones (10,11). On treatment of the mixture with 1542 K. TAKAHASHI, T. SOMEYA, S. MURAKI and T.~YosHlDA cone.…”

Section: Resultsmentioning

confidence: 99%

“…8. A mixture of 100 g of 13, 400 ml of methanol and 0.3 g of Rose Bengal was irradiated with an 8 x natrium lamp NX-55 (55W) (Matsushita Electric Industrial Co., Ltd.) in a 600 ml Pyrex cylindrical reactor under an oxygen flow of 3 liters per minute and cooling according to Foote et al 19 ) After 3 hr, 16 liters of oxygen was absorbed.…”

Section: S )mentioning

confidence: 99%

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A New Keto-alcohol, (−)-Mintlactone, (+)-isoMintlactone and Minor Components in Peppermint Oil

Takahashi

Someya

Muraki

et al. 1980

Agricultural and Biological Chemistry

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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A New Keto-alcohol, (−)-Mintlactone, (+)-isoMintlactone and Minor Components in Peppermint Oil

Takahashi

Someya

Muraki

et al. 1980

Agricultural and Biological Chemistry

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“…The solution is photolyzed with a stream of oxygen purging through the solution. That singlet oxygen is generated efficiently is shown by the fact that when 1 g of 2-methylfuran is used as the substrate, a 10-min photolysis using the above procedure results in complete conversion of the furan (to a hydroperoxide derivative), which is a known singlet oxygen trap (25). When 2 is irradiated under this setup for 30 min, no reaction is observed (similar time scale as for direct photolysis runs without Rose Bengal).…”

Section: A-h)idroperoq~-m-nitrobenzyl Methyl Ether 11mentioning

confidence: 91%

Photooxygenation of nitrobenzyl derivatives. Mechanisms of photogeneration and hydrolysis of α-hydroperoxy nitrobenzyl ethers

Wan¹,

Muralidharan²,

McAuley³

et al. 1987

Can. J. Chem.

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Can. J. Chem. 65, 1775 (1987. ' The photooxygenation of nitrobenzyl derivatives 1-10 has been studied in aqueous solution as a function of pH. For m-nitrobenzyl ethers 2-4 and 9, stable a-hydroperoxy ethers (11)(12)(13) are the primary photochemical products. Acid hydrolysis of 11-13 gives m-nitrobenzaldehyde and hydrogen peroxide. Quantum yields for photooxygenation are reported for a number of derivatives as a function of pH. Acid and base catalyses of photooxygenation are observed for several compounds. A mechanism involving photogenerated nitrobenzyl carbanion intermediates is proposed.PETER WAN, S . MURALIDHARAN, IAIN MCAULEY et CHRISTOPHER A. BABBAGE. Can. J. Chem. 65, 1775 (1987. Operant en solutions aqueuses, on a CtudiC la photo-oxydation des dCrivCs nitrobenzyliques (1-10) en fonction du pH. Dans les cas des Cthers m-nitrobenzyliques (2-4 et 9), les produits photochimiques primaires sont les Cthers a-hydroperoxylCs stables (11-13). L'hydrolyse acide des composCs 11-13 conduit au m-nitrobenzaldkhyde et au peroxyde d'hydroghe. Dans les cas d'un certain nombre de derives, on rapporte les rendements quantiques pour la photo-oxygenation en fonction du pH.Dans les cas de plusieurs composCs, on a observe que la photo-oxygenation est soumise i une catalyse acidelbase. On propose un mCcanisme impliquant, comme intermkdiaires, des carbanions nitrobenzyliques gCnCrCs photochimiquement.[Traduit par la revue]The photochemistry of aliphatic and aromatic nitro compounds has received considerable attention and several reviews (1-4) have been published. Recently, we (5-7) and others (8, 9) have noted that some m-and p-nitro-substituted benzenes display unexpected reactivity when irradiated in aqueous solution, especially in the presence of hydronium and hydroxide ions as catalysts for the transformations (5-8). Whereas it is well known (1-4) that o-nitrobenzyl systems are photolabile due to the proximity to the substituent of the reacting nitro chromophore, resulting in initial intramolecular hydrogen abstraction via the n, T" triplet excited state, it had been assumed for many years that the corresponding meta and para derivatives should not be photolabile, except for simple photoreduction. However, in aqueous solution, a number of m-and p-nitro-substituted derivatives have been found to react via new photochemical processes (5-9). In a preliminary report (10) we had demonstrated that molecular oxygen can react with photoexcited nitrobenzyl derivatives, which represent an additional example of the rich and sometimes unpredictable photochemistry of m-and p-substituted nitroaromatic compounds. In this work, we report the generality and proposed mechanisms for the photooxygenation reaction of a variety of m-and p-nitro-substituted derivatives. In addition, the thermal aqueous chemistry of several photogenerated a-hydroperoxy m-nitrobenzyl ethers isolated in these studies will be presented. Results Product studiesThe compounds chosen for the study, 1-10, are shown below. Both m-and p-nitrobenzyl alcohols 1 and 7, respec...

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“…Hydroperoxides react with lead tetraacetate releasing oxygen (11). Also in the nmr spectrum the exchangeable proton absorbed at 6 4.53 whereas the proton of a hydroperoxide absorbs around 6 9-9.5 (10). There are two sharp three-proton singlets at 6 3.47 and 3.84 assigned to the -0Me acetal and -0Me ester groups respectively.…”

mentioning

confidence: 97%

C-Nucleosides and related compounds. VI. Carbocyclic analogues of C-nucleosides: synthesis and derivatives of some useful intermediates

Just¹,

Reader²,

Chalard-Faure³

1976

Can. J. Chem.

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GEORGE JUST, GRANT READER, and BERNADETTE CHALARD-FAURE. Can. J. Chern. 54, 849 (1976).The Diels-Alder adduct of cyclopentadiene and 8-brorno acrylic acid 1 was converted to ~,~-exo-6,7-(dihydroxy-di-O-isopropylidene)-2-hydroxy-3-oxabicyclo[3.2.1]octane (9) in an eight-step sequence and a 24% yield based on 1. Alternatively, the hemiacetal9 was obtained in five steps and 22% yield from norbornadiene through the intermediate lactone 11. The thiosernicarbazone and sernicarbazone of 9 were prepared. The synthesis of the free aldehyde 13 as well as that of the Wittig reaction products 12 and 19 are described. GEORGE JUST, GRANT READER et BERNADETTE CHALARD-FAURE. Can. J. Chern. 54, 849 (1976).La rkction de l'acide 8-bromo acrylique 1 sur le cyclopentadkne conduit au produit d'addition de Diels-Alder correspondant; ce dernier peut Ctre transformi en huit Ctapes avec un rendernent global de 24y0 bask sur 1 en D,L-exo-(dihydroxy-di-0-isopropylidene-6,7 hydroxy-2-oxa-3 bicyclo[3.2.l]octane 9. L'hCmiacCtal 9 a Cgalernent Ct C obtenu en cinq Ctapes avec un rendement de 22'g ? i partir du norbornadikne et en passant par la lactone 11. On d k r i t la preparation de la thiosernicarbazone et de la semicarbazone de 9 ainsi que la synthtse de 1'aldChyde 13 et des produits 12 et 19 provenant de rkctions de Wittig.In a preliminary communication (I), we reported the synthesis of lactol9 and lactone 11. In this paper, we are giving a full account of this work and the description of a second pathway leading to 9 and 11. The syntheses of related derivatives and of the free aldehyde 13 are also described. These compounds are potential intermediates for the preparation of carbocyclic analogues of C-nucleosides.Condensation of 0-bromoacrylic acid 1 with cyclopentadiene in benzene (2) gave the DielsAlder adduct 2 in 75% yield. This compound was almost exclusively the endo carboxylate isomer (3). Treatment of the acid 2 with diazomethane gave, in essentially quantitative yield, the ester 2a which was oxidized to the diol 3 with hydrogen peroxide and a catalytic (4) amount of osmium tetroxide. The diol3, mp 145 "C, was obtained in 50% yield. The stereochemistry of the hydroxy groups in 3 was assigned on the basis of previous work (4, 5) which had shown the preferential exo-hydroxylation of bicyclic[2.2.1] systems of type 2.Attempts to hydroxylate the acid 2 directly were unsuccessful. Crude diol3 was converted to its isopropylidene derivative 3a in 60% yield based on adduct 2. Elimination of hydrogen bromide by treatment of 3a with 1,Sdiazabicyclo[5.4.0]undec-Sene afforded the olefinic ester 4. Upon treatment of diol 3 with acetic anhydride -pyridine, the olefinic diacetate 4a was obtained. Similarly, the olefinic carbonate derivative 4b was the major product from the reaction of diol 3 with phosgene in pyridine. It was not possible to obtain a pure sample of 3a for elemental analysis, although the compound was otherwise well characterized. Attempts at purification by column chromatography, on either silica gel or alumina (activity 1 or...

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Photosensitized oxygenation of alkyl-substituted furans

Cited by 181 publications

References 24 publications

A New Keto-alcohol, (−)-Mintlactone, (+)-isoMintlactone and Minor Components in Peppermint Oil

A New Keto-alcohol, (−)-Mintlactone, (+)-isoMintlactone and Minor Components in Peppermint Oil

Photooxygenation of nitrobenzyl derivatives. Mechanisms of photogeneration and hydrolysis of α-hydroperoxy nitrobenzyl ethers

C-Nucleosides and related compounds. VI. Carbocyclic analogues of C-nucleosides: synthesis and derivatives of some useful intermediates

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