ChemInform Abstract: REACTIONS OF COMPLETE PHOSPHITES WITH CONJUGATED BROMONITROALKENES

Gareev, R. D.; Loginova, G. M.; Zykov, I. N.; Pudovik, A. N.

doi:10.1002/chin.197931312

Chemischer Informationsdienst

1979

DOI: 10.1002/chin.197931312

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ChemInform Abstract: REACTIONS OF COMPLETE PHOSPHITES WITH CONJUGATED BROMONITROALKENES

R. D. Gareev¹,

G. M. Loginova²,

I. N. Zykov³

et al.

Abstract: Aus dem Trimethylphosphit (I) und dem Brom‐nitroalken (II) entsteht das Oxazaphospholenderivat (III).

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2005

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“…The presence of an easily leaving nucleofugal halogen in the gemposition to the nitro group and a mobile hydrogen atom at the P(O)(OR) 2 group evidently favors dehydrohalogenation and formation of bicyclooctadiene V. Note that the possibility of preparing substituted bicyclooctadienes from adducts of diene synthesis was considered in the works [10,11] devoted to synthesis of benzene derivatives. The instability of compound V is evidently connected with the cisoid location of the phosphoryl and nitro groups (steric factor) [12]; as a result, cleavage of the ethylene bridge and formation of arene VI occurs. The presence of compound VI in the mixture is confirmed by the presence of characteristic signals in the downfield region of the 1 H NMR spectrum (d 6.4038.20 ppm).…”

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Reaction of (2-Nitro- and 2-Bromo-2-nitroethenyl)phosphonates with 1,3-Cyclohexadiene

Anisimova¹,

Кужаева²,

Berkova³

et al. 2005

Russ J Gen Chem

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Specific features of the reactions of bis(chloroethyl) 2-nitro-and 2-bromo-2-nitroethenylphosphonates with 1,3-cyclohexadiene were studied. It was found that the reaction with 2-nitroethenylphosphonate occurs stereoselectively and provides bis(2-chloroethyl) endo- (3-nitrobicyclo[2.2.2]oct-5-en-2-yl)phosphonate. 2-Bromo-2-nitroethenylphosphonate under the same conditions gives a mixture of the endo and exo isomers of the corresponding nitrobicyclooctenes. Enhanced tendency of adducts derived from gem-bromonitroethenylphosphonates for intramolecular transformations, such as dehydrohalogenation and aromatization, under the cycloaddition conditions was revealed.We have previously shown that nitro-and halonitroethenylphosphonates act as highly active dienophiles in the Diels3Alder reaction with aliphatic dienes, cyclopentadiene, and furan [133]. In the present work we have studied reactions of nitro-and gem-bromonitroethenylphosphonates I and II with cyclohexadiene, aiming at revealing specific features of these reactions compared with similar reactions with cyclopentadiene. Such reactions are interesting to study in terms of development of convenient synthetic approaches to polyfunctional bicyclooctenes, important intermediates in the synthesis of fragments of natural compounds, such as hormones, vitamin D 3 , etc. [4,5].It is known that cyclopentadiene reacts with nitroethenylphosphonate I in benzene under reflux for 1 h to give a mixture of the endo and exo diastereomers of the corresponding phosphorylated norbornene in 80% yield [1]. Unlike cyclopentadiene, 1,3-cyclohexadiene reacts under more rigid conditions, viz. in benzene under reflux for 36 h. The reaction results in exclusive formation of the endo isomer of bis(2-chloroethyl)(3-nitrobicyclo[2.2.2]oct-5-en-2-yl)phosphonate (IIIa) in 69% yield (see table). Yields, R f values, and IR and 1 H and 31 P NMR spectral parameters of phoshorylated nitrobicyclooctenes IIIa, IVa, and IVb ÄÄÄÂÄÄÂÄÄÄÂÄÄÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄ ³ ³ R f ³ IR spectrum ³ 1 H NMR spectrum (CDCl 3 ), d, ppm (J, Hz)

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confidence: 99%

Reaction of (2-Nitro- and 2-Bromo-2-nitroethenyl)phosphonates with 1,3-Cyclohexadiene

Anisimova¹,

Кужаева²,

Berkova³

et al. 2005

Russ J Gen Chem

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ChemInform Abstract: REACTIONS OF COMPLETE PHOSPHITES WITH CONJUGATED BROMONITROALKENES

Abstract: Aus dem Trimethylphosphit (I) und dem Brom‐nitroalken (II) entsteht das Oxazaphospholenderivat (III).

Cited by 1 publication

References 0 publications

Reaction of (2-Nitro- and 2-Bromo-2-nitroethenyl)phosphonates with 1,3-Cyclohexadiene

Reaction of (2-Nitro- and 2-Bromo-2-nitroethenyl)phosphonates with 1,3-Cyclohexadiene

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