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1.
2.
3-exo-Hydroxymethyl-5,5,6-trimethylbicyclo[2.2.1]heptan-2-one was prepared by treatment of isocamphanone with Paraform in the presence of alkali in DMF. The product reacts with acetonitrile in the presence of sulfuric acid (Ritter reaction) to form a mixture of 2-(acetylamino)-3-(acetylaminomethyl)-5,5,6-trimethylbicyclo[2.2.1]hept-2-ene and 2,2-bis(acetylamino)-3-(acetylaminomethyl)-5,5,6-trimethylbicyclo[2.2.1]heptane in a 1:1 ratio. Attempted hydroxymethylation of isocamphanone in DMSO gave bis(isocamphanon-3-endo-yl)methane. 相似文献
3.
Fenchone (1,3,3-trimethylbicyclo[2.2.1]heptan-2-one) in reaction with acetonitrile in the presence of sulfuric acid (Ritter reaction) due to steric hindrances preventing geminal addition of two nucleophile molecules gives rise to a mixture of 1,2-exo-diacetamido-6-endo,7,7-trimethylbicyclo[2.2.1]heptane, 2-endo6-exo-diacetamido-3,3,6-trimethylbicyclo[2.2.1]heptane, and 2-exo,6-exo-diacetamido-1,3,3-tri- methylbicyclo[2.2.1]heptane in the ratio of 6:4:1. Fenchone oxime under condition of this reaction affords a mixture of stereoisomeric cis- and trans-acetamido-1-methyl-3-(-cyanoisopropyl)cyclopentanes in 2:3 ratio. 相似文献
4.
Paul G. Gassman Kentaro Okuma Aline Lindbeck Richard Allen 《Tetrahedron letters》1986,27(52):6307-6310
-2,3-Epoxy-1,7,7-trimethylbicyclo[2.2.1]heptane reacted with trimethylsilyl cyanide in the presence of zinc iodide to produce a complex mixture of products. The major product,
-7-trimethylsiloxy-
-2,3,3-trimethyl-
-2-isocyanobicyclo[2.2.1]heptane was obtained in 72% yield. In addition, eight other products were identified in yields ranging from 10% to 1%. All of the products could be rationalized on the basis of initial generation of a carbocationic intermediate. 相似文献
5.
Dikusar E. A. Kozlov N. G. Moiseichuk K. L. 《Russian Journal of Organic Chemistry》2002,38(2):182-187
By treating 1-octyne and phenylacetylene with butyllithium the corresponding lithium acetylides were obtained that with camphor and isocamphanone provided along streospecific process 2-exo-(1-octynyl or 2-phenyl-1-ethynyl)-2-endo-lithiumoxy-5,5,6-trimethylbicyclo[2.2.1]heptane and 2-endo-(1-octynyl or 2-phenyl-1-ethynyl)-2-exo-lithiumoxy-1,7,7-trimethylbicyclo[2.2.1]heptane. The hydrolysis of these lithium alcoholates occurred selectively and resulted in individual tertiary terpene alcohols containing exo-acetylene substituent in the case of camphor, endo-acetylene fragment in the case of isocamphanone. The alcohols reacted with methyl, ethyl, or butyl iodides in the presence of hexamethylphosphoramide to afford ethers, and with benzoyl chloride to furnish disubstituted esters of benzoic acid. 相似文献
6.
Kuvshinov G. V. Surovegin A. V. Bakanov M. O. Maslov A. V. 《Russian Journal of General Chemistry》2021,91(12):2606-2612
Russian Journal of General Chemistry - Surface modification of the diatomite adsorbent Hezasorb AW-HMDS by tetra(1,7,7-trimethylbicyclo[2.2.1]heptane[2,3-b]pyrazino)porphyrazine Pd(II) was... 相似文献
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Three (-)-fenchyl alcohol derivatives, ?(1R,2R,4S)-exo-(2-Ar)-1,3, 3-trimethylbicyclo[2.2.1] heptan-2-ol, Ar = o-anisyl (2), 2-N-methylimidazolyl (3), 2-N,N-dimethylbenzylamine (4)? were synthesized, characterized by X-ray analyses, and employed as precatalysts in diethyl zinc additions to benzaldehyde. Directions and relative degrees of enantioselectivities are rationalized by QM/MM ONIOM computations of mu-O transition structure models. Enantioselectivities arise from repulsive interactions between "transferring" or "passive" alkyl groups at the zinc centers and the substituents at donor groups or the bicyclo[2.2.1]heptane moieties. These results enable predictions for ligand-tuning to improve catalyst efficiency of fenchone-based ligands in dialkylzinc additions to aldehydes. 相似文献
9.
Ponomarev D. A. Vishnyakova E. V. Rudometova N. V. 《Russian Journal of Applied Chemistry》2010,83(4):695-699
Organocuprate reagents were used for introducing bornane (1,7,7-trimethylbicyclo[2.2.1]heptane) moiety into the carbon skeleton
of α,β-unsaturated carbonyl compounds. Prospects for use of the products obtained as fragrant substances were assessed. 相似文献
10.
S. S. Koval’skaya N. G. Kozlov E. A. Dikusar 《Russian Journal of Organic Chemistry》2005,41(6):832-837
2-(Phenylethynyl)isoborneol was synthesized by treatment of camphor with lithium phenylacetylide. Skeletal rearrangements of the title compound under the Ritter reaction conditions afforded a mixture of N-(4-phenylethynyl- and 4-benzoylmethyl-1,7,7-trimethylbicyclo[2.2.1]hept-2-yl)acetamides at a ratio of 8:3. The reaction of 2-(phenylethynyl)isoborneol with formic acid involved mainly Meyer-Schuster rearrangement instead of the expected Rupe rearrangement, and the major product was 2-(1,7,7-trimethylbicyclo[2.2.1]hept-2-ylidene)-1-phenylethanone. The minor product (∼6%) was 1-(2-hydroxy-1,7,7-trimethylbicyclo[2.2.1]hept-2-yl)-2-phenylethanone. The Ritter reaction of 2-(1,7,7-trimethylbicyclo[2.2.1]hept-2-ylidene)-1-phenylethanone selectively yielded N-(4-benzoylmethyl-1,7,7-trimethylbicyclo[2.2.1]hept-2-yl)acetamide.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 6, 2005, pp. 853–858.Original Russian Text Copyright © 2005 by Koval’skaya, Kozlov, Dikusar. 相似文献
11.
F. Makaev L. Bets L. Vlad S. Pogrebnoi A. Barba A. Besolov S. Malinovskii R. Lyubodarskii 《Russian Journal of Organic Chemistry》2006,42(6):849-854
A procedure was developed for the stereoselective synthesis of aminated derivatives of (+)-1-{(1R,3R,6S)-4,7,7-trimethylbicyclo[4.1.0]hept-4-en-3-yl}ethan-1-one. The configuration of the side-chain chiral center in (+)-1-{(1R,3R,6S)-4,7,7-trimethylbicyclo[4.1.0]hept-4-en-3-yl}ethan-1-ol was determined by X-ray analysis. Diketene and Meldrum’s acid were proposed as initial compounds for the synthesis of, respectively, 3-oxobutanoic and malonic acid esters having a 1-ethyl-4,7,7-trimethylbicyclo[4.1.0]hept-4-ene fragment. 相似文献
12.
N. F. Bondar' S. S. Koval'skaya R. V. Skupskaya F. S. Pashkovskii E. A. Dikusar N. G. Kozlov F. A. Lakhvich 《Russian Journal of Organic Chemistry》2001,37(1):23-28
endo-2-Ethynyl-1,7,7-trimethylbicyclo[2.2.1]heptan-exo-2-ol reacts with nitrile oxides, yielding endo-2-(3-R-isoxazol-5-yl)-1,7,7-trimethylbicyclo[2.2.1]heptan-exo-2-ols. Treatment of the latter with methanesulfonyl chloride in pyridine leads to dehydration and formation of mixtures of the corresponding 1-(3-R-isoxazol-5-yl)-3,3-dimethyl-2-methylenebicyclo[2.2.1]heptanes and 2-(3-R-isoxazol-5-yl)-1,7,7-trimethylbicyclo[2.2.1]hept-2-enes at a ratio of 2:1. 相似文献
13.
A method is proposed for the selective conversion of oximes of terpene ketones of the pinane (2,6,6-trimethylbicyclo[3.1.1]heptane) series into the corresponding bicyclic lactams which consists in the action on these oximes of sulfuric acid in a weak nucleophile — a nitrile. The fact that the interaction takes place through the stage of formation of N-acylamidines — products of the nucleophilic stabilization of the intermediate carbocations — permits the rearrangement of the latter and the formation of monocyclic products to be avoided, which makes it possible to obtain in good yields bicyclic lactams, the synthesis of which by other methods is problematical. 相似文献
14.
N. S. Vostrikov V. Z. Vasikov M. S. Miftakhov 《Russian Journal of Organic Chemistry》2006,42(7):962-965
Ethenylmagnesium bromide (1.5 equiv) forms a chelate with (?)-1-{(1S,2R,4R)-1-ethenyl-2-hydroxy-7,7-dimethylbicyclo[2.2.1]hept-2-yl} ethanone in THF and promotes its fast primary α-ketol rearrangement into 1-ethenyl-2-hydroxy-2,8,8-trimethylbicyclo[3.2.1]octan-3-one. The latter reacts with excess magnesium reagent (0.5 equiv) according to common 1,2-addition pattern at the carbonyl group and is simultaneously involved in the second α-ketol rearrangement which leads to 1-ethenyl-3-hydroxy-3,8,8-trimethylbicyclo[3.2.1]octan-2-one as thermodynamically more stable regioisomer. 相似文献
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16.
Using a relative rate method, rate constants for the gas-phase reactions of the OH radical with trans-pinane [(1R, 2R)-2, 6, 6-trimethylbicyclo[3.1.1]heptane], tricyclene (1, 7, 7-trimethyltricyclo[2.2.1.02, 6]heptane), and quadricyclane (quadricyclo[2.2.1.02, 6.03, 5]heptane) of (1.34 ± 0.29) × 10?11 cm3 molecule?1 s?1, (2.86 ± 0.62) × 10?12 cm3 molecule?1 s?1 and (1.83 ± 0.41) × 10?12 cm3 molecule?1 s?1, respectively, have been determined at 296 ± 2 K. These rate constants are compared with values calculated from an empirical estimation method and used to refine this estimation technique for the calculation of OH radical reaction rate constants for polycyclic systems. © John Wiley & Sons, Inc. 相似文献
17.
N. G. Kozlov L. A. Popova T. K. Vyalimyaé G. V. Nesterov V. O. Knizhnikov Yu. K. Ol'dekop 《Chemistry of Natural Compounds》1988,24(6):686-690
On the interaction of isocamphanone with butyllithium, 2-butyl-5,5,6-trimethylbicyclo[2.2.1]heptan-endo-2-ol is formed stereospecifically.
As a result of skeletal rearrangements of carbonium ions taking place in the course of the reaction, the Ritter reaction of
this tertiary alcohol with acetonitrile and benzonitrile has given endo-3-butyl-1,7,7-trimethylbicyclo[2.2.1]hept-exo-2-ylacylamines
and endo-6-butyl-1,7,7-trimethylbicyclo[2.2.1]hept-2-ylacylamines.
Institute of Physical Organic Chemistry, Academy of Sciences of the Belorussian SSR, Minsk. Translated from Khimiya Prirodynkh
Soedinenii, No. 6, pp. 807–812, November–December, 1988. 相似文献
18.
Ya. A. Gur’eva O. A. Zalevskaya L. L. Frolova I. N. Alekseev A. V. Kuchin 《Chemistry of Natural Compounds》2011,46(6):920-923
The new chiral derivatives of benzylamine and 2α-hydroxypinan-3-one (1R,2R,5R)-3-[(1S)-α-methylbenzylamino]-2,6,6-trimethylbicyclo[3.1.1]heptan-2-ol (2), (1S,2S,3S,5S)-3-(benzylamino)-2,6,6-trimethylbicyclo[3.1.1]heptan-2-ol (3), and (1R,2R,3R,5R)-3-[(1S)-α-methylbenzylamino]-2,6,6-trimethylbicyclo[3.1.1]heptan-2-ol (4) were synthesized and characterized. It was shown that reduction
of the benzylimines by sodium triacetoxyborohydride formed stereoselectively 3β-substituted pinanamines. 相似文献
19.
A method is proposed for the selective conversion of oximes of terpene ketones of the pinane (2,6,6-trimethylbicyclo[3.1.1]heptane) series into the corresponding bicyclic lactams which consists in the action on these oximes of sulfuric acid in a weak nucleophile — a nitrile. The fact that the interaction takes place through the stage of formation of N-acylamidines — products of the nucleophilic stabilization of the intermediate carbocations — permits the rearrangement of the latter and the formation of monocyclic products to be avoided, which makes it possible to obtain in good yields bicyclic lactams, the synthesis of which by other methods is problematical.Institute of Physical Organic Chemistry, Belarus Academy of Sciences, Minsk. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 365–369, May–June, 1993. 相似文献
20.
Hedin-Dahlström J Rosengren-Holmberg JP Legrand S Wikman S Nicholls IA 《The Journal of organic chemistry》2006,71(13):4845-4853
[structures: see text] A class II aldolase-mimicking synthetic polymer was prepared by the molecular imprinting of a complex of cobalt (II) ion and either (1S,3S,4S)-3-benzoyl-1,7,7-trimethylbicyclo[2.2.1]heptan-2-one (4a) or (1R,3R,4R)-3-benzoyl-1,7,7-trimethylbicyclo[2.2.1]heptan-2-one (4b) in a 4-vinylpyridine-styrene-divinylbenzene copolymer. Evidence for the formation of interactions between the functional monomer and the template was obtained from NMR and VIS titration studies. The polymers imprinted with the template demonstrated enantioselective recognition of the corresponding template structure, and induced a 55-fold enhancement of the rate of reaction of camphor (1) with benzaldehyde (2), relative to the solution reactions, and were also compared to reactions with a series of reference polymers. Substrate chirality was observed to influence reaction rate, and the reaction could be competitively inhibited by dibenzoylmethane (6). Collectively, the results presented provide the first example of the use of enantioselective molecularly imprinted polymers for the catalysis of carbon-carbon bond formation. 相似文献