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1.
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
2.
A. V. Bogdanov V. F. Mironov N. R. Khasiyatullina D. B. Krivolapov I. A. Litvinov A. V. Kuchin A. I. Konovalova 《Russian Chemical Bulletin》2006,55(2):396-398
The reaction of 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione with hexaethyltriamido-phosphite in the presence of diethylammonium
chloride afforded a stable quasiphosphonium salt, viz., (1,7,7-trimethyl-2-oxobicyclo[2.2.1]hept-3-yloxy)tris(diethylamino)phosphonium chloride, as one diastereomer (racemate,
1R*,3S*,4S*).
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 383–385, February, 2006. 相似文献
3.
S. S. Koval’skaya N. G. Kozlov E. A. Dikusar 《Russian Journal of Organic Chemistry》2010,46(8):1121-1134
Three-component condensation of [(1S,4S)-1,7,7-trimethylbicyclo[2.2.1]hept-2-ylidene]acetaldehyde with naphthalen-1-amine and cyclic β-diketones gave 7-[(1S,4S)-1,7,7-trimethylbicyclo[2.2.1]hept-2-ylidenemethyl]-7,8,9,10,11,12-hexahydro-7H-benzo[c]acridin-8-one derivatives possessing three or more asymmetric carbon atoms. Steric factors were found to be responsible for
the predominant formation of the (7R)-isomers (R/S ≈ 7: 5) and orientation of substituents in the cyclohexenone fragment. The same factors determined complete regioselectivity
of the reaction with methyl 2,4-dioxocyclohexane-1-carboxylates as dicarbonyl component, which led to exclusive formation
of methyl 8-oxobenzoacridine-11-carboxylates. In the reaction of [(1S,4S)-1,7,7-trimethylbicyclo[2.2.1]hept-2-ylidene]acetaldehyde with naphthalen-1-amine and barbituric acid as dicarbonyl component,
the only product was that formed by two-component condensation of barbituric acid with bicyclic aldehyde. 相似文献
4.
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
5.
Khalid A. Al-Farhan Ismail Warad Saud I. Al-Resayes Moustafa M. Fouda Mohamed Ghazzali 《Central European Journal of Chemistry》2010,8(5):1127-1133
Borneol is a monoterpene that is a part of traditional Chinese and Japanese medicine. (−) borneol reacted with methanesulfonyl
chloride in THF/pyridine to afford the new 1,7,7-trimethylbicyclo[2.2.1]hept-2-yl methane sulfonate derivative in excellent
yield. The product is characterized by H1NMR, C13NMR, mass spectroscopy as well as elemental analysis and its structure was identified by X-ray single crystal diffraction.
The packing of 1,7,7-trimethylbicyclo[2.2.1]hept-2-yl methanesulfonate exhibits the non-classical C-H···O hydrogen bonding
in C(4) and R2
2(8) chain and ring motifs as structural determinants. This was also confirmed by the analysis of Hirshfeld surfaces. The 1,7,7-trimethylbicyclo[2.2.1]hept-2-yl
methane sulfonate antimicrobial activity was tested and compared with its parent (−) borneol against three different pathogens.
Particularly, 1,7,7-trimethylbicyclo[2.2.1]hept-2-yl methane sulfonate showed high sensitivity, compared to Chloramphenicol
reference material, against Escherichia coli.
相似文献
6.
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
7.
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
8.
《Tetrahedron: Asymmetry》2006,17(1):79-91
Reductions of (1R,3R,4R)-3-([1,2,4]triazolo[4,3-x]azin-3-yl)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-ones and their lactone analogues, prepared from (1R)-(+)-camphor, were studied. Catalytic hydrogenation selectively led to partial saturation of the [1,2,4]triazolo[4,3-x]azine residue, while in reactions with borane–methylsulfide coordination of borane to the 1-position of [1,2,4]triazolo[4,3-x]azine system took place. On the other hand, activation of the carbonyl group in (1R,3R,4R)-3-([1,2,4]triazolo[4,3-x]azin-3-yl)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-ones with boron trifluoride etherate followed by reaction with borane–methylsulfide furnished the corresponding isoborneols, stereoselectively. The structures of all representative compounds were confirmed by X-ray diffraction. 相似文献
9.
M. N. Aboul-Enein A. A. EL-Azzouny Y. A. Maklad Y. S. Sokeirik H. Safwat 《Journal of the Iranian Chemical Society》2006,3(2):191-208
Starting from (1,7,7-trimethyl-bicyclo[2.2.1]hept-2-ylideneamino)-acetic acid methyl esters 6a, 6b, the aryl esters of exo-2-[methyl-(1,7,7-trimethyl-bicyclo[2.2.1]hept-2-yl)-amino]-ethanol (10a-f) and exo-2-[methyl-(1,7,7-trimethyl-bicyclo[2.2.1]hept-2-yl)-amino-2-phenyl-ethanol (10g-n) are prepared. Also, from the reaction of 1,7,7-trimethyl-bicyclo[2.2.1]heptan nitramine 4 with either 2-amino-1-(4-nitrophenyl)-propane-1,3-diol (17) or 1-aminomethyl-cyclohexanol (18), the alcohol exo-1-[(1,7,7-trimethyl-bicylo[2.2.1]hept-2-ylamino)-methyl]-cyclohexanol (13), exo-1-(4-aminophenyl)-2-(1,7,7-trimethyl-bicyclo[2.2.1]hept-2-ylamino)-propane-1,3-diol (14) and 1-(4-aminophenyl)-2-[methyl-1,7,7-trimethylbicyclo[2.2.1]hept-2-yl]-amino]-propane-1,3-diol (16) are synthesized. At a dose level of 12.5 mg/kg, compounds 16 and 14 show a significant anticonvulsant protection against pentylenetetrazole seizures (100% and 83% protection, respectively) compared with diphenylhydantoin sodium (50 mg/kg, 100%) and deramciclane fumarate (25 mg/kg, 83%), used as reference drugs. Compound 10b at dose level of 50 mg/kg displayed 41%, hypoglycemic activity, compared with gliclazide (10 mg/kg, 23%) as reference drug. Furthermore, the prepared compounds are screened for their anti-inflammatory potential at a dose level of 50 mg/kg. Compounds 10i, 10g, 14 and 10m exhibited 92%, 90%, 88% and 80% inhibition in rat paw weight, respectively, with no sign of ulcerogenicity, compared with indomethecin (5 mg/kg, 81%). 相似文献
10.
G. G. Mazgarova A. A. Fatykhov R. R. Gataullin 《Russian Journal of Organic Chemistry》2014,50(9):1346-1350
Heating of N-benzoyl-N-[2-(1-methylbut-2-en-1-yl)-4-methylphenyl]glycine with ethyl chloroformate or acetic anhydride gave (5R*) and (5S*) isomers of (1R*,3aS*,4S*,11S*)-5,7,11-trimethyl-3a-phenyl-4,5-dihydro-3aH-1,4-methano[1,3]oxazolo[3,2-a]quinolin-2-one. 相似文献
11.
《Tetrahedron: Asymmetry》2006,17(8):1217-1237
Stereoselective additions to the exocyclic CC double bond of some (1R,3E,4S)-3-alkylidene-1,7,7-trimethylbicyclo[2.2.1]heptan-2-ones and (1R,4E,5S)-4-alkylidene-1,8,8-trimethyl-2-oxabicyclo[3.2.1]octan-3-ones were studied. All additions took place predominantly from the less hindered endo-face of the methylidene compounds to give the corresponding exo-adducts as the major isomers. Thus, catalytic hydrogenations afforded the α-alkylated (1R,3R,4R)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-ones and (1R,4R,5R)-1,8,8-trimethyl-2-oxabicyclo[3.2.1]octan-3-ones in 28–100% de. Similarly, 1,3-dipolar cycloadditions of 2,4,6-trisubstituted benzonitrile oxides gave the corresponding spiro cycloadducts in 66–100% de. The structures were determined by 2D NMR techniques, NOESY spectroscopy and X–ray diffraction. 相似文献
12.
I. Yu. Chukicheva L. V. Spirikhin A. V. Kuchin 《Russian Journal of Organic Chemistry》2008,44(1):62-66
The alkylation of phenol with camphene in the presence of boron trifluoride in glacial acetic acid was accompanied by tandem molecular rearrangement with formation of a mixture of ortho- and para-substituted phenols having 1,7,7-trimethylbicyclo[2.2.1]hept-exo-2-yl and 5,5,6-trimethylbicyclo[2.2.1]hept-exo-2-yl substituents. The same products were obtained by rearrangement of 1,7,7-trimethylbicyclo[2.2.1]hept-exo-2-yloxybenzene under analogous conditions. Similar reactions performed in the presence of aluminum phenoxide as catalyst resulted in predominant formation of the corresponding ortho-substituted phenols. 相似文献
13.
14.
The structural characteristics of (±)-(exo,exo)-3-(hydroxymethylene)-5,6-(isopropylidenedioxy)bicyclo[2.2.1]heptan-2-one make the reactions between this β-diketone and hydrazines particularly interesting for elucidating the mechanism of pyrazole formation. The isolation and X-ray structure determination of two 5-hydroxy substituted Δ2-pyrazolines [(±)-(3aR*,4R*,5R*,6S*,7R*,7aR*)-7a-hydroxy-5,6-(isopropylidenedioxy)-3a,4,5,6,7,7a-hexahydro-4,7-methano-1H-indazole] and [(±)-(3aS*,4R*,5R*,6S*,7R*,7aR*)-7a-hydroxy-5,6-(isopropylidene-dioxy)-1-phenyl-3a,4,5,6,7,7a-hexa-hydro-4,7-methano-1H-indazole] has been determinant for proposing a mechanism. Besides B3LYP/6-31G* calculations have been carried out on all intermediate dihydroxypyrazolidines and 5-hydroxypyrazolines. Finally, the annular tautomerism of the NH-methanotetrahydroindazoles has been studied both experimentally (13C NMR) and theoretically: the Mills-Nixon effect favours the 2H-tautomer. 相似文献
15.
V. R. Kartashov K. V. Malkova A. V. Arkhipova T. N. Sokolova 《Russian Journal of Organic Chemistry》2006,42(7):966-968
Some nitriles reacted with camphene in the presence of heteropolyacids (H3PW12O40, H4SiW12O40, H7PMo12O40) as catalyst to give N-(1,7,7-trimethylbicyclo[2.2.1]hept-2-yl)-substituted amides in fairly high yields. 相似文献
16.
《Tetrahedron: Asymmetry》2007,18(19):2365-2376
Stereoselective [3+2] cycloadditions of trimethylenemethane (TMM) to the exocyclic CO and CN double bonds of (1S,3EZ,4R)-3-arylimino-1,7,7-trimethylbicyclo[2.2.1]heptan-2-ones gave the corresponding spiro[bicyclo[2.2.1]heptane-2,2′-furan] and spiro[bicyclo[2.2.1]heptane-3,2′-pyrrolidine] derivatives. Further stereoselective reductions of the CN or CO bond in these cycloadducts furnished new chiral amines, diamines, and a new aminoalcohol. All cycloadditions and reductions of the CN double bonds took place from the less hindered endo-face of the (1S,3EZ,4R)-3-arylimino-1,7,7-trimethylbicyclo[2.2.1]heptan-2-ones, exclusively, thus giving the corresponding products in 100% de. The structures were determined by NMR, NOESY spectroscopy, and by X-ray diffraction. 相似文献
17.
The asymmetric aza-Diels-Alder reaction of the (1R)-8-phenylmenthyl or (1R)-8-phenylisoneomenthyl glyoxylate-derived N-benzylimine with cyclopentadiene resulted in the enantioselective synthesis of the corresponding pure [(1S,3-exo)-2-benzyl-2-azabicyclo[2.2.1]hept-5-ene]-3-carboxylates (80 or 69% yield, respectively). Reduction of these cycloadducts with LiAlH4 afforded pure (−)-[(1S,3-exo)-2-benzyl-2-azabicyclo[2.2.1]hept-5-en-3-yl]methanol. Furthermore, a reaction sequence based on Barbier-Wieland degradation of both (1S,3-exo)-adducts afforded pure (+)-(1R)-2-benzoyl-2-azabicyclo[2.2.1]heptan-3-one. In the course of the two transformation sequences referred, the chiral auxiliaries were recovered in a virtually quantitative way. 相似文献
18.
《Tetrahedron: Asymmetry》2014,25(6-7):554-562
Five tridentate Schiff bases have been prepared from (1R,2S,3R,4S)-3-amino-1,7,7-trimethylbicyclo[2.2.1]heptan-2-ol and salicylaldehydes. X-ray structure investigation revealed differences in their molecular conformation, and their titanium(IV) complexes have been studied with NMR techniques. Among them the complex with the Schiff base obtained from 2-hydroxy-3-isopropylbenzaldehyde, is the most selective catalyst for the cyanosilylation of aliphatic, alicyclic, aromatic, and heteroaromatic aldehydes. The highest enantioselectivity, >99%, was achieved for the addition of trimethylsilyl cyanide to cinnamaldehyde. 相似文献
19.
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
20.
N. G. Kozlov L. A. Popova T. K. Vyalimyaé G. V. Nesterov V. O. Knizhnikov Yu. K. Ol'dekop 《Chemistry of Natural Compounds》1989,24(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