- Captodative Formyl- and Acyl(amino)alkenes Containing a Terminal Double Bond or a Weakly Basic Tertiary Amino Group
-
Piperidine reacts with 3-bromo-3-buten-2-one to give a mixture of 3,4-dipiperidinobutan-2-one and 3-piperidino-3-buten-2-one. The latter is also formed by the action of a strong base (Et3N in THF or MeONa in MeOH) on the dipiperidino derivative. Analogous reaction of 2-bromo-3-phenylpropenal with N-methylaniline affords 2-[methyl(phenyl)amino]-3-phenylpropenal which is the first captodative formyl-(amino)alkene having a weakly basic tertiary amino group.
- Rulev,Fedorov,Chuvashev,Voronkov
-
-
Read Online
- METHOD FOR PRODUCING 2-ACETYL-4H,9H-NAPHTHO[2,3-B]FURAN-4,9-DIONE
-
The invention addresses the problem of providing a method for producing 2-acetyl-4H,9H-naphtho[2,3-b]furan-4,9-dione that is suited to industrial production. The invention provides a method for producing 2-acetyl-4H,9H-naphtho[2,3-b]furan-4,9-dione by reacting 3-bromo-3-buten-2-one and 2-hydroxy-1,4-naphthoquinone in the presence of a solvent, then obtaining crystals of 2-acetyl-4H,9H-naphtho[2,3-b]furan-4,9-dione by adding an alcohol-based solvent and/or water to the reaction system, and treating the crystals by using a specific adsorbent in the presence of a solvent.
- -
-
Paragraph 0089; 0129; 0130; 0133
(2018/08/03)
-
- 2-ACETYLNAPHTHO[2,3-B]FURAN -4,9-DIONE FOR USE ON TREATING CANCER
-
The invention provides naphthofuran compounds, polymorphs of naphthofuran compounds, naphthofuran compounds in particle form, purified compositions that contain one or more naphthofuran compounds, purified compositions that contain one or more naphthofuran compounds in particle form, and methods of using these naphthofuran compounds, polymorphs, purified compositions and/or particle forms to treat subjects in need thereof.
- -
-
Paragraph 0241
(2016/02/20)
-
- A NOVEL GROUP OF STAT3 PATHWAY INHIBITORS AND CANCER STEM CELL PATHWAY INHIBITORS
-
The present invention relates to the composition and methods of use of Stat3 pathway inhibitors or cancer stem cell inhibitors in combination treatment of cancer.
- -
-
Paragraph 0156; 0157
(2016/08/17)
-
- Compounds and compositions for targeting cancer stem cells
-
The invention provides naphthofuran compounds, polymorphs of naphthofuran compounds, naphthofuran compounds in particle form, purified compositions that contain one or more naphthofuran compounds, purified compositions that contain one or more naphthofuran compounds in particle form, methods of producing these naphthofuran compounds, polymorphs, purified compositions and/or particle forms, and methods of using these naphthofuran compounds, polymorphs, purified compositions and/or particle forms to treat subjects in need thereof.
- -
-
Page/Page column 56; 57; 65
(2016/08/07)
-
- Ruthenium-lewis acid catalyzed asymmetric diels-alder reactions between dienes and α,β-unsaturated ketones
-
The complex [Ru(Cp)(R,R-BIPHOP-F)(acetone)][SbF6],(R,R)-1a. was used as catalyst for asymmetric Diels-Alder reactions between dienes (cyclopentadiene, methylcyclopentadienc, isoprene, 2,3-dimethylbutadiene) and α,β-unsaturated ketones (methyl vinyl ketone (MVK). ethyl vinyl ketone, divinyl ketone, α-bromovinyl methyl ketone and α-chlorovinyl methyl ketone). The cycloaddition products were obtained in yields of 50-_90% and with enantioselectivities up to 96% ee. Ethyl vinyl ketone, divinyl ketone and the halogenated vinyl ketones worked best and their reactions with acyclic dienes consistently provided products with >90% ee. α-Chlorovinyl methyl ketone performed better than α-bromovinyl methyl ketone. The reaction also provided a [4.3.1]bicyclic ring system in 95% ee through an intramolecular cycloaddition reaction. Crystal structure determinations of [Ru(Cp)((S,S)-BIPHOP-F)(mvk)]-[SbF6], (S,S)-1b, and [Ru(Cp)((R,R)-Me4BIPHOP-F)(acrolein)][SbF6], (R,R)-2b, provided the basis for a rationalization of the asymmetric induction.
- Rickerby, Jenny,Vallet, Martial,Bernardinelli, Gerald,Viton, Florian,Kuendig, E. Peter
-
p. 3354 - 3368
(2008/03/27)
-
- Structure-dependent oxidative bromination of unsaturated C-C bonds mediated by selectfluor
-
A number of olefins were subjected to oxidative bromination using Selectfluor/KBr. For different types of substrates, addition, monobromine-substituted, or Hunsdiecker-Borodin reaction products can be readily afforded.
- Ye, Chengfeng,Shreeve, Jean'Ne M.
-
p. 8561 - 8563
(2007/10/03)
-
- A radical based addition-elimination route for the preparation of indoles
-
Indoles, including tricyclic derivatives, are produced by cyclisations of aryl radicals onto vinyl halides followed by elimination of halide radical and tautomerism of the resulting product; the aryl radicals are produced using "clean methodology" either by reaction of iodide ions with arenediazonium salts or by reaction of phosphorus-centred radicals with aryl iodides. The Royal Society of Chemistry 2000.
- Murphy, John A.,Scott, Karen A.,Sinclair, Rhoha S.,Martin, Concepcion Gonzalez,Kennedy, Alan R.,Lewis, Norman
-
p. 2395 - 2408
(2007/10/03)
-
- A new synthesis of indoles
-
Aryl radical cyclisation onto appropriate vinyl bromides leads to a new route to indoles.
- Murphy, John A.,Scott, Karen A.,Sinclair, Rhona S.,Lewis, Norman
-
p. 7295 - 7298
(2007/10/03)
-
- SYNTHESIS OF 2,3,5,6-TETRAHYDROIMIDAZOTHIAZOLES
-
The reactions of 2-amino-2-thiazoline with alkylating and acylating agents give initial reaction on the endocyclic nitrogen.Acyl groups, however, readily rearrange to the exocyclic nitrogen to give the products usually observed in these reactions.These observations clear up a considerable amount of confusion in the literature and lead to the efficient synthesis of 2,3,5,6-tetrahydroimidazothiazoles.
- Kaugars, Girts,Martin, Scott E.,Nelson, Stephen J.,Watt, William
-
p. 2593 - 2604
(2007/10/02)
-
- Zeolite and Lewis Acid Catalysis in Diels-Alder Reactions of Isoprene
-
The use of zeolites as catalysts in Diels-Alder reactions of isoprene, 2, has been studied.The regioselectivity in zeolite-catalyzed reactions was compared with the regioselectivity of the same reaction using Lewis acid catalysts.The reaction was studied with seven dienophiles: but-3-en-one (1a), 3-bromobut-3-en-2-one (1b), methyl propenoate (1c), cyclohex-2-enone (1d), phenylethene (1e), ethyl propynoate (1f) and propenenitrile (1g).The following catalysts were investigated: zeolites: ZSM-5, mordenite, zeolite Y-152, zeolite Y-45, and zeolite β Lewis acids: aluminum tribromide, aluminum trichloride, antimony pentachloride, antimony triiodide, boron trifuoride-diethyl ether, manganese difluoride and zinc dichloride.The zeolite-catalyzed reactions afforded the Diels-Alder product with the denophiles 1a-1d, but not with the other dienophiles, 1e-1g.The dienophiles which failed to undergo cycloaddition in the presence of zeolites also did so or afforded poor results with the Lewis acid catalysts.With the exception of the reaction of 1b catalyzed by ZSM-5, which afforded a regioisomeric ratio of 13/87, the other zeolite-catalyzed reactions afforded regioisomeric ratios in the range 6/94-0/100 which is similar to that obtained by Lewis acid catalysis.The experimental conditions were studied in detail for two zeolite catalysts (mordenite, zeolite beta) in the reaction of isoprene with 1d.The optimum experimental conditions with respect to yield and selectivity were established by multivariate techniques.In this reaction, zeolite catalysis was found to afford high yields of cis-6-methyl-6(7)-1-octalone.Under Lewis acid catalyzed conditions, this product is rapidly epimerized into the trans isomer.Full experimental details are given for the preparative use of the method.Examples are provided by the reactions with the dienophiles 1a, 1c and 1d catalyzed by zeolite beta.Factors determining the regioselectivity of zeolite-catalyzed Diels-Alder reaction are briefly discussed.
- Eklund, Lars,Axelsson, Anna-Karin,Nordahl, Ake,Carlson, Rolf
-
p. 581 - 591
(2007/10/02)
-
- Three bacteriorhodopsins with ring-didemethylated 6-s-locked chromophores and their properties
-
Three novel, 6-s-locked rigidified retinals, racemic all-E 1,5-didemethyl-8,16-methanoretinal, all-E, 1,1-didemethyl-8,18-methanoretinal and all-E 8a,18-didehydro-1,1-didemethyl-8,18-methanoretinal were prepared in good yield in high purity on a 100-mg scale.For the preparation of the key intermediate in the synthesis of 1,5-didemethyl-8,16-methanoretinal, reductive cyanation of an unsaturated cyanohydrin to the corresponding conjugated nitrile was accomplished using triethylsilane and trifluoroacetic acid.The three locked retinals interact with bacterioopsin to form bacteriorhodopsin with about the same rate as the native chromophore.This work proves that steric interaction of the 1,1-dimethyl group in the chromophore is an important factor in binding to bacterioopsin.
- Groesbeek, M.,Galen, A. J. J. van,Ippel, J. H.,Berden, J. A.,Lugtenburg, J.
-
p. 237 - 246
(2007/10/02)
-
- Cyanoguanidine derivative and process for preparation thereof
-
A novel cyanoguanidine derivative represented by the following general formula (I): STR1 wherein X stands for a hydrogen atom, a chlorine atom or a bromine atom, and R stands for a lower alkyl group, is an effective precursor for the synthesis of N-cyano-N'-methyl-N"-(2-(5-methyl-4-imidazolylmethylthio(ethyl)-guanidine (Cimetidine) which has an action of controlling secretion of gastric acid and is valuable as an agent for the remedy of a gastric ulcer. This cyanoguanidine derivative is prepared by reacting a methylvinylketone derivative with a mercaptoguanidine derivative or by reacting an amidinoketone derivative with a halogenating agent.
- -
-
-
- Reactions of α-Diazo Ketones with Selenium-based Reagents. A General Synthesis of α-Chloro-, α-Bromo, α-Phenylseleno-, α-Acetoxy-, and α-Methoxy-αβ-unsaturated Ketones
-
Benzeneselenenyl derivatives, PhSe-X (X=Cl, Br, OCOCH3, and SCN) react readily with α-diazo ketones, RCOC(N2)R1 (R1=H or alkyl), with loss of nitrogen, furnishing αα-adducts of the type RCOCR1(X)SePh.The α-chloro and α-bromo adducts can be converted into α-methoxy adducts in methanol-sodium hydrogen carbonate.The utility of these adducts in synthesis is illustrated by their conversion (where structural considerations permit) via selenoxide fragmentation into α-heterosubstituted αβ-unsaturated ketones.Treatment of the series RCOCR1(X)SePh (R1=alkyl; X=Cl, Br, OCOCH3, and OCH3) with hydrogen peroxide-pyridine produces α-chloro-, α-bromo-, α-acetoxy-, and α-methoxy-αβ-unsaturated ketones, whereas treatment of series RCOCR1(X)SePh (R1=alkyl; X=Cl and Br) with lithium carbonate in dimethylformamide produces α-phenylseleno-αβ-unsaturated ketones.Several α-substituted cyclopentenones, cyclohexenones, and cycloheptenones have been synthesised in this way and acyclic examples are illustrated by the synthesis of 3-chloro-, 3-bromo-, 3-acetoxy-, 3-methoxy,-and 3-phenylselenobut-3-en-2-one from 3-diazobutan-2-one.
- Buckley, Daniel J.,McKervey, M. Anthony
-
p. 2193 - 2200
(2007/10/02)
-
- The electrophilic addition of dimethylbromosulfonium bromide to conjugated enones: efficient synthesis of α-bromo enones
-
Dimethylbromosulfonium bromide reacted readily with many enones at 0 deg C or lower to precipitate α-bromo-β-sulfonium conjugated enones.These salts eliminate a proton and dimethylsulfide readily with aqueous potassium carbonate to give excellent yields o
- Chow, Yuan L.,Bakker, Bert H.
-
p. 2268 - 2273
(2007/10/02)
-