2.6- Dimethyl-4/7-pyran

In 1991, Furukawa et al. reported the isolation of pyrayafoline B (170) from the stem bark of M. euchrestifolia collected in May in Taiwan (87). In the same year, the same group isolated a further pyrano[2,3- ]carbazole alkaloid, pyrayafoline E (171), from the stem bark of M. euchrestifolia. Pyrayafoline E was isolated from Nature in racemic form (70). These alkaloids are the first members of the naturally occurring 2,7-dioxygenated-3-methylcarbazole alkaloids having a dimethyl pyran ring fused to C-6 and C-7 of the carbazole nucleus (70,87) (Scheme 2.35). 

The direct condensation of pentan-3-one with ethyl formate failed to give 3,5-dimethyl-pyran-4-one. Instead, the diketone was produced, the enolate of which is apparently of insufficient reactivity to undergo condensation with a second molecule of ester. However, the isopropyl derivative (407) of the enol condensed with ethyl formate, and the potential triketone cyclized to the pyran-4-one (408) under acid conditions (Scheme 133) (64JOC2678). 

Furukawa, H., M. Yogo, C. Ito, T.S. Wu, and C. Kuoh New Carbazoloquinones Having Dimethyl Pyran Ring System. Chem. Pharm. Bull. 33, 1320 (1985). 

D-fMO MO-Nonitol, 2,6-anhydro-3,S,7-trideoxy-l-C-([hydroxy-(tetrahydro-2-methoxy-5,6-dimethyl-4-methylene-2 H-pyran-2-yl) acetyl] amino)-5,5-di methyl-1, S,9-tri-0-rriethyl-, 2R-[2( j(,2[S (5-q], 5P,6P] -... 

J-Pyran-2-acetamid, Ai-[[6-(2,3-dimethoxypropyl)tetrahydro-4-hydroxy-5,5-dimethyl-2H-pyran-2-yl]rriethoxymethyl]tetrahydro-a-hydroxy-2-methoxy-5,6-dimethyl-4-rTiethylene]-... 

Cyclization. Constmction of ben2otrifluorides from aHphatic feedstocks represents a new technique with economic potential. For example, l,l,l-trichloro-2,2,2-trifluoroethane [354-58-5] and dimethyl itaconate [617-52-7] form 4-methoxy-6-trifluoromethyl-2JT-pyran-2-one [101640-70-4] which is converted to methyl 3-(trifluoromethyi)ben2oate [2557-13-3] ixh. acetjdene or norbomadiene (125). 

Pyrans and related compounds react with ammonia to give pyridines. A commercially useful example is the reaction of dehydroacetic acid (derived from diketene) with ammonia to give 2,6-dimethyl-4-pyridinone [7516-31 -6] via 2,6-dimethyl-4-pyridinone-3-carboxyhc acid [52403-25-5]. Chlorination of the pyridone gives clopidol [2971-90-6] (56), a coccidiostat (72,73). 

H- Pyran-4-one, 3,5-diacetyl-2,6-dimethyl-dipole moment, 3, 626 (37JCS1088) 4H-Pyran-4-one, 2-dichloromethyl- C NMR, 3, 588 (82S500)... 

Pyran, 4-arylimino- C NMR, 3, 585 Pyran, 4-arylimino-2,6-dimethyl-synthesis, 3, 762 Pyran, 2-aryloxytetrahydro-X-ray studies, 3, 621 Pyran, 4-benzyl-isomerization, 3, 666 Pyran, 3-bromodihydro-synthesis, 3, 769 Pyran, -bromodihydro-halogen-metal exchange with t-butyllithium, 1, 474 Pyran, 2-bromotetrahydro- H NMR, 3, 579... 

Pyran, 2,6-dimethyl-4-(p-nitrophenylimino)-crystal structure, 3, 621 Pyran, 4,4-diphenyl-synthesis, 3, 757 Pyran, 2,6-diphenyltetrahydro-conformation, 3, 629 Pyran, ciY-diphenyltetrahydro-synthesis, 3, 774 Pyran, epoxydihydro-synthesis, 1, 475 Pyran, 2-ethoxytetrahydro-dehydration, 3, 773 Pyran, 2-formyl-5-methyl-3,4-dihydro-synthesis, 3, 771... 

Beckmann rearrangement, 3, 710 Pyran-4-carbaldehyde, 2,2-dimethyl-tetrahydro-Reformatsky reaction, 3, 732 4H-Pyran-4-carbaldehydes synthesis, 3, 760-761 Pyran-2-carbonitrile, 5,6-dihydro-reactions, 3, 732... 

H-Pyran-2,6-dicarboxylic acids synthesis, 3, 758 Pyran-2,4-dione, 3,3-dimethyl-photodimerization, 3, 720 reactions... 

Pyran-2-one, 5,6-dibromo-5,6-dihydro-reactions, 3, 735 Pyran-2-one, 5,6-dihydro-allylic bromination, 3, 799 dehydrogenation, 3, 724, 799 H NMR,3, 581 synthesis, 3, 841, 843 Pyran-2-one, 4,6-dimethyl-irradiation, 3, 677 photochemistry, 3, 678 Pyran-2-one, 5,6-dimethyl-chloromethylation, 3, 680 conformation, 3, 631 Pyran-2-one, 5-f ormyl-IR Spectra, 3, 595 Pyran-2-one, 6-formyl-IR spectra, 3, 595 Pyran-2-one, 5-halo-synthesis, 3, 799 Pyran-2-one, 3-hydroxy-IR spectra, 3, 595 Pyran-2-one, 4-hydroxy-methylation, 2, 57 3, 676 pyran-4-one synthesis from, 3, 816 reactions with phosphorus oxychloride, 2, 57 synthesis, 3, 792, 794, 795, 798 tautomerism, 2, 56 3, 642 Pyran-2-one, 4-hydroxy-6-methyl-methylation, 3, 692 reactions... 

Pyran-4-one, 2,6-dimethyl-2,3-dihydro-photochemistry, 3, 719 Pyran-4-one, 2,6-dimethyl-3,5-diphetiyl-synthesis, 3, 813... 

Dimethyl[1,1 -dimethyl-3-(tetrahydro-2H-pyran-2-yloxy)propylsilyl, 657... 

Thiopyrones and selenopyrones can be alkylated more readily than pyrones. Thus 2,6-dimethyl-4/f-pyran-4-thionc (4,6-dimethyl-4-thiopyrone) (23, Y = S) reacts rapidly with methyl iodide yielding a 4-methylmercaptopyrylium iodide (24, Y = S, R = Me, X = I). Many alkylating agents were investigated by King et al. The kinetics of the reaction between 2,6-dimethyl-4-thiopyrone and substituted phenacyl bromides was found to be described by the Hammett... 

Chemical Name 1-Hvdroxy-3-(1, 1 -dimethylheptyl)-6,6-dimethyl-6,6a,7.8,10,10a-hexahy-dro-9H-dibenzo(b/Jl pyran-9-one... 

The mixture was then allowed to warm to room temperature in a nitrogen atmosphere during which process the ammonia evaporated. The reaction mixture was then acidified with 1 N aqueous hydrochloric acid, and the organic constituents extracted with ethyl acetate. The ethyl acetateextracts were combined, washed with water and dried. Evaporation of the ethyl acetate under reduced pressure yielded 1.4 g of crude dl-trans-3-(r,r-dimethylheptyl)-6,6a, 7,8,10,10a -hexahydro-1 -hydroxy-6,6-dimethyl-9H-dibenzo(b/J] pyran-9-one. The... 

Propanol with magnesium in reduction of chlorobenzene, 47, 104 Propionyl fluoride, 46, 6 n Propylamine, 46, 85 n Propylhydrazine, 46, 85 C ( Propyl) N phenylmtrone, genera tion from phenylhydroxylamme and n butyraldehyde, 46, 97 Purification of tetrahydrofuran (Warning), 46,105 4H Pyran 4-one, 2 6 dimethyl 3,5 diphenyl, 47, 54... 

Starting from l.l-dichloro-7b-ethoxy-2-methyl-1,1 a,2,7-tetrahydrobenzo[/)]cyclopropa[prepared from the corresponding benzothiopyran by addition of dichlorocarbene, the three 1-benzothiepins 6a-c are formed upon treatment with strong bases, i.e. sodium methoxide or ethoxide in dimethyl sulfoxide.73 The optimal yield of each 1-benzo-thiepin compound depends on the molar equivalents of base, as follows from different ring-opening mechanisms. 

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