4- acetyl-3-thienyl

Nitration of 4-(2-thienyl)- (301) and 4-(3-thienyl)-pyrazoles (302) mainly occurs on the thiophene ring, but when acetyl nitrate is used as the nitration agent small quantities of products nitrated on the pyrazole ring are isolated (position of the nitro group uncertain) (80CS( 15)102). Pyrazol-l -ylpyridines (303) undergo electrophilic reactions (bromination, chlorination and nitration) preferentially in the pyrazole ring. Thus, the nitration of (303 R = R = = H) either with a mixture of nitric acid and sulfuric acid at 10-15 °C or with... 

The reactions of (174) with various amines has been studied." " Hydrolysis of the hexamine salt of (174) gave not the symmetric diamine but (184) via a cyclic intermediate. The pyrolysis of 5-methyl-2-thenyltrimethyl ammonium hydroxide (185) is claimed to give (186) through a 1,6 Hofmann elimination reaction. The Bischler-Napieralski cyclization has been applied to acetyl derivatives of 2-(2-thienyl) ethylamine and 2-(3-thienyl) ethylamine for the preparation of sulfur analogs of isoquinoline. ... 

Many stilbenelike thiophene compounds have been prepared for a study of estrogenic activity, especially by Buu-Hoi et al. Thiophene derivatives of nonhydroxylated stilbene types showed no significant activitywhereas weak estrogenic activity was found in 5-acetyl-, 5-propionyl-, and 5-benzoyl-2-(-stilbenyl)thiophene. 1-Bromo-l,2-diphenyl-2-(5-bromo-2-thienyl)ethylene (258) was found to inhibit body growth and to produce extensive testicular atropy in male rats. A thiophene analog of estrogenic isoflavones (259)... 

Also as noted above any substituents present have little effect upon such oxidations. In 2,2 -methylenedifuran (118) the rings are attacked simultaneously giving a tetramethoxy derivative.297 Even the bulk of the fert-butyl group has little effect.298 The only marked substituent effect is that exerted by an aromatic (benzene, thiophene, furan) residue which, if directly attached at the 2-position, promotes elimination instead of the addition of another methoxy group. The net process then becomes one of arylation, as when 2-(2-thienyl)furan (119) is oxidized to 120.298 There are reports that acetyl and carboxy groups can be ejected during oxidation, but that ester groups are usually retained.287... 

The stereochemical characterization of the adduct 53 follows from its NMR spectrum and a comparison with that of the l-(2-thienyl) compound (54). The aSY-exo configuration for the adducts 51 and 52 is consistent with the NMR spectra (hydrogen atoms at C-2, C-3, C-5, and C-6 all equivalent), with the proposed mechanism of formation, and with the failure of the related tetramethyl ester to xmdergo N-acetylation even in very vigorous conditions. N-substituted derivatives of compounds such as 51-53 may be obtainable directly from similar dipolar cycloaddition reactions of mesoionic N-substituted oxazolium 5-oxides, although the formation of only the N-methyl derivative of (52) has so far been reported. ... 

The preparation of various alkenylbenzo[6]thiophenes by dehydration of side-chain alcohols is discussed in Section VI, J. l,l-Di(2-benzo[6]thienyl)ethylene may be prepared by treating 2-benzo[6]-thienyllithium with acetyl chloride,132 and the olefins (158a-d) may... 

Reaction of 2-benzo[6]thienyllithium (and its 7-methyl derivative 90) with aldehydes 486,5fl4, 620 or ketones 467 483 affords a secondary or tertiary alcohol, respectively. Treatment of 2-benzo[6]thienyl-lithium with acetyl chloride gives mainly l,l-di(2-benzo[6]thienyl)-ethylene.132 Side-chain alcohols in positions other than the 2-position are most easily prepared by reaction of the appropriate benzo[6]-thienylmagnesium halide with aldehydes 460,471 or ketones,186,3o9, 349, 4 7,466,479,498 or foy reaction of a benzo[fe]thiophene aldehyde, ketone, or ester with an alkylmagnesium halide.358,427 465 The preparation of alcohols from 2- and 3-benzo[6]thienylmethyl-magnesium chloride485,528 is discussed in Section VI, D, 4. 

Similar treatment of the C-heteroarylhydrazonoyl bromide 28c with sodium acetate in glacial acetic acid gave the hydrazide 305 in 85% yield. Heating 305 in dimethylformamide in the presence of bases afforded 4-acetyl-7-bromo-2-(5-bromo-2-thienyl)-4//-l, 3,4-benzoxadiazine 306 in 6% yield [72JCS(P1)2915]. 

Acetyl-3-methylthiophene (Methyl 3-methyl-2-thienyl ketone) COCHj CH3... 

Similar reactions starting with the ethylene acetals of 3-formyl- or 3-acetyl-2-thienyl dimethyl telluronium iodides yielded 3-formyl- or 3-acetyl-2-thienyl methyl tellurium. The acetals were hydrolyzed before the products were isolated2. 

Butyl 3-thienyl tellurium was lithiated exclusively in the 5-position of the thiophene ring upon treatment with lithium diisopropylamide. The lithiated compound reacted with dimethylacetamide to produce 5-acetyl-3-thienyl butyl tellurium1. 

Preparation of /V -acetyl-A,-(2-methylpropyl)-/V-[3-ethoxycarbonyl-5-(l-naphthalenylmethyl)-2-thienyl]urea... 

Oxiran trans-3-(Diazo-acetyl)-2-(2-thienyl)- E14b, 1194 (Oxiran-Bild.)... 

Propansaure 2-Acetamino-3-(2-thienyl)- E18, 535/542 (En - An) Thiophen 2-Acetyl-5-amino-4-... 

Catalyst or with acetyl chloride and aluminum chloride catalyst have been reported. o-Nitrophenyl 2-thienyl ketone has been prepared. ... 

Benzylidene-3-oxo-2,3-dihydro-l-benzotellurophene reacted with hydrogen bromide in glacial acetic acid to produce 2-(2 -phenylethenylcarbonyl)phenyl tellurium bromide. Thienyl ethoxycarbonylmethyl tellurides with a formyl or acetyl group in the orf/to-position to tellurium were also converted to tellurium bromides upon treatment with 48% aqueous hydrobromic acid or glacial acetic acid saturated with hydrogen bromide. Only polymeric materials were obtained from 4-formyl-3-thienyl ethoxycarbonylmethyl tellurium. ... 

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