2.4- Dimethyl-5-formyl

Dimethyl- -formyl-azulen169 3-Formyl-l,4,7-trimethyl-azulen169 1 -Formyl-4,6,8-trimeth y l-azulen1 h R / - Formyl-2,4,6,8-tetramethyl-azulen172... 

Vilsmeier reagent The reagent obtained from POCI3 mixed with either N,N-dimethyl-formamide or N-methylformanilide. Used for introducing the methanoyl (formyl) (-CHO) group into activated aromatic substrates. 

The 2-[2-thienyl]selenazole is formylated in the 5-position by action of n-butyllithium. dimethyl formamide. and hydrolysis (106). 

Hydroformylation. Esters of maleate and fumarate are treated with carbon monoxide and hydrogen in the presence of appropriate catalysts to give formyl derivatives. Dimethyl fumarate [624-49-7] is hydroformylated in 1 1 CO/H2 at 100°C and 11.6 MPa pressure with a cobalt [7440-48-4] catalyst to give an 83% yield of dimethyl formylsuccinate [58026-12-3] product (72). 

Dimethylisoxazol-5-amine is easily acylated to its formyl derivative (697) which, on catalytic hydrogenation, undergoes ring cleavage and recyclization to yield 5,6-dimethyl-pyrimidin-4(3H)-one (698) other acyl derivatives give analogous 2-substituted pyrimidines... 

Acridine, 9,10-dihydro-9,9-dimethyl-as antidepressant, 1, 169 Acridine, 9-formyl-synthesis, 2, 507 Acridine, 3-hydroxy-formylation, 2, 322 Acridine, 9-hydroxy-N-oxide... 

Imidazole, 2-ethyl-1 -(o-nitrophenyl)-cyclization, S, 431 Imidazole, 4-ethyl-2-phenyl-oxidation, S, 405 Imidazole, ethynyl-Michael addition, S, 437 Imidazole, 4-ethynyl-2-phenyl-synthesis, S, 494 Imidazole, 1-formyl-reactions, S, 452 Imidazole, 2-formyl-mass spectra, S, 360 Imidazole, 4-formyl-synthesis, S, 475-476 Imidazole, 2-formyl-1,5-dimethyl-mass spectra, S, 360 3-oxide... 

Vilsmeier-Haack formylation, 4, 222 Indole, dimethyl- C NMR, 4, 172 Indole, 1,2-dimethyl-bis-allylation, 4, 357 Indole, 1,3-dimethyl-nitration, 4, 211 reactions... 

Isoindole, l-benzyl-3-formyl-, 4, 222 Isoindole, 1-cyano-synthesis, 4, 148 Isoindole, 2-cyano-synthesis, 4, 149 Isoindole, 1,3-dimethyl-... 

Pterin, 6,7-dimethyl-5,6,7,8-tetrahydro-configuration, 3, 281 conformation, 3, 281 Pterin, 6,7-diphenyl-chlorination, 3, 296 methylation, 3, 297 reduction, 3, 307 Pterin, 6,7-diphenyl-5,6-dihydro-properties, 3, 306 UV spectrum, 3, 279 Pterin, 6-ethyl-5,6,7,8-tetrahydro-configuration, 3, 281 Pterin, 6-formyl-synthesis, 3, 318 Pterin, 6-formyl-5,8-dihydro-synthesis, 3, 306... 

Pterin, 5-formyl-6,7-dimethyl-5,6,7,8-tetrahydro-structure, 3, 281 Pterin, 6-hydroxymethyl-reactions, 3, 304 structure, 3, 273 Pterin, 7-hydroxymethyl-synthesis, 3, 311... 

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... 

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... 

Pyrazole, 3-ethoxycarbonyl-3 (5 ),5-dimethyl-5 (3 )-pyrazol-l-yl-reduction, 5, 260 Pyrazole, ethynyl-reactions, 5, 261 Pyrazole, 4-formyl-IR spectra, S, 201 NMR... 

Pyrrole-2-carboxylic acid, 4,5-dimethyl-ethyl ester formylation, 4, 217 Pyrrole-2-carboxylic acid, 3-hydroxy-... 

Thieno[3,4-h]thiophene, 2-methoxycarbonyl-formylation, 4, 1052 Thieno[3,4-c]thiophene, 1,3-dimethyl-synthesis, 4, 1058... 

Thiophene, 3-pentadeuterophenyl-chemical shifts, 4, 730 Thiophene, 2-phenyl-oxidation, 4, 800 phototranspositions, 4, 743 rearrangement, 4, 42 reduction, 4, 775 synthesis, 4, 865, 914 UV spectrum, 4, 735 Thiophene, 3-phenyl-photochemical rearrangements, 4, 735 phototranspositions, 4, 743 lsmeier formylation, 4, 759 Thiophene, 2-pivaloyl-Birch reduction, 4, 775 Thiophene, polybromo-reactivity, 4, 829 Thiophene, polylithio-synthesis, 4, 831 Thiophene, (propargylthio)-rearrangement, 4, 746 Thiophene, 2-(3-pyridinyl)-synthesis, 4, 781 Thiophene, 2-(5-pyrimidinyl)-synthesis, 4, 781 Thiophene, 3-pyrrolidinyl-cycloaddition reactions, 4, 68 with dimethyl acetylenedicarboxylate, 4, 788-789... 

The reaction of isocyanates with enamines disubstituted at the -carbon gives -amino- -lactams (107,108). Thus the enamine (16) reacted exothermally with phenylisocyanate to give (33) dimethyl-l-phenyl-4-dimethylamino-2-acetidinone (157), which was converted by acid hydrolysis to 2-formyl-2-methyl propionanilide (158). 

I, 4- and 3,4-Dihydroquinazolines are tautomeric but any attempts to prepare the former w ithout a 1-substituent have led to the latter. The greater stability to proto tropic change of 1,2-dihydronaphthalene over 1,4-dihydronaphthalene is also found in 3,4-dihydroquinazoline. Earlier claims to the preparation of l,4-dihydroquinazolines ° were erroneous and based on incomplete experimental data. The first 1,4-dihydroquinazoline was prepared as recently as 1961. 1-Methyl and l-benzyl-l,4-dihydroquinazolines were obtained from o-methylamino-and o-benzylamino-benzylamines (42) by formylation and ring closure. Attempts to remove the benzyl group gave 3,4-dihydroquinazoline. These 1,4-dihydro compounds are susceptible to oxidation, and attempts made to prepare 1,2-dimethyl-1,4-dihydroquinazoline from o-... 

A somewhat similar method to that mentioned above involves alkylation of 4,4-dimethyl-1,3-oxathiolane 5,5-dioxide 32 at the 2 position followed by FVP at 400°C, which results in fragmentation with loss of SO2 and isobutene to give the aldehydes 33. Other electrophiles that may be used include aldehydes, ketones, and McsSiCl, making this a convenient formyl anion equivalent (79TL3375). 

A highly modified methyl testosterone derivative also exhibits antiandrogenic activity. One synthesis of this compound Involves initial alkylation of methyl testosterone (3 ) by means of strong base and methyl iodide to afford the 4,4-dimethyl derivative Formylation with alkoxide and... 

For example, 5 mols of dimethyl amine and 5 mols of formic acid and water are distilled to 135°C distilling off most of the water. To the remaining liquid, consisting for the most part of the formyl derivative of dimethyl amine, 1 mol of furfural mixed with 1 mol of formic acid is slowly added with heating, the temperature being maintained at 150°C to 170°C, until the reaction is complete. The mixture is then distilled into a receiver. The course of this reaction may be illustrated as follows ... 

The Vilsmeier formylation of copper deuteroporphyrin dimethyl ester (6) in which unsubstituted /3-positions are present yields a complex mixture of mono- and disubstituted formylation products which can be partially separated by chromatography on neutral alumina.106... 

Treatment of m-butyl (S )-4-formyl-2,2-dimethyl-3-oxazolidinccarboxylate ( Garner aldehyde, 3), readily available from /V-Boc-l-serine and configurationally extremely stable49,50, with various nucleophiles preferentially yields the n n(nonchelation)-diastereomeric amino alcohols 4 in high chemical yield51 -55,57-61. 

Under a nitrogen atmosphere 0.23 g (1 mmol) of tm-butyl (S)-4-formyl-2,2-dimethyl-3-oxazolidinecar-boxylate(3) is dissolved in 5 mL ofabs. THF. The clear solution is stirred, cooled to —78 °C, then a solution of 1.3 mmol of the Grignard or lithium reagent is added dropwise. The mixture is stirred at — 78 °C for a further 1 h, then quenched by the addition of 20 mL of sat. aq NH4C1. After dilution with II20 the aqueous... 

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