Formanilides

Julolidine has been prepared by the reaction of trimethylene chlorobromide with formanilide, aniline, methylaniline, and tetrahydroquinoline by the reduction of 8,10-diketojuloli-... 

Samal et al. [25] reported that Ce(IV) ion coupled with an amide, such as thioacetamide, succinamide, acetamide, and formamide, could initiate acrylonitrile (AN) polymerization in aqueous solution. Feng et al. [3] for the first time thoroughly investigated the structural effect of amide on AAM polymerization using Ce(IV) ion, ceric ammonium nitrate (CAN) as an initiator. They found that only acetanilide (AA) and formanilide (FA) promote the polymerization and remarkably enhance Rp. The others such as formamide, N,N-dimethylformamide (DMF), N-butylacetamide, and N-cyclohexylacetamide only slightly affect the rate of polymerization. This can be shown by the relative rate (/ r), i.e., the rate of AAM polymerization initiated with ceric ion-amide divided by the rate of polymerization initiated with ceric ion alone. Rr for CAN-anilide system is approximately 2.5, and the others range from 1.04-1.11. 

Addition of up to a tenfold molar excess of hydrogen chloride did not appreciably alter the reaction rate. Orton and Bradfield227 obtained the same kinetic form for the chlorination of formanilide, acetanilide, benzanilide, and benzene-sulphonanilide in 99 % aqueous acetic acid at 20 °C reaction rates were higher than previously obtained with the less aqueous medium, and this medium effect has been subsequently found to be general. 

Formanilid" Eine Mischung von 2,4 g (0,02 Mol) Phenyl-isocyanat und 16 g (0,043 Mol) Triphenyl-zinnhy-drid wird 4 Stdn. auf 100° erhitzt. Man kiihlt ab, extrahiert iiber Nacht kontinuierlich mit Wasser, engt den Aus-zug i. Vak. ein und kristallisiert den Riickstand aus Diathylather/Pentan urn Ausbeute 1,35 g (55% d.Th.) F 45,4-47°. 

Manganese(III)-promoted radical cyclization of arylthioformanilides and a-benzoylthio-formanilides is a recently described microwave-assisted example for the synthesis of 2-arylbenzothiazoles and 2-benzoylbenzothiazoles. In this study, manganese triacetate is introduced as a new reagent to replace potassium ferricyanide or bromide. The 2-substituted benzothiazoles are generated in 6 min at 110°C imder microwave irradiation (300 W) in a domestic oven with no real control of the temperature (reflux of acetic acid) (Scheme 15). Conventional heating (oil bath) of the reaction at 110 °C for 6 h gave similar yields [16]. 

Meth-Cohn has developed an efficient one-pot synthesis of isatins 108 by the sequential treatment of iV-substituted formanilides 107 with oxalyl chloride, Hunig s base, and bromine... 

Formamides have applications as solvents (particularly dimethylformamide (DMF) and formamide itself), as intermediates for insecticides and pharmaceuticals, and (for formanilide, PhNHC(O)H) as an antioxidant [95]. Formamides are prepared either from CO or from methylformate or formamide, which are themselves prepared from CO. 

To 42 g 1,3,5-trimethoxybenzene, 30 g formanilide and 200 ml ether add 19 g POCI3 and let stand twelve hours. Evaporate in vacuum, add 900 ml 5% NaOH and steam distill residue to get the aldehyde (recrystallized benzene-ligroin). 

To 13 g 3,4-dimethoxyphenol in 20 ml methanol add a solution of 5.3 g KOH in 100 ml methanol and then 12 g methyl iodide. Reflux two hours, add 300 ml water and make pH 10 with 5% NaOH. Extract with ether and dry, evaporate in vacuum the pooled extracts to get a clear oil. Mix 17.3 g N-methyl-formanilide and 19.6 g POCI3 and let stand at room temperature for one-half hour. Add 8.5 g of the oil, heat two hours on steam bath (or boiling water) and pour... 

Guo et al. prepared N-(3-chloro-4-fluorophenyl)aminomethylenemalo-nate (256, R = 3-C1, R1 = 4-F, R2 = R3 = Et) in 60-70% yields when 3-chloro-4-fluoroaniline was reacted with triethyl orthoformate and diethyl malonate in the presence of a Lewis acid. From the reaction mixture, ethyl A-(3-chloro-4-fluorophenyl)-2-[(3-chloro-4-fluorophenyl)-aminomethylene]malonamate and A-(3-chloro-4-fluorophenyl)formanilide were also isolated as byproducts (88MI3). 

Further A -alkylation of A -alkylcarboxamides always requires the more vigorous solidtliquid two-phase conditions [4-7], whereas it has generally been found [8, 9] that the more acidic A -aryl derivatives can be alkylated under the milder liquiddiquid conditions (Table 5.11). (It has been shown that, with sufficiently vigorous mixing of the two liquid phases, it is possible to A -methylate formanilides without recourse to a phase-transfer catalyst [8]). 

In contrast to the other large cats, the urine of the cheetah, A. jubatus, is practically odorless to the human nose. An analysis of the organic material from cheetah urine showed that diglycerides, triglycerides, and free sterols are possibly present in the urine and that it contains some of the C2-C8 fatty acids [95], while aldehydes and ketones that are prominent in tiger and leopard urine [96] are absent from cheetah urine. A recent study [97] of the chemical composition of the urine of cheetah in their natural habitat and in captivity has shown that volatile hydrocarbons, aldehydes, saturated and unsaturated cyclic and acyclic ketones, carboxylic acids and short-chain ethers are compound classes represented in minute quantities by more than one member in the urine of this animal. Traces of 2-acetylfuran, acetaldehyde diethyl acetal, ethyl acetate, dimethyl sulfone, formanilide, and larger quantities of urea and elemental sulfur were also present in the urine of this animal. Sulfur was found in all the urine samples collected from male cheetah in captivity in South Africa and from wild cheetah in Namibia. Only one organosulfur compound, dimethyl disulfide, is present in the urine at such a low concentration that it is not detectable by humans [97]. 

Soil A reversible equilibrium is quickly established when aniline covalently bonds with humates in soils forming imine linkages. These quinoidal structures may oxidize to give nitrogen-substituted quinoid rings. The average second-order rate constant for this reaction in a pH 7 buffer at 30 °C is 9.47 x 10 L/g-h (Parris, 1980). In sterile soil, aniline partially degraded to azobenzene, phenazine, formanilide, and acetanilide and the tentatively identified compounds nitrobenzene and jD-benzoquinone (Pillai et ah, 1982). 

Dimethoxy-5-ethoxybenzaldehyde. A mixture of N-methyol formanilide 17.3 g in 19.6 g of POCI3 is allowed to stand for % hour at room temp. Then add 9.2 g of the above ether and heat this mixture for 2 hours on a steam bath. The resulting black viscous product is poured onto 800 ml of cracked ice and allowed to stand overnight. The crude aldehyde is removed by filtration and is recrystallized from 100 ml of MeOH. Yield 8.8 g of fluffy white crystals. 

A similar reversal of the signs of the N—C—H coupling with stereochemistry is not, however, found for the geometric isomer, fi-formanihde (74) and Z-formanilide (75). In both cases, the one- and two-bond reduced couphng constants have been shown to be positive. 

More vigorous conditions were required for the formylation of thienothiophene 3 with an electron acceptor group in the molecule. Thus, refluxing methyl thieno[3,4-6]thiophene-2-carboxylate, iV-methyl-formanilide and phosphorus oxychloride for 1 hour gave a mixture (1 1)... 

A few cases have been recorded (Dreyer, Zeit Phys, Ghem, XLVlii. 487, 1904) where the effect of the addition agent on the crystallisation velocity is to be attributed to an alteration in the diffusion constant of the solute in the solution, thus the velocity of crystallisation of formanilide is increased and not decreased by the addition of methyl or ethyl alcohol to the fused salt. 

Zugabe von geschmolzenem Formanilid zu einem heiBen Gemisch von Natrium und 4-Chlor-l-nitro-benzol in Toluol/Dimethylformamid und weiteres Erhitzen fuhrt zur Bil-dung von (4-Nitro-phenyl)-phenyl-amin (85-94%)2. 

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