N-Formyl

The important synthesis of pyrazoles and pyrazolines from aldazines and ketazines belongs to this subsection. Formic acid has often been used to carry out the cyclization (66AHQ6)347) and N-formyl-A -pyrazolines are obtained. The proposed mechanism (70BSF4119) involves the electrocyclic ring closure of the intermediate (587) to the pyrazoline (588 R = H) which subsequently partially isomerizes to the more stable trans isomer (589 R = H) (Section 4.04.2.2.2(vi)). Both isomers are formylated in the final step (R = CHO). 

Dibenzo[6,/][l,4]selenazocine, N-formyl-6,11-dihydro-synthesis, 6, 34l Dibenzoselenophene, 2-amino-diazotization, 4, 951 Dibenzoselenophene, 2-nitro-reduction, 4, 951 Dibenzoselenophene, 3-nitro-5-oxide... 

HCO2H, DCC, Pyr, 0°, 4 h, 87-90% yield. These conditions produce N-formyl derivatives of r-butyl amino acid esters with a minimum of race-mization. -... 

The enamine (191) from isobutyraldehyde on treatment with p-nitrophenyl-diazonium chloride, on the other hand, gave the p-nitrophenylhydrazone of acetone (192) and presumably N-formyl piperidine, although the latter was not isolated. 

The Madelung indole synthesis has been employed in the preparation of some complex indole systems. Uhle et al. reported the conversion of N-formyl-5,6,7,8-tetrahydronaphthylamine 28 into 1,3,4,5-tetrahydrobenz[c,ti]indole 29 with t-BuOK in 11% yield in regard to synthesis of ergot alkaloids. ... 

Alternately, amifloxacin can be prepared via the ofloxacin/difloxacin route using an addition-elimination reaction with unsymmetiical N-methyl-N-formyl hydrazone to give 49 [14]. 

After the addition is complete, the whole Is cooled on an ice bath and there is added drop-wise a solution of 144 parts dl-N-formyl-N-[(ethoxycarbonyl)methyl] -1-phenylethylamine in 133 parts ethyl formate. After the addition is complete, the mixture is stirred overnight at room temperature. 

The dl-2-(N-formylamino)isocamphane (193 g) was dissolved in 1.9 liters n-heptane by heating on a steam bath. After clarifying the solution by filtration, the clear filtrate was allowed to stand at room temperature until crystallization was complete. The crystalline product is filtered by suction, washed with a little cold n-heptane and air dried. The dl-2-(N-formyl-amino)isocamphane melted at 169° to 174°C. 

Preparation of 3-(N-Formyl-N-Methyl)-Aminopropanol-1 A mixture of 40 grams of 3-methylaminopropanol-1 and 20 grams of formamide Is heated while stirring for 4 hours at 165°C. The crude product is fractionated in vacuo using a Widmer column yielding substantially pure 3-(N-formyl-N-methyl)-aminoprOpanol-1. 

Preparation of 5-[3-(N-Formyl-N-Methyl)-Aminopropyl]-SH-Dibenzo[a,d] Cycloheptene ... 

To a suspension of 3.9 grams of potassium amide is slowly added a solution of 19.2 grams (0.1 mol) Of 5H-dibenzo[a,d] cycloheptene in 600 ml of ether with stirring. The suspension is refluxed with stirring for 3 hours, then cooled to room temperature and a solution of 0.1 mol of 3-(N-formyl-N-methyl)-aminopropyl chloride in 100 ml of ether added. The mixture is then refluxed with stirring for 5 hours and then 100 ml of water added. The ether layer is then washed with dilute hydrochloric acid, then water and then dried over magnesium sulfate and evaporated to dryness yielding 5-[3-(N-formyl-N-methyl)-amino-propyl] -5H-dibenzo[a,d] cycloheptene. 

Preparation of 5-(3-Methylaminopropyl)-5H-Dibenzo[a,d]Cycloheptene from 5-[3-(N-Formyl-N-Methylj-Aminopropyl]SH-Dibenzo[a/i]Cycloheptene 29.5 grams of 5-[3-(N-formyl-N-methyD-aminoprOpyl] -5H-dibenzo[a,d] cycloheptene is refluxed for 24 hours under nitrogen in a solution of 36.3 grams of potassium hydroxide in 378 ml of n-butanol. After cooling to room temperature, the solvent Is evaporated in vacuo, the residue is stirred with 200 ml of water, 300 ml of n-hexane, the layers separated, the water layer extracted with 100 ml of n-hexane and the combined hexane layers washed with water (2 x 100 ml) and then with... 

N-Carboxy-a -amino-carbonsaure-anhydride (Leuchs-Anhydride, 2,4-Dioxo-tetrahy-dro-l,3-oxazole) werden durch Lithiumalanat reduktivzu 2-Amino-alkoholen (neben wenig N-Formyl-aminosaure) aufgespalten z.B.2 ... 

Dies wird zur selektiven Reduzierung der N-Formyl-Gruppe bei N-Formyl-dipeptid-estern ausgenutzt5. Auch die Reduktionen von Halogen-carbonsaure-amiden verlaufen selektiv. 

Die kathodische Reduktion von l,4-Dibrom-bicyclo[2.2.1]heptan in DMFergibt neben Bicyclo[2.2.1]nonan (I) und Pentacyclo 4.2.2.22 sl1,bl2 s]tetradecan (II) 1-(N-Methyl-N-formyl-amino)-bicyclo[2.2.1, ]heptan (III)4 ... 

N-Formyl-2-nitro-anilin wird in acetatgepuffertem wabrigem Athanol zu Benzimida-zol-3-oxid reduziert3 ... 

Figure 6.37 Peptide deformylase-catalyzed hydrolysis of N-formyl amino acids.

Pr)4, " borohydride-exchange resin,and formic acid. When the last is used, the process is called the Wallach reaction. Conjugated aldehydes are converted to alkenyl-amines with the amine/silica gel followed by reduction with zinc borohydride.In the particular case where primary or secondary amines are reductively methylated with formaldehyde and formic acid, the method is called the Esch-weiler-Clarke procedure. It is possible to use ammonium (or amine) salts of formic acid, " or formamides, as a substitute for the Wallach conditions. This method is called the Leuckart reaction,and in this case the products obtained are often the N-formyl derivatives of the amines instead of the free amines. Primary and secondary amines can be iV-ethylated (e.g., ArNHR ArNREt) by treatment with NaBH4 in acetic acid. Aldehydes react with aniline in the presence of Mont-morillonite KIO clay and microwaves to give the amine. Formaldehyde with formic acid converts secondary amines to the N-methyl derivative with microwave irradiation. 

CJ6H13I2NO5 94298-44-9) see Dextrothyroxine L-/V-formyl-3,5-diiodothyronine (CifiHi3l2NOj) see Levothyroxine D(-)-A/-formyl-3,5-diiodothyronine ( i6Hi3l2N05 120408-14-2) see Dextrothyroxine N-formyl-l,5-dimethyl-4-hexenamine (CyH,7NO) see Heptaminol 10-formylfolic acid... 

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