Formamide, dimethyl-, compound with

Compound 1567 CB and chloracetone are caused to react as in (B), the mineral salts subsequently filtered, 12 ml of concentrated hydrochloric acid are added to the solution in dimethyl formamide without dilution with water, and the mixture heated for 40 minutes on a water bath. The product crystallizes in the warm mixture, the mixture is cooled to room temperature, filtered, the residue washed with water and crystallized from acetic acid. MPc = 222°C. Yield 60% based on compound 1567 CB. 

Spirothiopyrans 45b including a benzopyrylium ring have been prepared in one step by condensation of 2-aminovinyl-3-formyl chromone-4-thione 47 with 1,2,3,3-tetramethylindolinium salts in ethanol (Scheme 25).90 The precursor 47 is prepared from 3-carboxymethylene-2-methyl-chromone-4-thione 48. First, oxidation of 48 with pyridinium dichromate in CH2C12, and then condensation with dimethyl formamide dimethyl acetal in benzene gave compound 47. 

L = dimethyl formamide (DMF), dimethyl sulfoxide (DMSO), and triphenylphos-phine oxide (OPPh3). The former illustrates how simple polyethers may stabilize the hydrated dioxomolybdenum(VI) bromide core. The others are representative examples of addition compounds with ligands that are able to displace water from the coordination sphere of molybdenum but at the same time are not sufficiently basic toward the proton to cause formation of hydrobromides and molybdates. 

C) Preparation of 2-Acetyl-3-Methyl-5-(2-Oxo-2,5-Dihydro-4-Furyl)Benro[b]Furan (3556 CB) (1) A suspension of 2 grams of the compound prepared according to (B) in 20 ml of concentrated hydrochloric acid, is heated to about 50°C, just until it dissolves. There after it is heated for 2 minutes to 70°C, just until precipitation commences. The mixture is allowed to cool, diluted with water, filtered, the residue washed, dried, and sublimed at 200°C and 0.1 mm pressure. 1.4 grams of product (Yield 70%) is obtained. MPc=218°-221°C. A second sublimation produces a chemically pure product. MPC= 221°-222°C. (2) Compound 1567 CB and chloracetone are caused to react as in (B), the mineral salts subsequently filtered, 12 ml of concentrated hydrochloric acid are added to the solution in dimethyl formamide without dilution with water, and the mixture heated for 40 minutes on a water bath. The product crystallizes in the warm mixture, the mixture is cooled to room temperature, filtered, the residue washed with water and crystallized from acetic acid. MPC= 222°C. Yield 60% based on compound 1567 CB. 

The oxyphosphoranes are made from the reaction of a trivalent phosphorus compound with a carbonyl compound. 6 DMF=dimethyl-formamide HFIP=hexafluoroisopropyl alcohol. c l-Phospha-2,8,9-trioxaadamantane. d ca. 0-2m soln. ca. 1m soln. tea. 2m soln. 

The electrically neutral marker substance employed to measure the velocity of the electro-osmotic flow has to fulfill the following requirements. The compound must be soluble in the electrolyte solution and neutral in a wide pH range and no interaction with the capillary wall must occur. In addition, the electrically neutral marker substance should be easily detectable in order to allow a small amount to be injected. If the electrically neutral marker interacts with the capillary wall or becomes partially charged by complexation with the components of the electrolyte solution, the measured electro-osmotic velocity may appear slower or faster than the real flow. Some compounds that adequately serve as electrically neutral markers include benzyl alcohol, riboflavin, acetone, dimethyl-formamide, dimethyl sulfoxide, and mesityl oxide. 

The commercially available isomer of dehydroascorbic acid is a crystalline, symmetric dimer comprising a system of five fused rings (4, 22), IV, and not the traditional textbook compound with the formula V. The latter has not been isolated and characterized, and is presumably not present in significant amount when the vitamin is oxidized. If the oxidation of L-ascorbic acid takes place in inert solvents such as dimethyl-formamide or dimethyl sulfoxide, it has been shown by Hvoslef and Pedersen (5), using NMR methods, that at low temperatures a dimer identical to the crystalline compound is formed. When the temperature... 

At high temperatures (140-180 °C), dibenzylcarbonate (DBzlC) is an efficient benzylating agent of phenol and methylene acidic compounds, such as phenylacetonitrile and benzyl phenylacetate (77). At reflux temperature in N,N-dimethyl-formamide (DMF) solvent with KjCOs as the catalyst, DBzlC react with phenol to yield the benzyl phenyl ether (Eq. 9). Phenylacetonitrile yields the monobenzylated compound (2,3-diphenyl-propionitrile) (Eq. 10). 

Abstract - This work is concerned with the origin of effects on rate equilibrium processes when reactions are performed in dipolar aprotic media such as dimethyl sulfoxide and dimethyl-formamide compared to typical hydroxylic media. An example of processes studied in our laboratory is the competition between proton abstraction and a-complex (Meisenheimer adduct) formation in the interaction of nitroaromatic compounds with basic systems (e.g. 1,3-dinitrobenzene in DMF-D20-Na0D). Other reactions studied are the base catalyzed isotopic exchange of D2 in aqueous DMSO mixtures, and also isotopic exchange of fluoroform. It has been found possible in certain cases to dissect the initial state and transition state contributions to the reaction rates from the kinetically measured enthalpies of activation and the thermodynamically evaluated enthalpies of transfer of the reactants. This procedure affords insight into transition state properties and behaviour. 

The Leuckart reaction (reductive amination of carbonyl compounds with formamide and formic acid) of 2-norbornanone and (lR)-(V-(3,3-dimethyl-2-oxo-l-norbornyl) acetamide furnishes the expected A-(2-norbornyl)formamides. (l/()-AI-(7,7-Dimethyl-2-0X0-l-norbornyl)acetamide, on the other hand, gives a product resulting from a Wagner-Meerwein rearrangement of the usual cationic intermediate followed by an unprecedented transamination, which affords an A,A-diacylammonium ion. Hydrolysis gives (15 )-A-(3,3-dimethyl-2-oxo-l-norbornyl)acetamide, which then undergoes the normal Leuckart reaction. 

The methodology presented can also be exploited for the preparation of six-membered heterocyclic systems, as illustrated in Figure 5.29. For example, [ C]formylation of the precursors 84 and 88 with acetic r CIfoimic anhydride (Af C1FA. 831 and dimethvlf C1-formamide dimethyl acetal (87), respectively, provided 8-[2- C]azaadenine 85 and 5-r6- " C1azacvtidine 89 in excellent yields. Compound 85 was used as akey intermediate... 

The desired pyridylamine was obtained in 69 % overall yield by monomethylation of 2-(aminomethyl)pyridine following a literature procedure (Scheme 4.14). First amine 4.48 was converted into formamide 4.49, through reaction with the in situ prepared mixed anhydride of acetic acid and formic acid. Reduction of 4.49 with borane dimethyl sulfide complex produced diamine 4.50. This compound could be used successfully in the Mannich reaction with 4.39, affording crude 4.51 in 92 % yield (Scheme 4.15). Analogous to 4.44, 4.51 also coordinates to copper(II) in water, as indicated by a shift of the UV-absorption maximum from 296 nm to 308 nm. 

In the examples, a nitro group is substituted for a hydrogen atom, and water is a by-product. Nitro groups may, however, be substituted for other atoms or groups of atoms. In Victor Meyer reactions which use silver nitrite, the nitro group replaces a hahde atom, eg, I or Br. In a modification of this method, sodium nitrite dissolved in dimethyl formamide or other suitable solvent is used instead of silver nitrite (1). Nitro compounds can also be produced by addition reactions, eg, the reaction of nitric acid or nitrogen dioxide with unsaturated compounds such as olefins or acetylenes. 

Amino-pyridazines and -pyridazinones react with monomethyl- or iV,A-dimethyl-formamide and other aliphatic amides in the presence of phosphorus trichloride, thionyl chloride, phosgene or benzenesuUonyl chloride to give mono- or di-alkylaminomethyl-eneamino derivatives. The same compounds can be prepared conveniently with A,iV-dimethylformamide dimethyl acetal in high yield (Scheme 50). 

---