Bis- acetamide

Included among other differentiating cell lines which have been established in culture, is the human promyelocytic cell line HL-60, which differentiates into more mature myeloid cells upon treatment with retinoic acid and prostaglandin E] (PGEi). Friend erythroleukemia cells differentiate into hemoglobin-producing cells when treated with either dimethyl sulfoxide, or hexamethylene bis-acetamide. 

Methylenedinitramine (l,3-dinitro-l,3-diazapropane) (168) can be prepared from the nitration of the bis-acetamide (166), followed by hydrolysis of the product (167) with barium hydroxide and subsequent acidification.Methylenedinitramine has no practical value as an explosive due to its facile decomposition in solution. 

The synthesis of a water-soluble diphenylmethano-bridged fullerene 122 was achieved by hydrolyzing the bis (acetamide) 121 with acetic acid-aqueous hydrochloric acid and then converting it into the bis(succinamide) 122 by treatment with succinic anhydride (Scheme 4.25) [158]. Compound 122 is soluble in water at pH > 7. This is an important requirement for the investigation of the biological activity of fullerenes. Remarkably, 122 is an inhibitor for the HIV enzymes protease (HIV-P) and reverse transcriptase (HIV-RT) [159]. As suggested by molecular modeling. 

They found that a good yield of ethylenedinitramine may also be obtained from ethylenediamine through diacetylethylenediamine (ethylene-bis-acetamide). The nitration of the latter involves the use of nitric acid (98%) mixed with acetic anhydride ... 

It is important to bear in mind that ethylene-bis-acetamide (earlier prepared by A. W. Hofmann [20]) cannot be nitrated with nitric acid alone or nitric and sulphuric acids. The product of nitration is readily hydrolysed by the action of 30% NaOH solution or ca. 15% NH3 solution at room temperature. 

The reductive cyclization of 2-nitrobenzyl-A, A -bis(formamide) with zinc in acetic acid to quinazoline was first described by RiedelT ° The reaction is used successfully for the synthesis of larger quantities of quinazoline and its benzene-ring-substituted derivatives 12 from 2-ni-trobenzyl-A, A -bis(formamides) 11. The method is suitable only for the preparation of 4-un-substituted quinazolines, because 2-nitro-substituted phenones do not condense with aliphatic amides to yield bis(amide) derivatives. Zinc in acetic acid is the reducing agent of choice, but iron in hydrochloric acid or Raney nickel can also be used. " Applications of compounds other than bis(formamides) [e.g., bis(acetamides) ] and preparation of 2-substituted quinazolines by Riedel s synthesis are scarce. 

Other amides have been used for ring closure with only limited success. The bis-acetamides were used to give only 20-25% yields of the macrocycle (Biernat et al., 1979 Mikiciuk-Olasik and Kotelko, 1984). A bis-formamide was used for ring closure to also give very poor yields (Krakowiak and Bradshaw. 1991). 

GC-MS analysis is an indirect method to detect TTX in a crude extract which is difficult to purify for other advanced analysis. In this method, TTX and its derivatives (0.2 ml with 25 MU) are dissolved in 2 ml of 2 mol/liter NaOH and heated in a boiling water bath for 45 minutes. After being cooled at room temperature, the alkali-decomposed compounds are adjusted to pH 4.0 with 1 mol/liter HCl and extracted thrice with three volumes of 1-butanol. The extracts are combined and evaporated to dryness in vacuum, and to the residue is added a mixture of N,0-bis acetamide, trimethylchlorosilane, and pyridine (2 1 1), in order to derive trimethylsilyl (TMS) Cg-base compounds. The derivatives are then submitted to GC-MS analysis. The column temperature is maintained from 180 to 250° C at a rate of 5°C/minute. The flow rate of inlet helium carrier gas is maintained at 20 ml/minute. The ionizing voltage is usually kept at 70 eV with the ion source temperature at 200°C. 

Friend et al. [1] made the striking observation that dimethyl sulfoxide (DMSO)-treated Friend erythroleukemia cells (FEE) differentiate in vitro. Subsequently, a number of other chemicals, including butyric acid,hypoxanthine andhexamethylene bis-acetamide were shown to induce Friend cells [2], These inducers appear to remove a block in the differentiation process but the mechanisms involved are unknown. The finding that benzamide and nicotinamide induced Friend cells [3, 4] suggested that since both compounds were inhibitors of poly(ADP-ribose) polymerase, poly(ADP-ribosylation) may have a role in the differentiation process. Furthermore, since poly(ADP-ribose) polymerase requires DNA strand breaks for activity [5], these observations implicated DNA strand breaks in FEE differentiation. 

GiHgll tS N.N - niio-bis-acetamid 8II184. 3liioaUophaii8jiine-S-5thyIeMer 3,139. Caib thozy-tfaiohamstcdf 8,191,177,... 

A newer method for the preparation of nitronic esters, namely utilizing the (9-trimethyl-silyl ester, has been reported and these are prepared by the reaction of alkylnitro compounds and (V,(V-bis(trimethylsilyl)acetamide. These nitronic esters also undergo cycloaddition with alkenes to produce isoxazolidines (equation 54) (74MIP41601, 74DOK109, 78ACS(B)ll8). 

Me3SiNHS020SiMe3, CH2CI2, 30°, 0.5 h, 92-98% yield. Higher yields of trimethylsilyl derivatives are realized by reaction of aliphatic, aromatic, and carboxylic hydroxyl groups with A, <9-bis(trimethylsilyl)sulfamate than by reaction with N,<9-bis(trimethylsilyl)acetamide. ... 

A,<9-Bis(trimethyIsilyl)trifluoroacetamide. The reagent is suitable for the silylation of carfjoxylic acids, alcohols, phenols, amides, and ureas. It has the advantage over bis(trimethylsilyl)acetamide in that the byproducts are more volatile. 

The high reactivity of N-H bonds has also been exploited to produce N-F denvatives without significant substitution on neighbonng C-H bonds, Diethyl-phosphoramidates of ammonia, alkylammes, and a,polar solvents to produce difluoroamine [57], N,N-difluoroalkylamines, and a,to-bis(At,7V-difluoroamino)alkanes [52] Acetamide undergoes fluonnation to give modest yields of N,N difluoroacetatnide and acetyl fluonde when fluorinated... 

TMSOCH2CH2OTMS, TfOH or FsOH (fluorosulfonic acid), BTMSA [bis(trimethylsilyl)acetamide] orBTMSU [bis(trimethylsilyl)urea], 76-97% yield-" ... 

DBU, A,0-bis(trimethylsilyl)acetamide." Thiophosphorylated derivatives are cleaved more rapidly than the phosphorylated counterpart. 

In another example treating anilines 40 with acetone under similar conditions gave the desired quinoline 41 as a single regioisomer. It has been reported that the addition of silylating reagents, in particular bis(trimethylsilyl)acetamide, may be beneficial for these types of substrates. ... 

Use of bis(trimethylsilyl)acetamide and bis(trimethylsilyl)urea for protection and as control reagents in reactions with participation of heterocycles 98S357. 

Treatment of the substrate (34) with catalytic (Ph3P)4Pd and dppe provided the desired bicyclo[3.3.0]octanes (35) and the acetate elimination product (36). The choice of ligand is crucial in this case since using only dppe or Ph3P increased the amount of (36). On the other hand addition of BSA (N,0-bis(trimethylsilyl) acetamide) minimized this side product (Scheme 2.12) [24]. 

Preparation of 7-(D-0t-phenyigiycyiamido)-3-chioro-3-cephem-4-carboxyiic acid To a suspension of 280 mg (1.2 mmol) of 7-amino-3-chloro-3-cephem-4-carboxylic acid in 14 ml of acetonitrile was added with stirring at room temperature 0.5 ml of N, 0-bis-(trimethylsilyl)acetamide to form the soluble disilylmethyl derivative thereof. The solution was cooled to 0°C and was slowly added to a solution of the mixed anhydride formed by reacting 408 mg (1.5 mmol) of methyl-3-a-carboxybenzylaminocrotonate sodium salt with 161 mg (1.7 mmol) of methyl chloroformate in the presence to 2 drops of N, N-dimethylbenzyl amine in 7 ml of acetonitrile. 

A suspension of 37.3 g (0.1 mol) of 7/3-amino-3-methoxy-3-cephem-4-carboxylic acid hydrochloride dioxanate in 500 ml methylene chloride is stirred for 15 minutes at room temperature under an argon atmosphere and treated with 57.2 ml (0.23 mol) of bis-(trimethylsilyl)-acetamide. After 45 minutes the faintly yellow slightly turbid solution is cooled to 0°C and treated within 10 minutes with 31.2 g (0.15 mol) of D-Ct-amino-Ct-d, 4-cyclohexadienyl (acetyl chloride hydrochloride. Thirty minutes thereafter 15 ml (about 0.21 mol) of propylene oxide is added and the mixture is further stirred for 1 hour at 0°C. A cooled mixture of 20 ml of absolute methanol in 200 ml of methylene chloride is added within 30 minutes, after another 30 minutes the precipitate is filtered off under exclusion of moisture, washed with methylene chloride and dried under reduced pressure at room temperature. The obtained hygroscopic crystals of the hydrochloride of 7j3-[D-a-(1,4-cyclohexadienyl)acetylamino] -... 

Methoxyimino-2-(2-amino-1,3-thiazol-4-yl)acetic acid Bis(Trimethylsilyl)acetamide 7-Aminocephalosporanic acid... 

Phosphorus oxychloride (2.0 g) was added at one time at 5°C to 10°C to a suspension of 2-methoxyimino-2-(2-amino-1,3-thiazol-4-yl)acetic acid (syn isomer) (2 g) in dry ethyl acetate (20 ml). After stirring for 20 minutes at 7°C to 10°C, bis(trimethylsilyl)acetamide (0.4 g) was added thereto at the same temperature. After stirring for 10 minutes at 7°C to 10°C, phosphorus oxychloride (2.0 g) was dropwise added thereto at the same temperature. The resulting mixture was stirred for 10 minutes at 7°C to 10°C, and dry dimethylformamide (0.8 g) was dropwise added thereto at the same temperature. The mixture was stirred for 30 minutes at 7°C to 10°C to give a clear solution. On the other hand, trimethylsilylacetamide (7.35 g) was added to a suspension of 7-aminocephalosporanic acid (2.45 g) in dry ethyl acetate (8 ml), after which the mixture was stirred at 40°C to give a clear solution. 

Chemical Name 4-[4,4-Bis(4-fluorophenyl)butvU -N-(2,6-dimethylphenyl)-1-piperazine-acetamide... 

BIs-triethylammonium pyrophosphate Adenosine triphosphate Bis(trimethylsilyl) acetamide Cefaclor Cefroxadine Ceftizoxime... 

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