Acetamide Chloride

Hinkel and Treharne (1945) did not refer to Hantzsch s observation and stated that hydrogen chloride readily combines with acetonitrile at low temperatures (ice-salt) to form the crystalline acetamide dichloride MeCCl2NH2, mp 6°C, although it was stated that at 40 C/11 mm the solid dichloride lost its crystalline structure. At ordinary temperatures methyl cyanide, acetamide chloride [CH3C(C1)=NH], and hydrogen chloride were obtained, but there was no stated evidence for the existence of the monochloride. 

A certain amount of hydrolysis of the original acetamide to acid and ammonia always occurs, and the final amine always contains traces of ammonia. This is separated by extracting the mixed anhydrous hydrochlorides with absolute ethanol, which dissolves the amine hydrochloride but not the ammonium chloride filtration of the hot ethanolic extract removes the ammonium chloride, whilst the amine hydrochloride crystallises readily from the filtrate on cooling. 

Place 45 g. of benzamide (Section IV, 188) and 80 g. of phosphorus pentoxide in a 250 ml. Claisen flask (for exact experimeutal details on the handling and weighing out of phosphoric oxide, see under Acetamide, Section 111,111). Mix well. Arrange for distillation (Fig.//, 29, 1 or Fig. II, 20, 1) under reduced pressure use a water pump with an air leak in the system so that a pressure of about 100 mm. is attained. Heat the flask with a free flame until no more liquid distils the nitrile will pass over at 126-130°/100 mm. Wash the distillate with a little sodium carbonate solution, then with water, and dry over anhydrous calcium chloride or magnesium sulphate. Distil under normal pressure (Fig. II, 13, 2 or II, 13, 6) from a 50 ml. flask the benzonitrile passes over as a colourless liquid at 188-189° (compare Section IV,66). The yield is 28 g. 

Ohta (344) prepared 2,4-dimethylthiazole (10), Rj=R2 = Me, Rj H, in fairly low yield by condensing a-mercaptoacetone with acetamide in the presence of anhydrous zinc chloride. 

Acetyl chloride Acetic anhydnde Methyl acetate Acetamide... 

Solubility. Acryhc fibers are insoluble in methanol, acetone, and methylene chloride and soluble in dimethylform amide, dimethyl acetamide, and... 

Dimethylformamide [68-12-2] (DME) and dimethyl sulfoxide [67-68-5] (DMSO) are the most commonly used commercial organic solvents, although polymerizations ia y-butyrolactoae, ethyleae carboaate, and dimethyl acetamide [127-19-5] (DMAC) are reported ia the hterature. Examples of suitable inorganic salts are aqueous solutioas of ziac chloride and aqueous sodium thiocyanate solutions. The homogeneous solution polymerization of acrylonitrile foUows the conventional kinetic scheme developed for vinyl monomers (12) (see Polymers). 

MPD-1 fibers may be obtained by the polymeriza tion of isophthaloyl chloride and y -phenylenediamine in dimethyl acetamide with 5% lithium chloride. The reactants must be very carefully dried since the presence of water would upset the stoichiometry and lead to low molecular weight products. Temperatures in the range of 0 to —40° C are desirable to avoid such side reactions as transamidation by the amide solvent and acylation of y -phenylenediamine by the amide solvent. Both reactions would lead to an imbalance in the stoichiometry and result in forming low molecular weight polymer. Fibers are dry spun direcdy from solution. 

Technora. In 1985, Teijin Ltd. introduced Technora fiber, previously known as HM-50, into the high performance fiber market. Technora is based on the 1 1 copolyterephthalamide of 3,4 -diaminodiphenyl ether and/ -phenylenediamine (8). Technora is a whoUy aromatic copolyamide of PPT, modified with a crankshaft-shaped comonomer, which results in the formation of isotropic solutions that then become anisotropic during the shear alignment during spinning. The polymer is synthesized by the low temperature polymerization of/ -phenylenediamine, 3,4 -diaminophenyl ether, and terephthaloyl chloride in an amide solvent containing a small amount of an alkaU salt. Calcium chloride or lithium chloride is used as the alkaU salt. The solvents used are hexamethylphosphoramide (HMPA), A/-methyl-2-pyrrohdinone (NMP), and dimethyl acetamide (DMAc). The stmcture of Technora is as follows ... 

The aramids are formed in the low temperature reaction, -10 to 60°C, of equimolar amounts of the diacid chloride and the diamine in an amide solvent, typically dimethyl acetamide (DMAc) or A/-meth5i-2-pyrrohdinone (NMP) and usually with a small amount of an alkaU or alkaline-earth hydroxide and a metal salt, such as LiOH [1310-65-2] LiCl, Ca(OH)2 [1305-62-0] or CaCl2 added to increase the solubiUty of the polymer and neutralize the hydrochloric acid generated in the reaction. 

Aqueous salt solutions such as saturated 2inc chloride [7646-85-7] or calcium thiocyanate [2092-16-2] can dissolve limited amounts of cellulose (87). Two non-aqueous salt solutions are ammonium thiocyanate [1762-95-4]— uoamonia. and lithium chloride /744Z-4/A/—dimethyl acetamide [127-19-5]. Solutions up to about 15% can be made with these solvents. Trifluoroacetic acid [76-05-17—methylene chloride [75-09-2] and /V-methy1morpho1ine N-oxide [7529-22-8]—(92—94) are two other solvent systems that have been studied (95). 

The heHcoidal stmcture of such Hquid crystals can be carried to the soHd state by cross-linking (119,120) or by careful evaporation of solvent (121,122). Underivatized ceUulose can also form ordered mesophases (123,124), and gel films precipitated from lithium chloride—dimethyl acetamide retain some mesophase stmcture (122). 

Several triazinyl ketones isomerize to 4-acetamidopyrimidines. TTiis is seen in the C-acylation of 2,4,6-trimethyl-l,3,5-triazine (708) with benzoyl chloride in the presence of sodium amide to give the ketone (709) which undergoes a Dimroth-like rearrangement in boiling water to afford A-(2-methyl-6-phenylpyrimidin-4-yl)acetamide (710) it can be seen that the acylating agent determines the identity of the 6-substituent 64JHC145). 

Amino-5-nitrosopyrimidines also condense with benzoylacetonitrile, phenacyl-pyridinium bromide and acetonylpyridinium chloride in the presence of sodium cyanide to produce. 7-amino-6-pteridinyl ketones (63JOC1197). Pteridine syntheses from pyridinium salts are not limited to the preparation of pteridyl ketones since pyridinium acetamide... 

The simplest method for acetamide preparation involves reaction of the amine with acetic anhydride or acetyl chloride with or without added base. Some other methods are listed below. 

In a 1-1, three-necked, round-bottomed flask equipped with a calcium chloride drying tube, a mechanical stirrer, and a ground-glass stopper are placed 28.2 g. (0.184 mole) of freshly distilled methyl bromoacetate, 500 ml. of anhydrous iV,iV-dimethy]acetamide (Note 1), and 20.0 g, (0.168 mole) of methyl nitroacetate (Note 2). The solution is stirred vigorously while 146 ml. (0.168 mole) of 1.15N sodium methoxide in... 

Figure 20.1 shows the structures of various derivatives of acetic acid (acetyl chloride, acetic anhydride, ethyl thioacetate, ethyl acetate and acetamide) arranged in order... 

In a later paper Speziale and Smith 109) investigated the reaction of trivalent phosphorus compounds with N-monosubstituted a-trichloro-acetamides and a-trichloroacetamide. The products were imidoyl chlorides (129) and dichloroacetonitrile (130), respectively. The intermediacy of enamines (131) was assumed. For the monosubstituted amides the enamine... 

A general method for malting Camps precursors has been developed/ Treatment of an anthranilic acid 15 with an acid anhydride or chloride in the usual way results in the corresponding benzoxazinone (16). Subsequent treatment with the dianion of an N-substituted acetamide furnishes P-keto amide 17. The reactions were run with crude 16, yields typically 50-80% overall. The effect of substituents on the reaction has not been extensively investigated. 

Finally, attachment of a rather complex side chain to the para position of the benzene ring on the sulfonamide leads to the very potent, long-acting oral antidiabetic agent, glyburide (215). Preparation of this compound starts with the chlorosul-fonation of the acetamide of 3-phenethylamine (209). The resulting sulfonyl chloride (210) is then converted to the sulfonamide (211) and deacylated (212). Reaction with the salicylic acid derivative, 213, in the presence of carbodiimide affords the amide, 214. Condensation of that with cyclohexylisocyanate affords glyburide (215). ... 

Preparation of 1 -(/3-D-arabinofuranosyl)-2-thiocytosine A solution of 2.0 g of 1 -(2, 3, 5 -0-triacetyl-/3-D-arabinofuranosyl)-2,4-dithiouracil in 100 ml of methanol is saturated with anhydrous ammonia at 0°C. The mixture, in a glass liner, is heated in a pressure bomb at 100°C for three hours. The reaction mixture is concentrated to a gum in vacuo, and most of the byproduct acetamide is removed by sublimation at 60°C/0.1 mm. The residue is chromatographed on 100 g of silica gel. Elution of the column with methylene chloride-methanol mixtures with methanol concentrationsof 2-25% gives fractions containing acetamide and a series of brown gums. The desired product is eluted with 30% methanol-methylene chloride to give a total yield of 0.386 g (30%), MP 175°-180°C (dec.). Recrystallization from methanol-iso-propanol furnishes an analytical sample, MP 180°-182°C (dec.). 

D(-) mandelic acid Thionyl chloride Monotrimethyl sllyl acetamide... 

To 13 of ethyl acetate were added 85.1 g (2.59 mols) of 7-emino-3-(1 -methyl-1H-tetrazol-5-ylthiomethyl)-3-cephem-4-carboxylic acid and 1,361 g (10.37 mols) of monotrimethylsilyl acetamide, and the mixture was stirred at 50°C until a clear solution was obtained. The solution was cooled to 20°C and 514 g (2.59 mols) of 0-formyl mandeloyl chloride was added at a rate such that the temperature of the reaction solution was maintained between about 20°C to 25°C with ice-cooling. 

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] -... 

The purified intermediate melted at 210°C. 70.9 g (0.10 mol) of the intermediate was dissolved in 150 ml dimethyl acetamide, and 15 g (0.08 mol) tributylamine was added. The mixture was heated to 50°C, and 56.6 g (0.62 mol) 1,3-dihydroxyisopropylamine (2-amino-1,3-pro-panediol) dissolved in 80 ml dimethylacetamide was added drop by drop. The reaction went to completion within a few hours, and the reaction mixture was evaporated to dryness in a vacuum. The oily residue was added to 350 ml methylene chloride with vigorous agitation, and the resuiting precipitate was filtered off and purified by repeated suspension of warm methyiene chioride. 

A. Ammonia reacts with acetyl chloride (CH3COCI) to give acetamide (CH3CONII2). Identify the bonds broken and formed in each step of the reaction, and draw curved arrows to represent the flow of electrons in each step. 

DNA sequencing and. 1113 Electrospray ionization (ESI) mass spectrometry, 417-418 Electrostatic potential map, 37 acetaldehyde, 688 acetamide, 791,922 acetate ion. 43. 53, 56, 757 acetic acid. 53. 55 acetic acid dimer, 755 acetic anhydride, 791 acetone, 55, 56. 78 acetone anion, 56 acetyl azide, 830 acetyl chloride, 791 acetylene. 262 acetylide anion, 271 acid anhydride, 791 acid chloride, 791 acyl cation, 558 adenine, 1104 alanine, 1017 alanine zwitterion, 1017 alcohol. 75 alkene, 74, 147 alkyl halide, 75 alkyne. 74... 

Oxalyl chloride, reaction with a chloro-acetamide, 46,16... 

N,N-Dimethylamlme, condensation with oxyalyl chloride, 41, 1 in reaction of cyanoacctyl chloride and lert-butyl alcohol, 41, 6 N-(2,4-Dimethylbenzyl)-acetamide, 42, 18... 

A related process reacts acetamide with amines and aluminum chloride to give the N-acetyl amine. ... 

---