Ethyl, amine iodide

N-Methylethylamine has been prepared by heating ethyl-amine with methyl iodide in alcohol at 100° 3 by the hydrolysis of N-methyl-N-ethylarenesulfonamides,4-5 -nitroso-N-methyl-N-ethylaniline,6 or methylethylbenzhydrylidene ammonium iodide 7 by catalytic hydrogenation of ethyl isocyanate or ethyl isocyanide 8 and by the reduction of ethyl isocyanate by lithium aluminum hydride,9 of N-methylacetisoaldoxime by sodium amalgam and acetic acid,10 or of a nitromethane/ethylmagnesium bromide adduct by zinc and hydrochloric acid.11... 

Trifluoroalanine has also been prepared by reducing trifluoropyruvate imines (ethyl trifluoropyruvate is available commercially it is prepared either from per-fluoropropene oxide or by trifluoromethylation of ethyl or f-butyl oxalate). These imines are obtained by dehydration of the corresponding aminals or by Staudinger reaction. They can also be obtained by palladium-catalyzed carbonylation of trifluoroacetamidoyl iodide, an easily accessible compound (cf. Chapter 3) (Figure 5.4). Reduction of the imines affords protected trifluoroalanines. When the imine is derived from a-phenyl ethyl amine, an intramolecular hydride transfer affords the regioisomer imine, which can further be hydrolyzed into trifluoroalanine. ... 

Adolph Wurtz, 1817—1884. Professor of chemistry at the ficole de Medecine in Pans. Discoverer of methyl and ethyl amines and the synthesis of hydrocarbons from alkyl iodides and sodium. He studied the oxidation products of the glycols and the homologs of lactic acid The proof of the elementary nature of gallium was demonstrated in his laboratory by Lecoq de Boisbaudran. 

The silyl enol ether may be obtained from the Fluka Chemical Corp., 255 Oser Avenue, Hauppauge, NY 11788. Alternatively, it may be prepared by the following modification of the procedure of Walshe and co-workers.2 The Walshe procedure is followed exactly with 36 g (0.30 mol) of acetophenone, 41.4 g (0.41 mol) of tri ethyl amine, 43.2 g (0.40 mol) of chlorotri-methylsilane, 60 g (0.40 mol) of sodium iodide, and 350 nt of acetonitrile. After extraction, the organic layer is dried over potassium carbonate and then concentrated with a rotary evaporator under reduced pressure. The crude product is a mixture of 97% of the desired silyl enol ether and 3% of acetophenone, as shown by gas chromatography. The crude product is distilled in a Claisen flask at a pressure of about 40 mm. After a small forerun (ca. 3... 

The only synthesis of 1-dialkylaminoindazoles is based on a recyclization reaction (83CC1344). Under the action of ethylmagnesium iodide on 4-phenylbenzo-l,2,3-triazine followed by treatment with methyl iodide, the formation of 1-aminoindazole 26a in 44% yield was observed. The same compound (23% yield) with a small amount of amine 26b is formed when methylmagnesium iodide and ethyl iodide are taken instead of ethyl-magnesium iodide and methyl iodide. Supposedly, the reaction occurs as shown in Eq. (7). 

Amines such as ethyl amine, at 25% in water or higher concentrations, swell hair to a greater extent than water. These solutions rupture amide and peptide linkages and ultimately disintegrate (dissolve) the hair (after several days) [56, 97]. Concentrated solutions of alkah halides (25 to 60%), after several days, produce extensive dimensional changes to hair [56, 97]. Barnard and White [90] found extensive swelhng by potassium iodide, sodium bromide, lithium bromide, and lithium chloride solutions, but not for sodium chloride. See the section on supercontraction in Chapter 3. 

Allow a mixture of 0-5 g. of the tertiary amine and 0-5 ml. of colourless methyl iodide to stand for 5 minutes. If reaction has not occurred, warm under reflux for 5 minutes on a water bath and then cool in ice water. The mixture will generally set solid if it does not, scratch the sides of the tube with a glass rod. RecrystaUise the solid product from absolute alcohol, ethyl acetate, acetone, glacial acetic acid or alcohol-ether. 

Apart from tertiary amines, the reaction may be catalyzed by phosphines, e.g. tri- -butylphosphine or by diethylaluminium iodide." When a chiral catalyst, such as quinuclidin-3-ol 8 is used in enantiomerically enriched form, an asymmetric Baylis-Hillman reaction is possible. In the reaction of ethyl vinyl ketone with an aromatic aldehyde in the presence of one enantiomer of a chiral 3-(hydroxybenzyl)-pyrrolizidine as base, the coupling product has been obtained in enantiomeric excess of up to 70%, e.g. 11 from 9 - -10 ... 

A mixture of 2.3 parts of 2-(4-methoxyphenyl)ethyl methanesulfonate, 4.9 parts of 1-[(4-fluorophenyOmethyl] -N-(4-piperidinyl)-1H-benzimidazol-2-amine dihydrobromide, 3.2 parts of sodium carbonate, 0.1 part of potassium iodide and 90 parts of N,N-dimethylformamide is stirred overnight at 70°C. The reaction mixture is poured onto water. The product is extracted with methylbenzene. The extract is washed with water,dried, filtered and evaporated. The residue is purified by column-chromatography over silica gel using a mixture of trichloro-methane and methanol (98 2 by volume) as eluent. The pure fractions are collected and the eluent is evaporated. The residue is crystallized from 2,2 -oxybispropane, yielding 2.2 parts (48%) of 1 -(4-fluorophenvlmethyl)-N-[1 - [2-(4-methoxvphenyl)ethvl] -4-piperidinyl] -1H-benzlmidazol-2-amine MP 149.1°C. 

It is prepd by the action of methylamine on 4-chloro-l-nitrobenzene (Ref 5) by the action of methyl iodide (Ref 6), or methyl sulfate on 4-nit roaniline (Ref 7) or by the hydrolysis of 4-nitro-N-methylformanilide with hot coned aq HC1 (Ref 8). In a study of the effect of nitric acid concn on the prods of the nitration of N,N-dimethylaniline to form Tetryl, it was isolated in low yield by the action of nitric acid, d 1.046g/cc, plus Na nitrite on N,N-dimethylaniline (Ref 10). A eutectic mixt with N-ethyl-4-nitroaniline has been patented as a stabilizer for NC (Ref 12). Studies at NPF indicate that 4-nitro-N-methyl-aniline is superior to Centralite, 2-nitrodiphenyl-amine, or Acardite in stabilizing. NC Refs 1) Beil 12, 586, (295) 1125 ... 

Solvent effects" on the rate of reaction between triethyl-amine and ethyl iodide... 

Carboxylic esters where R is methyl or ethyl can be cleaved by heating with lithium iodide in refluxing pyridine or a higher boiling amine. " The reaction is useful where a molecule is sensitive to acid and base (so that 10-10 cannot be used) or where it is desired to cleave selectively only one ester group in a molecule containing two or more. For example, refluxing O-acetyloleanolic acid methyl ester... 

Alkyl esters are efficiently dealkylated to trimethylsilyl esters with high concentrations of iodotrimethylsilane either in chloroform or sulfolane solutions at 25-80° or without solvent at 100-110°.Hydrolysis of the trimethylsilyl esters serves to release the carboxylic acid. Amines may be recovered from O-methyl, O-ethyl, and O-benzyl carbamates after reaction with iodotrimethylsilane in chloroform or sulfolane at 50—60° and subsequent methanolysis. The conversion of dimethyl, diethyl, and ethylene acetals and ketals to the parent aldehydes and ketones under aprotic conditions has been accomplished with this reagent. The reactions of alcohols (or the corresponding trimethylsilyl ethers) and aldehydes with iodotrimethylsilane give alkyl iodides and a-iodosilyl ethers,respectively. lodomethyl methyl ether is obtained from cleavage of dimethoxymethane with iodotrimethylsilane. 

A general synthesis of the secondary amines RNHMe and RNHEt has been developed starting from the iminophosphoranes (181). Alkylation with methyl or ethyl iodides (all other halides gave olefins) gave the salts (182) from which secondary amines were obtained on alkaline hydrolysis. 

All ionic liquids were made by alkylation of their parent amine or phosphine with methyl iodide or ethyl iodide. The following abbreviations for the various ionic liquids will be used throughout the manuscript ... 

Titanium(IV) iodide is extremely hygroscopic. It dissolves in water with decomposition, and it fumes in air owing to hydrolysis. It forms 2 1 adducts with ammonia,7 pyridine,33 and ethyl acetate.34 With excess ammonia it undergoes ammo-nolysis to give ammonobasic titanium(IV) iodides.7 Analogous aminolysis reactions occur when titanium(IV) iodide is treated with an excess of primary or secondary amine.36 Titanium(IV) iodide is sparingly soluble in petroleum ether, moderately soluble in benzene, and even more soluble in chlorinated hydrocarbons and carbon disulfide. At elevated temperatures it... 

The structure of cryptowoline iodide (2) was determined by a similar set of reactions. Both O-methyl and 0-ethyl ethers were subjected to exhaustive meth-ylation, elimination, reduction, and ozonolysis. The key compounds obtained from the ethyl ether were 26 and 6-aminopiperonal. The amine fragment showed the methylenedioxy group to be at the 9,10 position in cryptowoline, and the fact that the same aldehyde 26 was obtained from 0-ethylcryptowoline iodide fixed the position of the free OH as in cryptaustoline to C-2. 

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