Acetonitrile diethylamino

The structure of the 1 1 methanol solvate of olanzapine has been reported, where pairs of olanzapine molecules form a centrosymmetric dimer by means of C—H—-7t interactions [66]. The solvent molecule was linked to the drug substance through O—H-N, N—H O, and C—interactions. In a new polymorph of the 1 1 dioxane solvatomorph of (+)-pinoresinol, the structure was stabilized by O—H O hydrogen bonds between the compound and the solvent [67], Two new polymorphs of 2-cyano-3-[4-(/Y,jV-diethylamino)-phenyl]prop-2-enethioamide and its acetonitrile solvatomorph have been characterized [68], Although crystallization of the title compound was conducted out of a number of solvents, only the acetonitrile solvatomorph could be formed. 

Man erhalt auf diese Weise z.B. aus Triethylamin-oxid und 1-Brom-octan bzw. Brom-essigsaure-ethylester als Elektrophil 1-Diethylamino-octan (51%) bzw. Diethylamino-essigsaure-ethylester (31%) und aus l-Methyl-piperidin-1-oxid und 1-Brom-octan bzw. Bromessigsaure-ethylester 1-Octyl-piperidin (47%) bzw. Piperidinoessigsaure-ethylester (38%). Nach dem zweiten Reaktionsweg erhalt man z. B. aus Cyclohexyl-dimethyl-amin-oxid mit Cyan-trimethyl-silan als Nukleophil (Cyclohexyl-methyl-amino)-acetonitril (71%). 

A 1,4-dipolar cycloaddition between tetrahydropyrido[l,2-a]pyrimidi-none 114 (R = Me) and 4-methyl-l, 2,4-triazoline-3,5-dione 666gave stable adduct 667 in acetonitrile or in acetic acid at room temperature for 1 hour (Scheme 44) (85CB4567). When ethyl cyanoformate was used as dienophile in boiling toluene for 20 hours, ethyl 3-methyl-4-oxo-6,7,8,9-tetrahydro-4//-pyrido[ 1,2-a]pyrimidine-2-carboxylate 669 was obtained (86CB1445). Pyrido[l,2-a]pyrimidine-2-carboxylate 669 was formed from the initial adduct 668 by elimination of phenyl isocyanate. Reaction of tetrahydropyr-ido[l,2-a]pyrimidinone 114 (R = Me) with l-(diethylamino)-l-propyne in... 

Sequential SET desilylation has been used to generate a-amino radicals. The mechanistic and synthetic aspects of the reaction have been briefly surveyed.283 Thus irradiation of A, N- d i e t h y 11 r i m e t h y I si I yl meth y I a m i n e with acenaphthenequinone in acetonitrile or methanol produces 2-hydroxy-2-[(diethylamino)methyl]acenaphthylen-1-one.284... 

Upon treatment with acid (or on contact with an acidic surface), many spiropyrans give the salt of the open form or the open form itself, depending upon the relative base strengths of the spiro and open forms. Thus, treatment of several BIPS (7-diethylamino, 6-nitro, and 5 -nitro) with trifluoroacetic acid in the nonprotic solvents acetonitrile and chloroform gave the protonated merocyanine form, which upon neutralization with base gave the open colored form.180 This sequence of operations causes coloration by a non-thermal, non-photochemical route the adsorption coloration was utilized in the early applications of spiropyrans in carbonless (pressure-sensitive) copy papers. In this application, dialkylamino-substituted spirodi(benzopyrans) were preferred paper containing BIPS compounds turned pink on storage. 

The method has been further improved." Trimethyl(perfluoroalkyl)silanes RpTMS (Rp = c, -C, perfluoroaliphatic groups) are prepared by reaction of perfluoroalkyl halides RpX (X = Br, I) with chlorotrimethylsilane in the presence of tris(dialkylamino)phosphanes in acetonitrile. For example, chlorotrimethylsilane was treated with bromotrifluoromethane and tris(diethylamino)phosphane in acetonitrile at — 40"C for 1 hour to give trimethyl(trifluo-romethyl)silane in 90% yield. Bis(dimethylamino)(trifluoromethyl)silane is available from the reaction of chlorobis(dimethylamino)silane with the system bromotrifluoromethane/tris-(diethylamino)phosphane, while trichloro(trifluoromethyl)silane is prepared by nucleophilic trifluoromethylation of tetrachlorosilane with bromotrifluorornethane/tris(diethylamino)phos-phane. " ... 

SYNS (DIETHYLAMINO)ACETONITRILE NJM-DIETHYLGLYCINONITRILE NITRIL KISEUNY DIETHYLAMINOOCTOVE (CZECH)... 

Imine formation in adenines is presumably a factor of some importance to reactivity towards electrophiles since in A -dialkylated derivatives where imine formation is not possible, further alkylation becomes more difficult. Thus 6-diethylamino-9-methylpurine required prolonged heating with methyl iodide to produce the quaternary salt (92) (65JOC3597) and similarly 6-dimethylamino-9-benzylpurine required 3 days boiling with benzyl bromide in acetonitrile to produce 3,9-dibenzyl-6-dimethylaminopurinium bromide (93) (66JOC2202). Under these circumstances it is clearly difficult to control the alkylation step and quaternization is the normal rule. 

On irradiation with a high-pressure mercury lamp, 9-phenyl-8-azapurine in dioxane gave 9i/-pyrimido[4,5-i>]indole in 33% yiel whereas 54% was obtained in methanol. Nine derivatives of this azapurine, carrying various substituents in the 6 position, behaved similarly (32-91% yields). The principal by-products arose from (1) replacement of hydrogen in the 4 position of the pyrimidoindole by dioxane or methanol residues, (2) reaction with benzene, when used as a solvent, to yield 4-anilino-5-phenylpyrimidine, and (3) reaction with dioxane to furnish 4-anilinopyrimidines. l,3,7-Trimethyl-8-azapurine-2,4-dione, irradiated with diethylamine in acetonitrile, gave 6-diethylamino-1,2-dimethyl-5-methylaminopyrimidine-2,4-dione (66% yield). However, photolysis in methanol gave 5-hydroxy-l,3-dimethyl-6-methoxypyrimidine-2,4- one (22% yield). 

These numerous attempts to synthesize cyclopropanethiones demonstrate the difficulty in obtaining access to these elusive species. While it has not been possible to obtain direct experimental evidence for the trapping of cyclopropanethione, recently it proved possible to provide such evidence for cyclopropanethione 5-oxide (24) and cyclopropanethione 5,5-dioxide (21). Fluorodesilylation of l-(trimethylsilyl)cyclopropanesulfonyl chloride (20) with cesium fluoride in acetonitrile at room temperature in the presence of A, lV-diethylprop-l-yn-l-amine led to the isolation of 6-diethylamino-5-methyl-4-thiaspiro[2.3]hex-5-ene 4,4-dioxide (22) via the intermediacy of cyclopropanethione 5,5-dioxide (21). ... 

Methoxy-3-mcthyl-4-phenylazo-l,2-oxazole spalten thermisch (110°) Acetonitril ab unter Bildung von Nitrilimin-Dipolen, die bei Anwesenheit von Dipolarophilen (z. B. Butindisaure-diester, 1,1-Diethoxy-cthen, 1-Diethylamino-propin) zu Gemischen aus 2-Phenyl-l, 2,3-triazolen und 1 -Phenyl-1 H-pyra-zolen reagieren (vgl. S. 512)1175 v 1-1179. 

Table 28 summarizes pAf value determined in acetonitrile " along with pAf values in 50% MeCN-50% water for the complexes where these are available (values in parentheses). They were obtained spectrophotometrically from measurements of the equihbrium constants of the reaction of the carbene complex with strong amine bases such as TMG (1,1,2,2-tetramethyguanidine), DBU (1,8-diazabicyclo[5.4.0]undec-7-ene), BEMP (2-(tert-butylimino)-2-(diethylamino)-... 

A detailed description of the preparation of (diethylamino)acetonitrile from formaldehyde-bisulfite, diethylamine, and sodium cyanide is to be found in Organic Syntheses 1 ... 

Analogously TV -methylgraminium iodide and potassium cyanide yield 3-indole-acetic acid in 76% yield by way of the nitrile.807,808 This nitrile can also be obtained, in 33-44% yield, from indole and (diethylamino)acetonitrile 809... 

A mixture of the aminal and 2,4-dimethylphenol was treated in acetonitrile with sulphur dioxide (22 equivts.) at ambient temperature during 14h. to give 2-diethylamino-methyl-4,6-dimethylphenol. 

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