Ethanol 1-cyclopropyl

Ethanole 1-Cyclopropyl-2,2,2-tri-fluoro-1-phenyl- E10 (Ketone +-F3C-SiR3)... 

Reaction of 2,3-dichloroquinoxaline 367 with sodium azide in ethanol has been used to synthesize bistetrazolo-[l,5- 5, l -c]quinoxaline 368 in 65% yield (Scheme 28) <1997JOC4082>. Similarly, reaction of 2,3-dichloroquinoxaline 367 with thiosemicarbazide 366 has been used to generate l,6-diamino-bis-l,2,4-triazolo[4,3- 3,4-f]quinoxaline 365 in 67% yield <2002AP389>. Condensation of cyclopropanecarboxylic acid hydrazide 369 meanwhile gives rise to the cyclopropyl-substituted tetracycle 370 in 93% yield in the presence of l,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as base (Scheme 28) <2005JOC2878>. 

The high-pressure carbonylation of dimeric palladium derivatives 183 (R = Me or cyclopropyl) in ethanol or methanol/ chloroform leads in moderate yields to fused isoindoles 184 as mixtures with their alkoxy derivatives 185, easily separated by flash chromatography (Equation (25) a991JOM371)). 

On the other hand, solvolysis of the tosyl derivative of 1-cyclopropyl-cyclopropanol (112) in aqueous ethanol does not lead to ring enlarged products. 91 Apparently, the incipient cyclopropyl cation is better stabilized by conjugative interactions with another cyclopropyl system than with a vinyl group. 

The reaction of basic ZnEt2 with pyrrolidine norephedrine 10 and one equivalent of trifluoroethanol as auxiliary ligand leads to the chiral zinc alkoxide 309 under loss of ethane after deprotonation of the hydroxy groups of 10 and trifluoro ethanol as additive. 30 is not isolated but subjected to addition of cyclopropyl acetylene magnesium... 

A mixture of ethyl l-cyclopropyl-6,7,8-trifluoro-l,4-dihydro-4-oxoquinoline-3-carboxylate (933 mg), 3-acetamidopiperidine (710 mg), triethylamine (400 mg) and dimethylsulfoxide (10 ml) was heated at 100°C for 2 hours with stirring. Thereafter the mixture was cooled down and ice water was added thereto. The resulting mixture was extracted with chloroform and the chloroform layer was washed with water three times before being dried over anhydrous sodium sulfate. Removal of the solvent in vacuum followed by purification by silica gel column chromatography (chloroform-ethanol) gave ethyl 7-(3-acetamidopiperidin-l-yl)-l-cyclopropyl-6,8-difluoro-l,4-dihydro-4-oxo quinoline-3-carboxylate (930 mg). Re-crystallization from ethanol-ether afforded a colorless crystalline substance (MP 217°-218°C). 

A mixture of ethyl l-cyclopropyl-5,6,7,8-tetrafluoro-l,4-dihydro-4-oxoquinoline-3-carboxylate (28.2 g), benzylamine (9.8 ml), anhydrous potassium carbonate (23.6 g), and acetonitrile (140 ml) was heated at 100°-110°C for 1 h to give ethyl 5-benzylamino-l-cyclopropyl-6,7,8-trifluoro-l,4-dihydro-4-oxoquinoline-3-carboxylate (21.4 g), which was recrystallized from ethanol, melting point 134°-135°C. 

A mixture of 5-amino-l-cyclopropyl-6,7,8-trifluoro-l,4-dihydro-4-oxoquinoline-3-carboxylic acid (1.25 g), cis-2,6-dimethylpiperazine (2.0 g), and dimethylformamide was stirred at room tempersture for 24 h. The reaction mixture was evaporated to dryness under reduced pressure and water was added to the residue. The mixture was extracted with chloroform and the extract was dried. After evaporation of chloroform, ethanol was added to the residue. The resulting crystals were filtered and recrystallized from chloroform-ethanol to give 5-amino-l-cyclopropyl-6,8-difluoro-7-(cis-3,5-dimethyl-l-piperazinyl)-l,4-dihydro- 4-oxoquinoline-3-carboxylic acid (1.4 g), melting point 258°-260°C. 

The a-cyclopropyl substituent was foundto accelerate the rate of hydrolysis of 1-cyclopropylcyclopropyl tosylate (2) in 50% aqueous ethanol at 70°C over that of 1-isopropylcyclopropyl tosylate by a factor of about 16000 1. With the 1-cyclopropyl substituent, the non-ring-opened 1-cyclopropyl cyclopropanol was the major product. Also, there was no degenerate rearrangement in the ion. 

In its relative reactivity toward toluene, ethylbenzene and cumene the more highly substituted 1-methyl-2,2-diphenylcyclopropyl radicaP , derived from the decomposition of the precursor diacyl peroxide, resembles the chlorine radical more than it does the phenyl radical (Table 3). Similarly, comparison of the relative reactivities of primary, secondary and tertiary aliphatic hydrogens toward chlorine atoms (1.0 3.6 4.2) and phenyl radicals (1.0 9.3 44) with the relative reactivities of the C-H bond in the methanol/ethanol/2-propanol series toward the 1-methyl-2,2-diphenylcyclopropyl radical (1.0 2.4 15) further confirms the low selectivity of the cyclopropyl radical. Again, this radical resembles the chlorine atom in its reactivity more than it does the phenyl radical. 

Poisoning with mushrooms in this group occurs when ethanol is consumed shortly before or within 5 days after eating the mushrooms. Coprine (N(5)-(l-hydroxy cyclopropyl)-L-glutamine) is the active constituent in these mushrooms and has been shown to inhibit liver aldehyde dehydrogenase. The active metabolite, cyclopropanone hydrate, has also been shown to possess similar activity. This inhibition of ethanol metabolism at the point of aldehyde dehydrogenase results in accumulation of acetaldehyde. In the absence of concurrent ethanol consumption, these mushrooms are edible. 

Zinc in various solvents, most frequently acetic acid and ethanol, is a powerful reducing agent for monoreduction of 1,1-dihalocyclopropanes. Mechanistic studies indicate that cyclopropyl radicals as well as cyclopropyl anions, are involved as intermediates. In most cases the monohalides are obtained as stereoisomeric mixtures. Typical examples are compiled in Table 3, other examples can be found in refs 38,42,47, 51,69,108,112-121,774,782 (dibromo derivatives), refs 108, 112, 122, 762, 777, 888, 936 (dichloro derivatives), ref 47 (bromofluoro derivatives) and ref 112 (bromochloro derivatives). Thus, reduction of 2,2-dichlorocyclopropyl-methanol using a mixture of zinc and copper(II) chloride in ethylene glycol gave 2-chlorocyclo-propylmethanol (30) in 74% yield as an equimolar mixture of the cis- and tranj-isomers. ... 

Cyclopropyl sulfones 3 are easily reduced to cyclopropanes 4 by treatment with sodium amalgam in refluxing ethanol. Yields above 80% have been reported.However, quite different reaction conditions are required to perform reductive desulfurization of cyclopropanesulfinic acids 5, i.e. the use of mercury(II) chloride, concentrated hydrochloric acid, and heat ethylmagnesium bromide followed by acid has also been used but yields were poor. ... 

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