Chloro-triethyl

The side chain is prepared by the interaction between either ethylene oxide or l-chloro-2-hydroxy ethane with diethyl amine in methanol yields 2-hydroxy-triethyl hydrochloride. This on chlorination with thionyl chloride yields 2-chloro-triethyl amine whieh on treatment with ethyl aceto-acetate in the presence of sodium ethoxide gives an intermediate eompound. Alkaline hydrolysis produces l-acetyl-3-diethylamino propane which on reduction with Raney Nickel followed by oximation yields 4-amino-1-diethylamino pentane. 

CH2CH2N(C2H5)2 (Lactam-form) 1-Chloro-triethyl-... 

Chloro-1 -methyl-5-phenyl-s-trizolo[4,3-a]quinoline A stirred mixture of 6triethyl-orthoacetate (0.925 g,0.0057 mol) and xylene (100 ml) was refluxed, under nitrogen, for 2 hours 40 minutes. During this period the ethanol formed in the reaction was removed by distillation through a short,glass helix-packed column. The mixture was concentrated to dryness In vacuo and the residue was crystallized from methanol-ethyl acetate to give 1.28 g of 7-chloro-1-methyl-5-phenyl-s-triazolo[4,3-a]-quinoline (83.9% yield). The analytical sample was crystallized from methylene chloride methanol and had a melting point 252.5°-253.5°C. 

In general, the O-alkylation of benzoxepinones is accomplished via the anion. Alternatively, an acid-catalyzed process employing ortho esters may be used. For the acid-catalyzed formal O-alkylation of l-chloro-8-methoxydibenz[ft,/]oxepin-10(ll//)-ones with triethyl orthoformate rather drastic conditions are required (hot concentrated sulfuric acid) to give the 10-ethoxy derivative 12 in excellent yield.109... 

Cyclization of 8-hydrazinO 3-phenyl-l-azaazulenes 69 with triethyl orthoformate gave 4,5-triazabenz[c(f]azulene derivative 70 which was easily hydrolyzed on silica gel and gave (2-chloro-8-imino-3-phenyl-l-aza-l,8-dihydoazulen-l-yl) formaldehyde oxime (87H767) (Scheme 17). 

The Suzuki reaction has been successfully used to introduce new C - C bonds into 2-pyridones [75,83,84]. The use of microwave irradiation in transition-metal-catalyzed transformations is reported to decrease reaction times [52]. Still, there is, to our knowledge, only one example where a microwave-assisted Suzuki reaction has been performed on a quinolin-2(lH)-one or any other 2-pyridone containing heterocycle. Glasnov et al. described a Suzuki reaction of 4-chloro-quinolin-2(lff)-one with phenylboronic acid in presence of a palladium-catalyst under microwave irradiation (Scheme 13) [53]. After screening different conditions to improve the conversion and isolated yield of the desired aryl substituted quinolin-2( lff)-one 47, they found that a combination of palladium acetate and triphenylphosphine as catalyst (0.5 mol %), a 3 1 mixture of 1,2-dimethoxyethane (DME) and water as solvent, triethyl-amine as base, and irradiation for 30 min at 150 °C gave the best result. Crucial for the reaction was the temperature and the amount of water in the... 

The interesting observation has been made that 3 -amino-3 -deoxy-adenosine as a suspension in phosphoryl chloride-triethyl phosphate at 4° is converted into the 5 -chloro-5 -deoxy derivative in 80% yield, but that predissolution of the nucleoside in triethyl phosphate, followed by treatment with phosphoryl chloride at 0°, yields the 5 -phosphate in 62% yield.382... 

The reaction of 7-chloro-6-fluoro-2-hydrazinobenzothiazole 398 with triethyl orthoformate at reflux leads to the 4//-thiazolo[2,3-f][ 1,2,4] triazole derivative 399 (unreported yield), that has been further reacted with different substituted anilines to afford compounds 396 (unreported yields) (Scheme 46) <1998IJH23>. 

Guo et al. prepared N-(3-chloro-4-fluorophenyl)aminomethylenemalo-nate (256, R = 3-C1, R1 = 4-F, R2 = R3 = Et) in 60-70% yields when 3-chloro-4-fluoroaniline was reacted with triethyl orthoformate and diethyl malonate in the presence of a Lewis acid. From the reaction mixture, ethyl A-(3-chloro-4-fluorophenyl)-2-[(3-chloro-4-fluorophenyl)-aminomethylene]malonamate and A-(3-chloro-4-fluorophenyl)formanilide were also isolated as byproducts (88MI3). 

When the reaction mixture of 4-chloroaniline, triethyl orthoformate, and isopropylidene methylmalonate in Dowtherm A was heated slowly, stirred to reflux, and maintained at reflux for 3 minutes, 6-chloro-4-hydroxy-3-methylquinoline (1167) was obtained (69BRP1147760). 

Nucleophilic Reactions.—Attack on Saturated Carbon. Selected examples of the Arbusov reaction include phosphorylation of the chloroacetophenones (1) to give phosphonates, which cyclized to (2) in the presence of acid chlorides,1 formation of the azodiphosphonate (3) from 2,2 -dichloro-2,2 -azopropane,2 3 and the reaction of 2-chloro-3,4-dihydro-3-oxo-2//-l,4-benzothiazine (4) with triethyl phosphite to give the 2-phosphonate (5), which is used as an olefin synthon.8 Bis(trimethylsilyl) trimethylsiloxymethylphosphonite (6) has been synthesized by silylation of hydroxy-methylphosphonous acid, and, as expected, undergoes a normal Arbusov reaction with alkyl halides to give the phosphonates (7).4 This series of reactions, followed by... 

Diazoxide 7-chloro-3-methyl-2-//-l,2,4-benzothiadiazin-l,1-dioxide (21.3.14), is synthesized by condensating 2-aminosulfonyl-4-chloroaniline with triethyl orthoacetate [34-36]. 

A. Triethyl a-phtkalimidoethane-a,a, -tricarboxylate. Three hundred and twenty-seven grams (1.0 mole) of diethyl sodium phthalimidomalonate and 735 g. (6.0 moles) of ethyl chloro-acetate (b.p. 144-145°) are placed in a 2-1. Claisen flask fitted with a reflux condenser and rubber stoppers. The mixture is heated under reflux in an oil bath at 150-160° for 2.25 hours. The excess ethyl chloroacetate is removed by distillation at 30 mm. until the heating bath temperature reaches 150° and no more distillate is obtained (Note 1). The brown residual mass is... 

E. mwis-CHLORO (civ-1,2-DIPHENYLETHENYL)BIS(TRIETHYL-PHOSPHINE)PLATINUM(II)... 

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