L-Ethoxy-2-ethoxycarbonyl

Die reduktive Cyclisierung von Benzofuroxan mit (Ethoxycarbonyl-methylen)-triphenyl-phos-phan liefert nach einem komplizierten Mechanismus neben 2-Ethoxycarbonyl-benzimidazol (18%) l-Ethoxy-2-ethoxycarbonyl-benzimidazol (16%)186 ... 

H r CXn ch2 s cooc R- H R = CH3 R-OCjH5 5 HN(C4H9)2 HN(C6Hn)2 hv) 40%iges CHjO/HjO 20", 3 h l-( Dihutylamino-methyl)-2-( ethoxyearbonyl-methyl-thio) -... l-( Dicyclohexylamino-methyl) -2- ( ethoxy carbonyl-methyl-thio)-5-methyl-... 5-Ethoxy-2- ( ethoxycarbonyl-methylthio)-l-(piperidino-methyl)-... 33,5 31 40 237-239 177-179 118-119 445... 

Ethoxycarbonyl-l-hydroxy-benzimidazol wird offensichtlich auch bei der Umsetzung von Benzofurazan-l-oxid mit (Ethoxycarbonyl-methylen)-triphenyl-phosphoran als Zwischenpro-dukt durchlaufen nach weiterer Reaktion mit (Ethoxycarbonyl-methylen)-triphenyl-phospho-ran wird letztlich ein Gemisch aus J-Ethoxy-2-ethoxycarbonyl- und 2-Ethoxycarhonyl-henz-imidazol erhalten299. 

A cyclopropane containing a C-N bond was also obtained when a mixture of ethyl azidoformate and 1-ethoxy-1-trimethylsiloxycyclopropane in acetonitrile was photolyzed at room temperature. The product, l-ethoxy-2-(ethoxycarbonylamino)-l-trimethylsiloxycyclopropane(19), formally resulted from a substitution reaction, but the product is in fact generated by insertion of (ethoxycarbonyl)nitrene into a cyelopropyl C-H bond, keeping the cyclopropane ring intact.Interestingly, if the reactants are dissolved in dimethylformamide or dimethyl sulfoxide and are heated instead, quite different reactions take place. 

Considerable synthetic use has been made of ethyl azidoformate. Typical reactions of this are the additions to double bonds as a path to aziridines. Thus addition of ethoxycarbonyl nitrene to l-ethoxy-2-methyl-l-trimethylsilyloxypropene affords the aziridine 612 that can be ring opened to yield (75%) the diester 613. Addition of the same nitrene to siloxydienes has also been reported One of the common reactions of ethoxycarbonyl nitrene is addition to arenes as a route to azepines. An example of this process is seen in the synthesis of the hexafluoroazepine 614 by addition of the nitrene to... 

Reaction of 2-aminopyridine with ethyl 2-cyano-3-ethoxy-3-methyl-, -3-ethyl-, -3-phenylacrylates and ethyl 2-ethoxycarbonyl-3-ethoxy-3-methyl-, -3-phenylacrylates in boiling xylene yielded 2-substituted 4/f-pyrido[l,2-u]pyrimidine-3-carbonitriles and -3-carboxylates (99MI7). Similar reactions of 2-aminopyridine with 2-cyano-3-ethoxyacrylonitrile and its 3-methyl, 3-ethyl, -3-phenyl derivatives in boiling MeCN afforded 4-imino-4//-pyrido[l,2-u]-pyrimidine-3-carbonitrile and its 2-substituted derivatives. 

In addition to the typical cyclization procedures described above, methods involving the use of other mild, cyclodehydrating agents have been published. For example, cyanuric chloride in the presence of triethylamine, 2-ethoxy-A-ethoxycarbonyl-l,2-dihydroquinoline (EEDQ) or 2-isobutoxy-A-isobutoxy-carbonyl-1,2-dihydroquinoline (IIDQ), ° A,A-dimethylchlorosulfitemethanimi-... 

Die Reduktion von 6-Ethoxy-3-ethoxycarbonyl-5,6-dihydro-4H-l,2-oxazin mit Aluminium-amalgam in waBrigem Tetrahydrofuran ergibt unter Ringverengerung Prolin-ethyl-ester (96%)5 ... 

Indazole, 5,5-dimethyl-3-trifluoromethyl-4,5-dihydro-trichomonacidal activity, S, 291 Indazole, 2-ethoxycarbonyl-reactions, 5, 269 Indazole, 3-fluoro-synthesis, 5, 263 Indazole, 1-germyl-synthesis, 5, 236 Indazole, 1-glycosyl-synthesis, 5, 289 Indazole, 2-glycosyl-synthesis, 5, 289 Indazole, halo-reactions, S, 266 Indazole, 2-hydroxy-methylation, S, 269 Indazole, 3-hydroxy-reactions, S, 264 Indazole, 6-hydroxy-diazo coupling, S, 86 Indazole, hydroxyphenyl-synthesis, S, 288 Indazole, 3-iodo-synthesis, S, 241 Indazole, l-isopropyl-3-phenyl-reduction, S, 243 Indazole, 3-mercapto-1-substituted tautomerism, 5, 265 Indazole, m ethoxy-pharmaceutical activity, 5, 294 Indazole, 1-methyl-lithiation, S, 245 melting point, S, 207... 

In the case of 1,3-thiazine-2-ylidene compounds, hydrolysis of N-methylimino-5-ethoxycarbonyl-l,3-thiazine 188 (R = Me) is carried out in an acid medium. Formic acid does not react. Incorporation of water was found in the course of subsequent research (formic acid/aqueous triethyla-mine either formic acid or acetic acid/water 50-50 formic acid/aqueous formaldehyde) and resulted in the isolation of three compounds 5-ethoxy-carbonyl-2-oxo-2,3-dihydro-6//-l, 3-thiazine (189), 5-ethoxycarbonyl-l-methyl-2-thioxo-l,2,3,4-tetrahydropyrimidine (190) and 5-ethoxy-car-bonyl-3-methyl-2-thioxo-l, 2,3,4-tetrahydropyrimidine (191). The authors have proposed a mechanism involving cleavage of the C-6-S bond and reclosure of the six-membered ring by a Michael addition (Scheme 75). 

Benzyl-diethoxy- E2, 134 Benzyl-diisopropyloxy- E2, 134 Benzyl-ethyl-phenyl- -tosylimid E2, 113 Benzyl-methyl-phenyl- -tosylimid E2, 113 Benzyloxy-diphenyl- E2, 17, 18 Benzyloxy-ethoxy-hydroxy- E2, 187 Bis-[2-biphenylyl]- E2, 876 [2,6-bis-(2-tetrahydropyranyloxy-methyl)-phenyl]-Bis-[4-brom-anilino]-phenyl- E2, 416 Bis-[2-brom-ethoxy]-(2-brom-ethyl)- E2, 196 Bis-[butylthio]-ethyi- E2, 79, 408 Bis-[2-chlor-cthoxy]-butyl- E2, 196 Bis-[2-chlor-ethoxy]-(2-chlor-ethyl)- E2, 196 Bis-[2-chlor-ethoxy]-methyl- E2, 196 Bis- 2-chlor-ethoxy]-phenyl- E2, 196, 197, 202 Bis- 2-ehlor-ethoxy]-(2-phcnyl-vinyl)- E2, 196 Bis-(2-ehlor-ethoxy]-vinyl- E2, 196 Bis-j 2-chlor-ethyl]-methyl- E2, 205 Bis-[chlormethyl]-dodecyl- E2, 22 Bis-12-cyan-ethyl]- E2, 223 Bis- diethylamino]-butyl- E2, 486 Bis-[ l-cthinyl-butyl]-phenyl- E2, 197 Bis-[ethoxycarbonyl-methyl]-chlor- E2, 251 Bis-[ethylthio]-ethyl- E2, 408 Bis-[4-methoxy-aniliiio]-phenyl- E2, 416 Bis-[4-methyl-phenylJ-phenyl- K2, 105 Bis- 4-methyl-phcnyl]-phenyl- -phenylsulfonvlimid E2, 105... 

Ethoxycarbonyl-vinyl)-phenyl- E2, 140 (2-Ethoxycarbonyl-viny )-phenyl- -chlorid E2, 225 (1-Ethoxy-ethyl)-ethyl- -chlorid E2, 156 (2-Ethoxy-ethyl)-phenyl- -ethylester XII/1, 256 (2-Ethoxy-vinyl)-cthyl- -chlorid E2, 163 Ethyl-( 1-ethyl-l-methyl-3-oxo-pentyl)- -butylester XII/1, 258... 

Ethoxycarbonyl-l-mcthyI-ethan)-methyl- -O-cthylester XII/1, 566 Ethoxycarbonylmethyl-phenyl- -O-etbylester aus Ethoxy-phenyl-phosphansulfid, Natrium-ethanolat und Chloressigsaure-etbylcster XII/1, 280... 

O.O-divinylester-O-ethylester XII/2, 646 -0,0-divinylester-O-phenylester XII/2, 646 -O-dodecylester-O-methylester XII/2, 603 -O-cstcr-halogcnid-isothiocyanat E2, 680 O-Elhoxycarbonyl- -0,0-diethylester XII/2, 821 -S-(ethoxycaibonyl-methylestei)-0-metliylestei-0-(1,2,2,2-tetrachlor-cthylcstcr) E2, 588 -0-(2-ethoxycarbonyl-l-methyl-elhylester) E2, 678 -(ethoxymethylen-amid)-0,S-diethylester E2, 635 -(ethoxymethylen-amid)-O.S-dimethylester E2, 635 -(ethoxymethylen-amid)-0-(2-isopropyloxycarbonyl-phenylester)-0-methylester E2, 745 S-(Ethoxy-thiocarbonyl)- -chlorid-diethylamid XII/2, 822... 

Cyclohexen ( + )-l-Acetoxy-2,6-dimethyl-6-ethoxycarbonyl-E15/1, 76 (Keton + R-COOH) Cyclopentan 2-(3-Ethoxy-allyl)-2-ethoxycarbonyl-l-oxo- E15/1. 295 (Claisen-Umlager.) Cyclopropan 2,3-Diethoxycarbonyl-l-(2-methyl-l-propenyl)- E17a, 237 (subst. Cyclopropen + ROOC en-COOR) E18, 891 (Cyclopropen 4- En) 5,8-Dioxa-spiro 3.4 oct-l-en 2-Butyl-(or tert.-ButyI)-1 -isopropyloxy-3-oxo- E17f, 805 [l,2-(OR)j —4 OSiRj — 4-R — 3-oxo —cyclobuten + l,2-(OSiR3)2 — ethan] Ethan 1,1-Diethoxy-2-(4-methoxy-phenoxy)- E6b/1, 94 f, [OH -> 0-CH2-CH(0R)2]... 

Pyran 2-[Ethoxycarbonyl-(l-methoxy-1 -methyl-ethoxy)-methyl]-2-hydroxy-tetrahydro-E14a/1, 624 [Lacton + R — C(OR)2 - O - CH2 - COOR]... 

A -Aryl-A -(ethoxyearbonyl)iinidamides and 2-alkyl-l-aryl-3-(ethoxycarbonyl)isothioureas 12 cyclize thermally to yield 2-substituted quinazolin-4(3//)-ones 13. When an A-aryl-A -(ethoxy-carbonyl)imidamide is boiled briefly in quinoline, ethanol is evolved and the corresponding 2-arylquinazolin-4(3//)-one is formed in 49-88% yield. Presumably elimination of ethanol yields an imidoyl isocyanate which undergoes cyclization to form the 2-arylquinazolin-4(3//)-one. These cyclizations are most likely simple thermal processes, since they proceed equally well when diphenyl ether is used instead of quinoline or when the imidamide is heated at 50-70 C above its melting point in the absence of a solvent.This reaction is also suitable for the synthesis of benzo-fused quinazolin-4(3//)-ones. °... 

Irradiation of 2,5-bis(methoxycarbonyl)-3,6-dimethylpyrazine in diethyl ether with a 450-W high-pressure mercury lamp (330 nm) gave two significant photoproducts 2-hydroxy-5-methoxycarbonyl-3,6-dimethylpyrazine and l-(l -ethoxy-ethyl)2,5-dimethoxycarbonyl-3,6-dimethyl-l, 4-dihydropyrazine (74). Similar products were isolated when tetrahydrofuran was used as solvent. Corresponding reactions were observed with 2,5-bis(ethoxycarbonyl)-3,6-dimethylpyrazine, 2,5-diacetyl-3,6-dimethylpyrazine, and 2,5-dibenzoyl-3,6-dimethylpyrazine. The mechanism of these reactions were investigated and the initial stage was found to be... 

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