3.4- Dimethyl-4-nitro- -nitril

Diazo- -ethylester E14b, 1128/1146 (Hydrazon-Oxidat.) 2,2-Dimethyl-3-nitro- -nitril X/l, 415 Pyrazolidin l,2-Dimethyl-3,5-dioxo-VII/4, 301... 

In ahnlicher Weise erhalt man aus 4-Chlor-l-nitro-benzol und 3-Dimethylamino-propan-saure-nitril in Isoamylalkohol bei 130 (130 h) N,N-Dimethyl-4-nitro-anilin in guter Aus-beute. 

Nickel, dichloro [ethylenebis(dimethyl-phosphine)], 58, 133 Nickel, dichloro[ethj lenebis(diphenyl-phosphine)], 58,133 [Ni (-)-diop Cl2 ], (-)-diop=2,3-0-iso-propylidene-2,3-dihydroxy-l,4-bis(di-phenylphosphino)butane, 58, 133 Nickel, dichloro [ trimethylenebis(diphenyl-phosphine)], 58,133 NITRILES, alkylation of, 55, 91 NITRILES FROM KETONES, 58, 101 NITRILES, a vinyl, 55, 99, 101 p-Nitrobenzenesulfonyl cyanide, 57, 89 p-Nitrobenzyl alcohol, 57, 72 p-NITROBENZYL FLUORIDE, 57, 72 Nitro compounds, 56, 36 Nitronates, 56, 36... 

Nitrodienes undergo intermolecular Diels-Alder reactions with appropriate dienophiles. The resulting nitro compounds can then be cyclized via a nitrile oxide intermediate.49 Thus, the 2-chloroacrylonitrile Diels-Alder adduct of 8-nitro-l,3-octadiene was prepared and cyclized to give (105) as a 3 1 mixture of diastereomers (Scheme 30). The Diels-Alder adduct of dimethyl acetylenedicarboxylate and 8-nitro-l,3-octadiene cyclized exclusively at the conjugated double bond, activated by the ester groups. Similarly, the quinone Diels-Alder adduct (106) cyclized at the conjugated double bond reduction of the conjugated double bond permitted cyclization on the cycloalkenyl double bond. 

The reaction of allenic nitrile and 2-amino-6-methyl- and -4,6-dimethyl-pyridine gave a mixture of mono- and bis-adducts tentatively formulated as 75, 76, and 77 [88JCS(P1)975], while 2-amino-3-nitro-, 2,6-diamino-, and 2-amino-3,5-dibromopyridines do not react even after refluxing for 120 hours. 

Propansaure 3-(l-Nitro-cyclohexyl)- -nitril E5, 1518 (Ar —N02 + H2C = CH-CN) lH-Pyrazol 3,5-Dimethyl-l-(ethoxycarbonyl-methyl)- E8b,... 

Cyclopropan 2,2-Dimethyl-3-methylen-l-[3(or4)-nitro-phenyl]- El7a, 352 (Ar —CHN2 + 1,2-Dien) 2,4,6,8-Decatetraendisaure -ethyl-ester-nitril V/ld, 137... 

A simultaneous reduction-oxidation sequence of hydroxy carbonyl substrates in the Meerwein-Ponndorf-Verley reduction can be accomplished by use of a catalytic amount of (2,7-dimethyl-l,8-biphenylenedioxy)bis(dimethylaluminum) (8) [33], This is an efficient hydride transfer from the sec-alcohol moiety to the remote carbonyl group and, because of its insensitivity to other functionalities, should find vast potential in the synthesis of complex polyfunctional molecules, including natural and unnatural products. Thus, treatment of hydroxy aldehyde 18 with 8 (5 mol%) in CH2CI2 at 21 °C for 12 h resulted in formation of hydroxy ketone 19 in 78 % yield. As expected, the use of 25 mol% 8 enhanced the rate and the chemical yield was increased to 92 %. A similar tendency was observed with the cyclohexanone derivative. It should be noted that the present reduction-oxidation sequence is highly chemoselective, and can be utilized in the presence of other functionalities such as esters, amides, rert-alco-hols, nitriles and nitro compounds, as depicted in Sch. 10. 

A similar reaction is found in the formation of 5-amino-l-cyano-2,4-dimethyl-3.106-dihydrobenzo[c][2,7]naphthyridine by reduction of 3,5-dicyano-2,6-dimethyl-4-(2-nitro-phenyl)-l,4-dihydropyridine [87] and tetrahydroquino[2,l-c]benzodiazepines from 2-cyano-l-(2-nitrobenzyl)-l,2,3,4-tetrahydroquinoline [88], When the hydroxylamino group has a choice between a nitrile or an ester group, as in 3-ethoxycarbonyl-5-cyano-2,6-dimethyl-4-(2-nitrophenyl)-1,4-dihydropyridine, it condenses with the nitrile in acidic solution and with the ester in basic media [89]. 

Zur Reduktion von 4-Nitro-pentansaure-nitril mit nachfolgendem RingschluB zum 4-Imino-1 -hydroxy-2,2-dimethyl-tetrahydropyrrol s. Bd. X/l, S. 440. 

In another one-pot reaction, chiral isoxazoline-fused benzazepines 31 were formed from the reaction of P-nitrostyrene derivatives 30 and 1,3-dicarbonyl species such as dimethyl malonate. The first step is a nitro-Michael addition reaction between the nitro olefin and dimethyl malonate catalyzed by a chiral thiourea organocatalyst, followed by addition of DMAP and Boc anhydride with heating to promote nitrile... 

Amjno-hezan-/3-carbon8iaie-nitril 4, 460. a-Amino uy-dimethyl-n-Taleiians iire-nitrO 4, 461. 

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