N-Benzyl-4-nitro

N-Benzylmaleimide (500 g, 2.67 mole), 90% bromonitromethane (831 g, 5.34 mole), powdered molecular sieves 200 mesh (2020 g) and toluene (12 dm3) were stirred under nitrogen at -10°C. 1,2-Dimethyl-l,4,5,6-tetrahydropyrimidine (616 g, 5.49 mole) was added slowly over about 3 h maintaining the reaction temperature at <-8°C throughout the addition. After completion of the addition, the reaction mixture was stirred for 1.5 h at 25°C, filtered under a nitrogen atmosphere in a sealed pressure filter to remove sieves and resulting tar, and the sieves were washed with toluene (2 L). The combined filtrates were washed with 2 N dilute hydrochloric acid (3 times 750 cm3), treated with carbon (50 g) at 70°C, 1 h filtered, concentrated, and triturated with 2-propanol (about 4 dm3) to obtain crystals of the (la,5a,6a)-3-N-benzyl-6-nitro-2,4-dioxo-3-azabicyclo[3.1.0]hexane (223 g, 34%) melting point 116°-118°C. 

Tetrahydrofuran (350 cm3), sodium borohydride (14.1 g) and (la,5a,6a)-3-N-benzyl-6-nitro-2,4-dioxo-3-azabicyclo[3.1.0]hexane (35.0 g, mmol) obtained above were stirred under nitrogen for 0.25 h and then treated dropwise with boron trifluoride-THF complex containing 21.5% BF3 (44.9 cm3) so that the exotherm was controlled to <40°C. After addition was completed, the reaction mixture was stirred for 3 h at 40°C, quenched slowly with water/THF 1 1 (70 cm3) to avoid excessive foaming, and stirred for 0.5 h at 50°C to ensure that the quench of unreacted diborane generated in situ was completed. The quench formed a salt slurry which was filtered and washed with THF (140 cm3) the combined filtrate was partially concentrated, diluted with water (350 cm3) and further concentrated to remove most of the THF, and extracted with ethyl acetate (140 cm3). The resulting ethyl acetate solution was concentrated to afford the (la,5a,6a)-3-N-benzyl-6-nitro-3-azabicyclo[3.1.0]hexane as a clear oil (30.6 g, 97%). 

The slurry was filtered, and the compound was isolated as a white solid (75.5% yield based on (la,5a,6a)-3-N-benzyl-6-nitro-2,4-dioxo-3-azabicyclo[3.1.0]hexane 96.6% based on ethyl 7-chloro-l-(2,4-difluorophenyl)-6-fluoro-l,4-dihydro-4-oxo-l,8-naphthyridine-3-carboxylic acid). The ethyl (la,5a,6a)-7-(6-benzylidenylamino-3-azabicyclo[3.1.0]hex-3yl)-l-(2,4-difluorophenyl)-6-fluoro-l,4-dihydro-4-oxo-l,8-naphthyridine-3-carboxylate was recrystallized from acetonitrile, melting point 148°-155°C decomp. 

Aryl bromides were also perfluoroethylated under these conditions [205] The key to improved yields was the azeotropic removal of water from the sodium perfluoroalkylcarboxylate [205] Partial success was achieved with sodium hepta-fluorobutyrate [204] Related work with halonaphthalene and anthracenes has been reported [206 207] The main limitation of this sodium perfluoroalkylcarboxylate methodology is the need for 2 to 4 equivalents of the salt to achieve reasonable yields A trifluoromethylcopper solution can be prepared by the reaction of bis(tri-fluoromethyl)mercury with copper powder in /V-methylpyrrolidone (NMP) at 140 °C [208] (equation 138) or by the reaction of N-trifluoromethyl-A-nitro-sotnfluoromethane sulfonamide with activated copper in dipolar aprotic solvents [209] This trifluoromethylcopper solution can be used to trifluoromethylate aro matic [209], benzylic [209], and heterocyclic halides [209]... 

Meibyl-phenyl)-(4-methyl-benzy1iden)- 664 Methyl-propyl-phenyl- 361 Methyl-(2,2,2-trifluor-athyl)- 239 Methyl-undecyl- 130 N-Nitro- 3641, 4791, 489 (4-Nitro-benzyl)- 116, 377 N-Nitroso- 479/., 696/. 

N-Diphenylmethylen- 374 N-Diphenylmethylen-O-aminocarbonyl- 612 N-[l,3-Diphenyl-propyl-(2) - 374 N-[l,3-Diphenyl-propyliden-(2)]- 374, 377, 380 N-(4-Halogen-phenyI)- 683 N-Heptyl- 375 N-Heptyl-N-acetyl- 376 N-Heptyliden- 375 N-Hcptyliden-O-acetyl- 376 0-(2-Hydroxy-athyl)-N-athoxycarbonyl- 133 N-(4-Hydroxy-phenyl)- 683 0-(2-Hydroxy-l-phenyl-athyI)-N-athoxycarbonyI-aus 0-(ci-AthoxycarbonyI-benzyl)-N-athoxycar-bonyl-hydroxylamin und Lithiumalanat 133 N-Isopropyl- 682 N-Isopropylidcn- 613 N-Methyl- 133, 682 O-Methyl-N-bcnzyliden- 377 O-Methyl-N-benzyliden- 375 0-Methyl-N-(4-chlor-benzyl)- 375 0-Methyl-N-(4-chlor-benzyliden)- 375 N-Methy -N,0-diacetyI- 682 N-(4-Methyl-phenyl)- 683 0-McthyI-N-( 1 -phenyl-athyliden)- 375 N-(4-Methylthio-phenyl)- 684 N-(4-Nitro-benzyl)- 374 N-[4-Nitro-benzyliden - 374, 377 N-(2-Nitro-phenyl)- 562 N-(4-Nitro-phenyl)- 682 N-Nitroso-N-cyclohexyl- 697 N-Octyl- 374 N-Octyl-(2)-N-acetyl- 376 N-Octyliden- 374 N-0ctyliden-(2)-0-acctyl- 376 N-(Pentafluor-phenyl)-0,N-diacetyl- 697 N-Phenyl- 474, 481, 682, 783 N-Phenylacetyl-O-benzoyl- 265 N-(l-Phenyl-athyl)- 374 N-(l-Phenyl-athyl)-N-acetyl- 376 N-(l-Phenyl-athyliden)-374, 613 N-( l-Phenyl-athyliden)-0-acetyl- 376 N-[ 1 -Phenyl-buten-( 1 )-yl-(3)-iden]- 582 N-f4-Phenyl-butyl-(2)-iden]- 581 N-Phcnyl-N,0-diacetyl- 682 N-(4-Phenylthio-phenyl)- 684 N-Propyl-N-cyclohexyl- 376 N-Propyl-N-isopropyl- 376 O-Sulfonyl- 481 N-(4-Sulfonyl-phenyI)- 683 N-(2-Vinyl-phenyl)- 698... 

Phenyl-[3- (bzw. -4)-chIor-benzyl]- 569 Phenyl-[3- (bzw. -4)-cyan-benzyI]- 569 Phenyl-(n-halogen-benzyl)-. 569 Phenyl-[a-haIogen-3- (bzw. -4)-chlor-benzyI] 569 Phenyl-[a-halogcn-3- (bzw. -4)-cyan-benzyl]-569 Phenyl-(a-halogen-4-nitro-benzyI)- 569 PhenyI-(4-nitro-benzyI)- 569 (1,2,2-TriphenyI-vinyI)-phenyl - 464 Vinyl-phenyl- 633f. 

Nitroglycals65 are excellent Michael-type acceptors,66 where O-, N-, S-, C- and P-nucleophiles can be used as donors.67 An application of this kind of reaction was reported by Schmidt et al. for a new synthesis of 2-deoxy-2-nitro-D-galactose nucleoside 86 and of /V-acetyl-D-galactosamine nucleoside 88, based on addition reactions to 3,4,6-tri-0-benzyl-2-nitro-D-galactal 85 (Scheme 28).68... 

Comparable effects were observed in the catalysis of the dehydrofluorination of 4-fluoro-4-(p-nitrophenyl)-2-butanone using Mi-polymers or even Ml-pro-teins (see later) imprinted with suitable TSA templates. Focusing on the two sp3 hybridized carbons (C2 and C3) of the butanone which are converted to sp2 carbons as a result of dehydrofluorination, the search for the right TSA led to N-benzyl-AT-isopropylamine (Fig. 13) either containing a nitro-group [62] at the aromatic ring or not [63,64]. 

OzN- -N2 Hs-CsHb HsCs-N (CH2)2-C00C2Hg CH2—Cek QzN—N = N —N ch2)2-c 4 -[Benzyl-( 2-ethoxy-car bonyl-ethyl)-5 amino]-4-nitro-azo-henzol ooc2H5 91 122-123 3... 

CHj-C6H5 HsC6 P Tac"s 0 N-OH MethyT3-0-benzyl-4,6-0-benzyliden- 2-deoxy-2-nitro-at-D-glucopyranosid lb 121-122 3... 

Benzyloxy-phenyl)-1-nitro-ethen mit Lithium-N,N-dimethyl-acetamid 3-(2-Benzyl-oxy-phenyl)-4-nitro-butansaure-dimethylamid (99%) ... 

Eine weitere Alternative zur Gabriel-Synthese von primaren aliphatischen Aminen ist die Reaktion von Alkyl-bromiden mit den N-Lithium-Derivaten von Bis-[benzolsulfensaure]-oder Bis-[4-chlor-benzolsulfensaure]-imid, gefolgt von Spaltung der N-Alkylierungspro-dukte mit 3N-Salzsaure in Ether5,6. Man erhalt auf diese Weise z. B. Benzylamin bzw. (4-Nitro-benzyl)-amin aus den entsprechenden Brom-Verbindungen in 86% Ausbeute. 

N-Allyloxy-6-fluoro-N-(2-imidazo-lyl)-2-ti ifluoromethyl- E16a/1. 296 (OH -> OR) N-(2-Amino-phenyl)-pcntafluoro-E10b2. 458 (E,C6-NH2/Basc) N-(Amino-thiocarbonyl)-pentafluo-ro- ElOb, 617 (F.duct) N-Bcn7oyl-N-( 1 -ethenyl-butyl)-4-trifluoroinethyl- ElOb, 230 [Ar-N = C(Ar) O CII2 CH = CH-Aik A] N-Benzyl-N-(cyano-phenyl)-nitro-tnfluoromethyl- ElOb,. 641 (Cl - NR-Ar)... 

N 14.14%. The following isomers are known 2-Nifro-, solid, mp 28°, prepd by refluxing 2-nitrobenzyl chloride with finely powdered Ag nitrate for 7 days(Ref 4) 3-Nitro-, pale-yel crysts mp 42.5-43°, prepd as above from 3 nitrobenzyl chloride(Ref 4) and 4 Nitro-, yel crysts, mp 71° (Ref 1), 52°(Ref2) and 68.2° (Ref 3) can be prepd by nitration of p-nitrobenzyl alcohol(Refs 1 3) by gradual introduction of benzyl nitrate into an excess of 95% nitric acid cooled to -10°(Ref 2)... 

Nitrobenzyl-2,4,6-trimUo-nitranilinj 4 -Nitro-benzyl-2,4,6-trimtrophenyl-nitramine or Picryl-(4 -nitrobenzyl)-nitr amine nearly col crysts, mp 141 -2° (with evoln of gas) was first prepd by Blank-sma(Ref 2) by heating N-(4-nitrobenzyl)-4-nitro-aniline with nitric acid(d 1.52) and then later by van den Berg(Ref 3), who showed that this compd can also be obtd by nitration of 4 -nitrobenzyl-2 -ni tro aniline, benzyl-2,4-dinitroaniline, benzyl-2, 4,6-trinitroaniline, 4 -nitrobenzyl-2,4-dinitroani-line or 4 -nitrobenzyl-2,4,6-trinitroaniline. 

Methyl-5-nitro-phenyl)- E16a, 260 (O-Umarylier.) 0-(3-Methyl-4-nitro-pheny])- E16a, 260 (O-Umarylier.) 0-(5-Methyl-2-nitro-phenyl)- El 6a, 260 (O-Umarylier.) N-(3-Nitro-benzyl)- E16a, 39 (Oxim-Red.)... 

N-(4-Nitro-benzyl)- IV/ld, 374 (Oxim-Red.) X/I, U67f. (Nitron-Spalt.) Elba, 36 (Oxim-Red.)... 

Amin Benzyl-chlormethyl-nitro-E16a, 1171 (N-Chlormethylier.) Anitin 2-Chlor-N,N-dimethyl-4-ni-tro- V/3, 710 Benzol... 

Methy -nitro-(4-nitro-benzyl)-E16a, 1161 (N-Alkylier.)... 

Guanidin N-Benzyl-N"-nitro-N-nitroso- X/4, 543 1-Tetrazen 4-Acetyl-1-(4-nitro-phenyl)- X/3, 735... 

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