Phthalimides, hydroxy

Hydroxy-l-oxo-2,3-dihydro-lH-(isoindol)Zu einer Suspension von 147 g (1 Mol) Phthalimid in 1 / 90%igem Methanol wird unter Riihren bci 25-30° innerhalb 30 Min. eine Losung von 76 g (2 Mol) Natriumbo-ranat in 1,5/ Methanol getropft. Man riihrt 10 Stdn. bei 25-30 nach, laBt 12 Stdn. bei 20° stchcn, sauert mit Es-sigsaure an, engt i.Vak. ein, verdiinnt mit Wasser und filtriert. Das Rohprodukt wird aus Wasser umkristallisicrt Ausbeute 98 g (66% d.Th.) F 179°. 

Auf analoge Weise erhalt man aus N-Anilino-phthalimid in schwach saurer Losung2-Anilino-3-hydroxy-1-oxo-2,3-dihydro-isoindol (79% d.Th. F 1480)1 ... 

Eine ahnliche Umwandlung von sekundaren Alkoholen in primare Amine mittels der Mit-sunobu-Reaktion ist am Beispiel dcr 7-Hydroxy- untersucht worden1. Behandlung dieser Alkohole mit Triphenylphosphan, Phthalimid und Dieth-oxycarbonyl-diazen in Tetrahydrofuran ergibtdie 2-Phthalimido-Derivate, die isoliert und mittels Hydrazin unter Bildung der freien Amine gespalten werden. Bei dem beschriebenen System entstehen auf diese Weise aus den 7-m/o-Alkoholen die 7-exo-Amine und aus den 7-exo-Alkoholen Gemische der 1-endo- und 7-eJto-Amine. 

Various nucleophilic attacks at C(3) and C(4) of -lactams have been employed to introduce desired functionalities. Nucleophilic displacement of a halogen at C(3) by nucleophiles, for example, potassium phthalimide, has been performed (93JCS(Pl)2357). The a-azidation of l-hydroxy-2-azetidi-nones, for example (37), with arenesulfonyl azides in the presence of triethylamine affords 3-azido-2-azetidinones (38) via Otosylation and SN2 -type of displacement of the tosyloxy group (92JA2741, 93JA548, 93BMC2429). 

Very few compounds of this type are known, and none bear a 2-hydroxy group. The phthalimides (322), on cathodic reduction in anhydrous aceto-... 

The alkylation products are synthetically useful because simple subsequent transformations furnishes precursors of important natural products as illustrated in Scheme 8E.23. Simple oxidative cleavage of allylic phthalimide 45 generates protected (5)-2-aminopimelic acid, whose dipeptide derivatives have shown antibiotic activity. The esterification via deracemization protocol is not limited to the use of bulky pivalic acid. The alkylation with sterically less hindered propionic acid also occurs with high enantioselectivity to give allylic ester 116, which has been utilized as an intermediate towards the antitumor agent phyllanthocin and the insect sex excitant periplanone. Dihydroxylation of the enantiopure allylic sulfone gives diol 117 with complete diastereoselectivity. Upon further transformation, the structurally versatile y-hydroxy-a,(f-un-saturated sulfone 118 is readily obtained enantiomerically pure. 

The formation of dibenzopyrrolizines (51) on irradiation of N-(2-alkylphenyl)phthalimides (50) with a high-pressure mercury lamp was reported. Phthalimides containing electron-donating groups resisted cyclization. Hydroxy compounds 51 were dehydrated to dibenzopyrrolizinones by treatment with acids.38... 

Karimi, B. Rajabi, J. Efficient aerobic oxidation of acetals to esters catalyzed by N-hydroxy phthalimide and Co(II) under mild conditions. Synthesis 2003, 2373-2377. 

Finally, as examples of similar types of reactions, photolytic treatment of O-acyl ester (D) of benzophenone oxime, A-acyloxy-phthalimide (E), and O-acyl ester (F) of A-hydroxy-2-pyridone with a mercury lamp generates the corresponding alkyl radicals via decarboxylation. However, these reactions can be used only for the alkylation of aromatics (solvents such as benzene) and reduction [86-89], so their synthetic utility is extremely limited. 

The progress of intramolecular PET-reactions involving alkenyl phthalimides in essentially influenced by the solvent [29]. Upon irradiation in MeCN, [n2 + a2]-addition to the C(0)-N bond takes place and benzazepinediones are obtained. In alcohol, the intermediary formed radical cation is trapped in an aw/z -Markovnikov fashion depending on the polarity as well as the nucleophilicity of the solvent [30]. Recently, Xue et al. described an interesting modification of the latter process using tetrachloro-phthalimides with remote hydroxy alkyl substituents (13) [31]. During... 

HYDROXY-3-METHYL-1-PHENYL-1-BUTANONE 1-BUTANONE, 3-HYDROXY-3-METHYL-1-PHENYL- (43108-74-3), 65, 6, 12 1-(3-HYDROXY-2-METHYL-3-PHENYLPROPANOYL)PIPERIDlNE, ERYTHRO PIPERIDINE, 1 -(3-HYDROXY-2-METHYL-1-OXO-3-PHENYLPROPYL)-, R, R )-( )- (99114-36-0), 69, 44 N-Hydroxymethylphthalimide Phthalimide, N-(hydroxymethyl)- ... 

The substitution pattern of TfOH-mediated electrophilic aminomethylation of psoralens (furo-coumarins) by V-(hydroxymethyl)phthalimide has been elucidated <85JHC73>. Multiple phthal-imidoylated adducts were obtained when a B-ring hydroxy or methoxy activating group was present, and these resisted simple cleavage with NH2NH2. However, this two-step procedure to aminomethyl group introduction worked well when the psoralens contained only methyl substituents. 

Hydroxy phenyl aceto acetate coumaphos N-Hydroxy phthalimide clethodim... 

Another example of ring enlargement is provided by the aminomethylation of the potassium salt of N-hydroxy-phthalimide (Fig. 70), whieh affords the Mannich base 198 of dihydro-benzoxazine-dione, instead of the O-Mannich base of N-hydroxy-phthalimide, as previously proposed. -... 

Fig. 70. Simultaneous ring cniargement-aminomcthylation reaction of N-hydroxy-phthalimide salt.

Phthalazine 4-Amino-l-hydroxy-E9a, 753 (2-CN-l-COOR-benzene/N2H4), 758 (Thio-phthalimid + N2H4) Pyrido 2,3-b pyrazin... 

Phthalazine 4-Hydrazino-l-hydroxy-E9a, 759 (Phthalimid-l-imid/ N2H4) E16a, 719f. 

Methyl-2-oxo- E21e, 5260 6-[n(Acyl) —SR] — en Cyclisier. 8-Aza-bicycIo]4.3.0]non-3-en 8-Hydroxy- E16a, 188 (N-OH —phthalimid-Red.) Azetidin 4-Ethenyl-3-isopropyl-2-oxo- E16b, 246 (Imin + R-C-COOR) Bicyclo 2.2.1]bept-2-en S-endo-(Hydroxyamino-methyl)- E16a, 26 (Oxim-Red.)... 

Phthalazine 4-Hydroxy-l-methyl-E9a, 751 (2-Acetyl-benzoesaure/ N2H4), 756 (l,2-H2-Der./Oxid.) Phthalazinium-l-olate 3-Methyl-E9a, 785 (OT -+ O or N-Methylamino-phthalimid/ NaBH4)... 

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