8- Phthalimido-7-

Glutaric acid, 2-phthalimido-polymerization, 1, 273 Glutaric anhydride polymers, 1, 313... 

Bei 2-Phenylthio-, 2-Cyan- und 2-Alkoxycarbonylazido-athylhalogeniden verlaufen die reduktiven Eliminierungen unvollstandig, 2-Nitrato-, 2-Sulfonyloxy-, 2-Benzoylami-no- und 2-Phthalimido-athylhalogenide werden nicht angegriffen. 

Imides can also add to alkenes or alkynes. Ethyl 2-propynoate reacted with phthalimide, in the presence of a palladium catalyst, to give ethyl 2-phthalimido-2-propenoate. ... 

MDL 73005 = 8,2 (2,3-dihydro-l,4-benzodioxin-2yl) methylamino-ethyl-8-azaspirol (4,5) decan-7,9-dione NAN 190 = l-(2-methoxyphenyl) 4-(4(2-phthalimido)entyl-piperazine)... 

Phthalimido-methyl)-l-[4- ( 2-pyridyl-sulfonyl)-phenylazo]-benzimidazol ... 

Neben Hydrazin-Hydrat werden auch verschiedene primare Amine zur Spaltung der N-substituierten Phthalimide empfohlen, z. B. eine 40%ige waBrige Losung von Methylamin zur Spaltung von 2-Phthalimido-carbonsauren zu den entsprechenden tx-Aminosauren (Glycin 97% Alanin 100%),... 

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. 

Acetamido-4-0-(3,4,6-tri-0-acetyl-2-deoxy-2-phthalimido-fi-D-glucopyranosyl)-3-0-acetyl-6-0-(a-L-fucopyranosyl)-2-deoxy- -D-glycopyranosyl Azide... 

To a solution of 2-(trimethylsilyl)ethyl 3-O-allyl-6-0-benzyl-2-phthalimido-2-deoxy-p-D-glucopyranoside (250 mg, 0.49 mmol) and 18 p,L of 1M MeOTf solution in 0.5 mL of dry dichloromethane was added dropwise 18.8 mg (0.07 mmol) of 3-methoxy-2-pyridyl p-L-fucopyranoside in 0.5 mL of solvent over 15 min. The mixture was stirred at room temperature for 30 min, and processed as described in the foregoing. The residue was purified by flash chromatography on silica gel column using EtOAc-hexane, (2 1) as eluant to recover the excess of acceptor. Elution of the column with EtOAc-hexane, (1 1) containing 10% methanol gave 20 mg of the title product in 43% yield as a syrup. 

Trimethylsilyl)ethyI 0-(2,3,4-tri-0-henzyl-a-r.-Jucopyranosyl)-(l->3)-2-phthalimido-4,6-0-benzylidene-2-deoxy- -D-glucopyranoside (28)... 

Trimethylsilyl)ethyl 0-(2,3,4-tri-0-benzyl-a-L-fucopyranosyl)-(l—>3)-0-benzyl-2-deoxy-2-phthalimido-fi-D-glucopyranoside (29)... 

Propanoate Methyl 3-(3-fluoro-4-hydroxy-2-phthalimido-4-phenyl- ElOa. 443 (H -> F)... 

Synthesis from 2C-B. To a solution of 7.24 g 2,5-dimethoxy-4-bromophenethylamine (2C-B) and 4.5 g phthalic anhydride in 100 mL anhydrous DMF there was added molecular sieves. After 16 h reflux, the reaction mixture was cooled and the sieves removed by filtration. The addition of a little CH2C12 prompted the deposition of yellow crystals which were recrystallized from EtOH. The resulting l-(2,5-dimethoxy-4-bromophenyl)-2-(phthalimido)ethane weighed 7.57 g and had a mp of 141-142 °C. Anal. (C]gH 6BrN04) C,H,N,Br. 

A solution of 14.94 g of l-(2,5-dimethoxy-4-bromophenyl)-2-(phthalimido)ethane and 4.5 g cuprous chloride in 300 mL anhydrous DMF was heated for 5 h at reflux. The cooled mixture was poured into 20 mL H20 that contained 13 g hydrated ferric chloride and 3 mL concentrated HC1. The mixture was maintained at about 70 °C for 20 min, and then extracted with CH2C12. After washing the pooled organic extracts with dilute HC1 and drying with anhydrous MgS04, the volatiles were removed under vacuum to provide a solid residue. This was recrystallized from EtOH to provide 12.18 g of l-(2,5-dimethoxy-4-chlorophenyl)-2-(phthalimido)ethane as yellow needles that had a mp of 138-140 °C. Anal. (C. CINOJ C,H,N,C1. 

To 60 mL absolute EtOH there was added 12.2 g 1-(2,5-dimethoxy-4-chlorophenyl)-2-(phthalimido)ethane and 2.9 mL of 100% hydrazine. The solution was held at reflux for 15 min. After cooling, the cyclic hydrazone by-product was removed by filtration, and the alcoholic mother liquors taken to dryness under vacuum. The residue was distilled at 145-155 °C at 0.05 mm/Hg to give 5.16 g of a clear, colorless oil. This was dissolved in anhydrous Et20 and treated with hydrogen chloride gas, producing 2,5-dimethoxy-4-chlorophenethylamine hydrochloride (2C-C) as white crystals with a mp of 220-221 °C. Anal. (Ci0H 5C12NO2) C,H,N. 

Compound was treated with phthalic anhydride in pyridine at 90° for 0.5 hr, then acetic anhydride was added, and the mixture was stirred for another hour at 90° and worked up. The product 39 (34) was isolated as needles in 80% yield, and was then converted into 3,4,6-tri-0-acetyl-2-deoxy-2-phthalimido-8-D-glucopyranosyl bromide ("glycosyl donor") according to the method reported... 

Figure 12. Preparation ofa glycosyl acceptor, allyl3-0-benzoyl-2-deoxy-2-phthalimido-P-D-glucopyranoside (51).

Synthesis of Derivatives of V-acetyllactosamine from Lactal Hexa-acetate. Hexa-0-acetyl-2-deoxy-2-phthalimido-/l-D-lactosyl Chloride, R. U. Lemieux, S. Z. Abbas, H. M. Burzynska, and R. M. Ratcliffe, Can. J. Chem., 60 (1982) 63-67. 

K. I. Kanno and K. Hatanaka, Synthesis of l,6-anhydro-4-0-benzyl-2-deoxy-3-0-p-methoxybenzoyl-2-phthalimido-/ -D-glucopyranose and its oligomer, Polym. J. (Tokyo), 30 (1998) 678-680. 

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