Ethyl with phthalimide

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. ... 

Theil et al. developed a method for chemoenzymatic synthesis of both enantiomers of cispentacin [89]. frans-2-Hydroxymethylcyclopentanol, obtained by the sodium borohydride reduction of ethyl 2-oxocyclopentanecarboxylate, was monosilylated with tert-butyldimethylsilyl (TBDMS) chloride to afford 55. Lipase PS-catalysed transesterification with vinyl acetate in /erf-butyl methyl ether furnished the ester 56 and the alcohol 57. The deacetylated 58 was obtained by the Mitsunobu reaction with phthalimide, triphenylphosphine and diethyl azodicarboxylate (DEAD) to furnish the cis oriented 59 with inversion of configuration (not retention as mentioned in the original article) (Scheme 9). Desilylation, Jones oxidation and subsequent deprotection with aqueous methylamine gave the ( R,2S) enantiomer 5 [89]. The (15, 2/f) enantiomer was prepared by the same route from the silyl alcohol 57. 

N,0-Diacetyl-N-methylethanolamine heated with phthalimide at 200° to remove acetic acid N-[2-(N-methylacetamido)ethyl]phthalimide. Y 82-91%. F. e. s. K. Nakajima, T. Shinuchi, and M. Tauchi, Nippon Kagaku Zasshi 88, 976 (1967) (Japan) C. A. 69, 58928. 

The noncovalent binding of a series of oxo-squaraine dyes 9a-e to BSA was evaluated by measurement of absorption, emission, and circular dichroism [63]. The magnitude of the association constants (Ks) for the dye-BSA complexes depended on the nature of the side chains and ranged from 34 x 103 to 1 x 107 M-1. Depending on the side chains, the Ks increase in the order [R1 = R2 = butyl-phthalimide] < R1 = R2 = cetyl] <[RJ = R2 = ethyl] <<[R = butyl-phthalimide, R2 = butyl-sulfonate] <<[RJ = R2 = butyl-sulfonate]. These dyes seem to interact mainly with a hydrophobic cavity on BSA. However, the association constants Ks increase substantially when the side chains are selected from butyl sulfonate. 

The palladium-catalyzed substitution of the less reactive racemic ethyl 3-cyclohexe-nyl carbonate could, in a similar fashion, be completed with dimethyl malonate, p-methoxyphenol, or phthalimide as nucleophiles, with satisfactory ee (Eq. 11.38) [55]. These reactions, when irradiated for 1 min with temperatures up to 100 °C, delivered yields (91-96%) and ee values (94—95%) identical with those performed in... 

In a 6oo-cc. beaker 210 g. (0.87 mole) of ethyl bromomal-onate (p. 34) (Note 1) and 165 g. (0.89 mole) of potassium phthalimide (p. 8) are intimately stirred together. The mixture is stirred approximately every ten minutes. If no spontaneous reaction starts in half an hour (Note 1), it is necessary to initiate the reaction by heating to no-1200. The mixture then becomes liquid and can be stirred easily. It turns to a light brown color, especially near the top where it comes in contact with the air. When the temperature begins to drop, the mixture is heated in an oil bath at no0 for one hour to insure completion of the reaction. The mixture is then poured into a mortar where it solidifies to a solid mass (Note 2). When cold, the mixture is ground up with water and filtered to remove most of the potassium bromide. The precipitate is then reground with water and refiltered, finally washing the precipitate well with water. The solid material on the filter consists of some potassium bromide, some phthalimide, and the phthalimidomalonic ester. 

Phthalimide. C<,H4 (CO), NH, is an imide of commercial and industrial importance, forming a number of interesting derivatives. With alcoholic potash, phthalimide forms a potassium derivative. C(,H4 (COb -NK. which, when reacted with ethyl iodide (or other alkyl halides), yields eihylphthalimidc. C(,H4 (COi N - C2Hj Ihe latter product, when hydrolyzed wilh an acid or alkali, further yields ethylamine. Such reaction chains are useful in ihe preparation of certain primary amines and their derivatives. 

About the same time McKervey reported A-sulfonamidoprolinate catalysts [53] (17), and later Ikegami, Hashimoto, and co-workers described uses of dirhodium(II) catalysts with ligands that were phthalimide derivatives of phenylalanine [54] (18a), fer/-leucine [55] (18b), and alanine (18c), but they were similarly unselective in intermolecular cyclopropanation reactions of ethyl diazoacetate. Only when Davies applied chiral prolinate 17a and those that he reported for the first time (17c, X = rBu, C12H25) to cyclopropanation reactions of vinyldiazocarboxylates (Eq. 5.12) did the value of these catalysts for cyclopropanation reactions become fully expressed (Table 5.6) [56,57], The advantage of 17c (X = C12H25) is its solubility in pentane, even at -78°C. 

Treatment of perhydro-4-azaazulene (3) with mercuric acetate produces a mixture of dehydro derivatives 31a and 31b, which, with acids, yields homogeneous salts of structure 32 (56JOC344). The enamine 34, which was obtained by the same route from 33, served as a model compound in a study of the synthesis of cephalotaxine (72JOC3691). A reaction with ethyl y-bromo-acetoacetate surprisingly yielded the quinolizidine 36, which was formed by rearrangement of the intermediate annellation product 35 (Scheme 3) Phthalimides 38 were obtained from a Baeyer-Villiger oxidation of 4-azaazulen-3-ones 37 (77JOC1093). 

The Gabriel-malonic ester synthesis begins with (V-phthalimidomalonic ester. Think of (V-phthalimidomalonic ester as a molecule of glycine (aminoacetic acid) with the amino group protected as an amide (a phthalimide in this case) to keep it from acting as a nucleophile. The acid is protected as an ethyl ester, and the a position is further activated by the additional (temporary) ester group of diethyl malonate. 

McAlees and McCrindle found that phthalimides with electron-withdrawing substituents such as an acyl or alkoxycarbonyl on the imide nitrogen were hydrogenated to the corresponding 3-hydroxyisoindolin-l-ones over 10% Pd-C in ethyl acetate or ethanol (eq. 10.51).83... 

The present procedure is that described by the submitters.3 a-Phthalimido-o-toluic acid has also been prepared by the acidolysis of the corresponding ethyl ester, obtained from the reaction of ethyl a-bromo-o-toluate with potassium phthalimide.8... 

Table 8. Phthalimide Anion Displacement Reactions with 2-(2-Bromoacyl)-2-ethyl-1,3-dithiane 1-Oxide Substrates...

Acylation of tris(methylsulfanyl)methyllithium (496) has been performed with esters713, lactones714-716, ethyl chloroformate689 and carbon disulfide717. A complete study on the reaction of the intermediate 496 with aromatic, heteroaromatic and aliphatic esters showed that a-keto trithioorthoesters 509 and a-keto dithioacetals 510 are formed713 (Scheme 133). Compounds 509 were obtained mainly with a reagent/anion ratio of 1/1.25 at — 95 °C for 5 min and subsequent addition of (V-(methylsulfanyl)phthalimide to the reaction mixture. 

An alternative method for preparing is by reacting N-(2-hydroxyl-ethyl)phthalimide with ethyl 4-chloroacetoacetate in the presence of sodium hydride as illustrated in Eq. 1 and described elsewhere (2). 

Other amidoselenenylation reactions have been described. Salazar [50] reported that the carbamatoselenenylation of alkenes can be effected using hT-(phenylseleno)phthalimide, in the presence of tetrafluoboric acid, and ethyl carbamate as the nucleophile. The reaction is a stereospecific anti addition and works well with monosubstituted and 1,2-disubstituted alkenes. In the case of monosubstituted alkenes mixtures of regioisomers were obtained. 

Cyclic anhydrides of dibasic acids react with ammonia and certain amines to give cyclic imides, such as phthalimide (97%) and a-ethyl-glutarimide (85%). Aqueous ammonia, ammonium carbonate, and dry ammonia gas have been used. 2-Aminopyridine and phthalic anhydride react at 180° to yield N-(2 pyridyl)-phthalimide (76%). t-Butylphthali-mide is made by the action of phthalic anhydride on /-butylurea at 200-240°. The use of alkylureas in this reaction is general. ... 

Alkylation ofimutes. Ethyl chloroformale in DMF reacts with lithium phthalimide at temperatures of 60-110° to give N-ethylphthalimide (2) in 80% yield. 

With the development of W-(ethoxycarbonyl)phthalimide (78) an efficient and mild phthaloylation reagent was obtained which upon reaction with amino acids liberates ethyl carbamate as shown in Scheme 40. ... 

---