Chloro phthalimide

Phases with phenyl groups are less retentive than C8 bonded phases. They show a pronounced selectivity and retention toward solutes with aromatic ring systems, attributed to n-n interactions. These n-n interactions can be improved when nitro substituted phenyl groups are bonded to silica. The strongest interactions have been reported with tetra nitro or tetra chloro phthalimide substituents. 

The synthesis of poly(ether imide)s by condensation of the disodium salt of bisphenol-A with bis(chlorophthalimide)s under microwave irradiation conditions has been described by Zhang et al. (Scheme 14.21) [50]. The polymerization reactions were performed under phase-transfer catalysis (PTC) conditions in o-dichlorobenzene solution. For this purpose a mixture of 16.12 mmol bis(chloro-phthalimide)s and 16.12 mmol disodium salt of bisphenol-A in 60 mL o-dichlorobenzene with 0.56 mmol hexaethylguanidinium bromide was irradiated in a domestic microwave oven for 25 min and the product was precipitated by addition of methanol. The polymerization reactions, in comparison with those under the action of conventional heating, proceeded rapidly (25 min compared with 4 h at 200 °C) and polymers with inherent viscosities in the range 0.55 to 0.90 dL g were obtained. 

The discovery of the imidazolinotte herbicides had its beginnings in a random screening test some 12 years ago. The phthalimide 1 prepared originally as an anticonvulsant at Cyanamid s Lederle Laboratories had sufficient herbicidal activity to warrant the synthesis of additional members of this series. One of these, the chloro analog was essentially devoid of herbicidal activity but had instead a pronounced... 

A detailed study of the conversion of 3,4-dichloro-l,2,5-thiadiazole into 3,4-diamino-l,2,5-thia-diazole has been carried out <76JHC13>. Reaction with lithium or sodium amide produces only 4% of the diamine together with cyano-containing by-products, a consequence of direct attack on sulfur. Use of a less powerful nucleophile, ammonia or potassium phthalimide, resulted in an increased attack on carbon and produced the diamine in 24% and 66% yields, respectively. Secondary amines, e.g. morpholine <76JOC3l2l> and dimethylamine <72JMC315>, produce the normal displacement products. The reaction of dichlorothiadiazole with potassium fluoride in sulfolane gives a mixture of 3-chloro-4-fluoro and 3,4-difluoro-l,2,5-thiadiazole <82CB2135>. 

Polystyrene-bound amines can be converted into the corresponding phthalimides by heating with other phthalimides (BuOH, 85 °C, 18 h [33]). Support-bound phthalimides have also been prepared by N-alkylation of phthalimide derivatives [295] or by amidomethylation of cross-linked polystyrene with /V-(hydroxymethyl) or /V-(chloro-methyl)phthalimide [296,299]. 

Treatment of free sucrose with phthalimide under Mitsunobu conditions affords modified derivatives in which the primary 6-OH and 6 -OH groups are replaced by a phthalimido moiety, with concomitant epoxide formation at C-3 and C-4 (Scheme 19).253 Chloro-anhydro derivatives were formed similarly under Mitsunobu conditions in the presence of zinc chloride.254... 

Substitution. Copper phthalocyanine is preferred as starting material. Very little is known about the position of substitution. With the exception of hexadeca-chloro CuPc, all commercial Pc substitution products, as well as the tetrasubsti-tuted derivatives synthesized from monosubstituted phthalic acids, are mixtures of isomers. Despite the 16 hydrogen atoms that can be substituted, only two different monosubstituted Pc s are possible. The number of disubstituted isomers is higher. Mono- to heptasubstituted Pc derivatives have not yet been isolated in isomerically pure form. In addition, only a limited number of isomers are accessible in pure form by synthesis. Only symmetrically substituted phthalic acids, phthalimides, or phthalodinitriles (3,6-di-, 4,5-di-, or 3,4,5,6-tetrasubstituted derivatives) yield pure isomers of octa- or hexadecasubstituted phthalocyanine derivatives. All other substituted phthalic acids give mixtures of isomers. 

For example (+)-43a was obtained after two purifications at 55 % ee and 10 % yield. Treatment of (+)-43a with hydrazine and KOH gave (+)-45a at 55 % ee and 40 % yield. The chiral host (S)-(—)-40 has been found to be extremely effective as a chiral selector towards comparatively bulky molecules of the phthalimide formed from of l- < r -butyl-3-chloro-azetidin-2-one, 47. A crystalline inclusion complex of 1 1 stoichiometry was formed between one mole of (S)-(—)-40 and two moles of rac-47 dissolved in benzene/hexane 1 1 solution. After one recrystallization, the complex was chromatographed on silica gel, and the crystalline product was treated with hydrazine. Optically pure (—)-3-amino-l-ieri-butyl-azetidin-2-one (—)-47, was obtained at 100% ee and 44% yield [51]. Primary diamines, like 1,3-dibromobutane (49), can undergo a similar reaction with potassium phthalimide, yielding diphthalimide, 50. The complexation process between rac-diphthalimide 50 and host (S,S)-(—)-6 gave a 1 1 complex containing (—)-50... 

It has been proposed that the reaction of 2-chloro-5-nitropyridine (183) with the anions of benzotriazole, imidazole, pyrrole and phthalimide in DMF occurs by the S l mechanism. Thus, the reaction of 183 with the anion of benzotriazole gives 95% of the substitution product 184 (equation 125)229. 

The phthalimidoalkylsulfanylcarboxylic acid 592 was easily available from the corresponding chloro-iV-(pro-pyl)phthalimide 589 and methyl mercaptopropionate ester 590 and subsequent hydrolysis of ester 591 were obtained. Under standard irradiation conditions at 300 nm in acetone/water, the potassium salt of 592 cyclized with concomitant extrusion of C02 to give the isoindolothiazocine 561 in low yield (15 %) (Scheme 117). 

A mixture of l-(5-chloro-2-methoxyphenyl)piperazine (28.64 g), K2CO3 (44.6 g) and N-(3-bromopropyl)phthalimide (33.65 g) were dissolved in 250ml acetonitrile and refluxed 8 hours. The mixture was cooled, poured into 800 ml water, filtered, recrystallized in methyl alcohol, and the product isolated in 91% yield, mp = 131-133 °C. 

As an extension of this chemistry, the [3+2] cycloaddition reaction of new atropisomeric 4-dialkylamino-5-chloro-l,2-dithiole-3-thiones 130 and DMAD or its diethyl analogue has been utilized to give thioacid chlorides 131 (Scheme 13) <20030L929>. These have been converted into thioamides 132 with 2 equiv of pyrrolidine (or morpholine) by substitution of the 5-chloro substituent and phthalimide ring opening. Similar reactivity toward 1 or 2 equiv of pyrrolidine was noted for 130, which was obtained according to the general method described. 

The reaction of a-chloro carbonyl compounds with ammonia is not always successful, for example, w-chloro-o-methoxyacetophenone and w-chloro-o,p-dimethoxyacetophenone yield only resinous products (236), but in these cases potassium phthalimide may be used for the ammonation to the a-amino carbonyl compound. This last method was developed by Gabriel (116) and co-workers (187). 

AMIDES Bis(o-nitrophenyl)phenyl-phosphonate. N,N-Bis(2-oxo-3-oxazoli-dinyl)phosphordiainidic chloride. 2-Chloro-2-oxo-l, 3,2-benzodioxa-phos-phole. Iodine azide. N-Methyl-N-phenyl-benzohydrazonyl bromide. Phase-transfer catalysts. N-Phenylseleno-phthalimide. (Sl-Prohnol. 

An imide monomer was synthesised from 4-nitrophthalic anhydride N-(4 -carboxyphenyl)>4-(4 -carboxyphenoxy)phthaHmide. (14). This was reacted (via its dimethyl ester) with chloro- or phenylhydroquinone to form wholly aromatic co-poly(esterimide)s which were found to exhibit a nematic phase in the melt. Similar PEIs derived from aliphatic diols produced only isotropic polymers. Thus, PEI derived from 4-(4 -carboxyphenoxy)phthalimide and n-do-decane diol melted at 162 °C, Tg=66 °C, and was isotropic [28]. The above imide monomer based on phthalic anhydride was therefore shown to be a poor mes-ogen compared with its trimellitic anhydride analogue (4). 

Phthalimide is chlorinated with CBT in benzene at reflux to form a chloro derivative in 44% yield (72MI1). 

CCRIS 7991 Chloromethylphthalimide N-(Chloro-methyljphthalimide N-Chloromethyltrimeilitimide EINECS 241-541-4 1 H-lsoindole-1,3(2H)-dione, 2-(chloromethyl)- NSC 29558 Phthalimide, N-(chloromethyl)- Phthalimide, N-chloromethyl-. 

A large number of substituted alkyl halides, for instance, chloro ethers,266 chloro sulfides,267 and halo carboxylic esters,268 provide syntheses of phosphonic esters containing also other functional groups. A-(2-Bromoethyl)-phthalimide leads, after hydrolysis, to / -amino phosphonic esters.269... 

---