Phthalide hydroxy

Carboxyphenyl-(2-methyl-3-indoleninjdidene)methanol (303) was said to be formed by the action of phthalic anhydride on 2-methyl-indole magnesium bromide. Skatole magnesium bromide, on the other hand, apparently gave 2-carboxyphenyl-(3-methyl-2-indole-ninylidene)methanol (304) and 3-hydroxy-3-(3-methyl-l-indolyl)-phthalide (305) on treatment with 1 mole of phthalic anhydride. The derivative 305 was easily hydrolyzed in alkali, giving skatole and phthalic acid, and was thus formulated as a 1-skatolyl derivative. ... 

One of the more complex local anthetics in fact comprises a basic ether of a bicyclic heterocyclic molecule. Condensation of 1-nitropentane with acid aldehyde, 79, affords the phthalide, 81, no doubt via the hydroxy acid, 80. Reduction of the nitro group... 

D. Taub et al., Tetrahedron 24, 2443 (1968) 3-Hydroxy-5,7-dimethoxy-phthalid (4,6-Dimethyl-phthal-2-al-... 

Analog erhalt man aus 3-Acetoxy-phthalsaure-2-methylester mit 0,13 Mol Lithiumala-nat 4-Hydroxy-phthalid (68% d.Th. F 252—254°). 

Mit einem kleineren Natriumboranat-OberschuB kann sich neben 3-Hydroxy-l-oxo-2,3-dihydro-IH-isoindolen und 2 -Hydroxymethyl-benzoesaure-amiden ebenfalls Phthalid bilden1 2. 

The lactones are the intramolecular esters of the corresponding hydroxy fatty acids. They contribute to the aroma of butter and various fruits. 15-Pentadeca-nolide is responsible for the musk-like odor of angelica root oil. Of the naturally occurring bicyclic lactones, phthalides are responsible for the odor of celery root oil, and coumarin for woodruff. 

Protoberberine Alkaloids.—In the course of the bioconversion of the proto-berberine scoulerine (65) into chelidonine (62) and phthalide-isoquinolines, e.g. narcotine (63), C-13 becomes oxidized.61 Ophiocarpine (68), with a hydroxy-group at C-13, represents an intermediate stage in the modification of the protoberberine skeleton, and results62 of tracer experiments have shown that scoulerine (65) is also to be included in the biosynthesis of this alkaloid. Tetrahydro-protoberberine (67) is also a precursor, its incorporation indicating that C-13 hydroxylation is a terminal step. As for other protoberberine derivatives,63 nandinine (64) was not assimilated,62 and it follows then that (65) is probably converted into (67) by way of isocorypalmine (66). 

It will be recalled that in the case of succinyl chloride both of these forms are obtained, but mostly the symmetrical (p. 282). Now from phthalic anhydride only one phthalyl chloride is obtained. This chloride acts like the unsymmetrical succinyl chloride, not like the symmetrical. The positive proof, however, that phthalyl chloride is the unsymmetrical compound is the following Sodium amalgam reduces phthalyl chloride by replacement of the chlorine with hydrogen. The compound formed is known as phthalide. This phthalide takes up water as anhydrides do and the product is hydroxy-methyl benzoic acid. 

Hydroxy-methyl Benzoic Acid.—The first example given above is important in connection with the constitution of phthalide (p. 693) and phthalyl chloride (p. 692). By the addition of water phthalide is converted into o-hydroxy-methyl benzoic acid. 

The synthesis of phthalides and dihydroisocoumarins however, has drawn much attention [424-427]. A novel AlCb-catalyzed conversion of ( )-3-benzyl-7-methoxyphthalides to ( )-3-aryl-8-hydroxy-3,4-dihydro-isocou-marin and related compounds in a single step has been elaborated (Scheme 13) [427]. Chemical transformation from dihydroisocoumarin into benzylidene-phthalide has also been realized [122]. 

A recent method to introduce a carboxyl group ortlw to hydroxy methyl group may be mentioned here. This involves thallation of a benzyl alcohol The reaction is governed by orientation rules observed for acid catalysed electrophilic substitution reaction. Thus m-methoxy benzyl alcohol gives 5-methoxy phthalide... 

Hydroxyphthalide is. the cyclic lactol of phthalaldehydic acid. This compound can be readily obtained by lithiation of a benzoic acid derivative (N-methyl amide, N,N-diethy amide or oxazole derivative) and treatment either with N-methylform-anilide (MFA) or DMF. When an N-methylamide is the starting compound quite often, the intermediate 25 can be isolated which can be hydrolysed to 3-hydroxy-phthalide . 

Phthalide enolates (145), which can be viewed as dihomoenolates, add to Schiff bases to produce intermediate adducts (146) that cyclize to mixtures of cis and trans 3-aryl-4-hydroxy-3,4-dihydro-l(2W)-isoquinolones (147) and (148) (Scheme 30). As originally described by Dodsworth, Sammes and... 

Beilstein Handbook Reference) acid eosin BRN 0063410 Bromeosin Bromoeosin C.l. 45380 2 C.l. Solvent Red 43 CCRIS 4904 Cl 45380 2 D C Red no. 21 D and C Red No. 21 D C Red No. 21 2-(3,6-Dihydroxy-2,4,5,7-tetrabromoxanthen-9-yl)-benzoic acid 3,6-Dihydroxy-2,4,5,7-tetrabromospiro-(xanthene-9,3 -phthalide) EINECS 239-138-3 Eosin Eosin A Eosin acid Eosin 3J Eosin 4J extra Eosin A extra Eosin B Eosin C Eosin DH Eosin G Eosin G Extra Eosin GGF Eosin JJS Eosin KS Eosin yellowish Eosin Y spirit soluble Eosine acid Fluorescein, 2, 4, 5 ,7 -tetrabromo- Japan Red 223 Japan Red No. 223 NSC 244436 Red No. 223 Solvent Red 43 Spira(isobenzofuran-1(3H),9 -(9H)-xanthen)-3-one, 2, 4, 5, 7 -tetrabromo-3 ,6 -di-hydroxy- Water soluble eosin. The alkali salts of tetrabromo-fluoresceine, dyes wool and silk yellowish red used as a microscopic stain and a fluorescent tracer dye red writing ink cosmetic products and a colorant for motor fuel. Red solid. 

Beilstein Handbook Reference) 3,3-Bis(4-hydroxy 3,6-diiodophenyl)phthalide 3,3-Bis(4-hydroxy-3,5-diiodophenyl) ... 

Provided that they have at least one hydrogen atom on the amide-nitrogen, the hydroxy carboxamides formed from lactones can be converted by heat into lactams. For example, the above o-(hydroxymethyl)-A -methylbenzamide (2) cyclizes to the lactam (3) at 160° however, the removal of water involved in the change (2) -> (3) competes with the loss of methylamine that leads back to phthalide, so that pressure is required in preparation of the lactam.786... 

Senkyunolide Q (3Z-Butyl idene-4,5,6,7-tetrahydro-7/ -hydroxy-6 R-( 1 -oxobutyl)phthalide) 142235-81-2 Ligusticum chuanxiong [109]... 

A dimethyl 1-naphthol-2.3-dicartx)xylate compound has been synthesised from phthalide. Thus 2-methoxyphenyllithium, prepared from 2-bromoanisole and n-butyllithium, was reacted with phthalide in tetrahydrofuran solution at -78°C during 30 minutes and after the reaction mixture had attained ambient temperature during a further 30 minutes, 4 moles of dimethyl acetylene (DMAD) in dichloromethane were introduced. Following completion of reaction overnight, and removal of excess reagent, the crude product was aromatised by refluxing for 4 hours with a benzene solution of toluenesulphonic acid to afford dimethyl 1 -hydroxy-4-(2-methoxyphenyl)naphthalene-2,3-dicarboxylate (ref.53). 

Photo-oxygenation of either dihydrocoralyne (77) or 13-hydroxy-coralynium betaine (78) in sodium ethoxide solution has been found to give the dihy-droisoquinolone (79) and the phthalide (80), and these two products and 13-hydroxycoralydine (81) are obtained if the reaction is carried out in the... 

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