Über Keto‐phylloporphyrine und ihren Übergang in Desoxo‐phyllerythrin‐Derivate

Fischer, Hans; Müller, Kurt; Leschhorn, Otto

doi:10.1002/jlac.19365230111

Cited by 10 publications

(5 citation statements)

References 15 publications

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“…The spectrum of the recrystallized product was identical with that produced by the catalytic hydrogenation of phylloerythrin in formic acid containing palladium black (6,11).…”

mentioning

confidence: 65%

Reduction of Chlorophyllides, Chlorophylls and Chlorophyll Derivatives by Sodium Borohydride.

Holt

1959

Plant Physiol.

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Sodium borohydride is a well known reducing agent. In methanol at room temperature formyl and keto groups are readily reduced to alcohol groups, while ester and carboxyl groups, carbon-carbon and carbon-nitrogen double bonds are only reduced with difficulty (2, 17). Of the groups present in chlorophyll b the C3 formyl and the C9 keto groups should be amenable to reduction, while the C2 vinyl and the C7 and Ci0 ester groups should be unaffected. Similar considerations apply to chlorophyll a and other derivatives containing formyl and keto groups.Since previous methods of reducing pheophorbides a and b had caused either reduction of the C2 vinyl group (6, 8) or had proceeded poorly (10), it was of interest to investigate the action of sodium borohydride upon these compounds and their magnesium salts (phyllins). Furthermore, there remained the possibility that reduction of the C9 keto group might involve formation of an intermediate similar to the pink product of the "Krasnovsky reaction" (the reversible photobleaching of chlorophyll a by ascorbic acid in pyridine) (23).This communication dlescribes the preparation and the properties of the products obtainecl by treating methyl chlorophyllides a and b and other chlorophyll derivatives with sodium borohydride. HCl numbers, wave lengths and relative absorbancies of visible absorption maxima and minima, useful for identification purposes, are included. MATERIALS AND METHODSSolvents were reagent grade and were used without further purification. Sodium borohydride was obtained from Metal Hydrides Inc., Beverly, Mass. andl was about 99 % pure.Methyl chlorophyllides a and b, chlorophylls a and b. andl pheoporphyrin a5 and phylloerythrin were obtained pure by standard procedures (13,15,19,20,22,25). "Meso" derivatives were prepared bv catalytic hydrogenation of the parent compounds in acetone containing palladium black as the catalyst (14). Free acids were obtained by hydrolysis of the C7 ester in strong hydrochloric acid for 30 minutes at room temperature (12). For the phase test, 0.1 ml of methanolic magnesium methoxide (18 mg Mg/ml) was

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“…The spectrum of the recrystallized product was identical with that produced by the catalytic hydrogenation of phylloerythrin in formic acid containing palladium black (6,11).…”

mentioning

confidence: 65%

Reduction of Chlorophyllides, Chlorophylls and Chlorophyll Derivatives by Sodium Borohydride.

Holt

1959

Plant Physiol.

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“…Hence there must be at least one asymmetric center somewhere else than in positions 10 and in the chlorophyll molecule. Fischer therefore then placed the two surplus hydrogen atoms of the dihydroporphin nucleus of chlorophyll, the phorbides, and the chlorins and purpurins, in positions 5 and 6 of nucleus III, thus forming a dihydropyrrole nucleus (50). Conant (3) had previously made a similar suggestion on the basis of titration results on the basicity of chlorophyll derivatives (vide infra).…”

Section: XXVImentioning

confidence: 97%

“…The latter is obtained from phylloporphyrin by the action of bromine, to yield 6-bromophylloporphyrin, followed by treatment with methyl alcoholic alkali, which converts the bromine to the primary alcoholic group (-CH2OH). Similarly phylloerythrin was obtained by a condensation between positions 6 and y in chloroporphyrin e4 ( -methylrhodoporphyrin) under the influence of sodium ethylate (XIX b) (50).…”

Section: Allomerizationmentioning

confidence: 99%

“…If the formyl group is introduced into phylloporphyrin (Vc) by the method outlined above, the ester of the resulting 6-formylphylloporphyrin gives rise to an interesting series of 9-substituted derivatives of desoxophylloerythrin methyl ester (50), by the same type of ring closure. For instance, 6-formylphylloporphyrin ester condensed with malonic acid gives the 9-acetic acid derivative of desoxophylloerythrin ester, while with methyl alcohol and concentrated hydrochloric acid, the 9-methoxy derivative is obtained.…”

Section: Allomerizationmentioning

confidence: 99%

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Recent Progress in Determining the Chemical Structure of Chlorophyll.

Steele¹

1937

Chem. Rev.

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“…Recently (35) we have demonstrated in another manner by direct synthesis the constitution of phylloerythrin, employing the action of sodium ethylate on chloroporphyrin e4, according to the following formulation. Through the proof of the constitution of phylloerythrin, that of phylloporphyrin as a methyl-substituted pyrroporphyrin was also determined, and the 7-position once more proved.…”

Section: H3cfi-cjh6mentioning

confidence: 99%

Chlorophyll.

Fischer¹

1937

Chem. Rev.

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Über Keto‐phylloporphyrine und ihren Übergang in Desoxo‐phyllerythrin‐Derivate

Cited by 10 publications

References 15 publications

Reduction of Chlorophyllides, Chlorophylls and Chlorophyll Derivatives by Sodium Borohydride.

Reduction of Chlorophyllides, Chlorophylls and Chlorophyll Derivatives by Sodium Borohydride.

Recent Progress in Determining the Chemical Structure of Chlorophyll.

Chlorophyll.

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