Phosphorylation of lignins I. Phosphorylation of piperidinomethylated dioxane lignin from cottonseed husks

The phosphorylation of piperidinomethylated dioxane lignin has been studied. It has been shown that the reaction takes place with the formation of quaternary ammonium phosphates, while the transesterification of dimethyl phosphite with an aliphatic hydroxy group of the lignin is also possible.Institute of Chemistry of Plant Substances, Uzbekistan Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 275–277, March–April, 1993.     

Dioxane lignin from shoots of the cotton plant of variety 108-F. I

The dioxane lignin has been isolated by Pepper's method from two-week shoots of the cotton plant of variety 108-F and has been separated into two fractions — insoluble and soluble in ether — DLA-A and DLA-B, respectively. It has been shown that in the early stage of development of the cotton plant a low-molecular-weight lignin with a low degree of methoxylation and distinctly different from the lignin from ripe stems of the same cotton plant is synthesized.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 96–98, January–February, 1984.     

Hydrogenolysis of Willst?tter lignin

Summary 1. The hydrogenolysis of Willstätter spruce lignin has been performed under the optimum conditions. It has been shown that on hydrogenolysis in an aqueous alkaline medium in the presence of an inhibitor (phenol) the lignin macromolecules can be converted into low-molecular-weight ether-soluble products with a yield of about 80%.2. A comparative study of the ether-soluble fractions of Willstätter spruce lignin and hydrolysis spruce lignin has shown that hydrogenolysis takes place similarly in the two cases: the yields of phenols and the proportion of cresols in them are similar. In the Willstätter spruce lignin, the yield of acids is higher and that of neutral products lower than in the hydrolysis spruce lignin.3. Investigations of the group compositions of the hydrogenolysis products and of model substances have permitted the hypothesis that the Willstätter lignin contains a considerable amount of biphenyl structures.Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 106–112, January–February, 1972.     

Study of the lignin of cotton plants of the variety AN Bayaut-2. I

The dioxane lignin has been isolated from ripe stems of a cotton plant of the variety AN Bayaut-2. Its developed empirical formula has been derived, its UV, IR, and PMR spectra have been recorded, and its molecular weight has been determined. It has been shown that the dioxane lignins of the stems of cotton plants of different varieties differ in chemical structure.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 101–104, January–February, 1986.     

The lignin of the algaFucus vesiculosus

Summary 1. The plant material ofFucus vesiculosus has been treated with metallic sodium in liquid ammonia. The total yield of products extractable by ether was 1.1%.2. In the products of the decomposition of the lignin ofFucus vesiculosus 12 phenols and acids have been identified by paper chromatography and gas-liquid chromatography and it has thereby been established that the lignin of algae consists of p-coumaryl, guaiacyl, and syringyl structural units.3. The composition of the decomposition products confirms the hypothesis expressed previously that the brown algaFucus vesiculosus contains lignin.S. M. Kirov Belorussian Technological Institute, Minsk. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 645–647, September–October, 1978.     

Influence of the potential of the oxidizing system on the exothermic stages in the oxidation of lignin

It has been shown that on the oxidation of soda lignin by the potassium ferriferrocyanide system thermal and luminous energy due to exothermic processes are evolved. The heat effect and also the total amount of light emitted are determined by the potential of the oxidizing system.Siberian Scientific-Research Institute of Cellulose and Board, Bratsk. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 223–225, March–April, 1983.     

Cleavage of the natural lignin and the dioxane lignin of kenaf by thioacetic acid

The dioxane lignin and the natural lignin of kenaf undergo 37.62% and 94.6% cleavage, respectively. The combined monomeric degradation products have been studied by the GLC method. The presence of substances relating to three types of structural units has been established: p-coumaryl, gualacyl, and syringyl. It has been shown by chromatography on Sephadex LH-20 (with ethanol-water (9:1) as solvent and eluent) that the phenolic products of degradation extracted by ethyl acetate at pH 2 consist of five fractions: oligomers, tetramers, trimers, dimers, and monomers.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 234–235, March–April, 1986.     

Destruction of aspen wood by the fungusPhanerochaete sanguinea quantitative1H and13C NMR spectroscopies of biologically degraded lignin

The lignin of mechanically ground aspen wood and lignins isolated from aspen wood attacked by the fungusPhanerochaete sanguinea have been investigated by quantitative¹H and¹³C NMR spectroscopies. It has been shown that the biodestruction of the lignin takes place through the cleavage of alkyl-aryl and aryl-aryl bonds and is accompanied by demethylation (demethoxylation) reactions, and the oxidation of C and C atoms. In addition to reactions in which the C—C bonds are cleaved, the formation of ether bonds has been observed. An interconnection has been shown between the variations in the amount of functional groups, fragments, and the bonds in biolignins and the loss in mass of the wood. A method is proposed for evaluating the carbohydrate content in lignin preparations using the NMR method.Wood Chemistry Branch of the Institute of Organic Chemistry, Siberian Division of the Russian Academy of Sciences, Irkutsk. Irkutsk State University. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 547–557, July–August, 1994.     

An investigation of the dioxane lignin of cotton bolls

Summary 1. Dioxane lignin has been isolated from mature stems of the cotton plantGossypium hirsutum by mild acidolysis in an atmosphere of nitrogen.2. Its expanded semiempirical formula has been established by elementary and functional analyses.3. The molecular-weight distribution of the dioxane lignin has shown that it consists of high-molecular-weight and low-molecular-weight fractions.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 645–648, September–October, 1974.     

Influence of electrochemically activated water on lignin

It has been shown that under the action of electrochemically activated water a change in the functional composition of the macromolecule of hydrolysis lignin and of lignin sulfonate takes place and, in addition, the latter is desulfurated.M. V. Frunze Simferopol' State University. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 425–427, 1987.     

A study of the dioxane lignin of the stems of the cotton plant of variety S-4880

The dioxane lignin (DLA) has been isolated from the ripe stems of a cotton plant of the variety S-4880 B by a modification of Pepper's method. The yield was 16.9% on the Komarov lignin. The semiempirical formula of a phenylpropane structural unit has been calculated on the basis of elementary and functional analyses. It has been established that the amount of the main functional groups in the DLA and in the lignins isolated from the varieties of 108-F and Tashkent-2 basically coincide, but the DLA investigated was appreciably more highly methoxylated. The IR, UV, and PMR spectra of the DLA have been taken. The molecular-weight distribution of the DLA has been investigated and it has been shown that is is poly-disperse and has a weight-average molecular weight of 7400. Nitrobenzene oxidation and cleavage with sodium and liquid ammonia of the isolated DLA has shown that guaiacyl structural units predominate in it.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 430–434, May–June, 1987.     

Enzymatic oxidation of lignin and compounds modeling it. III. Formation of singlet oxygen in the peroxidase oxidation of lignin

The main emitters of radiation in the aerobic oxidation of lignin are the carbonyl groups in an excited state and singlet oxygen. It has been shown that the main source of O₂(¹) may be the radical anion O^–·₂. Singlet oxygen and the radical anion are by-products of the radical oxidation of lignin.Siberian Scientific-Research Institute of Cellulose and Board, Bratsk. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 510–514, July–August, 1984.     

Phosphorylation of hydrolysis lignin by dialkyl phosphorochloridates

It has been established that the phosphorylation of lignin by dialkyl phosphorochloridates takes place through the hydroxy groups of the lignin macromolecule.Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 750–752, September–October, 1997.     

PMR spectra of the lignins ofCystoseira barbata at different ages

The PMR spectra of the dioxane lignins from the brown algaCystoseira have been studied. It has been established that the lignins isolated from specimens ofCystoseira of different ages have different degrees of substitution of the C₃ side chain and differ in their degree of condensation. The most highly condensed is the dioxane lignin of young specimens ofCystoseira (age up to one year) and the least condensed the Björkman lignin ofCystoseira aged more than three years. All the PMR spectra of preparations of the lignin of the alga under investigation contain the signals of protons present in coumaran structures, their amount being the greatest in the lignins of the youngest samples and decreasing with increasing age of the alga.Odessa Institute of Structural Engineering. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 91–94, January–February, 1983.     

A study of dioxane lignin from bolls of the cotton plant of variety AN Bayaut-2 II

The dioxane lignin was isolated from ripe bolls of a medium-fiber cotton plant of the variety AN Bayaut-2. Its developed empirical formula was derived, its UV, IR, and PMR spectra were recorded, and its molecular weight was determined. It was shown that the boll lignin is more condensed than the stem lignin. It differs from the stem lignin by a lower content of methoxy groups and a higher content of hydroxy and carbonyl groups.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 428–429, May–June, 1987.     

Change in the structural elements of cotton-plant lignins in the various vegetation periods

Summary 1. The dioxane lignins of the cottonplant of various vegetation periods have been studied, and it has been shown that the lignin changes in the course of the development of the plant: the amount of methoxy groups increases and the amount of phenolic hydroxy groups decreases.2. Gel chromatography of the lignins has shown that they are all polydisperse with a predominance of the high-molecular-weight fraction.3. The 3,4-diethoxybenzaldehyde detected in the products of the alkaline nitrobenzene oxidation of dioxane lignin of the early vegetation period after its ethylation with diethyl sulfate is a direct proof of the presence of catechol structural units in cotton-plant lignin.4. A quantitative determination of the catechol structures in the lignins of the cottonplant has shown that their amount decreases as the plant develops.5. By decomposing the lignins with sodium and liquid ammonia, the presence in them of guaiacyl, syringyl, and p-coumaryl structural units has been confirmed and it has been shown that the lignin becomes less condensed as the plant grows, which is apparently connected with an increase in the degree of its methoxylation.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 100–107, January–February, 1977.     

Study of the fractional composition of the dioxane lignin from the cotton plant

Summary 1. The dioxane lignin of ripe cotton-plant stems has been separated into six fractions of different molecular weights which were fairly homogeneous and differed considerably in their molecular weights.2. It follows from the semiempirical formulas that in all the fractions guaiacyl structural units predominated. The chemical nonidentity of the fractions is shown by the different amounts of functional groups in the phenylpropane structural units and by the relative optical densities of the main bands in the IR spectra of the fractions.3. The low-molecular-weight fraction differed markedly from the others by a higher content of carbohydrates bound to the lignin and by a greater degree of oxidation.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 69–74, January–February, 1979.     

Investigation of the dihydroxylignin ofAlthaea rhyticarpa

1. The developed semiempirical formula for the dioxane lignin from the stems ofAlthaea rhyticarpa has been found from the results of elementary and functional analyses. 2. It has been shown that the lignin consists of high- and low-molecular-weight fractions.     

Formation of peroxide compounds on the oxidation of lignin by oxygen in an organic solvent

The results are given of a determination of the steady-state concentrations of peroxide compounds on the oxidation of lignin by oxygen in dioxane. An iodometric method of determining peroxides was used, with spectrophotometric control of the amount of iodine formed. It was established that the achievable steady-state concentration of peroxide compounds on the oxidation of lignin is 0.28–0.44 wt. % of O_act (oxygen pressure 1 atm, temperature 50–80°C). With a rise in the temperature, the steady-state concentration of peroxide compounds decreased. The addition of water (30 vol. %) to the organic solvent led to an increase in the rate of accumulation of peroxide compounds. It has been shown that the presence of alkaline and acidic catalysts exerts no appreciable influence on the achievable steady-state concentration and the rate of accumulation of peroxide compounds during the oxidation of lignin.Bratsk Industrial Institute. All-Union Scientific Production Combine of the Pulp and Paper Industry, Leningrad. Translated from Khimiya Prirodnykh Soedinenii, Nos. 3,4, pp. 413–417, May–August, 1992.     

Synthesis of model dimers of lignin from (1-hydroxyalkyl)phenols

It has been shown that model (1-hydroxyalkyl)phenols of lignin condense in an acid medium with heating to form dimers of the indan and Ar-C₃-Ar series, depending on the substituents in the aromatic ring.Institute of Chemistry of Plant Substances, Uzbekistan Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 564–567, September–October, 1992.