Studies on Lignin. III. Oxidation of Wood from Picea abies (L.) Karst. (Norway Spruce) with Nitrobenzene and Alkali.

Leopold, Bengt; Malmström, Inga-Lill; Motzfeldt, K.; Finsnes, Ernst; Sörensen, Jörgine Stene; Sørensen, Nils Andreas

doi:10.3891/acta.chem.scand.06-0038

Cited by 63 publications

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“…Biphenyl products obtained by NBO of cedar wood Leopold (1952) demonstrated that, among alkaline nitrobenzene oxidation (NBO) products of wood meal, two biphenyl compounds can be found, namely, dehydrodivanillin (DV) and, in a smaller amount, dehydrodivanillic acid (DVA). These compounds could be isolated as crystals by means of a multistep purification procedure.…”

Section: Resultsmentioning

confidence: 99%

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Revisiting alkaline nitrobenzene oxidation: quantitative evaluation of biphenyl structures in cedar wood lignin (Cryptomeria japonica) by a modified nitrobenzene oxidation method

Tamai

Goto

Akiyama³

et al. 2014

Holzforschung

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A modified alkaline nitrobenzene oxidation (NBO) method was developed to enable the analysis of the biphenyl structures of cedar wood lignin. The most essential point of the process is a modified work-up process in pyridine and a prolonged gas chromatography analysis of the silylated products. By applying this mean to cedar wood meal, a novel biphenyl product, dehydrovanillin-vanillic acid (1-carboxy-1′-formyl-4,4′-dihydroxy-3,3′-dimethoxy-5,5′-biphenyl), was detected together with known products, dehydrodivanillin and dehydrodivanillic acid. The highest total yield of biphenyl products was detected when NBO was carried out for 2-4 h at 170°C. The workup procedure was slightly modified so that the biphenyl products can be quantified. The NBO conversion rates of biphenyl linkages of lignin were also examined with a biphenyl-type lignin model compound, and this gave rise to 75% biphenyl-type NBO degradation products. Under the same condition, the total yield of vanillin and vanillic acid (VA) from a non-condensed-type β-O-4 model compound was 89%. Because the latter did not exhibit any peak of the biphenyl products, it can be concluded that all the biphenyl products obtained by NBO (0.17 mmol g -1 ) were from the lignin of the native wood. It was calculated that at least 6.7 of 100 phenylpropanoid units of cedar lignin were involved in biphenyl structures even if the NBO conversion rate was not taken into consideration. The synthesis and analytical data of 11 lignin model compounds is described.

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Section: Resultsmentioning

confidence: 99%

“…For example, dehydrodivanillin is a biphenyl compound and it was isolated in crystalline form from NBO products of spruce wood (Leopold 1952;Pew 1963). In general, the data of chemical degradation methods complement well the spectroscopic data and are helpful for their interpretation.…”

Section: Introductionmentioning

confidence: 97%

Revisiting alkaline nitrobenzene oxidation: quantitative evaluation of biphenyl structures in cedar wood lignin (Cryptomeria japonica) by a modified nitrobenzene oxidation method

Tamai

Goto

Akiyama³

et al. 2014

Holzforschung

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“…for two hours the best yields were obtained. Subsequently Leopold and co-mo1-1~ers (10,11,12) used these conditions to study the oxidation products of a wide variety of both hardwoods and softwoods. I t is significant that almost all the conifers studied gave small amountsof p-hydroxybenzalclehyde while several (Pi~zaceue family) gave small amounts of syl-ingaldehyde, this latter observation representing the first isolation of syringaldehyde from softwoods.…”

mentioning

confidence: 99%

The Alkaline Nitrobenzene Oxidation of Aspen Wood and Lignin Model Substances

Kavanagh¹,

Pepper²

1955

Can. J. Chem.

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The yields of vanillin and syringaldehyde obtained by the allcaline nitrobenzene oxidation of aspen wood meal have been determined a t various temperatures for various times. The maximum yield of each of these aldehydes, ca. 15 and 36y0 respectively, was obtained under the same conditions. Similar maximum yields result at 130&5°C. as at 170&5"C. if the reaction time is markedly increased. Treatment of the wood meal with sodium hydroxide a t 160°C. for two and one half hours prior to the addition of nitrobenzene and subsequent heating under the same conditions decreases, by over 30y0, the yields of aldehydes. Samples of 3,4,5-trimethoxybenzaldehyde, @ -~-g l~c o~a n i l l i~~, and 8-D-glucosyringaldehyde were oxidized by alkaline nitrobenzene a t 160°C. for two and one half hours and yields of the corresponding phenolic aldehydes of 10.7, 69.6, and 71.9% respectively were obtained. These results are discussed with respect to the chemistry of aspen lignin.Little has been reported regarding the establishment of the optimum conditions for obtaining the maximum yields for each of vanillin and syringaldehyde by the alkaline nitrobenzene oxidation of hardwood lignins. Brauns (2) has summarized the value of this tcchnique in lignin chemistry. The major part of this work was concerned with softwood lignins and various reaction temperatures, ranging from that of boiling alkaline sulphite spent liquor to 200°C., and various reaction times from 10 min. t o three hours. Since this book was published Leopold (9) has determined the vanillin yields obtainable from synthetic model lignin substances as a function of temperature and time and found that a t 180°C. for two hours the best yields were obtained. Subsequently Leopold and co-mo1-1~ers(10, 11, 12) used these conditions to study the oxidation products of a wide variety of both hardwoods and softwoods. I t is significant that almost all the conifers studied gave small amountsof p-hydroxybenzalclehyde while several (Pi~zaceue family) gave small amounts of syl-ingaldehyde, this latter observation representing the first isolation of syringaldehyde from softwoods. Stone and Blundell (14) used a temperature of 160°C. for two and one half hours in their analytical niicromethod for the alkaline nitrobenzene oxidation of plant materials.A detailed study of these conditions of oxidation as applied to hal-dwoocls was ~~nclertaken, therefore, with the belief tliat some useful information would be obtained wit11 respect,to tlie following problenl. If vanillin and syringaldehyde ai-ise by the hydrolysis and/or oxidative cleavage of different type linkages in tlie protolignin, then maximum yields of each might be obtained under different conditions. In this way a greater combined yield of aldehydes could rcsult than tliat now obtai~led under conditions whereby both yields are deter-

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“…This salnple was then charged to a 10-g column. Using solvent B, I appeared in fractions [3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19], and I1 in . After changing to solvent D , I11 appeared in fractions 4-13. illdchydes and Acids (See procedure below.)…”

Section: Elution Techn Iqziementioning

confidence: 99%

“…Along nritli both these compouncls much smaller yielcls of p-liydroxj7benzaldehyde have bee11 found in the oxidation products of monocot~~leclons. This technique has been used by several \vorl;ers interested i l l lignin clienlistry and from various lignified materials the followiiig other derivatives liave been isolated and characterized (2,3,4 ) : vanillic acid, syringic acicl, P-hydroxybenzoic acid, acetovanillone, acetos)~ringone, 5- 13-15, 1960. 2Colon~bo Plan S t z~d c~~t i n Canada a1 the U~riversity of Saskatchewan, 1957-1960. vanillin, syringaldehyde, vanillic acid, syringic acid, p-hydroxybenzoic acid, acetovanillone, acetosyringone, ferulic acid, p-coumaric acid, 5-carboxyvanillin, 5-carboxyvanillic acid, dehydrodivanillin, dehydrodivanillic acid, vanillil, 5-forrnylvanillin, 4,A'-dihydroxy-3,3'-dimethoxj.chalcone, vanillovanillone, and vanilloyl fornlic acid. Apart from these lignin fragments that have been obtained from lignin under oxidizing conditions, Inany of the same compounds have been obtained by alkaline hydrolysis of the whole wood or of an isolated lignin.…”

Section: Introductionmentioning

confidence: 99%

Cellulose Column Chromatographic Separation of Lignin Oxidation Products

Pepper¹,

Siddiqueullah²

1960

Can. J. Chem.

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X brief review is presented of the che~nical nature and the methods of separation of those lignin derivatives obtained by the oxidation and/or alkaline hydrolysis of woody plants and isolated lignin or lignosulphonates. Nine such closely related derivatives, vanillin, syringaldehyde, p-hydroxybenzaldehyde, acetovanillone, acetosyringone, p-hydrosyacetopheno~~e, vanillic acid, syringic acid, and p-hydroxybenzoic acid, were selected for a detailed study of their separation by cellulose column chromatography. Methods are presented whereby, by either a one-or two-stage process, a mixture of from any two to all nine of these compounds may be separated and the components recovered, using solvent systems which are suitable for subsequent quantitative spectrophotolnetric analysis. The applicatioll to a study of lignin chemistry is discussed. INTRODUCTIONIn recent years considerable attention has been given to tlie chro~~~atographic separation of the products of oxidation and/or alltalilie li~~clrolysis of the lignin component of woody plants ancl cereal straws. Froill the earlier \\rorl; the characterization of these various lignin clerivatives has colitributed substantially to the present I

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Studies on Lignin. III. Oxidation of Wood from Picea abies (L.) Karst. (Norway Spruce) with Nitrobenzene and Alkali.

Cited by 63 publications

References 0 publications

Revisiting alkaline nitrobenzene oxidation: quantitative evaluation of biphenyl structures in cedar wood lignin (Cryptomeria japonica) by a modified nitrobenzene oxidation method

Revisiting alkaline nitrobenzene oxidation: quantitative evaluation of biphenyl structures in cedar wood lignin (Cryptomeria japonica) by a modified nitrobenzene oxidation method

The Alkaline Nitrobenzene Oxidation of Aspen Wood and Lignin Model Substances

Cellulose Column Chromatographic Separation of Lignin Oxidation Products

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