Butea frondosa(CHAPTER VI. The Chalkone and Flavanone Groups.)(Osa artikkelista)

The Natural Organic Colouring Matters
By
Arthur George Perkin, F.R.S., F.R.S.E., F.I.C., professor of colour chemistry and dyeing in the University of Leeds
and
Arthur Ernest Everest, D.Sc., Ph.D., F.I.C., of the Wilton Research Laboratories; Late head of the Department of Coal-tar Colour Chemistry; Technical College, Huddersfield
Longmans, Green and Co.
39 Paternoster Row, London
Fourth Avenue & 30th Street, New York
Bombay, Calcutta, and Madras
1918

Kaikki kuvat (kemialliset kaavat) puuttuvat // None of the illustrations (of chemical formulas) included.

The Butea frondosa, also called Dhak or Pulas, is a fine tree, 30-40 feet high, belonging to the order Leguminosæ. It is common throughout India and Burma, and is found in the North-West Himalaya, as far as the Jhelum River. The flowers, which in the dried condition are known as tísu, késú, kesuda or palás-képpúl, have a bright orange colour, and, although they are much larger, closely resemble in appearance the common gorseflower (Ulex europæus) with which, indeed, they are botanically allied. Large quantities of the flowers are collected in March and April, and employed by the natives to produce a yellow dye, much used during the "Holi" festival. The dyeing operation, which consists in steeping the material in a hot or cold decoction of the flowers, is virtually a process of staining, because the colour can be readily washed out. On the other hand, a more permanent result is sometimes produced either by first preparing the cloth with alum and wood ash or by adding these substances to the dye-bath.

From the Butea frondosa is also obtained the so-called "Butea gum" or "Bengal kino," employed by the natives for tanning leather, and the tree is of additional interest because in many parts of India the lac insect (Coccus lacca) is reared upon it. This latter, as is well known, causes the formation of stick lac, from which shellac and lac dye are prepared.

Butin, C₁₅H₁₂O₅. The flowers are extracted with water, and the extract digested boiling with a little sulphuric acid. A light viscous precipitate devoid of dyeing property separates, and this is removed while hot and the filtrate left over-night. The clear liquid is now decanted from a small quantity of tarry substance, and partially evaporated on the water-bath. A further quantity of a black viscous precipitate thus separates, and when this has been removed the filtrate, after some days, deposits crystals of the colouring principle. For purification the product is dissolved in a little alcohol, the mixture poured into ether, and the solution well washed with water. The liquid is evaporated, and the residue repeatedly crystallised from dilute alcohol (Perkin and Hummel, Chem. Soc. Trans., 1904, 85, 1459).

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* This result has been criticised by Goschker and Tambor, who by the employment of mordanted calico obtained from butin very weak shades. It is, however, certain that by the use of mordanted wool a conversion of butin into butein occurs.Butin and butein dye mordanted woollen cloth identical shades, though as butin gives with an alcoholic lead acetate a practically colourless precipitate, it is not to be regarded as a colouring matter. In other words, butin is merely a colouring principle, and is converted during the dyeing operation by the action of the mordant into the colouring matter butein.*

The following shades are obtained: Chromium. Reddish-brown,
Aluminium. Brick-red
Tin. Full-yellow
Iron. Brownish-black,
and these are strikingly similar to those yielded by some of the hydroxybenzylidenecoumaranones artificially prepared by Friedlander and Rüdt (Ber., 1896, 29, 879) (see above).

The butea flowers contain but a trace of free butin or butein, and the glucoside present, which has not yet been isolated, is probably that of butin. This glucoside does not decompose readily during the dyeing process, hence the flowers do not dye mordanted cotton. In wool-dyeing, where acid-baths are employed, a better result is obtained, although in this case the shades possess but little strength. If the glucoside is first hydrolysed by boiling the flowers with dilute hydrochloric acid, or if sulphuric acid is employed, and the acid then neutralised with sodium carbonate, on evaporation a material is obtained which readily dyes by the usual methods. Such products give the following shades: with chromium, deep terra-cotta; with aluminium, a bright orange; with tin, bright yellow; and with iron, a brownish-olive. The chromium colour is characteristic, and is much redder in tint than that yielded by any known natural yellow dye.

Scoparin, Scutellarein(CHAPTER V. The Flavone Group.)(Osa artikkelista)

The Natural Organic Colouring Matters
By
Arthur George Perkin, F.R.S., F.R.S.E., F.I.C., professor of colour chemistry and dyeing in the University of Leeds
and
Arthur Ernest Everest, D.Sc., Ph.D., F.I.C., of the Wilton Research Laboratories; Late head of the Department of Coal-tar Colour Chemistry; Technical College, Huddersfield
Longmans, Green and Co.
39 Paternoster Row, London
Fourth Avenue & 30th Street, New York
Bombay, Calcutta, and Madras
1918

Kaikki kuvat (kemialliset kaavat) puuttuvat // None of the illustrations (of chemical formulas) included.

Cytisus scoparius Jänönpapu, jänönvihma

Scoparin, the colouring matter of the Cytisus scoparius (Link.), has been investigated by Stenhouse (Annalen, 78, 15), by Hlasiwetz (Annalen, 138, 190), and by Goldschmiedt and Hemmelmayer (Monatsh., 14, 202).

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Scutellarin. If the flowers and leaves of Scutellaria altissima are extracted with water the solution on keeping deposits crystals of scutellarin, C₂₁H₁₈O₁₂ (Molisch and Goldschmiedt, Monatsh., 1901, 22, 68; Goldschmiedt and Zerner, ibid.) 1910, 31, 439). It melts above 310, is sparingly soluble in the usual solvents, and the alcoholic solution gives with lead acetate a red precipitate, and with ferric chloride a green coloration passing into red on heating. With the haloid acids and sulphuric acid in the presence of acetic acid orange-red crystalline oxonium compounds separate, which are readily decomposed in contact with water.

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Fukugi(CHAPTER V. The Flavone Group.)

The Natural Organic Colouring Matters
By
Arthur George Perkin, F.R.S., F.R.S.E., F.I.C., professor of colour chemistry and dyeing in the University of Leeds
and
Arthur Ernest Everest, D.Sc., Ph.D., F.I.C., of the Wilton Research Laboratories; Late head of the Department of Coal-tar Colour Chemistry; Technical College, Huddersfield
Longmans, Green and Co.
39 Paternoster Row, London
Fourth Avenue & 30th Street, New York
Bombay, Calcutta, and Madras
1918

Kaikki kuvat (kemialliset kaavat) puuttuvat // None of the illustrations (of chemical formulas) included.

The Japanese dyestuff "fukugi" (botanical origin unknown) [EDIT: Garcinia subelliptica] has, at least until recently, been employed to a considerable extent in Japan as a mordant dyestuff. It consists of the wood of a tree which when ground forms an almost colourless powder, the extract of which is sold in the form of brittle rectangular cakes of a yellowish-brown colour.

Fukugetin, C₁₇H₁₂O₆, the colouring matter, forms minute canary-yellow prismatic needles melting at 288-290° (Perkin and Phipps, Chem. Soc. Trans., 1904, 85, 58). It dissolves in alkaline solutions with a yellow colour, and gives with alcoholic lead acetate an orange-yellow precipitate and with alcoholic ferric chloride a brown-black coloration.

Crystalline acetyl and benzoyl derivatives of this colouring matter could not be obtained, but the bromine compound, C₁₇H₁₀O₆Br₂, minute flat needles, melting-point 280°, is readily prepared by the action of bromine on fukugetin in the presence of acetic acid. Fukugetin dyes mordanted fabrics shades which are almost identical with those given by luteolin - Chromium. Dull orange-yellow,
Aluminium. Orange-yellow,
Tin. Bright yellow,
Iron. Olive brown,
and resembles this colouring matter in that its alkaline solution is not oxidised on exposure to air. By fusion with alkali fukugetin gives phloroglucinol and protocatechuic acid.

The dyeing properties of "fukugi" are analogous to those of weld. The similarity in shade indeed is so marked that except in point of strength for fukugi is a stronger dye than weld it is impossible to distinguish between them.

Dyer's Broom.(CHAPTER V. The Flavone Group.)

The Natural Organic Colouring Matters
By
Arthur George Perkin, F.R.S., F.R.S.E., F.I.C., professor of colour chemistry and dyeing in the University of Leeds
and
Arthur Ernest Everest, D.Sc., Ph.D., F.I.C., of the Wilton Research Laboratories; Late head of the Department of Coal-tar Colour Chemistry; Technical College, Huddersfield
Longmans, Green and Co.
39 Paternoster Row, London
Fourth Avenue & 30th Street, New York
Bombay, Calcutta, and Madras
1918

Kaikki kuvat (kemialliset kaavat) puuttuvat // None of the illustrations (of chemical formulas) included.

Genista tinctoria, Linn. {Dyer's broom, Dyer's greenweed; Genet, Genestrole, Trentanel, Fr.; Ginster, Ger.) is found in the pastures, thickets, and waste places throughout Central and Southern Europe, across Russian Asia to the Baikal, and northward to Southern Sweden. It is frequent in the greater part of England, but rare in Ireland and Scotland. The fact that it contains a yellow colouring matter is recorded by numerous writers, and the following embody the principal references to the dyeing and general properties of the plant: Bancroft ("Philosophy of Permanent Colours," 1813, 2, 108); Gmelin ("Handbook of Chemistry," 16, 517); Berthollet ("On Dyeing," 1824, 2, 242); Gonfreville ("L'Artdela Teinturedes Laines," 501); Leuchs ("Farben u. Farbekunde," 1846, 2, 309), and Schützenberger ("Traite des Matieres Colorantes," 1867, 4, 422).

To isolate the colouring matters, a hot aqueous extract of the plant is treated with lead acetate solution, and the pale yellow viscous precipitate is collected and decomposed by means of boiling dilute sulphuric acid. The clear liquid decanted from the lead sulphate deposits on cooling a dull yellow powder; this is filtered off, dissolved in a little alcohol, and the solution poured into a large volume of ether, causing the separation of a dark-coloured resinous impurity. The clear liquid is evaporated, yielding a yellow crystalline residue, which consists of two substances. To separate these, advantage is taken of the fact that, with sulphuric acid in the presence of acetic acid, one only of these compounds gives an insoluble sulphate. This is collected and decomposed with water and the product crystallised from dilute alcohol. It is obtained as yellow needles, and was found to be identical with the luteolin of weld (Reseda luteola) (Perkin and Newbury, Chem. Soc. Trans., 1899, 75, 830).

Genistein, C₁₄H₁₀O₅, the second colouring matter of dyer's broom, is present in the mother liquors obtained during the purification of the luteolin, and also in considerable quantity in the filtrate from the lead precipitate, from which it is most readily isolated. To the boiling liquid ammonia is added, causing the separation of a lemonyellow precipitate, which is collected and decomposed with boiling dilute sulphuric acid. The clear liquid is extracted with ether, and the extract evaporated, leaving a brownish crystalline mass. It is purified by crystallisation from acetic acid, and by conversion into the acetyl derivative.

Genistein crystallises in long colourless needles; melting-point 291-293° (Perkin and Horsfall, Chem. Soc. Trans., 1900, 77, 1312); soluble in alkalis with a pale yellow coloration. Alcoholic ferric chloride gives a dull-red violet coloration, and alcoholic basic lead acetate a lemon-yellow precipitate.

Triacetylgenistein, C₁₄H₇O₅(C₂H₃O)₃, colourless needles, melting-point, 197-201°; and tetrabromgenistein, C₁₄H₆Br₄O₅, colourless needles, melting-point above 290°, have been described.

On digestion with boiling 50 per cent, potassium hydroxide, genistein gives phloroglucinol and p-hydroxyphenylacetic acid.

By methylation with methyl iodide in the usual manner, genistein dimethyl ether and methylgenistein dimethyl ether are produced.

Genistein dimethyl ether, C₁₄H₈O₃(OCH₃)₂, forms colourless leaflets, melts at 137-139°, and gives the monacetyl compound, C₁₄H₇O₃(C₂H₃O)(OCH₃)₂, minute colourless needles, melting-point 202-204°. When decomposed with alcoholic potash, it forms methoxyphenylacetic acid and phloroglucinol-monomethyl ether (identified by means of its disazobenzene derivative).

Methylgenistein dimethyl ether,
CH₃.C₁₄H₇O₃(OCH₃)₂, melts at 202°; and the acetyl derivative,
CH₃.C₁₄H₆O₃(C₂H₃O)(OCH₃) ₂,
forms colourless needles, melting-point 212-214°. With alcoholic potash it gives methoxyphenylacetic acid and probably methylphloroglucinol-monomethyl ether.

Genistein diethyl ether, C₁₄H₈O₃(OC₂H₅)₂, forms colourless needles, melting-point 132-134°; whereas acetylgenistein diethyl ether, C₁₄H₇O₃(C₂H₃0)(OC₂H₅)₂, melts at 168-170°. Alcoholic potash gives p-ethoxyphenylacetic acid.

According to Perkin and Horsfall, genistein is most probably a trihydroxyphenylketocumaran.

Genistein is a feeble colouring matter, and upon woollen cloth gives, with chromium mordant, a pale greenish-yellow; with aluminium mordant, a very pale yellow; and with iron mordant, a chocolate- brown shade.

Dyeing Properties of Dyer's Broom.

-In this respect there is a close resemblance between dyer's broom and weld. The dyeing power of the former is distinctly the weaker of the two; otherwise the only point of difference worthy of mention is that shown by the iron mordant, which, in the case of dyer's broom, gives a duller and more drab-coloured shade. Luteolin is also present in the Digitalis purpurea (digito-flavone), (Fleischer and Fromm, Ber., 1899, 32, 1184; v. Kostanecki and Diller, ibid.) 1901, 34, 3577), and in the flowers of Antirrhinum majus (Wheldaleand Bassett, Biochem. Jour., loc. cit.).

Weld(CHAPTER V. The Flavone Group.)(Osa artikkelista)

The Natural Organic Colouring Matters
By
Arthur George Perkin, F.R.S., F.R.S.E., F.I.C., professor of colour chemistry and dyeing in the University of Leeds
and
Arthur Ernest Everest, D.Sc., Ph.D., F.I.C., of the Wilton Research Laboratories; Late head of the Department of Coal-tar Colour Chemistry; Technical College, Huddersfield
Longmans, Green and Co.
39 Paternoster Row, London
Fourth Avenue & 30th Street, New York
Bombay, Calcutta, and Madras
1918

Kaikki kuvat (kemialliset kaavat) puuttuvat // None of the illustrations (of chemical formulas) included.

Weld is the dried herbaceous plant known as Reseda luteola formerly cultivated to a considerable extent in France, Germany, and Austria. Its cultivation in this country has nearly ceased, because not only is the quantity of colouring matter it contains very small, but the carriage of the plant, owing to its bulky nature, is expensive. A special interest, however, attaches to weld, for it is said to be the oldest European dyestuff known, and was used by the Gauls and other nations dwelling north of the Alps in the time of Julius Caesar.

The plant attains a height of about 3 feet, is pale brown in colour, and is sold in sheaves like straw. The colouring matter is disseminated throughout the entire plant, but the greater quantity occurs in the upper extremity and the seeds.

Luteolin, the main colouring matter of weld, was examined by Chevreul (J. Chim. Med, 6, 157; Annalen, 82, 53), who obtained it in a crude condition; its isolation in a state of chemical purity was first achieved by Moldenhauer (Annalen, 100, 180), who assigned to it the formula C₂₀H₁₄O₈. It was subsequently investigated by Schützenberger and Paraf (Bull. Soc. Chim., 1861, (i.), 18), who proposed the formula C₁₂H₈O₅ and purified it in a somewhat novel manner which is worthy of mention. Weld was exhausted with alcohol, the extract evaporated, and treated with water, which threw down a dirty greenish precipitate. This was collected, introduced with a little water into a sealed tube and heated to 250°. On cooling the sides of the tube were found to be coated with golden-yellow needles of luteolin, and the impurities had collected at the bottom of the tube to form a resinous cake.

Hlasiwetz suggested that luteolin had the formula C₁₅H₁₀O₆ and was isomeric with the paradiscetin, which he obtained during the fusion of quercetin with alkali (Annalen, 112, 107).

For the preparation of luteolin in quantity, Perkin (Chem. Soc. Trans., 1896, 69, 206, 799) employs weld extract.

300 gms. of the extract dissolved in 3 litres of water is treated with 100 c.c. of hydrochloric acid (33 per cent.), and the mixture is digested at the boiling temperature for some hours. A quantity of a black resinous substance separates, which is collected while hot, and the filtrate, which contains the colouring matter, is allowed to stand for twelve hours. A brown precipitate of impure luteolin is slowly deposited, and is collected, washed, and dissolved in a little hot alcohol. On pouring this solution into ether, the main bulk of the impurity is precipitated, and the ethereal liquid on evaporation yields a yellow residue, which is crystallised from dilute alcohol. The product in addition to luteolin contains apigenin (Chem. Soc. Trans., 1900, 77, 1315), and the latter can only be removed with certainty by the following method: -

The mixture dissolved in boiling glacial acetic acid is treated with a few drops of strong hydrochloric acid; this causes the almost immediate separation of luteolin as hydrochloride, whereas the apigenin remains in solution. The hydrochloride is collected, decomposed by water, and the luteolin crystallised from dilute alcohol.

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It has already been stated that weld contains a second colouring matter, Apigenin (v. Parsley).

Dyeing Properties of Weld.

The importance of weld as a dyestuff in silk and wool dyeing has greatly diminished in consequence of its low colouring power compared with quercitron bark, flavin, and old fustic. This in one respect is unfortunate, because, of all the natural yellow colouring matters, it yields the purest and fastest shades. In conjunction with aluminium and tin mordants it gives very bright pure lemon-yellow colours, and these do not change to an olive or reddish tint as in the case with other vegetable yellows. With chromium and iron mordants weld gives yellowish and greenish olives respectively. For yellow, wool and silk are mordanted with alum and tartar in the usual manner and dyed subsequently in a decoction of weld with the addition of chalk to the dye-bath. Weld alumina yellow is to some extent still employed in this country for certain army cloths and braid. For silk dyeing, weld extract is manufactured in small quantity, and is used for the production of yellow and olive colours.

Lotus arabicus(CHAPTER V. The Flavone Group.)

The Natural Organic Colouring Matters
By
Arthur George Perkin, F.R.S., F.R.S.E., F.I.C., professor of colour chemistry and dyeing in the University of Leeds
and
Arthur Ernest Everest, D.Sc., Ph.D., F.I.C., of the Wilton Research Laboratories; Late head of the Department of Coal-tar Colour Chemistry; Technical College, Huddersfield
Longmans, Green and Co.
39 Paternoster Row, London
Fourth Avenue & 30th Street, New York
Bombay, Calcutta, and Madras
1918

Kaikki kuvat (kemialliset kaavat) puuttuvat // None of the illustrations (of chemical formulas) included.

The L. arabicus (Linn.) is a leguminous plant, indigenous to Egypt and Northern Africa, and in the young condition is extremely poisonous. It has been investigated by Dunstan and Henry (Phil. Trans., 1901, 194, 515).

Lotusin, the active principle, can be isolated by extracting the dried plant with methyl alcohol. The extract is evaporated, the residue treated with water to remove chlorophyll and resin, and from the aqueous solution tannin and other impurities are precipitated by means of lead acetate. The nitrate, on evaporation, leaves a syrupy residue, from which crystals of lotusin slowly separate. In the pure condition lotusin, C₂₈H₃₁NO₁₆, forms yellow needles, and when hydrolysed by digestion with hydrochloric acid, or by means of an enzyme lotase, also found in the plant, yields dextrose, lotoflavin, and hydrocyanic acid, according to the following equation:
C₂₈H₃₁O₁₆N + 2H₂O = 2C₆H₁₂O₆ + C₁₅H₁₀O₆ + HCN

When warmed with alcoholic potash (20 per cent.) lotusin is gradually decomposed with production of ammonia and lotusinic acid:
C₂₈H₃₁O₁₆N + 2H₂O = C₂₈H₃₂O₁₈ + NH₃ (Lotusinic acid.)

This compound is monobasic, gives yellow crystalline salts, and is hydrolysed by dilute hydrochloric acid with formation of lotoflavin dextrose and heptogluconic acid:
C₂₈H₃₂O₁₈ + 2H2 = C₁₅H₁₀O₆; + C₆H₁₂O₆ + C₇H₁₄O₈

Lotoflavin, C₁₅H₁₀O₆, crystallises in yellow needles, soluble in alkaline solutions with a yellow colour. By fusion with alkali, phloroglucinol and β-resorcylic acid are produced.

With acetic anhydride lotoflavin gives a tetra-acetyl compound, C₁₅H₆O₆(C₂H₃O)₄, colourless needles, melting-point 176-178°, and when methylated by means of methyl iodide the trimethyl ether, C₁₅H₇O₃(OCH₃)₃, is obtained. This latter compound exists in two forms, viz. the a-form yellow rosettes, melting-point 125°, and the -form glistening needles, melting-point 175°, which are mutually convertible. Both varieties give by means of acetic anhydride the same monoacetyl-lotoflavin trimethyl ether, C₁₅H₆O₃(C₂H₃O)(OCH₃)₃, yellow needles, melting-point 147°.

According to Dunstan and Henry, lotoflavin is probably a tetrahydroxyflavone, possessing the formula [KUVA PUUTTUU]

The hydrolysis of the cyanogenetic glucoside lotusin, with formation of maltose, lotoflavin and hydrocyanic acid, may be expressed by the equation
C₂₈H₃₁NO₁₆ + H₂O = C₁₂H₂₂O₁₁ + C₁₅H₁₀O₆ + HCN

The following constitutions are respectively assigned to lotusin (1) and lotusinic acid (2): [KUVA]

Saponaria officinalis(CHAPTER V. The Flavone Group.)(Osa artikkelista)

The Natural Organic Colouring Matters
By
Arthur George Perkin, F.R.S., F.R.S.E., F.I.C., professor of colour chemistry and dyeing in the University of Leeds
and
Arthur Ernest Everest, D.Sc., Ph.D., F.I.C., of the Wilton Research Laboratories; Late head of the Department of Coal-tar Colour Chemistry; Technical College, Huddersfield
Longmans, Green and Co.
39 Paternoster Row, London
Fourth Avenue & 30th Street, New York
Bombay, Calcutta, and Madras
1918

Kaikki kuvat (kemialliset kaavat) puuttuvat // None of the illustrations (of chemical formulas) included.

The epidermal cells of the leaves of certain flowering plants contain, dissolved in their cell sap, a substance which is coloured blue by iodine. The colour disappears on warming and returns on cooling, as is the case with starch. On this account the compound was regarded as an amorphous variety of starch by Sanio, its discoverer (Botanische Zeitung, 1857, 15, 420). Schenck (ibid., 1857, 15, 497, 455) doubted whether this substance was identical with starch, and the correctness of this view was confirmed by Nageli (Beitrage zur wissensch. Botanik, 1860, 2, 187). For the chemical examination of this substance the dried shoots of the S. officinalis were selected by Barger (Chem. Soc. Trans., 1906, 89, 1210) as the raw material, because this plant is relatively rich in the compound, and is grown on the Continent for pharmaceutical purposes, so that large quantities are easily obtainable.

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