Mustard seed was known during antiquity and was esteemed for one reason or another as becomes evident from the symbolic references made to it in the New Testament.5) It appears to have been utilized first as spice,1) and later also as external remedy. As the latter it is referred to by Theophrastus,2) Dios-corides,3) Pliny,4) Scribonius Largus5) and Alexander Trallianus. In the writings of Columella are found the oldest directions for the preparation of table mustard.6) About the year 800 mustard was cultivated in the neighborhood of Paris.7) Its cultivation was directed by Charlemagne in his Capitulare of 812.8) In Spain it was cultivated by the Arabians.9) From here its cultivation spread to Germany and France in the 10. century and thence to England10) during the 12. century.
1) Dioscorides, De materia medica libri quinque. Editio Kuhn-Sprengel. 1829. Vol. 1, p. 53. - Palladius, De re rustica. II. 7. Editio Nisard. p. 554. - Plinii Naturalis historiae libri. Lib. 7. - Editio Littre. Vol. 1, p. 548. - Hildegardis Abbatissae Physica. Editio Migne. Patrologiae Cursus completus. Vol. 197. 15, p. 1228.
2) Douet-d'Arcq, Comptes de I'Argenterie des rois de France au XIVme siecle. 1851. Vol. 1, p. 207.
3) Joh. Wier (Piscinarius), Medicarum observationum rararum liber. Basilias 1567. pp. 32-34.
4) Fluckiger, Dokumente zur Geschichte der Pharmacie. 1876.
5) Matth., 13:31. - Luke, 13:18 and 19.
The first statement which indicates a knowledge of the fact that mustard oil can be obtained by distillation with water, is found in the writings of Porta;11) another in the writings of the Parisian apothecary Nic. le Febvre.12) Boerhaave, however, seems to have been the first to prepare the volatile mustard oil in 1732 and to have called attention to its properties.13) That it contains sulphur was observed by Thibierge of Paris in 1819.14) Boerhaave and Murray15) observed the great density of the oil;
1) Mommsen, Berichte der Sachsischen Gesellschaft der Wissenschaften. Leipzig 1851, 1-80.
2) Theophrasti Eresii opera, quae supersunt, omnia. Editio Wimmer. 1866. p. 109.
3) Dioscoridis de materia medica libri quinque in Kuhn-Sprengel. Medicorum graecorum opera quae extant. 1829. Vol. 1, p. 52, 191 and 293.
4) Plinii Naturalis historiae libri. Lib. 19, p. 54 and Lib. 20, p. 87.
5) Scribonii Largi Compositiones medicamentorum. Editio Helmreich. 1887. 9, p. 56.
6) Columellae De re rustica et de arboribus. Editio Nisard. 1877. p. 493.
7) Guerard, Polyptique de I'abbe Irminon. Paris 1844. p. 716.
8) Capitulare de villi's et cortis imperialibus. Explained by A. Thaer in Fuhling's Landwirtschaftliche Zeitung. Berlin 1878, 241 - 260.
9) Dozy, Le Calendrier de Cordue de I'annee 961. Leyde 1873.
10) Rogers' History of agriculture and prices in England. 1866. p. 223. - Pharmaceutical Journ. III. 8 (1878), 852.
11) Portae Magiae naturalis libri viginti. Liber de destillatione. Romas 1608. p. 153.
12) N. le Febvre, Traite de la Chymie. Paris 1660. Tom. 1.
13) Boerhaave, Elementa chemiae, quae anniversario labore docuit inpublicis privatisque scholis. Lugduni Batavorum1732. Editio Londini. 1732. Pars 2, p. 38.
14) )Journ. de Pharm. 5 (1819), 20, 439 and 446. - Trommsdorff's Neues Journ. d. Pharm. 4, II. (1820), 250.
15) J. A. Murray, Apparatus medicaminum tarn simplicium quam prae-paratorum et compositorum. Gottingen 1794. Vol.2, p. 399.
Jul. Fontenelle determined the specific gravity in 1824, also its solubility in water.1)
Undoubtedly those who prepared mustard oil knew that the volatile oil does not preexist in the seed but is produced by the action of water. Yet the first to call attention to this fact were Glaser2) in 1825, Boutron and Robiquet3) in 1831, and independently of these Faure4) as well as Guibort,5) both in 1831. Shortly after (1833), Dumas and Pelouze6) made the first elementary analysis of the oil and discovered the thiosinamine, which mustard oil forms with ammonia. That mustard oil is produced by the action of a ferment was noticed by Boutron and Fremy.7) They isolated my rosin by extracting the seed with alcohol and obtained mustard oil by allowing this substance to act on the aqueous extract of the seed which had previously been extracted with alcohol. Sinigrin or myronate of potassium, was first prepared by Bussy.8) He termed the underlying acid acide myronique and with Robiquet9) determined its physical constants and its behavior toward reagents. The knowledge of the chemical composition of the oil was advanced materially by Will10) and simultaneously by Wertheim11) who regarded the mustard oil as allyl sulphocyanate.
Ludwig and Lange12) confirmed the existence of sinigrin and its decomposition by ferment action into mustard oil, sugar and potassium acid sulphate. This reaction was made more clear by the detailed studies of Will and Kcerner.13)
1) Journ. de Chim. medicale 1 (1825), 130. - Trommsdorff's Neues Journ. der Pharm. 15, II. (1827), 210.
2) Repert. f. d. Pharm. I. 22 (1825), 102.
3) Journ. de Pharm. II. 17 (1831), 294. - Geiger's Magazin f. Pharm. und Exper. Kritik 36 (1831), 64 and 67.
4) Journ. de Pharm. II. 17 (1831), 299 and 21 (1835), 464. 5) Ibidem 17 (1831), 360.
6) Ann. de Chim. et Phys. II. 53 (1833) 181. - Liebig's Annalen 10 (1834), 324.
7 ) Journ. de Pharm. II. 26 (1840), 48 and 112. - Liebig's Annalen 34 (1840), 230.
8) Journ. de Pharm. II. 26 (1840), 39. - - Liebig's Annalen 34 (1840), 223.
9) Journ. de Pharm. II. 26 (1840), 110. 10) Liebig's Annalen 52 (1844), 1. 11) Ibidem 52 (1844), 54.
12) Zeitschr. f. Chemie und Pharm. 3 (1860), 430, 577. 13) Liebig's Annalen 125 (1863), 257.
Artificial mustard oil had been prepared by the action of allyl iodide on potassium sulphocyanate by Zinin1) and by Berthelot and de Luca.2) The natural oil was therefore regarded as an ester of thiocyanic acid. Oeser,3) however, showed that allyl thiocyanate and natural mustard oil possess different properties.
The true constitution of mustard oil as the ester of the iso-thiocyanic acid was recognized by Billeter4) also by Gerlich.5) They showed that by the interaction of allyl iodide and potassium sulphocyanate, allyl sulphocyanate is first formed and that upon heating this is converted into its isomer, the allyl isosulphocyanate.
As an explanation of this form of isomerism, A. W. Hofmann6) had suggested that in the true thiocyanates the carbon is directly united with the sulphur, but in the isocompounds with the nitrogen.
Inasmuch as the possibility was not excluded that by the ferment action on sinigrin allyl sulphocyanate may first by formed, E. Schmidt7) allowed this action to take place at low temperature. He ascertained that even at 0° allyl isosulphocyanate is formed and only traces of the normal isomer.
The last uncertainty in connection with the hydrolysis of sinigrin was removed by Gadamer.8) He showed that the formula of sinigrin is C10H16NS2KO9 and not C10 H18 NS2 KO10 as was supposed by Will and Kcerner, also that the hydrolysis takes place by the addition of the elements of one molecule of water.