PERKIN ON SOME NEW DERIVATIVES, ETC. 211 XXIV.-Ort some New Derivatives of Anisoil (Anisol). By W. H. PERKIN, F.R.S. A SHORT time since I showed that methylparoxyphenyl-acrylic, -crotonic, and -angelic acids, when heated,-or, better, in the case of the two latter acids,-when converted into the hydrobromo-additive com- pounds, and then treated with sodium carbonate, yield para-deriva- tives of anisoil. I have now extended my experiments to the corre- sponding ortho-acids, and obtained the following results. Or f hovinglanisoi2. On boiling F-methylorthoxyphenylacrylic acid, it gradually decom- poses, carbonic anhydride being given off, and an oil distilling over. “his is purified by washing with dilute potassium hydrate and distillation with water; but with the view of obtaining it in a still purer state, i t was thought desirable to see if an additive derivative of the acid could be formed, which would decompose when treated with an alkahe solu- tion, and yield this body.For this purpose dry precipitated methylorthoxyphenylacrylic mid was placed in contact with hydriodic acid, sp. gr. 1.94, for two or three days, the mixture being frequently agitated. The resulting product was drained from the excess of hydriodic acid by means of a filter-pump. It was found best not to wash it, &s it is very unstable, and soon decomposes when in contact with water. It was then added in small quantities to a cold saturated solution of sodium carbonate, the mixture being well stirred and not allowed to get warm during the reaction, otherwise considerable quantities of a pol ymerised product are formed; this, however, rjometirnes happens even when great care is taken.The resulting milky fluid is then placed in a retort and boiled212 PERKIN ON SOME NEW DERIVATIVES until no more oily product distils over. The distillate is then warmed to promote the separation of the oil into a layer, whichis then collected and dried with potwium carbonate. On analysis if gave the follow- ing numbers : '- -2138 of substance gave -6364 of CO, and * l a 8 of H,O. Theory for CSHloO. Experiment. Carbon ............ 80.59 80.42 Hydrogen .......... 7.40 7.43 The formation of this substance, which I propose to call orthovinyl- awiso21, may be written thus :- Methylorthoxyphenylac~~c acid. Ort hovinylanieo'il. Hydriodomethylorthoxyphenylacrglic acid.Orthovinyhimdil. . Orthovinylanisoil polymerises so quickly when heated, that its boiling point could not be determined with certainty, but it seems to be between 195" and 200" C. When heated to 150" for about an hour, it solidifies to a transparent glassy substance, which is easily soluble in benzene, but insoluble in alcohol. This solid product when heated strongly distils, orthovinylanisoil being regenerated. The odour of orthovinylanisoll is very different from that of its isomeride, paravinylanisoll, being somewhat similar to that of high- boiling coal-tar naphtha, but more fragrant and not so strong. * Its specific gravity is- at 15" 1.0095 at 30" 1.000 When agitated with bromine-water it decolorises the latter, forming a nearly solid product.Heated with dilute nitric acid, it changes to a yellowish-brown heavy oil, becoming quite thick on cooling ; this product is partially soluble in aqueous potassium hydrate. With con- centrated sulphuric acid it becomes solid and of a bright-red colour. Orthallylanisooi. Methylorthoxyphenylcrotonic acid, when left in con tact with hydro- bromic acid, sp. gr. 1.74, for two or three days, combines with i t ; but the resulting acid, unlike the corresponding para-compound, when treald with an alkaline carbonate and then distilled, yields but a * Compared with water at the mme temperature.OF ANISO~L ( AXISOL). 213 small quamtity of oily prodact ; a large quantity of an uncrystallisable acid is, however, found in combination with the alkali; this is pro- bably an oxy-acid. If, however, hydriodic acid, sp.gr. 1.94, be used in place of hydrobromic, the resulting acid yields a large quantity of an oil when treated with an alkaline carbonate or acetate. A specimen of this dried over potassium carbonate and then distilled gave, on analysis, the following numbers :- I. -1894 of substance gave -5647 of COz and -1384 of H20. 11. -2178 of substance gave *6482 of CO, and -1631 of HZO. Theory for C10H120. I. 11. Hydrogen ...... 8-10 8.11 8.3 E sperimen t. Carbon ........ 81.08 81.3 81.17 This substance I propose to call orthaZlylanisoiZ ; the formula may be expressed thus :- Hy driodomethylorththoxyphenylcrotonic acid. Orthallylaniso'il. + HI + CO,. Orthallylanisoi'l is a highly refracting liquid boiling without poly- merising at 222-223" C.Its specific gravity is- at 15" 09972 at 30" 9884 at 45" *9793. Its odour is similar to that of its vinylic homologue, but fainter, When cooled in ft freezing mixture of snow and hydrochloric acid, it thickens but does not solidify. Cold nitric acid, sp. gr. 1.3, does not appear to act upon it in the cold, but on heating the mixture, red fumes are given off, and a brownish-yellow viscid oil, gradually solidifying to a resinous mass, results. With con- centrated sulphuric acid it becomes solid and of a red colour ; but on addition of water, it changes to a white opaque product soluble in benzene. Ort ho bzcteny lanksoil. Methylorthoxyphenylangelic acid, when treated with hydrobromic acid, combines with it, but the resulting compound yields only a very VOL.XXXIII. B It combines with bromine, forming a thick heavy oil.214 PERKIN ON SOME DERIVATIVES sniall quantity of oily product when treated with an alkaline carbon- ate ; but if hydriodic acid be employed, the yield of pi*oduct is good. The specimen of oil analysed was distilled with water and dried over potassium carbonate. -2083 of substance gave *6228 of CO, and -1634 of H,O. Theory for CIIHIOO. Experiment. Carbon ............ 81.48 81.54 Hydrogen .......... 8.64 8.71 The formation of this substance, which I propose to call orthobutenyl- anisozl, may be cxpressed thus :- Hydriodome thy lorthoxy phenylangelic acid. . Orthobutenylanisoil. + HI + CO,. Orthobutenylanisoil boils at 232-234" without polymerisiug. Its specific gravity is- at 15' -9817 at 30" *9740.When cooled in snow and hydrochloric acid, it does not solidify, but becomes thick. Like its homologues it combines with bromine, and also becomes solid and of a red colour when treated with concentrated snlphuric acid, the product losing its colour when washed with water. Boiled with dilute nitric acid it becomes yellow, but is only slowly acted upon, Strong nitric acid acts upon it with violence and dis- solves it; water precipitates from this solution a brown resin, which is mostly soluble in aqueous potassium hydrate. Paravinylanisoil. I mentioned in my paper, already referred to, that I endeavoured to produce paravinylanisoil from methylparoxyphenylacrylic acid by treating it with hydrobromic acid, hoping to obtain an addition-pro- duct which would decompose with alkaline carbonates in the usual manner ; but no result was obtained, as the methylparoxyph.eny1acrylic acid decomposed when brought in contact with hydrobromic acid.As, however, I have succeeded in obtaining orthovinylanisoil by a modifi- cation of this process, vie., by substituting hydriodic for hydrobromic acid, I applied this form for the preparation of this body. Dry precipitated methylparoxyphenylacr$ic acid, when left in con-OF ANISOk (ANJSOL). 215 tact with hydriodic acid, sp. gr. 1.94, for two or three days, combines with it? and the product, when drained from the excess of hydriodic acid and treated with an alkaline carbonate, yields the desired pro- duct. Unfortunately a good deal polymeriscs and becomes solid. The pure paravinylanisoil, however, was easily separated from this by distillation with water.Thus obtained, it differed but little from that prepared by the distil- lation of methylparoxyphexiylacrylic acid ; it was, however, somewhat purer, fts its fusing point was higher, viz., +3" instead of -1". Its specific gravity is- at 15" 1.002 at 30" -9956. It will be, perhaps, worth while to notice in what respects the para- and ortho-derivatives of anisojil I have obtained differ from each other. The difference in the boiling points appears to be about 10'. Paravinylanisoil ........ 204-205' Orthovinylanisoll ........ uncertain Parallylanisojil .......... 232" Parabutenylaniso'il ...... 242-245" Orthallylanisoil.. ........ 222-223' Orthobutenylanisoll ...... 232-234" The density is also slightly higher in the ortho-derivatives. 15' 30" 4s" - Paravinylanisojl ...... 1.0029 -9956 Ortho ,, ...... *9972 09884 09793 Parabntenylanisojil .... - -9i33 - Ortho ,, .... *9817 -9740 - Ortho ,, ...... 1.0095 1.000 Parallylanisoil ...... - *9852 *9761 - The ortho-compounds also refuse to crystallise, even when placed in a freezing mixture ; the para-derivatives crystaJlise freely. a-Methylorthoxyphenylacrylic acid obtained from coumarin, when treated with hydriodic acid and then with an alkaline carbonate, yields an oil which is appnently identicrtl with the orthovinglanisoll pre- pared from the B-acid. I am at present investigating this remarkable a-acid, and endeavouring to obtain some of its homologues.