87 TIT.-On the Chemical Composition of Canauba Wax. By NEVILSTORY-MASKELYNE, M.A. THEwax-like coating which protects the leaves and fruits of many plants has received little attention at the hands of chemists mainly probably because its quantity is small and the difficulties of collecting it in many cases almost insuperable. In Canaiiba wax however commerce supplies us with a material directly derived from a plant which furnishes such a wax in appreciable quantities. This vegetable wax is the pm- duct of a palm the Copernicia cerifera of botanists the'canauba tree of the Brazilians. It grows to a height of 20 ta 40 feet and when young its trunk is covered with leaves which however in the older plants are found only at its summit in a globular cluster.Its sap yields an amylaceous food its wood is a valuable timber while its younger leaves furnish in the gIaucous coating that protects them the wax-like body the chemical nature of which the following investigation may con-tribute to elucidate. The leaves are ghaken after being detached from the tree and the wax which they yield to the amount of some 50 grains per leaf is melted into a mass. In this state itpis a pale yellow body with a f'a.int tinge of green considerably harder at ordinary temperatures than bees- wax and from the descriptions of the wax made from the noble palm the Ceroxylon AndicoZa of the Cordilleras it would seem to be also harder and less resinous than this latter body. The specific gravity of Cawaiiba wax is 0.99907 and its melt-ing point is about $4"C.On being incinerated it yields 0.14 per cent. of ash for the most part consisting of dica and iron with some sodic chloride. Many trials were made as to the best way of breaking this body up into its cmstituent compounds. The following methods were those ultimately adopted for the purpose. A quantity of tlie crude substance was boiled with alcoholic solution of potash containing one-sixth of its weight of alkali till the liquid became clear when the spirit was distilled off. The residue in which are contained the saponified products STORY-MASKELYNE ON THE was poured into a solution of neutral plumbic acetate a yellow colour immediately developing itself throughout the mass. The whole was then carefully dried powdered and extracted with ether.Wax alcohols dissolve in this liquid in large quantities and mere successive crystallisation will give one of them which seems to be melissin in great purity. The insoluble lead salt can afterwards be decomposed by hydric chloride. In another experiment 12 oz. of the wax were sa,ponified with an alcoholic solution of potash as already mentioned; as soon as the liquid was clear it was precipitated by cold water the alcohol was then distilled 0% and from the mixed soap and alcohols which dissolve in the boiling water the acids were set free by hydric chloride. The mingled mass of acids and alcohols thus formed was then dissolved in boilingalcohol and the acids were saturated with ammonia ; the ammonia soap produced by this means was next thrown down by baric chloride.The alcohol was now distilled off and the precipitate after having been thoroughly extracted with boiling water was thrown on a filter. This precipitate was dried powdered and extracted several times with spirit. The residue was reserved for an examination of the acids contained in it. The part dissolved by alcohol was extracted with ether. Repeated crystallisations from this liquid yield at length a substance melting at first at 87O but ultimately rising to 88'. In this state the substance when fused on a watch-glass exhibits as it cools the concentric undulating rings characteristic of cooled wax alcohols. In appearance it is a very hard semi- transparent electric body exhibiting when in mass but little crystalline structure soluble in hot alcohol and in ether though not in large amount in either of theBe liquids.From its alcoholic dolution it separates on cooling as a gelatinous mass. From ether on the other hand it separates in small foliated crystals. Its analysis produced the following numbers :-I. 0.2858 grm. gave 0.8632 grm. carbonic acid and 0.365 grm. water. 11. 0.2914 grm. gave 0*8824grm. carbonic acid and 0.3738 grm. water. III. 0.2942 grm. gave 0.8898 grm. carbonic acid and 0.3768 grm. water. These results correspond to the following percentages :- CHEXICAL COllIPOSITION OF CANAUBA WAX. Experiment. Theory. I. 11. 111. (C3lHfX0)* Carbon .... 82.37 82.6 82-46 82.30 Hydrogen .. Oxygen ....14.21 - 14.28 - 14.24 - 14-16 3-54 100*00 The alcohol from these numbers was assumed to be melissin. In order to determine its constitutioii with greater exactitude the homologous acid resulting from its oxidation was formed. This was effected in the usual manner the tube containing an intimate mixture of the alcohol and potash-lime was kept by means of an air-bath at a nearly constant temperature of 270° this point being never exceeded. Pure hydrogen was evolved for some hours and when this gas ceased to be developed the substance in the tube was removed and the acids were separated by boiling with hydric chloride. The eliminated acids were dissolved in alcohol and their solution was filtered whilst hot ; when cold the alcohol was re- moved by filtration.The precipitated acid was again dissolved in a very large amount of cold alcohol and then boiled after which this alcoholic solution was converted into an ammonia soap and precipitated with baric chloride. This barium salt was filtered off from the boiling liquid and repeatedly exhausted of any unoxidized wax alcohol it might contain with boiling ether the process being continued till the ether dissolved no further trace of substance. The barium was then removed by boiling the pure salt with hydric chloride. Dissolved in hot alcohol and filtered from the remains of undecomposed barium salt the melissic acid after recrystallisstion presented on being fused and broken a fracture of highly crystalline aspect; and a fkagment fused on a watch-glass gave on cooling the needle-like crystalline radiations which mark the cooling of the wax acids.This substance was found to be in a high degree electrical; it melted at 91" and was only with the greatest difficulty at all soluble in alcohol. Its analysis gave the following results :-I. 0.2981 grm. gave 0.872 grm. carbonic acid and 0.36 grm. water. 11. 0-2972 grm. gave 08666 grm. carbonic acid and 0.3621 grm. water. STORY-MASKEEYNE ON THE 111. 0.2842 grm. gave 0.8286 grm. carbonic acid and 0.3462 grm. water. Them numbers corresponding to a percentage composition of-Experiment. Theory. I. 11. 111. (C31Hfi202). (CYOHfiOOt). Carbon.. . . 79.78 79.51 79.49 79-83 79.65 Hydrogen 13.42 13.53 13-55 13.30 13.27 Oxygen... . -6.87 7*08 I 100*00 100.00 The silver-salt of this acid was now prepared. An alcoholic solution of the acid after saturation with ammonia in slight excess was precipitated by an alcoholic solution of argentic nitrate and the pure white precipitate filtered off and washed in the dark. Dried at looo it presented the appearance of a greyish-white powder devoid of any waxy lustre and veiy readily affected by the light. Its analysis gave the following results :-I. 0.3692 grm. of the salt gave 0,8726 grm. of carbonic acid and 0.357 grm. of water. 11. 0.3276 grm. of the salt yielded 0.0632 grm. of silver. 111. 0.4192 grm. of the salt yielded 0.0816 p.of silver. These numbel-correspond to the following percentage composition:-Experiment.Theory. I. 11. 111. (C30H59Ag02) !C31Hfi1AIS02.) c Carbon .... 64.46 -64.4 64-92 10.75 -10.55 10.65 Hydrogen. Silver.. ... -19-29 19.45 19.32 18.85 . --5.7’3 5-58 Oxygen.. 100~00 100.00 In consequence of the large amount of alcohols yielded by the former process I was convinced that these alcohols were present in the free state. ‘1’0 establish this I endeavoured in a fresh quantity to aepnrate them by direct crystallisation with alcohol my preliminary experiments having proved the wax to be oidy partially soluble in t1ui.t liquid. 400 grainmes treated in this manner after an enormom number and continuation of boillngs which at last barely removed a trace of substance gave- CHEMICAL COMPOSITION OF CANAUBA WAX.91. 126 grarnmes of rsoluble ingredients which melted at 81"; 274 granimes of insoluble ingredients which melted at 86'. The insoluble portion when saponified by potash did not turn of 80 bright a yellow as the whole mass of wax does under the same treatment. This potash solution was then thrown down as before by a solution of lead and the precipitated lead-salt again dried pulverised and exhausted with alcohol. That part of the lead-salt insoluble in spirit corresponded to 85 grammes of acids which were liberated from it by hyclric chloride. From the portion dissolved in alcohol that solveiit was distilled off and the dried mass treated with ether. The boiling ether dis- solved a number of wax alcohols and left a residuary lead-salt which corresponded to 30 grammes of acids.The ethereal solution on cooling deposited mixtures of alcohols from which as before successive crystallisations yielded large amounts of melissin. The soZu62e portion of this fresh quantity weighing 126 gramrnes though repeatedly cryst,allised first from alcohol and afterwards from ether yieldedno products that after fusion on a watch-glass mould give any cq-stalline substance as they cooled. This appeared to be due to a resinous body which though very soluble in these liquids adhered pertinacioiisly to the alcohols as they separated out on cooling. With a view to saponifying and precipitating this substance a minute amount of potash was added to the alcoholic solution which instantly turned very yellow and of a much brighter colour than was observed on subjecting the insoluble ingredients of the wax to like treatment ; plumbic acetate threw down a precipitate com- paratively trifling in quantity; and on boiling it in alcohol it was noticed that the bodies which dissolved in this liquid no longer gave any yellow colour with potash.The resinous body thus eliminated in the form of a lead-salt was too small in amount and too readilF decomposed to invite further enquiry. The mass of substance now dissolved ,in alcohol began after a single crystallisation to exhibit on cooling from fusion on a watch-glass the concentrically annular ridges peculiar to the class of wax alcohols. The ridges were far lem coarse than in the case of cerotin and a few crystallisations from alcohol and ether yielded an individual alcohol of great purity which crystallised at 86O and was in fact melissin.The existence in the free state of a wax alcohol in Canaiiba STORY-MASKELYNEON THE wax to the amount of about one-third of its mass is a fact in vegetable physiology of no little interest. The melissin thus obtained is invariably accompanied by another body in very small relative proportions to it which is deposited in the flasks in fine cryslals; it does not yield annular surfaces on fusion but exhibits a crystalline structure of an entirely different kind. It is a circumstance important to remark that the melissin is present in much larger proportion to the mass of the other alcohols in the part soluble in spirit than it is in the portioii insoluble in this liquid.The whole of the residuary alcohols both from the fi-ee alcohols in the soluble and from the alcohol bases set fiee from the insoluble part of the wax were after the separation of t.he first crystallisations of the melissin mixed and treated together. Dissolved in boiling alcohol and filtered when cold these mixed substances fused at a variable melting point of from 81" to 86O and did not give a clear liquid at any temperature. By several recrystallisations more melissin waa extracted and a body obtained which had a melting point of 87" but which neither solidified in annular concretions nor presented the silky crystals characteristic of melissin. After these had been separated the residues began to melt at 81",and only became clear at tempera- tures over 90".On treating them with benzol there crystallised out a body having a melting-point of 88" which by repeated recrystallisation from this liquid could be raised to 96". After it had been crptallised from ether a few times its melting-point was furt.her raised to 105O and at this stage it solidified with crystalline characters similar to those of cerotic acid but did not saponify with an aqueous solution of potash. The residues of the solvents from which this body melting at 105" had separated yielded at once a substance that melted quite clearly at 84" whence it may be concluded that they con-tained no compound with a higher point of fusion. Substances crystallking between 80" and 84" are separated by the solvents from which this last body was obtained but they are devoid of cryst alliiie structure.Owing to the small amount of these substances obtained from even so large an amount of wax as 400 grammea a much larger quantity of the Caiiauba wax was next worked upon and the reaidues from the various stages of the treatment of these CHEMICAL COMPOSITION OF CANAUBA WAS. 400 grammes were mixed with the corresponding substances furnished by the new mat8eiial. Two pounds of the wax were treated with a mixture of ordinary benzol and alcohol a liquid which not to mention its greater solvent power has its extrac- tive influence enhanced by its higher boiling point. A result of the latter fact is that the wax fuses and is thus more readily acted upon by the solvent.Each portion as before was saponified by an alcoholic solution of potash. The insoluble part was precipitated. by plumbic acetate. By operating on small quantities at a time and allowing the flask to stand until the lead salt had fallen the melissin could be poured off in a state of partial precipitation from the solvent before the latter had become cold; or it may be allowed to cool when the lead salt will be found clotted into a lump at the bottom of the flask thus enabling the overlying portion con- taining the wax alcohols to be mechanically separated with great facility. The lead salt of course is in this way only partially freed from melissin ; it contains however none of the substance which melts at 105O.By again treating the mass thus separated fiom the lead salts with the same solventfi the melissin may be obtained in considerable purity; it still how- ever contains some lead salt. The soluble part was saponified by potash in quantities of about 6 oz. at a time. By filtering the liquid before it had become quite cold the solution of the soap was separat.ed from a quantity of very nearly pure melissin which a few crystallisa- tions rendered colourless and absolutely pure. The soap in the filtrate was precipitated by plumbic acetate and in this way a little more melissin was obtained. It must here be remarked that the mixture of benzol and alcohol used in treating this last quantity of the wax dissolved some of the compounds of melissic and other alcoholic bases with wax acids and that t>here-fore the precipitate produced by plumbic acetate in the soluble part contained a small quantity of lead salts and of acids which properly belong to the insoluble portion.After all the melissin had been crystdlised out as far as could be from both the soluble and the insoluble parts their residues were inixed and treated as one. Solution in alcohol and repeated crystallisatiou added to the amount of melissin obtained. The residuary matter contained in the filtrates from these last quan- tities no longer exhibited annular crystallisation on a watch- STORY-MASKELY~ON THE glass; they consisted in fact of a mixture of the substance melting at 105q with a number of lower wax alcohols whose chemical isolation is a problem for which at present there is perhaps no known satisfiLctory solution.In order to separate the body which melts at 103",these rcsidues were trhen dissolved in a very large quantity of alcohol sufficient in short to retain even when cold the more soluble of the wax alcohols. When cold this liquid was filtered and upon the filter there was left a substance which though it began to melt at 84O did not become transparent till it reached a temperature of 92O. Crystallisa-tion from pure benzol rapidly brought its melting point to 97O and this degree attained no amount of re-cry stallisat ion could raise it above this temperature. With ether however as already mentioned several cry stallisations gave a body having a melting point of 105" which cannot by any means be further raised and this was in fact the Substance previously dewxibed.Although the filtrates from the preparation of this compound yield by a repetition of the process of crystallisa- tion fiom ether a further amount of it this body is present in but very small proportions in Canaiibn wax. Enough however was at last obtained for examination and analysis. It crystal-lises from its ethereal solution in little bosses or lumps radiating fiom a centre. Fused on glass it solidifies with crystalline characters unlike however those of wax alcohols; and it is far less electric than melissin. Its analysis furnished the follow- ing results :-I. 0-271 grm. of the substance gave 0.778 grm.of carbonic acid and 0,3352 grm. of' water. These numbers correspond to the subjoined percentages :-Experiment. Theory. I. '(C39HdL03.) Carbon ........ 78.3 78.30 Hydrogen . . .. 13-73 13.71 Oxygen ........ -7.99 -I 100*00 It is very difficult however to assign a formula to this aiionia- lous substance in the -abHence of more experiments as to its nature. The filtrates from which the above body had crystalliaed CHEMICAL COMPOSITION OF CANAUBA WAX. yielded a series of substances melting respectively at 90" to 9 lo 92* and 95"; these however were obviously miutnres. The alcoholic bodies clissolved by the large amount of alcohol were next treated wit*h a view to a separation of the wax alcohols that they contain.The benzol residues from which the substance melting at 105' had been procured were distilled to remove the benzol and a considerable quantity of the spirit of the alcoholic solution of the lower wax alcohols was likewise driven off; these two residues were then mixed. On cooling a large mms of mixed bodies was deposited which were filtered off. This precipitate of a dark coloiir was then boiled with alcohol and animal char- coal filtered once more whilst hot arid the spirit removed by distillation. By repeatedly crystallising this purified residue from ether several bodies of the nature of wax alcoholp were obtained; they were however necessarily in a state of only approximate isolation. Their melting points were more or less definite being 72" 73" 71j3 78" 80' 81" to 82" 83" and (a little melissin) 85'.There was moreover a small quantity of a substance melting at 84O very similar to one melting at 78'; this however was not melissin aad though cooling from fusion with highly crystalline characters did not exhibit the annular kind of crystallisation. The alcohol melting at 78O appears to be that present in largest quantity and is probably cerotin. The remainder of the above series were present in small but pretty equal quantities. Sufficient of the alcohol which melts at 78O was obtained for the following analysis :-I. 0.2'722 grm. of the substance gave 0.809 grm. of carbonic acid and 0.3428 grm. of water. These results correspond to the following percentage com- positiou.:-Experiment.Theory. I. (C2s&O.) Carbon ........ 81.04 81.17 Hydrogen ...... 13.99 14.12 Oxygen ........ -4.7 1 100*00 It may here be mentioned that every attempt to obtain acids fiom these alcoholic bodies by submitting them to the action of soda-lime proved unsucceasful fkom the fact of the lower acids STORP-MASKELYNE ON THE undergoing decomposition at the temperature necessary for the reaction with the higher ones. In the endeavour to determine with greater exactness the nature of the alcohol the iodide of its radical was formed. In the first instance this body was produced by the action of phosphorus and iodine warmed gradually and subsequently treated by boiling with water and a little sodic carbonate. The resulting substance was dissolved in benzol and crystallised in large granular crystals.A similar preparation boiled with a strong solution of sodic carbonate gave a body with a melting point of 67". Subsequently the alcohol was treated by Von Fridau's method;* it was fused at a tempeyature of 120° to 135' C. in a sulphuric acid bath a small quantity of' phosphorus being dis- solved in it and iodine then added in excess. After being retained for 8ome time at a temperature of 130"C. the mass wa8 washed out with cold water fused and shaken with water at 80' C. It was then dried and digested with ether which left it with a melting point of 67" having dissolved a body that separates from it with a fusing point of 70" to 70O.5. The comportment of the iodide with argentic oxide was then observed.A quantity heated with this oxide and a little water in a sulphuric acid bath to a temperature of looo to 120' C. was converted into a pasty mass which when dried and boiled with alcohol was found to be soluble in this menstruum. Ats the solution cooled an abundant deposit was formed of a body the fusing point of which was found to be 67". Hence it appears that this reagent does not act upon the iodide. Analysis of the iodide produced by the above methods gave the following results :-I. 0.249 gim. of iodide prepared by means of phosphoric iodide when burnt with plumbic chromate in a current of air gave 0.2493 grm. water and 0.5946 of carbonic acid. A residue of urlburnt carbon weighing 0.0015 grm. remained in the platinum boat.11. 0*1009 grm. of the same preparation when heated with lime and sodic carbonate gave 0.0406 grrn. of argentic iodide. The smallness of the quantity employed magnifies the error of analyis. 111. 0.2085 gm.of iodide prepared by Von Fridau's method * Liebig's Handwarterbuch Bd. 11 924. CHEMICAL COMPOSITION OF CANAUBA WAX. gave when burnt 0.2095 gim. of water and 0.4902 grm. of carbonic acid. A residue of unburnt carbon weighing 0.0009 grm. remained in the. platinum boat. These numbers comespoiid with the following percentage composition:-Experiment. Theory. I. 11. HI. (CBOHB1~.) (C3IH63I*) Carbon .. .. 65.722 -64.556 65-693 66.193 Hydrogen.. 11.121 -11-16 11.132 11.209 Iodine .... -21.744 -23-175 22.598 100~000 100.000 The behaviour of the iodide with ammonia and aniline was next examined.When dry ammonia was passed through the fused iodide at 150"to 160"C. it soon became turbid and after the lapse of some time a white granular precipitate was formed in the fused mass. Heated with strong aqueous ammonia in sealed tubes it invariably became opaque and on breaking the points of ther;re tubes under water they immediately filled. The compound resulting from each experiment when boiled with water evolved much ammonia and had then a melting point of 68'05 to 69"C. indicating a return to the state of simple iodide. This body moreover appeared to decompose spon- tan eously. On boiling some of the iodide with aniline and allowing the solution to cool a precipitate formed.This was washed with cold ether in which it is almost insoluble and then boiled in this liquid which dissolved it with great ease and deposited it again in fine crystals. The product when fused evolved aniline leaving a residue with a melting point of 68' to 69O. The preparation of a corresponding chloride of the alcohol radical was next attempted. A quantity of melissin afier repeated treatment with phosphoric pentachloride yielded a compound with a melting point of about 65" which however sank to about 61" afterwarming the body with water. Boiling alcohol extracted from the above product a substance which fused at 64O.5 but after two crystallisations from ether was ob-served to melt at 65" to 65O.5. Two analyses of this substance gave the following results :-I.0.2201 grm. burnt in oxygen gave 002568grm.of water and 0.6035 grm. of carbonic acid. VOL. XXII. I STORY-MASKELYNE ON THE 11. 0.2154 grm. of a specimen once more crystallised from ether gave 0.246 grm. of water and 0.5913 grm. of carbonic acid. These numbers correspond with the following percentage composition:-Experiment. Theory. I. 11. (C3OH6lc1*) ((&1&&1*) Carbon.. 4.0. 74-784 74.865 18.861 79,065 Hydrogen .. 12.962 12.684 13.362 13.390 Chlorine . . . . -7.777 7.545 I 100*000 100*000 These closely agreeing numbers at first suggested that a chlorine replacement had taken place or that a bi-chloride of the biatomic radical had been formed; an inspection of their com- position however renders thig searcely probable.C30H60C12* Ca1H&12. Carbon.. . . . . 73.32 73.66 Hydrogen .. 12.22 12-27 Chlorine .. . . 14.46 1406 100*00 100*00 The body was therefore probably a mixture a view which the change of melting point after treatment with water might be considered to confirm. The acid produced by the action of sulphuric acid on melissin was also prepared and its potash salt submitted to analysis. For this purpose the wax alcohol was heated with sulphuric acid in a water-bath and continually pressed against the sideB of the tube in which the operation was conducted until it became completely dissolved or rather perhaps suspended ; by careful heating merely a trace of discoloration is noticed. If however the temperature of the sulphuric acid be raised too high and the wax be not stirred the liquid soon becomes black and much sulphurous acid is evolved.The wax therefore should never enter into more than incipient fusion. When taken up by the acid it was dissolved in alcohol and saturated witn alcoholic potash which threw down a large white precipitate. Boiled repeatedly with water this precipitate left a large flocculent residue which when mashed free from all sulphuric acid was dried and examined. It was scarcely soluble in alcoholor ether CHEMICAL COMPOSITION OF CANATJBA WAX. and consecutive portions of these solvents removed about an equal amount pointing to a slight solubility of the substance and not an impurity of melissin.The purified body thus obtained fused at 96". An analysis gave the following results :-I. 0.165 grm. when burnt gave 0.1681 grm. of water and 0.3975 grm. of carbonic acid and left in the platinum boat a residue of sulphate of potash which amounted to 0.0249 grm. These numbers correspond with the following percentage compositions:-Theory. Experiment. (C30H61KS04.)(C31HeKS04.) Carbon. ..... 65.69 64-75 65.26 Hydrogen .. 11.27 10.97 11.05 Potassium .. 6-74 7-01 6-84 so,. ....... -17.27 16.85 100.00 100~00 The above analysis like many of the earlier mentioned ones of the alcohol and its acid points to the formula C,,H,,KSO, unless the trifling amount of blackening at its first formation may have caused an increase of carbon and hydrogen in the body.The examination of the acids combined in the Gmaiiba wax -with the alcohol bases remains to be completed. The pertinacity with which a resinous body adheres to these ;acids and refuses to be separated from them by any amount t either of crystallisation fkom solvents or of partial precipita- *tion by any one or by different salts suggested the cautious 'use of a high temperature. By gradually raising the tern- ]peratare to about 240" in an air-bath the resinous sub-r3tance was successfully grappled with and acids obtained by czrystallisation fiom alcohol and ether which on fusion and c;ooling came to present the characteristic features of wax acids (3n a watch-glass. Acids with melting points &om 90O-5 and 13Oo-78O to 40°,were thus obtained but their further isolation 1md examination remains to be worked out.* * The greater part of the investigation of which this memoir is an account was carried out by the author in the years 1855-7; other duties then interfered and lime since prevented its completion.It is published nowJbecause no one having t'aken up the subject exhaustively in the interval the author trusts the interetit a,ttached to the composition of Canauba wax may induce some other chemist to c omplete its chemicd history. 12