The Chemistry of Essential Oils and Artificial Perfumes 1

7/27/2019 The Chemistry of Essential Oils and Artificial Perfumes 1

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V O L U M E I .T H E C H E M I S T R Y O F

E S S E N T I A L O I L SAND

A R T I F I C I A L P E R F U M E S

BYE R N E S T J . P A R R Y B .S c . ( L O N D . ) , F . I . C , F . C . S .

OF GRAYS INN, BARRISTKK-AT-LAWAUTHOR OF "FOOD AND DRUGS," "THE CHEMISTRY OF PIGMENTS," LTC.

FOURTH EDITION, REVISED AND ENLARGED

V O L U M E I .M O N O G R A P H S O N E S S E N T I A L O I L S

WITH FIFTY.TWO ILLUSTRATIONS

L O N D O NS C O T T , G R E E N W O O D A N D S O N

8 B R O A D W A Y , L U D G A T E , E .G . 41 9 2 1

[All rights reserved]NEW YORKD . V A N N O S T R A N D C O M P A N YEIGHT WARREN STREET


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BIBLIOGRAPHICAL NOTE.First Edition (Demy 8vo) 1899Second Edition, Revised and Enlarged (Demy 8vo) 1908Third Edition, Revised and Enlarged to Two Volumes (Royal8vo),of which this is Volume I May, 1918Fourth Edition (Vol. I.), Revised and Enlarged . . . . April, 1921

PRINTED IN GREAT BRITAINBY THE ABERDEEN UNIVERSITYPRESSLTD.,ABERDEEN.


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P R E F A C E T O T H E T H I R D E D I T I O N .T H E m ass of accum ula ted in form at ion in rega rd to e s sen t i a l o il sand the i r cons t i tuents has necess i ta ted the divis ion of th is workin to tw o vo lumes . T h e p res en t vo lum e dea l s en t i re ly w i th theessent ia l o i l s themselves in a ser ies of monographs .

The second vo lume covers the necessa ry g round re la t ing toth e analyses of essent ia l o i ls an d th e cha rac te rs of th e i r i sola tedcons t i tuen ts . I t a lso dea ls w i th art if icia l a ro m at ic bodies w hic hare not pre sen t in essen t ia l o i l s , bu t wh ich form th e gro un dw orkof sy nt he tic perf um ery . I t is believed* th a t th is divis ion of thesub jec t wi l l be found m ore co nv en ie n t t h an the a r ran ge m ent ofthe sub jec t -ma t te r in p rev ious ed i t ions .I have to acknow ledge m y inde b tedn ess to M ess rs . B ak er andSmi th o f the Technolog ica l Museum, Sydney , who have beenexceedingly kind in p la c ing m uc h inform at ion and severa l i l lus t ra-t ions a t my disposa l .- I am al so indeb ted to M . Ga t te fosse , M ess rs . Eo ur e -B er t ran dFi l s , t h e M o n o p o l y B u re a u o f t h e G o v e rn me n t o f Fo rmo s a , t h eIn d i a n Fo re s t ry D e p a r t me n t , t h e E d i t o r o f t h e Chemist andDruggist, a n d t h e E d i t o r of t h e Perfumery and Essential Oil

Record for pe rm iss ion to reprodu ce nu m ero us i l lus t ra t ions andmuch useful informat ion.E E N E S T J . P A E E Y .

56A GREAT DOVER STREET,LONDON, S.E., April,1918.

74000


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P K E F A C E T O T H E F O U R T H E D I T I O N .T H E rap id sa le of the Thir d Ed i t io n of th is work has necess i-ta ted the pub l ica t ion of th i s , the F o u r t h Ed i t ion . No a l te ra t ionhas been made in the a r r angemen t o f the sub jec t -mat te r , wh ichha s been b rou gh t up to da te , so th a t a l l work of im po r ta nc epubl ished up to the end of 1920 has been included.

E K N E S T J . P A K E Y .56A GREAT DOVER STREET,

LONDON, S.E., March,1921.


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C O N T E N T S O F V O L U M E I .PAGEPARMELIACE.E

JUNGERMANNIACE ^ 1CONIFERS 2-60N. 0. GRAMINE ^ 6 0 - 8 8PALMÊ 88-89N. Q. AROIDEÊ 89-91N. 0. LILIACE .E92-94AMARYLLIDACE .E94IRIDE.32 96-98ZINGIBERACEÊ 98-108PIPERACE.E . 109-116CANNABINACE .E116-118JUGLANDACEJE 118MYRICACE ^ 1 1 9 - 1 2 0SALICINEiE 120URTICACEÊ 120-121CHENOPODIACE ^ 1 2 1 - 1 2 2LAURACE ^ E 1 2 2 - 1 7 2PROTEACEJE 172MYRISTICE ^ E 1 7 2 - 1 7 6MONIMIACEÊ 177-178EUPHORBIACE ^ 1 7 8 - 1 7 9SANTALACE ^ E 1 7 9 - 1 9 1ARISTOLOCHIACE.E 191-192LABIATE 192-270VERBENACE .E270-272CONVOLVULACE^ . . 2 7 2P R I M U L A C E .E272-273RUBIACE ^ : 2 7 3 - 2 7 4OLEACE .E274-278ERICACE A E 2 7 8 - 2 8 4APOCYNACEJi 284


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vi i i CONTENTS OF V O L U M E I.PAGEVALERIANACEÊ 284-285COMPOSITE 285-304UMBELLIFERE ^ l 3 0 4 - 3 2 9MYRTAOE 329-390ROSACES 390-412CALYCANTHACEÊ 412-413RUTACE .E413-461ZYGOPHYLLACEÊ 461-462

ANACARDIACE ^ E 4 6 2 - 4 6 4BURSERACEÊ 464-475LEGUMINOS ^ 4 7 5 - 4 8 6GERANIACE.E 486-493T R O P ^ E O L A C E ^ . " * 4 9 4M E L I A C E J E 494CRUCIFERÊ . . 4 9 5 - 5 0 1MAGNOLIACEÊ 501-512ANONACEÊ 512-524PITTOSPORACEÊ 524-525HAMAMELIDACEÊ 525-526-CISTINE ^ E 5 2 6 - 5 2 7RESEDACEÊ 527-528TURNERACEiE 528CANELLACE ^ E 528-529DIPTEROCARPACE ^ E 5 2 9 - 5 3 1THEACEÊ 532MALVACEAE 532R ANUNC ULAC E ^ 532-53a'FLACOURTIACEÊ 533APPENDIX (Oil ofChenopodium) 534-536INDEX 537-549


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PARMELIACE/E.O A K M O S S O I L .

UNDER the nam e " Mousse de C he ne " an extract of various lichensgrowing on oak and other trees has been placed upon the market, andis of the greatest value in perfumery. The principa l plan ts yieldingthis extract are Evernia furfuracea, Evernia prunastri and Ramalinacalicarisand num erou s varieties of the latter. Va rious types ofU$nea,Alectoria,and Parmelia also yield a similar extract in less qua ntity andof poorer odou r. If the pla nts are extracted by mean s of a volatilesolvent, and the extra ct is steam distilled, a colourless esse ntial oil isobtained, which has an intense odour and, according to Gattefosse, 1consists almost entirely of a phenol which he has termed lichenol.On standing the lichenol crystallises out, and when pure melts at 72 to73 . Gattefosse originally considered this phenol to be identical w ithcarvacrol, but now (in a private com mun ication to the author) con-siders th at io is of low er mo lecular we ight, an d closely related tocetrarine, a phenol-ketone occurring in the oil from Cetraria islandica.JUNGERMANNIACE>E.

O I L S O F L I V E R W O R T S .When the dry plant Mastigobryum trilobatum, one of th e well-known

liverworts, is distilled, a small quantity of an orange-yellow essentialoil is obtained, having a powerful odour recalling those of sandal and


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2 T H E C H E M IST R Y O F E SS E N T IA L O IL SSpecific gravity 0'856 at 16Optical rotation - 72 14'Saponification value 5'56

Alicularia scalarisyields a lemon-yellow essential oil hav ing th e fol-lowing characters:Specific gravity 0-965 at 15Optical rotation 33 49'

It appears to contain a sesquiterpene alcohol.C O N I F E R S .

C E D A R - W O O D O I L .The oil usually known as cedar oil or cedar-wood oil is obtained bydistillatian of the wood of Juniperus virgmiana, the Virginia cedar, oneof the family of the Cupressinece. Oth er cedar-wood oils are occasion-ally met with, and will be mentioned later, but the present remarksapply to the above-mentioned oil.T hs oil is generally distilled from the waste shav ings from lead-pencil manufacture, which are usually plentiful when the pencils are

cut from logs. W hen thin sawn boards are impo rted and used, the re-ius e is m uch sm aller in amo unt, and the price n aturally rises. Ow ingto the m ethod s of distillation, the oil manufactured from pencil w asteis of less value to perfum ers tha n norm ally prep ared oil. The yield ofoil obtained varies from 2*5 to 5 per cent. Juniperus virginiana occursover a very wide area in America, and some of the finest oil is obtainedfrom the Florid a ced ar. This oil is one of those w hich are indispen -sable in certain classes of perfumery, especially in fine soap-making,where intensely " sw ee t" odou rs are not required. The wood in finepowder finds its way into m uch of the incense and sim ilar pre pa ratio nsused either for ceremonial or fumigating purposes.Th e oil is usually of a brow nish colour, bu t it can be obtained al-most wa ter-white, and although we know nothin g definitely of wh atchang e occu rs, it is certainly amon gst those oils wh ich improv e inquality by keeping. Occasionally samp les will be found to deposit asmall amount of crystal line "ce da r cam ph or" .] P ur e ce dar-wo od oil has a specific gra vity of from O9 40 to 0*962,and is alway s laevo-rotatory. Th e lim its, how ever, are wide, the oilvaryin g from - 25 to 47. According to Schim m el, 80 per cent,distils at between 125 and 155 at a pre ssure of 14 m m . Th e refrac-tive index is very high, usually exceeding 1*5, and often rising to 1'51.It is very insoluble in alcohol, 1 part requ iring 10 to 20 p ar ts of 90 p ercen t, alcohol for solution. Th e acid value is from 0 to 2, an d th e estervalue from 2 to 7. A sm all am oun t of free alcohols is prese nt, theeste r value of the acetylated pro duc t being from 15 to 44. The know nconstituents of the oil are the sesquiterpene cedrene, C 15 H 24 , and theoxygenated bodies cedar camphor, or cedrol, C15H26O, cedrenol C 16H 24O,and pseudo-cedrol, C15H 26O. Cedrol, wh en pure , is a silky crys tallinemass, with pleasant arom atic odour, m elting at 84. It is suggested bySchimmel that cedrol is not a normal constituent of fresh wood, but isformed in it by keeping it und er favourable conditions. Th is sup pos i-


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C O N IFE B ^E 3tion has not, however, been experimentally justified except in so far asvery old wood yields a semi-solid oil, wh ich d epo sits m uc h cedrol oncooling. At all events, only a small qu antity occurs in norm al oils, asis shown by the low acetylation figure. If the oil be acted upon b yacetic anhy dride, and the resu lting prod uct saponified, no m ore th an from6 to 8 per cent, of cedrol will be indicated. It m ust be rem em bered,however, that dehydration takes placet to a small extent with acetic an-hydride, so that the result m ay be som ewh at under-estim ated. Ten percent, m ay be reg arded as the m axim um usually occurring in good oils.The figures found by the au tho r for four p ure sam ples (p ercentage ofKO H to saponify the acety lated oils) are as follow s: 2-32, 2-21, 2*13,1-72.

Cedrenol, wh ich was isolated from cedar-wood oil by Se m m ler1 andhis pupils is a primary sesquiterpene alcohol, having the following char-acters :

Boiling-point at 9-5 m m . 1 6 6 to 169Refractive index 1-5212Specific gravity at 2 0 . 2 - 0 0 8 3Optical r o t a t i o n 0It forms an acetate of specific gravity 1-0168at 20 and refractive index1-5021.According to Sem m ler cedrenol stan ds in the same relation towardscedrene as the two primary alcohols of the santalol series towards thesesquiterpenes, C16H24, the sa nta lan es ; an d as m yrte no l and th e gin ger-grass alcohol stand towards p inene and limonen e. The prim aryCH 2OH group in the cedrenol molecule occupies the same positionwhich is occupied by the CH 3 group in cedrene and in solid cedrol.Hence the relation of cedrene towa rds cedrol and cedrenol is asfollows:

6 : CH G(OH) . CH2CH., CH3 CH2OHCedrene, C15H24. Cedrol, C15H260. Cedrenol, C15H240.Pseudo-cediol is a satu rate d alcohol, boiling at 1473to 152 at 10mm., and having a specific gravity 0*9964 at 20 , optical rotation + 21*5,and refractive index 1-5131. It ap pe ars to be a phy sical isome ride ofcedrol.Bousset2 has studied the oxidation products of cedrene, from whichhe obtained the ketone cedrone, C 15H 24O, by means of chromic acid.On reduction this yields an alcohol, isocedrol, isomeric with cedrol.Schimm el & Co.3 have examined a cedar-wood oil sent over from

Hayti, of whose botanical origin they were unable to ascertain anythingdefinite, but which according to microscopical results was derived froma conifer, which gave on distillation a yield of 4*33 per cent., of oil oflemon-yellow colour and the odour of the common cedar-wood obtainedfrom Juniperus virginiana L. B ut it differs from the latter by itshigher specific gravity (d 15 0*9612), th e lower rotation ( a D - 1458'),1Berichte,45 (1912), 355, 786, 1553. *Bull. Soc. Chim.,iii., 17 (1897), 4^5.Bericht,April, 1906, 10.


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4 T H E C H E M ISTK Y O F E SS E N T IA L O IL Sand the high er conten t of alcoholic constituents (e ster num ber afteracetylation 64-0). The acid num ber was 2*7, the ester num ber 5*0.The oil was not completely soluble in 10 volumes of 90 per cent, alcohol,but dissolved in every proportion in 95 per cent, alcohol.A cedar-wood oil has been distilled during the past few years fromthe wood of Cedrus Atlantica, the so-called Atlas cedar, which is prob-ably a variety of Cedrus Libani, the cedar of Leban on. Th is oil ha sthe following characters :

Specific gravity at 15 0-950 to 0-970Optical rotat on + 45 ,, + 62Refractive index 1-5119 1-5175Acid value 0 to 2Ester . 3 , , 3 11,, (after acetylation) 30 48

It is soluble in 1 to 10 vo lumes of 90 p er cent, alcoh ol. Acco rdingto Grimal,1 the oil co ntains traces of acetone, and about 5 per cent, ofa ketone, C9H14O, wh ich he term s libanone. This substance yields asemi-carbazone, melting at 159 to 160, and a liquid oxime, which onbrom ination yields a dibromide melting at 132 to 133. The principalcon stituent of the oil is dextro-cadinene, wh ich was obtained from it ina sufficiently pu re condition to hav e an optical rotatio n of + 48.Th e wood of t he ord inary L ebano n cedar, Cedrus Libani, yields,about 3 to 4 per cent, of oil, havin g an odour recalling those of m eth ylheptenone and thujone. Its characters are as follows:Specific gravity at 15 0 940 to 0'950Optical rotation + 66 + 86Refractive index at 20 1-51201-5140Acid value 0 to 1-8Ester 2 4 (after acetylation) 18 25

A sample examined by M essrs. S chim mel & Co. gave the followingresults on fractionation :270 to 2 7 5 . . . 3 0 per cent.275 280 40280 285 14285 290 6Residue . . . . . . . . . . 10 ,,

A cedar wood from E as t Africa, the pro du ct of Juniperus procera,,yields an essen tial oil, wh ich ha s been examined by S chim m el & Co.2and found to have the following characters :Oil fromSawdust. Boards.Yield of essential oil . . . 3*2 per cent. 3-24 per centDensity at i5 0..0-9876 1-0289Refractive index at 20 C. . . . 1-50893 1-51011Optical rotationAcid value . . . .Ester .... ,, (after acetylation)Solubility in 60 per cent, alcohol90

-37 10' - 32 30'14-9 27-068-4 7-9370-0 89-61-6 vol. 2 vols.0-5 vol. 0'5 vol.1Comptesrend.,185 (1902). b2, 1067. 2Bericht,October, 1911, 110-


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0-9549+ 52 16'1-51955-619-330-8

0-9756+ 346'1-52254-54-934-4

C O N I F B E ^ 5Th e essen t ia l o il der ived f rom th e bo ar ds i s fi ll ed w i th cry s ta l s

which have been ident i f ied as cedar camphor; a f te r pur i f ica t ion th eyme lt at 86 to 87 C. , an d h av e a specific rot at io n of + 10-12E o b e r t s 1 has examined the ceda r o i l d i s t i l l ed f rom the wood o f t heDeodar t ree , Cedrus deodara, a n a t i v e of t h e W e s t e r n H i m a l a y a s , w h i c hi s w i de ly d i s t r i b u t e d in N o r t h e r n I n d i a . T h e s a m p l e s e x a m i n e d w e r eof a redd i sh co lou r an d cha rac t e r i s t i c ba l samic odour . T he y ha d th efo l lowing cha rac t e r s :Specific gravityOptical rotationRefractive index at 21Acid value . . . . . . .Ester , , (after acetylation) . . . .

One w as mi sc ib l e in a l l p ro po r t i o ns w i th 90 pe r cen t , a l co ho l ; t heo t h er wa s n o t s o lu b l e i n t w e n t y v o l u m e s . A k e t o n e w a s is o l a t ed w h i c hd id no t combine wi th ac id su lph i t e s , bu t had an odour re sembl ing amylace ta te , an d form ed a sem i-ca rbaz on e me l t in g a t 163 to 164 , an d a d i -b r om o x i m e m e l t i n g a t a b o u t 1 3 0 . S c h i m m e l 2 con s ide r s t ha t i t i sp os si bly j ) - m e t h y l - t e t r a h y d r o a c e t o p h e n o n e . De c o m p o s i t i o n of t h e s e m i -carbazone by d i lu te su lphuric ac id gave a ke tone d i f fer ing f rom the or i -g ina l , bo i l ing a t 220 to 224 , an d form ing a s em i-car baz one m el t i ng a t204 t o 205 , an d fo rming p - to lu i c ac id on ox ida t ion . A ph eno l w as i so -la ted w hich gave a b lood-red co lo ur w i th fe rr ic c h lo r id e and pos sesse d asweet pheno l i c odo ur . I t y i e lded a benzoy l de r iva t ive w h ic h c rys t a l l i sedfrom d i lu t e a l coho l i n sm a l l need le s m e l t i n g a t 70 . Th e qu an t i t y foundwas less tha n 10 per cen t , of th e o i l . O n hy dro lys i s of the o i l , hexoic ,hep to i c, and s t ea r i c ac id s w ere ob t a ined . Th e p r in c ipa l co ns t i t u en t s ofth i s o il a re s e squ i t e rpen es , a s soc i a t ed w i th a va r i ab l e am ou n t of se squ i t e r -pene a l coho l s . Th e se sq u i t e rp ene f rac ti on bo i led a t 1 5 1 to 153 at 19mm . , o r 262 t o 265 a t o rd ina ry p r es su re . I t w as a co lou r l e ss , mob i l el iqu id , wi th a spec if ic gra v i ty of 0*9319, op t ica l ro ta t io n (1 ) + 16 5 1 ' , (2 ) +58 34 ' , an d refract ive ind ex 1*5150 ( 23) . I t gave a co lou r reac t ion wi thsu lphur i c ac id s imi l a r t o t ha t of cad in ene . A t t em pt s t o p r epa re so l id de -r iva tives w ere unsuc cessfu l . T h e com pos i t ion of the o i l w as as fo l lows :Ketone 2 per cen t . , phenol 0*07 to 0*4 per cen t . , es te rs of hexoic , hep to ic ,and s tear ic ac ids 3 t o 12 per cen t . , an d ses qu i te rp ene s 50 to 70 pe r cen t . ,the rem aind er of th e o il con sis t ing ch iefly of se sq ui te rp en e a lco hols , w i thh igh bo i l i ng v i scous decompos i t i on p roduc t s .

O I L O F C E Y P T O M E R I A .The wood of t he Ja pa ne se ceda r , Cryptomeria japonica, y i e l d s a b o u t1 '5 per cen t , o f an essen t ia l o i l hav ing the fo l lowing charac ters :

Specific gravity 0-945Optical rotation - 23Ester number 3'9The o i l con ta in s abou t 60 pe r cen t , o f se squ i t e rpenes and 40 pe rcen t, of se squ i t e rpen e a l coho l s . Th e p r in c ipa l se sq u i t e rpe ne i s p rob -ably cadinene , as ind ic a ted by th e fo l lowing f igures in c om par ison w i ththose for cadinene obtained from oi l of cade :

1Jour. Chem. Soc.(1916),791. 2Bericht,1917,23.


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6 TH E C H EM I S TEY O F ES S E N TI A L O I L SSesquiterpene from Cadinene fromCryptom ria Oil. Oil of Cade.Specific gravity . . . . 0-925 0-927Optical rotation . . . . - 98 45' - 97 30'Melting-point of dihydrochloride . 117 to 118 117 to 118

A second sesquiterpene is present, which only yields liquid halogenacid derivatives. This body, to which the discoverer h as given th ename suginene, has a specific gravity 0*918 and specific rotation- 10 34 '. I t yields a liquid hydrobro mide , of specific gravi ty 0*988and specific rotatio n - 11 15 '. One of the fractions obtained ondistillation was analysed and found to correspond w ith the formulaC 15H 25 OH , and is app aren tly one or more sesquiterpene alcohols. -By conversion into the xanthogenic esters the alcoholic portion ofthe oil was separated into two distinct portions, which on saponifica-tion yielded two isom eric sesquiterpene alcohols. One of these, iso-cryptomeriol, C 15H 25 OH , is a liquid of specific rota tion 3 25 '. Theisomeric alcohol has been termed cryptomeriol, and is an oil of specificrotatio n - 37 5', an d has a specific gravi ty 0'964.By dehydration by m eans of formic acid, cryptom eriol yields asesqu iterp ene hav ing a specific gravity 0*918, and a specific rota tion- 1 5'. It boils at 143 to 144 at 12 m m . pres sure . By dehy dra-tion by m ean s of phosph orus pentoxide an entirely different sesquite r-pen e results , having a specific grav ity 0*917 a nd a specific rotatio n+ 56 26'.The essential oil from the leaves has been investigated by So Uchida.1On distillation w ith steam th e green leaves yielded 0*70 per cent, ofvolatile oil, wh ich w as brownish-yellow in colour and had a fresharom atic odour. It ha s the following cha rac ters:

Specific gravity 0-9217 rotation + 19-29Refractive index 1*4895Acid value 1-0Ester 6-56 (after acetylation) 14-35

On fractional distillation th e following con stitue nts we re separa ted :d-a-pinene, together w ith a small qua ntity of dipe ntene formed about34 per cen t, of the oil. An alcohol, C ao H 18 O, having a fresh odour re-sembling that of cam phor and pep perm int, was found to the extent of4-5 pe r cent., par tly combined a s the capry lic ester. It had a specificgravity of 0'9414, refractive index1-4832,an d specific rota tion + 56*07in chloroform solution. Th is alcohol, though sm all in am oun t, is re-garded as the chief odorous constituent of t he oil. Sesqu iterpenes werepresent to the extent of about 30 per cent., consisting partly of cadineneand partly of a sesquiterpene with two double linkings, boiling-point266 to 268, specific gra vity 0*9335, refractive index 1*5041, and specificrotation + 15*19 in chloroform solution. A ses quit erpe ne alcohol, oc-curring to the extent of about 12 per cent., had boiling-point 284 to 286,specific gravity 0*9623, refractive inde x 1*5048, an d specific rot ati on+ 16*76 in chloroform solution. A new crystalline dite rpene, rep re-senting about 18 per cen t, of the oil, ha s been isolated, to w hich th eUchida has given the nam e a-cryptomerene. On passing dry hydro-.Amer.Chem. Soc.(1916),687.


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CONI F E E JE 7chloric acid into a well-cooled solution of this dipentene in ether a crys-talline isomer was obtained, which is term ed /2-cryptomerene. Trac esof a lactone, C20H 32O 2, free fatty acids, and a blue oil, azulene, were alsoseparated.

OIL OF TAXODIUM DISTICHUM.The oil extracted from the wood of Taxodium distichum (" SouthernCypress") by m eans of alcohol, ha s been examined by Odell.1 H efractionated the resin ous resid ue in vacuoand has thu s isolated a hydro-carbon C15H24 which he callscypressene; it is an inodorous oily liquid ,boiling-point (35 m m.) 218 to 220 C., boiling-point (778 m m.) 295 to

300 C .; [a]2D + 6*53. H e has also extracted a com pound C12H20O , abright yellow oil w ith a stro ng o dour, possessing th e pro perties of analdehyde; it has received the name of cypral (boiling-point, 35 mm.,182 to 185 G.) ; it is dex tro-rota tory.Cypressene yields, on oxidation with nitric a cid, an amorpho us yel-low produc t and an acid possessing the odo ur of isovaleric ac id ; theamorphous product dissolves in alkalies with a red coloration.Odell has also examined the oil from the cones of the same tree.When harvested in September the cones yield 1 per cent, of a greenish-yellow essential oil, with a strong odour of pinene, w7hilst the conesharvested at a la ter period yield on distillatio n 1*5 to 2 per cen t, of adarker oil possessing an odou r of lemon . Th ese two oils po ssess thefollowing characters:

Specific gravity 0-860 0-850Optical rotation +18 + 35 30'They contain about 85 per cent, of J-a-pinene, 5 per cent, of rf-limonene,and 2 per cent, of an alcohol. Sm all am ou nts of carvo ne, and of a ses-quiterpene, which is probably cypressene, are also present.

CHAM.ECYPAKIS OIL.Gham cecyparis obtusata, the hinoki tree which is extensively grownin Japan, furnishes a valuable timber wood, and the tree thrives well inthe mountainous districts of Form osa. U ch ida 2 has examined a sampleof the crude oil obtained by the dry distillation of the wood in Formosa.It is a reddish-brown mobile liquid possessing a woody and empyreu-matic smell and con taining tar ry m atter. The yield wa s 2-4 per cent,of the wood. Th e rectified oil obtaine d by distillation with steam w aslemon yellow in colour, and after treatment with sodium carbonate solu-tion to remove pyroligneous acids it had a specific gravity of 0*8821,refractive index, 1-4990, an d specific rot atio n + 50*37 in chlordformsolution. Th e co nstituen ts identified we re d-a-pinene and cadinen e,with a small amount of oxygenated compounds, the amount of terpenesbeing about 70 per cent., and tha t of th e se squiterpenes about 24 percent.The leaves of Cham cecyparis Lawsoniana yield about 1 per cent, ofoil having the following ch ara cter s :

1Jour.Amer. Chem. Soc.,33, 755. 2Jour.Amer. Chem. Soc.(1916),699.


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T H E C H E M I S T E Y O F E S S E N T I A L O I L SSpecific gravityOptical rotationRefractive indexAcid value . . . .Ester . . . . ,, (after acetylation)

0-9308+ 23 48'1-48843-761-678-8The oil contains laurinic aldehyde.\The oil distilled from the wood of Chamc&cyparis Lawsoniana andrectified by steam has been examined by Schorger.1 The oil ha s thefollowing characters:

Specific gravity 0-8905Refractive i n d e x . 1 - 4 7 5 8 at 15Optical rotation + 39-6Acid value 0-3Ester 32-8 (after a c e t y l a t i o n ) . . . . : . 7i-6

The oil behaved as follows on fractional distillation :(760 mm.) 155 to 157157 , 170170 , 180(15 mm.) 100 , 130130 , 160160 , 190

60-5 per cent.3-04-020-57-01-0The oil contains d-a-pinene to the extent of 60 per cent., dipentene (6 to7 per cent.), Z-borneol (11 per cent.), cadinene (6 to 7 per cent.), formicand acetic acids in the free state, and formic and capric acids as esters.

OLL OF JUNIPEBUS OX YCEDEUS WOOD.Juniperus oxycedrus is the ju nipe r which furnishes th e wood fromwhich the tarry empyreumatic oil, known as cade oil, is obtained by de-structive disti llation. H ue rr e 2 has submitted the same material , suit-ably com minu ted, to ordina ry steam distillation. The essential oil th usobtained com es over very slow ly; th e yield va ries from 1*6 to 3*4 pe r

cent. Th e higher yield w as obtained from the au tum n cut wood. Theoil is a dark yellow viscous liquid ; having the following characters :Specific gravityOptical rotation 0-915 to 0-927- 31 42'

At no rm al atm osp heric pressu re it boils between 260 and 300 C.Soluble 1 : 1 in 95 per cent, alcohol, and 1 : 12 in 90 per c ent, alcohol.On rectifying the crude oil in a current of steam, under reduced pressure,70 per cent, of the original oil distilled as a bright yellow liquid with apenetrating odour; i t was much less viscous than the original oil . Theresidue ( 30 per cent.) w as very viscous, dark in colour, and had a feeblesweet odour.

OLLS OF LLBEOCEDEUS DECUEEENS.Librocedrus decurrens,a tree found in California and know n as theIncen se ceda r, yields a leaf and twig oil and a bark oil. Th e leaf an dtwig oil has the following characters:

lJour. Ind. Eng.Chem.,6 (1914), 631.2Jour.Pharm. Chim.(1915), 12, 273.


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C O N I F E E ^ 9Specific gravity 0-865 to 0-874Optical rotation - 3 20' + 36-68Ester value 18-5 27-8 (after acetylation) . . . . 28'6 48-2

It contains furfural, a-pinene, sylvestrene, limonene, dipe nten e,borneol, esters, and a sesquiterpene, which has been named librocedrene,. having the following characters:Specific gravity at 20 0-929Boiling-point 270 (approximate)Refractive i n d e x . 1-4994Optical rotation + 6-4The bark oil has the following characters :Specific gravity 0-862Refractive index 1-4716at 15Optical rotation + 1'1Ester value 3-2 (after acetylation) 9-5

The oil contains furfural, a-pinene, dipentene, and borneol.O I L O F T U R P E N T I N E .

Numerous members of the family of the Conifera contain largequantities of resin, and an oil consisting almost entirely of terpenes, inwell-characterised resin duc ts in th e wood. Th is is especially th e casewith the variou s species of pin e. Th e exudation from th e wood, anoleo-resin, is often know n as crud e turp enti ne. Oil of turpen tine, or,as it is generally called, turpe ntin e or " tu rp s, " is the oil obtained bydistilling this, leaving the crude resin or " rosin " behind.At the present time Am erican turp entin e is the chief comm ercialvariety, although a considerable amount is produced in France, Eussia,and many other countries, and India produces a fair qua ntity which,although at present consumed in the East, may before long find its wayto Western markets.In the Un ited States the turpentine (i.e.the oleo-resin) is obtainedeither by what is known as th e " box sy st e m " or by the " cup andgutter " system . The box system , briefly, is carried out as follows : Asspring ap proach es, a- groove is cut diagona lly across the tru nk of th etree, and inclined inwards, ending in a hollow excavation about 12 to18 ins. above the ground level. Th is wound in the sapwood induces th eflow of the oleo-resin, and as the w arm er we ather app roach es, the barkabove and on both sides of th e excav ation or " box " is peeled off andshortly afterwards the flow of oleo-resin comm ences. Eve ry two orthree weeks fresh cuts are made so as to open up fresh passages for theexudation. The oleo-resin collects in the " box " and is baled out in tobarrels and transferred to th e distillery. Tre es are not considered worthtapping after four to six yea rs. Th e cup and gu tter sys tem is a com-bination of the older box system and of the usual method employed inFrance . The cuttin g of a large hollow in the trunk is obviated, and itsplace is taken by a receptac le wh ich is suspended from a nail in thetrunk . As in the " box " sys tem , here also the first work is cu tting st ripsin the bark, and as the work proceeds, the space above the receptacle isgradually cleared of ba rk. In order to let th e exu ding resin collect inthe earthenware pots or vessels placed below, two strips or gutters ofgalvanised sheet-iron about 2 ins. wide by 6 ins. to 12 ins. long are em-


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10 TH E C H EM I S TEY O F ES S EN TI A L O I LSployed. These are placed in grooves cut into the tru nk w ith a broadaxe in su ch m ann er, tha t each of the two c uts forms an angle of 60with the longitudinal axis of the itree, and the two together therefore

FIG. 1.Still of a ' Turpentine Farm " in the " Landes ".[liiiitte Jieitntiid /dsform an an gle of 120 open at the top. The two gutt ers, how ev er, arenot placed at the sam e heigh t, hut one about 1 in. or 2 ins. above theother, so tha t the resin flowing along the upper gutter only passe s theother one when flow ing down, and then passing thro ugh the lower g ut te r


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C O N I F E K JE 11reaches the vessel placed below the latter . W hen the cuts in the tru nkand the peeling of th e bark are continued in an upw ard direction, thegutters and the vessel are also m oved upw ards . In older trees con tain-

FIG> 2.Collection of the crude turpentine in the " Landes ".[Roure Bertrand Fils.ing more oleo-resin, several such vessels can of course be placed aroundthe tree.The Fre nch tu rpe ntin e ind ustry is practically confined to the L an de rdistrict, where the following method of collection is followed :^1Vezes,Roure-Bertrand's Bulletin(1909), 2, 9, 3.


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1 2 T H E CHBM I S T E Y OF E S S E N T I AL OI L SThis crude material the "gemme,"to give it the nam e u nde r w hich it

is known in the L andes exudes during the warm season (from M arch toOctober) from an incision m ade by the axe of the resin collector in thestem of the m aritim e pine . K ept open by the rem oval of a thin sliceevery week, this incisionthe "carre "rises gradually up the trunk ofthe tree until it reaches, after five years' working, a height of nearly4 m etre s. The tree is then left alone for two or three years, after w hichtime a fresh " carre " is ma de at an oth er point of the base. The sam etree is tapped in this manner for about forty years, after which it is" bled to death " ( that is, it is worked by me ans of several " c a r re s "simultaneously), before being felled and delivered to the timber mer-ch an ts. Th e forest is, moreover, rapid ly reconstituted, by m ean s ofsowings m ade at the proper t ime, so tha t the resin production of theLandes district is not diminished by the work of the wood-cutters andthe operations of th e mec hanical saw -mills. So far, th is principle hasnot been followed in the Un ited State s, wh ere every tree was " tapp ed todeath " from the beginning, and every plot which was subjected to tap-ping was thereby practically destroyed after four years' working, withoutan y steps being take n for its reco nstitution . Fo r some ye ars, howe ver,a serious movement has been set on foot in America to save what re-mains of the pine forests by a more rational and less destructive systemof exploitation ; and this appears to be producing good results.From the top of the " ca rre, " the drops of " gemm e " as they exu defrom the res in ducts of the tr ee , run down into the rec eiver placed tocollect th e m ; this was in former time s in the La ndes (and w as u ntilthree or four years ago in America) a holethe "crot "hollowed outof the stem of the treeitself,at the base of the " carre " ; at th e pre sen tday it is, both in A merica and in the La ndes, an earthe nw are or me talpot, suspended at the base of the " carre " and raised every year so as tobring it near the upper part of the incision and reduce the distance overw hich the drop s of the exudation have to run . -The imp ortan ce of thischange and w hy it is advantageou s tha t th e pa th of the " gemm e " downthe " carre " should be as short as possible, is obvious when one remem-

bers how easily the turpentine is oxidised.From the pots the " ge m m e" is transferred, about once a m onth,into casks and carried from th e forest to the factor y; this harves t,"I'amasse,"take s place in the La nde s from five to eight tim es a y ear.In India, the chir, as the Pinus longifolia is termed, is treated by amethod based on the French method.1An initial blaze about 6 ins. long, 4 in s. broad and not mo re tha n1 in. deep is cut n ear the base of the tree , a nd the blaze is freshenedevery six or seven days throughout the summer, until i t is about 18 ins.long by the end of the year : if the freshening is carefully done the useof a ladde r is thu s as a rule unn ece ssary till the fifth year. Th e resincollects in a cu p fixed at the base of t he curre nt yea rs' blaze, and thecon tents are emptied periodically. A curved ch ann el, in place of theformer rectangular chan nel , is now universally adopted in the U nitedProvinces, as it works easily, does not injure the tree so much, gives acleaner cut, and so far shows promise of giving a higher out-turn.There are two classes of tapping : (1) light tapping and (2) heavy tap-ping, sometimes termed tapping to death. The latt er is carried out in1IndianForest Memoirs(Sylviculture series), Vol. I, Part I, p. 100.


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oIIhrjW

FIG, d Turpentine Farm " in the '*Landes "Interior. Bitiand FUb


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1 4 T H E C H E M IST E Y O F E SSE N T IA L O IL Sthe case of tree s due to be felled within five years, a nd consists in m ak ing;as many blazes as the tree will hold the former consists in m aking am oderate num ber of blazes, and is carried out in the case of trees notdue to be felled with in the next few years. In the N ain i Tal Divisionlight tapping un der the presen t system' is comm enced when the treesxeach a girth of 3-J ft., and t he following n um be r of blazes are c u t:

(1) Trees over 6 ft. in girth . . . . . . 3 blazes(2) 4J to 6 ft. in girth 2 (3) 3 | to 4 | ft. in g i r t h . 1 blazeIn the maritime pine forests of Bordeaux no tree is tapped lightly till itreac hes a girth of 1*10 m etres (3 ft. 7 ins.), wh en one blaze is m ad e: thetree is then about fifty yea rs old. A second blaze is added w hen the treerea che s a girth of 1*30 me tres (4 ft. 3 ins.) . In the Ch akr ata Division.tapping is confined to fire-protected forests of th e first an d second p eri od icblocks in Jau nsa r-B aw ar; no tapping is at present don e in the Tehri-G arhw al forests owing to the cost of carr iage . At presen t no heavy tap -ping is done in this Division : light tapping commences when the treesrea ch 4 J ft. in gi rth . In perio dic block I. tree s 4-J- to 6 ft. in girt h h avetw


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C O N I F E E ^ 1 5years. The cycle was shortene d in orde r to avoid the use of a ladder,which was found necessary in the fifth year. The highest yield of resinis obtained in the third and fourth years of tapping, and thus by reducingthe tapping period to three years considerable loss is involved, which isavoidable considering that a ladder is not required in the fourth seasonif reasonable care is taken in freshening the blazes.If a tapping-cycle at all is to be decided on, twelve years (i.e. fouryears' tapping and eight years' rest) appears to be preferable to either nineor fifteen years. The objection to the former ha s been mentio ned, whilein the case of the latter it cannot be made to fit in with a suitable schemeof thinnings.In the maritime pine forests of Bordeaux light tapping, once begun,continues without interruption, no rest being given unless a tapped treeshows signs of becoming sickly, when a res t of five yea rs is given : s uchcases are rare. Now in the case of the chir pine, experiments haveshown that the tree possesses remarkable vitality even under the strainof heavy tapping. Th ere seems to be no reason, therefore, w hy the con-tinuous light tapping system of France should not be employed in thechirforests. Not only would it increase largely the ou t-tu rn of resin,but it would avoid the com plication in the gene ral sch eme of m anage-ment which is inevitable if a tapping-cycle is adopted.Much has been written in reference to the adulteration of oil of tur-pentine, most of which is of little more than historical interest to-day.The chief difficulty the expert has to contend with at the present time isthe detection of th e so-called wood or stu m p turp en tine oil. This oil isclearly entitled to the description " tur pentine oil," on accoun t of itsorigin and character, which are exceedingly close to those of normal or" gum " turpen tine ; but it is generally conceded th at it properly requiresthe qualification " wood " o r " stu m p, " so tha t users may know exactlywhat they are dealing with.Wood turpe ntine , " stum p turpen tine ," or " wood spirits of turpe n-tine," as the product is variously known, is turpentine oil made from cutpine,fir, or spruce, by distilling the wood in closed retorts . W hen pro-perly refined it closely resem bles gu m spirits of turp en tine , obtained bydistilling th e oleo-resin exud ing from th e cut surface of the living tree.The turpentine made by distilling the wood with steam below a tempera-ture of 150 C. more closely resembles gum spirits than that obtained bydestructively distilling the wood. The la tter is alw ays contaminatedwith other oils derived from th e break ing down of th e wood an d the re-sins which it contains.As a result of the reckless devastation of the pine forests which hasbeen practised for many years, in the United States, the tree-stumpswhich have been left standin g, and which a re know n as " light wood "are now often distilled. The stu m ps w hich are being used u p in Am ericaat present have remained in the ground many years after the trunk hadbeen removed, an d yield a pine wood wh ich is very rich in resin . Itwould appear that a chemical process is taking place in these stumps bywhich oil is formed subsequent to the removal of the trunk, for the oil-yield from new stu m ps is very low. Th is fact would also explain wh ythe oil thus obtained is somewhat different from ordinary oil of turpen-tine, and why the percentage is so high.The stumps which are mostly employed for distilling purposes arethose of Pinuspalustris (long leaf p ine) , whence the oil is called "l on g


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16 T H E C H E M IST R Y O F E SSE N T IA L O IL Sleaf pine oil ". Similar produc ts are brought to m arket und er the n am esof "lig ht wood oil " and " oil of fir";. while the designations " w h it e '*and "yellow pine oil " app ear to apply to separate fractions of the o il.According to Teeple l ord inary com mercial long leaf pin e oil in it scrude state has a specific gravity 0-935 to 0*944, optical rotation -11,and refractive index T4 830. These values, however, are often exceeded,and genuine samples may have a specific gravity 0 *954 and may bedextro-rotatory up to + 8. A sam ple was examined by Schimm el &Co.2 which had the following characters :

Specific gravity .Optical rotation .Refractive i n d e x .Ester n u m b e r . . .Total alcohols (by acetylation) .

0-9536. - 3 26'. 1-4853714-2. 58 per cent.

The bulk of th e oil boiled between 190 and 220. Th e following ter~penes we re identified in the o il : a-pinene, /3-pinene, Z-limonene, dip en-tene,and A-terpinene. A considerable a m oun t of a-terpinene was foun d(this had previously been identified by Teeple), as well as borneol andmethy l-chavicol. Fe nc hy l alcohol w as also found as a con stituen t of theoil, and traces of cam pho r and cineol. Th e presen ce of fenchyl alcoholis of particula r in terest as it occurs in the inac tive varie ty. It is wellknown that this body results from the reduction of fenchone, but it hasnever before been discovered as a natural constituent of an essential oil.The table below shows the character of the fenchyl alcohol occurringin this oil and of those prepared by the reduction of active and inactivefenchone.

FENCHYL ALCOHOL AND ITS DERIVATIVES.From Ye

m.p.33to35159to160142to143

93to94

b.p.202to20 S192to193

154to156

ellow Pine Oil.d.

0-9501(15)

0-8687(15)

nD.

1-47023(20)

1-47240(20)

FenchylAlcoholFenchoneFenchoneOxime

AcidPhthalicEsterFenchene

IsofenchylPhenyl-urethane

From Active Fenclione.m.p.45+ 6164to165145to145-5

106to107

b.p.201to202192to193

154to156

d.

0-952(15)

0-8660to0-8665(15)

nD.

1-46337(17)

1-46733to1-46832(17)

From Inactive Fenchone.m.p.33to35

153to160

94

b.p.201to

d.

202

_154to156

0-8665(15)

nD.

1-46733to1-46832

1Jour. Amer. Chem. Soc.,30 (1908), 412. Report,April,1910,104.


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C O N I F E E ^ 1 7The crude oil obtained by any distillation process is redistilled or re-

fined before it is m arketed. Crude oils from the destru ctive processare agitated with alkali whereby the greater part of the phenols, cresols,and related bodies are dissolved, and separated by settling from theturpentine; rosin spirits and rosin oils are run off and separated byredistillation with steam a s steam -distilled w ood turpen tine is. Th is isusually done in a copper-pot still of suitable size, live steam being con-ducted directly into the cru de oil. Ordinarily this distillation is notconducted with care, and but little attempt is made to ensure that thewood turpentine obtained does not conta in con siderable qu an tities of theheavier " pine oils," as the heavier oils present in the c rude pro duct arecalled.The principa l source of A merican turp en tine is the long-leafed pin e,Pinus palustris (Pinus australis M ch x . ) ; Pinus heterophylla and Pimisechinataalso furnish turp en tine .American oil of turpentine consists practically entirely of terpenes,of which pinene is the chief. De xtro-a-pinene, laevo-a-pinene and fi-pinene are all prese nt, as well as small qu antities of cam phen e. Thequestion as to whether firpene, 1 wh ich has been described as a consti-tuent of the oil, is a distinct individual or not, is a matter of some doubt.Crude wood turpen tine differs from norm al turp en tine primarily inthat it contains additional terpenes, and terpene derivatives, togetherwith other non-terpene derivatives. In tha t obtained by the destructivedistillation of long-leaf yellow pine , dipe nten e, penta ne , p en ten e, to luen e,heptine, etc., have been identified, in addition to pinene.Steam-distilled wood turpentine consists essentially of pinene, to-gether with camphene, limonene, dipentene, cineol, and (depending onc^re of fractionating), terpineol, borneol, terpinene, etc.The pine oils contain chiefly te rpin eol, borne ol, and fenchyl alcoho l,with small quantities of limonene, dipentene, terpinene, cineol, and evenless pinene and cam phen e.American oil of turpentine varies in character to a considerable ex-tent, the optical rotation, especially, having steadily decreased in thepast few years. Such var iation s are to be expected w hen one remembers-that the gathering grounds have been extended in various directions, themethods of prepar ation alt er from time to tim e, and the use of differentspecies of tree s is not unc om m on.Any standards for these oils must therefore be understood to be fairworking figures, to which by care, oils can be ma de to attain , a lthou gh pu redistillates may, obviously, give va lues widely outside the accepted figures.The United State s De pa rtm en t of Agriculture in 1911 issued sug-gested standards for pure turpentine, of which that for No. 1 or " stand-ard " turpentine is the most im portant. The suggested stand ards areas follows: Specific gravity at 20 = 0-862 to O870; refractive indexat 20 = 1-4680 to1*4760; 95 pe r cent, shou ld distil below 170. Onpolymerisation w ith sulp hu ric acid ( thirty-eig ht time s norm al) the re-sidue should not exceed 1 per cen t, and shou ld h ave a refractive indexof 1-500 to1-520.The author, 2 as the result of the examination of a very large numberof pure commercial samples, finds the following limits to embrace prac-tically all genuine normal samples as met with in commerce :

1Frankforter and Frary,Jour.Amer. Chem. Soc., 28(1906),1461.2E. J. Parry,ChemistandDruggist,24 August, 1912.VOL. I 2


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18 T H E C H E M I S T R Y OF E S S E N T I A L O I L SSpecific gravityat 15 0-862 to0-870Refractive index 1-4680 1-4730Initial boiling-point 154 155-5Distillate under160 72 74-5percent. 170 95,,97-5 Bromine value 1-96 ,, 2-31Iodine value (Hiibl) 360 , 375 (Wijs) 335 , 350 ,, oflast 10percent,ondistillation (Hiibl) 349 , 369(Wijs) 350 , 365Refractive indexof 1st 20 percent. . . . 1-4700 , 1-4722 2nd ,, . . . . 1-4700 1-4724 3rd . . . . 1-4710 1-47354th . . . . 1-4710 1-4740

5th , , . . . . 1-4780 1-4821The charactersof wood turpentine,and theeffect ofth isand of o theradulterantsonthe ss figures isshownin thefoliowing tab leby theauthor(loc. dt.):

Specific G r a v i t y . . . .Refractive IndexInitial Boiling-pointDistillate under160., 170Bromine Value * .Iodine Value (Hiibl).. (Wijs)

. . .

. . .

. . . oflast10 percent. (Hiibl).., (Wijs) .Refractive Indexof 1st 20 percent.2nd .3rd . . .4 t h .5 t h .

1)

Pe

Amec

upn

0-8661-47201557 4 9 4 2-23723503603551-47191-47001-47121-47121-4781

(2

Wo

upn

0-8731-47451596 1 %1-462642402512421-47311-47301-47341-47321-4842

(3)J3

rce

L

a(2

8 "0-8691-47371576 8 8 4 1-823212983042981-47281-47201-47221-47-211-4821

(4)

eoem

upn

0-8081-4490984 8 75%0-05908-49-08-51-4481-4191-44811-44701-4495

(5)i il ls~

0-8381-4610996 2 8 2 1-1190*51791841771-46601-46751-47211-47211-4735A s H e r t z 1 hasshown,the optical rotationof Americanoil of tu rpen-t ine isvery variable. NM.JThe experimentson theopposite page by the United States Govern-ment Chemists with the oil from named trees show how widely therotationmay vary even withtheproductof the same tree:

1Jour. Amer. Chem.Soc., 30, 863.


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C O N I F E E ^ L 19

TreeDesigna-tion.AlA2A3A4A5A6Cl02C304DlD2D3D4

Species.

P.heterophyllaMttP.palustris . P .heterophylla?iP.palustris .

P.heterophylla

Dia-meter(inches).7-014-524-57-315-021-012-38-213-08-79 013-513-09-0

Character of Chipping.

1st year, normal depth> t )> I*2nd year, shallow . > M > t 2nd year, normal depth '

OpticalRotation100 mm.Tube.20"C.- 20 50'+ 015'- 15 0'+ 15 40'+ 8 9'+ 18 18'- 27 11'- 26 28'- 7 26'+ 7 31'+ 10 50'+ 123'- 18 35'- 29 26'

In a general way the figures sup port the view tha t the oils of Pinuspalustrisare dextro-rotatory and those from Pinus heterophylla laevo-rotatory. Th at this is not strictly tru e, h ow ever, is evidenced by thedextro-rotation of A2(P. heterophylla),and more especially by the laevo-rotation of 03 (P. palustris).With these variations in the first collection from the several trees,the question natura lly arose, would the variations change as the seasonadvanced or would the figures prove co nsta nt for th e individ ual tree s ?The rotations for the successive collections are as follows:

OPTICAL KOTATION IN 100 MM. TU BE , 20 C.

Collection.1234567Collection.12

84567

Al.- 20- 22- 21- 21-20-20- 22C2.-26-25

- 26- 26- 26- 26- 26

50'5'45'7'30'15'15'28'37'20'30'r0'28'

A2.+ 0- 0 + 0- 1-2- 3- 503.- 7- 6

- 4- 4 3- 4- 6

15'30'15'15'5'30'45'26'42'45'29'55'5'6'

A3.- 15- 14- 15-15- 15- 15- 17C4.+ 7+ 7

0'26'55'50'15'27'52'31'20'

A4.+ 15+ 15+ 14+ 14+ 14+ 14+ 12Dl.+ 10+ 11

+ 13+LV4+ 13+ 13+ 10

40'22'15'20'21'35'49'50'23'7'46'0'0'48'

A5.+ 8 9'+ 8 50'+ 8 27'+ 8 34'+ 8 32'+ 8 4'+ 7 6'D2.+ 1 23'+ 2 40'

+ 2 25'+ 2 22'+ 1 13'+ 1 15'- 055

A6.+ 18+ 17+ 19+ 18+ 19+ 1">+ 14D3.- 18- 17

- 15- 15- 14- 14- 14

18'43'30'46'24'16'47'35'0'20'0'38'7'19'

01.- 27- 26 11'48'- 26 25'-23- 21- 21- 21D4.- 29- 27

- 28- 27- 27- 26- 26

32'12'46'35'26'45'19'38'48'11'12'

Wood turpe ntine can, how ever, be so rectified as to distil at tem pera -tures much closer to those of normal turpentine than is shown in thetable on p. 18, so tha t w hilst positive re su lts in dicate th e presence of woodturpentine, negative results do not necessarily exclude its presence.


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20 T H E C H E M IST R Y O F E SSE N T IA L O IL SThe lower iodine value, especially of the last 10 per cent, remainingon distillation is very char acteristic of wood turp entin e, and is, in theauthor's opinion, the most valuable evidence that can be obtained of its-presence.The fact that wood tur pe ntin e usually conta ins dip ente ne is also ofconsiderable assistance to the analyst in some cases. In norm al turp en -t ine, if the successive fractions of 5 per cent, be examined, they will befound to increase regularly in specific gravity and refractive index, witheach rise in the distillation temp erature. Dipentene, however, h as ahigh er boiling-point than pinene, but a lower specific gravity. So th atin a wood turpen tine containing dipentene, when about 70 per cent, has

distilled over, some of th e fractions will be found to hav e increa sed inboiling-point, increased in refractive ind ex, but decrea sed in specificgravity. In such a case, the presence of wood turp enti ne may safelybe assumed.When adulterated with most types of petroleum products , the tem-pera ture of distillation rises gradua lly, and no large fractions are obtainedat any definite tem per atur e when the adu lteration is at all excessive.The presence of ordinary petroleum spirit low ers the flash-point of tu r-pentin e. W he n pu re it flashes at 92 to 95 F . when tested in Abel'sflash-point appa ratus . W ith only 1 per cent, of ord inary petroleumspirit this temperature is reduced by 10.According to Arm strong, a good indication of the pre senc e of th eusual adu lteran ts is obtained by distillation with steam. A current ofsteam is allowed to pass into a definite volume of the tur pe ntin e con-tained in a flask attached to a con denser. Un less it has been allowedfree access to the air for some time, the genuine oil leaves only tracesof non-volatile matter, but old samples may leave up to 2 per cent.Usu ally, h owever, th e presence of mo re tha n '5 per c ent, after steamdistillation indica tes the presen ce of unvolatilised petroleum oil. Th isis easily recognised by its low specific gravity and its fluorescence whendissolved in eth er . If the residu e con sists of resin oil, it will form a.bulky soap wh en rubbed with slaked lim e. The specific g ravity of thefractions com ing over with the steam will largely assist in det erm inin gthe presence of volatile adulterants.For the approximate estimation of the amount of petroleum nap hth ain adulterated turpentine , Ar m strong 1 recommends the following pro-cess : 500 c.c. of the sam ple is placed in a sepa rato r an d treated w ithabout 150 c.c of sulphuric acid (2 volumes of acid to 1 of water).The mixture is cautiously agitated, and, if much rise of temperature isobserved, the separator must be placed in cold water for a short time.The turpentine is gradually converted into a viscid oil, and when this has.taken place, and no more heat is developed on repeated agitation, the

acid is tapp ed off. Th e oily layer is the n tran sferr ed to a flask andsubjected to steam distillation. W hen all tha t is volatile with steamhas passed over, the oily portion of the distillate is separated from theaqueo us layer, and heated with half its volume of sulp hur ic acid pre -viously diluted with one-fourth of its m easure of wa ter. The m ixtureis well agitated, the acid liquid separated , and the oily layer again dis-tilled with steam. W hen genuine turp entine is operated upon, thevolatile portion of this second treatment consists merely of cymene1Jour. Soc.CJem.Ind.,1882, 1, 480.


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C O N I F E E ^ 2 1and a small qua ntity of paraffinoid hyd roca rbo ns. It never exceeds4 to 5 per cent, of the volume of the original sam ple, and w ith care isas low as 3* per cent. If the volu me no tably exceeds 5 per cent., it isadvisable as a precaution to repeat th e tre atm en t w ith the ( 4 to 1) acid.When treated in this manner, petroleum naphtha is not appreciablyaffected; hence the prop ortion m ay be fairly estim ated by m aking anallowance of 4 to 5 per cent, from the volum e of volatile oil which ha ssurvived the repeated trea tm en t w ith sulph uric acid. A further puri-fication may be effected by violen tly ag itati ng th e su rviv ing oil w ithseveral times its volume of concentrated sulphuric acid heated to 50 or60. This treatm ent can be repeated if necessary , after w hich th eresidual hydrocarbon is separated, steam distilled and again measured,when the surviving oil from pure turpentine oil will not exceed fromJ- to 1 per cent, of th e origin al sam ple. Any excess over this will bethe minimum quantity of petroleum nap htha present. Shale n aph thacannot be at all estimated in this w ay. Th e behaviour of th e oil ondistillation is the best indication of the presence of rosin spirit, as thetemperature rises gradually, and no considerable fraction is obtained at158 to 160 if m uch rosin spirit be pr ese nt .Allen (Comm ercial Organic Analysis) gives the table on page 22 asindicating some of the properties of some substances which have beenused as adulterants for turpentine oil.

More empirical methods for detecting adulteration in turpentine havebeen published t ha n is the case for any oth er esse ntial oil. The se areprincipally based on colour reactions, and are, in very many cases, quiteuseless, especially wh en th e ad ul ter an t is carefully purified. M any mod i-fications of processes described above ha ve been pu blish ed, but do no tappear to possess any advantages over those which have been described.It is, therefore, considered unnecessary to reproduce so large a bulk ofpublished work, w hich ha s so little bearing on the practical exa m inationof this oil ; but reade rs who wish for inform ation on these or oth er little-used processes or tes ts, or for deta ils of metho ds wh ich for a ny otherreason are not dealt with here, are referred to the following papers :J. M. McC andless (J. Amer. Chem. Soc.,1904 (26), 981).Marcusson and Winterfeld (Chem. Zeit., 1909,987).W. Burton ( / . Amer. Chem. Soc., 1890 (12), 102).P . H. Conradson (J. Soc. Chem. Lid., 1897 (16), 519).H. Wolff (Farbenzeit., 1912 (17), 1553).Grimaldi (Chem . Zeit., 1908 (32), 8, and 1910 (34), 721).Dunwody (Amer. Jour. Pharm., 1892 (33) 131).H. Herzfeld (Chem. Zentralblatt, 1903 (1) , 258).P. van der Wielen (Pharm. Weekblad.,1911 (8) , 35).Nicolardot and Clement (Bull. Soc. Chim., iv. (1910), 7, 173).V6zes (Bull. Soc. Chim.,iii. (1903), 29, 896).C. Piest (Chem . Zeit., 1912 (36), 198).Utz (Chem . Zentralblatt, 1905 (1), 1673).A. W. Schorger l has examined the oils from a number of pine-trees

1U.S.Departmentof Agriculture, Bulletin119.


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1. Optical A c t i v i t y . . . .2. Specific Gravity . . . .3. Temperature of Distillation4. Action in the Cold on Coal-tarPitch5.Behaviour with Absolute Phenolat 206. Behaviour on Agitating 3 vols.with 1 vol. Castor Oil7. Bromine Absorption (Dry).8. Behaviour with H2S04

Turpentine Oil.

active860 to -872156 to 180

readily dissolveshomogeneousmixturehomogeneousmixture

203 to 236almost entirelypolymerised

Rosin Spirit.

usually none856 to -880gradual rise

readily dissolveshomogeneousmixturehomogeneousmixture

184 to 203polymerised

Petroleum Naphtha.

none700 to -740gradual rise

very slight actionno apparentsolutiontwo layersof nearly equalvolume

10 to 20very little action

Shale Naphtha.

none700 to -750gradual rise

very slight actionhomogeneous mix-ture, crystalliseson cooling

like petroleumnaphtha60 to 80

considerableaction

Coal-tar SolventNaphtha.none860 to ;875

gradual risereadily dissolves

homogeneousmixture

moderate action

pMGQ

KOMCQCQ

OQ


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C O N I F E E ^E 23foundin theWestern p artsof theUnited S tates,andA d a m slhasreportedupon similar"wood turpentines". These resultsare as follows:

TUKPENTINE FROM PlNUS PONDEROSA (LAWS).The specific gravity of the oil was 0-8625; the indexof refraction1*4772; and thespecific rotation [a]D'= - 14-39. On fractionationof500 gramsof oil the following results were obtained:

Temperature(corrected).

C.164-0-168-2168-6169-0169-2170-5171-0171-61724175-0179-5179-5+

Distillate.Observed.Per Cent.5-019-949-369-2010-4510-7110-289-6910-367-047-74

Cumulative.Per Cent.5-0114-9524-3133-5143-9654-6764-9574-6485-2092-24

99-98

SpecificGravityat15.

0-85788595860186068608861286158619862186319186

IndexofRefractionat15.

1-47401-47501-47521-47531-47541-47571-47601-47621-47631-47751-5063

SpecificRotationat 20.

-13-81-13-70-13-17-12-92-12-73-12-98- 13-33-14-17-17-15-24-13+ 0-86Laevo-a-pinene, /2-pinene,and laevo-limonene were detectedin the oil.

TURPENTINE FROM PINUS PONDEROSA SCOPULORUM (ENGELM).Theoil had the following characters: specific gravity0'8639at 15;indexof refraction 1*4727at 15.The physical constants of the fractions obtainedondistillationare asfollows:Temperature(corrected).

C.157-6-158-5159-5159-9160-1160-9161-7162-6165-2170-2173-0177-1183-3183-3+

Distillate.Observed.Per Cent.2-039-699-9710-2110-069-39

9-979-1210-505-946-252-194-60

Cumulative.Per Cent.2-0311-7221-6931-9041-9651-35

61-3270-4480-9486-8893-1395-3299-92

dl5.SpecificGravityat15.0-8586-8621862086208620-86208623862686268615-85938576

ND15IndexofRefractionat15.1-46861-47011-47021-47051-4706147111-47141-47221-47351-47521-47581-4769

a-Pinene, /3-pinene,and limonene were found in the oil.1Jour.Ind. Eng.Chem.,1915 (7), 957.


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2 4 T H E C H E M I S T E Y O F E S S E N T I A L O I L ST U R P E N T I N E F R O M P I N U S S A B I N IA N A .

T h e oil had a p l e a s a n t o r a n g e - l i k e o d o u r ; s p e c if i c g r a v i t y , 0 * 6 9 7 1 ;a n d i n d e x of r e f r a c t i o n , 1-3903. On f r a c t i o n a l d i s t i l l a t i o n of 500 g r a m sof th e oil th e f o l lo w i n g r e s u l t s w e r e o b t a i n e d :

Temperature(corrected).C.

96-1-97*397-998-398-398-498-498-598'598'598-598-698-798-898-8+

DistillateObserved.Per Cent.

4-247-939-048-448-898-978-067-136-926-946-836-195-664-66

Cumulative.Per Cent.

4-2412-1721-2129-6538-5447'5155-5762-7069-6276-5683-3989 -5895-2499-90

SpecificGravityat15C.

0-68896885-68826882688068816881-6882688168806879687968817393

XD15-IndexofRefractionat15C.

1-38901-38981-38981-38981-38981-38981-38981-38981-38981-38991-38991-38991-39001-4140Thisoil isvery notewo rthy,as it consists almost entirelyof thehydro-carbon heptane,a lowboiling paraffin hyd roca rbon , quite distin ct fromthe terpenes, which are thenorma l constituentsof practicallyall o therturpentine oils.

TUR PENT INE FROM PIN US OONTOBTA.Two samplesofthisoil had thefollowing chara cters:

Specific gravityRotation.Refractive index

1.0-8518-20-121-4862

2.08549

1-4860A b o u t 400 g r a m s w e r e s u b m i t t e d to f r a c t i o n a l d i s t i l l a t i o n w i t h t h ef o l l o w i n g r e s u l t s :

Temperature(corrected).

C.164-4-1706171-6172-6173-6175-3177*2177-6177-9178-4178-9178-9+

Distillate.Observed.Per Cent.

2-898-559-0810-7710-229*7910-0310-239-264-1514'83

Cumulative.Per Cent.

2-8911-4420-5231-2941-5151-3061-3371-5680-8284-9799-80


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C O N I F E E ^ 25The oil had a very characteristic odour; it was pungent when freshly

distilled, and, after stan ding some ti m e, was oran ge-like. Th e oil poly-merised very considerably at its boiling-po int. The 15 pe r cen t, residueremaining in the distilling flask solidified to a solid, amber-coloured massresembling colophony, insoluble in alcohol, but soluble in ether andchloroform. To avoid loss of oil by polym erisation it m ust be distilledunder reduced pressu re. Th e oil carefully purified a nd finally distilledover metallic sodium, had the following properties: Boiling-point, 60 at2111 m m .; specific gravity, ^ 0*8460; refractive index, 1-48 61; specificrotation [a]D = - 12'36.This oil is also no tew orth y, as it c onsists ma inly of /2-phellandrenewhich has.not previously been detected in any turpentine oil.

TURPENTINE FROM PINUS LAMBEKTIANA.An oil obtained from oleo-resin collected d ur ing 1 911 had the followingpro per ties: specific grav ity, 0'86 63 ; ind ex of refraction, 1-4728; specificrotation [A]O = + 10*42. Ano ther sam ple of the oil h ad a specificgravity of 0*8658 and an index of refraction of 1*4727, and gave the fol-lowing results on fractionation :

Temperature(corrected).C155-8-157-3158-6153-9159-3159-7160-3161*3162-5168-4178-8178-8 +

Distillate.Observed.

2-989-3310*7810-3410-709-799*949-547-675-1113-62

Cumulative.Per Cent.2-9812-3123-0933-4344-1353-9263-8673-4081-0786-1899-80

d 5SpecificGravity at15 C.0-9531S620862986328633863386348633862485489011

ND15Index ofRefractionat 15 C.1-46571-46931-46981-47011-47031-47081-47161-47261-47361-47211-4912

The oil contains a-pinene, /?-pinene, a very small amount of phellan-drene (?), a hydrocarbon, prob ably of the aliph atic series, and a sesqui-terpene which is probably aromadendrene.TUEPENTINE FROM PLNUS EDULIS.

The oil had th e cha ract eristi c odou r of thuja leaf oil, due to the pre -sence of a ses qu iterp en e; th e specific grav ity was 0*8680; the index ofrefraction, 1-4707; and the specific rotation, [O]D = + 19-26.The oil contains a-pinene, /3-pinene, and cadinen e, a compo und whichhas not previously been recorded as occurring in turpentine oils.On fractional distillation the following results were obtained :


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26 T H E C H E M I S T E Y O F E S S E N T I A L O I L S

Temperature(corrected).C.155-9-157-4157-6157-9158-4158-9160-0162-4176-5194-9194-9+

Distillate.Observed.Per Cent.5-10 '10-6610-288-9910-5411-04

8-769-723-8720-74

Cumulative.Per Cent.5-1015-7626-0435-0345-5756-61

65-3775-0978-9699-70

6/15Specific( ravity at15 C.0-861786178621861986168611

8609860586169129

ND 15Index ofRefractionat 15 C.1-46771-46831-46871-46891-46891-46931-46961-47131-47231-4837

T U R P E N T I N E FR OM P I N U S J E F F R E Y I .Schorger l states th at the norm al turpe ntine from this tree consists ofabout 95 per cent, of heptane and 5 per cent, of an aldehyde, probablycitronellal. Schimmel &Co.2 have examined this oil and found it to havethe following characters:

Specific gravityOptical rotationEster value ,, (after acetylation)0*70511-396535-28-7

They agree with Schorger that the principal constituent of the oil ishep tane. They do not agree, however, tha t citronellal is prese nt, b uthav e identified decylic ac id ; possibly trace s also of octylic and no ny licaldehydes m ay be prese nt. Linalol and m ethyl-chavicol are also pro -bably present.The " wood turpentine " of Pinus Jeffreyi was found to consist of 90to 95 per cent, of hep tane, with traces of limonen e and citronellal. That,from Pinus monophylla had a specific gravity 0*9702, rotation + 21-15,and refractive index 1*4771. In it were identified a-pinene, /3-pinene, a n dcadin ene. The corresp ond ing oil from Pinus ponderosa had a specificgrav ity 0*8626, ro tat ion - 13*15, an d refractive index1-4727. It containsa-pinene, /3-pinene, and limonene.Russian oil of turpentine is a product, the importance of which hasincreased during the past few years, and appreciable quantities are nowim ported into this cou ntry . Th e oil is obtained princ ipally from Pinussylvestris, but Pinus Ledebourii also contributes to its prod uction . Th ecrud e oleo-resin is, wh ilst still mixed with a large percentag e of im pu rities,distilled over a naked fire without the use of water (essence de t^reben-thine de resine) or the wood is crudely distilled directly (essence de t6r6-benthine de four).The resulting oil is brown ish in colour with a most unpleasa nt odou r,due to the presence of decomposition produ cts , which include phe no ls ,furfural, and benzenoid hydrocarbons.The principal constituents of Eussian turpentine are, according toSehindelmeiser, 3 /2-pinene, sylvestrene, and dipe nten e. A little dextro-a-

lJoiir. Ind. Eng. Chem .6 (1914), 541. *Report,October,1914,45.3ChemikerZeitung,1908 (32), 8.


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C O N I F E R S 27pinene is also pre sen t. Ze linski a nd Alexandroff1 isolated a highlylaevo-rotatory hydrocarbon [OJD = - 70 45', wh ich they believed to belaevo-pinene, but Schindelmeiser2 ha s shown it to be Zaevo-camphenecontaminated with some im pu rity. Acetone and a-terpineol have beenfound in some samples of Eussian turpentine oil.According to Sch katelo w 8the following tree s yield " Eussi an " tur pe n-tine oils, having th e following cha ract ers:

PinusSylvestris Abies(Abies excelsa)Larix Sibirica .PinusCembra,, TauricaAbies Sibirica

Field of Oil.15 to 16 per cent.

13-414-162028

[JD.+ 22 to + 24

- 13-2- 14-3+ 14-04- 75-9- 35-6

Specific Gravity.0-867 at 150-873 150-870 190-865 150-861 190-875 19

The oil of tu rpe ntin e arrivin g on this m arke t from Eu ssia does notcorrespond in ch ara cter wjth an y of th e above oils. Th is is d ue to twofacts; firstly, tha t the oil is a mixtu re derived from m ore than o ne species,and, secondly, that the bulk of the exported oil has been deprived of its" middle runnings " in Eussia, the so purified middle fractions being usedin the country, so that much of the Eussian turpentine as we know it is -a fractionated oil. Th e au th or 4has examined samp les of pur e unfraction-ated Eussian tur pe nti ne supplied to him byProf. Schindelmeiser, andfound them to contain over 60 pe r cent, of oil distilling betw een 155 to160, which fractions are missing in nearly all the commercial oil ex-ported. Two such typical sam ples had the following ch ara cte rs:

Specific gravityOptical rotationBefractive indexAbsorbed by 5 per cent. KOHDistilled below 155155 to 160160 165165 170170 180above 189

1.0-b67+ 750'1-47185 per cent,traces only65 per cent.H 13 7-5 3-5

2.0-865+ 101-47366 per cent,traces only63 per cent.915 7 6 ample No. 1, after remov al of the acid bodies and ta rr y m atter , ga vea rectified turpentine oil having the following characters :

Specific gravity .Opt--*+8ical rotation .Refractive index .Absorbed by KOHDisbils below 155155 to 160160 165165 170170 180above 180

0*8646+ 81-4890nonenone68 per cent.13 10 72 1ChemikerZeitung, 1902 (26), 1224. 2Chem. Zen tralblatt, 1908 (1), 2097.*M oniteur Scwn tifique,1908, iv.,22,i., 217.4Chemist and Druggist,26 October,1912,


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28 T H E C H E M I S T E Y O F E S S E N T I A L O I L SThe se fac t s a r e r ecogn i sed in the tu r pe n t in e m ark e t , an d use r s a r e.con ten t to accep t the f r ac t iona ted o i l a s Eu ss ia n tu rpe n t ine . B u t i t i scons idere d n eces s a ry tha t i t shou ld be in a r eason ab ly good cond i t ion an das w ha t i s kn ow n as of good m er ch an ta bl e qu al i ty . T he di ff iculty of f ix-ing em pi r i ca l s t an da rds un de r these con d i t ion s is obv ious , bu t as the r e -su l t of cons iderab le exp er i en ce in d i sp u te s on sh ipm en t s of th i s o il t heauthor i s able to say that the points to which object ion i s taken are (1 )the p resence of pheno lo id bod ies ( absorbed by caus t i c p o t as h ) ; ( 2 ) t h eprese nce of m uc h o i l bo i ling over 180 wh ich r en de r s th e o il u nr em un er a -t ive to refine , as the se f ract ions are usele ss for m os t p u rp o se s ; (3 ) th epre sen ce of im pu r i t ie s d is t i l l ing below 155. As a resu l t of th i s exp er i -

e n c e , the fo l lowing va lu es m ay be l a id do wn as r ep res en t ing w ha t i s ac -c e p te d on t h e L o n d o n m a r k e t s a s E u s s i a n t u r p e n t i n e of f ai r m e r c h a n t a b l equa l i ty . Th e f igures re la te to four typic al sa m p le s : I n i t i a l b o i l i n g - p o i n t .D i s t i l s b e l o w 1 5 5 155 t o 160 160 165 165 170 170 180, , a b o v e 1 8 0 S p e c i f ic g r a v i t y a t 1 5 R e f r a c t i v e i n d e x a t 2 0 O p t i c a l r o t a t i o nA b s o r b e d b y 5 p e r c e n t . K O H

1.1 5 7 n o n e1 p e r c e n t .4 4 37 1 5 3 0 - 8 6 31-4730+ 4 2 8 'n i l

2 .1 5 6 n o n e1 p e r c e n t .45 , ,3 5 1 6 30 - 8 6 3 51-4726+ 4 30 'n i l

3 .1 5 7 n o n e5 p e r c e n t .4 0 4 2 1 0 3 0 - 8 6 31-4725+ 9 n i l

4 .1 5 8 n o n e1 1 p e r c e n t .18 4 8 19 40 - 8 6 8 41-4748+ 8n i l

A v e r y l a r g e n u m b e r of s a m p l e s , h o w e v e r , h a v e b e e n e v e n m o r ela rge ly dep r ived of the i r mid d le runn ing s , an d con ta in a con s ide rab leam ou nt of hy dro carb on s bo i l ing over 180 , and a l so a co ns iderab lea m o u n t of a c i d b o d ie s , w h i c h a r e a b s o r b e d b y c a u s t i c p o t a s h . S u c hsamples a re qu i t e use les s to the r ec t i f i e r , a s the i r r ed i s t i l l a t ion mus t en-su re the rem ov al of th e acid bodie s a nd a lso of t he bod ies boi l ing ov er180, w i th a r esu l t ing los s wh ich , a s m ent io ned above , caus es the r ec t i f i-c a t i o n t o b e u n r e m u n e r a t i v e .Th e fo l lowing a re typ ica l s a m ple s of th i s k ind w hic h r e pre sen tn u m e r o u s d e li v er ie s o n t h e L o n d o n m a r k e t : 1. 2. 3.148 146 146per cent. 3 per cent. 5-5 per cent.3 5

Initial boiling-point . .Distils below 155155 to 160160 165\165 170J '170 ,, 180above 180Specific gravity at 15 Refractive index at 20Optical rotation .Absorbed by KOH .

F i nn i sh tu rpe n t in e o il c lose ly r esem bles Eus s ia n o i l. Asc han l h a siden t if ied i t i n the fo llowing com po un ds ; d i ace ty l , f u rane , me thy l - fu rane ,m e t h y l - i s o b u t y r a t e , b e n z e n e a n d i t s h o m o l o g u e s , p i n e n e , s y l v e s t r e n e ,^ - l imonene , and d ipe n ten e . H e ha s a l so r ecen t ly i so la t ed a new te rp en efrom thi s oi l, boil ing at 163 to 165, specif ic grav ity 0-8628 at 20, and spe ci-f ic rota t ion + 7 *7 . I t i s a sa tu rat ed bicycl ic terp en e , c losely re la te d to

23

3 54 81 20 - 8 6 31-47628(

345 01 00 - 8 6 6 5

1-4756+ 9 '

224 621-50 - 8 7 81-4780+ 11

4 .1 5 3 1 p e r c e n t .3 36 5 0 10 0-8691-4792+ 1 2 4 5 ' 8 + 9 + 1 1 + 1 2 4 5 '6 p e r c e n t . 8 - 5 p e r c e n t . 7 p e r c e n t . 3 p e r c e n t ,

1 Farm. Notisblad., 1 9 0 7 , 9 3 , and Chem. Zeit. ( 1 9 1 9 ) , 1 , 2 8 4 .


35/555

CONI F E E ^ E 2 9pinene. A terpene alcohol, and a sesquiterpene (cadinene ?) are alsopresent. A somew hat similar product is ma nufactured in No rwa y, as aby-product in cellulose m anufa ctu re. It ha s a specific gravity 0*874and optical rotation + 13. It contains pinene, cadinene, andsylvestrene.1French oil of turpentine is characterised by a high laevo-rotation.It is obtained principally from Pimis Pinoster (Pinus maritima Poir)>(vide supra),and has the following cha racte rs :

Specific gravity at 15 0*863 to 0*875Optical rotation - 20,, -38 Initiial boiling-point 152 155Distillate below 165 80 to 90 per cent.It resembles A merican oil in other respects, the pinene present merelydiffering by co nsisting mo re largely of the laevo-rotatory var iety.Norm al Italian turpe ntine is the product of Pinus piceaand Pinuspinaster. Palazzo2 gives the following values for a typ ical pur e com-mercial sample :

Specific gravity 0-863Optical rotation - 48 15'Refractive index 1*4678at 25Eigh ty per cen t, distilled between 155 an d 165-5". Th e first fraction,,distilling up to 159 had a specific gra vity O8576 at 20, optical rotatio n- 46 54', and refractive index1'4653at 25. The pu re sam ples fromPinus pinaster only had the following characters :Specific gravity at 1 5 , 0 - 8 6 7 0-871Befractive index at2 0 J . 1-4700 1-4707Optical r o t a t i o n . . . - 35 - 35

The high optical rotation is stated to be due to the presence ofl i m o n en e .Greek turpentine oil is a commercial article in the South of Europeand is obtained from the Aleppo pine (Pinus halepensis). It is producedin nearly all th e prov inces of G reece. It is usual either to m ake dee pincisions in the trunks through which the resin quickly flows away, or inthe French m anne r to c ut rathe r shallow notches and place a woodenreceptacle below these, in which the oleo-resin is collected. Pinus hale-pensisis the only tre e in Greece which is used for the produc tion ofturpentine.The crude oleo-resin contains from 20 to 25 per cen t, of oil and 7Oper cent, of resin. The essential oil consists princip ally of dextro-apinene. Gildemeister and K oh ler 3 isolated th is body in a fairly pu recondition, but Tsakalotos and Papaconstantinou 4 have more recentlyseparated it in an ap par ently pu rer condition. The ch ara cters of th ehydrocarbon so separated are as follows :Gildemeister. Tsakalotos.Specific gravity . . 0'8642 at 15 0-8548 at 25Refractive index . . 1-46565 20 1-4633 25Optical rotation . . + 40-23 + 47-7Boiling-point . . . 156 at 760 mm. 155 to 156 at 760 mm,Greek turpentine has the following characters :1Fosse,Ber.Deuts h.pharm. G es.,25(1915),303.2Ann.Chim.Applic. (1917),7, 88.'' Wallach-Festschr'ft,Gattingen,1909,429.4Jour, de Pharm. et deChim.,1916, 4. 97.


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3 0 T H E C H E M I S T E Y O F E S S E N T I A L O I L SSpecific gravity 0'860 to 0-866Optical r o t a t i o n . + 34 + 47Refractive index 1-46701-4740Distillate from 152 to 156 5 to 10 per cent. 156 160 80 85

Th e turp en tine oil from Pinus longifoliahas recen tly been examinedby Simonsen.1 H e found presen t\the following bodies: laevo-a-pinene,/3-pinene, a new terpene for which he proposes the name d-carene, and anew sesquiterpene which he term s longifolene. In the prev ious editionof this work (p. 28) it was stated that 3-sylvestrene was present in com-paratively large amount.It is probable that this is incorrect, but that another terpene has beenmistaken for sylvestrene on account of the fact that by the action ofhydrochloric acid, a molecular rearrangement takes place, with theformation of sylvestrene hydroch loride. This hydroc arbon is tha tisolated by Simonsen and nam ed by him d-carene . It is an oil havingthe following characters :Specific gravity@3 0 . 0-8586Refractive Index@30 1-4690Optical Rotation : + 7-69Boiling-point at 705 m m . 1 6 8 to 169

It yields sylvestrene hydrochloride when treated with hydroge n chloridein ethereal solution. It yields a crystalline nitrosate, decomposing at141-5.It s cons titution is not yet settled. Th e sesq uiterp ene ^-longifoleneboils at 150 to 151 at 36 mm ., or at 254 to 256 at 706 m m . It sspecific g rav ity is 0*9284 at 30, refractive index,1-4950at 30, and opticalrotation + 42'73.It yields a hydroc hloride m elting at 59 to 60, an d having a specificrotation + 7*1. It s hydro brom ide m elts at 69 to 70, and its hydrio -dide at 71.The characters of this oil fall within the following limits :Specific gravity 0*865 to 0-875Optical rotation 0 to + 4Initial boiling-point 165

Two sa mp les on fractionation by E ab ak 2 and by Schimmel &C o.3gave the following results:Rabak. Schimmel.165 to 170 56 per cent., aD = - 2 33 per cent., aD = - 3 30'170 175 20 = + 2 48' 31 ,. = + 0 40175 ,,180 9 ,, = + 6 50' 14 = + 4 32'above 180 . 15 = + 18 12' 22 = + 16 22'

Austrian turpentine oil is derived principally from Pinus laricio. I tscomposition has not been exhaustively studied, but it consists of terpenesan d is similar in compo sition to Fre nc h tu rpen tine oil. It s c hara ctersare as follows :1Jour. Chem. Soc.(1920), 570.2Pharm.Rev.,23(1905),229. sReport, April,1906, 63.


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C O N I F E R S 31Specific gravity .Optical rotationRefractive indexDistillate from 155 to 158 158 160,. 160 165 165 175

0-863 to 0-870-35 -401-46801-472545 to 50 per cent,about 30 165

TURPENTINE FROM AGATHIS EOBUSTA.The oleo-resinous exudation from this Australian tree, known as the" Queensland K au ri, " yields an essential oil, which has been exam ined

FIG. 4.Tree ofAgathis robusta,Queensland.[P.373,Pines ofAustralia.


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32 T H E C H E M I S T E Y O F E S S E N T I A L O I L Sby Baker and Sm ith.1 Th e yield of oil was 11*64 pe r cent, ha vin g the-following characters:Specific gravity at f C 0-8629Kotation aDin 100 mm. tube + 20-2Refractive index at 16 G. C.1*4766Thirty c.c. of the oil were distilled under atmospheric pressure, whennoth ing came over below 155 C .; between 155 and 156 C., 53'3 pe rcent, distilled; and between 156 and 159 C., 33*3 per cent, more cam eover. Th e residue in the flask, 13*3 per cent., wa s also determ ine d.The first fraction had the following characters :Specific gravity at f p C 0'8625

Kotation aD + 14-4Refractive index at 17 C. 1-4755The second fraction had the following characters :Specific gravity at lf 0 C 0 - 8 6 0 3Rotationo u a D + 20*4Refractive index at 17C. . . . . . . . 1-4763The portion remaining in the flask had the following characters :Specific gravity at $ C 0-8610Rotation aD + 38-6Refractive index at 17 C 1-4791Pinene was the only constituent identified.In addition to the above described turpentine oils, the following, al-though not of considerable importance, are of some interest :

Origin.SpanishPinuslialepensis . ) pinaster . . /2AlgerianPinushalepensisMexican3PhilippinePinusinsularis.BurmesePinusKhasyjb. Merkiisii .*JapanesePinusThunbergiiVariousPicea excelsa5" Strasburg Turpentine Oil"AbiesAlba.6Venetian Turpentine OilLarivdecidua .7Canada Balsam OilAbiesbalsamea (and otherspecies) . . . .Oregon Balsam OilPseudotsuga Douglasii

SpecificGravity.

0-8600-860-0-863

0'8690-8630-861

0-863-0-8700-860-0-8610-865-0-8780-862-0-8650-858-0-882

Rotation.

- 9+ 45 to +48

+ 34+ 13 to + 28+ 36+ 32

+ 3 to - 12

- 8 to - 12- 25 to - 38- 30 to - 48

RefractiveIndex.

1-46541-4638-1-4660

1-4700= }

1-47001-4730-1-4765

1-4730

Constituents.

d-pinenelimonene (?)d-a-pinene;-pinened-a-pinenea-pinene, di-pentene,limonenea-pinenea-pinene/-a-pineneZ-a-pinene

280 per cent, distils a t 155 to 156.4Distils chiefly at 165.1ThePinesof Australia,386.396 per cent, distils between 154 and 165-5.5Distils chiefly at 162 to 163.660 per cent, distils from 157 to 161; 20 per cent, from 161 to 164, and 6 per cent,from 164 to 168.7Distils chiefly between 160 and 167.


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C O N I F E E ^ 33O I L O F J U N I P E R .

The plant yielding this oil is Juniperus communis, a native of Greece,and widely distributed over E urop e. It is a small shrub or tree varyingfrom 2 to 6 ft. in height, but in parts of Norway it forms a forest treesome 30 to 40 ft. in height. The Itali an berries, however, are mo stvalued for oil. According to Pe reira , the jun ipe r of th e Bible was aleguminous plant, probably the broom or furze tree. F ra as considersthe Kt'8/)o fuxpa of Dioscorides was our juniper. Th e plant is usu allydioecious, and the scales of the cones, when ripe, become succulent, andcohere to form a kind of b erry (galbulus). The se berries are rich insugar, and by their ferm entation and d istillation th e w ell-known beverage,gin, is obtained, w hich owes its c ha ract eristi c flavour to the oil of juniper.It has been stated that the oil is distilled from the full-grown, but unripe,fruit. Bu t with reference to this po int, Sch immel and Co.1 states that"th is is an error, at least no such oil is distilled on a large scale. It isan antiquated idea, originating with Zeller, tha t u nr ipe fruits rend er alarger yield in oil th an rip e on es. In any case, the oil distilled fromunripe berries in all esse ntial qu alities is inferior to no rm al oil of rip efruits." The following are given by Schim me l as the average yields ofoil from plants grown in certain districts Bavarian . . 1/2 per cent.East PrussianThuringianSwedishItalianPolishHungarian

6751 to 1-598 to l

The oil is distilled on a very small scale in En gla nd , but, acc ordin gto the Perfumery and Essential OilRecord* hitherto it ha s not beenpossible to produce the oil competitively with southern Europe, becauseof the relative cheapness of labour and the vast tracts of land over whichthe trees grow wild. It also m ust be rem embered th at the foreign oil is.produced u nder somew hat different cond itions, and ma y be almost con -sidered a by-pro duct. Th ere is a conside rable dem and on the Continent,for an aqueous extra ct of th e berries, called " Boob ," or " Bob of Juniper,""and the distilled oil is in this case a by-prod uct, the berries being firstcrushed and macerated with water and then distilled with water, and theresidue in the still evaporated to a soft consistence.Much of the oil met with in commerce also is probably not normal incomposition, but is obtained as a by-product in the manufacture of ginand similar spirits.There can be no reason why it should not be possible for our northerndependencies to produce all that is required.The juniper plant is a small shrub 4 to 6 ft. high, or in shelteredwoods growing higher, widely distributed throughout the northern hemi-sphere, in E uro pe from the M editerranean to S candinavia, in A sianorthwards from the Himalaya Mountains, in North America from thesouthern states to Greenland. It requires a certain amou nt of m oisture,with some drainage, and a pp aren tly prefers some lime in the soil. Itoccurs freely on the slopes of the chalk downs near London, and onhealthy, and therefore silicious, soil w he re a little lime occu rs. Onmountains in the Arctic regions a small form of the plant occurs, viz.,

1Report,October, 1898, 30. 2P. and E.O.R.,March, 1915, 63.VOL. I. 3


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34 T H E C H E M IST E Y O F E SSE N T IA L O IL SJuniperus nanaW illd., with rath er longer berries and a pro strate h abit.Especially wh ere ban ds jof lim estone occur, as on some of the S cottishmountains and on the limestone hills in the Lake district, it is a commonplant.The berries take two years to come to maturity, so that there arealways mature and immature berries on the same plant, and the collec-tion by han d, unless the b ranch es are beaten over a tr ay, is, owing tothe sha rp points of the leaves, rath er a prickly m atter. The blackishberries that are imported are apparently all mature, indicating that thegreen imm ature berries are separated. The im m atur e berries, how ever,darken on keeping.W he the r imp orted o il of junipe r is alwa ys distilled from Juniperuscommunis is open to question, since the oil of some red juniper berriesimported from Smyrna, and attributed to Juniperus phoznicea, has beenfound to correspond in all its properties with those of Juniperus com-munis. B ut on exam ination of an oil distilled in Cy prus from the berr iesof Juniperus phanicea at the Imperial Institute, it was shown to differfrom that of Juniperus communis in optical rotation, which w as + 5,whilst that of Juniperus communis distilled from the berr ies is usu ally- 3 to - 15 0.1The yield of oil from imported berries varies from O5 to 1*5 per cent ,the Ita lian averag ing 1 to 1*5 per cent., the Ba va rian 1 to 1*2 per cen t.,the Hung arian O8 to 1 per cent. The berries

The Chemistry of Essential Oils and Artificial Perfumes 1

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