R A M A N S P E C T R A OF T E R P E N E S . BY W. ROGIE ANGUS. (From the University College of North Wales, Bangor.)
TH~ period dufing which Raman effect has been available a s a tool for the elucidation of molecular structure has been one in which much useful data have been accumulated. So much so, ir is now impossible for authors of monogTaphs or of bibliographies on the subject to include comprehensive and co-ordinating tables of data and deal with them critically. Consequently the exact position with respect to the usefulness of Raman spectral methods as applied to certain types of chemical substances is frequently uncertain. One group of substances for which a large volume of scattered data has been recorded is the terpenes and, arising from conversations with Professor J. L. Simonsen, the author has endeavoured to collect aU the existing results* and submits them in this paper. The purpose of the paper is to present in tabulated form, the experimental results of workers in this field ; to compare the results of different investigators for the same s u b s t a n c e ; to correlate data on substances considered chemically to be structurally related; to co-ordinate and examine critically the assertions made b y certain authors regarding the constaney of the Raman frequency of certain groups ; to consider whether the claims which have been made in the literature regarding the application of Raman spectral methods to the identification of terpenes and to the analysis of terpene mixtures ate spectroscopicaUy justifiable ; and to give a complete bibliography. Be/ore proeeeding to an examination of the data contained in the tables, ir is well to draw attention to some important facts. For a complete study of any molecule i t i s necessary to know its Raman and infra-red spectra. The more complicated the molecule, the more complex will both spectra be and, accordingly, ir will become increasingly difficult to work out the normal modes of vibration and to ascertain their spectroscopic activity. Every molecule, irrespective of its molecular complexity, should have 3n -- 6 (n ---number of atoms in the moleeule) normal modes of vibration. Whether these ate active in both Raman and infra-red spectra, of in one only, of ate forbidden in both will depend on ah application of spectroscopic selection * The bibliographies provided by Kohlrausch 45 and by Hibben42 have been of most valuable assis~ance in ~his connexion.
529
530
W. Rogie Angus
rules and on the symmetry of the molecule. F o r a full discussion of molecular structure a knowledge of the state of polarisation of the Raman lines and of their intensities (not visually estimated) is necessary. ~oreover, it must be borne in mind that spectroscopic selection rules, valid for the gaseous state, appear to break down when applied to the liquid state. 1 Consequently frequencies forbidden in one spectrum (Raman or infra-red) may appear faintly for the liquid state, although absent in the gaseous state. In many of the papers under review inadequate description of experimental technique is given. The duration of exposure, an important factor, is frequently omitted. Excitation b y unfiltered radiation from a mercury arc is always suspect because of the appearance of faint lines of mercury whieh may mask R a m a n lines of which, as sometimes happens, are mistaken for Raman lines. Important as these considerations are, there is a still more important fact particularly, but not peculiarly, applicable to terpenes. Ir is almost, if not absolutely, impossible to be certain that the substance is peffectly pure. For many terpene groups it is well known that members ate never completely separable, b u t that each member is always more or less contaminated with its isomerides.t This fact seems to llave been overlooked by many of the workers whose results ate under consideration. Yet the significance of it should be apparent. Since this difficulty of obtaining pure material for examination does exist, ir is quite impossible, for many substances, to draw conclusions regarding their structure from their Raman spectra.
Experimental V~lues. The data ate contained in Tables I - V I I I ; the intensities are given (in parenthesis) in the nomenclature of the paper from which the data ate taken since ir is obviously impossible to transform the various units employed into a uniform scheme. Before discussing these data critieally and comprehensively attention wiU be drawn to any particular features of interest in the tables. For comparative purposes the results for isoprene are ineluded in Table I. Table I I is interesting principally for the compa¡ of the data Ÿ limonene ; the agreement between the seven sets of results is good but not complete. The two sets of results given b y Dupont and his eollaborators'", ~3 differ in one important connection, viz., the numerical value of the t For instance, t0oo little attention would appear to have been paid to the wellknown " tautomerism " of the many members of the terpene series eontaining the isopropenyl-isopropyliclene group.
R a m a n Spectra o f Terpeu~s
531
frequeneies betweeu 1600 and 1700 cm. -~ As will be shown later the preeision with which these ffequeneies can be determŸ is of paramount importanee in deteeting the eonstituents of a mixture. Sueh vafiations in the same region are shown also in the data for a-phellandrene and A x-p-menthene. In Table III, whieh eontains the data for monoeyelie terpenie aleohols and esters, there is one point whieh ealls for speeial eomment. An examination of Boniehon's results 4 for a-terpineol, isopulegol, menthol, and their esters reveals the surprising faet that the majority of the lines of the alcohol appear in the identieal position in the esters and with unehanged intensities. I t is extremely doubtful if sueh elose agreement is indeed experimentally realisable, and eerta… ir is not so in the experienee of the present author. Furthermore, the eontention submitted here is fully substantiated b y examining the experimental values recorded for bornyl and isobornyl esters (Table VIII) and for myrtanol and fsomyrtanol and their esters (Table V I I ) ; although there is great similarity, there is not complete identity. Some of the data in Table IV is snbjeet to eritieism similar to that given in the last paragraph. Comparison of the data of Boniehon ~ with those of Dulou lo shows complete agreement in the numerieM values of praetically every displaeement for which these authors each report speetra. At first sight this would appear to arise from the reproduetion in one paper of data eommunieated originally in the other. I-Iowever, this does not seem to be the explanation sinee the two sets of intensities are often eonsiderably different (cf. ear 91 and earvomenthone) and d[splaeements marked " assez nette " in one paper are " raies floues " in the other. The more usual type of agreement expeeted in Raman effeet is exemplified, for instanee, b y comparison of the results of Bonino and Celia s for menthone with those of Dulou39 The derivatives of thujane all gire speetra very rich in lines (Table V). The speetrum of sabinene has been determined by three independent workers and their results are in very satisfaetory agreement. That reeorded b y l~atsuno and ~ a n 54 shows two displacements of 2964 and 2966 cm. -1 having visually estimated intensities of ( 6 ) a n d (4bd) respeetively. These eannot be experimental values because even with a speetrograph of very high resolving power, it would be extremely diffieult to separate two strong lines so close together. ~oreover the faet that one of the pair is broad and diffuse is a further argument in disproving their authentieity. The comment is made beeause of a great tendeney in mueh work on terpenes to elaim an unattainable aeeuraey of measurement. The derivatives of earane in Table VI eall for no speeial eomment exeept to mention here that data for two fraefions, said to eonsist Al9 ~'
532
W. Rogie Angus
predominantly of A3-carene, are reproduced from the paper of Dupont and Joffre. 27 On examining the data in Table VII it is found that by comparing the results obtained for a-pinene b y Dapont, Daure and Allard 2~ with those of Dttpont and Joffre .7 a very puzzling point emerges. Without a single exception, the values recorded b y the latter authors are exactly 5 cm. -a lower than those in the other paper ; even the broad band between 1400 and 1500 cm.-1 is shifted en bloc across the spectrum b y 5 cm.-1 The intensities of the lines are usually identical. Results for fl-pinene ate also contained in the same references and present the same extraordinary shifting of almost the entire speetrum b y 5 cm. -1 Ir is difficult to believe that such results were obtained either fortuitously or experimentally. Table V I I I calls for no special comment.
Discussion. The comments embodied in the preceding section generally indicate ah unfortunate tendency, not confined b y any means to the s t u d y of terpenes, for authors to extend the attainable accuracy and reproducibility of results to a quite impossible degree. There ate also in the tables certain results (e.g., limonene 6~ given to 0.1 cm. -1 Unquestionably, with a ~pectrograph of high resolving power, such aecuracy would be obtainable for a h intense, sharp line but the determination of faint or diffuse lines to this accuracy is, to say the least, a moot point. And, moreover, such high accuracy is not demauded b y the nature of the investigations being reviewed. I t would be impossible to deal in detail with the many points which emerge from ah examination of the results on terpenes. Accordingly only the salient features will be considered.
(a) Comparison of different sets of data on the same substance.--For most substances listed in the tables there exist 11o confirmatory results and it is thus better to await sucia confirmation before accepting existing data unreservedly. Where data can be compared, agreement between the different sets is, on the whole, satisfactory. Certain sets of data are obviously incomplete and ate therefore unsatisfactory for comparison purposes. For the others, apparently complete, there ate often discrepan-cies in the intensities assigned by different authors to corresponding displacements. This m a y or m a y not be serious beeause the assignment of the intensity of ah individual line in a complicated spectrum by visual estimation is more a question of physiology and psychology than of physics. Some of the recorded intensities must be accepted as very arbitrary. When the strongest line is
R a m a n Spectm oŸ Terpelzes
533
assigned a numerical intensity value of, s a y 15, ir is difficult to appreciate what is meant by the intensity of a diffuse line to which the value 1 has been assigned. Also ir is difficult to attach any value to fine intensity distinctions of (say) 4 and 5. Such criticism might be considered pedantic and academic, and the author would subscribe wholeheartedly to this view were ir not for the fact that, as will be shown later, the arbitrarily assigned intensity values have been applied to problems dealing with the detection of the constituents of a terpene inixture.
(b) The spectra of optically active substances.--The identity of the spectra of the dextro and lcevo forros of a substance has been amply demonstrated b y the results for a-pinene 2, 10. 11.44, 57, es, A3_carene,57 sabinene,57 borneol,O, camphor ~ and camphofic acid and campho¡ anhydride. 5s •ot only so b u t a dl-mixture has the same spectrum as the active forro. This is shown b y the results of J a t k a r and Padmanabhan 43 for dipentene and limonene (Table II). The differences which do, in fact, exist ate attributed by these authors to impurities in the dipentene. The nature of these impurities, and the evidence for their presente, will be discussed more conveniently later in this paper. (c) The frequency associated with certain links.--The danger of placing too much reliance on the constancy of the frequency of a link has been stressed by many authors (e.g., Sutherland61). The force fields exerted on the link by the rest of the molecule must play an important part in determining its frequency. I t i s well known, for Ÿ that a system containing double bonds in conjugation gives a spectrum in which the frequency characteristic of each double bond is considerably lowered. And ir is highly probable that other influences may alter the value for a link, although possibly, to a less extent. Many authors have attempted to attribute certain frequencies to particular links and groupings in terpenes and the assignments could be discussed a t a length out of keep~ng with the scope of this paper. The only link which will be considered will be the ethylenic C = C link. This occurs in the majority of the compounds listed in the tables. Ir is not always bound in the same way in the molecule ; sometimes ir is in the ring; sometimes ir is exocyclie ; and sometimes ir is conjngated to a second C = C or to a C = O link. Its ffequency has been the subject of considerable speculation, especially by the Japanese workers, I~ayashi 39-41 and Matsuno and I-Ian. ~ These authors have elaborated a scheme, based on Bourguel's work TM,whereby all substances containing a C =C link may be looked up0n as substituted ethylenes. When only one C = C link occurs its value wiU depend on how many of the four hydrogen atoms, originally attached to it in ethylene, have been replaced by substituents. Any group, other
534
W. Rogie Angus
than COOI-I, 014, C1, and Br, has the same effect on the frequency (1623 cm. -1) of pure ethytene. When the molecule contains two C = C links, substituted differently but not in conjugation, the appropriate values for each type of subsfitution will be found in the spectrum. These values are shown below : - C ~
H
C
1623
cm.-1
\H
R' N
ii 1642 cm. -1
l~'N
q or
t1 I~"~N
C = C" NR"
1653 cm.-t
R'" 1675 cm.- I
R'
1('" 1(66 cm. -1
R"
R ....
When the C = Clink is combined with a cyclohexane or a cyclohexene ring other slight modifications occur H ,\ /H
t%
,,/--\ 1655 cm. -1
1~/~ ~ - \ H\ /~
/
/ - ("- \ \
(7
/
tI~. C
c/--\
1676 cm. -1
q C
/ - - N
\ ....
/
HaC\
H~c\ . ~ S ~c~ c \/ - -.....\
/
16Ÿ cm. -~
\/
1655 cm. -1
1675 cm.-1
/q191
=
N
/
1675 cm.-1
This is applied to the published spectra of certain terpenic compounds, e.g.,
Z~x : s-m-Menthadlene (Sylvestrene)
I .6N //'~ ] |
)- ,,j
Pre dicted 1642,
1675
Found 1639,
1677
]r
Spec/ra o]c Ÿ
535
l
Terpinolene
/~ I
I
1674,
1675
1668,
1681
(19)
1580, 168[
1636
(~0)
1617,
1673
\/ /\
li
I
Pulegol,e
/~
(conjngated)
1714
/\
A 1-p-Menthene
/~N,
1675
(22)
(2:~)
(50)
1691
1681
1681
\/ / ' ,I . I-Iayashi has also applied the scheme to bridged compounds, derivatives of carane, thujane, pinane, and camphane, and he concludes that compounds containing a l : 3 - b r i d g e (thujane and pinane d e r i v a t i v e s ) f a l l into the scheme but that when a l:2-(carane) o r a l:4-(camphane) bridge is present the sctleme no longer holds. Ir will llave been observed that, for the four compounds for which predicted and ascertained values are given the agreement between them is tolerable but not complete. Such a scheme would be of immense value if ir were applicable to "non-bridged " and " 1:3-bridged " compounds. But when ir is tested out for all the data contained in the tables, its applicability is less than has been claimed for ir. A serious drawback to testing ir arises from the influence of conjugation on the value of the C = (3 frequency. Isoprene, CH2 : C (CHe).CK : C~2, has two links in conjugation, one disubstituted, the other monosubsti*uted. Its spectrum contains only one intense displacement of mean value 1638 cm. -1 According to tIle scheme outlined the two values 1642 and 1653 cm. -1, diminished on account of conjugation, should be found. Ir is, of course, possible that this does in fact occur and that the diminution of one type is greater than that of the other with the consequent overlapping of the two characteristic frequencies. On the other hand, ir
I is apparently impossible to incorporate ocimene, C H 2 : C (CI-i3).CI-I~.(91 II Iti CI-I : C (CI-I~) .CI-I : CI-I~, into the sctleme. Ir gives two displacements
W. Rogie Angus
536
of 1634 and 1666 cm. -1 whereas it would be anticipated t h a t the displacement 1653 cm. -1 for the non-conjugated disubstituted link (I) and decreased values (from 1675 and 1642 cm. -1) for the tri-(II) and mono-(III) substituted links would be found. MI the difficulties encountered in a figorous test of ttayashi's scheme cannot be discussed in detail here and consideration of ir will be terminated by reference to bridged compounds. The claim t h a t the 1 : 3-bridge ?tas no influence on the characteristic value f o r a substituted link is not justifiable. To support this claim t t a y a s h i has applied the scheme to
\ a-pinene
fl-pinene
sabinene
Mean Value from Tables
..
1662
1638
1655 cm. -1
Predicted Value
..
1675
1655
1655 cm. -1
Ir is unfortunate that, in advancing the claim, ~ a y a s h i cited only the value of Dupont, Daure and Allard ~o for a-pinene, viz., 1672 cm. -1. This value is much lfigher than t h a t obtained by other investigators (16571667 cm.-1). In addition, verbenol, which contains the same link,
gives 57 1642
cm.-1
Finally, in this connection, A S-carene -
and
A4-carene
each give two displacements of approximately 1640 and 1690
Raman Speclm o[ Terpenes
537
em. -~ (see Table VI), wheŸ according to the scheme, only one should be expected if the material under examination is pure. Quite apart from the laek of numerieal agreement, it is extremely doubtful whether the application of I-Iayashi's seheme would be expected to predict aceurately the (2 = (2 link frequeney of thujane and pinane derivatives. The derivatives Of both can eertainly be looked on as compounds containing a 1 : 3-bridge, but there is a very big differenee in that pinane contains a cyclobutane ring whilst thu]ane eontains a cyclopropane ring and thus resembles the earane derivatives whieh have a 1 : 2-bridge. I t is a wellestablished fact that the molecular refraetivities of bicyclie eompounds containing a cyclopropane ring show optieal exaltation when t h e y have a double bond in conjugation with either of the terminal carbon atoms of the bridge. Bieyclic compounds containing a cyclobutane show this to a much less extent. Ir might, therefore, be expeeted that this should be refleeted in Raman spectra b y a depression of the predicted value of the C ----C link in, for example, sabinene, a-thujene, and A4-carene. Actually A4-carene shows a considerable exaltation of the frequeney and has the same value as A3-earene which does not exhibit this " conjugation " (d) Detection of the constituents of a mixlure.--It is in this connexion that Raman effeet would find its most useful application in the ehemistry of the terpenes, and it is for this reason that some of the claims made must be considered in some detail. The principal workers in this branch have been Dupont and his eollaborators. Most of their evidence pivots round the consideration of the eharaeteristie frequeney of the ethylenie C----(2 link but ir is to some extent dependent also on the values of other frequeneies. All the work from this laboratory is similar in technique. A mixture of terpenes of terpenic eompounds is fraetionated. For the several fractions x~arious physieal constants ate reeorded. The Raman speetrum of eaeh fractioi1 is determined a n d a large number of the observed R a m a n displacements ate assigned to possible eonstituents of the mixture. I t is elaimed that the assignments ate supported by collateral ehemieal evidenee but the present author does not feeI competent to express ah opinion on the validity of this evidenee. I t is proposed, therefore, to consider the spectroscopie evidence on its own merits. Bonichon 4 claims to have found distinctive differenees between the speetra of spatial isomerides, e.g., bornyl and iso-bornyl esters (Table u earvomenthol and menthol, and isopulegol and dihydroearveol (Table III), based on the intensities of lines less than 1600 cm. -1 Already a carear regarding intensities has been expressed in this paper and it is strongly ielt that his elaims eannot be accepted--nor reieeted--until independent
538
W . Rogie A n g u s
confirmation of his experimental data has been obtained. Yet, on examining the data (Table VIII) for the esters of borneol and isoborneol, the assertion of Boniehon that the speetra of these esters are very different is not strongly supported. Consequently, i t i s rather doubtful if Raman speetral methods would be serviceable at present in detecting these isomerides in a mixtnre. Bourguel and Piaux 14 stated in 1931 that they could deteet the presente of isoprene as an impurity in dimethyl-1 9 1-allene, without mentioning the referenee lines of isoprene on which they base their claim. Late~ Gehman and OsterhoP 5 consider that it is possible to deteet not less than 5 per eent. isoprene in trimethylethylene because of the appearanee of a weak C = C displaeement at 1640 cm. -1 This is eonceivable. But it must be remembered t h a t these moleeules ate mueh less eomplex t h a n terpenie molecules and, aeeordingly, have simpler spectra. A large number of papers--too large to examine in detail here--dealing with the deteetion of isomerides in a mixture of terpenes llave appeared. Not only so but Dupont and his collaborators have elaimed to establish the occurrence and eonstitution of some hitherto unknown eomp0unds, as well as to establish the existente of certain (five in number) unidentifiable terpene analogues of isomers. And aetually, from the Raman speetrum of Amerieam wood turpentine, Dupont, Rambaud, and Boniehon 29 give the following composition to the turpentine 9 a-Pinche 76, Limonene 9.8, a-Terpenine 8.2, fl-Pinene 4 (?), Terpinolene 2% and 7-Terpeninein traces. Spectroscopieally these quantities are almost eertainly unjustifiable. I n Table VI the spectra of two fraetions containing &3-carene are given. Fraetion 19 shows the two displaeements 1640 (an 4) and 1690 (n 8) cm. -1 ; fraction 27 gives 1640 (f l) and 1690 (n 8) cm. -1 From this it is reasoned that 1640 cm. -1 must originate from an impurity eontaining ah exoeyclie C = C link and present in greater amount in fraetion 19 than in fraetion 27. This impurity could be fi-pinene but this is ruled out because no other eharacteristie displaeements of fi-pinene ate observed. (Comparison witia the data in Table VII for fl-pinene makes this statement debatable.) It is eoncluded that the impurity must be an isomerie carene with ah exocyelie C - C link,
called fi-carene and presumably representable as
~~/.
The validity
of such a elaim, from a spectroseopie standpoint is very slender.
Raman Spectra of Terpenes
539
The existenee and eonstitution of a new type of terpenes, called pyronenes (C~0H~8), have been postulated by Dupont and-Dulou ~4, ~5 in the pyrolysis products of pinche. The independent ehemieal evidence on the strueture of these hydrocarbons is still slender and requires eonfirmation. In severa1 papers referenee is made to ehemically unidentifiable terpenes. For instanee, Dupont and Gachard z~ report that in the spectra of 54 fraetions of non-polymerised pinche, obtained by the isomerisation of pinche by 50 per eent. sulphuric aeid at approximately 50 o, four unidentifiable hydroearbons X, Y, Z, and T are eneountered. These have been eharaeterised by the frequencies X 1634, Y 1661, Z 1514 and I556, arld T 1702 cm. -1 The intensities of these displacements are never very great and consequently, the accuracy of measurements cannot be very high. One of the products confirmed in certain fractions by chemical and spectroscopic methods, is camphene, which is characterised by the frequency 1658-1663 cm. -1. Is it not possible that Y may be camphene even though tests for camphene were negative ? In the sarne paper m a n y displacements are assigned to a- and ~-terpenines and to terpinolene ; these assignments comprise all the available information regarding the spectra of these compounds and are listed in Table II. Such a procedure of deducing the spectra of compounds by examination of complicated mixtures of uncertain composition is quite unjustifiable. The spectroscopic evidence for the presence of these compounds in mixtures is not acceptable unless comparison with the spectra of the pure substances is possible. The same criticism can be levelled at the results for the dehydration products of commercial terpineol 2s in which the existence of the terpenines, terpinolene, and the unidentifiable compounds T, Z, and IJ (1608-1610 cm. -I) is postulated. (Ir may be significant to point out that a-terpenine is identified by the frequency, 1610-1614 cm.-~). It is not possible to gire a detailed discussion of the other work from Dupont's laboratory. Generally speaking the criticisms given are applicable to the whole of it and particularly to the other papers 52,5~ dealing with the analysis of mixtures. There is a lack of accurate--and verified--data on terpenes and terpene derivatives. Until such data become available the results on the spectroscopic examination of complicated mixtures must be considered as untrustworthy. Even when such data do become available they must be supported by rigorous chemical .and physical criteria of purity. The present position is thus somewhat nebulous. For instance, Jatkar and Padmanabhan 43 conclude that because their spectrum of dipentene contains frequencies, attributed by Dupont and Gachard 2~ to a-terpenine and terpinolene,
540
W. Rogie Angus
these are p r e s e n t a s impurities. I t has already been noted that, for these substances, no reliable spectroscopic data exist. Therefore, although from ehemical standards these ate likely impurities, it m u s t be repeated that the spectroscopic evidente of their presente is quite unacceptable. The dangers inherent in attempting to analyse mixtures of terpenic eompounds are indicated by Snitter's work £ on eamphenilene. By the methods of R a m a n spectra he concluded t h a t the hydrocarbon which he examined was pure camphenilene contaminated by 2-5 per cent. apobornylene, but containing no santene. Chemical evidenee has been adduced by Gratton and Simonsen, 37 by Komppa and N y m a n 4s and by Lipp 51 which proves t h a t this hydrocarbon is essentially apocyclene and santene. Summary.
The available Raman spectral data on terpenic compounds are tabulated and reviewed. It is concluded that the identification of the constituents of a mixture of terpenes by Raman effect methods cannot give trustworthy results until confirmatory results on possible constituents have been obtained. A cknowledgements.
The attthor acknowledges his deep indebtedness to Professor J . L . Simonsen, I*.R.S., for encouragement and for very helpful advice and criticism ; to Professor G. W. Robinson for kindly translating (from Italian) the papers of Bonino and bis collaborators ; and to Mr. W. K. Hill for valuable assistance in the compilation of the tables of data and bibliography. BIBLIOGRAPHY. 1. Angus, Bailey, Hale, Ingold, Leckie, Raisin, Thompson and Wilson 2. Bhag~v~ntam and Venkateswaran 3, Bonichon 4. 5. Bonino and Brª and Cella 6. 7. 8. 9.
10. 11. 12.
and ManzoniAnsidei .. .. ..
J; Chem. Soc., 1936, 966.
Na!ure, 1930, 125, 237. Bull. inst. pin., 1933, p. 249. Ibid., 1934, pp. 1 and 32. Gazz., 1929, 59, 728. Mero. Accad. Ifal., 1931, 2, 5. Nature, 1930, 126, 915. Mero. Accad. Ital., 1932, 3. Zeit. Phys. Chem., 1933, B 22, 169. Mero. Accad. IMl., 1933, 4, 759. Mero. Accad. Bologna, 1935, 9, 2. Ricerca Sci., 1935, 4, 2.
Rama~t Speclra of Ÿ 13.
:Bourguel
1.4.
- -
..
and Piaux
..
15.
..
16.
Dadieu and Kohh'ausch
17.
Daure
..
18.
..
19.
Dulou
20.
Dupont, Allard
..
21 .
. . Levy
22 .
.
.
.
23.
Daure and
and Levy
Compt. rend., 1931, 193, 934. Ibid., 1931, 193, 1333. Bull. Soc. Chito., 1932, 51, 1041. Ber., 1930, 63, 1657. Compl, rend., 1931, 193, 1364. lbid., 1934, 198, 725. Bull. inst. pin., 1934, p. 214. Bull. Soc. Ctdm., 1931, 49, 1 4 0 ] . Bull. inst. pin., 1931, p p . 14 an~l 2 7 l .
and
.
,
..
Ibhl., 1932, p. 35. Ibid., 1932, p p . 2 5 8 a n d 2 8 3 ; Bull. Soc. Chito., 1932,
51, 24.
----
25.
,
and Dulou
..
-
.
-
26.
----and
G achard
27.
----
28.
- - , Levy and Marot
29.
- - , Rambaud Bonichon
30.
- wicz
31.
,
541
.
..
921.
Compt. rend., 1935, 201, 2 1 9 ; BuU. inst. pin., 1935, p. 2 0 3 ; i b i d . , 1936, p. 172. Bull. Soc. Chito., 1936, 3, 1639. Ibid., 1933, 51, 1 5 7 9 ; .Bull. inzt. pin., 1933, p p . 42, 67. 79 a n d 97.
and Joffre
..
BuU. inst. pin., 1932, p. 142. Bull. Soc. Chito., 1933, 53, 393. Bull. inst. p i n , 1935, p. 121.
and
Ibid., 1934, p. 1 6 6 ; 1935, p. 7 3 ; Compt. rend., 1934,
and Zachare-
199, 365.
Bull. inst. pin, 1934, p. 1 0 1 ;
and Dulou
Compt. rend., 1934, 198,
1699. 32.
,
9 9
33.
Euler and Hellstrom
34.
Gehman and Ostevhof
..
35.
..
36.
Godehot and Cauquil ..
37.
Gratton and Simonsen
38.
Gredy
..
39.
ttayashi
..
40.
..
~1.
..
~2.
Hibben
43.
Jatkar bhan
.. and Padmana-
Bull. Soc. Chito., 1935, 2, 533. Zeit. Phys. Chem., 1932, B 15, 342. J. Amer. Chem. Soc., 1935, 57, 1382. Ibid., 1936, 58, 2 1 5 . Compt. rend., 1938, 206, 88. J. Chem. Soc., 1935, 1621. Compt. rend., 1932, 195, 313. Sci. Papers Inst. Phys. Chem. Res., Tokyo, 1934, 23, 274. Ibid., 1934, 25, 31. Ibid., 1935, 27, 99. Chem. Reviews, 1936, 18, 1. Indian J. Physics, 1935, 10, 55.
44.
Kastler
..
45.
Kohlrausch
..
46.
--, Pongratz and Seka
Compt. rend., 1930, 191, 565. Der Smekal-Raman Effekt--Erganzungsband, 1938. iViener Ber., 1937, 146, 213.
..
Monatsh., 1937, 70, 213.
47.
,
W. Rogie Angus
542 48. ~9. 50. 51. 52. 53. 54. 55. 56.
K o m p p a and N)maan .. Lespieau and Bourguel Lipp Marot Mafsuno and Han
Ber., 1936, 69, 334. Compt. rend., 1930, 190, 1504.
..
B u l l . Soc. Chito., 1930, 47/48, 1365.
..
Ber., 1936, 69, 586.
..
B u l l . inst. p i n , 1933, pp. 42 and 61.
..
B u l l . Soc. Chem., J a p a n ; 1935, 10, 220.
..
I b i d . , 1936, l i , 576.
Morris .. Naves. Brus and Allard
P h y s . Rey., 1931, 38, 141. Compt.
rend.,
1935, 200, 1112; B u l l . htst. p i n . ,
1935,
p. 52. 57. 58. 59. 60. (;l. 62. ~i3. 6t. 65. 66.
Nevgi and J a t k a r Singh and Misra Snitter Sviniw~san Sutherland Tabateau Todesco Thosar and Singh Venkateswaran and Bhagavantam Zacharewicz
..
J o u r . I n d i a n I n s t . Sci., 1934, A, 17, 189.
..
Proc. I n d . A c a d . Svi., 1937, A, 6, 90.
..
B u l l . in,st. p i n . , 1933, p. 209.
..
Proc. ITtd. A c a d . Sci., 1935, A, 2, 105.
..
A n n u a l Reporls of lhe Chemical Society, 1 935, p. 57.
..
Bull. i~aul, p i n . , 1933, p. 237.
..
ll N u o v o Cimento, 1932, 9, 138.
..
Proc. I n d . Acad. Sci., 1937, A, 6, 105. I n d i a n J . P h y s i c s , 1932, 7, 585. B u i l . insl. p i n . , 1935. p. 143.
TABLES
899(3)
952(1)
525.4(4 )
778(2)
899.s(s)
950.8(1)
99~. 1(1 )
lO66.6(4)
1292,5(5)
423(2)
5:~o(4)
779(2)
899(3 b)
9,54(4)
994(2)
lo7o(4)
1291(5}
423(0
52~m)
778(I)
90l(mB)
952(f)
992g)
lOTO(m)
129O(aF)
1292(8) 1330(l)
1148(l) 1190(1) 1233(1 )
11o~(1)
1059(2)
1003(1)
805(1)
587(l) 667(2) 735(I)
456(1) 5250 )
3.30(5) 403(I )
289(1)
(35)
286g)
(60)
(16)
Mvrcene
(15)
(Isoprene)
1285.3(1)
1235.3(3)
1069.5(I)
959.1(2)
855.4(1)
752 -8(~)
433(1)
(••
Ocimene
1185(15) 1236(15) 1273(8) 1307(15)
1151(15)
1o25(i 3)
953(f 2) 9o6(f s)
791(f 2) 843ff 2) 871(4)
442(2)
]45(3)
(25)
AlloOeimene
1016(3 d)
8160)
456(0
(8)
Geraniol
1292(4
928(4:
754(0)
551(])
456(2)
3:~6(1)
(8)
Linalool
1096(3 1103(2
998(2'
814(2)
788(2)
456(2)
(s)
1295(f 1) 1323(f 2)
1146(f 1)
11106 2)
(56)
Citronellol
Acyclic Terpenes and their Derivatives.
TABLE I.
1328('
995(1)
166(1) ilO(1)
~9s(2) 15](l)
(S)
a-Citral
1096(2d) 1123(1)
1o35(o)
9fi3(3)
930(I)
836(2 d)
756(2)
351(l)
(8)
1295(f I) 1323(f 1)
1233(I 1)
1077(f 2) 1087(f l ) llOS(f 2)
981(f I)
802(f 1)
(56)
Citronellal
129~(f I)
1084(bf 1)
1028(f 1)
956(bf 1)
851(Ÿ1)
867 ?(f 1)
(56)
Cit ronellic Aeid
o'q
>
9
r
142n(5)
|636(10)
2920(2)
298~(]) 3o10(5)
308~(3)
1426(aFb)
1640(TF)
2908(m) 2930(m)
298ti(m) 3012(F)
3090(aF)
2864(F)
138o(1)
~38s(f)
3004(6)
3083(6)
8092(2)
2913(12) 2965(2)
2981.2(2) 3015.7(5)
2914.3(3)
2852(6)
3055(l)
2983(])
29120)
1666(3)
1675(8)
14~0(1)
1376.6(1) 14o6.t(I)
1634(7)
1454(6)
1424(6)
1381(6)
1636.8(10) 1636(15)
1422-4(2)
1382-3(1)
1344.4(~)
(25:
16r~ ) (lO:
163o ~
1384(2)
2918(5)
2869(3)
1675(5)
1434 I(B 6) 1456) 1453(g) 1593 {10'~
]345(3) 1365•8) ]38.~(1o)
1387(3)
2983(3)
2923(5)
1672(5)
1646(1)
2~8(2)
2965(3)
1681(5)
16400)
1387(2)
29o1(3)
1677(n12)
1660ff :~)
1434~ (Bf 14593 . 10)
1382(n8)
2s9,~(5)
1675(5)
1456(3) H57(5)
1420(1)
1383(3)
1346(f2)
2959(3)
1675(5) 1719(2)
1452(5)
1385(5) 1100(3)
] 342(0) 138201 5)
1677(n 15) 1729([ 6)
1679(n 12)
1653(f l)
1439~ (Bt lff 1439~(Bf10) 14593 1465J
1343(f 1) 1348(f 3) 1382(n 8)
4--
q
W. Rogie Angus
546
TAnL~II Monocydic Terpenes and Some Limonene (7)
a6(D
(22)
304([3)
(23)
(43)*
a-Phellan=lrene (43)
(50)
(60)
(23)
(26)
581(n) 599(f|)
~sl(ft)
258(fl) 289(fl)
3O8(anl)
314(fl)
330(an2) 350(f3)
(22)
a-Terpenine
35061 ) 376(B2)
433(l~) (409)(1) 503(0) 5250) 5£
437(f2) 497(fl ) 5283 553 ) (B3)
4Ÿ 491(f2) 524(an4) 544(an2)
t 423(1b)
429(1)
434(f)
437(B2)
4470b) 487(0) 5690 b)
497(f)
5160)
526(f) 548(f)
569(lb)
643(0)
71t(o)
Ÿ
765(3)
766(a8)
802(2)
432(an2)
810(ah4)
639(n2)
633(2b)
638(f)
662(n1 )
66S(2b)
702(f2)
706('2b)
702(21,)
757(an10)
7~(4)
755(5)
790(an4) 800(ah4)
795(1) 807(1) 8lo0)
788(2b)
63~.7(D
603(B2) 043(Bl)
673.7(._',)
I
713.7(89 766(aF) 801(m)
707(an2)
~60.1(3)
667(fl)
644(B2)
7r 763(fi) 786(an3)
818.6(~)
815(B4) s~4 (fl)
893(1)
894(ah3)
895(f3)
9160)
918(a~:1)
918(f2)
963(0)
931(n)
956(f1)
1010(0)
995(fl) 1Olg(B3)
* Dipentene.
1020(B2)
s72(4) 919(1) 934(1) 948(1) 1013(0)
ss4(2) 912(1)
898(m)
879,2(3)
880(f4)
927(f)
lo18(1)
934(B3)
956((f)
957(B3)
I024(I)
1019(B3)
~9(B3)
Ramau SpeŸ
o/ Terpe~zes
547
Related CloH16 and CloHls Compounds. ,~rpenine ~1 : s-ro. I/k2 : -maorA3 :s 7" Terpinolene Menthadiene Al"m" (Sylvestrene) Menthad.iene Menthene
(26)
(26)
(23)
(36)?
(23)
&l-p-l~Ienthene (Carvomenthene)
&2"m"
Menthene
(36)~
226)
(7)
333(fff)
450(?)
473(?) 492(?)
356(F) 437(ff)
6o7.*(,4) 457(n4)
6437(n4)
42!(fl)
422,5(ff)
3~l(f) 4li(f) 418(|)
447(m)
449(?)
627(an4) 646(fl)
752(fff)
752(an2)
719(B~)
52s(m)
782(f3)
957(F) 1004(f2)
995(f)
766(v)
784 (an3) 799
sol(f)
859(an2)
ss8(f3)
834(m)
91862)
918(f2)
8t0(an3)
82o6|) 873(1)
889(?)
[ 921 ) ' 929j (B|) i 953(f1)
957(F)
lOO~(.~)
Iooo(f)
94s(2) 959(1 )
961(f2) 1019(B1)
Mixture of A2 : s and Az : S-m-Menthudiene. h 20
5~7(f)
764(an8)
791(F)
8o7(.*)
935(f|)
522(fl)
753(4) 766(n6
774(~u3)
879J (B4) 899 J 884(fff)
442
640(aF)
732(fff)
839(?)
432(0
553(fl)
648(f)
820(fff)
41661) 435(fl) 442(fl) 493(anl)
553(F)
603(F)
727(n7)
322(fl)
462,5(ff)
626(n6)
(5)
294(fl)
3st(fff)
525(F) 555(?)
(50)
339(fl )
339(an2)
429('.~)
(23)
|43(~) 29s(2)
364(fl)
(22)
&Z.p. i]~Ienthene
952(f3)
lo13(B1) lo]9(fl)
9os(f) 954(0
962
loo5(f)
:[: Mixture of A 2- and Aa-m-~enthene. F
548
W. Rogie Angus TABLE
Lhnonene (7)
(22)
(23)
(43)*
a-Phellandrene (43)
1054(f2) 1082(anl) 1129(anl)
]080(ah3) lll5(an3) lt55(ar.5)
1074(0) 1096(2b)
(50)
1062(f)
(60)
1051.5(B~)
(22)
(23)
a-Terpinene (26)
1037(B1)
1086(f)
1103(lb)
1115(B2) 1121(f)
1148(lb)
1153(3b)
1158(m)
1205(2) 1227(2)
1198(lt))
12o5(t.f.)
1139(m)
1168(n3)
1215(anl ) 1257(anl) 12991 13~7J 1379(B4) 1434~ 14-71J (BS)
1205(B!)
1207.3(3)
1239(1b)
n77(m;
1172ff~)
1219(a.n3)
t 2:,,s.:(f3)
12470[) 1293(f2) 131I(f2) 1333(f2) 1368 } (B5)
138of
W897(f2) 14351 1455 ~ (B15)
1293(2b)
1279(1b) 1306(lb)
1290(f) 1318(f)
1306,9(2)
1369(3 b)
1268(5b)
1374(m)
1375(21
1429(3) 1444(2)
14:,o(8)
1434~ (F)
1406(au3) 1438"
1440,2(2)
1453J(m)
9(BI)
146](B4)
1 ~67.
1690(B6) 1631 ?(ah3)
1591(an10) 1640(aa8)
1384(fl) 1430 ) - , 1448 f (1~8)
15o8(2)
1641(n8)
1647(au15) 1667(an15)
1691(~r,8)
2834(f2) 2856(~~ )
(3156)(?) * Dipent ene.
1549(3) }6o700) 1637(3) 1658(2)
164:1(}0)
1645(F)
1677(3)
1678(10)
1681(F)
2832(2bb)
2667(0 b) 2722(0b) 2820(lb)
] 610,6(6)
2 ~ 8 t (B4) 2924
2916(4b)
2915(5bb)
2835 ] (aE~ I 2882 [ (aF) 2916 |(F) I 293[J (F)
2964(f2)
2967(4b)
3048(at,2)
3047(4)
2959(1bb) 3009(0) 3044(8) 3083(0b)
2968(m) 2981(f) 30 l 8(f) 30826)
2867(4b)
1673(B1)
2868.5(2) 2922(2)
2971.5(2)
1681 ?(at13)
1615-4(n15)
Raman Spectra o/Terpenes II
549
(Contd.). 91
: 8-?1 91
rerl~inene Terpinolcne Menthadiene i(Sylvestrene) (26)
(26)
(23)
AZ:SorA3 : si
AI-t~B-
Al-p-Menthcne (C~rvomentb.ene)
l~~enthene ~e ni;hene (36) Ÿ
(23)
(36)~:
(7)
(22)
(23)
(50)
]o3s(f) lo63(?)
1064(?)
I 1062(B2)
~oss(3) 1109(?)
UlO(?) i
1152(?)
1228(an10)
1164(?) ll;l(ff)
Ht~(?)
1219(F)
1215(~)
1163(B3)
l171ff) 1219(f)
1243(B2)
1376(B6)
1291(3) 1299"[
1282(F)
1377(f5)
1360(F)
1332(fl) 1371(f2)
1444(TF)
1427~(B8 ) 1440(F) 1459J
1434(f10) 1457(f7)
I to4(B2)
11 lO(f)
115ti(B3)
I|58(m)
1221(f[)
1218(tf) 1247(ff)
I
I
1286(an3) 1321(91
1072(f)
1327 J
(B3)
1378(1) 1450(5)
1434" .(B10) 1471.
] 1252(?} 1.294 (f2) 1310(ah3)
i313(aF)}
1290(m)
1361(ft) 1372(f4) 1429(f10)
1374(aF) 1429(F)
(
1444(f8 ) t4ti4(f4)
[462(m)
16oo6.1) 1639(an9)
1638(n10) 1668 1681 } (lO)
1630(T.F.) 168t(~n8)
16SI(F)
2867(5)
2831(fl) 2874(B3)
2833(m) 2871 (aF)
29o8(m)
2918(5)
2917(f2)
2921(F)
2930(an6)
2934(5) 2952 } (B2) 2964 j"
2968(m)
1677(an8)
1676(an6)
2s~5"1 I(B3)
2836(f4) 2871(f6)
2911
I
I
2943 J (B4) 2964(f3)
29s4(f1)
3048(anl ) 3075(91 3094(anI ) 3126(f3)
1675(FI)
1673(4)
2962(5)
3065(.*) 3119(anl)
3074(1) (3166)(2)
1691(n8)
3015(F)
W. Rogie Angus
550
TABLE
Alcohols and Esters a-Terpinyl Acetate
a-Terpineol (54)
194(1 bbd)
[
(4)
434 (4)
(4)
182(f2)
182(f 1)
260(f 1)
260(f 1)
295(f 2) 323(3 d)
(47)
325(f 1) 375(f 1) 436(f 2)
289(2) 318(1) 368(1 b) 429(3)
31O(f 1)
413(f i) 436(f 2)
-TerpiIso-Pu[egyl Iso-Pulegyl '-neol* Iso-Pulegol Formate Acetate (8)
294(2) 324(1) 373(89 433(89
470(f l)
470(fl)
509(f 3)
502(2)
509(f 2)
545(f 3)
543(3)
545(f 2)
(89d) 612(f 1) 630(f 1)
‰
639(91b)
732(8) 765(4 bd)
756(an 1O)
758(7)
~02(4 bd)
778(f 3) 803(f 3)
756(an 10) 771(f 1)
8o1(l)
8o1(f 1) 81o(f 1)
651(3) 683(3)
339(1 d) ~64(3 d) ~9o(5) }28(2)
832(2) 867(f 2) 898(f 1) 913~ (B51 928 J
659(f 1) 677(f1)
550(2)
642(1)
725(3) 761(5)
867 ] 898~ (B 1) 917(2)
170(f 2)
237(f 1)
237(f 1)
237(f 1)
298(an 6)
292(f 1) 309(f 5)
298(f 1)
399(f 2)
399(f 1)
442(f 1) 458~(B2 ) 468 J
442(f 1) 458(f 1)
399(an 2) 428(an 2)
* Mixture of ~t- and b-terpineols.
528(an 3) 552(an 2) 583(f 1)
922(3)
512(a.,t 3) 528(f2) 542 (fl)
321(f 5)
468(f 1 ) 473(f 1) 528(an 3) 542(f 1)
633(f 1 ) 667(f 1 ) 717(f 1)
656(f3)
775(an 10)
761(an 4) 775(f l)
775(n 8)
819(f 1 )
794(f 3) 819((f 2)
819(f 2)
845(f l )
845(f 1)
891(f 3)
891 (f 4)
913(f 3)
891(f 3) 913(f 1)
925 [ (BI) 939
925(1) 939(1)
939(f 2)
913} (B2) 944
(4)
170(f 2)
468(an 2) 5~2(2)
(4)
170(f 2)
458(an 2)
455(89d)
495(89d) 518(3) 546(89
(4)
Raman Speclra of Terpenes
551
III.
of Monocyclic Terpenes. Dihydrocarveol
(4)
Carvoment,ho]
(4)
17o(f 2) 2221(B1) 243/ 287l 310 ~(B2)
286(f l )
Menthol
M'enthyl Formate
(4)
(4)
464(f 1) 502(f 2)
704 [ (B 1) 732 j 773(an 5)
s27(f t)
893(f4) 920(fl)
496(f 2) 512(f2)
752(an10) 771(an 6) 783(f 1) 792(fl) s3o~ (B 1) 864 J s75(Ÿ
(s)
230(,~)
220(0)
182(B 3) 193(?)
182( f l)
260(f 1)
241(f 2) 26o(f 1)
26o(f ~)
291(f 2)
289(f 5)
291(an 3)
293(3)
316(f 2)
316(an 3)
318(3)
409(f2) 427(f 2)
409(f 5)
387(f 1) -109 (f 2)
466(f 3)
466(f 2)
503(f 4)
506(f 3) 529(f 2)
449 (f 2)
OSl(f 1)
549(f 1)
600(f l )
598(f l)
253(4)
(409)(3) (424)(0)
465(2)
503(f 2)
£
538(f 3)
544(4 d)
598(f I)
596(2)
649(f 3)
651(3)
305(2) 391(1)
461(3)
£ 55S(3) 6O3(0)
665(7)
(717)?(89
771(ah 10)
755(an10) 771(f l)
771(an 10)
793(f 1) 806(f 4)
793(an 8) 6o6(an 6)
Ÿ 1) 806(f 3)
809(4)
846(f 4)
842(f 1)
846(f 1)
846(2)
875(an 4)
875(5)
875(f 3)
1 : 8-Cineol
04)
(4)
]82(n)
317(f 2)
445(f 1)
hIenthvl Acetate "
768(5) 776(6)
908(f 2)
sss(f 3) 908(f 3)
90S(f l)
(905)(2)
922(f 4)
922 (f 3)
922(f 2)
(924)(1) 930(l)
8~5(~) 87o(:)
933(3)
552
W. Rogie Angus TABLE
a-Terpinyl Aceta, te
a-Terpi p_eol (54)
(4)
(47)
(4)
951(5) 962(1 d) (996)(2) 1027(? b)
1021(f 4)
1o51(2) 1073(6) 1096(})
1060(f 2) 108!(f 4)
1131(8 bd)
ll17(f 2) I163(B 5)
1250(5 d)
1229(f 2) 1251(f 3)
1301 1312(6bbd) 1315 j (B5) 1327(f 2)
1452
1468(4)
1467
1682(8)
10783 I
m81(f3)
(3 sb) 1i17(f2)
1~45J
1244(2 b) 1295(4)
1362 ) (B 4) 1366(4) 1382 j
1428(6) 1449(6)
1432 } (B 8)
1681(n 8)
1021(f 3) I053(f 2)
I
1163(6 d)
1371(6 d)
1019(2)
14a8(8 b)
1673(5)
1148 } (B 3) 1158 1184(f I) 1229(f 1) 1249(f 3) 1301(f 1) 1315 (f 3) 1327(f 1) 1360 } (B4) 1382 1432 J. (B15 1452
f~-Terpi- /so-Pulegol neot* (8)
(4)
Iso-Pulegyl /£ Formate (4)
967(f2) 967(f ] ) 992(f i) 9921 }(B3) lOO6J lOO6(f 1) m23(2) 1029(f 3) 1029(f 1)
lo44(Ÿ3)
1053(an 5)
lO52(f 4)
1o85(f ~)
1085(f 4)
1119 1129• (B6)
Acef.af-e (4)
967(fl) 992(f 2) lO06(f 1)
1048 (f 3) Ja85(f 2)
1136(f 4) 1138(f 5) 1170 (B5) 1170(f 5)
11.70(Bf 6) 1186(f 3) 1217(f I) 1235(an4)
1217(f i) 1235(em 4)
121Ÿ i)
1279 (B2) 1295J 1310(f 2)
1310(f 1)
1299(f 1) 1310(fl)
1351(f 8)
1351(f4)
1403(f 4) 1433 } (B4) 1453 j 1459(an 12)
1403(Ÿ3)
1403(an 3)
I453(f 5) 1459(n 10)
1453 ; 1459(n 10)
1645(an 12)
1645(n 15)
1645(n 10)
11861
1360(f 2)
1384(f2)
1435(f 5)
135t(Ÿ3) 1360(Ÿ
1384(~2)
14331(B8)
1681(n 10) 1715(f 3)
2832(2 d) 2849(6 b) 287 9(6bbdl
2844(3 b) 2875(3 b) 2917(4 b)
2932(6) 2961(3) 2970(3 b)
3o2o(~)
* Mixture of g- and b-terpienols.
I739 ?(f 1)
1740(f 3)
/r III
Si@c/ra o~ Terpelzes
555
(Contd.)
Dihydroearveol Carvoment.hol 5[enthol (4)
952(f 1)) 971(f 1) 987(f 1)
(4)
958(an 7)
(4)
956"~ (B4) 980 J
5Ient.hvl Forma'te (~)
956(f'1) 980(f 4)
~{emhyl Acetate (4)
956(f 2) 980(f 4)
(5~)
1ooo(~4)
tOlO(f 3)
1039(an 4) 1063(f 4)
1046(an 8) 1079(f 3)
1041(ah 5) 1057(f 2) 1079(f 3) 1099(f 3)
1000 1 lOl4 " ( B 2 ) t0~2(4) 1041(ah S) (1o62)(~.) 1057(f 2) 10991079} (B4) 1081(6 bd)
tHo ~(B ]) 1152(f4) 1149J
1!48(fl)
1148(f 3)
ll50(f 5)
1178(f2)
11si(f s)
1181(f S)
ll8t(an 8)
1150(6 I)bd) 1163(6 bbd) 118~(6 d)
1261(f 3)
1245(an 3) 1270(f 2)
1245(an 5) 1270(f4)
1245(Pm5) 1270(f 3)
1242(5) 1271(4)
1310(f 1) 1327(f 1)
1310(f 21 1327(f 3) 1350(an 4) 1370i (B4) 1379[
1310(f 1) 1327(f l) 13.50(f3) 1373(f 3) 1379(f 3)
1347(3)
135o 1
1.370 ~(B2) 1379J 1433(f 5) 1459(f 5)
14341470} (BI3)
138l(3<1)
1440l (B 12) 1440 1 (BS) 144o l (B 8) 1467 J
1467 J
1467
J
(8)
(954) (3) 975(3)
1002(f 1) 1044(f 1) 1057(fl)
1 :8-Cineo!
1033(2) 1098(0) 1121(2)
1166(6) 1.230(1) 1280(2)
1363(2) t~09(O) I452(5).
1462(6 ',t)
14Sa(l)
1645(an10) 1.679(f 1) 1725(f 3)
1739(f 3)
1737(2 el) 28t8(664) 2870(6 bbd) 2930(4 d)
2925(5)
2966((; d)
2o71(.5)
62,q(f3)
)40(U ~75(3)
638(fl)
802(f2)
898(fi)
7oG(3)
809C)
893(1)
683(f3) 702(f3)
$02(f2)
S98(f3) ~13(f2)
685(f4) 702(f4)
574(f2)
i75(2)
523(f2) 531(fl)
57~(fl )
523(fl) 531(fl)
:s8(2)
43S(f2) 462(f2) 482(f2)
43~(fl) 462(fl) 482(fl)
175(f2)
(19)
4o3(f2)
25(3)
(8)
403(fl)
(4)
Carvone
9o4(fl)
859(f2)
839(fl)
808(~2)
696(f2) 714(f2)
639(f3) 679(f2)
538(fl 560(fl)
494(f 1) 507(f3)
462(fl)
36o(f3) 381(fl)
32o(~] )
(19)
375(2
7400
644(2) 679(1)
569(2)
194(3)
~5(1)
(8)
891(f2)
768(f2) 787(f2) 827(f2)
732(f2)
707(f2)
615(f2)
585ff2)
553(f2)
494(Ÿ
~25(fl ) r
392(fi)
~84(fI)
~22(fl) ~53(fl)
(19)
/ Carvotan- Carve- I T)ihydroacetone none | earvone
874(1)
790(89
646(5)
597(0)
543(I)
~95(0)
t:40(0) ~61(o)
393(0) tll(O)
~55(2)
(8)
9o9(fD
875(Ÿ
867(f2)
756(f2)
650(f2)
532(f8)
482(f3)
421(f3) 440([4)
35o(f2) 383(f2)
(19)
Pulegone
849(f4) 866(f4)
790(f2) 808(f])
732(f7)
849(:f4) 865(f4)
790(f2) 8os(fl)
732(Ÿ
603(fl) 616(~2) 657(f5)
557(fl )
557(fi)
6o3(f2) 616(ft) 657(f5)
528(f2)
491(f2)
423(f2)
528(fi)
491(f2)
423(f2)
31O(fl) 329(fl)
310(fl) 329(fl)
(19)
274(f2)
(4)
Carvomenthono
274ff2)
Monocyclic Terpene Kelones.
TABL]~ I r .
913(~)
848(2)
746(3
~77(1:
320(3:
~63(2)
~o3(2)
;83(3)
(8)
(,B-Ionone)
s75(f3) 898(f3)
839(f3)
742(fl) 748(f4)
677(f4)
618(f2)
464(f3)
399(f3)
378(fl)
793(2)
5s50)
482(1) 495( 1 )
435(l)
338(1)
.211(1)
(19) [ (33)
285(f3)
Menthone
r/1
C~
r >
72
r
1438(4:
1448(f5)
1378(4: 1371(f5)
1262(f4)
3c8~(3)
2923(3 2978(3
2877(21
1646(an8: 164~(51 1646(f10) 1680(an7) 1673(51 1680(f10)
1448(f3)
1371(f1 )
1262(f!)
1~58(f))
1158(n)
1254(?)
UlO(f3)
m62(~) 1062(f4)
1062(f4)
nlo(Ÿ
1000(f2)
moo(f2)
1~~~(2)
1223(3)
t106(3)
961(1)
2961(3: 2961(3' 3oas(1'
2856(21
1632(5) 1646(f]o) 16S0(f10) 1673(51
1461(f7)
1426(f6)
1371(f3)
1292(f2)
1267(fl)
1224(f1)
llS6(fl)
1138(fl) 1148(fl)
ms8(n) lI05(fl)
I055(fi)
1Ola(f1) 1029(fl)
957(fl) 995(f4) lO14(f4) 1027(f4)
ioo2(f2)
922(f2) 95o(f2)
1304(fl) 1338(f1)
1274(f1)
1251(fl)
1226(f5)
1636 J
1580 t (f14)
1462 J
2917(4: 2951(4:
2878(51
1673(3) I 1681(f11)
1617(5)
1450(41
1433 l (f9)
1360 ~ (f9) 1379(3) 1374J
1347(0)
~215(2)
120Ÿ
1135(2) u3465)
1078(3) 1073(f4) 1092(f5~
lO41(2)
938(1)
1178(f4) 1202(f4)
] 178(f4) 1202(fr
1361(f3)
1317(f7)
1263(f5)
1714(f13)
1714(f].3)
1429(f3) 1429(tl) 1443 ~ (B16) 14433 ~(B36) 1471 J 1471J
1361(f7)
1317(f6)
1263(f5),
1221(f4)
1150(f4)
11~(f4)
1221(f4)
1101(f2) 1t27(f12)
1060(f2)
1060(f2) 11o1(f2) 1127(f12)
1039(f2)
1002(f5) 1019(f5)
932(f2) 960(f10)
1039(f2)
1002(f5) 1019(f5)
932(f2) 960(Ÿ
1226(f2)
1186(f3) 1205(f2)
1150(f3)
1077(f3) 1092(f3) 1121(f3)
1040(f3)
]382(fl) 1409(fl) 1~2o(fl)
1364ff2)
1426(2)
1239(4)
1140(4)
981(3b) 1003(3b)
2957(5',
2874(51
1714(3: 1710(f14)
2975(1) 3o54(1)
2878(4) 2898(3) 2923(4)
1658(~) 1674(5)
1448(1 ) 1463(4~ 1469(an15) 14560) 1588(5b) 1609(5b)
1345(2)
1273(f4) 1290(fl) 1311(f2) 1337(fl)
1247(.~) 1248(f3)
lO51(1)
lO17(1)
956(f3) 977(f3) 99o(f3)
r
c.J1
u3
q~
556
W. Rogie Angus TABI.,~ V.
Thujane
a-Thujene
(6)
(57)
Thujane and its Derivatives. Sabinene
(6)
(54) (120)(3bd) (169)(2bd) (214)(1)
312(2)
443(2) 479(0) 493(1) 559(2)
669(3) 693(1)
(299)(1) (335)(1) (372)(1)
497(1) 553(1) (621)(1)
3o8(u 373(2)
732(3) S07(3) 843(1)
953(4)
947(1) 979(1)
(265)(1) 317(2)
269(2) 313(3)
370(2) 448(2)
503(2) 573(0)
491(ld) 509(3) 566(2) 634((U
503(2) 570(1)
645(3)
655(5)
641(3)
781(1) SOS(2)
785(5) 808(4d)
789(2) S15(2)
863(3)
866(4bd) 882(2d) 915(6d) 930(1) 954(6bb) 989(3)
869(3)
963(3) 1038(2)
11o3(89 1123(1)
~io3(1) 1123(3)
(8)
441(3)
915(2)
lO15(2) lO41(o)
(57)
448(2)
670(1)
768(5) 8o8(o) 838(i) 867(1)
306(3) 333(1) 362(3d) (373)(~)
~-Thujone
1155(0)
lO31(5) 1067(4) 1t09(6bd)
434(~) 496(89
57o(f6) 325(f9)
720(1) 758(,4)
712(f7) 751(f15) 82o(f12)
832(1) 877(3)
963(3)
950(3) 973(1)
1036(3) 11m(2) 1133(5) 1209(3)
1168(2) 12100)
1291(0) 1305(0) 1318(2) 1383(2)
(1274)0)
127o(o)
1270(4bd)
1276(1)
1262(1)
1382(1)
1308(0) 1385(0) 1421(3)
1311(3)
1320(1)
1453(5)
1445(3)
1448(4)
1663(89
1642(3)
1656(5)
1308(4bb) 1379(3d) 1415(8) 1438(4d) 1447(5d) 1468(4d) 1656(10bd)
2863(5)
2875(2) 2910(3)
2878(4)
2923(4) (2950)(?2) 2964(5)
2963(4) 2980(3) 3050(2)
(3139)(2)
2918(4)
2998(2) 3043(3) 3076(3) 3152(1)
2913(2)
2940(2) 2964(6) 2966(4bd) 3070(4b)
396(fl) 416(f8) 459(Ÿ 474(f3)
867(f12)
921(2)
1145(4d) 1170(3d) 1197(6) 11214(ld)
2830(4)
256(f8) 3o6(rlO) 338(f7) 362(f8)
574(2) 628(2)
1183(2) 1218(1)
12J20)
(19)
1425(3)
1456(3) 1653(5) 2875(3) 2923(3)
147o(4) 1688(2) 1750(3) 2875(3) 2940(.}) 2966(3)
2990(3) 3040(1)
3067(4)
942(f15) 971(f12) 1014(f15) 1039(f12) lO65(f15) 1085(f13) 1123(f12) 1133(f6) 1153(f5) 1174(f5) 1213(f5) 1240(f5) 1259(f5) 1312(f5) 1384(f7) 1413(f8) 1446 1471(f13) 1637(f4) 1682(f4) 1747(f12)
Rarna;~ SŸ
557
o f Terpeues
EABLn VI. Carane and its Derivatives. A3-Carene
q
C~rano (20) (20)
(27) Fraction 19 (27) Fraotion 27
350(f2) 432(f21 467(fl ) 507(f2) 573(f2) 677(an4)
356(f2) 427(f3)
353(2) 424(2)
517(f4) 568(f3) 677(an4)
513(11 573(2) 68:),(2)
722(n61 761(an2)
719(3) 761(2) 825(2) 94O(l)
424(B4)
355(f2) 432(f31
52761) 568([l) 682(an4)
517(f4) 573(f3) 682(an4)
727(an2)
727(n6) 766(an3) 796(anl) 825(an4)
20(an3)
722(n6) 761(an3) 791(~nl) 820(an4)
947(n61
947(n6)
942(t~6)
ll05(fl)
l ]0O(fl)
1111(3)
1120(B2) 1.181(o) 1234(fl)
(57)
(57)
311(1) 415(11 4850) 517(2) 670(2) 704(2) 758(3) 831(2) 862(3) 9o80) 958(3) 9880) lO67(21 n41(2)
1163(f2)
I 158(f21
1158(f2 )
1162(21
1229(B1 )
1224(f2)
1224(fl)
]231.(21
1216(11 12580) 1304(21 1333(1) 1397(21 142o(11
1209(f2)
1313(~n4)
1308(B2)
1308(an4)
131l(1)
1383(B21
i383(n6)
1378(an41
1378(an6)
1377(2)
]434}147l(B10)
1430 [ (B10) 1460 ]1568(f2) 1645(f1 )
t425 t 1457; (B8)
1.438(4)
1640(an4)
1442 ) 1449; (B10) 1563(B2) ]640(fl)
1695(n8)
1690(n8)
1690(n8)
1684(3)
1~410)
2834(2) 2876(3) 2918(3) 3008(2)
1448(5) 1554(2) 1639(1) 1670(31
2g76(3) 2918(41 3005(3)
217(an2)
(27) (54)
864(tn7)
957(B4)
048(2)
752(f5)
822(2) 844(5)
956(2)
951
962(B5)
957(B5)
953(3bd)
9300)
835(an5)
774(4)
934(~)
83o(n5)
771(f3)
667(6)
9o8(1)
813 833
776(f3)
667(tn7)
62o(3)
885(1) 905(3)
823(89 848(3)
774(2)
672(tn7)
618(n3)
623(n3)
623(4)
669(5)
568(n4)
573(n4)
568(1) 564(4)
(465)(2) (488)(8)
472(B2)
477(bf2)
388(3bd)
306(2d) (333)(0)
261(3d)
472(f2)
386(an2)
273(an4) 304(ab2)
(426)(2)
39163)
278(an4) 3O962)
465(4) 464(~)
213(89
423(~)
389(89
3o9(1) 335(89
260(2)
644
222(B2)
(20)
(208)(2bd)
08)
2o5(~)
123(2)
(6)
134(3bd)
(.5)
/-'~~t~91 a n a ~ts 1 . ) e r w a t , ves.
134(2)
(l!)
a-Pinene
V I l (~1).
42761)
366(fl)
(20)
858(3)
814(2)
764(2)
660(4)
4780)
401(0)
8o8(o)
(6)
Pinane
TABLE
(57)
(65)
937(B3)
879(an3)
879(n5)
942(f7)
845(an3)
771(anl)
722(an1)
643(an5)
471(fl)
(27)
850(n5)
778(f2)
648(tn5)
480(n2)
391(fl)
(20)
~-Pinene r
~(2bblr225
949(2b)
918 931(2b)
872(3b)
814(2) 848(2b)
761(2)
712(2b)
639((4s)
552(3s)
4ssj
462 1
385(lbb)
296(2bb) 327(2bb)
03)
(3121)(1)
2924(4)
2873(4)
]453(5)
1298(1)
117o(])
lO88(2)
1038(2)
(B4
14~ J
i
1439]
(B8)
1351(I1)
1304(B2)
1229 J
I
1167 1
1096(an4)
1029(B5)
1174(89
117o(89 1185(}) 12o8(89
2931(2d) 2953(1) 2987(2) 3o26(1)
2874(Id)
2836(l)
1661(3)
I437(?) I448(?) 1457(?) 1476(?)
1376(89
1334(89
13o~(~)
1269(I)
2923(5) 2987(3) 3034(3) 3110(3) 3157(?)
3038 3O50
2863(2)
1656(3)
1449(5)
1378(89
1328(89
1268(89
2918 2925 2921
2848
1549
143O
1264
1218(D
1127(89
1129(])
1222(~)
1124
]o86(89
1659
1377
1309 1330 1339
1269
1223
1166 1184 1205
1047 1070 1085
1081
1o45(~)
1030
1001 1018'
1049(1) 1069(0) 1o87(1)
lO18(o)
(B5)
1672(tn8)
143o] I }(~1o) I 149oj
1383(an4)
1332(an3)
1299(an3)
1271(B3)
I
1234J
I
1177l
1134(an4)
1091(~n4)
1048(an4)
(BL10
1667(an)
I 14853
1425] I
1377(an4)
1327(an3)
1294(an3)
1266(B3)
1229(B5)
1129(an4)
1086(an4)
1043(an4)
2951(3bd) 2988(5d) 303l(4bd)
2874(4bd) 2912 } (5b) 2925 f (bd)
2833(4d)
1660(6)
1468(2)
1433(5d) 1444(3bd)
1374(33)
1308(2) 1328(3bd)
1264(4bd)
1223(3bd)
1163(4) 1183(3bd)
1125(2)
lO85(3)
1042(3d)
998(0) 1015(1d)
2993(3) 3031(3)
2883(2) 2918(5)
1658(4)
145o(4)
1381
133o(2)
1269(2)
1222(2)
1173(2)
I128(2)
1087(2)
1045(2)
2948(3b) 2989(4) 3o29(3b)
2876(4b) 2918(6b)
2833(2)
1661(4s)
1436(4d)
1375(0d)
1,~ 1332(1)
1270(0)
1224(0b)
1175(0b)
1131(o)
lO87(1)
1042(1)
994(0)
1086(fl)
1298(2b)
1254(3)
ns4(5b) 1194(2b) 1214(5b)
1126(5b)
lO96(3)
1045(2b)
1641(ta10)
3074(4)
2987(2b)
2933(2b)
2869(lb)
1636(an8) 1638(5s)
1411(2b) 1425] 1432(2b) 1430 l I I (BLS) i- (B8 I I 149o j 1485J
1378(an4)
1318(~nl)
1214(i3) 1224(f4) 1251(an2) 1257(anl)
1134(an3) 1129(fl)
1091(fl)
1048(an3) 1043(fl)
1019(2b)
r
%
930 ~ (B6) 962 J
884(an3) 906(an3)
s2]((n4) 845(nS)
782789}(B4)
684(an5)
656(an4)
626 J B3
c,oo [
499(~n3)
464(an3)
(31)
1V[yrtenol
946(lbd) 973(2d)
(925)(3d)
843(2d)
(799)(1)
777(3)
730(2)
(6s9)(89
651(1)
614(2)
517(2)
(470)(1)
402(2)
(313)(2)
(204)(3)
141(4)
(54)
Verbenol
(f5)
938 } 95s; (B4)
906(f2)
857(an3) 877(f3)
792(an3) 802(an3) 821(anl)
666 J
653 ]
535(f2) 549(fl)
368(32) 379(f2)
(.30)
Myr$anol
938 [ (B4) 958)
914(f2)
78890 so4 l (B3) 821 ~(an2) 841 862 J (f4)
666(fl)
530(f2) 55061)
387(an2)
311(31)
(30)
939(n) 957(Ÿ
859(an4)
861(n10)
937(f4) 961(B3)
821(f2)
646(an4) 661(f3) 678
(30)
819(n5)
796 } (89
771
663(an5) 676(an3)
355(f2)
(30)
Myrt~nyl I vu-l~lyrtanol /~o-M~yrtanyl ~xeetate Aeet~te
933(n3) 945(n3) 963(n6)
885(n3) 906(n3)
777(n3)
695(n4)
631(n4)
441(n5) 460(n3)
411(.5)
374(n3) 389(n2)
268(n5)
168175} (f3)
118102} (f5)
(31)
.~yr~enal
955(f3)
916(f3) 921(n3)
s63(fT) 874(f3)
824(f3)
753(n4) 784(n3)
652(n10)
60 9(f2)
472(32) 477(f3) 5o7(fl) 546(32) 569(f2)
432(f3)
388(f2)
353(f2)
263(fl)
lSO(fl)
(19)
Nopinono
967(n10)
912(f2)
889(f2)
802(f2) 823(39) 846(tn8)
7so(32)
694(33)
593(n7) 634(3(3)
570(f2)
444(n4) 462(f3)
416(n5)
376(f4) 391(f2)
272(35)
237J
170(f6) 191 t (]33
(197 (31)
945(f3) 978(n5)
893(n3) 907(n3)
746(n2) 758(n2)
623(n12)
960(fl)
930(Ÿ
s12(f2) s36ff2) 856(f3) s73(f3)
698(f6)
657(f3)
544(f4) 562(fl) 5so(fD 601(fl) 627(35)
396(fl)
371(fD
351(fi)
286([1)
211(fl)
l~(ft)
(19)
(B2)
957 [ 960 ) (BS)
901(n7) 919(fl)
s2o(fl) 842(anl) 857(anl)
783(f3)
695(fl)
544(an2)
424(fl)
356(fl) 3S8(fl)
267(fl)
233(fl)
202(fl)
142 161
(66)
>
O
O
r C~
(/~
PinoMyrtenilidene C~mphono Aeetone
/"'/
550(n10) 570(n5)
350(n4)
294(f3)
25l(f3)
117 134
Verbenone
(1037)(lbd)
(lOO7)(~)
1046(n6)
992(an4)
1671
1655 } (fs)
1469(f5)
1434(an12) 1451(an10)
L~ ) 1330(an3)
2972(3)
2908(3bd)
2860(3)
1657(5)
1593(o)
1446(5d)
1376(3) (1395)(1d)
(1338)(1)
(1312)(~)
1446(an8) 1460(an8)
1100(ah3) 1120 1129} (B4) 1153l .... p J!50(5bbd) 1141 / 1169 J (B3) 1167 f t~" # 1184(an5) (ilS5)(3b) 1196 [ 1201(anS) 1213 J (B3) 1216(3) 1234(f3) 12250~n5) 1258(3) 1263(I3) 1264(n6) 1287(f3)
1085(n6) I 1o92(3d)
1063(an4)
1025(an4)
1747(an3)
1444(an5) 1460(an5)
1293(f2) 1315(B2)
1266(an2)
1481J
(B8)
1746(anl)
1483 J
14451 (B10 1444 t
1238(B1)
1190(an3)
1159(an4)
1157(Ÿ 1182
1085(an3)
1046J (B3)
1024]
1084(an4)
lO64 j
~(mo)
1008(f3) 1021 ]
1191 l (m) ll91 } (B3) 1213 ~ (m~2) 1211(f2) 1236(an2) 1233(f4)
1149 { 62) 1169I
1109(an3)
1047(an4)
997(an3)
1677(f25)
1616(an25)
1713(f6)
1670 [ 1694 j (tnl8)
1613 ) 1628 ~ (tnl0:
1562(f2)
1520(fl)
1472(f3)
145063)
1418(n15) 1445(f5) 1459] 1490 J~(BS)
1418(n15)
1416(i7)
1386(f3)
1332(f2)
1300(f5)
12~7(Ÿ
1170(tn12) 1185(f2) 1204(f2) 1219(f3)
1128(tn8)
1047(I3) 1057(f3) 1085(tn8)
]ooo(m)
1362([1 ) 1385(f3)
1314(f3)
1286(f3)
1229 ) 1258 ) (B4)
1198(f2)
tiso(f~)
114[i(f6)
103263) 1o56(f3) 1o78(f3)
995(f3)
1338(f2) 1360(f1) 1382(fl)
1299(n3)
1217(n3)
1172(n8)
1126(n6)
1083(n6)
1042(n3)
1301(i3)
1183(f2) 1203(f2)
1053(P2) 1087(fl) ll00(fll 1133(f2) 1154(13)
1028(Ÿ
1679(f15)
1619(anl0)
1457(f3)
1439(n4)
1379(n8)
1340(n3)
1713(f5)
]49lJ
1444 t (B5)
1412(n4)
133~~(f3)
1224(f2) 1242(n5) 1259(f2) 1273"~ (B3) 1267(fl) 1293 J
1131(n3)
I092(n8)
1037(f3)
996(fl )
1655 t
167o f (B20)
1577 ) (B25) 1620
1421(n20)
1368(f5)
t
1216 ~ (B175) 1281(fl) 1296(f3) 1318(fl)
124s
11831170} (B20) 1203(fl) 1219(an8)
1131(.I0)
1044 } 1056 (B2) 1083(ar~5)
993 ) 1007 J (B15)
562
W. Rogie Angus TABL~ V I I I .
Bornyl Camphane Camphene Borneol Formate (20)
(20)
(64)
(4)
I~o-Bornyl Bornyl Formate Aeeta.te (4)
(4)
i.r (4)
Derivatives of
Acetate
Bornyl Propionate
(54)
(4)
Iso.Borny Propionat (4)
170(fl) 223(f1) 236(f2) 258(f2) 279(fl) 306(fl) 337 }
237(B3) 287(an3)
237(f3) 266
3?;
389(f4) 437(f2)
391(f2)
434(fl)
942(0)
966~4)
976(1)
1053(B3)
1077(0)
589(f2)
573(fl) 593(an6)
578(f3)
1188(0) 1223(0)
627(n8) 655(n8)
729(f3} 763(f2) 822(f5) 840(i2)
913(an4) 937 [ (B6) 961 973 (B4) 990 / too7 } (]33) 1031 j" 1048(B) 1083(an6)
345(1)
760(f1) 832(f2) 857(an4) 875(f])
64t(an10) 654(an10)
747(f2) 781(f2) 824(f2} 835(f2)
375(B1) 416387} (B1)
586(~)
5~~(fl) 59s(f5)
624(an10)
621(5)
655(f3)
655(3)
655(an10)
747(2d) 803(ld)
749(90 786(f2) 823(f3) 84l(f3) 875(f4) 899(f3)
73262) 798(fl)
859(4)
855(f3) 87063) 898(f3)
897(2)
987(2) 1022(3)
1045(f2) 1083(an3)
1077(1)
1114(f3) 1134(f2)
lllO(f?)
1104(4) 1131(2)
1170 1180 1207}( TM (B8) 1192(B5) 1230(f7) 1223 1230(f4) 1243 (B4) 1257(f4) 1260 1252(f3)
242(fl) 258(f2)
330(fl) 340
518(f2) 527(f2)
921(f3) 934(f2) 942(f 1) 957(f3) 981(f2) 1019(an3}
1112(f3) 1134 } 1148 (B3) II69(B3)
243[(B2)
262(f2)
526(3)
888(f3) 906(f3) 921(f3) 937. (B5) 947 (B5) 962 971 982 l (B1) 987(f2) 1004(I2) 1014J 1023(a,n4) 10M(f3) 1049(fl) 1047(f3) 1085(an5) 1083(an8) 913(f2)
223
387(fl)
4~7(f2)
586(f3) 6oo(f5)
1147(B3)
1210(Bl)
387(2b)
535(an3)
1114(f4)
1115(B3)
392(fl)
514(fl) 527(fl)
881(,4)
932(an7)
315(89
530(an3)
65o(4a) 655(n10)
889(an6)
310(f2) 340(fl)
526(f2)
672(n6)
820(fl)
402
237(f2) 234(1) ~~09}(B2) 2600)
465(fl )
501(an5)
737(0) 7~(o)
272(f3) 352(fl) 361(fl)
467(fl)
643(n6)
243(f3)
942(3)
117o(f5) 1223(f5) 1238(B2) 1258
1164(s)
i1246(3) i i
~36(f2)
628(f5) 655{f4) 734(fl)
845 (B3 871 893(f3)
918(an4) 915(an2 938(i5) 957(I4) 952 l (B2 973 [ (B4) 976 ) 988 ) 988 1007(fl) 1024 1024(f3) 1050 j (B3) 1082(n8) 1085(f4) 1104(fl)
1113(f3) 1148(f3) 1158 12o4(]38) 1~30(f8) 1254(f4)
1116(f2)
1134(f1) 1158
1249(f)
Raman Spec/ra of Terpenes
563
Camphane and Fenchane. Bornyi Butyrate (4)
lso-Bornyl Camphenilone Butyrate (4)
170(f 1) 211 ]f(BI ) 243 J
(19)
205(f5)
272(fl)
287
371(f3) 391(fl)
464(f2)
425(f2) 453(f2)
507(f2)
490(fl)
523(f2)
v~)4(n)
573(fl) 585(f3) 652(~n6)
575(fl) 624(f3) 652(f2)
592(fi) 650(tn18) 705(f2)
Camphor (12)
(19)
Fenchone (43)
(64)
139(I)
217(4)
301(2) 360(0b) 394(25)
392(0) 414(0) 476(89
612(fl) 649(5) 704(f2)
652(f8) 709(f2)
645(8)
834(fl) 864(f2) 873(fl) 893 (B1) 923 947(f2) 1000(ti)
1026 [ (B4) 1050 I 1081(an4)
1021(f2) 1048(fl) 1084(f2)
llll(f2) ]134 ) (B1) 1148 )
lll.0(fl)
1191)(B3) 1206 ) 1221 . 12321" (B3) 1252(f2)
1152(fl)
86o(1~4)
913(f6) 936(f10) 957(f8)
910(89 931(1) 950(1)
997(f4) 1010(Ÿ 1033(f5)
1034(2d)
859(f3)
1155 t (B4)
1229(f6)
30064) 33O(fl)
293(3b)
371(2)
371(f3)
364(2)
436(2) 458(2)
424(f3) 454(f3)
521(2)
513(f2) 528(f2) 561(fl)
509(0b)
606(5)
601(n10)
594(2)
651(n10) 663(n10)
658(2)
703(2b)
724(2)
695(fl) 716(f3)
708(0)
777(89
776(fl) 827(f5)
771(1) 819(0)
852(3)
854(1s)
889(n6)
850(0) 881(4)
923(f5)
927(4)
955(f5)
943(2)
995(f2) 1013(1) 1017(f2)
988(2) 1012(1)
1076(1) 1072(f2)
1066(2)
837(4) 889(2)
914(2) 954(f3)
947(3)
981(fl)
982(0) lO17(o)
953(1S)
1053(fl) 1090(1)
952(5)
1094(ld)
1088(Ÿ
li6t0d)
l 1.63(fl )
1194(89
1200(f2) 1.188(1)
1193(f])
1218(89
1222(f2)
1219(fl)
1244(1)
1245(f2)
1104(f6) 1132(f6) 1170 1183(f5)
301(3)
668(5}
816(f2) 875(f2)
260(3)
650(4s)
747(f2) $24(fl) 835(f2) 864(fl) 881 )(B2) 9O2 f 917(f3) 939 (B4) 959) 981(Ÿ
260(f3)
546(1) 595(0)
1147(o)
1238(1)
1169(2)
1243(0)
(43)
202(3b)
500(0) 556(fl)
(19)
221(f2)
276(3)
254(2b)
269(0)
553(89 566(89
(8)
418(2) 445(2)
ll10(f6)
1103(3b)
U55(f3)
1150(1)
1243(3) 1241(f3) 1258(f2)
1241(1)
564
W. Rogie Angus TABLE u
Camphane (20)
Camphene Borneol (20)
(~4)
1298(89
Bornyl Format.e (4)
1281(f4) 1306(f5) 1334(f2) 1377 ) 1395 ) (B5)
1388(fl) 1439 ] 1494 J
1430~(B8 )
(B4)
1467J 1672(an10)
1442(2b) 1438 ) (us) 1474(2b) 1463 j 148s(fs)
1725(Ÿ 2738(0b) 2S73(1) 2922(2) 2948(4b) 2981(2)
i.~o-Bornyl Formate (1)
1276(f2) 1293(o,n3) 1315(f3) 1367 ) 1392 f (B4)
1436(f8) 1464(f8) 1491(f3) 1725ff3)
Borny! Acetate
lso-BornylAcetate
(4)
(4)
1276(f2)
1278(fl) 1296(fl)
|304(an4) 1329(f]) 1360(fl)
1373(f2)
1323(fl) 1357(f1)
04)
1323(2b) 1376(3b)
Bornyl Propior~ate
/•o-Bornyl Propionat,e
(4)
(4)
1284(f3)
1274(f2)
1308(an5) !334(f2)
1304 ] 1332 1 (B1)
13~i9(?)
1360 t (B2
1295(?)
1386(?) 1406(fl)
1382(f2)
1437 } (Bl5) 1460 1483(f2)
]437(f6) 1462(f5) ]480(f2)
1440(4bd 1473(5)
1438 1 (B4) 1466 (B 6) 1467 ] 1492(?)
1~39(i3)
1739(f2)
1735(3)
1739(3)
1409J
2874(2) ;932 l (8B? :968J
1430 ]
1739(fl)
Raman Spec/ra of Terpenes
565
(Contd.) Bornyl Butyrate
I.~o-Bornyl Buty~ate
(4)
(4)
1270(fl ) 1301(f3)
Camphevilone
(19)
1299(f4)
f'a,mph,~r
(12)
(19)
(43)
Fenchooc
((,',4)
(S)
(19)
12~5(1 )
1267(~) 1297(89
1273(fl) 1293(f2)
129!(0)
1322(~)
1323(f2)
1319(0)
1329(fl)
13;38(1)
1373 ] ~-(Bl) 140~ J
lm4(i)
1315(f3) 1338(f2) 13S5(f2)
1418(2)
1-117(f3) 1412(l) 1443(f4) 1440([) 1.172(f3)
1437 (BI0) 1460 J
1439} (B10) 1469 j1492(f4)
1446(289 1476(2d)
1739(f2)
1745(f tO)
1734(189 1747(f6) 1738(5) 2868(1~) 2931(2d) 2970(2d)
(43)
2872(2b)
2946(5bb)
1423(0)
131o(o) 1334(0) 1582(tl b)
1415(fl)
1455(4) 1436 } (B8) 1478 j
1450(5)
1731(4) 1745(f8)
1736(3 i
2838(:3) 2925(5)
287.t(3)
2s7o(5) 2923(1 )
2968(6b
2961(5)
29~2(I)
