Title

Autoxidation of Terpinolene

Author(s)

Fushizaki, Yasaburo; Saito, Masumi

Citation

Bulletin of University of Osaka Prefecture. Series A, Engineering and natural sciences. 1956, 4, p.145-151

Issue Date

1956-03-30

URL

http://hdl.handle.net/10466/7863

Rights

http://repository.osakafu-u.ac.jp/dspace/

145

Autoxidation of Terpinolene

Yasaburo FusHIzAKi* and Masumi SAITo*

'
(Received January 31, 1956)
The oxidation of terpinolene with rnolecular oxygen at low temperature and its oxidation mechanism have been studied. The autoxidation of terpinolene was carried out under the following conditions: (A) absence of initiator, (B) presence of benzoyl peroxide (BPO), and (C) irradiation of ultra-violet light. Terpinolene hydroperoxide (HPO) was obtained as a primary oxidation product, and from the decomposition and reduction products of HPO, it was found that oxygen attacks terpinolene at the carbon
atom of 3 position in its structure under the conditions of (A) and (B), and of 8 position

'

under (C).

1. Introduction
Terpinolene has a methylene group activated by two double bonds. As in the autoxi-

dation of ethyl linolenatei) which has a 1,4--diene system, it was known that oxygen
attacks the methylenic carbon atom, similar results can be expected in the case of terpinolene autoxidation.

Aithough terpinolene has such an interesting character, there is no data to be available

on the oxidation with molecular oxygen. This may have been due to the fact that terpinolene of satisfactory purity was not readily obtained. Fairly pure terpinolene was obtained

and oxidized with air at a temperature below 500C under the conditions of (A) absence
of initiator, (B) presence of BPO and (C) irradiation of ultra-violet light.

The rate of its formation and the content of HPO under each condition was compared.

From the decomposition and reduction products of HPO, the structure of HPO was determined and the mechanism of autoxidation was discussed.

2. Experiment
Materials:- Terpinolene prepared by dehydration of a-terpineo12) contains other ter-

penes. So the terpinolene used in this research was obtained by fractionation of the
monocyclic terpenes produced from hydration of wood terpentine,3) and had the following
physical constants, b. p. : 63.5-65.00C/10 mm Hg, n2.' : 1.4895-1.4907, db5 : O.8654-O.8703,

m. p. of tetrabromide: 115.5-115.90C, absorption frequency: 4043-i cm.

Benzoylperoxide (BPO) was recrystallized with methanoi from commercial material, and had m.p. of 1040C. Apparatus:- The oxidation apparatus consisted of a cylindrical grass vessel (4cm
diameter, 15cm length) equipped with a condenser, an air in!et tube and a thermometer.
In the case of photo-oxidation by ultra-violet light, a quartz vessel of similar type was

used. The photo source wasaIKW. mercury lamp. The reaction vessel was held in a
* Department of Applied Chemistry, College of Engineering.

146 Y. FusmzAKI and M. SAiTo

constant temperature bath which could be regulated within O.50C.

Procedure:- Reaction (A) was carried out by the use of 100g terpinolene without an initiator. In reakction (B) O.1g of BPO was added to the sample. And in reaction
(C) 60g of terpinolene was charged in a quartz vessel and irradiated from a distance of

10cm. Dried air treated with concentrated H2SO,, NaOH, and CaC12 was inserted into the sample at a rate of 14-16 liters per hour, and then conveyed a water-trap in order to

catch water soluble materials. ,

The temperature of the thermostant was regulated to 100, 200, 300, 400, and 500C in

each experirnent. In the first step of oxidation reaction, terpinolene HPO was formed and

was quantitatively determined by iodometry every 3hours. Each oxidation reaction

requires at least 50 hours, so reaction was not continuous throughout the whole course and

stopped daily, and the reactor kept at a temperature of less than OOC. ,
Table 1. Results of oxidation of terpinol,ene without an initiator. (Reaction A)
Experi-

3. Results

mental

Temperature
10 20 as 40 50 30

Reaction

No.
9 11

(oC)

time
(hr)
374

Maximum Time to maxlmum HPO content HPO content (%) (hr)

35 24 27 23 16
5

(1) Formation of HPO

The relation between HPO content in the terpinolene and'reaction

4* 6* 10 8**

2e5 76 83 244 257

300 150 40 70 180 130

time is summarized in Tablel,2

and 3.

It was observed that the quantity of HPO formed during the oxidation process increases with reac-

* Weight of terpinolene used was 100g. in experiments 9, 11, 10 and 8, and 30 g. in experiments 4
** 3g. of manganese acetate was used as catslyser. Table 2. Results of oxidation of 100g. Qf terpinolene containing O.1g. of BPO. (Reaction B)
Experi-

and 6.

tion time, reaches a maximum value

and then decreases when oxidation

was continued further, as shown in
Fig. 1. This is due to the fact that

mental

Temperature
10 20 30 40 50

Reaction

No.
41

(eC)

time
(hr)

HPO leontent

Maximum (%)
31 25 15 14 13

HPO content

maxlmum
(hr)

Time to

decomposition of HPO predominates

over its formation above a certain concentration at each temperature.

45 47 46 43

115 110 110 90 65

105 105 100 80 48

When BPO was used the HPO value

measured by iodometry contames

quantity of BPO present. Therefore

true HPO content was obtained by

Table 3. Results of oxidation of 60g. of terpinolene irradiated with ultra-violet light. (Reaction C)
Experi-

mental

Tempra-

Reaction

No.
26 25 23

ture
10 20 30 40 50

(oC)

time
(hr)

maxlmum HPO content HPO content

(hr)
19 21

Maximum (%)
20 17
8

Time to

subtraction of BPO content from apparent HPO value. BPO content

was determined by following

method; that is, BPO was decomk
posed in terpinolene in the atmos-

m or

120 loe 90 64 62

115 92 80 58
' 57

phere of nitrogen under the same

tempeatures as in reaction (B), and

BPO undecomposed was measured

-,

Autaxidation of Tet:Pinolene

147

by iodometry every 3hours. By

means Qf this method the influence

(B) tooc .rtK} {odc

-p-'tr-eh

of primary decomposition of BPO 30 was eliminated but of secondary n

ge In reactions (A) and (B) the ". fv 20

frvN' /

/ o/o

decrease with ' the reaction tem- U

maximum values of HPO content ? o

./V /o st//toBt/'/1/s[-J"i"tat

//

perature' increase. This shows aO

that increasing temperature facili = to

tates the decomposition of HPO.

In these reacticms the maximum value of HPO content are nearly

equal at each temperature, so it is

ti/ /./e
O
o/"e

found in the case of air oxidation

O 1co 200 300

Retctlert time (hr)

that BPO can accelerate the oxidation reaction but net increase the

Fig. 1. Formation of HPO.

o (A) looc o (A) sooc e (A) 3ooc v (B) 100C A (B) 500C [] (c) loec [ (c) sooc
manganese acetate

HPO content. When manganese

acetate which is available as an

oxidation cataJyser was used (reaction (A) No. 8) the maximum value of HPO content was

lowered extremely. This also shows that such a catalyser facilitates the decomposition of HPO tather than its formation.
In the photochemical oxidation a different result was obtained: that is, at the reaction

temperature 100-400C the maximum values of HPO content were almost equal, 20%, but at 500C it was 'lowered to 8%. This'is feature of photoxidation and shows that the influences of ultra-violet light are greater than those of temperature on the formation and

decomposition of HPO and that particularly at 100-400C the change of temperature does not infiuence the HPO content. Even in' the case of irradiation of ultra-violet light, HPO can not be further accumulated at these temperatures. '
(2) Identification of products.

After the HPO content reached its maximum value the oxidation reaction was ,stopped. The reaction product was a viscous, yellowish liquid. Terpinolene HPO is so unstable that it decomposes by it$elf and the HPO content decreases when standing at room temperature. HPO could be neither concentrated nor isolated, and therefore the reaction products were used in their crude state. On reduction with a 10% aquous solution of sodium sulfite by agitating and cooling with ice water, the HPO contained there in
became corresponding alcohol.

The oil layer was extracted with ether and washed several times with water. By
fractional distillation in vacuo, thismixture can be separated into 6 fractions as shown in '

Table4 and 5. From these fractions alcohol, ketone and traces of aldehyde were found
but acid was not detected. Alcohol was detected only in reaction (C), by Nesseler's
reagent in the' water in the trap which conveyed the reaction exhaust gases.

148

Y. FusHizAKi and M. SATTo

Table 4.

Components from reaction products in reaction

(A) and (B).
nbO

!t is almost impossibl to
separate these components from

B.P.
(1) (2) (3) (4) (5) (6) (7)

oClmmHg
404715
47-51/5 53-62/5

component ' Terpinolene and isomerized } Monocyclic terpenes

Alcohol rich fraction Mixture containing alcohol Ketone rich fraction Viscous liquid Resinous material

each other by means of even

repeated distilation owing to
the influence of other related

60S8/5
65-11215 90-140/5 Residue

1.4920-1.4927 1.4890-1.4906 1.4955-1.4959 1.5055-1.5080 1.5075-1.5087

and ketone

compoundspresent. Eachfraction shown in Table4 and 5,

therefore, is not pure but con-

1.5166-15183

Table 5. Components from reaction products in

reaction (C).
B.P. (1) (2) (3) (4) (5) (6)

tains other components considerably. The relations between percentages in weight

of each fraction and reaction

oc/mmHg
47-5215 50-77/5

nbO

component
Terpinolene and isomerized monocyclic terpenes
Alcohol rich fraction Fraction not containing alcohol Alcohol rich fraction Mixture containing alcohol

1.4912-1.4988 1.4932-1.4958 1.4946-1.5070

temperature were summerized

in Table6 and 7.

68B815
93-112/5 115-125/5 Residue

In reaction (A) and (B)

the unoxidized terpenes are less

15031-1.5162
1.5089-1.5162

Resinous material

and ketone

and the high molecular weight

compounds formed are greater

in ratio to the height of the

Table 6. Percentages (in weight) of fractions in each . experlment ln reactlon (A) and (B).
reactlon temperature

reaction temperature. But in

reaction (C) the terpenes re-

100C 2ooc 3oec 4ooc sooc

42
11 11

component (1), (2) Terpenes

(3) (4) (5) (6) (7)

maining unoxidized are iess

25
3 8

Alcoholic fraction

25 13
i6 9 9 os

23
11

21 5

and the resinous materials

formed are greater in all cases,

Mixture containing alcohol and ketone Ketonic fraction Viscous liquid Resinous material

2
8

26

13 22 29

17 10
9

12
9

showing no relation between

the weight of each component
and reaction temperature.

30

17 36

Table 7. Percentages (in weight) of fractions in each

experlrnent in reaction (c).
'Sh xxsss!teaction

Alcohols were determined

by the phthalic acid method.`)

temperature

componell;N-Nts-x---xtt-(1) (2) (3) (4) (5) (6)

100C
22
7

2ooc 3ooc 4oec sooc

o 7

Calculation as p-menthadienol

shows that 10--25% of alcohol

is centained in each alcoholic
fraction. It'is very diMcult to

Alcoholic fraction Non alcoholic fraction Alcoholic fraction

Terpenes

25 12
9

8 as

22
7

4 27 13
11 38

8 34
6 3

4 10 36
3

Mixture containing alcohol and ketone

Resinous material

25

35

18 31

10 37

give benzoate derivatives from

the fractions (3), (4) in reac-

tion (A), (B) and (2), (4),

(5) in reaction (C),' owing to the presence of a double bond adjacent to OH group as
known empirically5); or to isolate benzoate derivatives even if they are prepared because

of the presence of terpene hydrocarbons. 3,4,5.Tribromobenzoate could be isolated only

from the fraction (3) in reaction (A).

Autouiddtion of Tet:Pinolene

.149

3, 4, 5-tribromobenzoate 1260-1280C 41.4

'

'- m. p. Analysis

C% H% 3.5
4.0
But

calculated for Ci,Hi,02Br3 -- 41.8

The identificatian of alcohols by the ceric nitrate method6) was not successful.
infra-red absorption spectra of these alcohol fractions show an absorption band of a

OH
a

group at 2.9-3.0pt as seen in With Fig.2. phthalic

anhydride the saturated compound obtained by hydrogenation of fraction (3) in reaction (B) gives monophthalate melting at 1190C which agrees with that of menthol. In reaction (C) infra-red absorption spect-

b' 1

N 'v

.7 v i
,fv'

x 7i , "N N'K if' .

N

IL-

a
6,O
li'"'"'
S,5

rum of the fraction (2) almost agrees with that of

the alcoholic fractions in reaction (A) and (B), but
there exists another band at 6.0pt in that of fraction
c

s.5 S N

3.0 "

"X,.;' x:t'"t

}
k
1

r i
'

t Sl

il

k
iis t t

.v l
t

(4) which disappears when hydrogenated. These

results are also shown in Fig. 2. Moreover the saturated ketone obtained from the fraction (4) in reaction

: ,

IN

tc

.-I

-l

GO 5,5 3 b' 3,Ov

Wave Lengtlt
Fig. 2. Infra-red absorption spectra of alcoholic fractions.

(C), when hydrogenated and oxidized with chromic

acid, gives iodoform by the iodoform reaction.')
Ketonic fractions gave red crystals of 2, 4-dinitro-

a: The fraction (3) in reaction

phenylhydrazone. Those obtained from the ketonic

fractions in reaction (A) and (B) had m.p. of 23002320C and the following results of their analysis agree

(A) and (B). (C).

b: The fraction (2) in reaction c: The fraction (4) in reaction the fraction (4) in reaction

with the calculated value of piperitenone which is

formed by decomposition of terpinolene HPO.

(c). d: The hydrogenated sample of (c).

m. p. Analysis N%
observed valve
piperitenone, calculated for Ci6His04N4

2300-2320C 16.85

- 16.96

From the ketonic fraction in reaction (C) 2,4- dinitrophenylhydrazone melting at 1300-

1320C was obtained, analysis of which indicate that the original ketone has one less
methylene group than piperitenone in its structure, as follows.

m. p. observed value

Analysis N% ,
17.71

1300-1320C 18.11
4. Discussion

calculated for CisH!604N4 r

(1) The reaction mechanism of the uninitiated and BPO initiated autoxidation.
According to the prevailing ideas of high reactivity of a-methylene group and experimental results of non-formatian of acids, the most likely place of attack by oxygen is not

methyl but the 3carbon atom which is flanked by two double bonds on each side. Addition first of an oxygen molecule and then of a hydrogen atom occurs on the radical center

150 Y. FvsHrzAK! and M. SAiTo

Qf free radical (X) (Fig. 3), resulting in HPO (I). Reduction of HPO thus formed with
sodium sulfite should lead to the alcohol (II), while decomposition of HPO during oxida-

tion should produce the ketone (III). If an allylic mesomery takes place between 3 and
1 or 3 and 8 positions as was investigated by Farmeri), then addition of an oxygen mole-

cule and a hydrogen atom leads to HPO (IV) or (VII). Reduction and decomposition of
these HPO, therefore, should give alcohols (V) or (VIII) and ketones (VI) or (IX) respeciili/,',,-`'Bp'o'9.b'9i'fi)OOgtops">,fiili):)/l;i.ls.'IC:ea/"/l,:lkaailielXd:lilrlilfi':,/I,:,i',i,g,'g,'ge.ak//lif:la,i,l2,

tively.

I,'!'

c4;i{li?-gi-k.,Ht&t-.El.il,Hiiigig:11T/ial',o/qh,,Eai?,eg',ic,x-illkh,2"/1,l,lb/ig/leX.llP,C!l,li-'%e,i.i'l'

""---#}ti2ii:l!ikiiir,E"'ii//fdgS'/3/7,(.io,ig,llli/k,l-li,eieglldOiM,ge/1/e/si,"i?d.',./hOG/s

X I (V) elementary analysis of 2,4-dinitrophenyl-

Fig. 3. Reaction scheme mery does not occur in free radical (X)
(2) The reaction mechanism of photochemical autoxidation. Judging from the data of beiling point, refractive index and infra-red absorption spectrum, the fraction (2) contains the same alcohol (II) as in reaction (A) and (B). It
is therefore beyound doubt that HPO (I) is formed, according to the above idea. Fraction (4) is different from these alcohols in boiling point, refractive index and
particularly infra-red absorption spectrum. As seen in Fig. 2 (c), there are different bands

at 5.9pt and 6.0pt, the former being that of C==O group of ketone present together. The

latter seems to be that of conjugation between two double bonds or a double bond and a C=O group. But the fact that the ketone of formula (Iil) did not sh6w this band indicates that band should belong to conjugated double bonds. Of course hydrogenation of
this fraction extinguishes this band as shown in Fig.2 (d). Therefore this alcohol has a conjugated double bonds, and so (V) or (VIII) is considered to be its formula.

Thus the original HPO should be (IV) or (VII), decompositian of which gives ketone of (VI) or (IX) and methanol eliminating the methyl group adjacent to carbonyl group,

considering the evidence of p-cymene- and cumene-HPO. This idea is supported by the
experimental results that analysis of 2, 4-dinitrophenylhydrazone of ketone in fraction (5)

agreed with the calculated value of that Qf ketone (VI) or (IX), and that methanol was

A"toxiddtion of Te2PinQlene 151

found in the water in the trap. Thus HPO, except one with formula (I), has formu!a

(IV) or (VII). .
Saturated ketone obtained by hydrogenation and then oxidation of alcoholic fraction

(4) showed the formation of iodoform by the iodoform reaction. This result shows that
alcohol in fraction (4) has formula (V) rather than (VIII).

It is evident from the above consideration that photochemical autoxidation gives HPO (I) and (IV) as primary products. For the production of HPO (IV), Schenck suggested8),9) that a double bond was activated by u!tra-violet light, the oxygen molecule added to the

carbon atom, and then hydrogen atom at allylic position migrated to the oxygen with
simultaneo' us movement of double bond.

On the other hand Farmer consideredi) that the oxygen molecule and hydrogen atom added to the radical center of radicals formed by mesomery of radical (X). Since the
mesomery of radical (X) was not found in reaction (A) and (B) as discussed in part (1)
of this section, Farmer'stheory is not applicable to this case. Photochemical autoxidation,

therefore, proceeds producing a radical by the activation of a double bond. Formation of HPO (IV) rather than (VII) seems to be due to the fact that the double bond outside the
ring is more unstable.

Acknowledgements
We are indebted to Arakawa Rinsan Kagaku Co. for supplying terpinolene. We also
wish to thank Mr. Y. Chijimatsu, T. Nakao, T. Matsuo for their assistances in this study.

Refere"ces ,
1) 2) 3) 4) 5) 6) 7) 8) 9) E. H. Farmer, D.A. Sutton, and H.P. Koch, J. Chem. Soc., 541 (1943). G.O. Wallach, Ann. 356, 249 (1907);368, 11 (1909). J.N. Borglin, et al. J. Am. Chem. Soc., 72, 4591 (1950). P.J. Elving, Ind. Eng. Chem., Anal. 19, 1006 (1947). E. Funakubo, "Identification of Organic Compounds", Vol. 1, p. 132 (1954). R.L. Shriner, "The Synthetic Identification of Organic Compounds", p. 96 (1948). E. Funakubo, "Identification of Organis Compounds", Vol, 1, p. 342 (1954). G.O. Schenck, Angew. Chem., 64, 12 (1952). G.O. Schenck, Ann., 586, 177 (1953)