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Патент USA US2136000

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2,130,000
‘Patented Nov. 8, 1938
S. PATENT
_ UNITED‘ STATE 2,136,000
OFFICE
TERPENE ALCOHOL ESTERS or DIBASIC
_ 'ACIDS AND METHOD OF PRODUCING
Joseph N. Borgliu, Wilmington, DeL, assignor to
Hercules Powder Company, Wilmington, Del., a
corporation of Delaware
1
,
No Drawing. Application December 18, 1934,
Serial No. 758,033
9 Claims. (01. 260-99)
This invention relates to terpene esters of di
basic acids and methodfor their production.
'Heretoiore it has been known to esterify
terpene alcohols and to subsequently purify the
*5 esters by distillationunder reduced pressure, or
by crystallization from alcohol (see United States
Patent No. 1,800,862, Humphrey). Such pro
cedure has not proved satisfactory in that the
products are dark colored and hence undesirable
for many'uses. ~
'
'l Now, in accordance with this invention there
is provided a method for the production of esters
of terpene alcohols which is e?icientand eco
nomical and which is productive directly of a
terpene ester product which is non-crystalline
and of 'a- light color, novel characteristics differ
entiating it from the prior art and vwhich adapt
for example, by re?uxing the pine oil, or pine oil
out, with, for example, alcoholic potash, and the
pine oil, or pine oil out may be, freed from
anethol, after-the refluxing, by decanting, water
Washing and fractionating at a temperature such ‘5
that the anethol’ and high boiling ethers will
remain in the residue.
In proceeding in accordance with this inven- 1
tion, pine oil containing terpene alcohols may be
used, though it will be preferable to use a pine ‘10
oil out rich in terpene alcohols, say, for example,
a pine oil out boiling within the range 200° C.
to 220° 0., though the particular boiling range of
the cut will not be material.
The pine oil, or pine oil out, will be ?rst treated 15
for the removal of oxidation products and such
it to wide use‘ in the commercial arts, for which
similar esters were not heretofore adaptable.
treatment may; for example, involve steam dis
tilling the pine oil, or pine oil out, from caustic
soda, by dry distilling from caustic, or by any
other effective procedure.
.20
' In accordance with this invention, terpene al-,
The pine oil, or pine oil out, after removal of
'cohols, pine oil‘containing terpene alcohols, or a oxidation products, will be esteri?ed with use
pine oil out ‘rich in terpene alcohols, are sub
of any suitable polybasic acid or anhydride, as,
jected to treatment for the removal of oxidation for example, phthalic acid or anhydride, maleic
products and the terpene alcohols then esteri?ed acid or anhydride, iumaric acid, sebacic acid, etc. :25
25 under conditions which will avoid oxidation, as
The esteri?cation will be carried out in any
by exclusion of air through carrying out the re
usual manner, using, if desired, any suitable es
action in an inert atmosphere. Inthe esteriiica
teri?cation catalyst. However, essentially the
tion the use of toluene, or an equivalent, to aid esteri?cation will be» carried out with avoidance
in the removal of water of reaction will desirably of oxidation and such may be accomplished by 130
30 be used; On completion of the esteri?cation
effecting the esteri?cation in an inert atmos
the product will desirably be distilled from the phere, as, for example, in an atmosphere of
reaction mass and the distillation will desirably hydrogen, nitrogen, carbon dioxide, or other inert
be carried out with avoidance of oxidation, as by
effecting the distillation in an inert atmosphere. gas.
‘Where it is desirable to remove ethers, such 35
35 The product will be non-crystalline and of a light as anethol and methyl chavicol, from the pine oil,
color.
.
i
or pine oil out, as has been indicated, such is
20
' More‘ speci?cally, in accordance with this in
vention‘ pine oil, or a pine oil out rich in terpene
‘alcohols, may be subjected to treatment for the
removal of tertiary terpene alcohols before ester
i?cation. The tertiary terpene alcohols may be
removed from the pine oil, or pine o-il'cut, by
effecting their dehydration, or splitting into ter
pene hydrocarbons and water, prior to treatment
45 of the pine oil, or pine oil out, for the removal
of oxidation products, by heating the pine oil, or
pine oil'cut, with a dehydrating agent, such as
fuller’s earth, iodine, sodium acid sulphate, etc.
Again, if it is desirable to avoid the presence of
50 others, such as anethol and methyl chavicol, in
the product, the pine oil, or pine oil out, may be
subjected‘to treatment to isomerize the methyl
chavicol to anethol and fractionated, leaving the
anethol in the residue. The isomerization of
55 methyl chavicol to anethol
may be accomplished, .
readily accomplished, for example, by isomeriz
ing the methyl chavicol, for example, by re?uxing
the vpine oil, or pine oil out, with alcoholic potash, 40
decanting, water-washing and fractionating the
pine oil, or cut,- from the high boiling ethers, be
fore treatment for the removal of oxidation prod.‘
ucts.
Where removal of the tertiary alcohols from 45
pine oil, or pine oil cut, is desired, such, as has
been indicated, can be accomplished by effecting
dehydration of the tertiary alcohols by, for ex
‘ample, heating the pine oil, or pine .oil out, with
fuller’s earth, iodine, sodium acid sulphate‘, etc., -‘50
prior to treatment of the pine oil, or pine oil out,
for removal of oxidation products.
7
In effecting dehydration of the tertiary alco
holds in the pine oil, or pine oil out, a tempera
ture within the range about 100° C‘. to about 55
2
2,136,000
200° C. may. be used and in eifecting the ester
i?cation a temperature within the range about
125° C. to about 250° C. will be found satisfactory.
Generally speaking, in carrying out the method in
accordance with this invention, temperatures in
of H+ (rosin, standard 7;” cube) and an acid
number of 52.
The product obtained by the above procedure
may be distilled under reduced pressure to ob
tain a 390% yield of ester which will have a color $1
excess of about 180° C. will be avoided in order
grade WW+ (rosin, standard 7A," g.) and an
to avoid c'arbonization, which will have a discol
oring ‘effect upon the ultimate product. The 'acidnumber of 20.
In the procedure described above the 3% ter
esteri?cation will desirably be carried out with
10 distillation over of oils and water of reaction in ’ tiary alcohols obtained from the original pine oil
order to avoid discoloration of the product and fcu't will be largely dehydrated during the esteri
sult from such cause may be avoided by e?ecting
The inert and unreacted materials such as h'y
15 drocarbons, excess pine oil alcohols, etc. on com
dehydration of the tertiary alcohols.
It will be understood that where in the claims
appended hereto the term “pine oil” is used, it
is intended that such term includes as equivalents
pletion of the esteri?cation will desirably be dis
tilled from the reaction mass in an inert at
mosphere.
.
.
pine oil as such and also pine oil cuts more or less
It will be understood that the method in ac
rich inosecondary terpene alcohols.
20 cordance with this invention, while more partic
What I claim and desire to protect by Letters 20
ularly, adaptable for the treatment of terpene
alcohols, and more especially of secondary ter
Patent is:
oil out rich in terpene alcohols, is adaptable for
It
in the reaction mass.
Will be appreciated that the product, where the
method is applied to the treatment of pine oil,
2. The method of producing a dicarboxylic acid
ester of a terpene alcohol which includes ester
ifying a terpene alcohol in an inert atmosphere.
. .or a pine oil out, will comprise a mixture of ter
.pene alcohol esters, since pine oil and pine oil
.
30 cuts richin terpene alcohols will contain a plu
an inert atmosphere.
esteri?cation of terpene alcohols as present in
pine oil, or in a pine oil cut, the tertiary alco~
hols will be dehydrated‘ rather than esteri?ed,
when the tertiary terpene alcohols 'are not de
will be present in the product.
As more speci?cally illustrative of the practical
‘ester of a terpene alcohol which includes remov~
adaptation of the method invaccordance with this '
ing oxidation products from pine oil and reacting
invention for the production of products in ac
cordance therewith, for example, 11,000 parts of a
the pin'eioil with av dicarboxylic acid to form an
‘while, avoiding oxidation of the pine oil.
pine oil out boiling Within the range 195° C. to
4.5
‘230° Grand, containing, for example, 54% sec
ondary alcohols and 3% tertiary alcohols, is steam
distilledv from caustic soda. To the dry distillate
is then added 250 parts of phthalic anhydride and
the reagents heated for about 80 hours at a tem
perature of about 180°C. , the reaction mass being
55
7 -
4. The method of producing a dicarboxylic acid
ester of a terpene alcohol which includes ester
ifying a terpene alcohol in an inert atmosphere
and distilling the resultant ester from, the reac
tion mass in an inert atmosphere.
5. The method of producing a dicarboxylic acid
hydrated by treatment of the pine oil, or a pine
oilcut, prior to ‘esteri?cation, the esters thereof
40
3. The method of producing a dicarboxylic acid
ester of a secondary terpene alcohol ‘which in 30
cludes esterifying a secondary terpene alcohol in
rality of terpene alcohols, as, for example, borneol
and fenchyl alcohol. Generally speaking, in the
35
v
1. The method vof producing a dicarboxylic acid
ester 'of a terpene alcohol which includes ester
ifying a terpene alcohol while avoiding oxidation
pene alcohols as present in pine oil, or in a pine
25 the treatment of terpene alcohols as such.
ester , of a terpene alcohol contained therein
,
6. The method of producing a dicarboxylic acid
ester of a terpene alcohol which includes remov
ing oxidation products from pine oil and reacting
the pine oil with a dicarboxylic acid to form an
‘ester of a terpene alcohol contained therein in
an inert atmosphere.
blanketed with carbon dioxide to prevent oxida
tion. Desirably, toluene will be added in small
quantities, from time to time to assist in the re
'7. The method of producing a dicarboxylic acid .~
,ester of a secondary terpene alcohol which in
moval of water of reaction.
pine oil and reacting the pine oil with a dicar
The water of ‘re
action will be distilled on togetherwith oils, which
will distill off atthe temperature used. The oils
will vdesirably not be returned to the reaction
mass, since they will become partially oxidized
and will e?ectdiscoloration of the product.
In
60 proceeding, any suitable form of apparatus may
be used and where the apparatus used is so de
signed as to exclude the possibility of entry of
air, the oils distilled oir may be returned to the
reaction mass.
'
‘
'
,
On completion of esteri?cation, the product will
be vsteam distilled in an inert atmosphere,'as car
bon dioxide, to remove hydrocarbons and excess
.terpene alcohols, from the product, which re
mains as a pale colored, amorphous residue. By
70 the procedure outlined aproduct amounting to
718 parts, or a yield of 97%, will be obtained. The
product will be amorphous, will have a colorgrade
10
?cation and will. cause some discoloration of the
ultimate product. Such discoloration as may re—
desirably an agent, as toluene, or the like, will be
‘used to aid in the removal of water of reaction.
cludes dehydrating tertiary terpene alcohols in
pine oil, removing oxidation products from the
boxylic acid to form an ester of a secondary ter- . ;
pene alcohol contained therein.
8. Thefmethod of producing a dicarboxylic acid
ester of a terpene alcohol which includes dis—
tilling pine oil from alkali to remove oxidation
products therefrom and reacting the distilled pine
oil with a dicarboxylic acid to form an ester of
a terpene alcohol contained therein While avoid
ing oxidation of the pine oil.
,
W 9. The method of producing a dicarboxylic acid
ester of a terpene alcohol which includes steam /
distilling pine oil from an'alkaline solutionv to re
move-oxidation products therefrom and reacting a
terpene alcohol in ‘the distilled pine oil with a
dicarboxylic acid to form an ester of a terpene
alcohol contained therein while avoiding oxida
tion of the pine oil.
JOSEPH N. BORGL'IN.
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