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Патент USA US2406106

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Patented Aug. 20, 1946
2,406,106
UNITED'STATES PATENT orrics
2,406,106.
TERPENE DERIVATIVES
Alfred L. Rummelsburg, Wilmington, Del., assign
or to Hercules Powder Company, Wilmington,
Del., a corporation of Delaware
No Drawing. Application December 8, 1943,
Serial No. 513,483
10 Claims.
1
of terpene derivatives resulting from the hydro
genation of condensation products of acyclic ter
penes having three double bonds per molecule and
acrolein. It also relates to a method for the
preparation of these derivatives.
By the method in accordance ‘with this inven
tion, a condensation product of an acyclic terpene
having three double bonds per molecule and
1
‘
-
2
A.
- from the ?rst and second fractions was hydro
genated in, the presence of 1.6v parts copper
chromite catalyst in a stainless steel autoclave.
The contents were heated under pressure. inac
. cordance with the following schedule: . f
'
1,9.
-'
Tune’ hours
‘
Tempera-
ture, ° 0.
Start ________________________________ _ _
1
ner there is obtained a, cyclic primary alcohol
which may or may not be saturated depending
upon the conditions under which the hydrogena
tion reaction is carried out.
a
(01. 260-617),’ " ‘
This invention relates to a new series of terpene
derivatives and more particularly to a new series
acrolein is reacted with hydrogen. ' In this man
'
.
Pressure,
lb. per sq. in.
28
2, 000
180
180
180
180
27
1, 960
1, 775
1, 740
l, 740
1, 225
‘
A condensation product of acrolein and-an
acyclic terpene having three double bonds per
About 1.5% hydrogen by weight was absorbed.
The theoretical amount of hydrogen for reduc
tion of the aldehyde group is 1.04% and for the
reduction of the aldehyde and hydrogenation of
molecule as, for example, allo-ocimene, ocimene,
myrcene, cryptotaenene, etc., is ?rst prepared.
This condensation product is then hydrogenated
to form a primary alcohol. Hereinafter, in this
speci?cation an acyclic terpene having three dou
ble bonds per molecule will be referredto for con
venience as an acyclic terpene.
"
.20
‘
'
The hydrogenated material was removed‘fromv
‘the autoclave and diluted with ethyl alcohol. The
catalystrwas removed fromtheproduct by ?ltra
I
tion and the ?ltrate was distilled at 18mm. to a
bath temperature of 100° C. to remove the alco
hol. The residue was distilled at 1 mm. pressure
to a bath'_ temperature of 165° C. Nineteen parts
of distillate, which was a nearly colorless oil, was
obtained. This product was analyzed with the
The method in accordance with" this invention
is illustrated by the examples which follow. All»
parts and percentages are by weight unless oth
erwise speci?ed.
two double bonds is 3.12%.
'
Example 1
following results:
A condensate of myrcene and acrolein was pre 30
pared by heating a mixture containing 80 parts ‘
(1420 _________________________________ __
of myrcene, (n2°1.475, 1142008023) 50 parts acro
nD2° ________________________________ __ 1.4910
0.9344
Per cent OH (by acetyla-tion) __ 8.6 (theory 8.75)
lein, and 0.5 part tert-butyl catechol as a poly—
merization inhibitor, to 175° C. in a nitrogen at
Example 2
mosphere in a stainless steel autoclave for 6 35
hours. After cooling to 30° C., the mixture was
Twenty-?ve parts of myrcene-acrolein con
removed and distilled at 18 7mm. pressure until
densate, prepared by the method described in
the bath temperature reached 104° C. and the
Example 1,,were mixed with 5.2 parts Raney
vapor temperature reached 70° C., in order to
nickel catalyst which had previously been washed
remove the excess acrolein. The distillation was 40
with isopropyl alcohol. The condensate was then
hydrogenated in a stainless steel autoclave. The
contents were heated under pressure according
then continued at 1 mm. The results of the dis;
tillation are shOWn in the following table:
to the following schedule:
Fraction
pgg?ggftué‘
Percent
combined
acrolein as
Yield, parts ‘
45
v
acrolein >
100-126
126-150
Residue ____ ._
71 (pale liquid) ______ ._
13 (pale liquid) ____ -'.__
>
28. 3
27. 0
10 (viscous resin) ____ __
‘ Time, hours
Tem§%atm_e’
Pressure, lb. per sq. in.‘
2,000.
800 (H: added to 2,000).
2 125
Calculated percentage of combined aldehyde
211401
1,400.
as acrolein for a condensate ‘containing one mole
acrolein per mole of myrcene is 29.3 %. >
2
About 2.90% hydrogen by weight was absorbed.
Twenty-?ve parts myrcene-acrolein condensate 155 .The theoretical amount of hydrogen foruthere-j
‘
‘
2,406,106
3
4
was carried out in a stainless steel autoclave ac
duction of the aldehyde and the hydrogenation
cording to the following schedule:
of two double bonds is 3.12%.
The mixture was ?ltered to separate the prod
‘not from the catalyst. The ?ltrate was distilled
‘at 18 mm. to a bath temperature of 100° C. to
Time, hours
Temgeéature’i
jremove traces of isopropyl alcohol. The residue
2,000.
1,925.
1,925.
1,210.
characteristics:
(1420
'
_
___
~
800 (H2 added 1:0 2,000).
;Was a nearly colorless oil having the following
‘ nnzo _
Pressure, lb. per sq. in.
0.9014
-V
___
; 1.74670
About 3.38% hydrogen was absorbed. The
Per cent on (by acetylation)_._ 8.4 (theory 8.6%) 7 i 7 mixture was ?ltered to separate the catalyst. The
?ltrate was distilled at a pressure of 16 mm. to a
Example 3v
‘
A mixture containing 80 parts allo-ocimpene
bath temperature of 100° C. to remove traces of
The yield was 13.1 parts of
nearly colorless oil having the following charac
‘
15 isopropyl alcohol.
(d42°0.8139, nD2°1.5417), 50 parts acrolein, and
‘ teristics:
1 0.5 part tert-butyl catechol (to inhibit polymer- ‘
1
d42°__ _________________ “I; ____ __' ________ __ 0.9015
ization) was heated in a stainless steel autoclave
; under a nitrogen atmosphere to 175° C. for 6 20 11.132“ __________________________________ ___ 1.4670
Per cent OH (by acetylation)
8.4 (theory 8.6)‘
1 hours, then. cooled to room temperature. "The
j
1
;
.
mixture was distilled at '18 mm. to a bath tern
Example 5
perature of 130° C., to remove excess acrolein..
Twenty
parts
of
allo-ocimene-acrolein
conden
Distillation was continued at 1 mm. The‘ follow
'ing table shows the results of the distillation:
25 sate from the ?rst fraction of Example 3 are
mixed with 10 parts of isopropyl alcohol as a
solvent and then hydrogenated in the presence
‘
'
Vapor
Fraction
of 5 parts of Adams’ platinumoxide catalyst in
Percent
-
.
temperature, géilg’ gfr?gt?eads
0'
.
a Parr shaker. The contents were heated at
40-55" C. at a pressure of 30-55 lbs. per sq. in. for
acrolein
6 hours. vAbout 3.2% of hydrogen was absorbed 77
28. 8
11
.
20
after correcting for that required to reduce the
29 '
platinum oxide. The mixture was ?ltered to re
move the catalyst. The ?ltrate was distilled at
35 a pressure of 16 mm. to a bath temperature of
100° C. in order to remove the solvent. ‘The re
____________ __
The calculated percentage of combined alde
sulting colorless oil had thefollowing character
hyde as acrolein for a condensate containing one
mole allo-ocimene per mole acrolein is 29.1%.
Twenty-?ve parts of allo-ocimene-acrolein con
densate. from the ?rst fraction was hydrogenated 40
in the presence of 1.6 parts of a copper chromite
catalyst in a stainless steel autoclave. The con
'nD
'
'
.
Per cent OH (by acetylation)___
In accordance with this invention a condensa
' tion product of an acyclic terpene hydrocarbon
tents were heated under pressure according to
the following schedule.
istics:
'
having theformula C10H1e with acrolein i5 hy
drogenated. in the presence of a catalyst.
Time, hours
'gfrtg’xtexa
Start ________________________________ - _
P53555355?‘ .
30
180
180
180
2, 000
1, 940
1', 825
1,200
180‘
’
180
180
29
1, 000
875
875
580
About 2.83%‘ of hydrogen was absorbed; The
V theoretical amount of hydrogen for the reduction
of the aldehyde and the hydrogenation of» two
double bonds is 3.12%. The mixture was ?ltered
to separate the catalyst. The ?ltratewas distilled
at v1 mm; to-a bath temperature of 160°
1 The
For
example, the acyclic terpenes operable in ac
cordance with the invention include allo-c-cimene,
myrcene, ooimene, and cryptotaenene.
The
50 acyclic terpenes may ‘be used either in pure form
or mixed with other substances.
_
r The condensation product of an acyclic ter
pene with acrolein is obtained by heating an
acyclic'terpene with acrolein. The major por
65 tion of condensate results~from a Diels-Alder re
action between the acyclic terpene and acrolein
and are unsaturated cyclic aldehydes. ' In addi-,
tion to the Diels-Alder reaction, in which one
molecule of acrolein adds to one molecule of an
acyclic .terpene, other types of reaction may oc
cur, for. example; two molecules of acrolein may
react with one molecule of the terpeneor vice
distillate yield was 16.4‘ parts of nearly colorless
versa. The extent to which each of these reac
oil having the following characteristics:
tions takes place will depend upon the relative
proportions of the reactantsand the conditions
114.2"; ___
mm
7
‘
__ 0.9087
'
__
I »-1.4740
Per cent OH (by acetylation) __' 8.5 (theory 8.75)
‘
Example 4
Twenty-?ve parts of allo-ocimene-acrolein con
densate from the ?rst fraction of Example 3, were
hydrogenated. in the presence of 5.2 parts Raney
of the reaction. Furthermora'during this con
densation any of the above condensation prod-7
ucts or reactants may polymerize. It is desirable
to add a polymerization inhibitor, suchfasterfte
70 butyl 'catechol, phenyl-beta-naphthylamine,~ etc.,
in order to hinder the formation of polymerized
. '
products. The compound which will greatlypre_
dominate in the mixture/‘will be thatiormed
when one molecule-of acyclic terpene condenses
nickel‘catalyst‘, which had been‘washed‘with iso 75 with one molecule’ oracrolein, particularly ‘so
propyl alcohol prior to use. The hydrogenation
2,406,106
a
5
when the latter is used in slight excess. ’ This
same compound can, if desired, be separated from
the other constituents by vacuum distillation, or
the crude condensate may be'reduced as such.
, The condensation products from the above pro
cedure are viscous yellow liquids. The product
resulting from the addition of one molecule of
acrolein to one molecule of allo-ocimene may be
referredv to‘v as dimethyl(butenyl)tetrahydro
benzaldehyde and the product resulting from the
addition‘of one molecule of acrolein totone mole
cule of myrcene may be referred to as isohexenyl
6
be‘ carried out in a batchwise or continuous man
ner.
.
I
I
~
-
‘
As hereinbefore describedfby proper choice of
conditions used in carrying outzthe hydrogena
tion reaction,'either an unsaturated or a satu
rated alcohol may be obtained. Thus, when ac
tive copper chromite catalyst is used under con
ditions 5f temperature and pressure within the
operable and preferred ranges for this catalyst,
as disclosed above, in most ‘cases the aldehyde
group is preferentially hydrogenated and an'un
saturated alcohol results. ‘On the other hand,
tetrahydrobenzaldehyde. If desired, the crude
the use of active noble or base metal catalysts,‘
condensate may be employedjin the process of
in particular, active nickel, platinum, or pal-.
the invention, as may any of the compounds sep 15 ladium catalysts, under conditions of tempera
arable therefrom.
’
‘
ture and pressure within the operable and pre
To form a cyclic primary alcohol, in accordance
ferred ranges for these catalysts as previously
with, my invention, any'oi" the aforesaid conden
given, results in hydrogenation of both the ethyl
sation products of acyclic terpenes with acrolein
enic double bonds and the aldehyde group and
may be reduced by hydrogen either with or ,with 20 saturated alcohols result. In between these two
out the use of a suitable hydrogenation catalyst.
extremes varying degrees of selectivity may be
Preferably, the condensate resulting when equi
obtained using varied conditions of temperature
molar proportions of the reactants are combined
and pressure, and using other catalysts under
will be employed. It is however, preferable to
varied conditions.
'
,
.
use a catalyst inasmuch as greater selectivity is
After hydrogenation, the catalyst is removed in
thereby obtainable. It is possible, by the use of
any desirable manner preferably by means of
a particular catalyst, as hereinafter described, to
?ltration. The solvent, if any is present, is re
hydrogenate only the aldehyde group of the con
moved by distillation. The product may then,
densate molecule. If only the aldehyde group is
if desired, be puri?ed by means of distillation,
reduced. the product is a substitution product of
preferably vacuum distillation. In this Way any
polymeric alcohols, which may be present in small
amounts, may be separated from the lower boil
tetrahydrobenzaldehyde. ‘ For’ example. it is be
lieved that dimethyl(butenyl)tetrahydrobenz
aldehyde forms 'dimethyl(butenyl)tetrahydro
benzyl ‘alcohol,’ isohexenyl tetrahydrobenzalde
ing monomeric alcohols. These polymeric alco
hols comprise products formed during the hydro
hyde eforms isohexenyl tetrahydrobenzyl alcohol.
genation, particularly, at high temperatures.
On the other hand, certain catalysts in conjunc
tion with the use of relatively high'conditions of
temperatures and pressure, lead to the hydro
genation of the ethylenic' bouble bonds of the
For example, the condensates of one molecule of
lieved that the products of’ this hydrogenation
are substitution products of hexahydrobenzyl al
lowed by polymerization. The monomeric alco
cohol; for example, dimethyl(butvDhexahydro
benzyl alcohol and isohexyl 'hexahydrobenzyl a1
are soft resins.
acrolein per‘ molecule of acyclic terpene may
polymerize and the polymer may then react with
hydrogen to form an alcohol. It is, possible, too,
molecule as well as the aldehyde group; It is be 40 that the monomeric alcohol may ?rst form, fol
cohnl.
'
"
'
Without regard to selectivity, the operable cat
hols are liquids, Whereas the polymeric alcohols
,45
,
In addition, if, for example; an acyclic terpene
acrolein condensate, ‘which does not consist en
tirely of the condensate which is formed from
alysts which may be used are active hydrogena
one molecule of acyclic terpene per molecule of
tion catalysts, and include active copper chro
acrolein, is used in the hydrogenation, alcohols
mite catalyst, the base metal catalysts. such as
formed upon hydrogenation may be separated
active nickel. Raney nickel, etc.. the noble metal 50 by vacuum distillation.
catalysts such as active platinum, palladium,
This process of vacuum distillation will enable,
rhodium, osmium. iridium. and ruthenium. The
in addition, the separation of any polymers of
quantity of catalyst, may vary up to about 10%
condensation products of acyclic terpenes and
of they weight of the acyclic terpene-crotonalde
acrolein, which may have been present originally
hyde condensate, preferably up to about 5.0%. 55 or which may have been formed during the hy
The foregoing catalysts may be used in unsup
drogen-aition. The probability is, however, that
ported form, or, if desired, supported on suit
this polymerized condensate will ultimately be
able inert support materials, such as kieselguhr, ’ hydrogenated and be separated from the mono
diatomaceous earth, activated clay, etc.‘ The hy
meric alcohols as a polymeric alcohol residue.
drogenation is desirably carried outat tempera 60 Vacuum distillation is also e?'ective in‘ separating
color bodies if they are present in the crude hy
tures ranging from about 25° C. to about 250° C.,
and at a pressure of 15 lbs. per sq. in. to 3000 lbs.
'per sq. in., depending upon the catalyst and the
drogenation product.
If desired, a suitable solvent may be employed
degree of hydrogenation desired. Using active
during the hydrogenation process. Such solvents
base metal or copper chromite catalysts the pref
erable pressure range is from about 250 to about
3000 lbs. per sq. in., and the preferable‘tempera
tures range from about 100° C. to about 200° C.
may be polar or non-polar in nature ‘and may
comprise saturated alcohols, such as methanol,
ethanol, propanol, isopropanol, butanol, etc.;
ethers such as ethyl ether, isopropyl ether, di
Using active noble metal catalysts, the prefer 70 oxane, etc.; esters such as ethyl acetate, butyl
acetate, etc.; saturated hydrocarbons, such as
able pressure range is from about 15 lbs. per sq.
gasoline, hexane, cyclohexane, petroleum ether,
in. to about 100 lbs. per sq. in., and the preferable
etc.; organic acids, such as acetic acid, propionic
temperature range from about 25° C. to about
acid, butyric acid,.etc. If an organic acid is em
100° C. Hydrogenation is continued until the de
sired degree of absorption has occurred and mayv 75 ployed as the solvent, it is preferable to use it
in conjunction with noble metal catalysts. The
2,406,106,
7
from a condensation product of acyclic Titer»
pene having three-doublebondsiper molecule with
3 solvent maybe-removed following separation; of"
the catalyst, ‘by means of distillation, preferably .‘
in vacuo.
acrolein, which comprises hydrogenating said;
As- an alternative procedure; inac- .
condensation product» in contact with an‘ activev
cordance-with?the invention,- any of the acyclic’
. noble metal hydrogenation catalyst.
iv ac'rolein condensates may be hydrogenated byv
6. The method of producing a primaryalcohol
‘
In "general; this i
means or a nascent hydrogen.
' methodis less satisfactory than that of catalytic
from a condensation product of .van acyclic ter-V '
pene having threedouble bonds per molecule with
hydrogenation. Reducing agents which‘may he
acrclein, which._ comprises :hydrogenating said
employed when nascent hydrogen is employed in
clude sodium am'algamedilute acid, 'zinc dust
glacial acetic acid, sodium and ‘ethyl ‘alcohol, ‘etc,
' usingftemperatures or froin240° "C. to 150°
condensation product in contact with an active
copper chromite catalyst.
with mono- or poly-basic acids.’ They may be‘
aorolein, which comprises hydrogenatingisaid
condensation product in contact with an active
base metal catalyst at a temperaturewithinthe
and at a pressure withinthe range ofirom about
20
suusing agents which are ‘used in the form ofv
their 'alkaltand organic biase salts. The mono-j
meric alcohols themselves possess ‘wetting and
detergent properties when emulsi?ed in‘ water.
' This application constitutes a continuation-1m
part of ‘my ‘application for U. '8. Letters Patent,
senators. ‘396,216, ?l'e'd May 31, 71"941.'_ i
I
What 1 claim and ‘desire to protect by Letters
~
~
‘
‘
'
250-lbs. per square inch to'about ‘3000'1bs-Hper
_ square inch.
-8. The method of producing a primary alcohol
from» a condensation product of w an ' acyclic» tor-
'pene having three doublebonds permolecule with
acrolein, which comprises - hydrogeneting 'said
condensation product inv contact with an active
noble metal catalyst-at a~temperatureof~irom
about 25° C. to ~aboutr100‘! (‘L-and at @a pressure
of from about 115 lbs. per square-inch to about
100 lbs. per square inch
"
'
9. The method of producing a-primary alcohol.’
‘
1; Dimetnyllbutyl)hexahydrobenzyl alcohol.
'2. Isohexyl henahydroben'z'yl alcohol.
n
range of 'from about; 100°C. toyaboutlo?tCa
- sulfonated , ‘to 7' produce emulsifying, wetting, and
‘
.;
pene having three double bondsper-moleculeiwith
15
tion ‘are useful in the manufacture of various
esters’ from which can be made insecticides, etc.,;
and in the manufacture of resins by ésteri?cation
Patent is:
, -
from’ a condensation product of’ an, acyclic- ter
general, these reducing agents are selective for
the‘ aldehyde group, the ethylenic double bonds
remaming substantially unhydrog'enated.
‘The-alcohols produced hy‘virtu'e of this inven
7.
'7. The method-0f producing a. primary alcohol.
‘In;
'
s. ‘The method 'or-produei' e a primary alcohol
rrom‘a condensation productcr ‘an acyclic ter
peire nevi g‘three ‘double bonds pe'r'molecule with
acme-m. "'hi'ch comprises ihydro‘ge'nating said
from a condensation product of an acyclic ten
pen-e havingthree double bonds per molecule
'
acrolein, which» comprises hydrogenating- said
condensation product in contact with annacti-ve
copper chromite catalyst at “a temperature :of
immanent-100° ‘(2.: to about 2009 G. andpat a
‘condensation product in contact With anactive
pressure of from aboutozéo lbs. per square inch
hydrogenation
' '4. The met Vodof
Ycfatal'y‘st.
‘producing a‘pr'imary alcohol
to about 3000 lbs-per square inch.
from 1a etude-seamen; product ‘of ‘an acyclic ‘ter;
pone having ‘three double bonds ‘per molecule
‘with aerolein, "which comprises 'l’iydi'ogenatin'g
said condensation product in contact'w'ith ‘an
active h'a’s’e metal hydrogenation catalyst.
' ‘V15.
'
‘methodof producing a primary ‘alcohol 1
~
J
> .
10-;v As a new product a substitutedhydrobenzyl
alcohol selected from the group consisting ofyldi
methyl(butylbhexahydrobenzyl alcohol-,3 isohexa
enyl tetrahydrobenzylalcohol and isohex l hexae
hydrobenzyl- alcohol. “
'
~>
'
'
ALFRED L. RUMMELSHJBHURQQ ‘ ’
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