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Патент USA US2115206

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April' 26, 1938.
N. ‘ A. MILAS
‘ 2,115,206
METHOD OF MAKING ORGANIC ZPEROXIDES
Filed April 5, 1955
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Invent-'02:;
jVZc?oZaa’ A
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Patented Apr. 26, 1938
2,115,205 ‘
I
"UNITED STATE 5, PATENT'OFFICE
-
‘
2,115,206
_
METHOD OF MAKING ORGANIC PE‘RoxmEs
Nicholas‘A. Milas, Cambridge, Mass.
’
Application April 5, 1935, Serial No. 14,787
.
21 Claims.
(Cl. 260—16) A '
' This invention relates to a process of producing
organic peroxides] and to the resulting products.
Although auto-oxidation is a well known and
well recognized process, the end products thereof
vary considerably in both chemical and physical
O
characteristics, such auto-oxidation processes
stable and can be easily isolated or obtained in
relatively pure concentrates.
As previously'pointed out, auto-oxidation un
der ordinary vconditions occurs to such a slight
usually producing relatively non-reactive organic
extent that it is practically’ impossible to detect
substances such as acids, aldehydes, ketones, etc. ‘
either such reactions or any products of such
reactions, but as I am able greatly to increase
During the course of such auto-oxidation rela
10
low rates of decomposition thereof are only
slightly affected these. peroxidic products are
the rate of formation of the peroxide ‘without 10
tively unstable, highly reactive intermediate sub
stances form, but under ordinary conditions
these substances decompose rapidly; the amount
appreciably increasing its rate of decomposition I am able to produce substances which were here—
‘present at any time during the process is very
small and their isolation is relatively» dii?cult.
tofore unknown and which could not-possibly be
produced by any process heretofore known.
Moreover, as the rate of decomposition of per
“ In the majority of auto-oxidation processes,
knowledge of the presence of the intermediate
products is based merely on theoretical consider
oxidic products is relatively slow, .the concen-'
trated solutions and also the relatively pure sub
ations and, as far as I am aware, their isolation
stances are stable over moderate lengths of time,
and, in fact, far more so than many of the stable
has ‘not-been accomplished except in a few lim
20 ited cases as, for example, in the auto-oxidation
.of ethyl ether and of certain aldehydes such as
acetaldehyde and benzaldehyde.
'
Although some workers have isolated the in
termediate products of a few selected auto-oxida
tion reactions, they invariably used methods
which involved refrigeration of the reaction mix-'
ture, and/or complete removal from the react ’
ants of substances capable of reacting with or
organic peroxides‘now known.
‘
Alcohol peroxides produced in accordance with
the present invention are of value for all purposes
for which the heretofore known peroxy com
pounds are now used, for example, germicides
(both contact and vapor), fungicides, oxidizing 25
agents, hemostats, etc., andv by reason of their
stability are of much greater value and utility.
accelerating the decomposition of peroxides.
The auto-oxidation of alcohols, in accordance
with the present invention differs fromand is a
Such processes are of limited applicability and
can only be applied to substances such as alde
marked advance over prior processes in that no
refrigeration or other means of preventing the
hydes which readily undergo auto-oxidation even
under ordinary conditions.
The auto-oxidation of alcohols is extremely
slow under ordinary conditions as is shown by the
fact that various alcohols remained substantial
ly unchanged when in contact with air or oxygen
for long periods of time.
Hence, the rate of for
mation of the intermediate peroxides is very
40 slow. Moreover, although their rate of ‘decom
position is also slow, it is apparently as fast as,
or faster than, their rate of formation, since
the concentration of peroxides found under these
ordinary conditions is negligible.‘ However, I
' have found that the rate of formation of per
oxides during the auto-oxidation of alcohols is
20
decomposition of the peroxides is required; in
fact it is often advantageous, when carrying out
the process, to employ temperatures above nor
mal room temperature. Further advantages will
be apparent from a consideration of the-follow:
ing description and the accompanying drawing,‘
vwherein
‘
The ?gure is a diagrammatic representation
of an apparatus suitable for carrying out the
auto-oxidation of alcohols in accordance‘ with
the present invention.
_
‘The term “alcohol” as hereinafter used desig
nates that class of organic compounds contain
ing one or more hydroxyl groups and which may
be designated by such formulae as -
considerably accelerated by ultra-violet light,
while the rate of decomposition of these products
is only slightly affected.
1
Since, under the joint in?uence of ultra-violet
light and oxygen, peroxides are produced from al
cohols at a much greater rate than that at which
they decompose, it follows that, under these spe
50
etc.,' wherein R1,‘ R2, etc. represent different or
ganic radicals.
-
\
In accordance with the present invention, the
cial conditions, high concentrations of peroxidic
alcohol to be treated is subjected to ultra-violet a‘
products can be reached, and since the original
irradiation in the presence of oxygen, air,‘or '55
2
2,115,206 '
other oxygen-containing gas, the'reaction pref
and alkylidene peroxides or their polymers, hav
erably being carried out in a quartz vessel such as
a ?ask, coil or the like. The time required to
ing the general formulas
carry out the process may vary from a few min
'
0
utes to several hours, or even days, depending
upon‘ the particular nature of the alcohol re
acted upon. At the end of the process‘fthe- un
oxidized alcohol, the solvent or volatile vmedium,
as the casevmaybe, may be removed by vacuum V
10 distillation at low temperatures, and ‘the perox
ide in the residue may be separated by preciph
tatlon or fractionation under low pressures.
The ‘auto-oxidation of a typical alcohol, for
example, an, alcohol having the general formula
19
I
respectively.
.
It is well known that peroxides of the type
15
.
15
HI
R-JLOH
wherein‘Rrepresents the organic radical, pro
20 ceeds, in all probability, substantially as follows:
'(alkylidine peroxides) polymerize very easily to
form dimers, t-rimers, etc., in the following man
nor:
a’ o,~ -o R’
wherein (I) may be dimeric, as:
30
As a result of the ultra-violet irradiation in the
presence of free oxygen, there is ?rst obtained
' a reaction mixture in which there is a high de
gree of active oxygen as determined by titration,
using acidi?ed potassium iodide and standard‘
thiosuli'ate solution. The initial peroxide formed
in the reaction mixture, being a derivative of the
alcohol
\
A
35
'
a-J:—on
> ,
Illa
i
is a peroxide of that alcohol and conforms in all
probability to the general formula
and so on.
~ The ?nal reaction products in the mixture com
prise alphahydroxy alkyl hydroperoxides, having
the general formula
,
I
’
>
H
'
_
,
R-Jl-QOH
alpha alpha dihydroxy dialkyl peroxides, having
_
45
Wvaer reaction, (Woker, Zeit. Allg. Phlsiol. 18,
340 (1914); Ber. 4'7, 1024 ‘(1914); whereas that 50
of the alkylidene peroxides is established by a
quantitative analysis in accordance with the usu
al procedures for ‘the identi?cation of organic
compounds.
H
the general formula
.
The presence of the hydroxy peroxides and
hydroperoxides is shown by the benzidene reac
tion of Woker, hereinafter referred to as the
.
To separate the alkylidene peroxide from the 55
other products, I subject the ?nal reaction mix
ture to vacuum distillation at or below room tem-\
peratures, thereby retaining it in the residue.
With secondary butyl alcohol (which is illus
trative of atypical alcohol) the auto-oxidation 60
proceeds, in all probability, as follows:
CHy- H1
70
TI
3
2,115,206 "
During the reaction a certain amount of the
duce water and as a result excess ketone is
In the figure I have shown an apparatus-par
tlcularly suitable for carrying out the auto-oxida
tion of lcohols in accordance with the present
formed. This ketone may combine with the alpha
inventio , it being understood that various other
hydroxy alkyl hydroperoxide to yield alpha di
types of apparatus may be used such, for exam- 5
ple, as a quartz ?ask disposed within a chamber
containing an ultra-violet light, in which case
the alcohol is exposed in .a static system to an
atmosphere of oxygen usually in a large excess.
liberated hydrogen peroxide breaks down to pro
hydroiw, dialkyl' peroxide, as shown in the fol
lowing equation:
oH'
10
-
'
“ on
(‘)3
cnrc-oon+cn,_-c=o->(m) crnJi-d-o-p-crn
CHr- H:
CHr- H2 7
CHF H1
The particular apparatus herein shown comprises 10
a quartz coil 5 circumposed about a Uviarc (ultra
' violet) light 6_ which is approximately six inches
CHI-CHI
The initial ‘peroxide (1) conforms, in all prob
ability, to the formula
J5
_ in length. A cylindricalre?ector or shield‘ 8 is
“
H
disposed about the coil 5, and this shield is pro
.
vided with openings. 9 and I0 adjacent to its top 16
and vbottom edges, respectively, through which
oHro-oo-on'
.
.
OF:-
H]
,
which may be expressed more generally by the
the ends of the coil extend.
,
The lower_ or inlet end ll of the coil is con-
_
nected preferably by a ground joint toione branch ‘
20
l2 of a T, another branch I‘ of the ‘I’ being 'con- 20
;nected to a U-tube or trap l5, and the lower
a-o—oo-on
~
branch l6 of the T ‘being connected to a delivery
tube l8 which is furnished with a tap 20. The
wherein R and R’ are organic radicals. Two oi’ U-tube I5 is connected by a return tube 22 to
25 the ?nal reaction products in the mixture, as
an outlet djlct 24 located at the lower end of a 25
identi?ed by the Woker reaction, comprise (II) ' cylindrical vessel‘ 25 which is disposed at a higher
formula
-
-
.
.
H
‘
an alpha hydroxy alkyl hydroperoxide, having the
level than the top of the coil 5, thus providing
formula
"a collecting chamber. The upper or outlet end
26 of the coil is connected by a ground joint to,
a tube 21 which leads to the inlet duct 28 of the 30
vessel 25. The top of the vessel is sealed ‘by a
0H
CHs-JJ-OOlI
30
CH:- H:
plug 30 having a vertically extending bore in‘
and (III) an alpha dihydroxy dialkyl peroxide,
35 having the formula
on
on
onr'd-o-oéo-cni
OKs-13H) (I'JHr-CHJ
40
(n1) _
Another of the ?nal products comprises (IV)’
an alkylidene peroxide or its polymer, having the
formulas
o .
which the lower end of an air condenser 32 tight
ly ?ts. The top of the condenser 32 is sealed
by aplug' 34 from which is suspended a ther- 35
mometer 35 which extends downwardly into the
_
vessel 25 so that its bulb is at approximately the.
same level of the normal level of ?uid therein.
A vent pipe 31 leads off the condenser 32 and ‘is
connected to a moisture trap, here shown as a 40’
tube 38 containing calcium chloride.
‘
The delivery tube I8 is connected to a chain
‘of drying tubes 39 which are connected to a suit
able oxygen supply, here shown as a tank 40 of
compressed oxygen gas, the-usual valve ll be- 45
ing provided to control the ?ow of ' gas through
' the delivery tube l8. If desired, a fan 45 'may
CHs-lH: ' '
o
50
being auto-oxidized.
.
CHr—-C/ l
parts of the apparatus should, of course, ,be leak
ens-cm
integral with the tubes, per se, (as by fusing the
\o
55 respectively‘.
be'employed to circulate cool air about the light
6 and thus prevent overheating of the alcohol
50
The various connections between the different
proof and where such connections are not formed
These peroxides may be isolated ‘ ends of glass tubing) or where ground joints are ‘55\
by subjecting the mixture to» a high vacuum
distillation when (H) and-(III) are more volatile
than (IV) which remains in the residue.
I have found that traces of water have a
not used, suitable coupling members may be used,
such couplings being of a material which will not
react with or dissolve in an alcohol; or' otherwise
introduce any impurity into the system.
60 marked effect upon the rate of peroxide forma»
In using the apparatus above described 100 to 60
tion; accordingly, it is advisable that each alcohol 125 cc. of the alcohol to be auto-oxidized may
be thoroughly dried. I have also found that the be introduced into the coil 5 either through the
relative rates of peroxide formation during the delivery-tube l8 or the vessel 25, the particular
irradiated auto-oxidation of impure alcohols dov amount varying with the type of alcohol. The‘
65 not necessarily conform to the relative rates of .
peroxidation of the same pure substances.
Furthermore, it is highly desirable, if not es,
sential for satisfactory yields, that the alcohol
. be either in liquid phase, or in a solution or dis
are light 6 may then be struck and the valve 4| 65 .
regulated so that a steady stream of dry oxygen is
passed through the delivery tube l8 and into the
coil 5. The rate of the ?ow of the oxygen through
the\alcohol within the coil is preferably of the
order of 1.5 liters per hour, ‘although a greater 70
70 persion, so that it may be agitated or kept in
motion during the reaction. With certain types . or less amount may be used. The small bubbles _ '
of alcohols, such as triphenyl carbinol, benz
hydrol, etc., it may be necessary to dissolve them
in a low boiling point solvent which is resistant
75
to peroxidation. -
'
of oxygen passing through the coil 5 and into the
vessel 25 and then out through the vent 31 are
not only e?ective to keep the alcohol constantly
agitated but also to maintain a steady circula- 75.
2,115,208
-4
tion of the alcohol through the coil 5, vessel 25.
tube 22 and back into coil 5, thus insuring a uni
form irradiation and complete saturation of the
alcohol with oxygen. Any alcohol which volatil
izes is condensed by the condenser 32 and is re
turned to the vessel 25 where it is carried back
into coil 5. The temperature of the alcohol dur_
ing the reaction may be determined by the ther
mometer 35 and the particular temperature de
10 sired may be maintained by varying the speed
and/or position of the fan 45.
v r
tively. Analysis of the irradiated product showed
0.090% active. oxygen, corresponding, to 0.67%v
alcohol peroxide (ROQH).
‘
.
. Example 7.—Secondarp amyl alcoh0l.—125 cc.
of secondary amyl alcohol, having _a boiling point 5
of 119.0 to 119.5° C., was irradiated for a period
of 20 hours, the temperature of the alcohol and
that of the room being 38 to 42° .C. and 20° C.,
respectively. Analysis of the irradiated product-“
showed 0.02% active oxygen, corresponding to 10
0.14% alkylidene peroxide.
_
v ' During the reaction samples may be withdrawn
through the tap 20 at intervals and analyzed for
active oxygen \in accordance with the procedure
Example 8._Cyclohexan0l.-This alcohol was ?rst puri?ed by extracting it with- saturated so->
dium bisul?te until no more 'cyclohexanone was
above set forth. As. previously noted, the'time removed. It was then carefully dried, ?rst with is
during which the alcohol is to be subjected to _ sodium sulfate and then with lime, after which
irradiation will vary in accordance with the par
ticular type used and the rate of reaction for any
it was fractionated, and the fraction boiling at
160.0 to 1'60.5° C. was removed and treated with
alcohol or any mixture of alcohols may be deter
2% aqueous permanganate until no further re
mined by titrating the samples withdrawn dur
duetion ensued. The cyclohexa’nol was then 20
dried again over lime and refractionated. 116
cc. of the treated cyclohexanol was then irra
diated for a period of 26 hours, the temperature of
the alcohol and that of the room being 42 to 48°
C. and 22° C., respectively. Analysis of the irra- 25
diated product showed 1.62% active oxygen, cor
ing the period of reaction; When the reaction
has been carried to the desired point the irradi-é
ated product may be withdrawn from the appa
ratus, cooled and either stored for'later use or
25 distilled under vacuum to produce a concentrated
solution, or a residue which, if desired, may be
mixed with ya suitable inert dilutent before use.‘
The following examples are illustrative of the
invention:
80
Example 1.-Isopropan0l.--125 cc. of isopro
panol having a boiling point of 81.9-82.0° C., was
irradiated, as above described, for a period of ap
proximately 13.5 hours, the room temperature be
responding to 11.5% alkylidene peroxide...»
Example 9.—-Benzyl alc0h0l.—120 cc. of benzyl
alcohol having a boiling point of 204.5°..t0 205.0°
C., was irradiated for a period of 23.5 hours, the 30
temperature of the alcohol and that of the room
being 42 to 46° C. and 22° C., respectively. An
alysis of the irradiated product showed 0.58%
ing 22° C. and that of the alcohol 40 to 45° C. ' active oxygen, corresponding to 4.5% alkylidene
.
At the end of the period the irradiation product. peroxide.
was analyzed, as above described, and found to
' Example 10.—Phenzllethyl alcohol-120 cc.‘ of
contain 0.60% active oxygen, corresponding to
2.8% alkylidene peroxide.
}
~
as
phenylethyl alcohol, having a boiling point of ' ‘I
. I 202 to 203° C., was irradiated for a period of 18
Example 2.--Secondary butan0l.--125 cc. of hours, the temperature of the alcohol and that of
secondary butanol, .having a boiling point of 995° 'the room being 40 to 44° C. and 21° C., respec- 40 I
C., was irradiated, as above described, for a period _ tively.
of approximately 13 hours, the temperatureof
the alcohol and that of the'room being 41‘ to 45°
Analysis oi.’ the irradiated product showed
0.040% active oxygen, .corresponding to 0.35%
' alkylidene peroxide.
C. and 20° C., respectively. Analysis of the ir
Example 11.-Tetrahydr0furfuryl alcohol-120
radiated product showed 1.07% active oxygen,_ cc. of tetrahydrofurfuryl alcohol, having a boil- 45 »
corresponding to 5.9% alkylidene peroxide.
Example '3.-Normal butanoL-IZO cc. of nor
mal butanol, having a boiling point of 117.6 to
117_.8° C., was irradiated for- a period of 19 hours,
the temperature of the alcohol and that of the
room being 40 to 43° C. and 22° C., respectively.
Analysis of the irradiated product showed 0.042%
active oxygen, corresponding to 0.25% alkylidene
peroxide.
.
' Example‘ 4.—-Tertiary butanol.—125 cc. of ter
tiary butanol, having a melting point of 25.3° C.
and a boiling point of 82.3 to 82.5“ C., was ir
radiated for a period of 48 hours, the temperature
of the alcohol and that of .the room being 42 to
60 45° C. and 22° C., respectively. Analysis of the
irradiated product showed 0.068% active oxygen,
corresponding to 0.45% alcohol peroxide (ROJH).
Example 5.—Isoamyl alcohol-120 -cc. of
isoamyl alcohol, having a boiling point of 130.1
to 130.4° C., was irradiated for‘ a period of 23
1 hours, the temperature of the alcohol and that
of the room being 40 to 44° C., and 20° C., respec
tively. Analysis of the irradiated product showed
ing point of 80 to 81° C. was irradiated for a pe
riod of 30 hours, the temperature of the alcohol
and that of the room being 39 to 45° C. and 20°
C.,‘ respectively. Analysis of the irradiated prod
uct showed 0.16% active oxygen, corresponding 50
to 1.2% alkylidene peroxide.
_
Example 12.--Triphenpl carbinoL-A quantity
of triphenyl carbinol, having a melting point~ of
162.00 C., was ?rst dissolved in tertiary amyl alco
hol andthe solution was irradiated for a period 55
of 25 hours, the temperature of the alcohol and,
that of the room'being 42 to>46° C. and 22° C.,
respectively. Analysis showed 0.035% active ox
ygen, corresponding to 1.1% alcohol peroxide
(ROJH) in the irradiated triphenyl carbinol, 00
these ?gures being derived by subtracting the cal
culated or estimated tertiary amyl alcohol perox
ide from the total peroxide to give that due to
the triphenyl carbinol peroxide.
Example 13.'--Benzhydrol.—'A quantity oi.‘ benz- 65
hydrol having a melting point of 67.4° C. was ?rst
dissolved in tertiary amyl alcohol, as in Example
12, and the solution was irradiated for a period of
0.035% active oxygen, corresponding to 0.23% ' 19 hours, the temperature of the alcohol and that
alkylidene peroxide. -
Example 6.--Tertiary amyl alcohol-120 cc. of
tertiary amyl alcohol, having a boiling point of
101.8 to 102.0° C., was irradiated fora period of
32 hours, the temperature of the alcohol and that
75 of the room being 40 to 45° and 22° C., respec
of the room being 40 to 45° C. and 20° C., respec- 70
tively. Analysis showed 0.15% active oxygen,
corresponding to 0.85% alkylidene peroxide in the
irradiated benzhydrol," these ?gures likewise be
ing obtained as in Example 12.
Example‘ 14.—Methanol.-100-cc. of methanol ‘16
anaaoo
having a boiling point of 66° C., was exposed in a
quartz" ?ask to irradiation for a period of 40
hours, an atmosphere of oxygen being main
tained within the ?ask. The temperature of both
the atmosphere and alcohol under irradiation was
maintained at 50° C. . Analysis of the irradiated
product showed 0.043% active oxygen, corre
sponding to 0.85% alkyledene peroxide.
_
Emample 15.-Ethanol.-100 cc. of ethanol was
I
.
5
vExample 19.-A sample of the peroxide ‘of sec- ondary butyl alcohol was treated‘an'd tested in .a "
manner similar to that described in Example 18
and an analysis of' the residue showed 78% of
methyl ethyl ketone against a theoretical of 81:8,
for C4H802, and- 17.71% active oxygen against a
theoretical of 18.18% for C4Ha0z, thus proving
the presence of the alkyledene peroxide.
The A
presence of alpha hydroxy alkyl peroxide was
10 subjected to irradiation under the same condi
tions as are set forth in Example 14 for a period
shown by a strong reaction with benzidene
of 80 hours. Analysis of the irradiated product
showed 0.36% active oxygen, corresponding to
Example 20.—A sample of isoamyl alcohol
which had been irradiated for twenty-?ve hours
and contained 0.04% active oxygen wasvevapo
1.4% alkylidene peroxide.
'
’
Example 16.—Normal pr0panol.—100 cc. of
normal propanol was subjected to irradiation for
a period of 80 hours and under the same condi
tions as set forth inExamples 14 and 15. Anal
ysis of the irradiated product showed 0.30%
20 vactive oxygen, corresponding to 1.4% alkylidene
16
peroxide.
'
‘
.
Example 17.—Mon0eth1/l ether of ethylene 911/
col.-120 cc. of monoethyl ether of ethylene gly
(Woker's reagent).
_
'
'
rated ?rst on a water pump and-then on an oil 15
pump, nearly a week of continuous evacuation
being ‘necessary to remove all the solvent. A
portion of the residue was weighed into a small
?ask and hydrolyzed with ,dilute sulfuric acid
and the product was then distilled into a solu
tion of 2,4-dinitro-phenyl hydrazine in hydro?
chloric acid. The precipitate was washed, dried
and recrystallized. The recrystallized precipitate '
, col was subjected to irradiation for a period of
showed a melting point of 122 to 122.4° vC. against
25 15.5 hours, the temperature of the alcohol and
that of the room being 44 to 48° C. and 21° C., re-
a melting point of 123°_ C. for isovaleraldehyde
2,4-dinitro-phenyl hydrazone. The precipitate
spectively. Analysis showed 0.43% active oxy
gen, corresponding to 2.8% alkyledene peroxide.
Miscellaneous alcohols.—_-Purther applications
30 of my process to various other alcohols have like
wise produced relatively stable peroxides. The
treatment of furfuryl alcohol (a primary hetero
cyclic alcohol), dodecyl alcohol (a further exam
ple of a primary aliphatic alcohol), menthol (a
35 typical alcohol of the terpene series), and ethyl
ene glycol (a typical polyhydric alcohol), in ac
cordance with the above procedures has in each
case produced peroxides having appreciable
amounts of peroxidic products, thus a?ording a
40 further con?rmation of the fact that my process
is applicable to alcohols as a class.
,
20
‘was weighed before puri?cation and an amount .
of isovaleraldehyde form was determined and
found to be 82.4% against a theoretical of ‘84.6%
for C5H1102.
30
~
Another portion of the residue was weighed
into a ?ask and analyzed for active oxygen. The
analysis showed 14.2% active oxygen against a
theoretical of 15.4 for C5H1102, thus showingv the '
presence of the alkyledene peroxide of isovaleral 35
dehyde.
In this case, as before, the original
solution gave a positive Woker’s. reaction, show
ihg the presence of a hydroxy hydroperoxide.
Example 21.-A sample of cyclohexanol which
had been irradiated for twenty-six hours and 40
contained 1.62% ‘active oxygen was diluted with
three times its volume of dry petroleum ether,
and 5 grams of silica gel were then added. The
solution was allowed to stand for one week with
In each of the preceding examples the irradia
tion product was also tested for stability at 0°
C. and at 20 to 23° C., and in all cases the
45 peroxide was found to be relatively stable at frequent shakings. A slow adsorption took place, 45
these temperatures for moderate lengths of time. , and at the end of this time 21% of the peroxide
The structure of the irradiated product may be had been adsorbed. The-gel was then ?ltered
off, washed with petroleum ether to remove ad
determined in the manner shown in the follow
ing examples, which illustrate the procedure as h'ering cyclohexanol, and extracted with cold
chloroform. The chloroform solution was evapo 50
.50 applied to di?erent types of representative al
rated as before and the residue was‘ hydrolyzed
cohols:
_
Example 1-8.-A sample of isopropanol which
has been irradiated for fourteen hours and con
tained 0.50% active oxygen was evaporated,,?rst
on a water pump and then overnight on an oil
pump, producing a viscous residue; A weighted
amount of‘ this residue was transferred to a ?ask,
then hydrolyzed with dilute sulfuric acid and the
mixture distilled into a solution of 2,4 .dinitro
60 phenyl hydrazine in hydrochloric acid. The pre
cipitate formed ‘was washed, dried and recrystal
lized. The recrystallized precipitate showed a
melting point of 126.5 to 127° C. against a melt
65
with dilute sulfuric acid, after which 2,4-dinitro
phenyl hydrazine solution was added. The pre
cipitate was then washed,dried and recrystallized.
The melting point of the recrystallized precipi v55
tate was found to be 158? C. against 160° C. for
cyclohexanone 2,4 ‘dinitro-phenyl hydrazone.
The amount of cyclohexanone formed was deter
mined, as before, and found to be 85.8 against a
theoretical of 86.2 for CeHuOz.
'
was determined as before and found to be 14.2
against a theoretical of 15.4 for CeHnOz, thus
ing point’ of 128° C. for ‘acetone 2,4 dinitro
showing the presence of alkyledene peroxide of
phenyl hydrazone. Before recrystallization the
cyclohexanone.
precipitate was weighed and the amount of
60
The presence of active oxygen in the residue
'
.
The present application is a continuation-in;
acetone formed was determined and found to be
part of my copending application Serial No.
77.5 against a theoretical of 78.4% for caHeQz.
Another portion of the residue was weighed
589,977, ?led January 30, 1932.
I claim:
1. The process 'of causing the production of 70
70 into a ?ask and analyzed for active oxygen. The
analysis showed 21.25% ‘active oxygen against a peroxides by the irradiated auto-oxidation of.re1-.
theoretical of 21.6 for CaHsOz, thus proving the atively pure alcohols substantially free from wa
‘
presence of the alkyledene peroxide of acetone. ter.
2. The process of causing the production of
The presence of isopropyl hydroxy hydroperoxide
. peroxide by the irradiated auto-oxidation of rel
75 was shown by Woker’s reaction.
2,110,206
6
atively pure monoethyl ether of ethylene glycol 1 wherein R and-R" represent hydrogen atoms or
substantially free from water.
,
hydrocarbon radicals.
'
--
.
3. The processof causing the production of
11. A’ composition oi matter containing an ap
peroxides by-the auto-oxidation of an alcohol preciable amount of a peroxide having the gen
having the general formula
eral
H
formula
_
‘
p
.
-
R,
-
.
.
R-(‘h-OH
10
whereijhR and R’ are di?erent hydrocarbon radi
wherein R and R' represent hydrogen atoms or
cals, which comprises subjecting the relatively
hydrocarbon radicals.
preciable amount of a peroxide having the gen- -
ultra-violet irradiation in the presence 01' oxygen. ,
_ 4. The process of causing the production of
15 peroxides by the ‘autoéoxidation of an alcohol
. having the general formula ROH, wherein R rep
resents a hydrocarbon radical, which comprises
"subjecting the relatively pure alcohol substan
vtially tree from water to ultra-‘violet irradiation
20 in the presence of oxygen.
'
-
12. A composition or matter containing an ap
pure alcohol substantially free vIrom water to
eral, formula
‘
r
‘R’!
16
In’!
rwo-o-o-o-a
on
011
wherein R and R’ represent hydrogen a’ ma orv
.hydrocarbon radicals.
~
'
13. A composition of matter containing an ap 20
5. The process of causing the production of
peroxides by the auto-oxidation of an alcohol "preciable amount of a peroxide having the general
formula
}
having the general formula ROH, wherein R rep
resents a cyclic hydrocarbon radical, which com
'
prises subjecting the relatively pure alcohol sub
stantially free from water to ultra-violet irradi
ation in the presence of oxygen.
112°
a
_
-\0
‘
I
.
_wherein R and R’ represent hydrogen atoms or
6. The process of causing the production of hydrocarbon radicals, and :1: equals '1, 2, . . . n.
peroxides .by the auto-oxidation of an alcohol ’
i4. Peroxides produced by the irradiated auto
30 having the general formula RQH, wherein R rep
oxidation of cyclohexanol.
resents a hydro-aromatic hydrocarbon radical
' and in which the OH group is directly attached
' to the ring, which comprises subjecting the rela
tively pure alcohol substantially free from water
to ultra-violet irradiation in the presence of
oxygen.
.
'
~-
‘
7. The process of causing the production 0
peroxides by the irradiated auto-oxidation of rel
atively pure cyclohexanol substantially free from
40
water.
‘
'
8. The process of causing the production of
peroxides by the irradiated auto-oxidation of rel
atively pure isopropanol substantially free irom
water.
'
9. Stable peroxides produced. by the auto-oxi
» dation of alcohols during the irradiation thereof
by ultra-violet light.
_
l0.‘ Acomposition of matter containing an ap
preciable amount of peroxides having the gen
eral formulas
‘
30
15. Pei-oxides produced by the irradiated auto-\
oxidation of isopropanol.
.
'
16. The process of making an alcohol perox
ide, which comprises subjecting a relatively pure
alcohol substantially free .Irom water to ‘ultra
violet irradiation in the presence 01' oxygen.
17. ‘A relatively pure and stable organic perox
ide consisting essentially of. an irradiated auto
oxidized alcohol.
18. A relatively pure and stable organic perox 40
ide consisting essentially of irradiated aut0~oxi~
dized
cyclohexanol.
I
Y
-
'
.
19. A relatively pure and stable organic perox-'
ide consisting essentially of irradiated auto-‘oxi
dized isopropanol.
-
20. Peroxides produced by the irradiated auto
oxidation of monoethyl ether of ethylene glycol.
21. A relatively pure and stableorganic perox
ide consisting essentially of the irradiated auto
oxidized monoethyl ether of ethylene glycol.
'
NICHOLAS A. mus.
45
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