CA1182843A - Process for the preparation of cumyl peroxides - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
An aliphatic or cycloaliphatic hydroperoxide or aliphatic dihydroperoxide, an olefin such as alpha-methylstyrene or a substituted alpha-methyl-styrene wherein the substituent is on the phenyl ring and a t-cumyl halide corresponding to the hydrohalogenated olefin such as t-cumyl chloride or a substituted t-cumyl chloride are reacted under relatively non-aqueous conditions, in the absence of a free acid and in the presence of a phenol catalyst, to obtain a cumyl (or substituted cumyl) peroxide or diperoxide corresponding to the hydroperoxide or dihydroperoxide. The cumyl peroxides prepared by this reaction are very useful as crosslinking agents for polyethylene and elastomers.

Description

Process for the Preparation of Cumyl Peroxides (IR 2477~

Field of the Invention This invention relates to an improved : process for the preparation of cumyl peroxides or cumyl diperoxides. More particularly, the invention relates to an improvement in the process of preparing cumyl peroxides by reacting an aliphatic or cycloaliphatic hydroperoxide or aliphatic dihydroperoxide, an olefin and a cumyl ~-, .

h~lide corresponding to the olefin under non aqueous conditions in the absence of a free acid and in the presence of a phenol catalyst.

Descri_tion of the Prior Art The preparation of aralkyl and alkyl peroxides is well known in the prior art that can best be summarized under four major methods of preparation:
1) The acid~catalyzed condensation of a hydroperoxide with an alcohol.

2) The acid-catalyzed addition of a hydro-peroxide to an olefin.

3) The displacement reaction between an alkali me~al salt of a hydroperoxide and an alkyl halide.

4) The displacement reaction between a hydrope:roxide or hydrogen peroxide and an alkyl.halide in the presence of an acid acceptor.
The fourth method is the only method relevant to this invention. The othe.r methods and their short-comings in the preparation of cumyl : peroxide are thoroughly diQCussed in U.S. Patent 4,133,835 (Bafford)O This invention is essentially an improvement over Baffordls process as taught in U.S. 4,133,835. Prior art per-taining to the fourth method above is:
Kato et. al. tAuslegeschrift 2,035,127) published a process for preparing t-cumyl type peroxides by reacting a tertiary hydroperoxide with an aralkyl halide, such as t-cum~l chloride~
at 0 80C in the presence of an acid binding agent such as a t-aicohol or an aliphatic olefin. The mole r~tio of the aralkyl halide to the hydro-peroxide could vary from l:l to l:l.5. In this process the hydroperoxide reacts with the ~ralkyl halide to ~orm the peroxide, t~e HCl generated is taken up by the acid binding agent. There is no regeneration of the t-cumyl chloride. Kato's ~ process was run with an acid sensitive aralkyl ; 15 hydroperoxide, cumene hydroperoxide, with t-cumyl chloride in the presence of t-butyl alcohol (see Example XX]. Although the reaction ran quite fast, only a 36% yield of dicumyl peroxide was obtained. There was a considerable amount of phenol generated during the reaction indicating the t butyl alcohol was not a good scavenger of the hydrogen chloride; consequently a large amount of the cumene hydroperoxide underwent acid catalyzed decomposition to form phenol and acetone.

Kloosterman et. al. (Auslegeschrift 1,216,305) describes a process for the prepara-tion of dicl~yl peroxide and its ring chlorinated derivatives by th.e reaction of t cumyl chloride or its ring chlorinated derivatives with an aqueous solution of hydrogen peroxide at 0~40C
in the presence of an acid binding medium so that the pH of the reaction mixture stays between -1 and ~.5 on a glass/Kalomel electrode. In a stronger acid medi~ decomposition exotherms were reported to occur. A mole ratio of t~cumyl chloride to hydrogen peroxide of 1:0O5 to 1:0.8 were used in this sys~em. The anhydrous basic acid binding agents, such as Na2CO3, K~CO3 or NH3, had to ~e added portionwise throughout the reaction so that the pH held between -1 and 2.5.
Bafford's ~.S. 4,133,835) process consisted of adding an aliph.atic or cycloaliphatic hydro-peroxide to an olefin such as a l-aromatic~l-sub-stituted ethylene and a halide corresponding to the ethylene under essentially anhydrous condi-tions in the absence of a free aci.d, at a temperature below the decomposition temperature of the halide. The main ob~ect of this invention was to provide a process for the preparation of certain peroxides, especially acid-sensitive peroxides by a procedure that does not use a free-acid catalyst. ~he process is similar to that of Kato's except Bafford uses the l-aromatic-l-subs~ituted ethylene as the acid binding agentO
By doing this aralkyl halide is regenerated.
Consequently, a low concentration of the aralkyl halide in the olefin can be used; the reaction becomes less acid sensitive and the economics are : much ~etter. Bafford stresses the importance of having an excess of hy~roperoxi~e over the olefin/aralkyl halideO
None of the prior art teaches the use of phenols as catalysts; to the best of our knowledge there never has been any mention in the literature of u~ing phPnols as catalysts for making peroxides.
Statement of the Invention .
This invention is directed to an impro~ement in the process o~ preparing the cumyl peroxides comprising reacting an aliphatic or cycloaliphatic hydroperoxide or aliphatic dihydroperoxide, an olefin ~such as alpha-methylstyrene or a substi-tuted alpha-methylstyrene, and a t-cumyl halide corresponding to the hydrohalogenated olefin such as t~cumyl chloride (or bromide) or a subs-tituted t~cumyl chloride (or bromide) in the presence of a phenol ca~alyst under reiati~ely no~-a~ueous conditions to form a cumyl (or substituted cumyl~ peroxide or diperoxide corresponding to the hydropero~ide or dihydroperoxide.
Detailed Description of the In~ention The olefin is alpha-methylstyrene or a sub~
stituted alpha-methylstyrene of Formula I
~H3 z (I) where the substituent Z is an inert group substi-tuted on the phenyl ring of the alpha-methylstyrene.
Suitable substituents include hydrogen, lower alkyl groups of 1 to 6 carbons such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, amyl, t-amyl or hexyl, halo groups such as chloro, bromo or fluoro, ether groups such as methoxy, ethoxy, propoxy, iso-propoxy or phenoxy and aryl groups such as phenyl or naphthyl.
The reactive halide is t-cumyl chloride or bromide or a substitu-ted t-cumyl chloride or bromide of Formula II

~ (II) Z
~. , where the su~stituent Z is an inert group substi-tuted on the phenyl ring of the t-cumyl halide, Y
is chloride or bromide and the reactive halide is the addition product of hy~rogen chloride or hydrogen bromide to the particular olefin employed.
The organic hydroperoxide is an aliphatic or cycloaliphatic hydroperoxide or aliphatic dihydro-peroxide having the general formula III
R -[OOH] y (III) where y is 1 or 2;
when y is l, R is selected from lower t-alkyl of 4 to 8 carbons, lower t-alkynyl or 5 to 8 carbons, t-aralkyl of 9 to 12 carbons or t-cycloalkyl of 5 to lO carbons; and lS when y is 2, R is selected from H3 1 3 f 3 CH3 C~C---or -C ~ C-C~3 CH3 where R' is an alkyl of 1 to 6 carbons.
Suitable hydroperoxides include t-butyl hydro-peroxide, t~amyl hydroperoxide, t-he~yl hydro~
peroxidel 1,1,3,3 tetramethylbutyl hydroperoxide, cumene hydroperoxide, cymene hydroperoxide, p-menthane hydroperoxide, l~methylcyclohexyl hydro-peroxide~ l-methylcyclopentyl hydroperoxide, 3-hydro-peroxy-3 methylbutyne~1, 2-hydroperoxy-2 methyl-; 4-hydroxypentane and 1-hydroperoxycyclohexylacetylene.
Suitable dihydroperoxides include 2,5--dim thyl~2,

5-dihydroperoxyhexane, 2 r 7-dimethyl-2, 7-dihydro-peroxyoctane, 2,5-dimethyl-2,5-dihydroperoxy-hexyne-3 and diisopropylbenzene dihydroperoxidesO
The phenol catalyst has the formula, ; 15 ~,0~ X~OEI

X' X' (V) (IV) and is phe.nol or naphthol or a substituted phenol or naphthol of Formula IV or V with inert sub-stituents X and X' which may be the same or different but when neither is hydrogen both X and X' cannot be subskituted ortho to the hydroxyl group at the same tLm~. X and X' axe selected from hydrogen, lower alkyl groups of 1 to 6 3~ 3 carbons, lower alkoxy groups of 1 to 6 carbons, aryloxy groups of 6 to 10 carbons, also groups such as chloro, bromo, fluoro or aryl groups of 6 to 10 carbons. It should be understood that when X and X' are hydrogen atoms, the phenol or naphthol are unsubstituted~ Preferably the sub-stituents should not be in the position ortho to the OH group where they would create steric hindrance to the OH group. For example, the hydroxyl group in 2,6-diisopropylphenol is too sterically hindered to ~enerate any catalytic effect on the reaction. o-Cresol is not as effective as p-cresol.
The following is a list of suitable phenols and naphthols: phenol, ortho, meta and para cresols, chlorophenols, bromophenols, methoxy-phenols, ethylphenols, isopropylphenols, para-t~
butylphencl, paraphenylphenol, 3,4-dichlorophenol, 3,4-dimethylphenol, alpha-naphthol and beta-na~hthol.
From a practical standpoint it is advantageous to use a cheap low molecular weight phenol which can be readily extracted out of the reaction mixture with aqueous caustic. Phenol and the meta and para cresols or mixtures thereof are especially suitable. alpha- and beta-Naphthols are also suitahle.
The reaction is run in the temperature range of 10-50C prefera~ly 15-45C. Since the phenol acts as a catalyst, the reaction temperature and reaction time are quite dependent on the amount of phenol added. When small amounts of phenol are added, the reaction will take longer and should be run at a higher temper-ature than when larger amounts of phenol are added. In practice we have found tha~ it is advisable to start the reaction ou~ at a low temp~ratur~, 15-25C, while the bulk of t~e reaction is going on and then progr~m the reaction temperature up as the reaction slows down. In mos~ cases ~he reaction can be monitored by gas chromatography.
: The mole ratio of olefin groups to hydro-peroxide groups can vary from 0.5.1 to 5:1. The yield of peroxide based on the hydroperoxide increases as the mole ratio of olefin to hydro-peroxide increases frcm 1:1 to 2:1. Increasing the mole ratio of olefin to hydroperoxide above 2:1 does not improve the yield and would only be applied when there is a problem of solubility of the hydroperoxide in the reaction system. In practice a mole ratio of approximately l.3:1 is optimum in regards to yields and the amount of product that can be made per gi~en reactor volume.
Although one could run the reaction at a mole ratio less than l ol ~ in most cases it would not be economically advisable.
- The t-cumyl halide is charged in an amount of a~out 5-20 mole percent based on the olefin charged. Generally one would use 7 12 mole percent. Increasing the mole percent t-cumyl halide increases the reaction rate but usually increases the amount of i~purities generated as well.
The components of the feed may be charged to the xeaction zone in any order; but it has been found pxeferable to add the t-cumyl halide to a solution of the hydroperoxide, olefin and phenol or to add a solution of the phenol in th~ hydro-peroxide to the solutlon of t-cumyl halide in the alpha-methylstyrene or add the phenol last since a mixture of the olefin, t-cumyl halide and phenol, in~the absence of hydroperoxide, under-goes some degree oE oligomerization of the olefin.
When the t-cumyl halide is added last, the t-cumyl halide can be added neat or as a solution in the olefin or e~en in an inert diluent. The adaition of thR t-cumyl halide sh.ould be carried out at such a rate and temperature th.at the reaction can be easily controlled. If th.e halide is added too fast at a high temperature in the presence of a considerable amount of phenol, a runaway reactïon could occur.
The system does not have to be completely anhydrous but water does have a rate retarding effect. I-t has been found beneficial in some cases, from an ease in handling stanapoint~ to use liquifi.ed phenol which so~tains about 9~ water~
When using liquified phenol you have to increase the amount of phenol used by about lO~ to overr.i~e the rate retarding effect of the water.
For each peroxide, the mole ratios, temper-ature, addition rate and phenol level have to be adjusted slightly to obtain the optimum reslllts.
The cumyl peroxide compounds produced in process of this invention are useful crosslinking agents for high and low density polyethylene, elastomers and rubbers.

Examples The examples will demonstrate the prepara-tion of various cumyl peroxides using the phenol catalyzed system, the effect of the phenol on the time requixed to complete the reaction and the advantages of the phenol catalyzed system over the prior art systems. They will also demonstrate that various phenols are effective ; catalysts an~ that alcohols, kètones and organic acids are not.
Most reactions were monitored by gas chromatography (G.C. or VPC) and the values given in the example tables will be area percentage values obtaine~ by integration of the VPC scans.
Although these values are not absolute ta small percentage ~rv2~) of rnaterial does not come through the VPC], they are relative and will clearly demonstrate the catalytic effect of the phenol. The gas chromatographic analyses were carried out on a Hewlett Packard 5710A gas chromatograph coupled to a 3380S integrator. An 18 inch 1/8 inch diameter 3% OV-17 column was uæed. The injection port t~mperature was 110C
and the thermal detector temperature was 250C.
For dicumyl peroxide the temperature was pro-grammed at 8C per minute from 45C to 210C and the helium f 10W rate ~as approxlmately 90 cc per minute. The dicumyl peroxide was diluted about ~:1 in pentane to flush it through the injection point. A .25 minute delay was carried on the integr~tor so the pentane would not integrate.
The temperature program rate and helium flow were cut back for the more volatile peroxides.
Final assays and yields in mos t cases were determine~ accurately by liquid chromatography using analytically pure standards and internal standards.
Example I
Preparati~n of t-Cumyl Chloride Into a jacketed 2 liter reactor equipped with a thermometer~ gas inlet tube, mechanical stirrer, bottom outlet and a water~cooled con-denser connected to a gas bub~ler was added 708 grams (6 moles) of alpha methylstyrene. Hydrogen chloride was passed into the alpha-methylstyrene over 2 l/2 hours at 27-29C at a slow enough rate that complete absorption was obtained. After 226.3 grams (6.2 moles) of hydrogen chloride had been added, absorption ceased and the hydrogen chloride bubbled through the gas ~ubbler. The addition was stopped and the solution was stirred l/2 hour at 28 29 C. The product was drained - 15 ~

into a tared glass bottle and weighed. The bottle was tightly capped and stored in the freezer compartment of a refrigerator. The pxcduct weighed 927 grams for a 100% yield~ The ; 5 product was used as a stock solution for the subsequent reactions.
Although it is more practical on a commercial basis to prepare a solution of cumyl chloride in ; alpha-methylstyrene, it was found much easier on a labor~tory scale to make the solution by adding a weighed amount of 100% t-cumyl chl~ide to a predetermined amount of alpha-methylstyrene. It was much easier to obtain accurate concentrations of the t-cumyl chloride in the alpha~methylstyxene operating in this manner xather than trying to accurately weigh small amounts of hydrogen chloride into the alpha-methylstyrene each time.
Exampl II
Preparation of Dicumyl Peroxide This example demonstrates the difference between a phenol catalyzed reaction and a non-catalyzed reaction in the preparation of dicumyl peroxide. The reactions were monitored by gas chromatography.

A. Phenol Catalyzed Reaction Six grams ~0.064 m) of phenol were dissolved in 57,4 grams (0.315 m~ of 83.5~ cumene hydro-peroxide by stirring the solid phenol in a beaker with the cumene hydroperoxide with a magnetlc stlrrer at roo~ temperature.
Into a ZOQ ml jacketed reactor equipped wi~h a mechanical stirrer, thermometer, water-cooled , condenser and addition funnel were added 47.2 grams ~0.4 m) alpha-methylstyrene and 6~7 grams (0.043 mJ t-cumyl chloride. T~e stirrer was activated and the temperature of the solutlon was adjusted to 15C by circulating cold water through the reactor jacket. The cumene hydroperoxide solution was transferred to the ad~ition funnel and added to the reactorover 8 minutes at 15C.
Tne reaction was stirred an additional 5 minutes at 15C; then the reaction was warmed to 30C
over 5 minutes and stirred ~5 mlnutes at 30C, and 1 1/4 hours at 45C at which point the cumene hy~roperoxide was completely consumed.
The reactisn was termlnated ~y a~ding 50 mls o~
water, stirring 15 minutes, adding 10 mls of 50%
NaOH, stirrlng an a~ditional 15 mlnutes and separating the aqueous caustic layer. ~l~he organic layer was successively washad with 50 ml portions oE water, 15~ Na~S03 solution, water, saturate~ Na~C03 solution, 1/2 % EICl and water.
~he volatiles were steam distilled out of the crude product under vacuurn ~See Example III~.
The organic resldue after isolation and arylng weighed 61.5 grams ana assayed 96.1% by liquid chromatography to give a 69.5~ corrected yield.
Bo Non-Catalyzea ~eaction lhe non-catalyzed reaction was run the same ; as the reaction in part A except no phenol was dissQlved in ~he cumene hy~roperoxi~e. The same temperature progrc~m was used for the reaction except the raaction had to be run 5 1/4 hours at 45 C instead of 1 1/5 hours to ccmplete the reaction. The volatiles were steam dlstilled out of the crude product under vacuum ~see Example III). The organic residue after isolation and drying ~eighed 57.0 grams and assayed ~4.~% by liquid chromatography to give a 57~ corrected yield~
Table I gives a summary of the % dlcumyl peroxide in the reaction mixtures after various lengths of reaction. The values in parenthesis .are normalized for the amount of phenol added to the system, so a direct comparison can be dra~n.

Table I
% Dicumyl Peroxide in Reaction Mixtures Phenol Reaction Tlme Temp C Catalyzed Non-catalyzed 5 minutes 15 6.4 ~6.~ 1.7 1/2 hour 30. 25.7 (~7~0) 7.5 1 hour 45 53.7 (56.5) 23.5 1 1/2 hours 45 ~0O~ (63.3~ 36.
1 ~/4 hours 45 61.4 ~64.5)*
2 hours 43.8 3 houxs 5~.6 4 hours 57.~
5 hours 59.6 5 1/2 hours 60.3 5 3/4 hours 61.3*
:

* Reaction complete - Example III
Steam Stri~pin~ of DicumYl Peroxiqe This example describes the procedur~ for steam distillLng off the volatiles from the crude washRd dicumyl peroxide and the isolation and drying of the final product~
The washed dicumyl peroxide was trangferred to a 2 liter 3 neck flask with a thermometer, steam inlet line, magnetic stirrer and distilling head connected to a condenser, receiver and dry ice trap connected ko a manometer and vacuum p~p. Approximately 400 mls of water were added to the flask/ the magnetic stirrer activated and a vacuum of 100~120 mm Hg drawn on the system.
Then the steam line was cracked open and the glass inlet lowered below the level of the liquid. The volatile components were s~eam distilled out of the flask and co~lected in the receiver and the dry ice trap. The temperature in the flask was held around ~5-60C throughout the steam dis-tillatio~. The steam stripping required approxi-mately 1 l/2 hours at 55-60C and 100-120 mm Hg~
At the end of the steam stripping (no organic film in the condenser~, the steam inlet was raised above the level of the liquid, the steam shut off and then the vacuum pump was turned off.

The vacuum ~as released and the contents of th~
flask cooled to about 30 C. The mixture was ~ransferred to a 2 liter separatory funnel and the stripped dlcumyl peroxide taken up in 400 mls of pentane by shaking for 5 minutes. The pentane layer was separated, ~ried over an~ydrous sodium sulfate, filtered and the pentane stripped off under reduced pressure on a rotating evaporator.
; A water aspirator was used to remove mos~ of the pentan~ and the last traces were removed by stripping with a vacuum pump at 50 C. The residue was weighed and assayed by liquid chromatography using an internal standard.
Exc~mPle IV
Preparation of Dicumyl Peroxide Usin~_~arious Amounts of~Phenol This example ~emonstrates how varying the amount of phenol catalyst in the reactlon effec~s the reaction time required to complete the reac-tion. All the reactions were monitored by gas chromatography to determine when the reactions were complete.
A series of 5 reactions were run where the amount of phenol added was varied from 2 to 10 grclms in 2 gram intervals. The reactions were run at 40C and the reaction time varied from greater than 5 1/2 hours to 1 1/~ hours. The .

- 21 _ reactlons were run in the 200 ml jackQted reactor described in Example II. The phenol was dissolved in 47.2 grams (0.4 m) alpha-methyl-styre~e and ad~ed to tne reactor. The t-cumyl chloride, S.0 grams (0.0323 m), was added to the reactor and the temperature adjusted to 25 CO
The ~l.Y% cumene hydroperoxlde, 58.6 grams (0.315 m~, was added with vigorous stirring over 5 minutes at 25 C from an addition funnel. At the-end of the addition the temperature was ralsed to 40C a~d the reaction stirred until xeaction was complete, i.e. less than 1~ unreacted cumene hydroperoxide in the VPC scan. (In the case of the run made with only ~ gr~ms of phenol the reaction was terminated after 5 1/2 hours al-though there was still about 4~ cumene hydro-peroxide present in the reaction mix~ure due to insufficient time to complete the reaction. This accounts for the low yield in this runl. The reactions were terminated and worked up in the usual manner. The results are illustrated in Table II.

Table II
Effect of tne Amount of Phenol Present on the Reaction Time Grams C6~I OH Reaction Time Strlpped L. C. Corrected Run #added 5 at 40 C Weight Assay ~ Yield 1 2 5 1/2 hours* 57.1 97.3 65.3 2 ~ 5 hours 61.0 95.9 ~8.~
3 6 ~ 1/2 hours 64.3 96.~ 72.8 4 ~ 1 3/4 hours 64~8 96.0 73.2 1~ 1 1/2 hours 66.0 95.7 74.

* Reaction incomplete ~xample_~
Preparation of Dicumyl Peroxide Usinq Various Amounts of Phenol and Excess Cumene ~ydroperoxide.
This example also demonstrates how varying the amount of phenol catalyst in the reaction effects the reaction tLme required to complete the reaction but in thls reaction an excess of cumene hydroperoxlde is used. All the reactions ,i were monitored by gas chromatography to deter-mine when the reactions were c~mplete.
A series of 4 reactions were run where the amount of phenol added was varied from 0 to 3 grams in 1 gram intervals. The reactions were run for 1/2 hour at 30, the temperature raised to 45 C and the reac~ion completed at 45 C. The reaction time at 45C varied from 3 1/~ hours to 1 1/4 hours.
The reactions were run in a 250 ml ~-neck round bottom flask equlpped with a magnetic stirrer, thermometer, condenser and addition funnel. The phenol was dlssolved in 27.2 grams (0.231 m) alpha-methylstyrene in the reaction flask. The t-cumyl chloride, 5.8 grams ~0.37 m~, was added to the flask and the temperature adjus~ed to 20C. Then 81.9~ cumene hydro-peroxide, 58.6 grams ~00315 m~, was added with - ~4 -vigorous stirring over 5 minutes at 2QC from the addition funnel. At the end of the addition the temperature was ralsed to 30C for 1/2 hour and then raised to 45C and the reaction stirred until reaction was complete, i.e. less than 1~6 unreacted cumene hydroperoxide in the VPC scan.
The reactions were terminated and worked up in the usual manner. The results are illustrated in Table III. The corrected ~ yields are based on the cumene hydroperoxide despite the fact it was used in excess.

Table III
Effect of the Amoun~ of Phenol Present on the ReactiQn Time Grams C6H5OH Reactio~ Time Stripped L. C. Corrected Run #Adaed at 45 CWeight As~ay ~ Yield 1 0 3 1/2 hours51.2 91.7 55.2 2 1 2 1/2 hours52~2 92.6 56.9 3 2 1 3/4 hours51.~ 93.8 56.8 4 3 1 1/4 hours 5~.7 93.3 57,9 Example VI
Preparation of Dicumyl Peroxide Using Liquified _ ?~e~ Cata~
This example demonstrates that liquified phenol~ which contains about 9% water to keep lt in the liquid state, is also a very effecti~e catalyst fox tne preparation o~ ~icumyl peroxide.
In~o a ~ ter jacketed reactor equipped with a mechanical stirrer, thermometer, water-cooled condenser and addition funnel, were added 141 grams (1.2 m) alpha-methylstyrene, 229.6 grams ~1.26 m) o~ 83.3~ cumene hydroperoxide and 26.7 ~rams (0.255 m~ of 91~ aqueous phenol (liquified).
A solution of 26.8 grams (00173 ml t-cumyl chloride in 47 grams (0.4 m3 alpha-methylstyrene was transferred to the addition funnel. The t-cumyl chloride solution was added to the stirred hydroperoxide solu~ion over 5 minutes whlle adjusting the reaction temperature at l~ 0C by ~0 circulating water through the reactor jacket.
The reaction temperature was raised from ~0 to 25 C over ~0 minutes, th.e reactlon stirred 20 minutes at 25 C, the reaction temperature raised to 35C over 20 minutes, the reaction s~i.rred 15 ~5 minutes at 35C, the reaction temperature raised to 45C over 1~ minutes and the reaction stirred 4~ minutes at 45C to complete the reaction.

~ 26 _ The reaction was terminated by adding ~5 mls of water, stlrxing 5 minutes, addlng 150 mls of Na2S03 solution and stirring another 5 minutes.
The aqueous layer was separated and the organic layer was washed successively with 2~0 ml portions of 3~% NaOH (twicel, and water (4 timesl. After drying, the crude product weighed 395 gram~ and assayed 6~.7% by liquid chromatography to give a , /6.5% ylel~.
Example vII
Preparati~ ~ Cumyl ~-Butyl Peroxide This example demonstrates the difference between a phenol catalyzed reaction and a non-cataly~ed reaction in the preparation of cumyl t-butyl peroxiae. The reactions were monitored by gas chromatography to detenmine the extent of reaction.
. Phenol Catalyze~ Reaction Into a 500 ml erlenmeyer flask equipped with a magnetic stirrer and a thermometer were added 141.6 grams (1.~ m~ alpha-methylstyrene, 92.7 grams (0.945 m) 91.9% t-butylhydroperoxide and l.8.0 grams ~0.192 m~ of phenol. The solution was stirred 10 minutes and the temperature adjusted to 18C~ To this solution was added 1~.4 grams ~U~0~6 m) of t-cumyl chlorlde over 8 minutes with the temperature slowly rising to 22 C. Tne flask was placed in a cool water ha~h and the reaction stirred for 1j2 hour at 25C. The water bath was removed and the temperature rose to 35 C over ~he nex~ 1~2 hour and ~o 3~C over the next 15 minutes where it leveled off and remained constant for the next hour an~ then slowlv dropped to 35C over the ne~t 1 1/2 hours. Aftex ,~ a total of 3 3/4 hours s~irring the reaction was essentially comple~e so 150 mls of water were added, the mixture stirred 1~ minutes to hydrolyze the t-cumyl chloride an~ then 30 mls of 50% NaOH
were added. The brown mixture was stirred 15 minutes and the ~rown aqueous layer separated.
The organic layer was washed witn 100 mls of 15%
NaOH then 3 tlmes with 100 mls of water and once with 100 mls of saturated NaHC03 solution. The crude product was dried over anhydrous sodium su]fate and filtered. The drying agent was rinsed down with pentane and the pentane stripped off on a rotating evaporator. The residue weighed 2~4.~ grams and assayed 77~5% cumyl t-butyl peroxide ~y gas chromatography for an 88.5~ yield.
The pure product was lsolated by fractional dis tillatLon under vacuum. A summary of the extent of reaction at v æ ious time lntervals frQm - 28 -o integra~ion of the VPC scans can be found Ln Table IV. Th.e values in parenthesis are values corrected ~or the amount of phenol in the system so they czn be dlrectly compared to the non-catalyzed system.
B. Non-Ca~alyze~ Reaction Into a ~00 ml erlenmeyer flask equipped with a magnetlc stirrer and a thermometer were ad~ed l41.6 grams ~1.2 m~ alpha-methylstyrene and 9~.7 grams ~0.945 m) ~1.9% t-butylhydroperoxide.
The solution was stirred lO minutes and the temperature stabilized at 24C.
To this solution ~a~ added 1~.4 grams cn .0~6 m~ of t:-cumyl chlorlde over 7 minutes. The reaction was stirred 30 minu-tes at Z5C and then the flask was placed in a warm water bath and the temperature raised to 35 C over l/2 hour. The reaction was then stirred 3 hours at approximately 3~ C. Since there was a large amount of unreacted t-butylhydroperoxide left, the.reaction was stirred 2 hours at 40~45C, allowed to stand over-night at room temperature and then stirred another hour at 40-45C. Since there was still about ~5%
of the t-butylnydroperoxide unreacted an additional 3 grams of t-cumyl chlorlde were added and the reaction stirred 3 hours at 40 C - 5C. Ano~her - 2~ -3 grams of t-cumyl chloride were adaed and the reaction was stirred another hour at 40 C ~ 5 .
Si.nce very little reaction was occuxring the reaction was terminated by adding 100 mls of water followe~ by 30 mls of 50% NaOH 5 minutes later. The same workup procedure was used as in part A. The crude product weiyhea 211 grams and assayed 67.~% for a 7~% yleld. Thus using the non-catalyzed system, the reaction time was much longer, higher temperatures had to be employed, the reaction did not go to completion,the yield was lower and the assay was lower. A summary of the extent of reaction at various time intervals can be found in Table IV.

~ C~ U~ ~ o ~ C~ o ~
~ O ~ ~ ~ ~D ~> O ~r o\O ~ ~ ,, ~ ~ ~P ~ ~
__ _ _ _ _ N O~ N~)NLl'l a~ Lt~ I
~ OO r-lCO~ N O ~D I`
~ m~ ~N N N N r~l ~ ~ _ ___ .
Y __ U~
O ~ N In ~D N ~ ~1 00 ~7 Z U~ ~ Ir~ 00 N O ~ CO O
0~o ~ ~r X '6 O __ __ _ _ _ ~ _ ~1 _ _ _ _ _ P~ ~ ~:7 r~ ~ U~ r~
~1 ~ ~ o~a~ ~~n ~
~1 ~I ~ If) U~ ~D
_ ~_~___~ ~_ d~
Oo:~ I~ ~ ~In u~
S~ . . . . .
~> ~) P~~_ Ln ~ ~ ~ 11') )-1 ~ N~r ~U l 11 Q~ ~ -- -- - - - - --Q ~r a~ 00 _ ~ . , . N ~ a~
E~ S ~D r~ O . . .
u~ 0 N N ~ ~ ~ N
O ~ 0~ _ _ _ _ _ _ '~
~: ~ m I` In ,~ r~a~ ~g , ~i N ~ ~ ~ ~ ~ N N .C
~ _ _ _ _ _ .
h ~ ~ ~1 n c~ ~o N ~1 ~ N ~ O~ ~ ~
~1 o\ O o o o o o cn U
1:4 ~1 ~ ~1 ~1 ~1 ~1~1 I .,1 O ~ ~ O
~:: . ___ __ __ .
.~ ~ _~ _ _~ _ ~ O U~
P~,1 Ln ~ ~ O ~ ~ '~
~ ~9 o ~1 r- u~ ~r O ~) ~ t~ ~ N ~1 ~1 ~J ~1 0\o U~ _ ~_ _, _ _ _ .
,......... :~ 1~ ~r 1~ oo ~D O
N r~ a~, In ~) ~ N ~1 ~1 ~1 ~1 _ _ ~ ~ In ~ IS~ In Lr Ul O O O
a~ o ~ ~`J ~- ~ ~- ~ ~ ~r ~ S 1 5 1 E~ ~ a~
_ _ __ _ . ___ _ __ ~ ~

~ h ~
O ~1 o u~ ~n u~In s U~ U1 .~ ~¢ rl 1: ~ ~15 1 ~1 ~ ~ S~ O
.,1 .,_1 ~ ~ ~ ~r :~ ~ ~ S
o o o ~ o o o a (d ~3'd o o ~ ~ ~ ~ ~:: ~: S ,I p:;
~ E~ 1 ~ ~ ~ ~ ~ ~ ~ ~ *
.... ~f ., :..

~ æ~
Pre~aration Qf Cum~ AmyL Peroxide This example demonstrates th~ difference ~etween a phenol catalyzed reaction rat two levels of phenol~ and a non-catalyzed reaction in the preparation of cumyl t-amyl peroxide.
rrhe reactions were monitored ~y gas chromato-graphy to determlne the extent of reaction.
A. Phenol Catalyzed Reaction - High Level of Phenol Into the 203 ml jacketed reactor descri~ed in Example II were added 15 . n grams (0.127 m) alpha-methylstyrene, 15.5 grams (0.1 m) 67~%
t-amy:L hydroperoxïde and ~.8 grams (0. 041 m;
phenoL~ The mixture was stirre~ to obtain a clear solution and the temperature was adjusted to 20C by pumping cool watPr tnrough the reactor jacket. To this solution was ad~ed 1.4 grams (00009 m) of t-cumyl chloride from t~e addition funnel over 10 minutes while holding the temperature at 21-2~ C0 The reaction was stirre~ 5 minutes at 2~C, the temperature raised to 25 C and the reaction stirred 1/2 hour at ` 30 C, 1/2 hour at 35 C, 1 1/2 hours at 40 C and 1/2 hour at 45 C for a total reaction time of 3 1/2 hours. At this point essentlally all the t-amyl hydropero~ide had ~een consumed. The ;

reaction was termina~ed ~y adding 25 mls of water~ stirring 5 minutes, adding 5 mls of 50%
NaO~, stirring another S minutes and then separating the aqueous caustic layerO The organic layer was washed with saturated NaHCO3 solution, ~ater, 15% NaHS03, saturated NaHC03 again and water. The dried material weighed 24.6 grams and contained 54.6% cumyl t-amyl peroxide for a corrected ylel~ of 13.4 grams and a 60~5% yield~ The pwre cumyl t-amyl peroxi~e was isolated by fractional distillation under vacuum.
B. Phenol Catalyzed Reaction - Low Level of Phenol This reac-tion was run the same as the reaction in part A except the mole ratio of phenol to hyclroperoxide was cut ln half. The same temperature programs was used for the reaction except the reaction had to be run 3 hours at 45 C
instead o~ 1/2 hour at 45 C to essentially com-plete the reaction. The ~ yield was only 49.~.
C. Non-Catalyzed Reaction The reaction was run the same as the reaction in part A except no phenol was used.
The same temperature program was used for the reaction except the reaction was run 3 1/~ hours at 45 C instead of 1/2 hour and only ahout 1/~

~2~3~3 of the t-amyl hydroperoxide had reacted. The reaction was terminated at this point due to a lack of -time. The % yield was only 20.6%.
Table V gives a su~nary of the % of cumyl t-amyl ~eroxide in the reaction mixture at various stages of the reaction. The values in parenthesis are normalized for the amount of phenol added to the system so that a direct comparison can be drawn.

Table V
C-umyl t-Amyl Pe~roxide~in Reaction Mixture _ . _ _ Phenol Cc Italyzed Non Catalyzed Reaction Time Temp. C H ~ Level Low Level 1/2 hour 25 18 (20.5) 7.4 (7.9) 2.4 1 hour 30 29.7 (34.2) 1408 (15.8) 5.4 1 1/2 hours 35 22.1 123.7) 9.4 2 hours 40 46.2 (53.3) 29.2 (31.3) 13.6 2 1/2 hours 40 50.0 (58.0) 33.9 (36.4) 3 hours 40 50.8 (59.1~ 37.7 (40.5) 16.4 3 1/2 hours 45 53.4 (6109)* 40.3 (43.1) 4 hours 45 42.8 (45.7)21.9

6 hours 45 53.2 (55.9)*25.6 6 1/2 hours 45 26.1 * Reaction complete a ~

- 3~ -Example_IX
Preparation of CumYl t-Hexyl_3Q~
This example demonstrates the difference ~etween a phenol catalyzed reaction ~at two levels of phenol~ and a non-catalyz~d reaction in the preparation of cumyl t-hexyl peroxide.
The reactions were monitored by gas chromato-graphy to determine the extent of reaction.
A. Phenol_Catal~ed Reaction - High Level of Ph nol Into the 200 ml ~acketed reactor described in Example II were added 15 .6 grams (0.13 m) alpha-methylstyrene, 15.0 grams (0.104 m~ ~2 t-hexyl hydroperoxi~e and 4.0 grams (0.04~ m) :~ - pheno:L. The mixture was stirred to~obtain a : 15 clear solution and the temperature was ad justed : to 20C. To this solution was added 1.5 grams ~0.0095 m) of t-cumyl chlo~iae from the addition funnel over 5 minutes while holding the tempera-ture at 21-22C. The reaction self-exothermed to 25C over lO minutes and then was stirred an additional l/2 hour at 25C. The reaction was then stirred 80 minutes at 35C and 90 minutes at 40C at which point the reaction was complete.
The reaction was terminated ~y adding 25 mls of water, stirring 5 minutes~ addlng 5 mls of ~0%
NaoEr~ stirring another 5 minutes and separating the aqueous caustic layer. ~he organic layer was successively washed with ~5 mls of 15% NaOH, saturated NaHCO3 solution, watex, 15% Na~S03 solution, saturated NaHCO3 solution and water.
After drying with anhydrous sodium sulfate the cru~e product weighed 26.7 grams and contained 80.6% cumyl t-hexyl peroxide ~or a corre~ted yield of 21.5 gr~ms and a 87.8% yield. The pure c~nyl t-hexyl peroxide was isolated by fractional distillation under vacuum.
B. Phenol Catalyzed Reaction - Low Level of Phenol This reaction ~as run the same as the reac~ion in part A except only ~.0 grams (0.021 m) of phenol were used. The same temperature program - 15 was u~3e~ for the reaction except the reaction had to ~e stirxed an additional 95 minutes at 45 C to complete the reaction~ The crude product weighed 26.4 grams and assayed 74.0% cumyl t-hexyl peroxi~e for a corrected yield of 19.5 grams and a % yield of 79.7%.
C. Non-Catalyzed Reaction The reaction was run the same as the reaction in part A except no phenol was used.
The cumyl chloride was added over 5 minutes at 20-21 C. After 40 mlnutes stirring the tempera ture had only risen to 23 C. The reaction was warmed to 35C, stirred 80 minutes at 35C, 90 minutes at 40C and ~ 1/4 hours at 45C. At this point about ~5% of the t hexyl hydroperoxide had still not reacted but the reaction was terminated and worked up as in Part A due ~o lack of t~le. The crude product weighed 13 . 8 grams and assayed 29 . 8% for a corrected yield of 5.9 grams and a % yield of 24%.
Table VI gives a summary of the % cumyl t-hexyl peroxide in the reaction at various stages of the reaction. The values in parenthesis are normalized for the amounts of phenol added to the system so that a direct ccmparison can ~e made.

' Table VI

_____ _ % C lmyl t-~ex~r 1 Peroxide in Reaction M xtu re Phenol Ca talyzed Non-Catalyzed Reaction Time Temp. C igh Level Low Level 3.1 1 hour 35 49.0 (53.6)20.7 (21.6) 1 1/2 hours 35 62.0 (68.3)31.4 (32.8) 2 hours 35 71.4 (77.8)41.0 (42.4) 8.8 3 hours 40 75.5 (83.7)55.1 (57.8) 13.3 3 1/2 hours 40 77.2 (84.-6)*60.2 (63.1) 15.3 4 hours 45 64.9 ~67.5) 4 1/2 hours 45 65.8 (69.0) 19.4 5 1/2 hours 45 70.8 (74.2) 21.6 6 1/2 hours 45 74.9 (78.5)* 24.7 * Reaction complete , - 37 -,~

Example P aration of Cumyl t-Octyl Peroxide Into ~he ~00 ml jackete~ reactor described in Example II were added l8.0 grams ~0.l52 ml alpha-methylstyrene, 1~.4 grams (0.ll ml ~7.6~
l,l,3,3-tetr~methyl~utyl hy~roperoxide and 4.6 grams ~0.04~ ml phenol. The mixture was stlrred to obtain a clear solution and the temperature was adjusted to 20 C. To thiS solution was added l.7 grams ~0.0ll m~ of t-cumyl chlorlde from the addition funnel over S minutes whlle holding the temperature at 20-21C. The reaction was stirre~ 5 minutes at 21-2~ C, warmed to 25 C
and stirred l/2 hour at 25C, l/~ hour at 30C, 1/2 hour at 35C, 1 1/2 hours at 40C and finally 1/2 hour at 45C. At thls poin~ the t-octyl hydroperoxlde had been completely consumed and the reac~ion ~as terminated by adding ~0 mls of water, stirring 5 minutes, adding 10 mls of 50% NaOH, stirring another 5 minutes and separating the aqueous caustic layer. The organic layer was successively washed with 50 mls 15% NaOH, saturated NaHCO~ solutlon, H2O, 15% NaHSO3 solution, saturated NaHCO3 solution and water.
After drylng over anhydrous sodi~n sulate the crude product weighed ~2.6 grams and contained 3~3 72.6~ cumyl t-octyl peroxide for a corrected yield of 23.7 grams and a Rl.5% yield.
The crude product was purified ~y steam dis-tilling off the volatiles under vacuum and chramatographing the residue over alumina using pentane as the eluent.
Example XI
Preparatlon of ~ eroxY 2~methYl-4-h~roxy~entane The reaction was run in the same manner as the preparation of cumyl t-octyl peroxide excep~
16.1 grams C0.12 m) of 2-hydroperoxy-2-methyl-4-hydroxypentane were used instead o~ the t-octyl hydroperoxide. The reaction was stirred 1/~ hour at 25 C, 1/2 hour at 30 C, 1/2 hour at 35 C, 1 1/2 hours at 40C and finally 3 hours at 45C
to complete the reaction. The reaction was worked up in the normal manner. The crude product weigned ~8.~ grams and assayed approximately 67%
for a 64% yield.
ExampZe XII
Preparation of 3-~t-cumylperoxy)-3-methylbutyne The reaction was run in the same manner as ` the preparation of cumyl t-oc~yl peroxi~e except 16~4 grams ~0.12 ml of 73.3% 3-hydroperoxy-3-methyl~utyne-l were used instead of the t-octyl hydroperoxide. T~e reaction was stirred 1/2 hour at 25C, 1/2 hour at 30 C, 1/2 hour at 35C, 1 1/2 hours a~ 40C and flnally 1/2 houx at 45C
to complete the reac~ion. The reaction was worked up ïn -the normal manner. The crude product weighed 29.8 grams and assayed appxo~i-mately 74% for an 84% yleld.
Example XIII
Prep ration of 2,~-Di-t-cumylperoxY-2,5-dimethylhexane Into a 100 ml 3-neck round bottom flask were added 35.4 grams ~0.~ m) alpha-methylstyrene and 3.8 grams (0.04 m~ phenol. The flask was equipped with a magnetic stirrer, thermometer, condenser and addition funnel. The phenol was dissolved in tne alpha-methylstyrene with stlrrlng at 20 C.
To this solution was added 9.1 grams ~0.05 m~ of 98~ 2,~~dihydroperoxy-2,5-dimethylhexane. To the resulting slurry was added ~.1 grams ~0.0~
m) t cumyl chloride dropwise from the addltion f~mnel. The temperature slowly rose to 29C
over 1/2 hour and a clear solution formed. At this point an additional 4.5 grams ~0O~25 m) of the dihydroperoxide was added. The temperature slowly aropped to 26 C over the next 1 1/4 hours at which point the solution became clear again.
Another 4.5 grams ~0.025 m) of the dihydroperoxide was ad~ed. The reaction was stirred 2 1/4 hours at 26C but the solution was s~lll cloudy so it was warmed to 35C ~solution cleared) and stlrred at 30-35C for another hour. The reaction was terminat~d by adding 40 mls of water and stirring 10 minutes. T~e contents of the flask were poured lnto a 1~5 ml erlenmeyer flask, the reaction flask rinsed out with a small amount of pentane and 10 mls of water. Wlth rapld stirring, 10 mls of 50% NaOH were a~de~ and the mixture stirred 15 minutes and the aqueous layer separated. Th~ organic layer was washed successively with 50 ml portions of water, saturated NaHCO3 solution and water. The volatiles we~e steam distilled out of the crude product under vacuum. The organic residue after solation and drying weighed 36.5 grams for an 88% crude yield. The product slowly solidi~ied into a whlte solid. The crude product was further purified by recrystallization from methanol ~0 to give a white powder. The compound was not shock sensitive and had a melting point of ~8-3sc - 4~ -Exam~le XIV
Preparation of 2,5-Di t-c~mylperox~-2,5-dimethylhexyne-3 ..
Into a 250 ml 3-neck rouna bottom flask, equipped with a condenser, ~hermomet~r, magnetic stirrer and addition funnel, were added 35O4 grams (O ~ 3 m~ alpha-methylstyrene and 6 . O grams (0 . 063 m~ phenol. The phenol was dissolved ln the alpha-methylstyrene with st~rriny at 25 C. To this solution was added 12 . 7 grams (0.05 m) of 68~ wet 2,5-dihydroperoxy 2,5-dlmethylhexyne~3 and the mixture stlrred for 10 minutes ~efore adding 6.2 grams (0.04 m) t-cumyl chloride from the dropping funnel over-2 minutes. The reaction mixture was stirrecl 1/2 hour at 24-~5 C and a clear solution resulted. An additional ~ . 2 grams ~0.0125 m) of the dihydroperoxide were added. The temperature slowly rose from 24C to 31C over 15 minutes.
l~he reaction was stirred an additional hour ana the temperature yraaually aropped ~ack to 24C
and a clear solution formed. Another 3.2 grams (0.0125 m) of the dihydroperoxide were added.
The reaction was stirred an adaitional 2 1/2 hours at 24-25 C. The solution was s~ cloudy so 1 yram of t-cumyl chloride was add~d~ t~P
reaction warmed to 35 C ana stirred 2 hours at 30-3SC. The reaction was terminated ~y a~ding 50 mls water~ stirring l0 minutes, addlng 10 mls NaO~, stirring 15 mlnutes and separating the aqueous phase. The organic layer was washed successively with 50 ml portions of water, satuxated NaHCO3 solutlon and wat~r. The vo1ati1es were steam ~is~illed out of the crude product under vacuum~ The organic residue after isolation and ~rylng weighed 41.7 grams. It was recry~ta11ized from methanol at -20C to give 31.~ grams of a white powder. The compound was not shock sensitive and had a melting point of 49 51C.

Example XV
Prepara~ion of_Dicumy1 Peroxide Using Methanol as a Catalyst In this example we attempted to use methanol as a catalyst for the preparation of dicumyl peroxide. The reaction was monitored by gas cnromatography to determine the extent of reactionO Into the 200 ml jacketed reactor described in Example II were added 27.2 grams ~0.23 m) alpha-methylstyrene and 5.8 grams (0.0~75 m~ t-cumyl chloride. The stirrer was activated and with the temperature around 25C, 56.5 grams (0.315 m~ of 85% cumene hydroperoxid~
and 5 m1s of methanol were quickly adde~. The I

- 44 _ reaction temperature was brought up to 45 ~ over 3 mlnutes ~y circulating warm water through the reactor jac~cet. The reaction was stirred 1 1/2 hours at ~5C at which point the hyaroperoxide was completely consumed. The reaction mixture was cooled to 3QC and washed with 50 mls of 20%
sodium sulflte solution for 10 minutes, separated, washed twice with 50 ml portions of 39~ NaOH, once wlth saturated Na~C03 and three tLmes with water. The volatiles were steam dis-tilled out of the crude p.roduct under vacuum.
Tne crude residue after isolation and drying weighed 3~.7 grams and assayed 91.1% by liquid chromatography to give a 38.2% corrected yield.
:15 The crude product contained ~.7~ cumyl methyl ether.
The reaction ran faster than normal but there was a greater degree of ~ecomposition of ~he cumene hyaroperoxide, the yield was lower and thexe was a considerable amount of cumyl methyl ether formed from the reaction of the methanol with the t-cumyl chlorlde.

Example XVI
Prepax_tion of Dicumyl Peroxlde ~sin~ t-B~annl aa ~ ~tal~s~
In this example we tried to use t~bu~anol as a c:atalyst for the preparation of dicumyl S peroxi~e. The reaction was monitored by ga~
chromatography to determine the extent of r action.
The reactlon was run the same as Example XV
except 5 mls of ~-butanol were used instead of 5 mls of met~anol. The reaction had to be stirred 3 1~2 hours at 45 C to complete the reaction.
This :is 2 hours longer than required in the methanol reaction and a~out l/~ to ~/4 hours longer than when no addltive is used. The reaction was worked up the same as in Example XV.
The volatlles were steam distilled out of the cru~e product under vacuum. ~rhe crude residue after isolation and drying weighed 45.7 grams and assayed 88~ by liquid chrcmatography to give a 4~.5% corrected yield.
The t butanol did not catalyze the reaction in fact it slowe~ it down somewhat and the yield was slightly low.

Exam~le XVII_ Preparation of Dicum~l Peroxide Uslnq Ethano1 as a Catalyst In this example we attempted to use ethanol as a catalyst for the preparation of ~icumyl peroxide. The reaction was monitored by gas chromatography to determine the extent of reaction. Into the 200 ml jackete~ reactor described in Example II were added 27.2 grams ~0.23 m~ a1pha-methylstyrene and 5.8 grams t~.0375 m) t-cumyl chloride~ The stirrer was ac~ivated and with the temperature around 25 C, 56.5 grams (0.315 m) of 85% cumene ~yaroperoxide and 5 mls of ethanol were qulck1y a~ded. The reaction temperature ~as ~rought up to 40C over .
3 mlnutes by cixculating warm water t~rough the reactor jacket. The reaction was stirrea 2 l/2 hours at 40C at which point the hyaroperoxide was essentia~ly consumed~ The reaction mixture was cooled to 30 C and 50 mls of a solution composed of 3 parts methanol and l part 50% NaOH
by volume was added and the mixture stirred for .2~ minutes, ~0 m1s o~ water and 50 m1s of hexane added, the mixture stirred l minute and the aqueous caustic layer separated. The hexane so1ution was washed successively with 50 ml po.rtions of water, 5% NaHSO3, saturated ~aHC03 J

and water. The volatiles were steam distllled out of the crude product under vacuum, the crude resldue after lsolation and drying ~eighed 42.1 grams and assayed 91.8~ by liquid chromato-graphy to glve a 45~5~ corrected yield.
The adaition of the e~hanol reduced the reaction time slightly but lt gave approx~lately 25% Lower yiel~.
Example XVIII
Preparation of_D cumyl Peroxide Usin~ Acetic Acid as_a Catalyst In this example we attempted to use acetic - acid as a catalyst for the preparation of dicumyl peroxide. The reaction was monitored by gas chromatography.
lnto the 20U ml ~acketed reactor described in Example II were added 47.2 grams (0.4 m) alpha-methylstyrene and 6.7 grams ~.0433 m) t-c~yl chloxide. The stirrer was activated and the temperature adjusted to 15C by circulatlng cold water through the reactor jacket. TO the cooled solution was added 57.4 grams ~0.315 m) of ` 83.5~ cumene hydxoperoxlde. The mixtura was stirred S minutes and then 6.0 grams (0.1 m) of acetic acid were added aropwise from the addltion funnel over 5 minutes at 15-17 C. The reaction was stirred L/2 hour at 15-20 C, the temperature - ~8 -raised to 30C and the reaction stirred 1 hour at 30C and the temperature raised to 45C.
Tne reaction had to be stirred 5 hours at 45 C
to complete the reactlon. The reaction was term'nated by adding 75 mls of water, stirring 15 minutes, adding 15 mls of 50% NaOH and stlrring another 15 minutes. The aqueous layer was separated and tha organic layer was washed with water untii neutral. The volatiles were steam disti:L1ed out of the crude product under vacuum. The crude residue after isolation and drying weighed 5~ grams and assayed 91.5% by liquid chromatography to give a 6U% yleld.
The reaction took much 1Onger than the normal reaction and the yield was about 10 lS~
lower than the pheno1 catalyze~ reactions run under siml1ar conditions.
Example XIX
Preparation of ~iClmyL Peroxlde Usinq Acetone as a Catalyst In thls example we attempted to use acetone as a catalyst for the preparation of dicumyl peroxide. The reaction was monitored ~y gas chromatography.
Into the ~00 ml jacketed reactor described in Example II were a~ded 27.2 grams (0.23 m~
alpha-methylstyrene and 5.8 grams ~0.0433 m) - 4~ -t-cumyl chlori~e. ~l~he stirrer was activated ana the temperature adju~ted to 20C. To this ~o1ution was added 56.0 grams ~Q.315 m~ of 85%
c~nene hydroperoxide and kh.an 5 mls of acetone were added dropwisa from the addition funne1.
The reaction temperature rose to 22C upon addition of th~ acetone. The reaction mixture was warmed to 40C over 10 minutes, stirred 85 minutes at 40C and 9.0 minutes at 4SC at which point most of the cumene hyaroperoxi~e had been consumed. rl~he reaction was terminated by adding 25 mls of water and then slowly addlng 50 mls of 1~% Na~SO3. The aqueous layer was separated and the organic layer was was~ed successively with :~ 15 50 ml portions of 30~ NaOH v water, saturated NaHCO~ solut~.on and watPr. The volatiles were steam aistilled out of the crude prcduct under vacuum. The organic residue after lsolation and drylng weighed 25.0 grams ana assayed 84.5~ by 2Q Liquid chromatography to give a ~4.2% corrected yleld .
The reaction was not catalyzed by the acetone, the yiel~ of aicumyl peroxide was low, the assay of the steam stripped ~icumyl peroxlde was low and a consi~erable amount of di-t-cumyl pe.roxypropane was formed.

Exam~le XX
Preparation of Di-cumyl Peroxide fr~m t-Cumyl Chloride and Cumene ~ydroperoxide Using t~Butano1 as an Aci~ Bindina Aqent Th1s example ~emons~ra~es ~hat t-butanol is not as efficient an acid bindlng agent as alpha-methy1styrene and that the Kato process does not work very well for acid sensitive hy~roperoxides.
The reaction was monltored by gas chromatography.
Into a lOo ml ~-neck round ~ottcm flask, equipped with a magnetic stirrer, thermometer, water-cooled condenser and dropping funnel, were added 29 4 grams (0.16 m) of 83% cumene hy~ro~
peroxide and ~5 grams (0.34 m) t-butanol. The temperature of the solution was a~justed to 20C
and 26.Q grams ~0.165 mJ t-cumyl chloride were transferred to the dropping funnel. A dropwise addition of the cumyl chlori~e was ~egun. After 3 m1nutes there was no noticeable exotherm so the addition was stopped and the temperature of the solution ra:ised to 3QC with a warm water bath.
The addition was restarted and the remainder of the t-cumyl chlor1de was added over 18 m1nutes wi~h the temperature ho1ding at 30C. VPC
analysis indicated the presence of 28% dicumyl peroxide in ~he reaction mlxtureO The tempera-ture remained constant for most of the next hour - 51 _ and then rose to 4].C toward the end of the hour.
It was cooled to 35C ko s~op the exotherm and then warmed back up to 40C. VPC analysls indi cated the cwmene hydroperoxide was campletely consumed at this point. The reaction ~as stirred an additional hour at 45 C + and then stirred lnto 100 ml warm H2O. The aqueous layer was ~eparated washed with another 100 ml warm H2O twlce. In the second washing 25 ml of 50%
NaOH were added and the mlxture stirred 10 minutes at 50 C. T~e aqueous layer was separated and the organic layer was washed success1vely wlth water ~3 times~, satuxated NaHCO3 solu-tion and waterO The volatlles were steam distille~ out of the crude product under vacuum. The organic resi-due aiter isolation and drying weighed 15.5 grams and assayed 83.6% by llquid chromatography to give a 30.0% corrected yield.
A VPC scan at the end of the reaction period indicated ~here was approximately 21% alpha-methyl-styrene, 13% p~lenol and 3~% dicumyl peroxiae present. This indicates that a considerable amount of the cumyl chloride eliminated HCl to form alpha~methylstyrene and a considera~le amount of the cumene hydroperoxide decomposed in the presence of the HCl to form phenol.

Example XXI

Thls example demonstrates that substituted phenols also work as catalysts in the prepara~ion S of dicumyl p~roxide.
A solution o~ 6.9 grams ~0.064 m) p-cresol in 47.2 grams (Q.4 ml alpha-methylstyrene was prepared and ~iltered to remove any iron par-ticles. The solution was transferred to a 200 ml 3-neck round bottom flask equipped with a thermometer, magnatic stlrrer, dropping f unnel containing 58.6 grams (0.315 m) of 81.9% cumene hydroperoxide and a water-cooled condens~r. To the a.Lpha-methylstyrene was added 6.7 grams I5 (0.0433 m) t-cumyl chloride and the temperature of the resulting solution was adjusted to 25 C.
The cl~ene hydroperoxide was added from a dropplng fullnel over 5 mlnutes at 25C. Without a bath around the flask, there was no apparent exotherm during the ad~ition but the temperature began to slowly rise after the additlon was com-plete. After 2~ minutes the temperature had risen to 37C and after 40 minutes it had reached 45C. At this point the reaction was cooled to 40C and t~e hath removed~ The t~mperature dropped to 37C over 20 m1nutes.

34~

The reaction was then warmed back up to 47-48 C
for another 45 minutes to complete the reaction.
The reaction was termlnated ~y adding 50 mls of watex, stirred 5 minutes, 10 mls of 50% NaOH
addedl stirred 15 minutes and the aqueous layer separated. The organic layer was washed wit~
water, 15~ NaHS03 solution, water, saturated Na~C03 solution and water. The volatiles were steam distilled out of the cru~e product under vacuum. The organic residue after isolation and drying weighed 62.2 grams and assayed 95.4~ by liquid chromatography to give a 69.7~ corrected yield.
Example XXII
Preparation of Dicumyl P ox de Using Varlous Phenols as Catalysts`
This example demonstrates that phenols ~lncluding naphtholsl containing inert ~ubstit-uents also wor~ as catalys~s and some work better -than others depending upon the nature and posi-tion of the substituent. The reactions were monitored by gas chromatography to determine when the reaction was complete.
The following general procedure was used ~or the preparation of the dicumyl peroxide, substituting an equimolar amount of the desired phenol in each case. A control experiment was run without any phenol for comparison sake. All the runs w~e maae with Eastman alpha-methyl~
styrene which seemed to react faster than the commercial grade alpha-methylstyrene we had ~een using for the other examples~ The results are summarizea in Table VII.
A solution of ph~nol or su~stituted phenol in cumene hydroperoxide was prepared by adding .064 mole of the phenol to 57.6 grams ~0O315 m~
lQ of 83.5% cumene hy~roperoxiae and stirring until the phenol dissolved.*
Into a 200 ml ~ackete~ reactor equlpped with a mechanical stirrer, thermometer, water-cooled co~denser and addition funnel weré adaed 47.2 grams (0.4 m) alpha~methylstyrene and 6~7 grams (0.043 m) t-cumyl chloride. The stirrer was activatea and the temperature of the solution was adjusted to 15C by circulating cold water through the reactor jac~et. After the phenol had dis-solved, the cumene hydroperoxide solution was transferre~ to the addition fumlel and adde~ at a unifonm rate to the stirred alpha-methyl-styrene solution over 10 minutes at 13 15C.
The reaction mlxture was stirred an add1tional 5 minut s at 15 C, the reac~ion warmed to 30 C
over 5 minutes and stirre~ an addltional 25 ~ 55 -minutes at 30C. The reaction mix~ure was then ~armed to 45C and stirred until the cumene hydroperoxide was con.sumed (1% or le~s ~y VPC~.
A comparison of the reaction tImes requ'red at 45 C to comple~e the reaction is found in Table VII. Upon consumption of all the hydroperoxide, the reaction was terminated by adaing 50 mls of water, stirring 15 minutes, adding 10 mls o~ 50%
NaOH and stirring an additional 10 minutes at 45-55C. The aqueous caustic layer was separated and savea for waste disposal. The organic layer was-s~anned by gas chromatography to see if the aqueous caustic had removed the su~stituted phenol. If the phenol had not beén removed, the organic layer was washed twice for 10 minute periods with 30 mls of methanolic caustic ~3 parts by volume metha~ol and l part 50% NaOH).
After the phenols had been removed, the organic layer was washed with 50 mls of saturated NaHCO3 and tnen 3 times with 50 ml portions of water.
The organic layer was cooled to room temperature, taken up in 25 mls of pentane, dr1ed over an~
` hydrous sodium sulfate, filtered and the pentane stripped off on a rotating evaporator under reduced pressure. The crude product was weighed, assayed by liquid chromatography and the % yiel~

~etermlned. The volatiles were ~team dlstll].ed out of the crude product under vacuum. The organic residue after isolation and drying was reassayed.

* p-Phenylp~enol was insoluble in the cumene hydroperoxide an~ was adaed directly to the 20~
ml reactor ju~t prior to the cumene hydroperoxide adaitlon .

~ t.) ~r 1-- 0~ ~1 N ~ O ~ ~Cl CO ~P O
~ ~ ~ . . . . . . . . . . .
t_) h O a:l ~1 N ~1 r~l a~ Cl~ C~ N ~ ~ ~

h rl ~1 ~ ~r 1 ~ OD ~ O t~l ~1 ~r ~1 h ~ cn ~_1 ~) 1_ l` ~ 11~ r l Ll~ ~1 11 ) ~ ~ojO Ir) U~ ~O ~D ~ U~ ~ 1_ ~D ~C 1~ In ~ ~ O~ ~ ~' CO ~ ~ 1-V ~O . . . . . .
U) ~ ~ ~ r-l ~ ~ C~ ') N (~l ~r ~
~ ~ Ul W ~O ~ ~D 10 ~n ~ u:~ ~D ~ 1~
U~
Q~
rl O O ~ N cn CO ~ ~1 Ci~ (~ O ~1 a~
.. . . . . . . . . . . .
P~ ~ ~ 'd ~ ~1 U~ ~ N 0~ ~ ~r cn ~ o ~r ~ ~VP~ ~ CO OD ::n ~ ~ a~ ~ a: o~ ~ cr~

O U
Hl~rl h 1~n v~
O O O O O O O O O ~ O O
z :~ z z z z z z z :~ ~; ~;

E~ ,1 X U~ U~ U~ U~
rl 11~ S ~: S S h h S u~
E-l ~r S l ~ ~ ~1 h ~ ~ ~_ X~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ S
~ u~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~r ,~ l Q ~1 ~1 ~1 ~1 ~0 0~ ~ ~ O ~0 1~ ~0 1~
o ~ ~ ~ ~ ~0 ~ P~ ~
.~~ O r~ ~ ~ ~ ~0 ~1 S~ ~ ~ ~0 o ,_l ~1 ~ O ~ h ~) ~ (~I ,C IYl ~ a) s~ v ~D ~ ~ V m ~ ~ z ~ ~ ~ o O ~P, ~ ~r ~r ~r ~ ~ ~ ~ ~ Z

-X ~1 N ~ /7 ~r Ll ) ~C) 1~ C~ C~ O ~1

Claims (6)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE:
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A process for preparing cumyl peroxides comprising reacting in a temperature range of 10-50°C an aliphatic or cycloaliphatic hydro-peroxide or aliphatic dihydroperoxide with an olefin and a t-cumyl halide corresponding to the hydrohalogenated olefin in the presence of a phenol catalyst under substantially anhydrous conditions, said phenol having the formula IV or V

or and where X and X ' are independently selected from the group consisting of -H, Cl-, Br-, F-, alkyl of 1 to 6 carbons, alkoxy of 1 to 6 carbons, aryloxy of 6 to 10 carbons or aryl of 6 to 10 carbons; and when neither X nor X' is hydrogen, neither X nor X' can be substituted in positions ortho to the hydroxyl group a t the same time.

2. A process for preparing a cumyl peroxide consisting essentially of reacting a hydroperoxida or dihydroperoxide with an olefin and a t-cumyl halide corresponding to the hydrohalogenated olefin in the presence of a phenol or naphthol catalyst under substantially anhydrous conditions in a temperature range of about 10°-50°C, where a) said hydroperoxide having the formula R -[OOH]y (III) where y is 1 or 2; when y is 1, R is selected from t-alkyl of 4 to 8 carbons, t-alkynyl of 5 to 8 carbons, t-aralkyl of 9 to 12 carbons or t-cycloalkyl of 6 to 10 carbons; and when y is 2, R is selected from or where R1 is selected from alkyl of 1 to 6 carbons;

b) said olefin having the formula (I) (I) where Z is selected fran -H, alkyl of 1 to 6 carbons, Cl-, Br-, F-, alkoxy of 1 to 5 carbons, phenoxy, phenyl or naphthyl;
c) said t-cumyl halide has the formula (II) (II) where Z is defined as in b and Y is Cl or Br; and d) said phenol has the formula IV or V

and IV V

where X and Xl are independently selected from the group consisting of -H, Cl-, Br-, F-, alkyl of 1 to 6 carbons, alkoxy of 1 to 6 carbons, aryloxy of 6 to 10 carbons or aryl of 6 to 10 carbons; and when neither X nor X' is hydrogen, neither X nor X' can be substituted in positions ortho to the hydroxyl group at the same time;
e) the mole ratio of olefin to hydro-peroxide is 0.5:1 to 5:1; and f) the t-cumyl halide is charged in an amount of about 5-20 mole percent based on olefin charged.

3. The process of Claim 2 wherein the hydroperoxide is selected from cumene hydroperoxide, t-butyl hydroperoxide, t-amyl hydroperoxide, t-hexyl hydro-peroxide, 1,1,3,3-tetramethylbutyl hydro-peroxide, 2-hydroperoxy-2-methyl-4-hydroxy-pentane, 3-hydroperoxy-3-methyl-butyne-1, 2,5-dihydroperoxy-2,5-dimethyl-hexane, or 2, 5-dihydroperoxy-2, 5-di-methylhexyne-3.

4. The process of Claim 2 wherein the phenol catalyst is selected from o-cresol 4-t-butylphenol, 4-chlorophenol, 4-bromophenol, 4-methoxyphenol, beta-naphthol, 2-t-butylphenol, 4-phenyl-phenol, 3-methoxyphenol or phenol.

5. The process of Claim 2 wherein the cata-lyst is liquified phenol containing about 9% water.

6. The process of Claim 2 where the reaction is initiated at 20-25°C and the temperature is allowed to rise to 40-45°C over 3/4 - 1 hour and the reaction is completed at 40-45°C.