Patent Description:
Peroxyesters and percarbonates find a wide variety of uses in the chemical field. They are typically produced by reacting an organic hydroperoxide with a reactive carbonyl species, such as an acid halide, an acid anhydride, or a haloformate.

An issue with peroxyesters and percarbonates is that they often contain undesirably high levels of hydroperoxide, which can be problematic from a regulatory and/or application viewpoint. Additionally, peroxyesters and percarbonates often have poor storage stability.

The standard workup process for this reaction comprises one or more washing steps in an attempt to reduce the residual organic hydroperoxide present in the organic layer (e.g., <CIT>). In <CIT> the reaction workup was performed at pH <NUM>-<NUM>, which was found by the present inventors to yield a poor product (see Comparative Example <NUM> below). The present inventors unexpectedly found that the hydroperoxide content in the peroxide product could be substantially reduced whilst simultaneously giving rise to a peroxy product with much improved storage stability by a specific process that manipulates the reaction mixture pH during the initial workup process.

In a first aspect, the present disclosure relates to a process for preparing a peroxyester or peroxycarbonate comprising:.

wherein the process is characterized in that:.

Steps a) and b) follow the normal process for producing peroxyesters or peroxycarbonates, wherein the organic hydroperoxide is reacted with an acid halide, an acid anhydride, or a haloformate, in the presence of a base. The equivalent amount of the reactive carbonyl compound (acid halide, acid anhydride, or haloformate) relative to the organic hydroperoxide is not particularly limited, but typically is in the range of about <NUM>-<NUM> equivalents, preferably in the range of about <NUM>-<NUM> equivalents, more preferably in the range of about <NUM>-<NUM> equivalents, and most preferably in the range of about <NUM> - <NUM> equivalents.

The reaction conditions of step a) are conventional. The temperature generally is in the range of -<NUM> to <NUM> and suitably between <NUM> to <NUM>. The pH is basic, i.e., above <NUM>. Generally, the pH is in the range of <NUM>-<NUM>. In practice, the pH is above <NUM>, and the common pH range is from <NUM> to <NUM>. The reaction may proceed under ambient pressure and in free contact with the atmosphere. Any suitable base may be used to adjust the pH to a basic pH, such as, but not limited to, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, and mixtures thereof. Such bases are typically used in the form of aqueous solutions thereof. The reaction mixture may also comprise conventional auxiliaries, such as NaCl(aq. ) to assist phase separation (for step b)). The reaction can be performed neat or in the presence of solvent(s).

The organic hydroperoxide may be selected from an organic hydroperoxide of the general formula (II):
<CHM>
wherein:.

Preferred organic hydroperoxides include tert-butyl hydroperoxide, tert-amyl hydroperoxide, cumyl hydroperoxide, <NUM>,<NUM>,<NUM>,<NUM>-tetramethylbutyl hydroperoxide, <NUM>-hydroperoxy-<NUM>-methylpentan-<NUM>-ol, <NUM>,<NUM>-dihydroperoxy-<NUM>,<NUM>-dimethylhex-<NUM>-yne, <NUM>,<NUM>-dihydroperoxy-<NUM>,<NUM>-dimethylhexane, or mixtures thereof. The most preferred organic hydroperoxide for use in this process is tert-butyl hydroperoxide (TBHP), preferably tert-butyl hydroperoxide obtained from an air oxidation process.

The acid halide, acid anhydride, or haloformate may be a reactive carbonyl compound of the general formulae (la) or (Ib) :
<CHM>
wherein:.

Preferably, the acid halide or acid anhydride is derived from any of the following carboxylic acids: acetic acid, phenylacetic acid, phenoxyacetic acid, propanoic acid, isobutyric acid, n-butyric acid, benzoic acid, <NUM>-methyl-benzoic acid, <NUM>-methylbutanoic acid, <NUM>-butenoic acid, <NUM>-phenylpropenic acid, <NUM>,<NUM>-dimethylpropanoic acid, <NUM>,<NUM>-dimethylbutanoic acid, <NUM>,<NUM>-dimethylpentanoic acid, <NUM>-ethylbutanoic acid, <NUM>,<NUM>,<NUM>-trimethylhexanoic acid, <NUM>-ethylhexanoic acid, neohexanoic acid, neoheptanoic acid, neodecanoic acid, octanoic acid, nonanoic acid, lauric acid, hexanedioic acid, <NUM>,<NUM>,<NUM>-trimethylhexanedioic acid, <NUM>,<NUM>,<NUM>-trimethylhexanedioic acid, decanedioic acid, undecanedioic acid, dodecanedioic acid, cyclohexanecarboxylic acid, <NUM>,<NUM>-cyclohexanedicarboxylic acid, cyclohexane-<NUM>,<NUM>-diacetic acid, maleic acid, citric acid, methylsuccinic acid, citraconic acid, fumaric acid, oxalic acid, terephthalic acid, propenoic acid, and phthalic acid.

Preferably, the process uses an acid halide or a haloformate.

Preferably, the acid halide is an acid chloride. Preferably, the acyl portion of the acid chloride corresponds to the acyl portion of any of the following carboxylic acids: acetic acid, phenylacetic acid, phenoxyacetic acid, propanoic acid, isobutyric acid, n-butyric acid, benzoic acid, <NUM>-methyl-benzoic acid, <NUM>-methylbutanoic acid, <NUM>-butenoic acid, <NUM>-phenylpropenic acid, <NUM>,<NUM>-dimethylpropanoic acid, <NUM>,<NUM>-dimethylbutanoic acid, <NUM>,<NUM>-dimethylpentanoic acid, <NUM>-ethylbutanoic acid, <NUM>,<NUM>,<NUM>-trimethylhexanoic acid, <NUM>-ethylhexanoic acid, neohexanoic acid, neoheptanoic acid, neodecanoic acid, octanoic acid, nonanoic acid, lauric acid, hexanedioic acid, <NUM>,<NUM>,<NUM>-trimethylhexanedioic acid, <NUM>,<NUM>,<NUM>-trimethylhexanedioic acid, decanedioic acid, undecanedioic acid, dodecanedioic acid, cyclohexanecarboxylic acid, <NUM>,<NUM>-cyclohexanedicarboxylic acid, cyclohexane-<NUM>,<NUM>-diacetic acid, maleic acid, citric acid, methylsuccinic acid, citraconic acid, fumaric acid, oxalic acid, terephthalic acid, propenoic acid, and phthalic acid.

Preferably, the haloformate is a chloroformate. Preferred haloformates include <NUM>-(<NUM>-methylethoxy)phenyl chloroformate, <NUM>-methylpropyl chloroformate, <NUM>-methylphenyl chloroformate, heptyl chloroformate, cyclohexyl methyl chloroformate, ethylene glycol bis(chloroformate), phenyl chloroformate, <NUM>-methoxybutyl chloroformate, <NUM>-phenoxyethyl chloroformate, <NUM>,<NUM>-dimethyl-<NUM>,<NUM>-propane diol bis(chloroformate), phenyl methyl chloroformate, <NUM>-octadecenyl chloroformate, <NUM>-methylphenyl chloroformate, bisphenol A bis(chloroformate), <NUM>,<NUM>-dimethyl butyl chloroformate, <NUM>,<NUM>-dimethyl butyl chloroformate, <NUM>,<NUM>-dimethyl phenyl chloroformate, <NUM>,<NUM>-butane diol bis(chloroformate), <NUM>,<NUM>-bis (ethoxycarbo)ethyl chloroformate, <NUM>,<NUM>-dimethyl phenyl chloroformate, octyl chloroformate, ethyl chloroformate, octadecyl chloroformate, (<NUM>-oxo-<NUM>,<NUM>-dioxolan-<NUM>-yl)methyl chloroformate, <NUM>,<NUM>-hexane diol bis(chloroformate), <NUM>-chlorobutyl chloroformate, <NUM>-methoxyphenyl chloroformate, <NUM>-methylpropyl chloroformate, , dodecyl chloroformate, <NUM>,<NUM>-cyclohexane dimethanol bis(chloroformate), <NUM>-chloro-<NUM>-phenyl ethyl chloroformate, <NUM>-acryloyloxyethyl chloroformate, <NUM>-nitrophenyl chloroformate, n-butyl chloroformate, decyl chloroformate, <NUM>-ethylhexyl chloroformate, <NUM>-propenyl chloroformate, <NUM>-chlorocyclohexyl chloroformate, <NUM>-methyl-<NUM>-propenyl chloroformate, cyclohexyl chloroformate, <NUM>-chloroethyl chloroformate, [<NUM>-(phenylazo)phenyl]methyl chloroformate, hexadecyl chloroformate, <NUM>-naphthalenyl chloroformate, chloroformate, <NUM>,<NUM>,<NUM>-trimethyl hexyl chloroformate, isotridecyl chloroformate, tridecyl chloroformate, <NUM>-(<NUM>,<NUM>-dimethylethyl)cyclohexyl chloroformate, chloroformate, <NUM>-chloropropyl chloroformate, tetradecyl chloroformate, chloroformate, methyl chloroformate, <NUM>-(<NUM>-methylethyl)phenyl chloroformate, triethylene glycol bis(chloroformate), <NUM>-methoxyethyl chloroformate, <NUM>-methylethenyl chloroformate, <NUM>-methylphenyl chloroformate, <NUM> chloroformate, diethylene glycol bis(chloroformate), <NUM>-methyl-<NUM>-(<NUM>-methylethyl)phenyl chloroformate, , <NUM>-ethoxyethyl chloroformate, <NUM>-methyl-<NUM>,<NUM>-pentane diol bis(chloroformate), <NUM>-methoxy carbophenyl chloroformate, ethenyl chloroformate, <NUM>-methylethyl chloroformate, <NUM>-(<NUM>-methylpropyl)phenyl chloroformate, chloroformate, pentyl chloroformate, cyclodecyl chloroformate, <NUM>-(<NUM>,<NUM>-dimethylethyl)phenyl chloroformate, hexyl chloroformate, n-propyl chloroformate, <NUM>-methoxy-<NUM>-methylbutyl chloroformate, <NUM>-propoxyethyl chloroformate, <NUM>-methoxy-<NUM>-methylethyl chloroformate, <NUM>-butoxyethyl chloroformate, <NUM>,<NUM>-dimethyl propyl chloroformate, <NUM>,<NUM>-dihydro-<NUM>,<NUM>-dimethyl-<NUM>-benzofuranyl chloroformate, <NUM>-chloroethyl chloroformate, cyclobutyl chloroformate, <NUM>-methyl-<NUM>-(<NUM>-methylethyl)cyclohexyl chloroformate, <NUM>,<NUM>-dimethyl ethyl chloroformate, <NUM>-methylheptyl chloroformate, and mixtures thereof.

After completion of step a), the reaction mixture is allowed to settle, thereby forming an aqueous layer and an organic layer (i.e., two separate/immiscible phases). The aqueous layer that forms upon allowing the mixture to settle is separated in step b). The organic layer that remains is taken through to step c).

In step c), the reducing agent is added to the organic layer. Preferably, the reducing agent is a sulfur based reducing agent, such as a dithionite, hydrosulfite, metabisulfite, sulfide or a sulfite. The reducing agent serves to reduce any remaining hydroperoxide to the corresponding alcohol. Preferred sulfites include metal sulfites, metal bisulfites, and/or metal metabisulfites. Preferred metals include the alkali and alkaline metals, such as sodium or potassium. Preferably, the reducing agent added in step c) is sodium metabisulphite and/or sodium sulfite, preferably sodium metabisulphite. The reducing agent is preferably added in step c) as an aqueous solution of the reducing agent. As such, in a most preferred embodiment, the reducing agent added in step c) is an aqueous solution of sodium metabisulphite. The reducing agent (RA) to hydroperoxide (HP) molar ratio (RA:HP) is preferably ><NUM>:<NUM>, preferably ><NUM>:<NUM> to about <NUM>:<NUM>, preferably ><NUM>:<NUM> to about <NUM>:<NUM>, more preferably ><NUM>:<NUM> to about <NUM>:<NUM>, and most preferably about <NUM>:<NUM> to about <NUM>:<NUM>. It is preferred if the reaction mixture is agitated (e.g., stirred) for at least about <NUM> minute (e.g., about <NUM>-<NUM> minutes) before proceeding to the next step of the process.

In a preferred embodiment (step i)), the pH of the mixture of step c) is lowered to a pH of less than <NUM> before proceeding to step d), preferably to a pH of about <NUM> or lower, and most preferably to a pH within the range of about <NUM> to <NUM>. The pH drop may be achieved by any conventional means, such as by adding an acid, e.g., H<NUM>SO<NUM>(aq. ), by adding a buffer with a pH of less than <NUM>, and/or by using a reducing agent with a pH of less than <NUM>. The pH of the mixture of step c) may be decreased as a consequence of dosing the reducing agent to the organic layer (preferred reducing agents, such as aqueous sulfite solutions, can be weakly acidic, so dosing those acidic reducing agents to the organic layer in step c) may result in the mixture having a pH of <<NUM>). Preferably, a buffer with a pH in the range of about pH <NUM> - <NUM> is used to effect the pH drop. Preferred buffers include acetate buffer with a pH of from about <NUM> to <NUM> (other suitable buffers include, but are not limited to, citrate acid buffer or monopotassiumphosphate buffer). The mixture is preferably agitated (e.g., stirred) at this reduced pH for at least about <NUM> minute (e.g., about <NUM> to about <NUM> minutes) before proceeding to the next step of the process.

Step d) ensures that the pH of the mixture of step c) is at a pH of greater than <NUM>, preferably greater than <NUM>, preferably greater than <NUM>, and more preferably greater than <NUM>. For example, the pH may be ><NUM>. This is achieved either by maintaining the pH of the mixture (if the mixture of step c) is already at a pH of ><NUM>) or by increasing the pH of the mixture to a pH of greater than <NUM> (particularly if the pH of the mixture of step c) is adjusted to a pH of less than <NUM> before step d)). A pH increase may be achieved by adding a base in an amount necessary to reach the desired pH value. Suitable bases include, but are not limited to, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, and mixtures thereof. Such bases are typically used in the form of aqueous solutions thereof.

In step e), the pH of greater than <NUM>, preferably greater than <NUM>, preferably greater than <NUM>, and more preferably greater than <NUM>, is maintained for at least <NUM> seconds, preferably at least <NUM> seconds, preferably at least <NUM> seconds, preferably at least <NUM> seconds, and more preferably at least <NUM> seconds, such as from about <NUM> seconds to about <NUM> seconds. The mixture is preferably agitated (e.g., stirred) during step e).

In a preferred embodiment, the process further comprises step f) (step f) = step ii)), wherein after completion of step e) the pH of the mixture is subsequently decreased to a pH of less than <NUM>, preferably to a pH of about <NUM> or lower, and most preferably to a pH within the range of about <NUM> to <NUM>. The pH drop may be achieved by any conventional means, such as by adding an acid, e.g., H<NUM>SO<NUM>(aq. ) or by adding a buffer with a pH of less than <NUM>. Preferably, a buffer with a pH in the range of about pH <NUM> - <NUM> is used to effect the pH drop. Preferred buffers include acetate buffer with a pH of from about <NUM> to <NUM> (other suitable buffers include, but are not limited to, citrate acid buffer or monopotassium phosphate buffer). The pH of the mixture of step f) is preferably maintained for at least <NUM> seconds, preferably at least <NUM> seconds, preferably at least <NUM> seconds, preferably at least <NUM> seconds, such as from about <NUM> seconds to about <NUM> seconds, during which time the mixture is preferably agitated (e.g., stirred). Optionally, at the end of step f) the pH may be increased to a pH of greater than <NUM> (i.e., step d) may be optionally repeated at the end of step f)).

The aqueous layer of step f) (that forms after the mixture is allowed to settle into an aqueous layer and an organic layer, i.e., two immiscible phases) is separated, and the remaining organic layer may be subjected to one or more washing steps g) (to remove any residual water-soluble impurities, such as excess sulfite, alcohol and sulfate generated during the reaction). The washing step(s) may comprise one or more water washes and/or one or more alkaline aqueous washes (e.g., washing with NaOH(aq) and/or NaHCO<NUM>(aq)). The washing step(s) preferably comprises one or more neutral to alkaline aqueous washes. For the avoidance of doubt, the peroxyester or peroxycarbonate is present in this organic layer. The final organic layer may be dried using conventional means, such as drying agents (e.g., MgSO<NUM>), vacuum, and/or air drying.

It is preferable for the temperature of the mixture during steps c)-g) to be maintained at about <NUM>-<NUM>, more preferably about <NUM>-<NUM>.

In a preferred embodiment, the present disclosure relates to a process for preparing a peroxyester or peroxycarbonate comprising:.

This process is particularly relevant for processes which use hydroperoxides manufactured by air oxidation (notably t-butyl hydroperoxide). In that respect, a surprising observation was that, using the preferred processes disclosed herein, it was possible to consistently produce peroxyesters and peroxycarbonates from t-butyl hydroperoxide that have an initial (t = <NUM> weeks) tert-butylhydroperoxide (TBHP) content of less than <NUM> ppm and a four-week stability (<NUM>-<NUM> week ΔTBHP) value of <NUM> ppm or less (the initial TBHP content and the four-week stability value are determined in accordance with the "TBHP Protocol" described in the Worked Examples below). This very high product purity and stability profile was unexpected.

Accordingly, in another aspect, the present disclosure relates to a tert-butyl peroxyester or a tert-butyl peroxycarbonate, preferably a tert-butyl peroxyester, characterized in that the tert-butyl peroxyester or tert-butyl peroxycarbonate has an initial (t = <NUM> weeks) tert-butylhydroperoxide (TBHP) content of less than <NUM> ppm and a four-week stability (<NUM>-<NUM> week ΔTBHP) value of <NUM> ppm or less, wherein the initial TBHP content and the four-week stability value are determined in accordance with the "TBHP Protocol" as set out in the worked examples below. For the avoidance of doubt a "tert-butyl peroxyester" is a peroxyester that is obtainable by reacting TBHP with an acid halide or an acid anhydride (i.e., t-Bu-OO-C(O)R), and a "tert-butyl peroxycarbonate" is a peroxycarbonate that is obtainable by reacting TBHP with a haloformate (i.e., t-Bu-OO-C(O)OR). Non-limiting examples of tert-butyl peroxyesters include tert-butyl peroxy-<NUM>,<NUM>,<NUM>-trimethyl hexanoate (<NPL>), tert-Butyl peroxy-<NUM>-ethylhexanoate (<NPL>), and tert-Butyl peroxybenzoate (<NPL>).

It has also been found that this process is particularly effective for preparing peroxyesters or percarbonates that do not contain any free acid groups. Accordingly, in a preferred embodiment, the process disclosed herein is for preparing a peroxyester or peroxycarbonate, wherein the peroxyester or peroxycarbonate contains no free acid groups.

The following examples provide a detailed method for working the invention. These worked examples are exemplary in nature and not intended to be limitative.

To a <NUM> jacketed glass reactor, equipped with baffles, a pH electrode, an overhead mechanical stirrer (pitch blade agitator, size <NUM>/<NUM> of the diameter of the reactor) and glycol/water temperature control, <NUM> TBHP (<NUM> wt% in water) was added. The reaction medium was cooled to <NUM>° C under agitation (<NUM> rpm) and <NUM> NaOH-<NUM> solution (<NUM> wt% NaOH in water) was added in <NUM>. After the addition, agitation was increased to <NUM> rpm and <NUM> gram Isononanoyl chloride was dosed in <NUM> and the temperature was allowed to rise to <NUM>° C and maintained at that temperature. In a second addition step <NUM> isononanoyl chloride and <NUM> NaOH-<NUM> were added simultaneously in <NUM> during which the temperature was allowed to rise to <NUM>° C and maintained at that temperature. After the second addition the reaction mixture was stirred for <NUM> at <NUM>° C and <NUM> rpm. The reaction mixture was quenched with <NUM> demineralized water and stirred for <NUM>. Agitation was stopped and the organic phase and water phase were allowed to separate. The water phase was drained from the reactor and discarded.

Agitation was restarted (1000rpm) and <NUM> buffer solution (<NUM> wt% AcOH, <NUM> wt% water and <NUM> wt% NaOH-<NUM>) was added followed by the addition of <NUM> gram water. The temperature was set to <NUM>° C by adjusting the jacketed temperature. The pH was adjusted to pH = <NUM> by addition of a few drops of NaOH-<NUM>. To the buffered solution <NUM> grams of a freshly prepared sulfite solution (<NUM> wt% water, <NUM> wt% sodium metabisulfite Na<NUM>S<NUM>O<NUM> (s) and <NUM> wt% NaOH-<NUM>) was added dropwise over a period of <NUM> minutes. During the dosing a pH of <NUM> was maintained by the addition of NaOH-<NUM> (approximately <NUM> grams in total).

After the addition of the sulfite solution, the reaction mixture was stirred for <NUM> minutes at a pH of <NUM>. The pH of the reaction mixture was then increased to pH <NUM> by the dropwise addition of NaOH-<NUM> (approximately <NUM> over <NUM> minutes) (steps d) and e)), followed by workup (see below).

After the addition of the sulfite solution, the reaction mixture was stirred for <NUM> minutes at a pH of <NUM>. The pH was then increased to pH <NUM> by the dropwise addition of <NUM> NaOH-<NUM> over <NUM> minutes (step d)). The mixture was stirred for <NUM> minutes at pH <NUM> (step e)). The pH was then lowered back to <NUM> by the dropwise addition of <NUM> HCl (<NUM> wt% HCl in water) over <NUM> minutes (step ii)). The reaction mixture was stirred for <NUM> minutes at a pH of <NUM>. Total reduction time was <NUM> minutes (cf. Example <NUM>). The pH of the reaction mixture was then increased to pH <NUM> by the dropwise addition of NaOH-<NUM> (approximately <NUM> over <NUM> minutes), followed by workup (see below).

Agitation was stopped and the organic phase and water phase were allowed to separate. The water phase was drained from the reactor and discarded. Next, <NUM> NaCl-<NUM> (<NUM> wt% NaCl in water), <NUM> demineralized water and <NUM> NaHCO<NUM>-<NUM> (<NUM> wt% NaHCO<NUM> in water) were added to the remaining organic layer. After the addition the mixture was stirred (<NUM> rpm) at <NUM>° C for <NUM> minutes. Agitation was stopped and the organic phase and water phase were allowed to separate. The water phase was drained from the reactor and discarded. Subsequently the organic phase was drained and collected separately in a <NUM> Erlenmeyer flask. The organic phase was dried over <NUM> grams MgSO<NUM>. <NUM><NUM>O for <NUM> minutes. The mixture was filtered over a glass filter and the clear organic peroxide product <NUM> gram (assay <NUM>%) was collected and stored at <NUM>° C.

The following reagents and apparatus were used in the determination of the TBHP content of the peroxide product:.

The TBHP content of the final peroxide product was determined by dissolving <NUM> of peroxide product in <NUM> Solution B. The solution was titrated immediately with the Sulphur dioxide solution A until slightly beyond the potential jump. The measurement was performed in duplicate. Two blanks were also performed, and the average blank was calculated. The following formula was used to calculate the hydroperoxide content (TBHP) <MAT> Where:.

For the avoidance of any doubt, the term "four-week stability (<NUM>-<NUM> weeks ΔTBHP) value" as used herein means the difference in TBHP, in ppm, between the TBHP value measured at week <NUM> (i.e., the initial TBHP value) and the TBHP value measured after a storage period of four weeks, wherein both the week <NUM> and week <NUM> values are determined in accordance with the above "TBHP protocol". For the purposes of the present disclosure, the "four-week stability (<NUM>-<NUM> weeks ΔTBHP) value" is determined by storing the peroxide for a period of <NUM> weeks at <NUM>.

To a <NUM> jacketed glass reactor, equipped with baffles, a pH electrode, an overhead mechanical stirrer (pitch blade agitator, size <NUM>/<NUM> of the diameter of the reactor) and glycol/water temperature control, <NUM> TBHP (<NUM> wt% in water) was added. The reaction medium was kept at <NUM>° C under agitation (<NUM> rpm) and <NUM> NaOH-<NUM> solution was added in <NUM>. After the addition, agitation was increased to <NUM> rpm and <NUM> <NUM>-ethyl hexanoyl chloride and <NUM> NaOH-<NUM> were added simultaneously over <NUM> minutes during which the temperature was allowed to rise to <NUM>° C and maintained at that temperature. After the addition the reaction mixture was stirred for an additional <NUM> minutes at <NUM>° C and <NUM> rpm. The reaction mixture was cooled to <NUM> and <NUM> NaOH-<NUM> was added. The reaction mixture was stirred for <NUM> minutes. The reaction mixture was quenched with <NUM> demineralized water and stirred for <NUM>. Agitation was stopped and the organic phase and water phase were allowed to separate. The water phase was drained from the reactor and discarded.

To the unstirred reactor content, <NUM> buffer solution (<NUM> wt% AcOH, <NUM> wt% water and <NUM> wt% NaOH-<NUM>) were added followed by the addition of <NUM> water. The temperature was kept at <NUM>° C by jacketed temperature control. The pH was adjusted to pH <NUM> by addition of a few drops of NaOH-<NUM>. To the buffered solution <NUM> of a freshly prepared sulfite solution (<NUM> wt% water, <NUM> wt% sodium metabisulfite Na<NUM>S<NUM>O<NUM> (s) and <NUM> wt% NaOH-<NUM>) was added dropwise over a period of <NUM> minutes. During the dosing a pH of <NUM> was maintained by the addition of NaOH-<NUM> (approximately <NUM> in total).

After the addition of the sulfite solution, the reaction mixture was stirred for <NUM> minutes at a pH of <NUM>. The pH of the reaction mixture was then increased to <NUM> by the dropwise addition of approximately <NUM> gram NaOH-<NUM> in <NUM> minutes (steps d) and e)), followed by workup (see below).

After the addition of the sulfite solution the reaction mixture was stirred for <NUM> minutes at a pH of <NUM>. The pH was then increased to <NUM> by the dropwise addition of <NUM> NaOH-<NUM> over <NUM> minutes (step d)). The mixture was stirred for <NUM> minutes at a pH of <NUM> (step e)). The pH was lowered back to <NUM> by the dropwise addition of <NUM> HCl (<NUM> wt% in water) over <NUM> minutes (step ii)). The reaction mixture was stirred for <NUM> minutes at a pH of <NUM>. Total reduction time was <NUM> minutes (cf. Example <NUM>). The pH of the reaction mixture was then increased to <NUM> by the dropwise addition of approximately <NUM> gram NaOH-<NUM> in <NUM> minutes, followed by workup (see below).

Agitation was stopped and the organic phase and water phase were allowed to separate. The water phase was drained from the reactor and discarded. Next, <NUM> gram NaCl-<NUM> (<NUM> wt% in water), <NUM> gram demineralized water and <NUM> gram NaHCO<NUM>-<NUM> (<NUM> wt% NaHCO<NUM> in water) were added to the unstirred reaction mixture. After the addition the reaction mixture was stirred (<NUM> rpm) at <NUM>° C for <NUM> minutes. Agitation was stopped and the organic phase and water phase were allowed to separate. The water phase was drained from the reactor and discarded. Subsequently the organic phase was drained and collected separately in a <NUM> Erlenmeyer. The organic phase was dried over <NUM> grams MgSO<NUM>. <NUM><NUM>O for <NUM> minutes. The mixture was filtered over a glass filter and the clear organic peroxide product <NUM> gram (assay <NUM>%) was collected and stored at <NUM>° C.

Analysis: Examples <NUM> and <NUM> were analyzed using the same method as is described for Examples <NUM> and <NUM> ("TBHP Protocol").

To a <NUM> jacketed glass reactor, equipped with baffles, a pH electrode, an overhead mechanical stirrer (pitch blade agitator, size <NUM>/<NUM> of the diameter of the reactor) and glycol/water temperature control, <NUM> NaCl-<NUM>% (aq. ) and <NUM> TBHP (<NUM> wt% in water) were added. The reaction medium was kept at <NUM>° C under agitation (<NUM> rpm) and <NUM> NaOH-<NUM> solution was added in <NUM> minutes. After the addition, <NUM> benzoyl chloride was added in <NUM> minutes during which the temperature was maintained at <NUM>° C. Next, <NUM> benzoyl chloride and <NUM> NaOH-<NUM> solution were added simultaneously over <NUM> minutes during which the was maintained at <NUM>° C. After the addition the reaction mixture was stirred for an additional <NUM> minutes at <NUM>° C and <NUM> rpm. After the post reaction <NUM> NaOH-<NUM> was added and the mixture was stirred for an additional <NUM> minutes. Agitation was stopped, and the organic phase and water phase were allowed to separate. The water phase was drained from the reactor and discarded.

Examples <NUM> and <NUM>: To the unstirred reactor content, <NUM> water and <NUM> NaCl-<NUM> (aq) were added, and the agitator was restarted (<NUM> RPM). The pH was adjusted to pH <NUM> with <NUM> NaOH-<NUM>. The temperature was kept at <NUM>° C by jacketed temperature control. To the stirred solution <NUM> freshly prepared sulfite solution (<NUM> wt% water, <NUM> wt% sodium metabisulfite Na<NUM>S<NUM>O<NUM> (s) and <NUM> wt% NaOH-<NUM>) was added dropwise over a period of <NUM> minutes. During the dosing a pH of <NUM> was maintained by the addition of NaOH-<NUM> (approximately <NUM> in total).

Examples <NUM> and <NUM>: To the unstirred reactor content, <NUM> water, <NUM> NaCl-<NUM> (aq. ) and <NUM> buffer solution (<NUM> wt% AcOH, <NUM> wt% water and <NUM> wt% NaOH-<NUM>) were added. The temperature was kept at <NUM>° C by jacketed temperature control. The pH was adjusted to pH <NUM> by addition of a few drops of NaOH-<NUM>. To the buffered solution <NUM> of a freshly prepared sulfite solution (<NUM> wt% water, <NUM> wt% sodium metabisulfite Na<NUM>S<NUM>O<NUM> (s) and <NUM> wt% NaOH-<NUM>) was added dropwise over a period of <NUM> minutes. During the dosing a pH of <NUM> was maintained by the addition of NaOH-<NUM> (approximately <NUM> in total).

The reaction mixture was stirred for an additional <NUM> minutes after the sulfite solution was dosed and the pH was maintained at pH <NUM>, followed by workup (see below).

The reaction mixture was stirred for an additional <NUM> minutes after the sulfite solution was dosed and the pH was maintained at pH <NUM>. The pH was subsequently lowered to pH <NUM> by the addition of <NUM> HCl (<NUM> wt% in water) in <NUM> minutes (step i)). The reaction mixture was stirred for <NUM> minutes at pH of <NUM>. (total time <NUM>; cf. Comparative Example <NUM>). The pH was then brough to <NUM> with the addition of NaOH-<NUM> (steps d) and e)), followed by workup (see below).

After the addition of the sulfite solution, the reaction mixture was stirred for <NUM> minutes at a pH of <NUM>. The pH of the reaction mixture was then increased to <NUM> by the dropwise addition of approximately <NUM> NaOH-<NUM> in <NUM> minutes (steps d) and e)), followed by workup (see below).

After the addition of the sulfite solution the reaction mixture was stirred for <NUM> minutes at a pH of <NUM>. The pH was then increased to <NUM> by the dropwise addition of <NUM> NaOH-<NUM> over <NUM> minutes (step d)). The mixture was stirred for <NUM> minutes at a pH of <NUM> (step e)). The pH was lowered back to <NUM> by the dropwise addition of <NUM> HCl (<NUM> wt% in water) over <NUM> minutes (step ii)). The reaction mixture was stirred for <NUM> minutes at a pH of <NUM>. Total reduction time was <NUM> minutes (cf. Example <NUM>). The pH of the reaction mixture was then increased to <NUM> by the dropwise addition of approximately <NUM> NaOH-<NUM> in <NUM> minutes, followed by workup (see below).

Agitation was stopped and the organic phase and water phase were allowed to separate. The water phase was drained from the reactor and discarded. Next, <NUM> NaCl-<NUM> (<NUM> wt% in water) and <NUM> demineralized water were added to the unstirred reaction mixture. After the addition the reaction mixture was stirred (<NUM> rpm) at <NUM>° C for <NUM> minutes. Agitation was stopped and the organic phase and water phase were allowed to separate. The water phase was drained from the reactor and discarded. Subsequently the organic phase was drained and collected separately in a <NUM> Erlenmeyer. The organic phase was dried over <NUM> MgSO<NUM>. <NUM><NUM>O for <NUM> minutes. The mixture was filtered over a glass filter and the clear organic peroxide product <NUM> gram (assay <NUM>%) was collected and stored at <NUM>° C.

Analysis: Examples <NUM>-<NUM> were analyzed using the same method as is described for Examples <NUM> and <NUM> ("TBHP Protocol").

These data show that having a pH of less than <NUM> in step c) before proceeding to step d) ("step i)') reduces the hydroperoxide content in the product (><NUM>% reduction at t=<NUM>) and increases storage stability (C. <NUM> vs. Ex. <NUM>/<NUM>). These data also demonstrate that reducing the pH following completion of step e) ("step ii)") reduces the hydroperoxide content in the product (><NUM>% reduction at t=<NUM>) and increases storage stability (Ex. <NUM> vs. Ex. <NUM> vs. Ex. <NUM> vs. Ex.

The overall improvement obtained by combining steps i) and ii) is remarkable (><NUM>% reduction in hydroperoxide content at t=<NUM>, substantial improvement in storage stability; C. <NUM> vs. Ex. As shown above, this most preferred process (Ex. <NUM>) consistently generated t-butylperoxy products with an initial TBHP content of less than <NUM> ppm TBHP and a <NUM>-week stability (ΔTBHP, <NUM>-<NUM> weeks) of less than <NUM> ppm.

Claim 1:
A process for preparing a peroxyester or peroxycarbonate comprising:
a) reacting an organic hydroperoxide with an acid halide, an acid anhydride, or a haloformate, in the presence of a base,
b) separating the aqueous layer after completion of step a),
c) adding a reducing agent to the organic layer after the aqueous layer has been separated in step b), wherein the reducing agent is an agent capable of reducing the organic hydroperoxide to the corresponding alcohol,
d) ensuring that the mixture of step c) has a pH of greater than <NUM> by maintaining or increasing the pH of the mixture of step c), and
e) maintaining the pH of greater than <NUM> for at least <NUM> seconds,
wherein the process is characterized in that:
i. the mixture of step c) has a pH of less than <NUM> before step d), and in step d) the pH of the mixture of step c) is increased to a pH of greater than <NUM>; and/or
ii. after completion of step e) the pH is decreased to a pH of less than <NUM>.