US3479394A - Process for the oxidation of cycloalkanes - Google Patents

Process for the oxidation of cycloalkanes Download PDF

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Publication number
US3479394A
US3479394A US598635A US3479394DA US3479394A US 3479394 A US3479394 A US 3479394A US 598635 A US598635 A US 598635A US 3479394D A US3479394D A US 3479394DA US 3479394 A US3479394 A US 3479394A
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Prior art keywords
cyclohexane
tri
hydroperoxide
orthoborate
cycloalkane
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US598635A
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English (en)
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Jean Claude Brunie
Noel Crenne
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Rhone Poulenc SA
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Rhone Poulenc SA
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/28—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of CHx-moieties
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
    • C07C29/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only
    • C07C29/52—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only in the presence of mineral boron compounds with, when necessary, hydrolysis of the intermediate formed
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Definitions

  • Cycloalkanols and cycloalkanones are prepared by contacting a cycloalkane having 6 to 12 ring carbon atoms with a tri(organoperoxy)borane.
  • the present invention concerns the oxidation of cycloalkanes (alicyclic hydrocarbons), and more especially cyclohexane.
  • the reaction can be carried out in the presence of certain oxygen-containing boron compounds.
  • oxygen-containing boron compounds For example, it is Well known to oxidise cyclohexane with an oxygen-containing gas in the presence of a boric acid or of a boric anhydride capable of reacting with the cyclohexanol formed (see Belgian patent specification No. 635,117).
  • this process involves either the elimination of water formed during esterification with the anhydride or the dehydration of the boron derivatives when acids are used. The only simple procedure for doing this consists in distilling the water-cyclohexene azeotrope.
  • the process of the invention may be carried out by heating a solution of the tri(organoperoxy)borane (II) in the cycloalkane (I), optionally in the presence of a lower alkyl orthoborate of Formula IV given hereafter, at a temperature between and 180 'C. and preferably between and C.
  • the lower alkanol formed from the lower alkyl orthoborate may, if desired, be eliminated as it is formed.
  • Any cycloalkyl orthoborate formed may be treated by any known means to liberate the cycloalkanol.
  • the reaction time will ordinarily be from /2 to 6 hours but the reaction is best continued until all the hydroperoxide is consumed or until substantially all the volatile lower alkanol has been removed.
  • the saturated alicyclic hydrocarbon of Formula (I) which may be oxidised by the process of the invention are cycloalkanes having from 6 to 12 ring carbon atoms, and are ordinarily unsubstituted cycloalkanes such as cyclohexane, cyclooctane and cyclododecane.
  • the tri(organoperoxy)boranes of formula B(OOR) include those wherein R represents the residue of a primary, secondary or tertiary alcohol containing at least 4 carbon atoms which may be aliphatic, alicyclic or arylaliphatic.
  • R may represent, for example, a butyl, pentyl, hexyl, octyl, dodecyl, cyclohexyl, methylcy-clohexyl, ethylcyclohexyl, cyclohexenyl, benzyl, phenylethyl, cumyl, p-nitrocumyl, tetrahydronaphthyl, methyltetrahydronaphthyl, decahydronaphthyl, indanyl, or pinanyl radical.
  • the tri(organoperoxy)boranes may be obtained by the action of boron trichloride on hydroperoxides [Davis and Moodie, J. Chem. Soc. 2372 (1958)].
  • Another (more advantageous) method of preparation consists in reacting a hydroperoxide at a temperature below 90 C. with a lower alkyl orthoborate, under a pressure at which the alcohol liberated is removed by distillation as it is formed. This reaction may be generally represented by the equation:
  • inert solvents saturated aliphatic or alicyclic hydrocarbons and benzene hydrocarbons, which hydrocarbons may be unsubstituted or substituted by substituents such as halogen atoms, e.g. chlorine and fluorine.
  • the solvent should desirably be chosen to give an efiicient elimination from the reaction mixture of the alcohol liberated by the reaction of the alkylorthoborate with the hydroperoxide and preferably solvents which favour the removal of the alcohol.
  • solvents forming a binary azeotrope with the alcohol are particularly suitable.
  • stoichiometric quantities of hydroperoxide and alkyl orthoborate can be employed, but, as stated above, we prefer to operate with an excess of orthoborate, the precise molar ratio depending on the reactants.
  • the molar ratio of orthoborate to hydroperoxide may be between 0.4 and 2.
  • the proportion by weight of hydroperoxide relative to the solvent may vary widely, for example it may vary between 1% and preferably between 2% and 10%. Such solutions may be obtained by diluting relatively pure hydroperoxide.
  • the process of the invention is particularly applicable to tri(organoperoxy)boranes of the Formula (II) wherein R represents a saturated alicyclic radical
  • These tri(cycloalkylperoxy)boranes may be prepared by reacting a solution of the cycloalkyl hydroperoxide in the corresponding cycloalkane with an alkyl borate.
  • the hydroperoxide solutions may be prepared by dissolving the pure hydroperoxide in the cycloalkane.
  • the hydroperoxide should preferably have been purified, for example by converting it into its sodium salt and then treating it with carbon dioxide [Farkas et al. J. Amer. Chem. Soc. 72, 3333 (1950)].
  • the solutions may also be obtained directly and continuously without having first to isolate the hydroperoxide, by partially oxidising the cycloalkane in air, provided that the traces of acid formed in the course of this oxidation are removed. Not only do these acid by-products serve no purpose, but they may subsequently impair the stability of the peroxide derivatives. Besides the hydroperoxide, the
  • partial oxidation of the cycloalkane by air generally leads to small quantities of cycloalkanone and cycloalkanol which is converted into cycloalkyl borate during the preparation of the peroxyborane; these products do not interfere with the subsequent operations.
  • tri(cyclohexylperoxy)boranes as defined above, tri(cyclohexylperoxy)borane may be employed with particular advantage. It may be prepared, for example, by treating in the manner hereinbefore stated a cyclohexyl hydroperoxide in solution in cyclohexane with a lower alkyl borate such as methyl orthoborate or ethyl orthoborate, the operation being carried out under atmospheric pressure. Ethyl orthoborate is preferably employed, because the ethanol liberated by the reaction may be easily eliminated by distillation of the ethanol-cyclohexane azeotrope.
  • the process of the invention may be carried out in a diluent which is inert under the operating conditions, but it is generally preferred to employ as diluent an excess of the cycloalkane which may thereafter be recovered or recycled. This excess is usually large; between 2% and 5% of tri(organoperoxy)borane calculated on the weight of the cycloalkane is generally suitable.
  • the reactants may be introduced into an apparatus under greater than atmospheric pressure, in order to maintain the mixture in the liquid phase, preferably at boiling point.
  • This pressure usually from 3 to 10 kg./cm. absolute, is generally supplied by a gas which is inert under the operating conditions, such as nitrogen.
  • the reaction of the tri(organoperoxy)borane with the cycloalkane may advantageously be carried out in the presence of a lower alkyl orthoborate of Formula (IV) given hereinbefore, which protects the cycloalkanol formed by transesterifying it as it is formed into the cycloalkanol orthoborate.
  • the lower alkanol thus liberated is best removed from the reaction mixture.
  • the proportion of orthoborate employed is not critical and quantities between 2 and 5 mol per mol of tri(organoperoxy)borane are generally suitable.
  • the excess of orthoborate (IV) and the unoxidised cycloalkane (I) may be recovered or recycled.
  • the residue consisting essentially of cycloalkyl borate of Formula B (OR) (V), orthoborate B (OR) (VI) and cycloalkanone, lends itself preferably to the known methods of liberating a cycloalkanol from its borate, for example, by alcoholysis by means of a lower alkanol. Either the compound (V1) is eliminated before the residue is subjected to the alcoholysis, or the residue is reacted as it is and thereafter the alcohol ROH and the cycloalkane ROH are separated, for example by distillation.
  • the residue consisting mainly of cycloalkylborate and cycloalkanone is subjected to alcoholysis to liberate the cycloa kanol from its borate
  • the lower alkanol removed during the formation of the tri(organoperoxy)borane and during the reaction of the solution of tri(organoperoxy)borane with the the cycloalkane may be used.
  • a particular embodiment of the process of the invention consists in employing a tri(cycloalkylperoxy)borane obtained from the hydroperoxide derived from the cycloalkane to be oxidised, i.e. employing a hydrocarbon (I) and a tri(organoperoxy)borane (II) in which the radicals R and R are identical.
  • the diluent in the preparation of the tri(cycloalkylperoxy)borane is the cycloalkane to be reacted according to the process of the invention and if a suitable quantity of lower alkyl orthoborate is used, the solution of tri(cycloalkylperoxy)borane thus obtained may then be directly reacted with the cycloalkane. It may however be found desirable to dilute the tri(cycloalkylperoxy)borane solution with the cycloalkane, so as to bring the concentration of the former to the desired value.
  • the process according to the invention is particularly useful for oxidising cyclohexane into cyclohexanol and cyclohexanone and the simplicity of its technical aspects is such that it meets the requirements for continuous industrial operation.
  • a solution of hydroperoxide in cyclohexane and ethyl borate may be injected into a first column heated at a temperature below C., and the reaction mixture may thereafter be introduced into a second column heated between and C, under the above-described pressure conditions.
  • the cyclohexane and the ethyl borate may be separated from the residual mixture and recycled, respectively, into an apparatus for air oxidation, and into the first column.
  • the heavy (non-volatile) products may then be introduced into a third column into which the ethanol-cyclohexane azeotrope is distilled from the first and second columns is simultaneously injected.
  • the cyclohexanol and the cyclohexanone formed are then separated, and the ethyl borate can be recycled into the first column.
  • Example 1 The apparatus employed consists of a 1 litre cylindrical vessel which may be externally heated, and which is provided with an efficient distillation column connected to a receiving system.
  • the vessel and the column are made of stainless steel and the apparatus has seals for operation under greater than atmospheric pressure.
  • the heating is stopped and the greater part of the cyclohexane is removed by expansion to atmospheric pressure.
  • the residual cyclohexane and ethyl orthoborate are thereafter distilled.
  • Example 2 The apparatus consists of a 3.6 litre autoclave provided with a stirring system and an efiicient distillation column connected to a receiving system, and is scalable for operation under pressure.
  • the tri(cyclohexylperoxy)borane is obtained as a cyclohexane solution prepared from a technical solution in cyclohexane of cyclohexyl hydroperoxide and ethyl orthoborate by heating the reactants and simultaneously distilling the ethanol-cyclohexane azeotrope.
  • the cyclohexyl hydroperoxide is obtained as a solution in cyclohexane prepared from the oxidation of cyclohexane by air, in the liquid phase, without catalyst, the oxidation being limited to about 4% conversion. Before being used, this solution was washed with Water and then with an aqueous sodium bicarbonate solution.
  • the solution is heated to 160 C. under pressure.
  • the boiling is effected under a pressure of 6.5 bars (6.6 kg./cm. and 112.5 g. of a mixture of ethanol and cyclohexane are distilled for 30 minutes.
  • the heating is then stopped and the greater part of the cyclohexane is removed by expansion to atmospheric pressure and the re mainder by distillation. 1150 g. are thus obtained of cyclohexane containing 6.32 g. of entrained cyclohexanone.
  • the residual product which contains mainly cyclohexyl orthoborate and cyclohexanone, is alcoholysed by the addition of 400 cc. of methanol and heating at boiling point. 427 g. of a mixture of methyl orthoborate and methanol, containing 1.1 g. of entrained cyclohexanone, are simultaneously distilled.
  • the residual volatile products are distilled under 100 mm. Hg pressure.
  • the residue consists of 105.5 g. of heavy products containing 80.55 g. of cyclohexanol and 12.85 g. of cyclohexanone, 1.23 mol of cyclohexanol and 0.09 mol of cyclohexanone per mol of hydroperoxide employed.
  • Example 3 An apparatus consisting of a cylindrical vessel (height: 2 metres) having a useful capacity of 3.3 litres, and surmounted by an efficient distillation column connected to a receiving system is employed.
  • the cylinder and the column are made of stainless steel and the apparatus is scalable for operation under pressure.
  • the cylinder has an external jacket through which a fluid maintained at C. is circulated.
  • the residue consists of 34.5 g. of heavy products containing 28 g. of cyclohexanol and 3 g. of cyclohexanone, 1.24 mol of cyclohexanol and 0.16 mol of cyclohexanone per mol of the hydroperoxide.
  • R is such that RH is the said cycloalkane.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
US598635A 1965-12-10 1966-12-02 Process for the oxidation of cycloalkanes Expired - Lifetime US3479394A (en)

Applications Claiming Priority (1)

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FR41807A FR1466528A (fr) 1965-12-10 1965-12-10 Procédé d'oxydation de cycloalcanes

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AT (1) AT266072B (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
BE (1) BE690989A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
DE (1) DE1593343B1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
FR (1) FR1466528A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
GB (1) GB1128089A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
LU (1) LU52547A1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
NL (1) NL6617026A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011064135A1 (fr) 2009-11-30 2011-06-03 Rhodia Operations Procede de preparation d'un catalyseur de deperoxydation
WO2011073053A1 (fr) 2009-12-17 2011-06-23 Rhodia Operations Procédé d'oxydation d'hydrocarbures par l'oxygène
FR2955322A1 (fr) * 2010-01-21 2011-07-22 Rhodia Operations Procede de fabrication d'un hydroperoxyde d'alkyle
WO2011089074A1 (fr) 2010-01-21 2011-07-28 Rhodia Operations Procede d'oxydation d'hydrocarbures
WO2021122955A1 (en) 2019-12-18 2021-06-24 Performance Polyamides, Sas Process for producing cyclohexanol and cyclohexanone

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB892723A (en) * 1959-11-04 1962-03-28 Distillers Co Yeast Ltd Production of alkanols
FR1361232A (fr) * 1963-06-28 1964-05-15 Ici Ltd Procédé d'oxydation catalytique d'hydrocarbures
GB1008314A (en) * 1961-04-27 1965-10-27 Halcon International Inc Production of cycloalkanones

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1346607A (fr) * 1963-01-15 1963-12-20 Stamicarbon Fabrication d'alcools cycliques

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB892723A (en) * 1959-11-04 1962-03-28 Distillers Co Yeast Ltd Production of alkanols
GB1008314A (en) * 1961-04-27 1965-10-27 Halcon International Inc Production of cycloalkanones
FR1361232A (fr) * 1963-06-28 1964-05-15 Ici Ltd Procédé d'oxydation catalytique d'hydrocarbures

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8853461B2 (en) 2009-11-30 2014-10-07 Rhodia Operations Method for preparing a deperoxidation catalyst
WO2011064135A1 (fr) 2009-11-30 2011-06-03 Rhodia Operations Procede de preparation d'un catalyseur de deperoxydation
US8835695B2 (en) 2009-12-17 2014-09-16 Rhodia Operations Method for oxidizing hydrocarbons with oxygen
WO2011073053A1 (fr) 2009-12-17 2011-06-23 Rhodia Operations Procédé d'oxydation d'hydrocarbures par l'oxygène
WO2011089075A1 (fr) 2010-01-21 2011-07-28 Rhodia Operations Procede de fabrication d'un hydroperoxyde d'alkyle
CN102725267A (zh) * 2010-01-21 2012-10-10 罗地亚经营管理公司 烷基过氧化氢的生产方法
WO2011089074A1 (fr) 2010-01-21 2011-07-28 Rhodia Operations Procede d'oxydation d'hydrocarbures
US8846980B2 (en) 2010-01-21 2014-09-30 Rhodia Operations Process for the production of an alkyl hydroperoxide
FR2955322A1 (fr) * 2010-01-21 2011-07-22 Rhodia Operations Procede de fabrication d'un hydroperoxyde d'alkyle
CN102725267B (zh) * 2010-01-21 2014-10-08 罗地亚经营管理公司 烷基过氧化氢的生产方法
RU2530896C2 (ru) * 2010-01-21 2014-10-20 Родиа Операсьон Способ получения алкилгидропероксида
US9156757B2 (en) 2010-01-21 2015-10-13 Rhodia Operations Process for the oxidation of hydrocarbons
WO2021122955A1 (en) 2019-12-18 2021-06-24 Performance Polyamides, Sas Process for producing cyclohexanol and cyclohexanone
CN114845983A (zh) * 2019-12-18 2022-08-02 巴斯夫欧洲公司 制备环己醇和环己酮的方法
JP2023506663A (ja) * 2019-12-18 2023-02-17 ベーアーエスエフ・エスエー シクロヘキサノール及びシクロヘキサノンを製造する方法

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GB1128089A (en) 1968-09-25
NL6617026A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1967-06-12
LU52547A1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1967-02-09
BE690989A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1967-06-09
FR1466528A (fr) 1967-01-20
DE1593343B1 (de) 1971-09-16
AT266072B (de) 1968-11-11

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