DE1907532A1 - Process for the preparation of cycloaliphatic alcohols - Google Patents

Description

BI YOU POFJ? BE HEHDUH3 & COHPAFf
10th and Market Streets, "Wilmington, Del. 19898, Y.StJl.

Process for the production of cycloaliphatic alcohols

The present invention relates to an ancestor sur Ker ^
Position of cycloaliphatic alcohols on cycloaliphatic compounds and oloolofins.

It is already known that gyalododecane can be oxidized with air or a mixture containing cyclododeeanol. Organic mixtures usually contain or other oxyclation products,
like Cyclodoäeeanon and Gyclododecylhyclroperosyd. Such air oxidation systems often contain boric acid or one other

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its boron compound, see the British patents 1 052 390 and 1 064 167 is referred to.

A convenient route to cyelododecane is the irimerization of Butadiene with subsequent hydrogenation of this product. A A convenient route to cyclooctane is the dimerization of Butadiene and the subsequent hydrogenation of this product.

It has now been found that daa product IiuftoxydatioHS-systems of Cyelododeeans, contains a T to 30 $ £ öyelododecylhydroperoxyd, can be used as an oxygen source for the conversion of cyclododecatriene in Cyclododecatrienoxyd-Zwiachenprodukte, (tie in the hydrogenation cyclododecanol in high yields with only The cyclododecyl hydroperoxide is reduced in the reaction with the cyclododecatriene and also forms cyclododecanols.

Cyclododecane is oxidized with air au a mixture which contains from 1 to 30 f * öyclododecylhydroperoxyd. This mixture also contains small amounts of .oyclododecanol, cyclododecanone and other oxidation products. "The cyclododecanol does not enter any chemical reaction in the remaining stages." Cyclododecatriene is then added to this mixture in more than stoichiometric amounts, based on the amount of hydroperoxide present, usually in an amount of 1.1 to 3 times the amount of the hydroperoxide present is released and the cyclododecstriene is oxidized, with oxidized olefinic intermediates being formed. the

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Mixture is then hydrogenated and the cyclododecatx'ienoxycl intermediates are converted into öyclododecanol. That unused cyclododecatriene, which in an excess has been admitted to. Hydrogenated cyclododecane. In the hydrogenation reaction, the cyclododecane is also used reduced to the cyclododecanol. The cyclododecanol is then for example by distillation, obtained and the cyclododecane is returned to the air oxidation stage.

The air oxidation of cyclodoecane in a mixture? containing cyclododecyl hydroperoxide can be carried out by any of the several methods already known, either with or without a modifier such as boric acid. The conditions are preferred under which the formation of hydroperoxide is maximal. Suitable conditions for bubbling air through Cyclodoclecan are 140 to 17O ⁰ G, preferably as close to * HO ⁰ G as possible, and atmospheric. Ozone can be added to the air in order to reduce idle times . enable.

The mixture containing the cyclododecyl hydroperoside is then magesetat with Cyclodoöecatrien. This latter reaction is preferably carried out at temperature einar In Seraich of etv / a 60 to about 140 ° _C? preferably at 80 to 120 ^{° C.} , since at this temperature the mixture is solid and since above this temperature the reaction takes place in a low yield. Yorzugvioise is also present a catalyst. Suitable catalysts include boric acid compounds, such as orthoboric acid, boron oxide, borate ester, for example ^: riaeth; flborate, triethyl borate _? Vanadius compounds, for example VanaßiUKpentoxyd, boron

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vanadic acids and oxides, molybdenum compounds such as molybdic anhydride, molybdic acid, boron molybdic acids, peroxymolybdic acid _f molybdenum blue, holybdenum oxide, and mixtures of these substances. When the catalyst is boric acid or a derivative, the amount added will range from about 0.5 to 5 moles per mole of cyclododecyl hydroperoxide present. If the catalyst is one of the other catalysts mentioned, it accounts for about 0.005 to 0.5 weight percent of the total amount of organic substances present (oyclododecane, oyclododecanol, cyolododecanone, cyclododecyl hydroperoxide, other oxidation products and added oyclododecatriene). The reaction pressure is not critical and can vary from about 20% to 1 or 2 atmospheres absolute.

The hydrogenation of the mixture containing the intermediates is carried out using conventional hydrogenation methods, for example with a fixed bed catalyst made of nickel oxide, Ifiekel on diatomite or aluminum oxide, platinum on a support, palladium black, Raney nickel, cobalt molybdate or nickel tungsten sulfide. Such reactions are herköiamlicherweise kg at 100 to 25O ⁰ C and at pressures from 2.81 to 352 / cm ² (40 to 5000 psi), preferably of 3? 52 carried out until 35.2 kg / cm (50 to 500 psi), v / whether the special conditions are selected so that the olefinic ITsaturation is essentially completely saturated and ketone to alcohol. _{: is} reduced. _; .

The method according to the invention is illustrated by the attached Flow chart explained further. Cyclododecane and air will be fed into an air oxidation reactor 1, wherein the Cyclododecane is oxidized to a product, the cyclo-

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contains dodecyl hydroperoxide. This product is fed into the peroxide reactor 2, v / o it is mixed with cyclododecatriene and reacted in the presence of added catalyst. The reaction mixture is then poured into a. Catalyst removal and neutralization step where it is appropriately treated to remove the catalyst and to neutralize any organic acids formed by the oxidation steps and any acidic catalyst residues present. The particular catalyst removal step that is performed depends on the catalyst used. When boric acid is the catalyst, the bulk of the catalyst is removed by washing only with water at a! Temperature above about '60 ⁰ O. The remainder is neutralized by the subsequent addition of a mild alkali solution with a pH of 8 to 12. The 3oric acid is then dehydrated and transferred to the peroxide reactor. returned. What if the catalyst is not boric acid, but instead Mclybdenum trioxide or something like that _? so the catalyst by washing with water, the small amounts of alkali · at pH 8 can contain up to 12, located in contact times of 1 to 30 minutes and at Semperatüren of 60 to 11O ⁰ G werden.-Such catalysts may be discarded or cleaned and returned will.

The reaction mixture is then put into the hydrogen reactor where in the presence of a hydrogenation catalyst the Main amount of Oyclododecatrienoxyde and Cyclododeeanons is reduced to cyclododecanol, while cyclododecatriene, which is added in excess in the peroxide reaction, to Cyclododecane is reduced. The reaction mass then becomes to the cyclododecane recovery distillation plant 5 ge

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directs where Gyolododeean is recovered and to the air oxidation stage is returned. The rest of the Eeaktionsaiasse is then sent to the recovery distillation plant 6 for non-hydrogenated product, where products, which are not completely au cyclododecane or cyelododecanol are removed and returned to the hydrogenation reactor 4. Eventually the reaction room becomes into the cyclododecanol no-waste distillation plant 7 Gelsitet where this product differs from the higher boiling organic Substances is separated that have been formed in the previous reactions.

The reaction scheme can be modified in various ways, for example more than one hydrogen reactor 4 can be used and long residence times in a single reactor 4 can be used, eliminating the need for 3Χ12Θ G-ewinnungßdestillatlonsanlage 6 for non-hydrogenated product.

The following examples are intended to further illustrate the invention. All ^r feil3 and Pro a entangab s are gewichtsbszogen. unless otherwise stated.

example 1

Oycloäoäeean is used in conventional :; Manner-oxidized with air to form a mixture containing about 5.1 & Cyclod'odeoylhydroperozyd. 2.1 mol and 1.8 Gyclodödecatrien Hol Metaboroäure vrerden per haul hydroperoxide was added and the mixture is heated to 120 ⁰ C for 1.75 hours. After this period of time, 99 Ά of the hydroperoxide have been converted. 0.49 moles of boric acid added per mole of cyclododecylhydroperoxyä

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go into solution. The boric acid is removed by hydrolysis and extraction with hot water. On analysis of the product it is found that 0.85 moles of cyclododecatriene per mole of Oyclododeeylhydroperoxyä present has been oxidized in. The product is hydrogenated by adding 1 wt. JS PallEdiunischwara-KatE.lysator and with hydrogen under a pressure of 2.81 kg / cm (40 psi) is set while the product is agitated and ^{heated to about 100 °} C. until the pressure remains constant. Analysis of the product shows that 95 5j of the oxidized cyclododecatriene in cyclododecane! or are converted into products which form cyclododecanol on further hydrogenation. A total of 0.73 moles of these products are obtained per mole of peroxide introduced.

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Cyclodoaecane is oxidized with air to form a mixture which contains 6.9 5 * cyclododecyl hydroperoxide. Cyclododecatriene is used in an amount of 2.1 mol / mol hydroperoxide zugegeben3 there are added about 500 ppm Parmolybdänoxyd catalyst and the temperature is maintained for 1 hour at 10O ⁰ C. -L molybdenum trioxide (MoO) water is suspended in 20 parts * 5 and ropes of a 30 jiigen Wasserstoffperoxydlösuug are added The solution is heated to 90 to 100 ⁰ G, until a yellow solution klare-: (The catalyst is prepared by 1 50e. is obtained, then it is dried on a steam bath. The yellow solid shows 81 # HgMoOc) on iodometric analysis. After 1 hour the hydroperoxide is reduced to 98%. The product is filtered off. Analysis of the filtered product shows that 0.80 moles of cyclodo & ecatriene per. Mole of cyclo-

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dodecyl hydroperoxide are converted into products that the reduction produce oyclododecanol. The product is washed with water in a small amount of sodium hydroxide is included to remove the catalyst and about the organic acids and the catalyst residues to neutralize,

The product is then mixed with about 2.5 parts by weight Jo Raney Uiekelpulver and hydrogenated at 10O ⁰ O with 2.81 biting 3.52 kg / cm (40 to 50 pnig) until the hydrogen absorption ceases. Me hydrogen absorption is 100 ^c / * the value which has been calculated from the analysis of the feedstock necessary to unuragesetzte everything Cyclodode * - Catrien in cyclododecane and everything oxidized product in Gyclododeeanol r "m au wan yours. The catalyst is removed by filtration and the product is analyzed. It contains 10.5% by weight of cyclododecanol, 0.27% by weight of cyclododecanone and 0.04% of cyclododecyl epoxide.

The product is subjected to vacuum distillation and. in four fractions separated, resulting in a recovery of 99.1% by weight.

(1) B & will remove a praction at 104 to 105 ⁰ G and at a pressure of 10! Eorr ep / c. This fraction makes up about 86.6 % of the product introduced and contains mainly cyclododeoane with about 0-5% by weight of cyclododecanol and cyclododecanols. This fraction can aur LuftO3cyda * tionss m £ e be suriickgeleitet.

(2) * Dei pressure then wirel on etv / a 6 üorr reduced and viird a fraction ait a boiling point of 97-132 ⁰ C mitferat. This praction makes about 3.5 wt .- ^

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of the introduced product. This fraction contains about 54 wt. -Fi Cyclododecanole 5.1 wt .- # Cyclododeeanon, 0.4 part by weight 5a Cyolododecanepoxyd and 43 wt .- # A Cyolododecan This fraction can be returned to the hydrogenation stage to the Cyclododecanepoxya and Converting Oyclododecanone into Cyclododecanol.

(3) The temperature is then increased while maintaining the pressure at about 6 torr and a fraction is recovered which is about 8.0% by weight of the charged product. This fraction contains more than 96% by weight of cyclododeeanol, 0.3% by weight of cyclododecane epoxide, 1.0% by weight of cyclododeeanone and 2.5% by weight of cyclododecane. This product is of sufficiently high purity to be used in this form, however, a further distillation can be performed to further purify the product aas'.

(4) A high-boiling residue remains, about 0.88 percent by weight of the charge. This faction contains about 5 wt .- $ cyclododeeanol.

The inventive method can also be used to produce alcohols from other cyclic olefins can be used, for example the cyclic butadiene dimer to provide the alcohol used in further oxidation yields octanedia acid.

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Claims (2)

AD-4326 "| 0 ** · February 1969 Claims! 1 \ Process for the production of Cyclododecane ^, daduTch marked! that he (1) Cyclododecane is oxidized with air to form a mixture, the cyclododecanols cyclododecanone and 1 bia 30 wt .- ^ Cyolododeoyl hydroperoxide contains » (2) Cyolododecatriene by reaction with this mixture in the presence of a catalyst “selected from Mo-, B- and V-containing catalysts, ^{oxidized at a temperature of 60 to HO 0} O to form a mixture containing cyclododecatriene oxides”, the molar ratio of oyolododeoatriene increasing to Cyclododecyl hydroperoxide is about 1.5 to 3 »preferably the catalyst used for the oxidation of the cyclododecatriene is removed, if necessary the oxidized product is neutralized by washing with dilute aqueous alkali, (3) the obtained mixture using a hydrogenation catalyst at 100 to 25O ⁰ C and at a pressure of 2.81 kg to 352 / om ² (40 to 5000 psi) was hydrogenated cyclododecane preferably from the hydrogenated product is isolated and dtr luftOxydationsstufe returns, preferably a mixture containing cyclododecanone and cyclododecane epoxide, recovered from the hydrogenated product and returned to the hydrogenation stage, and - 10 - 90 9 838/15 35 AD-4326 (4) Cyclododecatiol wins from the hydrogenated »product, 2. The method according to claim 1 »characterized» that in the oxidation of Oyclododecatrien as a catalyst Orthoboric acid in an amount from 0.5 to 20 hol per mole of cyclododecyl hydroperoxide or one molybdenum or Vanadium-containing catalyst used in an amount of 0.005 to 0.5 wt .- # of the total present organic substances are present. - 11 - 909838/1535 Blank page