DE1518981A1 - Process for the preparation of amine oxidation products - Google Patents

Description

DR. IM MAAS no. WG PFEILER β TENIAMWÄ! - "1, UNCHEN 7" ■ UNGERERSTa. » - IEL 333; 6

Gases 762

HalGon International Iac ", Lew York, H.Y. T.St, A.

Process for the production of aninoxidation products

The invention relates sioh to a method for Heratel-. amine oxidation products such as oxines and hydroxylamines! except primarily "" Aaißen. The invention relates to 'a method of Heratellung of Aminoxydationsprodukten, with an amine, oxygen, and a Kohlenwaeeergtoffrerbindung Kit atoms at least one Waeseretoffatom at an at least 2 other carbon or eineis aromatic Hing adjacent carbon atom (preferably Ouiaol, Xthylbensol or isobutane) are the only required Auegangestoffe represent laugh before ", suggested execution form of the process according to the invention, such amine oxidation products are made from" one "amine

IQf84.
BATH ORIGINAL

Oxidation with a! J.pha- "Phenylethylhydroperoxide produced" Here the amine, oxygen and ethylbenaol are the only starting materials required. In addition to the oxidized amine is a by-product is obtained which alpha-phenylethanol, styrene or acetophenone may Ain * laugh another Off · fUhrungaform is the alcohol formed as a by-product back into the ®ingeeetst "n Kohlenwaaeeratoff converted _f whereby in operation the by-products, but with Consumption of hydrogen is possible.

The importance of ketoxisien and other oxygen-containing amine oil rates as raw materials for the chemical industry is constantly increasing. In this field of technology there has been a need for aaoh usable decay for the production of 70η ketoximes wad hydroxylamines from the entepreötienä®® amides. Be was already vn ^ vorgfeehla using Waaserstoffperoxyd in a wäaerigea system to be arbeiten.Hiermit Although no byproducts formed praktieon no or dooh has this Arbeitavaiae * that it vrerwendete medium T "rhältnismäSig is sohwer sugänglioh especially & qh Haehteil. Hydroperoxides were found to be extremely useful for such a process and it was believed that they would form by-products.

909848 / 1'3'3S-

BATH ORIGINARY

Eb is dither the task of a process for the production of Hydroxylamino !! and. Olimes from appropriate prairies Find amines in simple and economical ffeioe eu.

Through the process according to the invention, the task is to Oxime or hydroxylamines in economic rock solved while avoiding or reducing the loss of valuable waste materials.

The subject matter of the invention is a process for the production of clay aeinoxidationejurodiurte "such as oxime" or HydroxyXejdnen aua the breaking prairie amines, whose eel group "is bound to a primary or natural carbon off β to", because a combination of the amine is not necessary (1) a lustful Xet & llcatalyst from the group of peracid-forming or hydroxylation catalysts (namely compounds Ton Tl, V ₉ Gr _v Cb, Se, Zr, Sb, Mo ₁ Te, Ta, W, Re and U), etc. (2) An organic hydroperoxide is treated as the essential oxidizing agent, with the amount of oxygenation in the range from 0.01 to 8 10 mol per mole of the algae and the amount of metal torzugeveiee in the range from 0.00001 to 0.1 ! fol je. Get the hydroperoxyde.

BAO QRIOlfoAL

The following describes a number of measures that preferred when carrying out the process according to the invention can be applied:

1. The temperatures used are in the range from about 10 to + 175 ⁰ C;

™ 2. sui * Production of cyclohexanone oxime becomes cyclohexyl hydroperoxide, Cumene hydroperoxide or a hydroxy hydroperoxide is used f

3 · A molybdenum or vanadium bond is used as a catalyst used}

4ο an amine is used as the starting material, its

Amino group on a secondary carbon atom of a cyclo- ^. an alkyl group having 4 to 16 carbon atoms is bonded;

5 · the hydroperoxide is made by converting gaseous Oxygen with ethylbenzene in the presence of an oxidation » Initiator produced and with an amine nit 1 to 20 Carbon atoms mngeeetatj ale by-product is

909Θ / 3/133 & SADOfilGlNAL ,,

£ lpha «Phenylethanol obtained;

6 »The not converted ethylbenzene is in the stage of Production of the hydroperoxide aurlioXgöfUhr15

7. The alpha-fhesylethanol is dehydrated to styrene

8. The hydration stage is over in the vapor phase a titanium dioxide catalyst at a temperature in the range from 180 to 280 ° 0 öurchgcfiflartj

as a catalyst, a catalytic amount of a molyb Danish Balsea of a Carbons & ur «used)

Every catalyst becomes a catalytic amount of hollybda diacid sulfide

11. daa alpha-phenylethanol is dehydrated to acetophenone, that is won;

12 * daa alpha-phenylethanol is hydrogenated to JithylbenBol, daa is used to make its hydroperoxide j

909848/1335
BAD ORfQlNAt

- ■ 6

13. The hydroperoxide is produced by converting gaseous oxygen with cumene in the presence of an oxidation initiator prepared and unset with an amine with 1 or 20 carbon atoms; Oumy alcohol is obtained as a by-product;

14. A catalytic amount of a Holybdänealzes is used as a catalyst a carboxylic acid used;

15. The cumyl alcohol is overfilled into cumene, since it is used in the manufacture of its hydroperoxide;

16. the cumyl alcohol is converted into alpha-methylstyrene?

17. starting from n-Hexylaaln, n-Haxylaldoxlra is produced;

18 _a starting from one of the lines mentioned, aaa corresponding hydroxylemin is produced

19 «for the production of cyclobexy! Hydroxylamine, <3us! Ol is used» related to hydroperoxide as an oxidizing agent; ·

Surprisingly, it was found that peroxy by the oxidation of the above hydrocarbons without further "educated Hydro de special" good for dio OxyJaljloa of

90 3348 / 133S BATH

primary amines, the amino group of which is bonded to a primary or secondary carbon atom, are suitable for adoximes or ketoximes. Although the process according to the invention involves a number of process steps, it is not necessary to isolate the products of these individual steps, so that the entire reaction sequence is particularly advantageous

Way can be done * Λ

In the first stage of the process according to the invention the hydrocarbon is oxidized e.g. with atmospheric oxygen, for example cumene to cuaol hydroperoxide. You oxidation of the hydrocarbon, b.B. of cumene, can be

lungs of up to $ 40> can be carried out with high selectivity. Aliphatic hydroperoxides are formed with somewhat lower selectivities on oxidation with Q £. The oxidation mixture obtained contains the starting material and the hydroperoxide formed during the oxidation. It also contains β ore small amounts of by-products The jSlnfUhrung of the primary amine in this mixture (or a concentrate thereof) either during or after addition of the catalyst £ üiirt to the corresponding oxine or hydroxylamine and using üümolhydroperoxyd to Cumy! Alcohol.

9.848 / 1-3.3

" 8th

The mixture of reaction products obtained as described above contains some acetophenone in addition to alcohol. Pan area oxidation product passes through without difficulty Separate distillation or other suitable measures from the mixture »

If the hydroperoxide concentration, for example the concentration of alpha-phenylethyl hydroperoxide or cumene hydroperoxide, is above about $ 30-40, it can be useful to add an inert solvent. The solvent used in each case should not react with the Peroacydsaueretoff or the amino acid formed during the reaction. The solvents that can be used include, inter alia, "tert _e " -buty alcohol, elpha-phenylethanol, cumyl alcohol, benzene, toluene, ethylbenzene and cumene.

The secondary alcohols can be dehydrated to ketones in a manner known per se, e.g. to acetophenone (from alpha-phenylethanol), which is a tradable substance. Instead you can use the alcohols (secondary or tertiary alcohols) readily in a manner known per se by dehydration in styrene or substituted styrenes or isobutene, which are also tradable substances. Brushes are easily known Way by vacuum distillation in a substance of

9G984S / 133I BAD ORIGINAL -k

"" 9 -

transfer to a higher degree of purity * Furthermore, eo is without Difficulty possible, the alcohol or the olefin obtained therefrom in a known way in the Torwendet'en as a starting material To transfer hydrocarbons, which is recycled. This measure results in one of Processes free of byproducts, although hydrogen is consumed.

The following examples illustrate the invention without ale to restrict. Parts and percentages are calibrated to dan Weight, unless otherwise stated, lot.

example 1

A mixture of 10.1 g of tert-butanol, 2.0 g of cyolobexylamine, 0.1 g of yanedin naphthenate in naphthenic acids with a content of 3.4% vanadium and 4/9 g of uuaol hydroperoxide is produced at Zinmer temperature, to 80 ° ^O The mixture formed contains Oyclohexanonoxia and is heated and kept at this temperature for 2 hours without stirring. The hydroperoxide conversion is about 62 ? *.

In relation to ußigewandeltee Ouraolhydropei'opxyd baträgt the oxime yield 45 i>"The analysis can be performed on .beliebige 'Weis * beis-pielo'7 / eiae gaachroffiatographiach.

BATH ORIGINAL

■■ - ίο - ·

The oxine can be prepared in the usual way, for example by action with diethyl ether and removal of the solvent . separated extract phase has been obtained. In cases where the area of the oxine forms a co-forklift compound, it is used as a solid subatana, for example in an aqueous syiitem. The Oxira can be separated from it by distillation, extraction with cyclohexane or equivalent measures.

Beiapial 2

The bsschriebene in Example 1 "operation will be repeated except that 10.0 g Cyolohexylhydroptit> xyd as Oxidant at aimmerteaiperatur (24 hours) and 11 g Molybdännaphthsnat be used with a Mo-content of 5 1". Daa hydroperoxide is known ISS Whiteness by conversion of cyclohexane old air and afterlisend vacuum daatillatlon of not uagaeoteteB Cy <Jlohii: ßa. Here one obtains the Auegangematarial used, which contains 2.28 mmol Hydroperoaj'd ja Qranu & on, After the conversion the mixture contains the Oxide is 90 'i » and the oxime selectivity-« bassogen on uagaattates hydroperoxide - 26 %.

909 348 / t3T3; S ''

BATH ORIGINAL Example 3

The procedure described in BoiBpiel 2 is repeated with the Auonahme that a temperature of 60 ⁰ C and a time are applied by 17 hours. The reaction mixture contains the Cxim. The hydroperoxide conversion is 100 # and the selectivity based on the converted hydroperoxide is 45 # »

Example 4 .

The procedure described in Example 2 is repeated using 0.1 g of a catalyst containing 3.4 $ vanadium in naphthenic acids. The hydroperoxide conversion is 100 f *. and the related oxime selectivity $ 55. ,

5-

in Example 4, described ".Arbeitaweise is again · brings -with: except that one temperature of 6O ⁰ C. and a .Zeit;? to be used with JI voices . The conversion is the same (100 #) and the oxime selectivity is $ 60. Furthermore, cyclohexylhydroxylamine is formed with a selectivity of a few percent «

9 m 8 _: 4.8 / 1 3 3 5 BATH

Ti.v,. - '

Example 6 .. _;

The procedure described in Example 2 is repeated, but with. 10 g of cyclohexylamine are used and reacted for 24 hours at room temperature. The conversion of the peroxide is; 93 $> and the selectivity to cyclohexy! Hydroxylamine 63 ° «

■ ■ · .. ■. ^ - ■■;. ·, - ■■■ Example 7 ... -..-., · .- ■ -_ .....

The procedure described in Example 6 is repeated, but using 4.9 g CumoIhydroperoxyd used, and a 6-stUndige implementation are applied at 60 ⁰ C. The results given in Example 6 are obtained.

. ■ /..- ■ Example β

About 7.5 g of 88% alpha-phenylethyl hydroperoxide, 7.5 g of alpha-phenylethanol, D ₍ 6 g of molybdenum naphthenate (with a Mo content of 2 %) and 16.0 g of amine are reacted as described in Example 5. Practically the same results as those given in Example 5 are obtained.

BATH

Example 9

The oxidation is practically described as in Example 8 carried out with the exception that 0.016 g as a catalyst Permolybdic acid can be used. Doing so will be the same Results as given in Example 8 were obtained.

In the case of oxidations of the type described above, obtained very good results with molybdenum disulphide as a catalyst,

Example 10

The procedure described in Example 2 is repeated with the exception that 10 g of a solution of the hydroperoxide of para-ethyltoluene in ethyltoluene, 16.8 g of the amine and 0.03 g Mo naphthenate with a Mo content of 5 S ^ used will. The results correspond to those described in Example 2

Example 11 .

According to the procedure described in Example 10, 5 g of cumene hydroperoxide, 5 g of curoyl alcohol, 0.2 g of a Catalyst solution with a vanadium content of 3 to 4 pounds (ale

u -

Naphthenate) and 10 g of the amines a Hydroperoxydumwandlung of about 90 # and a Oximaelektivität of about 30 fo generated

After the procedure described in Example 10 is obtained from n-hexylamine the corresponding n-hexylaldoxia in good yield.

The use of tungsten carbonyl as a catalyst in the The procedures described in the above examples also lead to good results.

The results achieved by the method according to the invention are proportionate, taking into account the the low cost of the oxidizing agent and the simplicity of the process measures are extraordinary surprising and technically of great value · a Another advantage of the oxidation used according to the invention = medium is that they are not like Waseeratoffperoxyd experience adverse decomposition

The oxidation of alkyl, cycloalkyl or aralkyl hydrocarbons such as ethylbenzene or cumene can in itself be carried out in a known manner in such a way that only the formation of the hydroperoxide is favoredc Palis Absats-

909848/1135

BAD ORIÖINÄ

O '**' Γ

There are possibilities for alcohol formed as a by-product, it can be won and sold Bring «Otherwise you can use the alcohol su styrene or dehydrate a styrene derivative. Secondary alcohols can also be dehydrated to acetophenone in a known manner will. Both and valuable substances. Styrene can also hydrogenated again to form coal.

! Alpha-phenylethanol _r consisting of the hydroperoxide in a ratio of about / mole per mole is formed, can be calibrated in a yield of 80 ^ or more by Cfaaphasendehydratieierung at 200 - 250 ° C over granular! Convert titanium dioxide or similar oxide catalysts into styrene at atmospheric pressure. Other catalysts that can be used include silicon dioxide and aluminum oxide. The styrene is purified by distillation and provides a highly pure product.

Instead, ßlpha-PlienyläthiCinol can be dehydrogenated at 200-300 ⁰ C in the presence of a copper catalyst eu Aetoplienon, which is obtained in a known manner and purified by distillation.

909 ai8 / 1 ^ 3 δ

BATHROOM ORIGINAL.

After all, you can put the alcohol in the "well-known" way converting all starting material used hydrocarbons, which is returned in the cycle.

Ieobutene is reacted with oxygen sum tert.-Bvtylhydroperojyd, which is reacted with the amine to form the amino XJ - dation product and of terto-butanol. The latter can be marketed as such or used for the production of isobutene or converted into isobutene «

In the first stage isobutane is in the vapor phase with air and hydrogen bromide as a catalyst at a pressure τοη about one atmosphere and a temperature of 160 ⁰ C using 2 moles of oxygen per mole of isobutene and a throughput rate of about 1000 volumes of gas mixture per fe reactor volume and Hour implemented. Dan escaping gaseous mixture is abgskühlt to about 30 ⁰ C and condensed and teit-Butylhydroperozyd is ^{above sea level} by Deetilation at about 50 C in "known ffeiue recovered from the condensate. Me conversion of isobutane is 30 $> and the related unreacted isobutane selectivity to tert-butyl hydroperoxide 65 £ «Non-urageoetates inubutane is recovered and returned to the ■ cycle *

BATH

Another way of working is that the isobutane in the Way oxidized that one oxygen by 800 g of liquid Isobutane. ,, the 5 g of Dl-tert-butyl peroxide and 1 g of iron naphthenate contained, in a reactor made of corrosive

ο conducts permanent steel at a temperature of 110 C and a pressure of 42 atmospheres. This action continues when Us $ 25> dea isobutane are converted.

The analysis of the reaction products obtained (isobutane-free) gives a tert-butyl hydroperoxide equivalent of about 1.0 100 g each,

The oxidation of isobutane can be carried out in the manner that the almost exclusive formation of teifc butyl hydroperoxide is favored. However, it is also possible to use a mixture of tert-butyl hydroperoxide and tert-butyl alcohol to produce and these two substances by distillation separate * Where there are sales opportunities for teifc-butanol, can be placed on the market without excess of this substance will. Since texk butyl alcohol is a part of the for.die Oxidation of the amine with the hydroperoxide used mixtures has a beneficial effect is a separation of tert-butanol from the Hydroperoxide is not required for the Zweake according to the invention. The fact that such a separation is not necessary is, of course, from an economic point of view advantageous from a point of view. In addition to the operations described above

909848/1335 BAD ORIOlNAl. '

"at tfewei3cnkönnen also bsi lobige other for the implementation of Iaobu'lian with molelculm .- 'is an oxygen ζλ \ tert-butyl ^ hy di-operoxyd" known work are applied "wise,

In the second stage the hydroperoxide becomes practical ii.qulmolarem ratio converted into tert -butyl alcohol.

The tertiary butyl alcohol can be thermally or over a suitable catalyst, such as activated alumina or silica-alumina at a temperature in the range 150-500 ⁰ C in a known manner to Iaobutylen

are dehydrated, with practically $ 100 yields of olefin. A catalyst can also be used with 48% bromine acid.

The temperatures used for the oxidation can vary within wide limits depending on the reactivity and other properties of the other reaction participants. Quite generally one can temperatures in the range of about -10 to +175 ⁰ O, Eweckmäßigerweise of 25 - 13O ⁰ C, preferably apply from 60 -HO ⁰ C, üie reaction is under pressure sufficient to maintain a liquid Reaktionsphaae printing is performed "negative pressures can indeed may be used, but pressures in the range of about atmospheric pressure to slightly above are usually best »

G098A8 / 133 BAD i

The catalysts that can be used include compounds of the following elements: Ti »V, Gr, Se, Cb ₈ Zr, Nb, Mo, Te, Ta, W, Re and U. Such compounds can be characterized as peracid formers or hydroxylation catalysts.

The amount of as a catalyst for the process according to the invention The dissolved metal used can vary within wide limits. As a rule, it is useful at least 0.00001 Mo, preferably 0.001 to 0.01 mol per mol of existing hands NEN Hydroperoxyds to use, lying above about 0.1 mole Quantities evidently do not produce anything compared to smaller quantities Advantage = The catalysts remain during the entire process in the reaction mixture in solution and can be used again for the reaction after the removal of the reaction products be used. The ratio of hydroperoxide to. Ami η- "is in the range from 0.01 to 10 moles, preferably at 0.5 to 2 hol per mole of amine.

The molybdenum compounds that can be used include the organic MolyMänaalze, the oxides such as Mo ₂ O ,, KoO ^ p MoO ,, Molybdenum -Sulfide, Molybdenum-containing heteropolyseates and their salts can also be used * Examples are phosphoitfolybdanic acid and its sodium and potassium al z, - Analogous compounds of the other metals mentioned above can also be used «,

90984 8/133 5 BATH

The hydroperoxides used are derived from hydrocarbons. Stable aralkyl or cycloalkyl hydroperoxides are very suitable. Exemplary hydroperoxides can are represented by the formula ROOH, where R is an aralkyl, aralkenyl, hydroxyaralkyl, hydroxyalkyl, Cycloalkyl, cycloalkenyl, hydroxycycloalkyl, alkyl or a similar group of about 3 to 20 carbon atoms means »The analogous Hydroxyhyxroperoxyverbindungen can also be used.

Specific examples of organic hydroperoxides are Cyclohexylhydroperoxyd, cyclohex-2-enylhydroperoxyd, tert · - butyl hydroperoxide and the hydroperoxides of toluene, Ä'thylbenzol, cumene, ρ-ethyltoluene, isobutylbenzene, tetrahydronaphthalene, Diisopropylbensol _f p-isopropyl toluene, o-xylo], m -Xylene, p-xylene and PhenylCyClohexene. The preferred compounds are those derived from cumene, ethylbenzene and isobutane. It is also possible to use mixtures of such hydroperoxides and also cyclohexanol hydroperoxide and the like.

In the practical implementation of the process according to the invention, the catalytically active substances can be in the form use a compound or a mixture of compounds which are initially soluble in the reaction medium

90984 8/1 33 S BAD '

is «The solubility depends to a certain extent on depending on the reaction medium used, but belong In addition to the soluble substances which can be used according to the invention, in general the organometallic compounds which are soluble in hydrogen and have a methanol solubility of at least 0.1 g per liter at room temperature. Examples of soluble Forms of the catalytically active substances are the haphthenates, Stearate, Ootoate and Garbony! Compounds. Different Chelates, association compounds and bnol salts, * · Β «die Acetoacetonates can also be used «Pur die Catalytically active purposes preferred according to the invention Compounds of this type are the vaphthenates and carbonyl compounds of UoVMMn, vanadium and tungsten **.

Pie Bauer der Oxy <* »» tion reaction feltaft from the gtwunsohten Conversion from »Very curious reaction pages can be used where there are no low conversions and / or very active substances are usually used, reactions of about 10 minutes to 6 hours, usually from 2 to 24 hours. . .

They used aaine and prairie Asiine, and the aaino group can be linked to a prlaMrea or eecundary! Be bonded to carbon atom. The aaine can 1 ble 20 Carbon atoms, preferably 4 to 16 carbon atoms,

9098A8 / 1335

hold, Ala examples are bensylamine, Ieopropylamln » n-3utylamine, cyclohexylamine, cyclooctylaain and cyclododecylamine called-, Gan / 3 generally can ee aich amines act, the aminsubati-tuated, saturated "aliphatic" Contain groups that are cyclic or acyclic and can carry cyclic aryl or alkyl substituents «

The amine concentration in the Beaktionsgemlach can la Bereioh of 5 - · ■ 60 «, preferably 5 Ms 15 weight weights-J *.

Urdroperoxydkonentration in Oxidationtgtoiech litgt

Do usually start with a prostitute or above dooh there are also lower ion concentrations effective ■ aa. . ■■.; ...- ■

let eweükeaßig, the üaaettunf under practically TollatHadige · Auitehluß τοη faater throughEuflihren. Preventive little breathing problems can be tolerated during the training session be, dooh rortugaweiae the largest part of the uaaetiung is carried out in the absence of fatser.

Ii has shown special Tprttilhaft, 4m «UrehaufWatches. A preferred solvent or thinner

909 84 8/133 5

BAD ORlGfNAL

nung3mittel is. tort; »- butanol. However, it can _r other alcohols. for example, tert-amyl alcohol, Dimehtylpropylcarbinol, Hethyldi.äthylcarbinol and dimethylphenylcarbinol used werdenc Priinäre or secondary alcohols are also suitable, such _t as methanol, ethanol, n- or iso-propanol, iso ^ or n- or AI and analog Bitanol Pentanols and hexanols, too. iither _r eg ₀ Mäthyläther, and ketones such as cyclohexanone, are suitable In addition, provide the low aromatic. Hydrocarbons as / ie the lower boiling chlorinated hydrocarbons, for example chlorotoluene, are suitable solvents. ;

Should dan? formed oxime as a starting material for another Serve synthesis, then you can use the raw Oxira. If the intention is to rearrange the oxime, then one can Acid, e.g. Sulfuric acid, mix with the oxime and Erw & rinan and thereby in a known manner, for example, cyclohexenpnoxime convert into caprolactam.

An essential feature of the invention is that cyclohexylhydroxylamine can be produced and then further oxidized to the oxime with air. The preparation of this product has the advantage defl while only 1 mole of hydroperoxide is consumed _v whereas for the preparation of 2 moles Qxmie are needed.

9 09 8.4 8/1335 ORIGINAL BATHROOM

The dehydration catalyst for the production of styrene can be used in the form of a supported catalyst or as pellets. Examples of carriers a! Crushed sandstone, silicon dioxide, filterate and sintered or molten aluminum oxide, which is common in the ceramics industry. For example, the carrier can be wetted with water and powdered titanium dioxide in an amount of about 10 · ·? 15 fi - based on the support ~ followed by drying at 150 0 pollinate. The activity of the titanium dioxide can be increased by treatment with hot aqueous sulfuric acid (eg 10 # »- Ig) and subsequent thorough washing with Ϋ / water to remove the acid before the titanium dioxide is applied to the support. With titanium dioxide on granular aluminum oxide with a particle size of about 4.76 × 3.36 mm (4 x 6 mesh) melted by measures used in the ceramic industry, production ratios of 400 to 650 g of styrene per liter of catalyst per hour can be obtained. Even higher production ratios can be achieved with the titanium dioxide catalyst in granular form. For this, chemically pure anhydrous titanium dioxide powder is wetted with water, the paste formed is ^{dried at 130 150 0} C and the dried cake is powdered and granulated, whereupon the grains are burned in an oven at a temperature of at least 800 G and a very high temperature mechanical pestig

BATH

9 3 ^ 3 / 1335-

··· 25 ~

to attain. Then they warden 11, "a Aktlvierungeetufe by immersion in boiling aqueous nitric acid (concen tration 18 -? 20 <ο) during about 90 minutes, gründlichea washing with water and drying" at about 130 - ■ -. Subjected to 150 ⁰ C instead of nitric acid Hydrochloric acid, phosphoric acid or sulfuric acid can be used for the acid treatment. ^{The grains or pellets shrink between 800 and 1000 °} C., making them harder and denser. These denser, harder grains can obviously not be activated by nitric acid as easily as those ^{fired at 80O 0} C, even if concentrated nitric acid is used. However, they can be activated with the help of 20% aqueous phosphoric acid. By using the denser, harder grains, the dusting of the catalyst, for example during its introduction, is largely eliminated. For this reason, burning or roasting temperature is preferably from about 1,000 ⁰ C.

In general the production ratio is eo higher, the smaller the grain size. Grains whose largest dimension is less than 4.7 mm (3/16 inch) are also meehanlschen Less suitable for reasons «Good production conditions are obtained with grains up to about in diameter in one or more directions

9098Ä8 / 1335 ÖAO

9 _r 53 mm (3/0 inch).

The suitable for the dehydration Temperäuren Iiegan between 180 and ⁰ 2GO G. Usually ee advantageous to use temperatures below 220 ⁰ C or 250 ⁰ C. Less than 22O ⁰ O can steam or reduced pressure to turn to the evaporation to support the carbinol. When working at temperatures of about 250 - 28O ⁰ C high feed rates can be applied.

When using Cyelohexanolhydroperoxid as PeroxydeulK- stanz with a working method of the kind as it is in Bei. game 2 is described , good results are achieved. Another suitable substance of this type is isopropanol hydroperoxide. These substances contain an OH group bonded to the same carbon atom as the 00H = group. They can be prepared from the corresponding alcohol instead of the hydrocarbons as described above. If the alcohol is obtained as a by-product of an oxidation stage, it can be converted into its hydroperoxide and the latter can be used for an oxidation, with the corresponding ketone then being produced as a by-product »

909848/1335 ORIGINAL BATHROOM

BoIdie Hydroxy-Hydrop-Egg-Oxy compounds can also be used as "Ketonhydrnpei'oxyde" are designated.

Pure dehydration can also be used - if desired working methods other than those described above are used «

Par method according to the invention can intermittently, semicontinuously can be carried out nuely or continuously. When working continuously, the implementation can become long and drawn out

th reaction cut. z * B. a pipe or a tower or several series-connected heating vessels and the hydroperoxide at points spaced apart from one another along the flow path. the solution will be introduced »

90.9 8 C & / 133
BATH ORIGINAL

Claims (18)

Paten-tana ρ r Ü c h e 1. Process for the production of Arainoxidationaprodukte from the corresponding primary amines, their amino group a primary or secondary carbon atom is bonded, characterized in that the amine is in the presence a dissolved, metal-containing, peracid-forming or hydroxylation catalyst is reacted with an organic hydroperoxide, 2c The method according to claim 1, characterized in that a temperature in the range of about -10 to * 175 ° C _f the oxidizing agent in an amount of 0.01 to 10 mol per mole of amine and the metal in an amount in the range of 0 , 00001 to 0.1 mole per mole of the hydroperoxide applies » 3ο method according to claim 1 or 2, characterized in that that one cyclohexyl hydroperoxide or cumene hydroperoxide ale organic hydroperoxide is used. 4. The method according to claim 1 or 2, characterized in that that one is a molybdenum compound or a vanadium compound used. 9 0 98A8 / 1335 BATH ORIGINAL 5. The method according to claim 1 or 2, characterized in that that a Hydroxyhydroperoacyd as organiechea Bydroperoxyd used. 6 * The method according to claim 1, characterized in that daS an amine is used whose amino group is attached to a secondary one Carbon atom of a cycloalkyl group with 4 to 16 carbon atoms is bonded .7, method according to A & apruoh. 1, characterized »that a hydroperoxide is used ₅ which has been obtained by reacting gaseous oxygen with ethylbenzene in the presence of an oxidation initiator and the alpha-phenylethanol formed as a by-product in the reaction with an amine with T to 20 carbon atoms. 8. The method according to claim 7 »gekennseiolmet characterized in that the unreacted ethylbene sol is converted into the hydrop # roxjd ~ education level suxtiok leads. 9 »The method of claim ₉ characterized ge I & RAIII * @ 9l iizi9% _B Dafi to the alpha ^ su styrene Fhanyläthanol 9098487133§ BADORlGiNAt 10 · The method of claim 9 »characterized gekemuseiehnet in that the dehydration in the vapor phase over a Titandioxydkatalyaator hei a temperature in the range of 180 - 280 ⁰ C is carried out. 11. Procedure according to iaepyuch? _f gakennaeichnet characterized in that one uses a catalyst ala Molybdänealai a Gartoneäure or üiolybdäns & iaulfid. 12 »Procedure according to claim T ₉ date ^ ch gekemizoiohnet that the alpha» l? Iias! QrläthmnoX au Aoet@pfe.eaom is dehydrated and the latter wins » 13 « Procedure nsoSi tospiiucsia. T ₉ & a $ ssr © h gtgkejsnsslohnet by incorporation of the alj ^ ia Phenylattosol zn. Ithyl ^ saaol hydrogenated imd l @ tster®s ziiT manufacturing process a®ia @ s Hyd ^ opsroxyda ^ used »' 14 «Terfalir®E aaafe tespriaoh t _s ^ a € iss © h gelcsaaBseiehaet, dai Oxygen ait Ctool ia- @ © g @ awas? 'S; säsioa ators received, wasrfe ₉ .M ^ eineai iaim with 1 fcla carbon atoms umsatat uai öan as Sefessprodakt g® formed »Gimyl alcohol wins *""■'~" S09848 / 1335 BAD ORIGINAU 15. The method according to claim 4 *, characterized in that a molybdenum salt of a carboxylic acid is used as a catalyst used" 16. The method according to claim H _r, characterized in that the cumyl alcohol formed as a by-product is converted into cumene and the latter is used to produce its hydroperoxide. 17. The method according to Anepruch H, characterized in that the cumyl alcohol formed as a by-product in alpha-methyl styrene transferred «, 18. The method according to claim 1 or 2, characterized in that that n-hexylamine is used as the starting material and η-Hexylaldoxime wins as a product. ¹ Q. Process according to claim 1 or 2, characterized in that the AnIn used as the starting material is converted into the corresponding hydroxylamine. 909848/1335 Process according to Claim 19, characterized in that cyelohexylamine is used as the starting material and cyclohexylhydroxylamine is obtained. 21 «Method according to claim 19», characterized in that one uses Cuoio Ihy droperoxyd as an oxidizing agent. 9848/133