DE1913182A1 - Process for the preparation of ketone condensation products - Google Patents

Description

PATE N; TA NrW AL T Έ

Djpfelng,

800OvMUNGsHE ^ a

z & r

The Ei ^ firtiiXirig: Ije2rf; elife sicii on dii croton compounds of Kebon & n ,. i
.Position., The Crotonyei'binuurig-. from

from to -dm Eev urjd; on

i invention; is e * n- VeiPfaiiren for the cultivation of; Gro * onv.e3Plji; ßd «ngen: provided by Ifefeoneni, at; which a ketone with - a - methylene group in the aliphatic position to the carbonyl group with a - lcatalytisAtoeniIege of a compound of - titanium, vanadium, Clirom ^ manganese, iron, cobalt, nickel ,. Copper, zinc », zirconium * molybdenum ,. Cadmium, 2tinn or

1: 751

Where If pam

Under CKO ^ onvejebindUingen, (; σρ; ο &0ηθϊ> © \) according to ;; 4 Satisfaction are “condensation products: from Ketoßenv s partj. by. Implementation; onejs - (^ rjDQnyjlgpuppB * with; onej? · to a carbonyl group; is _: alpJaa position. befift & lijäfee ^ methylene group untfir WasseKaMSfcKiMi; ex * kaä £ & n _:

-QS ^ ;: ^ ■■■■ (%:

JedQcii. karin eats; some balls enter one of the product so that; the position binding is postponed; For example, the cyclohexanone gives 2- (l "-Cyclohexenyl) c, ycloiieixanoji ,, ^; The sation can be a homocondensation eJbies mixed condensation of two ketones ,,.

The ketone or different ketones omxm ketones are used) possess the. R'-CQ-GH ₂ R'S eat the - · '\ ^: ...

R 'an,: AJL.ky _y lgr.uppe with vor ^ ugsiiieisjev to,, in particular to ■:. ■ to 6 K ^ M ^ at ^ iftaMjnei ^ isfeünd: in

R ^Jf hydrogen: or an alkyl group :; boäsj · z « H aiy vorzagswei & e feil zä -6 ^; - ^:; K'öfe3i6j5s.tof f / Äfecwiezrv -sea » ^;:

can. The ketone can also be substituted by inert substituents, but it is preferably an alkanone, for example acetone and methyl ethyl ketone. The groups R ¹ and "R" can also form part of a ring structure to form a cyclic ketone, cycloalkanones as feedstock for the process according to Cycloalkanones with 5 to 12 carbon atoms in the ring, in particular cyclohexanone, are particularly preferred.Substituted cycloalkanones, in particular cycloalkanones substituted by alkyl substituents, for example methylcyclohexanone, are also suitable for use in the process according to the invention.

The term "catalytic amount" is understood to mean that an amount of a metal compound is present which is very small compared to the amount of ketone present, which metal compound exerts a catalytic effect and does not form part of the product of the reaction. Suitably the amount of metal compound is up to 0.5 moles of metal / moles of ketone present, preferably up to 0.05 moles of metal / moles of existing ketone, for example 10 ^-5 to 10 ^-2 moles of metal / moles of existing ketone. If vanadium compounds are used, slightly larger sizes can be used, e.g. up to 1 mole vanadium / mole ketone present, but it is further preferred that

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the amount of vanadium used does not exceed 0.5 mole vanadium / mole ketone present.

More than one metal compound can be used in the process according to the invention, e.g. mixtures of vanadium and titanium compounds and also mixtures of compounds of the same metal.

Organic compounds of the metals are particularly suitable for use in the process according to the invention, preferably metal salts of organic acids, in particular aliphatic carboxylic acids with up to 20 carbon atoms. Preferred acids are aliphatic carboxylic acids having 10 to 20 carbon atoms, for example vanadium stearate, titanium palmitate and vanadium oleate, and the naphthenic acids, for example vanadium naphthenate. If a metal carboxylate is used, it is advantageous to incorporate the corresponding carboxylic acid into the reaction medium, for example stearic acid can be added if vanadium stearate is the catalyst. The concentration of the carboxylic acid is preferably up to 5 % w / w. Organic complexes of the metals can also be used, for example with 1,3-di-ketones, such as acetylacetone and substituted acetylacetones, and formed with ethylenediaminetetraacetic acid

90 & 840 / 175t

Complexes. Metal alkoxides are also suitable, in particular from lower alkanols, e.g. alkanes with up to to 6 carbon atoms, such as' tetraisopropyl titanate, dissipative alkoxides.

Polyacids, e.g. tungstic acid and the anadic acids, and heteropoly acids such as phosphomolybdic acid, silicon dioxide If ramic acid and phosphorvanadlumic acid., Can be used as metal compounds used in the method according to the invention will-.

The process according to the invention is expediently carried out in the liquid phase using soluble metal compounds and, if it is necessary for the Ii oh _} , an increased pressure can be used which is at least sufficient to keep the reaction medium in the liquid phase at the working temperature. Working in a heterogeneous liquid phase is also possible. Working in the gas phase can be achieved by passing the ketone as a reactant over the catalyst, which can be contained on or in a suitable carrier such as silicon dioxide or carbon . ..-, -,

β Q mm t V

1913.1 6 : - * - ■ '

The genannte.Verfahren may suitably at a temperature of -50 "to 250 ⁰ C, preferably in the. Range of 120 ° ..bis l80 c are carried out. In many-Ke ... tone, for example, cyclohexanone, the temperature of the boiling point of the ketone in question is a suitable temperature.

The reaction is preferably using. . ■ of the ketone carried out as a solvent. However, if an inert solvent is used, it is desirable to keep a high concentration of ketone in the reaction zone. It is also desirable that water formed during the process be removed as soon as possible as soon as it is formed, since an accumulation of water in the reaction mixture slows the reaction rate. The removal of the water formed. It is convenient, if possible, to distill a. Azeotrops from the ketone and. Water: obtained from the reaction zone .: Many ketones, e.g. cyclohexanone, form- with water-. ■ ser azeotropes,. however, if necessary, an inert azeotrope-forming agent, for example toluene, can be added to the reaction mixture; will. - A Spülung-. ■ · apply kann'ferner-with an inert Sas to the WasseFentfernuhg "to

Preferably, oxygen is excluded from the reaction zone and the process is carried out in an inert one Atmosphere such as nitrogen or argon for prevention carried out an oxidation of the ketone.

The process can be carried out batchwise, but it is preferably carried out continuously. It is a particularly beneficial feature of using a catalytic amount of the metal compound, that the croton product of the process, which is obtained in high yield, is easily removed from the reaction medium, e.g. Distillation, separated and the catalyst can be recycled.

The process is particularly useful for homocondensation of cyclohexanone applicable. The croton product formed is 2- (l-cyclohexenyl) cyclohexanone, which is easily converted to ortho-phenylphenol becomes dehydrated, a product useful as a fungicide and preservative.

An embodiment of the method according to the invention .is a process for the .production of ortho-phenylphenol, in the case of cyclohexanone with a catalytic

Amount of a compound of titanium, vanadium, chromium, manganese, Brought into contact with iron, cobalt, nickel, copper, zinc, zirconium, molybdenum, cadmium, tin or tungsten and that on. 2- (1-cyclohexenyl) cyclohexanone formed in this way is dehydrated to ortho-phenylphenol.

Cyclohexanone is obtained industrially by the oxidation of cyclohexane with molecular oxygen, often in the presence of catalysts such as transition metal or boron compounds. The product of this oxidation is a " mixture of cyclohexanol and cyclohexanone; however, since cyclohexanol is essentially inert to the conditions of the process according to the invention, it does not have to be removed from the cyclohexanone and the cyclohexanol / cyclohexanone mixture can be used as a feedstock for the process in question be used.

Another embodiment of the method according to of the invention is therefore.ein a process for the production of ortho-phenylphenol, in which a mixture of cyclohexanol and cyclohexanone with a catalytic amount of a compound of titanium, vanadium, "chromium, manganese, iron, Cobalt, nickel, copper, zinc, zirconium, molybdenum, cadmium, tin or tungsten put on this 2- (l-Cyclohexenyl) cyclohexanone formed from the cyclo-

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Separated hexanol and the 2- (1-cyclohexenyl) cyclohexanone is dehydrated to ortho-phenylphenol.

In the above-mentioned embodiments of the process in which cyclohexanone is converted into 2- (1-cyclohexenyl) cyclohexanone is crotonized, it is preferred to use a catalytic amount of a vanadium compound, preferably Vanadium naphthenate to be used as a catalyst in the process.

The 2- (1-cyclohexenyl) cyclohexanone can be obtained from cyclohexanol in the above-mentioned embodiment of the Process can be separated by distillation. The dehydrogenation of 2- (l-cyclohexenyl) cyclohexanone can be about any convenient dehydrogenation catalyst such as a noble metal supported on an inert support such as Platinum worn on charcoal, silicon oxide or aluminum oxide, and catalysts containing combinations of metals on inert supports, e.g. Nickel and tin, supported on silica.

The invention is explained in more detail below by means of the following examples.

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Example 1 to 8

These examples illustrate the crotonization of Cyclohexanone using catalytic amounts of various metal stearates. The results are given in Table I.

In. Each pail was given 50 g of cyclohexanone at 155 ° C and atmospheric pressure: for 190 minutes with exclusion of air with 1.4 χ 10 mol of metal, added as metal stearate / heated. Water formed in the reaction was continuously azeotroped with cyclohexanone removed. The cyclohexanone removed in this way was returned to the reaction mixture and the Mixture analyzed by gas-liquid chromatography. The product, 2- (1-cyelohexenyl) cyclohexanone, became purified by means of fractional distillation. The results are shown in the table in which the ketone conversion and yield of 2- (1-cyclohexenyl) cyclohexanone are expressed in moles of the converted cyclohexanone.

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Table I.

Example no. as stearate ' Ketone Yield to used settlement 2- (1-cyclohexenyl) metal % cyclohexanone (%) 1 Vanadium 11th 94 2 manganese 11th 94 3 cobalt 11th 90 4th Zircon 8th 82 5 zinc 9 . -75 6th cadmium 11th • 70 7th tin 9 81 8th titanium 34 92 Example 9

. 50 g of cyclohexanone containing 1.4 × 10 "· moles of vanadium in the form of vanadium stearate were heated to reflux with the exclusion of air and at atmospheric pressure. The water was continuously removed from the reaction mixture by azeotropic distillation with cyclohexanone The reaction temperature rose as the concentration of 2- (l-cyclohexenyl) cyclohexanone in the reaction medium rose. After 190 minutes the temperature was 168 ^° C., the cyclohexanone conversion was 40 % and the yield of 2- (l-cyclohexenyl) cyclohexanone was 94 %. According to weather

ο For 120 minutes the temperature had risen to 193 C and the ketone conversion and product yield were now 71 % and 89 %, respectively. ■

. 9 0 9 8 4 0/1751 ^ 0-

- Mg "-

Examples 10 bis; 12th

In each of the examples given below: 50 g of cyclohexanone were heated at 155 ° C. for 190 minutes at atmospheric pressure in the presence of the catalyst. Water formed in the reaction was continuously removed by azeotropic distillation with cyclohexanone. The cyclohexanone thus removed was recycled to the reaction mixture the Reaktionspröi- 'diikt -was by gas-liquid chromatography ana' ^ '.' lysed the product, 2- (l-cyclohexenyl) cyclohexanone was purified by fractional distillation ER-.. ^': results of in the given in the table below; the / '"molar yield of 2- (1-cyclohexyl) cyclohexanone is;' based on "converted cyclohexanone. /"

Table TI - -

Example No. Catalyst Mol Kätaly- Ketoneum- molar ■ Aus

sator (as a set of booty.... .. metal) each,,. (%) 2- (1-CyCIo-

5OgCyCIo- hexehyl) cyclo-

. . ._. .... hexanone. hexanone (#)

MoNAF 14, 5x1 θ " ■ -. -.11, .- .;. 58 F.M.A. 5XiO- ⁴ ' 2S 77 S.W.A. 16, IxLQ 70 , 51

B ü BmB / ΛΜΛ '

MoNAP = molybdenum naphthenate P. M. A. = phosphomolybdic acid S.W.A. = silicon tungstic acid

Example 13

There were 25 g of methyl amyl ketone containing 1.5 g Vanadlumnaphthenat, at 155 ° C with exclusion of air and heated at atmospheric pressure for 190 minutes. While Water formed in the reaction was removed by azeotropic distillation with the ketone. Unreacted methyl amyl ketone was removed by distillation leaving a product consisting essentially of hydrated Methyl amyl ketone dimers.

Example l4

It has been Example 13 was repeated with the exception that Oj ^ 50 g of titanium tetrabutoxide instead of nat Yanadiumnaphthe used wurden- again methyl amyl ketone dimers were obtained as a product. ^:

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Claims (1)

Claims 1. Process for the preparation of croton compounds of ketones., Characterized in that one ketone with a methylene group in alpha position to the carbonyl group with a catalytic amount of a compound of titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, cadmium, tin, molybdenum or tungsten implements. 2. The method according to claim 1, characterized in that a ketone of the general formula R'-CO-CHp-R " implements in the. R 'is an alkyl group of up to 12 carbon atoms, preferably up to 6 carbon atoms, and R "is hydrogen or an alkyl group with up to 12 carbon atoms, preferably up to 6 carbon atoms, is or. - R 'and R "a part of a ring-shaped structure with the formation of a cyclic ketone, preferably a cycloal . canons with 5 to 12 carbon atoms in the ring. 90984 0/17 13: 12182 J5: Method according to one of the preceding claims., characterized in that the ketone is Cyclo- ■ hexanone used. 4. The method according to claim J>, characterized in that the process product 2- (l-CyclOhexenyl) cyclohexanor is dehydrated to ortho-phenylphenol. 5. The method according to claim 4, characterized in that that the 2- (l-cyclohexenyl) cyclohexanone over a catalyst made of a noble metal, supported on an inert carrier, preferably. Platinum worn on charcoal, Silica or alumina, or a combination of metals, supported on an inert support, preferably Nickel and tin, supported on silica, dehydrated . 6.- method according to one of the preceding claims, characterized in that the ketone used is cyclohexanone used in admixture with cyclohexanol :. 7 · method according to one of the preceding claims, characterized in that 'one. the. Metal compound present in an amount up to 0.5 mole metal / mole Ketone, preferably up to 0.05 mole metal / mole Away ' - ■ -5. · Existing · ketone and especially in the range ^ οίϊ ^: IG- to ' 10 moles of metal / mole of ketone present used. 8. Method according to one of the preceding claims ;; characterized in that a metal salt of an organic acid, preferably a metal salt of an aliphatic carboxylic acid having 10 to 20 carbon atoms or a naphthenic acid, in particular vanadium stearate, titanium palmitate, vanadium oleate or vanadium naphthenate, is used as the metal compound -. Process according to Claim 8, characterized in that the carboxylic acid corresponding to the metal salt is incorporated into the reaction medium, preferably in a concentration of up to 5 % w / wi 10 \ Method according to one of the preceding claims, characterized / that one as ^; Catalyst '■' -an organic complex of the metal, -preferably one formed with a 1,3-diketone or with ethylenediaminetetraacetic acid. ^ Complex used .. - '- ···'':^---': - ll; i · Verfahr'en-;. For 'a' DER preceding arrival - 'claims, characterized in' ^ - that man'als catalyst * '·''is a metal alkoxide preferably, one of a lower 9 0 904.0 / IfSi; ·: Metal alkoxide derived from alkanol, used. 12. The method according to any one of the preceding claims., characterized in that the metal compound used is a polyacid, preferably tungstic acid or vanadium acid, or a heteropoly acid, preferably phosphomolybdic acid, silicon tungstic acid or phosphorvanadic acid., used. 13. The method according to any one of the preceding claims., Characterized in that one carries out the reaction des'Ketons to Crotonverbindung at a temperature in the range of 50 ° to 25O ⁰ C. IH-. Process according to one of the preceding claims, characterized in that the conversion of the ketone to the croton compound is carried out at a pressure which is sufficient to keep the reaction medium in the liquid phase at the working temperature. 15 · The method according to any one of the preceding claims, characterized in that one in the implementation water formed from the ketone to the croton compound is removed as an azeotrope with the ketone, 90 98 413/1751 l6. Method according to one of the preceding claims, characterized in that the conversion of the ketone to the croton compound is carried out continuously and circulates the catalyst. 909840 / 175-1