DE1965377B2 - PROCESS FOR PRODUCING PRIMARY OR SECONDARY AETHYLENIC ALCOHOLS - Google Patents

Description

25th

It is known that certain ethylenic alcohols, in particular tertiary α-ethylenic alcohols, can be added to tsomerize primary or secondary alcohols with the help of acidic catalysts (E.A. Braude, Quaterly Rev, 4,407-417 [1950]). This isomerization is known as the allyl rearrangement

The use of acidic media in the liquid phase for the isomerization of ethylenic alcohols has various disadvantages when carried out on an industrial scale, in particular:

a) The separation of the reaction products requires im generally the neutralization of the reaction medium; on the one hand, this neutralization has the loss the acid used and on the other hand the formation of a salt of the acid in considerable Crowd.

b) The reaction medium is corrosive in nature.

c) There is a formation of reaction by-products through hydration or addition of the acid the double bonds of the reaction components and reaction products instead

It is also known that tertiary -ethylenic alcohols can be isomerized by a two-stage process, its first stage in a reaction by acetylation with acetic anhydride and its second stage in tine saponification (Dimroth, Ber. d. dtsch. former Ges. 7 !, 1340 [1938]).

There has now been a process for the catalytic isomerization of tertiary «-ethylenic alcohols do primary or secondary ethylenic alcohols found in a stage that does the above Does not have any disadvantages.

The invention therefore relates to a process for preparing primary or secondary ethylenic alcohols by catalytic isomerisation of tertiary "-äthylenischer alcohols, which is characterized in that the isomerization in the presence of the compound of a transition metal of sub-groups 5 to 7 at 50 to 25O ⁰ C in the liquid phase performs

The transition metals of subgroups 5-7 also become columns 5b to 7b of the periodic table mentioned by Mendelejev (Handbook of Chemistry and Physics _J 45th Edition, page B-2).

The oil-ethical alcohols according to the invention can be isomerized, correspond to the formula

C-CH = CH-R ₃ R ₂ OH

in the Ri and R2 either

a) can be identical to or different from one another and are saturated or unsaturated aliphatic or mean cycloaliphatic radicals, aromatic radicals or arylaliphatic radicals, these radicals optionally substituents such as halogen atoms or hydroxy, alkoxy, acyl or acyloxy radicals carry or through heteroatoms such as O, N or S, or through functional groups such as —CO— or —CO — NH-, may be interrupted, or

b) together represent a saturated or unsaturated divalent alkylene radical - R -, the optionally substituents such as alkyl, cycloalkyl, aryl, aralkyl, hydroxy, alkoxy, acyl or Acyloxy radicals and halogen atoms, carry or through heteroatoms, such as O, N or S, or through functional groups, such as —CO— or —CO — NH-, or cycloalkylene or arylene radicals, can be interrupted,

and R3 represents a hydrogen atom or the same Meanings as given for Ri and R2 under a) are owns

A particularly interesting class of alcohol in the process according to the invention consists of the Alcohols of the formula I for which R3 represents a hydrogen atom

Preferably, Ri, R2 and R3 contain a total of 2 to 30 carbon atoms, and at least one of the radicals Ri and R2 is a saturated or unsaturated alkyl radical which can optionally be substituted and contains 1 to 15 carbon atoms

The primary or secondary ethylenic prepared by isomerization of alcohols of the formula I Alcohols are generally-ethylenic alcohols of the formula

C = CH-CHOH-R ₃

in which Ri, R2 and R3 have the meanings given above own.

However, if Ri and R2 together form a bivalent A radical such as, for example, an optionally substituted pentamethylene radical, is also formed / f-Ethylenic alcohol with a double bond in the ring.

The catalysts which can be used in the process of the invention are essentially inorganic or organic compounds of Transition metals of subgroups 5 to 7 and preferably the compounds of metals from Group of vanadium, niobium, molybdenum, tungsten or rhenium.

In particular, the halides, chalcogenides, chalcohalides, nitrosochlorides, nitrosyl halides; the salts of oxygenated mineral acids,

such as sulfates, nitrates, phosphates, carbonates, arsonates, arsenates, germanates, perchlorates, sulfites, nitrites; the mixed salts of transition metals of subgroups 5 to 7 with other metals of the Periodic table; the salts of aliphatic, cycloaliphatic or aromatic organic acids, such as Acetates, propionates, stearates, benzoates, oxalates, Sucdnates, sulfonates, tartrates, citrates, salicylates, Naphthenates; the alcoholates and phenolates, which originate from transition metals of subgroups 5 to 7, to name.

These salts, alcoholates and phenates can also Salts of oxygen-containing metal residues, such as vanadyl and molybdenum salts.

As other inorganic or organic compounds of the above-mentioned metals, the seeds and Esters of acids derived from one or more of these metals, such as the vanadates, niobates, tantalates, Molybdates, wblframates and rhenates; the analog Connections in the form of per, poly, ortho, meta, Pyro, thio and halogen compounds; the mixed salts and esters such as tungstovanadates, phosphomolybdates, tartratoniobates, zirconium tungstates and Molybdocitrates, -formates, -lactates, -maleates, -mandelates, -mucates, -oxalates, -chinates, -saccharates, -tartrates and -wungframate, name it. Also suitable are the chelates, such as the acetylacetonates, which are optionally carried out by for example, aliphatic or cycloaliphatic groups or substituted by halogen atoms can, the Benzoylacetonate, the Glyoximate, Quinolinate, Salicylaldehydate and Benzylhydroxamate, the Derivatives and ethylenediamine, α, α '· bipyridyl, o-nitrosophenol, 0-nitrosonaphthol, salicylaldimidine and porphyrins. It can also be the metal complexes or Metal salts with coordinates such as carbon mono-olefins, diolefins, polyolefins, acetylenic ones Compounds, cyclopentadienyl, ammonia, cyanides, tertiary nitrogenous bases, phosphines, arsines, stibines and nitriles can be used. Furthermore can the organometallic compounds, such as metal alkyls, can also be used.

A particularly suitable class of catalyst for carrying out the invention consists of the products which is a grouping of one of the following formulas

45

-M = O

(Π1)

Ο - M = O (IV) M - O = (V) Ο-M <-O = (VI)

have, in which M eir metal atom means that also to other atoms by one or more ionic or covalent bonds can be bound. This class of catalysts includes the Metal oxides, the salts and esters of oxo acids of metals, the salts of metal oxo ions and the Chelates, such as those derived from jJ diketones.

The active metal derivative that forms the catalyst, can be applied to a carrier. As a carrier, for example: activated aluminum oxides and Silicas, pumice stone, fuller's earth, infusor earth and Activated carbon can be used.

The amount of metal contained in the catalyst is usually based on the weight of the Reaction mass, above 0.0001% and preferably between 0.05 and 2%. Higher amounts can can of course be used, but with no significant added benefit.

The catalyst can be soluble or insoluble in the reaction medium. You can do it with little Amounts of a cocatalyst or activator can be combined as an example of the cocatalyst Alcohols, the Lewis bases, such as ammonia, amines, Phosphine, Arsine, Stibine and Bismutine, as well as the Compounds capable of releasing a Lewis base under the reaction conditions, such as the Ammonium salts. An excess of cocatalyst is sometimes necessary for good yields disadvantageous. The optimum amount of cocatalyst varies depending on the kind of this cocatalyst and the Catalyst.

One can be in the presence or absence of one Solvent work. As a solvent can generally be compared to the catalyst and the Use reaction components that are chemically inert. The chlorinated ones are particularly suitable or non-chlorinated aliphatic, acyclic or aromatic hydrocarbons, ethers and amides.

Case * one is a sufficiently volatile Ethiopian Alcohol isomerized in the presence of a solvent, this alcohol can be converted into a gaseous form introduce liquid reaction medium brought to the temperature selected to carry out the reaction, wherein the liquid medium at the beginning mainly contains the solvent and the catalyst To keep the temperature constant, a distillation can then be carried out to the extent that the reaction products are formed.

The reaction temperatures are between 50 and 250 ⁰ C and preferably between 100 and 200 ⁰ C. Because the pressure is not a critical factor for the inventive method, one turns advantageous legally atmospheric pressure aa

If the catalyst used is an ester of an oxygen acid derived from a metal from subgroup 5 to 7, it is advantageous to use anhydrous Atmosphere to work to avoid hydrolysis of the catalyst.

The process according to the invention can be carried out continuously or batchwise. At the end The reaction can use the catalyst and the unreacted tertiary alcohol in general recover and reuse for a new isomerization operation. According to the invention The primary or secondary ethylenic alcohol produced can be prepared by any method known per se be isolated, for example by distillation in a sufficiently efficient column and below Working under suitable conditions.

The ethylenic alcohols prepared according to the invention are interesting starting materials or intermediates for organic synthesis, especially for the synthesis of natural products such as those of the terpene range. They are also useful in perfumery compositions.

Unless otherwise stated, the yields given in the following examples are the yields of ethylenic secondary or primary alcohol obtained, based on in the course of the reaction converted tertiary alcohol, and the degree of conversion is the ratio of the amount of the

Reaction consumed tertiary alcohol to the amount of tertiary alcohol used at the beginning.

example 1

In a 15-cm ^ flask, which with a device S for moving, is equipped with a rising cooler, a dropping funnel and a dip tube, 100 g of linalool [3,7-dimethyioctadien- (1,6) -ol- {3)] and 4 g of ammonium metavanadate are introduced.

Nitrogen is passed into the medium at a rate of 2 l / h in order to remove most of the ammonia formed in the course of the reaction. The mixture is heated for 6 hours at 150 ^° C. It is cooled and filtered over a glass frit. The flask and the glass frit are rinsed twice with 25 cm ^{3 of} ethyl ether each time. The FQtrat ι s is concentrated in order to evaporate the ether. 99.7 g of crude product are obtained, which is distilled under 0.1 mm Hg with the aid of a Vtgreux column with a height of 200 mm and a diameter of 25 mm. Between 60 and 100 ^° C., a total of 32.2 g of a mixture is obtained containing 16.2 g of geraniol, the fraction distilling between 70 and 75 ° C (12.7 g) containing 98% by weight of geraniol

The mixture is heated * for 2 hours at about 125 ° C. under an anhydrous atmosphere. It is cooled and distilled below 03 mm Hg. Between 78 and 112 ^° C., 4.77 g of a fraction which contains 0.7 g of farnesol are obtained

Degree of conversion%

yield

Degree of conversion yield

28.5% 57%

Example 2

50 cm ³ flask, which is as in Example 1, brings 20 g of linalool and 0.8 g

In a fitted Ammonium metavanadate.

It is flushed with nitrogen as in Example 1. The mixture is then heated for 5 1/2 hours at 130 ^° C. and then for 1 hour and 20 minutes at 150 ^° C. It is then cooled. The reaction mixture is distilled below 0.2 mm Hg.

Between 48 and 115 ^° C., 18.9 g of a mixture containing 53 g of geraniol are obtained

Degree of conversion yield

43.7%
60.5%

Example 3

Degree of conversion yield

32% 783%

Example 5

a) Preparation of the catalyst Tert-amyl orthovanadate is prepared from tert-amyl alcohol and V ₂ O ₅ by the method mentioned in Example 4.

b) isomerization

5 g of nerolidol are placed in an apparatus identical to that described in Example 3 and 03 g of tert-amyl orthovanadate.

The mixture is heated for 2 hours at 120 ° C. in an anhydrous atmosphere.

The reaction medium is cooled. It is poured into a separatory funnel into which 50 cm ^{3 of} water and 40 cm ^{3 of} ethyl ether are introduced. After shaking and decanting, the organic phase is separated off, to which 50 cm ^{3 of} water and 40 cm ^{3 of} ethyl ether are again added. The organic layer is decanted separated off, dried over sodium sulfate, filtered, concentrated and distilled under 0.1 mm Hg. 3.24 g of a mixture which contains 0.89 g of farnesol are obtained between 90 and 115 ° C

35

40

In a 50-cm ³ flask equipped with a stirrer, a vertical condenser and a dropping funnel, 5 g brings Nerolidol [3,7,11-Trimethyldode- catrien- (l, 6,10) -OL- (3 )] and 0.2 g of ammonium metavanadate.

The mixture is heated for 1 hour and 50 minutes at 150 ° C. Then it is cooled and distilled below 0.1 mm Hg. 4.83 g of a fraction are obtained between 70 and 115 ° C, which contains 1.26 g of farnesol [3,7,11-trimethyldodecatriene- (2,6,1O) -Ol- (I)]

55

Example 4 a) Preparation of the catalyst

Tert-butyl orthovanadate is made from tert-butanol and V2O5 according to that of N. F. OrIoν and M. G. Voronkov (Izv. Akad. Nauk. SSSR, Otdel. Khim. Nauk, 933-934 [1959]) described method.

b) isomerization

In a 50 cm ³ flask equipped with a stirrer, a dropping funnel and an ascending condenser, 5 g of nerolidol, 0.2 g of tert-butylnane vanadate and 1 cm ^{3 of} tert-butanol are introduced.

Degree of conversion yield

24.6%
723%

Example 6

20 g of nerolidol and 0.6 g as in example 4 are placed in an apparatus which is identical to that of example 3 produced tert-butyl orthovanadate.

The mixture is heated for 20 minutes at 150 ^° C. in an anhydrous atmosphere. It is then cooled and distilled under 0.05 mm Hg. One gets between 75 and 12O ⁰ C 19.27 g of a mixture containing 334 g Farnesol

Degree of conversion yield

28%
633%

Example 7

5 g of nerolidol, 0.1 g of ammonium molybdate and 1 cm ^{3 of} cyclohexanol are introduced into an apparatus which is identical to that of Betspiel 2.

The reaction medium is flushed with nitrogen in an amount of 2 l / h in order to remove the greater part of the im To remove ammonia formed in the course of isomerization.

The mixture is heated for 2 hours and 50 minutes at 130 ° C.

The mixture is cooled and distilled under 0.2 mm Hg. One gets between 100 and 12O ⁰ C 3.92 g of a fraction containing 0.76 g of farnesol

Degree of conversion yield

29% 523%

Example 8 a) Preparation of the catalyst

Cyclohexylorthovanadate is prepared from ammonium metavanadate and cyclohexanol according to the method described by F. C a r t ο η and N. C a u g h 1 a η (J. Physic Chem. 64, 1756 [1960]) described method. You heat them up

Reaction components up to the reflux temperature of the cyclohexanol, the water and the Ammonia is removed as it is formed. Then you cool off. The reaction mixture is filtered. By Distillation of the filtrate under reduced pressure, the cyclohexanol is removed and the Cyclohexyl ester as distillation residue.

b) isomerization

5 g of nerolidol and 0.5 g of cyclohexyl orthovanadate are placed in an apparatus identical to that of Example 3 a.

The mixture is heated for 20 minutes at 130 ° C. under an anhydrous atmosphere.

It is cooled and distilled below 0.15 mm Hg. 4.9 g of a fraction which contains 0.76 g of farnesol are obtained between 85 and 115 ° C

Conversion rate 34.2%

Yield 44.5%

Degree of conversion
yield

19.8%
22.2%

10

example

Into an apparatus which is identical to that of Example 3. 5 g of 3-methylpentene- (1) -ol- (3) and 0.2 g of cyclohexylorthovanadate prepared as in Example 8 are introduced .

The mixture is heated under an anhydrous atmosphere for 5 hours and 5 minutes. The temperature of the reaction mixture rises from 78 to 132 ° C. It is cooled. One destffliert below 15 mm Hg. One gets between 40 and 6O ⁰ C, 4.79 g of a fraction containing 0.71 g 3-methylpentene (2) -OH 1)

yield Degree of conversion

18.6%

15th

Example 9
a) Preparation of the catalyst

In a mixture of 11.3 VOSO ₄ -3.5 H ₂ O g, 100 cm ³ of distilled water and 11.3 cm ³ acetylacetone allowed stirring 15 cm ³ of an ammoniacal solution (20% NH ₃₎ incorporated. A pH of 9 is obtained. The mixture is stirred for one hour at room temperature. Then it is filtered. The precipitate is ^{washed with 100 cm 3 of} distilled water. It is dried to constant weight. Vanadyl acetylacetonate VO (C ₅ H rO ₂ ) 2- is obtained

b) isomerization

The procedure is as in Example 8, replacing the cyclohexyl orthovanadate with vanadyl acetylacetonate and heating for 2 hours instead of 20 minutes. Distillation below 0.15 mm Hg gives between 70 and 118 ° C. 4.01 g of a mixture containing 0.22 g of farnesol contains

40

45

Example 11 ^ ₀

3 g of 2-methylenene (3) -ol- (2) and 0.12 g of ammonemia metavanadate are introduced into an apparatus similar to that used in Example 2.

It is flushed with nitrogen in an amount of 2 l / h. around the main part of the isomerization * s to remove ammonia formed.

The mixture is heated at 130 ° C. for 2 hours and 50 minutes It is cooled and then distilled below 0.01 mm Hg.

2.58 g of a fraction which boils between 35 and 63 ° C. and contains 0.38 g of 2-methylnonene- (2) -ol- (4) are obtained.

yield
Degree of conversion

47% 27%

Example 12

4.5 g of 2,2,6-trimethyl-1-vinylcyclohexanol are placed in an apparatus which is identical to that of Example 2 and 0.2 g of ammonium metavanadate.

The reaction medium is flushed with nitrogen at a rate of 2 l / h to remove most of the in the course to remove ammonia formed in the reaction.

The mixture is heated for 5 hours at 150 ^° C. It is then cooled and filtered. The flask and the filter are rinsed twice with 20 cm ^{3 of} ethyl ether each time. Then you narrow down. By distillation under 0.1 mm Hg is obtained between 40 and 7O ⁰ C 4.16 g of a fraction which 034 g of 1 - contains -2,6,6-trimethyl (2-hydroxyethyl)

20 degrees of conversion
yield

17.3%
43.5%

Example 13

a) Preparation of the catalyst
(Tetrahydrohalyl orthovanadate)

In a 250 cm ³ flask. equipped with a device for agitation, a dip tube and a reflux head, 10 g of ammonium metavanadate and 100 cm ^{3 of} 3,7-dimethyloctanol- (3) are introduced.

The reaction medium is flushed with nitrogen in an amount of 6 l / h. The mixture is heated for 2 hours at 150 ^° C., the water and the ammonia being removed as they are formed

It is diluted with 100 cm ^{3 of} cyclohexane. 1 g of activated vegetable charcoal is added, the mixture is heated under reflux for 1 hour and filtered. The cyclohexane and the excess of dimethyl octanol are removed by distilling the filtrate. The mixture is heated for a further 30 minutes at 100 ^° C. below 02 mm Hg.

45.9 g of pure tetrahydrohalyl orthovanadate of the formula are thus obtained as the distillation residue

(CHj) ₂ CH- (CH ₂ ) JCOC ₂ H,

V = O

b) isomerization

In an apparatus identical to that of Example 3 is, you bring 20 g of Unalool, 0438 g of catalyst and 0.149 g of triethanolamine.

The mixture is heated under anhydrous atmosphere I ^1/2 hours at 150 ⁰ C and then for 1 hour and 50 minutes at 160 ⁰ C. The mixture is cooled and distilled under 0.03 mm Hg.

One gets between 47 and 6O ⁰ C 1932 g of a fraction containing 3 g geraniol.

Degree of conversion yield

23.4% 64%

Example 14

a) Preparation of the catalyst (Tetrahydrolinate orthovanadate)

In a 250- ^{cm 1} KoIbCn, which is equipped with a device for moving, an immersion tube and a reflux

709610/444

equipped head, 10 g of ammonium metavanadate and 100 cm ^{3 of} 3,7-dimethyloctanol- (3) are introduced.

Nitrogen is passed into the reaction medium in an amount of 6 l / h. The mixture is heated for 2 hours at 150 ^° C. with removal of the water and ammonia to the extent that they are formed.

It is diluted with 100 cm ^{3 of} cyclohexane. 1 g of activated vegetable charcoal is added and the mixture is refluxed for 1 hour. It is filtered. The cyclohexane and the excess of dimethyloctanol are removed by distilling the filtrate. The mixture is heated for a further 30 minutes at 100 ° C below 0.2 mmHg.

This gives 45.9 g of pure distillation residue Tetrahydrolinalyl orthovanadate of the formula

CH ₃

(CHj) ₂ CH- (CH ₂ J ₃ -C-O-V = O
C ₂ H ₅

b) isomerization

200 g of linaiool and 2.70 g of catalyst are placed in a 500 cm ^{3 flask equipped with a stirrer and a rising condenser.}

The mixture is heated for 2 hours at 161 ° C. under a nitrogen atmosphere. You cool off. By distillation under a reduced pressure of 0.2 mm Hg is obtained

between 45 and 78 ° C 191 g of a fraction containing 38.7 g Contains geraniol

Degree of conversion
yield

25.2%
763%

Example 15

150 g of nerolidol and 2.025 g are placed in an apparatus identical to that of Example 13 Tetrahydrolinolyl orthovanadate prepared according to Example 13 a.

The mixture is heated for 1 hour at 160 ° C. under a nitrogen atmosphere. It is then cooled and distilled in the presence of triethanolamine below to 0.25 mm Hg reduced pressure. 148.5 g of a fraction containing 293 g of famesol are obtained between 90 and 108 ° C.

Degree of conversion
yield

21.7%
89.9%

Example 16

18.8 g of 3-methylbutene- (1) -ol- (3) and 0.2 g of tetrahydrolinalyl orthovanadate prepared according to Example 13 are placed in a stainless steel autoclave with a capacity of 125 cm ^{3 under a nitrogen atmosphere.}

The mixture is heated for 7 hours at 150 ° C. under autogenous Pressure. It is cooled and distilled under reduced pressure to 112 mm Hg. You get that 3-methylbutene- (2) -ol- (l) with a degree of conversion of 25.6% and a yield of 83%.

Claims (4)

Patent claims: 1. A process for the preparation of primary or secondary alcohols by äthylsnischer katalytisehe isomerization tertiary "alcohols -äthylenischer" characterized in that a transition metal of subgroups 5 carries out the isomerization in the presence of the compound to 7 at 50 to 25O ⁰ C in the liquid phase Z The method according to claim 1, characterized in that the isomerization in the presence of a · " Compound of one of the transition metals vanadium, niobium, molybdenum, tungsten or rhenium performs 3. The method according to claim 2, characterized in that the isomerization is carried out in the presence of a compound of one of the transition metals vanadium or molybdenum 4. The method according to claim 2, characterized in that the isomerization is carried out in the presence of an orthovanadate