DE1965377C3 - Process for the production of primary or secondary ethylenic alcohols - Google Patents

Description

25th

It is known that certain ethylenic alcohols, in particular tertiary-ethylenic alcohols, can be isomerized to primary or secondary alcohols with the aid of acidic catalysts (EA B raude, -J ₀ 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 generally requires the neutralization of the reaction medium; this neutralization the one hand the loss of acid used and on the other ^ ₀ to form a salt of the acid in a considerable amount result.

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 tertiary a-ethylenic alcohols to isomerize by a two-stage process, the first stage of which in a reaction by acetylation with acetic anhydride and its second stage consists of saponification (Dimroth, Ber. d. dtsch. chem.Ges.71,1340 [1938]).

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

The invention therefore relates to a process for the ( ₁₀ production of primary or secondary ethylenic alcohols by catalytic isomerization of tertiary -ethylene alcohols, which is characterized in that the isomerization is carried out in the presence of a compound of a transition metal of the subgroups (, ₅ 5 to 7 at 50 to 250 ° C in the liquid phase.

The transition metals of subgroups 5-7 also become columns 5b to 7b of the periodic table C-CH-CH-R ₃

R, OH

in the ri and rj 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 R) denotes a hydrogen atom or has the same meanings as are given for Ri and R ₂ under a).

A class of alcohol which is particularly interesting in the process according to the invention consists of the alcohols of the formula 1 for which R _{3 represents} a hydrogen atom.

Ri, R2 and R ₃ preferably contain a total of 2 to 30 carbon atoms, and at least one of the radicals Ri and R ₂ 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 α-ethylenic alcohols the formula

C = CH-CHOH-R ₃

UD

in which Ri, R ₂ and Rj have the meanings given above.

However, if Ri and R ₂ together represent a divalent radical, such as, for example, an optionally substituted pentamethylene radical, a β-ethylenic alcohol with a double bond in the ring is also formed.

The catalysts that can be used in the process of the present invention are essentially inorganic or organic compounds of transition metals of subgroups 5 to 7 and preferably the compounds of metals from the group of vanadium, niobium, molybdenum, tungsten or Rhenium.

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

'd'e sulfates, nitrates, phosphates, carbonates, Arsona ^like . _rsenatei Germanates, perchlorates, sulfites, nitrites; Here mixed salts of transition metals of subgroups 5 to 7 with other metals of the periodic table; the salts of aliphatic, cycloali-

aromatic or aromatic organic acids, such as acetates, propionates, stearates, benzoates, oxalates, Succinates, sulfonates, tartrates, citrates, salicylates, Naohthenates; the alcoholates and the phenates produced by Transition metals of subgroups 5 to 7 originate, ι ο

"^ These salts, alcoholates and phenolates can also be salts of oxygen-containing metallic groups, such as vanadyl _and molybdenyl salts.

Other inorganic or organic compounds of the above-mentioned metals can be the salts and esters of acids derived from one or more of these metals, such as the vanadates, niobates, tantalates, molybdates, tungstates and rhenates; the analogous compounds in the form of the per, poly, ortho, meta, pvro, thio and halogeno compounds; the mixed salts and esters, such as tungstovanadates, phosphomolybdates, tartratoniobates, zirconium woiframates and molybdocitrates, formates, lactates, maleates, almondates, mucates, oxalates, quinates, saccharates, tartrates and wolframates. Also suitable are the chelates, such as acetylacetonates, which may be optionally substituted by, for example, aliphatic or cycloaliphatic groups or by halogen atoms, the Benzoylacetonate that Glyoximate, Chinoli- yo nate s'alicylaldehydate and Benzylhydroxamate, the derivatives and ethylene diamine, "oc'- Bipyridyl, o-nitrosoohenol / 3-nitrosonaphthol, salicylaldimidine and pornhyrins. It can also noolefinen the metal complexes or metal salts with coordinates which, like carbon monoxide, Mo y, diolefins, polyolefins, acetylenic compounds, cyclopentadienyl, ammonia, cyanides, tertiary nitrogen-containing bases, phosphines, arsines, stibines and nitriles may be used. Furthermore, 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

-M = O

.Q-M-O

-M <-0 =

(HD

(IV)

(V)

(Vl)

in which M denotes a metal atom which can also be bonded to other atoms by one or more ionic or covalent bonds. 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 <, 0} chelates, such as those derived from j9-diketones.

The active metal derivative which forms the catalyst can be applied to a carrier. As a carrier can for example: activated aluminum oxides and silicas, pumice stone, fuller's earth, infusoria earth and (, 5 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 Combine amounts of a cocatalyst or activator. An example of a cocatalyst is the Alcohols, the Lewis bases, such as ammonia, amines, phosphines, arsines, stibines and bismuthines, 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.

You can work in the presence or in the absence of a solvent. As a solution center! you can compounds which are generally chemically inert towards the catalyst and the reaction components use. Particularly suitable are the chlorinated or non-chlorinated aliphatic, acyclic or aromatic hydrocarbons, ethers and amides.

If a sufficiently volatile ethylenic alcohol is isomerized in the presence of a solvent, can this alcohol in gaseous form in a temperature chosen to carry out the reaction introduced liquid reaction medium, the liquid medium at the beginning mainly the Contains solvent and the catalyst. To keep the temperature constant, you can then use a Carry out distillation to the extent that the reaction products are formed.

The reaction temperatures are between and 250 ° C and preferably between 100 and 200 ° C. Since the pressure is not a critical factor for the process according to the invention, it is advantageous to use atmospheric pressure.

If the catalyst used is an ester of an oxygen acid, that of a metal of the subgroup 5 to 7, it is advantageous to work in an anhydrous atmosphere in order to prevent the hydrolysis of the Avoid 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 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 150 cm ³ flask, equipped with a device for moving, a vertical condenser, a dropping funnel and a Eintauchronr, bringing 100g linalool [3,7-Dimethyloctadien- (l, 6) -OL- (3) ] and 4 g of ammonium metavanadate.

Nitrogen is introduced into the medium in an amount of 2 l / h in order to remove most of the ammonia formed in the course of the reaction. The mixture is heated at 150 ^° C. for 6 hours. It is cooled and filtered through a glass frit. The flask and the glass frit are rinsed twice with 25 cm ^{3 of} ethyl ether each time. The filtrate is concentrated 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 Vigreux 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 containing 16.2 g of geraniol is obtained, the fraction distilling between 70 and 75 ° C. (12.7 g) containing 98% by weight of geraniol.

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 purged with nitrogen as in Example 1. The mixture is heated 5 '/ 2 hours at 130 ° C and then 1 hour and 20 minutes at 150 ⁰ C. Then the mixture is cooled off. The reaction mixture is distilled below 0.2 mm Hg.

18.9 g of one are obtained between 48 and 115 ° C Mixture containing 5.3 g geraniol.

Degree of conversion
yield

43.7%
60.5%

Example 3

Degree of conversion
yield

320/0
78.5%

The mixture is heated for 2 hours at about 125 ° C. under an anhydrous atmosphere. It is cooled and distilled below 0.3 mm Hg. It is recovered between 78 and 12 ° C 4.77 g of a fraction containing 0.7 g of farnesol.

Degree of conversion 18.6%

Yield 75%

Example 5

a) Preparation of the catalyst
Tertiary amyl orthovanadate is prepared from tertiary 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 0.5 g of tertiary amyl orthovanadate.

The mixture is heated for 2 hours at 12O ⁰ C in an anhydrous atmosphere.

The reaction medium is cooled. It is poured into a separating 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 and another 50 cm ^{3 of} water and 40 cm ^{3 of} ethyl ether are added. One decants. The organic layer is separated, dried over sodium sulfate, filtered, concentrated and distilled under 0.1 mm Hg. 3.24 g of a mixture are obtained between 90 and 115 ° C., since C, G contains 3 g of farnesol.

40

In a 50-cm ³ flask equipped with a stirrer, a vertical condenser and a dropping funnel, 5 g bringing Nerolidol [3,7,11-Trimethyldodecatrien- (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, the 1.26 g of farnesol [3,7,11-trimethyldodecatriene- (2,6,1O) -Ol- (I)] contains.

55

60

Example 4
a) Preparation of the catalyst

Tertiary butyl orthovanadate is prepared from tertiary butanol and V2O5 according to that of N. F. O r 1 ο ν 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 a ₅ & ascending condenser, bringing nerolidol 5 g, 0.2 g of tert-butyl orthovanadate and 1 cm ³ of tert-butanol.

Degree of conversion
yield

24.6%
72.5%

Example 6

In an apparatus identical to that of Example 3 20 g of nerolidol and 0.6 g of tert-butyl orthovanadate prepared as in Example 4 are introduced.

The mixture is heated for 20 minutes at 15O ⁰ C in anhydrous atmosphere. The mixture is then cooled and distilled below 0.05 mm Hg. 19.27 g of a mixture containing 3.54 g of farnesol are obtained between 75 and 120 ° C.

Degree of conversion
yield

28%
63.5%

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 Example 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.

It is thrown off and distilled below 0.2 mm Hg. 3.92 g of a fraction are obtained between 100 and 120 ° C. which contains 0.76 g of farnesol.

Degree of conversion
yield

29%
52.5%

Example 8
a) Preparation of the catalyst

Cyclohexylorthovanadate is prepared from ammonium metavanadate and cyclohexanol by the method described by F. C art η and N. C augh 1 an (J. Physic. Chem. 64, 1756 [1960]). You heat them up

Reaction components up to the reflux temperature of the Cyclohexanol, removing the water and ammonia as they are formed. Then cool one off. The reaction mixture is filtered. By distilling the filtrate under reduced pressure the cyclohexanol is removed and the cyclohexyl ester is obtained as the distillation residue.

b) isomerization

In an apparatus identical to that of Example 3 5 g of nerolidol and 0.5 g of cyclohexyl orthovanadate are added one.

The mixture is heated for 20 minutes at 13O ⁰ C under an anhydrous atmosphere.

It is cooled and distilled below 0.15 mm Hg. Man wins between 85 and 115 ° C 4.9 g of a fraction that Contains 0.76 g of farnesol.

Degree of conversion
yield

34.2%
44.5%

Example 9
a) Preparation of the catalyst

^{15 cm 3 of} an ammoniacal solution (20% NH ₃ ) are allowed to flow into a mixture of 11.3 g of VOSO ₄ -3.5 H ₂ O, 100 cm ^{3 of} distilled water and 11.3 cm ^{3 of} acetylacetone, while stirring a pH of 9. The mixture is stirred for one hour at room temperature. It is then filtered. The precipitate is ^{washed with 100 cm 3 of} distilled water. It is dried to constant weight. Vanadylacetyl-

b) isomerization

The procedure is as in Example 8, the cyclohexyl orthovanadate being replaced by vanadyl acetylacetonate replaced and heated for 2 hours instead of 20 minutes. Distillation below 0.15 mm Hg yields between 70 and 118 ° C, 4.01 g of a mixture containing 0.22 g of fernene oil contains.

Degree of conversion
yield

19.8%
22.2%

10

example

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

The mixture is heated under an anhydrous atmosphere for 5 hours and 2 minutes. The temperature of the reaction mixture rises here from 78 to 132 ^° C. It is cooled. It is distilled under 15 mm Hg. Between 40 and 60 ¹¹ C, 4.79 g of a fraction containing 0.71 g of 3-methylpylene- (2) -ol- (1) is obtained.

yield
Degree of conversion

76.3%
18.6%

55

to

Example

In an apparatus identical to that of Example 2 3 g of 2-methylnoncn- (3) -ol- (2) and 0.12 g of ammonium vanadate are introduced.

It is flushed with nitrogen at a rate of 2 l / h in order to remove most of the fts in the course of the isomerization 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-methyynonene- (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 15O ⁰ C. Then kühlit 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 70 ⁰ C. 4.16 g of a fraction which 034 g of 1 - contains -2,6,6-trimethyl (2-hydroxyethyl)

Degree of conversion
yield

17.3%
43.5%

25th

30th

35

45

Example 13

a) Preparation of the catalyst
(Tetrahydrolinalyl 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 placed.

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 Dinnethyloctanol are removed by distilling the filtrate. The mixture is heated for a further 30 minutes at 100 ^° C. below 0.2 mm Hg.

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

CH,

(CHj) ₂ CH- (CH _{2) 3} -C-O V = O
C ₂ H ₅

b) isomerization

In an apparatus identical to that of Example 3 20 g of linalool, 0.538 g of catalyst and 0.149 g of triethanolamine are introduced.

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 "C. The mixture is cooled and distilled under 0.03 mm Hg.

You win between 4? and 6O ⁰ C 19.52 g of a fraction which contains 3 g of geraniol.

Conversion rate 23.4%

Yield 64%

Example 14

a) Preparation of the catalyst
(Tctrahydrolinalylorthovanndal)

In a 250 cm ³ flask equipped with a device for agitation, a fine immersion tube and a reflux

709B44 / 11B

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. Filter. The cyclohexane and the excess dimethyloctanol are removed by distilling the filtrate. The mixture is heated for a further 30 minutes at 100 ° C below 0.2 mmHg.

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

CH ₃

(CH ₃ ) ₂ CH- (CH ₂ ) -, -C- O- V = O
C ₂ H ₅ .

b) isomerization

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

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

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

Degree of conversion
yield

25.2%
76.9%

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.

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 Hgi reduced pressure. 148.5 g of a fraction containing 29.3 g of farnesol 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

yo 3-methylbutene- (2) -ol- (l) with a degree of conversion

of 25.6% and a yield of 83%.

Claims (4)

Patent claims: 1. Process for the production of primary or secondary ethylenic alcohols by catalytic Isomerization of tertiary ac-ethylenic alcohols, characterized in that the isomerization in the presence of the compound one Transition metal of subgroups 5 to 7 at 50 to 250 ° C in the liquid phase. 2. 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 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. is mentioned by Mendelejev (Handbook of Chemistry and Physics, 45th Edition, page B-2). The Λ-ethylenic alcohols according to the invention can be isomerized, correspond to the formula