DE2516698A1 - NEW TUNGSTEN COMPOUNDS - Google Patents

Description

The invention relates to new tungsten compounds, complexes thereof, methods of making the same and uses thereof Links.

The tungsten complexes of the present invention can be made by the following general formula can be reproduced:

[WO (OR ₁ ) (OR ₂ ) (OR ₃ ) (OR ₄ )] _R L (I)

wherein R ₁ , R ₂ , R ₃ and R _{4 represent} a hydrocarbon group or a

Group of the formula: y R _c , where R _c , R _c and R ..

'ςί - ■ R bo /

R ₇

also represent a hydrocarbon group. All of the above-mentioned hydrocarbon groups may be substituted. R ₁ , R ₂ , R_ and R. can be the same or different groups. If the number of these hydrocarbon groups in the compounds of the general formula (I) is 2 or more, then

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2 of these groups form a condensed ring with the tungsten atom and the oxygen atoms. There can be 1 or 2 such condensed rings may be formed per tungsten atom. L stands for a monodentate or polydentate ligand that is an element which is selected from the class of typical elements of group V of the Periodic Table of the Elements, namely from N, P, As, Sb and Bi, the ligand being coordinated via the element with the tungsten atom in the above formula is. η is a value that fluctuates between 1 and the number of tungsten atoms that are coordinated with the ligand L. can be.

The tungsten compounds according to the invention can be represented by the general formula:

WO (OR ₁ ) (OR ₂ ) (OR ₃ ) (OR ₄ ) (II)

In this formula, R-, R ₂ , R ₃ and R. have the meanings given in connection with the general formula (I), the prerequisite that at least one of the substituents R ₁ , R ₉ ,

RR, and R. is a group of the formula: / 5, where R ^, R _fi and

^{J 4} -Si -— R, ^D

\ ⁶

R _{7 have} the meanings given in connection with the general formula (I).

Therefore, the compounds of the general formula (II) can also be written as follows:

/ 5
^ -R ₆ ) _m (0R-; ₄ _ _m 509844/1093

In this formula (II) ¹ , R ₁ , R ₅ , R _g and R _{7 have} the same meanings as have been given in connection with the general formula (I), m is an integer from 1 to 4. M means m a number of 2 or less then the two -OR ¹ groups can form a fused ring f-0 - ^ with the tungsten atom in the

W Z

Form a formula. In the condensed ring, Z is for example

an alkenylene group, a phenylene group or the residue of a polyoxyalkylene glycol, which after removal the terminal hydroxyl groups is available. The formation of such a condensed ring is not due to tungsten compounds of the general formula (II), it can also occur in tungsten complex compounds of the general formula (I).

The compositions and structures of the tungsten complex compounds and the tungsten compounds according to the present invention are explained in more detail below.

In the general formulas (I) and (II) (including the general formula (II ¹ ), R .., R-, R ₃ and R. represent a hydrocarbon group, for example an alkyl group containing 1 to 20 carbon atoms Alkenyl group with 2 to 20 carbon atoms, a cycloalkyl group with 3 to 10 carbon atoms, a cycloalkenyl group with 3 to 10 carbon atoms, an aryl group with 6 to 10 carbon atoms, an aralkyl group with 7 to 20 carbon atoms or an alkylaryl group with 7 to carbon atoms or a group of the formula ^ 5 _f

Si-R ₆

^ ^R 7 where R ₅ , Rg and R _{7 are} hydrocarbon groups that represent the

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Groups R ₁ , R ~, R ^ and R. are similar. These hydrocarbon groups R ₁ to R_ can have substituents, for example halogens, hydroxyl groups, alkoxy groups, carbonyl groups, amino groups, nitro groups, nitroso groups, mercapto groups, etc.

The ligand L in the tungsten complex compounds of the general Formula (I) is a compound containing at least one element selected from the class consisting of N, P, As, Sb and Bi, and those with the tungsten atom via such a typical element of Group V of the Periodic Table of the Elements can be coordinatively bound. The symbol Ty is used to represent the typical elements mentioned above, the belong to group V of the Periodic Table of the Elements, then the compound used in this way as a ligand is represented by one of the formulas (i) to (vi) (hereinafter referred to as "ligand compound"):

^ ^R 8

_Ty R

So

^V 9 R

R ₀ , R _n and R ₁ , - denote a hydrogen atom or a carbon y IU

hydrogen group, as it has been defined in connection with the general formula (I), where R _g , R _{1 and R 10 can be} identical or different.

This type of ligand compound includes various amines such as primary amines, secondary amines and tertiary amines as well as alkyl or ary! phosphines. Alkyl or aryl arsines, alkyl or arylstibines and alkyl or aryl bismuthines.

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Ty (ii)

Rg has the meaning given above, while B is a Is an atom or an atomic group which is connected to the element Ty via a double bond.

Among the ligand compounds of this type, Schiff bases, isonitriles, azo compounds or the like can be mentioned.

Ty -sr Y (iii)

Y is an atom or a group of atoms linked to the element Ty by a triple bond.

Examples of ligand compounds of this type are nitriles mentioned.

Ro

• ⁸ (iv)

Ty Q

R ₀ has the meaning given above under (i), wäho

rend Q is an atomic group which, together with Ty, forms a cyclic structure.

Typical ligand compounds of this type are imines, aziridine, pyrrolimidazole, pyrazole, indole, carbazole, pyrrolidine, pyrroline, Imidazolidine, piperidine, piperazine or morpholine.

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-β-

Ty Q ¹ (ν)

A ¹ ''"

A, A ¹ and Q ¹ each represent an atom or a group of atoms which are taken together and form a cyclic structure with Ty.

Of the ligand compounds in this series are pyridine, picoline, Pyrazine, pyrimidine, pyridazine, triazine, quinoline, naphthyridine, quinoxaline, pteridine, etc. mentioned.

Ty - Q "(vi)

Q "means an atomic group which, together with Ty, forms a polycyclic Structure forms.

Examples of this type of ligand are indolizine, quinuclidine, hexamethylenetetramine, 1,5-diaza bicycloundecen etc.

The ligand compounds in the categories outlined above also include compounds having a Ty atom with a solitary one Electron pair or a multitude of functional groups that contain the same per molecule (compounds with lower and high molecular weight). Although many compounds belonging to each of the above categories are in accordance with the invention can be used as ligand compounds, nitrogen compounds are nevertheless particularly useful in With regard to their low cost and easy availability in larger quantities and also with regard to the fact that a variety of derivatives are available. What such

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As far as nitrogen compounds are concerned, in general they can all Compounds are used which contain one or more basic nitrogen atoms. As particularly suitable compounds be primary amines, such as methylamine, ethylamine, propylamine, ß-ethoxyethylamine, butylamine, cyclohexylamine, aniline, Naphthylamine etc., acyclic and cyclic secondary amines, such as dimethylamine, diethylamine, dibutylamine, dicyclohexylamine, Methylaniline, methylcyclohexylamine, piperidine, piperazine, morpholine, pyrrolidine etc., acyclic as well as cyclic tertiary amines, such as trimethylamine, triethylamine, ethyldibutylamine, tricyclohexylamine, dimethylaniline, pyridine, Picoline, quinoline, isoquinoline, N-methylpyrrolidine, N-methylmorpholine etc., as well as polyamines such as jithylenediamine, pyrazine, piperazine, pyrimidine, triethylenediamine, and 1,8-diazabicyclo- (5,4,0) -undecene-7-polyethyleneimine, as well as ion exchange resins mentioned, which have a larger number of intramolecular amino groups exhibit. In addition to the nitrogen-containing ones mentioned above Compounds can also be used with Schiff's bases, imines, nitriles, isonitriles or the like. Besides such Nitrogen-containing compounds can optionally also trialkyl, Tricycloalkyl and triary compounds of phosphorus, Use arsenic, antimony or bismuth, such as triphenylphosphine, Tributylphosphine, tricyclohexylphosphine, triphenylarsine, tributylarsine, triphenyl bismuth, or the like.

The tungsten complex compounds of the general formula (I) and the tungsten compounds of the general formula (II) (including the compounds of the general formula (II) ¹ ) can be successfully synthesized by the following method:

1. According to a process which consists in _{using a tungsten oxytetrahalide (WOX 4} , where X is Cl, Br or J) with

5 0 9 8 A kl 1 0 9 3

a monohydroxy compound and / or a polyhydroxy compound (Both compounds are hereinafter referred to as "starting hydroxy compounds" are designated) to implement in the presence of the above-mentioned ligand compound.

The reaction is usually carried out in the presence of a solvent. Preferred solvents are those which are inert towards the tungsten halide and the starting hydroxy compounds. Benzene, toluene, xylene, tetrahydrofuran, dioxane or the like may be mentioned as examples. Since tungsten oxytetrahalides are very unstable in the presence of water, it is advisable if the solvent, the starting hydroxyl compound and the reaction atmosphere are absolutely anhydrous. The reaction temperature is conveniently below the temperature range within which the starting hydroxy compound remains stable in the reaction mixture. It is generally between -50 and approximately 150 ^° C.

The starting hydroxy compound must be per mole of tungsten oxytetrahalide (also in the case that 2 or more hydroxy compounds are used) in an amount not less than 4 moles in the case of monohydroxy compounds or in an amount of not more than 4 / m mol can be used in the case of polyhydroxy compounds with m-hydroxyl groups. So that the reaction is within In a reasonable period of time, it is usually preferable to use 4 to 20 moles of a monohydroxy compound or 4 / m to 20 / m mol of a polyhydroxy compound.

As for the ligand compound used in the reaction system is present, a tungsten complex compound (I) is obtained if not less than 5 equivalents of the ligand compound per Mol of tungsten oxytetrahalide are used during a preparation (hereinafter referred to as preparation (I))

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which is a mixture of a tungsten complex compound (I) and a ligand-free Wolfrain connection accordingly (I) minus the ligand is when the amount of the ligand compound used is not less than 4 equivalents and less than 5 molar equivalents. A compound of formula (I) is also used obtained when two or more different ligand compounds in a total amount of not less than 5 equivalents per mole Tungsten oxytetrahalide can be used.

2. By a process which consists in tungsten trioxide to react with the starting hydroxy compound in the presence of a ligand compound, while the water formed as a by-product is constantly azeotropically removed with a suitable solvent such as benzene or a benzene analog.

When carrying out the above reaction, the amount of the starting hydroxy compound per mole of tungsten oxytrioxide must not be used less than 4 moles in the case of monohydroxy compounds and not less than 4 / m moles in the case of polyhydroxy compounds with m-hydroxyl groups be. For the same reason as set out above, it is generally appropriate to use a to use excess of the starting hydroxy compound. In particular then, when a low boiling hydroxy compound is used or the hydroxy compound is unstable, it is preferable to proceed in such a way that the starting hydroxy compound is added in individual portions, while that as a by-product resulting water is constantly distilled off.

The compound (I) can also be produced in this way.

3. By a process which consists in using a tungsten oxytetrahalide to react with an alkali metal alcohol of the starting hydroxy compound in the presence of a ligand compound.

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This reaction is usually carried out in the presence of a solvent. This solvent is preferably a Solvents that do not contain active hydrogen atoms, for example Benzene, toluene, xylene, hexane, heptane, tetrahydrofuran or dioxane. Per mole of tungsten oxytetrahalide it is necessary to use at least 4 mol of the alkali metal alcoholate, although a larger excess is not favorable Results. A preferred range is between 4 and molar equivalents. Although the reaction is within a temperature range from -80 to 150 ° C, it is preferable to do it at 0 to 100 ° C. As in the case of the one described under 1) In the process, the reaction is conveniently carried out under strictly anhydrous conditions. After In the above method, the compound (I) or the preparation (I) 'can be produced selectively.

When carrying out the above methods 1) to 3) there are depending on the type of starting hydroxy compound as well as the Ligand compound Cases where the yield of the tungsten complex compound is low or where the complex compound cannot be produced with high purity. It has been found that when performing either of the following procedures 4) and 5) these disadvantages no longer occur. The tungsten complex compound can be used in high yield as well with high purity, regardless of the type of starting hydroxy compound and the ligand compound.

4. The process consists in using a tungsten oxytetra-lower alkylate (which can be a raw preparation, but is preferably purified) of a transesterification reaction with a starting hydroxy compound or an organic carboxylic acid ester thereof in the presence of a ligand compound. As tungsten oxytetra-lower alkylates are for example the appropriate

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Methylates, ethylates, propylates, butylates or the like mentioned. They can also be mixed alkylates or mixtures of alkylates.

5. This method consists of using any tungsten complex compound (I) in advance by one of the above-mentioned methods 1) to 3) using a selected hydroxy compound, which is able to produce a tungsten complex compound (I) in high yield with ease, or to synthesize according to the above-mentioned method 4) using any starting hydroxy compound or an organic one To produce carboxylic acid esters thereof and the tungsten complex compound (I) obtained then to an esterification reaction with another starting hydroxy compound or an organic one To subjugate carboxylic acid esters thereof.

In carrying out the above-mentioned methods 4) and 5), if the starting hydroxy compound is in the form of a organic carboxylic acid ester is used, usually a lower fatty acid ester, for example an ester of acetic acid, Propionic acid or butyric acid, can be used in a convenient manner. The esterification reactions described above are preferably carried out in the presence of a solvent, while the hydroxy compound or the organic Acid ester, which is released during the ester exchange, either alone or azeotropically with the solvent is constantly distilled off will. As the solvent, one which is free from active hydrogen atoms, such as, for example, is preferred Benzene, toluene, xylene, hexane, heptane, tetrahydrofuran, dioxane or the like. Those solvents are also preferred which boil higher than the hydroxy compound or the organic carboxylic acid ester that is released during ester interchange. Further those solvents are to be preferred which have the lowest

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Form boiling azeotrope. The transesterification reaction can in general between 0 and 200 C and preferably between 60 and 150 ° C. When performing method 4) then, if not per mole of tungsten oxy-tetra-lower alkylate less than 1 mole of the ligand compound and less than 4 moles of the starting hydroxyl compound or the organic carboxylic acid ester are used thereof, a tungsten complex compound (I) or a preparation (I) 'obtained as a partially transesterified product. When 4 moles or more of the starting hydroxy compound or the organic carboxylic acid ester thereof is used, it is obtained a tungsten complex compound (I) as a completely transesterified product. To the completely transesterified tungsten complex compound (I), it is generally preferable to use the ligand compound in an amount of 1.1 to 5.0 moles per mole of the tungsten oxytetra-lower alkylate and the starting hydroxy compound or the organic carboxylic acid ester thereof in an amount of 4.4 to Use 20 moles on the same basis. If the amount of the ligand compound is below 1 mole per mole of the tungsten oxytetra-lower alkylate, then a preparation (I) 'is obtained.

Used when performing the method 5) per mole of the tungsten complex compound (I) which is subjected to transesterification, the starting hydroxy compound or the organic carboxylic acid ester thereof used in an amount of less than 4 moles, a tungsten complex compound (I) or a preparation is obtained (I) 'as a partially interesterified product. Becomes 4 moles or more of the starting hydroxy compound or the organic If carboxylic acid ester thereof is used, the tungsten complex compound (I) is obtained as a completely transesterified product. To the Preparation of the completely transesterified tungsten complex compound (I), it is advantageous to use the starting hydroxy compound or the organic carboxylic acid ester thereof in an amount of 4.4 to

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To use 20 moles per mole of the Wolf rainkomplexverbindungen (I) with which the intended transesterification is to be carried out. If two or more of the tungsten complex compounds (I) are mixed by one of the methods described above 1) to 5) have been prepared, then another complex compound (I) and / or a preparation (I) 'can be obtained.

Synthesis of tungsten compounds of the general formula (II)

1) The synthesis can be carried out by a method which consists in using a tungsten oxytetrahalide with a

^ * R
Compound of formula: ^ 5, wherein R _c , R _c and R_ die

HOSi R. ^{5 6 7}

^R 7
Have the meanings given above, to implement in the presence of a neutralizing agent for hydrogen halide, for example ammonia.

This reaction is usually carried out in the presence of a solvent. As solvents not containing active hydrogen atoms, benzene, toluene, xylene, hexane, heptane, tetrahydrofuran, dioxane or the like are preferred. The reaction temperature should not be higher than the range within which ^^ 5 remains stable in the reaction system. HOSi R,

^ ^R 7
It is usually between -50 and 150 ° C. The amount of

^ ^R 5
HOSi R, must not be less than 4 moles per mole of the tungsten

oxytetrahalide. Any large excess of / 5

HOSl-R, -

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does not produce favorable results. The preferred amount is between 4 and 20 molar equivalents. The hydrogen halide neutralizer, like ammonia, is usually used in large excess and conveniently in one Amount sufficient to completely neutralize the hydrogen halide.

2) The synthesis is possible by a method which is therein

is a tungsten oxytetrahalide with / , wherein M is a

MOSi R,

^ ^R 7

Alkali metal, such as potassium or sodium, and R ₁ , R _{1 and R 3 have} the meanings given above.

This reaction is also preferably carried out in a solvent, as has been described in connection with process 1). Although the reaction at a temperature from -80 to 200 ⁰ C goes well, it is preferable to carry out this reaction at a temperature from -50 to 150 ° C. The amount of

MOSi R _fi must not be less than 4 moles per mole of the tungsten oxy-

^ R ₇

tetrahalide, an extremely large excess of the former Connection is just harmful. An amount between 4 and 10 molar equivalents is preferred.

3) The synthesis is possible by a method which is therein

consists to implement tungsten trioxide with ^ / 5, with that as

HOSi - R, ^ - ^

^R 7

By-product resulting water is continuously removed azeotropically with a suitable solvent, such as benzene or a benzene analog will.

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The reaction is conveniently carried out at a temperature which does not exceed the range in which the

• p

Connection ^ y 5

HOSi-R _fi when it reacts in the reaction system

^ ^R 7

is stable and is converted to the desired product compound with a high selectivity. Usually there is one Range between room temperature and approximately 150 ° C. The amount

at y ~ ^R 5

HOSi - R _ß must not be below 4 moles per mole of tungsten trioxide

^ ^R 7
lie. The preferred range is between 4 and 20 moles.

4) The synthesis can be carried out by a method which consists in using a tungsten oxytetra-lower alkylate, for example a methylate, ethylate, propylate, butylate or the like

• p

Chen with / 5

HOSi- R, or a reactive derivative thereof, for example

R ^R?
wise RCOSi — R _p (where R is a hydrocarbon group, pre-

0 ^ ^R 7 is preferably a lower alkyl group) to implement.

This reaction is preferably carried out in the presence of a solvent carried out, the alcohol formed as a by-product or the organic carboxylic acid ester alone or as an azeotropic mixture is removed with the solvent. The solvent is preferable a solvent that does not contain active hydrogen atoms, for example benzene, toluene, xylene, hexane, heptane, tetrahydrofuran, Dioxane or the like. Preferably it is a solvent that has a higher boiling point than that of the by-product occurring alcohol or the organic carboxylic acid ester,

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or it is a solvent which forms the lowest boiling point azeotrope with the alcohol. The reaction temperature can between 0 and 200 ° C and preferably between 60 and 150 ° C.

5) The synthesis can be carried out according to a method

■ p

according to which ^ 5

WO (OSi - R,) ^ a partial transesterification reaction

\ R ₇

with HOR 'or HO-Z-OH (where R ¹ and Z have the meanings given above) or a reactive derivative thereof.

This reaction occurs in the presence or absence of a solvent carried out. If a solvent is used, it is preferably one that is not active Contains hydrogen atoms, as already in connection with the process 4) has been explained. The reaction temperature can vary between 0 and 200.degree. C. and preferably between 60 and 150.degree.

When carrying out the procedures 1) to 4) described above generally a tungsten compound of the general formula is obtained (II) where m is 4. When carrying out process 5), a tungsten compound of the general formula (II) can be obtained, in which m stands for 1, 2 or 3.

When carrying out the process 4), the molar ratio of

HOSi-R or a reactive derivative thereof to the tungstenoxy- \
^R 7

lower alkylate selected in a suitable manner to carry out a partial transesterification reaction, then one can also obtain a tungsten compound of the general formula (II) in which m is 1, 2 or 3, with the proviso that R ¹ in the product compound is a is lower alkyl group. It is also possible to have a

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To obtain mixture of tungsten compounds (II), for example by using two or more different compounds

^ ^R 5 " X ^R 5
HOSi R, or MOSi R _c in performing the above

^R 5 or MOSi ^R 5 ^R 6 ^R 6 ^R 7 ^R 7

Method 1) to 4) or by using two or more different compounds ^ 5

WO (OSi R _c ). and / or HOR ¹ (or HO-Z-OH)

R ₇
when carrying out the procedure 5). For production of

Rr

WO (OSi— ^R g) 4, the method 4) is particularly suitable with regard to

^ R ₇ ρ

¹ ^ ^R 5

booty and purity of the product. Used WO (OSi R) as a catalyst

^ ^R 7 used for the isomerization of allyl alcohols, then a higher purity of the catalyst has a reduced tendency to the effect that a dehydration reaction takes place, with a higher selectivity of the reaction with respect to the desired isomer is achieved. For this reason, too, the method 4) described above is preferred.

As connections HOSi - R _fi or MOSi - R _fi , which output

^ R ₇ ^ R ₇

represent bonds for the synthesis of the complex compounds (I) or the compounds (II), the compounds given below are particularly suitable with regard to their availability and the simplicity of the synthesizer etc. as well as the corresponding alkali metal silanolates. As connections HOR ¹ and

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HO-Z-OH can be mentioned as follows: saturated alcohols, such as methanol, ethanol, butanol, amyl alcohol, ethyl cellulose, Methyl cellulose, lauryl alcohol, stearyl alcohol etc., unsaturated alcohols, such as allyl alcohol, crotyl alcohol, Prenyl alcohol, linalol, geraniol, citronellol, farnesol, phytol etc., phenols such as phenol, cresol alkoxyphenols, Naphthols etc., alcohols containing aromatic rings, such as naphthols, benzyl alcohols, β-phenylethyl alcohol etc., as well as polyhydric alcohols such as ethylene glycol, propylene glycol, 1,4-butanediol, etc.

Use of the tungsten complex compounds according to the invention and tungsten compounds

The tungsten complex compounds according to the invention and also tungsten compounds as well as their mixtures (compounds (I), which only consist of the tungsten complex compounds of the general formula (I), Compounds (II), which consist only of the tungsten compounds of the general formula (II), and preparations (I) ', which consist of a tungsten complex compound of the general formula (I) and a tungsten compound of the general formula (II)) new and can be used for various purposes. They are particularly suitable as catalysts for carrying out Isomerization reactions of allyl alcohols of the following general formulas (oi, ß-unsaturated alcohols)

^ 12 ^ 13 ^ 14, ^R 12 ^R 13 ^R 14

R ₁ , -CC = CR ₁₁ -C = CC-OH

111 ι Il ι

OH R ₁₅ R ₁₅

(III) (IV)

1093

In the above general formulas (III) and (IV), R ₁₁ , R ₁ Of R ₁ ~> i Ri 4 and R ₁ , - denote a hydrogen atom or a hydrocarbon group which may optionally be substituted, where Rj., and R ₁₂ ' ^R i ι ^{and R} 13' ^R 11 ^un ^ ^R 14 ' ^R 13 ^{and R} 14 ^{or R} -] 4 ^{and R} -] together can form a cyclic group. Halogens, hydroxyl groups, alkoxy groups, carbonyl groups, amino groups, nitro groups, nitroso groups, mercapto groups, alkylthio groups, sulfyl groups, sulfonyl groups, carboxyl groups, alkoxycarbonyl groups, acyloxy groups, cyano groups, etc. may be mentioned as substituents for such hydrocarbon groups.

In the allyl alcohols of the general formulas (III) and (IV), R ₁₁ / R-io ' ^R i V ^R i 4 b ^zw · ^R i 5 ^e ^ ⁿ hydrogen atom, an alkyl group with 1 to 20 carbon atoms, a cycloalkyl group with 3 to 10 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkenyl group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms or an alkylaryl group having 7 to 20 carbon atoms.

Typical examples of compounds of the general formulas (III) and (IV) are as follows: 3-buten-2-ol, 2-methyl-3-buten-2-ol, Linalol- (3,7-dimethyl-1,6-octadien-3-ol), 3-methyl-7-ethyl-1,6-octadien-3-ol, 3,7-dimethyl-7-ethoxy-1-octen-3-ol, 3,7-diethyl-1,6-octadien-3-ol, Nerolidol- (3,7,11-trimethyl-1,6,10-dodecatrien-3-ol), 3-methyl-7,11-diethyl-1,6, iO-dodecatrien-3-ol, isophytol- (3,7,11,15-tetramethyl-1-hexadecen-3-ol), 3,7,11,15-tetramethyl-1,6,10,14-hexadecatrien-3-ol, 2-benzyl-3-buten-2-ol, 1-phenyl-2-propen-1-ol, 1-vinylcyclohexanol, cyclonerolidol- (5-J2 ', 6', 6'-trimethyl-1-cyclohexyl] -3 -methyl-1-penten-3-ol), 1-hexen-3-ol, cyclohexen-i-ol-3, 2-methylenecyclohexanol-1, 1-hydroxymethylcyclohexen-1, ß-Cyclohexylidene ethyl alcohol, crotyl alcohol, frenyl alcohol (3-methyl-2-buten-1-ol), Geraniol (3,7-dimethyl-2,6-octadien-1-ol), 3-methyl-7-ethyl-2,6-octadiene-1-oil, 3,7-dimethyl-7-ethoxy-2-octene-1-oil, 3,7-diethyl-2,6-octadiene-1-oil, farnesol- (3,7,11

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trimethyl-2,6,1O-dodecatrien-1-oil), - 3-methyl-7,11-diethyl-2,6,10-dodecatrien-1-ol, Phytol (3,7,11,15-tetramethyl-2-hexadecene-1-oil), 3,7,11,15-tetramethyl-2,6,10,14-hexadecatrien-1-ol, 3-benzyl-2-buten-1-ol, Cinnamyl alcohol (3-phenyl-2-propen-1-ol), 2-cyclohexylidene ethanol, Cyclofarnesol, 2-hexen-1-ol etc.

The rearrangement reactions of allyl alcohols in the presence of acids as catalysts are known, but so far they have been of limited value due to the preponderance of side reaction products. Recently, however, protective right publications have appeared in which it is stated that compounds of transition metals of Groups V, VI and VII of the Periodic Table of the Elements are effective as catalysts for the rearrangement of tertiary allyl alcohols to secondary or primary allyl alcohols (cf. GB-PS 1 256 184 and JA-OS 23 407/1974). It it has now been found that compounds of the transition metals of groups V, VI and VII not only cause the rearrangement of tertiary Allyl alcohols catalyze to primary or secondary allyl alcohols, but also the reverse rearrangement of primary ones or secondary allyl alcohols to tertiary allyl alcohols and the rearrangement of primary allyl alcohols to secondary allyl alcohols and vice versa, etc. It was also found that these reactions in the presence of such transition metal compounds are reversible equilibrium reactions (cf., for example, FR-PS 2 175 772).

It has also been found that of the aforementioned Transition metal compounds only certain vanadium compounds are suitable, while the rest are practically of no value is due to a low catalytic activity or a high level of side reactions such as dehydration reactions, and consequently a low selectivity

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did. Thus, in the aforementioned GB-PS 1 256 184 only refers to compounds of vanadium and molybdenum in the examples, while the aforementioned JA-OS refers to vanadium and molybdenum compounds is limited. In addition, the reaction results obtained when using molybdenum compounds are achievable are unsatisfactory. Vanadyl alkylates are particularly suitable, but these compounds have many disadvantages, for example, they are expensive and have poor catalytic activity. They have to be used in large quantities, their separation or catalyst inactivation being difficult. The difficulties encountered in separating these catalysts occur are explained in more detail below.

If the conversion of linalol to geraniol is carried out using such a vanadium compound as a catalyst, then the reaction occurs automatically at an equilibrium composition of 60% linalol, 15% nerol and 25% geraniol. Around To separate the geraniol from the equilibrium mixture, it is generally easiest and cheapest to do a distillation perform. The boiling points increase from linalol to nerol to geraniol, so that linalol is the first to distill off. Varsity one therefore, to separate linalol from such a reaction mixture by distillation, then the equilibrium is disturbed, which results in a reverse rearrangement of nerol and geraniol to linalol, so that the yield is reduced Consequence is. To prevent this, it is necessary to separate or inactivate the catalyst, in view of the high Cost as well as the difficulty of inactivating such a vanadium catalyst, it is preferable to use the catalyst for to disconnect a reuse. However, since the catalyst is homogeneously dissolved in the reaction system, there is no pending

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Separation methods other than distillation are available. Since a distillation, however, the above-described equilibrium disturbs, it would be useful to set the number of distillation stages for distilling off a mixture of linalol, geraniol and Decrease nerol and pull the vanadium catalyst off the bottom. Due to the comparatively high vapor pressure of the catalyst compound, however, it is inevitable that part of the catalyst gets into the distillate. The use of a high boiling vanadium catalyst can be considered during the However, in reaction, such a compound would undergo transesterification, resulting in the formation of an alkylate of the product allylic alcohol so that the problem is not solved in the slightest. The invention is based on the knowledge that an excellent Catalyst for the conversion of allyl alcohols in the form of the new tungsten complex compounds (I) is available. These compounds have an excellent catalytic effect and are free from the disadvantages described above of the known catalysts. From the comparative examples below shows that conventional tungsten compounds have the ability to catalyze these conversion reactions, however, the rate of the dehydration reaction is so high that the reaction product is practically from the Dehydration product consists. The selectivity for the desired compound is extremely low. Hence these are tungsten compounds of no ..practical value. In contrast, it was found that the inventive tungsten complex compounds cause essentially no dehydration reaction and have an unusually high catalytic activity. It it was also found that the selectivity of the reaction is markedly by the production method of the complex compound as well is influenced by the cleaning method used, and that the complex compound is affected by one described in more detail below Transesterification method is produced, particularly suitable

609844/1093

is. Furthermore, it has been found that an even further improved selectivity is achieved if a solution of such a complex compound (including a tungsten complex compound (I) synthesized elsewhere) beforehand with a porous substance, for example silica gel, diatomaceous earth, aluminum oxide, silicon dioxide-aluminum dioxide, magnesia, Activated carbon or the like. The selectivity of the novel catalysts generally moves in the order tungsten complex compound (I) "> Preparation of tungsten complex compound and tungsten compound (I) 'J ^? Tungsten compound (II). Therefore, the tungsten complex compounds of formula (I) are extremely effective.

A comparison of the catalytic activity of an inventive Tungsten complex compound (I) having the activity of a conventional vanadium compound is shown in Table I. It is it can be seen that the activity of the tungsten complex compound is extremely high. Furthermore, tungsten is cheaper than vanadium. These Fact together with the lower amount required, due to the higher activity, has a significant decrease in the Catalyst costs result.

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Table I.

Isomerization of linalol; Changes in the course

currently

Catalyst VO (O-tert-Bu), WO (O-L).

Catalyst concentration

(x 10 ³ mol%) 54 74

Reaction ^{temperature, 0} C 200 195-197

Isomerization reaction change, _A _ change, * 2

Selectivity selectivity%%%%

Response time, hours

1.0 1.5 2.0 2.5 3.0

* 1 "L" stands for the remainder, which is Linalol minus OH. * 2 selectivity = product (geraniol + nerol) χ 100

Reacted linalol

As can be seen from the following examples, the inventive Tungsten complex compounds (I) are generally solid and have low vapor pressures. You can be more beneficial. Way to separate them completely by a simple distillation, which in the case of vanadium compounds is entrained into the distillate has the consequence. The technical significance of these advantages cannot therefore be overlooked.

20th 97 28 95 28 95 34 96 36 96 39 95 38 97 40 95 40 98

B098A4 / 1093

It should be noted that Wolfraitikomplexverbxndungen (I) and tungsten compounds (II) in which R .., R ", R ₃ and R ₄ are hydrocarbon groups, respectively, are also catalytically active. However, if at least one of these substances is

■ D

do at / 5

Si - R,, then the selectivity in terms of one

^X R
R ₇

Conversion product compound markedly improved. Also is the stability of the catalyst is increased, so that its handling is facilitated.

It was found that although all tungsten complex compounds (I) and tungsten compounds (II) are suitable as catalysts, those compounds synthesized by the transesterification method 4) are most suitable and have a particularly high reaction selectivity. It is also advisable to use the complex compound, which has been synthesized according to one of the methods 1) to 4) to be treated with a porous substance. Through this Treatment will not only decrease the selectivity of the reaction by about 5 increased to 30%, but also the fluctuations in the selectivity when carrying out the various methods for the preparation of Compounds of formula (I) observed in the individual batches is reduced. In all cases a selectivity of not less than 90% is achieved. As for the treatment with the porous As for substance, it consists in dissolving a tungsten complex compound (I) in a suitable solvent and contact the solution with the porous substance. For example, a solution of the complex compound (I) by a with Column filled with silica gel powder or mixed thoroughly with diatomaceous earth and then filtered.

The unsaturated alcohols that can be prepared according to the invention,

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in the form in which they occur, are suitable for use as perfumes or as starting materials for the manufacture of pharmaceuticals, agricultural chemicals or other products. To carry out the allyl rearrangement reaction, it is only necessary to heat the allyl alcohol (III) or (IV) in the presence of, for example, a complex compound (I). Usually, in appropriate manner, the reaction temperature between 300 ⁰ C and to achieve even better results between 150 and 25O ⁰ C. The usable amount of catalyst is between 1 χ 10 and 1 χ 10 mol%, while the preferred range is between 1 χ 1o ~ and varies by 1 χ 10 mol%. The reaction with a high concentration of catalyst not only means wasting the catalyst, but also has the effect of lowering the selectivity of the reaction. Even if the use of a solvent is not necessary, a solvent still has a beneficial effect if a solid substance takes part in the reaction. The allyl rearrangement reaction can be carried out in the atmosphere, but since, for example, the oxygen or moisture present in the air will decompose the catalyst and lower the reactivity and selectivity of the system, the reaction is preferably carried out in the absence of oxygen and / or moisture, for example in an atmosphere from molecular nitrogen or in a vacuum. There are no particular restrictions with regard to the reaction pressure. In general, the reaction can be carried out satisfactorily under atmospheric pressure. However, if the boiling point of the compounds (III) or (IV) is lower than the aforementioned suitable reaction temperature or the reaction is carried out while the compound (IV) is constantly driven off, as will be explained below, then the reaction is preferably under a carried out according to increased or reduced pressure.

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For example, the complex compound (I) can be deposited in Form on a carrier, such as aluminum oxide, silicon dioxide, diatomaceous earth, Pumice stone, Fuller's earth or the like or in the form of a solid catalyst preparation, for example together with a basic ion exchange resin, can be used. As mentioned above, the reaction of the present invention is one Equilibrium reaction. Regardless of whether the compound (III) or (IV) is used as the starting material, one is obtained Equilibrium mixture of compounds (III) and (IV). After this equilibrium is established, the reaction proceeds no longer gone. Therefore, in order to obtain the desired product compound, it must be separated from the equilibrium mixture. This separation can be carried out by any suitable separation method which is found to be suitable. Is the The boiling point of the product compound, for example the compound (IV), is lower than that of the starting material and can be separate this compound by distillation, then the reaction proceeds in one direction to the formation of the compound (IV), so that consequently the compound (IV) with a conversion of practically 100% can be obtained when the reaction is carried out while the compound (IV) is constantly coming out of the reaction system Will get removed. Of course, similar results can be obtained using other suitable methods for separating the compound (IV) will.

The following examples illustrate the invention without restricting it.

Examples of the synthesis of tungsten complex compounds and reaction examples

example 1

In 100 ml of an anhydrous benzene, 11.05 g of tungsten oxy-

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tetrachloride dissolved by adding 30 ml of methanol dropwise in an atmosphere of molecular nitrogen at room temperature. The solution is refluxed for a period of approximately 1 hour. After the reaction temperature has been reduced to 20 to 30 ⁰ C, ammonia gas is bubbled through the solution for a period of about 3 hours, followed by ammonium chloride abscheidet.Das reaction vessel is heated to drive out the excess methanol and other low-boiling fractions. The transesterification reaction is then carried out in such a way that 13 g of triethylsilanol and 6 ml of pyridine are added dropwise. The end point of the reaction corresponds to a distillate ^{temperature of 80 °} C. The reaction mixture is allowed to cool, whereupon the ammonium chloride crystals are filtered off in the air. The solvent is removed from the filtrate by vacuum distillation. This gives 22.2 g of WO (OSiAt.,). · ^ V

(Where Ät stands for ethyl / in the form of white needles. Yield: 85%. This compound is easily soluble in petroleum ether, n-hexane, benzene and acetone. A fluorescence X-ray analysis of this compound shows a Si / W ratio of 3.96. The purity is about 99% The infrared absorption spectrum of this compound by the KBr disk method is shown in Fig. 1. Fig. 2 shows the NMR spectrum of the compound measured in a cyclohexane solution at 100 MHz Cyclohexane is added, whereupon the changes obtained in the chemical shifts of the ty, β / ^ protons ^{are measured at 30 °} C. The results are shown in Fig. 3. In Fig. 3, the chemical shifts (ppm) of οί , β, Τ protons of pyridine from cyclohexane protons (vertical axis) plotted against the [pyridine / jpyridine + WO (OSiAtO , J molar ratio (horizontal axis). From FIG. 3 it can be seen that in the above product compound the pyridine koor is dinatively connected to tungsten via its nitrogen atom.

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Elemental analysis of the above product compound (C ₂₉ H ₆₅ NO ₅ Si ₄ W)

Calculated: C 43.32, H 8.15, N 1.74 Found: C 43.10, H 8.16, N 1.62

Reaction example 1

0.0067 mol% of the catalyst prepared according to Example 1, WO (OSiAt-O ₄ · N \ , is added to linalol, whereupon the

Reaction is carried out in an atmosphere of molecular nitrogen at 182 to 183 ⁰ C for a period of 1 hour. A gas chromatographic analysis of the reaction mixture shows that the conversion of the linalol is 22.3%. The selectivity for nerol and geraniol is 92.7%.

Example 2

In the manner described in Example 1, 10.9 g of tungsten oxytetrachloride and 30 ml of methanol are reacted in benzene with the introduction of ammonia. The transesterification reaction is then carried out in such a way that 13 g of triethylsilanol and 10 ml of cyclohexylamine are added. After cooling, the ammonium chloride crystals are filtered off, whereupon the solvent is removed from the filtrate by distillation in vacuo. The method described provides 21.6 g of WO (OSiAt-). * NH ₉ - / s ~ \ ((S) stands for one

Cyclohexy! Group) in the form of white plates. Yield: 82%.

The infrared spectrum of this compound is shown in FIG. That NMR spectrum in benzene at 100 MHz is given by Fig. 5,

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Cyclohexylamine is added to a solution of this compound in benzene. The change in the chemical shift of the d proton of cyclohexylamine:

is being measured. The result is shown in FIG. 6. In FIG. 6, the chemical shift Q (ppm) of the d-proton is of cyclohexylamines in benzene at 80 ⁰ C (vertical axis) against the [cyclohexylamine / [WO (OSiAt _{3) 4} + C ₆ H ₁ - | NH ₂ 3 Molar ratio (horizontal axis) plotted. It can be seen from FIG. 6 that in the above product compound the cyclohexylamine is coordinatively bonded to the tungsten through its nitrogen atom.

Elemental analysis of the product compound described above:

(C ₃₀ H ₇₃ NO ₅ Si ₄ W)

Calculated: C 43.72, H 8.93, N 1.70 Found: C 43.48, H 9.12, N 1.58

Reaction example 2

0.0047 mol% of the catalyst which has been prepared according to Example 2 is added to linalol. The reaction is carried out in a stream of molecular nitrogen at 190 to 193 ^° C. for a period of 3 hours. A gas chromatographic analysis of the reaction mixture shows that the conversion of the linalol is 32.3% and the selectivity for nerol and geraniol is 94.2%.

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Example 3

According to the procedure described in Example 1, 12.06 g of framoxytetrachloride and 35 ml of methanol are reacted in benzene with the introduction of ammonia. A transesterification reaction is then carried out in such a way that 10 ml of pyridine and a solution of 21 g of trimethylsilylacetate (synthesized according to the method according to Schuyten et al, J. Amer. Chem. Soc., 69, 2110 (1947)) in 20 ml of benzene can be added. The reaction is how to accept, then stopped when the distillate temperature reached 80 ⁰ C. The reaction mixture is passed over silica gel and filtered through a glass filter with suction. A benzene solution of WO (OSiMe _1. ) - · N ^ (Me stands for a methyl group) is obtained.

Reaction example 3

3 0 μΐ of the benzene solution of the catalyst WO (OSiMe ₃ J ₄ · N ^, prepared according to Example 3, are added to 5 ml of linalol, whereupon the reaction takes place in a ^ atmosphere at 190 to 193 ° C for a period of 2.5 A gas chromatographic analysis of this reaction mixture shows that the conversion of the linalol is 38.8%, while the selectivity for nerol and geraniol is determined to be 89.3%.

Example 4

Following the procedure described in Example 1, 14.2 g of framoxytetrachloride and 45 ml of ethanol are introduced into benzene implemented by ammonia. The transesterification reaction is then carried out in such a way that a solution of 25 g of trimethylsilanol in 12 ml of pyridine is added. The reaction mixture is then filtered through a glass filter. You get a

Γ-

Benzene solution of WO (OSiMe ₃ ) ₄ · Ν _χ Α

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Reaction example 4

40 μg of the benzene solution from WO (OSiMe.) Are added to 5 ml of linalol. * jsj. j,

given according to Example 4, whereupon the reaction is carried out in an N_ atmosphere at 185 to 187 ⁰ C for a period of 1 hour. A gas chromatographic analysis of the reaction mixture shows that the linalol conversion is 28.4% and the selectivity for nerol and geraniol is 88.6%.

Example 5

According to the procedure described in Example 1, 4.38 g of framoxytetrachloride and 15 ml of ethanol are reacted in benzene with the introduction of ammonia. The transesterification reaction is then carried out by adding a solution of 6.5 g of triethylsilanol in 2.7 g of dicyclohexylamine. The reaction mixture is then passed over silica gel and filtered through a gas filter. The solvent is distilled off from the filtrate in vacuo. This gives 9.68 g of WO (OSiAt-). * NH - (- (S)) ₉ in the form of white needles. The end-

loot: 83%.

Reaction example 5

0.0023 ml of the WO (OSiAt-) are added to linalol. NH -f- (S)) _o , produced

^{6 4} \ / ^Δ

is given according to Example 5, whereupon the reaction is carried out in an N "atmosphere at 180 to 183 ° C. for a period of 3 hours. A gas chromatographic analysis of this reaction mixture shows that the linalol conversion is 29.4% and the selectivity for nerol and geraniol is 93.1 % .

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Example 6

According to the procedure described in Example 1, 10.95 g Tungsten oxytetrachloride and 35 ml of ethanol in 1 x 50 ml of benzene Implementation of ammonia. Subsequent to the addition of 10 ml of pyridine will reflux the reaction for a period of time continued for 1 hour.

The reaction mixture is filtered through a glass filter. The solvent is distilled off from the filtrate obtained under reduced pressure. In this case, one obtains 13.75 g of WO (OCT) ₄ * N,

in the form of white needles. This product is relatively stable in solution, even in air, but its crystals must be in handled in an inert atmosphere. Fig. 7 shows the infrared absorption spectrum of this product in carbon tetrachloride solution, while Fig. 8 shows the NMR spectrum (100 MHz) of the same product in methylene chloride.

Elemental analysis (for C ₁ ^ H _{51 -NO 1} -W)

Calculated: C 34.00, H 5.49, H 3.05 Found: C 33.81, H 5.26, H 2.79

Reaction example 6

Linalol becomes 0.0021 mol% of the WO (OAt). · N)> given according to example 6. The reaction is carried out at 190 to 192 ° C for a Carried out over a period of 3 hours. A gas chromatographic analysis of this reaction mixture shows that the linalol conversion 30.0% and the selectivity for nerol and geraniol is 92.4%.

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Example 7

Following the procedure described in Example 1, 9.14 g of tungsten oxytetrachloride and 25 ml of tert-butanol are introduced into benzene implemented by ammonia. Subsequent to the addition of 10 ml of pyridine, the reaction is refluxed for a Period of 1 hour continued. When the reaction is complete, diatomaceous earth is added and the mixture filtered through a glass filter is filtered. A benzene solution of

WO (O-BUt) ₄ · N Λ (But stands for a tert-butyl group). Reaction example 7

30 μΐ of the benzene solution of WO (O-But) · N Λ are added to 5 ml of linalol

⁴ \ i J /

given according to Example 7, whereupon the reaction is continued in a ^ atmosphere at 190 ⁰ C for a period of 2 hours. A gas chromatographic analysis of this reaction mixture shows that the linalol conversion is 30.4% and the selectivity for nerol and geraniol is 90.3%.

Example 8

According to the procedure described in Example 1, 10.42 g Tungsten oxytetrachloride and 30 ml of methanol in benzene with introduction implemented by ammonia. Then the transesterification reaction is carried out in such a way that a mixture of 10 ml of pyridine and 25 ml tert-butanol is added. The reaction mixture is passed over silica gel and filtered through a glass filter. One obtains

a benzene solution of

WO (O-BUt) ₄ * N ^ S (

Butyl group).

WO (O-BUt) ₄ N ^ S (BUt stands for a tertiary

S09844 / 1093

Reaction example 8

20 μΐ of the benzene solution of WO (O-BUt) ₄ 'are added to 5 ml of linalol

given according to Example 8, whereupon the reaction in a ^ atmosphere is carried out at 195 to 197 ° C for a period of 3 hours. A gas chromatographic analysis of this reaction mixture shows that the linalol conversion is 36.8% and the selectivity for nerol and geraniol is 91.6%.

Example 9

According to the procedure described in Example 1, 21.94 g of framoxytetrachloride and 60 ml of methanol are reacted in benzene with the introduction of ammonia. Then the transesterification reaction is carried out in such a way that 60 ml of linalol and 15 ml of pyridine are added. The end point of the reaction corresponds to a distillate ^{temperature of 80 °} C. After the reaction mixture has cooled, it is passed over silica gel and filtered through a glass filter. A linalol solution of

WO (O-linalyl). ■ N Λ

(LinalyL stands for the linalyl group). Reaction Example 9 To 100 ml of linalol, 0.6 ml of the linalol solution of

WO (O-linalyl). 'N,) given according to Example 9. The reaction is carried out at 190 ⁰ C. A gas chromatographic analysis after a 1 hour reaction shows that the linalol conversion is 32.5% and the selectivity for nerol and geraniol is 94.3%. After 2 hours, the linalol conversion is 39.4% and the selectivity for nerol and geraniol is 91.9%.

50984A / 1093

Example 1O

According to the procedure described in Example 1, 9.60 g of tungsten oxytetrachloride and 30 ml of methanol are reacted in benzene with the introduction of ammonia. The transesterification reaction is then carried out in such a way that 40 ml of linalol and 10 ml of triethylamine are added. The reaction mixture is passed through silica gel and filtered through a glass filter. A linalol solution of WO (O-linalyl) is obtained. · NAt ₃ .

Reaction Example 1 0

50 μg of the linalol solution from WO (O-linalyl) are added to 5 ml of linalol . -NÄt_ given according to example 10. The reaction is carried out in a N "atmosphere at 200 ⁰ C for a period of 3 hours. A gas chromatographic analysis of the reaction mixture shows that the linalol conversion is 35.5% and the selectivity with regard to nerol and geraniol is 91.9%.

Example 11

If 1 molar equivalent of tert.-butanol is converted into a benzene solution (1.60

Mol%) of ^/ " ^{: =} \

WO (OSiAt ₃ ) ₄ N. Λ , manufactured according to Example 1, tensile

sets then takes place no ligand exchange, as shown in Fig. 9 seen (NMR spectrum at 30 ⁰ C of the reaction product which has been obtained in the manner that a molar equivalent of tert-butanol

to a benzene solution (1.60 mol%) of ^{/ ==} \

WO (OSiAt ₃ ) ₄ · Ν _χ )> ) is added). A reaction takes place in an autoclave by heating to 200 ^° C. for a period of 10 minutes. The NMR spectrum is then measured at 30 ° C. and 100 MHz. As can be seen from FIG. 10, the signal to be assigned to the WO-But appears at

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CA 1.82 ppm, while at the same time the signal corresponding to the -Si-CH - from The etching released is to be assigned to SiOH, at cfo.5O to 0.88 ppm

appears. The / ^ A

W N.,) linkage is not split off,

and even not if the reaction is carried out at 200 ⁰ C. Fig. 11 shows the signal of WO-But at 1.82 ppm on an enlarged scale.

In Fig. 11, the left signal is the WO (OBut) _ (OSiAt ₀ ) _o · N _v )>

2 3 3 ^ /

assign. The signal in the middle can be assigned to the WO (OBUt) ₂ (OSiAt ₀ ) ₂ * n '/>. The signal on the right belongs to

I- V

WO (OBUt) ₀ (OSiAt) * N ^ f.. A small signal further to the right corresponds to WO (OBut) .. N '··>. This NMR spectrum is confirmed

the formation of products of the formula WO (OSiAt ₀ ) "/ η · (OBut)" N, _{t /} Ä? where η stands for 1, 2, 3 and 4, respectively.

From an analysis of the intensities of the signals in the preceding In the NMR spectrum, the relative amounts can be assumed as follows:

WO (OSiAt ₃ J ₃ (OBUt) -N ^ ^ 5 WO (OSiAt) ₂ (OBUt) ₂ N. ^ : WO (OSiÄt ₃ )

(OBut).,. N Γ ~ λ: WO (OBut). . N \ Λ = 0.0322: 0.0272: 0.0086: 0.00048.

The transesterification reaction according to the invention is a sequence equilibrium reaction, where the equilibrium constants are as follows:

0.0044 for WO (OSiAt ₃ ) ₃ (OBut). N ^ /); 0.11 for

WO (OSiAt ₃ ) ₂ (OBu ^ _2. K \)> ; 0.041 for WO (OSiAt ₃ ) (OBut) ₃ . N ~ \ and 0.0072 for WO (OBut). N Λ.

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Reaction Example 11

0.0032 mol% of a benzene solution of

WO (OSiAt ₃ ) ₄ / n (O-But) _n . N _v β given to the (n = 1-4) mixture obtained according to Example 11. The reaction is carried out in an N “atmosphere at 190 to 192 ^° C. for a period of 3 hours. A gas chromatographic analysis of the reaction mixture shows that the linalol conversion is 36.8% and the selectivity for nerol and geraniol 9 is 6.2%.

Example 12

0.25 g (0.0019 mol) of triethylsilanol and 0.20 ml (0.0025 mol) of pyridine are dissolved in 5 ml of benzene. While the solution is at Room temperature is stirred, a solution of 0.16 g (0.00047 mol) of tungsten oxytetrachloride in 60 ml of benzene is added dropwise during added over a period of 20 minutes. The mixture is stirred for a period of 15 hours. Then she gets under Heat refluxed for 1 hour. After cooling, the insoluble components are filtered off, whereupon the solvent, etc. are removed from the filtrate by distillation. This gives 0.010 g (yield "=

^{2/6 %)} W

Reaction example 12

In Linalol becomes WO (OSiAt ₃ ). . N Λ, synthesized according to Example 12, dissolved in a concentration of 0.005 mol%. In a hermetically sealed vessel which has been flushed with nitrogen, the solution is ^{heated to 200 °} C. for a period of hours. A gas chromatographic analysis of the reaction

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mixture shows a linalol conversion of 24.1% and a nerol and Geraniol selectivity of 85.8%.

Example 13

The procedure described in Example 12 is repeated with with the exception that trimethylsilanol is used instead of triethylsilanol. Performing this example yields

WHERE (QSiMe) ₄ . N ~ £ reaction Example 13

Using WO (OSiMe). . N. λ, synthesized according to

game 13, the isomerization reaction of linalol to nerol and Geraniol carried out under the conditions described in reaction example 1. The linalol sales is 27.6% as well the selectivity of converted linalol with respect to nerol and geraniol 85.8%.

Example 14

7.2 g (0.080 mol) of trimethylsilanol are dissolved in 100 ml of benzene. While the reaction temperature door is maintained at 5 ⁰ C, 1.84 g (0.080 mole) of sodium metal are added. After the release of hydrogen has ceased, a benzene solution of 6.84 g (0.020 mol) of tungsten oxytetrachloride is gradually added dropwise so that the reaction temperature remains ^{between 5 and 10 ° C.} The reaction mixture is stirred as such for a period of 30 minutes. 4 ml of pyridine are then added and the mixture is refluxed with heating for a period of 2 hours. After cooling to room temperature, the reaction mixture is filtered to remove the insoluble

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remove all components. The solvent etc. will be distilled off from the filtrate. 0.78 g are obtained (yield =

^7/0%

WHERE (OSiMe ₀ ) .. ".

3 4 ^ //

Reaction example 14

The isomerization reaction of linalol to nerol and geraniol is performed using _{W0 (0SiMe)} . _Ν ^ = Λ _# synthesized according to

Example 14 was carried out. The reaction will be among the same Conditions as described in reaction example 2 are carried out. This gives results that are essentially with the results of Reaction Example 2 are comparable.

Example 15

3.42 g (0.010 mol) of tungsten oxytetrachloride are added to 50 ml of benzene added. 5 ml of a completely anhydrous methanol are added with stirring. The mixture is made by heating during a Held at reflux for 30 minutes. After cooling to room temperature, ammonia gas is passed through the reaction mixture pearled for a period of 3 hours. The excess methanol and benzene become azeotropic from the reaction mixture removed. A solution of 11.0 g (0.040 mol) of triphenylsilanol and 2 ml of pyridine in 150 ml of benzene is then added dropwise added. The released methanol is distilled off as an azeotrope with benzene. The insoluble components are then filtered off, whereupon the solvent etc. from the filtrate by distillation

removed. The residue obtained is t == ^

WHERE (OSiPh ₃ J _4. N \,

* - ~ y (Ph stands for a phenyl group).

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Reaction Example 1 5

In Linalol becomes WO (OSiPh). N. J , synthesized according to

game 15, dissolved in a concentration of 3x10 mol%, based on the linalol. In a hermetically sealed vessel which is flushed with nitrogen, the solution is ^{heated to 200 °} C. for a period of 4 hours. The linalol conversion is 34.8% and the selectivity of the converted linalol with respect to nerol and geraniol is 95.5%.

Example 16

50 ml of benzene are added to 3.42 g (0.010 mol) of tungsten oxytetrachloride and, with stirring, 5 ml of completely anhydrous ethanol are added. The mixture is made by heating for a period of time refluxed for 30 minutes. It is then allowed to cool to room temperature. Then dry ammonia gas passed through the reaction mixture over a period of 2 hours. After the excess ethanol azeotropes with benzene has been removed, a solution of 6.96 g (0.053 mol) of triethylsilanol and 2.8 g (0.010 mol) of tricyclohexylphosphine in 30 ml of benzene are added while the released ethanol is removed azeotropically with the benzene. After the reaction mixture on Has cooled to room temperature, the insoluble constituents are filtered off, whereupon the solvent etc. from the filtrate through Distillation can be removed. The rest is obtained

WHERE (OSiAt ₃ ) ₄ . Pl / S) 4-3. Reaction example 16

In Linalol becomes WO (OSiAt ₃ ). . .4 P / S) -4- _3, synthesized according to Example 16, in a concentration of 5 χ ~ 10 mol, based on

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the linalol, dissolved. In a closed vessel flushed with nitrogen, the solution is ^{kept at 200 °} C. for a period of hours. A gas chromatographic analysis of the reaction mixture shows that the linalol conversion is 35.8% and the selectivity of the converted linalol with respect to nerol and geraniol is 96.8%.

Examples 17-19

After tungsten oxytetrachloride reacted with ethanol as in Example 7 triphenylstibine, triphenylarsine and triphenyl bismuth, respectively added to aliquots of the reaction mixture to synthesize the appropriate catalysts. Using this Catalysts the isomerization reaction of linalol is carried out. The results are summarized in Table I.

The results of the isomerization reaction using conventional tungsten compounds including WO (OCH ₃ ) and WO (OC ₂ H ₅ ). are shown in Table II. It is found that when conventional compounds of this type are used, the dehydration of allyl alcohols predominates, which causes a considerable decrease in the selectivity with regard to the isomerized allyl alcohols.

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Table I.

Example starting game material

17th

Sb

(C ₆ H ₅ J ₃ As

(C ₆ H ₅ ) ₃ Bi

catalyst

WO (OAt) ₄ .Sb (C ₆ H ₅ ) WO (OAt) ₄ .As (C ₆ H ₅ ) WO (OAt) ₄ -Bi (C ₆ H ₅ )

Catalyst concentration, mol% based on the linalol

0.0038 0.0052 0.0023

% Sales of
Linalols

35.2
40.3
28.9

selectivity
regarding nerol
and geraniol

94.3
, 7
95.4

catalyst

0WO (OMe) ₄

Catalyst concentration, mol% based on the linalol

0.04 0.005

Table II

% Conversion of linalol

40.2 30.3

selectivity
regarding nerol
and geraniol

20.8
45.6

CO CD CD OO

Examples of the synthesis of tungsten compounds and reaction examples

Example 20

50 ml of one are added to 3.42 g (0.010 mol) of tungsten oxytetrachloride anhydrous benzene and, while stirring the mixture at room temperature, 5 ml of a completely anhydrous methanol added. The mixture is in an N - stream for a period of time treated at reflux for 30 minutes. After cooling to room temperature, dry ammonia gas is bubbled through the reaction mixture over a period of 2.5 hours. After this the excess methanol has been removed azeotropically with benzene, a solution of 6.7 g of triethylsilanol in 30 ml of benzene is added dropwise added while the liberated methanol is removed azeotropically with the benzene. After cooling down to room temperature the insoluble components filtered off. The solvent, etc. are removed from the filtrate by distillation. Receives one 7, Oq (yield = 97%) tetrakis (triethylsiloxy) tungsten oxide, a new connection.

This compound is a colorless viscous liquid that ^{boils at 202 °} C. (0.3 mmHg). The NMR spectrum of this compound (in a benzene solution, 100 MHz) is shown in FIG. The σ (ppm) values are plotted on the horizontal axis and the signal intensities are plotted on the vertical axis. The signal at 7.20 (cT) in Figure 12 is attributable to benzene as the solvent. The infrared absorption spectrum measured by sandwiching the above product between KBr disks is shown in FIG. In this figure, the permeabilities are plotted on the vertical axis and the wave numbers (cm) on the horizontal axis.

509844/1093

Elemental analysis

Calculated: C 39.77, H 8.34, Si 15.50, W 25.36 Found: C 40.01, H 8.45, Si 15.33, W 25.27 '

Reaction example 20

The tetrakis (triethylsiloxy) tungsten oxide, synthesized according to Example 1, is dissolved in linalol in a concentration of 3-10 mol%, based on the linalol. ^{The solution is kept at 200 °} C. for a period of 4 hours in a closed vessel flushed with nitrogen. A gas chromatographic analysis of the reaction mixture shows that the linalol conversion is 46.3% and the selectivity of the converted linalol with respect to nerol and geraniol is 71.9%.

Example 21

The procedure described in Example 1 is repeated, wherein Trimethylsilanol is used instead of triethylsilanol. Included one obtains 4.8 σ (yield = 86%) tetrakis (trimethylsiloxy) tungsten oxide, a new connection.

Elemental analysis for C ₁₂ H-DrOcSi ₄ W

Calculated: C 25.90, H 6.52, Si 20.18, W 33.03 Found: C 25.98, H 6.64, Si 20.00, W 32.75

Reaction Example 21

In Linalol is "tetrakis- (trimethyloxy) -wolframoxyd synthesized according to Example 21, in a concentration of 3 χ 10 mol%, based on the Linalol dissolved. The solution is stirred at 200 ⁰ C in a nitrogen-purged sealed reaction vessel held for a period of 4 hours.Gaschromatographic analysis of the reaction product shows that the

509844/1093

Linalol conversion 38.7% and the selectivity for nerol and Geraniol, based on the converted linalol, is 74.3%.

Example 22

The procedure described in Example 20 is essentially repeated, using triphenylsilanol instead of triethylsilanol is used. When carrying out this example, 12.5 g (yield = 96%) of tetrakis (triphenylsiloxy) tungsten oxide, get a new connection.

Elemental analysis for C ₇₂ H ^ ₀ O

Calculated: C 66.45, H 4.65, Si 8.63, W 14.12 Found: C 66.63, H 4.91 *, Si 8.42, W 13.98

Reaction Example 22

The tetrakis (triphenylsiloxy) tungsten oxide is dissolved in linalol in a concentration of 3x10 mol%, based on the linalol. ^{The solution is kept at 200 °} C. for a period of 3 hours in a closed reaction vessel flushed with nitrogen. A gas chromatographic analysis of the reaction product mixture shows that the linalol conversion is 30.2%. The selectivity for nerol and geraniol, based on the converted linalol, is determined to be 92.4%.

Example 23

7.20 g (0.080 mol) of trimethylsilanol are dissolved in 100 ml of benzene. 1.84 g (0.080 mol) of sodium metal are added with stirring. After the hydrogen release has stopped, that will The reaction vessel was cooled in an ice / water bath. While the

509844/1093

Reaction temperature is held in this manner on 5 to 10 ⁰ C, a benzene solution of 6.84 g (0.020 mole) WoIframoxytetrachlorid is added dropwise. As such, the reaction mixture is stirred for a period of 30 minutes and then refluxed for a period of 2 hours. The reaction mixture is cooled to room temperature. The insolubles are removed by filtration. The solvent etc. are distilled off from the filtrate. The product obtained is identified as tetrakis (trimethylsiloxy) tungsten oxide, which is the same compound that was obtained according to Example 21.

Reaction Example 23

Using tetrakis (trimethylsiloxy) tungsten oxide, synthesized according to Example 23, the isomerization reaction of linalol to nerol and geraniol is carried out under the same conditions carried out as in the case of Reaction Example 21. The results are essentially identical to the results of the Reaction Example 21.

Example 24

6.7 g of triethylsilanol are dissolved in 30 ml of benzene. While the reaction vessel is maintained at 5 to 10 ⁰ C, dry ammonia gas is bubbled through the solution. A benzene solution of 3.42 g (0.010 mole) tungsten oxytetrachloride is added. The mixture is stirred for a period of 1 hour and then refluxed for a period of 1 hour. After cooling to room temperature, the insoluble constituents are filtered off, whereupon the solvent etc. are removed from the filtrate by distillation. This is how

5098U / 1093

The product is kept as tetrakis (triethylsiloxy) tungsten oxide identified, which is the same compound that was obtained according to Example 21.

Reaction Example 24

In Linalol, the tetrakis (triethylsiloxy) tungsten oxide, syn-

-3 thetisiert according to Example 24, in a concentration of 3x10 mol%, based on the linalol, dissolved. ^{The solution is kept at 200 °} C. for a period of 3 hours in a closed reaction vessel which is flushed with nitrogen. A gas chromatographic analysis of the reaction product mixture shows that the linalol conversion is 28.7%. The selectivity for nerol and geraniol, based on the converted linalol, is 68.5%.

Examples of the isomerization of allylic alcohols using of the tungsten complex compounds or tungsten compounds according to the present invention as catalysts.

Manufacture of the catalyst (1)

In 150 ml of an anhydrous benzene, 21.94 g of tungsten oxytetrachloride are added dissolved. Under a stream of nitrogen and at room temperature, 60 ml of methanol are added dropwise. After this When the dropwise addition is complete, the reaction mixture is in a stream of molecular nitrogen for a period of time refluxed from 0.5 to 1 hour. Ammonia gas is then passed through the reaction mixture during a water bath Time span of about 3 hours sent through.

Without removing the precipitated ammonium chloride, it becomes a solution of 60 ml of linalol in 15 ml of pyridine is added, followed by heating. The methanol and the benzene are called azeotropes

B098U / 1093

Mixture is distilled off, whereupon the reaction is ended after the distillate temperature has reached ^{80 0 C.} The reaction mixture is allowed to cool and then filtered through a glass filter with suction. A linalol solution of WO (O-linalyl) is obtained. Py (Py stands for pyridine).

Manufacture of the catalyst (2)

Using dry Hyflo-Supercel (available from Johns Manville Products, USA) as a filter aid, the linalol solution from WO (O-linalyl). . Py according to the preparation of the catalyst (1) filtered through a glass filter with suction. In this way, a purified linalol solution of WO (O-Linalyl) . . Py can be obtained.

Manufacture of the catalyst (3)

The linalol solution from WO (O-Linalyl). . Py according to manufacture the catalyst (1) is passed through silica gel and filtered through a glass filter with suction. This is how you get one purified linalol solution from WO (O-linalyl). . Py.

Manufacture of the catalyst (4)

10.95 g of tungsten oxytetrachloride are dissolved in 150 ml of benzene. In a stream of nitrogen and at room temperature, 35 ml Ethanol added dropwise. After the dropwise addition is completed, the mixture is poured in a nitrogen stream during refluxed for a period of 0.5 to 1 hour. Then ammonia gas is passed through the mixture while on a water bath about 3 hours.

509844/1093

Following the addition of 5 g of pyridine, the mixture is heated, whereupon the ethanol and benzene are removed azeotropically. The reaction is ended when the distillate temperature has reached ^{8 0 0 C.} The reaction mixture is then allowed to cool and filtered through a glass filter with suction. This gives a benzene solution of WO (OÄt) .. Py.

Manufacture of the catalyst (5)

Using the method as described in connection with the preparation of the catalyst 4, 11.2 g of tungsten oxytetrachloride are obtained dissolved in 150 ml of benzene, followed by the dropwise addition of 40 ml of ethanol. After the drop by drop The addition is complete, the reaction mixture is refluxed for a period of 0.5 to 1 hour. Then on ammonia gas was passed through the reaction mixture over a period of approximately 3 hours in a water bath.

A solution of 9 g of triphenylphosphine in 50 ml of benzene is then added, followed by heating. The ethanol and benzene are removed by azeotropic distillation. The reaction is complete when the Destxllattemperatur reaches 80 ⁰ C. The reaction mixture is allowed to cool and filtered through a glass filter with suction. This gives a benzene solution WO (OAt). . PPh., (PPh-. Stands for triphenylphosphine).

Method of identifying the structure of the catalyst

From the benzene solution of WO (OAt). . Py obtained according to the preparation of the catalyst 4, the solvent is completely removed, resulting in white needles. These crystals are in

509844/1093

Methylene chloride dissolved, followed by the solution by NMR spectroscopy is analyzed. The NMR spectrum shows the formation of a

W N Λ bond. As for the catalyst concentration,

so the crystals can be weighed, a quantitative determination however, by fluorescent X-ray analysis is easier.

Example 25

0.0035 mol% of the benzene solution of WO (O-linalyl) are added to 50.0 g of linalol . . Py added according to the preparation of the catalyst 3, whereupon the reaction is ^{carried out in an atmosphere of molecular nitrogen and at room temperature at 95 °} C. for a period _of 2.5 hours. A gas chromatographic analysis of the reaction mixture shows that the linalol conversion is 30.4%, while the selectivity for nerol and geraniol is increasing

96.7%, based on the converted linalol, is determined. the Distillation of the reaction mixture under reduced pressure gives

43.8 g of a distillate that boils at 45 to 85 ° C (1 mmHg). The linalol: nerol; geraniol ratio of this fraction is 70:18:12. This distillate is heated in an atmosphere of molecular nitrogen to 200 ^° C. for a period of 18 hours and then analyzed by gas chromatography. The linalol: nerol: geraniol ratio of this product is unchanged compared to the corresponding ratio of the original distillate, which shows that there is no distillation of the catalyst

WO (O-linalyl) ₄ . Py took place.

Comparative example 1

0.026 mol% of n-butyl-o-vanadate (VO (0-Bu ¹¹ K)) are added to 100 g of linalol, whereupon the

5098 4 4/1093

Mixture is ^{reacted at 200 0} C for a period of 1 hour. A gas chromatographic analysis of the reaction product mixture shows that the linalol conversion is 19.4%, while the selectivity for nerol and geraniol is determined to be 98.0%. Distillation of the same mixture under reduced pressure gives 90.3 g of a distillate which ^{boils at 51 to 93 °} C. (2 mmHg). The linalol: nerol: geraniol ratio of this fraction is 81: 7: 12. This distillate is heated in a nitrogen atmosphere over a period of 18 hours to 2 00 ⁰ C and then analyzed by gas chromatography. In this case the linalol: nerol: geraniol ratio is 75: 9: 16. The difference is due to a distillation of n-butyl-o-vanadate. A determination of the V content by atomic absorption spectrometry shows that the vanadium is present in a concentration of 18 ppm.

Examples 26 to 39

According to the procedure described in connection with the preparation of the catalyst 3, WO (OR). L (where R is allyl alcohol and L is an amine) dissolved in the corresponding alcohol to synthesize a catalyst. Using the Different catalysts, which have been prepared in the manner described above, the isomerization of different Alcohols carried out. The results are shown in Table III (an autoclave is used if the boiling point of the starting alcohol is lower than the reaction temperature, with all reactions being carried out in a nitrogen atmosphere will).

9 844/1093

Φ Ti ■ Η

-rl > + J

φ · Η ad IO +> -P

-μ cd Dl

I. in β ω O H -H tn H
approx O Τ5 C -P , CU 3 fj IO Λ Tue O c4 U O I. + J CD φ pi

ca tn β

in cn

ro

ο +> ro co cn

UO ο +3

o cn

τ— VD

ο 4J O CO

cn ir- in

UO O Τ3 CJd

ο 4J ο + J ο +)

O CO O CO UXO

r- ο ο

t - VO CM ro. CM ¹ O

M. I. O dP in CM tn co in O co O β -H I. in ^ J * • co . r— co "ro T— I. +> φ -P CM O O O ο ' O O approx approx N approx O CM O O O O O O O -P CQ G • ■ te CD > i O -P O O O O O O O Ai

pi

ro

I Φ VO r- co cn O ro CM -H-H CM CM CM CM m ro Φ Οι

B098A4 / 1093

Example

RO -

L =

Catalyst concentration, MoI- * * 2

Table III (continued)

Starting alcohol reaction * ³

conditions

Production turnover selek alcohol * 5 * 6 tivi-

ity * 7

O CD CO -P-

O CD CO

33

34 35

36 37 38

\ = a / 0.0150

39 ( 7-CH-CH = CH ₂ ^{N == /} OH

S> 0.0035

NH ₂ - (S.

0.0035

/ ^ Λ 0.0030

0.0025

0.0040

OH

7 \ o, oo35 AaAa ₀ ^

OH

165 ° C
10 hours

195 ° C
3 hours.

3 hours.

3 hours. '

i180 ° C
8 hours

OH

OH

OH

CH-CH = CH ₂₁₈₀ O ₀ f \. _{CK = cu} _

OH 3 hours

21.6 96.6 53.8 95.1

40.6 96.3

29.2 97.5

32.7 91.2 27.1 92.3 '

CH = CH-CH ₂ OH 35.8 96.0

CO CD OO

Example 40

The linalol solution from WO (L-Linalyl). Py according to manufacture of the catalyst 1 is diluted with linalol to a concentration of 0.0045 mol%, whereupon in an atmosphere of molecular Nitrogen the reaction is carried out at 195 ° C for a period of 1 hour. A gas chromatographic analysis of the Reaction product mixture shows that the linalol conversion is 14.3%, while the selectivity for nerol and geraniol is found to be 51.6%.

Example 41. '

The linalol solution from WO (O-Linalyl). . Py according to manufacture of the catalyst 2 is diluted with linalol to a concentration of 0.0035 mol%, whereupon in a nitrogen atmosphere the Reaction is carried out at 185 ° C for 1.5 hours. A gas chromatographic analysis of the reaction mixture shows that the linalol conversion is 18.6%, while the selectivity with regard to nerol and geraniol is determined to be 85.5%.

Example 42

Linalol becomes 0.0025 mol% of a benzene solution of WO (OAt). Py, described in connection with the preparation of the catalyst 4, was added, whereupon the reaction is ^{carried out in an atmosphere of molecular nitrogen at 190 °} C. for a period of 3 hours. A gas chromatographic analysis of the reaction product mixture shows that the linalol conversion is 30.0%, while the selectivity for nerol and geraniol is determined to be 91.4%.

50984W109 3

Example 43

0.003 mol% of a benzene solution of WO (OBu) ₄ -Py prepared from Wolfraitioxytetrachlorxd and tert-butanol according to the method of the preparation of the catalyst 4 are added to linalol. In an atmosphere of molecular nitrogen, the reaction is carried out at 190 ^° C. for a period of 1.5 hours. The reaction product mixture is analyzed by gas chromatography. The linalol conversion is 29.6%, while the selectivity for nerol and geraniol is found to be 54.8%.

Example 44

The benzene solution of WO (OBu) ₄ . Py, described in Example 43, is purified with silica gel as has been described in connection with the preparation of catalyst 3, after which it is added to linalol in an amount of 0.003 mol%, based on the linalol. In an atmosphere of molecular nitrogen, the reaction is carried out at 190 ^° C. for a period of 3 hours. The reaction mixture is analyzed by gas chromatography. The linalol conversion is 34.9%. The selectivity for nerol and geraniol is found to be 86.2%.

Example 45

The WO (O-Geranyl). . Py, made as in connection with the Preparation of the catalyst 3 described, is with geraniol up to a concentration of 0.0025 mol%, based on the geraniol, diluted, followed by the addition of 20 ml of polyethylene glycol as a high-boiling solvent. The solution obtained is placed in a three-necked flask fitted with a thermometer and a 30 cm distillation column. After the reaction apparatus Has been purged with molecular nitrogen, the reaction will

5098 ^^ / 1093

carried out with heating to 195 to 197 ⁰ C under a reduced pressure of 600 to 650 mmHg. The Isomerisxerungsprodukt, namely linalol, is obtained as a fraction (94.5 g), boiling at 185-190 ⁰ C (600 to 650 mmHg). Gas chromatographic analysis shows that fraction ^{1 has} a purity of 97.8%. The yield, based on the geraniol, is 92.4%.

Example 46

As in the case of Example 30, the catalyst WO (OPr ¹¹ ) .NÄt- (Pr stands for n-propyl) is added to 3-methyl-1-penten-3-ol to a concentration of 0.005 mol%, whereupon the addition of 20 ml squalane follows. In an autoclave flushed with nitrogen, the reaction is carried out at 180 ^° C. for a period of 5 hours. The conversion of 3-methyl-1-penten-3-ol is found to be 32.6%. The selectivity for cis- and trans-3-methyl-2-penten-1-ol is 94.1%. Subjecting this reaction mixture to distillation under reduced pressure in a stream of nitrogen, 32.6 g of the starting material, namely 3-methyl-1-penten-3-ol, and 14.9 g of cis- and trans-3-methyl are obtained -2-penten-1-ol. Yield = 29.8%.

50 g of 3-methyl-1-penten-3-ol are added to the distillation residue indicated above, whereupon the reaction is carried out in a similar manner in a nitrogen atmosphere and at 180 ^° C. for a period of 5 hours. In this case, the conversion of 3-methyl-1-penten-3-ol is 31.8%, while the selectivity for cis- and trans-3-methyl-2-penten-1-ol is found to be 94.3% .

5 09844/1093

- 5ο -

Example 47

The Lxnalol solution from WO (O-Lxnalyl). . PPh ₃ prepared according to the preparation of Catalyst 5 is diluted to 0.0045 mol%, and the reaction is carried out in a nitrogen atmosphere at 195 ° C. for a period of 2 hours. A gas chromatographic analysis of this reaction mixture shows that the linalol conversion is 33.9%, while the selectivity for nerol and geraniol is determined to be 90.2%.

Comparative Examples 2 to 9

The results of isomerization reactions with ligand-free catalysts such as WO (OR) ₄ are shown in Table IV. These catalysts are prepared essentially by the method described by Funk et al in "Z. Anorg. Chem.", 304, 239-240 (1960).

5098A4 / 1093

Table IV

Ver catalyst and starting same catalyst alcohol example concentration, mol ~% * 3 * * 2

WO (OMe) ₄ 0.02 WO (OAt) ₄ 0.02 W0 (0Pr ^iso ) ₄ 0.02 W0 (0Bu ^fc ) ₄ 0.02 WO (OAlIyI) ₄ 0.04 W0 (0Lina-0.04

W0 (0Pre- 0.06

W0 (0Gera- 0.06 reactive production alcohol
condition- * 5
worked
* 4

13O ⁰ C
10 min.

65 ° C
60 min.

100 ⁰ C
30 min.

65 ⁰ C
60 min.

100 ⁰ C
30 min.

OH

OH

ti?

Sales,
%
* 6 , 96 Selek
tivi
activity ^ '
* 7 I.
Ul
VO 8th , 2 27.1 I. 37 , 6 22.4 65 12.0 lOO ,1 0 12, , 2 28.4 40, 9 20.8 18 5 25.4 50, 17.5

ro

ΟΙ

-Λ CD

cn co co

Example 48

50 ml of benzene are added to 3.42 g (0.010 mol) of tungsten oxytetrachloride added, whereupon 5.3 ml of anhydrous methanol are added with stirring. The reaction mixture is refluxed in a stream of nitrogen for a period of 30 minutes, after which, after cooling to room temperature, dry ammonia gas was passed through the mixture over a period of 5 hours is pearled. The excess methanol becomes from this reaction mixture removed azeotropically with the benzene. While a mixed solution of 2.6 g (0.020 mol) of triethylsilanol and 2 ml of pyridine in 30 ml of benzene is added, the methanol which is released during the ester exchange with the triethylsilanol becomes azeotropic removed with the benzene. After the addition of the triethylsilanol has ended and no more methanol has been drawn off with the distillate the heat is stopped and the reaction mixture is allowed to cool to room temperature. The rainfall are removed from the mixture by filtration. The benzene and the excess of triethylsilanol are removed from the filtrate distilled off under reduced pressure. The residue obtained is:

WO (OCH ₉ CH ) ₀ [OSi (CH ₀ CH.,) "] _0. N _x a

Using this compound in an amount of 3 10 mol%, the isomerization reaction of linalol is carried out. 8.0 g of the above-described catalyst compound are dissolved in 50 ml of anhydrous benzene, and 20 ml of the resulting solution are added to 31 g of linalol. In a reaction vessel flushed with nitrogen, the reaction is carried out at 200 ^° C. for a period of 7 hours. The reaction mixture is then analyzed by gas chromatography. The linalol conversion is 37.3%, while the selectivity for nerol and geraniol, based on the converted linalol, is 93.2%.

Β0984Λ / 1093

Examples 49 to 51

Using the catalysts synthesized by methods similar to the method described in Example 48, is the isomerization of linalol to nerol and geraniol in one nitrogen-purged kettles at predetermined temperatures for predetermined periods of time. Table V shows the results of gas chromatographic analysis. In the table, "sales" means the percentage of sales of linalol, while under "selectivity" the percentage of selectivity with respect to nerol and geraniol, based on the converted linalol, increases understand is.

Table V

At- catalyst cat- reac- reac- conversion, selecti-

play lysation% vity,%

gate contemporaneous time,

centra- hour

tion, door,

Mole%, ⁰ ° C

related to

Linalol

49 WO [OSX (CH ₃ ) ₂ PhJ ₄ .N ⁷ J ^ 3x10 " ³ 200 7 34.8 95.1

50 WO [OSi (CH ₂ CH ₃ ) ₃ ] ₄ • """35.8 95.3 N (CH ₂ CH ₃ J ₃

51 WO [OSi (CH-.CH, J,] - · """36.7 94.8 PPh ₃ ^J - ^J

pin in the table, Ph stands for a phenyl group)

509844/1093

Examples 52 to 58

Using the catalyst prepared according to Example 1 the following isomerization reactions are carried out in closed vessels flushed with nitrogen:

R "- C - C = CH ₂ R ¹ -C = C- CH ₂ OH

OH

The reaction mixtures obtained are subjected to gas chromatography analyzed. The results are summarized in Table VI. In the table, "Sales" means the percentage of sales the corresponding starting alcohol, while under "Selectivity" the percentage of the selectivity with respect to the corresponding product alcohol, based on the starting alcohol. "Catalyst concentration" means the concentration of

/ = r \
WO (OSiAt ₃ ), · N ^ ή (where Ät means ethyl), based on the

Starting alcohol.

509844/1093

Table VI

At- starting alcohol cat- reac- conversion, selectiv-

game lysation% act,%

tor- tem-

concentra-

door,

tion, ⁰ C

Mol%

52 Isophytol 2x1θ " ³ 200 10 21.5 94.3

53 3-butyn-2-ol 5x10 ^-3 150 4 16.8 93.8

54 1-Vxnylcyclohexanol 5x10 ~ ³ 150 4 13.8 91.4

55 1-phenyl-2-propen-1-ol 3x10 ^-3 180 5 30.2 93.1

56 cyclonerolidol 4x10 ~ ³ 200 3 35.0 90.7

QC *

57 nerolidol 3x10 150 4 13.8 87.4 2-methyl-3-buten-2-ol 3x1 θ " ³ 150 3 12.9 82.2

58 3 -ethyl 1-7 -methyl-1,6- _.

octadien-3-ol 3x10 180 3 40.3 75.6

Example 59

Using the catalyst prepared according to Example 1 is Geraniol isomerized to linalol. It becomes 40 g of geraniol

WO (OSiAt-). · N * y / ^{111 to} a concentration of 2 10 mol%, based on the geraniol, was added, followed by the addition of 4 g of polyethylene glycol. In a three-necked flask provided with a distillation column, said piston is sufficiently purged with nitrogen molekluarem, the above mixture is heated to an internal temperature of 180 ⁰ C. The pressure in the column head is kept at 100 to 200 mmHg. The reaction is carried out under rectification conditions until no more distillate emerges. In this way, 37 g of linalol are obtained as a distillate (yield 93%). The purity of this linalol

B0984A / 1093

is determined to be 98.7%. Examples 60 to 66

Using the catalyst prepared according to Example 1 the following isomerization reactions are carried out in closed vessels flushed with nitrogen:

R ₁ -C = C-CH ₂ OH> R ₁ -CC = CH ₃

OH

Table VII summarizes the results of the gas chromatographic analyzes of the reaction mixtures. In the table means "Catalyst concentration" is the concentration of the catalyst, based on the starting alcohol, while "Conversion" is the percentage the conversion of the starting alcohol is to be understood. "Selectivity" means the percentage of selectivity with respect to the corresponding Product alcohol.

509844/1093

_ 65 _

Example starting game alcohol

Catalysis

sator

focus

tration,

Mol%

Table VII

Reac-reac conversion,
tion%
Temporary time,
pera- hour
door, ° C

Crotyl alcohol 5x10 Prenyl alcohol 2x10 Farnesol 6x10 Phytol 4x1

3,7-diethyl- 2x10 2,6-octadiene-

-3 -3 -3

Γ ³ -3

2,3-dimethyl 5x10 2-butene-1 oil

Geranylgera- 2x10 niol

-3

-3

Example 67

150
150
200
200
200

160
200

3 3 1 1 2

3 5

Selectivity, p

15.0 92.3 20.1 94.8 43.5 96.2 35.8 95.7 48.8 97.3 20.3 91.4 42.5 92.2

WO [bsi (CH ₂ CH ₃ ) ₃ 3 ₄ · N, )> according to Example 1 is added to 50.0 g of linalol up to a concentration of 3 × 10 mol%, based on the linalol. The reaction is carried out at a temperature of 200 ^° C. in a closed vessel flushed with nitrogen
carried out over a period of 2 hours. After cooling down
5 ml of polyethylene glycol (average molecular weight 400) are added to the reaction mixture. The mixture is distilled in a rotary flask under a reduced pressure of 1 mitiHg. This gives 48.8 g of a distillate which boils at 45 to 85 ⁰ C. Analysis of the distillate by gas chromatography shows that
the linalol: nerol: geraniol ratio is 77.9, 8.4: 13.7. These

509844/1093

The fraction is heated again in a closed vessel flushed with nitrogen to 200 ^° C. for a period of 18 hours and then examined by gas chromatography. The linalol: nerol: geraniol ratio is, as is determined, completely identical to the ratio given above. This shows ^that WO [bsi (CH ₀ CHO J „· N, /) cannot be achieved by simple distillation

^u Δ i Jr 4 ^ ¹ J

is distilled off, but can easily be separated from the reaction mixture.

Comparative example 10

To 15.4 g Linalol 0.12 g tungsten trioxide are added, and the mixture is heated to 140 ⁰ C in a nitrogen-purged sealed vessel. The reaction mixture is then analyzed by gas chromatography. * The results are shown in Table VIII. In the table, “conversion” means the percentage of the conversion of linalol, while “selectivity” means the percentage of selectivity with regard to geraniol and nerol, based on converted linalol.

Reaction
time, hours Sales,
% Selectively
% 0.75 0.83 37.1 2.00 2.78 39.2 5.80 5.76 39.3

Comparative Example 11

2.31 g of tungsten trioxide are added to 15.4 g of linalol, whereupon with stirring in a closed reactor flushed with nitrogen

5098A4 / 1093

Reaction time, 1.50 sales Hours. 2.25 3.00 16.5 5.25 37.3 54.2 85.9

tion vessel the mixture is heated ^{to 140 0 C.} The reaction mixture is then examined by gas chromatography. The results of the analysis are shown in Table IX. “Conversion” and “selectivity” have the same meanings as have been given above.

Table IX

Selectivity,

43.7 32.9 19.9 0.75

Comparative example 12

0.95 g of tungsten hexaphenoxide are added to 15.4 g of linalol. In a closed reaction vessel flushed with nitrogen, the mixture is ^{heated to 180 °} C. for a period of 5 minutes. The reaction mixture is then analyzed by gas chromatography. When this comparative example is carried out, although the conversion of linalol is 83.8%, neither geraniol nor nerol is found in the reaction product.

Comparative Example 13

While 4.54 g of tungsten hexachloride in 150 ml of an anhydrous benzene are stirred, 20 ml of acetylacetone are added. The reaction mixture is refluxed for a period of 5 hours whereupon it is allowed to cool to room temperature. Subsequent to the addition of a further 17.7 g of linalol

50984 W1093

_ 68 _

the benzene and excess acetylacetone are distilled off under reduced pressure. 5 ml of linalol are added to 1 ml of the residue. The mixture is then heated in a closed reaction vessel flushed with nitrogen to 180 ° C. for a period of 5 minutes. The reaction mixture is then analyzed by gas chromatography. The linalol conversion is 34.3%, while the selectivity for geraniol and nerol, based on the converted Linalol, is determined to be 24.9%.

Comparative example 14

Tetramethoxy-tungsten oxide, WO (OMe)., Is synthesized according to the method described by H. Funk et al (cf. Z. Anog. U. General Chem., 304, 238 (1960)). Using this compound as a catalyst, the isomerization reaction of linalol to geraniol and nerol is carried out. A linalol solution containing the catalyst in a predetermined concentration is prepared, whereupon the solution is heated to a predetermined temperature for a predetermined period of time in a reaction vessel purged with nitrogen. The reaction mixture obtained is analyzed by gas chromatography. The t · ¹ results obtained are summarized in Table X. “Conversion” and “selectivity” have the same meanings as have been given above.

S0984A / 1093

React
functional
tem-
pera-
temperature, ° C Table X Sales,
% Selectivity,
% Catal
gate concentra
tration
(Mol%, be
pulled up
Linalol) 65 Reak
ions
Time,
Min. 8.96 27.1 0.02 100 60 37.2 22.4 0.02 130 30th 65.6 12.0 0.02 180 10 100 0 0.02 65 2 12.1 28.4 0.04 100 60 40.2 20.8 0.04 65 30th 18.9 25.4 0.06 100 60 50.5 17.5 0.06 65 30th 28.2 23.1 0.08 100 60 48.4 19.4 0.08 30th

S09844 / 1093

Claims (31)

- 70 claims where R, R, R or R ₄ stand for hydrocarbon groups, substituted hydrocarbon groups or groups of the formula S 5, "" £ 51t \ - where R ₅ , R ₆ or R _{7 represent} a hydrocarbon group which can optionally be substituted, where R ₁ , R 1, R ₃ and R _{4 can be} identical or different and, if two or more of the groups R ₁ , R ", R ₃ and R _{4 are} hydrocarbon groups, regardless of whether they are substituted or unsubstituted, two such groups can form a cyclic structure together with the adjacent tungsten and oxygen atoms in the formula, while L is a monodentate or polydate ligand , which contains a typical element of group V of the Periodic Table of the Elements and is coordinatively linked to the tungsten atom in the formula via this element, and η is a value between 1 and the number of tungsten atoms that can be coordinated with the ligand L. 2. Tungsten compound of the general formula: WO (OR ₁ ) (OR ₂ ) (OR ₃ ) (OR ₄ ) (II) wherein R ₁ , R ₂ , R ₃ or R _{4 represent} a hydrocarbon group, a substituted hydrocarbon group or a group of the formula: -Si R ₆ , where at least one substituent of the formula: ^R 7 509844/1093 -Si-R corresponds to, where R ₅ , R-. or R ₇ hydrocarbon are groups or substituted hydrocarbon groups and R., R ₂ , R ₃ and R. can be identical or different, and where, if two or more of the groups R., R ₃ , R ₃ and R. are hydrocarbon groups, regardless of whether if they are substituted or unsubstituted, two such groups can form a cyclic structure together with the adjacent tungsten and oxygen atoms in the formula. 3. Tungsten complex compound of the general formula (I) according to claim 1, characterized in that R., R_, R ₃ , R., R-, R _fi and R _{7 represent} a hydrocarbon group from the class consisting of alkyl groups with 1 to 20 carbon atoms, alkenyl groups with 2 to 20 carbon atoms, cycloalkyl groups with 3 to 10 carbon atoms, cycloalkenyl groups with 3 to 10 carbon atoms, aryl groups with 6 to 10 carbon atoms, aralkyl groups with 7 to 20 carbon atoms and alkylaryl groups with 7 to 20 carbon atoms. 4. Tungsten compound of the general formula (II) according to claim 2, characterized in that R ₁ , R ", R ₃ , R ₄ , R ₅ , R _g and R _{7 represent} a hydrocarbon group from the class consisting of alkyl groups with 1 up to 20 carbon atoms, alkenyl groups with 2 to 20 carbon atoms, cycloalkyl groups with 3 to 10 carbon atoms, cycloalkenyl groups with 3 to 10 carbon atoms, aryl groups with 6 to 10 carbon atoms, aralkyl groups with 7 to 20 carbon atoms and alkylaryl groups with 7 to 20 carbon atoms. 50984A / 1093 5. Tungsten complex compound of the general formula (I) according to claim 1, characterized in that the ligand L is a typical Contains element selected from the class consisting of N, P, As, and Bi. 6. Tungsten complex compound of the general formula (I) according to claim 1, characterized in that L is one of the following Formulas corresponds to: ^R 10 Ty - Q " where Ty is a typical element selected from the class consisting of N, P, As and Bi, R _g , R _g and R .. _{Q are} from the class consisting of hydrogen atoms, alkyl groups having 1 to 20 carbon atoms , Cycloalkyl groups with 3 to 10 carbon atoms, alkenyl groups with 2 to 20 carbon atoms, cycloalkenyl groups with 3 to 10 carbon atoms, aryl groups with 6 to 10 carbon atoms, aralkyl groups with 7 to 20 carbon atoms and alkylaryl groups with 7 to 20 carbon atoms, where Rg, Rg and R ^ _{0 can be the} same or different, B an atom or a 509844/1093 Represents a group of atoms which is linked to the element Ty by a double bond, Q is an atomic group which together with Ty forms a cyclic structure, A, A ¹ and Q ^{1 represent} atoms or groups of atoms which together form a cyclic structure, and Q. "is a group of atoms which together with Ty forms a polycyclic structure. 7. Tungsten complex compound of the general formula (I) according to claim 1, characterized in that L is selected from the class is made up of primary, secondary and tertiary monoamines, polyamines, Schiff’s bases, imines, nitriles and isonitriles consists. 8. Tungsten complex compound of the general formula (I) according to claim 1, characterized in that L is selected from the class which is composed of a primary amine selected from methylamine, ethylamine, propylamine, ß-ethoxyethylamine, butylamine, cyclohexylamine, Aniline and naphthylamine, a secondary monoamine selected from dimethylamine, diethylamine, dibutylamine, dicyclohexylamine, Methylaniline, methylcyclohexylamine, piperidine, morpholine and pyrrolidine, a tertiary amine selected from trimethylamine, Triethylamine, ethyldibutylamine, tricyclohexylamine, dimethylaniline, Pyridine, picoline, quinoline, isoquinoline, N-methylpyrrolidine and N-methylmorpholine, ethylenediamine, pyrazine, piperazine, pyrimidine, Triethylenediamine, 1,8-diaza-bicyclo £ 5.4, (TJundecen-7, Polyäthyleniminen as well as ion exchange resins with a large number of amino groups within the molecules. 9. Tungsten complex compound of the general formula (I) according to claim 1, characterized in that L is selected from the class $ 09844/1093 is derived from triphenylphosphine, tributylphosphine, tricyclohexylphosphine, Triphenylstibine, triphenylarsine, tributylarsine as well Triphenyl bismuth exists. 10. Tungsten complex compound of the general formula (i) according to claim 1, characterized in that R .., R ₂ , R ₃ and R ₄ each represent hydrocarbon groups. 11. tungsten complex compound of the general formula (I) according to claim 1, characterized in that at least one of the substituents R _1, R _3, R ₃ and R ₄ '.C t ₃₁ HrS _stand, while the remainder ^{Each R} 7 is a hydrocarbon group. 12. Wolframkomplexverbindurfg of the general formula (I) according to claim 1, characterized in that * that R ₁ , R ₂ , R-, and R ₄ each for _y R ₅ -Si - Rg groups stand. 13. Tungsten compound of the general formula (II) according to claim 2, characterized by being of the formula WO (OSi- Rg) _1n (OR ₁ ) ^ _1n (II) corresponds to, wherein R ₁ , R-, R _fi and R ₇ are selected from the class consisting of hydrocarbon groups and substituted hydrocarbon groups, m is an integer corresponding to a value from 1 to 4 inclusive, where, if m is a number of 2 or more that <, R ₁ . OSi'-R _fi groups equal or different 509844/1093 can be different, and, if m corresponds to a number of 2 or below, the OR groups have a cyclic structure together with the neighboring tungsten atom in the formula. 14. Tungsten compound of the general formula (II) according to claim 2, characterized in that R ₁ , R ₂ , R ₃ and R. each represent .--- ^R 5
-Si * "■ —R _fi groups are available. 15. Mixture of a tungsten complex compound of the general formula (I) and a tungsten compound of the general formula (II). 16. Process for the preparation of a tungsten complex compound of general formula (I), wherein [WO (OR ₁ ) (OR ₂ ) (OR ₃ ) (OR ₄ )] _n L (II) where R ₁ , R ₂ , R or R _{4 are} substituted for hydrocarbon groups Hydrocarbon groups or groups of the formula _ ^ 5 -Si — R, stand, where Rr, R _g or R ^ represent a hydrocarbon group which can optionally be substituted, where R ₁ , R_, R_ and R. can be identical or different and, if two or more of the groups R ₁ , R ₂ , R ₃ and R _{4 are} hydrocarbon groups, regardless of whether they are substituted or unsubstituted, two such groups can form a cyclic structure together with the adjacent tungsten and oxygen atoms in the formula, while L is a monodentate or polydentate ligand, which is a typical Element of group V of the Periodic Table of the Elements 5098ΛΛ / 1093 contains and is coordinatively linked to the tungsten atom in the formula via this element, and η is a value which is between 1 and the number of tungsten atoms which can be coordinated with the ligand L, characterized in that a tungsten oxy-tetrahalide of the formula WOX ₄ , where X stands for chlorine, bromine or iodine, is reacted with a hydroxy compound which contains groups which R .., R ₂ , R ₃ and R ₄ according to the definitions of the general formula (I), in the presence of a ligand compound. 17. A method for producing a tungsten complex compound the general formula (WO (OR ₁ ) (OR ₂ ) (OR ₃ ) (OR ₄ ) J ₁₁ L (I) wherein R, R, R ₃ or R _{4 represent} hydrocarbon groups, substituted hydrocarbon groups or groups of the formula -Si R, where R-, Rg or R _{7 is} a hydrocarbon "" ^R 7
represent a group which may optionally be substituted, where R-, R ₂ , R ₃ and R _{4 can be} identical or different, and, if two or more of the groups R ₁ , R-, R_ and R are hydrocarbon groups, independently whether they are substituted or unsubstituted, two such groups can form a cyclic structure together with the adjacent tungsten and oxygen atoms in the formula, while L is a monodentate or polydentate ligand, the typical element of Group V of the Periodic Table of FIG Contains elements and is coordinatively linked to the tungsten atom in the formula via this element, and η is a value between 1 and the number of with 509844/1093 the ligand L is coordinatively connectable tungsten atoms, characterized in that tungsten trioxide is reacted with a hydroxy compound containing groups which R ₁ , R ₃ , R and R ₄ correspond to the general formula (I), in the presence of a ligand compound, the water occurring as a by-product is removed azeotropically with a solvent which is able to form an azeotropic mixture with water. 18. The method according to claim 17, characterized in that the solvent used consists of benzene, toluene or xylene . 19. Process for the preparation of a tungsten complex compound of the general formula (I) [WO (OR ₁ ) (OR ₂ ) (OR ₃ ) (OR ₄ )] _n L (I) wherein R ₁ , R ₃ , R ₃ or R _{4 represent} hydrocarbon groups, substituted hydrocarbon groups or groups of the formula stand, where R ₅ , Rg and R ₇ ^R 7 represent a hydrocarbon group which may optionally be substituted, where R ₁ , R ₂ , R ₃ and R _{4 may be the} same or different, and if two or more of the groups R ₁ , R ₃ , R ₃ and R _{4 are} hydrocarbon groups, regardless of whether they are substituted or unsubstituted, two such groups can form a cyclic structure together with the adjacent tungsten and oxygen atoms in the formula, while L is a monodentate or polydentate ligand which is a typical element of group V of the periodic Contains system of elements and is coordinated via this element with the tungsten atom in the formula, and η is a value between 1 and the number of tungsten atoms that can be coordinated with the ligand L, characterized in that a tungsten oxy- 509844/1093 tetrahalide is reacted with an alkali metal alcoholate of a hydroxy compound with groups which _{correspond to R 1} , R ₂ , R and R ₄ according to the general formula (I) in the presence of a ligand compound. 20. Process for the preparation of a tungsten complex compound of the general formula (I) [WO (OR ₁ ) (OR ₂ ) (OR ₃ ) (OR ₄ J _n L (I) wherein R ₁ , R ₂ , R ₃ or R _{4 represent} hydrocarbon groups, substituted hydrocarbon groups or groups of the formula / 5 -Si R _c ^R 7 ' stand, where R_, R, or R _{7 represent} a hydrocarbon group which may optionally be substituted, where R ₁ , R ₂ , R-. and R _{4 may be the} same or different and, if two or more of the groups R ₁ , R 1, R 1, R and R are hydrocarbon groups, regardless of whether they are substituted or unsubstituted, two such groups have a cyclic structure together with the neighboring tungsten and oxygen atoms in the formula, while L is a monodentate or polydentate ligand which contains a typical element of group V of the Periodic Table of the Elements and is coordinated via this element with the tungsten atom in the formula, and η is a value which is between 1 and the number of tungsten atoms which can be coordinated with the ligand L, characterized in that a tungsten oxytetra-lower alkylate and a hydroxy compound with groups which R ₁ , R _{1, R 3} and R ₄ according to the general formula (I), or an organic carboxylic acid ester thereof can be subjected to an esterification reaction in the presence of a ligand compound. 50984 4/1093 21. The method according to claims 16 to 20, characterized in that the hydroxy compound used is an alcohol with groups _{corresponding to R 1} , R 1, R 1, R 1 and R according to the general formula (I). 22. The method according to claims 16 to 20, characterized in that that the hydroxy compound used is a compound of the formula: ^R 5 or MOSi ^R 5 HOSi ^R 6 \ ^R 6 ^R 7 ^R 7 where R ₁ -, R _fi and R_ have the meanings given in connection with the general formula (I), and M is an alkali metal consisting of sodium or potassium. 23. Process for the preparation of a tungsten compound of the general Formula (II): WO (OR ₁ ) (OR ₂ ) (OR ₃ ) (OR ₄ ) (II) wherein R, R, R ₃ or R. for a hydrocarbon group, a substituted hydrocarbon group or a group of the formula / 5 -Si R_, where at least one substituent of the formula: ^R 7 - ^R 5
-Sx-R, where R_, R _g and R _{7 are} hydrocarbon groups ^Xr 7 or substituted hydrocarbon groups and R ₁ , R ", R ₃ and R _{4 can be the} same or different, and where, if two or more of the groups R ₁ , R", R ₃ and R _{4 are} hydrocarbon groups, regardless of whether they substituted or unsubstituted, two such groups can form a cyclic structure together with the adjacent tungsten and oxygen atoms in the formula, characterized in that a tungsten oxytetrahalide 5098 U A / 109 3 with a compound of the formula: ^ ^R 5 HOSi R _c ^R 7 wherein R _n ., R _fi and R _{7 are} a hydrocarbon group, which may optionally be substituted, is reacted in the presence of a halogen hydrogen neutralizing agent. 24. The method according to claim 23, characterized in that the hydrogen halide neutralizing agent used consists of ammonia consists. 25. Process for the preparation of a tungsten compound of the general Formula: WO (OR ₁ ) (OR ₂ ) (OR ₃ ) (OR ₄ ) (II) wherein R ₁ , R «, R-. and R. for a hydrocarbon group, a substituted hydrocarbon group or a group of the formula / ^R 5
-Si R, where at least one substituent of the formula ' 5
-Si R corresponds to, where R ₅ , R or R _{7 are} hydrocarbon groups ^ ^R 7 or substituted hydrocarbon groups and R ₁ , R, R and R _{4 can be the} same or different, and where, if two or more of the groups R ₁ , R ₃ , R ₃ and R _{4 are} hydrocarbon groups, regardless of whether they are substituted or are unsubstituted, two such groups form a cyclic structure together with the adjacent tungsten and oxygen atoms in the formula 509844/1093 can, characterized in that a tungsten oxytetrahalide with a compound of the general formula: ^ ^R 5
MOSi R, -, ■ " ^R 7 in which M stands for an alkali metal and R ₅ , R _g and R ₇ respectively mean a hydrocarbon group, which may optionally be substituted, is reacted. 26. A method for producing a tungsten compound of general formula (II): WO (OR ₁ ) (OR ₂ ) (OR ₃ ) (OR ₄ ) (II) wherein R, R ₂ , R ₃ or R _{4 represent} a hydrocarbon group, a substituted hydrocarbon group or a group of the formula: S- ^R 5
-Si R, where at least one substituent of the formula: ^ ^R 7 / ^R 5
-Si Rg corresponds, where R ₅ , R, or R _{7 is} hydrocarbon ^ ^R 7 are groups or substituted hydrocarbon groups and R ₁ , R_, R_ and R. can be identical or different, and where, if two or more of the groups R ₁ , R ₂ , R. » and R _{4 are} hydrocarbon groups, regardless of whether they are substituted or unsubstituted, two such groups can form an eyelic structure together with the adjacent tungsten and oxygen atoms in the formula, characterized in that tungsten trioxide with a compound of the general formula : 509844/1093 ^ ^R 5 HOSi R _c , wherein R ₁ -, R _g or R- denote a hydrocarbon group which may optionally be substituted, is reacted in the presence of a solvent which is able to form an azeotropic mixture with water, the water occurring as a by-product being removed azeotropically with the solvent will. 27. The method according to claim 26, characterized in that the solvent used consists of benzene. 28. Process for the preparation of a tungsten compound of the general Formula (II): WO (OR ₁ ) (OR ₂ ) (OR ₃ ) (OR ₄ ) (II) wherein R ₁ , R_, R ₃ or R. for a hydrocarbon group, a substituted hydrocarbon group or a group of the formula ^ ^R 5
-Si R _c , where at least one substituent of the formula: ^ 5
-Si R ₆ corresponds, where RR or R ^ hydrocarbon- ^ ^R 7 are groups or substituted hydrocarbon groups and R ₁ , R ₂ , R3 and R _{4 can be} identical or different, and where, if two or more of the groups R ₁ , R ₂ , R ₃ and R _{4 are} hydrocarbon groups, regardless of whether they are substituted or unsubstituted, two such groups can form a cyclic structure together with the adjacent tungsten and oxygen atoms in the formula, characterized in that 509844/1093 a tungsten oxytetra-lower alkylate with a compound of general formula ^ ^R 5 HOSi R ₆ \ R ₇ wherein R _1. , R ₆ and R _{7 are} a hydrocarbon group, which can optionally be substituted, or an organic one Carboxylic acid ester thereof is reacted. 29. Process for the preparation of an allyl alcohol of the general formula (IV) ^R 12 ^R 13 ^R 14
R "- C = C - C - OH (IV) ^R 15 wherein R ₁₁ , R ₁ O ' ^R i3' ^R i4 b ^zw · ^R -ic ^e ^ - ⁿ hydrogen atom or a hydrocarbon group, which may optionally be substituted, are characterized in that an allyl alcohol of the general formula (III) R ₁₂ R ₁₃ R ₁₄ III R "- C - C = C (III) I I OH R ₁₅ in which R ₁₁ , R ₁ o ' ^R i3' ^R -i 4 ^{un <} ^ ^R i 5 d-ie have the meanings given in connection with the general formula (IV), is isomerized or, conversely, an allyl alcohol of the general formula (III) an allyl alcohol of the general formula (IV) 509844/1093 is generated, wherein in the presence of a tungsten complex compound or a tungsten compound according to one of claims 1 to 14 or a mixture of such tungsten compounds is worked as a catalyst. 30. A process for the preparation of an allyl alcohol of the general formula (III) or (IV) according to claim 29, characterized in that that the tungsten complex compound, the tungsten compound or the mixture of these compounds with a porous substance is treated before use as a catalyst. 31. Process for the preparation of an allyl alcohol of the general Formula (III) or (IV) according to claim 29, characterized in that the allyl alcohol (III) used is made from linalol and the allyl alcohol (IV) consists of geraniol and / or nerol. 509844/1093 Blank page