The present invention relates to a selective transfer hydrogenation of citral to geraniol/nerol and ethyl citral to ethyl geraniol/ethyl nerol.

Citral (lUPAC: 3,7-dimethyl-2,6-octadienal) is the compound of formula (la)

The chemical formulae as drawn above cover all isomeric configurations these compound can have.

Citral is usually a mixture of the E- and the Z-isomer. The E-isomer is known as geranial or citral A (compound of formula (la'):

and the Z-isomer

The same applies for the ethyl citral. It also exists in different isomeric configurations due to both double bonds. Each carbon-carbon double bond can independently have the E or Z configuration.

Citral can be extracted from various plants such as for example lemon myrtle, Litsea citrata, Litsea cubeba, lemongrass, lemon tea-tree, Ocimum gratissimum, Lindera citriodora, Ca- lypranthes parriculata, petitgrain, lemon verbena, lemon ironbark (26%), lemon balm, lime, lemon, and orange.

It also possible and more common to chemically synthesize citral. Citral is available commercially from various companies.

The goal of the present invention was to find an improved way to provide geraniol/nerol (compound of formula (Ma)) and ethyl geraniol/ethyl nerol (compound of formula (lib)),

which are the selectively hydrogenated products of citral and ethyl citral respectively. In nature geraniol, can be found in rose oil, palmarosa oil, and citronella oil (Java type). It also occurs in small quantities in geranium, lemon, and many other essential oils. It appears as a clear to pale- yellow oil that is insoluble in water, but soluble in most common organic solvents. It has a rose-like scent and is commonly used in perfumes. It is used in flavors such as peach, raspberry, grapefruit, red apple, plum, lime, orange, lemon, watermelon, pineapple, and blueberry. In nature nerol, which is the compound of formula (I la")

can be found in many essential oils such as lemongrass and hops. It was originally isolated from neroli oil, hence its name. This colourless liquid is used in perfumery. Like geraniol, nerol has a sweet rose odor but it is considered to be fresher.

Geraniol and nerol (as well as the mixture of these compounds) are very important com- pounds in fragrance and flavour applications. Therefore there is always a need for an improved way for obtaining these compounds.

Some specific transfer hydrogenations of citral are known from the prior art, but they have some disadvantages in regard to selectivity and/or conversion and/or yield and/or reaction conditions.

Surprisingly we found that the using specific kind of catalysts and reduction agents it is possible to hydrogenate citral selectively by a transfer hydrogenation reaction whereas the selectivity, the conversion as well as the yield of the hydrogenation are excellent.

The present inven und of formula (I)

to a compound of wherein R signifies -CH ₃ or -CH ₂ CH ₃ ,

characterized in that the hydrogenation is carried out in the presence of an amino-amide-transition-metal catalyst of formula (III)

MX[Z-(-H)][Y] (III)

wherein

M is a transition metal, preferably chosen from the group consisting of Ir, Rh and Ru, and

signifies H or a halogen atom, and

signifies a ligand, preferably an aromatic ligand, and

signifies a group of formula (IV) or (V)

wherein

R ¹ signifies d-d-alkyl which may be substituted with one or more fluorine atoms, C ₂ -C ₈ -alkenyl, C ₂ -C ₈ -alkynyl, C ₄ -C ₇ -cycloalkyl, aryl which may be substituted, het- eroaryl, or camphor-10-yl, and

R ² and R ³ each independently signify hydrogen, d-d-alkyl, C ₄ -C ₇ -cycloalkyl, or aryl which may be substituted, and

R ⁴ signifies hydrogen or Ci-Ce-alkyI , and

R ⁵ signifies hydrogen or d-d-alkyl, and

R ⁶ signifies hydrogen or d-Ce-alkyl, and

n signifies 0,1 ,2 or 3, and

m signifies 0,1 ,2 or 3, and

with the proviso that in formula (V) the sum of n and m is 2, 3, 4 or 5, and

b) a H ₂ donor.

A preferred transfer hydrogenation (TH ¹ ) is (TH), characterized in that the hydrogenation carried out in the absence of water. This ("by the absence of water") means that water is not added intentionally to the reaction solution. The water content is usually below 3 weight-% (wt-%), preferably below 2 wt-%, based on the total weight of the reaction solution. The selectivity, the yield and the conversion of the transfer hydrogenation according to the present invention are excellent.

The monosulphonylated diamine is present in the complex as a monoanion and is accordingly denoted in formula III as "Z-(-H)".

By the term "amino-amide transition metal catalyst" it is meant that the transition metal is complexed to Z via the amine and the amide of Z.

Transfer hydrogenation is the addition of hydrogen to a compound (molecule) from a source other than gaseous H ₂ .

The use of H ₂ gas has some issues with the handling of the explosive gas in regard to safety and in regard to the apparatus needed.

Instead of H ₂ gas a H ₂ donor system is used for transfer hydrogenation. Any H ₂ donor sys- tern known from the prior art can be used.

The H ₂ donor (= reduction agent), which is used in the process according to the present invention, can be any commonly known H ₂ donor in the field of transfer hydrogenation. In principle a transfer hydrogenation can be carried out by using

(option a) at least one solvent which also serves as hydrogen donor or

(option b) at least one hydrogen donor and at least one inert solvent.

Therefore a further embodiment of the present invention is a transfer hydrogenation (TH ² ), which is (TH) or (TH ¹ ), wherein the hydrogenation is carried out by using at least one solvent which also serves as hydrogen donor.

Therefore a further embodiment of the present invention is a transfer hydrogenation (TH ³ ), which is (TH) or (TH ¹ ), wherein the hydrogenation is carried out by using at least one hydrogen donor and at least one inert solvent.

As the hydrogen donor and at the same time (option a) the solvent there can be used especially alcohols, preferably secondary alcohols, e.g. isopropanol. Therefore a further embodiment of the present invention is a transfer hydrogenation (TH ⁴ ), which is (TH), (TH ¹ ) or (TH ² ), wherein the hydrogenation is carried out by using isopropanol as hydrogen donor and solvent.

As mixtures of hydrogen donors with an inert solvent (option b) there are conveniently used mixtures of alcohols with inert solvents, preferably a mixture of an alcohol with a lower aliphatic halogenated hydrocarbon, e.g. methylene chloride or 1 ,2-dichloroethane. Other suitable hydrogen donor/solvent mixtures are mixtures of formic acid with an inert solvent or a salt of formic acid with an inert solvent.

Suitable inert solvents are i.e. hydrocarbons, esters, alcohol and ethers.

Suitable salts of formic acids are any commonly known salts. Preferred salts are those of the following formula (VI)

QOOCH (VI) ,

wherein

Q is an alkali cation or NH ₄ ⁺ , NH ₃ (R ⁷ ) ⁺ , NH ₂ (R ⁷ ) ₂ ⁺ , NH(R ⁷ ) ₃ ⁺ or N(R ⁷ ) ₄ ⁺ , wherein all R ⁷ are independently from each other -CH ₃ or -CH ₂ CH ₃ .

Preferably Q is Na ⁺ , K ⁺ , NH ₄ ⁺ , more preferably Q is K ⁺ .

Therefore a further embodiment of the present invention is a transfer hydrogenation (TH ⁵ ), which is (TH), (TH ¹ ) or (TH ³ ), wherein the hydrogenation is carried out by using formic acid (or a salt of formic acid QOOCH) and triethylamine and wherein

Q is an alkali cation or NH ₄ ⁺ , NH ₃ (R ⁷ ) ⁺ , NH ₂ (R ⁷ ) ₂ ⁺ , NH(R ⁷ ) ₃ ⁺ or N(R ⁷ ) ₄ ⁺ , wherein all R ⁷ are independently from each other -CH ₃ or -CH ₂ CH ₃ .

Therefore a further embodiment of the present invention is a transfer hydrogenation (TH ⁵ ), which is (TH ⁵ ), wherein Q Na ⁺ , K ⁺ , NH ₄ ⁺ , more preferably Q is K ⁺ .

Therefore a further embodiment of the present invention is a transfer hydrogenation (TH ⁵ ), which is (TH ⁵ ), wherein Q is K ⁺ .

When mixtures of hydrogen donors and inert solvents are used, in principle all mixture rati- os can apply.

When a mixture of QOOCH and (CH ₃ CH ₂ ) ₃ N (=QOOCH/(CH ₃ CH ₂ ) ₃ N) is used then ratio is from 1 :1 to 10:1 , preferably 1 :1 to 6:1 (molar ratio). Therefore a further embodiment of the present invention is a transfer hydrogenation (TH ⁶ ), which is (TH), (TH ¹ ), (TH ³ ), (TH ⁵ ), (TH ⁵ ) or (TH ^5" ), wherein a mixture of QOOCH and (CH ₃ CH ₂ ) ₃ N wherein Q is an alkali cation or NH ₄ ⁺ , NH ₃ (R ⁷ ) ⁺ , NH ₂ (R ⁷ ) ₂ ⁺ , NH(R ⁷ ) ₃ ⁺ or N(R ⁷ ) ₄ ⁺ , wherein all R ⁷ are independently from each other -CH ₃ or -CH ₂ CH ₃ , is used in a ratio from 1 :1 to 10:1 , preferably 1 :1 to 6:1 .

In the scope of the present invention the term "substituted with one or more fluorine atoms", otherwise expressed as "mono- or multiply-fluorinated", means having at least one fluorine substituent to as many fluorines as the alkyl group so modified is capable of accepting; however one to five fluorines is preferred.

In the scope of the present invention the term "alkyl" embraces straight-chain or branched alkyl groups with 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. Methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl and tert. -butyl, are examples such alkyl groups. Trifluromethyl, 2,2,2-trifluoroethyl and pentafluoroethyl are examples of mono- or multiply-fluorinated alkyl groups.

The term "alkenyl" embraces straight-chain or branched alkenyl groups with 2 to 8 carbon atoms, preferably 2 to 6 carbon atoms, e.g. allyl, 2-butenyl and 3-butenyl.

The term "alkynyl" signifies a straight-chain or branched alkynyl group with one triple bond and 2 to 8 carbon atoms, preferably 2 to 6 carbon atoms, e.g. propynyl and butynyl.

The term "cycloalkyl" signifies a 4- to 7-membered alicyclic group, namely cyclobutyl, cyclo- pentyl, cyclohexyl or cycloheptyl, of which cyclopentyl and cyclohexyl are preferred.

The term "unsubstituted or substituted aryl" or equally "aryl which may be substituted" or "optionally mono- or multiply-substituted aryl" preferably embraces a phenyl or naphthyl group, which can be unsubstituted, mono-substituted or multiply-substituted. As substi- tutents there come into consideration e.g. phenyl, halogen and straight-chain and branched alkyl and alkoxy groups with in each case 1 to 5 carbon atoms, whereby the multiply- substituted phenyl or naphthyl groups can have the same or different substituents. Of the alkyl and alkoxy groups the methyl and, respectively, the methoxy group is preferred. Examples of optionally substituted aryl groups are phenyl, chloro-, bromo- and fluorophenyl, tolyl, anisyl, as well as naphthyl. The place of the substitution can be at any position of the aromatic ring. The term "heteroaryl" embraces 5- or 6-membered heterocyclic groups featuring O, S or N as a ring member, i.e. heteroatom, such as, for example, furyl, thienyl, benzofuryl, dibenzo- furyl, xanthenyl, pyrrolyl and pyridinyl. The heterocyclic groups featuring O as the heteroatom are especially preferred.

A preferred embodiment of the present invention relates to a transfer hydrogenation of citral or ethyl citral, wherein the catalyst of formula (III)

M is chosen from the group consisting of Ir, Rh and Ru, and

X signifies H or a halogen atom, and

Y signifies an aromatic ligand, preferably a 6π electrons aromatic system - ligand, and

signifies a group of formula (IV) or (V)

wherein

R ¹ signifies C ₁ -C ₂ -alkyl which may be substituted with one or more fluorine atoms, C ₂ -C ₆ -alkenyl, C ₂ -C ₆ -alkynyl, C ₄ -C ₇ -cycloalkyl, aryl which may be substituted, heteroaryl, or camphor-10-yl, and

R ² and R ³ each independently signify hydrogen, Ci-C ₂ -alkyl, C ₄ -C ₇ -cycloalkyl, or aryl which may be substituted, and

R ⁴ signifies hydrogen or d-C ₂ -alkyl, and

R ⁵ signifies hydrogen or Ci-C ₂ -alkyl, and

R ⁶ signifies hydrogen or d-C ₂ -alkyl, and

n signifies 0,1 ,2 or 3, and

m signifies 0,1 ,2 or 3,and

with the proviso that in formula (V) the sum of n and m is 3 or 4. Therefore a further embodiment of the present invention is a transfer hydrogenation (TH ⁷ ), which is (TH), (TH ¹ ), (TH ² ), (TH ³ ), (TH ⁴ ), (TH ⁵ ), (TH ⁵ ), (TH ^5" ) or (TH ⁶ ), wherein the catalyst is a compound of formula (III) MX[Z-(-H)][Y], wherein

M is chosen from the group consisting of Ir, Rh and Ru, and

X signifies H or a halogen atom, and

Y signifies an aromatic ligand, preferably a 6π electrons aromatic system - ligand, and

signifies a group of formula (IV) or (V)

wherein

R ¹ signifies C ₁ -C ₂ -alkyl which may be substituted with one or more fluorine atoms, C ₂ -C ₆ -alkenyl, C ₂ -C ₆ -alkynyl, C ₄ -C ₇ -cycloalkyl, aryl which may be substituted, het- eroaryl, or camphor-10-yl, and

R ² and R ³ each independently signify hydrogen, C ₁ -C ₂ -alkyl, C ₄ -C ₇ -cycloalkyl,or aryl which may be substituted, and

R ⁴ signifies hydrogen or d-C ₂ -alkyl, and

R ⁵ signifies hydrogen or Ci-C ₂ -alkyl, and

R ⁶ signifies hydrogen or Ci-C ₂ -alkyl, and

n signifies 0,1 ,2 or 3, and

m signifies 0,1 ,2 or 3, and

with the proviso that in formula (V) the sum of n and m is 3 or 4.

In the catalyst of formula (III) preferably Y is chosen from the group consisting of pentame- thylcyclopentadienyl, benzene, p-cymene, toluene, anisole, xylene, 1 ,3,5-trimethylbenzene, p-dicyclohexylbenzene, naphthalene and tetralin. Therefore a further embodiment of the present invention is a transfer hydrogenation (TH ), which is (TH), (TH ¹ ), (TH ² ), (TH ³ ), (TH ⁴ ), (TH ⁵ ), (TH ⁵ ), (TH ^5" ), (TH ⁶ ) or (TH ⁷ ), wherein the ligand Y in the catalyst of formula (III) is chosen from the group consisting of pentamethyl- cyclopentadienyl, benzene, p-cymene, toluene, anisole, xylene, 1 ,3,5-trimethylbenzene, p- dicyclohexylbenzene, naphthalene and tetralin.

A more preferred embodiment of the present invention relates to a transfer hydrogenation of citral or ethyl citral, wherein the catalyst of formula (III)

M is chosen from the group consisting of Ir, Rh and Ru, preferably Ru, and

X signifies H or CI, and

Y signifies an aromatic ligand, preferably a 6π electrons aromatic system - ligand, and

Z signifies a group of formula (IV)

wherein

R ¹ signifies d-C ₂ -alkyl which may be substituted with one or more fluorine atoms,

C ₂ -C ₆ -alkenyl, C ₂ -C ₆ -alkynyl, C ₄ -C ₇ -cycloalkyl, aryl which may be substituted, het- eroaryl, or camphor-10-yl, and

R ² and R ³ each independently signify hydrogen, C ₁ -C ₂ -alkyl, C ₄ -C ₇ -cycloalkyl, or aryl which may be substituted, and

R ⁴ signifies hydrogen or d-C ₂ -alkyl, and

R ⁵ signifies hydrogen or d-C ₂ -alkyl, and

R ⁶ signifies hydrogen or d-C ₂ -alkyl, and

n signifies 0,1 ,2 or 3.

Therefore a further embodiment of the present invention is a transfer hydrogenation (TH ⁹ ), which is (TH), (TH ¹ ), (TH ² ), (TH ³ ), (TH ⁴ ), (TH ⁵ ), (TH ⁵ ), (TH ⁵ ), (TH ⁶ ), (TH ⁷ ) or (TH ⁸ ), wherein wherein the catalyst of formula (III)

M is chosen from the group consisting of Ir, Rh and Ru, preferably Ru

X signifies H or CI, and Y signifies an aromatic ligand, preferably a 6π electrons aromatic system ligand, and

Z signifies a group of formula (IV)

wherein

R ¹ signifies C ₁ -C ₂ -alkyl which may be substituted with one or more fluorine atoms,

C ₂ -C ₆ -alkenyl, C ₂ -C ₆ -alkynyl, C ₄ -C ₇ -cycloalkyl, aryl which may be substituted, het- eroaryl, or camphor-10-yl, and

R ² and R ³ each independently signify hydrogen, Ci-C ₂ -alkyl, C ₄ -C ₇ -cycloalkyl, or aryl which may be substituted, and

R ⁴ signifies hydrogen or d-C ₂ -alkyl, and

R ⁵ signifies hydrogen or Ci-C ₂ -alkyl, and

R ⁶ signifies hydrogen or d-C ₂ -alkyl, and

n signifies 0,1 ,2 or 3.

Therefore a further embodiment of the present invention is a transfer hydrogenation (TH ¹⁰ ), which is (TH ⁹ ), wherein the ligand Y in the catalyst of formula (III) is chosen from the group consisting of pentamethylcyclopentadienyl, benzene, p-cymene, toluene, anisole, xylene, 1 ,3,5-trimethylbenzene, p-dicyclohexylbenzene, naphthalene and tetralin.

Furthermore the present invention also relates to preferred transfer hydrogenations of citral or ethyl citral, wherein the catalyst is of formula (III ^* )

wherein

M is Ru, Rh, Ir, preferably Ru, and

Y is an aromatic ligand chosen from the group consisting of

Therefore a further embodiment of the present invention is a transfer hydrogenation (TH ^{1 1} ), which is (TH), (TH ¹ ), (TH ² ), (TH ³ ), (TH ⁴ ), (TH ⁵ ), (TH ⁵ ), (TH ^5" ), (TH ⁶ ), (TH ⁷ ), (TH ⁸ ), (TH ⁹ ) or (TH ¹⁰ ), wherein

the catalyst is of formula (III')

wherein

M is Ru, Rh, Ir, preferably Ru, and

Y is an aromatic ligand chosen from the group consisting of

Preferred transfer hydrogenations according to the present invention are such wherein the following catalysts are used:

Therefore a further embodiment of the present invention is a transfer hydrogenation (TH ¹² ), which is (TH), (TH ¹ ), (TH ² ), (TH ³ ), (TH ⁴ ), (TH ⁵ ), (TH ⁵ ), (TH ^5" ), (TH ⁶ ), (TH ⁷ ), (TH ⁸ ), (TH ⁹ ), (TH ¹⁰ ) or (TH ^{1 1} ), wherein the catalyst is chosen from the group consisting of

More preferred transfer hydrogenations according to the present invention are such wherein the following catalysts are used:

Therefore a further embodiment of the present invention is a transfer hydrogenation (TH ¹³ ), which is (TH), (TH ¹ ), (TH ² ), (TH ³ ), (TH ⁴ ), (TH ⁵ ), (TH ⁵ ), (TH ^5" ), (TH ⁶ ), (TH ⁷ ), (TH ⁸ ), (TH ⁹ ), (TH ¹⁰ ), (TH ¹¹ ) or (TH ¹² ), wherein the catalyst is chosen from the group consisting of

consisting of

Preferably the catalyst is prepared in situ starting from a metal precursor complex and vari- ous ligands:

0.5 Mol [M(Y)X ₂ ] ₂ and 1 Mol Z, which is as stated above represented by formula (IV) or (V)

wherein all the substituents have the same meanings as defined above,

are mixed to form the catalyst.

All the substituents have the same meanings as defined above as well as the same prefer ences.

The reaction temperature of the process of production of the catalyst (compound of formula (III)) is usually 0 - 100°C. The reactants are usually mixed for a period of time and then all the reactants for the selective transfer hydrogenation of the present invention are added and the necessary reaction conditions of the hydrogenation are applied.

The selective transfer hydrogenation reaction is usually carried out at a temperature of 0 - 100 °C, preferably 25 - 90 °C. Therefore a further embodiment of the present invention is a transfer hydrogenation (TH ¹⁴ ), which is (TH), (TH ¹ ), (TH ² ), (TH ³ ), (TH ⁴ ), (TH ⁵ ), (TH ⁵ ), (TH ^5" ), (TH ⁶ ), (TH ⁷ ), (TH ⁸ ), (TH ⁹ ), (TH ¹⁰ ), (TH ^{1 1} ), (TH ¹² ) or (TH ¹³ ), wherein the transfer hydrogenation reaction is carried out at a temperature of 0 - 100 °C, preferably 25 - 90 °C.

The selective transfer hydrogenation reaction is usually carried out at a normal (ambient) pressure. It could also been carried out at elevated and preferably at reduced pressure. Usually the transfer hydrogenation according to the present invention is carried out at a pressure of 50 - 1 000 mbar.

Therefore a further embodiment of the present invention is a transfer hydrogenation (TH ¹⁵ ), which is (TH), (TH ¹ ), (TH ² ), (TH ³ ), (TH ⁴ ), (TH ⁵ ), (TH ⁵ ), (TH ^5" ), (TH ⁶ ), (TH ⁷ ), (TH ⁸ ), (TH ⁹ ), (TH ¹⁰ ), (TH ^{1 1} ), (TH ¹² ), (TH ¹³ ) or (TH ¹⁴ ), wherein the transfer hydrogenation reaction is carried out at a pressure of 50 - 1000 mbar.

The substrate to catalyst ratio (s/c ratio) in the selective transfer hydrogenation is usually from 20:1 to 10000:1 , preferably 50 :1 to 1000:1 . This ratio is related to Mol of substrate (which is compound of formula (I)) to mol of catalyst (compound of formula (III)). Therefore a further embodiment of the present invention is a transfer hydrogenation (TH ¹⁶ ), which is (TH), (TH ¹ ), (TH ² ), (TH ³ ), (TH ⁴ ), (TH ⁵ ), (TH ⁵ ), (TH ^5" ), (TH ⁶ ), (TH ⁷ ), (TH ⁸ ), (TH ⁹ ), (TH ¹⁰ ), (TH ^{1 1} ), (TH ¹² ), (TH ¹³ ), (TH ¹⁴ ) or (TH ¹⁵ ), wherein substrate to catalyst ratio (s/c ratio) is from 20:1 to 10000:1 , preferably from 50:1 to 1000:1 . The transfer hydrogenation according to the present invention allows the preparation of nerol/geraniol or ethyl nerol/ethyl geraniol in excellent yield.

The nerol/geraniol or ethyl nerol/ethyl geraniol which is obtained by the transfer hydrogenation according to the present invention can be used in any application wherein such fragrance compounds are used.

The invention is illustrated by the following Examples. All temperatures are given in °C and all parts and percentages are related to the weight. Examples

Example 1 : Production of the catalysts

In a 25 mL 2-necked round bottomed flask equipped with thermometer and a magnetic stirrer, 0.020 mmol of metal complex (M(Y)X ₂ ] ₂ ) and 0.044 mmol of a ligand (Z) were dissolved in 9 mL solvent at room temperature. The mixture was stirred for 30 min.

The solvent was ethyl acetate, isopropanol or methanol.

All of the following catalysts [(C1 ) - (C8)] were produced according to the process of Example 1

Catalyst 1 (CD

Catalyst 3 (C3)

Catalyst 4 (C4)

Catalyst 5 (C5)

Catalyst 6 (C6)

with Y= Catalyst 7 (C7)

Catalyst 8 (C8)

Example 2: Selective transfer hydrogenation of Citral To the solution (obtained according to Example 1 ) 6 mL solvent, 4 mmol (621 mg=700 μΙ_) citral and 20 mmol reducing agent were added and stirred at the desired temperature (for all the following hydrogenation room temperature = 23 °C was used)..

The reaction mixture was concentrated at 100 mbar by 40 °C. The residue was filtered over 10 g Si0 ₂ and washed with 50 mL ethyl acetate. The solution was concentrated at 100 mbar, 40 °C and the residue analyzed by gas chromatography with internal standard.

In the following table the results of the transfer hydrogenation with the catalysts of Example 1 are summarized. Exp. Cat. Red .Agent Solvent Conversion Yield

[%] [%]

2a C1 HCOOH/EtsN (5:2) Ethyl acetate 99 97

2b C1 i-propanol/KOH i-propanol 98 87

2c C3 HCOOH/Et ₃ N (1 :1 ) Ethyl acetate 99 99

2d C3 HCOONa Methanol 99 83

2e C4 HCOOH/Et ₃ N (1 :1 ) Ethyl acetate 99 99

2f C5 HCOOH/Et ₃ N (1 :1 ) Ethyl acetate 86 86

2g C6 HCOOH/EtsN (1 :1 ) Ethyl acetate 99 99

2h C7 HCOOH/Et ₃ N (1 :1 ) Ethyl acetate 99 99

2i C8 HCOOH/Et ₃ N (1 :1 ) Ethyl acetate 96 95

Examples 3 and 4

In the following examples the catalyst is formed in situ. The following ligands have been used to form the catalyst in situ. The numbering of the ligands corresponds to the Examples they are used in.

Examples 3a - 3e: Transfer hydrogenation of citral (to nerol/geraniol); in situ formation of the catalyst

9 mg of dichloro(p-cymene)ruthenium(ll) dimer (CAS No 52462-29-0) and the ligand (see table for the amount; the numbering of the Example corresponds to the numbering of the ligand) were dissolved in 3 ml of ethyl acetate. After stirring for 5 minutes, a solution of 500 mg citral in 2 ml ethyl acetate was added. The mixture was stirred for an additional 5 minutes and afterwards 1 .30 ml of a 5:2 mixture of formic acid:triethylamine was added and the reaction mixture was stirred at room temperature. After 20 hours, the reaction mixture was analysed by HPLC. For the results (in regard to the conversion and the yield) see the table below.

Examples 4a - 4e: Transfer hydrogenation of ethyl citral (to ethyl nerol/ethyl geraniol); in situ formation of the catalyst

9 mg of Dichloro(p-cymene)ruthenium(ll) dimer (CAS No 52462-29-0) and the ligand (see table for the amount; the numbering of the Example corresponds to the numbering of the ligand) were dissolved in 3 ml of ethyl acetate. After stirring for 5 minutes, a solution of 530 mg of ethyl citral in 2 ml ethyl acetate was added.

The mixture was stirred for an additional 5 minutes and afterwards 13.0 ml of a 5:2 mixture of formic acid:triethylamine (5:2, Fluka, 1 .30 ml) was added and the reaction mixture was stirred at room temperature. After 20 hours, the reaction mixture was analysed by HPLC. For the results (in regard to the conversion and the yield) see the table below.

Exp. Amount of ligand Conversion [%] Yield [%]

4a 8 mg 96.9 92.5

4b 9 mg 99.1 95.1

4c 10 mg 99.0 94.7

4d 9 mg 99.2 95.1

4e 10 mg 98.8 93.4