GB2387595A

GB2387595A - Osmium-catalysed dihydroxylations of olefins using a hypohalite in the presence of nitrogen compounds

Info

Publication number: GB2387595A
Application number: GB0307128A
Authority: GB
Inventors: Matthias Beller; Gerald Mehltretter; Christian Doebler; Uta Sundermeier; Markus Klawonn; Santosh Bhor; Markus Eckert; Hans-Christian Militzer
Original assignee: Bayer AG
Current assignee: Bayer AG
Priority date: 2002-03-28
Filing date: 2003-03-27
Publication date: 2003-10-22
Anticipated expiration: 2023-03-27
Also published as: GB0307128D0; GB2387595B; DE10213981A1; FR2839511A1

Abstract

A process for preparing vicinal diols comprises the conversion of olefins in the presence of hypohalite, catalysts comprising at least one osmium compound, water and nitrogen compounds. The reaction mixture may further comprise an organic solvent, particular tert-butanol. The hypohalite is preferably an alkali metal or alkaline earth metal hypochlorite or hypobromite, especially sodium hypochlorite. The nitrogen compound used is preferably (DHQD)2PHAL (dihydroquinidine-1,4-phalazinediyl diether) or (DHQD)2Pyr (hydroquinidine(2,5 -diphenyl-4,6-pyrimidinediyl) diether). The osmium compound used is preferably potassium osmate dihydrate. The diols prepared may be used for preparing polymers, herbicides, fungicides, insecticides, pharmaceuticals and cosmetics or their precursors.

Description

-a-; 1 2387595 Preparation of vicinal dials The present invention relates

to a process for preparing vicinal dials from olefins in the presence of catalysts comprising osmium compounds and of nitrogen compounds using hypochlorites as oxidizing agents.

5 Vicinal diols find use on the industrial scale, for example as starting materials for polyesters. Furthermore, stereoisomerically enriched vicinal dials especially have a great industrial significance as herbicides, fungicides, insecticides and pharma ccuticals and also their respective precursors.

10 A common method for synthesizing vicinal diols is dihydroxylation of olefns in the presence of catalysts comprising osmium compounds. A specific variant of the reaction is the asymmetric dihydroxylation in which chiral ligands are additionally used. This method is summarized, for example, in M. Beller, K. B. Sharpless, "Asymmetric Dihydroxylation Reactions", p. 1009-1024, in B. Cornils, W. A. 15 Herrmann (Eds.), VCH, 1996, Weinheim.

For industrial application, it is essential to achieve high substratecatalyst ratios and to be able to use readily available and easily handled oxidizing agents.

20 The use of air or oxygen and also of hydrogen peroxide as oxidizing agents for dihydroxylations has been described, for example, in Dobler et al., J. Am. Chem. Soc. 2000, 122, 10289-10297 and Jonsson et al., Organic Letters 2001, 3, Vol. 22, 3463 3466. 25 A disadvantage of the use of air or oxygen is the fact that, to achieve acceptable conversion rates, operation has to be effected under pressure and elevated temperatures which, according to the above-cited literature, may lead to explosive

l - mixtures in the presence of organic solvents. The industrial scale use of this process would therefore be associated with expensive safety measures.

A disadvantage of the use of hydrogen peroxide as an oxidizing agent is the necessity 5 of co-catalysts and biomimetic flavins.

It is also common to such processes that the yields and, in the case of asymmetric dihydroxylations, additionally the stereoselectivities do not satisfy industrial requirements. Another process (US 3,488,394) describes the use of osmium tetroxide as catalyst and sodium hypochlorite as oxidizing agent.

However, this process only achieves disappointing yields between 51 and 76%.

There was therefore a need for a process for optionally asymmetric dihydroxylation of olefns which allows high substrate-catalyst ratios and delivers high yields when using readily available and easy-to-handle oxidizing agents.

20 A process has now been found for preparing vicinal dials, which is characterized in that olefins are converted in the presence of hypohalite, - catalysts comprising at least one osmium compound, - water and 25 - nitrogen compounds and - optionally an organic solvent.

It is pointed out that any desired combinations of areas of preference are also encompassed by the scope of the invention.

r

- 3 For the process according to the invention, the olefins used are, for example and with preference, of the formula (I) R'R2C=CR3R4 (I)

5 where R' to R4 are each independently hydrogen, iodine, bromine, chlorine, fluorine, nitro, nitroso, cyano, free or protected forrnyl, C C -alkyd, C' -C ' s-haloalkyl, C4 Cx-aryl, Cs-C-arylalkyl, C-Cihydroxyalkyl, C'-Cs-hydroxyalkoxy, 10 -PO[(C -Ce)-alkyl]2, -PO[(C4-C 2)aryl]2, -PO[-[(C -Cs-alkyl)(C4-C'2)-aryl], tri(C -C6-alkyl)siloxyl, tri(C -C6-alkyl)silyl, tri(C -C6-alkyl)silyl-(C -C6 alkyl) or a radical of the general formula (II) A-B-D-E (II)

where, each independently, A is absent or is a C'-Ca-alkylene radical and 20 B is absent or is oxygen, sulphur or NR where R' is hydrogen, C'-Csalkyl, C5-C'o-arylalkyl or C4-C'O-aryl and D is a carbonyl group and E is R2, oR2, NHR3 or N(R3)2 where R2 is C-Cs-alkyl, C7-C,O-arylalkyl, C'-Cshydroxyalkyl, C-Cs-

haloalkyl or C4-CO-aryl and

R3 is in each case independently C,-C-alkyl, C,-C8-hydroxyalkyl, Cs-

C0-arylalkyl or C4-C'0-aryl, or N(R3)2 together is a cyclic amino radical, or a radical of the general formulae (IIIa-e) s A-E (IIIa) A-SO2-E (IIIb) 10 A-B-SO2R2 (IIIc) A-SO3X (IIId) A-COX (IIIe) where A, B. E and R2 are each as defined above and X is OH, NH2, or OM where M may be an alkali metal ion, half an equivalent of an alkaline earth metal ion, an ammonium ion or an organic ammonium ion.

20 The Rat and R2 and/or R3 and R4 radicals together may also be part of a 5- to 9 membered carbo- or heterocyclic radical, although carbocyclic radicals are preferred.

For example and with preference, Rat and R2 and/or R3 and R4 together are a 1,1 cycloalkylene radical such as 1, I -cyclopentylene or I,1 cyclohexylene.

25 The formula (I) may also be part of an unsaturated mono- or bicyclic ring which may in each case be 5- to 9-membered and carbo- or heterocyclic.

For example and with preference, R' and R2 and/or R3 and R4 together with the double bond of the olefin are a 1,2-cycloalkenylene radical such as 1, 2 30 cyclopentenylene or 1,2-cyclohexenylene.

l - 5 For the purposes of the invention, aryl is, for example and with preference, a carbocyclic aromatic radical or heteroaromatic radical, each of which may also be fused. The heteroaromatic radicals may contain no, one, two or three heteroatoms per cycle, but at least one heteroatom in the entire molecule which is selected from the 5 group of nitrogen, sulphur or oxygen.

The carbocyclic aromatic radicals or heteroaromatic radicals may also be substituted by up to five identical or different substituents per cycle which, for example and with preference, are selected from the group of hydroxyl, C-C'2-alkyl, cyano, COOH, 10 COOM, COO-(C-C,2-alkyl), COO-(C4C0-aryl), CO-(C'-C2-alkyl), CO-(C4-C'o aryl), O-(C -C 2-alkyl), (C -C 2alkyl)-O-(C -C 2-alkyl), (C4-C 0-aryl)-O-(C -C 2 alkyl), O-(C4-C'0-aryl), O-CO-(C4-C0-aryl), O-CO-(C'-C'2-alkyl), OCOO-(C-C2 alkyl), N-(C-C'2-alkyl) 2, NH-(C-C2-alkyl), N(C4-C0-aryl)2, NH-(C4-C'0-aryl), NO, NO2, NOH, aryl, fluorine, chlorine, bromine, iodine, NO2, Si(C'-C2-alkyl)3, CHO, 15 SO3H, SO3M, SO3(C-C2-alkyl), SO2(C-C2-alkyl), SO(C-C'2-alkyl), C-C2 haloalkyl, NHCO-(C'-C2-alkyl), CONH2, CONH-(C'-C2-alkyl), NHCOO-(C'-C'2 alkyl), PO(C4-C0-aryl)2, PO(C-C2-alkyl)2, PO3H2, PO3M2 PO3HM, PO(O(C-C'2 alkyl)2, where M may in each case be an alkali metal ion, half an equivalent of an alkaline earth metal ion, an ammonium ion or an organic ammonium ion. The same 20 applies to the aryl moiety of an arylalkyl radical.

In the contexts specified, alkyl is in each case independently a straightchain, cyclic, branched or unbranched alkyl radical which may be further substituted by C-C4 alkoxy radicals. The same applies to the alkyl moiety of an arylalkyl radical.

For the purposes of the invention, C-C6-alkyl is, for example, methyl, ethyl, 2 ethoxyethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, cyclohexyl and n-hexyl, C-Cs-alkyl is additionally, for example, n-heptyl, n-octyl or isooctyl, C-C,z-alkyl is further additionally, for example, norbornyl, n-decyl and n-dodecyl, and Cl-Cl8-alkyl 30 is still further additionally n-hexadecyl and n-octadecyl.

In the abovementioned contexts, haloalkyl is in each case independently a straight chain, cyclic, branched or unbranched alkyl radical which may be singly, multiply or fully substituted by halogen atoms independently selected from the group of fluorine, chlorine and bromine.

For the purposes of the invention, C-C6-haloalkyl is, for example, 1 trifluoromethyl, 2,2,2-trifluoroethyl, chloromethyl, fluoromethyl, bromomethyl, 2-bromoethyl, 2 chloroethyl, nonafluorobutyl, C'-Cxhaloalkyl is additionally, for example, n perfluorooctyl, and C'-C'xhaloalkyl is still further additionally, for example, n 1 0 perfluorododecyl.

In the abovementioned contexts, hydroxyalkyl is in each case independently a straight-chain, cyclic, branched or unbranched alkyl radical which is substituted by one or more hydroxyl groups in such a way that each carbon atom of the 15 hydroxyalkyl radical bears at most one oxygen, sulphur or nitrogen atom. For the purposes of the invention, C'- Cx-hydroxyalkyl is, for example, 2-hydroxyethyl.

Protected formyl is a formyl radical which has been protected by conversion to an aminal, acetal or mixed aminalacetal, each of which may be acyclic or cyclic.

Particular preference is given to using olefins for the process according to the invention which are of the formula (I) where R1 to R4 are each independently hydrogen, C'-Cg-alkyl, cyano, COOH, 25 COOM, COO(C'-C2alkyl), CO(C,-C'2-alkyl), CO(C4-C'0-aryl), O(C-C'x alkyl), O(C4-C0-aryl), (C-C4-alkyl)-(C4-C,0-aryl), (C4-C'0-aryl), fluorine, chlorine, bromine, free or protected formyl, tri(C'-C4-alkyl)silyl-(C-C4-alkyl) or NHCO(CC'x-alkyl).

- 7 < Very particular preference is given to using olefins for the process according to the invention which are of the formula (I) R'R2C=CR3R4 (I)

5 where R1 to R4 are each independently hydrogen, C'-C2-alkyl, cyano, COOH, COOM where M = Li, Na, K, COO(C,-C4-alkyl), CO(C-C,2-alkyl), CO phenyl, O(C-C4-alkyl), O-phenyl, fluorine, chlorine, bromine, free or protected formyl, NHCO(C'-C,-alkyl), (C-C4-alkyl)-O-(C-C4-alkyl), (C4 C'0aryl)-O-(C-C4-alkyl), trimethylsilylmethyl, benzyl and also phenyl or 10 naphthyl, each of which may be substituted by up to three further radicals which are each independently selected from the group of hydroxyl, C'-C2 alkyl, cyano, COOH, COOM where M = Li, Na, K, COO-(C-C4-alkyl), CO (C'-C4-alkyl), O-(C-C4-alkyl), N(C-C4-alkyl)2, NH-(C'-C4-alkyl), NO2, fluorine, chlorine, bromine, SO3H, SCAM where M = Li, Na, K, C'-C'2 15 haloalkyl, such as in particular trifluoromethyl, CONH2.

The olefins of the general formula (I) are most preferably styrene, amethylstyrene, 1 -phenyl- 1 -cyclohexene, trans-5-decene, 1 -octene, allyltrimethylsilane and allyl phenyl ether.

The process according to the invention is carried out in the presence of water.

In a preferred embodiment, the process according to the invention is carried out in the presence of water and organic solvent.

Suitable organic solvents are organic solvents inert towards the reactants. Preference is given to aromatic and/or aliphatic ethers, for example anisole, tetrahydrofuran, dioxane, dimethoxyethane, methoxyethanol, aliphatic alcohols, for example methanol, ethanol, npropanol, isopropanol, tert-butanol, n-butanol, isobutanol, 30 aromatic and/or aliphatic hydrocarbons, for example toluene, xylenes, aliphatic ketones, for example acetone, ethyl methyl ketone, esters, for example ethyl acetate,

- 8 . halogenated aromatic or aliphatic hydrocarbons, for example chlorobenzene and methylene chloride, sulphoxides, for example dimethyl sulphoxide, sulphones, for example tetramethylsulphone or diethylsulphone, and amidic solvents, for example N,N-dimethylformamide and Nmethylpyrrolidinone and also mixtures of such 5 solvents. The preferred ratio of water to an organic solvent is 1:10 to 10:1, and particular preference is given to a ratio of 1:5 to 5:1.

10 The preferred ratio of water to olehm is 1000:1 to 1:1, and particular preference is given to a ratio of 100:1 to 10:1.

The aqueous phase which optionally contains organic solvents is preferably adjusted to a pH of 8 to 14, more preferably 10 to 12, based on 25 C. The pH may be adjusted 15 in a sufficiently well-known manner, for example by adding a base.

For example and with preference, suitable bases are carbonates, hydrogencarbonates, hydroxides and alkoxides of alkali metals and alkaline earth metals or mixtures of such bases.

Particular preference is given to carbonates, hydrogencarbonates and hydroxides of sodium or potassium, or mixtures thereof. Very particular preference is given to sodium carbonate and potassium carbonate.

25 It may be advantageous for the removal of the products if inorganic salts are also added to the aqueous phase. Such inorganic salts may be, for example, alkali metal or alkaline earth metal halides, for example sodium chloride.

The amount of salt added may range, for example, from O to 25% by weight.

30 _

The oxidizing agents used in the process according to the invention are hypohalites or their aqueous solutions. Preferred hypohalites are alkali metal or alkaline earth metal hypochlorites or hypobromites, or mixtures thereof.

Particular preference is given to using sodium hypochlorite, in particular in the form 5 of its aqueous solutions.

The oxidizing agent is advantageously added to the reaction mixture in the form of an aqueous solution. However, it may also be generated in situ, for example by passing chlorine into the reaction mixture (HollemanWiberg, Lehrbuch der Anorganischen lO Chemie, 1985, 95th- 100th Edition, Chapter 4.3.1.1, p. 422 95).

The reaction temperature may be, for example, -30 to 100 C, and preference is given to -20 to 80 C, particular preference to O to 50 C.

15 The pressure in the reaction is uncritical and may be, for example, 0. 5 to lOO bar.

Preference is given to ambient pressure.

The process according to the invention is carried out in the presence of nitrogen compounds. For example and with preference, the nitrogen compounds used are 20 tertiary mono- or diamines, unsubstituted, mono- or polysubstituted N heteroaromatics, or mono- or polysubstituted Nheteroaromatics in which at least one substituent is or bears a tertiary amino group.

Particular preference is given to using unsubstituted, mono- or polysubstituted 25 pyridines or quinolines where the substituents are each selected independently from the group of C-C'4-alkyl, C4-C4-aryl, CsC,s-arylalkyl, monoamines of the general formula (IVa) 30 NRsR6R7 (IVa)

- 10 where R5, R6 and R7 are each independently Cl-C20-alkyl, C4-Cl4-aryl or C5-C5-

arylalkyl, or in each case two or three of the R5, R6 and R7 radicals together with the nitrogen atom may form a mono-, hi- or tricyclic, aliphatic heterocycle having from 4 to 8 carbon atoms per cycle, and diamines of the formula (IVb) R8R9N-B-NR'0R'' (IVb) 10 where R8, R9, R' and Rut are each independently Cl-C20-alkyl, C4-C4-aryl or Cs-Cs arylalkyl, or, in each case independently, the Rg and R9 and also R' and Rid radicals together form a C2-Cg-alkylene or C5-C's-N-alkyl-N-arylene radical, or, each independently, Rg and/or R9 with R' and/or Rig are each a radical bridging two nitrogen atoms which is selected from the group of C2-Cg 1 S alkylene, Cs-C'5-N-alkyl-N-arylene and C4-CO-arylene and B is C2-Cs-alkylene, Cs-C's-N-alkyl-N-arylene, bis(C4-C'o-aryl)ene or C4-Co arylene. 20 Preferred pyridines are, for example, pyridine, 2,2'bipyridine; preferred quinolines are, for example, quinuclidine, quinine and quinidine' cinchonidine and cinchonine; preferred monoamines are trin-butylamine and triethylamine; a preferred diamine is l,4-diazabicyclo[2. 2.2]-octane (DABCO).

Preference is given to using stereoisomerically enriched nitrogen compounds for the process according to the invention. For the purposes of the invention, stereo isomerically enriched (enantiomerically enriched, diastereomerically enriched) means stereoisomerically pure (enantiomerically pure or diastereomerically pure) nitrogen 30 compounds or mixtures of stereoisomeric (enantiomeric or diastereomeric) nitrogen compounds in which one stereoisomeric (enantiomeric or diastereomeric) nitrogen r

. - 11

-l compound is present in a larger absolute proportion, preferably 70 to 100 mol% and very particularly preferably 95 to 100 mol%, than another diastereomeric or the other enantiomeric nitrogen compound.

5 Particular preference is given to using stereoisomerically enriched nitrogen compounds. Very particular preference is given to using stereoisomerically enriched nitrogen compounds whose content of one stereoisomer is at least 95%.

Greatest preference is given to using dihydroquinidine-1,4phthalazinediyl diether, 10 dihydroquinidine-2,5-diphenyl-4,6pyrimidinediyl diether, dihydroquinidine(anthra quinone-1,4-diyl) diether, dihydroquinidine-9-phenanthryl ether, dihydroquinine-1,4 phthalazinediyl diether, dihydroquinine-2,5-diphenyl-4,6-pyrimidinediyl diether, dihydroquinine(anthraquinone- 1,4-diyl) diether or dihydroquinine-9phenanthryl ether or compounds of the formulae (Va) and (Vb) \,,H:,H

R3C R'3Co i, R12,,, R12

(Va) (Vb) where, in each case independently, R12 is hydrogen or methoxy and R13 is Cl-C8-alkyl, C4-C'4-aryl, C5-Cl5-arylalkyl or di(CI-C4)alkylamino.

Preferred compounds of the formulae (Va) and (Vb) are those in which Rl2 is methoxy and Rl3 is selected from the group of methyl, ethyl, n-propyl, cyclohexyl, tert-butyl, isopropyl, methoxymethyl, dimethylamino, phenyl, 2-, 3-, 4-chlorophenyl,

- 1 2 2-, 3-, 4-methoxyphenyl, 4-nitrophenyl, 2-naphthyl, 4-phenylphenyl, 2,6-dimethoxy phenyl. The catalysts used for the process according to the invention are those which comprise osmium compounds.

s In principle, it is also possible to use such compounds in the form of copolymers, as have been described in WO 91/16322.

Preference is given to using those catalysts which comprise osmium compounds 10 which have been generated from osmium compounds and nitrogen compounds.

Preference is given to using osmium compounds in the formal oxidation states +8 and +6. Examples of useful osmium compounds include: osmium oxides such as OsO4 and OsO4 on vinylpyridine, alkali metal hydroxy 15 osmates, for example K2OsO2(OH)4 and Na2OsO2(OH)4, osmium carbonyls, for example Os3(CO)2, osmium halides, for example OsCl3, haloosmic acids, for example H2OsCI6, osmium complexes, for example [CF3SO3Os(NH3)s] (O3SCF3)2, imidoosmiumoxides, for example (tert-butylimino)OsO3.

20 In the process according to the invention, the amount of catalyst comprising osmium compounds is such that, for example, between 0.05 and 0. 0000001 mol. preferably 0.02 to 0.00005 mol and more preferably 0.01 to 0. 0001 mol. of osmium is used per mole of olefin.

25 The ratio of nitrogen compound to osmium is, for example and with preference, between 0.01:1 and 1000:1, more preferably 0.1:1 to 100:1 and most preferably 1:1 to 50:1.

Ihe Final dials which can be prepared according to the invention are suitable in 30 particular for use as building blocks for polymers and may be used in particular in

t - 13 stereoisomerically enriched form for preparing herbicides, fungicides, insecticides, pharmaceuticals and cosmetics, and also their respective precursors.

The process according to the invention has the advantage that the dihydroxylation of 5 olefins in high yields is possible with high chemoselectivity and using easily obtainable and handled hypohalites as oxidizing agents. Furthermore, high reaction rates are observed which make the process particularly economical in respect of the space-time yield.

l O Also, outstanding stereoisomeric excesses are observed in the case of the asymmetric reaction.

- 14 Examples

The examples which follow serve to illustrate the process according to the invention, without restricting it thereto.

Example 1

A 100 ml Schlenk vessel equipped with a magnetic stirrer is charged with 2.95 mg of K2OsO4 2H2O (0.008 mmol; 0.4 mol%), 78 mg of (DHQD)2PHAL 10 (dihydroquinidine-1,4-phthalazinediyl diether) (0.1 mmol, 5 mol%) and 550 mg of potassium carbonate (4 mmol, 200 mol%). The addition of 10 ml of distilled water and 10 ml of tert-butanol with stirring transfers everything into a solution.

Afterwards, the reaction mixture is cooled to 0 C in an ice bath. 1.5 ml of aqueous sodium hypochlorite solution (11.7% of active chlorine titrimetrically, 150 mol%) 15 and afterwards 230 pi of styrene (2 mmol) are added at this temperature with further stirring. The reaction is terminated after stirring at 0 C for one hour by adding approx. 1 g of sodium sulphite and the reaction mixture is extracted using 20 ml of ethyl acetate. The organic phase is removed and dried over magnesium sulphate.

After the addition of a standard, the reaction product and also unconverted substrate 20 are determined quantitatively by gas chromatography.

Yield of (R)-l-phenyl-1,2-ethanediol: 84% (selectivity 84%), 91% ee (HPLC) .

Example 2

25 In a similar manner to Example 1, 260 pi (2mmol) of a-methylstyrene are reacted and worked up as described.

Yield of (R)-2-phenyl-1,2-propanediol: 99% (selectivity 99%), 91% ee (HPLC).

- 15 Example 3

In a similar manner to Example 1, 318 pi (2 mmol) of 1-phenyl-1cyclohexene are reacted. 5 Yield of (lR,2R)-1-phenyl-1,2-cyclohexanediol: 88% (selectivity 88%), 95% ee (HPLC).

Example 4

10 380 Ill (2 mmol) of trans-5-decene are reacted as stated in Example 1.

Yield of (R,R)-5,6-decanediol: 92% (selectivity 94%), 93% ee (HPLC).

Example 5

15 As detailed in Example 1, except in a reaction time of 2 hours, 258 pi (2 rnmol) of trans-,8-methylstyrene are reacted.

Yield of (R,R)-I-phenyl-1,2-propanediol: 93% (selectivity 99%), 95% ee (HPLC).

Example 6

In a similar manner to Example 5, 314 Ill (2 mmol) of 1 -octene are reacted.

Yield of (R)-1,2-octanediol: 97% (selectivity 97%), 73% ee (HPLC).

Example 7

275 Al of allyl phenyl ether (2 mmol) are reacted in a similar manner to Example 5.

Yield of (S)-3-phenoxy-1,2-propanediol: 88% (selectivity 94%), 73% ee (HPLC).

- 16 ExamnIe 8 In a similar manner to Example 5, 2 mmol of allyltrimethylsilane are reacted, except that the ligand used is (DHQD) 2Pyr(hydroquinidine(2,5-diphenyl-4,6-pyrimidinediyl) 5 diether). Yield of (S)-3-(trimethylsilyl)-1,2-propanediol: 87% (selectivity 93%), 80% ee.

It will of course be understood that the present invention has been described above purely by way of example, and that modifications of detail can be made within the 10 scope of this invention.

Claims

- 17 Claims:

1. Process for preparing vicinal diols, characterized in that olehms are converted in the presence of 5 - hypohalite, - catalysts comprising at least one osmium compound, - water and - nitrogen compounds.

10 2. Process according to Claim 1, characterized in that it is carried out in the presence of an organic solvent.

3. Process according to one or more of Claims 1 to 2, characterized in that the olefins used are of the formula (I) RIR2C=CR3R4 (I)

where 20 R' to R4 are each independently hydrogen, iodine, bromine, chlorine, fluorine, nitro, nitroso, cyano, free or protected formyl, CC's-alkyl, C'-Cg haloalkyl, C4-C'g-aryl, Cs-C's-arylalkyl, C'-Cshydroxyalkyl, C-Ca hydroxyalkoxy, -PO[(C -Cs)-alkyl]2, -PO[(C4-C 2)-aryl] 2, -PO[-[(C Ca-alkyl)(C4-C 2)-aryl], tri(C -C6-alkyl)siloxyl, tri(C -C6alkyl)silyl, 25 tri(C-C6-alkyl)silyl-(C-C6-alkyl) or a radical of the general formula (II) A-B-D-E (II)

30 where, each independently,

- 18 A is absent or is a C-C8-alkylene radical and B is absent or is oxygen, sulphur or NR' where Rat is hydrogen, C-Ca-alkyl, C5-C0-arylalkyl or C4-C'0-aryl and s D is a carbonyl group and E is R2, oR2, NHR3 or N(R3) 2 where R2 is Cl-C8-alkyl, C7-Cl0-arylalkyl, Cl-C8-hydroxyalkyl, C'-C8 10 haloalkyl or C4-C' 0-aryl and R3 is in each case independently Cl-C8alkyl, Cl-Cs-hydroxyalkyl, Cs C0-arylalkyl or C4-C'0-aryl, or N(R3)2 together is a cyclic amino radical, or a radical of the general formulae (IIIa-e) A-E (IIIa) 20 A-SO2-E (IIIb) A-B-SO2R2 (IIIc) A-SO3X (IIId) ACOX (IIIe) where A, B. E and R2 are each as defined above and X is OH, NH2, or OM where M may be an alkali metal ion, half an equivalent of an alkaline 30 earth metal ion, an ammonium ion or an organic ammonium ion or

- 19 the Rat and R2 and/or R3 and R4 radicals together are part of a 5- to 9-

membered Garbo- or heterocyclic radical.

4. Process according to one or more of Claims I to 3, characterized in that the 5 olefins of the formula (I) used are styrene, a-methylstyrene, 1-phenyl-1 -cyclo hexene, trans-5-decene, 1-octene, allyltrimethylsilane or allyl phenyl ether.

5. Process according to one or more of Claims 2 to 4, characterized in that the organic solvent used is an aromatic and/or aliphatic ether, aliphatic alcohol, 10 aromatic and/or aliphatic ketone, ester, halogenated aromatic or aliphatic hydrocarbon, sulphoxide, sulphone, amidic solvent or a mixture of such organic solvents.

6. Process according to one or more of Claims 1 to 5, characterized in that the 15 aqueous phase which optionally contains organic solvents is preferably adjusted to a pH of 8 to 14, based on 25 C.

7. Process according to one or more of Claims 1 to 6, characterized in that the base used to adjust the pH is a carbonate, hydrogencarbonate, hydroxide or 20 alkoxide of alkali metals or alkaline earth metals, or a mixture thereof.

8. Process according to one or more of Claims 1 to 7, characterized in that inorganic salts are added to the aqueous phase which optionally contains organic solvents.

9. Process according to one or more of Claims 1 to 8, characterized in that the oxidizing agent used is an alkali metal or an alkaline earth metal hypochlorite or hypobromite or a mixture thereof.

30 10. Process according to Claim 9, characterized in that the oxidizing agent used is sodium hypochlorite.

- 20 Process according to one or more of Claims 9 to 10, characterized in that the oxidizing agent is used in the form of an aqueous solution.

5 12. Process according to one or more of Claims I to 11, characterized in that the reaction temperature is -30 to 1 00 C.

13. Process according to one or more of Claims 1 to 12, characterized in that the nitrogen compound used is 1,4-diazabicyclo[2.2.2]octane.

14. Process according to one or more of Claims 1 to 12, characterized in that the nitrogen compound used is dihydroquinidine-1,4-phthalazinediyl diether, dihydroquinidine-2,5-diphenyl-4,6-pyrimidinediyl diether, dihydroquinidine (anthraquinone- l,4-diyl) diether, dihydroquinidine-9phenanthryl ether, IS dihydroquinine-1,4-phthalazinediyl diether, dihydroquinine-2,5-diphenyl-4,6 pyrimidinediyl diether, dihydroquinine(anthraquinone- 1,4-diyl) diether or dihydroquinine-9phenanthryl ether or one of the formulae (Va) and (Vb) \,,H:,H

R13C:,] R13Co R12 R12

20 (Va) (Vb) where, in each case independently, R12 is hydrogen or methoxy and Rl3 is Cl-C8-alkyl, C4-C,4-aryl, Cs-C,5-arylalkyl or di(CI-C4) -alkylamino.

- 21 15. Process according to one or more of Claims 1 to 14, characterized in that the osmium compounds used are those in the formal oxidation states +8 and +6.

16. Process according to one or more of Claims 1 to 15, characterized in that the 5 catalysts used for the process according to the invention are those which comprise osmium compounds which are obtained from nitrogen compounds and osmium compounds which are selected from the group of osmium oxides, alkali metal hydroxyosmates, osmiumcarbonyls, osmiumhalides, haloosmic acids and imidoosmium oxides.

17. Process according to Claim 16, characterized in that OSO4, OSO4 on vinylpyridine, K2OsO2(OH)4 Na2OsO2(OH)4, Os3(CO)2, 0SC13, H2OSC16, [CF3SO3Os(NH3)s](O3SCF3)2 or (tert-butylimino)OsO3 are used.

15 18. Process according to one or more of Claims 1 to 17, characterized in that, for example, between 0.05 and 0.0000001 mol of osmium is used per mole of Glenn. 19. Process according to one or more of Claims 1 to 18, characterized in that the 20 ratioofnitrogencompoundtoosmiumisO.01:1 to 1000:1.

20. Process according to Claim 1 substantially as hereinbefore specifically described in any one of Examples 1 to 8.

25 21. Use of the vicinal dials prepared according to one or more of Claims 1 to 20 for preparing polymers, herbicides, fungicides, insecticides, pharmaceuticals and cosmetics and also their respective precursors.