FR2839511A1 - PROCESS FOR THE PREPARATION OF VICINAL DIOLS AND THEIR USE - Google Patents

Abstract

The invention relates to a process for the preparation of vicinal diols in which olefins are reacted in the presence of a hypohalogenite, to catalysts containing at least one osmium compound, to water and to nitrogen compounds, as well as their use for the production of polymers, herbicides, fungicides, insecticides, drugs and cosmetics and their precursors.

Description

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 The present invention relates to a process for the preparation of vicinal diols from olefins in the presence of catalysts containing osmium compounds and nitrogen compounds using hypohalogenites as oxidants, as well as the use of these diols.

 Vicinal diols are used on an industrial scale, for example as starting materials for polymers such as polyesters and, in addition, vicinal diols enriched in stereoisomers are of great industrial importance as herbicides, fungicides, insecticides and medicaments as well as precursors. of these substances.

dans "Asymmetric Dihydroxylation /?<?<9<yo/75", p. 1009-1024, dans B. The dihydroxylation of olefins in the presence of catalysts containing osmium compounds is a common process for the synthesis of vicinal diols. Asymmetric dihydroxylation further using chiral ligands is a particular variant of this reaction. This process is described for example by M. Bélier, KB Sharpless,

in "Asymmetric Dihydroxylation /? <? <9 <yo / 75", p. 1009-1024, in B.

Cornils, W. A. Herrmann (Eds.), VCH, 1996, Weinheim.

 With a view to industrial implementation, it is essential to achieve high substrate / catalyst ratios and to be able to use widely used and easy-to-handle oxidants.

 The use of air or oxygen as well as hydrogen peroxide as an oxidant for dihydroxylations has been described for example by Döbler et al., In J. Am. Chem. Soc. 2000, 122, 10289-10297 and by Jonsson et al., In Organic Letters 2001.3, Vol. 22.3463-3466.

 The use of air or oxygen has the disadvantage that it is necessary to operate under pressure and at high temperature to obtain acceptable conversion rates, which can lead, according to the literature cited above. , to explosive mixtures in the presence of organic solvents. This is why, the industrial implementation of this process would be linked to very expensive security measures.

 The disadvantage of using oxygen peroxide as an oxidant is that it is necessary to use co-catalysts and biomimetic flavins.

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 In addition, these processes have in common that the yields and, in the case of asymmetric dihydroxylations, the stereoselectivities do not meet industrial requirements.

 Another process (US 3,488,394) describes the use of osmium tetroxide as catalyst and sodium hypochlorite as oxidant.

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

 This is why it is necessary to have a possibly asymmetric dihydroxylation process of olefins making it possible to obtain high substrate / catalyst ratios and high yields by using oxidants of easy access and easy handling.

 Thus, the present invention relates to a process for the preparation of vicinal diols in which olefins are reacted in the presence of a hypohalogenite, of catalysts containing at least one osmium compound, of water and of nitrogen compounds and optionally d 'an organic solvent.

 It should be noted that the method according to the invention also includes any combinations of preferred domains.

-PO[aryle en C4-Clz]z, -PO[alkyle en C1-C$ -aryle en C4-Clz], tri(alkyle en Cl-C6)SilOXY, tri(alkyle en Cl-C6)SilYle, tri(alkyle en Ci-C6)silyle-alkyle en Ci- C6 ou des restes de formule générale (II)
A-B-D-E (II) For the process according to the invention, for example preferably using olefins of formula (I)
R1R2C = CR3R4 (I) where R1 to R4 independently of one another represent hydrogen, iodine, bromine, chlorine, fluorine, a nitro, nitroso, cyano group, a free or protected formyl group, a group C1-C18 alkyl, C1-C18 haloalkyl, CrCis aryl, C5-C18 arylalk, C1-C6 hydroxyalkyl, C1-C8 hydroxyalkoxy, -PO [C1-C8 alkyl] 2,

-PO [C4-Clz aryl] z, -PO [C1-C $ alkyl-C4-Clz aryl], tri (C1-C6 alkyl) SilOXY, tri (C1-C6 alkyl) SilYle, tri ( C1-C6 alkyl) silyl-C1-C6 alkyl or residues of general formula (II)
ABDE (II)

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where A is absent or represents a C1-C8 alkylene residue, B is absent or represents oxygen, sulfur or NR * where R * represents hydrogen, C1-C8 alkyl, arylalkyl in
C5-C10 or C4-Clo aryl, D represents a carbonyl group and E represents R **, OR **, NHR *** or N (R ***) 2, where R ** represents a C1 alkyl group -Cs, arylalkyl in
C7-C10, C1-C5 hydroxyalkyl, C1-C8 haloalkyl or C4-C10 aryl and
R *** independently represents in each case a C1-C6 alkyl, C1-C6 hydroxyalkyl, C5-C10 arylalkyl or C4-C10 aryl group or else N (R ***) 2 represents a cyclic amino residue or remnants of general formulas (IIIa-IIIe)
AE (IIIa)
A-S02-E (IIIb) AB-S02R ** (IIIc) A-S03X (IIId)
A-COX (Ille) where A, B, E and R ** have the meaning indicated above and X represents OH, NH2 or OM where M represents an alkali metal ion, a half equivalent of a metal ion alkaline earth, an ammonium ion or an organic ammonium ion.

 Furthermore, the residues R1 and R2et / and R3and R4may be part of a 5 to 9-membered carbocyclic or heterocyclic residue, the carbocyclic residues being preferred. For example, and preferably, R1 and R2 and / or R3 and R4 can together form a 1,1-cycloalkylene residue as a 1,1-cyclopentylene or 1,1-cyclohexylene residue.

 In addition, formula (I) can also be part of an unsaturated mono or bicyclic ring, where the rings can be 5 to 9-membered carbocyclic or heterocyclic rings.

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 Preferably, R1 and R2et / or R3 and R4 represent, with the double bond of the olefin, a 1,2-cycloalkenylene residue such as 1,2cyclopentenylene or 1,2-cyclohexenylene.

 According to the present invention, aryl represents for example carbocyclic aromatic residues or heteroaromatic residues which can optionally be condensed. The heteroaromatic radicals can contain one, two or three heteroatoms per cycle, but at least one heteroatom chosen from the group of nitrogen, sulfur and oxygen in the total molecule.

en C4-C1o), 0-(alkyle en C1-Clz), (alkyle en CI-Cl2)-O-(alkyle en C1-C12), (aryle en C4-Clo)-O-(alkyle en C1-C12), 0-(aryle en C4-Clo), O-CO-(aryle en C4-Cio), O-CO-(alkyle en Ci-Ci2), OCOO-(alkyle en C1-C12), N-(alkyle en Ci-Ci2)2, NH-(alkyle en Cl-Cl2), N-(aryle en C4-Clo)2, NH-(aryle en C4CIO), NO, N02, NOH, aryle, fluor, chlore, brome, iode, N02, Si-(alkyle en Ci-Ci2)3, CHO, S03H, S03M, S03-(alkyle en CI-Cl2), S02(alkyle en Ci-C,2), SO-(alkyle en Ci-Ci2), halogénoalkyle en C1-C12, NHCO-(alkyle en CI-CI2), CONH2, CONH-(alkyle en C1-C12), NHCOO-(alkyle en C1-C12), PO-(aryle en CrCio)2, PO-(alkyle en C1-C12)2, P03H2, P03M2, P03HM, PO(O)(alkyle en Ci-Ci2)2, où M représente un ion de métal alcalin, un demi-équivalent d'un ion de métal alcalino-terreux un ion ammonium ou un ion ammonium organique. Ceci vaut également pour la partie aryle d'un reste arylalkyle. In addition, the aromatic carbocyclic residues or the heteroaromatic residues can be substituted per cycle with up to five identical or different substituents which are chosen, for example, from the following group: hydroxyl, C1-C12 alkyl, cyano, COOH, COOM, COO - (C1-C12 alkyl), COO- (C4-Clo alkyl), CO- (C1-C12 alkyl), CO- (aryl

C4-C1o), 0- (C1-Clz alkyl), (C1-Cl2 alkyl) -O- (C1-C12 alkyl), (C4-Clo aryl) -O- (C1-C12 alkyl ), 0- (C4-Clo aryl), O-CO- (C4-Cio aryl), O-CO- (C1-C12 alkyl), OCOO- (C1-C12 alkyl), N- (alkyl Ci-Ci2) 2, NH- (C1-Cl2 alkyl), N- (C4-Clo aryl) 2, NH- (C4CIO aryl), NO, NO2, NOH, aryl, fluorine, chlorine, bromine, iodine, NO2, Si- (C1-C2 alkyl) 3, CHO, S03H, S03M, S03- (C1-C2 alkyl), SO2 (C1-C2 alkyl), SO- (C1-C2 alkyl ), C1-C12 haloalkyl, NHCO- (C1-CI2 alkyl), CONH2, CONH- (C1-C12 alkyl), NHCOO- (C1-C12 alkyl), PO- (CrCio aryl) 2, PO - (C1-C12 alkyl) 2, P03H2, P03M2, P03HM, PO (O) (C1-C12 alkyl) 2, where M represents an alkali metal ion, half an equivalent of an alkali metal ion- an ammonium ion or an organic ammonium ion. This also applies to the aryl part of an arylalkyl residue.

 Alkyl represents in all cases a linear or cyclic alkyl radical, branched or unbranched, which can be further substituted by C1-C4 alkoxy radicals. This also applies to the alkyl part of an arylalkyl residue.

 For example, C1-C6 alkyl can represent a methyl, ethyl, 2-ethoxyethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, cyclohexyl or n-hexyl group, C1-Cs alkyl can represent in addition, for example, an n-heptyl, n-octyl or isooctyl, C1-C12 alkyl group may also represent, for example, a

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 norbornyl, n-decyl or n-dodecyl and C1-C18 alkyl may further represent an n-hexadecyl or n-octadecyl group.

 Haloalkyl represents in all cases linear or cyclic alkyl radicals, branched or unbranched, which can be partially or totally substituted by one or more halogen atoms chosen independently from each other from fluorine, chlorine and bromine atoms .

 For example, C1-C6 haloalkyl may represent a trifluoromethyl, 2,2,2-trifluoroethyl, chloromethyl, fluoromethyl, bromomethyl, 2-bromoethyl, 2-chloroethyl, nonafluorobutyl, C1-C8 haloalkyl group and further for example a group n-perfluorooctyle, and C1-C18 haloalkyl can also represent for example an n-perfluorododecyl group.

 Hydroxyalkyle represents in all cases linear or cyclic, branched or unbranched alkyl radicals, which can be substituted by one or more hydroxyl groups in such a way that each carbon atom of the hydroxyalkyl radical contains at most one oxygen, sulfur atom. or nitrogen. For example, C1-C8 hydroxyalkyl may represent a 2-hydroxyethyl group.

 Protected formyl represents a formyl residue which is protected by conversion to a mixed aminal, acetal or aminal acetal, which may be acyclic or cyclic.

O-(alkyle en Ci-C,8), O-(aryle en C4-Co), (alkyle en C1-C4)-(aryle en C4Clo), aryle en C4-Clo, un atome de fluor, de chlore, de brome, un groupe formyle libre ou protégé, un groupe tri(alkyle en C1-C4)silyle-(alkyle en Ci- C4) ou un groupe NHCO-(alkyle en C1-C18). Preferably, for the process according to the invention, olefins of formula (I) are used where R1 to R4 represent, independently of each other, hydrogen, a C1-Cis alkyl group, cyano, COOH, COOM, COO- ( C1-C12 alkyl), CO- (C1-C12 alkyl), CO- (C4-Clo aryl),

O- (C1-C8 alkyl), O- (C4-Co aryl), (C1-C4 alkyl) - (C4Clo aryl), C4-Clo aryl, a fluorine, chlorine atom, bromine, a free or protected formyl group, a tri group (C1-C4 alkyl) silyl- (C1-C4 alkyl) or an NHCO- group (C1-C18 alkyl).

Ci-C:4), CO-(alkyle en C1-C12), CO-phényle, 0-(alkyle en Cl-C4), 0-phényle, un atome de fluor, de chlore, de brome, un groupe formyle libre ou In a particularly preferred manner, olefins of formula (I) are used for the process according to the invention in which R1 to R4 independently represent hydrogen, a C1-C12 alkyl group, cyano, COOH, COOM with M = Li, Na, K, COO- (alkyl in

Ci-C: 4), CO- (C1-C12 alkyl), CO-phenyl, 0- (C1-C4 alkyl), 0-phenyl, a fluorine, chlorine, bromine atom, a free formyl group or

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protégé, NHCO-(alkyle en Ci-C,8), (alkyle en Ci-C4)-0-(alkyle en Cl-C4), (aryle en C4-Clo)-0-(alkyle en Ci-C4), triméthylsilylméthyle, benzyle et phényle ou naphtyle, qui peuvent être substitués chacun par jusqu'à trois autres restes qui peuvent être choisis indépendamment dans le groupe suivant : hydroxyle, alkyle en C1-C12, cyano, COOH, COOM avec M = Li, Na, K, COO-(alkyle en C1-C4), CO-(alkyle en C1-C4), O-(alkyle en Ci-C4), N- (alkyle en Ci-C4)2, NH-(alkyle en C1-C4), N02, un atome de fluor, de chlore, de brome, un groupe SO3H, S03M avec M = Li, Na, K, halogénoalkyle en C1-C12 comme trifluorométhyle, CONH2.

protected, NHCO- (C1-C8 alkyl), (C1-C4 alkyl) -0- (C1-C4 alkyl), (C4-Clo aryl) -0- (C1-C4 alkyl), trimethylsilylmethyl, benzyl and phenyl or naphthyl, which may each be substituted by up to three other residues which may be independently selected from the following group: hydroxyl, C1-C12 alkyl, cyano, COOH, COOM with M = Li, Na, K, COO- (C1-C4 alkyl), CO- (C1-C4 alkyl), O- (C1-C4 alkyl), N- (C1-C4 alkyl) 2, NH- (C1- alkyl C4), NO2, a fluorine, chlorine, bromine atom, an SO3H, SO3M group with M = Li, Na, K, C1-C12 haloalkyl as trifluoromethyl, CONH2.

 As olefins of general form (I), preference is given in particular to styrene, a-methylstyrene, 1-phenylcyclohex-1-ene, trans-dec-5-ene, oct-1-ene, allyltrimethylsilane and allylphenyl 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 an organic solvent.

 The suitable organic solvents are organic solvents which are inert with respect to the reactants, preferably aromatic or aliphatic ethers such as anisol, tetrahydrofuran, dioxane, dimethoxyethane, methoxyethanol, aliphatic alcohols such as methanol, ethanol , n-propanol, isopropanol, tert-butanol, n-butanol, isobutanol, aromatic or aliphatic hydrocarbons such as toluene, xylenes, aromatic or aliphatic ketones such as acetone, ethyl methyl ketone, esters like ethyl acetate, halogenated aromatic or aliphatic hydrocarbons like chlorobenzene or methylene chloride, sulfoxides like dimethylsulfoxide, sulfones like tetramethylsulfone or diethylsulfone and amide solvents like N, N-dimethylformamide or N-methylpyrrolidinone, as well as mixtures of such solvents.

 Preferably, the ratio of water to organic solvent is 1: 10 to 10: 1, more preferably 1: 5 to 5: 1.

 Preferably, the ratio of water to olefin is 1000: 1 to 1: 1, more preferably 100: 1 to 10: 1.

 The aqueous phase optionally containing an organic solvent is preferably brought to a pH of 8 to 14, preferably

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 still from 10 to 12, at 25 C. The pH can be adjusted in a known manner, for example by adding a base.

 Suitable bases are, for example, carbonates, hydrogen carbonates, hydroxides and alcoholates of alkali or alkaline earth metals, or mixtures of such bases.

 Particular preference is given to carbonates, hydrogen carbonates and sodium or potassium hydroxides or mixtures thereof. Particular preference is given to sodium carbonate and potassium carbonate.

 In order to separate the products, it may be advantageous to additionally add inorganic salts to the aqueous phase, which can be, for example, alkali or alkaline earth halides such as sodium chloride.

 The amount of added salts is for example from 0 to 25% by mass.

 As the oxidant, hypohalogenites or their aqueous solutions are used in the process according to the invention, and alkaline or alkaline earth hypochlorites or hypobromites or their mixtures are preferred as hypohalogenites.

 It is particularly preferred to use sodium hypochlorite, in particular in the form of its aqueous solutions.

 The oxidant is advantageously added in the form of an aqueous solution to the reaction mixture. However, it is also possible to form it in situ, for example by introducing chlorine into the reaction mixture (Holleman-Wiberg, Lehrbuch der Anorganischen Chemie, 1985, 95-100ème, Edition, Chapter 4. 3.1.1, p. 422 and following).

 The reaction temperature can be, for example, from -30 to 100 ° C., preferably from -20 to 80 ° C., more preferably from 0 to 50 ° C.

 The pressure for the reaction is not critical and may be, for example, from 0.5 x 105 Pa to 100 x 105 Pa (0.5 to 100 bar). Room pressure is preferred.

 The process according to the invention is carried out in the presence of nitrogen compounds which may preferably be tertiary mono- or diamines, N-heteroaromatic compounds substituted one or more times or N-heteroaromatic compounds substituted one or more

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 times in which at least one substituent is or carries a tertiary amino group.

It is particularly preferred to use pyridines or quinolines which are unsubstituted or substituted one or more times where the substituents are chosen independently of one another from C1-C14 alkyl, C4-C14 aryl, C5-C15 arylalkyl, monoamines of general formula (IVa) NR5R6R7 (IVa), where R5, R6 and R7 represent, independently of one another, C1-C20 alkyl, C4-C14 aryl or C5-C15 arylalkyl or two or three of the R5 residues , R6 and R7 can form, with the nitrogen atom, a mono-, bi- or tricyclic aliphatic heterocycle having 4 to 8 carbon atoms per cycle, and diamines of formula (IVb)
R8R9N-B-NR10R11 (IVb), where R8, R9, R10 and R11 each independently represent a C1-C2o alkyl, C4-C14 aryl or C5-C15 arylalkyl group or else the residues R8 and R9 as well as R10 and R11 independently form together a C2-C8 alkylene residue or N-alkyl-N-arylene of C5-C15 or else R8 and / or R9 independently represent with R10 and / or R11 a residue connecting the two nitrogen atoms which is chosen among the C2-C8 alkylene groups, N-C5-C15 alkylN-arylene and C4-Clo arylene and B represents a C2-C8 alkylene group, N-alkyl-N-arylene in
C5-C15, bis (C4-Clo aryl) or C4-C10 arylene.

 The preferred pyridines are pyridine and 2,2'bipyridine, the preferred quinolines are quinuclidines, quinines and quinidines, cinchonidines and cinchonines, the preferred monamines are tri-n-butylamine and triethylamine, and the preferred diamine is 1,4-diazabicyclo- [2.2.2] -octane (DABCO).

 Preferably, nitrogen-containing compounds enriched in stereoisomers (enriched in enantiomers, enriched in diastereoisomers), that is to say nitrogen compounds, are used for the process according to the invention.

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 stereoisomerically pure (enantiomerically pure or diastereoisomerically pure) or mixtures of stereoisomeric nitrogen compounds (enantiomers or diastereoisomers), in which a stereoisomeric nitrogen compound (enantiomer or diastereoisomer) is present in a greater absolute proportion, preferably from 70 mol% to 100 mol% and more preferably from 95 to 100 mol%, than another diastereoisomeric nitrogen compound or than the other enantiomeric nitrogen compound.

 More preferably, nitrogen compounds enriched in stereoisomers are used and it is very particularly preferred to use nitrogen compounds enriched in stereoisomers whose stereoisomer content is at least 95%.

où R12 représente l'hydrogène ou un groupe méthoxy et R13 représente indépendamment un groupe alkyle en Ci-Cs, aryle en C4-C14, arylalkyle en C5-C15 ou di-(alkyle en Ci-C4)-amino. It is particularly preferred to use dihydroquinidine-1,4phthalazinediyldiether, dihydroquinidine-2,5-diphenyl-4,6-pyrimidinediyldiether, dihydroquinidine- (anthraquinone-1,4-diyl) diether, dihydroquinidine-9-phenanthrylether, dihydroquinine -1,4-phthalazinediyldiether, dihydroquinine-2,5-diphenyl-4,6-pyrimidinediyldiether, dihydroquinine- (anthraquinone-1,4-diyl) diether and dihydroquinine-9-phenanthryl ether, and the compounds of formulas (Va) and (Vb)

where R12 represents hydrogen or a methoxy group and R13 independently represents a C1-C5 alkyl, C4-C14 aryl, C5-C15 arylalkyl or di- (C1-C4 alkyl) -amino group.

 The compounds of formulas (Va) and (Vb) that are preferred are those in which R12 represents a methoxy group and R13 is chosen from methyl, ethyl, n-propyl, cyclohexyl, tert-butyl groups,

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 isopropyl, methoxymethyl, dimethylamino, phenyl, 2-, 3-, 4-chlorophenyl, 2-, 3-, 4-methoxyphenyl, 4-nitrophenyl, 2-naphthyl, 4phenylphenyl, 2,6-dimethoxyphenyl.

 For the process according to the invention, catalysts are used which contain osmium compounds.

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

 Preferably, catalysts containing osmium compounds are used which are produced from osmium compounds and nitrogen compounds.

d'osmium comme [CF3SO30S(NH3)51-(03SCF3)2, des imidooxydes d'osmium comme (tert-butylimino)Os03. Preferably, osmium compounds are used in the formal oxidation states +8 and +6. For example, osmium oxides such as OsO4 and OsO4 can be used on vinylpyridine, alkaline hydroxyosmas such as K2OsO2 (OH) 4 and Na20s02 (OH) 4, osmium carbonyls such as Os3 (CO) i2, osmium halides OsCl3, halogenoosmic acids like H20SCI6, complexes

osmium such as [CF3SO30S (NH3) 51- (03SCF3) 2, osmium imidooxides such as (tert-butylimino) Os03.

 In the process according to the invention, an amount of catalyst containing osmium compounds is used such that there is per mole of olefin, for example 0.05 to 0.0000001, preferably 0.02 to 0 , 00005 and more preferably 0.01 to 0.0001 mol of osmium.

 The ratio of nitrogen compound to osmium is preferably between 0.01: 11000: 1, more preferably between 0.1: 1100: 1, particularly preferably between 1: 1 50: 1.

 The vicinal diols which can be prepared according to the invention are particularly suitable for the production of polymers and can be used in particular in form enriched in stereoisomers for the production of herbicides, fungicides, insecticides, medicaments and cosmetics as well than for their precursors.

 The process according to the invention has the advantage of allowing the dihydroxylation of olefins with high yields and in a very chemoselective manner using as oxidants hypohalogenites of easy access and easy handling. Furthermore, high reaction rates are observed which make the process particularly profitable.

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 In addition, remarkable excess of stereoisomers are observed when the reaction is carried out asymmetrically.

 The present invention will be better understood on reading the following nonlimiting examples.

Example 1
2.95 mg of K2OsO4 x 2H20 (0.008 mmol; 0.4 mol%), 78 mg of (DHQD) 2PHAL (1,4-dihydroquinidine) are introduced into a 100 ml Schlenk container fitted with a magnetic stirrer. phthalazinediyldiether) (0.1 mmol, 5 mol%) and 550 mg of potassium carbonate (4 mmol, 200 mol%). By adding 10 ml of distilled water and 10 ml of tertbutanol with stirring, the entire mixture is brought into solution. Then, the reaction mixture is cooled to 0 C on an ice bath. Continuing to agitate at this temperature, 1.5 ml of aqueous sodium hypochlorite solution (11.7% of active chlorine by titrimetry, 150 mol%) is added, then 230 l of styrene (2 mmol). After one hour of stirring at 0 C, the reaction is stopped by adding about 1 g of sodium sulfite and the reaction mixture is extracted with 20 ml of ethyl acetate. The organic phase is separated and dried over magnesium sulfate. After adding a standard, the reaction product and the unreacted substrate are quantitatively determined by gas chromatography.

 Yield in (R) -1-phenylethane-1,2-diol: 84% (selectivity 84%), enantiomeric excess ee 91% (HPLC).

Example 2
Analogously to Example 1, 260 l (2 mmol) of α-methylstyrene are reacted and the procedure is carried out as described.

 Yield in (R) -2-phenylpropane-1,2-diol: 99% (selectivity 99%), enantiomeric excess ee 91% (HPLC).

Example 3
Analogously to Example 1, 318 μl (2 mmol) of 1-phenylcyclohex-1-ene are reacted.

Yield in (1R, 2R) -1-phenylcyclohexane-1,2-diol: 88% (selectivity 88%), enantiomeric excess ee 95% (HPLC)

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Example 4
380 μl (2 mmol) of trans-dec-5-ene are reacted as described in Example 1.

 Yield of (R, R) -decane-5,6-diol: 92% (selectivity 94%), enantiomeric excess ee 93% (HPLC).

Example 5
258 l (2 mmol) of trans-p-methylstyrene are reacted as described in Example 1 but for a reaction time of 2 h.

Yield in (R, R) -1-phenylpropane-1,2-diol: 93% (selectivity 99%), enantiomeric excess ee 95% (HPLC).

Example 6
314 μl (2 mmol) of oct-1-ene are reacted in a similar manner to example 5.

Yield in (R) -octane-1,2-diol: 97% (selectivity 97%), enantiomeric excess ee 73% (HPLC).

Example 7
275 μl of allylphenyl ether (2 mmol) are reacted in a manner analogous to Example 5.

 Yield of (S) -3-phenoxypropane-1,2-diol: 88% (selectivity 94%), enantiomeric excess ee 73% (HPLC).

Example 8
2 mmol of allyltrimethylsilane are reacted in a similar manner to Example 5 but using as ligand (DHQD) 2Pyr (hydroquinidine- (2,5-diphenyl-4,6-pyrimidinediyl) -diether).

Yield in (S) -3- (trimethylsilyl) propane-1,2-diol: 87% (selectivity 93%), enantiomeric excess ee 80%.

Claims (20)

1. Process for the preparation of vicinal diols, characterized in that olefins are reacted in the presence of a hypohalogenite, of catalysts containing at least one osmium compound, of water and of nitrogenous compounds.  2. Method according to claim 1, characterized in that it is carried out in the presence of an organic solvent.  3. Method according to any one of claims 1 and 2, characterized in that one uses olefins of formula (I) R1R2C = CR3R4 (I) where R1 to R4 independently of one another represent hydrogen, iodine, bromine, chlorine, fluorine, a nitro, nitroso, cyano group, a free or protected formyl group, a group C1-C18 alkyl, C1-C6 haloalkyl, C4-C18 aryl, C5-C18 arylalk, C1-C8 hydroxyalkyl, C1-C8 hydroxyalkyl, -PO [C1-C8 alkyl] 2, -PO [ C4-C12 aryl] 2, -PO [C1-C8 alkyl -C4-C12 aryl], tri (alkyl

 Cl-C6) SilOXY, tri (C1-C6 alkyl) Silyl, tri (C1-C6 alkyl) silyl-C1-C6 alkyl or residues of general formula (II) A-B-D-E (II) where A is absent or represents a C1-C8 alkylene residue, B is absent or represents oxygen, sulfur, or NR * where R * represents hydrogen, C1-C8 alkyl, arylalkyl in C5-Clo or C4-Clo aryl, D represents a carbonyl group and E represents R **, OR **, NHR *** or N (R ***) 2, where R ** represents a C1 alkyl group -C8, arylalkyl in C7-C10, C1-Cs hydroxyalkyl, C1-Cs haloalkyl or C4-Cio aryl and <Desc / Clms Page number 14> A-COX (Ille) where A, B, E and R ** have the meaning indicated above and X represents OH, NH2 or OM where M represents an alkali metal ion, a half equivalent of a metal ion alkaline earth, an ammonium ion or an organic ammonium ion, or else the residues R1 and R2 and / or R3 and R4 are together part of a carbon or heterocyclic residue with 5 to 9 members. A-B-SO2R ** (IIIc) A-S03X (IIId) A-S02-E (IIIb) A-E (IIIa) R *** independently represents in each case a C1-C6 alkyl, C1-C8 hydroxyalkyl, C5-C10 arylalkyl or C4-Clo aryl group or else N (R ***) 2 represents a cyclic amino residue or remains of the general formulas (IIIa-IIIe)  4. Method according to any one of the preceding claims, characterized in that the olefins of formula (I) used are styrene, a-methylstyrene, 1-phenylcyclohex-1-ene, trans-dec- 5-ene, oct-1-ene, allyltrimethylsilane or allylphenyl ether.  5. Method according to any one of claims 2 to 4, characterized in that one uses as organic solvent aliphatic or aromatic ethers, aliphatic alcohols, aromatic or aliphatic ketones, esters, halogenated aromatic or aliphatic hydrocarbons , sulfoxides, sulfones, amide solvents or mixtures of such organic solvents.  6. Method according to any one of the preceding claims, characterized in that the aqueous phase optionally containing organic solvents is brought to a pH of 8 to 14 to 25 C.  7. Method according to any one of the preceding claims, characterized in that, for the adjustment of the pH, carbonates, hydrogencarbonates, hydroxides or alcoholates of alkali or alkaline earth metals or mixtures of these are used as bases -this. <Desc / CRUD Page number 15>  8. Method according to any one of the preceding claims, characterized in that inorganic salts are added to the aqueous phase optionally containing organic solvents.  9. Method according to any one of the preceding claims, characterized in that as the oxidant is used alkaline or alkaline earth hypochlorites or hypobromites or mixtures thereof.  10. Method according to claim 9, characterized in that sodium hypochlorite is used as oxidant.  11. Method according to any one of claims 9 and 10, characterized in that the oxidant is used in the form of an aqueous solution.  12. Method according to any one of the preceding claims, characterized in that the reaction temperature is from -30 to 100 C.  13. Method according to any one of the preceding claims, characterized in that 1,4-diazabicyclo- [2.2.2] octane is used as the nitrogen compound.  14. Method according to any one of claims 1 to 12, characterized in that the nitrogen compounds used are dihydroquinidine-1,4-phthalazinediyldiether, dihydroquinidine-2,5-diphenyl-4,6pyrimidinediyldiether, dihydroquinidine- (anthraquinone-1,4-diyl) diether, dihydroquinidine-9-phenanthrylether, dihydroquinine-1,4-phthalazinediyldiether, dihydroquinine-2,5-diphenyl-4,6-pyrimidinediyldiether, dihydroquinine- (anthraquinone-1, 4-diyl) diether and dihydroquinine-9phenanthryl-ether, or compounds of the formulas (Va) and (Vb)

<Desc / Clms Page number 16>  where R12 represents hydrogen or a methoxy group and R13 independently represents a C1-C8 alkyl, C4-C14 aryl, C5-C15 arylalkyl or di- (C1-C4 alkyl) -amino group.  15. Method according to any one of the preceding claims, characterized in that compounds having osmium compounds are used having formal oxidation states of +8 and +6.  16. Process according to any one of the preceding claims, characterized in that catalysts containing osmium compounds which have been obtained from nitrogen compounds and osmium compounds chosen from osmium oxides, alkaline hydroxyosmates, osmiumcarbonyls, osmium halides, haloemoic acids and osmium imidooxides.  17. Method according to claim 16, characterized in that

 we use OS04, Os04 on vinylpyridine, t <20s02 (OH) 4, Na20s02 (OH) 4, OS3 (CO) 12, Osais, H20SCI6, [CF3SO3OS (NH3) 5] (O3SCF3) 2 or (tert- butylimino) OsO3.  18. Method according to any one of the preceding claims, characterized in that one uses per mole of olefin 0.05 to 0.0000001 mol of osmium.  19. Method according to any one of the preceding claims, characterized in that the ratio of the nitrogenous compound to the osmium is 0.01: 1 to 1000: 1.  20. Use of the vicinal diols prepared by the process according to any one of the preceding claims for the production of polymers, herbicides, fungicides, insecticides, drugs and cosmetics as well as their precursors.