WO1997037981A1

WO1997037981A1 - Process for the production of oxazolidine-2,4-diones

Info

Publication number: WO1997037981A1
Application number: PCT/EP1997/001425
Authority: WO
Inventors: Lutz Heuer
Original assignee: Bayer Aktiengesellschaft
Priority date: 1996-04-03
Filing date: 1997-03-21
Publication date: 1997-10-16
Also published as: DE19613333A1; AU2158897A

Abstract

The invention relates to the production of oxazolidine-2,4-diones by reaction of amides with carbon dioxide in a solvent and in the presence of one or a plurality of basic compounds.

Description

Process for the preparation of Qxazolidin-2,4-diones

The present invention relates to a particularly advantageous and simple to carry out process for the preparation of oxazolidine-2,4-diones from amides and

Carbon dioxide

Processes for the preparation of oxazolidine-2,4-diones are already known, for example from DE-OSs 3 1 15 650, 3 003 653, 2 542 453 and 1 81 1 843. In the processes described there, isocyanates are used as starting materials to be made from phosgene. Phosgene requires very complex safety measures in order to be able to be handled safely.

Other known processes are based on amines, carbon dioxide and 2-halocarboxylic acid esters, a strong organic base, for example N-cyclohexyl-N ', N', N ", N" -tetraethylguanidine being used as an auxiliary (see for example WO 94 / 18 181). The bases required are not only expensive, but are also lost in the aqueous workup, which makes no ecological or economic sense. An analogous reaction is also described in Collect Czech Chem Commun 54, 1005 (1989)

Another process for the preparation of oxazolidine-2,4-diones uses the reaction of amides with carbon dioxide using a so-called

"Electrochemical catalysis" (s J Chem Research (S), 1995. 166 and Tetra¬ hedron 51, 5891 (1995), a probase, for example (EtO ₂ C) ₂ C = C (CO ₂ Et) _2, to be added The yields in this process are sometimes good, but they often leave something to be desired. The probase must be added in double stoichiometric proportions if the yield is to be brought to the desired order. The electrodes for the electrochemical catalysis contain mercury. Finally, the reaction mixture is also still capable of ignition (eg due to the simultaneous presence of dimethylformamide and electrical current) Therefore, overall it is not suitable for use on an industrial scale

Another process uses amides, potassium carbonate and chloroformate in dimethylformamide (Heterocycles 32 1697 (1991)). Here too, phosgene is used as a precursor for the chloroformate used, which means great technical outlay A process for the preparation of oxazolidine-2,4-diones of the formula (I) has now been found

R °

R (I),

in the

R, R ² and R are the same or different and each for one of the following

Leftovers stand.

C, -C ₃₀ alkyl, C ₃ -C ₃₀ alkenyl, C ₃ -C ₃₀ alkynyl, C ₃ -C, ₂ cycloalkyl, C ₅ -C, ₂ -

Cycloalkenyl, C ₈ -C ₁₂ cycloalkynyl, C ₆ -C ₁₄ aryl, C ₅ -C ₁₃ hetaryl with up to 3

Oxygen, sulfur and / or nitrogen atoms in the ring system, C ₇ -C ₂₀ aralkyl,

C. ₉₉ --Cv. ₂₀ aralkenyl, C ₉ -C ₂₀ aralkynyl, C ₇ -C ₂₀ alkaryl, C ₈ -C ₂₀ alkenaryl or

C, ₀ -Alkinaryl,

optionally one to five times by OC, -C, -, - alkyl or OC ₆ -C _{] 0} aryl, N (C _r C ₁₂ alkyl or C ₆ -C ₁₀ aryl) ₂ , COO-C _r C ₁₂ -Alkyl or COO-C ₆ -C ₀ aryl, CONH-C _r C ₁₂ alkyl, CONH-C ₆ -C ₁₀ aryl, CON (C, -C _{] 2} alkyl) ₂ , CON (C ₆ -C ₁₀ - aryl) ₂ halogen, OP (OC _r C, ₂ - alkyl or OC ₆ -C ₁₀ aryl) ₂ , Si (C, -C ₁₂ alkyl and / or C ₆ -C ₁₀ aryl) ₃ , Si (OC _r C ₁₂ alkyl and / or C ₆ -C ₀ aryl) ₃ , Si (C _r C ₁₂ alkyl and C ₆ -C ₁₀ aryl) (OC _r C ₁₂ alkyl and / or OC ₆ -C ₁₀ aryl) ₂ , Si (C _r C ₁₂ alkyl and / or C ₆ -C ₁₀ aryl) ₂ (OC _r C ₁₂ alkyl or OC ₆ -C ₁₀ aryl), OS (C , -C ₁₂ - alkyl or C ₆ -C ₁₀ aryl, O ₂ S (C, -C ₁₂ alkyl or C ₆ -C ₁₀ aryl), CHO, CN, C (OC _r C ₁₂ alkyl or OC ₆ -C ₁₀ aryl) ₂ , OC (C, -C _{] 2} alkyl or C ₆ -C ₀ aryl), NO ₂ , CF ₃ ,

OCF ₃ , OCF ₂ H, OCFH ₂ , OCF ₂ CF ₃ , OCH ₂ CF ₃ , OCO (C _r C ₁₂ alkyl or C ₆ -C ₁₀ aryl), OP (C, -C ₁₂ alkyl or C ₆ -C, ₀ -aryl) ₃ , OP (OC, -C ₁₀ - alkyl or O- (C ₆ -C ₁₀ -

or C ₆ -C ₁₀ aryl) can be substituted

and / or can optionally be interrupted by oxygen or sulfur atoms or N (C ₁ -C _P alkyl or C ₆ -C ₁₀ aryl) groups.

or represent an optionally protected peptide residue and where R ² and K ^{λ can} independently represent hydrogen,

in the amides of the formula (II)

R, R> 2 ~, u, "ndJ R D3 have the meaning given for formula (I) and

X for a leaving group

stand,

and carbon dioxide, which is characterized in that the reaction is carried out in a solvent and in the presence of one or more basic compounds

In formula (II) X represents halogen may, for example, a sulfonate group or one or more sulfonate group-containing radical preferably stands for chlorine, bromine, C, -C ₄ alkyl phenyl sulfonate, tosylate, perfluoro-C _r C ₄ -alkylsulfonate, Tπfluormethanesulfonat or mesylate

Compounds of the formula (II) are, for example, accessible from the corresponding acids, esters, acid chlorides, acid anhydrides or acid amine salts in a known manner by reaction with amines of the formula (III A)

R - NH ₂ (IIIA),

m the

R ^{1 has} the meaning given for formula (1), or of the formula (III B)

B- (NH ₂ ) _n (IIIB),

in the

B for an aliphatic radical with 3 to 30 C atoms, an aromatic

Radical with 6 to 14 carbon atoms or a heterocyclic radical with 5 to 13 carbon atoms and up to 3 oxygen, sulfur and / or nitrogen atoms in the ring system and

n represents an integer from 2 to 30,

and ketones of the formula

in the

R ² and R have the meaning given for formula (I) and X for formula (II) and

Y represents hydroxy, halogen, C, -C ₆ alkoxy or C ₆ -C ₁₀ aryloxy or OCO-R,

where R has the meaning given for formula (I)

(see e.g. Organicum, Berlin 1990, S 387, 388, 408, 409, 412, 61 1 and 622)

Halogen can mean e.g. fluorine, chlorine, bromine or iodine

Individual, not exhaustively listed examples of alkyl groups, even in compound residues, are methyl, ethyl, propyl, butyl, pentyl, hexyl,

Heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl and hexadecyl, each of which can be straight-chain or branched and / or optionally substituted with fluorine.

Individual, non-exhaustive examples of alkoxy groups, even in compound radicals, are methoxy, ethoxy, propyloxy, butyloxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy and

Dodecyloxy, each of which can be straight-chain or branched and / or optionally substituted with fluorine.

Individual, non-exhaustive examples of hetaryl groups are pyrazolyl, imidazolyl, 1,2,4-triazolyl, pyrrolyl, furanyl, thienyl, thiazolyl, oxazolyl, pyridinyl, pyrimidinyl, triazinyl, quinolinyl, isoquinolinyl, quinazolinyl,

Indolyl, benzothienyl, benzofuranyl, benzothiazolyl, benzimidazolyl, pyrazolylmethyl, imidazolylmethyl, 1,2,4-triazolylmethyl, pyrrolylmethyl, furfuryl, thienylmethyl, thiazolylmethyl, oxazolylmethyl, pyridinylmethyl, pyriazinylmethylmethyl, pyriazinylmethyl Indolylmethyl, benzothienylmethyl, benzofurfuryl, benzothiazolylmethyl or benzimidazolylmethyl, where each of these groups can optionally be monosubstituted to trisubstituted, identical or different, for example by fluorine, chlorine, bromine, methyl, ethyl and / or tert-butyl.

Amines of the formula (III B) are, for example: ethylene, butylene, hexylene, pentylene, octylene, decylene and dodecylene diamine, 1,4-diaminobenzene, 1,4'-benzidine,

2,5-diaminopyridine, so-called TAN amines as described in EP-OS 51 1 948 or amines as described in WO 94/18181

Instead of amines of the formulas (III A) or (IIIB), hydrazine derivatives of the formula (V) can also be used, optionally in proportion

R!

N-NH, (V) / ²

FT in the

R and R ^{~ have} the meaning given for formula (I). Amides of the formula (II) in which R ¹ , R ² and R ¹ independently of one another each represent one of the following radicals are preferred

C, -C ₁₄ alkyl, C ₃ -C ₁₀ alkenyl, C ₃ -C _{] 0} alkyl, C ₃ -C ₁₂ cycloalkyl, C ₅ -C ₇ cycloalkenyl, C ₆ -C _{] 0} aryl, C ₅ -C _{] 0} -hetaryl with up to 3 oxygen, sulfur and / or nitrogen atoms in the ring system, C ₇ -C ₁₂ aralkyl or C ₇ -C, ₀ -alkaryl,

optionally one to five times by 0-Cτ-Q-alkyl or OC ₆ -C ₁₀ aryl, N (C, -C ₆ alkyl or C ₆ -C ₁₀ aryl) ₂ , COO-C, -C ₆ -Alkyl, COO-C ₆ -C ₁₀ -aryl, CONH- C, -C ₆ -alkyl, CON (C, -C ₆ -alkyl) ₂ , OS (C _r C ₆ -alkyl or phenyl), O ₂ S (C _r C ₆ - alkyl or phenyl), CHO, CN, OC (C _r C ₆ alkyl or phenyl), NO ₂ , CF ₃ , OCF ₃ , OCF ₂ H, OCFH ₂ , OCO (C _r C ₆ - Alkyl or phenyl) or HNCO (C, -C ₆ -alkyl or phenyl) may be substituted,

and / or can optionally be interrupted by oxygen or sulfur atoms or N (C _] -C ₆ -alkyl or phenyl) groups and,

where R ² and / or R ^{3 can} also represent hydrogen

Amides of the formula (II) in which R ^{1 represents} one of the following radicals are particularly preferred: methyl, ethyl, n-propyl, l-propyl, butyl, cyclohexyl, phenyl, pyrazolyl, imidazolyl, pyrrolyl, furanyl, thienyl, pyπdinyl, Quinolinyl, isoquinolinyl, quinazolyl, indolyl, benzyl, tolyl and xylyl, which are optionally once or twice by methoxy, ethoxy, phenyl, CHO, CN, Cl, F, Br, OCF ₃ , OCF ₂ H, C arb oxymethyl, carboxyethyl or NO ₂ can be substituted and

which may be interrupted once or twice by an oxygen atom or an N-methyl, N-ethyl or N-phenyl group

The following amines of the formula (III A) may be mentioned individually

Methylamine, ethylamine, n-propylamine, l-propylamine, n-butylamine, l-butylamine, s-butylamine, n-pentylamine, amylamine, l-amylamine, hexylamine, heptylamine, octylamine, nonylamine, dodecylamine, undecylamine, dodecylamine, tπdecylamine , Tetra-decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, cyclohexylamine, benzylamine, phenylamine, allylamine, aniline, 2-ethylaniline, 2-propylaniline 2-cyclohexylaniline, 3,5-dichloroaniline, 4-chloro-5-fluorine hvdroxvanιlιn and l-fluoro-4-chloro-5-chloro-5-cyclopentyloxyanιlιn as well as the methyl and ethyl esters of the following amino acids and the peptides with the following amino acid end groups alanine, arginine, asparagine, aspartic acid, cysteine, glutamine, glutamic acid, glycine, Histidine, isoleucine, leucine, lysine, methionine, phenylalanine, Prohn, Senn, threonine, tryptophan, tyrosine, valm, t-butylglycine,

Ornithine, norleucine and sarcosine

The usual commercial product, optionally also known as dry ice, can be used as carbon dioxide in the process according to the invention. In addition, especially for special purposes, for example for analytical or diagnostic uses or for such uses of the products which can be produced therefrom, isotope-enriched, e.g. B ¹³ C and / or ¹⁴ C containing carbon dioxide can be used

R ² and R ³ can also together stand for one of the following radicals in divalent form C, -C ₃₀ alkyl, C ₄ -C ₁₂ cycloalkyl, C ₅ -C ₃₀ alkenyl, C ₈ - C ₃₀ alkynyl, C ₇ -C ₂₀ aralkyl, C ₈ -C ₂₀ aralkenyl, C ₈ -C ₂₀ alkenaryl and up to 3

Oxygen, sulfur and / or nitrogen atoms in the ring system contained C ₅ - C _π -Alkenhetaryl and C ₅ -C, ₃ -Alkιnhetaryl,

where together with the carbon atom to which R ² and R ^{3 are} bound, 3- to 7-glιedπge rings result and

chain-like molecular parts, linear, branched and / or optionally by

Oxygen, sulfur, N (C, -C ₁₂ alkyl or C ₆ -C ₁₀ aryl) -, CO-, COO-, SO-, SO ₂ - or SO (O) O- or OP (C _] -C ₁₂ alkyl or C ₆ -C ₁₀ aryl) groups can be interrupted

For each amide equivalent used, for example 0.01 to 10,000 equivalents of carbon dioxide can be used in the process according to the invention. This ratio is preferably 1 0.5 to 1 1000, in particular 1 1 to 10

It is an essential feature of the present invention that one works in the presence of one or more basic compounds, in particular basic compounds of the elements lithium, sodium, magnesium, potassium calcium, rubidium, strontium, cesium, barium and / or ammonium are favorable The basic compounds include, for example, basic salts, oxides, Hydrides and hydroxides in question. Examples include: lithium hydride, sodium hydride, potassium hydride, calcium hydride, lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, lithium oxide, sodium peroxide, potassium oxide, potassium peroxide, calcium oxide, barium oxide, magnesium oxide, ^• strontium oxide,

Lithium carbonate, lithium hydrogen carbonate, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, rubidium carbonate, rubidium hydrogen carbonate, cesium hydrogen carbonate, cesium carbonate, lithium cyanide, sodium cyanide, potassium cyanide, rubidium cyanide, ammonium hydrogen carbonate, ammonium carbonate, ammonium carbamate, potassium hydrogen sulfide, potassium

Sodium sulfide, sodium hydrogen sulfide and / or their naturally occurring or synthetically obtainable mixtures, such as, for example, dolimite or magnesium oxide carbonate and / or compounds which contain sodium or potassium metal in dispersed form on the corresponding carbonates.

Al potassium carbonates and / or hydrogen carbonates are preferred, very particularly preferably potassium carbonate.

The basic compounds can be used in anhydrous form or, in the case of salts which crystallize with water of hydration, also in hydrated form. Anhydrous compounds are preferably used

The basic compounds can be used, for example, in amounts of 0.5 to 10 mol per mol of the amide of the formula (II) used. This amount is preferably in the range from 0.8 to 5 mol, particularly preferably in the range from 1 to 2.5 mol, in each case per mol of amide of the formula (II) used.

The process according to the invention can optionally be carried out in the presence of auxiliary bases, i.e. in the presence of further bases, for example in an amount of less than 1.0 mol, preferably less than 0.5 mol, in each case based on 1 mol of the basic compound.

Examples of such auxiliary bases are: halides of alkali metals, zeolites, potassium acetate, potassium formate, sodium acetate, titanium alkonates, titanium acid amides, amidine bases or guanidine bases such as 1,5-diazabicyclo-

(4.3.0) non-5-ene (DBN), 1,8-diazabicyclo (5.4.0) undec-7-ene (DBU), 7-methyl-1,5,7-triazabicyclo (4.4.0) dec -5-ene (MTBD), cyclohexyl-tetrabutylguanidine, cyclohexyl- tetramethylguanidine, N, N, N, N-tetramethyl-1, 8-naphthalιndιamιn, pentamethyl-pipeπdin, N, N-Dιmethylamιnopyπdιn, N-butyl-tetraethylguanidine, Nt-butyl-N ', N'-diethylformamidine, tetramethylguanidine Nt-butyl-N ', N'-dimethylacetamidine, N-cyclohexyl-tetraethylguanidine and Nt-butyl-tetraethylguanidine as well as 1,4-diazabyclo (2 2 2) octane (DABCO), tertiary amines such as

Triethylamine, Tπmethylamin, N-methylmorphohn, pyridine and tetramethylethylenediamine, pπmare and secondary amines of the same structure as the amine used for the reaction, alkyl and aryl metal compounds, such as butyl, methyl, phenyl and neopylithium, as well as Ggnard reagents

The process according to the invention is carried out in the presence of solvents. The solvent is advantageously used in such an amount that the reaction mixture remains readily stirrable throughout the process. Examples of suitable solvents are hydrocarbons such as petroleum ether, benzene, toluene, chlorobenzene and dichlorobenzene , Hexane, cyclohexane, methane, cyclohexane, pentane, heptane, octane and technical hydrocarbon mixtures, for example so-called white spins with components with boiling points in the range from, for example, 40 to 250 ° C., ethers such as dimethyl, diethyl, dipropyl, diisopropyl , Dibutyl, methyl t-butyl ether, tetrahydrofuran, 1,4-dioxane and polyethers of ethylene oxide and / or propylene oxide, amines such as tπmethyl, triethyl, tπpropyl, tπbutylamine, N-methylmorpholine, pyridine and

Tetramethylethylenediamine, esters such as methyl, ethyl and butyl acetate, as well as dimethyl, dibutyl and ethylene carbonate, nitro compounds such as nitromethane, nitroethane, nitropropane and nitrobenzene, nitπle such as acetonitrile, propionite and benzonite, as well as compounds such as tetrahydroth- thylene sulfoxide and dimethyl sulfoxide, diphenoxide and sulfonium oxide, dimethyl sulfoxide and dimethyl sulfoxide, diphenoxide and sulfonium oxide, dimethyl sulfoxide and diphenyl sulfoxide, diphenoxide and sulfonium oxide, dimethyl sulfoxide and diphenoxide, diphenoxide and sulfonium oxide, , Benzylmethyl sulfoxide, dnsobutyl sulfoxide, dibutyl sulfoxide, dnsoamyl sulfoxide, ketones such as acetone, methyl butyl ketone and methyl ethyl ketone, liquefied carbon dioxide, polyethers of ethylene oxide and / or propylene oxide and amides such as hexamethylene-phosphorotamin, N-methylpyrrolactam, N-methylpyrrolamone -Dιmethyl- 3, 4,5,6-tetrahydro-2 (lH) -pyπmιdιn, octylpyrrohdon, octyl caprolactam, 1, 3-

Dimethyl-2-ιmιdazolιndιon, dimethylformamide, dimethyl-acetamide, formamide, diethylformamide, N-formylpyrrodone, N-formylmorpholine, N-formylpipeπdin, N, N'-l, 4-dimethylpιperazιn, dipropylformamide and dimethyl sulfone come into question -, Diethyl, dipropyl, dibutyl, dipentyl, dihexyl, methylethyl, ethylpropyl, ethyl isobutyl and pentamethylene sulfone in

Question as well as 3-Sulfolen Auxiliaries such as cryptands, for example crown ethers or polyethers as complexing agents, can optionally be added to the solvents

Of course, mixtures of solvents can also be used in the process according to the invention

Preferred solvents are dimethylformamide and dimethyl sulfoxide and mixtures of these with other of the solvents mentioned

The process according to the invention is generally carried out by bringing the amide and the carbon dioxide together in the presence of a basic compound and a solvent and allowing them to react with one another

The process according to the invention can be carried out, for example, at temperatures of

Carry out -50 to + 180 ° C. Temperatures in the range from -30 ° C. to + 150 ° C. are preferred, in particular those in the range from -10 ° C. to + 100 ° C.

The pressure is not critical in the process according to the invention. In principle, it is possible to work with normal pressure, but also with increased or reduced pressure. The process is preferably carried out under normal pressure or with pressures of up to

15 bar. At higher temperatures it is advantageous to work under increased pressure, possibly also above 15 bar

The process according to the invention can be carried out under a carbon dioxide atmosphere, but also in an atmosphere which contains carbon dioxide and still other, preferably inert, gases. When working in liquid carbon dioxide, this is preferably done in a closed vessel at the autogenous pressure which arises. You can also work in supercritical carbon dioxide, but then you have to apply pressure of e.g. 80 to 200 bar

The process according to the invention has a number of surprising advantages. It allows the preparation of compounds of formula (I) in a technically simple, economically advantageous manner while avoiding the use of phosgene, chlorine, formic acid esters, isocyanates, carbamoyl chlorides and carbonates, which in many cases are entirely require considerable effort for plant safety. It can be carried out under mild reaction conditions and the reaction mixtures can often be used directly, for example for hydrogenations, Chlorination, bromination, oxidation, condensation, polymerization and / or for nucleophilic substitutions as described in WO 94/18 181

It can be used to easily introduce radioactive or labeled C atoms into organic molecules. If the compound of formula (I) is to be isolated in pure form, this can also be done in a simple manner, for example by separating the salt mixture present in the reaction mixture, removing the volatile constituents of the reaction mixture and then removing the product, for example by Distillation or crystallization, isolated. Since the process according to the invention is heterogeneous, it is also suitable for continuous implementation, in which case solvents and

Base, optionally after regeneration, can be returned to the reaction mixture. This is particularly favorable for the solvent, since it allows direct reuse without the use of an aqueous phase during processing.

It is also possible and useful to prepare the oxazolidine-2,4-diones from the amines, compounds of the formula (III), carbon dioxide and base in one pot in two steps

Products of the formula (I) are important substances in the chemical industry which can be used, for example, as intermediates for active ingredients or as active ingredients in crop protection (in particular insecticides, pesticides, fungicides and herbicides) and in the pharmaceutical sector. They can also be used as intermediates for plastics, Lacquers and polymers serve

Some particularly important compounds of the formula (I) which can be prepared according to the invention are e.g. Trimethadione, paramethadione, malidone, vinclozolin, ethadione, propazone, chlozolinate, RN 24 261 -46-9, 129 143-39-1,

1 10 956-75-7 and 1012-87-9, myclozolin, dichlozolin and the like. Oxazolidine-2,4-diones prepared according to the invention can also be used as protective groups, for example peptide chemistry, or as formulation auxiliaries if R = C ₆ -C ₃₀ alkyl and R ² , R ³ = H, methyl or ethyl Examples

The reaction was carried out in a manner similar to that described in DE-OS 4 318 889, but with the difference that all the reactants were introduced together and carbon dioxide was introduced at the same time under pressure or over a longer period of time without significant pressure.

example 1

N-hexyloxazolidine-2,4-dione

5.15 g of hexylchloroacetic acid amide, 8.02 g of potassium carbonate and 70 ml of dimethyl sulfoxide were stirred at 25 ° C. for 12 hours, a carbon dioxide atmosphere being maintained. The mixture was then heated to 50 ° C. and stirred for a further 8 hours. Finally, the reaction mixture was discharged onto 250 ml of water and extracted with ethyl acetate, and the residue obtained after the volatile components had been driven off was distilled in a bulb tube. Yield: 5.0 g (= 99.6% of theory; bp: 1 12-1 13 ° C / 0.3 mbar)

The other examples were carried out analogously. The reaction time at 25 ° C. was varied in part, no noteworthy changes in yield being observed, and in the case of products which were solid at room temperature or could not be distilled under normal conditions, the aqueous work-up was dispensed with and the product was isolated directly after filtration and removal of the solvent . The use of DBU instead of potassium carbonate reduced the yield.

The results are summarized in the following table, in each case the product produced is indicated and R ^{3 was} hydrogen in all cases. table

Claims

1 Process for the preparation of oxazolidin-2,4-diones of the formula (I)

OR ^z

^

R ^J

R ^[ N (D,

C o o in the

R, R and R "are the same or different and each represents one of the following radicals:

C _r C ₃₀ alkyl, C ₃ -C ₃₀ alkenyl, C ₃ -C ₃₀ alkynyl, C ₃ -C ₁₂ cycloalkyl, C ₅ -C _{] 2} cycloalkenyl, C ₈ -C _{] 2} cycloalkynyl, C ₆ -C ₁₄ aryl, C ₅ -C _{] 3} hetaryl with up to 3 oxygen, sulfur and / or nitrogen atoms in the ring system, C ₇ -C ₂₀ aralkyl, C ₉ -C ₂₀ aralkenyl, C ₉ -C ₂₀ aralkynyl, C ₇ -C ₂₀ alkaryl, C ₈ -C ₂₀ -

Alkenaryl or C ₈ -C ₂₀ -alkinaryl,

optionally one to five times by OC _j -C _p alkyl or OC ₆ -C ₁₀ aryl, N (C _r C ₁₂ alkyl or C ₆ -C ₁₀ aryl) ₂ , COO-C _r C _{l 2} alkyl or COO-C ₆ -C _U) aryl, CONH-C, -C ₁₂ alkyl, CONH-C ₆ -C ₁₀ aryl, CON (C _r C ₁₂ alkyl) ₂ , CON (C ₆ -C ₁₀ -Aryl) ₂ halogen, OP (OC, -C ₁₂ -Alky! Or OC ₆ -

C ₁₀ aryl) ₂ , Si (C _r C ₁₂ alkyl and / or C ₆ -C ₁₀ aryl) ₃ , Si (OC _r C ₁₂ alkyl and / or C ₆ -C _{] 0} aryl) ₃ , Si (C _r C ₁₂ alkyl and C ₆ -C _{] 0} aryl) (OC _r C ₁₂ alkyl and / or OC ₆ -C ₁₀ aryl) ₂ , Si (C _r C ₁₂ alkyl and / or C ₆ -C _1Q aryl) ₂ (OC _r C _{I 2} alkyl or OC ₆ -C ₁₀ aryl), OS (C, -C ₁₂ alkyl or C ₆ -C ₀ aryl, O ₂ S (C , -C ₁₂ alkyl or C ₆ -C ₁₀ aryl), CHO, CN, C (OC, -C ₁₂ alkyl or

OC ₆ -C ₁₀ aryl) ₂ , OC (C, -C ₁₂ alkyl or C ₆ -C ₁₀ aryl), NO ₂ , CF ₃ , OCF, OCF ₂ H, OCFH ₂ , OCF ₂ CF ₃ , OCH ₂ CF ₃ , OCO (C, -C, ₂ alkyl or C ₆ -C ₁₀ aryl), OP (C _r C ₁₂ alkyl or C ₆ -C ₁₀ aryl) ₃ , OP (OC _r C ₁₀ - Alkyl or O- (C ₆ -C ₁₀ aryl) -, (C _] -C _p -alkyl or C ₆ -C, _0- aryl) may be substituted

and / or optionally by oxygen or sulfur atoms or N (C _j -

C _p alkyl or C ₆ -C _ι aryl) groups can be interrupted, or represent an optionally protected peptide residue

and where R ² and R ^{3 can} independently represent hydrogen,

in the amides of the formula (II)

in the

R 1, R τ> - ~, u, "nΛd D R3 have the meaning given for formula (I) and

X for a leaving group

stand,

and carbon dioxide are reacted, characterized in that the reaction is carried out in a solvent and in the presence of one or more basic compounds

Process according to Claim 1, characterized in that in formula (II) X represents halogen, a sulfonate group or a radical containing one or more sulfonate groups

Process according to Claims 1 and 2, characterized in that amides of the formula (II) are used which have been obtained from the corresponding acids, acid chlorides, esters, acid anhydrides or acid amine salts by reacting amines of the formula (III A)

R'-NH-, (III A),

in the R ^{1 has} the meaning given in claim 1 for formula (I) or the formula (III B)

B- (NH ₂ ) "(III B),

in the

B for an aliphatic radical with 3 to 30 C atoms, an aromatic radical with 6 to 14 C atoms or a heterocyclic radical with 5 to 13 C atoms and up to 3 oxygen, sulfur and / or nitrogen atoms in the Ring system and

represent an integer from 2 to 30,

and ketones of the formula (IV)

in the

R ² and R ^{3 have} the meaning given in claim 1 for formula (I) and

Y for hydroxy, halogen, C _r C ₆ alkoxy, C ₆ -C ₁₀ aryloxy or OCO-

R ¹ is where R ^{1 has} the meaning given in claim 1 for formula (I).

Process according to Claim 3, characterized in that amides of the formula (II) are used which have been obtained by using hydrazine derivatives of the formula (V) instead of amines of the formulas (III A) or (III B) R

\

N - NH, (V),

/

FT

R and R> 2 have the meaning given in claim 1 for formula (I)

Process according to Claims 1 to 4, characterized in that 0.01 to 10,000 equivalents of carbon dioxide are used per amide equivalent used

Process according to Claims 1 to 5, characterized in that those of the elements lithium, sodium, magnesium, potassium, calcium, rubidium, strontium, cesium, barium and / or ammonium are used as basic compounds

Process according to Claims 1 to 6, characterized in that 0.5 to 10 mol of basic compound are used per mol of amide of the formula (II) used

Process according to Claims 1 to 7, characterized in that, based on 1 mol of basic compound, less than 1.0 mol of auxiliary bases are used

Process according to Claims 1 to 8, characterized in that hydrocarbons, ethers, amines, esters, nitro compounds, nitπle, terahydrothiophene dioxide, dimethyl sulfoxide, tetramethylene sulfoxide, dipropyl sulfide, benzyl methyl sulfoxide, dnsobutyl sulfoxide, dibutyl sulfoxide are used as solvents,

Dnsoamyl sulfoxide, ketones, liquefied carbon dioxide, polyethers of ethylene and / or propylene oxide, amides and / or sulfones

Process according to Claims 1 to 9, characterized in that it is carried out at temperatures in the range from -50 to 180 ° C and pressures up to 15 bar