DE102005023858A1 - Preparation of spiro-orthoester comprises reaction of a lactone with an epoxide in the presence of a catalyst e.g. heterogeneous acid catalyst - Google Patents

Abstract

Preparation of spiro-orthoester comprises reaction of a lactone with an epoxide in the presence of a catalyst such as a heterogeneous acid catalyst; excluding fluorinated sulfonic acid group containing ion exchanger resin.

Description

The The invention relates to a process for the preparation of spiroorthoesters by reacting a lactone with an epoxide in the presence of a catalyst.

• 1. die Polymerisierung der Epoxide und
• 2. eine Umlagerung der gebildeten Spiroorthoester.

It is known to prepare spiroorthoesters by adding lactones to epoxides in the presence of catalytic amounts of a Lewis acid. K. Bodenbrenner, Liebigs Ann. Chem. 623, 183 (1959) describes the reaction of lactones with epoxides to give spiroorthoesters in the presence of catalytic amounts of boron trifluoride etherate or tin tetrachloride in carbon tetrachloride as solvent. As epoxides, ethylene oxide, propylene oxide, epichlorohydrin and phenoxypropylene oxide are reacted. As lactones, 5- and 6-membered lactones are reacted, in detail γ-butyrolactone, α-chloro-γ-butyrolactone, δ-valerolactone and coumarin. The spiroorthoesters are obtained in yields of between 20 and 70%. For the non-quantitative formation of orthoester side reactions are attributed, which are catalyzed by the Lewis acids used, namely

• 1. the polymerization of epoxides and
• 2. a rearrangement of the formed Spiroorthoester.

DD 275,687 describes a process for the preparation of spiroorthoesters from lactones and epoxides, in which a mixture of boron trifluoride or boron trifluoride etherate and tin tetrachloride or antimony pentachloride is used as the catalyst. By using the Lewis acid mixture, a significant reduction of side reactions while avoiding long reaction times to be achieved. In the examples, a hydroxylactone, namely 3-hydroxy-4,4-dimethyldihydrofuran-2-one (pantolactone) is reacted with ethylene oxide or epichlorohydrin in dichloromethane as the solvent, wherein in the presence of tin tetrachloride / boron trifluoride etherate or antimony pentachloride / boron trifluoride etherate Catalyst is worked. There are yields of 28% of theory, based on ethylene oxide, or 55% of theory, based on epichlorohydrin, achieved.

lee et al., Chem. Lett. 1990, 2019-2022 disclose the reaction of γ-butyrolactone with propylene oxide and γ-valerolactone with epichlorohydrin in the presence of N- (4-methoxybenzyl) -2-cyanopyridinium hexafluoroantimonate as a catalyst in the absence of a solvent. It will be Yields of 45% and 72%, respectively.

In Zh. Prikl. Khim. 59 (3), 600-604 (1986), the reaction of γ-butyrolactone with epichlorohydrin on a perfluorinated, containing sulfonic acid groups Ion exchange resin (F-4SK) described.

The in the literature described manufacturing process for spiroorthoester using Lewis acid catalysts are predominantly homogeneously catalyzed process. These have the disadvantage that the catalyst is deactivated quickly and therefore not insignificant Quantities must be used. The yields are low and are dependent on the starting materials, between 20 and 70%. These are by-products, especially polymers formed. The workup of the product mixture obtained is complicated, since the catalyst is separated consuming or must be deactivated. A recovery and return of the Lewis acid catalyst is also not possible.

task The invention is an improved process for the production of spiroorthoesters of epoxides and lactones and to remedy the disadvantages of the prior art. Object of the invention in particular, it is a process for producing spiroorthoesters to provide which is characterized by high yields and a simplified workup of the obtained in the reaction Product mixture allows. The object of the invention is also to provide such a method, in which the catalyst is easily separated and reused can be.

Is solved the object by a process for the preparation of spiroorthoesters by reacting a lactone with an epoxide in the presence of a Catalyst, characterized in that the catalyst an acidic heterogeneous catalyst, except fluorinated, containing sulfonic acid groups Ion exchange resins, is.

The use of heterogeneous catalysts considerably simplifies the preparation of spiroorthoesters. The heterogeneous catalyst can be easily separated from the product mixture obtained and reused or recycled in continuous implementation of the method in the reaction. The heterogeneous catalyst is not or only slightly deactivated in the reaction and can be used repeatedly. The product mixture can be separated by distillation after separation of the catalyst without further elaborate workup in the individual components. Due to the possible recycling of the heterogeneous catalyst and unreacted educts can also at partial conversion the educts used are an economic process can be realized. Furthermore, the process according to the invention can be carried out continuously, for example in a fixed bed or fluidized bed reactor.

The used in the process according to the invention Lactones preferably have a ring size of 4 to 13 ring atoms on. Besides unsubstituted lactones, substituted lactones can also be used can be used, for example with halogen, alkyl, haloalkyl or hydroxy substituted lactones. The lactone structure can be simple or multiple times in the molecule to be available. In any case, all lactones are already suitable according to the methods of the prior art using Homogeneous catalysts successfully with epoxides to spiroorthoesters have been implemented. Suitable epoxides include all epoxides already according to the methods known from the prior art in the presence of homogeneous catalysts reacted with lactones to spiroorthoesters were. The epoxides can the oxirane structure single or multiple in the molecule. Examples are ethylene oxide, propylene oxide and epichlorohydrin. The Epoxides can Be polymers with an epoxy end group.

worin
X eine gegebenenfalls substituierte, gesättigte oder ungesättigte Alkylengruppe mit 2–12 C-Atomen, wobei eine oder mehrere nicht direkte benachbarte Methylengruppen durch -O-, -C(O)O-, -C(O)-, -S- und -NR- und zwei direkt benachbarte Methylengruppen durch die Kohlenstoffatome eines annellierten aromatischen Rings, bevorzugt 1,2-Phenylen, ersetzt sein können,
bedeutet,
mit einem Epoxid der allgemeinen Formel (II)

worin
R¹–R⁴ unabhängig voneinander Wasserstoff, eine gegebenenfalls substituierte Alkylgruppe mit 1–18 C-Atomen, eine gegebenenfalls substituierte Alkenylgruppe mit 2–18 C-Atomen, eine gegebenenfalls substituierte Phenylgruppe oder -COOR⁵, worin R⁵ eine Alkylgruppe mit 1–8 C-Atomen ist, und wobei auch jeweils zwei der Reste R¹–R⁴ eine gesättigte oder ungesättigte Alkylengruppe mit 2 bis 18 C-Atomen bilden können,
bedeutet,
zu einem Spiroorthoester der allgemeinen Formel (III)

worin R¹–R⁴ und X wie oben definiert sind,
umgesetzt.Preferably, a lactone of the general formula (I)

wherein
X is an optionally substituted, saturated or unsaturated alkylene group having 2-12 C atoms, where one or more non-adjacent, adjacent methylene groups are represented by -O-, -C (O) O-, -C (O) -, -S- and - NR and two directly adjacent methylene groups can be replaced by the carbon atoms of an annulated aromatic ring, preferably 1,2-phenylene,
means
with an epoxide of the general formula (II)

wherein
R ¹ -R ^{4 are} independently hydrogen, an optionally substituted alkyl group having 1-18 C atoms, an optionally substituted alkenyl group having 2-18 C atoms, an optionally substituted phenyl group or -COOR ⁵ , wherein R ^{5 is} an alkyl group having 1- 8 C atoms, and wherein in each case two of the radicals R ¹ -R ^{4 can form} a saturated or unsaturated alkylene group having 2 to 18 C atoms,
means
to a spiroorthoester of the general formula (III)

wherein R ¹ -R ⁴ and X are as defined above,
implemented.

is X in formula (I) is a substituted alkylene group, this is for example with halogen (F, Cl, Br, I, preferably Cl and Br, in particular Cl), alkyl and / or -OH- or substituted several times. Preferably, X in formula (I) is an unsubstituted one or one or more times substituted alkylene group having 3, 4 or 5 C atoms, i. connection (I) is preferably unsubstituted or substituted γ-butyrolactone, δ-valerolactone or ε-caprolactone. examples for substituted γ-butyrolactone, δ-valerolactone or ε-caprolactone are derived from γ-hydroxy, δ-hydroxy or ε-hydroxy fatty acids alkyl- or alkenyl-substituted γ-butyrolactones, δ-valerolactones or ε-caprolactones, for example γ-decalactone, δ-decalactone or δ-dodecalactone.

Especially preferred lactones of the general formula (I) are γ-butyrolactone, δ-valerolactone, ε-caprolactone, Coumarin, γ-decalactone, δ-decalactone and δ-dodecalactone.

If R ¹ -R ⁴ in formula (II) is a substituted alkyl group, this is preferably monosubstituted or polysubstituted by halogen (F, Cl, Br, I, preferably Cl and Br, in particular Cl). Preferably, the optionally substituted alkyl group has 1-18 C atoms. If R ¹ -R ⁴ in formula (II) is a substituted phenyl group, this is preferably substituted by alkyl or halogen. R ⁵ in -COOR ⁵ is preferably an alkyl group having 1-18 C atoms, in particular methyl, ethyl or tert-butyl.

Especially preferred epoxides of the general formula (II) are ethylene oxide, Propylene oxide, epichlorohydrin, glycidyl methyl ester (oxirane-2-carboxylic acid methyl ester), Styrene epoxy, butylene oxide, isobutylene oxide and vinyloxirane.

• – Ionenaustauscherharze, ausgenommen fluorierte, Sulfonsäuregruppen enthaltende Ionenaustauscherharze,
• – Tonmineralien
• – Zeolithe
• – auf oxidische Trägermaterialien geträgerte Brönsted-Säuren
• – Alkali- und Erdalkalimetallfluoride
• – saure Metalloxide der Elemente Al, Ce, Th, Ti, Zr, Sn, Pb, As, Bi, Sb, V, Cr, Mo, W, Zn, Cd
• – saure Metallsulfide der Elemente Cd und Zn
• – Sulfate, Phosphate und Halogenide der Elemente Mg, Ca, Sr, Ba, Cu, Zn, Cd, Al, Fe, Co, Ni, Cr, K, B, Ti, Sn und Ag
• – Mischoxide
• – Heteropolysäuren

Suitable acidic heterogeneous catalysts are generally selected from one of the following groups:

• Ion exchange resins, excluding fluorinated ion exchange resins containing sulfonic acid groups,
• - clay minerals
• - zeolites
• - Brönsted acids supported on oxidic support materials
• - alkali and alkaline earth metal fluorides
• Acidic metal oxides of the elements Al, Ce, Th, Ti, Zr, Sn, Pb, As, Bi, Sb, V, Cr, Mo, W, Zn, Cd
• Acidic metal sulfides of the elements Cd and Zn
• Sulfates, phosphates and halides of the elements Mg, Ca, Sr, Ba, Cu, Zn, Cd, Al, Fe, Co, Ni, Cr, K, B, Ti, Sn and Ag
• - mixed oxides
• - Heteropolyacids

Suitable ion exchange resins, for example, Amberlyst ^{®, ®} and Anberlite Dowex ^®.

suitable Clay materials are, for example, kaolins, bentonites, attapulgites, Montmorillonite, Sepiolite, Halloysite and other silicates with Layer, network, chain or island structure.

suitable Zeolites are, for example, X, Y and A zeolite, mordenite, pentasils, ZSM-5, ZSM-11, Beta, ZSM-22, MCM-22, ZBM-11, ZBM-10, Ferrierite, Chabazite, Erionite, zeolite-analogous alumino- and silico-aluminophosphates, MeAlPO-, MeAPO- and MeAPSO compounds and Atlas of Zeolite Framework Types, Ch. Baerlocher, W.M. Meier, D.H. Olson, Elsevier 2001, 5th Edition, cited zeolites.

Examples of supported Brönsted acids are homogeneous acids such as sulfuric acid, phosphoric acid or acetic acid supported on SiO ₂ , Al ₂ O ₃ , TiO ₂ , CrO ₂ , Fe ₂ O ₃ and aluminosilicates as support materials.

Suitable acidic metal oxides are, for example, ZnO, CdO, Al ₂ O ₃ , CeO ₂ , ThO ₂ , TiO ₂ , ZrO ₂ , SnO ₂ , PbO, As ₂ O ₃ , Bi ₂ O ₃ , Sb ₂ O ₅ , V ₂ O ₅ , Cr ₂ O ₃ , MoO ₃ , WO ₃ , suitable metal sulfides are CdS and ZnS.

Suitable mixed oxides are, for example, SiO ₂ -Al ₂ O ₃ , SiO ₂ -TiO ₂ , SiO ₂ -SnO ₂ , SiO ₂ -ZrO ₂ , SiO ₂ -BeO, SiO ₂ -MgO, SiO ₂ -CaO, SiO ₂ -SrO, SiO ₂ -ZnO, SiO ₂ -Ga ₂ O ₃ , SiO ₂ -Y ₂ O ₃ , SiO ₂ -La ₂ O ₃ SiO ₂ -Mo ₂ O ₃ SiO ₂ -WO ₃ , SiO ₂ -V ₂ O ₅ , SiO ₂ -ThO ₂ , Al ₂ O ₃ -MgO, Al ₂ O ₃ -ZnO, Al ₂ O ₃ -CdO, Al ₂ O ₃ -B ₂ O ₃ , Al ₂ O ₃ -ThO ₂ , Al ₂ O ₃ -TiO ₂ , Al ₂ O ₃ -ZrO ₂ , Al ₂ O ₃ -V ₂ O ₅ , Al ₂ O ₃ -MoO ₃ , Al ₂ O ₃ -WO ₃ , Al ₂ O ₃ -Cr ₂ O ₃ , Al ₂ O ₃ -Mn ₂ O ₃ , Al ₂ O ₃ -Fe ₂ O ₃ , Al ₂ O ₃ -Co ₃ O ₄ , Al ₂ O ₃ -NiO, TiO ₂ -CuO, TiO ₂ -MgO, TiO ₂ -ZnO, TiO ₂ -CdO, TiO ₂ -ZrO ₂ , TiO ₂ -SnO ₂ , TiO ₂ -Bi ₂ O ₃ , TiO ₂ -Sb ₂ O ₅ , TiO ₂ -V ₂ O ₅ , TiO ₂ -Cr ₂ O ₃ , TiO ₂ - MoO ₃ , TiO ₂ -WO ₃ , TiO ₂ -Mn ₂ O ₃ , TiO ₂ -Fe ₂ O ₃ , TiO ₂ -Co ₃ O ₄ , TiO ₂ -NiO, ZrO ₂ -CdO, ZnO-MgO, ZnO-Fe ₂ O ₃ , MoO ₃ -CoO-Al ₂ O ₃ , MoO ₃ -NiO-Al ₂ O ₃ , TiO ₂ -SiO ₂ -MgO and MoO ₃ -Al ₂ O ₃ -MgO.

preferred Acidic heterogeneous catalysts are selected from zeolites and ion exchange resins.

Especially Preferred acidic heterogeneous catalysts are zeolites, for example Boron-zeolite.

The Reaction of lactone with epoxy is at temperatures of generally 0 to 300 ° C, preferably 80 to 220 ° C and when pressed of generally 1 to 200 bar, preferably 1 to 40 bar performed. The depend optimal reaction conditions from the activity of the catalyst used and of the educts and leave easily identify themselves through orientation experiments.

The Reaction of lactone with epoxide can be carried out in a solvent or in the absence of a solvent respectively. Suitable solvents are for example, dichloromethane, chloroform, carbon tetrachloride, Methyl tert-butyl ether, benzene and toluene.

The Reaction can be carried out batchwise or continuously. If the reaction is carried out batchwise, the acidic heterogeneous catalyst generally in amounts of 0.1 to 20 wt .-%, based on the Reaction mixture used. The process according to the invention can be discontinuous for example in a stirred autoclave carried out become. For example, the process according to the invention can be continuous in a tubular reactor with fixed catalyst bed or in a fluidized bed reactor carried out become. The catalyst may, depending on the procedure, as a powder, Granules, grit or in the form of ordinary Moldings, For example, rings, tablets and strands are used. Becomes the process is carried out continuously, then the product mixture preferably for the removal of traces of acid before work-up preferably passed through a guard bed, which is a basic Component, for example, basic carbonates or oxides or basic Contains ion exchanger.

Of the Acidic heterogeneous catalyst can be easily separated from the product mixture be separated, for example by filtration, and used again be, or in continuous implementation of the Be returned to the implementation process.

The Invention will be explained in more detail by the following examples.

example 1

In an inerted glass autoclave are 4.8 g of epichlorohydrin and 2.32 g γ-butyrolactone submitted and 0.46 g of boron zeolite (β-B zeolite) added. The autoclave is closed and heated to 200 ° C. After 4 hours, cool to room temperature and the catalyst becomes filtered off. The filtrate is analyzed by gas chromatography. It will an epichlorohydrin conversion of 64% was found. The selectivity of formation of 2-chloromethyl-1,4,6-trioxaspiro [4.4] nonane (syn- and anti-adduct) is 98 regarding Epichlorohydrin and 99% with respect to γ-butyrolactone.

Subsequently was the reaction is repeated using the filtered catalyst, wherein under the same conditions an epichlorohydrin conversion of 62% was achieved. The spiroorthoester was changed to epichlorohydrin with a selectivity made up of 98%. activity and selectivity of the catalyst used have thus practically not decreased.

Example 2

In an inerted glass autoclave, 5.27 g of oxirane-2-carboxylic acid methyl ester (Glycidyl methyl ester) and 2.22 g of γ-butyrolactone submitted and 0.53 g of boron zeolite (β-B zeolite) was added. The autoclave will closed and then with stirring at 160 ° C heated. After 4 hours, the autoclave is cooled to room temperature, the Catalyst filtered off and the filtrate analyzed by gas chromatography. It becomes an oxirane-2-carboxylic acid methyl ester conversion found from 39%. The 1,4,6-trioxaspiro [4.4] nonane-2-carboxylic acid methyl ester is with a selectivity of 97 for γ-butyrolactone formed, with syn and anti-adduct in the ratio 1: 2 are formed.

Claims (10)

A process for the preparation of spiroorthoesters by reacting a lactone with an epoxide in the presence of a catalyst, characterized in that the catalyst is an acidic heterogeneous catalyst, except fluorinated, sulfonic acid groups containing ion exchange resins. A method according to claim 1, characterized in that a lactone of the general formula (I)

wherein X is an optionally substituted, saturated or unsaturated alkylene group having 2-12 C atoms, wherein one or more non-adjacent vicinal methylene groups represented by -O-, -C (O) O-, -C (O) -, -S- and -NR- and two directly adjacent methylene groups may be replaced by the carbon atoms of a fused aromatic ring, means with an epoxide of the general formula (II)

wherein R ¹ -R ^{4 are} independently hydrogen, an optionally substituted alkyl group having 1-18 C atoms, an optionally substituted alkenyl group having 2-18 C atoms, an optionally substituted phenyl group or -COOR ⁵ , wherein R ^{5 is} an alkyl group with 1 In which in each case two of the radicals R ¹ -R ^{4 can form} a saturated or unsaturated alkylene group having 2 to 18 C atoms, to give a spiroorthoester of the general formula (III)

wherein X and R ¹ -R ^{4 have} the meaning given above, is reacted. Method according to claim 1 or 2, characterized that the lactone of the general formula (I) is selected from β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, Coumarin, γ-decalactone, δ-decalactone and δ-dodecalactone. Method according to one of claims 1 to 3, characterized that the epoxide of the general formula (II) is selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, Styrene epoxide, glycidyl alkyl esters, butylene oxide, isobutylene oxide and Vinyl oxirane. Method according to one of claims 1 to 4, characterized in that the acidic heterogeneous catalyst is selected from ion exchange resins, except fluorinated, containing sulfonic acid ion exchangers resins - clay minerals - zeolites - Brönsted acids supported on oxidic support materials - alkali and alkaline earth metal fluorides - acidic metal oxides of the elements Al, Ce, Th, Ti, Zr, Sn, Pb, As, Bi, Sb, V, Cr, Mo, W , Zn, Cd-acidic metal sulfides of the elements Cd and Zn sulfates, phosphates and halides of the elements Mg, Ca, Sr, Ba, Cu, Zn, Cd, Al, Fe, Co, Ni, Cr, K, B, Ti, Sn and Ag mixed oxides -hetero polyacids Method according to one of claims 1 to 5, characterized that after the reaction, the catalyst is separated and recycled. Method according to one of claims 1 to 6, characterized that the process is carried out continuously. Method according to claim 7, characterized in that that the process in a tubular reactor with fixed catalyst bed carried out becomes. Method according to claim 7, characterized in that that the process is carried out in a fluidized bed reactor. Method according to one of claims 1 to 9, characterized the acidic heterogeneous catalyst is a zeolite or an ion exchange resin is.