DE2055814A1 - 1 5.7 Trioxa spiro square bracket to 2 5 square bracket to octane - Google Patents

Description

Cologne, 11/11/1970 Eg / Ax / Hz

Ugine Kuhlmann, Io rue du General Foy, Paris 8e /
France

The invention relates to novel 1 _t 5,7-trioxa spiro ^ ~ 2.j> 7octane, namely 1.5 * 7 * T Ioxa-spiro _i / 2. _i 57octanes of the formula (I) and
Bis (1,5 »7-trioxa-spiro ^ 5. ^ octane) of the formula (H):

0-OH ₀

• ν ,

0OH O

O CH ₂ -OHH 0-0H ₂ 0

and their preparation by epoxidation of 5-methylene-1 ₉ 3-dioxanes of the formula (III) and bis (5-methylene-1 | 3- <3 ioxanen) of formula (IV):

R ¹ ,, 0-0H ₂

0 C-OH ₂ (III)

T09822 / 2217

CH ₀ - O R_ O- CH ₀

^0H 2 = ° v Λ Λ / ^CH 2 ^(IV)

-OH H Ό - "" '

The 5-methylenedioxanes (III) and (IV) are known compounds, the preparation of which is described in the applicant's French patent specification 1,387,099. They are cyclic acetals of 2-methylene-1,3-propanediol and a carbonyl, aldehyde or ketone compound of the type R ¹ , - CO-R'p in the case of the compounds (III) or a dialdehyde compound of the type OCH-R ^ -CHO in the case of compounds (IV).

In the products of the formula (III), H ¹ ^ and R ' _{2 can represent} a hydrogen atom, a monovalent alkyl radical, cycloalkyl radical or arylalkyl radical with up to 18 carbon atoms, an aryl radical, in particular a phenyl radical, a heterocycle, especially a 5- or 6-membered heterocycle containing oxygen or nitrogen as a hetero atom. They can also together form a divalent alkylene radical with 3 to 14 carbon atoms. These residues R ',. and R ¹ ρ can optionally contain ethylenic double bonds which, depending on their reactivity, can optionally be epoxidized during the epoxidation reaction, as well as substituents stable under the epoxidation conditions, for example halogen atoms such as chlorine or bromine, alkoxy radicals and cyclic acetal groups. In the case of epoxidizable residues, the epoxidation can be partial or complete.

In the products according to (IV), the dialdehyde used as starting material can be a carboxyl derivative OGH-R ^ -CHO, in which R is a divalent alkylidene radical with 1 to 12 carbon atoms or a phenylene radical, or the glyoxal can be OCH-CHO, which corresponds to the case in which R, stands for zero.

R ^ j and Rg have the same meaning as R ¹ ^ and R ' ₂ "except for the cases" in which the latter are epoxidizable

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Contain double bonds and R ^ and Rg are therefore epoxidized radicals which correspond to the olefinic radicals R ¹ ^ and R'g.

The scope of the invention is indicated by an enumeration of some aldehydes or ketones that are necessary for the preparation of the compounds (III) and (IV) can be used, more recognizable.

When starting from an aldehyde, the formula R ¹ ^ -CO-R ¹ 2 becomes R '^ ₁ -GHO, where H is R ⁽ ₂ and a compound of type (III) is obtained.

If a non-ethylene radical is selected from the above-mentioned radicals R ¹ ^, R, j is identical to R ¹ ^. Of the aldehydes of this type, the following may be mentioned: formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, valeraldehyde, isovaleraldehyde, önanthaldehyd, 2-ethylhexanol, cyclopentanecarbaldehyde, cyclohexane arbaldehyde and its methyl-substituted aldehyde, carbaldehyde and its methyl-substituted derivatives, nododecanane-2-aldehyde Benzaldehyde, p-tolualdehyde, naphthalene-1-acetaldehyde, tetrahydrofurfurylaldehyde, tetrahydropyran-2-carbaldehyde, nicotihaldehyde, chloroacetaldehyde, chloral, p-chlorobenzaldehyde, piperonal, methoxyacetaldehyde and 3-methoxypropionaldehyde

When a radical R ^1,. is chosen which contains one or more ethylenic bonds, R ^. be identical to R ¹ ^ and / or the Spoxydrest, which ^{corresponds to R 1} , -. Of the aldehydes of this type, the following may be mentioned: acrolein, methacrolein, crotonaldehyde, 2-ethyl-2-hexenal, 3-cyelohexenecarbaldehyde, S-methyl-J-cyclohexenecarbaldehyde, ^ -methyl ^ -cyclohexenearbaldehyde, 5-norboimen-2-carbaldehyde and 3-methyl-5-no bornene-2-carbon aldehyde

When starting from a dialdehyde of the type OCH-Rx-CHO, one obtains, as already mentioned, a compound (, TV) The following dialdehydes, for example, can be used for this purpose: glyoxal, malonaldehyde, succinic

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aldehyde, glutaraldehyde, adipaldehyde, phthalaldehyde, isophthalaldehyde and terephthalaldehyde.

If from a ketone, ie. a compound R ¹ ^ -CO-R ¹ g, in which R ' _{2 is} not a hydrogen atom, is assumed, the compounds (III) are obtained.

If R ¹ ^ and R ¹ ρ are unsaturated, compounds of the formula (III) are obtained in which R ^ and Rp have the same meanings as R '/ j or R ¹ ^. For example, the following ketones can be used for this purpose: acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, cyclobutanone, cyclopentanone, cyclohexanone, methylcyclohexanone, cyclooctanone and cyclododecanone.

If R '^ and / or R ¹ ^ or the Alkylenre st R' / jR ¹ ο contain ethylenic double bonds, R, - and R ^ with R'y. or R ¹ ρ be identical and represent the corresponding epoxidized radical or the corresponding epoxidized radicals. Examples of ketones of this type are: methyl vinyl ketone, methyl isopropenyl ketone, mesityl oxide, cyclohexen-2-one, isophorone and cyclododecadien-5,9-one.

To prepare the epoxidized compounds according to the invention, the compounds (III) or (IV) with a known epoxidation agents treated. Organic peracids are particularly suitable, e.g. performic acid, Peracetic acid, perbenzoic acid or substituted derivatives, e.g. p-Nxtroperbenzoic acid or m-Chloroperbenzoic acid, Monopuccinic acid, monopermaleic acid, monoperphthalic acid or a peroxycarboximidic acid. Preferably be Peroxycarboximidic acids used, which are produced by reacting hydrogen peroxide with a nitrile The preferred procedure consists in preparing the epoxidation agent in the reaction medium itself by gradually an aqueous hydrogen peroxide solution to a mixture of the nitrile and that to be epoxidized Acetals there. Suitable nitriles are, for example, alkyl

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nitrile, Oycloalkylnitrile or Arylnitrile, which do not contain Ethylenic or acetylenic bonds or other! functions that contain a constituent of the reaction medium can react. Particularly suitable are the alkyl nitriles or cycloalkyl nitriles with 2 "to 8 0 atoms, preferably acetonitrile, or a benzene nitrile, preferably benzonitrile.

The hydrogen peroxide is preferably in a stoichiometric amount or in a slight excess, namely in one Amount of about 1 to 2 moles per equivalent of the ethylenic double bonds used · It can be in the form of a aqueous solution containing 30 to 90 wt .-% B ^ Og, such as it is commercially available can be used.

The nitrile is used in at least the stoichiometric amount compared to HpOo or in excess, in an amount from about 1 to 10 moles per mole of HoOo is used.

It is also useful in the presence of a solvent to work to facilitate the homogenization of the mixture. Aliphatic solvents are preferably used monohydric alcohols with 1 to 4 carbon atoms, e.g. methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, isobutanol and tert-butanol are used.

The reaction requires a control of the Pjr value of the Medium, which must be kept at p "8 to 10 by adding a basic compound during the reaction, to neutralize the acidic by-products formed · For this purpose, for example, sodium or Potassium hydroxide, sodium or potassium carbonate, calcium and ammonia. These compounds can be used as such or be added in the form of an aqueous solution. It can also be useful to reduce the p «fluctuations by adding for example a mono-, di- or tri-sodium phosphate to buffer.

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The optimal temperature is between 20 and 100 ° C and preferably between 40 and 75 ° C

The reaction time, which varies with the nature of the reactants and with the temperature, is a few hours.

After the reaction, the epoxidized product can be isolated by extraction with a solvent which is insoluble or sparingly soluble in the reaction medium. It may be useful to separate off the excess nitrile and the solvent beforehand by fractionation. Then, if necessary, the epoxy can be obtained by simply decanting the aqueous medium. Examples of suitable extraction solvents are aliphatic and cycloaliphatic or benzene hydrocarbons with 5 to 8 carbon atoms or chlorinated solvents with 1 to 6 carbon atoms, for example methylene chloride, chloroform, carbon tetrachloride, tetrachlorethylene and o-dichlorobenzene.

The new compounds according to the invention are used for a wide variety of purposes. The monoepoxies of the Structure (I), whose R. * and Ro radicals have no oxirane groups are reactive solvents or diluents for epoxy resins or intermediates, for example for the production of polyacetal resins. The diepoxides of structure (II) or, when R ^ or Rg is a OxJ-Tangruppe contains, the structure (I) or the tri- or Polyepoxides of structure (I), wherein R, - or R ~ one or contains several oxirane groups, are intermediates for the manufacture of thermosetting resins, paints and Adhesives. They can also be used as stabilizers for multiply halogenated compounds, in particular for polyvinyl chloride, be used.

example 1
6-isopropyl-i, 5,7-trio: x: a-spiro ^ 2. ^ 7octane

0-0H ₂ ö

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14-3 6 (A mol) of 2-isopropyl-5-methylene-1,3-dioxane are dissolved in 160 g of methanol and 82 g of acetonitrile (2 mol). 10 ml of an aqueous 1 molar monosodium phosphate solution are added to the solution. Then, within 3 hours at 60 O 73 E be an? O # aqueous hydrogen peroxide solution (1.5 mol H2O2) were added, the _pH value is kept by addition of a 10% sodium hydroxide solution at 9.0. The temperature and the p ^ value are then kept constant for 2 hours.

The solvents are removed by distillation under reduced pressure. The mixture is treated first with 280 g and then twice with 70 g of chloroform each time. The chloroform extracts are decanted, then combined and washed twice with 70 g of water each time. The chloroform is evaporated to give 146 g of a product which analysis shows that it contains 92 $ 6-isopropyl-1,5,7-trioxa-spiro ^ 2 \ £ 7octane. A product of 96-97% purity according to chemical analysis and analysis by gas chromatography with the following characteristics is obtained by distillation under reduced pressure: boiling point 90 ° C./5 mm Hg; Melting point 52 ⁰ C,

Example 2
6- (3 »4-epoxy-cyclohexyl) -1,5,7-trioxa-spiro / 2 \ j> 7octane

= 0-

/ 0-0H ₂ CH

63 g (0.35 mol) of 2- (3-cyclohexenyl) -5-methylene-1,3-dioxane are dissolved in 224 g of methanol and II5 g (2.8 mol) of acetonitrile. 5 nQ. given to an aqueous 1 molar monosodium phosphate solution. Subsequently (1.05 mole HgOg) wherein the _R p value is kept by addition of a sodium hydroxide solution at 9.0 1Obigen be added within 2 hours at 60 ⁰ C 5I g of an aqueous 70% hydrogen peroxide, · Subsequently, the temperature and the _pH value 3 hours kept constant.

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The subsequent work-up of the mixture in the manner described in Example 1 gives 64 g of a crystallized product which has a melting point of 32 0 and 77% 6- (3 »4 ~ epoxycyclohexyl) -1,5,7

and contains 22% of the monoepoxide derivative.

Example 3
- (5,6-epoxy-2-norbornyl) -1,5

In 224 g of methanol and 115 g of acetonitrile (2.8 mol), 67.2 g (0.35 mol) of 2- (5-norbornen-2-yl) -5-methylene-1,3-dioxane (boiling point 7O- 73 ° C / 1 mm Hg; n ^ ⁰ = 1.504-; d | ° »1.0698). Then 5 ml of an aqueous 1 molar monosodium phosphate solution are added. Subsequently (1.05 mol ^ Η Ο ^) are zugesezt wherein the p _H ~ value is kept by addition of a 10% liatriumhydroxydlösung in 9 »0 within 2 hours at 60 0, 51 g of an aqueous 70% hydrogen peroxide. The temperature and the p “value are then kept constant for 3 hours.

Subsequent work-up of the mixture in the manner described in Example 1 gives 68.9 g of an extremely viscous, colorless product which has a refractive index n ^ of 1.505 and about 75% that of diepoxide, i.e. 6- (5,6-epoxy-2-norbornyl-1,5 »7-trioxa-spiro / 2". ^ 7octane and 25% monoepoxides corresponding to a partial epoxidation of the starting product contains.

Example 4- 6- (1,2-epoxy-ethyl) -1,5 »7-trioxa-spiro ^ 2 ~ .j> 7octane

OHo-OH-OH

In 400 g of methanol and 205 g of acetonitrile (5 mol) 62 g

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(0.5 Hol) 2-vinyl-5-fifthyl «ri-1,3-dioxaa dissolved. For iösang be al optionally 14.5 of an aqueous 1 M monosodium phosphate solution "Then, within 2 hours at 60 ⁰ C, 170 g of an aqueous solution τοη 40ji Wasseratoffperoxyd (2 Hol H ₂ O ₂₎ was added, the PJJ value by adding a 10bigen Fatriuahydroxydlösung was kept at 9.2 * The temperature and the Pg value are kept constant for 1 hour.

The subsequent workup of the mixture to the way described in Example 1 · "rubs 48 g of a colorless" Tiekosen liquid "which contains 1.11 g I <iaiTalente Oociran per 100 · D" r 6- (t * ^ lpiJEy ⁱ "* ^ r3l) -1.5 _> 7 oxa-spiro- / 2 \ 5j7octane calculated theeretisohe value is 1.26 Iquiralente oxirane per 100 g »

IWSPECTEO

Claims (7)

- ίο - 20558U Pat ent an εη rüch e 1,5,7-Trioxa-spiro / 2. ^ octane of the formula IL O-CIL ⁰ C ' J ^ 0-0H ₂ and Bis (1,5 | 7-trioxa-spiro ^ 2, j> 7 ^oc i ^{; ane} ) ^ ^ΘΓ general formula ^ CH ₂ -O _x B ₃ ^ ^ ° - ^GH 2 ^ ¹ GH ₂ -OCC C-CH ₂ "V ^ CH ₂ -O ^ HH ^ 0-0H ₂ ^ y wherein R and R _{2 represent} hydrogen atoms, monovalent alkyl, cycloalkyl or arylalkyl radicals with up to 18 carbon atoms, aryl radicals, in particular phenyl radicals or heterocyclic radicals, in particular 5- or 6-membered heterocycles, which contain oxygen or nitrogen as a heteroatom , oder.gemeinsam form a divalent alkylene radical with 3 to 14 Q atoms, optionally contain epoxidizable or non-epoxidizable 'ethylenic double bonds or represent the epoxidized radicals corresponding to the above-mentioned radicals, while B * iüjfi ·' zero or a divalent alkylidene radical 1 to (12 carbon atoms or a phenylene radical stands · ^v 2. Process for the production of 1,5,7- Octanes of the general formulas (I) and (II) according to Claim 1, characterized! that one has 5-methylene-1,5-dioxBne of the formulas .C C-CH ₂ and 0CH ^ with known oxidizing agents, especially with organic ones Peracids such as performic acid, peracetic acid, per- 109827/2217 benzoic acid and substituted derivatives of these acids, or peroxycarboximidic acids 3. The method according to claim 2, characterized in that the epoxidation is carried out with a peroxycarboxylic acid is made by reacting hydrogen peroxide with a nitrile that does not contain any function that works with a the constituents of the reaction medium are reactive, has been made. 4-, method according to claim 3, characterized in that an alkyl nitrile or cycloalkyl nitrile with 2 to 8 carbon atoms or monobenzolisch.es nitrile, preferably acetonitrile or benzonitrile, is used 5. The method according to claim 3 or 4, characterized in that that the epoxidation agent is produced in the reaction medium itself by adding an aqueous hydrogen peroxide solution gradually added to a mixture of the nitrile and the 5-methylene-1,3-dioxane to be epoxidized, the Pjj value of the reaction medium by adding a basic The compound is kept between 8 and 10, the hydrogen peroxide in an amount of 1 to 2 moles per equivalent of the ethylenic double bonds and the ITitrile in one Amount of 1 to 10 moles per mole of hydrogen peroxide used will. 6. The method according to claim 2 to 5, characterized in that it is carried out in the presence of a solvent, preferably a monohydric aliphatic alcohol having 1 to M carbon atoms. 7. The method according to claim 2 to 6, characterized in that the reaction ^{temperature between 20 and 100 0} C, preferably between MO and 75 ° O is kept. 109827/2217 _ I