PL215559B1 - New non-saturated �-diketone derivatives and process for the preparation thereof - Google Patents

Description

The subject of the invention is new allylic β-diketone derivatives and a method for the preparation of new allylic β-diketone derivatives.

The aim of the invention was to produce new allylic β-diketone derivatives and to develop a method for the preparation of new allylic β-diketone derivatives.

In a first aspect, the invention relates to novel allylic β-diketone derivatives of the general formula 1,

in which ₁

- R ¹ is an alkyl group having 1-18 carbon atoms, both of which may be the same or different, ₂

- R ² is an alkoxy substituent having from 1 to 4 carbon atoms.

The compounds according to the invention can be successfully used as agents for removing metal ions, in particular copper (II) from solutions, for modifying silica supports and as monomers for the preparation of functionalized polysiloxanes.

In a second aspect, the invention relates to a process for the preparation of novel allylic β-diketone derivatives of general formula 1

in which ₁

- R ¹ is an alkyl group having 1-18 carbon atoms, both of which may be the same or different, ₂

- R ² is an alkoxy substituent having from 1 to 4 carbon atoms, which comprises reacting a cross-metathesis of the allyl derivative of β-diketones of the general formula 2,

₁ wherein R ¹ is as defined above, with etenylosilanami of the general formula 3

₂ wherein R ² is as defined above, in the presence of a ruthenium complex as a catalyst for metathesis reactions.

The known catalysts for olefin metathesis reactions are used as catalysts, in particular compounds of the general formulas 4-12:

PL 215 559 B1

in which

345

- R ³ , R ⁴ , R ⁵ are equal or different and represent an alkyl group with a carbon content of 3-8 or a cycloalkyl group with a carbon content of 5-8, in particular a cyclopentyl or cyclohexyl group,

- R ⁶ , R ⁷ are equal or different and represent any anionic ligand, in particular chloride ligand, acetate, fluoroacetate, difluoroacetate, trifluoroacetate, tert-butoxy, (CF3) (CH3) 2CO-, (CF3) 2 (CH3) CO-, PhO, MeO-, EtO-, toluylsulfone, methylsulfone, trifluoromethylsulfone, - aryloxy group,

- R ⁸ is hydrogen, a substituted or unsubstituted alkyl group with a content of 1-20 carbon atoms, a substituted or unsubstituted mono- or polycyclic aryl group, in particular a phenyl group,

- R ⁹ and R ¹⁰ may be equal or different, represent an alkyl group having 1-18 carbon atoms, a substituted or unsubstituted single or multi-ring aryl aryl group, in particular a mesityl group,

PL 215 559 B1

- R ¹¹ represents an alkyl group containing 1-18 carbon atoms, in particular an isopropyl group,

- R ¹² is pyridine or substituted pyridine with the exception of N-substituted derivatives. 12

^{R 12} in particular is 3-bromopyridine.

The catalyst is used in an amount of not less than 1x10 ^-3 mol per 1 mol of Ru dione, wherein najko -2-3 rzystniejsze catalyst is used in an amount of 3x10 ^-3 - 5x10 ^-2 mol per 1 mol dione. It is preferable, but not necessary, to add the catalyst in several portions during the course of the reaction evenly throughout the course of the reaction. This way of conducting the reaction results in an increase in the efficiency of the process.

It is preferable, but not necessary, to use an excess of olefin over the dione to speed up the reaction. An excess of 10 moles of olefin is preferred for each mole of CH2 = CH (ethenyl groups) moieties in the dione.

It is preferable to carry out all operations under an inert gas atmosphere, and it is particularly preferable to use a gas purified from oxygen and moisture. Reactions are carried out in an open system at a temperature not higher than the boiling point of the solvent. The reactions are carried out in solvents selected from the groups: aromatic organic compounds, chlorinated aliphatic compounds, and chlorinated aromatic compounds. It is preferable to carry out the reaction in methylene chloride, benzene and toluene.

In the process according to the invention, an appropriate amount of the β-diketone derivative of the general formula 2, the ethenylsilane of the general formula 3, the solvent and the catalyst are introduced into the reactor under an inert gas atmosphere. The reaction mixture is stirred with heating until the reaction temperature is reached. The reaction is carried out for 1-24 hours at a temperature of 20 ° C, most preferably at the reflux temperature of the reaction mixture.

It is preferable to introduce the catalyst into the stirred and boiling reaction mixture. It is preferred that all reagents be dried and deoxygenated prior to the reaction.

The crude product is separated from the reaction mixture by distillation under reduced pressure. The crude product, depending on its intended use, is further purified using known methods.

The use of the metathesis process in the method according to the invention enables the synthesis of new compounds with satisfactory efficiency and selectivity.

The product analysis was performed on:

13

- ¹ H and ¹³ C NMR spectra were made on a Varian Gemini 300 spectrometer. All measurements were made in NMR tubes filled under argon atmosphere. Deoxygenated and dried deuterated benzene was used as a solvent. Measurements were made at room temperature.

- GC-MS analyzes were performed on a Varian Saturn 2100T apparatus.

P r z k ł a d 1

The synthesis was carried out in a 50 ml round-bottom flask equipped with a magnetic stirrer, a reflux condenser with an attached adapter enabling connection to a gas-vacuum line, ending with a bubble. All synthesis operations were performed under an argon atmosphere. Down

-3 -2 boiling solution containing 0.5 mL (3.4x10 ^-3 mole) of 3- (allyl) pentane-2,4-dione and 7.18 mL (3.4x10 ^-2 mol) etenylotrietoksysilanu in 20 mL of benzene was added 0.1399 g (1.7x10 ^{- 4} mol) benzylidene dichlorobis (tricyclohexylphosphine) rutene (IV) as a catalyst in three portions with an interval of about 3 hours.

The reaction was carried out at the reflux temperature of benzene (80 ° C) for 24 h. After this time, the product was isolated by fractional distillation under reduced pressure. 0.31 g of 3 - [(3 ₁

- (triethoxysilyl) allyl] pentane-2,4-dione representing 30% of theory. ¹ H NMR analysis of the benzene solution of the product indicates the presence of two stereoisomers, tautomers which are E.

₁

The ratio of ketone to enol form in solution C6D6 calculated based on ¹ H NMR spectrum is equal to 1: 2.

Spectroscopic analysis:

^1H NMR (C6D6, δ (ppm)): 1.18 (t, J = 7 Hz, 9H, CH 3) (enol form); 1.20 (t, J = 7 Hz, 9H, CH3) (keto); 1.68 (s, 6H, CH3) (ketone form); 1.71 (s, 6H, CH3) (enol form); 2.422.46 (m, 2H, CH2) (ketone form); 2.58-2.63 (m, 2H, CH2) (enol form); 3.27 (t, J = 7.5 Hz, 1H, CH) (ketone form); 3.82 (q, J = 7.0 Hz, 6H, OCH2) (enol form); 3.84 (q, J = 7.0 Hz, 6H, OCH2) (ketone form); 5.52 (dt, J = 18.7 Hz; J = 2.0 Hz, 1H, = CHSi) (enol form); 5.56 (dt, J = 18.7 Hz, J = 1.6 Hz, 1H, = CHSi) (ketone form); 6.40 (dt, J = 18.7 Hz, J = 6.4 Hz, 1H, = CH ₂₎ (keto form);

PL 215 559 B1

6.47 (dt, J = 18.7 Hz, J = 4.9 Hz, 1H, = CHCH2) (enol form); 17.47 (s, 1H, OH) (enol form);

¹³ C NMR (C ₆ D ₆ ; δ (ppm)): 18.56 (CH ₃ CH ₂ ) (enol and ketone forms overlap); 22.57 (CH ₃ C = OH) (enol form); 28.67 (CH ₃ C = O) (ketone form); 33.78 (CH ₂ C = C) (enol form); 34.82 (CH ₂ C = C) (ketone form); 58.63 (OCH ₂₎ (enol form); 58.67 (OCH ₂₎ (keto form); 67.18 (C = COH) (ketone form); 106.16 (CHC = O) (enol form); 120.38 (= CHCH ₂ ) (enol form); 123.55 (= CHCH ₂ ) (formaketone); 148.46 (= CHSi) (ketone form); 149.95 (= CHSi) (enol form); 191.58 (COH) (enol form); 202.26 (C = O) (ketone form);

MS m / z (int. Rel): 303 (M ⁺ +1, 4), 284 (8), 269 (28), 256 (20), 241 (55), 213 (85), 177 (20) , 169 (53), 163 (68), 135 (65), 127 (17), 107 (66), 79 (100), 45 (35).

P r z k ł a d 2

Under the conditions of example 1 to a boiling solution containing 0.5 mL (3.4x10 ^-3 mol) -2

3- (allyl) pentane-2,4-dione and 7.18 mL (3.4x10 ^-2 mol) ethenyltriethoxysilane in 20 mL of methylene chloride was added 0.1399 g (1.7x10 ^-4 mol) benzylidene dichlorobis (tricyclohexylphosphine) -rutene (IV) as a catalyst in three portions with an interval of about 3 h. The reaction was carried out at the boiling point of methylene chloride (40 ° C) for 24 h. After this time, the product was isolated by fractional distillation under reduced pressure. 0.17 g of 3 - [(3- (triethoxysilyl) allyl] pentane-2,4-dione was obtained, which was ₁

17% of theory. ¹ H NMR analysis of the benzene solution of the product indicates the presence of two stereoisomers, tautomers which are E. ratio to the enol form of the ketone in solution ₁

C6D6 calculated based on the ¹ H NMR spectrum is equal to 1: 2.

P r z k ł a d 3

Under the conditions of example 1 to a boiling solution containing 0.5 mL (3.4x10 ^-3 mol) -2

3- (allyl) pentane-2,4-dione and 7.18 mL (3.4x10 ^-2 mol) ethenyltriethoxysilane in 20 mL of benzene was added 0.1443 g (1.7x10 ^-4 mol) benzylidene dichloro (tricyclohexylphosphine) [(1,3-bis (trimethylphenyl) ) imidazolidinylidene] ruthenium (IV) as a catalyst in three portions with an interval of about 3 hours. The reaction was carried out at the reflux temperature of benzene (80 ° C) for 24 hours. After this time, the product was isolated by fractional distillation under reduced pressure. 0.52 g of 3 was obtained. - (3- (triethoxysilyl) allyl) pentan-2.4 ₁

-dione, which was 51% of theoretical yield. ¹ H NMR analysis of the benzene solution of the product indicates the presence of two tautomers, stereoisomers which form E. The ratio of ketone to enol _one in C6D6 solution calculated on the basis of ¹ H NMR spectrum is equal to 1: 2.

P r z k ł a d 4

Under the conditions of example 1 to a boiling solution containing 0.5 mL (3.4x10 ^-3 mol) -2

3- (allyl) pentane-2,4-dione and 7.18 mL (3.4x10 ^-2 mol) ethenyltriethoxysilane in 20 mL of toluene was added 0.1443 g (1.7x10 ^-4 mol) benzylidene dichloro (tricyclohexylphosphine) [(1,3-bis (trimethylphenyl) ) imidazolidinylidene] ruthenium (IV) as a catalyst in three portions with an interval of about 3 hours. The reaction was carried out at the boiling point of toluene (110 ° C) for 24 hours. After this time, the product was isolated by fractional distillation under reduced pressure. The yield was 0.73 g 3 - [(3- (triethoxysilyl) allyl] pentane ₁

-2,4-dione which was 71% of theory. ¹ H NMR analysis of the benzene solution of the product indicates the presence of two tautomers, stereoisomers which form E. The ratio of ketone to enol _one entry in C6D6 solution calculated on the basis of ¹ H NMR spectrum is equal to 1: 2.

P r z k ł a d 5

Under the conditions of example 1 to a boiling solution containing 0.5 mL (3.4x10 ^-3 mol) -2

3- (allyl) pentane-2,4-dione and 7.18 mL (3.4x10 ^-2 mol) ethenyltriethoxysilane in 20 mL of toluene was added 0.1065 g (1.7x10 ^-4 mol) dichloro [1,3-Bis- (2.4, 6-trimethylphenyl) imidazolidinylidene)] (2-isopropoxyphenylmethylene) ruthenium (IV) as a catalyst in three portions with an interval of about 3 hours. The reaction was carried out at the reflux temperature of toluene (110 ° C) for 24 hours. At this time, the product was isolated by fractional distillation under reduced pressure. Was obtained 0.48 g of 3 - [(3- (triethoxysilyl) -allyl] pen _tan-1 2,4-dione, which was 47% of theory. Analysis of ¹ H NMR of the benzene solution of the product indicates the presence of two tautomers, stereoisomers which form E. The ratio of ketone ₁ input to the enol solution C6D6 calculated based on ¹ H NMR spectrum is equal to 1: 2.

P r z k ł a d 6

Under the conditions of example 1 to a boiling solution containing 0.5 mL (3.4x10 ^-3 mol) -2

3- (allyl) pentane-2,4-dione and 7.18 mL (3.4x10 ^-2 mol) ethenyltriethoxysilane in 20 mL of toluene to give 0.1613 g (1.7x10 ^-4 mol) dichloro (tricyclohexylphosphine) [(1,3-bis ( trimethylphenyl) imidazolidinylidene] (3-phenylinden-1-ylidene) ruthenium (IV) as a catalyst in three portions with an interval of about 3 hours.

The mixture was refluxed with toluene (110 ° C) for 24 hours. At this time, the product was isolated by fractional distillation under reduced pressure. Yielding 0.34 g of 3 - [(3- (triethoxysilyl) ₁ -allyl] pentane-2,4-dione, which was 33% of theory. Analysis of ¹ H NMR of the benzene solution of the product indicates the presence of two stereoisomers, tautomers which are E. ratio for ₁ we keto enol solution C6D6 calculated based on ¹ H NMR spectrum is equal to 1: 2.

P r z k ł a d 7

Under the conditions of example 1 to a boiling solution containing 0.5 mL (3.4x10 ^-3 mol) -2

3- (allyl) pentane-2,4-dione and 5.1 mL (3.4x10 ^-2 mol) ethenyltrimethoxysilane in 20 mL of toluene were added

0.1443 g (1.7x10 ^-4 mol) benzylidene dichloro (tricyclohexylphosphine) [(1,3-bis (trimethylphenyl) imidazolidinylidene] ruthenium (IV) as a catalyst in three portions with an interval of about 3 hours. All operations were carried out under an argon atmosphere. at the boiling point of toluene (110 ° C) for 24 hours, at which time the product was isolated by fractional distillation under reduced pressure to give 0.60 g of 3 - [(3- (trimethoxysilyl) allyl] pentane-2,4-dione, accounted for 68% of the theoretical _one. ¹ H NMR analysis of the benzene solution of the product indicates the presence of two tautomers, stereoisomers which form E. the ratio of ketone to enol in C6D6 solution calculated on the basis of the ₁ H NMR spectrum of ¹ is equal to 1: 1.3.

Spectroscopic analysis:

¹ H NMR (C ₆ D _6, δ (ppm)): 1.81 (s, 6H, CH ₃₎ (enol form); 1.90 (s, 6H, CH ₃₎ (keto form); 2.41-2.46 (m, 2H, CH2) (ketone form), 2.58-2.61 (m, 2H, CH2) (enol form); 2.83 (t, J = 7.26 Hz, 1H, CH) (ketone form); 3.44 (s, 9H, OCH3) (enol form); 3.45 (s, 9H, CH3) (ketone form); 5.42 (dt, J = 1.9 Hz, J = 18.8 Hz, 1H, = CHSi) (enol form); 5.46 (dt, J = 1.6 Hz, J = 18.8 Hz, 1H, = CHSi) (ketone form); 6.34 (dt, J = 6.4 Hz, J = 18.6 Hz, 1H, = CH-CH ₂₎ (keto form); 6.39 (dt, J = 4.9 Hz, J = 18,8Hz, 1H, = CH-CH ₂₎ (enol form); 17.42 (s, 1H, -OH) ¹³ C NMR (C ₆ D ₆ ; δ (ppm)): 22.57 (CH ₂ C = C) (ketone form); 28.70 (CH ₂ C = C) (enol form);

33.85 (CH ₃ ) (enol form); 34.83 (CH ₃ ) (ketone form); 50.34 (OCH ₃ ) (ketone and enol forms overlap); 68.16 (CH ₂ C = O) (ketone form), 106.46 (C = COH) (enol form); 118.75 (= CHCH ₂ ) (enol form); 121.88 (= CHCH ₂ ) (ketone form); 145.50 (= CHSi) (ketone form); 150.80 (= CHSi) (enol form); 190.64 (COH) (enol form); 202.24 (C = O) (ketone form)

MS m / z (int. Rel): 261 (M ⁺ +1.4), 229 (10), 217 (26), 213 (42), 185 (99), 139 (12), 121 (100) , 107 (88), 91 (96), 77 (53), 45 (19)

P r z k ł a d 8

Under the conditions of example 1 to a boiling solution containing 0.5 mL (3.4x10 ^-3 mol) -2

4- (allyl) heptane-3,5-dione and 7.18 mL (3.4 × 10 ^-2 mol) ethenyltriethoxysilane in 20 mL of toluene was added 0.1443 g (1.7 × 10 ^-4 mol) benzylidene dichloro (tricyclohexylphosphine) [(1,3-bis (trimethylphenyl) ) imidazolidinylidene] ruthenium (IV) as a catalyst in three portions with an interval of about 3 hours. All operations were carried out under argon. The reaction was carried out at the boiling point of toluene (110 ° C) for 24 hours. After this time, the product was isolated by fractional distillation under reduced pressure. The resulting 0.71 g of 4 - [(3- (triethoxysilyl) -allyl] heptane-3,5-dione, which accounted for 63% of the theoretical _one. ¹ H NMR analysis of the benzene solution of the product indicates the presence of two tautomers, stereoisomers which form E ratio keto enol in C6D6 solution calculated on the basis of the ₁ H NMR spectrum of ¹ is equal to 1: 2.3

Spectroscopy, ¹ H NMR (C6D6, δ (ppm)): 1.18 (t, J = 7 Hz, 9H, CH 3) (enol form); 1.21 (t, J = 7 Hz, 9H, CH3) (ketone form); 1.35 (t, J = 6.9 Hz, 6H, CH ₂ CH ₃ ) (ketone form); 1.38 (t, J = 6.9 Hz, 6H, CH ₂ CH ₃ ) (enol form); 2.40-2.45 (m, 2H, CH ₂₎ (keto form); 2.59-2.65 (m, 2H, CH ₂₎ (enol form); 2.52 (q, 4H, J = 7.1Hz, CH ₂ CO) (ketone form); 2.65 (q, J = 7.1 Hz, 4H, CH2CO) (enol form); 3.37 (t, J = 7.5 Hz, 1H, CH) (ketone form); 3.78 (q, J = 7.0 Hz, 6H, OCH2) (enol form); 3.85 (q, J = 7.0 Hz, 6H, OCH2) (ketone form); 5.50 (dt, J = 18.7 Hz; J = 2.0 Hz, 1H, = CHSi) (enol form); 5.62 (dt, J = 18.7 Hz, J = 1.6 Hz, 1H, = CHSi) (ketone form); 6.36 (dt, J = 18.7 Hz, J = 6.4 Hz, 1H, = CH ₂₎ (keto form); 6.40 (dt, J = 18.7 Hz, J = 4.9 Hz, 1H, = CH ₂₎ (enol form); 17.44 (s, 1H, OH) (enol form);

¹³ C NMR (C ₆ D ₆ ; δ (ppm)): 8.02 (CH ₃ CH ₂ ) (ketone and enol forms are overlapping); 18.23 (CH ₃ CH ₂ O) (ketone and enol forms are overlapping); 32.88 (CH ₂ C = C) (form

PL 215 559 B1 (enol); 33.23 (CH ₂ C = C) (keto); 34.57 (CH ₂ COH) (enol form); 35.67 (CH ₂ C = O) (ketone form); 58.63 (OCH ₂ CH ₃ ) (enol form); 58.77 (OCH ₂ CH ₃ ) (ketone form); 106.16 (C = COH) (enol form); 63.31 (CHC = O) (keto); 120.38 (= CHSi) (enol form); 123.55 (= CHSi) (ketone form); 148.46 (= CH ₂₎ (keto form); 149.55 (= CHCH ₂ ) (enol form); 191.58 (COH) (enol form); 201.26 (C = O) (ketone form).

Claims (6)

1. New allylic derivatives of β-diketones of the general formula 1, in which ₁ - R ¹ is an alkyl group having 1-18 carbon atoms, both of which may be equal or different ₂ - R ² is an alkoxy substituent having from 1 to 4 carbon atoms 2. The method of obtaining new allylic derivatives of β-diketones of the general formula 1 in which ₁ - R ¹ is an alkyl group having 1-18 carbon atoms, both of which may be equal or different ₂ - R ² is an alkoxy substituent having from 1 to 4 carbon atoms by reacting a cross-metathesis of the allyl derivative of β-diketones of the general formula 2 _of claim ₁ wherein R ¹ is as defined above, with etenylosilanami of the general formula 3 SiR ² 3 = ⁷ (3) ₂ where R ² is as defined above, in the presence of a ruthenium complex as a metathesis catalyst. 3. The method according to p. A process according to claim 1, characterized in that known catalysts for olefin metathesis are used as catalysts. 4. The method according to p. A process according to claim 2, characterized in that the catalysts are compounds of general formulas 4-12: PL 215 559 B1 in which 345 - R ³ , R ⁴ , R ⁵ are equal or different and represent an alkyl group with a carbon content of 3-8 or a cycloalkyl group with a carbon content of 5-8, in particular a cyclopentyl or cyclohexyl group, - R ⁶ , R ⁷ are equal or different and represent any anionic ligand, in particular chloride ligand, acetate, fluoroacetate, difluoroacetate, trifluoroacetate, tert-butoxy, (CF3) (CH3) 2CO-, (CF3) 2 (CH3) CO- PhO, MeO-, EtO-, toluylsulfone, methylsulfone, trifluoromethylsulfone, - aryloxy group, - R ⁸ is hydrogen, a substituted or unsubstituted alkyl group with a content of 1-20 carbon atoms, a substituted or unsubstituted mono- or polycyclic aryl group, in particular a phenyl group, - R ⁹ and R ¹⁰ may be equal or different, represent an alkyl group having 1-18 carbon atoms, a substituted or unsubstituted single or multi-ring aryl aryl group, in particular a mesityl group, - R ¹¹ represents an alkyl group containing 1-18 carbon atoms, in particular an isopropyl group, - R ¹² is pyridine or substituted pyridine with the exception of the N-substituted derivatives, R ¹² in particular is 3-bromopyridine. 5. The method according to p. 3 or 4, characterized in that the catalyst is used in an amount not less than the st-3 1x10 ^-3 mol per 1 mol of Ru dione. -3-3 6. The method according to p. 5, characterized in that the catalyst is used in an amount of 3x10 ^-3 - 5x10 ^-3 mol per 1 mol dione.