PL215560B1 - New non-saturated �-diketone derivatives and process for the preparation thereof - Google Patents

Description

The subject of the invention is new 4-ethenylbenzyl derivatives of β-diketones and a method for the preparation of new 4-ethenylbenzyl derivatives of β-diketones.

The aim of the invention was to produce new 4-ethenylbenzyl β-diketone derivatives and to develop a method for the preparation of new 4-ethenylbenzyl β-diketone derivatives.

In a first aspect, the invention relates to novel 4-ethenylbenzyl derivatives of β-diketones of the general formula I

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 represents an alkoxy group having 1-4 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 method for the preparation of novel 4-ethenylbenzyl 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 equal or different.

₂

- R ² represents an alkoxy group having 1-4 carbon atoms, which comprises reacting a cross-metathesis 4-etenylobenzylowej derivative of β-diketones of the general formula 2,

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

SiR ² 3 = ⁷ (3) where R ² is as defined above, in the presence of a ruthenium complex as a catalyst for the metathesis reaction.

PL 215 560 B1

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

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 and represent an alkyl group having 1-18 carbon atoms, a substituted or unsubstituted mono- or polycyclic 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 N-substituted derivatives.

^{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, the most -2-3 is preferable to use a catalyst in an amount of 3x10 ^-3 - 5x10 ^-2 mol per 1 mol dione.

It is preferred, but not necessary, to add the catalyst in several (2-3) portions during 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 the olefin of general formula III is preferred for each mole of CH2 = CH- (ethenyl groups) in the reagent of general formula II.

PL 215 560 B1

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, the appropriate amount of reagents, solvent and 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 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 25 ml round-bottom flask equipped with a magnetic stirrer, a reflux condenser with a cap fitted, enabling connection to a vacuum-gas line, ending with a bubble, used to remove ethylene, which was released during the reaction. All synthesis operations were performed under an argon atmosphere.

To a boiling solution containing 0.6 mL of 3- [4- (ethenyl) benzyl] pentane-2,4-dione (3,4x10 -2 ^-3 mol) and 3.6 mL etenylotrietoksysilan (1,7x10 ^-2 mol) 20 mL of methylene chloride was added 0.1399 g (1.7x10 ^-4 mol) of benzylidene dichlorobis (tricyclohexylphosphine) 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 methylene chloride (40 ° C) for 24 hours. hours. All operations were performed under an argon atmosphere. The product was isolated by fractional distillation under reduced pressure. The obtained 0.67 g of 3- {4- [2- (triethoxysilyl) ₁ ethenyl] benzyl} pentane-2,4-dione was 52% of theory. ¹ H NMR analysis of the benzene solution of the product indicates the presence of two stereoisomers, tautomers which are _one hundred and E. The ratio of ketone to enol form in solution C6D6 calculated based on ¹ H NMR spectrum was defined as 1: 1.8.

Spectroscopic analysis:

¹ H NMR (C ₆ D ₆ ; δ (ppm)); 1.24 (t, 9H, CH ₃₎ (enol form); 1.25 (t, 9H, CH ₃₎ (keto form); 1.64 (s, 6H, CH3) (ketone form); 1.68 (s, 6H, CH3) (enol form); 2.91 (d, J = 7.6 Hz, 2H, CH ₂ Ph) (ketone form); 3.12 (s, 2H, CH ₂ Ph) (enol form); 3.55 (t, J = 7.16, 1H, CHC = O); 3.92 (q, 6H, OCH ₂₎ (keto form); 3.93 (q, 6H, OCH ₂₎ (enol form), 6.34 (d, J = 19,3Hz, 1H, J = CHSi) (keto form); 6.41 (d, J = 19.2 Hz, 1H, = CHSi) (enol form); 7.45 (d, J = 19.3 Hz, 1H, = CH) (ketone form); 7.52 (d, J = 19.2 Hz, 1H, = CH) (enol form); 6.82 (d, J = 8.4 Hz, 2H, C6H4) (enol form); 6.87 (d, J = 8.0 Hz, 2H, C6H4) (ketone form); 7.22 (d, J = 8.0 Hz, 2H, C6H4) (ketone form); 7.28 (d, J = 8 Hz, 2H, C6H4) (enol form); 17.52 (s, 1H, OH).

¹³ C NMR (C ₆ D ₆ ; δ (ppm)): 18.6 (OCH ₂ CH ₃ ) (ketone and enol forms overlap); 22.90 (CH ₃ ) (enol form); 29.15 (CH ₃ ) (ketone form); 32.77 (CH ₂ C = C) (enol phase); 34.02 (CH ₂ C = C) (ketone form); 58.78 (OCH ₂₎ (keto-form and enol overlapping); 69.69 (CHC = O) (ketone form); 108.21 (C = COH) (enol form); 118.58 (= CH) (enol form); 118.80 (= CH) (ketone form); 127.36 (C ₆ H ₄ ) (ketone form); 127.46 (C ₆ H ₄ ) (enol form); 127.90 (C ₆ H ₄ ) (enol form); 129.26 (C6H4) (ketone form); 136.44 (C6H4) (enol form); 136.66 (C6H4) (ketone form); 139.42 (C6H4) (ketone form); 140.92 (C6H4) (enol form); 148.68 (= CHSi) (ketone form); 148.81 (= CHSi) (enol form); 191.82 (COH) (enol form); 202.18 (C = O) (ketone form)

PL 215 560 B1

P r z k ł a d 2

Under the conditions of example 1, to a boiling solution containing 0.6 mL of 3- (4-ethenylben-3 -2-yl) pentane-2,4-dione (3.4x10 ^-3 mol) and 3.6 mL of ethenyltriethoxysilane (1, 7x10 ^-2 mol) in 20 mL of benzene, 0.1399 g (1.7x10 ^-4 mol) of benzylidene dichlorobis (tricyclohexylphosphine) ruthenium (IV) as a catalyst was added in three portions with an interval of about 3 hours. The reaction was carried out at the boiling point of benzene (80 ° C). C) for 24 h. The product was isolated by fractional distillation under reduced pressure. 0.81 g of 3- {4- [2- (triethoxysilyl) ethenyl] benzyl} pentane-2,4-dione was obtained, 63% of theory.

₁

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 _one ¹ H NMR spectrum was defined as 1: 1.8.

P r z k ł a d 3

Under the conditions of example 1, to a boiling solution containing 0.6 mL 3- (4-ethenyl-3 -2 benzyl) pentane-2,4-dione (3.4x10 ^-3 mol) and 3.6 mL ethenyltriethoxysilane (1, 7x10 ^-2 mol) in 20 mL of benzene, 0.0991 g (1.7x10 ^-4 mol) of dichloro (tricyclohexylphosphine) (2-isopropoxyphenylmethylene) ruthenium (IV) was added in three portions, after about 3 hours. The reaction was carried out at the boiling point of benzene (80 ° C) for 24 h. The product was isolated by fractional distillation under reduced pressure. 0.76 g of 3- {4- [2- (triethoxysilyl) ethenyl] benzyl} pentane-2,4-dione was obtained, which was ₁

59% of theory. ¹ H NMR analysis of the benzene product solution indicated the presence of two E stereoisomers. The ketone to enol ratio of solution ₁ calculated from the ¹ H NMR spectrum was found to be 1: 1.8.

P r z k ł a d 4

Under the conditions of example 1 to a boiling solution containing 0.6 mL 3- (4-3 -2

-etenylobenzylo) pentane-2,4-dione (3,4x10 ^-3 mol) and 3.6 mL etenylotrietoksysilan (1,7x10 ^-2 mol) in 20 mL of benzene was added 0.1505 g (1,7x10 ^-4 mol), dichlorobis (tricyclohexylphosphine) (3-phenylinden-1-ylidene) 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 benzene (80 ° C) for 24 hours. The product was isolated by fractional distillation under reduced pressure. pressure. Was obtained 0.68 g of 3- {4- [2- (triethoxysilyl) ethenyl] benzyl} _{pentane-2,4-1}

-dione, which was 53% 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 was defined as 1: 1.8.

P r z k ł a d 5

Under the conditions of example 1, to a boiling solution containing 0.6 mL 3- (4-ethenyl-3 -2 benzyl) pentane-2,4-dione (3.4x10 ^-3 mol) and 2.5 mL ethenyltrimethoxysilane (1, 7x10 ^-2 mol) in 20 mL of benzene, 0.1399 g (1.7x10 ^-4 mol) of benzylidene dichlorobis (tricyclohexylphosphine) ruthenium (IV) as a catalyst was added in three portions with an interval of about 3 hours. The reaction was carried out at the boiling point of benzene (80 ° C). C) for 24 h. The product was isolated by fractional distillation under reduced pressure. 0.70 g of 3- {4- [2- (trimethoxysilyl) ethenyl] benzyl} pentane-2,4-dione was obtained, which was ₁

61% of theory. ¹ H NMR analysis of the benzene product solution indicates the presence of two tautomers. The ratio of ketone to enol form a benzene solution based on ₁ ¹ H NMR analysis was determined as 1.8: 1. Only the E isomer was observed.

Spectroscopic analysis:

¹ H NMR (C ₆ D ₆ ; δ (ppm)); 1.66 (s, 6H, CH ₃₎ (keto form); 1.70 (s, 6H, CH ₃₎ (enol form); 2.46-2.55 (m, 2H, CH2) (ketone form); 2.69-2.75 (m, 2H, CH2) (enol form); 3.32 (t, J = 7.5 Hz, 1H, CH); 3.55 (s, 9H, OCH3) (enol form); 3.49 (s, 9H, OCH3) (ketone form); 5.75 (d, J = 18.7 Hz; 1H, = CHSi) (enol form); 5.86 (d, J = 18.7 Hz, 1H, = CHSi) (ketone form); 6.52 (d, J = 18.7 Hz, 1H, = CHCH) (ketone form); 6.59 (d, J = 18.7 Hz, 1H, = CHCH3) (enol form); 6.85 (d, J = 8.4 Hz, 2H, C6H4) (enol form); 6.90 (d, J = 8.0 Hz, 2H, C6H4) (ketone form); 7.24 (d, J = 8.0 Hz, 2H, C6H4) (ketone form); 7.30 (d, J = 8 Hz, 2H, C6H4) (enol form); 17.36 (s, 1H, OH);

¹³ C NMR (C6D6; δ (ppm)): 24.56 (CH3COH); 28.56 (CH3CO); 32.34 (CH ₂ C = C) (enol form); 33.61 (CH ₂ C = C) (ketone form); 48.4 (OCH ₃ ) (enol form); 48.5 (OCH ₃ ) (ketone form); 69.3 (CHC = O) (ketone form); 108.2 (C = COH) (enol form); 120.3 (= CHSi) (keto); 118.7 (= CHSi) (enol form); 149.9 (= CH) (enol); 149.4 (= CH) (ketone form); 127.2 (C ₆ H ₄ ) (ketone form); 127.4 (C6H4) (enol form); 127.9 (C6H4) (enol form); 129.3 (C6H4) (ketone form); 136.5 (C6H4) (enol form); 136.7 (C6H4) (ketone form); 139.5 (C6H4) (ketone form);

141.1 (C6H4) (enol form); 194.5 (COH); 204.2 (C = O)

PL 215 560 B1

P r z k ł a d 6

Under the conditions of example 1, to a boiling solution containing 0.83 g of 4- (4-ethenyl-3 -2 benzyl) heptane-3,5-dione (3.4x10 ^-3 mol) and 3.6 mL of ethenyltriethoxysilane (1, 7x10 ^-2 mol) in 20 mL of benzene, 0.1399 g (1.7x10 ^-4 mol) of benzylidene dichlorobis (tricyclohexylphosphine) ruthenium (IV) as a catalyst was added in three portions with an interval of about 3 hours. The reaction was carried out at the boiling point of benzene (80 ° C). C) for 24 h. The product was isolated by fractional distillation under reduced pressure. 0.83 g of 4- {4- [2- (triethoxysilyl) ethenyl] benzyl} heptane-3,5-dione was obtained, which was ₁

60% of theory. ¹ H NMR analysis of the benzene product solution indicates the presence of two tautomers. The ratio of ketone to enol form a benzene solution based on ₁ ¹ H NMR analysis was determined as 1.8: 1. Only the E isomer was observed.

Spectroscopic analysis;

^1H NMR (C6D6, δ (ppm)): 1.02 (s, 6H, CH 3) (keto); 1.09 (s, 6H, CH3) (enol form); 1.20 (t, J = 7.0 Hz, 9H, CH3) (ketone form); 1.23 (t, J = 7.0 Hz, 9H, CH3) (enol form); 2.65 (q, 7.0 Hz, 4H, CH2C = O) (keto); 2.42 (q, J = 7.0 Hz, 4H, CH2CO) (enol form); 2.56-2.61 (m, 2H, CH2) (keto); 2.67-2.72 (m, 2H, CH2) (enol form); 3.39 (t, J = 7.5 Hz, 1H, CH) (ketone form); 3.90 (q, J = 6.9 Hz, 6H, OCH2) (enol form); 3.97 (q, J = 6.9 Hz, 6H, OCH2) (ketone form); 5.55 (d, J = 18.7 Hz; 1H, = CHSi) (enol form); 5.61 (d, J = 18.7 Hz, 1H, = CHSi) (ketone form); 6.43 (d, J = 18.7 Hz, 1H, = CH) (ketone form); 6.52 (d, J = 18.7 Hz, 1H, = CH) (enol form); 6.82 (d, J = 8.4 Hz, 2H, C6H4) (enol form); 6.87 (d, J = 8.0 Hz, 2H, C6H4) (ketone form); 7.22 (d, J = 8.0 Hz, 2H, C6H4) (ketone form); 7.28 (d, J = 8 Hz, 2H, C6H4) (enol form); 17.42 (s, 1H, OH).

¹³ C NMR (C6D6; δ (ppm)): 7.5 (CH3) (keto); 7.7 (CH2) (enol form); 18.6 (OCH2CH3) (ketone and enol forms overlap); 24.8 (CH ₂ CH ₃ ) (enol form); 24.6 (CH ₂ CH ₃ ) (ketone form); 33.2 (CH2) (ketone phono); 34.0 (CH2) (enol form); 58.7 (OCH2) (ketone form); 58.8 (OCH2); (enol form), 107.4 (C = COH); 118.1 (= CHSi) (enol form); 118.4 (= CHSi) (ketone form); 148.5 (= CH) (enol form); 148.7 (= CH) (ketone form); 127.4 (C6H4) (ketone form); 127.5 (C6H4) (enol form); 127.9 (C6H4) (enol form); 128.0 (C6H4) (ketone form);

136.6 (C6H4) (enol form); 137.0 (C6H4) (ketone form); 139.42 (C6H4) (ketone form); 140.92 (C6H4) (enol form); 192.8 (COH); 203.2 (C = O)

Claims (6)

1. New 4-etenylobenzylowe derivatives of β-diketones of the general formula 1, wherein 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 4-ethenylbenzyl derivatives of β-diketones of general formula 1, in which PL 215 560 B1 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 4-etenylobenzylowej 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: in which PL 215 560 B1 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 of this three-st than 1x10 ^-3 mol per 1 mol of Ru dione. -3 -2 6. The method according to p. 5, characterized in that the catalyst is used in an amount of 3x10 ^-3 - 5x10 ^-2 mol per 1 mol dione.