Sulfur-containing organosilicon compounds and methods for their preparation

Abstract

The application relates to a sulfur-containing organosilicon compound and a preparation method thereof, and belongs to the technical field of organic materials. The sulfur-containing organosilicon compound is obtained by the reaction of a thiosulfonate substituent, an organosilicon compound and a catalyst in a solvent. The method can efficiently and simply realize the efficient synthesis of the sulfur-containing organosilicon compound, can realize the functional group modification of the compound, and the richness of the functional groups provides guarantee for the application of the sulfur-containing organosilicon compound in the material field.

Description

Technical Field

[0001] This invention relates to the field of organic materials technology, and in particular to a sulfur-containing organosilicon compound and its preparation method. Background Technology

[0002] With the rapid development of modern electronic information technology, electronic products are evolving towards miniaturization, portability, and multifunctionality, making electronic packaging materials and technologies particularly important. Electronic packaging, along with electronic design and manufacturing, is jointly driving the development of the information society. In recent years, the development of packaging materials has shown a rapid growth trend. As microelectronic packaging technology moves towards multi-chip modules (MCMs) and surface mount technology (SETs), traditional packaging materials can no longer meet the requirements of high-density packaging. Developing and producing green and environmentally friendly new epoxy composite materials that meet the rapidly developing market demands is a significant challenge.

[0003] Chinese invention patent CN 103897657B discloses a UV adhesive for glass lamination based on modified organosilicon materials and its application. The silicone-containing UV adhesive uses organosilicon-modified acrylic or methacrylic monomers to modify and adjust the adhesive's properties. Chinese invention patent CN 107189730B discloses a dual-curing UV adhesive based on acrylic-modified hyperbranched waterborne polyurethane and its preparation method, using organosilicon-modified polyethers to adjust the adhesive's properties. However, its properties are limited and cannot achieve further modification and adjustment of more functional groups. Summary of the Invention

[0004] To address the aforementioned technical problems, this invention provides a sulfur-containing organosilicon compound and its preparation method.

[0005] The first objective of this invention is to provide a sulfur-containing organosilicon compound with the structure shown in formula (I):

[0006]

[0007] Among them, R 1 R 2 and R 3 Independently hydrogen, halogen, substituted or unsubstituted C1-C 18 Alkyl, substituted or unsubstituted C6-C 18 Aryl, substituted or unsubstituted heterocyclic groups.

[0008] Furthermore, the substituted group is one or more of methyl, methoxy, and halogen.

[0009] Furthermore, the heterocyclic group is naphthyl, pyridine, or thiophene.

[0010] Furthermore, the sulfur-containing organosilicon compound is selected from the following compounds:

[0011]

[0012] Among them, R 5 It can be -CH3, -OCH3, -Cl, -Br, -F, or -CF3.

[0013] Furthermore, it is characterized in that R 1 R 2 Choose from any one of (1)-(4):

[0014] (1)R 1 =R 2 =Ph, 2-CH3Ph, 3-CH3Ph, 4-CH3Ph, 4-OCH3Ph, 4-FPh, 4-ClPh or 4-CF3Ph;

[0015] (2)R 1 =CH3,R 2 =Ph;

[0016] (3)R 1 =CH3,R 2 =4-FPh;

[0017] (4)R 1 =CH3,R 2 =2-CH3Ph.

[0018] The sulfur-containing organosilicon compound is selected from the following compounds:

[0019]

[0020] Furthermore, sulfur-containing organosilicon compounds can exist in the form of one or more stereoisomers, including enantiomers, diastereomers, and geometric isomers.

[0021] A second objective of this invention is to provide a method for preparing a sulfur-containing organosilicon compound, comprising the following steps:

[0022] The compounds of formula (II) and formula (III) are reacted in a solvent under the action of a catalyst to obtain the sulfur-containing organosilicon compound shown in formula (I);

[0023] The structural formulas of equations (I), (II), and (III) are as follows.

[0024]

[0025] Among them, R 1 R 2 R 3 and R 4Independently hydrogen, halogen, substituted or unsubstituted C1-C 18 Alkyl, substituted or unsubstituted C6-C 18 Aryl, substituted or unsubstituted heterocyclic groups.

[0026] Furthermore, the catalyst is one or more of copper salt, cobalt salt, and iron salt.

[0027] Furthermore, the copper salt is one or more of copper chloride, cuprous chloride, copper bromide, cuprous bromide, cuprous iodide, copper acetate, and copper sulfate.

[0028] Furthermore, the cobalt salt is one or more of cobalt bromide, cobalt chloride, cobalt iodide, and cobalt acetylacetonate.

[0029] Furthermore, the iron salt is one or more of ferric chloride, ferrous chloride, ferric bromide, and ferrous bromide.

[0030] Further, the solvent is acetonitrile, dichloromethane, ethanol, or N,N-dimethylformamide.

[0031] Furthermore, the reaction temperature is from -10°C to 80°C, and the reaction time is from 0.1 to 12 hours.

[0032] Furthermore, the molar ratio of the compound with structure (II) to the compound with structure (III) is 2:3 to 2:3.

[0033] Furthermore, the amount of catalyst used is 0.1-10% of the molar amount of the compound with structure (II) or the compound with structure (III).

[0034] A third objective of this invention is to provide an application of a sulfur-containing organosilicon compound in a cured material.

[0035] The technical solution of the present invention has the following advantages compared with the prior art:

[0036] (1) The metal catalyst described in this invention is an important factor in the synthesis of sulfur-containing organosilicon compound (I). Taking a copper catalyst as an example, under the action of copper salt and ligands, compound (II) is activated by the copper salt catalyst to generate a five-membered ring copper-silicon intermediate (IV), which undergoes a ligand exchange reaction with compound (III) to obtain intermediate (V), while releasing a sulfinic acid compound. Intermediate (V) undergoes an elimination reaction to obtain intermediate (VI), and (VI) reacts with the sulfinic acid compound to obtain intermediate (VII). Intermediate (VII) undergoes desulfinic acid removal to obtain the target compound (I).

[0037]

[0038] (2) Due to the tunable substituent groups of the raw material thiosulfonate, the sulfur-containing organosilicon compounds of the present invention can introduce various functional groups such as alkyl, aryl, and heteroaryl S-substituent groups, thereby achieving functional group modification and adjustment of the sulfur-containing organosilicon compounds. The silicon atom portion of the sulfur-containing organosilicon compounds, due to the formation of Si-OH functional groups, can easily achieve further Si derivatization reactions.

[0039] (3) The sulfur-containing organosilicon compounds described in this invention use readily available organosilicon and organosulfur compounds, combined with a catalyst, to achieve efficient and concise synthesis of sulfur-containing organosilicon compounds. At the same time, it can achieve functional group modification of these compounds. Moreover, the abundance of these functional groups provides a guarantee for the application of sulfur-containing organosilicon compounds in the field of materials.

[0040] (4) The sulfur-containing organosilicon compound of the present invention can be used as an additive in UV curing materials, low-temperature epoxy curing materials and medical encapsulation materials. The sulfur-containing organosilicon compound of the present invention has a more prominent effect on regulating the performance of curing materials. Detailed Implementation

[0041] The present invention will be further described below with reference to specific embodiments, so that those skilled in the art can better understand and implement the present invention, but the embodiments are not intended to limit the present invention.

[0042] Example 1

[0043] A sulfur-containing organosilicon compound 01 and its preparation method are described below:

[0044] Step 1: Synthesis of intermediate (a-1)

[0045]

[0046] A solution of 1,1-dichlorosilane (3.0 mmol, 1.0 equivalent) in anhydrous THF (15 mL) was added to a 50 mL round-bottom flask equipped with a stir bar and dried in an oven under an Ar atmosphere. Then, commercially available Grignard reagent (6.3 mmol, 2.1 equivalent) was added, and the temperature was 0 °C. The mixture was stirred at ambient temperature for 4 h. The mixture was then quenched with water (5 mL) and a saturated aqueous solution of NH4Cl (15 mL). The organic phase was separated, and the aqueous layer was extracted with EtOAc (20 mL × 2). The combined organic layers were dried over MgSO4 and concentrated under reduced pressure to provide the crude product. The residues were purified by rapid silica gel column chromatography using petroleum ether or petroleum ether / EtOAc to provide the corresponding intermediate (a-1).

[0047] Step 2: Synthesis of intermediate (a-2)

[0048]

[0049] A mixture of PhSO₂Na (4 equivalents), disulfide (1 equivalent), and NBS (2 equivalents) in MeCN was stirred at room temperature. After the reaction was complete, the reaction mixture was washed with water and extracted with ethyl acetate by TLC monitoring. The organic phase was separated, dried over anhydrous Na₂SO₄, and filtered. The filtrate was concentrated and the residue was purified by column chromatography to provide the desired aryl-thiosulfonate.

[0050] Step 3: Synthesis of sulfur-containing organosilicon compound 01

[0051]

[0052] In a glove box, 134.5 mg (0.6 mmol) of intermediate (a-1), 100 mg (0.4 mmol) of intermediate (a-2), and Cu(MeCN)4PF6 (5 mol%) were weighed into a dry 8 mL reaction flask. 1 mL of anhydrous N,N-dimethylacetamide was added, the flask was capped, and the reaction was carried out at 40 °C for 12 h. After the reaction was complete, the mixture was extracted twice with EtOAc (20 mL × 2). The aqueous layer was separated from the extract, dried over anhydrous sodium sulfate, and the organic solvent was removed by rotary evaporation. The product was purified by column chromatography to obtain a yellow oily product, which was the sulfur-containing organosilicon compound 01, with a yield of 68%.

[0053] Example 2

[0054] A sulfur-containing organosilicon compound O2 and its preparation method are described below:

[0055] Step 1: Synthesis of intermediate (a-3)

[0056]

[0057] Step 2: Synthesis of sulfur-containing organosilicon compound O2

[0058]

[0059] In a glove box, 134.5 mg (0.6 mmol) of intermediate (a-1), 76.4 mg (0.4 mmol) of intermediate (a-3), and Cu(MeCN)4PF6 (5 mol%) were weighed into a dry 8 mL reaction flask. 1 mL of anhydrous N,N-dimethylacetamide was added, the flask was capped, and the reaction was carried out at 40 °C for 12 h. After the reaction was complete, the mixture was extracted twice with EtOAc (20 mL × 2). The aqueous layer was separated from the extract, dried over anhydrous sodium sulfate, and the organic solvent was removed by rotary evaporation. The product was purified by column chromatography to obtain a yellow oily product, which was the sulfur-containing organosilicon compound O2, with a yield of 61%.

[0060] Example 3

[0061] A sulfur-containing organosilicon compound O3 and its preparation method are described below:

[0062] Step 1: Synthesis of intermediate (a-4)

[0063]

[0064] Sodium benzenesulfinate (10 g, 61 mmol) and sulfur (1.95 g, 61 mmol) were dissolved in anhydrous pyridine (60 mL) to give a yellow solution. The reaction was stirred under argon atmosphere, and a white suspension was obtained after 1 h. Diethyl ether was added to the suspension, the reaction mixture was filtered and washed with anhydrous diethyl ether. Recrystallization from anhydrous ethanol gave PhSO₂SNa (10.5 g, 88%) as a white crystalline solid.

[0065] Step 2: Synthesis of intermediate (a-5)

[0066]

[0067] Alkyl bromide (2 equivalents) was added to a DMF solution of PhSO₂SNa (1 equivalent), and the reaction mixture was stirred at room temperature. After the reaction was complete, the reaction mixture was monitored by TLC, diluted with ethyl acetate, and washed with water. The organic phase was separated, dried over anhydrous Na₂SO₄, and filtered. The filtrate was concentrated, and the resulting residue was purified by column chromatography to provide the desired alkyl thiosulfonate.

[0068] Step 3: Synthesis of sulfur-containing organosilicon compound O3

[0069]

[0070] In a glove box, 134.5 mg (0.6 mmol) of intermediate (a-1), 144.4 mg (0.4 mmol) of intermediate (a-5), and Cu(MeCN)4PF6 (5 mol%) were weighed into a dry 8 mL reaction flask. 1 mL of anhydrous N,N-dimethylacetamide was added, the flask was capped, and the reaction was carried out at 40 °C for 12 h. After the reaction was complete, the mixture was extracted twice with EtOAc (20 mL × 2). The aqueous layer was separated from the extract, dried over anhydrous sodium sulfate, and the organic solvent was removed by rotary evaporation. The product was purified by column chromatography to obtain a yellow oily product, which was the sulfur-containing organosilicon compound O3, with a yield of 45%.

[0071] Example 4

[0072] A sulfur-containing organosilicon compound 04 and its preparation method are described below:

[0073] Step 1: Synthesis of intermediate (a-6)

[0074]

[0075] A solution of 1,1-dichlorosilane (3.0 mmol, 1.0 equivalent) in anhydrous THF (15 mL) was added to a 50 mL round-bottom flask equipped with a stir bar and dried in an oven under an Ar atmosphere. Then, commercially available Grignard reagent (6.3 mmol, 2.1 equivalent) was added, and the temperature was 0 °C. The mixture was stirred at ambient temperature for 4 h. The mixture was then quenched with water (5 mL) and a saturated aqueous solution of NH4Cl (15 mL). The organic phase was separated, and the aqueous layer was extracted with EtOAc (20 mL × 2). The combined organic layers were dried over MgSO4 and concentrated under reduced pressure to provide the crude product. The residues were purified by rapid silica gel column chromatography using petroleum ether or petroleum ether / EtOAc to provide the corresponding intermediate (a-6).

[0076] Step 2: Synthesis of intermediate (a-7)

[0077]

[0078] A mixture of PhSO₂Na (4 equivalents), disulfide (1 equivalent), and NBS (2 equivalents) in MeCN was stirred at room temperature. After the reaction was complete, the reaction mixture was washed with water and extracted with ethyl acetate by TLC monitoring. The organic phase was separated, dried over anhydrous Na₂SO₄, and filtered. The filtrate was concentrated and the residue was purified by column chromatography to provide the desired aryl-thiosulfonate.

[0079] Step 3: Synthesis of sulfur-containing organosilicon compound O4

[0080]

[0081] In a glove box, 170.5 mg (0.6 mmol) of intermediate (a-6), 105.6 mg (0.4 mmol) of intermediate (a-7), and Cu(MeCN)4PF6 (5 mol%) were weighed into a dry 8 mL reaction flask. 1 mL of anhydrous N,N-dimethylacetamide was added, the flask was capped, and the reaction was carried out at 40 °C for 12 h. After the reaction was complete, the mixture was extracted twice with EtOAc (20 mL × 2). The aqueous layer was separated from the extract, dried over anhydrous sodium sulfate, and the organic solvent was removed by rotary evaporation. The product was purified by column chromatography to obtain a yellow oily product, which was the sulfur-containing organosilicon compound O4, with a yield of 53%.

[0082] Example 5

[0083] A sulfur-containing organosilicon compound 05 and its preparation method are described below:

[0084] Step 1: Synthesis of intermediate (a-8)

[0085]

[0086] In a 100 mL round-bottom flask, 1,2-dibromoethane (3 drops), magnesium (1.90 g, 80 mmol), and anhydrous THF (5 mL) were added and stirred for 30 min at ambient temperature under nitrogen. Then, 3-chloropropylmethyldichlorosilane (9.50 mL, 60 mmol) was added dropwise to THF (45 mL) over 15 min, and the reaction mixture was heated to 50 ± 8 °C for an additional 2 h. A solution of 1-chloro-1-methyl-siloxane (3.0 mmol, 1.0 equivalent) in anhydrous Et₂O (15 mL) was added to an oven-dried 50 mL round-bottom flask equipped with a stir bar under Ar atmosphere. The mixture was stirred for 4 h at ambient temperature by slowly adding commercially available RMgBr (3.3 mmol, 1.1 equivalent) at 0 °C. The mixture was then quenched with water (5 mL) and a saturated aqueous solution of NH₄Cl (15 mL). The organic phase was separated, and the aqueous layer was extracted with EtOAc (20 mL × 2). The combined organic layers were dried over MgSO4 and concentrated under reduced pressure to provide the crude product. The residues were purified by silica gel rapid column chromatography using petroleum ether or petroleum ether / EtOAc to provide the corresponding intermediate (a-8).

[0087] Step 2: Synthesis of sulfur-containing organosilicon compound 05

[0088]

[0089] In a glove box, 72.0 mg (0.6 mmol) of intermediate (a-8), 105.6 mg (0.4 mmol) of intermediate (a-7), and Cu(MeCN)4PF6 (5 mol%) were weighed into a dry 8 mL reaction flask. 1 mL of anhydrous N,N-dimethylacetamide was added, the flask was capped, and the reaction was carried out at 40 °C for 12 h. After the reaction was complete, the mixture was extracted twice with EtOAc (20 mL × 2). The aqueous layer was separated from the extract, dried over anhydrous sodium sulfate, and the organic solvent was removed by rotary evaporation. The product was purified by column chromatography to obtain a yellow oily product, which was the sulfur-containing organosilicon compound 05, with a yield of 32%.

[0090] Test case

[0091] The sulfur-containing organosilicon compounds 01-05 synthesized in Examples 1-5 of this invention were subjected to nuclear magnetic resonance testing.

[0092] Table 1 shows the structure of the compounds and their... 1 H NMR test results:

[0093] Table 1

[0094]

[0095] As shown in Table 1, we can achieve the efficient synthesis of sulfur-containing organosilicon compounds with alkyl, aryl, and amino acid skeletons. The rich functional groups provide possibilities for further modification of the compounds.

[0096] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. A method for preparing a sulfur-containing organosilicon compound, characterized in that, Includes the following steps: In the presence of a catalyst, compounds of formula (II) and formula (III) are reacted in a solvent to obtain the sulfur-containing organosilicon compound shown in formula (I); the catalyst is Cu(MeCN)4PF6. The structural formulas of equations (I), (II), and (III) are as follows: ， ， ； Among them, R 1 R 2 R 3 and R 4 Independently hydrogen, halogen, substituted or unsubstituted C1-C 18 Alkyl, substituted or unsubstituted C6-C 18 Aryl.

2. The method for preparing the sulfur-containing organosilicon compound according to claim 1, characterized in that, The solvent is acetonitrile, dichloromethane, ethanol, or N,N-dimethylformamide.

3. The method for preparing the sulfur-containing organosilicon compound according to claim 1, characterized in that, The reaction temperature is from -10℃ to 80℃, and the reaction time is from 0.1 to 12 hours.

4. The method for preparing the sulfur-containing organosilicon compound according to claim 1, characterized in that, The molar ratio of the compound with structure (II) to the compound with structure (III) is 2:3 to 2:3; the amount of catalyst used is 0.1-10% of the molar amount of the compound with structure (II) or the compound with structure (III).

Images