CN1108305C

CN1108305C - Method for preparing 1,3-dichloro-1,1,3,3-tetraphenyl disilazane

Info

Publication number: CN1108305C
Application number: CN 99123988
Authority: CN
Inventors: 谢择民; 周宁; 张志杰; 徐彩虹; 姚燕斌
Original assignee: Institute of Chemistry CAS
Current assignee: Institute of Chemistry CAS
Priority date: 1999-11-23
Filing date: 1999-11-23
Publication date: 2003-05-14
Anticipated expiration: 2019-11-23
Also published as: CN1303856A

Abstract

The present invention relates to a preparation method of 1, 3-dichloro-1, 1, 3, 3-tetraphenyl disilazane. In the preparation method, hexamethyl cyclotrisilazane or octamethyl cyclotetrasilazane reacts with diphenyl dichlorosilane after hexamethyl cyclotrisilazane or octamethyl cyclotetrasilazane and diphenyl dichlorosilane are stirred according to the molar ratio of 1:6 to 1:10, and the reaction for 45 to 60 hours is realized at the temperature of 140 DEG C to 200 DEG C; filtration and recrystallization are carried out; consequently, 1, 3-dichloro-1, 1, 3, 3-tetraphenyl disilazane is prepared. The method of the present invention has the advantages of convenient operation and high yield (78%).

Description

Process for preparing 1, 3-dichloro-1, 1, 3, 3-tetraphenyldisilazane

The invention relates to 1, 3-dichloro-1, 1, 3, 3-tetraphenyldisilazane (ClPh)₂Si-NH-SiPh₂Cl) (I)and processes for the preparation thereof.

For the preparation of (I), the document "1.3-dihalogengdilizane (Beitrage)Zur Chemie der silicon-sticksttoff-verindungen) "(mona. chem., 1971, 102: 1806) two methods are used. One method is hexaphenylcyclotrisilazane ((Ph)₂SiNH)₃) Reacting with Hydrogen Chloride (HCL), but this method requires the preparation of a hydrogen chloride-ether solution of precise concentration in advance and the work-up of by-product NH₄Cl is not easy to remove, so the whole operation process is complicated; process II hexaphenylcyclotrisilazane ((Ph)₂SiNH)₃) With diphenyldichlorosilane (Ph)₂SiCl₂) However, the yield of this process was low, only 21%.

The invention overcomes the defects of complex operation or low yield in the prior art, and provides a preparation method of 1, 3-dichloro-1, 1, 3, 3-tetraphenyldisilazane, which has simple operation and high yield (78%).

The reaction equation for preparing 1, 3-dichloro-1, 1, 3, 3-tetraphenyldisilazane according to the invention is as follows:

or

The preparation method of the invention is carried out according to the following sequence:

the hexamethylcyclotrisilazane or octamethylcyclotetrasilazane and diphenyldichlorosilane are reacted under stirring at a molar ratio of 1: 6 to 1: 10, and the reaction is carried out at 140-200 ℃ for 45-60 hours, wherein dimethyldichlorosilane (Me) generated by the reaction is continuously evaporated₂SiCl₂). After the reaction, the crystals were obtained by filtration. The crystals are recrystallized from organic solvents including: alkane with 6-12C atoms, aromatic hydrocarbon with 6-9C atoms and the like.

The method provided by the invention has the advantages of simple operation and high yield (78%), and the effect is shown in table 1.

Table 1: EXAMPLES 123456 yield (%) 78.077.269.969.970.473.0 melting point (. degree. C.) 117.1117.0117.0117.1117.2117.2

Example 1:

0.1mol of octamethylcyclotetrasilazane and 0.8mol of diphenyldichlorosilane were added to a three-necked flask, and reacted at 200 ℃ for 45 hours while dimethyldichlorosilane produced by the reaction was continuously distilled off. Cooling, filtering to obtain crystal, and recrystallizing with mixed solution of toluene and n-hexane (volume ratio of 1: 3) to obtain white crystal140.4g, 78.0% yield, mp 117.1 ℃. Elemental analysis: c63.70%, H4.56%, N2.91%, cl15.49% (the observed values of elemental analysis are in line with the theoretical values). Of the product²⁹The Si-NMR spectrum has only a single peak with a chemical shift at δ -7.75(TMS scale).¹H-NMR spectrum has peaks (-C) at delta 7.2-7.6₆H₅) And a single peak (-NH) at 2.5.

Example 2:

0.1mol of octamethylcyclotetrasilazane and 0.9mol of diphenyldichlorosilane were added to a three-necked flask, and reacted at 180 ℃ for 47 hours while dimethyldichlorosilane produced by the reaction was continuously distilled off. After cooling, the mixture was filtered to give crystals, which were recrystallized from a mixture of toluene and n-hexane (volume ratio 1: 3) to give 139.0g of white crystals, 77.2% yield and 117.0 ℃ melting point. Elemental analysis: c63.66%, H4.46%, N2.94%, Cl 15.238% (the observed values of elementalanalysis are in agreement with the theoretical values). Of the product²⁹The Si-NMR spectrum has only a single peak with a chemical shift at δ -7.76(TMS scale).¹H-NMR spectrum has peaks (-C) at delta 7.2-7.6₆H₅) And a single peak (-NH) at 2.5.

Example 3:

0.1mol of octamethylcyclotetrasilazane and 1.0mol of diphenyldichlorosilane were added to a three-necked flask, and reacted at 150 ℃ for 55 hours while dimethyldichlorosilane produced by the reaction was continuously distilled off. Cooling, filtering to obtain crystal, and mixing with toluene and n-hexane (1: 3 by volume)The solution was recrystallized to give 125.8g of white crystals, 69.9% yield, mp 117.0 ℃. Elemental analysis: c63.72%, H4.55%, N2.98%, Cl 15.39%, (the observed values of elemental analysis correspond to those of theory). Of the product²⁹The Si-NMR spectrum has only a single peak with a chemical shift at δ -7.76(TMS scale).¹H-NMR spectrum has peaks (-C) at delta 7.2-7.6₆H₅) And a single peak (-NH) at 2.5.

Example 4:

0.1mol of hexamethylcyclotrisilazane and 0.6mol of diphenyldichlorosilane are added into a three-neck flask, and the mixture reacts for 60 hours at the temperature of 140 ℃, and dimethyldichlorosilane generated by the reaction is continuously evaporated during the reaction. After cooling, the mixture was filtered to give crystals, which were recrystallized from a mixture of toluene and n-hexane (volume ratio 1: 3) to give 94.4g of white crystals, yield 69.9%, melting point 117.1 ℃. Elemental analysis: c63.81%, H4.60%, N3.01%, Cl 15.59%, (the observed values of elemental analysis correspond to theoretical values). Of the product²⁹The Si-NMR spectrum has only a single peak with a chemical shift at δ -7.73(TMS scale).¹H-NMR spectrum has peaks (-C) at delta 7.2-7.6₆H₅) And a single peak (-NH) at 2.5.

Example 5:

0.1mol of hexamethylcyclotrisilazane and 0.8mol of diphenyldichlorosilane are added into a three-neck flask, and the mixture reacts for 50 hours at 170 ℃, and dimethyldichlorosilane generated by the reaction is continuously evaporated during the reaction. After cooling, the mixture was filtered to give crystals, which were recrystallized from a mixture of toluene and n-hexane (volume ratio 1: 3) to give 95g of white crystals, 70.4% yield and 117.2 ℃ melting point. Elemental analysis: c63.86%, H4.57%, N3.10%, cl15.69% (the observed values of elemental analysis are in line with the theoretical values). Of the product²⁹The Si-NMR spectrum has only a single peak,chemical shifts are at δ -7.73(TMS scale).¹H-NMR spectrum has peaks (-C) at delta 7.2-7.6₆H₅) And a single peak (-NH) at 2.5.

Example 6:

adding 0.1mol of hexamethylcyclotrisilazane and 1.0mol of diphenyldichlorosilane into a three-neck flask, reacting for 45 hours at 200 ℃, and continuously distilling off dimethyl generated by the reactionDichlorosilane. After cooling, the mixture was filtered to obtain crystals, which were recrystallized from a mixture of toluene and n-hexane (1: 3 by volume) to obtain 98.5g of white crystals, 73.0% yield and 117.2 ℃ melting point. Elemental analysis: c63.89%, H4.56%, N3.13%, Cl 15.55%, (the observed values of elemental analysis are in line with the theoretical values). Of the product²⁹The Si-NMR spectrum has only a single peak with a chemical shift at δ -7.75(TMS scale).¹H-NMR spectrum has peaks (-C) at delta 7.2-7.6₆H₅) And a single peak (-NH) at 2.5.

Claims

The preparation method of 1, 3-dichloro-1, 1, 3, 3-tetraphenyldisilazane is characterized in that hexamethylcyclotrisilazane or octamethylcyclotetrasilazane and diphenyldichlorosilane are reacted at 140-200 ℃ for 45-60 hours in a molar ratio of 1: 6-1: 10, and the product is obtained through filtration and recrystallization.
2. The process for the preparation of 1, 3-dichloro-1, 1, 3, 3-tetraphenyldisilazane according to claim 1, characterized in that the reaction temperature is between 180 ℃ and 200 ℃.
3. The process for preparing 1, 3-dichloro-1, 1, 3, 3-tetraphenyldisilazane according to claim 1, wherein said recrystallization solvent is a mixed solvent of toluene and n-hexane in a volume ratio of 1: 3.