Process for the preparation of diisopropyl telluride

Abstract

The application relates to the field of metal organic source synthesis, in particular to a preparation method of diisopropyl telluride, which comprises the following steps: adding an alcohol solvent and tellurium powder into a reaction device, building an atmospheric reflux device, and starting stirring; then adding sodium blocks, continuously and slowly stirring, heating the reaction device to 50-60 DEG C after the sodium blocks are all added and the reaction is stable, and continuously stirring for 3-4 hours; then cooling to room temperature, slowly and dropwisely adding 2-halogenated propane into the reaction device, controlling the dropwise adding speed according to the reaction intensity, heating the reaction device to 50-60 DEG C after the dropwise adding is completed, and continuously stirring for 12 hours; after the stirring is completed, a reduced pressure distillation device is built, and diisopropyl telluride crude products are obtained through reduced pressure distillation; the diisopropyl telluride crude products are subjected to reduced pressure rectification to obtain high-purity diisopropyl telluride finished products; all the above steps are carried out under the protection of inert gas. The preparation method has the advantages of simple synthesis route, easily-obtained raw materials, high yield, high product purity, can be used for industrial production, and can meet the market demand.

Description

Technical Field

[0001] This invention relates to the field of organometallic source synthesis, and more particularly to a method for preparing diisopropyltellurium. Background Technology

[0002] Diisopropyltellurium is an important organometallic compound with wide applications in organic synthesis, semiconductor materials, optoelectronic materials, and medicine. In organic synthesis, it serves as a catalyst for catalyzing olefin addition, alkylation, and isomerization reactions. In semiconductor and optoelectronic materials, it acts as a precursor for the preparation of materials such as cadmium telluride, lead telluride, and indium telluride transparent conductive films. These materials possess excellent photoelectric properties and are widely used in solar cells, lasers, and photodetectors. In medicine, it serves as a precursor for anticancer drugs in the preparation of tellurium compounds. These drugs are widely used in cancer treatment.

[0003] Because diisopropyltellurium is easily oxidized in air and its oxides are toxic, the reaction is difficult to control and carries certain risks. Furthermore, its high boiling point makes the preparation and processing of high-purity diisopropyltellurium challenging. Currently, domestic research on diisopropyltellurium is relatively limited. One notable approach, by purchasing high-purity raw materials, rigorously cleaning experimental equipment, and employing the Grignard reagent method for synthesis, combined various experimental parameters and conditions during the purification phase to ultimately identify an efficient purification route, yielding electronic-grade diisopropyltellurium with a crude product yield of approximately 76.9% (Suzhou University, 2021 dissertation). This demonstrates that the low efficiency of domestic diisopropyltellurium preparation hinders the development of related industries in China. Therefore, developing a simple synthetic route, readily available raw materials, high yield, high product purity, and industrially viable preparation method for diisopropyltellurium is crucial. Summary of the Invention

[0004] To address the problems existing in the prior art, this invention provides a method for preparing diisopropyltellurium, which has a simple synthetic route, readily available raw materials, high yield, and high product purity, and can be used for industrial production, thus meeting the growing market demand.

[0005] To achieve the above objectives, the present invention provides a method for preparing diisopropyltelluride, comprising the following steps:

[0006] S1. Add alcohol solvent and tellurium powder to the reaction apparatus, set up an atmospheric pressure reflux device, and start stirring;

[0007] S2. Add sodium blocks to the reaction apparatus and stir slowly and continuously. After all the sodium blocks have been added and the reaction is stable, heat the reaction apparatus to 50-60°C and stir continuously for 3-4 hours.

[0008] S3. Then cool down to room temperature and slowly add 2-halopropane dropwise to the reaction apparatus. Control the dropping rate according to the intensity of the reaction. After the addition is complete, heat the reaction apparatus to 50~60℃ and stir continuously for 12 hours.

[0009] S4. After stirring, set up a vacuum distillation apparatus and distill under vacuum to obtain crude diisopropyltelluride.

[0010] S5. The crude diisopropyltelluride obtained was subjected to vacuum distillation to obtain a high-purity diisopropyltelluride product.

[0011] All steps are performed under the protection of an inert gas.

[0012] Optionally, the alcohol solvent is either ethylene glycol or isopropanol.

[0013] Optionally, the sodium block needs to be washed twice with dry n-hexane, then the n-hexane is vacuum-dried, and finally cut into small pieces, in order to remove impurities from the raw sodium block.

[0014] Optionally, the sodium blocks should be added in batches when the reaction is stable. If the reaction solution occupies less than 1 / 2 of the space, the sodium blocks can be added all at once, but slow stirring is required.

[0015] Optionally, the 2-halopropane is one of 2-chloropropane, 2-bromopropane, or 2-iodopropane, with 2-bromopropane and 2-iodopropane being preferred.

[0016] Optionally, the molar ratio of tellurium powder, sodium lumps and 2-halopropane is 1:(2.1~2.4):(2.5~2.8).

[0017] Optionally, the reduced pressure distillation is carried out at a controlled pressure of 100 Torr to remove the fore-distillate and receive the distillate at 93~95℃.

[0018] Optionally, the reduced pressure distillation removes the front and rear fractions at a ratio of 5-10% of the diisopropyltellurium content, and the resulting middle fraction is the high-purity diisopropyltellurium product.

[0019] Optionally, the purity of the high-purity diisopropyltellurium product is confirmed by NMR and ICP testing.

[0020] Optionally, the water and oxygen content of the inert gas is less than 1 ppm.

[0021] This invention provides a method for preparing diisopropyltellurium. The core of the method involves reacting tellurium powder with metallic sodium under an inert gas atmosphere using ethylene glycol or isopropanol as a solvent to generate sodium telluride, which is then reacted with 2-halopropane to produce diisopropyltellurium. The specific reaction equation is as follows:

[0022]

[0023] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0024] 1. This invention provides a method for preparing diisopropyltellurium, which has a simple synthetic route, readily available raw materials, stable reaction process, safe and controllable operation, and can be used for industrial production.

[0025] 2. This invention provides a method for preparing diisopropyltellurium, which significantly improves the yield and produces a product with higher purity compared to the traditional Grignard reagent method. Attached Figure Description

[0026] To more clearly illustrate the technical solutions in this invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in this invention. For those skilled in the art, other drawings obtained from these drawings without creative effort are also within the protection scope of this invention.

[0027] Figure 1 The present invention describes the process steps for preparing diisopropyltellurium according to an embodiment of the present invention. Detailed Implementation

[0028] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the specific embodiments.

[0029] It should be noted that, unless otherwise defined, the technical or scientific terms used in this invention should have the ordinary meaning understood by one of ordinary skill in the art to which this invention pertains. The terms "first," "second," and similar terms used in this invention do not indicate any order, quantity, or importance, but are merely used to distinguish different components. Terms such as "comprising" or "including" mean that the element or object preceding the word encompasses the elements or objects listed following the word and their equivalents, without excluding other elements or objects. Terms such as "connected" or "linked" are not limited to physical or mechanical connections, but can include electrical connections, whether direct or indirect. Terms such as "upper," "lower," "left," and "right" are used only to indicate relative positional relationships; when the absolute position of the described object changes, the relative positional relationship may also change accordingly.

[0030] like Figure 1 As shown in the figure, a specific embodiment of the present invention provides a method for preparing diisopropyltellurium, comprising:

[0031] S1. Add alcohol solvent and tellurium powder to the reaction apparatus, set up an atmospheric pressure reflux device, and start stirring;

[0032] S2. Add sodium blocks to the reaction apparatus and stir slowly and continuously. After all the sodium blocks have been added and the reaction is stable, heat the reaction apparatus to 50-60°C and stir continuously for 3-4 hours.

[0033] S3. Then cool down to room temperature and slowly add 2-halopropane dropwise to the reaction apparatus. Control the dropping rate according to the intensity of the reaction. After the addition is complete, heat the reaction apparatus to 50~60℃ and stir continuously for 12 hours.

[0034] S4. After stirring, set up a vacuum distillation apparatus and distill under vacuum to obtain crude diisopropyltelluride.

[0035] S5. The crude diisopropyltelluride obtained was subjected to vacuum distillation to obtain a high-purity diisopropyltelluride product.

[0036] All steps are performed under the protection of an inert gas.

[0037] In some optional embodiments, the alcohol solvent is either ethylene glycol or isopropanol.

[0038] In some optional embodiments, the sodium block needs to be washed twice with dry n-hexane, then the n-hexane is vacuum-dried, and finally cut into small pieces, in order to remove impurities from the raw sodium block.

[0039] In some optional embodiments, the sodium blocks need to be added in batches when the reaction is stable. If the reaction solution occupies less than 1 / 2 of the space, the sodium blocks can be added all at once, but slow stirring is required.

[0040] In some optional specific embodiments, the 2-halopropane is one of 2-chloropropane, 2-bromopropane or 2-iodopropane, wherein 2-bromopropane and 2-iodopropane are preferred.

[0041] In some optional embodiments, the molar ratio of tellurium powder, sodium lumps and 2-halopropane is 1:(2.1~2.4):(2.5~2.8).

[0042] In some optional embodiments, the reduced pressure distillation is controlled at 100 Torr, the fore-fraction is removed, and the fraction at 93-95°C is received.

[0043] In some optional specific embodiments, the reduced pressure distillation removes the front and rear fractions at a ratio of 5-10% of the diisopropyltellurium content, and the resulting middle fraction is the high-purity diisopropyltellurium product.

[0044] In some optional specific embodiments, the purity of the high-purity diisopropyltellurium product is confirmed by NMR and ICP testing.

[0045] In some optional embodiments, the water and oxygen content of the inert gas is less than 1 ppm.

[0046] The following are five specific examples:

[0047] Example 1

[0048] Add 500 mL of ethylene glycol and 127.6 g of tellurium powder to a 2 L reaction flask, set up an atmospheric pressure reflux device, and start stirring;

[0049] Add 48.3g of cleaned sodium blocks (washed twice with dried n-hexane, then vacuum-dried, and finally cut into small pieces) to the reaction apparatus at once, stir slowly and continuously until the reaction is stable, then heat the reaction apparatus to 50°C and stir continuously for 4 hours.

[0050] Then cool down to room temperature and slowly add 425g of 2-iodopropane to the reaction apparatus. Control the adding rate according to the intensity of the reaction. After the addition is complete, heat the reaction apparatus to 50°C and stir continuously for 12 hours.

[0051] After stirring, a vacuum distillation apparatus was set up, the pressure was controlled at 100 Torr, the fore fraction was removed, and the fraction at 93~95℃ was collected to obtain 171g of crude diisopropyltelluride.

[0052] The crude diisopropyltelluride obtained is then subjected to vacuum distillation, and the fractions before and after distillation are removed at a ratio of 5-10% of the total amount. The middle fraction obtained is the high-purity diisopropyltelluride product.

[0053] All steps were carried out under the protection of inert gas (water and oxygen content both less than 1 ppm), and product samples were taken for NMR and ICP testing to confirm purity.

[0054] In Case 2, the crude isopropyl telluride was synthesized with a yield of 80%. The product was analyzed by a JNM-ECZ400S nuclear magnetic resonance spectrometer. 1 HNMR (400 MHz, CDCl3): δ=3.38 (sept, 2H, -CH-); 1.61 (d, 12H, -CH3). Inductively coupled plasma atomic emission spectrometry (Optima8000) detected all inorganic elements <1ppm, with a purity of 6N.

[0055] Example 2

[0056] Add 800 mL of isopropanol and 191.5 g of tellurium powder to a 2 L reaction flask, set up an atmospheric pressure reflux device, and start stirring;

[0057] Add 82.8g of cleaned sodium blocks (washed twice with dried n-hexane, then vacuum-dried, and finally cut into small pieces) in batches to the reaction apparatus, and stir slowly and continuously. After all the sodium blocks have been added and the reaction is stable, heat the reaction apparatus to 55°C and stir continuously for 3.5 hours.

[0058] Then, cool the mixture to room temperature and slowly add 714g of 2-iodopropane dropwise to the reaction apparatus. Control the dropping rate according to the intensity of the reaction. After the addition is complete, heat the reaction apparatus to 55°C and stir continuously for 12 hours.

[0059] After stirring, a vacuum distillation apparatus was set up, and the pressure was controlled at 100 Torr. The fore fraction was removed, and the fraction at 93~95℃ was collected to obtain 269.3g of crude diisopropyltelluride.

[0060] The crude diisopropyltelluride obtained is then subjected to vacuum distillation, and the fractions before and after distillation are removed at a ratio of 5-10% of the total amount. The middle fraction obtained is the high-purity diisopropyltelluride product.

[0061] All steps were carried out under the protection of inert gas (water and oxygen content both less than 1 ppm), and product samples were taken for NMR and ICP testing to confirm purity.

[0062] In Case 2, the yield of crude isopropyl tellurium was 84%, and the product was analyzed by a JNM-ECZ400S nuclear magnetic resonance spectrometer. 1 HNMR (400 MHz, CDCl3): δ=3.38 (sept, 2H, -CH-); 1.61 (d, 12H, -CH3). Inductively coupled plasma atomic emission spectrometry (Optima8000) detected all inorganic elements <1ppm, with a purity of 6N.

[0063] Example 3

[0064] Under inert gas protection, add 800 mL of ethylene glycol and 191.5 g of tellurium powder to a 2 L reaction flask, set up an atmospheric pressure reflux device, and start stirring;

[0065] Add 75.9g of cleaned sodium blocks (washed twice with dried n-hexane, then vacuum-dried, and finally cut into small pieces) in batches to the reaction apparatus, and stir slowly and continuously. After all the sodium blocks have been added and the reaction is stable, heat the reaction apparatus to 60°C and stir continuously for 3 hours.

[0066] Then, the temperature was lowered to room temperature, and 479.7 g of 2-bromopropane was slowly added dropwise to the reaction apparatus. The dropping rate was controlled according to the intensity of the reaction. After the addition was completed, the reaction apparatus was heated to 60°C and stirred continuously for 12 hours.

[0067] After stirring, a vacuum distillation apparatus was set up, and the pressure was controlled at 100 Torr. The fore fraction was removed, and the fraction at 93~95℃ was collected to obtain 259.7g of crude diisopropyltelluride.

[0068] The crude diisopropyltelluride obtained is then subjected to vacuum distillation, and the fractions before and after distillation are removed at a ratio of 5-10% of the total amount. The middle fraction obtained is the high-purity diisopropyltelluride product.

[0069] All steps were carried out under the protection of inert gas (water and oxygen content both less than 1 ppm), and product samples were taken for NMR and ICP testing to confirm purity.

[0070] In this case, the yield of crude triethylantimony was 81%, and the product was analyzed by a JNM-ECZ400S nuclear magnetic resonance spectrometer. 1 HNMR (400 MHz, CDCl3): δ=3.38 (sept, 2H, -CH-); 1.61 (d, 12H, -CH3). Inductively coupled plasma atomic emission spectrometry (Optima8000) detected all inorganic elements <1ppm, with a purity of 6N.

[0071] Example 4

[0072] Under inert gas protection, add 500 mL of isopropanol and 127.6 g of tellurium powder to a 2 L reaction flask, set up an atmospheric pressure reflux device, and start stirring;

[0073] Add 51.7g of cleaned sodium blocks (washed twice with dried n-hexane, then vacuum-dried, and finally cut into small pieces) to the reaction apparatus at once, and stir slowly and continuously. After all the sodium blocks have been added and the reaction is stable, heat the reaction apparatus to 55°C and stir continuously for 3.5 hours.

[0074] Then, cool the mixture to room temperature and slowly add 208.1 g of 2-chloropropane dropwise to the reaction apparatus. Control the dropping rate according to the intensity of the reaction. After the addition is complete, heat the reaction apparatus to 55°C and stir continuously for 12 hours.

[0075] After stirring, a vacuum distillation apparatus was set up, and the pressure was controlled at 100 Torr. The fore fraction was removed, and the fraction at 93~95℃ was collected to obtain 163.5g of crude diisopropyltelluride.

[0076] The crude diisopropyltelluride obtained is then subjected to vacuum distillation, and the fractions before and after distillation are removed at a ratio of 5-10% of the total amount. The middle fraction obtained is the high-purity diisopropyltelluride product.

[0077] All steps were carried out under the protection of inert gas (water and oxygen content both less than 1 ppm), and product samples were taken for NMR and ICP testing to confirm purity.

[0078] In this case, the yield of crude triethylantimony was 76.5%, and the product was analyzed by a JNM-ECZ400S nuclear magnetic resonance spectrometer. 1 HNMR (400 MHz, CDCl3): δ=3.38 (sept, 2H, -CH-); 1.61 (d, 12H, -CH3). Inductively coupled plasma atomic emission spectrometry (Optima8000) detected all inorganic elements <1ppm, with a purity of 6N.

[0079] Example 5

[0080] Add 1000mL of ethylene glycol and 255g of tellurium powder to a 2L reaction flask, set up an atmospheric pressure reflux device, and start stirring;

[0081] Add 105.8g of cleaned sodium blocks (washed twice with dried n-hexane, then vacuum-dried, and finally cut into small pieces) to the reaction apparatus in batches, and stir slowly and continuously. After all the sodium blocks have been added and the reaction is stable, heat the reaction apparatus to 55°C and stir continuously for 4 hours.

[0082] Then, the temperature was lowered to room temperature, and 664.2 g of 2-bromopropane was slowly added dropwise to the reaction apparatus. The dropping rate was controlled according to the intensity of the reaction. After the addition was completed, the reaction apparatus was heated to 60°C and stirred continuously for 12 hours.

[0083] After stirring, a vacuum distillation apparatus was set up, and the pressure was controlled at 100 Torr. The fore fraction was removed, and the fraction at 93~95℃ was collected to obtain 354.9g of crude diisopropyltelluride.

[0084] The crude diisopropyltelluride obtained is then subjected to vacuum distillation, and the fractions before and after distillation are removed at a ratio of 5-10% of the total amount. The middle fraction obtained is the high-purity diisopropyltelluride product.

[0085] All steps were carried out under the protection of inert gas (water and oxygen content both less than 1 ppm), and product samples were taken for NMR and ICP testing to confirm purity.

[0086] In Case 2, the yield of crude isopropyl tellurium was 83%, and the product was analyzed by a JNM-ECZ400S nuclear magnetic resonance spectrometer. 1 HNMR (400 MHz, CDCl3): δ=3.38 (sept, 2H, -CH-); 1.61 (d, 12H, -CH3). Inductively coupled plasma atomic emission spectrometry (Optima8000) detected all inorganic elements <1ppm (see Table 1), and the purity reached 6N.

[0087] Table 1. Impurity content of diisopropyltelluride after purification (unit: ppm)

[0088]

[0089] Note: ND indicates not detected; a purity of 6N indicates a purity ≥ 99.9999%, meaning the total impurities are ≤ 1 ppm.

[0090] Therefore, this invention provides a method for preparing diisopropyltellurium. Under inert gas protection, using ethylene glycol or isopropanol as a solvent, tellurium powder and metallic sodium react to generate sodium telluride, which is then reacted with 2-halopropane to produce diisopropyltellurium. This preparation method has a simple synthetic route, readily available raw materials, high yield, and high product purity, making it suitable for industrial production and meeting the growing market demand.

[0091] Those skilled in the art should understand that the discussion of any of the above embodiments is merely exemplary and is not intended to imply that the scope of the invention (including the claims) is limited to these examples; within the framework of the invention, the technical features of the above embodiments or different embodiments can also be combined, the steps can be implemented in any order, and there are many other variations of the different aspects of the invention as described above, which are not provided in the details for the sake of brevity.

[0092] This invention is intended to cover all such substitutions, modifications, and variations that fall within the broad scope of the appended claims. Therefore, any omissions, modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this invention should be included within the scope of protection of this invention.

Claims

1. A method for preparing diisopropyl telluride, characterized by, The method comprises the following steps: S1, adding an alcohol solvent and tellurium powder into a reaction device, building an atmospheric reflux device, and starting stirring; S2, adding sodium blocks into the reaction device, continuously slowly stirring, heating the reaction device to 50-60 DEG C after the sodium blocks are all added and the reaction is stable, and continuously stirring for 3-4 hours; S3, then cooling to room temperature, slowly adding 2-halogenated propane into the reaction device, controlling the dropping speed according to the reaction intensity, heating the reaction device to 50-60 DEG C after the dropping is completed, and continuously stirring for 12 hours; S4, building a reduced pressure distillation device after the stirring is completed, and obtaining a crude diisopropyl telluride by reduced pressure distillation; S5, obtaining a finished diisopropyl telluride by reduced pressure rectification of the crude diisopropyl telluride; The steps are all carried out under the protection of inert gas; The alcohol solvent is one of ethylene glycol or isopropyl alcohol.

2. The method of claim 1, wherein the diisopropyl telluride is prepared by the process of: The sodium blocks need to be cleaned twice by dry n-hexane, then vacuum dried n-hexane, and finally cut into small pieces. ​ 3. The method for preparing diisopropyltellurium according to claim 1, characterized in that, The sodium blocks need to be added in batches when the reaction is stable, and if the reaction solution occupies less than 1 / 2 of the space, the sodium blocks can be all added at once, but slowly stirring is needed.

4. The method for preparing diisopropyltellurium according to claim 1, characterized in that, The 2-halogenated propane is one of 2-chlorinated propane, 2-brominated propane or 2-iodinated propane.

5. The method for preparing diisopropyltellurium according to claim 1, characterized in that, The molar ratio of the amounts of the tellurium powder, the sodium blocks and the 2-halogenated propane is 1:(2.1-2.4):(2.5-2.8).

6. The method for preparing diisopropyltellurium according to claim 1, characterized in that, The reduced pressure distillation controls the pressure to be 100 Torr, removes the front fraction, and receives a fraction of 93-95 DEG C.

7. The method for preparing diisopropyltellurium according to claim 1, characterized in that, The reduced pressure rectification removes the front and rear fractions according to the proportion of 5-10% of the diisopropyl telluride content, and the middle fraction obtained is the finished diisopropyl telluride.

8. The method for preparing diisopropyltellurium according to claim 1, characterized in that, The finished diisopropyl telluride is detected by nuclear magnetic resonance and ICP to confirm the purity.

9. The method for preparing diisopropyltellurium according to claim 1, characterized in that, The inert gas has a water and oxygen content of less than 1 ppm.

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