(3, 3-dimethyl-1-butyne) hexacarbonyl dicobalt and synthetic method thereof
By adding 3,3-dimethyl-1-butyne in batches and distillation and distillation, the problem of low synthesis yield of (3,3-dimethyl-1-butyne) hexacarbonyl dicobalt in the prior art was solved, and high yield and high purity preparation was achieved.
Patent Information
- Application Number
- CN202311089718.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2023-08-28
- Publication Date
- 2025-02-28
AI Technical Summary
The existing (3,3-dimethyl-1-butyne)hexacarbonyldicobalt synthesis method has low yields and complex steps.
The product is isolated by mixing the cobalt carbonyl carbonyl reagent with n-hexane and 3,3-dimethyl-1-butyne dropwise, including dropwise addition of one half, then dropwise addition of the remaining portion, and distillation and rectification treatment.
High yield and high purity (3,3-dimethyl-1-butyne)hexacarbonyl dicobalt preparation is achieved, simplifying the synthesis step and reducing the generation of by-products.
Smart Images
Figure CN119528993A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the field of fine chemicals, in particular to (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl and a synthesis method thereof. Background Art
[0002] There are few methods for synthesizing (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl. One method is to add graphene oxide material at the same time, which has many raw materials, complicated process and low yield. Another synthesis method is to mix the cobalt carbonyl reagent and n-hexane, and add 3,3-dimethyl-1-butyne to it, and separate (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl after the reaction. Although the above method has simple steps, the yield is low.
[0003] The information disclosed in this background technology section is only intended to enhance the understanding of the overall background of the invention and should not be regarded as an acknowledgment or any form of suggestion that the information constitutes the prior art already known to a person skilled in the art. Summary of the invention
[0004] The object of the present invention is to provide a method for synthesizing (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl, which has both high yield and purity and simple synthesis steps.
[0005] To achieve the above object, an embodiment of the present invention provides a method for synthesizing (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl, comprising the following steps:
[0006] S1. Weigh a certain amount of cobalt carbonyl reagent, n-hexane and 3,3-dimethyl-1-butyne;
[0007] S2, uniformly mix all the cobalt carbonyl reagent and n-hexane, dropwise add half of 3,3-dimethyl-1-butyne thereto, and continue the reaction after the dropwise addition is completed;
[0008] S3, adding the remaining 3,3-dimethyl-1-butyne dropwise, and continuing the reaction after the addition is completed;
[0009] S4. Separate and obtain (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl.
[0010] In one or more embodiments of the present invention, step S1 includes:
[0011] Weigh 400 parts by mass of a cobalt carbonyl reagent, 2000-2500 parts by mass of n-hexane, and 90-100 parts by mass of 3,3-dimethyl-1-butyne.
[0012] In one or more embodiments of the present invention, step S2 includes:
[0013] Under a protective gas atmosphere, all the cobalt carbonyl reagent was mixed with n-hexane, stirred for 10-15 minutes, and the temperature was maintained at 22-28°C.
[0014] In one or more embodiments of the present invention,
[0015] In step S2, the time for adding half of 3,3-dimethyl-1-butyne dropwise is 20 to 40 minutes, and the reaction is continued for 20 to 40 minutes; and / or,
[0016] In the step S3, the remaining 3,3-dimethyl-1-butyne is added dropwise for 20 to 40 minutes, and the reaction is maintained for 20 to 40 minutes.
[0017] In one or more embodiments of the present invention, in step S2, the reaction time is maintained to be the same as the dripping time; and / or, in step S3, the reaction time is continued to be the same as the dripping time.
[0018] In one or more embodiments of the present invention,
[0019] In step S2, the time for adding half of 3,3-dimethyl-1-butyne is 30 minutes, and the reaction time is continued for 30 minutes; and / or,
[0020] In step S3, the remaining 3,3-dimethyl-1-butyne is added dropwise for 30 minutes, and the reaction is continued for 30 minutes.
[0021] In one or more embodiments of the present invention, in step S4, the separation step includes:
[0022] The mixture after the reaction in step S3 is subjected to distillation to remove n-hexane;
[0023] Carry out distillation treatment.
[0024] In one or more embodiments of the present invention, the temperature of the distillation treatment is 32-38° C., and the vacuum degree is 20-30 kPa.
[0025] In one or more embodiments of the present invention, the temperature of the distillation treatment is 48-52° C., and the vacuum degree is 0.05-0.2 kPa.
[0026] An embodiment of the present invention provides (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl, which is prepared by the above-mentioned synthesis method.
[0027] Compared with the prior art, the method for synthesizing (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl according to the embodiment of the present invention has the following beneficial effects by dripping 3,3-dimethyl-1-butyne in batches into a mixed system of a cobalt carbonyl reagent (cobalt octacarbonyl) and n-hexane:
[0028] (1) The one-step method may result in excessive and violent gas production. Adding the gas in batches can reduce the intensity of the reaction.
[0029] (2) One-step addition may result in an excessively high concentration of 3,3-dimethyl-1-butyne in the mixed system, thereby generating by-products and resulting in a low yield. Batch addition reduces the generation of by-products.
[0030] (3) The contact area between 3,3-dimethyl-1-butyne and the unreacted cobalt carbonyl reagent was increased in batches, thereby improving the reaction efficiency. BRIEF DESCRIPTION OF THE DRAWINGS
[0031] Figure 1 is a flow chart of a method for synthesizing (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl according to one embodiment of the present invention;
[0032] Figure 2 This is the nuclear magnetic 1H spectrum of (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl prepared in Example 1 of the present invention. DETAILED DESCRIPTION
[0033] The specific implementation modes of the present invention are described in detail below in conjunction with the accompanying drawings, but it should be understood that the protection scope of the present invention is not limited by the specific implementation modes.
[0034] Unless explicitly stated otherwise, throughout the specification and claims, the term “comprise” or variations such as “include” or “comprising”, etc., will be understood to include the stated elements or components but not to exclude other elements or components.
[0035] like Figure 1 As shown, the method for synthesizing (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl according to a preferred embodiment of the present invention comprises the following steps:
[0036] S1. Weigh a certain amount of cobalt carbonyl reagent, n-hexane and 3,3-dimethyl-1-butyne.
[0037] Specifically, step S1 may include weighing 400 parts by mass of a cobalt carbonyl reagent, 2000-2500 parts by mass of n-hexane, and 90-100 parts by mass of 3,3-dimethyl-1-butyne.
[0038] Wherein, the cobalt carbonyl reagent is dicobalt octacarbonyl.
[0039] S2. Evenly mix all the cobalt carbonyl reagent and n-hexane, and dropwise add half of 3,3-dimethyl-1-butyne thereto. After the dropwise addition is completed, continue the reaction.
[0040] Specifically, under a protective gas atmosphere, all the cobalt carbonyl reagent is mixed with n-hexane, stirred for 10-15 minutes, and the temperature is maintained at 22-28°C.
[0041] The time for dropping half of 3,3-dimethyl-1-butyne is 20 to 40 minutes, and the reaction time is 20 to 40 minutes. It can be understood that during the process of dropping 3,3-dimethyl-1-butyne, 3,3-dimethyl-1-butyne and the carbonyl cobalt reagent have already reacted. The reaction time is 20 to 40 minutes, which means that after the dropwise addition of half of 3,3-dimethyl-1-butyne is completed, the reaction is continued for another 20 to 40 minutes.
[0042] The protective gas can be nitrogen, argon, etc.
[0043] S3. Add the remaining 3,3-dimethyl-1-butyne dropwise. After the addition is completed, continue the reaction.
[0044] Among them, the time for dripping the remaining 3,3-dimethyl-1-butyne is 20 to 40 minutes, and the reaction time is continued for 20 to 40 minutes. It is understandable that in the process of dripping 3,3-dimethyl-1-butyne, 3,3-dimethyl-1-butyne and carbonyl cobalt reagent have reacted. The continued reaction time is 20 to 40 minutes, which can be considered to be the remaining 3,3-dimethyl-1-butyne after the dripping is completed, and then react for 20 to 40 minutes. Preferably, during a large number of experiments by the inventor, it was accidentally found that when the dripping time in step S2 is the same as the dripping time in step S3, and in step S2 and step S3, and the continued reaction time in step 2 and step 3 is the same as the dripping time, the (3,3-dimethyl-1-butyne) hexacarbonyl dicobalt prepared finally has both a higher yield and a higher purity.
[0045] For example, in step S2, the time for adding half of the 3,3-dimethyl-1-butyne is 30 minutes, and the reaction time is continued for 30 minutes; in step S3, the time for adding the remaining 3,3-dimethyl-1-butyne is 30 minutes, and the reaction time is continued for 30 minutes.
[0046] S4. Separate and obtain (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl.
[0047] The separation step includes:
[0048] S41, distilling the mixture after the reaction in step S3 to remove n-hexane.
[0049] The temperature of the distillation treatment is 32-38°C, and the vacuum degree is 20-30 kPa.
[0050] S42, performing distillation treatment.
[0051] The temperature of the distillation treatment is 48-52°C, and the vacuum degree is 0.05-0.2 kPa.
[0052] Specifically, the distillation treatment may be performed using a distillation column, and a 5*5 mm Dixon filler may be installed in the distillation column.
[0053] Specifically, in step S4, the separation process may include:
[0054] The reaction container containing the mixture after the reaction in step S3 is heated to 32-38° C., and the vacuum degree of the reaction container is made to reach 20-30 kPa, so as to remove n-hexane (solvent). After no liquid (n-hexane) continues to be discharged, the reaction container is heated to 48-52° C., and the vacuum degree of the reaction container is made to reach 0.05-0.2 kPa. Distillation is performed from a discharge port of the reaction container, that is, the discharge port is connected to a distillation column, and a 5*5 mm Dixon filler can be installed in the distillation column, so as to obtain high-purity (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl.
[0055] An embodiment of the present invention provides (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl, which is prepared by the above-mentioned synthesis method.
[0056] The (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl and its synthesis method of the present invention will be described in detail below with reference to specific embodiments.
[0057] Example 1
[0058] Under nitrogen atmosphere, 400 g of cobalt carbonyl reagent (cobalt octacarbonyl) was added to the reactor, and then 2000 mL of n-hexane was added, followed by stirring for 10 min, while maintaining the reactor temperature at 25°C.
[0059] 45 g of 3,3-dimethyl-1-butyne was added dropwise into the reactor under stirring for 30 min. After the addition was completed, the reaction was continued for 30 min.
[0060] Then 45 g of 3,3-dimethyl-1-butyne was added dropwise to the reactor for 30 min. After the addition was completed, the reaction was continued for 30 min.
[0061] After the reaction is completed, the reactor is heated to 35°C and the reactor temperature is maintained. The vacuum degree is adjusted to 25kpa to distill and remove n-hexane, and the material is discharged when there is no liquid. The reactor temperature is increased to 50°C and the reactor temperature is maintained. The vacuum degree is adjusted to 0.1kpa, and distillation is performed from the other port of the reactor. The distillation chamber is filled with 5*5mm Dixon filler to obtain high-purity (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl.
[0062] The yield of (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl prepared in this example is 97%, and the prepared (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl is subjected to nuclear magnetic resonance and GC-MS detection, and the following is obtained: Figure 2 The 1H NMR spectrum shown and the data described in Table 1.
[0063] Table 1: GC-MS results of (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl are as follows:
[0064]
[0065]
[0066] It can be seen from Table 1 and the above data that the (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl prepared in this embodiment has an organic purity of 99.99%, and is a 7N product.
[0067] Example 2
[0068] Under nitrogen atmosphere, 400 g of cobalt carbonyl reagent (cobalt octacarbonyl) was added to the reactor, and then 2000 mL of n-hexane was added, followed by stirring for 10 min, while maintaining the reactor temperature at 25°C.
[0069] 45 g of 3,3-dimethyl-1-butyne was added dropwise into the reactor under stirring for 20 min. After the addition was completed, the reaction was continued for 20 min.
[0070] Then 45 g of 3,3-dimethyl-1-butyne was added dropwise into the reactor for 40 min. After the addition was completed, the reaction was continued for 40 min.
[0071] After the reaction is completed, the reactor is heated to 35°C and the reactor temperature is maintained. The vacuum degree is adjusted to 25kpa to distill and remove n-hexane, and the material is discharged when there is no liquid. The reactor temperature is increased to 50°C and the reactor temperature is maintained. The vacuum degree is adjusted to 0.1kpa, and distillation is performed from the other port of the reactor. The distillation chamber is filled with 5*5mm Dixon filler to obtain high-purity (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl.
[0072] The yield of (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl prepared in this example is 92.2%, and the organic purity is 99.99%.
[0073] Example 3
[0074] Under nitrogen atmosphere, 400 g of cobalt carbonyl reagent (cobalt octacarbonyl) was added to the reactor, followed by 2200 mL of n-hexane, and then stirred for 15 min, maintaining the reactor temperature at 22°C.
[0075] 45 g of 3,3-dimethyl-1-butyne was added dropwise into the reactor under stirring for 20 min. After the addition was completed, the reaction was continued for 40 min.
[0076] Then 45 g of 3,3-dimethyl-1-butyne was added dropwise into the reactor for 20 min. After the addition was completed, the reaction was continued for 40 min.
[0077] After the reaction, the reactor was heated to 32°C and maintained at this temperature. The vacuum was adjusted to 20 kpa to distill off the n-hexane and the material was discharged when there was no more liquid. The reactor temperature was raised to 48°C and maintained at this temperature. The vacuum was adjusted to 0.05 kpa and distillation was performed from the other port of the reactor. The distillation chamber was filled with a 5*5 mm Dickson filler to obtain high-purity (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl.
[0078] The yield of (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl prepared in this example is 89%, and the organic purity is 99.99%.
[0079] Example 4
[0080] Under nitrogen atmosphere, 400 g of cobalt carbonyl reagent (cobalt octacarbonyl) was added to the reactor, and then 2500 mL of n-hexane was added, and then stirred for 10 minutes, maintaining the reactor temperature at 28°C.
[0081] 50 g of 3,3-dimethyl-1-butyne was added dropwise into the reactor under stirring for 40 min. After the addition was completed, the reaction was continued for 40 min.
[0082] Then 50 g of 3,3-dimethyl-1-butyne was added dropwise to the reactor for 40 min. After the addition was completed, the reaction was continued for 40 min.
[0083] After the reaction, the reactor was heated to 38°C and maintained at this temperature. The vacuum was adjusted to 30 kpa to distill off the n-hexane, and the material was discharged when there was no more liquid. The reactor temperature was raised to 52°C and maintained at this temperature. The vacuum was adjusted to 0.2 kpa, and distillation was performed from the other port of the reactor. The distillation chamber was filled with a 5*5 mm Dickson filler to obtain high-purity (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl.
[0084] The yield of (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl prepared in this example is 95%, and the organic purity is 99.99%.
[0085] Comparative Example 1
[0086] Under nitrogen atmosphere, 400 g of cobalt carbonyl reagent (cobalt octacarbonyl) was added to the reactor, and then 2000 mL of n-hexane was added, followed by stirring for 10 min, while maintaining the reactor temperature at 25°C.
[0087] 30 g of 3,3-dimethyl-1-butyne was added dropwise into the reactor under stirring for 20 min. After the addition was completed, the reaction was continued for 20 min.
[0088] 30 g of 3,3-dimethyl-1-butyne was added dropwise into the reaction kettle under stirring for 20 min. After the addition was completed, the reaction was continued for 20 min.
[0089] 30 g of 3,3-dimethyl-1-butyne was added dropwise into the reaction kettle under stirring for 20 min. After the addition was completed, the reaction was continued for 20 min.
[0090] After the reaction is completed, the reactor is heated to 35°C and the reactor temperature is maintained. The vacuum degree is adjusted to 25kpa to distill and remove n-hexane, and the material is discharged when there is no liquid. The reactor temperature is increased to 50°C and the reactor temperature is maintained. The vacuum degree is adjusted to 0.1kpa, and distillation is performed from the other port of the reactor. The distillation chamber is filled with 5*5mm Dixon filler to obtain high-purity (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl.
[0091] The yield of (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl prepared in this example is 79%, and the organic purity is 99.1%.
[0092] Comparative Example 2
[0093] Under nitrogen atmosphere, 400 g of cobalt carbonyl reagent (cobalt octacarbonyl) was added to the reactor, and then 2000 mL of n-hexane was added, followed by stirring for 10 min, while maintaining the reactor temperature at 25°C.
[0094] 90 g of 3,3-dimethyl-1-butyne was added dropwise into the reactor under stirring for 60 min. After the addition was completed, the reaction was continued for 60 min.
[0095] After the reaction is completed, the reactor is heated to 35°C and the reactor temperature is maintained. The vacuum degree is adjusted to 25kpa to distill and remove n-hexane, and the material is discharged when there is no liquid. The reactor temperature is increased to 50°C and the reactor temperature is maintained. The vacuum degree is adjusted to 0.1kpa, and distillation is performed from the other port of the reactor. The distillation chamber is filled with 5*5mm Dixon filler to obtain high-purity (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl.
[0096] The yield of (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl prepared in this example is 87%, and the organic purity is 99.94%.
[0097] It can be seen from the above examples and comparative examples that the method for synthesizing (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl of the present invention has the advantage of simple synthesis steps, and the prepared (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl has a high yield and purity.
[0098] In addition, the inventors of the present case also conducted experiments with other process conditions described in this specification with reference to the aforementioned embodiments, and the yield and organic purity of (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl were both relatively high.
[0099] The foregoing description of specific exemplary embodiments of the present invention is for the purpose of illustration and demonstration. These descriptions are not intended to limit the present invention to the precise form disclosed, and it is clear that many changes and variations can be made based on the above teachings. The purpose of selecting and describing the exemplary embodiments is to explain the specific principles of the present invention and its practical application, so that those skilled in the art can realize and utilize various different exemplary embodiments of the present invention and various different selections and changes. The scope of the present invention is intended to be limited by the claims and their equivalents.
Claims
1. A method for synthesizing (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl, characterized in that: The following steps are involved: S1. Weigh a certain amount of cobalt carbonyl reagent, n-hexane and 3,3-dimethyl-1-butyne; S2, uniformly mix all the cobalt carbonyl reagent and n-hexane, dropwise add half of 3,3-dimethyl-1-butyne thereto, and continue the reaction after the dropwise addition is completed; S3, adding the remaining 3,3-dimethyl-1-butyne dropwise, and continuing the reaction after the addition is completed; S4. Separate and obtain (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl.
2. The method for synthesizing (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl according to claim 1, characterized in that: The step S1 comprises: Weigh 400 parts by mass of a cobalt carbonyl reagent, 2000-2500 parts by mass of n-hexane, and 90-100 parts by mass of 3,3-dimethyl-1-butyne.
3. The method for synthesizing (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl according to claim 1, characterized in that: The step S2 comprises: Under a protective gas atmosphere, all the cobalt carbonyl reagent was mixed with n-hexane, stirred for 10-15 minutes, and the temperature was maintained at 22-28°C.
4. The method for synthesizing (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl according to claim 1, characterized in that: In step S2, the time for adding half of 3,3-dimethyl-1-butyne dropwise is 20 to 40 minutes, and the reaction is continued for 20 to 40 minutes; and / or, In the step S3, the remaining 3,3-dimethyl-1-butyne is added dropwise for 20 to 40 minutes, and the reaction is maintained for 20 to 40 minutes.
5. The method for synthesizing (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl according to claim 4, characterized in that: In the step S2, the reaction time is maintained to be the same as the dropping time; and / or, in the step S3, the reaction time is continued to be the same as the dropping time.
6. The method for synthesizing (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl according to claim 1, characterized in that: In step S2, the time for adding half of 3,3-dimethyl-1-butyne is 30 minutes, and the reaction time is continued for 30 minutes; and / or, In step S3, the remaining 3,3-dimethyl-1-butyne is added dropwise for 30 minutes, and the reaction is continued for 30 minutes.
7. The method for synthesizing (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl according to claim 1, characterized in that: In step S4, the separation step includes: The mixture after the reaction in step S3 is subjected to distillation to remove n-hexane; Carry out distillation treatment.
8. The method for synthesizing (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl according to claim 7, characterized in that: The temperature of the distillation treatment is 32-38° C., and the vacuum degree is 20-30 kPa.
9. The method for synthesizing (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl according to claim 7, characterized in that: The temperature of the distillation treatment is 48-52° C., and the vacuum degree is 0.05-0.2 kPa.
10. A (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl, characterized in that The compound is prepared by the synthesis method according to any one of claims 1 to 9.