CN112159431A - Preparation method of tert-butyl arsenic - Google Patents
Preparation method of tert-butyl arsenic Download PDFInfo
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- CN112159431A CN112159431A CN202011028564.8A CN202011028564A CN112159431A CN 112159431 A CN112159431 A CN 112159431A CN 202011028564 A CN202011028564 A CN 202011028564A CN 112159431 A CN112159431 A CN 112159431A
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- tert
- butyl
- arsenic
- magnesium
- chloride
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- QTQRGDBFHFYIBH-UHFFFAOYSA-N tert-butylarsenic Chemical compound CC(C)(C)[As] QTQRGDBFHFYIBH-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- CQRPUKWAZPZXTO-UHFFFAOYSA-M magnesium;2-methylpropane;chloride Chemical compound [Mg+2].[Cl-].C[C-](C)C CQRPUKWAZPZXTO-UHFFFAOYSA-M 0.000 claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000011777 magnesium Substances 0.000 claims abstract description 32
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 32
- 239000003999 initiator Substances 0.000 claims abstract description 31
- NBRKLOOSMBRFMH-UHFFFAOYSA-N tert-butyl chloride Chemical compound CC(C)(C)Cl NBRKLOOSMBRFMH-UHFFFAOYSA-N 0.000 claims abstract description 26
- OEYOHULQRFXULB-UHFFFAOYSA-N arsenic trichloride Chemical compound Cl[As](Cl)Cl OEYOHULQRFXULB-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 21
- HCYZKGMAIJGVOQ-UHFFFAOYSA-N tert-butyl(dichloro)arsane Chemical compound CC(C)(C)[As](Cl)Cl HCYZKGMAIJGVOQ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 19
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 239000012043 crude product Substances 0.000 claims abstract description 13
- 239000011261 inert gas Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 11
- -1 lithium tri-t-butoxyaluminum hydride Chemical class 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 8
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 8
- CRWNQZTZTZWPOF-UHFFFAOYSA-N 2-methyl-4-phenylpyridine Chemical compound C1=NC(C)=CC(C=2C=CC=CC=2)=C1 CRWNQZTZTZWPOF-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- QBBWRNBMWSVXBB-UHFFFAOYSA-K aluminum;oxolane;trichloride Chemical compound Cl[Al](Cl)Cl.C1CCOC1 QBBWRNBMWSVXBB-UHFFFAOYSA-K 0.000 claims description 5
- 239000012280 lithium aluminium hydride Substances 0.000 claims description 5
- 239000012629 purifying agent Substances 0.000 claims description 5
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical group CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 claims description 4
- BYSWLWJOROIDHP-UHFFFAOYSA-N lithium;tris(3-ethylpentan-3-yloxy)alumane Chemical compound [Li].CCC(CC)(CC)O[Al](OC(CC)(CC)CC)OC(CC)(CC)CC BYSWLWJOROIDHP-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000011698 potassium fluoride Substances 0.000 claims description 4
- 235000003270 potassium fluoride Nutrition 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 2
- MDDPTCUZZASZIQ-UHFFFAOYSA-N tris[(2-methylpropan-2-yl)oxy]alumane Chemical compound [Al+3].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-] MDDPTCUZZASZIQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000013067 intermediate product Substances 0.000 abstract description 10
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 abstract description 4
- 238000007086 side reaction Methods 0.000 abstract description 3
- 238000000746 purification Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical group CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical class CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000003747 Grignard reaction Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012045 crude solution Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- HTBVGZAVHBZXMS-UHFFFAOYSA-N lithium;tris[(2-methylpropan-2-yl)oxy]alumane Chemical compound [Li].[Al+3].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-] HTBVGZAVHBZXMS-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/66—Arsenic compounds
- C07F9/70—Organo-arsenic compounds
- C07F9/72—Aliphatic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/02—Magnesium compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
The invention provides a preparation method of tert-butyl arsenic, which comprises the following steps: (1) under the protection of inert gas, reacting magnesium with chloro-tert-butane at 60-80 ℃ to generate tert-butyl magnesium chloride, wherein the magnesium and the chloro-tert-butane react under the condition of an initiator, the initiator is organic aluminum or inorganic aluminum, and the weight ratio of the initiator to the magnesium is (3-7): 100; (2) stirring arsenic trichloride and tert-butyl magnesium chloride at the temperature of below 10 ℃ to react to obtain tert-butyl arsenic dichloride; (3) stirring tert-butyl arsenic dichloride and a reducing agent at the temperature of below 10 ℃ to react to obtain a tert-butyl arsenic crude product; (4) and (4) purifying the crude tert-butyl arsenic obtained in the step (3). The method improves the reaction efficiency of magnesium and tert-butyl chloride, improves the purity of the intermediate product tert-butyl magnesium chloride, improves the conversion rate of arsenic trichloride, and avoids the arsenic trichloride from generating arsine by side reaction in subsequent reactions, thereby improving the purity of crude tert-butyl arsenic.
Description
Technical Field
The invention relates to the field of organic metal synthesis, in particular to a preparation method of tert-butyl arsenic.
Background
US2005/0033073 discloses a process for preparing tert-butyl arsine, comprising the following steps, synthesizing tert-butyl magnesium chloride by Grignard reaction; reacting tert-butyl magnesium chloride with arsenic chloride to synthesize tert-butyl arsenic dichloride; synthesizing crude tert-butyl arsine by tert-butyl arsenic dichloride reduction reaction; and adding a purifying agent for rectification and purification to obtain the pure tert-butyl arsine product. The method has the following disadvantages: the surplus of magnesium is excessive, the yield is low and impurities are more in the process of synthesizing the tert-butyl magnesium chloride by the Grignard reaction method; in addition, arsenic chloride can not completely participate in the reaction in the process of synthesizing tert-butyl arsenic dichloride through the reaction of tert-butyl magnesium chloride and arsenic chloride, so that arsenic alkane with high toxicity is reduced in the next step; the crude product of tert-butyl arsine has more impurities, the tert-butyl magnesium chloride has poor stability and difficult transportation, and the preparation of tert-butyl arsine by directly utilizing the purchased tert-butyl magnesium chloride has high cost and poor safety.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a preparation method of tert-butyl arsenic.
In order to achieve the purpose, the invention adopts the technical scheme that: a method for preparing tert-butyl arsenic, comprising the steps of:
(1) under the protection of inert gas, reacting magnesium with chloro-tert-butane at 60-80 ℃ to generate tert-butyl magnesium chloride, wherein the magnesium and the chloro-tert-butane react under the condition of an initiator, the initiator is organic aluminum or inorganic aluminum, and the weight ratio of the initiator to the magnesium is (3-7): 100;
(2) stirring arsenic trichloride and the tert-butyl magnesium chloride obtained in the step (1) at a temperature of below 10 ℃ to react to obtain tert-butyl arsenic dichloride;
(3) stirring and reacting the tert-butyl arsenic dichloride obtained in the step (2) with a reducing agent at the temperature of below 10 ℃ to obtain a tert-butyl arsenic crude product;
(4) and (4) purifying the crude tert-butyl arsenic obtained in the step (3).
The invention firstly prepares the tert-butyl magnesium chloride in the preparation process of the tert-butyl arsenic, and utilizes the initiator to react in the preparation process of the tert-butyl magnesium chloride, thereby improving the reaction efficiency of magnesium and tert-butyl chloride, improving the purity of the intermediate product tert-butyl magnesium chloride, reducing the purification burden of the intermediate product tert-butyl magnesium chloride, being beneficial to improving the reaction efficiency of arsenic trichloride and the tert-butyl magnesium chloride obtained in the step (1), improving the conversion rate of arsenic trichloride, and avoiding the generation of arsine by side reaction of arsenic trichloride in subsequent reactions, thereby improving the purity of crude tert-butyl arsenic and reducing the purification burden of crude tert-butyl arsenic.
Preferably, the organic aluminum is red aluminum, trimethylaluminum ethyl ether complex, aluminum tert-butoxide or aluminum chloride tetrahydrofuran complex.
The inventor finds that in the preparation process of tert-butyl arsenic, organic aluminum is used as an initiator, so that the reaction efficiency of magnesium and tert-butyl chloride is improved, the purity of an intermediate product tert-butyl magnesium chloride is improved, and the purification burden of the intermediate product tert-butyl magnesium chloride is reduced; the inventor further finds that when the aluminum chloride tetrahydrofuran complex in the organic aluminum is used as an initiator in the preparation process of the tert-butyl magnesium chloride, the method has better effect on improving the reaction efficiency of magnesium and tert-butyl chloride and is beneficial to improving the purity and yield of tert-butyl arsenic.
Preferably, the weight ratio of the initiator to the magnesium is (5-6): 100.
The inventor finds that when the weight ratio of the initiator to the magnesium is (5-6): 100, the yield of the tert-butyl magnesium chloride is higher and the cost is lower.
Preferably, in the step (1), the mass ratio of the magnesium to the chloro-tert-butane is 1.02: 1-1.05: 1.
The inventor discovers through research that in the preparation method of tert-butyl arsenic, when the mass ratio of magnesium to tert-butyl chloride is 1.02: 1-1.05: 1, the reaction is more complete, and the purity of the intermediate product tert-butyl magnesium chloride is higher.
Preferably, in the step (1), the magnesium reacts with the tert-butyl chloride in a way that: dispersing the magnesium and an initiator in an organic solvent A to obtain a reaction system B, and dropwise adding a tert-butyl chloride solution into the reaction system B in a stirring state, wherein the solvent of the tert-butyl chloride solution is the organic solvent A.
Preferably, the organic solvent A is diethylene glycol dibutyl ether.
Preferably, in the step (2), arsenic trichloride is dispersed in the organic solvent a to obtain a reaction system C, and tert-butyl magnesium chloride is added dropwise to the reaction system C while keeping the reaction system C in a stirring state.
Preferably, in the step (2), the mass ratio of the arsenic trichloride to the tert-butyl magnesium chloride obtained in the step (1) is 0.5: 1-0.9: 1.
Preferably, in the step (3), the reducing agent is: the reducing agent is diisobutylaluminum hydride, lithium tri-tert-butoxyaluminum hydride, lithium tris [ (3-ethyl-3-pentyl) oxy ] aluminum hydride, sodium borohydride or lithium aluminum hydride.
The inventor finds that, in the reaction process of tert-butyl arsenic dichloride and a reducing agent, when the reducing agent is diisobutyl aluminum hydride, lithium tri-tert-butoxyaluminum hydride, lithium tris [ (3-ethyl-3-pentyl) oxy ] aluminum hydride, sodium borohydride or lithium aluminum hydride, the conversion rate of tert-butyl arsenic dichloride is higher, the purity of tert-butyl arsenic in the obtained crude tert-butyl arsenic product is better, and the burden of subsequent purification is reduced.
Preferably, in the step (3), the amount ratio of the reducing agent to the tert-butyl arsine dichloride substance obtained in the step (2) is (0.5: 1-0.8: 1).
Preferably, in the step (4), the crude tert-butyl arsenic is purified by negative pressure rectification at 60-80 ℃, and the purifying agent of rectification is potassium fluoride.
Preferably, in the step (1), tert-butyl magnesium chloride is purified.
The purpose of purifying the tert-butyl magnesium chloride is mainly to remove tert-butyl chloride and impurities with low boiling point.
Preferably, in the step (2), tert-butyl arsenic dichloride is purified.
The purpose of purifying the tert-butyl arsenic dichloride is to remove unreacted arsenic trichloride and impurities with low boiling point.
The invention has the beneficial effects that: the invention provides a preparation method of tert-butyl arsenic, which comprises the steps of firstly preparing tert-butyl magnesium chloride, and utilizing an initiator to react in the process of preparing the tert-butyl magnesium chloride, so that the reaction efficiency of magnesium and tert-butyl chloride is improved, the purity of an intermediate product tert-butyl magnesium chloride is improved, the purification burden of the intermediate product tert-butyl magnesium chloride is reduced, the reaction efficiency of arsenic trichloride and the tert-butyl magnesium chloride obtained in the step (1) is improved, the conversion rate of arsenic trichloride is improved, the generation of arsine by side reaction of arsenic trichloride in subsequent reactions is avoided, the purity of crude tert-butyl arsenic is improved, and the purification burden of a crude tert-butyl arsenic product is reduced.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
The invention provides a preparation method of tert-butyl arsenic, which comprises the following steps:
(1) under the protection of inert gas, reacting magnesium with chloro-tert-butane at 60-80 ℃ to generate tert-butyl magnesium chloride, wherein the magnesium and the chloro-tert-butane react under the condition of an initiator, the initiator is organic aluminum or inorganic aluminum, the weight ratio of the initiator to the magnesium is (3-7): 100, and the mass ratio of the magnesium to the chloro-tert-butane is 1.02: 1-1.05: 1;
(2) stirring arsenic trichloride and the tert-butyl magnesium chloride obtained in the step (1) at a temperature of below 10 ℃ to react to obtain tert-butyl arsenic dichloride; the mass ratio of the arsenic trichloride to the tert-butyl magnesium chloride obtained in the step (1) is 0.5: 1-0.9: 1;
(3) stirring and reacting the tert-butyl arsenic dichloride obtained in the step (2) with a reducing agent at the temperature of below 10 ℃ to obtain a tert-butyl arsenic crude product; the mass ratio of the reducing agent to the tert-butyl arsine dichloride substance obtained in the step (2) is 0.5: 1-0.8: 1;
(4) and (4) purifying the tert-butyl arsenic crude product obtained in the step (3), wherein the tert-butyl arsenic crude product is purified to be subjected to negative pressure rectification at the temperature of 60-80 ℃, and a rectification purifying agent is potassium fluoride.
Example 1
The preparation method of tert-butyl arsenic provided by the embodiment of the invention comprises the following steps:
(1) mixing 35.1g of magnesium strip, 450mL of diethylene glycol dibutyl ether and 1.76g of aluminum chloride tetrahydrofuran complex to obtain a reaction system B, removing oxygen in the reaction system B, heating the reaction system B to 75 ℃ under the protection of nitrogen, dropwise adding a chlorinated tert-butane solution into the reaction system B in a stirring state by using a constant-pressure funnel, wherein the chlorinated tert-butane solution consists of 148mL of chlorinated tert-butane and 150mL of diethylene glycol dibutyl ether, keeping the temperature, stirring and reacting for 1.5 hours to obtain tert-butyl magnesium chloride, and cooling to room temperature;
(2) dissolving 180g of arsenic trichloride in 150mL of diethylene glycol dibutyl ether to obtain a reaction system C, refrigerating the reaction system C to-10 ℃, dropwise adding the tert-butyl magnesium chloride obtained in the step (1) into the reaction system C in a stirring state to ensure that the reaction temperature is not higher than 10 ℃, and stirring and reacting for 1.5 hours at 10 ℃ to obtain tert-butyl arsenic dichloride;
(3) dispersing 25.8g of lithium aluminum hydride in diethylene glycol dibutyl ether to obtain a reducing agent suspension, cooling to-10 ℃, dropwise adding the tert-butyl arsenic dichloride in the step (2) into the reducing agent suspension in a stirring state, stirring and reacting at 10 ℃ for 1.5 hours to obtain a tert-butyl arsenic crude product solution, and distilling the tert-butyl arsenic crude product solution at 65 ℃ under reduced pressure to obtain a tert-butyl arsenic crude product;
(4) and (4) purifying the tert-butyl arsenic crude product obtained in the step (3), wherein the tert-butyl arsenic crude product is purified by negative pressure rectification at the temperature of 75 ℃, and a rectification purifying agent is potassium fluoride.
Example 2
As a method for preparing tert-butyl arsenic according to an embodiment of the present invention, the only difference between this embodiment and embodiment 1 is: the initiator is anhydrous aluminum trichloride.
Example 3
As a method for preparing tert-butyl arsenic according to an embodiment of the present invention, the only difference between this embodiment and embodiment 1 is: the organic aluminum initiator is red aluminum.
Example 4
As a method for preparing tert-butyl arsenic according to an embodiment of the present invention, the only difference between this embodiment and embodiment 1 is: the organic aluminum initiator is trimethyl aluminum ethyl ether complex.
Example 5
As a method for preparing tert-butyl arsenic according to an embodiment of the present invention, the only difference between this embodiment and embodiment 1 is: the organic aluminum initiator is tert-butyl alcohol aluminum.
Example 6
As a method for preparing tert-butyl arsenic according to an embodiment of the present invention, the only difference between this embodiment and embodiment 1 is: the reducing agent in the step (3) is diisobutylaluminum hydride.
Example 7
As a method for preparing tert-butyl arsenic according to an embodiment of the present invention, the only difference between this embodiment and embodiment 1 is: the reducing agent in the step (3) is lithium aluminum tri-tert-butoxyhydride.
Example 8
As a method for preparing tert-butyl arsenic according to an embodiment of the present invention, the only difference between this embodiment and embodiment 1 is: the reducing agent in the step (3) is lithium tris [ (3-ethyl-3-pentyl) oxy ] aluminum hydride.
Example 9
As a method for preparing tert-butyl arsenic according to an embodiment of the present invention, the only difference between this embodiment and embodiment 1 is: the reducing agent in the step (3) is sodium borohydride.
Example 10
The only difference between the embodiment and the embodiment 1 is that: the amount of organoaluminum initiator used was 1.05 g.
Example 11
The only difference between the embodiment and the embodiment 1 is that: the amount of organoaluminum initiator used was 1.40 g.
Example 12
The only difference between the embodiment and the embodiment 1 is that: the amount of organoaluminum initiator used was 2.11 g.
Example 13
The only difference between the embodiment and the embodiment 1 is that: the amount of organoaluminum initiator used was 2.46 g.
Effect example 1
1. Examples 1 to 13, the amounts of chlorinated tert-butylalkane and tert-butylmagnesium chloride in the tert-butylmagnesium chloride obtained in step (1) were quantified by nuclear magnetism. The results are shown in Table 1.
TABLE 1 Effect of preparation of tert-butylmagnesium chloride
2. Examples 1 to 13, the content of arsine and tert-butylarsenic in the crude solution of tert-butylarsenic obtained in step (3) was quantified by nuclear magnetism, and the results are shown in table 2.
TABLE 2 Effect of the preparation method of Tert-butylarsenic
As can be seen from tables 1 and 2, in the preparation process of tert-butyl arsenic, organoaluminum is used as an initiator, so that the reaction efficiency of magnesium and tert-butyl chloride is improved, the purity of the intermediate product tert-butyl magnesium chloride is improved, and the purification burden of the intermediate product tert-butyl magnesium chloride is reduced; the inventor further finds that when the aluminum chloride tetrahydrofuran complex in the organic aluminum is used as an initiator in the preparation process of the tert-butyl magnesium chloride, the method has better effect on improving the reaction efficiency of magnesium and tert-butyl chloride and is beneficial to improving the purity and yield of tert-butyl arsenic. When the weight ratio of the initiator to the magnesium is (5-6): 100, the yield of the tert-butyl magnesium chloride is higher, the cost is lower, and the purity and the yield of tert-butyl arsenic are improved.
The inventor finds that, in the reaction process of tert-butyl arsenic dichloride and a reducing agent, when the reducing agent is lithium aluminum hydride, the conversion rate of tert-butyl arsenic dichloride is higher, the purity of tert-butyl arsenic in the obtained tert-butyl arsenic crude product is better, and the burden of subsequent purification is favorably reduced.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. A preparation method of tert-butyl arsenic is characterized by comprising the following steps:
(1) under the protection of inert gas, reacting magnesium with chloro-tert-butane at 60-80 ℃ to generate tert-butyl magnesium chloride, wherein the magnesium and the chloro-tert-butane react under the condition of an initiator, the initiator is organic aluminum or inorganic aluminum, and the weight ratio of the initiator to the magnesium is (3-7): 100;
(2) stirring arsenic trichloride and the tert-butyl magnesium chloride obtained in the step (1) at a temperature of below 10 ℃ to react to obtain tert-butyl arsenic dichloride;
(3) stirring and reacting the tert-butyl arsenic dichloride obtained in the step (2) with a reducing agent at the temperature of below 10 ℃ to obtain a tert-butyl arsenic crude product;
(4) and (4) purifying the crude tert-butyl arsenic obtained in the step (3).
2. The production method according to claim 1, wherein the organoaluminum is red aluminum, trimethylaluminum ethyl ether complex, aluminum tert-butoxide, or aluminum chloride tetrahydrofuran complex.
3. The preparation method according to claim 1, wherein in the step (1), the mass ratio of the magnesium to the tert-butyl chloride is 1.02: 1-1.05: 1.
4. The process according to claim 1, wherein in the step (1), the magnesium is reacted with tert-butyl chloride in such a way that: dispersing the magnesium and an initiator in an organic solvent A to obtain a reaction system B, and dropwise adding a tert-butyl chloride solution into the reaction system B in a stirring state, wherein the solvent of the tert-butyl chloride solution is the organic solvent A, and the organic solvent A is diethylene glycol dibutyl ether.
5. The production method according to claim 4, wherein in the step (2), arsenic trichloride is dispersed in the organic solvent A to obtain a reaction system C, and tert-butyl magnesium chloride is added dropwise to the reaction system C while the reaction system C is kept in a stirred state.
6. The method according to claim 1, wherein in the step (2), the mass ratio of arsenic trichloride to tert-butyl magnesium chloride obtained in the step (1) is (0.5: 1-0.9: 1).
7. The method of claim 1, wherein the reducing agent is diisobutylaluminum hydride, lithium tri-t-butoxyaluminum hydride, lithium tris [ (3-ethyl-3-pentyl) oxy ] aluminum hydride, sodium borohydride, or lithium aluminum hydride.
8. The production method according to claim 1, wherein in the step (3), the reducing agent is used in an amount of: the mass ratio of the reducing agent to the tert-butyl arsine dichloride substance obtained in the step (2) is (0.5: 1-0.8: 1).
9. The preparation method according to claim 1, wherein in the step (4), the crude tert-butyl arsenic is purified by negative pressure rectification at 60-80 ℃, and a purifying agent of the rectification is potassium fluoride.
10. The method according to claim 1, wherein in the step (1), tert-butyl magnesium chloride is purified, and in the step (2), tert-butyl arsenic dichloride is purified.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050033073A1 (en) * | 2003-05-08 | 2005-02-10 | Rohm And Haas Electronic Materials, L.L.C. | Alkyl group VA metal compounds |
| CN111647011A (en) * | 2020-07-16 | 2020-09-11 | 宁夏中星显示材料有限公司 | Preparation method of monohalogenated phenylboronic acid |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20050033073A1 (en) * | 2003-05-08 | 2005-02-10 | Rohm And Haas Electronic Materials, L.L.C. | Alkyl group VA metal compounds |
| CN111647011A (en) * | 2020-07-16 | 2020-09-11 | 宁夏中星显示材料有限公司 | Preparation method of monohalogenated phenylboronic acid |
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