CN112159431B - Preparation method of tertiary butyl arsenic - Google Patents
Preparation method of tertiary butyl arsenic Download PDFInfo
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- CN112159431B CN112159431B CN202011028564.8A CN202011028564A CN112159431B CN 112159431 B CN112159431 B CN 112159431B CN 202011028564 A CN202011028564 A CN 202011028564A CN 112159431 B CN112159431 B CN 112159431B
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- butyl
- tert
- arsenic
- magnesium
- chloride
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- BMZAJIYVAAFBTR-UHFFFAOYSA-N butylarsenic Chemical group CCCC[As] BMZAJIYVAAFBTR-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 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 41
- 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 27
- QTQRGDBFHFYIBH-UHFFFAOYSA-N tert-butylarsenic Chemical compound CC(C)(C)[As] QTQRGDBFHFYIBH-UHFFFAOYSA-N 0.000 claims abstract description 24
- 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
- 239000012043 crude product Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 20
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 16
- JADMTAKJPYAWOT-UHFFFAOYSA-N butyl(dichloro)arsane Chemical group CCCC[As](Cl)Cl JADMTAKJPYAWOT-UHFFFAOYSA-N 0.000 claims abstract description 8
- HCYZKGMAIJGVOQ-UHFFFAOYSA-N tert-butyl(dichloro)arsane Chemical compound CC(C)(C)[As](Cl)Cl HCYZKGMAIJGVOQ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011261 inert gas Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 13
- -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 group [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
- QBBWRNBMWSVXBB-UHFFFAOYSA-K aluminum;oxolane;trichloride Chemical group 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
- 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
- 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 2
- 239000002904 solvent Substances 0.000 claims description 2
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 abstract description 5
- 238000007086 side reaction Methods 0.000 abstract description 3
- 238000000746 purification Methods 0.000 description 12
- 239000013067 intermediate product Substances 0.000 description 9
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000012535 impurity Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000003747 Grignard reaction Methods 0.000 description 2
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 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 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- MJPPNOYSSOKENI-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-] MJPPNOYSSOKENI-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
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 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 tertiary butyl arsenic, which comprises the following steps: (1) Under the protection of inert gas, magnesium and tert-butyl chloride react at 60-80 ℃ to generate tert-butyl magnesium chloride, the magnesium and tert-butyl chloride 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 and reacting arsenic trichloride and tert-butyl magnesium chloride below 10 ℃ to obtain tert-butyl arsenic dichloride; (3) Stirring and reacting tertiary butyl arsenic dichloride with a reducing agent at the temperature of below 10 ℃ to obtain a tertiary butyl arsenic crude product; and (4) purifying the crude product of the tertiary butyl arsenic obtained in the step (3). The method improves the reaction efficiency of magnesium and tert-butyl chloride, improves the purity of intermediate tert-butyl magnesium chloride, improves the conversion rate of arsenic trichloride, and avoids the generation of arsine by side reaction of the arsenic trichloride in the subsequent reaction, 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 tertiary butyl arsenic.
Background
US2005/0033073 discloses a process for the preparation of t-butyl arsine comprising the following procedure, the synthesis of t-butyl magnesium chloride by the Grignard reaction; the tertiary butyl magnesium chloride reacts with arsenic chloride to synthesize tertiary butyl arsenic dichloride; synthesizing crude tertiary butyl arsine by reduction reaction of tertiary butyl arsine dichloride; adding a purifying agent for rectification and purification to obtain the pure tertiary butyl arsine. The method has the following defects: excessive magnesium remains in the process of synthesizing the tert-butyl magnesium chloride by the Grignard reaction method, the yield is low, and the impurities are more; in addition, arsenic chloride cannot completely participate in the reaction in the process of synthesizing tert-butyl arsenical dichloride by the reaction of tert-butyl magnesium chloride and arsenic chloride, so that arsine with larger toxicity is produced in the next reduction step; the crude product of tertiary butyl arsine has more impurities, the tertiary butyl magnesium chloride has poor stability and difficult transportation, and the purchased tertiary butyl magnesium chloride is directly utilized to prepare tertiary butyl arsine with high cost and poor safety.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of tertiary butyl arsenic.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: a process for the preparation of tertiary butyl arsenic, the process comprising the steps of:
(1) Under the protection of inert gas, magnesium and tert-butyl chloride react at 60-80 ℃ to generate tert-butyl magnesium chloride, the magnesium and tert-butyl chloride 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 and reacting arsenic trichloride with the tert-butyl magnesium chloride obtained in the step (1) below 10 ℃ to obtain tert-butyl arsenic dichloride;
(3) Stirring and reacting the tertiary butyl arsenic dichloride obtained in the step (2) with a reducing agent at the temperature of below 10 ℃ to obtain a tertiary butyl arsenic crude product;
(4) And (3) purifying the crude product of the tertiary butyl arsenic obtained in the step (3).
The inventor prepares tert-butyl magnesium chloride firstly in the preparation process of tert-butyl arsenic, and reacts by using an initiator in the preparation process of tert-butyl magnesium chloride, so that the reaction efficiency of magnesium and tert-butyl chloride is improved, the purity of intermediate product tert-butyl magnesium chloride is improved, the purification burden of intermediate product tert-butyl magnesium chloride is reduced, the reaction efficiency of arsenic trichloride and 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 the subsequent reaction is avoided, the purity of crude tert-butyl arsenic is improved, and the purification burden of crude product of tert-butyl arsenic is reduced.
Preferably, the organoaluminum is red aluminum, trimethylaluminum diethyl ether complex, aluminum tert-butoxide or aluminum chloride tetrahydrofuran complex.
The inventor finds that in the preparation process of tertiary 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 intermediate product tert-butyl magnesium chloride is improved, and the purification burden of intermediate product tert-butyl magnesium chloride is reduced; the inventor further discovers that when aluminum chloride tetrahydrofuran complex in organic aluminum is used as an initiator in the preparation process of tert-butyl magnesium chloride, the method has better effect on improving the reaction efficiency of magnesium and chloro tert-butane, 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 chlorobutane is 1.02:1-1.05:1.
The inventor finds that in the preparation method of the tertiary butyl arsenic, when the mass ratio of magnesium to chlorobutane is 1.02:1-1.05:1, the reaction is more complete, and the purity of an intermediate product tertiary butyl magnesium chloride is higher.
Preferably, in the step (1), the magnesium is reacted with tert-butyl chloride in the following manner: dispersing the magnesium and the 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 under 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 dropwise added to the reaction system C while keeping the reaction system C in a stirred 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 to 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 the tertiary butyl arsenical dichloride and the reducing agent, when the reducing agent is diisobutyl aluminum hydride, lithium aluminum tri-tert-butoxide hydride, lithium aluminum tri [ (3-ethyl-3-amyl) oxy ] hydride, sodium borohydride or lithium aluminum hydride, the conversion rate of the tertiary butyl arsenical dichloride is higher, the purity of the tertiary butyl arsenical in the obtained tertiary butyl arsenical crude product is better, and the subsequent purification burden is reduced.
Preferably, in the step (3), the amount ratio of the reducing agent to the tertiary butyl arsine dichloride obtained in the step (2) is (0.5:1 to 0.8:1).
Preferably, in the step (4), the crude product of tertiary butyl arsenic is purified to be subjected to negative pressure rectification at 60-80 ℃, and the rectification purifying agent is potassium fluoride.
Preferably, in the step (1), the tert-butyl magnesium chloride is purified.
The purpose of purifying tert-butyl magnesium chloride is mainly to remove tert-butyl chloride and impurities with low boiling point.
Preferably, in the step (2), the tertiary butyl arsenic dichloride is purified.
The purpose of the purification of t-butyl arsenic dichloride is to remove unreacted arsenic trichloride and low-boiling impurities.
The invention has the beneficial effects that: according to the preparation method of tert-butyl arsenic, firstly, tert-butyl magnesium chloride is prepared, and an initiator is utilized to react in the process of preparing tert-butyl magnesium chloride, so that the reaction efficiency of magnesium and tert-butyl chloride is improved, the purity of intermediate product tert-butyl magnesium chloride is improved, the purification burden of 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, arsine generated by side reaction of arsenic trichloride in the subsequent reaction is avoided, the purity of crude tert-butyl arsenic is improved, and the purification burden of crude tert-butyl arsenic is reduced.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples.
The invention provides a preparation method of tertiary butyl arsenic, which comprises the following steps:
(1) Under the protection of inert gas, magnesium and tert-butyl chloride react at 60-80 ℃ to generate tert-butyl magnesium chloride, the magnesium and tert-butyl chloride 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 tert-butyl chloride is 1.02:1-1.05:1;
(2) Stirring and reacting arsenic trichloride with the tert-butyl magnesium chloride obtained in the step (1) below 10 ℃ 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 tertiary butyl arsenic dichloride obtained in the step (2) with a reducing agent at the temperature of below 10 ℃ to obtain a tertiary butyl arsenic crude product; the mass ratio of the reducing agent to the tertiary butyl arsine dichloride obtained in the step (2) is 0.5:1-0.8:1;
(4) And (3) purifying the crude product of the tertiary butyl arsenic obtained in the step (3), wherein the purification of the crude product of the tertiary butyl arsenic is negative pressure rectification at 60-80 ℃, and the rectification purifying agent is potassium fluoride.
Example 1
As a preparation method of tertiary butyl arsenic, the embodiment of the invention comprises the following steps:
(1) Mixing 35.1g of magnesium strips, 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 tert-butyl chloride solution into the reaction system B in a stirring state by using a constant pressure funnel, wherein the tert-butyl chloride solution consists of 148mL of tert-butyl chloride and 150mL of diethylene glycol dibutyl ether, carrying out heat preservation and stirring for reaction 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, ensuring 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, refrigerating to-10 ℃, dropwise adding the tertiary butyl arsenical dichloride in the step (2) into the reducing agent suspension in a stirring state, stirring and reacting for 1.5 hours at 10 ℃ to obtain a tertiary butyl arsenical crude product solution, and carrying out reduced pressure distillation on the tertiary butyl arsenical crude product solution at 65 ℃ to obtain a tertiary butyl arsenical crude product;
(4) And (3) purifying the crude product of the tertiary butyl arsenic obtained in the step (3), wherein the purification of the crude product of the tertiary butyl arsenic is negative pressure rectification at 75 ℃, and the rectification purifying agent is potassium fluoride.
Example 2
As a preparation method of tertiary butyl arsenic in the embodiment of the present invention, the only difference between the embodiment and the embodiment 1 is that: the initiator is anhydrous aluminum trichloride.
Example 3
As a preparation method of tertiary butyl arsenic in the embodiment of the present invention, the only difference between the embodiment and the embodiment 1 is that: the organic aluminum initiator is red aluminum.
Example 4
As a preparation method of tertiary butyl arsenic in the embodiment of the present invention, the only difference between the embodiment and the embodiment 1 is that: the organic aluminum initiator is trimethyl aluminum diethyl ether complex.
Example 5
As a preparation method of tertiary butyl arsenic in the embodiment of the present invention, the only difference between the embodiment and the embodiment 1 is that: the organic aluminum initiator is aluminum tert-butoxide.
Example 6
As a preparation method of tertiary butyl arsenic in the embodiment of the present invention, the only difference between the embodiment and the embodiment 1 is that: the reducing agent in the step (3) is diisobutylaluminum hydride.
Example 7
As a preparation method of tertiary butyl arsenic in the embodiment of the present invention, the only difference between the embodiment and the embodiment 1 is that: the reducing agent in the step (3) is lithium aluminum tri-tert-butoxide.
Example 8
As a preparation method of tertiary butyl arsenic in the embodiment of the present invention, the only difference between the embodiment and the embodiment 1 is that: the reducing agent in the step (3) is lithium aluminum tri [ (3-ethyl-3-amyl) oxy ] hydride.
Example 9
As a preparation method of tertiary butyl arsenic in the embodiment of the present invention, the only difference between the embodiment and the embodiment 1 is that: the reducing agent in the step (3) is sodium borohydride.
Example 10
As a preparation method of tertiary butyl arsenic in the embodiment of the present invention, the only difference between the embodiment and the embodiment 1 is that: the amount of the organic aluminum initiator was 1.05g.
Example 11
As a preparation method of tertiary butyl arsenic in the embodiment of the present invention, the only difference between the embodiment and the embodiment 1 is that: the amount of the organoaluminum initiator was 1.40g.
Example 12
As a preparation method of tertiary butyl arsenic in the embodiment of the present invention, the only difference between the embodiment and the embodiment 1 is that: the amount of the organoaluminum initiator was 2.11g.
Example 13
As a preparation method of tertiary butyl arsenic in the embodiment of the present invention, the only difference between the embodiment and the embodiment 1 is that: the amount of the organoaluminum initiator was 2.46g.
Effect example 1
1. In the method for producing t-butylarsenic of example 1-example 13, the amounts of t-butylalkane chloride and t-butylmagnesium chloride in the t-butylmagnesium chloride obtained in step (1) were quantified by using a nuclear magnetic resonance. The results are shown in Table 1.
TABLE 1 effect of preparation of t-butylmagnesium chloride
2. In the method for producing t-butylarsenic of example 1-example 13, the content of arsine and t-butylarsenic in the crude t-butylarsenic solution obtained in step (3) was quantified by nuclear magnetism, and the results are shown in Table 2.
TABLE 2 effects of the preparation method of tert-butyl arsenic
As can be seen from tables 1 and 2, 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 intermediate product tert-butyl magnesium chloride is improved, and the purification burden of intermediate product tert-butyl magnesium chloride is reduced; the inventor further discovers that when aluminum chloride tetrahydrofuran complex in organic aluminum is used as an initiator in the preparation process of tert-butyl magnesium chloride, the method has better effect on improving the reaction efficiency of magnesium and chloro tert-butane, 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 the tert-butyl arsenic are improved.
The inventor finds that in the reaction process of the tertiary butyl arsenic dichloride and the reducing agent, when the reducing agent is lithium aluminum hydride, the conversion rate of the tertiary butyl arsenic dichloride is higher, the purity of the tertiary butyl arsenic in the obtained tertiary butyl arsenic crude product is better, and the subsequent purification burden is reduced.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (7)
1. A process for the preparation of tertiary butyl arsenic, the process comprising the steps of:
(1) Under the protection of inert gas, magnesium and tert-butyl chloride react at 60-80 ℃ to generate tert-butyl magnesium chloride, the magnesium and tert-butyl chloride react under the condition of an initiator, the initiator is organic aluminum, the organic aluminum is aluminum chloride tetrahydrofuran complex, the weight ratio of the initiator to the magnesium is (5-7): 100, and the mass ratio of the magnesium to the tert-butyl chloride is 1.02:1-1.05:1;
(2) Stirring and reacting arsenic trichloride with the tert-butyl magnesium chloride obtained in the step (1) at the temperature of below 10 ℃ to obtain tert-butyl arsenic dichloride, wherein 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 tertiary butyl arsenic dichloride obtained in the step (2) with a reducing agent at the temperature of below 10 ℃ to obtain a tertiary butyl arsenic crude product;
(4) And (3) purifying the crude product of the tertiary butyl arsenic obtained in the step (3).
2. The method according to claim 1, wherein in the step (1), the magnesium is reacted with the tert-butyl chloride in the following manner: dispersing the magnesium and the 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 under 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.
3. The method according to claim 2, wherein in the step (2), arsenic trichloride is dispersed in the organic solvent a to obtain a reaction system C, and t-butylmagnesium chloride is added dropwise to the reaction system C while keeping the reaction system C in a stirred state.
4. The method according to 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.
5. The 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 tertiary butyl arsine dichloride obtained in the step (2) is (0.5:1-0.8:1).
6. The method according to claim 1, wherein in the step (4), the crude product of tertiary butyl arsenic is purified to be subjected to negative pressure rectification at 60-80 ℃, and the rectification purifying agent is potassium fluoride.
7. The method according to claim 1, wherein in the step (1), t-butylmagnesium chloride is purified, and in the step (2), t-butylarsenic dichloride is purified.
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