CN109928988B - Preparation method and application of elemental zinc - Google Patents
Preparation method and application of elemental zinc Download PDFInfo
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- CN109928988B CN109928988B CN201910180905.4A CN201910180905A CN109928988B CN 109928988 B CN109928988 B CN 109928988B CN 201910180905 A CN201910180905 A CN 201910180905A CN 109928988 B CN109928988 B CN 109928988B
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Abstract
The invention relates to the technical field of chemical product preparation, in particular to a preparation method and application of elemental zinc. The high-activity simple substance zinc prepared by the preparation method can be directly synthesized into an organic zinc compound with most of bromide, and can replace a high-cost iodide method and preparation methods such as other metal exchange methods, derivative methods and the like; has the characteristics of high reaction efficiency and low cost.
Description
Technical Field
The invention relates to the field of chemical product preparation, in particular to a method for preparing simple substance zinc.
Background
The organic zinc reagent has relatively low activity and good reaction selectivity, and has important theoretical significance and practical value when being applied to the research of multifunctional compounds.
As early as 1849, Frankland heated metallic zinc together with iodoethane under the protection of hydrogen to synthesize an organozinc compound, diethyl zinc. In 1962, Gaudemar discovered that under mild conditions (25-50 ℃), zinc foil rapidly undergoes a metal insertion reaction with an alkyl iodide in tetrahydrofuran solvent. Later researches prove that the Gaudemar method is a general method for preparing the functionalized organic zinc reagent, and the reaction rate is mainly related to factors such as an activation method of elemental zinc, the structure of halogenated hydrocarbon, the halogen type and reaction conditions (concentration of a solvent and a substrate and reaction temperature). The chlorohydrocarbon is generally unreactive, and only benzyl bromide and allyl bromide with higher activity in the bromohydrocarbon can directly generate oxidation addition reaction with the simple substance zinc. When the organic zinc reagent is prepared by the method, the common simple substances of zinc comprise zinc foil, zinc powder, zinc particles and Rieke zinc. Knochel et al have found that when preparing benzyl-type zinc halide reagents, small amounts of coupling product are often incorporated into the organic zinc solution prepared using zinc particles, while relatively pure organic zinc reagents are obtained using zinc powder.
Among the many factors, the degree of activation of elemental zinc is a key factor in determining whether an organozinc reagent can be successfully prepared. Many activation methods have been reported such as dilute hydrochloric acid washing, Zn-Cu-Ag, 1, 2-dibromoethane, trimethylchlorosilane and the like, and physical methods such as ultrasonic irradiation can also be used to activate zinc. Of these, the combination of 1, 2-dibromoethane and trimethylchlorosilane (TMSCl) proposed by Knochel is a more successful activation method. Even commercial grade zinc powder, after activated by this method, can be oxidized and added with primary or secondary alkyl iodo hydrocarbon with lower reactivity under rather mild conditions to obtain organic zinc reagent with high yield, and functional groups of organic halohydrocarbon reagent such as ester group, halogen, ketone carbonyl group, amido group, cyano group, primary and secondary amino group, thioester group, sulfoxide group, thioether group and sulfone group are retained (formula 1). In the reaction of formula 1, satisfactory results were obtained with halides having various functional groups other than those having hydroxyl groups (undergoing deprotonation), nitro groups and azido groups (inhibiting insertion of metallic zinc). The general preparation method is as follows: A3M solution of alkyl iodocarbon was added at 40 ℃ to zinc powder suspended in tetrahydrofuran, which was treated with small amounts of 1, 2-dibromoethane and trimethylchlorosilane (TMSCl) before the addition of the halogenated hydrocarbon. Secondary iodocarbon reacts at 25 deg.C, while benzyl bromide reacts with allyl bromide at 0 deg.C. Meanwhile, the structure of the organic halogenated hydrocarbon has great influence on the insertion speed of the zinc monogen. The insertion zinc reaction of the halogenated hydrocarbon of the allyl and benzyl type proceeds relatively easily.
X＝I，Br；FG＝CO2R，enolate，CN，enone，halide，(RCO)2N，NH2，RNH，RCONH，(TMS)3Si，(RO)3Si，(RO)2PO，RS，RS(O)，RSO2，PhCOS；R＝alkyl，aryl，benzyl，allyl.
In particular, the alkylzinc halide can also be prepared by a Zn-Cu couple in a mixed solvent of benzene and N, N-Dimethylacetamide (DMACM) or Hexamethylphosphoramide (HMPA).
In 1973, Rieke reported a method for preparing highly active Zinc (Rieke Zinc) by reducing Zinc chloride with metallic potassium. In 1991, a method for preparing higher activity zinc by reducing anhydrous zinc chloride with a naphthalene lithium reagent was reported. Thereafter, the method is further refined and developed.
X＝CI，Br，I。
The high activity zinc prepared by this method can react completely with alkyl bromide in THF at 25 deg.C for several hours, and the corresponding organic zinc bromide can be obtained with aryl bromide with lower activity in refluxing THF in high yield. Adding copper salt CuCN 2LiBrl soluble in THF10bAfter the zinc reagent is converted into the corresponding organic copper reagent, the organic copper reagent can react with various electrophilic reagents such as acyl chloride, ketene, allyl or blocky propyl halide, and the yield is good. Various electron deficient heteroaromatic iodides are also capable of undergoing oxidative addition reactions with Rieke-Zinc to form heteroaromatic Zinc iodide reagents (25 ℃ C., several hours), after which they may be further coupled with aromatic or heteroaromatic halides in the presence of Pd (0). Many heterocyclic aromatic iodides and even heterocyclic aromatic bromides are sufficiently reactive to undergo zinc intercalation reactions directly with commercial grade zinc powder.
This direct insertion method of zinc powder is useful for the preparation of zincate of serine, which has become one of the practical reagents for synthesizing various pure amino acids having optical activity. Recently, this method has also been applied to the preparation of 4-hydroxyboryl-L-aminopropionic acid using a zinc-copper couple in a benzene/DMACM (N, N-dimethyllacenamide) mixed solvent under ultrasonic waves.
In addition, under the action of ultrasonic wave, alkyl, alkenyl or aryl bromide reacts with metallic lithium and ZnX2The direct reaction can prepare dialkyl zinc and diaryl zinc reagents, which is a preparation method with potential application value. The reaction is carried out under mild conditions, and the obtained active organic zinc reagent can perform 1, 4-addition reaction with conjugated ketene under the catalysis of Ni (II) salt.
In sharp contrast to organomagnesium and organolithium reagents, relatively acidic protons may be allowed to exist in the molecule of the organozinc reagent. For example, 5-iodopentyne can be converted to the corresponding organozinc reagent under moderate conditions (THF, 25-30 ℃ C.) with less than 5% deprotonation occurring. Similarly, organozinc reagents bearing an NH group and an amide group can also be prepared in the same way and then reacted with electrophiles catalyzed by metals Cu (I), Pd (0), etc.
The fluorine-containing organozinc reagent can also be prepared by direct insertion of metallic zinc, and the polyfluoro iodo hydrocarbon is completely converted into the corresponding organozinc reagent in dioxane or THF.
Disclosure of Invention
The invention aims to provide a preparation method and application of simple substance zinc, and high-activity zinc can be directly used for preparing organic zinc; the high-activity zinc has the characteristics of storage and relatively large-scale preparation, so that scientific research and production conditions are stable, and the efficiency is improved; the application of the ultrasonic strengthening technology can effectively remove oxygen, carbon dioxide and other gases adsorbed by the pores on the surface of the zinc, increase the specific surface area of the zinc and increase the reaction activity.
In order to achieve the purpose, the invention provides the following technical scheme:
the preparation method of the simple substance zinc comprises the following steps: under the protection of nitrogen, adding metal sodium and simple substance zinc into toluene, refluxing to activate and attach the simple substance sodium on the surface of zinc, and obtaining the high-activity simple substance zinc.
The method specifically comprises the following steps:
(1) under the protection of nitrogen, adding anhydrous toluene and dry simple substance zinc into a reaction bottle, and carrying out ultrasonic deoxidization;
(2) adding fresh metal sodium into the reaction bottle in proportion;
(3) heating and refluxing under the protection of nitrogen, stirring and the action of ultrasonic waves;
(4) standing and cooling under the protection of nitrogen; then most of toluene is removed to obtain high-activity simple substance zinc.
The preparation method of the simple substance zinc, provided by the invention, comprises the following steps of (1): 10-20.
The preparation method of the simple substance zinc, provided by the invention, comprises the following steps of (1): 50-100.
The preparation method of the simple substance zinc has the reflux time of 0.5 h.
The preparation method of the simple substance zinc, provided by the invention, comprises the following steps of preparing a zinc powder, zinc dust and zinc particles.
According to the preparation method of the simple substance zinc, the activities of zinc powder, zinc scraps and zinc particles are sequentially reduced, and the proportion of the metal sodium required to be added is correspondingly increased.
The simple substance zinc can be used for preparing organic zinc; the product is preserved in air-isolated state for 7 days before use.
Compared with the prior art, the invention has the beneficial effects that: the high-activity simple substance zinc obtained by the preparation method can be directly synthesized into an organic zinc compound with most of bromide, and can replace a high-cost iodide method and other preparation methods such as a metal exchange method, a derivative method and the like; has the characteristics of high reaction efficiency and low cost.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of high-activity elemental zinc comprises the following steps:
(1) under the protection of nitrogen, adding dry elemental zinc powder and anhydrous toluene into a reaction bottle according to the weight ratio of 1:10, and carrying out ultrasonic deoxidization;
(2) fresh metal sodium is added into the mixture according to the molar ratio of the metal sodium to the simple substance zinc of 1: 90, adding the mixture into the reaction bottle;
(3) heating and refluxing at 110 ℃ under the protection of nitrogen, stirring and ultrasonic action;
(4) standing and cooling under the protection of nitrogen; then most of toluene is removed to obtain high-activity simple substance zinc.
Example 2
A preparation method of high-activity elemental zinc comprises the following steps:
(1) under the protection of nitrogen, adding dry simple substance zinc chips and anhydrous toluene into a reaction bottle according to the weight ratio of 1:15, and carrying out ultrasonic deoxidization;
(2) fresh metal sodium is added into the mixture according to the molar ratio of the metal sodium to the simple substance zinc of 1: 75, adding the mixture into the reaction bottle;
(3) heating and refluxing at 110 ℃ under the protection of nitrogen, stirring and ultrasonic action;
(4) standing and cooling under the protection of nitrogen; then most of toluene is removed to obtain high-activity simple substance zinc.
Example 3
A preparation method of high-activity elemental zinc comprises the following steps:
(1) under the protection of nitrogen, adding dry simple substance zinc particles and anhydrous toluene into a reaction bottle according to the weight ratio of 1:50, and carrying out ultrasonic deoxidization;
(2) fresh metal sodium is added into the mixture according to the molar ratio of the metal sodium to the simple substance zinc of 1: 100, adding the mixture into the reaction bottle;
(3) heating and refluxing at 110 ℃ under the protection of nitrogen, stirring and ultrasonic action;
(4) standing and cooling under the protection of nitrogen; then most of toluene is removed to obtain high-activity simple substance zinc.
Experiments show that:
(1) in the experiment, ultrasonic waves are adopted to effectively drive steam drums (oxygen, carbon dioxide and the like) adsorbed on the surface of metal, so that the reaction efficiency and the product quality can be effectively improved, and the product quality is superior to that of a product prepared under the condition of not adopting the ultrasonic waves.
(2) The activity of the high-activity simple substance zinc prepared in the examples 1-3 is equivalent to that of zinc powder prepared by reducing zinc chloride by metal potassium or organic lithium, and is better than that of an activation method combining 1, 2-dibromoethane and trimethylchlorosilane (TMSCl).
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (3)
1. The preparation method of the elemental zinc is characterized by comprising the following steps:
(1) under the protection of nitrogen, adding anhydrous toluene and dry simple substance zinc into a reaction bottle, and carrying out ultrasonic deoxidization; the weight ratio of the simple substance zinc to the toluene is 1: 10-20 parts of;
(2) adding fresh metal sodium into the reaction bottle in proportion; the molar ratio of the metal sodium to the simple substance zinc is 1: 50-100 parts of;
(3) heating and refluxing for 0.5h under the protection of nitrogen, stirring and the action of ultrasonic waves;
(4) standing and cooling under the protection of nitrogen; most of the toluene is then decanted to obtain elemental zinc.
2. The method of preparing elemental zinc according to claim 1, characterized in that: the simple substance zinc is one of zinc powder, zinc filings and zinc particles.
3. The method of preparing elemental zinc according to claim 2, characterized in that: the activity of zinc powder, zinc dust and zinc particles is reduced in sequence, and the proportion of the required added metal sodium is correspondingly increased.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101291940A (en) * | 2005-08-19 | 2008-10-22 | 凯密特尔有限责任公司 | Highly reactive zinc form, method for the production thereof, and use of the same |
| CN102180901A (en) * | 2011-04-02 | 2011-09-14 | 绍兴文理学院 | Preparation method of 2,4,6,10-tetra-double bond pentadecyl carbon phosphonate ester |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101291940A (en) * | 2005-08-19 | 2008-10-22 | 凯密特尔有限责任公司 | Highly reactive zinc form, method for the production thereof, and use of the same |
| CN102180901A (en) * | 2011-04-02 | 2011-09-14 | 绍兴文理学院 | Preparation method of 2,4,6,10-tetra-double bond pentadecyl carbon phosphonate ester |
Non-Patent Citations (1)
| Title |
|---|
| Photoassociation and bound-bound excitation into the 2 2P state of LiZn, LiCd, and NaZn molecules;Davorka Azinovic et al.;《Physical Review A》;19960331;第1323-1329页 * |
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