CN1040870C - Reduction dehalogerating reaction of halohydrocarbon under action of active alkali metal hydride - Google Patents
Reduction dehalogerating reaction of halohydrocarbon under action of active alkali metal hydride Download PDFInfo
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- CN1040870C CN1040870C CN93111152A CN93111152A CN1040870C CN 1040870 C CN1040870 C CN 1040870C CN 93111152 A CN93111152 A CN 93111152A CN 93111152 A CN93111152 A CN 93111152A CN 1040870 C CN1040870 C CN 1040870C
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Abstract
The present invention relates to reduction and dehalogenation reaction of halogenated hydrocarbon and reaction that o-dihalogenated hydrocarbon is dehalogenated into alkene. The present invention is characterized in that high-activity alkali metal hydride (such as NaH) synthesized by a coordination catalysis method is used as reducing agents. Reaction is carried out in aprotic solvent at normal pressure and low temperature (-40 to 100 DEG C). Dehalogenation reaction can be carried out to aryl halogenated hydrocarbon and alkyl halogenated hydrocarbon. The present invention has high activity especially for the reaction that o-dihalogenated hydrocarbon is dehalogenated into alkene.
Description
The present invention relates to a kind of organic chemical reactions, promptly provide a kind of high activity alkali metal hydride that adopts can carry out reduction dehalogenation reaction as the halohydrocarbon that makes of reductive agent under normal pressure, low temperature, particularly adjacent dihalo hydrocarbon dehalogenation becomes olefine reaction.
The reduction dehalogenation reaction of halohydrocarbon is in organic synthesis, and especially (in order to remove the organic polyhalogenide of high toxicity that is difficult to the ordinary method processing) all has important use in environmental protection.This reaction needs composite metal hydride, fusion attitude basic metal or alkali-metal organometallics to make reductive agent usually.As Canadian Patent 1991, CA2,026,506 usefulness fused sodium and many halogenated aryl hydrocarbons are then used C 105 ℃ of effects down
1-3Pure termination reaction, can realize the dehalogenation of many halogenated aryl hydrocarbons.In the recent period similarly patent also has: United States Patent (USP) 1990, US4,950,833, European patent 1992, EP467,053 etc.United States Patent (USP) 1978, US4,466,870 with LiAlH
4Be reductive agent, under the ultrasonic wave effect, in glycol dimethyl ether, realize O-BrC
6H
4The OMe debrominate, 35 ℃ of reactions down, the 4h transformation efficiency is 98%.If there is not action of ultrasonic waves, above-mentioned being reflected under 100 ℃ carried out, and the 24hr transformation efficiency also has only 58%.United States Patent (USP) 1984, US4,447,667 usefulness naphthalene sodium make halohydrocarbon, and especially many halogenated biphenyls (PCB) dehalogenation is used CO
2Termination reaction.Relevant adjacent dihalo hydrocarbon dehalogenation becomes the reaction of alkene to yet there are no patent report.In addition, the dehalogenation poor ability of conventional base metal hydride, report such as Nelson (J.Org.Chem for example, 1974,39,1425) excessive 10 times common NaH dehalogenation reaction to bromonaphthalene under the THF reflux temperature is inoperative, and (101 ℃) carry out also non-activity under the diox reflux temperature even be reflected at.
The purpose of this invention is to provide a kind of reduction dehalogenation reaction of halohydrocarbon under the mild conditions and dehalogenation of adjacent dihalo hydrocarbon can realized and become alkene reaction.This reaction system is simple, the transformation efficiency height, and it not only can make aryl halogenide, aryl polyhalogenide dehalogenation, and can make halogenated alkyl thing dehalogenation, especially the dehalogenation to adjacent dihalo hydro carbons becomes alkene reaction high reactivity especially.
The present invention for achieving the above object, promptly under mild conditions, carry out the reduction dehalogenation reaction of halohydrocarbon and the dehalogenation of adjacent dihalo hydrocarbon and become alkene reaction, adopted high activity alkali metal hydride as reductive agent, this reductive agent utilizes the complex catalysis method prepared, promptly in the presence of polycyclic aromatic hydrocarbon compounds, with the ethers is solvent, as catalyzer, makes basic metal carry out hydrogenation with transistion metal compound.Under this condition, reaction can be carried out under normal pressure, low temperature (20~100 ℃).The reduction dehalogenation reaction of its halohydrocarbon can be by reaction formula 1 expression, and the dehalogenation of adjacent dihalo hydrocarbon becomes alkene reaction to be represented by reaction formula 2.
Wherein: R: alkyl, aryl;
M:Li,Na,K;
X:Cl,Br,I。Reaction (1), (2) can be carried out under normal pressure or high pressure, and temperature of reaction is-40~100 ℃, is solvent with aprotic organic solvent.In the reaction, the hydride consumption is advisable with 0.5~20 with the MH/X mol ratio.
The reaction that the invention described above provided, owing to use high activity alkali metal hydride as reductive agent, it is easy to prepare, need not specific installation, the reaction conditions gentleness, the hydride consumption is few, reaction system is simple, and the transformation efficiency height not only can make aryl halide, aryl polyhalohydrocarbon dehalogenation, also can make alkyl halohydrocarbon dehalogenation, especially the dehalogenation for adjacent dihalo hydrocarbon becomes olefine reaction to have very high activity.Below by example building-up reactions provided by the invention is described in detail.
Synthesizing of example 1 active alkali metal hydride
In 150ml glass reaction bottle, insert 100mmol basic metal (K, Na or Li are cut into small pieces) and 0.64g (5mmol) naphthalene, nitrogen three times is found time, filled to reaction flask after, under protection of inert gas, add 40ml tetrahydrofuran THF and 2mmol (about 0.23ml) TiCl
4, after finding time, fill hydrogen three times, in 40 ℃, normal pressure hydrogen, react.Question response finishes back (no longer inhaling hydrogen), and reaction solution is through the centrifugal solid of telling, and after THF washing three times, (60 ℃) vacuum-drying 2hr promptly gets product active alkali metal hydride under the low-grade fever.
The reaction of example 2 bromobenzene reduction-debrominations
(purity 90% 13.5mmol) is pressed the made active sodium hydride of example 1 method to (through finding time, fill nitrogen three times) adding 360mg, 10ml tetrahydrofuran (THF) (THF) and 0.53ml (5mmol) bromobenzene in 50ml glass reaction bottle.At normal pressure, the THF reflux temperature is reaction down, and the 4h transformation efficiency is 99%, and product is a benzene, does not have other side reactions and takes place.
Example 3 adjacent two bromo hexanaphthene debrominates become olefine reaction
In 50ml glass reaction bottle, (add 180mg (purity 90% three times through finding time, fill nitrogen, 6.75mmol) press the made adjacent two bromo hexanaphthenes of active sodium hydride, 10ml THF, 0.34ml (25mmol) of example 1, be reflected under the normal pressure, 40 ℃ and carry out, the 30min transformation efficiency is 100%, product is a tetrahydrobenzene, does not have other side reactions and takes place.
Example 4-12 presses example 2 or 3 described experiment conditions and operation steps embodiment 4-12, the results are shown in table 1.
The dehalogenation of the reduction dehalogenation reaction of some halogenated hydrocarbons of table 1 and adjacent dihalo hydrocarbon become alkene reaction real halogenated hydrocarbons hydride MH/X reaction time temperature inversion rate product example (h) (℃) (%) (%) 4 α-bromonaphthalene KH 1.35 8 THF 31.8 naphthalenes (100) 5 α-bromonaphthalene NaH 2.7 8 THF, 100 naphthalenes (100) 6 chlorobenzene NaH, 2.7 8 THF, 71.8 benzene (100) 7 iodobenzene NaH, 1.35 1 THF, 100 benzene (100) 8 m-dichlorobenzene NaH, 2.7 8 THF, 73.3 chlorobenzenes (50.0) that reflux that reflux that reflux that reflux that reflux
Benzene (50.0) 9 benzyl chloride NaH 1.35 8 THF 50.1 toluene (100) 10 1-iodo octane NaH, 1.35 3 THF, 36.5 octanes (100) 11 1,1-ethylene dichloride NaH, 1.35 8 60 68.7 monochloroethane (principal product) that reflux that reflux
Ethane (on a small quantity) 12 1,2-ethylene dichloride NaH 1.35 8 THF 100 ethene (100) that reflux
By above-mentioned example,, can realize that aryl halide and halogenated alkyl hydrocarbon reduction dehalogenation reaction and the adjacent dihalo hydrocarbon dehalogenation under normal pressure, low temperature (40~100 ℃) becomes olefine reaction when adopting reaction provided by the invention.This reaction system is simple, and reductive agent is easy to get, and is inexpensive, do not need specific installation, the reactive behavior height, and the dehalogenation of especially adjacent dihalo hydrocarbon becomes olefine reaction to have more high reactivity, is a kind of economic, practical reduction method dehalogenation method and the method for preparing corresponding alkene.
Claims (3)
1. the reduction dehalogenation reaction of a halohydrocarbon is characterized in that it being to have adopted to utilize the highly active alkalimetal hydride of complex catalysis method preparation to be reductive agent; So-called complex catalysis method be basic metal in the presence of polycyclic aromatic hydrocarbon compounds, be solvent with the ethers, with transistion metal compound as under the catalyzer, the alkali-metal hydrogenation of realization.
2. according to the described reaction of claim 1, it is characterized in that being reflected under normal pressure or the high pressure, temperature is-40~100 ℃, is to carry out under the solvent with aprotic organic solvent.
3. according to the described reaction of claim 1, the mol ratio that it is characterized in that halogen element in alkalimetal hydride consumption and the halohydrocarbon is 0.5~20.
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JPH0217140A (en) * | 1988-07-04 | 1990-01-22 | Nagase Sangyo Kk | Dehalogenation of aliphatic fluorinated hydrocarbon |
EP0493760A1 (en) * | 1990-12-21 | 1992-07-08 | Hoechst Aktiengesellschaft | Process for the removal of olefinic impurities from partially halogenated fluorochlorocarbons |
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JPH0217140A (en) * | 1988-07-04 | 1990-01-22 | Nagase Sangyo Kk | Dehalogenation of aliphatic fluorinated hydrocarbon |
EP0493760A1 (en) * | 1990-12-21 | 1992-07-08 | Hoechst Aktiengesellschaft | Process for the removal of olefinic impurities from partially halogenated fluorochlorocarbons |
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