CN101306968B - Process for synthesizing halogenated compounds by oxygenizing and halogenating reaction - Google Patents
Process for synthesizing halogenated compounds by oxygenizing and halogenating reaction Download PDFInfo
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- CN101306968B CN101306968B CN2008100626842A CN200810062684A CN101306968B CN 101306968 B CN101306968 B CN 101306968B CN 2008100626842 A CN2008100626842 A CN 2008100626842A CN 200810062684 A CN200810062684 A CN 200810062684A CN 101306968 B CN101306968 B CN 101306968B
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Abstract
The invention discloses a method for synthesizing halogenated compound through oxidation-halogenating reaction. The method is as follows: in the presence of an oxidizing agent and catalyst, compound SH and halide MXn as shown in formula (II) are fully reacted at a temperature of between -10 DEG C and 180 DEG C in the presence of excessive compound SH or added organic solvent, and the halogenated compound SX is obtained after post treatment of the reaction liquid; the halide (II) is added in the form of an aqueous solution; the compound SH is straight-chain or branched-chain alkane with the carbon number of between C1 and C30, polymethylene with the carbon number of between C3 and C30, alkyl substituted polymethylene with the carbon number of between C1 and C10, alkyl substituted arene with the carbon number of between C1 and C10, heterocyclic compound with the carbon number of between C2 and C30 or alkyl substituted heterocyclic compound with the carbon number of between C1and C10; and the X in the halide MXn is Cl, Br or I, while the M is H, Na, K, Ca or Mg. The method has simple making steps, no three-waste pollution and as high as more than 90 percent of yield.
Description
(1) technical field
The present invention relates to the method for a kind of structure suc as formula the synthesizing halogenated compounds of compound halogenation shown in (I).
(2) background technology
Halogenated alkane is a class synthetic intermediate very important in the chemical industry.Though synthesizing halogen alkane has various methods, getting haloalkane from the direct halo of alkane obviously is the ideal approach.People have been developed the halogenated method of a lot of alkane, as use the halogen halogenation, N-X compounds, many halogenated alkanes or the like.But because the reactive behavior of alkane is lower, the alkane bromination method is not a lot of efficiently.
Li C-Z report simple substance bromine can be realized the single bromo-reaction (productive rate is up to 99%) to hexanaphthene well under the Manganse Dioxide effect.Catalyzer MnO
2Simply recovery and reuse and need not further activating.
Top reaction has obtained almost quantitative yield at molecular bromine, but for bromine atoms, owing to generated the hydrogen bromide of a part, its yield has only 50% at most.The halide reagent commonly used for great majority all exists same problem, because the generation of by-product hydrogen halide, the utilization ratio of halogen atom has only 50% at most.
Therefore, utilize the oxidisability of oxygenant that the halogen negative ion in the by-product hydrogen halide is oxidized to the effective way that bromine atoms participates in reacting the Atom economy that is the raising bromination reaction again.For the needs of realizing growing Green Chemistry with go to realize higher efficient and reaction preference, the researchist more is absorbed in the commutable and ecological easier received bromo-reaction of development.Promptly to adopt the oxidation bromination of the bromide of a suitable oxygenant be exactly a reasonable thinking and add oxygenant in the employing halogenating reaction.
Since nineteen twenty-four begins one's study oxidative halogenation, attracted fervent concern to ion halo and free radical halo process.But up to the present, it is few to obtain reasonable result, has only the halogenated example result of bromine oxide of several ketone more satisfactory.Do not see good especially result's report for alkane, aromatic hydrocarbons etc.
Ca[V (HIDPA) such as Pombeiro
2] be catalyzer HBr-H
2O
2Oxidation bromination hexanaphthene, but have to yield [Reis P.M. about 10%; Silva J.L.; Fra ú sto da Silva J.J.R.; Pombeiro A.J.L., Chem.Commun., 2000,1845-1846.]
Iskra has reported a H
2O
2-HBr Aquo System effectively and the method for " green ", gentleness, without organic solvent and do not produce be used to prepare under the condition of organic liquid waste alpha-brominated 1,3-diketone, 'beta '-ketoester and ketone, the yield of reaction and selectivity all obtained good result [
A.; Stavber S.; Zupanab M.; Iskra J., Green Chem., 2007,9,1212-1218.].
And propose in the reaction system that contains the water hydrogen peroxide, the oxidation bromination reaction has experienced following process:
Gadde Ramachandraiah has reported NaBr-NaBrO
3System is to alkene, and the bromination of aromatic ring side chain and carbonyl α position has all obtained good effect [Adimurthy S.; GhoshS.; Patoliya P.U.; Ramachandraiah G.; Agrawal M.; Gandhi M.R.; Upadhyay S.C.; Ghosh P.K.; Ranu B.C., Green Chem., 2008,10,232-237].
Based on noted earlier, the utilization ratio of utilizing oxygenant to improve halogen atom in the halogenating reaction is to improve the key of halogenating reaction technology.
(3) summary of the invention
The technical problem to be solved in the present invention be to provide a kind of simple, green, compound (I) is by the novel process of oxidative halogenation synthesizing halogenated compounds efficiently.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows:
A kind of suc as formula compound shown in (I) with suc as formula the synthetic method of halogenide shown in (II): in the presence of oxygenant and catalyzer suc as formula the halogenated compound shown in (III), compound (I) and excessive or add under the organic solvent condition at compound (I) in-10～180 ℃ of fully reactions suc as formula the halogenide shown in (II), reaction solution obtains halogenated compound (III) through aftertreatment; Described halogenide (II) adds with the form of the aqueous solution;
SH (I) MX
n (II) SX (III)
In the formula (I), SH is that carbon number is C
1～C
30Straight or branched alkane, C
3～C
30The C that naphthenic hydrocarbon or one or more alkyl replace
3～C
30Naphthenic hydrocarbon, the aromatic hydrocarbons that one or more alkyl replace, C
2～C
30The C that heterogeneous ring compound or one or more alkyl replace
2～C
30Heterogeneous ring compound, described substituted alkyl independently are selected from C separately
1～C
10Alkyl; Wherein, at " the C that one or more alkyl replace
3～C
30Naphthenic hydrocarbon " and " C that one or more alkyl replace
2～C
30Heterogeneous ring compound " statement in, described carbon number " C
3～C
30" and " C
2～C
30" all do not comprise the carbon number of substituted alkyl.
SX is the halides of SH in the formula (III), and wherein X is Cl, Br or I;
X is Cl, Br or I in the formula (II); M is H or Na, K, metals such as Ca, Mg; N is MX
nIn the ratio of valence number of the valence number of M and X, n is 1,2...;
Described reaction is excessive or add under the organic solvent condition and carry out at compound (I), and the described organic solvent that adds can be selected halogenated alkane, as methylene dichloride, and 1,2-ethylene dichloride etc., the present invention preferably reacts under the excessive condition of compound (I).
In the reaction system of the present invention, halogenide (II) in the presence of oxygenant, is oxidized to halogen simple substance earlier, and halogen simple substance obtains corresponding halogenated compound (III) with compound (I) reaction again under the effect of certain catalyzer, and reaction process is as follows:
Oxygenant+MX → X
2
(II)
(I) (III)
Oxygenant+HX → X
2
W-response formula following (is example with the hexanaphthene)
Catalyzer used in the present invention is mainly metal oxide, Lewis acid or loaded catalyst commonly used in the halogenating reaction;
Described oxygenant is laboratory and industrial various oxygenants commonly used, and is one of following as being selected from: KMnO
4, NaBrO
3, NaClO
3, sodium dichromate 99,5%～90% hydrogen peroxide, iron nitrate, MnO
2, MnO
3, OsO
4, Pd (OAc)
4, ceric ammonium nitrate, iron(ic) chloride, H
2O
2-urea, TEMPO-NaClO.
It is one of following that described oxygenant can also be selected from: hypohalous acid, hypohalous acid sodium, hydracid, halate, high hydracid, perhalide.Specifically, can select one of following: NaBrO
3, NaClO, Mg (ClO
4)
2
When described be reflected at not have add when carrying out under the organic solvent condition, the described reactant amount of substance ratio that feeds intake is recommended as SH: oxygenant: catalyzer: MX
n=30～3: 5.0～0.8: 0.01～0.8: 1/n.
Described being reflected at adds when carrying out under the organic solvent condition, and the present invention recommends described reactant to feed intake amount of substance than SH: oxygenant: catalyzer: MX
n=0.8～1: 5.0～0.8: 0.01～0.8: 1/n.The amount of substance consumption of the described organic solvent that adds is 4～5 times of SH amount of substance.
Further, described catalyzer specifically can be selected from one of following: KF, TiCl
4, NiCl
2, CuSO
4, Cu (OAc)
2, ZnCl
2, AlCl
3, CuI, Fe (NO
3)
3, FeCl
3, Manganse Dioxide, V
2O
5, Fe
2O
3, MgO, CaO, CuO, TiO
2, aluminum oxide.
Perhaps, it is one of following that described catalyzer is selected from: silica gel, diatomite, various types of wilkinite, various types of molecular sieve, wherein molecular sieve comprises: the molecular sieve of various special constructions such as the molecular sieve of the adsorbed molecules sieve of various 3A or 4A type, H β, H γ, various forms such as Na β, Na γ, HTS.
Temperature of reaction of the present invention is-10～180 ℃, mainly in room temperature, and the more weak compound (I) of reactive behavior mainly is in its paraffin boiling points as the temperature of reaction of saturated alkane to wherein more active compound (I) as the temperature of reaction of aromatic ring and electron rich heterogeneous ring compound; Reaction times is as the criterion fully with the halogen atom primitive reaction, and generally speaking, the reaction times is at 0.2～24h.
Described reaction can be reacted under the natural light condition, adds certain illumination and then impels reaction, and selected illumination is mainly: carry out under the incandescent light of 10-1000W, high voltage mercury lamp, the ultra violet lamp.
Aftertreatment of the present invention can be taked following steps: after reaction finishes, from reaction solution, tell organic phase, organic phase with the sodium sulfite solution washing after, revolve to steam to remove and add organic solvent or raw material obtains product.Catalyzer is present in remaining aqueous phase, can drop into the reaction of next pot after removing most of water again, generally can recycle 5-10 time.
The present invention compares suc as formula the halogenation method of the compound shown in (I) with existing structure, and its main advantage is:
A) the present invention has added oxygenant in the halogenating reaction system, the by-product hydrogen halide of halogenating reaction is changed into halogen again participate in halogenating reaction, has improved the Atom economy of halogenating reaction greatly;
B) the present invention has introduced catalyzer in reaction system, has improved the efficient of oxidative halogenation greatly.
Thus, the present invention opened up one simple, green, efficiently by the route of compound (I) oxidative halogenation synthesizing halogenated compounds (III), preparation process is simple, three-waste free pollution, yield can be up to more than 90%.
(4) embodiment
The present invention is described further below in conjunction with specific embodiment, but protection scope of the present invention is not limited in this:
Embodiment 1:
40% hydrogen bromide of 20g normal hexane, 9.4g and 1.0g catalyzer MnO
2, stirring heating refluxes, and adds the 5%NaClO of 70g more slowly with peristaltic pump, reacts the color of 15 hours bromines to the reaction solution and takes off stopped reaction substantially.Tell organic layer, use sodium sulfite solution, sodium hydrogen carbonate solution, saturated common salt water washing respectively after, anhydrous magnesium sulfate drying, normal hexane is removed in underpressure distillation, obtains the normal hexane product (colourless liquid) of 2-bromo and 3-bromo.Productive rate is that 76%, 500 million nuclear-magnetism determines that the ratio of 2-bromo and 3-bromo is 3: 2.
Embodiment 2:
40% hydrogen iodide of 20g octane-iso, 9.4g and 0.5g catalyzer wilkinite, 120 ℃ of reactions of stirring heating add the KMnO of 7g more slowly with peristaltic pump
4, react the color of 5 hours bromines to the reaction solution and take off stopped reaction substantially.Tell organic layer, use sodium sulfite solution, sodium hydrogen carbonate solution, saturated common salt water washing respectively after, anhydrous magnesium sulfate drying, underpressure distillation obtains 2-bromo-iso-octane product (colourless liquid).Yield is 54%.
Embodiment 3:
40% hydrogen bromide of 20g hexanaphthene, 9.4g and 1.5g catalyzer diatomite, the stirring heating temperature is 70 ℃, adds 1.5 normal 30% hydrogen peroxide slowly with peristaltic pump again, reacts the color of 10 hours bromines to the reaction solution and takes off stopped reaction substantially.Tell organic layer, use sodium sulfite solution, sodium hydrogen carbonate solution, saturated common salt water washing respectively after, anhydrous magnesium sulfate drying, underpressure distillation obtains bromo normal hexane (colourless liquid).Boiling point is 166 ℃, and yield is 97%.
Embodiment 4:
40% aqueous sodium bromide and the 0.15g catalyzer silica gel of 20g toluene, 9.4g, stirring at room adds normal 30% hydrogen peroxide slowly with peristaltic pump again, reacts the color of 3 hours bromines to the reaction solution and takes off stopped reaction substantially.Tell organic layer, use sodium sulfite solution, sodium hydrogen carbonate solution, saturated common salt water washing respectively after, anhydrous magnesium sulfate drying, underpressure distillation obtains product benzyl bromine.Productive rate is 74%.
Embodiment 5:
50% hydrogen iodide of 20g thiophene, 9.4g and 3g HTS, 10 ℃ of stirring reactions add 0.8 normal NaBrO slowly with peristaltic pump again
3, react the color of 1 hour bromine to the reaction solution and take off stopped reaction substantially.Tell organic layer, use sodium sulfite solution, sodium hydrogen carbonate solution, saturated common salt water washing respectively after, anhydrous magnesium sulfate drying, underpressure distillation obtains product 2-iodo thiophene.Productive rate is 70%.
Embodiment 6:
4.5g methylcyclohexane is dissolved in the 15mL ethylene dichloride, adds 40% hydrogen bromide of 9.4g and the Na beta-molecular sieve of 2g, 90 ℃ of stirrings add 5 equivalent iron(ic) chloride slowly with peristaltic pump again, react the color of 20 hours bromines to the reaction solution and take off stopped reaction substantially.Tell organic layer, use sodium sulfite solution, sodium hydrogen carbonate solution, saturated common salt water washing respectively after, anhydrous magnesium sulfate drying, underpressure distillation obtains product 1-bromo-1-methylcyclohexane.Productive rate is 63%.
Embodiment 7:
The 40% magnesium bromide aqueous solution of the 2-methyl furan of 20g, 12g and 0.8g Fe (NO
3)
3, 50 ℃ of stirrings add 2 normal H slowly with peristaltic pump again
2O
2-urea reacts the color of 2 hours bromines to the reaction solution and takes off stopped reaction substantially.Tell organic layer, use sodium sulfite solution, sodium hydrogen carbonate solution, saturated common salt water washing respectively after, anhydrous magnesium sulfate drying, underpressure distillation obtains 1-bromo-2-methyl furan.Productive rate is 90%.
Embodiment 8:
40% hydrogen bromide of 20g hexanaphthene, 9.4g and 1.5g catalyzer diatomite, the stirring heating temperature is 70 ℃, and 100 watts of incandescent light irradiations add 1.5 normal 30% hydrogen peroxide with peristaltic pump down more slowly, react the color of 5 hours bromines to the reaction solution and take off stopped reaction substantially.Tell organic layer, use sodium sulfite solution, sodium hydrogen carbonate solution, saturated common salt water washing respectively after, anhydrous magnesium sulfate drying, underpressure distillation obtains bromocyclohexane (colourless liquid).Boiling point is 166 ℃, and yield is 98%.
Embodiment 9:
After most water is removed in the distillation of remainder water solution decompression among the embodiment 3, at 40% hydrogen bromide that adds 20g hexanaphthene, 9.4g, the stirring heating temperature is 70 ℃, add 1.5 normal 30% hydrogen peroxide slowly with peristaltic pump again, react the color of 10 hours bromines to the reaction solution and take off stopped reaction substantially.Tell organic layer, use sodium sulfite solution, sodium hydrogen carbonate solution, saturated common salt water washing respectively after, anhydrous magnesium sulfate drying, underpressure distillation obtains bromocyclohexane (colourless liquid).Yield is 94%.
Claims (8)
1. synthetic method suc as formula the halogenated compound shown in (III), it is characterized in that described method is: in the presence of oxygenant and catalyzer, compound (I) and excessive or add under the organic solvent condition at compound (I) in-10～180 ℃ of fully reactions suc as formula the halogenide shown in (II), reaction solution obtains halogenated compound (III) through aftertreatment; Described halogenide (II) adds with aqueous solution form;
SH (I) MX
n (II) SX (III)
SH is that carbon number is C in the formula (I)
1～C
30Straight or branched alkane, C
3～C
30The C that naphthenic hydrocarbon or one or more alkyl replace
3～C
30Naphthenic hydrocarbon, the aromatic hydrocarbons that one or more alkyl replace, C
2～C
30The C that heterogeneous ring compound or one or more alkyl replace
2～C
30Heterogeneous ring compound, described substituted alkyl independently are selected from C separately
1～C
10Alkyl;
SX is the halides of SH in the formula (III), and wherein X is Cl, Br or I;
X is Cl, Br or I in the formula (II); M is H, Na, K, Ca or Mg; N is MX
nThe ratio of the valence number of middle M and the valence number of X;
Described catalyzer is one of following: KF, TiCl4, NiCl2, CuSO4, Cu (OAc) 2, ZnCl2, AlCl3, CuI, Fe (NO3) 3, FeCl3, Manganse Dioxide, V2O5, Fe2O3, MgO, CaO, CuO, TiO2, aluminum oxide; Perhaps described catalyzer is one of following: silica gel, diatomite, wilkinite, molecular sieve, and wherein molecular sieve comprises: molecular sieve, the HTS of adsorbed molecules sieve, H β, H γ, Na β or the Na γ form of 3A or 4A type;
The described organic solvent that adds is a halogenated alkane;
And when M was Na, K, Ca or Mg in the formula (II), described oxygenant was one of following: hypohalous acid, high hydracid, 5%～90% hydrogen peroxide, H
2O
2-urea.
2. synthetic method as claimed in claim 1 is characterized in that M is H in the formula (II), and described oxygenant is one of following: KMnO
4, NaBrO
3, NaClO
3, sodium dichromate 99,5%～90% hydrogen peroxide, iron nitrate, MnO
2, MnO
3, OsO
4, Pd (OAc)
4, ceric ammonium nitrate, iron(ic) chloride, H
2O
2-urea, TEMPO-NaClO.
3. synthetic method as claimed in claim 1 is characterized in that M is H in the formula (II), and described oxygenant is one of following: hypohalous acid, hypohalous acid sodium, high hydracid, perhalide.
4. synthetic method as claimed in claim 1, it is characterized in that described be reflected at not have to add under the organic solvent condition carry out, described reactant feeds intake amount of substance than SH: oxygenant: catalyzer: MX
n=30～3: 5.0～0.8: 0.01～0.8: 1/n.
5. synthetic method as claimed in claim 1, it is characterized in that described be reflected to add under the organic solvent condition carry out, described reactant feeds intake amount of substance than SH: oxygenant: catalyzer: MX
n=0.8～1: 5.0～0.8: 0.01～0.8: 1/n, the described organic solvent amount of substance consumption that adds are 4～5 times of SH amount of substance.
6. synthetic method as claimed in claim 1 is characterized in that described reaction is to carry out under incandescent light, high voltage mercury lamp or the ultra violet lamp at 10-500W.
7. synthetic method as claimed in claim 1 is characterized in that the described reaction times is 0.2～24h.
8. synthetic method as claimed in claim 1 is characterized in that described aftertreatment is: after reaction finishes, from reaction solution, isolate organic phase, organic phase with the sodium sulfite solution washing after, revolve to steam and remove organic solvent or raw material obtains product; The catalyzer of aqueous phase recycles after removing most of water again.
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| CN103508862A (en) * | 2013-10-16 | 2014-01-15 | 连云港市华伦化工有限公司 | Method for preparing terephthalaldehyde through catalytic oxidation |
| CN106748809B (en) * | 2016-12-01 | 2019-05-31 | 浙江工业大学 | A method of adjacent halogen arylamine is prepared based on C-H activation arylamine class |
| CN108358748B (en) * | 2018-03-28 | 2021-04-20 | 上海交通大学 | Preparation method of alkane bromide |
| CN114539019B (en) * | 2022-03-01 | 2023-11-28 | 苏州大学张家港工业技术研究院 | Method for continuously synthesizing halogenated compound by photoinduction based on halogen salt instead of halogen simple substance |
| CN114591225B (en) * | 2022-03-02 | 2024-02-06 | 河南阿尔法医药科技有限公司 | Method for large-scale production of 2, 6-dibromo-4-methylpyridine |
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Non-Patent Citations (1)
| Title |
|---|
| Subbarayappa Adimurthy et al..An alternative method for the regio- and stereoselective bromination of alkenes, alkynes, toluene derivatives and ketones using a bromide/bromate couple.Green Chemistry.2008,10(2),232-237. * |
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