CN101508625B - Method for synthesis of alkyl substituted benzene with direct cross coupling of cobalt salt catalysed fragrant halogen and haloalkane - Google Patents
Method for synthesis of alkyl substituted benzene with direct cross coupling of cobalt salt catalysed fragrant halogen and haloalkane Download PDFInfo
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- CN101508625B CN101508625B CN200910058771A CN200910058771A CN101508625B CN 101508625 B CN101508625 B CN 101508625B CN 200910058771 A CN200910058771 A CN 200910058771A CN 200910058771 A CN200910058771 A CN 200910058771A CN 101508625 B CN101508625 B CN 101508625B
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Abstract
The invention discloses a novel method for synthesizing alkyl substituted benzene by directly and crossly coupling aryl halide catalyzed by cobalt salt and halogenated alkane in the presence of magnesium. The method comprises a step of directly adding cobalt salt, magnesium, aryl halide, halogenated alkane, solvent and ligand together into a reactor, at room temperature or a temperature lower than room temperature under the protection of inert gases, to synthesize alkyl substituted benzene in one pot. The method of the invention avoids a process of preparing Grignard reagent and has advantages of simple and feasible process, low cost, safe production and the like, in addition, the reactive materials used by the reaction system is easily obtained and the synthesized alkyl substituted benzene has high yield.
Description
Technical field
The present invention relates to a kind of compound method of alkyl substituted benzene, particularly a kind of with aryl halide and halogenated alkane novel method in the presence of magnesium and cobalt salt through direct cross-coupling reaction synthesis of alkyl substituted benzene.
Background technology
Transition metal-catalyzed cross-coupling reaction has vital role aspect Materials science and the medicine industry, and the formation instrument as a kind of irreplaceable C-C key is widely used [1. Cross-CouplingReactions:A Practical Guide in laboratory or industry; (Ed.N.Miyaura), Topics in Current Chemistry, Series 219; Springer-Verlag, New York, 2002; 2. Eur.J.Org.Chem.2004,2081].Through the coupling of transition metal-catalyzed Grignard reagent and halogenated alkane, can accomplish usually by S
N2The coupling of the irrealizable aryl-alkyl of substitution reaction, thus facilitate for the synthetic of some alkyl substituted benzenes, and in some medicine intermediates and biologically active substance synthetic, be used widely.Like number of patent application is 200410079508 patent, discloses aryl grignard reagent and bromine haloalkane coupling synthesizing coenzyme Q
10Method.And all adopt metals such as palladium and nickel to make catalyzer in most of instances, and the former costs an arm and a leg, and latter's toxicity is bigger.In recent years, more green, the inexpensive molysite and the cross-coupling reaction of the catalytic Grignard reagent of cobalt salt had been obtained than quantum jump.For example: people such as F ü rstner A. have reported the catalytic alkyl Grignard reagent of iron and the coupling (Angew.Chem.Int.Ed.2002,41,609 that contain aryl halide and the aryl grignard reagent and the bromine/alkane iodide of multiple functional group; Angew.Chem.Int.Ed.2004,43,3955), its productive rate is mostly more than 80%.OshimaK. wait the people to report CoCl
2The coupling of catalytic aryl grignard reagent and bromo alkane, and be used to have the prostaglandin A H13205 that reduces the intraocular pressure effect synthetic (J.Am.Chem.Soc., 2006,128,1886).Yet,, all need in advance one of them component to be made Grignard reagent in Grignard reagent link coupled report.Because kick off temperature is higher, add and follow heat releasely in a large number when Grignard reagent forms to have bigger danger at the initiating stage of Grignard reagent, especially for large batch of industrial preparation.And many functional groups suffer brokenly ring (J.Org.Chem.2003,68,3695, Org.Process Res.Dev.2006,10,1258, Org.ProcessRes.Dev.2007,11,1135) easily in the preparation process of Grignard reagent.Though, there is an instance to report in the presence of magnesium recently, the direct cross-coupling of catalytic halogenated aryl hydrocarbon of iron and halogenated alkane has been avoided the preparation in advance of Grignard reagent.But most examples all can only obtain moderate yield.This reaction system also need add the containing n-donor ligand of excessive costliness, and resource is produced waste, has increased production cost; And functional group's tolerance is not high, and reaction can not be carried out when containing itrile group; These defectives have all limited the practical application (Angew.Chem.Int.Ed.2009,48,607) of this method in industry.
Summary of the invention
The object of the invention to existing problem in the above-mentioned prior art, provides a kind of under room temperature or subambient condition just, cobalt salt, magnesium, aryl bromide and bromo alkane is directly added in the reaction vessel together the method for one kettle way synthesis of alkyl substituted benzene.This method need not the prepared beforehand Grignard reagent just can synthesis of alkyl substituted benzene, and that method of the present invention has is simple, with low cost, production safety and productive rate advantages of higher.
For realizing the object of the invention, the technical scheme that the present invention adopts following measure to constitute realizes.
The direct cross-coupling of catalytic aryl bromide of cobalt salt of the present invention and bromo alkane prepares the method for alkyl substituted benzene; It is characterized in that adopting cobalt salt, magnesium, aryl bromide, bromo alkane, part and solvent are directly added reaction vessel together; In temperature is under the 0-30 ℃ of condition, and under protection of inert gas, stirring reaction 2-6h; The one kettle way synthesis of alkyl substituted benzene, its reaction expression is following:
In the above-mentioned reaction formula, ArX represents aryl halide, comprises halogeno-benzene and naphthalene halide; Wherein halogeno-benzene has the structure of following i, and naphthalene halide has the structure of following ii;
X＝Cl，Br，I X＝Cl，Br，I
Wherein, R
1Being ortho position, a position, para-orienting group, can be alkyl, phenyl, ester group, itrile group, the alkoxyl group that contains 1-10 carbon; Or do not contain the amino of active hydrogen, the acetal of protection;
Naphthalene halide can be the α naphthalene halide, perhaps β naphthalene halide, R
2Being the optional position substituting group on the naphthalene nucleus, can be alkyl, phenyl, ester group, itrile group, the alkoxyl group that contains 1-6 carbon; Or do not contain the amino of active hydrogen, the acetal of protection;
RX represents disactivation or activatory halogenated alkane, the activatory halogenated alkane be meant halogen be in have electron-withdrawing group such as ester group, itrile group or unsaturated group such as thiazolinyl, the α position of alkynes, phenyl, halogen comprises chlorine, bromine, iodine;
Said cobalt salt consumption is the 1-5% molar percentage; The part consumption is 2 times of cobalt salt; The mol ratio of aryl halide and halogenated alkane is 0.8-1.2, and concentration is 0.1-0.2mol/L.
In the technique scheme, said cobalt salt is selected from CoCl
2, or CoSO
4, or Co (NO
3)
2, or Co (CH
3COO)
2, or Co (AcAc)
2, or Co (AcAc)
3, wherein (AcAc is a methyl ethyl diketone), or Co
2O
3
In the technique scheme, said cobalt salt Co (AcAc)
3Productive rate is higher during for catalyzer.
In the technique scheme, used part is the alkylate of diamine, like TMEDA (Tetramethyl Ethylene Diamine), or TMCHDA (tetramethyl-1,2-cyclohexanediamine).
In the technique scheme, when aryl halide and the reaction of secondary halogenated alkyl alkane, said TMCHDA provides higher productive rate.
In the technique scheme, when aryl halide and the coupling of primary alkyl haloalkane, said TMEDA is a better choice.
In the technique scheme, solvent for use is an ether solvent, like ether, or THF, or the 2-methyltetrahydrofuran.
In the technique scheme, said THF is optimal selection, handles with sodium before using.
In the technique scheme, said rare gas element is an argon gas, or nitrogen.
The present invention compared with prior art has following characteristics and useful technique effect:
1, the present invention adopts one kettle way to accomplish the direct cross-coupling of halogenated aryl hydrocarbon and halogenated alkane, need not the prepared beforehand Grignard reagent, so this method has and the productive rate advantages of higher simple for process, with low cost.
2, method of the present invention is no more than solvent boiling point in the temperature of entire reaction course, has strengthened the tolerance of functional group, and has improved reaction safety greatly.
3, used catalyzer and the part of the present invention is catalytic amount, practiced thrift resource and production cost.
Embodiment
Through specific embodiment the present invention is done the explanation of further detail below, but content of the present invention is not limited only to the content described in the embodiment.
The batching and the processing condition of the representative instance of one kettle way synthesis of alkyl substituted benzene according to the invention are following: adding 0.05mol halogenated aryl hydrocarbon, 0.05mol halohydrocarbon, 2.5mmol cobalt salt, 0.06mol magnesium rod, 5mmol part, 250mL newly steam THF in exsiccant 500mL flask; Under the protection of argon gas body, temperature is stirring reaction 2-6h under 0 ℃ of-30 ℃ of condition; Add saturated ammonium chloride solution again, ethyl acetate extraction, saturated common salt water washing; Anhydrous sodium sulfate drying, steam ETHYLE ACETATE after, again with underpressure distillation or post separate corresponding alkyl substituted benzene.
Embodiment 1:
CoCl
2Catalytic para-bromo toluene of/TMEDA and the synthetic 4-methyl-n-butylbenzene of positive NBB cross-coupling
In exsiccant 500mL flask, add para-bromo toluene 8.55g (0.05mol), positive NBB 6.85g (0.05mol), CoCl
265mg (0.5mmol), magnesium rod 1.44g (0.06mol), TMEDA 116mg (1mmol), 250mL newly steam THF, under the protection of argon gas body, at 25 ℃ of stirring reaction 2h; Add saturated ammonium chloride solution, ethyl acetate extraction, saturated common salt water washing; Anhydrous sodium sulfate drying, steam ETHYLE ACETATE after, underpressure distillation gets colourless liquid 6g, productive rate again: 81%.
Embodiment 2:
CoCl
2Dodecyl benzene is synthesized in catalytic bromobenzene of/TMEDA and bromododecane coupling
In dry 100mL flask, add bromobenzene 1.73g (0.011mol), bromododecane 2.49g (0.01mol), CoCl
264.9mg magnesium rod 0.29g (0.012mol), TMEDA 116mg (1mmol), 60mL newly steam THF, in the protection of argon gas body down, spends stirring reaction 5h for 20 ℃ (0.5mmol); Add saturated ammonium chloride solution, ethyl acetate extraction, saturated common salt water washing; Anhydrous sodium sulfate drying, steam ETHYLE ACETATE after, with sherwood oil do the eluent post separate colourless liquid 1.8g, productive rate: 78%.
Embodiment 3:
Co (AcAc)
3Dodecyl benzene is synthesized in catalytic bromobenzene of/TMEDA and bromododecane coupling
In dry 100mL flask, add bromobenzene 1.73g (0.011mol), bromododecane 2.49g (0.01mol), Co (AcAc)
3180mg (0.5mmol), magnesium rod 0.29g (0.012mol), TMEDA 116mg (1mmol), 60mL newly steam THF, under the protection of argon gas body, at stirring at room reaction 4.5h; Add saturated ammonium chloride solution, ethyl acetate extraction, saturated common salt water washing; Anhydrous sodium sulfate drying, steam ETHYLE ACETATE after, with sherwood oil do the eluent post separate colourless liquid 1.95g, productive rate: 84%.
Embodiment 4:
Co (AcAc)
3Catalytic bromobenzene of/TMCHDA and cyclohexyl bromide coupling synthesizing cyclohexyl benzene
In dry 100mL flask, add bromobenzene 1.57g (0.01mol), cyclohexyl bromide 1.63g (0.01mol), Co (AcAc)
3180mg (0.5mmol), magnesium rod 0.29g (0.012mol), TMCHDA 170mg (1mmol), 50mL newly steam THF, under the protection of argon gas body, and at 0 ℃, stirring reaction 5h; Add saturated ammonium chloride solution, ethyl acetate extraction, saturated common salt water washing; Anhydrous sodium sulfate drying, steam ETHYLE ACETATE after, make eluent with sherwood oil and get colourless liquid 1.18g, productive rate: 73.7%.
Embodiment 5:
Co (AcAc)
3Catalytic adjacent bromobenzylcyanide of/TMEDA and the synthetic adjacent butylbenzene-formonitrile HCN of positive NBB coupling
In exsiccant 500mL flask, add bromobenzene 9.1g (0.05mol), positive NBB 6.85g (0.05mol), Co (AcAc)
30.9g magnesium rod 1.44g (0.06mol), TMEDA 581mg (5mmol), 250mL newly steam THF, under the protection of argon gas body, at 0 ℃ of stirring reaction 6h (2.5mmol); Add saturated ammonium chloride solution, ethyl acetate extraction, saturated common salt water washing; Anhydrous sodium sulfate drying, steam ETHYLE ACETATE after, underpressure distillation gets colourless liquid 4.6g, productive rate again: 57.7%.
Embodiment 6:
Catalytic bromobenzene of CoCl2/TMEDA and METHYL BROMOACETATE coupling synthesize phenylacetic acid ethyl ester
In exsiccant 500mL flask, add bromobenzene 9.1g (0.05mol), METHYL BROMOACETATE 8.35g (0.05mol), CoCl
2324.5mg magnesium rod 1.44g (0.06mol), TMEDA 581mg (5mmol), 250mL newly steam THF, under the protection of argon gas body, at 0 ℃ of stirring reaction 5h (2.5mmol); Add saturated ammonium chloride solution, ethyl acetate extraction, saturated common salt water washing; Anhydrous sodium sulfate drying, steam ETHYLE ACETATE after, underpressure distillation gets colourless liquid 6g, productive rate again: 73.2%.
Embodiment 7:
CoCl
2The catalytic 1-bromo-of/TMEDA 6-methoxynaphthalene and 2 bromopropionic acid ethyl ester coupling Synthetic 2-(6-methoxynaphthalene-1-yl) ethyl propionate, structural formula:
In exsiccant 500mL flask, add 1-bromo-6-methoxynaphthalene 11.85g (0.05mol), 2 bromopropionic acid ethyl ester 9g (0.05mol), CoCl
2324.5mg magnesium rod 1.44g (0.06mol), TMEDA 581mg (5mmol), 250mL newly steam THF, under the protection of argon gas body, at 0 ℃ of stirring reaction 5h (2.5mmol); Add saturated ammonium chloride solution, ethyl acetate extraction, saturated common salt water washing; Anhydrous sodium sulfate drying, steam ETHYLE ACETATE after, with petroleum ether-ethyl acetate do the eluent post separate liquid 8.2g, productive rate: 63.5%.
Embodiment 8:
1-allyl group-4-methoxymethoxy benzene is synthesized in catalytic 1-bromo-4 methoxymethoxy benzene of CoCl2/TMEDA and bromopropylene coupling, structural formula:
In exsiccant 500mL flask, add 1-bromo-4 methoxymethoxy benzene 10.85g (0.05mol), bromopropylene 6.05g (0.05mol), CoCl
2324.5mg magnesium rod 1.44g (0.06mol), TMEDA 581mg (5mmol), 250mL newly steam THF, under the oxide gas protection, at 0 ℃ of stirring reaction 5h (2.5mmol); Add saturated ammonium chloride solution, ethyl acetate extraction, saturated common salt water washing; Anhydrous sodium sulfate drying, steam ETHYLE ACETATE after, with petroleum ether-ethyl acetate do the eluent post separate colourless liquid 6.4g, productive rate: 71.8%.
Embodiment 9:
CoCl
2Catalytic 4-Chlorotoluene 99.5 of/TMEDA and the synthetic 4-methyl-n-butylbenzene of positive butyl iodide coupling
In exsiccant 500mL exsiccant flask, add 4-Chlorotoluene 99.5 7.6g (0.06mol), positive butyl iodide 9.2g (0.05mol), CoCl
265mg (0.5mmol), magnesium rod 1.44g (0.06mol), TMEDA 116mg (1mmol), 250mL newly steam THF, under the oxide gas protection, at 30 ℃ of stirring reaction 6h; Add saturated ammonium chloride solution, ethyl acetate extraction, saturated common salt water washing; Anhydrous sodium sulfate drying, steam ETHYLE ACETATE after, underpressure distillation gets colourless liquid 3.1g, productive rate again: 41.8%.
Embodiment 10:
CoCl
2Catalytic iodobenzene of/TMEDA and the synthetic n-butylbenzene of positive chlorobutane coupling
In exsiccant 500mL exsiccant flask, add iodobenzene 10.2g (0.05mol), positive chlorobutane 5.78g (0.0625mol), CoCl
265mg (0.5mmol), magnesium rod 1.44g (0.06mol), TMEDA 116mg (1mmol), 500mL newly steam THF, under the oxide gas protection, at 25 ℃ of stirring reaction 2h; Add saturated ammonium chloride solution, ethyl acetate extraction, saturated common salt water washing; Anhydrous sodium sulfate drying, steam ETHYLE ACETATE after, underpressure distillation gets colourless liquid 5.8g, productive rate again: 86.5%.
Claims (7)
1. the method for catalytic fragrant halogen of cobalt salt and the direct cross-coupling synthesis of alkyl substituted benzene of haloalkane; It is characterized in that adopting cobalt salt, magnesium, aryl halide, halogenated alkane, part and solvent are directly added reaction vessel together; In temperature is under the 0-30 ℃ of condition, and under protection of inert gas, stirring reaction 2-6h; The one kettle way synthesis of alkyl substituted benzene, its reaction expression is following:
In the above-mentioned reaction formula, ArX represents halogeno-benzene and naphthalene halide; Wherein halogeno-benzene has the structure of following i, and naphthalene halide has the structure of following ii;
X＝Cl，Br，I X＝Cl，Br，I
Wherein, R
1Be ortho position, a position, para-orienting group, be selected from the alkyl, phenyl, ester group, itrile group, the alkoxyl group that contain 1-10 carbon; Or do not contain the amino of active hydrogen, the acetal of protection;
Naphthalene halide is the α naphthalene halide, perhaps β naphthalene halide, R
2Be the substituting group on the naphthalene nucleus, be selected from the alkyl, phenyl, ester group, itrile group, the alkoxyl group that contain 1-6 carbon; Or do not contain the amino of active hydrogen, the acetal of protection;
RX represents the activatory halogenated alkane, and the activatory halogenated alkane is meant that it is ester group, itrile group or thiazolinyl, alkynes, phenyl that halogen is in the described electron-withdrawing group in α position with electron-withdrawing group, and halogen is chlorine, bromine, iodine;
Said cobalt salt consumption is the 1-5% molar percentage; The part consumption is 2 times of cobalt salt; The mol ratio of aryl halide and halogenated alkane is 0.8-1.2, and concentration is 0.1-0.2mol/L.
2. the method for cross-coupling synthesis of alkyl substituted benzene according to claim 1 is characterized in that cobalt salt catalyst is selected from CoCl
2, or CoSO
4, or Co (NO
3)
2, or Co (CH
3COO)
2, or Co (AcAc)
2, or Co (AcAc)
3
3. the method for cross-coupling synthesis of alkyl substituted benzene according to claim 1 is characterized in that said part is the alkylate of diamine, is selected from TMEDA (Tetramethyl Ethylene Diamine), or TMCHDA (tetramethyl-1,2-cyclohexanediamine).
4. according to the method for claim 1 or 3 described cross-coupling synthesis of alkyl substituted benzene, when it is characterized in that aryl halide and the coupling of primary alkyl haloalkane, be selected from TMEDA.
5. the method for cross-coupling synthesis of alkyl substituted benzene according to claim 1 is characterized in that said solvent is an ether solvent, is selected from ether, or THF, or the 2-methyltetrahydrofuran.
6. according to the method for claim 1 or 5 described cross-coupling synthesis of alkyl substituted benzene, it is characterized in that said solvent is a THF, handle with sodium before using.
7. the method for cross-coupling synthesis of alkyl substituted benzene according to claim 1 is characterized in that said rare gas element is an argon gas, or nitrogen.
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| CN105884677A (en) * | 2016-04-21 | 2016-08-24 | 湘潭大学 | Method for carrying out cross coupling reaction on benzylmagnesium chloride under iron catalysis conditions |
| CN109529906B (en) * | 2018-12-25 | 2021-06-15 | 西安近代化学研究所 | Catalyst for synthesizing 1,1,2,3,3, 3-hexafluoropropyl methyl ether and preparation method thereof |
| CN109810001B (en) * | 2019-01-22 | 2022-04-01 | 深圳市第二人民医院 | Synthesis method of ropinirole hydrochloride intermediate 2-methyl-3-nitrophenylacetic acid |
| CN113045373B (en) * | 2021-03-12 | 2024-04-23 | 烟台盛华液晶材料有限公司 | Synthesis method of 4- (3-butene-1-yl) -4 '-alkyl-1, 1' -biphenyl liquid crystal monomer |
| CN113929577B (en) * | 2021-11-05 | 2023-09-29 | 安徽美致诚药业有限公司 | Synthesis method of 2- (4-methylphenyl) -propionate |
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| CN1228073A (en) * | 1996-08-20 | 1999-09-08 | 陶氏化学公司 | Process for production of alkylated benzenes |
| WO2008076722A1 (en) * | 2006-12-13 | 2008-06-26 | Chevron U.S.A. Inc. | Alkylation process using an alkyl halide promoted ionic liquid catalyst |
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2009
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1228073A (en) * | 1996-08-20 | 1999-09-08 | 陶氏化学公司 | Process for production of alkylated benzenes |
| WO2008076722A1 (en) * | 2006-12-13 | 2008-06-26 | Chevron U.S.A. Inc. | Alkylation process using an alkyl halide promoted ionic liquid catalyst |
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| Ge´ |
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