CN104876956A - One-pot synthesis process for boron-amine compounds - Google Patents
One-pot synthesis process for boron-amine compounds Download PDFInfo
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- CN104876956A CN104876956A CN201510321171.9A CN201510321171A CN104876956A CN 104876956 A CN104876956 A CN 104876956A CN 201510321171 A CN201510321171 A CN 201510321171A CN 104876956 A CN104876956 A CN 104876956A
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- amide compounds
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- 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
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
- C07F5/02—Boron compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/08—Hydrogen atoms or radicals containing only hydrogen and carbon atoms
-
- 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
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
- C07F5/02—Boron compounds
- C07F5/025—Boronic and borinic acid compounds
Abstract
The invention discloses a one-pot synthesis process for boron-amine compounds. The process comprises the steps of slowly dripping an anhydrous solvent, bromo-compounds RBr and XBY2 which are mixed into the anhydrous solvent containing metal lithium, maintaining the temperature at -20 to 20 DEG C in a dripping process, maintaining the temperature of -20 to 40 DEG C and reacting for 3-8h after the reaction initiation and the completion of adding the rest mixed solution, and separating to obtain the RBY2. An intermediate can be added with acid to be hydrolyzed to obtain organic boric acid, and reacted with diol to generate boric acid ester, or is directly conducted for coupled reaction with an aryl halogenate. The process is simple in process, few in by-product and high in reaction yield, and the ultralow temperature reaction and the dependency on the solvent by the stability of lithiated compounds can be prevented, therefore the process is applicable to industrial amplification and is beneficial for improving the core competitiveness of products.
Description
Technical field
The present invention relates to the technique of one pot process boron amide compounds, belong to fine-chemical intermediate synthesis field.
Background technology
In the last few years, along with people are to the pay attention to day by day of health degree, more and more faster along with corresponding new drug development paces, various organic chemical reactions also emerges in an endless stream.As the most effectively, the structure carbon-carbon bond mode of mild condition, Suzuki linked reaction is subject to the extensive favor of industry member naturally, and Successful utilization in the new drug synthesis of much having gone on the market.
As the important source material of Suzuki coupling, the synthesis of boric acid/ester mainly contains following two kinds of modes at present: lithium reagent and the trimethyl borate of the Grignard reagent that MAGNESIUM METAL participates in or metallic lithium/lithium alkylide participation react, and obtain corresponding boric acid after acid hydrolysis; With palladium metal/nickel/copper for catalyzer halides to connection boric acid ester carry out linked reaction after obtain corresponding boric acid ester.
Grignard reagent is often confined to ether or tetrahydrofuran (THF) due to the feature reaction solvent of self, and concentration is lower, easy crystallization when exceeding finite concentration.Lithium reagent is strong to solvent dependant, prepares majority often can only prepare in ether with metallic lithium direct reaction, all there is the risk that the transformation period degenerates in other solvent.The reactive mode that halides and butyllithium exchange often needs very low temperature to carry out.Usually all there is the by product that to produce secondary under general low temperature with trimethyl borate reaction and replace in grignard and lithium reagent method.The shortcomings such as linked reaction prepares boric acid ester, and to there is cost high, and easy heavy metal is remaining.
Summary of the invention
In order to overcome above-mentioned defect, emphasis of the present invention is studied lithium reagent method, have selected metallic lithium, bromo-derivative and halogen borane reagent and amplify in common industrialization the mode that in solvent, one kettle way carries out, synthesize stable intermediate, this intermediate acid hydrolysis can become boric acid, reacts generate corresponding boric acid ester or directly carry out Suzuki linked reaction to glycol.
The present invention relates to the technique of one pot process boron amide compounds, it is characterized in that: by anhydrous solvent, bromo-derivative RBr and XBY
2after three's mixing, be slowly added dropwise in the anhydrous solvent containing metallic lithium, in dropping process, holding temperature is at-20 ~ 20 DEG C, when in reaction solution, temperature rise is more than more than 3 DEG C, remaining all added complete, maintain-20 ~ 40 DEG C of reaction 3-8h subsequently, detection reaction is complete, add saturated ammonium chloride and adjust PH=4-6, separate organic layer, water layer extracts once again, merges organic layer, saturated common salt water washing, obtains the boron amide compounds RBY of purity more than 98% after underpressure distillation solvent
2.
Further, in technique scheme, described XBY
2middle X is chlorine or bromine, and Y is Diisopropylamine, diisobutylamine, two cyclopropylamines, Pyrrolidine, six hydrogen piperidines, morpholine.
Further, in technique scheme, described R is alkyl or aryl.Alkyl comprises: methyl, ethyl, sec.-propyl, cyclopropyl, normal-butyl, isobutyl-, cyclopentyl or cyclohexyl.Aryl comprises: phenyl, neighbour// p-methylphenyl, neighbour// p-methoxyphenyl, neighbour// to fluorophenyl, neighbour// rubigan, neighbour// to bromophenyl, 2/3-position furans, 2/3-position thiophene, N-methyl-4-pyrazoles or N-benzyl-4-pyrazoles.
Further, in technique scheme, described anhydrous solvent is tetrahydrofuran (THF), 2-methyltetrahydrofuran, methyl tertiary butyl ether, cyclopentyl-methyl ether, glycol dimethyl ether and methylene diethyl ether.
Further, in technique scheme, described RBr, XBY
2be 1:1-1.2:2-2.4 with the mol ratio of metallic lithium.
Further, in technique scheme, described reaction causes basis for estimation and is: in reaction solution, temperature rise is more than more than 3 DEG C.
The boron amide compounds RBY that aforesaid method obtains
2one of application: by RBY
2dissolve in organic solvent, after adding acid hydrolysis, obtain boric acid compound RB (OH)
2; Acid is hydrochloric acid, sulfuric acid or acetic acid; Hydrolysis temperature is 40 ~ 100 DEG C.
The boron amide compounds RBY that aforesaid method obtains
2application two: boron amide compounds RBY
2react with glycol and generate boric acid ester, glycol is: pinacol, neopentyl glycol or pyrocatechol; Operational condition is: by RBY
2add 1-1.1 equivalent weight diols, be slowly warming up to back flow reaction 1-3 hour, after distillation, obtain corresponding boric acid ester.
The boron amide compounds RBY that aforesaid method obtains
2application three: boron amide compounds RBY
2with 1-1.05 equivalent bromobenzene or iodobenzene under 1-3% mole of palladium catalyst and 1.5-3.0 equivalent alkali exist, 80 ~ 120 DEG C of linked reactions obtain PhR; Described alkali is: KOAc, K
3pO
4or K
2cO
3; Described solvent is: dioxane, dimethyl sulfoxide (DMSO), tetrahydrofuran (THF) or glycol dimethyl ether; Catalyzer is Pd (OAc)
2/ P
t-Bu
3, Pd (OAc)
2/ PCy
3, PdCl
2dppf or Pd (PPh
4)
3.
invention beneficial effect:
The mode that the present invention selects one kettle way reinforced, the moment of lithium reagent is generated at bromo-derivative and metallic lithium, just caught by corresponding borane reagent, solve the problem that lithium reagent synthesizes the transformation period in different solvents, expanded simultaneously and adopted metallic lithium to participate in the use range of reaction solvent.Select the halogen borane reagent of large steric hindrance, this reagent can a very convenient step prepare, and simultaneously boron nitrogen key stability is comparatively strong, even if temperature reaction, is carrying out after lithium reagent replaces with halogen boron, also can not forming the by product of secondary replacement.
In conjunction with both advantage above, this inventive method substrate universality is strong, all can carry out in the solvent of general cold condition and common applicable amplification, reaction yield is high, product stability is strong, also diversity can derive, provides the novel borane reagent that may be used for linked reaction of a class.
Embodiment
embodiment 1
Compound MeB (N
i-Pr
2)
2synthesis:
Under argon shield; in the there-necked flask being furnished with Dropping feeder; after adding metallic lithium (0.21 molar weight) and 2-methyltetrahydrofuran 20 milliliters; be cooled to-20 DEG C; start to drip monobromethane (0.1 mole) and two (N, N-di-isopropyl) boron bromide (0.11 mole) is dissolved in 150 milliliters of 2-methyltetrahydrofuran solution.After being added dropwise to 15-20 milliliter at first, continue stir about 10-20 minute, reacting liquid temperature rises to-15 DEG C from-20 DEG C, now shows that reaction causes, then holding temperature is no more than-10 DEG C of continuation and is dropwised by surplus stock, and system has bromination lithium salts to generate gradually.Extract reaction solution detection no longer include monobromethane residue time, stopped reaction.Add saturated ammonium chloride cancellation, regulator solution pH value is 4-5.Separatory, water layer 2-methyltetrahydrofuran extracts once again, merges organic layer, and saturated common salt is washed.Evaporated under reduced pressure solvent, obtains crude product, obtains 20.1 grams of MeB (N after rectifying
i-Pr
2)
2.This product is colourless liquid, GC purity more than 98%, yield 89%.
embodiment 2
Compd E tB (N
i-Pr
2)
2synthesis:
Under argon shield; in the there-necked flask being furnished with Dropping feeder; after adding metallic lithium (0.22 mole) and methylene diethyl ether 20 milliliters; be cooled to-20 DEG C; start to drip monobromethane (0.1 mole) and two (N, N-di-isopropyl) boron bromide (0.1 mole) is dissolved in 150 milliliters of methylene diethyl ether solution.After being added dropwise to 15-20 milliliter at first, continue stir about 10-20 minute, reacting liquid temperature rises to-16 DEG C from-20 DEG C, now shows that reaction causes, then holding temperature is no more than-10 DEG C of continuation and is dropwised by surplus stock, and system has bromination lithium salts to generate gradually.Extract reaction solution detection no longer include monobromethane residue time, stopped reaction.Carefully add saturated ammonium chloride cancellation, regulator solution pH value is 4-5.Separatory, water layer methylene diethyl ether extracts once again, merges organic layer, and saturated common salt is washed.Evaporated under reduced pressure solvent, obtains crude product, obtains 20.4 grams of EtB (N after rectifying
i-Pr
2)
2.This product is colourless to weak yellow liquid, GC purity more than 98%, yield 85%.
embodiment 3
Compound
synthesis:
Under argon shield; in the there-necked flask being furnished with Dropping feeder; after adding metallic lithium (0.24 mole) and tetrahydrofuran (THF) 25 milliliters; be cooled to-20 DEG C, start to drip Cyclopropyl Bromide (0.1 mole) and two (Pyrrolidine) boron chloride (0.12 mole) is dissolved in 150 milliliters of tetrahydrofuran solutions.After being added dropwise to 15-20 milliliter at first, continue stir about 10-20 minute, reacting liquid temperature rises to-16 DEG C from-20 DEG C, now shows that reaction causes, then holding temperature is no more than-10 DEG C of continuation and is dropwised by surplus stock, and system has bromination lithium salts to generate gradually.Extract reaction solution detection reaction complete, without Cyclopropyl Bromide residue, stopped reaction.Carefully add saturated ammonium chloride cancellation, regulator solution pH value is 5-6.Add separatory after ethyl acetate, water layer is extracted with ethyl acetate once again, merges organic layer, and saturated common salt is washed.Evaporated under reduced pressure solvent, after continuing rectification under vacuum, obtain purity more than 98% target product 23.7 grams, yield 81%, HNMR structure meets.
embodiment 4
Compound
synthesis:
Under argon shield; in the there-necked flask being furnished with Dropping feeder; after adding metallic lithium (0.2 mole) and glycol dimethyl ether 20 milliliters; be cooled to-15 DEG C, start to drip bromobenzene (0.1 mole) and two (six hydrogen piperidines) boron bromide (0.11 mole) is dissolved in 150 milliliters of ethylene glycol dimethyl ether solutions.After being added dropwise to 15-20 milliliter at first, continue stir about 10-20 minute, reacting liquid temperature rises to-11 DEG C from-15 DEG C, now shows that reaction causes, then holding temperature is no more than-5 DEG C of continuation and is dropwised by surplus stock, and system has bromination lithium salts to generate gradually.Extract reaction solution detection no longer include bromobenzene residue time, stopped reaction.Add saturated ammonium chloride cancellation, regulator solution pH value is 4-5.Add separatory after ethyl acetate, water layer is extracted with ethyl acetate once again, merges organic layer, and saturated common salt is washed.Evaporated under reduced pressure solvent, then after underpressure distillation, oil pump continues to vacuumize 1-2 hour again, obtains purity more than 98% target product 19.7 grams, and yield 77%, HNMR structure meets.
embodiment 5
Compound
synthesis:
Under argon shield; in the there-necked flask being furnished with Dropping feeder; after adding metallic lithium (0.21 mole) and methyl tertiary butyl ether 20 milliliters; be cooled to-20 DEG C, start to drip 3 bromo thiophene (0.1 mole) and two (morpholine) boron chloride (0.12 mole) is dissolved in 150 milliliters of t-butyl methyl ether solution.After being added dropwise to 15-20 milliliter at first, continue stir about 10-20 minute, reacting liquid temperature rises to-14 DEG C from-20 DEG C, now shows that reaction causes, then holding temperature is no more than-10 DEG C of continuation and is dropwised by surplus stock, and system has bromination lithium salts to generate gradually.Extract reaction solution detection no longer include 3 bromo thiophene residue time, stopped reaction.Add saturated ammonium chloride cancellation, regulator solution pH value is 4-5.Add separatory after ethyl acetate, water layer is extracted with ethyl acetate once again, merges organic layer, and saturated common salt is washed.Evaporated under reduced pressure solvent, then after underpressure distillation, oil pump continues to vacuumize 1-2 hour again, obtains purity more than 98% target product 20.7 grams, and yield 78%, HNMR structure meets.
embodiment 6
The synthesis (application example) of ethyl-boron dihydroxide:
Under nitrogen protection, by the EtB (N obtained in above-described embodiment 2
i-Pr
2)
2be dissolved in 65 milliliters of 2-methyltetrahydrofurans, control temperature 40 DEG C to 50 DEG C, be added dropwise in 10% salt aqueous acid gradually, after dropwising, insulated and stirred reacts 1 hour, and now detecting pH is 2-3.Cooling layering, water layer 2-methyltetrahydrofuran extracts once again, merges organic layer, after solvent evaporated, adds normal heptane making beating, after filtration, naturally dries and obtain white plates crystal ethyl-boron dihydroxide 5.9 grams, yield 94%, HNMR purity 97%.
embodiment 7
The synthesis (application example) of cyclopropylboronic acid pinacol ester:
Under nitrogen protection, the product obtained is dissolved in 70 milliliters of tetrahydrofuran (THF)s, is warming up to backflow in above-described embodiment 3, start the tetrahydrofuran solution being added dropwise to pinacol (0.85 mole) gradually.In whole process, keep the weak backflow of solution.In dropping process, have Pyrrolidine to generate gradually, after dropwising, continue stirred at reflux condition and react 1 hour, it is complete that GC detects raw material reaction.After cooling, after the complete solvent of underpressure distillation and Pyrrolidine, obtain colourless transparent liquid cyclopropylboronic acid pinacol ester 12.4 grams after the distillation that continues to heat up, yield 91%, GC:99.2%, HNMR structure meets.
embodiment 8
The synthesis (application example) of 3-tolylthiophene:
Under nitrogen protection; dioxane 220 milliliters is added in reaction flask; subsequently the product obtained in above-described embodiment 5, Glacial acetic acid potassium (1.95 moles) and bromobenzene (0.80 mole) are added, after stirring, finally by 3% mol catalyst PdCl
2dppf adds.Then, reaction mixture is warming up to 100 DEG C gradually, and maintains this temperature stirring reaction 3-5 hour.Above-mentioned reaction solution is in reaction process, and color deepens black gradually, and it is complete that GC detects raw material reaction.After cooling, diatomite filtration, filtrate decompression is distilled to dry, obtains 3-tolylthiophene 7.7 grams after rapid column chromatography, and yield 62%, HNMR structure meets.
Claims (8)
1. the technique of one pot process boron amide compounds, is characterized in that: by anhydrous solvent, bromo-derivative RBr and XBY
2after three's mixing, be slowly added dropwise in the anhydrous solvent containing metallic lithium, in dropping process, holding temperature is at-20 ~ 20 DEG C, when in reaction solution, temperature rise is more than more than 3 DEG C, remaining all added complete, maintain-20 ~ 40 DEG C of reaction 3-8h subsequently, detection reaction is complete, add saturated ammonium chloride and adjust PH=4-6, separate organic layer, water layer extracts once again, merges organic layer, saturated common salt water washing, obtains the boron amide compounds RBY of purity more than 98% after underpressure distillation solvent
2; Described R is alkyl or aryl; Described XBY
2middle X is chlorine or bromine, and Y is Diisopropylamine, diisobutylamine, two cyclopropylamines, Pyrrolidine, six hydrogen piperidines or morpholines.
2. the technique of one pot process boron amide compounds according to claim 1, is characterized in that: in described R, alkyl is selected from methyl, ethyl, sec.-propyl, cyclopropyl, normal-butyl, isobutyl-, cyclopentyl or cyclohexyl; In described R aryl be selected from phenyl, neighbour// p-methylphenyl, neighbour// p-methoxyphenyl, neighbour// to fluorophenyl, neighbour// rubigan, neighbour// to bromophenyl, 2/3-position furans, 2/3-position thiophene, N-methyl-4-pyrazoles or N-benzyl-4-pyrazoles.
3. the technique of one pot process boron amide compounds according to claim 1, is characterized in that: anhydrous solvent is selected from tetrahydrofuran (THF), 2-methyltetrahydrofuran, methyl tertiary butyl ether, cyclopentyl-methyl ether, glycol dimethyl ether or methylene diethyl ether.
4. the technique of one pot process boron amide compounds according to claim 1, is characterized in that: described RBr, XBY
2be 1:1-1.2:2-2.4 with the mol ratio of metallic lithium.
5. one of the application of the boron amide compounds of technique synthesis according to claim 1-4 any one, is characterized in that: boron amide compounds RBY
2dissolve in organic solvent, after adding acid hydrolysis, obtain boric acid compound RB (OH)
2.
6. acid is selected from hydrochloric acid, sulfuric acid or acetic acid; Hydrolysis temperature is 40 ~ 100 DEG C.
7. the application two of boron amide compounds of technique synthesis according to claim 1-4 any one, is characterized in that: boron amide compounds RBY
2react with glycol and generate boric acid ester, glycol is selected from: pinacol, neopentyl glycol or pyrocatechol; Operational condition is: by RBY
2add 1-1.1 equivalent weight diols, be slowly warming up to back flow reaction 1-3 hour, after distillation, obtain corresponding boric acid ester.
8. the application three of boron amide compounds of technique synthesis according to claim 1-4 any one, is characterized in that: boron amide compounds RBY
2with 1-1.05 equivalent bromobenzene or iodobenzene under 1-3% mole of palladium catalyst and 1.5-3.0 equivalent alkali exist, 80 ~ 120 DEG C of linked reactions obtain PhR; Alkali is selected from: KOAc, K
3pO
4or K
2cO
3; Solvent is selected from: dioxane, dimethyl sulfoxide (DMSO), tetrahydrofuran (THF) or glycol dimethyl ether; Palladium catalyst is selected from Pd (OAc)
2/ P
t-Bu
3, Pd (OAc)
2/ PCy
3, PdCl
2dppf or Pd (PPh
4)
3.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105566368A (en) * | 2016-01-11 | 2016-05-11 | 沧州普瑞东方科技有限公司 | Synthesis method of N-substituted piperidine-4-borate |
| CN105503926B (en) * | 2016-01-10 | 2017-04-26 | 沧州普瑞东方科技有限公司 | Method for synthetizing vinyl boronic acid ester |
| CN107892699A (en) * | 2017-12-17 | 2018-04-10 | 沧州普瑞东方科技有限公司 | A kind of synthesis technique of the boric acid of pyridine 4 |
| CN107987097A (en) * | 2017-12-17 | 2018-05-04 | 沧州普瑞东方科技有限公司 | The synthesis technique of 2,6- dichloropyridine -4- boric acid pinacol esters |
| CN107987096A (en) * | 2017-12-17 | 2018-05-04 | 沧州普瑞东方科技有限公司 | A kind of method of synthesis 2- aldehyde radicals furans -4- boric acid pinacol esters |
| CN109456350A (en) * | 2018-12-23 | 2019-03-12 | 沧州普瑞东方科技有限公司 | Dibenzofurans/thiophene -4- boric acid synthetic method |
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| CN105503926B (en) * | 2016-01-10 | 2017-04-26 | 沧州普瑞东方科技有限公司 | Method for synthetizing vinyl boronic acid ester |
| CN105566368A (en) * | 2016-01-11 | 2016-05-11 | 沧州普瑞东方科技有限公司 | Synthesis method of N-substituted piperidine-4-borate |
| CN107892699A (en) * | 2017-12-17 | 2018-04-10 | 沧州普瑞东方科技有限公司 | A kind of synthesis technique of the boric acid of pyridine 4 |
| CN107987097A (en) * | 2017-12-17 | 2018-05-04 | 沧州普瑞东方科技有限公司 | The synthesis technique of 2,6- dichloropyridine -4- boric acid pinacol esters |
| CN107987096A (en) * | 2017-12-17 | 2018-05-04 | 沧州普瑞东方科技有限公司 | A kind of method of synthesis 2- aldehyde radicals furans -4- boric acid pinacol esters |
| CN107987096B (en) * | 2017-12-17 | 2020-06-05 | 沧州普瑞东方科技有限公司 | Method for synthesizing 2-aldehyde furan-4-boronic acid pinacol ester |
| CN109456350A (en) * | 2018-12-23 | 2019-03-12 | 沧州普瑞东方科技有限公司 | Dibenzofurans/thiophene -4- boric acid synthetic method |
| CN109456350B (en) * | 2018-12-23 | 2021-04-16 | 沧州普瑞东方科技有限公司 | Synthetic method of dibenzofuran/thiophene-4-boric acid |
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