CN104478928B - The α that a kind of α diphenylphosphines replace, β unsaturated carboxylic ester compounds and its preparation and application method - Google Patents
The α that a kind of α diphenylphosphines replace, β unsaturated carboxylic ester compounds and its preparation and application method Download PDFInfo
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- CN104478928B CN104478928B CN201410820320.1A CN201410820320A CN104478928B CN 104478928 B CN104478928 B CN 104478928B CN 201410820320 A CN201410820320 A CN 201410820320A CN 104478928 B CN104478928 B CN 104478928B
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Abstract
The invention belongs to technical field of organic synthesis, the α that more particularly to a kind of α diphenylphosphines replace, β unsaturated carboxylic ester compounds and its preparation and application method.The present invention is reacted with simple reagent phosphorus ylide and aromatic aldehyde as raw material by Wittig, is reacted with the phosphorus ylide of carboxylate, halogenating agent is added, halo α, β esters of unsaturated carboxylic acids is generated, then react with diphenylphosphine under the catalysis of palladium reagent, generate target product in high yield.The carboxylic acid ester groups of the compounds of this invention can be transformed into other groups, so as to generate new organic phosphine catalyst.
Description
Technical field
The invention belongs to technical field of organic synthesis, the α that more particularly to a kind of α-diphenylphosphine replaces, beta-unsaturated carboxylic acid
Ester compounds and its preparation and application method.
Background technology
Organic phosphorus compound not only has a wide range of applications in the fine chemistry industry such as pesticide and medicine, past 40 years with
Come, in chiral synthesis field, organic phosphorus compound is increasingly taken seriously, and many organic phosphonate reagents are exploited and are applied to various urging
Change in reaction, some are had been applied in commercial production, such as BINAP, JosiPhos and Du-Phos etc. (Science, 1992,
258,584；Acc.Chem.Res.1983,16,106；J.Am.Chem.Soc.1991,113,8518.)
The phosphino- compound of different skeleton connections often shows different catalytic performances, shows solely in some reactions
Some characteristics.The present invention relates to the α that α-diphenylphosphine replaces, beta-unsaturated carboxylic acid ester structure.Structure double bond one end connection
Phosphine and carboxylate, ester group can derive as other groups, and such compound can further generate doubly linked phosphine-miscellaneous original
Sub- compound.During catalytic reaction, phosphorus and the big hetero atom of electronegativity and metal-complexing produce catalytic action.Have now been found that
Such skeleton controls two coordinating groups by double bond one end, adjusts the structure of its metal complex, shows in catalytic reaction
Go out good catalytic performance.The example (ZL200910087763.3) of only several relevant reports.α-hexichol according to the present invention
The α that base phosphine replaces, beta-unsaturated carboxylic acid ester compounds are there is not yet document report, can further convert preparation double bond by them
The phosphino- of connection-hetero atom catalyst.
Content of the invention
Not enough for prior art, the invention provides the α that a kind of α-diphenylphosphine replaces, beta-unsaturated carboxylic acid esterification conjunction
Thing and its preparation and application method.
The α that a kind of α-diphenylphosphine replaces, beta-unsaturated carboxylic acid ester compounds, the structural formula of compound are as follows：
Wherein Ar is aromatic radical or heterocyclic aromatic base, and R is alkyl or aromatic radical.
The Ar be Ph (phenyl), p-MePh (p-methylphenyl), p-MeOPh (p-methoxyphenyl), p-FPh (to fluorine
Phenyl), p-ClPh (rubigan), m-BrPh (m-bromophenyl), 2- thienyls, 5- methylthiophene bases, 2- furyls, 5- first
Base-furyl or 2- naphthyls；The R is CH3Or CH2CH3.
The α that a kind of α-diphenylphosphine replaces, the preparation method of beta-unsaturated carboxylic acid ester compounds, it is characterised in that include
Following steps：
(1) α of alpha-halogen, the preparation of beta-unsaturated carboxylic acid ester compounds：Existed with corresponding aromatic aldehyde by phosphorus ylide III
Under conditions of appropriate, reaction generates the α of alpha-halogen, beta-unsaturated carboxylic acid ester compounds；Phosphorus ylide III is according to usual way
Prepare and prepared by halogenated acetic acids ester and triphenylphosphine.(Can.J.Chem.1997,75,1315-1321；
Chem.Eur.J.2012,18,10362-10367.)
(2) α that α-diphenylphosphine replaces, the preparation of beta-unsaturated carboxylic acid ester compounds：In the presence of a catalyst by α-
The α of halo, beta-unsaturated carboxylic acid ester compounds obtain the α, β-unsaturation that a kind of α-diphenylphosphine replaces with diphenylphosphine reaction
Carboxylate compound.In existing document report, only there is coupling reaction with aryl halide in diphenylphosphine, finally obtain three
Aromatic yl phosphine compound, the present invention is first by the reactive applications to thiazolinyl halogen and the coupling reaction of phosphine, and obtains the phosphine of double bond skeleton
Yl carboxylic acid ester.(with reference to Journal of Organometallic Chemistry 2002,645,14-26.)
The α of the alpha-halogen, the structure of beta-unsaturated carboxylic acid ester compounds are as follows：
Wherein described X be I, Cl, Br, preferably I.
The structure of the phosphorus ylide III is as follows：
The α that the α-diphenylphosphine replaces, beta-unsaturated carboxylic acid ester compounds to prepare reaction process as follows：
Step (1) is reacted through Wittig reactions and halogenating agent；In step (2), catalyst is palladium salt catalyst.
Solvent used in step (1) is atent solvent, such as dichloromethane, chloroform, toluene, benzene, tetrahydrochysene
Furan etc.；Halogenating agent is X2(N- iodos acyl is sub- for molecule or NCS (N- chloro acid imides) or NBS (N- brominated imides) or NIS
Amine), wherein described X be I, Cl, Br, preferably I；Halogenating agent is 1 with the mol ratio of phosphorus ylide III：1.1；Reaction temperature
Room temperature is less than, -40～10 DEG C is optimal reaction temperature；Response time is 2～24 hours；Reaction is carried out in the basic conditions,
Add Na in reaction system2CO3, NaHCO3Or K2CO3, Na2CO3, NaHCO3Or K2CO3Addition be III mole of phosphorus ylide
1～10 times of ratio.
The α of alpha-halogen in step (2), beta-unsaturated carboxylic acid ester are 1 with the mol ratio of diphenylphosphine：1；Catalyst is
PdCl2, Pd (OAc)2Or Pd (PPh3)4, the α of catalyst and alpha-halogen, the mol ratio of beta-unsaturated carboxylic acid ester is 1：125；Solvent
For the α of atent solvent, benzene, toluene, dimethylbenzene, dichloromethane, tetrahydrofuran, solvent and alpha-halogen, beta-unsaturated carboxylic acid
The mol ratio of ester is 1：50～1：200；Addition organic base, the such as α of triethylamine, pyridine, piperidines, organic base and alpha-halogen, β-no
The mol ratio of saturated carboxylic acid ester is 1.25：1；Reaction temperature is 50 DEG C～150 DEG C, and 80 DEG C～110 DEG C optimal.
The α that a kind of α-diphenylphosphine replaces, the application process of beta-unsaturated carboxylic acid ester compounds, the α-diphenylphosphine take
The α in generation, beta-unsaturated carboxylic acid ester compounds are used as catalyst intermediate.Such as formula IV and V are potential in terms of catalytic reaction
There is the organophosphorus ligand of significant application value, can be prepared by Formulas I.
Beneficial effects of the present invention are：
The α that α-diphenylphosphine replaces in the present invention, beta-unsaturated carboxylic acid ester compounds are the compounds for having no document report,
Efficiently, high income, carboxylic acid ester groups can be transformed into other groups to simple synthetic method, so as to become new chiral phosphine catalyst
Part.The preparation method of the present invention, with simple reagent phosphorus ylide and aromatic aldehyde as raw material, selects appropriate catalyst to pass through
Two-step reaction obtains the organic phosphine compound being connected on double bond skeleton in high yield.The present invention achieves alkenyl halide and two first
Phenyl phosphine reaction prepares doubly linked organic phosphine compound, and further conversion can prepare new organic phosphine catalyst ligand.
Specific embodiment
The invention provides the α that a kind of α-diphenylphosphine replaces, beta-unsaturated carboxylic acid ester compounds and its preparation and application
Method, with reference to specific embodiment, the present invention will be further described.
The α that the α-diphenylphosphine replaces, beta-unsaturated carboxylic acid ester compounds are the one kind in following I-a～I-k：
I-a：Ar=Ph, R=CH2CH3；
I-b：Ar=p-MePh, R2=CH2CH3；
I-c：Ar=p-MeOPh, R2=CH2CH3；
I-d：Ar=p-FPh, R2=CH2CH3；
I-e：Ar=p-ClPh, R2=CH2CH3；
I-f：Ar=m-BrPh, R2=CH2CH3；
I-g：Ar=2- thienyls, R2=CH2CH3；
I-h：Ar=5- methylthiophene bases, R2=CH2CH3；
I-i：Ar=2- furyls, R2=CH2CH3；
I-j：Ar=5- methyl-furyls, R2=CH2CH3；
I-k：Ar=2- naphthyls, R2=CH2CH3；
The α that I-a～I-k α-diphenylphosphine replaces, the corresponding Formula II of beta-unsaturated carboxylic acid ester compounds and formula III
Compound is labeled as II-a～II-k and III-a～III-k respectively successively.
Embodiment 1
The synthesis of 3- phenyl -2- bromopropene acetoacetic esters (III-a)：
(document can be passed through in bromination triphenylphosphine ethyl acetate II-a (4.28g, 1.0mmol)《Minute Organic Synthesis -- have
Reaction and synthesis in chemical machine practice》, Zhang Jinqi compilings, publishing house of Nanjing University, P141) it is dissolved in anhydrous methylene chloride,
It is cooled to -20 DEG C, adds NBS (1.78g, 1.1mmol), stirs 30 minutes, be warmed to room temperature and be stirred overnight.It is subsequently adding K2CO3Solid
With benzaldehyde (1.06g, 1.0mmol), room temperature reaction 48 hours, sucking filtration, filtrate is collected, organic solvent is removed under reduced pressure, after concentration
Column chromatography (petroleum ether：Ethyl acetate (volume ratio)=5：1) grease 1.8g is obtained, and yield is 70.8%, and its nuclear magnetic data is such as
Under：
1H NMR(300MHz,CDCl3):δ7.39(s,1H),7.37–7.33(m,3H),7.32–7.27(m,2H),4.26
(q, J=7.1Hz, 2H), 1.24 (t, J=7.1Hz, 3H).
Embodiment 2
The synthesis of 3- phenyl -2- iodo ethyl acrylate：
Bromination triphenylphosphine ethyl acetate II-a (4.28g, 1.0mmol) (refer to document (《Minute Organic Synthesis --
Reaction and synthesis in organic chemistry practice》, Zhang Jinqi compilings, publishing house of Nanjing University, P141) it is dissolved in anhydrous methylene chloride
In, it is cooled to -20 DEG C, adds NIS (2.25g, 1.1mmol), stirs 30 minutes, be warmed to room temperature and be stirred overnight.It is subsequently adding K2CO3
Solid and benzaldehyde (1.06g, 1.0mmol), room temperature reaction 24 hours, sucking filtration are collected filtrate, organic solvent are removed under reduced pressure, dense
Column chromatography (petroleum ether after contracting：Ethyl acetate (volume ratio)=6：1) grease 2.4g, yield 79.5%, its nmr analysis are obtained
Data are as follows：
1H NMR(300MHz,CDCl3):δ 8.26 (s, 1H), 7.84 7.71 (m, 2H), 7.41 (dd, J=6.5,3.9Hz,
3H), 4.33 (q, J=7.1Hz, 2H), 1.37 (t, J=7.1Hz, 3H).
Compound III-b～III-k can be prepared according to example 1 or 2 operational approach of example, only changed aldehyde used
For corresponding aromatic aldehyde.
Embodiment 3
The synthetic method one of 3- phenyl -2- diphenylphosphino ethyl acrylate (I-a)：
Compound 3- phenyl -2- bromopropene acetoacetic esters (2.56g, 1.01mmol) is dissolved in toluene, Pd is subsequently adding
(PPh3)4(0.0924g, 0.08mmol), adds triethylamine 0.5mL and diphenylphosphine (1.86g, 1mmol), in 100 DEG C of oil bath
Middle heating 24 hours, removal of solvent under reduced pressure, remaining solid are filtered with kieselguhr, and filtrate concentration removes solvent, and then column chromatography (is washed
De- agent, petroleum ether：Ethyl acetate=10：1) separate, obtain grease 0.21g, yield 58%.
Embodiment 4
The synthetic method two of 3- phenyl -2- diphenylphosphino ethyl acrylate (I-a)：
Compound 3- phenyl -2- iodo ethyl acrylate (3.05g, 1.01mmol) is dissolved in dimethylbenzene, is subsequently adding
Pd(OAc)2(0.018g, 0.08mmol), adds triethylamine 0.5mL and diphenylphosphine (1.86g, 1mmol), in 100 DEG C of oil
Heat 4～24 hours in bath, removal of solvent under reduced pressure, remaining solid is filtered with kieselguhr, then column chromatography (eluant, petroleum ether：
Ethyl acetate=10：1).Obtain grease 0.27g, yield 75%.
Compound I-b～I-k can be prepared according to example 3 or 4 operational approach of example.
Embodiment 5
The preparation of organophosphorus ligand IV and V：
Compound 3- phenyl -2- diphenylphosphinos ethyl acrylate 0.56g (1.54mmol) is dissolved in ether, is added
LiAlH40.057g (1.55mmol), stirs 12 hours under room temperature, is slowly added dropwise 10mL saturated ammonium chloride solutions and reaction is quenched,
Add ethyl acetate to extract 3 times (20mL × 3), merge organic layer, vacuum distillation removes solvent, and crude product need not be further pure
Change, be directly used in following reaction.Tetrahydrofuran 30mL is added, then plus hydrogenated sodium 0.057g (1.54mmol) flows back 1 hour,
It is cooled to room temperature, adds iodomethane 0.22g (1.55mmol), stirring reaction 6 hours at 50 DEG C adds saturated aqueous common salt to be quenched instead
Should, vacuum distillation removes solvent, and dichloromethane is extracted three times, merges organic faciess, and anhydrous sodium sulfate drying, column chromatography obtain oily
Compound IV 0.21g, yield is 42%.
Its nucleus magnetic hydrogen spectrum data：1H NMR(300MHz,CDCl3):δ7.61–7.28(m,14H),7.25–7.09(m,1H),
6.44 (d, J=10.5Hz, 1H), 3.55 (s, 2H, CH2), 3.35 (s, 1H, CH3).
Compound 3- phenyl -2- diphenylphosphinos ethyl acrylate 0.56g (1.54mmol) is dissolved in ether, is added
LiAlH40.057g (1.55mmol), stirs 12 hours under room temperature, adds saturated ammonium chloride solution that reaction is quenched, adds acetic acid
Ethyl ester extracts 3 times (20mL × 3), merges organic layer, and rotary evaporation removes solvent, and crude product need not be further purified, directly
For ensuing reaction.30mL tetrahydrofurans are added, 0 DEG C is cooled to, is subsequently adding paratoluensulfonyl chloride 0.294g
(1.55mmol), with pyridine 0.25g (3.16mmol), after stirring 5 hours under ice bath, add the tetrahydrofuran of 1.0mL dimethylamine molten
Liquid (concentration is 2mol/L), is stirred at room temperature reaction 12 hours, and adding water stops reaction, and organic solvent, dichloromethane is removed under reduced pressure
Extraction (20mL × 3), sodium sulfate dry organic faciess, concentrate, and column chromatography obtains oily compound V 0.34g, and yield is 64%.
Nucleus magnetic hydrogen spectrum data (CDCl3, 300MHz)：δ 8.13 (d, J=20.9Hz, 1H), 7.52 7.28 (m, 15H),
6.26 (t, J=10.8Hz, 1H), 3.11 (2H, CH2, 2H), 2.28 (s, 6H, CH3).
The nuclear magnetic data of I-a～I-k compounds of the present invention is as follows：
The nuclear magnetic data table of 1 I-a～I-k compounds of the present invention of table
Claims (6)
1. the α that a kind of α-diphenylphosphine replaces, beta-unsaturated carboxylic acid ester compounds, it is characterised in that the structural formula of compound is such as
Under：
Wherein Ar is aromatic radical or heterocyclic aromatic base, and R is alkyl or aromatic radical.
2. the α that a kind of α according to claim 1-diphenylphosphine replaces, beta-unsaturated carboxylic acid ester compounds, its feature exist
In the Ar is Ph, p-MePh, p-MeOPh, p-FPh, p-ClPh, m-BrPh, 2- thienyl, 5- methylthiophene bases, 2- furan
Base, 5- methyl-furyls or 2- naphthyls；The R is CH3Or CH2CH3.
3. the α that a kind of α-diphenylphosphine replaces as claimed in claim 1 or 2, the preparation side of beta-unsaturated carboxylic acid ester compounds
Method, it is characterised in that comprise the steps：
(1) α of alpha-halogen, the preparation of beta-unsaturated carboxylic acid ester compounds：Given birth to corresponding fragrant aldehyde reaction by phosphorus ylide III
Into the α of alpha-halogen, beta-unsaturated carboxylic acid ester compounds；
(2) α that α-diphenylphosphine replaces, the preparation of beta-unsaturated carboxylic acid ester compounds：In the presence of a catalyst by alpha-halogen
α, the reaction of beta-unsaturated carboxylic acid ester compounds and diphenylphosphine obtains the α that a kind of α-diphenylphosphine replaces, beta-unsaturated carboxylic acid
Ester compounds；
The structure of the phosphorus ylide III is as follows：
The α of the alpha-halogen, the structure of beta-unsaturated carboxylic acid ester compounds are as follows：
Wherein described X be I, Cl, Br；
Step (1) is reacted through Wittig reactions and halogenating agent；In step (2), catalyst is palladium salt catalyst.
4. the α that a kind of α according to claim 3-diphenylphosphine replaces, the preparation side of beta-unsaturated carboxylic acid ester compounds
Method, it is characterised in that the solvent used in step (1) is atent solvent；Halogenating agent is NCS or NBS or NIS；Halogen
Mol ratio for reagent and phosphorus ylide is 1：1.1；Reaction temperature is less than room temperature；Response time is 2～24 hours；Reaction is in alkali
Property under the conditions of carry out, in reaction system add Na2CO3, NaHCO3Or K2CO3, Na2CO3, NaHCO3Or K2CO3Addition be
1～10 times of phosphorus ylide III mol ratios.
5. the α that a kind of α according to claim 3-diphenylphosphine replaces, the preparation side of beta-unsaturated carboxylic acid ester compounds
Method, it is characterised in that the α of alpha-halogen in step (2), beta-unsaturated carboxylic acid ester are 1 with the mol ratio of diphenylphosphine：1；Urge
Agent is PdCl2, Pd (OAc)2Or Pd (PPh3)4, the α of catalyst and alpha-halogen, the mol ratio of beta-unsaturated carboxylic acid ester is 1：
125；Solvent is atent solvent；With alpha-halogen α, the mol ratio ratio of beta-unsaturated carboxylic acid ester is 1：50～1：200；Add organic
The α of alkali, organic base and alpha-halogen, the mol ratio ratio of beta-unsaturated carboxylic acid ester is 1.25:1；Reaction temperature is 50 DEG C～150
℃.
6. the α that a kind of α-diphenylphosphine replaces as claimed in claim 1 or 2, the application side of beta-unsaturated carboxylic acid ester compounds
Method, it is characterised in that the α that the α-diphenylphosphine replaces, beta-unsaturated carboxylic acid ester compounds are used for preparing organophosphorus ligand, institute
The structural formula for stating organophosphorus ligand is as follows
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