CN104478928A - Alpha-diphenylphosphinesubstituted alpha, beta-unsaturated carboxylatecompound as well as preparation and application methods - Google Patents
Alpha-diphenylphosphinesubstituted alpha, beta-unsaturated carboxylatecompound as well as preparation and application methods Download PDFInfo
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- CN104478928A CN104478928A CN201410820320.1A CN201410820320A CN104478928A CN 104478928 A CN104478928 A CN 104478928A CN 201410820320 A CN201410820320 A CN 201410820320A CN 104478928 A CN104478928 A CN 104478928A
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Abstract
The invention belongs to the technical field of organic synthesis, and particularly relates to an alpha-diphenylphosphinesubstituted alpha, beta-unsaturated carboxylatecompound as well as preparation and application methods. A simple reagent phosphorus ylide and aromatic aldehyde are taken as raw materials, a Wittig reactionand a phosphorus ylidereaction of carboxylate ester are performed, a halogenating agent is added, halogenated alpha, beta-unsaturated carboxylate ester is generated and reacts with diphenylphosphine under catalysis of a palladium reagent, and a target product with high yield is generated. Carboxylate of the compound can be transformed into other groups, so that a novel organicphosphine catalyst is generated.
Description
Technical field
The invention belongs to technical field of organic synthesis, the α that particularly a kind of α-diphenylphosphine replaces, beta-unsaturated carboxylic acid ester cpds and preparation and application method thereof.
Background technology
Organo phosphorous compounds not only has a wide range of applications in the fine chemistry industries such as agricultural chemicals and medicine, since past 40 years, in chiral synthesize field, organo phosphorous compounds more and more comes into one's own, much organic phosphine reagent is applied in various catalyzed reaction by excavation, and some has been applied in industrial production, as BINAP, (the Science such as JosiPhos and Du-Phos, 1992,258,584; Acc.Chem.Res.1983,16,106; J.Am.Chem.Soc.1991,113,8518.)
The phosphino-compound that different skeleton connects often shows different catalytic performances, and some reaction demonstrates exclusive characteristic.The present invention relates to the α that α-diphenylphosphine replaces, beta-unsaturated carboxylic acid ester structure.This structure double bond one end connects phosphine and carboxylicesters, and ester group can derive the group for other, and this compounds can generate doubly linked phosphine-heteroatomic compound further.During catalyzed reaction, phosphorus and the large heteroatoms of electronegativity and metal-complexing, produce katalysis.Have been found that such skeleton controls two coordinating groups by double bond one end at present, regulate the structure of its metal complex, in catalyzed reaction, demonstrate good catalytic performance.Only there is the example (ZL200910087763.3) of several relevant report.The α that the α that the present invention relates to-diphenylphosphine replaces, beta-unsaturated carboxylic acid ester cpds there is not yet bibliographical information, can transform preparation doubly linked phosphino--heteroatoms catalyzer further by them.
Summary of the invention
Not enough for prior art, the invention provides the α that a kind of α-diphenylphosphine replaces, beta-unsaturated carboxylic acid ester cpds and preparation and application method thereof.
The α that α-diphenylphosphine replaces, beta-unsaturated carboxylic acid ester cpds, this structural formula of compound is as follows:
Wherein Ar is aromatic base or heterocyclic aromatic base, and R is alkyl or aromatic base.
Described Ar is Ph (phenyl), p-MePh (p-methylphenyl), p-MeOPh (p-methoxyphenyl), p-FPh (to fluorophenyl), p-ClPh (rubigan), m-BrPh (bromophenyl), 2-thienyl, 5-thiotolene base, 2-furyl, 5-methyl-furyl or 2-naphthyl; Described R is CH
3or CH
2cH
3.
The α that α-diphenylphosphine replaces, the preparation method of beta-unsaturated carboxylic acid ester cpds, is characterized in that, comprises the steps:
(1) α of alpha-halogen, the preparation of beta-unsaturated carboxylic acid ester cpds: react by phosphorus ylide III and corresponding aromatic aldehyde the α generating alpha-halogen under suitable condition, beta-unsaturated carboxylic acid ester cpds; Phosphorus ylide III is prepared by halogenated acetic acids ester and triphenylphosphine according to usual method preparation.(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 cpds: in the presence of a catalyst by the α of alpha-halogen, beta-unsaturated carboxylic acid ester cpds and diphenylphosphine are obtained by reacting the α that a kind of α-diphenylphosphine replaces, beta-unsaturated carboxylic acid ester cpds.In existing bibliographical information, be only diphenylphosphine and aryl halide generation linked reaction, finally obtain triaryl phosphine compound, the present invention first by the linked reaction of this reactive applications to thiazolinyl halogen and phosphine, and obtains phosphinocarboxylic acid's ester of double bond skeleton.(with reference to Journal ofOrganometallic Chemistry 2002,645,14-26.)
The α of described alpha-halogen, the structure of beta-unsaturated carboxylic acid ester cpds is as follows:
Wherein said X is I, Cl, Br, is preferably I.
The structure of described phosphorus ylide III is as follows:
The α that described α-diphenylphosphine replaces, the preparation feedback flow process of beta-unsaturated carboxylic acid ester cpds is as follows:
Described step (1) is through Wittig reaction and halogenating agent reaction; In step (2), catalyzer is palladium salt catalyst.
The solvent used in described step (1) is inert solvent, as methylene dichloride, trichloromethane, toluene, benzene, tetrahydrofuran (THF) etc.; Halogenating agent is X
2molecule or NCS (N-chloro imide) or NBS (N-brominated imides) or NIS (N-iodo imide), wherein said X is I, Cl, Br, is preferably I; The mol ratio of halogenating agent and phosphorus ylide III is 1:1.1; Temperature of reaction is lower than room temperature, and-40 ~ 10 DEG C is optimal reaction temperature; Reaction times is 2 ~ 24 hours; Reaction is carried out in the basic conditions, in reaction system, add Na
2cO
3, NaHCO
3or K
2cO
3, Na
2cO
3, NaHCO
3or K
2cO
3addition be 1 ~ 10 times of phosphorus ylide III mol ratio.
The α of alpha-halogen in described step (2), the mol ratio of beta-unsaturated carboxylic acid ester and diphenylphosphine is 1:1; Catalyzer is PdCl
2, Pd (OAc)
2or Pd (PPh
3)
4, the α of catalyzer and alpha-halogen, the mol ratio of beta-unsaturated carboxylic acid ester is 1:125; Solvent is inert solvent, benzene, toluene, dimethylbenzene, methylene dichloride, tetrahydrofuran (THF), the α of solvent and alpha-halogen, and the mol ratio of beta-unsaturated carboxylic acid ester is 1:50 ~ 1:200; Add organic bases, as triethylamine, pyridine, piperidines, the α of organic bases and alpha-halogen, the mol ratio of beta-unsaturated carboxylic acid ester is 1.25:1; Temperature of reaction is 50 DEG C ~ 150 DEG C, 80 DEG C ~ 110 DEG C the bests.
The α that α-diphenylphosphine replaces, the application method of beta-unsaturated carboxylic acid ester cpds, the α that described α-diphenylphosphine replaces, beta-unsaturated carboxylic acid ester cpds is used as catalyst intermediate.Than being the potential organophosphorus ligand having significant application value at catalyzed side reaction mask such as formula IV and V, can prepare by through type I.
Beneficial effect of the present invention is:
The α that α in the present invention-diphenylphosphine replaces, beta-unsaturated carboxylic acid ester cpds is the compound having no bibliographical information, and simple synthetic method is efficient, and yield is high, and carboxylic acid ester groups can be transformed into other group, thus becomes new chiral phosphine catalyst ligand.Preparation method of the present invention, with simple reagent phosphorus ylide and aromatic aldehyde for raw material, selects suitable catalyzer to be obtained the organic phosphine compound be connected on double bond skeleton by two-step reaction height yield.The present invention achieves haloolefin and diphenylphosphine first and reacts and prepare doubly linked organic phosphine compound, transforms further and can prepare new organic phosphine catalyst ligand.
Embodiment
The invention provides the α that a kind of α-diphenylphosphine replaces, beta-unsaturated carboxylic acid ester cpds and preparation and application method thereof, below in conjunction with embodiment, the present invention will be further described.
The α that described α-diphenylphosphine replaces, beta-unsaturated carboxylic acid ester cpds is the one in following I-a ~ I-k:
I-a：Ar＝Ph，R＝CH
2CH
3；
I-b：Ar＝p-MePh，R
2＝CH
2CH
3；
I-c：Ar＝p-MeOPh，R
2＝CH
2CH
3；
I-d：Ar＝p-FPh，R
2＝CH
2CH
3；
I-e：Ar＝p-ClPh，R
2＝CH
2CH
3；
I-f：Ar＝m-BrPh，R
2＝CH
2CH
3；
I-g:Ar=2-thienyl, R
2=CH
2cH
3;
I-h:Ar=5-thiotolene base, R
2=CH
2cH
3;
I-i:Ar=2-furyl, R
2=CH
2cH
3;
I-j:Ar=5-methyl-furyl, R
2=CH
2cH
3;
I-k:Ar=2-naphthyl, R
2=CH
2cH
3;
The α that described I-a ~ I-k α-diphenylphosphine replaces, the formula II that beta-unsaturated carboxylic acid ester cpds is corresponding and formula III compound are labeled as II-a ~ II-k and III-a ~ III-k respectively successively.
Embodiment 1
The synthesis of 3-phenyl-2-bromopropylene acetoacetic ester (III-a):
At bromination triphenylphosphine ethyl acetate II-a (4.28g, 1.0mmol) (by document " Minute Organic Synthesis--the reaction in organic chemistry practice and synthesis ", Zhang Jinqi compiles, press of Nanjing University, P141) be dissolved in anhydrous methylene chloride, be chilled to-20 DEG C, add NBS (1.78g, 1.1mmol), stir 30 minutes, rise to stirred overnight at room temperature.Then K is added
2cO
3solid and phenyl aldehyde (1.06g, 1.0mmol), room temperature reaction 48 hours, suction filtration, collect filtrate, decompression removing organic solvent, after concentrated, column chromatography (sherwood oil: ethyl acetate (volume ratio)=5:1) obtains oily matter 1.8g, productive rate is 70.8%, and its nuclear magnetic data is as follows:
1H NMR(300MHz,CDCl
3):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 propenoate:
At bromination triphenylphosphine ethyl acetate II-a (4.28g, 1.0mmol) (can reference (" Minute Organic Synthesis--organic chemistry practice in reaction and synthesis ", Zhang Jinqi compiles, press of Nanjing University, P141) be dissolved in anhydrous methylene chloride, be chilled to-20 DEG C, add NIS (2.25g, 1.1mmol), stir 30 minutes, rise to stirred overnight at room temperature.Then K is added
2cO
3solid and phenyl aldehyde (1.06g, 1.0mmol), room temperature reaction 24 hours, suction filtration, collect filtrate, decompression removing organic solvent, after concentrated, column chromatography (sherwood oil: ethyl acetate (volume ratio)=6:1) obtains oily matter 2.4g, productive rate 79.5%, its nmr analysis data are as follows:
1H NMR(300MHz,CDCl
3):δ8.26(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 all can be prepared according to example 1 or example 2 working method, only aldehyde used is changed into corresponding aromatic aldehyde.
Embodiment 3
The synthetic method one of 3-phenyl-2-diphenylphosphino ethyl propenoate (I-a):
Compound 3-phenyl-2-bromopropylene acetoacetic ester (2.56g, 1.01mmol) is dissolved in toluene, then adds Pd (PPh
3)
4(0.0924g, 0.08mmol), triethylamine 0.5mL and diphenylphosphine (1.86g, 1mmol) is added, heat 24 hours in the oil bath of 100 DEG C, removal of solvent under reduced pressure, remaining solid diatomite filtration, filtrate is concentrated except desolventizing, then column chromatography (eluent, sherwood oil: ethyl acetate=10:1) be separated, obtain oily matter 0.21g, yield 58%.
Embodiment 4
The synthetic method two of 3-phenyl-2-diphenylphosphino ethyl propenoate (I-a):
Compound 3-phenyl-2-iodo ethyl propenoate (3.05g, 1.01mmol) is dissolved in dimethylbenzene, then adds Pd (OAc)
2(0.018g, 0.08mmol), add triethylamine 0.5mL and diphenylphosphine (1.86g, 1mmol), heat 4 ~ 24 hours in the oil bath of 100 DEG C, removal of solvent under reduced pressure, remaining solid diatomite filtration, then column chromatography (eluent, sherwood oil: ethyl acetate=10:1).Obtain oily matter 0.27g, yield 75%.
Compound I-b ~ I-k all can be prepared according to example 3 or example 4 working method.
Embodiment 5
The preparation of organophosphorus ligand IV and V:
Compound 3-phenyl-2-diphenylphosphino ethyl propenoate 0.56g (1.54mmol) is dissolved in ether, adds LiAlH
40.057g (1.55mmol), stirred at ambient temperature 12 hours, slow dropping 10mL saturated ammonium chloride solution cancellation reaction, add extraction into ethyl acetate 3 times (20mL × 3), merge organic layer, underpressure distillation is except desolventizing, and thick product does not need to be further purified, and is directly used in reaction below.Add tetrahydrofuran (THF) 30mL, then plus hydrogenated sodium 0.057g (1.54mmol) is refluxed 1 hour, is chilled to room temperature, adds methyl iodide 0.22g (1.55mmol), stirring reaction 6 hours at 50 DEG C, add saturated aqueous common salt cancellation reaction, underpressure distillation removes desolventizing, dichloromethane extraction three times, merge organic phase, anhydrous sodium sulfate drying, column chromatography obtains oily compound IV 0.21g, and yield is 42%.
Its nucleus magnetic hydrogen spectrum data:
1h NMR (300MHz, CDCl
3): δ 7.61 – 7.28 (m, 14H), 7.25 – 7.09 (m, 1H), 6.44 (d, J=10.5Hz, 1H), 3.55 (s, 2H, CH
2), 3.35 (s, 1H, CH
3).
Compound 3-phenyl-2-diphenylphosphino ethyl propenoate 0.56g (1.54mmol) is dissolved in ether, adds LiAlH
40.057g (1.55mmol), stirred at ambient temperature 12 hours, add saturated ammonium chloride solution cancellation reaction, add extraction into ethyl acetate 3 times (20mL × 3), merge organic layer, rotary evaporation is except desolventizing, and thick product does not need to be further purified, and is directly used in ensuing reaction.Add 30mL tetrahydrofuran (THF), be cooled to 0 DEG C, then Tosyl chloride 0.294g (1.55mmol) and pyridine 0.25g (3.16mmol) is added, stir under ice bath after 5 hours, add the tetrahydrofuran solution (concentration is 2mol/L) of 1.0mL dimethylamine, stirring at room temperature reacts 12 hours, add water and reaction is stopped, decompression removing organic solvent, dichloromethane extraction (20mL × 3), dried over sodium sulfate organic phase, concentrated, column chromatography obtains oily compound V 0.34g, and yield is 64%.
Nucleus magnetic hydrogen spectrum data (CDCl
3, 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, CH
2, 2H), 2.28 (s, 6H, CH
3).
The nuclear magnetic data of I-a ~ I-k compound of the present invention is as follows:
The nuclear magnetic data table of table 1 I-a ~ I-k compound of the present invention
。
Claims (9)
1. the α that α-diphenylphosphine replaces, beta-unsaturated carboxylic acid ester cpds, is characterized in that, this structural formula of compound is as follows:
Wherein Ar is aromatic base or heterocyclic aromatic base, and R is alkyl or aromatic base.
2. the α that a kind of α according to claim 1-diphenylphosphine replaces, beta-unsaturated carboxylic acid ester cpds, it is characterized in that, described Ar is Ph, p-MePh, p-MeOPh, p-FPh, p-ClPh, m-BrPh, 2-thienyl, 5-thiotolene base, 2-furyl, 5-methyl-furyl or 2-naphthyl; Described R is CH
3or CH
2cH
3.
3. the α that a kind of α as claimed in claim 1 or 2-diphenylphosphine replaces, the preparation method of beta-unsaturated carboxylic acid ester cpds, is characterized in that, comprises the steps:
(1) α of alpha-halogen, the preparation of beta-unsaturated carboxylic acid ester cpds: react by phosphorus ylide III and corresponding aromatic aldehyde the α generating alpha-halogen under suitable condition, beta-unsaturated carboxylic acid ester cpds;
(2) α that α-diphenylphosphine replaces, the preparation of beta-unsaturated carboxylic acid ester cpds: in the presence of a catalyst by the α of alpha-halogen, beta-unsaturated carboxylic acid ester cpds and diphenylphosphine are obtained by reacting the α that a kind of α-diphenylphosphine replaces, beta-unsaturated carboxylic acid ester cpds.
4. the α that a kind of α according to claim 3-diphenylphosphine replaces, the preparation method of beta-unsaturated carboxylic acid ester cpds, is characterized in that, the α of described alpha-halogen, and the structure of beta-unsaturated carboxylic acid ester cpds is as follows:
Wherein said X is I, Cl, Br.
5. the α that a kind of α according to claim 3-diphenylphosphine replaces, the preparation method of beta-unsaturated carboxylic acid ester cpds, is characterized in that, the structure of described phosphorus ylide III is as follows:
6. the α that a kind of α according to claim 3-diphenylphosphine replaces, the preparation method of beta-unsaturated carboxylic acid ester cpds, is characterized in that, described step (1) is through Wittig reaction and halogenating agent reaction; In step (2), catalyzer is palladium salt catalyst.
7. the α that a kind of α according to claim 3-diphenylphosphine replaces, the preparation method of beta-unsaturated carboxylic acid ester cpds, is characterized in that, the solvent used in described step (1) is inert solvent; Halogenating agent is X
2molecule or NCS or NBS or NIS, wherein said X is I, Cl, Br; The mol ratio of halogenating agent and phosphorus ylide III is 1:1.1; Temperature of reaction is lower than room temperature; Reaction times is 2 ~ 24 hours; Reaction is carried out in the basic conditions, in reaction system, add Na
2cO
3, NaHCO
3or K
2cO
3, Na
2cO
3, NaHCO
3or K
2cO
3addition be 1 ~ 10 times of phosphorus ylide III mol ratio.
8. the α that a kind of α according to claim 3-diphenylphosphine replaces, the preparation method of beta-unsaturated carboxylic acid ester cpds, it is characterized in that, the α of alpha-halogen in described step (2), the mol ratio of beta-unsaturated carboxylic acid ester and diphenylphosphine is 1:1; Catalyzer is PdCl
2, Pd (OAc)
2or Pd (PPh
3)
4, the α of catalyzer and alpha-halogen, the mol ratio of beta-unsaturated carboxylic acid ester is 1:125; Solvent is the α of inert solvent, solvent and alpha-halogen, and the mol ratio of beta-unsaturated carboxylic acid ester is 1:50 ~ 1:200; Add organic bases, the α of organic bases and alpha-halogen, the mol ratio of beta-unsaturated carboxylic acid ester is 1.25:1; Temperature of reaction is 50 DEG C ~ 150 DEG C.
9. the α that a kind of α as claimed in claim 1 or 2-diphenylphosphine replaces, the application method of beta-unsaturated carboxylic acid ester cpds, is characterized in that, the α that described α-diphenylphosphine replaces, and beta-unsaturated carboxylic acid ester cpds is used as catalyst intermediate.
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Cited By (2)
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| CN108727179A (en) * | 2018-07-18 | 2018-11-02 | 信阳师范学院 | A kind of alpha, beta-unsaturated ketone of α-allyl substitution, the synthetic method of ester or nitrile compound |
| CN113242852A (en) * | 2018-12-20 | 2021-08-10 | 帝斯曼知识产权资产管理有限公司 | Specific alpha, beta-unsaturated carboxylic acid esters |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108727179A (en) * | 2018-07-18 | 2018-11-02 | 信阳师范学院 | A kind of alpha, beta-unsaturated ketone of α-allyl substitution, the synthetic method of ester or nitrile compound |
| CN108727179B (en) * | 2018-07-18 | 2021-04-30 | 信阳师范学院 | Synthetic method of alpha-allyl substituted alpha, beta-unsaturated ketone, ester or nitrile compound |
| CN113242852A (en) * | 2018-12-20 | 2021-08-10 | 帝斯曼知识产权资产管理有限公司 | Specific alpha, beta-unsaturated carboxylic acid esters |
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