CN112679546A - Cyclic triazophos ligand compound and preparation method thereof - Google Patents
Cyclic triazophos ligand compound and preparation method thereof Download PDFInfo
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- CN112679546A CN112679546A CN202011550644.XA CN202011550644A CN112679546A CN 112679546 A CN112679546 A CN 112679546A CN 202011550644 A CN202011550644 A CN 202011550644A CN 112679546 A CN112679546 A CN 112679546A
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 47
- 239000003446 ligand Substances 0.000 title claims abstract description 33
- 125000004122 cyclic group Chemical group 0.000 title claims abstract description 30
- AMFGTOFWMRQMEM-UHFFFAOYSA-N triazophos Chemical compound N1=C(OP(=S)(OCC)OCC)N=CN1C1=CC=CC=C1 AMFGTOFWMRQMEM-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 48
- 238000006243 chemical reaction Methods 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- 229940126214 compound 3 Drugs 0.000 claims description 14
- -1 1-ethyl- (3-dimethylaminopropyl) Chemical group 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- ICSNLGPSRYBMBD-UHFFFAOYSA-N 2-aminopyridine Chemical compound NC1=CC=CC=N1 ICSNLGPSRYBMBD-UHFFFAOYSA-N 0.000 claims description 10
- 229940125782 compound 2 Drugs 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 229940125904 compound 1 Drugs 0.000 claims description 9
- 229940125898 compound 5 Drugs 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 239000012074 organic phase Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 6
- ASOKPJOREAFHNY-UHFFFAOYSA-N 1-Hydroxybenzotriazole Chemical compound C1=CC=C2N(O)N=NC2=C1 ASOKPJOREAFHNY-UHFFFAOYSA-N 0.000 claims description 5
- 239000012280 lithium aluminium hydride Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 3
- 238000004440 column chromatography Methods 0.000 claims description 3
- 239000012043 crude product Substances 0.000 claims description 3
- 239000003480 eluent Substances 0.000 claims description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 3
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- XVDBWWRIXBMVJV-UHFFFAOYSA-N n-[bis(dimethylamino)phosphanyl]-n-methylmethanamine Chemical compound CN(C)P(N(C)C)N(C)C XVDBWWRIXBMVJV-UHFFFAOYSA-N 0.000 claims description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 5
- 238000004090 dissolution Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 238000007363 ring formation reaction Methods 0.000 abstract description 2
- 238000005576 amination reaction Methods 0.000 abstract 1
- 125000006239 protecting group Chemical group 0.000 abstract 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- KUXDQQMEFBFTGX-UHFFFAOYSA-N [N].P Chemical class [N].P KUXDQQMEFBFTGX-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a cyclic triazophos ligand compound, which has the structural formula as follows:
the invention also discloses a preparation method of the cyclic triazophos ligand compound, which mainly comprises four steps of amination, Boc protecting group removal, reduction and cyclization. The technical scheme disclosed by the invention provides the triazophos ligand compound with high stability and good catalytic activity.
Description
Technical Field
The invention relates to the field of organic synthesis, in particular to a cyclic triazophos ligand compound and a preparation method thereof.
Background
In recent years, nitrogen and phosphorus elements are introduced into one compound simultaneously, and the reaction activity of organic reaction is improved by utilizing the synergistic coordination effect of the nitrogen and phosphorus elements. Meanwhile, molecules containing nitrogen and phosphorus elements are generally unstable, particularly nitrogen and phosphorus elements connected with alkyl chains, and nitrogen-phosphine compounds connected with aromatic rings are generally prepared in the prior art to improve the stability of the molecules. However, the activity of nitrogen and phosphorus atoms is reduced due to delocalization of the aromatic ring pi electrons.
The nitrogen-or phosphorus-containing ligand compounds disclosed in the prior art are therefore not highly catalytically active.
Disclosure of Invention
One of the technical problems to be solved by the present invention is to provide a cyclic triazophos ligand compound.
The invention solves the technical problems through the following technical scheme:
a cyclic triazophos ligand compound of the formula:
preferably, the synthetic route of the cyclic triazophos ligand is as follows:
the second technical problem to be solved by the present invention is to provide a method for preparing a cyclic triazophos ligand compound,
the invention solves the technical problems through the following technical scheme:
a preparation method of a cyclic triazophos ligand compound comprises the following steps:
(1) preparation of compound 2:
respectively adding the compound 1, 2-aminopyridine and 1-hydroxybenzotriazole into a round-bottom flask, and adding dichloromethane and N, N' -dimethylformamide into the round-bottom flask to dissolve the mixture;
adding 1-ethyl- (3-dimethylaminopropyl) carbonyldiimine hydrochloride into the solution, stirring at room temperature, reacting while stirring, concentrating a reaction system to dryness, and performing post-treatment operation to obtain a compound 2;
(2) preparation of compound 3:
adding a compound 2, 5mL of trifluoroacetic acid and dichloromethane into a round-bottom flask, stirring the reaction system at room temperature, concentrating to dryness, adding dichloromethane into the residue to dissolve, adjusting the pH to alkalescence by using 1mol/L sodium hydroxide solution, and performing aftertreatment operation to obtain a compound 3;
(3) preparation of compound 4:
respectively adding a compound 3 and 1, 4-dioxane into a round-bottom flask, uniformly mixing, adding lithium aluminum hydride into the solution in an ice bath, slowly heating to room temperature while stirring, heating to reflux, carrying out reflux reaction, cooling to room temperature, and carrying out aftertreatment on the reaction liquid to obtain a compound 4;
(4) preparation of compound 5:
respectively adding a compound 4, tri (dimethylamino) phosphine and toluene into a round-bottom flask, refluxing the reaction system under the protection of nitrogen, cooling to room temperature after reflux reaction, and concentrating the reaction system to dryness to obtain a compound 5, wherein the compound 5 is a cyclic tri-nitrogen phosphine ligand compound.
Preferably, the molar ratio of compound 1 to 2-aminopyridine in step (1) is 1: 1.5;
the molar weight ratio of the compound 1 to the 1-hydroxybenzotriazole in the step (1) is 1: 1.0;
the molar weight ratio of the compound 1 to the 1-ethyl- (3-dimethylaminopropyl) carbonyldiimine hydrochloride in the step (1) is 1: 1.55.
preferably, the pH of the solution is adjusted to 8 in said step (2).
Preferably, the molar weight ratio of the compound 3 to the lithium aluminum hydride in the step (3) is 1: 5.
preferably, after stirring for 17 hours at room temperature in the step (1), concentrating the reaction system to be dry, adding ethyl acetate to dissolve, washing with saturated sodium carbonate solution and saturated saline water twice respectively, drying the organic phase with magnesium sulfate, and concentrating to be dry; separating the crude product by column chromatography, wherein the eluent is dichloromethane and acetone.
Preferably, in the step (2), the residue is extracted by dichloromethane, and the organic phase is dried by anhydrous sodium sulfate and concentrated to dryness to obtain the compound 3.
Preferably, in the step (4), after the reaction system is refluxed for 12 hours under the protection of nitrogen, the reaction system is cooled to room temperature.
Compared with the prior art, the invention has the following advantages:
the invention discloses a cyclic triazophos ligand compound, which enables an alkyl N-P compound to become stable after cyclization by improving the structure of the compound, has higher yield in each step of reaction and provides guarantee for synthesizing the compound in large quantity.
Therefore, the technical scheme disclosed by the invention provides the triazophone ligand compound with high stability and good catalytic activity.
Drawings
FIG. 1 is an H-NMR spectrum of a compound 2 prepared in example 3 of the present invention;
FIG. 2 is an H-NMR spectrum of Compound 3 prepared in example 3 of the present invention;
FIG. 3 is an H-NMR spectrum of compound 4 prepared in example 3 of the present invention;
FIG. 4 is an H-NMR spectrum of a cyclic triazophos ligand Compound 4 prepared in example 3 of the present invention.
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1A Cyclic triazophos ligand Compound
This example discloses a cyclic triazophos ligand compound, which has the following structural formula:
example 2 synthetic route to Cyclic triazophos ligand Compounds
The synthetic route of the cyclic triazophos ligand compound is as follows:
EXAMPLE 3 preparation of Cyclic triazophos ligand Compounds
(1) Preparation of compound 2: a50 mL round-bottom flask was charged with 2.15g (10mmol) of Compound 1, 1.4g (15mmol) of 2-aminopyridine, and 1.36g (10mmol) of 1-hydroxybenzotriazole, respectively, and 27.2mL of dichloromethane and 2.8mL of N, N' -dimethylformamide were added to the flask to dissolve the above mixture. To the above solution was added 2.88g (155mmol) of 1-ethyl- (3-dimethylaminopropyl) carbodiimides hydrochloride and stirred at room temperature for 17 hours. The reaction system was concentrated to dryness, dissolved in 50mL of ethyl acetate, washed twice with 50mL of saturated sodium carbonate solution and saturated brine, respectively, and the organic phase was dried over magnesium sulfate and concentrated to dryness. Column chromatography of the crude product, eluent dichloromethane: acetone is 30:1 (V/V). 1.6g of Compound 2 are obtained, yield 58.4%.
(2) Preparation of compound 3: a25 mL round-bottom flask was charged with 1.34g (4.6mmol) of Compound 2, and dissolved by adding 5mL of trifluoroacetic acid and 5mL of dichloromethane. The reaction system was stirred at room temperature for 30min, concentrated to dryness, and the residue was dissolved in 20mL of dichloromethane and adjusted to pH 8 with 1mol/L sodium hydroxide solution. The mixture was extracted with 20mL of dichloromethane and the organic phase was dried over anhydrous sodium sulphate and concentrated to dryness to give 0.82g of compound 3 in 94% yield.
(3) Preparation of compound 4: a25 mL round-bottom flask was charged with 0.82g (4.3mmol) of Compound 3 and 15mL of 1, 4-dioxane, respectively, and mixed well. 0.8g (21.5mmol) of lithium aluminum hydride was added to the above solution while cooling on ice, and after slowly raising the temperature to room temperature with stirring, the mixture was refluxed for 1 hour. Cooling to room temperature, adding 20mL of saturated sodium sulfate solution, filtering, extracting the filtrate with 20mL of dichloromethane, drying the organic phase with anhydrous sodium sulfate, and concentrating to dryness to obtain 0.74g of compound 4 with a yield of 98%.
(4) Preparation of compound 5: a25 mL round-bottom flask was charged with 0.55g (3.1mmol) of Compound 4, 0.74mL (4.7mmol) of tris-dimethylaminophosphine, and 6mL of toluene, respectively, and the reaction was refluxed for 12 hours under a nitrogen atmosphere. Cooling to room temperature, and concentrating the reaction system to dryness to obtain 0.7g of compound 5, wherein the compound 5 is a cyclic triazophos ligand compound, and the yield is 91%.
The structure of the compound 2-5 prepared above was identified, and the H-NMR spectra of the compound 2-5 are shown in FIGS. 1-4.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (9)
1. A cyclic triazophos ligand compound having the structural formula:
2. a cyclic triazophos ligand compound according to claim 1, wherein the synthetic route of the cyclic triazophos ligand is as follows:
3. a process for preparing a cyclic triazophos ligand compound according to any one of claims 1 to 2, comprising the steps of:
(1) preparation of compound 2:
respectively adding the compound 1, 2-aminopyridine and 1-hydroxybenzotriazole into a round-bottom flask, and adding dichloromethane and N, N' -dimethylformamide into the round-bottom flask to dissolve the mixture;
adding 1-ethyl- (3-dimethylaminopropyl) carbonyldiimine hydrochloride into the solution, stirring at room temperature, reacting while stirring, concentrating a reaction system to dryness, and performing post-treatment operation to obtain a compound 2;
(2) preparation of compound 3:
adding a compound 2, 5mL of trifluoroacetic acid and dichloromethane into a round-bottom flask, stirring the reaction system at room temperature, concentrating to dryness, adding dichloromethane into the residue to dissolve, adjusting the pH to alkalescence by using 1mol/L sodium hydroxide solution, and performing aftertreatment operation to obtain a compound 3;
(3) preparation of compound 4:
respectively adding a compound 3 and 1, 4-dioxane into a round-bottom flask, uniformly mixing, adding lithium aluminum hydride into the solution in an ice bath, slowly heating to room temperature while stirring, heating to reflux, carrying out reflux reaction, cooling to room temperature, and carrying out aftertreatment on the reaction liquid to obtain a compound 4;
(4) preparation of compound 5:
respectively adding a compound 4, tri (dimethylamino) phosphine and toluene into a round-bottom flask, refluxing the reaction system under the protection of nitrogen, cooling to room temperature after reflux reaction, and concentrating the reaction system to dryness to obtain a compound 5, wherein the compound 5 is a cyclic tri-nitrogen phosphine ligand compound.
4. The method for producing a cyclic triazophos ligand compound according to claim 3,
the molar weight ratio of the compound 1 to the 2-aminopyridine in the step (1) is 1: 1.5;
the molar weight ratio of the compound 1 to the 1-hydroxybenzotriazole in the step (1) is 1: 1.0;
the molar weight ratio of the compound 1 to the 1-ethyl- (3-dimethylaminopropyl) carbonyldiimine hydrochloride in the step (1) is 1: 1.55.
5. the method for producing a cyclic triazophos ligand compound according to claim 3,
and (3) adjusting the pH value of the solution to 8 in the step (2).
6. The method for producing a cyclic triazophos ligand compound according to claim 3, wherein the molar ratio of compound 3 to lithium aluminum hydride in the step (3) is 1: 5.
7. the method for preparing a cyclic triazophos ligand compound according to claim 4, wherein in the step (1), after stirring at room temperature for 17 hours, the reaction system is concentrated to dryness, ethyl acetate is added for dissolution, the reaction system is washed twice with a saturated sodium carbonate solution and a saturated common salt solution, respectively, the organic phase is dried over magnesium sulfate, and concentrated to dryness; separating the crude product by column chromatography, wherein the eluent is dichloromethane and acetone.
8. The method for preparing a cyclic triazophos ligand compound according to claim 5, wherein the residue in step (2) is extracted with dichloromethane, and the organic phase is dried over anhydrous sodium sulfate and concentrated to dryness to obtain compound 3.
9. The method for producing a cyclic triazophos ligand compound according to claim 3, wherein in the step (4), the reaction system is refluxed for 12 hours under nitrogen atmosphere and then cooled to room temperature.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999052915A1 (en) * | 1998-04-10 | 1999-10-21 | Chemi S.P.A. | Chiral phosphorated ligands useful in catalysts |
| WO2003010174A1 (en) * | 2001-07-23 | 2003-02-06 | Wisconsin Alumini Research Foundation | Diazaphosphacycles |
| CN111269147A (en) * | 2020-01-14 | 2020-06-12 | 浙江工业大学 | Chiral phosphine nitrogen phosphine ligand and chiral metal organic coordination complex and application thereof |
-
2020
- 2020-12-24 CN CN202011550644.XA patent/CN112679546A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999052915A1 (en) * | 1998-04-10 | 1999-10-21 | Chemi S.P.A. | Chiral phosphorated ligands useful in catalysts |
| WO2003010174A1 (en) * | 2001-07-23 | 2003-02-06 | Wisconsin Alumini Research Foundation | Diazaphosphacycles |
| CN111269147A (en) * | 2020-01-14 | 2020-06-12 | 浙江工业大学 | Chiral phosphine nitrogen phosphine ligand and chiral metal organic coordination complex and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| NICOLAS TOSELLI ET AL.: "New P-stereogenic triaminophosphines and their derivatives: synthesis, structure, conformational study, and application as chiral ligands", 《TETRAHEDRON: ASYMMETRY》 * |
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