CN102786421A - Method of preparing integral generation polypropyleneimine dendrimer by reducing cyano group - Google Patents
Method of preparing integral generation polypropyleneimine dendrimer by reducing cyano group Download PDFInfo
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- CN102786421A CN102786421A CN2012102903367A CN201210290336A CN102786421A CN 102786421 A CN102786421 A CN 102786421A CN 2012102903367 A CN2012102903367 A CN 2012102903367A CN 201210290336 A CN201210290336 A CN 201210290336A CN 102786421 A CN102786421 A CN 102786421A
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Abstract
The invention discloses a method of preparing a primary amine compound by reducing a cyano group. The method is characterized in that the primary amine compound is integral generation PPI (Polypropyleneimine) dendrimer. The method comprises a step of reducing half generation PPI dendrimer in alkaline solution with sodium borohydride under normal pressure by taking Raney Ni as a catalyst under an alkaline condition, wherein the reaction is performed in the solution; the mass ratio of the Raney Ni to the half generation PPI is 1:1-7.5:1; and the molar ratio of the sodium borohydride to the cyano group in the half generation PPI is 1.5:1-4:1. The preparation method can be performed under normal pressure; and a product has the advantages of high yield and high primary amine content.
Description
Technical field
The present invention relates to a kind of method for preparing primary amine, be specifically related to a kind of cyanic acid that reduces and prepare the method for primary amine.
Background technology
Vestolen PP 7052 imines (PPI) dendrimer has high-regularity; There is a large amount of cavitys in intramolecule; There are a plurality of amino in molecular surface, and the unique chemical structure makes Vestolen PP 7052 imines (PPI) be with a wide range of applications at pharmaceutical chemistry, sensitive materials, nano material and catalytic field.At present, the more sophisticated compound method of PPI is to be nucleus with the diamines, is repeating unit with the vinyl cyanide; Alternately repeat Michael reaction (Michael Addition; The N-alkylation) and the hydro-reduction of polynitriles reaction, obtaining terminal half for cyanic acid respectively is PPI (the 1.0G PPI in integer generation of primary amino for PPI (0.5G PPI, 1.5G PPI etc.) and end; 2.0G PPI etc.), to obtain increase (building-up process is as shown in Figure 1) of dendritic structure.Two crucial steps are that fine Michael reaction of aminocompound and propylene and polynitriles are reduced to primary amine under the effect of catalyzer, repeat the growth that these two steps can realize branch sub-branch, hole and ring.
Polynitriles needs under hyperbaric environment, to carry out in the reaction that is reduced to primary amine under the effect of catalyzer more in the prior art; Adopt Raney Ni in basic soln, hydrogenation of nitriles to be generated aminated compounds like a kind of prior art, have advantages of high catalytic activity, but in reaction, also generate a certain amount of by product secondary amine and tertiary amine; And this reaction needs (6MPa) under higher pressure just can be carried out; And the reaction times is grown (24h) (synthetic and sign, fine chemistry industry, 2001 of low algebraically Vestolen PP 7052 imines dendrimer; 18 (7), 414-416).Also have a kind of prior art to coat with lacquer former cobalt and 1,4-dioxane-water (10%) is reduction system (Wang Qin, the chemical reagent of many cyano compounds; 2005,27 (1), 8-10); Though the productive rate and the primary amine ratio of reaction are all higher, reaction still need just can be carried out (3MPa) under higher pressure.Another kind of prior art adopts Raney Co-Cr and water as reduction system (Meijler, Angew.Chem.Int.Ed.Engl., 1993; 32:1306-1308), successfully realized the conversion of polynitriles to primary amine, product need not to separate; The primary amine yield is high; But this reaction needs also that (4MPa) just can carry out under higher pressure, and the costing an arm and a leg of Raney Co, and is difficult for from the home market at present obtaining.
Also have in the prior art to be employed in and carry out hydro-reduction under the normal pressure; As adopt Peng Qinghuana and brill (II) salt reduction polynitriles (Vogtle, Angew.Chem.Int.Ed.Engl., 1992; 31:1571-1576); Be prone in the reaction process produce the side reaction that causes aminoethyl or aminopropyl side chain to break off, make product be difficult for purifying, the yield of primary amine is very low.
In the synthetic prior art of above Vestolen PP 7052 imines (PPI) dendrimer; Use catalyst n i and Co, polynitriles is reduced into primary amine through the high pressure catalytic hydrogenation, pressure that need be higher in hydrogenation (＞3MP) reach than the long reaction times (24h); To the requirement of conversion unit than higher; And have side reaction in the reaction process, the yield of primary amine is lower, and product is difficult for purifying.
Under normal pressure, successfully prepare 2.0 generation integer also do not appear in the newspapers for the example of Vestolen PP 7052 imines (PPI) dendrimer.
Summary of the invention
For one of solving the problems of the technologies described above, the invention provides a kind of cyanic acid that reduces and prepare the method for integer for the PPI dendrimer, under normal pressure, be catalyzer with Raney Ni, in basic soln with the sodium borohydride reduction half for the PPI dendrimer.
Preferably, preparation method of the present invention may further comprise the steps:
Half is mixed in solvent with Raney Ni for the PPI dendrimer, be preheated to temperature of reaction, obtain first reaction solution;
Peng Qinghuana is dissolved in pH greater than in 11 the strong alkali solution, obtains second reaction solution, second reaction solution is slowly splashed in first reaction solution mix, carry out reduction reaction, obtain the 3rd reaction solution;
Remove the Raney Ni in the 3rd reaction solution, obtain the 4th reaction solution;
Separate integer in the 4th reaction solution for the PPI dendrimer.
Preferably, described integer for the PPI dendrimer for being a generation, two generations or the three generations PPI dendrimer of core with quadrol, tetramethylenediamine, hexanediamine or diethylenetriamine.
Preferably, described Raney Ni and half are 1 for the mass ratio of PPI dendrimer: 1-7.5: 1.
Preferably, described Raney Ni and half are 1: 1,1.024: 1,6: 1 or 7.5: 1 for the mass ratio of PPI dendrimer.
Preferably, described Peng Qinghuana and half are 1.5 for the mol ratio of cyanic acid quantity in the PPI dendrimer: 1-4: 1.
Preferably, described Peng Qinghuana and half are 1.5: 1,3: 1 or 4: 1 for the mol ratio of cyanic acid quantity in the PPI dendrimer.
Preferably, temperature of reaction is 25-70 ℃.
Preferably, the reaction times is 3-4h.
Preferably, the method for removing the Raney Ni in the 3rd reaction solution is a suction filtration.
Preferably, separate integer in the 4th reaction solution for the method for PPI dendrimer for the solvent in the 4th reaction solution is concentrated, liquid concentrator is carried out organic extraction.
Preferably, the integer in described separation the 4th reaction solution for to remove gained the 4th reaction solution under reduced pressure solvent, obtains white solid for the method for PPI dendrimer; The white solid of gained is dissolved in the organic solvent, carries out suction filtration after the stirring at room, obtain filtrating, will filtrate concentrates, and gets integer for the PPI dendrimer.
Preferably, before removing the 4th reaction solution under reduced pressure solvent, regulate pH is the weakly alkaline of 9-10 to the integer in described separation the 4th reaction solution for the method for PPI dendrimer.
Preferably, described solvent is water, methyl alcohol, ethanol or 1, the 4-dioxane.
Beneficial effect of the present invention is: preparation method of the present invention carries out under normal pressure, and reaction conditions is gentle, less demanding to equipment.
Description of drawings
Fig. 1 is the synthetic route chart of PPI dendrimer.
Fig. 2 synthesizes the synoptic diagram of integer for the PPI dendrimer among the embodiment 3.
Fig. 3 is the 2.0G PPI of preparation among the embodiment 3
1H-NMR figure.
Fig. 4 is the 2.0G PPI of preparation among the embodiment 3
13C-NMR figure.
Fig. 5 is the 2.0G PPI of preparation among the embodiment 4
1H-NMR figure.
Embodiment
The invention provides a kind of method for preparing integer for the PPI dendrimer, under normal pressure, is catalyzer with Raney Ni, in basic soln with the sodium borohydride reduction half for the PPI dendrimer.
Concrete steps comprise:
(1), half is mixed in solvent with Raney Ni for the PPI dendrimer, be preheated to temperature of reaction, obtain first reaction solution;
(2), Peng Qinghuana is dissolved in pH greater than in 11 the strong alkali solution, obtain second reaction solution, second reaction solution is slowly splashed into carry out hydrogenation in first reaction solution, obtain the 3rd reaction solution;
(3), the 3rd reaction solution is carried out suction filtration, remove Raney Ni, obtain the 4th reaction solution;
(4), gained the 4th reaction solution removes solvent under reduced pressure, obtains white solid, and the white solid of gained is dissolved in the organic solvent, carries out suction filtration after the stirring at room, obtains filtrating, will filtrate concentrates, must integer for the PPI dendrimer.
Among the present invention prepared integer for the PPI dendrimer for being a generation, two generations or the three generations PPI dendrimer of core with quadrol, tetramethylenediamine, hexanediamine or diethylenetriamine.
The Raney Ni that uses is Powdered, and particle diameter is below 40 orders, like 50 μ m, 150 μ m or 20 orders.
The effect of the solvent in the step (1) is that half is dissolved for the PPI dendrimer, and described solvent can adopt water, methyl alcohol, ethanol or 1,4-dioxane.
Strong alkali solution in the step (2) can adopt NaOH solution or KOH solution.
Suction filtration can be regulated the weakly alkaline that pH is 9-10 earlier before going out behind the catalyzer Raney Ni and removing the 4th reaction solution under reduced pressure solvent in the step (4), can regulate with HCl solution.
White solid also contains inorganic salt (mainly being NaCl or KCl) except containing integer for the PPI molecule in the step (4), extracts with organic solvent, obtains integer for the PPI molecule, and used organic solvent can be chloroform.
Below in conjunction with specific embodiment and accompanying drawing, the present invention is further set forth.
Embodiment 1
Reduction reaction temperature is set to room temperature (25 ℃).
In a 250ml twoport flask that magneton is housed, add 0.5 generation PPI2.0g, Raney Ni (50 μ m) 2.0g and methyl alcohol 13ml, room temperature (25 ℃) stirs and obtains reaction solution 1; The 1.51g Peng Qinghuana is dissolved in the 8MNaOH aqueous solution of 16ml, obtains reaction solution 2; Reaction solution 2 is dropwise joined in the twoport flask that reaction solution 1 is housed, and the control rate of addition carries out reacting balance; After about 3h dropwises, under room temperature, stir, TLC (Thin Layer Chromatography, thin-layer chromatography) follows the tracks of and to react 1h consuming time when raw material 0.5 generation PPI disappears, and stopped reaction obtains reaction solution 3; Reaction solution 3 is carried out suction filtration, remove Raney Ni, obtain filtrating 1, remove under reduced pressure in the filtrating 1 behind most of solvent, with the CHCl of 50ml
3Extract 4 times, extraction liquid is concentrated, get 1.0 generation PPI (2.0G PPI) 1.8g, be faint yellow oily material.Warp
1H NMR analyzes, and confirms that the faint yellow oily material of gained is 1.0G PPI.
Embodiment 2
Reduction reaction temperature is set to 50 ℃.
In a 250ml twoport flask that magneton is housed, add 0.5 generation PPI5.0g, Raney Ni (50 μ m) 5.12g and methyl alcohol 32ml, stir also and under the oil bath condition, be heated to 50 ℃, obtain reaction solution 1; The 3.78g Peng Qinghuana is dissolved in the 8M NaOH aqueous solution of 40ml, obtains reaction solution 2; Reaction solution 2 is dropwise joined in the twoport flask that reaction solution 1 is housed, and the control rate of addition carries out reacting balance; After about 2h dropwises, stir down in 50 ℃, TLC follows the tracks of and reacts 1h consuming time when raw material 0.5 generation PPI disappears, and stopped reaction obtains reaction solution 3; Reaction solution 3 is carried out suction filtration, remove Raney Ni, obtain filtrating 1, remove under reduced pressure in the filtrating 1 behind most of solvent, with the CHCl of 100ml
3Extract 3 times, extraction liquid is concentrated, get 1.0 generation PPI (2.0GPPI) 4.8g, be faint yellow oily material.
Gained 1.0G PPI is carried out 1H NMR analyze, the gained chemical shift is following: CDCl
3, 500MHz, δ :=1.28 (m, 4H), 1.37 (m, 8H), 2.34 (m, 4H), 2.40 (t, J=7.0Hz, 8H), 2.67 (t, J=7.0Hz, 8H) ppm, the faint yellow oily material of gained is 1.0G PPI.
Embodiment 3
The quality that Raney Ni is set is 6 times of 1.5G PPI quality, and the Peng Qinghuana mole number is that 3 times of cyanic acid mole number carry out the synthetic of 2.0G PPI among the 1.5G PPI, and synthesis path is as shown in Figure 2.
In a 250ml twoport flask that magneton is housed, add 1.5 generation PPI2.0g, Raney Ni (50 μ m, Aladdin) 12.0g and methyl alcohol 50ml, stir also and under the oil bath condition, be heated to 70 ℃, obtain reaction solution l; The 2.45g Peng Qinghuana is dissolved in the 8MNaOH aqueous solution of 14ml, obtains reaction solution 2; Reaction solution 2 is dropwise joined in the twoport flask that reaction solution 1 is housed, and the control rate of addition carries out reacting balance; Dropwise the back and stir down in 70 ℃, reaction 3h, TLC (Thin Layer Chromatography, thin-layer chromatography) follow the tracks of reaction and display raw material 1.5 generation PPI and exhaust, and stop reduction reaction, are cooled to room temperature, obtain reaction solution 3; Reaction solution 3 is carried out suction filtration, remove Raney Ni, obtain filtrating 1, gained filtrating 1 usefulness 2M HCl regulates pH value, and making 1 the pH value of filtrating is 9-10, will filtrate 1 to remove solvent under reduced pressure, obtains white solid; The white solid of gained is dissolved in the CHCl of 200ml
3In, carry out suction filtration behind the stirring at room 1h, obtain filtrating 2; To filtrate 2 concentrates, 2.0 generation PPI (2.0G PPI), be faint yellow oily material, quality is 1.65g, yield is 79%.
Gained 2.0G PPI is carried out
1H NMR analyzes, and the gained chemical shift is following: CDCl
3, 500MHz, δ :=1.33 (m, 4H), 1.55 (m, 24H), 2.34 (m, 20H), 2.39 (m, 16H), 2.67 (t, J=6.5Hz, 16H) ppm (Fig. 3);
13C NMR analyzes, and the gained chemical shift is following: CDCl
3, 125MHz, δ=24.70,25.13,30.79,40.58,51.92,52.28,52.35,54.21ppm (Fig. 4), the faint yellow oily material of gained is 2.0G PPI.
Gained 2.0G PPI is measured primary amine groups content with primary amine group determination among the ISO9702 1996, calculate that primary amine content is 85% in the product.
Embodiment 4
The quality that Raney Ni is set is 7.5 times of 1.5G PPI quality, and the Peng Qinghuana mole number is that 4 times of cyanic acid mole number carry out the synthetic of 2.0G PPI among the 1.5GPPI.
In a 250ml twoport flask that magneton is housed, add 1.5 generation PPI2.0g, Raney Ni (50 μ m, Aladdin) 15.0g and methyl alcohol 50ml, stir also and under the oil bath condition, be heated to 70 ℃, obtain reaction solution 1; The 3.27g Peng Qinghuana is dissolved in the 8M NaOH aqueous solution of 14ml, obtains reaction solution 2; Reaction solution 2 is dropwise joined in the twoport flask that reaction solution 1 is housed, and the control rate of addition carries out reacting balance; Dropwise the back and stir down in 70 ℃, reaction 3h, TLC follow the tracks of reaction and display raw material 1.5 generation PPI and exhaust, and stop reduction reaction, are cooled to room temperature, obtain reaction solution 3; Reaction solution 3 is carried out suction filtration, remove Raney Ni, obtain filtrating 1, gained filtrating 1 usefulness 2M HCl regulates pH value, and making 1 the pH value of filtrating is 9-10, will filtrate 1 to remove solvent under reduced pressure, obtains white solid, the white solid of gained is dissolved in the CHCl of 200ml
3In, carry out suction filtration behind the stirring at room 1h, obtain filtrating 2; To filtrate 2 concentrates, 2.0 generation PPI (2.0G PPI), be faint yellow oily material, quality is 1.67g, yield is 80.2%.
Gained 2.0G PPI is carried out
1H NMR analyzes, and the gained chemical shift is following: CDCl
3, 500MHz, δ :=1.33 (m, 4H), 1.54 (m, 24H), 2.34 (t, J=7.0Hz, 20H), 2.39 (t, J=7.0Hz, 16H), 2.67 (t, J=7.0Hz, 16H) ppm (Fig. 5), the faint yellow oily material of gained is 2.0G PPI.
Gained 2.0G PPI is measured primary amine groups content with primary amine group determination among the ISO97021996, calculate that primary amine content is 90% in the product.
The consumption of Raney Ni and Peng Qinghuana is influential to the ratio of primary amine in the product in the reaction; As among embodiment 3 and the embodiment 4 during preparation 2.0 generation PPI dendrimers; At the consumption of Raney Ni 6 times of 1.5 generation PPI quality of cyano-containing; And when the Peng Qinghuana consumption was 3 times of institute's cyano-containing total mole number, the ratio of primary amine reached 85% in the product, further improves the consumption of Raney Ni and Peng Qinghuana; Be 7.5 times of 1.5 generation PPI quality of cyano-containing at the consumption of Raney Ni, and the Peng Qinghuana consumption when being 4 times of institute's cyano-containing total mole number in the product ratio of primary amine reach 90%.
It is understandable that; Although the present invention is a methyl alcohol at the solvent that half adopts during with Raney Ni mixing preheating for the PPI dendrimer; Yet; It will be understood by those skilled in the art that the solvent that half among the present invention adopts during with Raney Ni mixing preheating for the PPI dendrimer can also be water, ethanol or 1,4-dioxane.Although separating integer is chloroform for the used extraction solvent of PPI dendrimer, the extraction integer is not limited to chloroform for the employed organic solvent of PPI dendrimer.Although the particle diameter of used Raney Ni catalyzer is 50 μ m, the size of Raney Ni catalyzer is not limited to 50 μ m.The organic solvent that the solvent that described half adopts during with Raney Ni mixing preheating for the PPI dendrimer, extraction integer use for the PPI dendrimer, the size of Raney Ni do not produce materially affect to method of the present invention.
Above-described embodiment of the present invention does not constitute the qualification to protection domain of the present invention.Any modification of within spirit of the present invention and principle, being done, be equal to replacement and improvement etc., all should be included within the claim protection domain of the present invention.
Claims (10)
1. one kind is reduced cyanic acid and prepares the method for integer for the PPI dendrimer, it is characterized in that described method is under the normal pressure, is catalyzer with Raney Ni, in basic soln with the sodium borohydride reduction half for the PPI dendrimer.
2. reduction cyanic acid according to claim 1 prepares the method for integer for the PPI dendrimer, it is characterized in that, may further comprise the steps:
Half is mixed in solvent with Raney Ni for the PPI dendrimer, be preheated to temperature of reaction, obtain first reaction solution;
Peng Qinghuana is dissolved in pH greater than in 11 the strong alkali solution, obtains second reaction solution, second reaction solution is slowly splashed in first reaction solution mix, carry out reduction reaction, obtain the 3rd reaction solution;
Remove the Raney Ni in the 3rd reaction solution, obtain the 4th reaction solution;
Separate integer in the 4th reaction solution for the PPI dendrimer.
3. reduction cyanic acid according to claim 1 and 2 prepares the method for integer for the PPI dendrimer; It is characterized in that, described integer for the PPI dendrimer for being a generation, two generations or the three generations PPI dendrimer of core with quadrol, tetramethylenediamine, hexanediamine or diethylenetriamine.
4. reduction cyanic acid according to claim 1 and 2 prepares the method for integer for the PPI dendrimer, it is characterized in that, described Raney Ni and half are 1 for the mass ratio of PPI dendrimer: 1-7.5: 1.
5. reduction cyanic acid according to claim 4 prepares the method for integer for the PPI dendrimer, it is characterized in that, described Raney Ni and half are 1: 1,1.024: 1,6: 1 or 7.5: 1 for the mass ratio of PPI dendrimer.
6. reduction cyanic acid according to claim 1 and 2 prepares the method for integer for the PPI dendrimer, it is characterized in that, described Peng Qinghuana and half are 1.5 for the mol ratio of cyanic acid quantity in the PPI dendrimer: 1-4: 1.
7. reduction cyanic acid according to claim 6 prepares the method for integer for the PPI dendrimer, it is characterized in that, described Peng Qinghuana and half are 1.5: 1,3: 1 or 4: 1 for the mol ratio of cyanic acid quantity in the PPI dendrimer.
8. reduction cyanic acid according to claim 2 prepares the method for integer for the PPI dendrimer, it is characterized in that, temperature of reaction is 25-70 ℃.
9. reduction cyanic acid according to claim 2 prepares the method for integer for the PPI dendrimer, it is characterized in that, the reaction times is 3-4h.
10. reduction cyanic acid according to claim 2 prepares the method for integer for the PPI dendrimer, it is characterized in that, described solvent is water, methyl alcohol, ethanol or 1, the 4-dioxane.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103435814A (en) * | 2013-07-10 | 2013-12-11 | 中国科学院深圳先进技术研究院 | Non-viral genetic vector material and preparation method and application thereof, and brain-targeted gene transfer system and preparation method and application thereof |
| CN107216256A (en) * | 2017-05-19 | 2017-09-29 | 江苏斯威森生物医药工程研究中心有限公司 | A kind of synthetic method of N, N diisopropyl ethylenediamine |
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2012
- 2012-08-15 CN CN2012102903367A patent/CN102786421A/en active Pending
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| SIMON J. GRANT，ET AL.，: "Studies of pendant-arm macrocyclic ligands. Part 8. Synthesis of two pentaazamacrocycles based upon pyridine-containing tetraazamacrocycles with a single pendant co-ordinating 2-pyridylmethyl arm, and characterisation of their nickel(II), copper(II) and zi", 《J. CHEM. SOC., DALTON TRANS.》 * |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103435814A (en) * | 2013-07-10 | 2013-12-11 | 中国科学院深圳先进技术研究院 | Non-viral genetic vector material and preparation method and application thereof, and brain-targeted gene transfer system and preparation method and application thereof |
| CN103435814B (en) * | 2013-07-10 | 2015-09-16 | 中国科学院深圳先进技术研究院 | A kind of non-viral gene carrier material and its preparation method and application, brain targeting gene transmission system and its preparation method and application |
| CN107216256A (en) * | 2017-05-19 | 2017-09-29 | 江苏斯威森生物医药工程研究中心有限公司 | A kind of synthetic method of N, N diisopropyl ethylenediamine |
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Application publication date: 20121121 |