CN101624370B - Polymolybdate compounds and method of preparing same - Google Patents

Polymolybdate compounds and method of preparing same Download PDF

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CN101624370B
CN101624370B CN2008101405033A CN200810140503A CN101624370B CN 101624370 B CN101624370 B CN 101624370B CN 2008101405033 A CN2008101405033 A CN 2008101405033A CN 200810140503 A CN200810140503 A CN 200810140503A CN 101624370 B CN101624370 B CN 101624370B
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molybdic acid
acid compounds
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pyridine
dibromo
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牛云垠
吕效锐
侯红卫
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Zhengzhou University
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Abstract

The invention discloses polymolybdate compounds which have the general formula as follow, wherein R1 represents C4-C5 alkylidene, and the polymolybdate compounds are prepared through the reaction of the aqueous solution of [C14H18N2]2Br2 and [C15H20N2]2Br2 and the aqueous solution of (NH4)6Mo7O24.4H2O. The invention provides the polymolybdate compounds of [C14H18N2]2[Mo8O26] and [C15H2ON2]2[Mo8O26], and the two polymolybdate compounds can be used as catalysts, have advantages of high stability, insoluble in water, easy separation and strong repeatability and better catalytic performance on organic oxidation reaction. The invention prepares the two polymolybdate compounds by using the hydrothermal method and has simple preparation method, easily controllable process and low preparation cost.

Description

A kind of many molybdic acid compounds and preparation method thereof
Technical field
The present invention relates to a kind of compound, be specifically related to a kind of many molybdic acid compounds, relate to the preparation method of this compound simultaneously.
Background technology
The chemistry of polyacid compound (isopoly-acid and heteropolyacid and salt thereof) is an important research field in the chemistry, since Berzelius in 1862 finds first heteropolyacid salt---the 12-ammonium phosphomolybdate is so far, Chemistry of Polyacids has experienced nearly 100 years of development, become an important research field in the chemistry, the chemistry of relevant polyacid compound has had a lot of summaries.The research of early stage polyacid compound mainly concentrates on determining structure, from 1933 to nineteen sixty-eight heteropolyacid anions several frequently seen structure type be determined gradually, the common structure of fixed heteropolyacid anions is: Keggin, Dawson, Anderson, Silverton, five kinds of structure types of Waugh, the anion structure of most polyacid compounds all belongs to a kind of or derivatives thereof wherein, is the most stable and is easy to obtain with the Keggin structure in these five kinds of structure types.The Chemistry of Polyacids development except making progress to some extent, has also obtained breakthrough achievement in application facet rapidly aspect theoretical, in the various application of heteropoly compound, katalysis is most important.It is that catalyzer carries out the propylene hydration industrialization and succeeds that Japan in 1972 takes the lead in the 12-tungstosilicic acid, 1984 with 12-phospho-molybdic acid catalyzing iso-butane alkene hydration preparing tert-butanol, nineteen eighty-two is a catalyzer with the 12-phospho-molybdic acid, Methylacrylaldehyde gaseous oxidation system methacrylic acid, 1986 is 8 project industrialization successes such as catalyzer THF system polyoxy four methyne ethylene glycol with the 12-phospho-wolframic acid.
The most important advantage that polyacid compound is made catalyzer is their multifunctionality and the easy tonality of structure, and heteropolyacid has very strong Bronsted acidity on the one hand; Heteropoly compound is an oxygenant efficiently on the other hand, just showing quick reversible polyelectrons oxidation-reduction under mild conditions changes, add and self present very high proton mobile and " false liquid phase ", good stability can be used for homogeneous phase or inhomogeneous reaction, environmentally safe, selectivity is good, active high, corrosion is slight, so polyacid compound is widely used in catalyzer in the organic synthesis as a kind of efficient green catalyzer.Structural modification to polyacid compound comprises that mainly polyacid compound is as part by section Sauerstoffatom and bridging oxygen atom bonding or defect structure introducing metal ion formation title complex; Perhaps introduce organic cation as the counterion of polyoxoanion and form the polyacid super molecular compound, the polyacid compound of such novel structure is by continuous synthesis characterization.
Summary of the invention
A kind of many molybdic acid compounds that the object of the present invention is to provide.
Another object of the present invention is to provide a kind of preparation method of these many molybdic acid compounds.
For achieving the above object, the present invention by the following technical solutions: a kind of many molybdic acid compounds, its general formula is:
Figure S2008101405033D00021
R in the formula 1Alkylidene group for C4-C5.
Work as R 1During for the alkylidene group of C4, the structural formula of these many molybdic acid compounds is:
Figure S2008101405033D00022
Work as R 1During for the alkylidene group of C5, the structural formula of these many molybdic acid compounds is:
The preparation method of many molybdic acid compounds may further comprise the steps: (1) is with (NH 4) 6Mo 7O 244H 2O and 1,4-butane group two pyridine dibromo quaternary ammonium salt [C 14H 18N 2] 2Br 2Or 1,5-pentyl two pyridine dibromo quaternary ammonium salt [C 15H 20N 2] 2Br 2Difference formation solution soluble in water; (2) with [C 14H 18N 2] 2Br 2Or [C 15H 20N 2] 2Br 2The aqueous solution and (NH 4) 6Mo 7O 244H 2The aqueous solution of O, stirring reaction 20～30min produces white precipitate, and white precipitate and reaction soln are enclosed in the reactor, and control reaction temperature is 149～151 ℃, reacts 94～98 hours, is cooled to room temperature then, separates out crystal, and crystal is [C 14H 18N 2] 2[Mo 8O 26] or [C 15H 20N 2] 2[Mo 8O 26].
Described [C 14H 18N 2] 2Br 2[C 15H 20N 2] 2Br 2With (NH 4) 6Mo 7O 244H 2The amount of substance ratio of O is 1: 2.5～1: 3.
Speed when lowering the temperature in the described step (2) is 5～10 ℃/h.
Beneficial effect of the present invention is as follows: 1, the invention provides two kinds of many molybdic acid compound [C that do not appear in the newspapers 14H 18N 2] 2[Mo 8O 26] and [C 15H 20N 2] 2[Mo 8O 26], these two kinds of compound useful as catalysts, epoxidation, alcohols and the glycol oxidation that is mainly used in alkene becomes ketone and lactone, connects the fields such as oxygenolysis of two pure and mild alkene, have the advantages that stability is high, water insoluble, separation is easy and repeatability is strong, with respect to polyacid compound in the past, such product comprises long carbochain and good oxygen transfer function, so organic oxidizing reaction is had better catalytic performance, lays the first stone for further developing; 2, the present invention adopts hydrothermal method to prepare molybdic acid compound more than two kinds, and the preparation method is simple, and technology is controlled easily, the raw material ammonium paramolybdate aboundresources of use, is simple and easy to, and preparation cost is low.
Description of drawings
Fig. 1 is [C 14H 18N 2] 2[Mo 8O 26] the infrared colour spectrogram;
Fig. 2 is [C 15H 20N 2] 2[Mo 8O 26] the infrared colour spectrogram;
Fig. 3 is [C 14H 18N 2] 2[Mo 8O 26] structure iron;
Fig. 4 is [C 15H 20N 2] 2[Mo 8O 26] structure iron.
It is BRUKER TENSOR 27 type infrared spectrometers that infrared chromatography is analyzed used instrument, uses the KBr compressing tablet at 400～4000cm -1Test in the zone.
The used instrument of structure determination is that Japanese RAXIS-IV face of science is visited instrument.
Embodiment
Embodiment 1: many as described in the present invention molybdic acid compound [C 14H 18N 2] 2[Mo 8O 26], its preparation method is: (1) is with 0.0617g (0.05mmol) (NH 4) 6Mo 7O 244H 2O is dissolved in the 10mL water, 0.0561g (0.15mmol) [C 14H 18N 2] 2Br 2Be dissolved in the 10mL water, two kinds of aqueous solution are at room temperature mixed, stirring reaction 20min, produce white precipitate, white precipitate and reaction soln are enclosed in the reactor, control reaction temperature is 149 ℃, reacted 94 hours, speed with 10 ℃/h is cooled to room temperature then, separates out jade-green rhabdolith at the bottom of still, and rhabdolith is [C after testing 14H 18N 2] 2[Mo 8O 26].As follows through the infrared detection data: IR (KBr): 3745 (s), 1630 (s), 1483 (m), 1273 (m), 1173 (m), 937 (m), 864 (m), 622 (s) cm -1
Embodiment 2: many as described in the present invention molybdic acid compound [C 14H 18N 2] 2[Mo 8O 26], its preparation method is: (1) is with 0.0617g (0.05mmol) (NH 4) 6Mo 7O 244H 2O is dissolved in the 10mL water, 0.0468g (0.125mmol) [C 14H 18N 2] 2Br 2Be dissolved in the 10mL water, two kinds of aqueous solution are at room temperature mixed, stirring reaction 30min, produce white precipitate, white precipitate and reaction soln are enclosed in the reactor, control reaction temperature is 150 ℃, reacted 96 hours, speed with 8 ℃/h is cooled to room temperature then, separates out jade-green rhabdolith at the bottom of still, and rhabdolith is [C after testing 14H 18N 2] 2[Mo 8O 26].As follows through the infrared detection data: IR (KBr): 3745 (s), 1630 (s), 1483 (m), 1273 (m), 1173 (m), 937 (m), 864 (m), 622 (s) cm -1
Embodiment 3: many as described in the present invention molybdic acid compound [C 14H 18N 2] 2[Mo 8O 26], its preparation method is: (1) is with 0.0617g (0.05mmol) (NH 4) 6Mo 7O 244H 2O is dissolved in the 10mL water, 0.0524g (0.14mmol) [C 14H 18N 2] 2Br 2Be dissolved in the 10mL water, two kinds of aqueous solution are at room temperature mixed, stirring reaction 25min, produce white precipitate, white precipitate and reaction soln are enclosed in the reactor, control reaction temperature is 151 ℃, reacted 98 hours, speed with 5 ℃/h is cooled to room temperature then, separates out jade-green rhabdolith at the bottom of still, and rhabdolith is [C after testing 14H 18N 2] 2[Mo 8O 26].As follows through the infrared detection data: IR (KBr): 3745 (s), 1630 (s), 1483 (m), 1273 (m), 1173 (m), 937 (m), 864 (m), 622 (s) cm -1
Embodiment 4: many as described in the present invention molybdic acid compound [C 15H 20N 2] 2[Mo 8O 26], its preparation method is: (1) is with 0.0617g (0.05mmol) (NH 4) 6Mo 7O 244H 2O is dissolved in the 10mL water, 0.0582g (0.15mmol) [C 15H 20N 2] 2Br 2Be dissolved in the 10mL water, two kinds of aqueous solution are at room temperature mixed, stirring reaction 20min, produce white precipitate, white precipitate and reaction soln are enclosed in the reactor, control reaction temperature is 149 ℃, reacted 94 hours, speed with 10 ℃/h is cooled to room temperature then, and in separating out colourless transparent crystal at the bottom of the still and on the wall, colourless transparent crystal is [C after testing 15H 20N 2] 2[Mo 8O 26], as follows through the infrared detection data: IR (KBr): 3447 (s), 1632 (s), 1490 (m), 921 (s), 800 (s), 658 (s), 552 (m) cm -1
Embodiment 5: many as described in the present invention molybdic acid compound [C 15H 20N 2] 2[Mo 8O 26], its preparation method is: (1) is with 0.0617g (0.05mmol) (NH 4) 6Mo 7O 244H 2O is dissolved in the 10mL water, 0.0485g (0.125mmol) [C 15H 20N 2] 2Br 2Be dissolved in the 10mL water, two kinds of aqueous solution are at room temperature mixed, stirring reaction 30min, produce white precipitate, white precipitate and reaction soln are enclosed in the reactor, control reaction temperature is 150 ℃, reacted 96 hours, speed with 7 ℃/h is cooled to room temperature then, and in separating out colourless transparent crystal at the bottom of the still and on the wall, colourless transparent crystal is [C after testing 15H 20N 2] 2[Mo 8O 26], as follows through the infrared detection data: IR (KBr): 3447 (s), 1632 (s), 1490 (m), 921 (s), 800 (s), 658 (s), 552 (m) cm -1
Embodiment 6: many as described in the present invention molybdic acid compound [C 15H 20N 2] 2[Mo 8O 26], its preparation method is: (1) is with 0.0617g (0.05mmol) (NH 4) 6Mo 7O 244H 2O is dissolved in the 10mL water, 0.0543g (0.14mmol) [C 15H 20N 2] 2Br 2Be dissolved in the 10mL water, two kinds of aqueous solution are at room temperature mixed, stirring reaction 25min, produce white precipitate, white precipitate and reaction soln are enclosed in the reactor, control reaction temperature is 151 ℃, reacted 98 hours, speed with 5 ℃/h is cooled to room temperature then, and in separating out colourless transparent crystal at the bottom of the still and on the wall, colourless transparent crystal is [C after testing 15H 20N 2] 2[Mo 8O 26], as follows through the infrared detection data: IR (KBr): 3447 (s), 1632 (s), 1490 (m), 921 (s), 800 (s), 658 (s), 552 (m) cm -1
[the C that uses among the present invention 14H 18N 2] 2Br 2[C 15H 20N 2] 2Br 2Can adopt following method preparation: with BrCH 2(CH 2) 2CH 2Br or BrCH 2(CH 2) 3CH 2Br is dissolved in the pyridine, reacts down at 120 ℃ can make [C in 6 hours 14H 18N 2] 2Br 2Or [C 15H 20N 2] 2Br 2

Claims (6)

1. molybdic acid compound more than a kind, it is characterized in that: its general formula is:
R in the formula 1Alkylidene group for C4-C5.
2. many molybdic acid compounds as claimed in claim 1 is characterized in that: the structural formula of these many molybdic acid compounds is:
Figure FSB00000435648600012
3. many molybdic acid compounds as claimed in claim 1 is characterized in that: the structural formula of these many molybdic acid compounds is:
4. the preparation method of many molybdic acid compounds as claimed in claim 1, it is characterized in that: may further comprise the steps: (1) is with (NH 4) 6Mo 7O 244H 2O and 1,4-butane group two pyridine dibromo quaternary ammonium salts or 1,5-pentyl two pyridine dibromo quaternary ammonium salts are formation solution soluble in water respectively; (2) with 1,4-butane group two pyridine dibromo quaternary ammonium salts or 1, the aqueous solution of 5-pentyl two pyridine dibromo quaternary ammonium salts and (NH 4) 6Mo 7O 244H 2The aqueous solution of O, stirring reaction 20～30min produces white precipitate, and white precipitate and reaction soln are enclosed in the reactor, and control reaction temperature is 149～151 ℃, reacts 94～98 hours, is cooled to room temperature then, separates out crystal, and crystal is [C 14H 18N 2] 2[Mo 8O 26] or [C 15H 20N 2] 2[Mo 8O 26].
5. the preparation method of many molybdic acid compounds as claimed in claim 4 is characterized in that: described 1, and 4-butane group two pyridine dibromo quaternary ammonium salts and 1,5-pentyl two pyridine dibromo quaternary ammonium salts and (NH 4) 6Mo 7O 244H 2The amount of substance ratio of O is 1: 2.5～and 3.
6. as the preparation method of claim 4 or 5 described many molybdic acid compounds, it is characterized in that: the speed when lowering the temperature in the described step (2) is 5～10 ℃/h.
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