CN101693211A - Transition metal catalyst and method for preparing picoline through adopting catalyst - Google Patents
Transition metal catalyst and method for preparing picoline through adopting catalyst Download PDFInfo
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- CN101693211A CN101693211A CN 200910236478 CN200910236478A CN101693211A CN 101693211 A CN101693211 A CN 101693211A CN 200910236478 CN200910236478 CN 200910236478 CN 200910236478 A CN200910236478 A CN 200910236478A CN 101693211 A CN101693211 A CN 101693211A
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- picoline
- transition
- metal catalyst
- acetylene
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- 239000003054 catalyst Substances 0.000 title claims abstract description 72
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 55
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 54
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 28
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 73
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 25
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 25
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims abstract description 9
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 claims abstract description 7
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims abstract description 6
- -1 silicyl Chemical group 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000001188 haloalkyl group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical group [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 27
- 239000013078 crystal Substances 0.000 description 12
- 239000012299 nitrogen atmosphere Substances 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 7
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 238000000589 high-performance liquid chromatography-mass spectrometry Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000010183 spectrum analysis Methods 0.000 description 6
- 238000003828 vacuum filtration Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- NNSSHRACPMBEBC-UHFFFAOYSA-N sodium penta-1,3-diene Chemical compound [Na+].CC=CC=[CH-] NNSSHRACPMBEBC-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 description 2
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 description 2
- NTSLROIKFLNUIJ-UHFFFAOYSA-N 5-Ethyl-2-methylpyridine Chemical compound CCC1=CC=C(C)N=C1 NTSLROIKFLNUIJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 125000005647 linker group Chemical group 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- HHWFLQDBOJJRGU-UHFFFAOYSA-N Cl[SiH2]Cl.C(C)C=1C=CCC1 Chemical compound Cl[SiH2]Cl.C(C)C=1C=CCC1 HHWFLQDBOJJRGU-UHFFFAOYSA-N 0.000 description 1
- MDBWHBUZZKYRTQ-UHFFFAOYSA-N [SiH4].CC=1C=CCC1 Chemical class [SiH4].CC=1C=CCC1 MDBWHBUZZKYRTQ-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003266 anti-allergic effect Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- SOYKEARSMXGVTM-UHFFFAOYSA-N chlorphenamine Chemical compound C=1C=CC=NC=1C(CCN(C)C)C1=CC=C(Cl)C=C1 SOYKEARSMXGVTM-UHFFFAOYSA-N 0.000 description 1
- 229960003291 chlorphenamine Drugs 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000010977 jade Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- UDBORWKCIDLNIG-UHFFFAOYSA-N sodium;1h-inden-1-ide Chemical compound [Na+].C1=CC=C2[CH-]C=CC2=C1 UDBORWKCIDLNIG-UHFFFAOYSA-N 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Landscapes
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention provides a transition metal catalyst, wherein the structural general formula of the catalyst is R1(Z)yMR2, wherein R1 and R2 are same or different, and are respectively substituted or unsubstituted cyclopentadienyl, substituted or unsubstituted indenyl and substituted or unsubstituted fluorenyl, wherein y is 0 or 1, Z is a linked group for connecting R1 and R2, and M is transition metal element. The invention further provides a method for preparing picoline, wherein the method comprises leading acetylene and methyl cyanide to contact for reacting under the existence of catalyst, and the catalyst is the transition metal catalyst supplied by the invention. The transition metal catalyst can effectively prompt methyl cyanide and acetylene to react for preparing 2-picoline.
Description
Technical field
The present invention relates to a kind of transition-metal catalyst, and adopt described transition-metal catalyst to prepare the method for picoline.
Background technology
Picoline is a kind of important chemical intermediate, also is the important source material of fine chemistry industry, can be used for a plurality of fields, for example, and as medicine and agricultural chemicals raw material.In picoline series, the 2-picoline can be used for producing long-acting semi-annular jade pendant amine, antiallergic chlorpheniramine, pesticide intermediate, feed and feed intermediate, also can be used for preparing the medicine of herbicide.At present, the method for producing the 2-picoline mainly contains two kinds, and a kind of is to refine the 2-picoline with coal tar, the major defect of this method be yield poorly, of poor quality, and tar resource is also quite poor; Another kind is to adopt the ammonium aldehyde method to produce the 2-picoline, this method reaction temperature is up to 550 ℃, and comprise pyridine, 3-picoline, 4-picoline, 2-methyl-5-ethylpyridine in the product, it is too near that the boiling point of these accessory substances differs, the product separating difficulty is bigger, thereby influences the quality of 2-picoline.
Summary of the invention
The objective of the invention is to be provided for preparing the transition-metal catalyst that production security is good and catalytic efficiency is high of picoline in order to overcome the existing above-mentioned defective that is used to prepare the catalyst of picoline.
Another object of the present invention provides the method that adopts described transition-metal catalyst to prepare picoline.
The invention provides a kind of transition-metal catalyst, wherein, the general structure of this catalyst is R
1(Z)
yMR
2, wherein, R
1And R
2For identical or different, and be respectively cyclopentadienyl group, replacement or unsubstituted indenyl, replacement or the unsubstituted fluorenyl of replacement separately; Y is 0 or 1; Z is for connecting R
1And R
2Linking group; M is a transition metal.
The present invention also provides a kind of method for preparing picoline, and wherein, described method is included in and under the existence of catalyst acetylene is contacted to react with acetonitrile, and described catalyst is above-mentioned transition-metal catalyst.
Adopt transition-metal catalyst catalyst provided by the invention carry out acetylene, when acetonitrile reaction prepares picoline, the catalytic efficiency height of catalyst, production security is good, helps separating of product and catalyst in the reaction system simultaneously.
The specific embodiment
The general structure of transition-metal catalyst provided by the invention is R
1(Z)
yMR
2, wherein, R
1And R
2Can be for identical or different, be preferably identical, and R
1And R
2Can be cyclopentadienyl group, replacement or unsubstituted indenyl, replacement or the unsubstituted fluorenyl that replaces respectively separately.Under the preferable case, R
1And R
2Be respectively methyl cyclopentadienyl, ethyl cyclopentadienyl group, propyl group cyclopentadienyl group, butyl cyclopentadienyl group, isopropyl cyclopentadienyl group, indenyl or fluorenyl separately.
In the general structure of described transition-metal catalyst, y is 0 or 1, is preferably 1; Z is for connecting R
1And R
2Linking group, and Z can be the linking group of various routines, for example can be Si (X
1)
2, C (X
2)
2, C (X
3)
2C (X
4)
2, CX
5=CX
6Or C (X
7)
2Si (X
8)
2, wherein, X
1, X
2, X
3, X
4, X
5, X
6, X
7And X
8Can be that alkyl, silicyl, haloalkyl, the carbon number of 1-10 is aryl, halogenated aryl or the halo aralkyl of 6-10 for hydrogen atom, halogen atom or carbon number respectively separately, being preferably alkyl, silicyl, haloalkyl, the carbon number that hydrogen atom or carbon number are 1-4 is aryl, halogenated aryl or the halo aralkyl of 6-8, and X
3And X
4Can be preferably identical for identical or different; X
5And X
6Can be preferably identical for identical or different; X
7And X
8Can be preferably identical for identical or different.Under further preferred situation, Z can be SiH
2, Si (CH
3)
2, Si (C
2H
5)
2, Si (C
3H
7)
2, CH
2, C (CH
3)
2, C (C
2H
5)
2, C (C
3H
7)
2, CH
2CH
2, C (CH
3)
2C (CH
3)
2, C (C
2H
5)
2C (C
2H
5)
2, CH=CH, C (CH
3)=C (CH
3), CH
2SiH
2Or C (CH
3)
2Si (CH
3)
2
In the general structure of described transition-metal catalyst, M is a transition metal, for example can most preferably be cobalt for manganese, vanadium, chromium, iron or cobalt.When the transition metal in the described transition-metal catalyst is cobalt, its catalytic performance is very excellent, for example, described transition-metal catalyst is adopting acetylene, acetonitrile to prepare to have very high catalytic performance in the reaction system of 2-picoline and reaction generates the selectivity of 2-picoline, thereby makes the conversion ratio of acetonitrile reach more than 95%.
Described transition-metal catalyst provided by the invention can be by making replacement the slaine of slaine, replacement or unsubstituted Cong base of slaine, replacement or unsubstituted indenyl of cyclopentadienyl group and the halide of transition metal, be 1.5-3 with the mol ratio: thus 1, at room temperature, reaction made in 1-4 hour under inert atmosphere such as nitrogen atmosphere; Perhaps can make general structure is R
1ZR
2Organic matter (R wherein
1, R
2With identical in Z and the above-mentioned transient metal complex) with the halide of transition metal, be 0.8-1.4 with the mol ratio: thus 1, at room temperature, reaction made in 1-4 hour under inert atmosphere such as nitrogen atmosphere.The solvent that uses in the described reaction is generally the nonaqueous solvents of the low and easy removal of boiling point, for example can be oxolane, and the described transition metal halide with respect to 1 mole, and the consumption of described solvent can be the 50-1000 milliliter, is preferably the 100-600 milliliter.
The present invention also provides a kind of method for preparing picoline, and wherein, described method is included in and under the existence of catalyst acetylene is contacted to react with acetonitrile, and described catalyst is a described transition-metal catalyst provided by the invention.
In the preferred case, described acetylene is the acetylene gas through deoxidation, processed, and acetylene is carried out the method for deoxidation, processed for conventionally known to one of skill in the art.
In described method provided by the invention, the mol ratio of the consumption of acetylene and acetonitrile can be 1-8: 1, be preferably 1-3.5: 1.The weight ratio of the consumption of described catalyst consumption and acetonitrile can be 1: 50-10000 is preferably 1: 400-5000.
The condition that described acetylene contacts with acetonitrile can comprise: temperature is 100-200 ℃, is preferably 110-160 ℃; The pressure of acetylene is 0.3-2MPa, is preferably 0.6-1.2MPa, and described acetylene pressure is meant the dividing potential drop of acetylene in the reaction system of acetylene and acetonitrile; Time is 2-5 hour, is preferably 3-4 hour.The haptoreaction of described acetylene and acetonitrile is preferably carried out under inert atmosphere, for example can carry out under nitrogen atmosphere.
The present invention is further detailed explanation with Comparative Examples by the following examples.
Embodiment 1
Present embodiment is used to illustrate described transition-metal catalyst provided by the invention.
At room temperature, under nitrogen atmosphere, with 2 moles tetramethyl-ring pentadienyl sodium and 1.2 moles anhydrous CoCl
2Be added in 300 milliliters the oxolane and carried out haptoreaction 2 hours, the mixture that obtains after the reaction is carried out vacuum filtration (absolute pressure is that vacuum is 0.01MPa), obtain atropurpureus crystal by evaporative crystallization then, learn that by nuclear magnetic resonance spectroscopy and mass spectral analysis described crystal is the transition-metal catalyst A1 shown in the structural formula 1
Structural formula 1
Embodiment 2
Present embodiment is used to illustrate described transition-metal catalyst provided by the invention.
At room temperature, under nitrogen atmosphere, with 2 moles indenyl sodium and 1.2 moles anhydrous CoCl
2Be added in 200 milliliters the oxolane and carried out haptoreaction 2.5 hours, the mixture that obtains after the reaction is carried out vacuum filtration (absolute pressure is that vacuum is 0.01MPa), obtain atropurpureus crystal by evaporative crystallization then, learn that by nuclear magnetic resonance spectroscopy and mass spectral analysis described crystal is the transition-metal catalyst A2 shown in the structural formula 2
Structural formula 2
Embodiment 3
Present embodiment is used to illustrate described transition-metal catalyst provided by the invention.
At room temperature, under nitrogen atmosphere, with 2 moles Cong base sodium and 1.3 moles anhydrous CoCl
2Be added in 400 milliliters the oxolane and carried out haptoreaction 2.5 hours, the mixture that obtains after the reaction is carried out vacuum filtration (absolute pressure is that vacuum is 0.01MPa), obtain atropurpureus crystal by evaporative crystallization then, learn that by nuclear magnetic resonance spectroscopy and mass spectral analysis described crystal is the transition-metal catalyst A3 shown in the structural formula 3
Structural formula 3
Embodiment 4
Present embodiment is used to illustrate described transition-metal catalyst provided by the invention.
At room temperature, under nitrogen atmosphere, with 1 mole 2 (3-methyl cyclopentadiene)-monosilanes and 1.1 moles anhydrous CoCl
2Be added in 250 milliliters the oxolane and carried out haptoreaction 3.2 hours, the mixture that obtains after the reaction is carried out vacuum filtration (absolute pressure is that vacuum is 0.01MPa), obtain atropurpureus crystal by evaporative crystallization then, learn that by nuclear magnetic resonance spectroscopy and mass spectral analysis described crystal is the transition-metal catalyst A4 shown in the structural formula 4
Structural formula 4
Embodiment 5
Present embodiment is used to illustrate described transition-metal catalyst provided by the invention.
At room temperature, under nitrogen atmosphere, with 1 mole 2 (3-ethyl cyclopentadiene)-dichlorosilane and 1.1 moles anhydrous CoCl
2Be added in 200 milliliters the oxolane and carried out haptoreaction 3.2 hours, the mixture that obtains after the reaction is carried out vacuum filtration (absolute pressure is that vacuum is 0.01MPa), obtain atropurpureus crystal by evaporative crystallization then, learn that by nuclear magnetic resonance spectroscopy and mass spectral analysis described crystal is the transition-metal catalyst A5 shown in the structural formula 5
Structural formula 5
Embodiment 6
Present embodiment is used to illustrate described transition-metal catalyst provided by the invention.
At room temperature, under nitrogen atmosphere, with 1 mole 2 (3-propyl group cyclopentadiene)-carrene and 1.2 moles anhydrous CrCl
2Be added in 250 milliliters the oxolane and carried out haptoreaction 3.2 hours, the mixture that obtains after the reaction is carried out vacuum filtration (absolute pressure is that vacuum is 0.01MPa), obtain atropurpureus crystal by evaporative crystallization then, learn that by nuclear magnetic resonance spectroscopy and mass spectral analysis described crystal is the transition-metal catalyst A6 shown in the structural formula 6
Structural formula 6
Embodiment 7
Present embodiment is used to illustrate described transition-metal catalyst provided by the invention.
Method according to embodiment 1 prepares described transition-metal catalyst, the FeCl that different is with identical amount of substance
2Replaced C oCl
2With the reaction of tetramethyl-ring pentadienyl sodium, thereby obtain the transition-metal catalyst A7 that central metal atom is Fe.
Comparative Examples 1
Method according to embodiment 1 prepares described transition-metal catalyst, and different is, and replace wherein tetramethyl-ring pentadienyl sodium with 2 moles cyclopentadienyl group sodium, thereby obtain the transition Confucian classics catalyst D1 shown in the structural formula 7,
Structural formula 7
Embodiment 8
Present embodiment is used to illustrate the described method for preparing picoline provided by the invention.
The acetonitrile (9756 moles) of the described transition-metal catalyst A1 that makes among 0.5 kilogram the embodiment 1 and 400 kilograms is added in 1000 liters the reactor, under normal pressure, purged described reactor 0.5 hour with nitrogen, purged 0.1 hour with acetylene gas then through deoxidation, dehydration, in temperature be under 120 ℃ afterwards, pressure is under the 1.0MPa, 34104 moles of the acetylene gas of the deoxidation of injection process continuously again, dehydration, make the pressure in the reactor rise to 1.5MPa (dividing potential drop of acetylene is 0.8MPa), under this temperature and pressure, kept 3 hours.Then, reduce to room temperature, sampling is carried out high performance liquid chromatography-mass spectrometry (HPLC-MS) and is analyzed and to learn that the product that above-mentioned reaction generates is the 2-picoline, and the yield of conversion ratio by calculating acetonitrile and 2-picoline is as shown in table 1 below.
Embodiment 9-14
Present embodiment is used to illustrate the described method for preparing picoline provided by the invention.
Method according to embodiment 8 prepares picoline, and different is, replaces wherein transition-metal catalyst A1 with the described transition-metal catalyst A2-A7 that makes among the embodiment 2-7 respectively.Sampling is carried out high performance liquid chromatography-mass spectrometry (HPLC-MS) and is analyzed and to learn that the product that above-mentioned reaction generates is the 2-picoline then, and the yield of conversion ratio by calculating acetonitrile and 2-picoline is as shown in table 1 below.
Comparative Examples 2
Method according to embodiment 8 prepares picoline, and different is, replaces wherein transition-metal catalyst A1 with the described transition-metal catalyst D1 that makes in the Comparative Examples 1.Sampling is carried out high performance liquid chromatography-mass spectrometry (HPLC-MS) and is analyzed and to learn that the product that above-mentioned reaction generates is the 2-picoline then, and the yield of conversion ratio by calculating acetonitrile and 2-picoline is as shown in table 1 below.
Table 1
| Transition-metal catalyst | The conversion ratio of acetonitrile (%) | The yield of 2-picoline (%) | |
| Embodiment 8 | ??A1 | ??95.8 | ??91.6 |
| Embodiment 9 | ??A2 | ??96.1 | ??92.1 |
| Embodiment 10 | ??A3 | ??97.4 | ??93.5 |
| Embodiment 11 | ??A4 | ??100 | ??95.9 |
| Embodiment 12 | ??A5 | ??100 | ??98.4 |
| Transition-metal catalyst | The conversion ratio of acetonitrile (%) | The yield of 2-picoline (%) | |
| Embodiment 13 | ??A6 | ??99.5 | ??95.3 |
| Embodiment 14 | ??A7 | ??72.8 | ??56.2 |
| Comparative Examples 2 | ??D1 | ??68.1 | ??48.9 |
This shows that transition-metal catalyst provided by the invention can promote acetonitrile and acetylene reaction to make the 2-picoline effectively.Particularly, when having linking group in the described transition-metal catalyst provided by the invention, described transition-metal catalyst can significantly improve the selectivity of described acetonitrile and acetylene reaction generation 2-picoline.
Claims (10)
1. a transition-metal catalyst is characterized in that, the general structure of this catalyst is R
1(Z)
yMR
2, wherein, R
1And R
2For identical or different, and be respectively cyclopentadienyl group, replacement or unsubstituted indenyl, replacement or the unsubstituted fluorenyl of replacement separately; Y is 0 or 1; Z is for connecting R
1And R
2Linking group; M is a transition metal.
2. catalyst according to claim 1, wherein, Z is Si (X
1)
2, C (X
2)
2, C (X
3)
2C (X
4)
2, CX
5=CX
6Or C (X
7)
2Si (X
8)
2, X
1, X
2, X
3, X
4, X
5, X
6, X
7And X
8The alkyl, silicyl, haloalkyl, the carbon number that are respectively hydrogen atom, halogen atom, carbon number separately and are 1-10 are aryl, halogenated aryl or the halo aralkyl of 6-10.
3. catalyst according to claim 2, wherein, Z is SiH
2, Si (CH
3)
2, Si (C
2H
5)
2, Si (C
3H
7)
2, CH
2, C (CH
3)
2, C (C
2H
5)
2, C (C
3H
7)
2, CH
2CH
2, C (CH
3)
2C (CH
3)
2, C (C
2H
5)
2C (C
2H
5)
2, CH=CH, C (CH
3)=C (CH
3), CH
2SiH
2Or C (CH
3)
2Si (CH
3)
2
4. catalyst according to claim 1, wherein, R
1And R
2Be respectively cyclopentadienyl group, methyl cyclopentadienyl, ethyl cyclopentadienyl group, propyl group cyclopentadienyl group, butyl cyclopentadienyl group, isopropyl cyclopentadienyl group, indenyl or fluorenyl separately.
5. according to any described catalyst among the claim 1-4, wherein, M is manganese, vanadium, chromium, iron or cobalt.
6. a method for preparing picoline is characterized in that, described method is included in and under the existence of catalyst acetylene is contacted to react with acetonitrile, and described catalyst is any described transition-metal catalyst among the claim 1-5.
7. method according to claim 6, wherein, the mol ratio of the consumption of acetylene and acetonitrile is 1-8: 1.
8. method according to claim 6, wherein, the weight ratio of the consumption of described catalyst consumption and acetonitrile is 1: 50-10000.
9. method according to claim 8, wherein, the weight ratio of the consumption of described catalyst consumption and acetonitrile is 1: 400-5000.
10. according to any described method among the claim 6-9, wherein, the condition that described acetylene contacts with acetonitrile comprises: temperature is 100-200 ℃, and the pressure of acetylene is 0.3-2MPa, and the time is 2-5 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910236478 CN101693211B (en) | 2009-10-22 | 2009-10-22 | Transition metal catalyst and method for preparing picoline through adopting catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910236478 CN101693211B (en) | 2009-10-22 | 2009-10-22 | Transition metal catalyst and method for preparing picoline through adopting catalyst |
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