CN117551115A - Synthesis method of 1,2,3,4, 5-penta (3, 5-dimethylphenyl) -cyclopentadiene sodium salt - Google Patents
Synthesis method of 1,2,3,4, 5-penta (3, 5-dimethylphenyl) -cyclopentadiene sodium salt Download PDFInfo
- Publication number
- CN117551115A CN117551115A CN202311647190.1A CN202311647190A CN117551115A CN 117551115 A CN117551115 A CN 117551115A CN 202311647190 A CN202311647190 A CN 202311647190A CN 117551115 A CN117551115 A CN 117551115A
- Authority
- CN
- China
- Prior art keywords
- solvent
- solution
- brown
- drying
- dimethylphenyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- -1 1,2,3,4, 5-penta (3, 5-dimethylphenyl) -cyclopentadiene sodium salt Chemical compound 0.000 title claims abstract description 11
- 238000001308 synthesis method Methods 0.000 title claims abstract description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 7
- 239000002244 precipitate Substances 0.000 claims abstract description 7
- WRIKHQLVHPKCJU-UHFFFAOYSA-N sodium bis(trimethylsilyl)amide Chemical compound C[Si](C)(C)N([Na])[Si](C)(C)C WRIKHQLVHPKCJU-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011734 sodium Substances 0.000 claims abstract description 5
- 239000006228 supernatant Substances 0.000 claims abstract description 4
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 3
- ZRHJSDJDFVLVRB-UHFFFAOYSA-N 1,3-dimethyl-5-[2,3,4,5-tetrakis(3,5-dimethylphenyl)cyclopenta-1,4-dien-1-yl]benzene Chemical compound CC=1C=C(C=C(C=1)C)C1C(=C(C(=C1C1=CC(=CC(=C1)C)C)C1=CC(=CC(=C1)C)C)C1=CC(=CC(=C1)C)C)C1=CC(=CC(=C1)C)C ZRHJSDJDFVLVRB-UHFFFAOYSA-N 0.000 claims abstract 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 13
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 9
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 4
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 claims description 4
- WLPXNBYWDDYJTN-UHFFFAOYSA-N 1-bromo-2,3-dimethylbenzene Chemical group CC1=CC=CC(Br)=C1C WLPXNBYWDDYJTN-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000012043 crude product Substances 0.000 claims description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 2
- QMBQEXOLIRBNPN-UHFFFAOYSA-L zirconocene dichloride Chemical compound [Cl-].[Cl-].[Zr+4].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 QMBQEXOLIRBNPN-UHFFFAOYSA-L 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 3
- 239000012074 organic phase Substances 0.000 claims 3
- 239000001301 oxygen Substances 0.000 claims 3
- 229910052760 oxygen Inorganic materials 0.000 claims 3
- 239000002808 molecular sieve Substances 0.000 claims 2
- 229910052757 nitrogen Inorganic materials 0.000 claims 2
- 238000000746 purification Methods 0.000 claims 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 2
- 230000003213 activating effect Effects 0.000 claims 1
- 238000009835 boiling Methods 0.000 claims 1
- 230000005587 bubbling Effects 0.000 claims 1
- 239000003480 eluent Substances 0.000 claims 1
- 238000005580 one pot reaction Methods 0.000 claims 1
- 239000012047 saturated solution Substances 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 8
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical group C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 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 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- DCERHCFNWRGHLK-UHFFFAOYSA-N C[Si](C)C Chemical compound C[Si](C)C DCERHCFNWRGHLK-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- DBKDYYFPDRPMPE-UHFFFAOYSA-N lithium;cyclopenta-1,3-diene Chemical compound [Li+].C=1C=C[CH-]C=1 DBKDYYFPDRPMPE-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 125000001979 organolithium group Chemical group 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/04—Sodium compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the field of organic synthesis, and relates to a synthesis method of 1,2,3,4, 5-penta (3, 5-dimethylphenyl) -cyclopentadiene sodium salt. The synthesis method of the compound comprises the following steps: with 1,2,3,4, 5-penta (3, 5-dimethylphenyl) -1, 3-cyclopentadiene ((Cp) Ar* )H,Cp Ar* ＝C 5 Ar 5 ，Ar * ＝3,5‑Me 2 ‑C 6 H 3 ) And bis (trimethylsilyl) sodium amide (NHMDS) as raw materials, toluene as solvent, reacting at room temperature for 24 hr, filtering to remove supernatant, repeatedly washing precipitate with hexane until the washing solution is colorless, and drying to obtain pure Na CpAr* . Provides a high-efficiency synthesis method for the compound.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and in particular relates to a method for synthesizing 1,2,3,4, 5-penta (3, 5-dimethylphenyl) -cyclopentadiene sodium salt
Background
Since ferrocene was discovered in 1951, cyclopentadienyl ligands have evolved into the most basic ligand family in organometallic chemistry and have been widely used in the fields of asymmetric catalysis, small molecule activation and coordination chemistry such as single molecule magnets.
The steric and electronic properties of cyclopentadiene can be easily altered by introducing one or more substituents on the carbon atom of the cyclopentadiene. These substituents have a significant effect and can provide stronger steric protection for the coordinated metal center, making the metal complex more stable, or have higher catalytic activity.
Methyl penta-methylcyclopentadienyl C from 1960 5 Me 5 Due to its higher steric requirement and stronger electron donating property, has been developed as the most commonly used ligand, and cyclopentadiene with higher steric requirement, such as C, is also produced by introducing substituents with larger volumes such as tert-butyl or isopropyl 5 H 2 t Bu 3 And C 5 i Pr 5 . The latter ligands are of interest because of their ability to stabilize dysprosium metallocene single molecule magnets and linear uranium half-metallocenes.
In addition to alkyl substituents, the introduction of aryl substituents on the cyclopentadienyl ring is also an important direction of investigation. The appropriate aryl groups are selected for substitution on the carbocycle, so that the corresponding complex with better solubility and crystallinity can be obtained. It has been reported that (Cp) is substituted with 3, 5-diisopropylphenyl Ar# )H(Cp Ar# ＝C 5 Ar 5 ，Ar＝3,5- i Pr 2 -C 6 H 3 ) And 3, 5-dimethylphenyl-substituted (Cp) Ar* )H(Cp Ar* ＝C 5 Ar 5 ，Ar * ＝3,5-Me 2 -C 6 H 3 ) Etc.
Substituted (Cp) with 3, 5-dimethylphenyl Ar* ) LiCp can be obtained by reacting H with n-butyllithium Ar* (THF) 2 However, due to the unique manner in which lithium centers interact with organic molecules, organolithium complexes may be present in solution. In the subsequent Li removal reaction, lithium is coordinated with the solvent, and the solution is not easily removed.
The atomic radius of sodium in the same main group is larger than that of lithium, coordination is not easy to form with a solvent, and the sodium is easy to remove in subsequent reactions, so that the sodium is a more suitable choice for removing hydrogen on a cyclopentadiene ring.
Disclosure of Invention
In order to overcome the problem of serious coordination of lithium salt solvents, the invention provides a novel synthesis method of a compound, namely 1,2,3,4, 5-penta (3, 5-dimethylphenyl) -cyclopentadiene sodium salt. Meanwhile, the synthesis of the compound is simple, and the yield is high.
The specific synthesis method of the invention comprises the following steps: to (Cp) Ar* ) H and bis (trimethyl)Silicon-based) sodium amide (NHMDS) is reacted for 24 hours at room temperature by taking toluene as a solvent, filtering to remove supernatant, repeatedly washing precipitate with hexane until washing solution is colorless, and drying to obtain pure NaCp Ar* 。
The invention avoids using dangerous alkyl lithium reagents such as n-butyl lithium, selects relatively safe NaHMDS, improves experimental safety NaHMDS and (Cp) Ar* ) Products after H ion exchange other than NaCp Ar* In addition, the byproduct is hexamethyldisilazane, the hexamethyldisilazane is easy to dissolve in hexane, the product is insoluble in hexane, the hexamethyldisilazane can be removed by washing, and the post-treatment is simple.
The reaction was carried out at room temperature and very completely, with a yield of 92%.
Drawings
FIG. 1 is a NaCp Ar* Is of (2)
FIG. 2 is (Cp) Ar* ) H crystal structure containing chloroform
FIG. 3 shows (Cp) Ar* ) H stacking structure from a viewing angle of a direction
FIG. 4 is (Cp) Ar* ) H stacking structure from b direction viewing angle
FIG. 5 shows (Cp) Ar* ) H stacking structure from view angle of c direction
Detailed Description
The following detailed description of specific embodiments of the invention is provided. These embodiments are provided only for illustrating and not limiting the scope or practice of the invention, which is defined by the appended claims and includes obvious variations or modifications made thereon.
Example 1
(1) In a glove box (O) 2 <1ppm,H 2 O<0.1 ppm), zirconocene dichloride (14.6 g,50 mmol), m-bromoxylene (111.0 g,600 mmol), cesium carbonate (195.5 g,600 mmol), palladium acetate (2.8 g,1.25 mmol), tri-tert-butylphosphine (10.1 g,50 mmol) and 300mL of N, N-dimethylformamide were added to a 1L Schlenk flask, connected to a vacuum line, and the oil bath was heated to 130℃for 24 hours.
(2) After cooling to room temperature, 250mL of methylene chloride and p-toluenesulfonic acid (228.0 g,1200 mmol) were added to the mixture and reacted for 30 minutes, and the mixture was passed through a silica gel column to obtain a brown solution.
(3) The solvent was removed under high vacuum as a brown oil.
(4) The oil was dissolved in 300mL of chloroform, washed three times with 300mL of saturated sodium bicarbonate and three times with 300mL of saturated brine, and dried over magnesium sulfate for half an hour.
(5) And (3) passing the product obtained in the step (3) through a silica gel column to obtain a brown solution, and pumping the solvent under high vacuum to obtain a brown oily solid.
(6) The oily solid in step (4) was repeatedly washed with hexane until the wash liquid was colorless, to give the crude product as an orange solid (29.6 g, 51.2%).
(7) Dissolving the orange solid in the step (5) in chloroform, volatilizing at room temperature to obtain colorless crystals, repeatedly washing with hexane until the washing solution is colorless, and removing the solvent under high vacuum to obtain white powder, i.e. pure product (Cp) Ar* )H(17.5g，30.27％)。
Example 2
(1) In a glove box (O) 2 <1ppm,H 2 O<0.1 ppm) was added to a 100mL Schlemk bottle (Cp) Ar* )H(12.0g 20.8mmol)
Dissolved in 15mL of toluene, excess NaHMDS (5.49 g,30 mmol) was added and stirred at room temperature for 24 hours.
(2) Centrifuging the turbid liquid obtained in the step (1), discarding the supernatant, and repeatedly washing the precipitate with hexane until the washing liquid is colorless.
(3) Removing the solvent from the precipitate obtained in the step (2) in vacuum to obtain pure NaCp Ar* (11.5 g, 92% yield).
The foregoing is only for the understanding of the method and core idea of the invention, and it should be noted that it will be obvious to those skilled in the art that numerous changes and modifications can be made without departing from the principle of the invention, and these changes and modifications fall within the protection scope of the claims of the invention.
Claims (15)
1. A compound characterized in that the compound is 1,2,3,4, 5-penta (3, 5-dimethylphenyl) -cyclopentadiene sodium salt.
2. The process for the synthesis of a compound according to claim 1, wherein 1,2,3,4, 5-penta (3, 5-dimethylphenyl) -1, 3-cyclopentadiene ((Cp) is obtained in a glove box Ar* )H，Cp Ar* ＝C 5 Ar 5 ，Ar * ＝3,5-Me 2 -C 6 H 3 ) And sodium bis (trimethylsilyl) amide (NHMDS) in toluene as solvent for 24 hours. Filtering to remove supernatant, repeatedly washing precipitate with hexane until the washing solution is colorless, and drying to obtain Na CpAr* 。
3. NaCp of claim 2 Ar* The synthesis method of the compound is a one-pot method, and comprises the following steps:
(1) In a glove box, adding N, N-dimethylformamide as a solvent to disperse under the catalysis of palladium acetate by using zirconocene dichloride, m-bromoxylene, cesium carbonate and tri-tert-butylphosphine.
(2) The mixture was connected to a vacuum line and reacted at 130℃in an oil bath for 24 hours, and the resulting brown turbidity was cooled to room temperature.
(3) P-toluenesulfonic acid and methylene chloride were added to give a brown solution.
4. A preliminary purification of a compound according to claim 3, characterized in that
(1) The column was passed through the brown solution and then washed with dichloromethane and N, N-dimethylformamide until the solution was colorless.
(2) The solvent, i.e., dichloromethane and N, N-dimethylformamide, was removed under high vacuum to give a brown oil.
(3) The product was dissolved in chloroform and washed three times with saturated sodium bicarbonate solution to give a brown organic phase.
(4) The mixture was washed with saturated brine three times to obtain a brown organic phase.
(5) The organic phase was dried over magnesium sulfate.
(6) Then chloroform is used as eluent to pass through the column, and the solvent is removed under high vacuum.
(7) Washing with hexane gave an orange solid.
5. NaHMDS as claimed in claim 2, characterized in that colorless transparent crystals obtained are recrystallized in hexane.
6. The method according to claim 2, wherein the reaction temperature is about 25℃at room temperature.
7. The further purification process as claimed in claim 4, wherein the orange crude product is dissolved in chloroform and evaporated at room temperature until a small amount of crystals appear, resulting in a supersaturated solution thereof, and the resulting solution is filtered to give a clear saturated solution. Cooling in a refrigerator for one day. A large amount of colorless crystals are formed, and the pure product is obtained by washing with hexane and drying.
8. The method of claim 7, wherein the solvent is removed from the precipitate and the precipitate is placed under high vacuum for at least 10 minutes.
9. In claims 2 and 3, the glove box has a water content of less than 0.1ppm and an oxygen content of less than 1 ppm.
10. A nitrogen blanket is required within 24 hours of the step (2) reaction of claim 3.
11. The process of adding p-toluenesulfonic acid in step (3) as claimed in claim 3 is carried out in air without nitrogen protection.
12. The solvent N, N-dimethylformamide as claimed in claim 3, which is dried in advance in a molecular sieve for 2 days to have a water content of less than 10ppm, and oxygen in the solvent is removed by a bubbling method to have an oxygen content of less than 10ppm.
13. In the process of removing the solvent in the step (2) as claimed in claim 4, the solvent may be heated at about 100 to 130℃because the boiling point of N, N-dimethylformamide is too high.
14. Step (3) as claimed in claim 4 lasts at least 30 minutes and the magnesium sulphate is sufficient to allow the drying to be completed after the drying to be observed as a fine magnesium sulphate powder.
15. The molecular sieve of claim 9, wherein the activating step is performed by drying in a 160℃oven for at least 7 days, placing in a 1L yankee reactor, and placing at a high temperature of 260℃under a high vacuum of 10 -2 The sample is pumped at mbar for 12 hours. The piston was closed, cooled and placed in a glove box.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311647190.1A CN117551115A (en) | 2023-12-04 | 2023-12-04 | Synthesis method of 1,2,3,4, 5-penta (3, 5-dimethylphenyl) -cyclopentadiene sodium salt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311647190.1A CN117551115A (en) | 2023-12-04 | 2023-12-04 | Synthesis method of 1,2,3,4, 5-penta (3, 5-dimethylphenyl) -cyclopentadiene sodium salt |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117551115A true CN117551115A (en) | 2024-02-13 |
Family
ID=89810886
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311647190.1A Pending CN117551115A (en) | 2023-12-04 | 2023-12-04 | Synthesis method of 1,2,3,4, 5-penta (3, 5-dimethylphenyl) -cyclopentadiene sodium salt |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117551115A (en) |
-
2023
- 2023-12-04 CN CN202311647190.1A patent/CN117551115A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Michelman et al. | Synthesis, exchange reactions, and metallacycle formation in osmium (II) imido systems: formation and cleavage of osmium-nitrogen bonds | |
| Wehman et al. | Structural investigation of aryllithium clusters in solution I. A 13C and 7Li NMR study of phenyllithium and some methyl-substituted phenyllithium derivatives | |
| Okeya et al. | Reactions of the bis (. BETA.-diketonato) palladium (II) complexes with various nitrogen bases. | |
| Kowalczyk et al. | Synthesis, structure, and reactivity of chiral rhenium alkyne complexes of the formula [(. eta. 5-C5H5) Re (NO)(PPh3)(RC. tplbond. CR')]+ BF4 | |
| Gong et al. | Metal–organic frameworks built from achiral cyclohex-1-ene-1, 2-dicarboxylate: syntheses, structures and photoluminescence properties | |
| Rietveld et al. | An Aryllithium Complex with Intramolecular Coordination of an o-Diamine Substituent. X-ray and Solution NMR Structures of Dimeric [Li {C6H4 (CH2N (Me) CH2CH2NMe2)-2}] 2 | |
| Barash et al. | Anhydrous yttrium acetylacetonate and the course of thermal" dehydration" of Y (acac) 3.3 H2O | |
| Beachley Jr et al. | Synthesis and characterization of neopentylaluminum compounds | |
| Leung et al. | Resolutions involving metal complexation. Synthesis and resolution of (.+-.)-(2-mercaptoethyl) methylphenylarsine. Crystal and molecular structure of (-) 589-bis [(R)-[1-(dimethylamino) ethyl] naphthyl-C2, N] chloro [. mu.-(S)-(2-mercaptoethyl) methylphenylarsine] dipalladium. cntdot. 0.67 dichlomethane | |
| Reger et al. | Preparation of cationic. eta. 2-alkene and. eta. 2-alkyne complexes of the (. eta. 5-C5H5) Fe (CO)[P (OPh) 3] system and reduction of these complexes to. sigma.-alkyl and vinyl derivatives | |
| JPH0529371B2 (en) | ||
| CN116410224B (en) | Synthesis process of cyclopentadiene titanium trichloride | |
| Vaughan et al. | Synthesis and characterization of zinc complexes and reactivity with primary phosphines | |
| Frauenhoff et al. | Isolation, characterization, and substitution reactions of the osmium trinuclear triflate complex H2Os3 (CO) 9 (O3SCF3) 2. X-ray crystal structure of the mixed oxyligand cluster (. mu.-H) 2Os3 (CO) 9 (. mu.,. eta. 2-O2CCH3)(. eta. 1-O3SCF3) | |
| CN117551115A (en) | Synthesis method of 1,2,3,4, 5-penta (3, 5-dimethylphenyl) -cyclopentadiene sodium salt | |
| De Koning et al. | Synthesis, characterization and properties of some organozinc hydride complexes | |
| Benetollo et al. | Six-nitrogen macrocyclic complexes of the dioxouranium (VI) and praseodymium (III) ions | |
| Berry et al. | Synthesis and reactions of binuclear molybdenocene and tungstenocene derivatives | |
| CN109232586B (en) | Synthesis method of three-dimensional multi-imidazole salt cage-shaped compound | |
| CN107652206B (en) | Acenaphthylene skeleton large steric hindrance alpha-diimine compound and synthesis method thereof | |
| CN107903346B (en) | Binuclear rare earth catalyst, preparation method thereof and polymerization method of syndiotactic polystyrene | |
| Ritch et al. | Secondary diphosphine and diphosphido ligands: synthesis, characterisation and group 1 coordination compounds | |
| Niemann et al. | Zirconocene dipicolinate and related dicarboxylate complexes: coordination geometries and reactivities | |
| CN108440606B (en) | Method for synthesizing titanocene dichloride | |
| Hubbard et al. | Carbon-carbon double bond formation from a cis-bis (chloromethyl) ruthenium complex |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |