CN1291955C - Process for preparing cyclopentadiene or substituted cyclopentadiene - Google Patents
Process for preparing cyclopentadiene or substituted cyclopentadiene Download PDFInfo
- Publication number
- CN1291955C CN1291955C CN 03157352 CN03157352A CN1291955C CN 1291955 C CN1291955 C CN 1291955C CN 03157352 CN03157352 CN 03157352 CN 03157352 A CN03157352 A CN 03157352A CN 1291955 C CN1291955 C CN 1291955C
- Authority
- CN
- China
- Prior art keywords
- acid
- substituted
- pyrone
- gamma
- cyclopentadiene
- 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.)
- Expired - Fee Related
Links
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000004519 manufacturing process Methods 0.000 title 1
- 238000000034 method Methods 0.000 claims abstract description 39
- CVQUWLDCFXOXEN-UHFFFAOYSA-N Pyran-4-one Chemical compound O=C1C=COC=C1 CVQUWLDCFXOXEN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000002841 Lewis acid Substances 0.000 claims abstract description 5
- 230000002378 acidificating effect Effects 0.000 claims abstract description 5
- 230000007062 hydrolysis Effects 0.000 claims abstract description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 5
- 150000007517 lewis acids Chemical class 0.000 claims abstract description 5
- -1 substituted-cyclopentadienyl Chemical group 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 12
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 238000006722 reduction reaction Methods 0.000 claims description 8
- 230000002829 reductive effect Effects 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 229960003280 cupric chloride Drugs 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 150000007524 organic acids Chemical class 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
- 238000005406 washing Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 239000012280 lithium aluminium hydride Substances 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 239000011707 mineral Substances 0.000 claims description 4
- 235000010755 mineral Nutrition 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 229910021575 Iron(II) bromide Inorganic materials 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- NWZXFAYYQNFDCA-UHFFFAOYSA-N cyclopenten-1-ol Chemical compound OC1=CCCC1 NWZXFAYYQNFDCA-UHFFFAOYSA-N 0.000 claims description 2
- 125000002433 cyclopentenyl group Chemical class C1(=CCCC1)* 0.000 claims description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentenylidene Natural products C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 claims description 2
- 229940046149 ferrous bromide Drugs 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 claims description 2
- 235000005985 organic acids Nutrition 0.000 claims description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 239000011968 lewis acid catalyst Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 22
- 238000002360 preparation method Methods 0.000 abstract description 12
- 230000018044 dehydration Effects 0.000 abstract description 4
- 238000010531 catalytic reduction reaction Methods 0.000 abstract description 2
- VNPQQEYMXYCAEZ-UHFFFAOYSA-N 1,2,3,4-tetramethylcyclopenta-1,3-diene Chemical compound CC1=C(C)C(C)=C(C)C1 VNPQQEYMXYCAEZ-UHFFFAOYSA-N 0.000 abstract 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 21
- 238000005516 engineering process Methods 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 235000021050 feed intake Nutrition 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- XNMQEEKYCVKGBD-UHFFFAOYSA-N 2-butyne Chemical compound CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- 229910010082 LiAlH Inorganic materials 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000012797 qualification Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYILSJIMFKKICJ-UHFFFAOYSA-N 1,2-dimethylcyclopenta-1,3-diene Chemical compound CC1=C(C)C=CC1 RYILSJIMFKKICJ-UHFFFAOYSA-N 0.000 description 1
- NPRBXPWIWZJYDY-UHFFFAOYSA-N 2-(2-methylpropyl)cyclopenta-1,3-diene Chemical compound CC(C)CC1=CCC=C1 NPRBXPWIWZJYDY-UHFFFAOYSA-N 0.000 description 1
- CBQAACXHLISDSO-UHFFFAOYSA-N 2-ethylcyclopenta-1,3-diene Chemical compound CCC1=CCC=C1 CBQAACXHLISDSO-UHFFFAOYSA-N 0.000 description 1
- AHQZRFBZJSCKAV-UHFFFAOYSA-N 2-methylcyclopenta-1,3-diene Chemical compound CC1=CCC=C1 AHQZRFBZJSCKAV-UHFFFAOYSA-N 0.000 description 1
- HBZVNWNSRNTWPS-UHFFFAOYSA-N 6-amino-4-hydroxynaphthalene-2-sulfonic acid Chemical compound C1=C(S(O)(=O)=O)C=C(O)C2=CC(N)=CC=C21 HBZVNWNSRNTWPS-UHFFFAOYSA-N 0.000 description 1
- BZKFMUIJRXWWQK-UHFFFAOYSA-N Cyclopentenone Chemical compound O=C1CCC=C1 BZKFMUIJRXWWQK-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- NFWSQSCIDYBUOU-UHFFFAOYSA-N methylcyclopentadiene Chemical compound CC1=CC=CC1 NFWSQSCIDYBUOU-UHFFFAOYSA-N 0.000 description 1
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 150000004880 oxines Chemical class 0.000 description 1
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical compound C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 description 1
- WQIQNKQYEUMPBM-UHFFFAOYSA-N pentamethylcyclopentadiene Chemical compound CC1C(C)=C(C)C(C)=C1C WQIQNKQYEUMPBM-UHFFFAOYSA-N 0.000 description 1
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention provides a preparation process of cyclopentadiene or substituted cyclopentadiene, in particular to tetramethylcyclopentadiene, which takes gamma-pyrone or substituted gamma-pyrone as a reaction raw material, and is obtained by catalytic reduction in the presence of Lewis acid and dehydration of the product under acidic condition after hydrolysis. The process method provided by the invention can greatly improve the yield (up to more than 65%) of cyclopentadiene or substituted cyclopentadiene synthesized by gamma-pyrone or substituted gamma-pyrone, and can greatly simplify the process compared with the prior art.
Description
Technical field
The present invention relates to the preparation technology of cyclopentadiene or substituted-cyclopentadienyl, particularly the preparation technology of tetramethyl-ring pentadiene.
Background technology
Cyclopentadiene or substituted-cyclopentadienyl are one of most important parts in the transition metal chemistry.Cyclopentadiene, tetramethyl-ring pentadiene, pentamethyl-cyclopentadiene are very useful ligands in the process of preparation single site catalysts, use them can prepare multiple metallocene compound, these compounds are to produce polyolefinic good catalyzer such as polyethylene, polypropylene under the situation that methylaluminoxane (MAO) exists.In addition, cyclopentadiene is used as polymerization single polymerization monomer or the comonomer for preparing polycyclopentadiene.
Cyclopentadiene or substituted-cyclopentadienyl are to be difficult to obtain.A spot of cyclopentadiene and methyl cyclopentadiene can be from naphtha cracking or pyrolysis gasoline C
5Obtain the then more difficult acquisition of other substituted-cyclopentadienyl in the fraction.For example: the typical synthetic route of tetramethyl-ring pentadiene is to be starting raw material with pentanone-3 and acetaldehyde, obtains 2,3,5,6,-tetrahydrochysene-2,3,5,6-tetramethyl--gamma-pyrone carries out dehydration reaction then under acidic conditions, generate 2,3,4,5-tetramethyl-ring amylene-2-ketone passes through LiAlH again
4Or NaBH
4Be reduced to accordingly 2,3,4 Deng reductive agent, 5-tetramethyl-ring amylene-2-alcohol carries out dehydration reaction at last in the presence of sulfuric acid or hydrochloric acid, obtain target product tetramethyl-ring pentadiene.In entire synthesis process, serious side reaction causes the yield of target product not high, and the technical process of whole process of preparation is very complicated.
Therefore, in the building-up process of substituted-cyclopentadienyl, it is very important managing to improve the product yield of any single step reaction in the building-up process or the technical process of simplification preparation process.
Williams etc. (J.Am.Chem.Soc., 113,4843-4851,1991) have described a kind of ADOGEN464 of employing prepares substituted-cyclopentadienyl as phase-transfer catalyst method.The shortcoming of this method is: the ratio of three replacements and four substituted-cyclopentadienyls has reached 35: 65 in the reaction mixture, and the separation of reaction mixture is difficult.
It is the method for the synthetic tetramethyl-ring pentadiene of raw material with the 2-butyne that Garner (Tetrahedron Letters, 16:2463-2464,1994) has reported a kind of, and the yield of target product tetramethyl-ring pentadiene is 36%.
It is the synthetic technology of raw material with the vinyl ketone that US5329056 provides a kind of, can obtain target product with higher reaction yield.
US6388151 has reported a kind of with 2,3, and-dibromobutane is a raw material, and through the preparation technology of the synthetic tetramethyl-ring pentadiene of four-step reaction, the yield of target product tetramethyl-ring pentadiene is between 50%～75%.
US5648578 isobornyl carboxylicesters is the preparation technology of raw material through the synthetic substituted-cyclopentadienyl (as: tetramethyl-ring pentadiene) of three-step reaction.
US5434324 has reported with cyclopentenone and the effect of haloalkyl magnesium, is converted into corresponding alcohol, then the preparation technology of dehydration generation alkyl substituted-cyclopentadienyl in the presence of organic carboxyl acid.The yield of this method gained substituted-cyclopentadienyl is about 80%, and in the reaction product, the ratio of inside and outside type isomer is about 1.5: 1, and exo isomer is unsuitable for synthetic metallocene compound.
US5414173 provides a kind of more effective synthetic method, this method is after cyclopentenes-2-ketone or substituted cyclopentene-2-ketone are reduced to corresponding alcohol, adopt specific composition and the sieve peg-raking catalyst catalysis cyclopentenes-2-alcohol of structure or the dehydration of substituted cyclopentene-2-alcohol, make dehydration obtain higher reaction yield, but cyclopentenes-2-ketone or substituted cyclopentene-2-ketone are not reduced to the yield data of the process of corresponding alcohol.The actual recovery that therefore, can not reflect target product in the whole process.
Summary of the invention
The purpose of this invention is to provide a kind of technology for preparing cyclopentadiene or substituted-cyclopentadienyl.
The present invention relate generally to gamma-pyrone or replace gamma-pyrone (preparation process is according to document Organometallics1988,7, the described method of 1828-1829 is carried out) at reductive agent (as LiAlH
4Or NaBH
4) there is reduction down, and reduzate dewaters under acidic conditions and obtains the reaction process of target product cyclopentadiene or substituted-cyclopentadienyl.Its key problem in technology is gamma-pyrone or replaces gamma-pyrone without the reaction process that generates cyclopentenes-2-ketone or substituted cyclopentene-2-ketone, but through after the reduction dehydration reaction, directly obtains target product cyclopentadiene or substituted-cyclopentadienyl.
With the tetramethyl-ring pentadiene is example, and the typical synthetic route of tetramethyl-ring pentadiene is in the prior art:
The synthetic route that the present invention takes is:
In the implementation process of the best of the present invention, by gamma-pyrone or the reduction of replacement gamma-pyrone, the process that forms γ-pyrans alcohol or replacement γ-pyrans alcohol is carried out in the presence of lewis acidic.Lewis acid can be any Lewis acid, as: cupric chloride, iron(ic) chloride, iron protochloride, aluminum chloride, zinc chloride, ferrous bromide etc., be preferably aluminum chloride, iron(ic) chloride, cupric chloride, zinc chloride, preferably the binary or the ternary complex of above-claimed cpd composition.
After reaction to be restored is finished, can form cyclopentenol or substituted cyclopentene alcohol in the solutions of weak acidity hydrolysis.In the presence of protonic acid, directly carry out dehydration reaction again.Protonic acid of the present invention can be any mineral acid, organic acid, also can be mineral acid and organic acid mixing acid, can also be the mixture that different organic acids is formed.As: phosphoric acid, sulfuric acid, formic acid, acetate, acetate/phosphoric acid mixing acid, oxalic acid, tosic acid, phenylformic acid, oxalic acid/tosic acid mixing acid etc.Be preferably tosic acid, phenylformic acid.
By gamma-pyrone or replace temperature of reaction that the gamma-pyrone catalytic reduction generates intermediate product γ-pyrans alcohol or replace γ-pyrans alcohol according to the difference of solvent for use and different, the present invention does not do special qualification.But the present invention is recommended in-40～40 ℃ of scopes and carries out, and preferred-5～30 ℃, the reaction times is 2～5 hours; By γ-pyrans alcohol or replace the difference of the temperature of γ-acid dehydration reaction of pyrans alcohol according to the boiling point of solvent for use, generally in 50～150 ℃ temperature range, carry out, preferably temperature of reaction is 80～120 ℃.After reaction finished, reaction mixture was with strong base weak acid salt brine solution neutralization (being preferably saturated sodium carbonate or sodium bicarbonate), washed twice also after the drying, carried out rectification under vacuum and obtained.
Adopt method of the present invention that cyclopentadiene or the substituted-cyclopentadienyl that obtains be there is no special qualification, available general formula is expressed as: CpR
1(R
2) (R
3) (R
4).R
1, R
2, R
3And R
4Can be identical, also can be different; R
1, R
2, R
3And R
4Can be straight-chain alkyl, branched hydrocarbyl, phenyl, substituted-phenyl or cyclic hydrocarbon group etc., also can be hydrogen atom.R
1, R
2, R
3And R
4In carbon atom number do not have strict demand, be generally 1～30.Below exemplify out some concrete compounds, but the present invention is not limited to this: 1,2,3,4-tetramethyl-ring pentadiene, 3,4-dimethyl cyclopentadiene, 2-ethyl cyclopentadiene, 3-isobutyl-cyclopentadiene, the benzyl ring pentadiene, 2,3,4,5-tetramethyl-ring pentadiene, 1,2,3 ,-triethyl cyclopentadiene etc.
In technology disclosed by the invention, behind gamma-pyrone or replacement gamma-pyrone reduction formation γ-pyrans alcohol or the replacement γ-pyrans alcohol, reaction mixture need not separate or purify, can directly carry out dehydration reaction, thereby greatly simplify the technical process of synthetic cyclopentadiene or substituted-cyclopentadienyl.Simultaneously, the reaction yield of target product cyclopentadiene or substituted-cyclopentadienyl can reach more than 65%.
Embodiment
The present invention is further illustrated by the following examples, but should not be construed as limitation of the invention.
Embodiment 1
Reaction flask adds 250ml1 ether and 17g tetra lithium aluminium hydride after replacing through sufficient inertia successively, starts stirring, and mixture is cooled to 0 ℃, under constantly stirring, with 45g (0.29mol) 2,3,5,6-tetrahydrochysene-2,3,5,6 tetramethyl-s-gamma-pyrone slowly is added dropwise in the reaction flask.Reinforced finishing continues to stir 0.5 hour, slowly is warming up to 25 ℃ and stirs 3 hours, slowly drips the acid distilled water hydrolysis of PH=2.Add 200ml benzene and 62.8g tosic acid again, under boiling state, refluxed 12 hours stopped reaction.Liquid in the reaction mixture is separated with decantation, and remaining solid is washed twice with ether and with washings and decant gained liquid mixing, saturated sodium carbonate solution is neutralized to neutrality, organic layer washing twice, anhydrous magnesium sulfate drying removes by filter sal epsom, filtrate obtains 1,2 in removal of solvent under reduced pressure, 3,4-tetramethyl-ring pentadiene 17.2g is (to feed intake 2,3,4, the mole number meter of 5-tetramethyl-ring penta-2-alkene-1-ketone), calculated yield is 48.6%.
Embodiment 2
After reaction flask is replaced through sufficient inertia, add mixture, 250ml1 ether and 17g tetra lithium aluminium hydride that 1g is made up of iron trichloride (0.2g) and cupric chloride (0.8g) successively, start stirring, mixture is cooled to 0 ℃, under constantly stirring, with 45g (0.29mol) 2,3,5,6-tetrahydrochysene-2,3,5,6 tetramethyl-s-gamma-pyrone slowly is added dropwise in the reaction flask.Following steps and embodiment 1 obtain 1,2,3 together, 4-tetramethyl-ring pentadiene 23.4g, and (to feed intake 2,3,5,6-tetrahydrochysene-2,3, the mole number meter of 5,6 tetramethyl-s-gamma-pyrone) yield is 66%.
Comparative Examples 1
(1) get 45g (0.29mol) 2,3,5,6-tetrahydrochysene-2,3,5,6 tetramethyl-s-gamma-pyrone are pressed document
Organometallics 1988,7, and the described method of 1828-1829 is a dewatering agent with tosic acid/benzene, and reaction obtains 28g 2,3,4,5-tetramethyl-ring penta-2-alkene-1-ketone under boiling state;
(2) 28g 2,3,4 that obtains with above-mentioned reaction, 5-tetramethyl-ring penta-2-alkene-1-ketone reacts by the step of embodiment 2, obtains 1,2,3,4-tetramethyl-ring pentadiene 22g is (to feed intake 2,3,5,6-tetrahydrochysene-2,3, the mole number meter of 5,6 tetramethyl-s-gamma-pyrone) yield is 62.2%.
Comparative Examples 2
After reaction flask is replaced through sufficient inertia, add mixture, 250ml1 ether and 17g tetra lithium aluminium hydride that 1g is made up of iron trichloride (0.2g) and cupric chloride (0.8g) successively, start stirring, mixture is cooled to 0 ℃, under constantly stirring, with 45g (0.29mol) 2,3,5,6-tetrahydrochysene-2,3,5,6 tetramethyl-s-gamma-pyrone slowly is added dropwise in the reaction flask.Reinforced finishing continues to stir 0.5 hour, slowly is warming up to 35 ℃ and stirs 5 hours, slowly drips the acid distilled water hydrolysis of PH=2.
Liquid phase in the reaction mixture is separated with decantation, remaining solid is washed twice with ether and with washings and decant gained liquid mixing, be neutralized to neutrality with dilute hydrochloric acid solution, organic phase washing twice, anhydrous magnesium sulfate drying removes by filter sal epsom, filtrate is undertaken by the dehydration reaction step among the embodiment 2 after removal of solvent under reduced pressure, obtain 1,2,3,4-tetramethyl-ring pentadiene 21.9g, (to feed intake 2,3,5,6-tetrahydrochysene-2,3,5, the mole number meter of 6 tetramethyl-s-gamma-pyrone) yield is 62%.
Embodiment 3
With the Glacial acetic acid is dewatering agent, and other process and embodiment 2 obtain 1,2,3 together, 4-tetramethyl-ring pentadiene 22.4g (with 2,3,5,6-tetrahydrochysene-2,3, the mole number meter of 5,6 tetramethyl-s-gamma-pyrone), and yield is 63.4%.
Embodiment 4
With the phenylformic acid is dewatering agent, and other process and embodiment 2 obtain 1,2,3 together, 4-tetramethyl-ring pentadiene 23.6g, and (to feed intake 2,3,5,6-tetrahydrochysene-2,3, the mole number meter of 5,6 tetramethyl-s-gamma-pyrone) yield is 66.7%.
Embodiment 5
With the mixture as catalyst of iron trichloride and aluminum chloride, other process and embodiment 2 obtain 1,2,3 together, 4-tetramethyl-ring pentadiene 20.5g, and (to feed intake 2,3,5,6-tetrahydrochysene-2,3, the mole number meter of 5,6 tetramethyl-s-gamma-pyrone) yield is 58%.
Embodiment 6
With 2-methyl-gamma-pyrone is raw material, and preparation process and embodiment 2 obtain 2-methyl cyclopentadiene 14.7g together, and (in the mole number of the 2-methyl-gamma-pyrone that feeds intake) yield is 65%.
Claims (12)
1. the method for synthetic cyclopentadiene or substituted-cyclopentadienyl, it is characterized in that with gamma-pyrone or replacement gamma-pyrone be raw material, at-40～40 ℃ reduction reaction taking place generates γ-pyrans alcohol or replaces γ-pyrans alcohol, hydrolysis generates cyclopentenol or substituted cyclopentene alcohol under solutions of weak acidity, under acidic conditions, dewater again, washing, drying, rectification under vacuum obtains cyclopentadiene or substituted-cyclopentadienyl.
2. method according to claim 1 is characterized in that reductive agent is a tetra lithium aluminium hydride.
3. method according to claim 2 is characterized in that gamma-pyrone or replaces gamma-pyrone the reduction reaction takes place under 0～30 ℃ of condition.
4. method according to claim 1 is characterized in that adding lewis acid catalyst in the reduction reaction process.
5. method according to claim 4 is characterized in that Lewis acid is cupric chloride, iron(ic) chloride, iron protochloride, aluminum chloride, zinc chloride or ferrous bromide.
6. method according to claim 5 is characterized in that Lewis acid is selected from the binary or the ternary complex of aluminum chloride, iron(ic) chloride, cupric chloride, zinc chloride or above-claimed cpd.
7. method according to claim 1, it is characterized in that need not separate or purify after reduction reaction is finished directly carries out dehydration reaction.
8. method according to claim 1, the acid that it is characterized in that being used for dehydration reaction is any mineral acid, organic acid, or mineral acid and organic acid mixing acid, or the mixture formed of different organic acids.
9. method according to claim 8 is characterized in that the acid of dehydration reaction is selected from phosphoric acid, sulfuric acid, formic acid, acetate, oxalic acid, tosic acid or phenylformic acid.
10. method according to claim 9 is characterized in that 50～150 ℃ of dehydration reaction temperature.
11. method according to claim 10 is characterized in that 80～120 ℃ of dehydration reaction temperature.
12. the method one of described according to claim 1 to 11 is characterized in that the substituted-cyclopentadienyl for preparing is expressed as with general formula: CpR
1(R
2) (R
3(R
4), R wherein
1, R
2, R
3And R
4Can be identical, also can be different; R
1, R
2, R
3And R
4Be straight-chain alkyl, branched hydrocarbyl, phenyl, substituted-phenyl, cyclic hydrocarbon group or hydrogen atom; R
1, R
2, R
3And R
4In carbon atom number do not have strict demand, be 1～30.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03157352 CN1291955C (en) | 2003-09-19 | 2003-09-19 | Process for preparing cyclopentadiene or substituted cyclopentadiene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03157352 CN1291955C (en) | 2003-09-19 | 2003-09-19 | Process for preparing cyclopentadiene or substituted cyclopentadiene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1597647A CN1597647A (en) | 2005-03-23 |
| CN1291955C true CN1291955C (en) | 2006-12-27 |
Family
ID=34660269
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03157352 Expired - Fee Related CN1291955C (en) | 2003-09-19 | 2003-09-19 | Process for preparing cyclopentadiene or substituted cyclopentadiene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1291955C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102958971B (en) * | 2010-04-29 | 2014-12-31 | 陶氏环球技术有限责任公司 | Epoxy polycyclopentadiene compounds |
| CN102942511B (en) * | 2012-11-02 | 2014-01-08 | 东北师范大学 | Preparation method of cyclopentadiene |
| CN111217657B (en) * | 2018-11-25 | 2021-04-30 | 中国科学院大连化学物理研究所 | Method for synthesizing methyl cyclopentadiene from 3-methyl-2-cyclopentene-1-ketone |
| CN112723978A (en) * | 2020-12-28 | 2021-04-30 | 山东京博中聚新材料有限公司 | Preparation process of tetramethylcyclopentadiene |
-
2003
- 2003-09-19 CN CN 03157352 patent/CN1291955C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1597647A (en) | 2005-03-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5279275B2 (en) | Diarylphenoxyaluminum compounds | |
| JP2018023974A (en) | Aluminum catalyst | |
| JP5269084B2 (en) | Method for producing tetranorlabdane derivative | |
| CN1291955C (en) | Process for preparing cyclopentadiene or substituted cyclopentadiene | |
| CN1069629C (en) | Process for manufacture of alpha-beta-unsaturated organic carboxylic acids | |
| CN113896674B (en) | Synthesis method of apremilast | |
| CN116947695B (en) | Preparation method and application of 1,3, 6-hexanetrinitrile | |
| CN1298683C (en) | Synthesis method of cyclopentadiene or substituted cyclopentadiene | |
| CN100336787C (en) | Process for synthesizing1,3,5-triphenyl benzene | |
| CN1966476A (en) | Iron-catalysed allylic alkylation | |
| RU2109004C1 (en) | Method of synthesis of substituted indanones | |
| DE102005010329A1 (en) | New diarylphenoxy-aluminum compound, obtained by a reaction of bis(diarylphenol) ligand with aluminum compound and/or aluminum compound, useful as a catalyst | |
| CN1056134C (en) | Process for the preparation of a linear aldehyde organic compound | |
| CN1149572A (en) | Cyclopentadienyl derivative and its preparing method | |
| CN100422138C (en) | Process for producing optically active 1-alkyl-substituted 2,2,2-trifluoroethylamine | |
| EP2921228A1 (en) | Method for producing optically active isopulegol and optically active menthol | |
| JP5340297B2 (en) | Method for producing tetranorlabdane derivative | |
| CN113735673B (en) | Method for catalyzing cyclopropanation reaction of olefin by acidic molecular sieve | |
| JP4511093B2 (en) | Method for producing alicyclic monoolefin carboxylic acid | |
| CN101265201A (en) | Method for synthesizing tramadol hydrochloride | |
| CN115583874B (en) | Method for catalyzing asymmetric tandem reaction of internal alkyne by rhodium metal | |
| JPH08310975A (en) | Production of polyalkylated cyclopentadiene from isobornylcarboxylate | |
| US20010041742A1 (en) | Process for producing 2-substituted propionic acid | |
| RU2342392C2 (en) | Method of 6-ethyl-6-aluminaspiro[3,4] octane | |
| CN1622949A (en) | Improved method for the production of biphosphites |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20061227 Termination date: 20210919 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |