US3092647A - Preparation of dicyclopentadienyliron and dicyclopentadienylnickel - Google Patents
Preparation of dicyclopentadienyliron and dicyclopentadienylnickel Download PDFInfo
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- US3092647A US3092647A US312658A US31265852A US3092647A US 3092647 A US3092647 A US 3092647A US 312658 A US312658 A US 312658A US 31265852 A US31265852 A US 31265852A US 3092647 A US3092647 A US 3092647A
- Authority
- US
- United States
- Prior art keywords
- dicyclopentadienyliron
- dicyclopentadienylnickel
- sodium
- cyclopentadienyl
- halide
- 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 - Lifetime
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- NQLVCAVEDIGMMW-UHFFFAOYSA-N cyclopenta-1,3-diene;cyclopentane;nickel Chemical compound [Ni].C=1C=C[CH-]C=1.[CH-]1[CH-][CH-][CH-][CH-]1 NQLVCAVEDIGMMW-UHFFFAOYSA-N 0.000 title description 12
- 238000002360 preparation method Methods 0.000 title description 4
- 238000000034 method Methods 0.000 claims description 19
- OHUVHDUNQKJDKW-UHFFFAOYSA-N sodium;cyclopenta-1,3-diene Chemical compound [Na+].C=1C=C[CH-]C=1 OHUVHDUNQKJDKW-UHFFFAOYSA-N 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 6
- 150000004820 halides Chemical class 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- -1 bis-cyclopentadienyl iron Chemical compound 0.000 description 8
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 229910001507 metal halide Inorganic materials 0.000 description 4
- 150000005309 metal halides Chemical class 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 150000001649 bromium compounds Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- SFDZETWZUCDYMD-UHFFFAOYSA-N monosodium acetylide Chemical compound [Na+].[C-]#C SFDZETWZUCDYMD-UHFFFAOYSA-N 0.000 description 2
- 150000002816 nickel compounds Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 150000003388 sodium compounds Chemical class 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- AOPDRZXCEAKHHW-UHFFFAOYSA-N 1-pentoxypentane Chemical compound CCCCCOCCCCC AOPDRZXCEAKHHW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 238000003747 Grignard reaction Methods 0.000 description 1
- 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 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 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
- C07F17/00—Metallocenes
- C07F17/02—Metallocenes of metals of Groups 8, 9 or 10 of the Periodic Table
Definitions
- Dicyclopentadienyliron and dicyclopentadienylnickel are recently discovered organo metallic compounds which are of great theoretical and practical interest because they are the only known compounds in which these metals are directly attached by principal valence to a hydrocarbon radical.
- the iron compound is described and claimed in pending U.S. application Serial No. 291,567, filed June 3, 1952 now Patent No. 2,680,756 and the corresponding nickel compound is described and claimed in pending U.S. application Serial No. 298,170, filed July 10, 1952 now Patent No. 2,680,758.
- Several structural formulas have been proposed for these compounds, the simplest being the following:
- These compounds may also be called bis-cyclopentadienyl iron and bis-cyclopentadienyl nickel.
- Another method of preparing dicyclopentadienyliron involves reacting cyclopentadiene and a specially prepared iron catalyst.
- the main disadvantage with this process is that the catalyst loses its activity readily and becomes inoperable in a very short time.
- a further object is the provision of a method which employs inexpensive starting materials. Further objects will appear from the description of this invention which follows:
- dicyclopentadienyliron or dicyclopentadienylnickel is obtained by reacting an anhydrous halide of the corresponding metal with cyclopentadienyl sodium.
- the reaction is preferably carried out in a liquid medium which is inert with respect to the sodium compound and which has some solvent action with respect to the metal halide.
- the media ordinarily used for Grignard reactions are suitable. These include various ethers, such as diethyl ether, diamyl ether, anisole and the like, and tertiary amines such as diethylamine and dimethylaniline.
- the solvent may be diluted with hydrocarbons such as benzene or refined petroleum fractions. It is of course important to exclude moisture, both from the solvent and from the reactants. Any compounds capable of reaction with the cyclopentadienyl sodium should also be excluded.
- the preferred halides are the chlorides and bromides. Either ferrous or ferric halides may be employed, as the latter are reduced to the ferrous state by the cyclopentadienyl sodium.
- Cyclopentadienyl sodium is conveniently made by the reaction of cyclopentadiene with sodium acetylide, as described and claimed in my copending U.S. application Serial No. 312,659, filed October 1, 1952, now Patent No. 2,763,700.
- the reaction between the metal halide and the cyclopentadienyl sodium is preferably carried out at a temperature between 0 and 50 C., although higher and lower temperatures are operable.
- the product may be recovered by filtering off the sodium halide which is formed during the reaction and separating the dicyclopentadienyliron or dicyclopentadienylnickel from the filtrate by evaporation of the solvent.
- the products may be recovered and purified either by virtue of their solubility in organic solvents such as ethers, alcohols and aliphatic and aromatic hydrocarbons, or of their volatility at slightly elevated temperatures.
- Cyclopentadienyl sodium is prepared by adding 33 parts of freshly distilled cyclopentadiene to a solution of sodium acetylide, formed from 11.5 parts of sodium and an excess of acetylene, in 275 parts of liquid anhydrous ammonia. The charge is permitted to reflux at 32 C. with agitation and under a blanket of nitrogen. The ammonia is replaced by dry ethyl ether and the mixture is refluxed at 35% C. for one hour. Twenty-eight (28) parts of anhydrous ferric chloride dissolved in dry ethyl ether are added and the mixture is agitated at room temperature for 16 hours. The mixture is then filtered and the filter cake is washed with ethyl ether.
- the combined filtrate is concentrated :and the last traces of ether are removed under reduced pressure.
- the yield is dicyclopentadienyliron, M.P. 173 C., is 14.9 parts. This corresponds to a yield of 44.1% based on the ferric chloride.
- Example 2 'Cyclopentadienyl sodium is prepared as described in Example 1 and in the same amount. To the slurry of cyclopentadienyl sodium in ether are then added 22.4 parts of anhydrous nickel chloride, prepared by heating nickel chloride.
- the process of this invention is adaptable to operation on either a small or large scale, using cheap and readily available starting materials. It eliminates the use of expensive Grignard reagents and also the need for high temperatures and pressures. It permits the manufacture of either dicyclopentadienyliron or dicyclopentadienylnickel in commercially practical yield. These products are useful in the preparation of anti-knock fuels, as a source of free organic radicals and as concentrated sources of organic-soluble iron and nickel.
- metal halide is a member of the class consisting of chlorides and bromides.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
United States Patent 3,092,647 PREPARATION OF DICYCLOPENTADIENYLIRON AND DICYCLOPENTADIENYLNICKEL Charles L. Hobbs, Jr., Wilmington, Del., assignor to E. I. du Pont de Nemours and Company, Wilmington, Del., a corporation of Delaware No Drawing. Filed Oct. 1, 1952, Ser. No. 312,658 9 Claims. (Cl. 260439) This invention relates to a process for the manufacture of dicyclopentadienyliron and dicyclopentadienylnickel.
Dicyclopentadienyliron and dicyclopentadienylnickel are recently discovered organo metallic compounds which are of great theoretical and practical interest because they are the only known compounds in which these metals are directly attached by principal valence to a hydrocarbon radical. The iron compound is described and claimed in pending U.S. application Serial No. 291,567, filed June 3, 1952 now Patent No. 2,680,756 and the corresponding nickel compound is described and claimed in pending U.S. application Serial No. 298,170, filed July 10, 1952 now Patent No. 2,680,758. Several structural formulas have been proposed for these compounds, the simplest being the following:
These compounds may also be called bis-cyclopentadienyl iron and bis-cyclopentadienyl nickel.
One known method for their preparation is by the Gn'gnard reaction between a cyclopentadienyl magnesium halide and the anhydrous halide of iron or nickel dissolved in ether. The yields, particularly in the case of the nickel compound, are small and in addition the process is expensive and suitable only for small scale production.
Another method of preparing dicyclopentadienyliron involves reacting cyclopentadiene and a specially prepared iron catalyst. The main disadvantage with this process is that the catalyst loses its activity readily and becomes inoperable in a very short time.
Another method of making dicyclopentadienyliron, which is not applicable to the manufacture of dicyclopentadienylnickel, is described and claimed in pending U.S. application Serial No. 292,388, filed June 7, 1952 now Patent No. 2,791,597. It involves the reaction between cyclopentadiene and iron pentacarbonyl. This method is suitable for large scale production but involves the use of high temperatures and in some cases of high pressures.
It is an object of the present invention to provide a process for preparing dicyclopentadienyliron and dicyclopentadienylnickel which is adapted to commercial scale operation and which produces satisfactory yields without the use of elevated temperatures or pressures. A further object is the provision of a method which employs inexpensive starting materials. Further objects will appear from the description of this invention which follows:
ice
According to the present invention, dicyclopentadienyliron or dicyclopentadienylnickel is obtained by reacting an anhydrous halide of the corresponding metal with cyclopentadienyl sodium.
The reaction is preferably carried out in a liquid medium which is inert with respect to the sodium compound and which has some solvent action with respect to the metal halide. For this purpose, the media ordinarily used for Grignard reactions are suitable. These include various ethers, such as diethyl ether, diamyl ether, anisole and the like, and tertiary amines such as diethylamine and dimethylaniline. The solvent may be diluted with hydrocarbons such as benzene or refined petroleum fractions. It is of course important to exclude moisture, both from the solvent and from the reactants. Any compounds capable of reaction with the cyclopentadienyl sodium should also be excluded.
The preferred halides are the chlorides and bromides. Either ferrous or ferric halides may be employed, as the latter are reduced to the ferrous state by the cyclopentadienyl sodium.
Cyclopentadienyl sodium is conveniently made by the reaction of cyclopentadiene with sodium acetylide, as described and claimed in my copending U.S. application Serial No. 312,659, filed October 1, 1952, now Patent No. 2,763,700.
The reaction between the metal halide and the cyclopentadienyl sodium is preferably carried out at a temperature between 0 and 50 C., although higher and lower temperatures are operable. The product may be recovered by filtering off the sodium halide which is formed during the reaction and separating the dicyclopentadienyliron or dicyclopentadienylnickel from the filtrate by evaporation of the solvent. In general the products may be recovered and purified either by virtue of their solubility in organic solvents such as ethers, alcohols and aliphatic and aromatic hydrocarbons, or of their volatility at slightly elevated temperatures.
The process of this invention is illustrated by the following examples, in which parts are by weight.
Example 1 Cyclopentadienyl sodium is prepared by adding 33 parts of freshly distilled cyclopentadiene to a solution of sodium acetylide, formed from 11.5 parts of sodium and an excess of acetylene, in 275 parts of liquid anhydrous ammonia. The charge is permitted to reflux at 32 C. with agitation and under a blanket of nitrogen. The ammonia is replaced by dry ethyl ether and the mixture is refluxed at 35% C. for one hour. Twenty-eight (28) parts of anhydrous ferric chloride dissolved in dry ethyl ether are added and the mixture is agitated at room temperature for 16 hours. The mixture is then filtered and the filter cake is washed with ethyl ether. The combined filtrate is concentrated :and the last traces of ether are removed under reduced pressure. The yield is dicyclopentadienyliron, M.P. 173 C., is 14.9 parts. This corresponds to a yield of 44.1% based on the ferric chloride.
Example 2 'Cyclopentadienyl sodium is prepared as described in Example 1 and in the same amount. To the slurry of cyclopentadienyl sodium in ether are then added 22.4 parts of anhydrous nickel chloride, prepared by heating nickel chloride.
Analysis Theory Found Percent Carbon" 63. 60 63. 37 Percent Hydrogen 5. 30 5. 03 Percent Nickel 31. 30. 75
By the previously known reaction between a cyclopentadienyl magnesium halide and nickel halide, yields of only about 4% of dicyclopentadienylnickel are obtained.
The process of this invention is adaptable to operation on either a small or large scale, using cheap and readily available starting materials. It eliminates the use of expensive Grignard reagents and also the need for high temperatures and pressures. It permits the manufacture of either dicyclopentadienyliron or dicyclopentadienylnickel in commercially practical yield. These products are useful in the preparation of anti-knock fuels, as a source of free organic radicals and as concentrated sources of organic-soluble iron and nickel.
I claim:
1. The process of preparing a compound from the class consisting of dicyclopentadienyliron and dicyclopentadi- 4 I enylnickel which comprises reacting an anhydrous halide of the corresponding metal with cyclopentadienyl sodium.
2. A process according to claim 1 in which the reaction is carried out in the presence of a solvent for the metal halide which is inert with respect to the sodium compound.
3. A process according to claim 2 in which the solvent is an ether.
4. A process according to claim 1 in which the metal halide is a member of the class consisting of chlorides and bromides.
5. The process of preparing dicyclopentadienyliron which comprises reacting an anhydrous iron halide with cyclopentadienyl sodium.
6. The process of preparing dicyclopentadienyliron which comprises reacting an anhydrous iron chloride with cyclopentadienyl sodium in the presence of ethyl ether.
7. The process of preparing dicyclopentadienylnickel which comprises reacting an anhydrous nickel halide with cyclopentadienyl sodium.
8. The process of preparing dicyclopentadienylnickel which comprises reacting an anhydrous nickel chloride with cyclopentadienyl sodium in the presence of ethyl ether. 7
9. The process of preparing dicyclopentadienyliron which comprises reacting anhydrous ferric chloride With cyclopentadienyl sodium.
References Cited in the file of this patent February 1952.
Kealy et 31.: Nature, vol. 168, pp. 1039-; mp1s,
Claims (1)
1. THE PROCESS OF PREPARING A COMPOUND FROM THE CLASS CONSISTING OF DICYCLOPENTADIENYLIRON AND DICUCLOPENTADIENYLNICKEL WHICH COMPRISES REACTING AN ANHYDROUS HALIDE OF THE CORRESPONDING METAL WITH CYCLOPENTADIENYL SODIUM.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US312658A US3092647A (en) | 1952-10-01 | 1952-10-01 | Preparation of dicyclopentadienyliron and dicyclopentadienylnickel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US312658A US3092647A (en) | 1952-10-01 | 1952-10-01 | Preparation of dicyclopentadienyliron and dicyclopentadienylnickel |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3092647A true US3092647A (en) | 1963-06-04 |
Family
ID=23212434
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US312658A Expired - Lifetime US3092647A (en) | 1952-10-01 | 1952-10-01 | Preparation of dicyclopentadienyliron and dicyclopentadienylnickel |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3092647A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3306917A (en) * | 1965-08-02 | 1967-02-28 | Ethyl Corp | Process for preparing group viii metal cyclopentadienyl compounds |
-
1952
- 1952-10-01 US US312658A patent/US3092647A/en not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| None * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3306917A (en) * | 1965-08-02 | 1967-02-28 | Ethyl Corp | Process for preparing group viii metal cyclopentadienyl compounds |
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