GB1579038A - Substituted heterofulvalenes - Google Patents

Substituted heterofulvalenes Download PDF

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GB1579038A
GB1579038A GB3295977A GB3295977A GB1579038A GB 1579038 A GB1579038 A GB 1579038A GB 3295977 A GB3295977 A GB 3295977A GB 3295977 A GB3295977 A GB 3295977A GB 1579038 A GB1579038 A GB 1579038A
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substituted
alkali metal
heterofulvalene
ttf
metal compound
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International Business Machines Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/022—Electrolytes; Absorbents
    • H01G9/025—Solid electrolytes
    • H01G9/028—Organic semiconducting electrolytes, e.g. TCNQ
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D339/00—Heterocyclic compounds containing rings having two sulfur atoms as the only ring hetero atoms
    • C07D339/02—Five-membered rings
    • C07D339/06—Five-membered rings having the hetero atoms in positions 1 and 3, e.g. cyclic dithiocarbonates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D345/00—Heterocyclic compounds containing rings having selenium or tellurium atoms as the only ring hetero atoms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte

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  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Heterocyclic Compounds Containing Sulfur Atoms (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)

Description

(54) SUBSTITUTED HETEROFULVALENES (71) We, INTERNATIONAL BUSINESS MACHINES CORPORATION, a Corporation organized and existing under the laws of the State of New York in the United States of America, of Armonk, New York 10504, United States of America, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: The invention relates to substituted heterofulvalenes.
Considerable interest has been found recently in the study of highly conducting organic charge transfer salts. Most attractive of these systems are the tetracyano - p - quinodimethane (TCNQ) salts of tetrathiafulvalene (TTF), tetraselenafulvalene (TSeF) and dithiadiselenafulvalene (DTDSeF). These salts display exceptional electrical conductivity and metallic behavior over a wide temperature range.
Presently, interest has been focused on substituted derivatives of the tetraheterofulvalenes, where hetero means S and/or Se which are hereafter referred to as fulvalenes. Substituting fulvalenes are of interest because they alter the conductivity of their charge transfer salts.
Prior attempts to synthesize unsymmetrically substituted fulvalenes have been by a cross coupling reaction described by M. Narita and C. Pittman Jr. Synthesis, 1976, 495. The reaction can be generalized as follows:
where R1, R2, R3 and R4 are selected from various organic groups such as alkyl, aryl, ester and sulfur containing compounds. This method of synthesis, however has its obvious drawbacks, in that there are three possible products, which are most difficult to separate. For cross coupling reactions multi-step procedures are sometimes required to obtain just one of the components to be coupled. The variety of substituents that can be substituted is severely limited to reagents that will not react with the coupling reagents. Attempted substitution of TTF by direct action of a reagent such as a halogen has been shown to yield not the substituted derivative, but rather the unsubstituted radical cation salt. (F. Wudl et al, JCS Chem. Commun. 1970, 1453). This points up the difference between the chemistry of TTF and other sulfur heterocycles such as thiophene TTF. Thiophene is related to TTF in that they both have the C-S-C=C linkage in common. However while direct substitution can be made to thiophene by a number of methods (F. F. Blicke Heterocyclic Compounds, John Wiley & Sons, N.Y. pg. 208) it appears that the only substitution common to both TTF and thiophene is that if lithiation and subsequent reaction thereof.
In summary; prior art attempts to prepare unsymmetrically substituted TTF or TSeF derivatives have used mixed coupling reactions that give multi-product mixtures that are difficult to separate and which yield only a limited variety of substituents. Direct substitution methods have resulted in oxidative attack on the central double bond and have yielded only radical cation salts.
According to the invention there is provided a substituted heterofulvalene having the general formula
where Y is S or Se; Z is S or Se; R is C2H5, -CH=CH2, CO2H, R'R"COH, R'CHOH, COR', Cl, Br, I, SR', SO2Li+, SnR3,, SiR3,, CH2OH, CO2R', R'CHOH, CHO, CR2'OH or an alkali metal radical and where R' and R" are alkyl, aryl, alkaryl, ether substituted alkyl, halogen substituted alkyl or halogen radicals.
Further, according to the invention, there is provided a method of preparing a substituted heterofulvalene as above, which comprises reacting a heterofulvalene of the formula
with an organo-alkali metal compound in the absence of oxygen to give an alkali metal compound of the formula
wherein M is an alkali metal, and thereafter reacting said alkali metal compound with a suitable reagent to replace the alkali metal M in said alkali metal compound with a radical R.
The following scheme is illustrative of the many novel substituted fulvalene compounds that become available by the method of this invention. It should be noted that while lithium is used to illustrate the invention, other alkali metals such as sodium and potassium are also contemplated for use herein.
where Z is S and Y is S, or Z is S and Y is Se, or Z is Se and Y is Se, and it is understood that when Z is S and Y is Se that two isomers exist.
The substituted fulvalenes of the invention can be used to form charge-transfer salts with TCNQ. These charge-transfer compounds are now finding numerous electrolytic and semiconductor applications in capacitors, conductive films and antistatic agents. The substituted compounds of the present invention can be coupled to polymers to thereby provide highly conducting or semiconducting polymers. These polymers are useful in integrated circuits and solid electrolytic condensers. The utility of these compounds is disclosed in the following Japanese patents 75-52,594, 73-37,569, 75-27,098, 74-16,895, 75-56,593 and 74-54,484.
Suitable organo-lithium compounds for use as starting materials in the preparation of the compounds of the present invention can be selected from any of a number of commercially available compounds, such as butyl lithium, phenyllithium, ethyliithium and lithium diisopropyl amide (LDA). The lithium compound is usually in an ethereal or hydrocarbon solution and is of reagent grade.
LDA however, is purchased as a solid. Sodium or other alkali metals are expected to function similarly although lithium is generally preferred for ease in handling.
The fulvalene compounds are prepared according to known methods. For example, several schemes for their preparation are given in the publication entitled "Preparation of Tetrathiafulvalene (TTF) and their Selenium Analogs Tetraselenafulvalenes (TSeF)", by Mitsuaki Narita et al Synthesis pp. 489-514 August 1976.
All reactions in the present invention are carried out in the absence of 02. The atmosphere can be N or an inert gas such as argon.
The lithiated fulvalenes formed in the present invention are not isolated and are not characterized in the usual manner because of their instability at elevated temperatures. They are used in solution and are characterized by the products formed therefrom. The lithiated fulvalenes are generally reacted with the desired reagent at a temperature of from -40"C to 80C C.
The following is a list of general reactions contemplated by the present invention. These reactions are similar to those known for other organolithium reactions. See J. M. Mullan et al Chemical Reviews 69, 693-755(1969).
It should be noted that FLi is the lithium compound of TTF, TSeF or DTDSeF, R' and R" are as defined above and X is a halogen selected from Cl, Br and I.
Fulvalene Lithium Comp.+Reactant Product FLi+CO2 FCO2H FLi+R'R"C=O FR'R"COH FLi+R'CHO FR'CHOH FLi+R'C3N FCOR' FLi+X2 FX FLi+R'X+S FSR' FLi+SO2 FSO2Li+ FLi+R3,SnCl FSnR3, FLi+R2,SiCl Fir,' FLi+HCHO FCH2OH FLi+CICO2R' FCO2R' FLi+R'CO2R" FR'CHOH FLi+DMF FCHO The following examples are by way of illustration and in no manner restrictive of the present invention.
Example 1 Preparation of monocarboxylic acid of TTF (TTF-CO2H) and its methylester (TTFCO2Me) - Method 1.
A quantity of TTF 1 gram (0.0049 mole) is dissolved in 100 ml of dried diethyl ether in a flask dried and purged with nitrogen. A solution of 1.96 M butyl lithium in hexane (2.5 ml, 0.0049 mole) is added dropwise into the TTF solution with stirring for a period of about 15 minutes and at a temperature of about 25"C. The solution is further stirred for about 30 minutes and then poured onto a large excess of solid carbon dioxide (dry ice). After a 30 minute period, the reaction mixture is allowed to warm to about room temperature. Diethyl ether is then added and the solution extracted with 5Vn NaOH solution. Unreacted TTF is removed in the ethereal layer. The aqueous layer is acidified with 100/, HC1 and extracted with ether. The ether solution is dried and evaporated to yield 0.1 g of a red solid ( /O yield=807) the product has a melting point of about 176 to about 178"C with decomposition.
Esterification of the acid is carried out by dissolving the solid in methanol and refluxing the solution to which 2 drops of concentrated H2SO4 has been added, for 16 hours.
NMR of the Ester gave 1 proton â=7.4 (singlet), 2 protons ô=6.3 (singlet) and 3 protons ô=3.8 (singlet) relative to tetramethylsilane (TMS).
TTF CO2H infrared spectrum C=O stretch 1660 cm-'.
TTF CO2Me infrared spectrum C=O stretch 1720 cm-'.
Example 2 Preparation of Monocarboxylic Acid of TTF (TTFCO2H) - Method 2 A reaction flask containing 1.02 gram (0.005 mole) of TTF dissolved in 50 ml of ether is placed in a dry box under an argon atmosphere. The reaction flask is fitted with a thermometer, magnetic stirring bar, an addition funnel and a rubber syringe cap. Lithium diisopropylamide (LDA) (5.35 grams -0.005 mole) is dissolved in 10 ml of ether and added to the addition funnel. The flask is stoppered and brought outside of the dry box and purged with nitrogen. The TTF solution is cooled to about -50"C with a dry ice acetone external bath. The LDA solution is added dropwise for about 15 minutes at about -500C to about 600C with stirring. The mixture is then stirred for an additional 30 minutes. The slurry in the reaction flask is then pressed over through a teflon tube by applying nitrogen pressure into a flask containing dry ice. The dry ice and solvent is allowed to evaporate after which a weak sodium hydroxide solution is added to the resultant red solid residue. The mixture is filtered to recover unreacted TTF. The filtrate is then acidified with a 5% hydrogen chloride solution and the resulting red precipitate is collected on a filter and dried under vacuum to yield 0.78 (57 /,, yield). The precipitate is recrystallized from chloroform to obtain 0.5 grams of red needles having a melting point of about 182"C to about 184 C. An infrared spectrum of the product via KBr pellet indicate the carbonyl group stretch to appear at 1660 cm-'. The NMR analysis in D6 acetone indicated I proton ;=7.6 (singlet) 2 protons b=6.7 (singlet), I proton (CO2H) =4.7 (singlet) (CO2H proton moves to ô 5.35 in benzene D6). This disappears with the addition of D2O to the example. Elemental analysis C7H4O2S2.
Element /" Found Theory /" C 34.03 33.85 H 1.50 1.62 0 13.03 12.89 S 51.18 51.64 Mass spectrum parent peak 248 AMU.
Electrochemical Data; 2 reversible waves. ElPeak=+O.475 v vs saturated calomel electrode (SCE); E2peak=+0.385 v vs SCE; 0.1 M tetraethylammonium perchlorate (TEAP) CH3CN; 0.2 v/sec scan rate; Pt electrode.
Example 3 Preparation of ethyl ester of TTF (TTFCO2ET) Lithium TTF is prepared according to the method disclosed in Example 2. To a solution of lithium TTF (0.0049 mole) maintained at a temperature of about -700C is added a 5 fold excess (0.27 grams) of ethylchloroformate (ClCO2Et). The mixture is stirred, slowly warmed to about room temperature, added to water and extracted with ether. The ether layer is then separated and dried over MgSO4. The ether and ethylchloroformate are removed under vacuum. A crystalline compound having a melting point of about 79.5"C to about 80.5"C (uncorrected) is obtained. The IR spectrum indicated the carbonyl group stretch to appear at 1690 cm-' (KBr). The NMR analysis indicated 1 proton o > =7.3 singlet (methine), 2 protons ô=6.3 singlet (methine); 3 protons ô=4.25 (methylene) J=7 Hz: 3 protons ô=1.35 triplet (methyl) J=7 Hz.
Electrochemical data: 2 reversible oxidation waves E1peak=+0.47 V; E2peak=+0.83 V vs. SCE 0.1 m TEAP/CH3 CN 0.2 volts/sec scan. rate, Pt electrode.
Example 4 Preparation of Ethyl TTF Lithium TTF (0.0049 mole) is prepared according to Example 2. The lithium TTF solution is maintained at a temperature of about -70"C to a flask containing 1.36 grams (ET3O±PF6) (0.0055 mole) and is added in 25 ml of ether by pressing through a teflon tube using nitrogen pressure. The mixture is stirred for about I hour and then brought slowly to about room temperature. It is then added to water and extracted with ether. The ether layer is separated, dried over MgsO4, and evaporated. The product is separated from unreacted TTF using dry column chromatography with a 1.25 inch by 24 inch column of neutral grade 3 alumina with hexane as the eluent. The product which is a yellow band is cut out and again chromatographed to yield 0.1 grams of a yellow oil which does not crystallize at room temperature. NMR analysis in CCl4 relative to TMS gave 2 protons S=7.3 singlet (Methine); 1 proton ô=5.8 singlet (methine); 2 protons ô=2.45 (methylene) quartet J=8 Hz; 3 protons ô 1.25 (methyl) triplet J=7 Hz. The infrared spectral analysis indicated the following major peaks at 3070, 2970, 2930, 1450, 820, 795, 780, 735, and 645 cm-'. The electrochemical data indicate 2 reversible oxidation waves Elpeak=+O.33 volts; E2pcak=+O.70 volts vs. SCE; 0.2 m TEAP CH3CN; platinum electrode 0.2 V/sec. scan rate.
Example 5 Preparation of TTFCOCH3 (TTF Methyl Ketone) Lithium TTF (0.005 mole) is prepared according to Example 2 and is prepared at -70 C.
The lithium TTF solution is added to a five fold molar excess solution (2 g) of CH3COCI in ether at -700C with stirring. After the addition is completed the mixture is warmed for about 1 hour to about room temperature. The ether and excess acetylchloride is removed under vacuum. The resultant solid is dissolved in benzene and the LiCI is removed by filtration. The mixture is purified by dry column chromatography on a silica gel (grade III) column (4.5x10 cm) by first eluting with hexane to remove unreacted TTF and then with benzene to remove the product band from the column. Deep red crystals are obtained with a melting point of about 152"C to about 153"C. (uncorrected) A 67% yield (0.08 g) is obtained.
NMR ô=7.32 1 proton (methine) singlet, ô=6.35 2 protons (methine) singlet, =2.40 3 protons (methyl) singlet.
IR spectrum shows the carbonyl stretch at 1635 cm-' (KBr Pellet).
Electrochemical data Elpeak=+0.47 V vs SCE; E2peak=+0.83 V vs SCE.
Pt electrode; 0.1 M TEAP/CH3CN; scan rate 0.2 V/sec.
Example 6 Preparation of TSeFCO2H Lithium TSeF and TSeFCO2H are prepared exactly according to the procedure for the preparation of TTFCO2H in Example 2, except that TSeF 100 mg, (0.00026 mole) and LDA 28 mg (0.00026 mole) are used. A yield of 13 mg of TSeFCO2H is obtained. Melting point: -The product decomposed at about 165 C before melting.
Electrochemical Data 2 reversible waves Pt electrode Ep=+0.63 V vs. SCE CH3CN/0.1 M TEAP Ep=+0.90 V vs. SCE Scan rate 0.2 V. sec.
IR spectrum indicated that the carbonyl peak appears at 1670 cm-l.
Example 7 Preparation of TTFCHO TTF Li (0.0049 mole) is prepared according to method 2 at -700C. This was added at -70 C to a stirred solution of ether containing a five fold molar excess of N,N-dimethylformamide (DMF) at -70 C. The mixture is allowed to come to room temperature and then added to water (which had been purged with N2 to remove 02). This is extracted with ether. The ether layer is dried and the ether removed under vacuum. The mixture is purified by dry column chromatography on a silica gel (grade III) column (4.5x8 cm) by first eluting with hexane to remove unreacted TTF and then with benzene to isolate the product. Deep red crystals (0.58 g 44% yield) are obtained having a melting point of about 98 to about 99 C (uncorrected).
IR spectrum indicated that the aldehydic carbonyl appears at 2810 cm-l and 1660 cm-'.
NMR ô=9.52 (aldehydic) 1 proton, ô=7.48 (methine) 1 proton, ô=6.38 (methine) 2 protons.
Electrochemical data 2 reversible waves 0.1 M TEAP/CH3CN Elpeak=+0.53 V vs SCE 0.2 V/sec scan rate Pt electrode E2peak=+0.89 V vs SCE Example 8 Preparation of Vinyl TTF
e A slurry of #3P+CH3Br (0.39 g, 0.0011 mole) in 25 ml of dry ether is prepared under nitrogen. To this is added dropwise at 220C, 0.61 ml of 1.8 M BuLi in 10 ml of ether over a 10 min. period. The resulting orange solution was stirred for 1 hr. Then 0.25 g (0.0011 mole) of TTFCHO in 30 ml of ether was added dropwise over 10 min.
A white-tan precipitate separated. The mixture is stirred for 1 hr. and the precipitate (3PO and LiCI) is filtered off. The ether solution is evaporated under vacuum and the residue is purified by dry column chromatography using Grade III silica Gel.
The product is eluted from the impurities with hexane. There is obtained 0.1 g (39 /O vield of a bright vellow oil
Hx 1 proton Quartet b=6.38 JbX=17 Hz J =11 Hz Ha 1 proton Doublet b=5.11 J =11 Hz.
Hb 1 proton Doublet b=5.03 JbX=17 Hz.
Hv=Hz 3 protons (coincidently) b=6.07 (singlet).
Ir spectrum indicates that the C=C stretch appears at 1610 cm-', other IR peaks occur at 3070(S), 2960 (W), 2920 1800 (W), 1610(S), 1532(S), 1415(W), 1290(W), 1258 (W), 1240(M), 1150 (S), 1095 (M), 973 (S), 902 (S), 829 (S), 800 (S), 780 (S), 770 (S), 740 (M), 645 (S) cm-'.
Electrochemical Data 2 reversible waves 0.1 M TEAP/CH3CN Elpeak=+0.415 V vs. SCE 0.2 V/sec Scan rate E2pxak=+0.770 V vs SCE Pt electrode Example 9 Preparation of TTFCO2H-TCNQ Equimolar portions of TTFCO2H and TCNQ are mixed in CH3CN. After several minutes a black precipitate separates and is collected on a filter. The crystals are compressed into a pellet which shows a conductivity of 8.3 ohm-l cm- at 25"C.
Example 10 Preparation of Ethyl TTF TCNQ Equimolar portions of ETTF and TCNQ are mixed in CH3CN. The resulting black precipitate shows a resistance when pressed between the electrodes of an ohm-meter of 40 ohms.
WHAT WE CLAIM IS: 1. A substituted heterofulvalene having the general formula
where Y is S or Se; Z is S or Se; R is C2H5, -CH=CH2, CO2H, R'R"COH, R'CHOH, COR', Cl, Br, I, SR', CO-2Li+, SnR3,, SiR3,, CH2OH, CO2R', R'CHOH, CHO, CR2'OH or an alkali metal radical and where R' and R" are alkyl, aryl, alkaryl, ether substituted alkyl, halogen substituted alkyl or halogen radicals.
2. A substituted heterofulvalene according to Claim 1, wherein R is -CO2C2H5, C2H5, -COCH3, -CHO, -CH=CH2 or CO2CH3.
3. A substituted heterofulvalene according to Claim 1, wherein R is lithium.
4. A tetracyano - p - quinodimethane salt of a substituted heterofulvalene as claimed in any one of Claims 1 to 3.
5. A method of preparing a substituted heterofulvalene as claimed in Claim 1, which comprises reacting a heterofulvalene of the formula
with an organo-alkali metal compound in the absence of oxygen to give an alkali metal compound of the formula
wherein M.is an alkali metal, and thereafter reacting said alkali metal compound with a suitable reagent to replace the alkali metal M in said alkali metal compound with a radical R.
6. A method according to Claim 5, wherein said alkali metal compound is a lithium compound which is added to said reagent at a temperature of from -40"C to -800C.
**WARNING** end of DESC field may overlap start of CLMS **.

Claims (8)

  1. **WARNING** start of CLMS field may overlap end of DESC **.
    Ir spectrum indicates that the C=C stretch appears at 1610 cm-', other IR peaks occur at 3070(S), 2960 (W), 2920 1800 (W), 1610(S), 1532(S), 1415(W), 1290(W),
    1258 (W), 1240(M), 1150 (S), 1095 (M), 973 (S), 902 (S), 829 (S), 800 (S),
    780 (S), 770 (S), 740 (M), 645 (S) cm-'.
    Electrochemical Data 2 reversible waves 0.1 M TEAP/CH3CN Elpeak=+0.415 V vs. SCE 0.2 V/sec Scan rate E2pxak=+0.770 V vs SCE Pt electrode Example 9 Preparation of TTFCO2H-TCNQ Equimolar portions of TTFCO2H and TCNQ are mixed in CH3CN. After several minutes a black precipitate separates and is collected on a filter. The crystals are compressed into a pellet which shows a conductivity of 8.3 ohm-l cm- at 25"C.
    Example 10 Preparation of Ethyl TTF TCNQ Equimolar portions of ETTF and TCNQ are mixed in CH3CN. The resulting black precipitate shows a resistance when pressed between the electrodes of an ohm-meter of 40 ohms.
    WHAT WE CLAIM IS: 1. A substituted heterofulvalene having the general formula
    where Y is S or Se; Z is S or Se; R is C2H5, -CH=CH2, CO2H, R'R"COH, R'CHOH, COR', Cl, Br, I, SR', CO-2Li+, SnR3,, SiR3,, CH2OH, CO2R', R'CHOH, CHO, CR2'OH or an alkali metal radical and where R' and R" are alkyl, aryl, alkaryl, ether substituted alkyl, halogen substituted alkyl or halogen radicals.
  2. 2. A substituted heterofulvalene according to Claim 1, wherein R is -CO2C2H5, C2H5, -COCH3, -CHO, -CH=CH2 or CO2CH3.
  3. 3. A substituted heterofulvalene according to Claim 1, wherein R is lithium.
  4. 4. A tetracyano - p - quinodimethane salt of a substituted heterofulvalene as claimed in any one of Claims 1 to 3.
  5. 5. A method of preparing a substituted heterofulvalene as claimed in Claim 1, which comprises reacting a heterofulvalene of the formula
    with an organo-alkali metal compound in the absence of oxygen to give an alkali metal compound of the formula
    wherein M.is an alkali metal, and thereafter reacting said alkali metal compound with a suitable reagent to replace the alkali metal M in said alkali metal compound with a radical R.
  6. 6. A method according to Claim 5, wherein said alkali metal compound is a lithium compound which is added to said reagent at a temperature of from -40"C to -800C.
  7. 7. A method of preparing a substituted heterofulvalene as claimed in Claim 1
    substantially as described in any one of the Examples 1 to 10.
  8. 8. A substituted heterofulvalene prepared by the method claimed in any one of Claims 5 to 7.
GB3295977A 1976-12-03 1977-08-05 Substituted heterofulvalenes Expired GB1579038A (en)

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Publication number Priority date Publication date Assignee Title
US20140134502A1 (en) * 2012-11-09 2014-05-15 Samsung Fine Chemicals Co., Ltd. Electrolyte for secondary lithium battery and secondary lithium battery using the same

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Publication number Priority date Publication date Assignee Title
US4405515A (en) * 1979-05-10 1983-09-20 International Business Machines Corporation Heterofulvalene geminal dithiolate compounds and their selenium and tellurium analogs and a method of fabricating the same
US4362662A (en) * 1979-05-10 1982-12-07 International Business Machines Corporation Heterofulvalene geminal dithiolate compounds and their selenium and tellurium analogs and a method of fabricating the same
US4312991A (en) * 1979-05-10 1982-01-26 International Business Machines Corporation Dithiobenzoate 4,5-dicyano-1,3-(dithiolidene-2-yl)methylene
US4363919A (en) * 1979-05-10 1982-12-14 International Business Machines Corporation Heterofulvalene geminal dithiolate compounds and their selenium and tellurium analogs and a method of fabricating the same
DE2937225A1 (en) * 1979-09-14 1981-04-02 Basf Ag, 6700 Ludwigshafen CYCLICALLY SUBSTITUTED FULVALENOPHANES, THEIR PRODUCTION AND USE
US4439505A (en) * 1982-01-21 1984-03-27 Eastman Kodak Company Electrical conductive compositions
US4478922A (en) * 1982-01-21 1984-10-23 Eastman Kodak Company Electrically conductive compositions
US4465845A (en) * 1982-04-26 1984-08-14 Koppers Company, Inc. High pressure synthesis of sulfur-selenium fulvalenes
JPS61100586A (en) * 1984-10-22 1986-05-19 コツパ−ス　コムパニ−　インコ−ポレ−テツド Substituted furvalene
FR2659486B1 (en) * 1990-03-09 1995-10-13 Europ Composants Electron ELECTROLYTIC CAPACITOR WITH SOLID ELECTROLYTE AND METHOD FOR IMPREGNATING SUCH A CAPACITOR.

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140134502A1 (en) * 2012-11-09 2014-05-15 Samsung Fine Chemicals Co., Ltd. Electrolyte for secondary lithium battery and secondary lithium battery using the same

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