CN1045966C - Novel trifluorovinyl phosphonic acid diester monomer and its synthesis - Google Patents
Novel trifluorovinyl phosphonic acid diester monomer and its synthesis Download PDFInfo
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- CN1045966C CN1045966C CN97106460A CN97106460A CN1045966C CN 1045966 C CN1045966 C CN 1045966C CN 97106460 A CN97106460 A CN 97106460A CN 97106460 A CN97106460 A CN 97106460A CN 1045966 C CN1045966 C CN 1045966C
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Abstract
本发明涉及一类新型含氟膦酸酯单体，即三氟乙烯基膦酸二酯单体及其合成，其是以CF2BrCFClBr为原料，在0-80℃的有机溶剂和水的混合溶液中，应用Na2S2O4/NaHCO3和表面活性剂存在的亚磺化脱卤反应，与端烯基膦酸二酯发生加成反应，再在Zn粉和CuCl2催化下发生脱邻二卤和还原去溴反应得到，由该单体合成的材料不仅具有PTFE材料的优异耐腐蚀，耐高温的化学稳定性，还具有膦酸酯的广泛用途，可用作金属萃取剂和燃料电池中的固体电解质；该合成方法的反应条件温和，操作简便，得率高。The present invention relates to a new type of fluorine-containing phosphonate monomer, i.e. trifluorovinyl phosphonic acid diester monomer and its synthesis, which uses CF 2 BrCFClBr as raw material and mixes organic solvent and water at 0-80°C In the solution, use Na 2 S 2 O 4 /NaHCO 3 and the sulfination dehalogenation reaction in the presence of surfactants to undergo addition reaction with terminal alkenyl phosphonic acid diesters, and then de-halogenate under the catalysis of Zn powder and CuCl 2 It is obtained by the reaction of ortho-dihalide and reductive debromination. The material synthesized from this monomer not only has the excellent corrosion resistance and high temperature chemical stability of PTFE materials, but also has a wide range of uses of phosphonates, which can be used as metal extractants and fuels. A solid electrolyte in a battery; the synthesis method has mild reaction conditions, simple operation and high yield.
Description
The present invention relates to a class novel fluorine phosphonic acid ester monomer.It is trifluoro vinyl phosphonate diester monomer and synthetic.
In recent years, the research of tetrafluoroethylene monomer and polymkeric substance thereof is paid much attention to because of its special excellent properties always.Multipolymer Tefzel as tetrafluoroethylene and ethene, fluoro-containing plastic tetrafluoroethylene R 1216 FEP, the terpolymer of excellent fluorocarbon elastomer-tetrafluoroethylene, vinylidene, R 1216, tetrafluoroethylene and end group are sulfonic acid fluoride or carboxylic acid resin's the monomeric multipolymer of trifluoro vinyl ethers.P.Mougenot, P.Mertens, M.Nguyen, R.Touillaux and J.Marchand-Brynaert., J.Org.Chem., 61,408 (1996); M.-H.Hung, W.B.Farnham, A.E.Fieringand S.Rozen., J.Am.Chem.soc., 115,8954 (1993); M.-H.Hung, S.Rozen.and B.E.Smart., J.Org.Chem., report trifluoro vinyl ethers are monomeric synthetic and receive much attention in 59,4332 (1994), and contain fluorinated phosphonic acid and phosphonic acid ester has stronger physiologically active, its widely purposes also caused the research interest of people to it, at S.D.Lindell., Tetrahedron.Lett., 37,5381 (1990); S.F.Mattin.Tetrahedron.Lett., 39, in 1839 (1992) to α, the phosphinic acid compounds that α-fluoroalkyl replaces has more research, it can be used as tensio-active agent, lubricant additive, fire-retardant material, defoamer in agricultural chemicals and the insecticidal formulation, releasing agent, the biological sequestrant that is used for biological study, electrolyte, and phosphonyl group has stronger complexing action to metal ion, therefore the compound that contains phosphonyl group also is commonly used for extraction agent and uses, be exactly to use the fluorine-containing phosphonic acid resin enriched uranium element from seawater that contains in Japanese Patent-" the little field; limit, mountain; add rattan; special permission is open, clear 54-122616 ".Therefore utilize corrosion-resistant, the high temperature resistant and high chemical stability of the excellence of PTFE material, with PTFE is that basic framework is introduced phosphonate groups, and synthetic novel material with fluorine-containing and phosphonate groups of good complexing of metal ion extracting power is the problem of current research.
Purpose of the present invention just provide a kind of novel have corrosion-resistant, high temperature resistant and a high chemical stability contain novel fluorophosphonate monomer and synthetic method thereof, it is as follows to contain the monomeric general molecular formula of novel fluorophosphonate:
n=3-7,R=Me、Et、n-Pr、i-Pr、n-Bu、i-Bu、s-Bu、t-Bu.
Synthetic method provided by the present invention is achieved by the following scheme, promptly with CF
2BrCFClBr is fluorine-containing raw material, is the diethyl phosphonate of thiazolinyl with end group in the sulfinatodehalogenation system
The generation addition reaction gets
This adduct is at the CuCl of Zn powder and catalytic amount
2Effect is taken off down adjacent dihalo-and reduction and is gone bromine reaction to obtain final product to contain the novel fluorophosphonate monomer.CF wherein
2BrCFClBr can make by trifluorochloroethylene and bromine water addition reaction are synthetic.The condition of sulfinatodehalogenation is to carry out in the miscible solution of polarity and non-polar solvent and water, at Na
2S
2O
4/ NaHCO
3Exist down with tensio-active agent, under 0-80 ℃ of condition, react, wherein CF
2BrCFClBr with
Feed ratio be 1: 2-4: 1, the miscible solution of polarity and non-polar solvent and water is C
2H
5OH/H
2O, CHCl
3/ H
2O, CH
3CN/H
2O, THF/H
2O, DMSO/H
2O, CH
2Cl
2/ H
2O,
Deng, the volume ratio of the solvent and the aqueous solution is 1: 2-3: 1; The mol ratio of sodium bicarbonate and V-Brite B is 0: 1-1: 2.Tensio-active agent is R
4N
+Br
-, as ceryl trimethylammonium amine bromide, tetran-butylphosphonium bromide amine etc.; And take off adjacent dihalo-and reduction go bromine reaction be under the cupric chloride effect of Zn powder and catalytic amount in the DMF solvent, being heated to 30-100 ℃ of condition reacts next time and obtains final product and contain the novel fluorophosphonate monomer, wherein the Zn powder is the 1.5-3 equivalent, CuCl
2Amount is the 2-10% of raw material mol number.
It is the corresponding product of addition reaction preparation of raw material that present method also is suitable for other ω-alkenyl phosphonic acid diethyl ester.
The present invention has successfully introduced phosphonic acid ester in the fluoro-containing macromolecule material, has overcome the deficiency of phosphonic acid ester, has widened the purposes of phosphonic acid ester, and the present invention can be widely used in the solid electrolyte in the enrichment of uranium element and ore dressing, the fuel cell.
Synthetic method provided by the invention has avoided prior art with the method for superoxide as the initiator fluoroalkylation, and it is few not only to have possessed reactions steps, and mild condition can be carried out under aqueous phase and normal temperature, and is easy to operate and safe, the high advantage of reaction yield.And, therefore have broad application prospects and economic worth because this contains the characteristics that the phosphonic acid ester polymer of monomers has the PTFE material.
Following examples help to understand the present invention, but are not limited to the present invention:
Embodiment 1
With compound allyl group diethyl phosphonate 20mmol, CF
2BrCFClBr30mmol is added to 50ml methylene dichloride and 50ml water, in the mixing solutions of 0.8g cetyl trimethylammonium bromide CTMAB, and vigorous stirring, oil bath is heated to 40 ℃, adds V-Brite B 6g, sodium bicarbonate 3g,
19FNMR follows the tracks of reaction and adds 50ml water with dissolve inorganic salts to the back that reacts completely, and the solution extracted with diethyl ether merges organic phase saturated common salt water washing, anhydrous sodium sulfate drying, and removal of solvent under reduced pressure obtains oily matter, obtains adduct 6.6g by column chromatography for separation.
Adding 1.3g in 30ml DMF is the 20mmolZn powder, 0.2gCuCl
2With the above-mentioned adduct of 10mmol, oil bath is heated to 50 ℃, induction stirring,
19FNMR follows the tracks of reaction and extremely reacts when finishing, continue 5 hours postcooling of reaction again to room temperature, reaction mixture is moved into adding 20ml5%HCl solution in the separating funnel, extracted with diethyl ether, merge organic phase saturated common salt water washing, anhydrous sodium sulfate drying, removal of solvent under reduced pressure obtains oily matter, obtains adduct by column chromatography for separation
Experimental data is as follows:
1HNMR(CDCl
3),σH(ppm):1.30(6H,t,CH
3CH
2O-)；1.85(4H,m)；2.4(2H,m,-(CH
2)
3-)；4.1(4H,q,CH
3CH
2O-).
19FNMR(CDCl
3),σF(ppm):29.5(dXd,1F,J=100,40Hz)；97.5(dm,1F,J=120Hz).
Ms(m/e):261(15.94,M
++1)；233(18.13,M
+-Et+1)；125(100).
IR(film):3010,2900,1750,1390,1200,1050.
HRMS(C
9H
16F
3PO
3):Cal:260.0776
Found:260.0763
Embodiment 2
With compound allyl group dimethyl phosphonate 20mmol, CF
2BrCFClBr10mmol is added to 30mlCH
3CN/60mlH
2O water, in the mixing solutions of 0.8g tetra-n-butyl ammonium bromide, vigorous stirring, oil bath is heated to 70 ℃, adds V-Brite B 6g, sodium bicarbonate 1g,
19FNMR follows the tracks of reaction and adds 50ml water with dissolve inorganic salts to the back that reacts completely, and the solution extracted with diethyl ether merges organic phase saturated common salt water washing, anhydrous sodium sulfate drying, and removal of solvent under reduced pressure obtains oily matter, obtains adduct by column chromatography for separation.
In 30mlDMF, add 30mmolZn powder, 0.3gCuCl
2With the above-mentioned adduct of 10mmol, oil bath is heated to 40 ℃, induction stirring,
19FNMR follows the tracks of reaction and extremely reacts when finishing, continue 5 hours postcooling of reaction again to room temperature, reaction mixture is moved into adding 20ml5%HCl solution in the separating funnel, extracted with diethyl ether, merge organic phase saturated common salt water washing, anhydrous sodium sulfate drying, removal of solvent under reduced pressure obtains oily matter, obtains adduct by column chromatography for separation
1HNMR(CDCl
3),σH(ppm):1.85(4H,m)；2.4(2H,m)；3.9(6H,s).
19FNMR(CDCl
3),σF(ppm):29.5(dXd,1F,J=100,40Hz)；97.5(dm,1F,J=120Hz).
Ms(m/e):247(12.5,M
++1)；233(27.5,M
+-Et+1)；125(100).
IR(film):3010,2900,1750,1390,1200,1050.
Embodiment 3
With compound allyl group phosphonic acids diisopropyl ester 20mmol, CF
2BrCFClBr80mmol is added to 60ml trichloromethane and 20ml water, in the mixing solutions of 0.8g cetyl trimethylammonium bromide CTMAB, and vigorous stirring, room temperature reaction adds V-Brite B 6g, sodium bicarbonate 2g,
19FNMR follows the tracks of reaction and adds 50ml water with dissolve inorganic salts to the back that reacts completely, and the solution extracted with diethyl ether merges organic phase saturated common salt water washing, anhydrous sodium sulfate drying, and removal of solvent under reduced pressure obtains oily matter, obtains adduct by column chromatography for separation.
In 30mlDMF, add 20mmolZn powder, 0.2gCuCl
2With the above-mentioned adduct of 10mmol, oil bath is heated to 80 ℃, induction stirring,
19FNMR follows the tracks of reaction and extremely reacts when finishing, continue 5 hours postcooling of reaction again to room temperature, reaction mixture is moved into adding 20ml5%HCl solution in the separating funnel, extracted with diethyl ether, merge organic phase saturated common salt water washing, anhydrous sodium sulfate drying, removal of solvent under reduced pressure obtains oily matter, obtains adduct by column chromatography for separation
1HNMR(CDCl
3),σH(ppm):1.40(12H,m)；1.85(4H,m)；2.4(2H,m)；4.5(2H,q).
19FNMR(CDCl
3),σF(ppm):29.5(dXd,1F,J=100,40Hz)；97.5(dm,1F,J=120Hz).
Ms(m/e):275(10.2,M
++1)；125(100).
IR(film):3010,2900,1750,1390,1200,1050.
Embodiment 4
With compound allyl group phosphonic acids di-n-butyl ester 20mmol, CF
2BrCFClBr40mmol is added to 50mlTHF/H
2O50ml water, in the mixing solutions of 0.8g cetyl trimethylammonium bromide CTMAB, vigorous stirring, oil bath is heated to 80 ℃, adds V-Brite B 3g, sodium bicarbonate 3g,
19FNMR follows the tracks of reaction and adds 50ml water with dissolve inorganic salts to the back that reacts completely, and the solution extracted with diethyl ether merges organic phase saturated common salt water washing, anhydrous sodium sulfate drying, and removal of solvent under reduced pressure obtains oily matter, obtains adduct by column chromatography for separation.
In 30mlDMF, add 30mmolZn powder, 0.2gCuCl
2With the above-mentioned adduct of 10mmol, oil bath is heated to 100 ℃, induction stirring,
19FNMR follows the tracks of reaction and extremely reacts when finishing, continue 5 hours postcooling of reaction again to room temperature, reaction mixture is moved into adding 20ml5%HCl solution in the separating funnel, extracted with diethyl ether, merge organic phase saturated common salt water washing, anhydrous sodium sulfate drying, removal of solvent under reduced pressure obtains oily matter, obtains adduct by column chromatography for separation
1HNMR(CDCl
3),σH(ppm):0.9(6H,t)；1.7-2.0(12H,m)；2.4(2H,m)；4.1(4H,q).
19FNMR(CDCl
3),σF(ppm):29.5(dXd,1F,J=100,40Hz)；97.5(dm,1F,J=120Hz).
Ms(m/e):289(7.6,M
++1)；125(100).
IR(film):3010,2900,1750,1390,1200,1050.
Embodiment 5
With compound alkene butyl phosphonic acids di-t-butyl ester 20mmol, CF
2BrCFClBr60mmol is added to 80mlC
2H
5OH/40mlH
2O water, in the mixing solutions of the positive Tetrabutyl amonium bromide of 0.53g, vigorous stirring, oil bath is heated to 60 ℃, adds V-Brite B 4g, sodium bicarbonate 3g,
19FNMR follows the tracks of reaction and adds 50ml water with dissolve inorganic salts to the back that reacts completely, and the solution extracted with diethyl ether merges organic phase saturated common salt water washing, anhydrous sodium sulfate drying, and removal of solvent under reduced pressure obtains oily matter, obtains adduct by column chromatography for separation.
In 30mlDMF, add 25mmolZn powder, 0.2gCuCl
2With the above-mentioned adduct of 10mmol, oil bath is heated to 30 ℃, induction stirring,
19FNMR follows the tracks of reaction and extremely reacts when finishing, continue 5 hours postcooling of reaction again to room temperature, reaction mixture is moved into adding 20ml5%HCl solution in the separating funnel, extracted with diethyl ether, merge organic phase saturated common salt water washing, anhydrous sodium sulfate drying, removal of solvent under reduced pressure obtains oily matter, obtains adduct by column chromatography for separation
1HNMR(CDCl
3),σH(ppm):1.30(6H,t)；1.7-1.9(6H,m)；2.4(2H,m)；4.1(4H,q).
19FNMR(CDCl
3),σF(ppm):29.5(dXd,1F,J=100,40Hz)；97.5(dm,1F,J=120Hz).
Ms(m/e):275(27.5,M
++1)；247(30.5,M
+-Et+1)；125(100).
IR(film):3010,2900,1750,1390,1200,1050.
Embodiment 6
With compound alkene amyl group diethyl phosphonate 20mmol, CF
2BrCFClBr30mmol is added to 50mlDMSO/40mlH
2O water, in the mixing solutions of 0.8g cetyl trimethylammonium bromide CTMAB, vigorous stirring under the normal temperature adds V-Brite B 5g, sodium bicarbonate 4g,
19FNMR follows the tracks of reaction and adds 50ml water with dissolve inorganic salts to the back that reacts completely, and the solution extracted with diethyl ether merges organic phase saturated common salt water washing, anhydrous sodium sulfate drying, and removal of solvent under reduced pressure obtains oily matter, obtains adduct by column chromatography for separation.
In 30mlDMF, add 20mmolZn powder, 0.2gCuCl
2With the above-mentioned adduct of 10mmol, oil bath is heated to 90 ℃, induction stirring,
19FNMR follows the tracks of reaction and extremely reacts when finishing, and continues again
5 hours postcooling of continuous reaction move into adding 20ml5%HCl solution in the separating funnel to room temperature with reaction mixture, and extracted with diethyl ether merges organic phase saturated common salt water washing, anhydrous slufuric acid
The sodium drying, removal of solvent under reduced pressure obtains oily matter, obtains adduct by column chromatography for separation
1HNMR(CDCl
3),σH(ppm):1.30(6H,t)；1.7-2.1(8H,m)；2.4(2H,m)；4.1(4H,q).
19FNMR(CDCl
3),σF(ppm):29.5(dXd,1F,J=100,40Hz)；97.5(dm,1F,J=120Hz).
Ms(m/e):289(19.6,M
++1)；261(26.1,M
+-Et+1)；125(100).
IR(film):3010,2900,1750,1390,1200,1050.
Embodiment 7
With compound alkene hexyl diethyl phosphonate 15mmol, CF
2BrCFClBr30mmol is added to 50ml
60ml water, in the mixing solutions of 0.8g cetyl trimethylammonium bromide CTMAB, vigorous stirring, oil bath is heated to 50 ℃, adds V-Brite B 4g, sodium bicarbonate 3g,
19FNMR follows the tracks of reaction and adds 50ml water with dissolve inorganic salts to the back that reacts completely, and the solution extracted with diethyl ether merges organic phase saturated common salt water washing, anhydrous sodium sulfate drying, and removal of solvent under reduced pressure obtains oily matter, obtains adduct by column chromatography for separation.
In 30mlDMF, add 25mmolZn powder, 0.2gCuCl
2With the above-mentioned adduct of 10mmol, oil bath is heated to 60 ℃, induction stirring,
19FNMR follows the tracks of reaction and extremely reacts when finishing, continue 5 hours postcooling of reaction again to room temperature, reaction mixture is moved into adding 20ml5%HCl solution in the separating funnel, extracted with diethyl ether, merge organic phase saturated common salt water washing, anhydrous sodium sulfate drying, removal of solvent under reduced pressure obtains oily matter, obtains adduct by column chromatography for separation
1HNMR(CDCl
3),σH(ppm):1.30(6H,t)；1.6-1.9(10H,m)；2.4(2H,m)；4.1(4H,q).
19FNMR(CDCl
3),σF(ppm):29.5(dXd,1F,J=100,40Hz)；97.5(dm,1F,J=120Hz).
Ms(m/e):303(10.7,M
++1)；275(17.8,M
+-Et+1)；125(100).
IR(film):3010,2900,1750,1390,1200,1050.
Embodiment 8
With compound alkene heptyl diethyl phosphonate 20mmol, CF
2BrCFClBr40mmol is added to 50ml methylene dichloride and 50ml water, in the mixing solutions of 0.8g cetyl trimethylammonium bromide CTMAB, and vigorous stirring, oil bath is heated to 80 ℃, adds V-Brite B 4g, sodium bicarbonate 2g,
19FNMR follows the tracks of reaction and adds 50ml water with dissolve inorganic salts to the back that reacts completely, and the solution extracted with diethyl ether merges organic phase saturated common salt water washing, anhydrous sodium sulfate drying, and removal of solvent under reduced pressure obtains oily matter, obtains adduct by column chromatography for separation.
In 30mlDMF, add 20mmolZn powder, 0.1gCuCl
2With the above-mentioned adduct of 10mmol, oil bath is heated to 70 ℃, induction stirring,
19FNMR follows the tracks of reaction and extremely reacts when finishing, and continues again
5 hours postcooling of continuous reaction move into adding 20ml5%HCl solution in the separating funnel, extracted with diethyl ether to room temperature with reaction mixture, merge organic phase saturated common salt water washing, anhydrous sodium sulfate drying, removal of solvent under reduced pressure obtains oily matter, obtains adduct by column chromatography for separation
1HNMR(CDCl
3),σH(ppm):1.30(6H,t)；1.7-1.9(12H,m)；2.4(2H,m)；4.1(4H,q).
19FNMR(CDCl
3),σF(ppm):29.5(dXd,1F,J=100,40Hz)；97.5(dm,1F,J=120Hz).
Ms(m/e):317(7.5,M
++1)；289(12.5,M
+-Et+1)；125(100).
IR(film):3010,2900,1750,1390,1200,1050.
Claims (8)
1. novel fluorine phosphonic acid ester monomer is characterized in that general molecular formula is as follows:
n=3-7,R=Me、Et、n-Pr、i-Pr、n-Bu、i-Bu、s-Bu、t-Bu.
2. the monomeric synthetic method of novel fluorine phosphonic acid ester is characterized in that with CF
2BrCFClBr is fluorine-containing raw material, in the miscible solution of polarity or non-polar solvent and water, at Na
2S
2O
4/ NaHCO
3And/or tensio-active agent exists down, is the phosphonic acid diester of thiazolinyl with end group under 0-80 ℃ of condition
The generation addition reaction gets
This adduct in the DMF solvent, is heated to and takes off adjacent dihalo-under the 30-100 ℃ of condition and reduction goes bromine reaction to obtain under the cupric chloride effect of Zn powder and catalytic amount.
3. the monomeric synthetic method of novel fluorophosphonate that contains as claimed in claim 2 is characterized in that CF
2BrCFClBr with
Feed ratio be 1: 2-4: 1.
4. as claim 2 or the 3 described monomeric synthetic methods of novel fluorophosphonate that contain, it is characterized in that the miscible solution of polarity and non-polar solvent and water is C
2H
5OH/H
2O, CHCl
3/ H
2O, CH
3CN/H
2O, THF/H
2O, DMSO/H
2O, CH
2Cl
2/ H
2O,
The volume ratio of the solvent and the aqueous solution is 1: 2-3: 1.
5. as claim 2 or the 3 described monomeric synthetic methods of novel fluorophosphonate that contain, the mol ratio that it is characterized in that sodium bicarbonate and V-Brite B is 0: 1-1: 2.
6. as claim 2 or the 3 described monomeric synthetic methods of novel fluorophosphonate that contain, it is characterized in that tensio-active agent is R
4N
+Br
-, i.e. ceryl trimethylammonium amine bromide, tetran-butylphosphonium bromide amine.
7. as claim 2 or the 3 described monomeric synthetic methods of novel fluorophosphonate that contain, it is characterized in that the temperature of sulfinatodehalogenation is 30-50 ℃, taking off adjacent dihalo-and reduction, to go the temperature of reaction of bromine reaction be 40-60 ℃.
8. the monomeric purposes of novel fluorophosphonate that contains as claimed in claim 1 is characterized in that as the solid electrolyte in metal extraction agent and the fuel cell.
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|---|---|---|---|
| CN97106460A CN1045966C (en) | 1997-06-11 | 1997-06-11 | Novel trifluorovinyl phosphonic acid diester monomer and its synthesis |
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| CN1045966C true CN1045966C (en) | 1999-10-27 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8445142B2 (en) | 2009-05-21 | 2013-05-21 | Samsung Sdi Co., Ltd. | Organic electrolytic solution and lithium battery employing the same |
| US8568920B2 (en) | 2009-05-08 | 2013-10-29 | Samsung Sdi Co., Ltd. | Electrolytic solution and lithium battery employing the same |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100695110B1 (en) | 2005-05-18 | 2007-03-14 | 삼성에스디아이 주식회사 | High Temperature Fuel Cell Using Alkyl Phosphoric Acid |
| CN113277474A (en) * | 2021-07-07 | 2021-08-20 | 福建富仕新材料有限责任公司 | Preparation method of hydrogen chloride |
-
1997
- 1997-06-11 CN CN97106460A patent/CN1045966C/en not_active Expired - Fee Related
Non-Patent Citations (4)
| Title |
|---|
| A GENERAL METHOD FOR THE SYNTHESIS OF 1,1-DIFLUOROALKYL-PHOSPHONATES * |
| TETRAHEDRON LETT 1990,NO.37 P5381-5384,VOL31 1990. 1. 1 S.D.LINDELL SYNTHEIS OF POTENTIAL INHIBITORS OF THE ENZYML ASPARTATL TRANSC ARBAMOYLACE * |
| TETRAHEDRON LETT 1990,NO.37 P5381-5384,VOL31 1990. 1. 1 S.D.LINDELL SYNTHEIS OF POTENTIAL INHIBITORS OF THE ENZYML ASPARTATL TRANSC ARBAMOYLACE;TETRAHEDRON LETT 1992,VOL33(14)P1839-1842 1992. 1. 1 S.F.NATTIN;A GENERAL METHOD FOR THE SYNTHESIS OF 1,1-DIFLUOROALKYL-PHOSPHONATES * |
| TETRAHEDRON LETT 1992,VOL33(14)P1839-1842 1992. 1. 1 S.F.NATTIN * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8568920B2 (en) | 2009-05-08 | 2013-10-29 | Samsung Sdi Co., Ltd. | Electrolytic solution and lithium battery employing the same |
| US8445142B2 (en) | 2009-05-21 | 2013-05-21 | Samsung Sdi Co., Ltd. | Organic electrolytic solution and lithium battery employing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1165826A (en) | 1997-11-26 |
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