GB1559565A - Production of phosphoric acid esters of n-hydroxyalkyl perfluoroalkane sulphonamides - Google Patents
Production of phosphoric acid esters of n-hydroxyalkyl perfluoroalkane sulphonamides Download PDFInfo
- Publication number
- GB1559565A GB1559565A GB11374/78A GB1137478A GB1559565A GB 1559565 A GB1559565 A GB 1559565A GB 11374/78 A GB11374/78 A GB 11374/78A GB 1137478 A GB1137478 A GB 1137478A GB 1559565 A GB1559565 A GB 1559565A
- Authority
- GB
- United Kingdom
- Prior art keywords
- phosphoric acid
- perfluoroalkyl
- acid ester
- radical
- substituted phosphoric
- 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
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- 150000003014 phosphoric acid esters Chemical class 0.000 title claims description 12
- 150000003456 sulfonamides Chemical class 0.000 title description 4
- 238000004519 manufacturing process Methods 0.000 title description 3
- 150000001875 compounds Chemical class 0.000 claims description 20
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 4
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 claims description 4
- 229940124530 sulfonamide Drugs 0.000 claims description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000004480 active ingredient Substances 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 239000000413 hydrolysate Substances 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims 1
- 150000002431 hydrogen Chemical group 0.000 claims 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- -1 perfluoroalkyl radical Chemical class 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 3
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- 229940086542 triethylamine Drugs 0.000 description 3
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- FUVKFLJWBHVMHX-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonamide Chemical compound NS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F FUVKFLJWBHVMHX-UHFFFAOYSA-N 0.000 description 1
- XKQMKMVTDKYWOX-UHFFFAOYSA-N 1-[2-hydroxypropyl(methyl)amino]propan-2-ol Chemical compound CC(O)CN(C)CC(C)O XKQMKMVTDKYWOX-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001348 alkyl chlorides Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical compound O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000000565 sulfonamide group Chemical group 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/14—Derivatives of phosphoric acid
-
- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/091—Esters of phosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
(54) PRODUCTION OF PHOSPHORIC ACID
ESTERS OF N-HYDROXYALKYL
PERFLUOROALKANE SULPHONAMIDES (71) We, BAYER AKTIENGESELLSCHAFT, a body corporate organised under the Laws of Germany of 509 Leverkusen, Germany 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 :- This invention relates to perfluoroalkyl-substituted phosphoric acid esters and to a method for their production.
Thus, the present invention provides perfluoroalkyl-substituted phosphoric acid esters corresponding to the general formula (I) :
in which Ri, represents a straight-chain or branched-chain perfluoroalkyl radical having 1
to 6 carbon atoms, preferably 3 to 5 carbon atoms;
R represents hydrogen, or an alkyl, alkenyl, aralkyi, aryl or cycloalkyl radical
having up to 20 carbon atoms and optionally substituted by a non-interfering
inert radical, or the group
R'represents a CH2CH2or CH (CHSCH2-group ; and
M represents hydrogen and/or an alkali metal, an ammonium radical or sub
stituted ammonium group.
The optional substituents of the groups represented by R are radicals which are inert in that environment i. e. radicals which do not interfere with other radicals of the esters.
The compound according to the invention are produced by reacting an N-hydroxy- alkyl perfluoroalkane sulphonamide corresponding to the general formula:
in which RF, R'and R are as defined in claim 1, and R may also represent the group
R'OH with an excess of phosphorus oxychloride based on the OH groups at a temperature of from 0 to 60 C, followed by hydrolysis of the dichlorides primarily formed and, optionally, by neutralisation of the resulting hydrolysate with a base such as an alkali metal hydroxide, ammonia or an amine. For example, where N- (2-hydroxyethyl)- N-methyl perfluorobutane sulphonamide is used, the process according to the invention takes place in accordance with the following equations :
1. CdFg502 i-CHZ-CH2-OH + POC13 CH3 C4F9SO2N-CH2-CH2-OPCI2+ HCI CH2 0 C H3 O 0 2 Hydrolysis H20 C4FgSO2N-CH2-CH2-O-P CH3 (OH) 2 /'O 3. Neutralization 8--% 3. 5 2 N-CH2-CH2-O-F or ) OM 0 C4F9S 2N CH2CH2 0 P C H3 (OM) 2 Cl3 It is surprising that, in the process according to the present invention, only the monosubstitution products of POC13 are formed in a substantially quantitative yield and that the hydrogen chloride or hydrochloric acid formed as by-product does not enter into any secondary reactions during the hydrolysis step. In particular, no splitting of the sulphonamide group occurs, nor is any alkyl chloride formed (cf. Houben-WeyI, Methoden der Organischen Chemie, 1964, Vol. XII/2, page 164, and Vol. IX, page 630). The N- (hydroxy-alkyl)-perfluoroalkane sulphonarnides which may be used as starting materials in accordance with the present invention are readily obtainable (for example, in accordance with German Offenlegungsschrift No. 2,024,909 by reacting perfluoroalkane sulphonamides with ethylene or propylene carbonate in the presence of bases).
Examples of suitable starting materials are:
CF3SO2N(CH3)--CH2CH2OH
C, F, SO, N (C, H,) CH, CH, OH CaFSQN (C3HrIZCH20H C3F11SO2NHCH2CH2OH
C4F9SO2N(C6H5)--CH2CH2OH
CF3SO2N(CH2--CH=CH2)
CH (CH3)CH2OH and
C2F8SO2N(C18H37)CH2--CH2OH
The process according to the present invention is generally carried out by using one component viz. phosphorus oxychloride as solvent. The reaction temperature should best be in the range from 10 C to 30 C, more particularly 15 C to 23 C, and most preferably the reaction is carried out at room temperature. The hydrogen chloride formed is suitably removed under reduced pressure (approximately 200 to 300 Torr) during the actual reaction. Towards the end of the reaction, the temperature may be briefly increased to 40 C--60 C and, at the same time, the excess phosphorus oxychloride may be recovered by vacuum distillation.
The phosphoric acid ester dichlorides formed are converted into the ester acids
by treating with water, optionally under heat and in the presence of an organic solvent which enables excess water to be azeotropically removed, for example a chlorinated hydrocarbon, such as dichloroethane. The ester acids are reacted optionally in a molar ratio of about 1: 1 or 1: 2 with a base preferably alkali metal hydroxide, ammonia, a primary, secondary or tertiary amine or heterocyclic nitrogen compound, such as pyridine or morpholine, in an organic solvent, for example an alcohol or halogenated hydrocarbon, resulting in the formation of the add or neutral salt.
The products according to the invention may be used for a variety of purposes.
They may be used as biocides, wetting agents, levelling agents, defoaming agents, emulsifiers, impregnating agents, for example for the hydrophobic or oleophobic finishing of paper and other fibre-based materials, or as additives to fire-extinguishing agents.
It is surprising that the compounds according to the present invention are suitable for use as surfactants. Interfacially active effects are obtained even with short-chain perfluoroalkyl groups, for example, the C3F"C, F, or C5Fl,-group. Thus, according to another aspect, the invention provides a surface active agent comprising as active ingredient at least one perfluoroalkyl-substituted phosphoric acid ester according to the invention.
The process according to the invention is illustrated by the following examples :
EXAMPLE 1
In a three-necked flask provided with a heatable dropping funnel, reflux condenser, internal thermometer and stirrer, 165 g (0.46 mole) of molten N- (2-hydroxy- ethyl)-N-methyl perfluorobutane sulphonamide were added dropwise with cooling at 20 C to 25 C to 457 g (3 moles) of phosphorus oxychloride. The hydrogen chloride evolved was removed by applying a vacuum (200300 Torr). 5 Hours after the dropwise addition, the temperature was increased to approximately 30-35 C and, after another hour, the excess phosphorus oxychloride was transferred in vaqua (approximately 1 to 3 Torr) to a cooled receiver. The residue was taken up with 250 ml of dichloroethane, 25 g of water were added and the mixture was gradually heated to reflux temperature. After 2 hours, the excess water and dichloroethane were azeotropically distilled off. Drying in vacuo gave 192 g (95.5% of the theoretical yield) of the compound.
(m. p.: 134-136 C). The compound was identified by NMR-spectroscopy and by titration.
EXAMPLE 2
21.7 g (0.05 mole) of the compound of Example 1 were dissolved in 50 ml of methanol, followed by the addition of 4 g (0.1 mole) of sodium hydroxide (in the form of a 10% aqueous solution). The solvents were removed in vacuo after 30 minutes, leaving 24 g (quantitative amount) of the compound
EXAMPLE 3
134 g (0.31 mole) of the compound of Example 1 were suspended in 200 ml of methylene chloride, followed by the gradual addition of 70 g (0.69 mole) of triethyl- amine. After a clear solution had formed, the solvent and excess triethylamine were distille off in vacuo at 60 C. 163 g (quantitative) of the compound
were obtained. The existing structure of the compound as an acid salt was confirme by NMR-spectroscopy and by titration.
EXAMPLE 4
40.6 g (0.0928 mole) of the compound of Example 1 were suspended in 50 g of water, 9.4 g (0.0928 mole) of triethylamine were added and the mixture was heated to 70 C. The 50% solution of the compound formed which corresponded to the formula in Example 3 may be further diluted with water as required.
EXAMPLE 5
20 g (0.046 mole) of the compound of Example 1 were suspended in 50 ml of methylene chloride, followed by the addition of 6.8 g (0.046 mole) of N-methyl diiso propanolamine. After a clear solution had formed, the solvent was distille off in vacvo at 60 C. 26.7 g (quantitative amount) of the compound
were obtained.
Reduction in surface tension 18. 2 dyn/cm for 750 mg/l of H, 0j EXAMPLE 6
50.2 g (920/,', of the theoretical yield) of the compound
were obtained by the method described in Example 1 from 184 g (1.3 moles) of phosphorus oxychloride, 39 g (0. 1 mole) of N, N-bis- (2-hydroxy-ethyl)-per8uorobutane sulphonamide and 18 g (1 mole) of water.
Reduction in surface tension wu18. 8 dyn/cm for 500 mg/l of water3
EXAMPLE 7
167.5 g (95.5,, o of the theoretical yield) of the compound
were obtained by the method described in Example 1, but without using the heatable dropping funnel, from 368 g (2.4 moles) of phosphorus oxychloride, 124 g (0.64 moles) of N- (2-hydroxyethyl)-N-methyl trifluoromethane sulphonamide and 27 g (1. 5 moles) of water.
The structure of the compound was confirme by NMR-spectroscopy and by titration.
EXAMPLE 8
17.2 g (0.06 mole) of the compound of Example 7 were dissolved in 50 ml of methanol and 4.8 g (0.12 mole) of sodium hydroxide (in the form of a 10% aqueous solution) were added to the resulting solution. After about 0.5 hour, the solvents were distille off, leaving 19.8 g (quantitative) of the compound.
EXAMPLE 9 47 g (93 of the theoretical yield) of the compound
were obtained by the method described in Example 7 from 153 g (1 mole) of phos phorus oxychloride, 42.7 g (0.1 mole) of N-hexyl-N- (2-hydroxyethyI)-pernuorobutane sulphonamide and 5.4 g (0.3 mole) of water.
Claims (10)
1. A perfluoroalkyl-substituted phosphoric acid ester corresponding to the general formula (I) :
in which RF represents a straight-chain or branched-chain perfluoroalkyl radical having 1
to 6 carbon atoms ;
R represents hydrogen, or an alkyl, alkenyl, aralkyl, aryl or cycloalkyl radical
having up to 20 carbon atoms and optionally substituted by a non-mterfering inert radical, or the group
R'represents a--CHj-CH=-or-H (CHaHZ-group and
M represents hydrogen and/or an alkali metal, an ammonium radical or a sub
stituted ammonium group.
2. A perfluoroalkyl-substituted phosphoric acid ester as claimed in claim 1, wherein RF is a straight-chain or branched-chain perssuoroalkyl radical having 3 to 5 carbon atoms.
3. A perfluoroalkyl-substituted phosphoric acid ester substantially as herein described with reference to any of the specific Examples.
4. A process for producing a compound of general formula (I) as defined in claim 1, wherein an N-hydroxyalkyl perfluoroalkane sulphonamide corresponding to the general formula:
in which RF, R'and R are as defined in claim 1, and R may also represent the group
R'OH, is reacted with an excess of phosphorus oxychloride at a temperature of from 0 to 60 C wherein the dichloride formed is isolated and hydrolysed with water, and
wherein the resulting hydrolysate is optionally neutralised by reaction with a base.
5. A process as claimed in claim 4, wherein the temperature is from 10 C to 30 C.
6. A process as claimed in claim 5, wherein the temperature is from 15 C to 25 C
7. A process as claimed in any of claims 4 to 6, wherein the base is an alkali metal
hydroxide, ammonia or an amine.
8. A process for producing a perfluoroalkyl-substituted phosphoric acid ester substantially as herein described with reference to any one of the specific Examples.
9. A perfluoroalkyl-substituted phosphoric acid ester when prepared by a process as claimed in any of claims 4 to 8.
10. A surface-active agent comprising as active ingredient at least one perfluoro- alkyl-substituted phosphoric acid ester as claimed in any of claims I to 3 and 8.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19772713498 DE2713498A1 (en) | 1977-03-26 | 1977-03-26 | PERFLUORALKYL-SUBSTITUTED PHOSPHORIC ACID ESTERS AND METHOD FOR THEIR MANUFACTURING |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB1559565A true GB1559565A (en) | 1980-01-23 |
Family
ID=6004805
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB11374/78A Expired GB1559565A (en) | 1977-03-26 | 1978-03-22 | Production of phosphoric acid esters of n-hydroxyalkyl perfluoroalkane sulphonamides |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPS53119827A (en) |
| DE (1) | DE2713498A1 (en) |
| ES (1) | ES468143A1 (en) |
| FR (1) | FR2384788A1 (en) |
| GB (1) | GB1559565A (en) |
| IT (1) | IT7848593A0 (en) |
| NL (1) | NL7803214A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0296661B1 (en) * | 1987-06-23 | 1992-01-22 | ENIRICERCHE S.p.A. | Single-phase composition containing a perfluorinated oil and one or more surfactant(s), useful as an excipient for cosmetic and dermatologic formulations, as well as for biomedical applications |
| DE3723198A1 (en) * | 1987-07-14 | 1989-02-16 | Bayer Ag | FOAM-RESISTANT ADDITIVE IN ACID SOURS AND GALVANIC BATHS |
-
1977
- 1977-03-26 DE DE19772713498 patent/DE2713498A1/en active Pending
-
1978
- 1978-03-22 GB GB11374/78A patent/GB1559565A/en not_active Expired
- 1978-03-22 ES ES468143A patent/ES468143A1/en not_active Expired
- 1978-03-23 NL NL7803214A patent/NL7803214A/en not_active Application Discontinuation
- 1978-03-24 JP JP3318378A patent/JPS53119827A/en active Pending
- 1978-03-24 FR FR7808826A patent/FR2384788A1/en not_active Withdrawn
- 1978-03-24 IT IT7848593A patent/IT7848593A0/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| FR2384788A1 (en) | 1978-10-20 |
| DE2713498A1 (en) | 1978-09-28 |
| IT7848593A0 (en) | 1978-03-24 |
| JPS53119827A (en) | 1978-10-19 |
| NL7803214A (en) | 1978-09-28 |
| ES468143A1 (en) | 1978-12-16 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| CSNS | Application of which complete specification have been accepted and published, but patent is not sealed |