AU642350B2 - Synthesis of perfluoroalkyl bromides - Google Patents
Synthesis of perfluoroalkyl bromides Download PDFInfo
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- AU642350B2 AU642350B2 AU17038/92A AU1703892A AU642350B2 AU 642350 B2 AU642350 B2 AU 642350B2 AU 17038/92 A AU17038/92 A AU 17038/92A AU 1703892 A AU1703892 A AU 1703892A AU 642350 B2 AU642350 B2 AU 642350B2
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C19/00—Acyclic saturated compounds containing halogen atoms
- C07C19/08—Acyclic saturated compounds containing halogen atoms containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
- C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
- C07C17/204—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being a halogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
Abstract
Preparation of perfluoroalkyl bromides RF-Br, RF denoting a linear or branched perfluoroalkyl radical containing from 2 to 12 carbon atoms. The continuous process according to the invention consists in reacting bromine and a perfluoroalkyl iodide RF-I in the gas phase at a temperature of between 200 and 600 DEG C, it being possible for the Br2/RFI molar ratio to range from 0.1 to 2. The selectivity for RF-Br is virtually complete.
Description
AUSTRALIA 6 4 PATENTS ACT 1990 COMPLETE SPECIRCATION FOR A STANDARD PATENT
ORIGINAL
S F Ref: 211650 350 I 1 ~~111~ Name and Address of Applicant: Actual Inventor(s): Address for Service: Invention Title: Elf Atochem S.A.
4 8 Cours Michelet La Defense 92800 Puteaux
FRANCE
Gilles Drivon Spruson Ferguson, Patent Attorneys Level 33 St Martins Tower, 31 Market Street Sydney, New South Wales, 2000, Australia Synthesis of Perfluoroalkyl Bromides
C
The following statement is a full description of this invention, including the best method of performing it known to me/us:- 5845/4 2 The present invention relates to the preparation of perfluoroalkyl bromides or bromoperfluoroalkanes R,-Br, R, denoting a linear or branched perfluoroalkyl radical CnF 2 n+1, containing from 2 to 12 carbon atoms.
These known compounds are employed in many fields, in particular in medicine as radioopacifiers (X-ray contrast agents) or as oxygen carriers in blood substitutes. A compound more particularly investigated in this field is nperfluorooctyl bromide CgF 1 7 Br.
Among the known methods for preparing these compounds there may be mentioned in particular: the action of bromine on a compound RFSF 5 at 500°C in the presence of nickel (US Patent 3,456,024); the gas phase photolysis of a compound RFH with 15 Br-Cl or Br-F Adcock et al., CA 100, 34092 e) or with Br 2 (French Patent FR 1,512,068).
*2 The poor yields obtained and/or the use of fluorine derivatives which are not available industrially mean that economical production of the RFBr compounds on an 20 industrial scale is not possible.
European patent EP 0,298,870 and European patent application EP 90403118.4 describe processes for the manufacture of RFBr compounds from the corresponding perfluoroalkane-sulphonyl chlorides RFSO 2 Cl which are reacted S 25 either with gaseous HBr in the presence of a catalyst (EP 0,298,870), or with a quaternary ammonium or phosphonium bromide (EP 90403118.4). The yields obtained are generally 3 high but the sulphochloride RFSOgCl, employed as starting material, is very complex to produce, since its synthesis from the corresponding iodide RFI requires two reaction stages, according to the equation: Zn 2C1 2 2 Rp I 2 SO 2
(RFSO
2 2 n 2 RFSO 2 CI ZnC 2 The most direct route for obtaining the compounds RFBr would comprise radical bromination of the corresponding iodides RFI, the latter being products which are available in industrial quantities.
International Journal of Chemical Kinetics, vol.
II, 273-285 (1975), E.N. Okafo et E. Whittle, describes the kinetics of thermal bromination of CF 3 I in a photochemical reactor between 173 and 321°C, wi;:h a view to determining the 15 dissociation energy of the C-I bond.
J. Chem. Soc. 1953, 3761-8, R.N. Haszeldine, describes a photochemical process for reacting RFI wi-th bromine, the operation being carried out in a sealed tube with an excess of bromine (10 and while irradiating with a 20 UV light for seven days. The reaction temperature and the purity obtained are not stated; it is merely indicated that the yield is higher than or equal to 90 depending on the length of the perfluorinated chain Rp.
In examples of Japanese Application Iokai 85-184,033, which describes the reaction of RI with Br 2 in 4 e the presence of a chemical radical initiator, the yields indicated do not exceed 42 The poor yields obtained and/or the slow kinetics of these techniques do not make it possible to envisage their industrial exploitation.
According to the present invention, there is provided a continuous process for the preparation of a perfluoroalkyl bromide Rn-Br (wherein RF represents a linear or branched perfluoroalkyl radical containing from 2 to 12 carbon atoms) which process comprises reacting in gaseous phase bromine with the corresponding perfluoroalkyl iodide RI-I (wherein RF represents a linear or branched perfluoroalkyl radical as defined above).
The process of the present invention permits 15 continuous production of perfluoroalkyl bromides RFBr containing from 2 to 12, preferably 6 to 10, carbon atoms, from the corresponding R I, with very high selectivity for RpBr. The process according to the invention is characterised in that an RI and bromine are reacted continuously in gaseous 20 phase.
The reaction can be carried out in a tubular
S
reactor at a temperature ranging from 200 to 600°C, but is advantageously operated at a temperature of between 300 and 500 C, preferably between 350 and 500*C. The reactor can be a hollow tube, but it may optionally contain an inert solid substrate (for example glass or quartz) to facilitate the contact between the two gases (Br 2 and RFI). The operation may also be carried out in the presence of an inert gaseous diluent, for example nitrogen, although this is not essential.
Since the reaction of bromine with RFI in gaseous phase is very fast, the contact time, that is to say the residence time of the reactants in the reactor, is not a critical parameter and may vary within wide limits. A contact time of from 1 second to 2 minutes is generally suitable but, on an industrial scale, it is preferred to operate with a contact time ranging from 5 to 30 seconds.
On an industrial scale it is preferred to work at atmospheric pressure, but working at a pressure above atmospheric pressure would not constitute a departure from the scope of the present invention, provided that the reaction system remains in the gaseous state.
To recover the RFBr formed and optionally unconverted RFI the gases leaving the reactor may be cooled, and the mixture is then distilled directly or after treatment with a reducing agent.
20 The process according to the invention may be implemented by operating with an excess or a deficiency of too bromine in relation to the theoretical quantity (0.5 mol of Br 2 per mol of RFI). The Br 2 /RFI molar ratio may therefore vary within wide limits, generally between 0.1 and 2.
S" 25 However, for process economy, the operation is advantageously carried out at a Br 2 /RFI molar ratio of between 0.3 and 1.
When the operation is carried out with an excess 6 of bromine, and whatever the temperature and the contact time, the reaction takes place according to the scheme: RI Br 2 RFBr BrI (1) Depending on the operating conditions used, it is then possible to obtain substantially complete conversion of the RFI, and this makes it easier to recover the RFBr in a very pure state merely by distillation. However, because of the thermodynamic equilibrium: BrI B Br 2 I12 10 a mixture containing bromine and iodine is inevitably found at the reactor exit.
When the operation is carried out with a deficiency of bromine and depending on the operating conditions (molar ratio, temperature, contact time), the reaction takes place either according to the scheme (1) Sabove, or according to the scheme 2 RFI Br 2 2 RFBr I 2 (2) Bearing in mind the deficiency of bromine, only partial conversion of the RFI will be obtained. However, it is possible to combine the operating conditions such as to permit a substantially complete conversion of the bromine 7 (equation and this simplifies the recovery and the upgrading of the iodine obtained as a by-product in its oxidised or reduced form. After separation of the iodine, the RFBr/RFI mixture can be distilled to separate off the unconverted RFI and to recycle it to the reactor. It is also possible to add supplemental bromine to the RpBr/RpI mixture and to complete the reaction in a second reactor.
The bromine and the RI may be introduced into the reactor separately. However, since bromine is partially soluble in the RFI, it is advantageously possible, when working at a molar ratio below the solubility limit, to introduce both reactants by starting with a homogeneous mixture of these two compounds; this then makes it possible to operate with a single feed pump and thus to ensure a 15 constant molar ratio.
The process according to the invention applies both to the preparation of a specific RFBr (for example
C
6
F
1 3 Br, C 8
F
17 Br, C 10
F
21 Br, etc.) and to that of a mixture of different RFBr compounds from a mixture of the corresponding 20 RI compounds.
In the following Examples, which further illustrate the invention, the degree of conversion (DC) of the RFI is crlculated using the relationship:
S
S" RFI moles input RI moles output DC 100 x RFI moles input 8 and the selectivity for RBr using the relationship: S 100 of miscellaneous output of impurities input) EXAMPLE 1 SYNTHESIS OF PERFLUOROOCTYL BROMIDE A glass tubular reactor (internal diameter: 30 mm; height: 300 mm) is employed, with 1/5 of it packed with rings to ensure good gas mixing, equipped with a thermometer sheath for checking the temperature and with a dip tube for introducing the reactants.
Test No. 1 This reactor is fed simultaneously and continuously for 2 hours, with the aid of two metering pumps, with 0.261 mol of bromine and 0.560 mol of perfluorooctyl iodide (purity: 99.3 together with 2 i/h of nitrogen.
S15 The operating conditions are the following: temperature 300°C contact time e 30 seconds
B
2
/CF,
1 L molar ratio 0.47 The gases leaving the reactor are collected in an 20 excess of aqueous solution of sodium sulphite. After 6 settling, two phases are obtained: an upper aqueous phase which is analysed quantitatively by argentimetry to determine the content of bromide and iodide which are present 0.374 eq. and Br' 0.150 eq.); 9 a lower organic phase which weighs 283.5 g and whose analysis by gas phase chromatography with a Varian 3300 apparatus (catharometer detector; 30 m macrobore DB 1 column:) gives the following composition by weight:
CF
17 Br 62.55
C
8
F
17 36.80 miscellaneous 0.65 which corresponds to a degree of conversion of CF1 7 I of 66 and a selectivity for CgF 17 Br of 100 Tests No. 2 to 26 These tests, carried out in the same apparatus and operating in the same way as in the case of Test No. 1, show the influence of the various parameters on the degree of conversion and the selectivity.
The operating conditions, the quantities employed and the results obtained in these tests are summarised in Tables I to V, which follow.
g* oo TA13LE I EFFECT OF THE REACTION TEMPERATURE Contact time :30 2 seconds Br 2
/CF
17 1 molar ratio 1 0. 1 Purity of the starting C 8
,F,
7 1 99.3 Duration of a test :approximately 2 hours operating conditions Quantities used REACTOR EXIT TEST IOrganic phase Aqueous phase No. Temperature Br 2 1CF 1 7 I Br. CaF 17 I Weight C 8
F,
7 Br C 8
F
1 DC Misc. S I- eq. Br- eq.
0 C molar ratio mol mol mol mol 2 250 1.07 0.423 0.396 200.8 0.153 0.228 42.5 0.64 100 0.155 0.716 3 300 0.92 0'.340 0.368 179.2 0.294 0.058 84 0.70 100 0.312 0.419 4 350 0.99 0.342 0.344 167.6 0.334 0.001 99.7 0.66 100 0.356 0.357 400 0.94 0.303 0.322 156.6 0.314 f #100 0.66 100 0.336 0.312 6 450 0.91 0.269 0.297 145.3 0.290 f #100 0.72 100 10.312 0.2-66 7 500 1.09 0.300 0.276 133.4 I0'.264 f #10011.42 99.310.287 0.343 S. *S* I. S S TABLE II EFFECT OF THE Brd/C8E 17 I MOLAR RATIO AT 300 C Contact time 30 2 seconds Purity of the starting CF 17 1 :99.3 Duration of a test approximately 2 hours Quantities used REACTOR EXIT TEST Br 2
/C
8
F
17 1 Organic phase Aqueous phase No. molar ratio Br. CF 1 7 1 Weight C 8
F
17 Br C.F 17 1 DC Misc. S I- eq. Br- eq.
mol mol mol -Mol 8 0.30 0.200 0.669 344.5 0.311 0.344 48.5 0.70 100 0.316 0.072 9 0.32 0.199 0.621 319.2 0.315 0.293 53 0.8 99.9 0.328 0.060 0.36 0.225 0.621 315.4 0.345 0.256 59 0.95 99.75 0.354 0.090 1 0.47 0.261 0.560 283.5 0.356 0.191 66 0.65 100 0.374 0.150 11 0.52 0.326 0.621 313.4 0.420 0.187 70 0.70 100 0.432 0.208 13 0.92 I0.340 0.368 179.2 0.294 0.058 84 0O.70 100 0.312 j0.419
S
S S TABLE III EFFECT OF THE Br 9
/C
1 17I MOLAR RATIO AT 350 0
C
Contact time 30 2 seconds Purity of the starting CF, 7 1 :99.3 Duration of a test approximately 2 hours Quantities used REACTOR EXIT TEST Br./CF 1 7 1 organic phase Aqueous phase No. molar ratio Br 2
C
8
F
17 1 Weight CF 1 7Br C 8
F
17 1 DC Misc. S I- eq. Br- eq.
mol mol inol mol 12 0.30 0.182 0.606 310.7 0.341 0.255158 0.4 100 0.334 13 0.385 0.216 0.562 271.8 0.405 0.123 78 0.9 99.8 0.404 0.014 14 0.54 0.279 0.513 251.8 0.471 0.028 94.5 0.6 100 0.494 0.066 4 0.99 0.342 0.344 167.6 0.334 0.001 99.7 0.66 100 0.356 0.357 I __1 TABLE IV EFFECT OF THE Br 8.- 1 7 L ±P AI A 0 0 Contact time 30 2 seconds Purity of the starting CF 17 1 :99.3 Duration of a test approximately 2 hours Quantities use REACTOR EXIT TEST Br 2
/CBF
17 1 Organic phase Aqueous phase No. molar ratio Br. CBF 17 1 Weight C 8
F
17 Br JC 8
,F.
7 1 DC Misc. Is I- eq. Br- eq.
mol mol j(g) mol mol 0.30 0.36 0.37 0.52 0.52 0.59 0.94 0.161 0.171 0.178 0.250 0.248 0.285 0.303 0.533 0.478 0.478 0.478 0.478 0.478 0.322 283.8 2316 7 240.2 234.1 237. 1 232.5 156.6 0.300 0.337 0.355 0.447 0.454 0,463 0.314 0.231 0.123 0.112 0.017 0.016 56.5 74 76.5 96.5 96.5 100 100 0.60 0.70 0.90 0.70 0.70 0.60 0.66 100 100 99.8 100 100 100 100 0.304 0.348 0.364 0.478 0.486 0.491 0.336 0. 040 0.032 0 .087 0.312 I I J .1 TABLE V Cotc tim 10 1* seconds.
Conato tim 10 tes 1prxmtl seconds Nitrogen flow -rate :2.2 to 4.3 1/hi f operating conditions Quantities used REACTOR EXIT 1 TEST organic phase Aqueous phase No. Temperature Br 2 1CBF 17 I Br 2
C
8
F
17 1 Weight C 8
F
1 7Br CBF 1 7I DC I.isc. S I- eq. Br- eq..
cc molar ratio niol mol mol mol 21 300 0.30 0.329 1.100 563.1 0.511 0.554 49.5 1.0 99.9 0.518 0.114 22 350 0.30 0,300 0.996 513.6 0.569 0.412 58.5 0.9 100 0.564 0.018 23 400 0.30 0.278 0.927 475.5 0.553 0.356 61.5 1,0 99.9 0.536 f 24 300 0.98 0.660 0.670 330 0.562 0.085 87.5 0.9 100 0.560 0.750 350 0.89 0.539 0.608 293.2 G.574 0.008 98.5 0.9 0 0.605 0.430 26 400 0.84 0.469 0.558 1270.8 0.530 0.007 98.5 0.9 j100 0.56510.350 15 EXAMPLE 2 SYNTHESIS OF PERFLUOROHEXYL BROMIDE Test No. 27 71 g (0.444 mol) of bromine and 180 g (0.404 mol) of perfluorohexyl iodide (purity: 99.5 are introduced over 40 minutes simultaneously and continuously, in the presence of 8.4 1/h of nitrogen, into the same apparatus as in Example 1, under the following operating conditions: temperature 350°C contact time 8.6 seconds Br,/CF 13 I molar ratio 1.1 At the reactor exit, after neutralisation in an aqueous solution'of sodium sulphite and settling, an organic phase is recovered, containing 98.8 by weight of C 6 F Br and 0.65 of C 6
F
1 3 1, which corresponds to a selectivity for C 6
F
13 Br close to 100 Test No. 28 The starting material is a homogeneous mixture of 441.7 g (0.99 mol) of C 6
F
13 I and of 67.2 g (0.42 mol) of bromine, which is introduced over 168 minutes with the aid of a 'ingle metering pump into the same reactor as in Example 1, in the absence of nitrogen, under the following operating conditions: temperature 350°C contact time 28 seconds Br 2
/C
6
FI
3 I molar ratio 0.42 After reduction with sulphite and settling, an organic phase is recovered at the reactor exit, containing, -16on a weight basis, 77.7 of C 6
F
13 Br and 21.8 of C 6
F
13 1, which corresponds to a selectivity for C 6
F
13 Br of 100 9O
S
S
S
S
S. S
Claims (15)
1. A continuous process for the preparation of a perfluoroalkyl bromide RF-Br (wherein RF represents a linear or branched perfluoroalkyl radical containing from 2 to 12 carbon atoms) which process comprises reacting in gaseous phase bromine with the corresponding perfluoroalkyl iodide RF-I (wherein RF represents a linear or branched perfluoroalkyl radical as defined above).
2. A process according to claim 1, in which the reaction is carried out at a temperature of 200 to 600°C. A process according to claim 1, in which the reaction is carried out at a temperature between 350 and 5000C.
4. A process according to any preceding claim, in which the Br 2 /RFI molar ratio is between 0.1 and 2. A process according to any of claims 1 to 3, in which the Br 2 /RFI molar ratio is between 0.3 and 1.
6. A process according to any preceding claim in which the reaction is carried out in the presence of an 4 inert diluent.
7. A process according to claim 6, in which the inert diluent is nitrogen.
8. A process according to any preceding claim in which the contact time is from 1 second to 2 minutes.
9. A process according to any of claims 1 to 7, in which the contact time is from 5 to 30 seconds. A process according to any preceding claim 18 in which the reaction is carried out at atmospheric pressure.
11. A process according to any preceding claim in which a homogeneous mixture of bromine and RFI is introduced into the reactor.
12. A process according to any preceding claim in which the reaction is carried out with a Br 2 /RFI molar ratio below 0.5, and the iodine is then separated from the reaction mixture to obtain a RFBr/RFI mixture which is either distilled and the RFI is recycled, or to which supplemental bromine is added and the reaction is completed in a second reactor.
13. A process according to any preceding claim for the preparation of perfluorooctyl bromide.
14. A process according to any one of claims 1 to 12 for the preparation of perfluorohexyl bromide.
15. A process according to any one of claims 1 to 12 for the preparation of perfluorodecyl bromide. 6e
16. A process according to any one of claims 1 to 12 for the preparation of a mixture of perfluoroalkyl bromides.
17. A process according to claim 1 substantially 55 "as described in Example 1 or 2.
18. A perfluoroalkyl bromide prepared by the process claimed in any preceding claim. DATED this NINETEEtMl day of MAY j 992 Elf Atochem S.A. Patent Attorneys for the Applicant SPRUSON ERGUSON ABSTRACT SYNTHESIS OF PERFLUOROALKYL BROMIDES The invention relates to the preparation of perf luoroalkyl bromides RF-Br, R F denoting a linear or branched perfluoroalkyl radical containing from 2 to 12 carbon atoms. According to the invention, the perfluoroalkyl bromides are prepared by a continuous process which comprises reacting bromine and an iodide RF-I in gaseous phase, suitably *at a temperature of 200 to 6G&0 0 C. The Br 2 /R FI molar ratio is suitably 0.1 to 2. High selectivity for R,~-Br is obtained. *06 000 09
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9106114A FR2676731A1 (en) | 1991-05-21 | 1991-05-21 | SYNTHESIS OF PERFLUOROALKYL BROMIDES. |
| FR9106114 | 1991-05-21 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU1703892A AU1703892A (en) | 1992-11-26 |
| AU642350B2 true AU642350B2 (en) | 1993-10-14 |
Family
ID=9412960
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU17038/92A Ceased AU642350B2 (en) | 1991-05-21 | 1992-05-20 | Synthesis of perfluoroalkyl bromides |
Country Status (15)
| Country | Link |
|---|---|
| EP (1) | EP0515258B1 (en) |
| KR (1) | KR950012995B1 (en) |
| CN (1) | CN1032306C (en) |
| AT (1) | ATE110705T1 (en) |
| AU (1) | AU642350B2 (en) |
| CA (1) | CA2069018C (en) |
| DK (1) | DK0515258T3 (en) |
| ES (1) | ES2057968T3 (en) |
| FI (1) | FI922293A (en) |
| FR (1) | FR2676731A1 (en) |
| HU (1) | HU207506B (en) |
| IE (1) | IE64724B1 (en) |
| IL (2) | IL101772A0 (en) |
| NO (1) | NO177636C (en) |
| ZA (1) | ZA923664B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4027766A1 (en) * | 1990-09-01 | 1992-03-05 | Riedel De Haen Ag | METHOD FOR PRODUCING LARGE FLUORINATED ALKYLBROMIDES |
| FR2710053B1 (en) * | 1993-09-16 | 1995-11-03 | Atochem Elf Sa | Manufacture of solid perfluoroalkyl bromides. |
| CN116903433A (en) * | 2023-07-12 | 2023-10-20 | 安徽科芯微流化工科技有限公司 | Method for preparing perfluorooctyl bromide by micro-channel reaction |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0199781A1 (en) * | 1984-10-24 | 1986-11-05 | RORER INTERNATIONAL (OVERSEAS) INC. (a Delaware corporation) | BICYCLIC BENZENOID ALKYLENE AMINO THIENO AD3,4-d BDISOTHIAZOLE ETHERS AND THIOETHERS, AND THEIR PHARMACEUTICAL USES |
| AU605325B2 (en) * | 1987-07-10 | 1991-01-10 | Atochem | Synthesis of perfluoroalkyl bromides |
| AU635985B2 (en) * | 1989-11-24 | 1993-04-08 | Atochem | Synthesis of perfluoroalkyl bromides |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60184033A (en) * | 1984-03-02 | 1985-09-19 | Daikin Ind Ltd | Production of perfluoroalkyl bromide |
| IT1200594B (en) * | 1985-02-26 | 1989-01-27 | Montefluos Spa | PROCEDURE FOR THE PREPARATION OF ALFA-OMEGA-ALOPERFLUOROCARBURI |
| JP2797626B2 (en) * | 1990-04-03 | 1998-09-17 | 旭硝子株式会社 | Method for producing perfluoroalkyl bromide |
| DE4116361A1 (en) * | 1990-06-23 | 1992-01-02 | Hoechst Ag | Per:fluoroalkyl mono:bromide(s) prodn. - by reacting per:fluoroalkyl mono:iodide(s) with bromine at elevated temp. |
-
1991
- 1991-05-21 FR FR9106114A patent/FR2676731A1/en active Pending
-
1992
- 1992-05-04 IL IL101772A patent/IL101772A0/en unknown
- 1992-05-04 IL IL19177292A patent/IL101772A/en not_active IP Right Cessation
- 1992-05-18 EP EP92401350A patent/EP0515258B1/en not_active Expired - Lifetime
- 1992-05-18 AT AT92401350T patent/ATE110705T1/en not_active IP Right Cessation
- 1992-05-18 ES ES92401350T patent/ES2057968T3/en not_active Expired - Lifetime
- 1992-05-18 DK DK92401350.1T patent/DK0515258T3/en active
- 1992-05-20 NO NO921992A patent/NO177636C/en unknown
- 1992-05-20 ZA ZA923664A patent/ZA923664B/en unknown
- 1992-05-20 FI FI922293A patent/FI922293A/en not_active Application Discontinuation
- 1992-05-20 HU HU9201683A patent/HU207506B/en not_active IP Right Cessation
- 1992-05-20 AU AU17038/92A patent/AU642350B2/en not_active Ceased
- 1992-05-20 CA CA002069018A patent/CA2069018C/en not_active Expired - Fee Related
- 1992-05-21 CN CN92103936A patent/CN1032306C/en not_active Expired - Fee Related
- 1992-05-21 KR KR1019920008640A patent/KR950012995B1/en not_active IP Right Cessation
- 1992-07-01 IE IE921621A patent/IE64724B1/en not_active IP Right Cessation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0199781A1 (en) * | 1984-10-24 | 1986-11-05 | RORER INTERNATIONAL (OVERSEAS) INC. (a Delaware corporation) | BICYCLIC BENZENOID ALKYLENE AMINO THIENO AD3,4-d BDISOTHIAZOLE ETHERS AND THIOETHERS, AND THEIR PHARMACEUTICAL USES |
| AU605325B2 (en) * | 1987-07-10 | 1991-01-10 | Atochem | Synthesis of perfluoroalkyl bromides |
| AU635985B2 (en) * | 1989-11-24 | 1993-04-08 | Atochem | Synthesis of perfluoroalkyl bromides |
Also Published As
| Publication number | Publication date |
|---|---|
| FI922293A (en) | 1992-11-22 |
| DK0515258T3 (en) | 1995-02-13 |
| KR950012995B1 (en) | 1995-10-24 |
| CN1032306C (en) | 1996-07-17 |
| IL101772A (en) | 1996-01-19 |
| CN1067239A (en) | 1992-12-23 |
| EP0515258B1 (en) | 1994-08-31 |
| CA2069018C (en) | 1997-05-13 |
| ZA923664B (en) | 1993-02-24 |
| NO921992L (en) | 1992-11-23 |
| NO177636C (en) | 1995-10-25 |
| EP0515258A1 (en) | 1992-11-25 |
| HU9201683D0 (en) | 1992-08-28 |
| IE64724B1 (en) | 1995-08-23 |
| NO177636B (en) | 1995-07-17 |
| FR2676731A1 (en) | 1992-11-27 |
| FI922293A0 (en) | 1992-05-20 |
| IE921621A1 (en) | 1992-12-02 |
| CA2069018A1 (en) | 1992-11-22 |
| HU207506B (en) | 1993-04-28 |
| ATE110705T1 (en) | 1994-09-15 |
| IL101772A0 (en) | 1992-12-30 |
| NO921992D0 (en) | 1992-05-20 |
| AU1703892A (en) | 1992-11-26 |
| HUT60987A (en) | 1992-11-30 |
| KR920021478A (en) | 1992-12-18 |
| ES2057968T3 (en) | 1994-10-16 |
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