DE1643766A1 - Perhalogenated iodides and processes for their preparation - Google Patents

Description

Munich 5

Polio V1204

W / H

Allied Chemical Corporation, New York "N" Y _ef USA Ftrhalogenated iodides and processes for their preparation

Because of the reactivity of the iodine atom, they are perhalogenated Iodides are capable of various reactions which other relatively inert perhalogenated compounds, especially those which contain a relatively large amount of fluorine, do not enter into. Perhalogenated iodides, especially however, those containing much fluorine are difficult to prepare, as can be seen from the fact that many of them At present, iodides can only be produced by very time-consuming methods and with the use of koatapieliger reagents can, such as by the implementation of anhydrous em iodine with the. Silver salt of a fluorocarboxylic acid The invention relates to compounds of the formula

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wherein the radicals R are fluorine, chlorine or a perfluoroalkyl radical with 1 to 5 carbons, the radicals R fluorine or a perfluoroalkyl radical with 1 to 5 carbons, η 0 or 1 and X and Y, which are different, mean iodine or fluorine «as well as a process su their production, which is characterized is that one is an olefin of the ütorael:

CI ₁

wherein R ₉ . R * and η have the meaning given above, with a Gemiaoh of iodine and iodine pentafluoride, in which the ratio of iodine ze. Iodine penteflupride is at least 1: 1 * umeetet.

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The compounds of the invention were prepared in the simple and convenient manner described above

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can is, surprisingly _for considering that the Sohwefelpentafluoridgruppe known undergoes decomposition to sulfur tetrafluoride and sulfur hexafluoride, and certain other transformations. For example, it is known that perfluoroalkylsohulphurpentafluorides decompose at elevated temperature to the corresponding perfluoroalkyl compounds, sulfur tetrafluoride and sulfur hexafluoride, and chlorides of perfluoroalkylsulphurpentafluoride compounds, for example compounds of the formula Si ¹ C (CgIiV) _n Cl, easily to form chloride such as aluminum trichloride, at room temperature in the presence of a Lewis acid Sulfur chlorides react. In addition, iodides of perfluoroalkylsulfur pentafluoride compounds cannot be prepared in a conventional manner, for example by reaction with sodium iodide or hydrogen iodide.

They treat new compounds as fumigants to combat various insects and insect larvae «Because of the reactivity of the iodine atoms, the compounds go many reactions that fluorine compounds generally do not enter into, such as the conversion of chlorosulfone- or fluorosulfonic acid to the corresponding chlorine or fluorosulfonates. In addition, the iodides are suitable as Intermediate products for the production of a large number of compounds, when it comes down to introducing a lot of fluorine into a molecule,

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such as in the production of water and oil resistant as well as fleece-insensitive coatings or from Sizing and impregnating agents for natural or artificial fibers and textiles, paper products and objects made of HoIs, metal and plastics

Some of the olefins used as ^A usgangsinaterialien in making the erfindungsgemäseen iodide are known from US Patent 3,131,217. These olefins can be prepared by dehydrohalogenation of the corresponding saturated chlorides with a base, for example with an alkali hydroxide.

Although iodine monofluoride has not been isolated, it is believed to be in situ from a mixture of iodine and iodine pentafluoride that the molar ratio of iodine to iodine pentafluoride is at least 1: 1. This procedure is from J.Am.Chem.Soc. £ 8, 2383 (1961) known and runs probably according to the equation

• 2Y ₂ + JP ₅ > 5 JP

The iodine is preferably used in excess, as iodine pentafluoride acts as a fluorinating agent alone or in a mixture with small amounts of iodine. That is why one generally uses a molar ratio of iodine to iodine pentafluoride of

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about 1.8; 1 to about 2.5 i 1 * The iodine can also be present in a large excess, no? This, however, is unnecessary and generally uneconomical =, the mixture of iodine and iodine antafluoride preferably contains a metal catalyst such as metallic aluminum, magnesium, etherium, beryllium, calcium or strontium. The metals should be free of impurities such as iron, copper, or zinc ,, which inhibit the reaction. A catalyst geoisoh made of aluminum and aluminum triiodide can also be used. The metal catalyst can for example be present in an amount of about 0.1 to about 10 wt .- ^ of the iodine monofluoride theoretically present in the iodine / iodine pentafluoride mixture; Usually it is used in an amount of about 1 to 5% by weight. Before the reaction with the olefin, the mixture of iodine and iodine pentafluoride and, if used, the metal catalyst is left to stand for a few hours. The best results are achieved when the mixture is kept at a temperature of about 100 to about 250 ^° C. before the olefin is added.

The molar ratio of olefin to iodine monofluoride is not particularly important. The molar ratio of olefin to iodine monofluoride is preferably about 0.5> 1 to about 3 liters.

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The temperature of the reaction may vary τοη about 5O ° C to about 15O ⁰ C and depends on the reactivity of the olefin used. It must be carefully controlled so that such rapid decomposition and thus loss of product is prevented. In general, the conversion and the yield of perhalogenated iodide increase with increasing temperature. However, it is important that the temperature is not increased too quickly, otherwise the reaction can proceed explosively.

In a preferred form of implementation of the inventive method, the Reaktlonstsilnehmer are always kept at least 24 hours at a temperature below about 75 ⁰ O. Then the temperature can be increased to a value between 75 ° C and 150 ⁰ O- *

The response time is not important; oils generally decreases with increasing temperature. By increasing the Reaction time one obtains a higher yield, and with a higher * action temperature requires less time for the Achieve a certain yield than at low temperature.

'The reaction can be carried out at atmospheric pressure « In most cases, however, it becomes two-pounded under massive

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superatmospheric pressure performed by either the system under an inert gas eetz'j or the TJmsetsung at the self-pressure that has set in during its course can drain · Suitable pressures are in the range of about 1.4 to 70 atm. However, depending on the load limits of the reaction vessel, higher pressures can be applied.

The following examples illustrate the invention. declarations about parts refer to the weight «

example 1

153 ropes of iodine, 5 parts of aluminum triiodide and 5.5 parts (1.9 x 10 hol) of pure aluminum chips were placed in a Dru'ok vessel from Hiokel. The vessel was closed, cooled to -78 ⁰ O and evacuated · The vacuum Tutsen 60 parts iodine pentafluoride were introduced. The vessel was then closed. The mixture was shaken 1.75 hours to 140 bie 150 ⁰ C erhitet, then cooled to -78 ⁰ C and 310 ropes Irifluorrinylechwefelpentafluorit beeohlokt · Benson nitrogen was eingedrüekt, WLE 4p bridge had risen at within the vessel to 2.1 " Denaeh was DAEA Found äse sealed and Sohütteln about 75ι5 hours at 48 ⁰ C and 15 hours at 125 ⁰ C "rhitut. The resulting mixture was fractionally distilled, whereby two main fractions were obtained.

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1-Jodtetrafluoroäthyl- was obtained in 15 »4 # yield

sohvrefelpentafluorid as a white solid at -78 ⁰ C and colorless liquid from stinging and the insoles irritating odor at room temperature. The structure was through

Infrared: and KMR analysis confirmed. The Elenientaranalyse

resulted in the following values:

C ₂ P ₉ SJ

Ber. "C 6.8; P 48.3; S 9.1; J 35.9

Found: C 6.9 $ P 47.11 S 8.7v J 32.0

They "wide main fraction beatand from a small amount of 2-Jodtotrafluor * thyleoaw" felpentafluorid _f whose structure -was confirmed by Infrarotanalyee.

The I-iodetrafluoroethylsohulphurous peirtafluoride would make them Fumigants tested as follows:

5 test ineects of each species to be investigated below were tested in Tins of 3.8 en Durehaeeeer pit-perforated deodorants are set, which also contain a little putter (grains, flour, ground Dog cows, etc.), and the buoheen were placed in a 3.8-1 sewing-in glass. Thereupon 1-iodetetrafluoroethylsohulphurpentafluoride was sugesetst so that its concentration in the jar was about 16 g / m ⁵ . The glass was then turned off. After 24 hours, the in-

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Champagne cans removed and mortality immediately and then for another week at a distance of ^ e one lay "for sure .

After 5 say a 100% mortality was observed in Imagenes ron Sribolium confusum, Alphitobium diaperinus and Attagenus piceus _o

Example 2

250 ropes of iodine, 5 ropes of aluminum triiodide and about 5 ropes of pure aluminum shavings were placed in a pressure vessel as described in Example 1. The vessel was cooled to -78 ⁰ O, evacuated and charged with 100 iodine pentafluoride ropes Bas mixture was heated for about 3 hours at 140 to 150 ⁰ C. Thereafter, the vessel was cooled to -78 ⁰ C and charged with 370 ropes Srifluorvinylsohwefelpentafluorid. Nitrogen was injected until the pressure in the vessel had reached 2.1 atm. The vessel was then heated under Sohtttteln 18 hours 5O ⁰ C, 26 hours at 70 ⁰ O, and 19.5 hours at 90 ⁰ C, Anschlleseend .wurde it cooled to -30 ⁰ C ,,

11.6 in 56-yield was obtained by fractional distillation of the product Gemischee 1-Jodtotrafluoräthylschwefelpentafluorid, as determined by analysis gaeohroeatogrophlsohe "

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The reaction mixture was combined again and returned to the pressure vessel, which was then placed under a Set nitrogen pressure of 2.1 at and 21.5 hours 95 ° C and 19.5 hours to 100 ° 0 was heated.

Naoh fractionated destination of the product mixture received a final yield of 1-iodetetrafluoroethylsulphurpentafluoride of 21.9 # »

The experiment was repeated, the reaction mixture is the addition of the NaOH Trifluorvinylschwefelpentafluorids directly to 125 ⁰ C heated # The reaction proceeded aueeeretheftig .and gave virtually no product "

Example 3 The procedure of Example 2 was followed with the exception

repeats that 2-perfluoroprapenyl sulfur pentafluoride is used as the olefin. The product mixture contained 2-iodoperfluoropropyl sulfur pentafluoride and 3-joaperfluorpropyl sulfur pentafluoride. The compounds were duroh fractional destination separated and its structure confirmed by infrared optical analysis.

Example 4

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S * · Method according to Example 2 became old with the deviation

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the β is obtained as the olefin I-sifluoromethylperfluorovinylsulfur pontafluorid used «The product contained 1-trifluoromethyl-t-sodperfluoroethylaohulphurpentafluoride and 1-Trifluoromethyl-2-3odperfluoräthylschv / efelpentafluorid. The compounds were separated by fractional distillation and their structure was determined by infrared spectrographic Analysis confirmed "

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Claims (1)

Claims 1, compounds of the formula C R wherein the beds H are fluorine, chlorine or a perfluoroalkylreat with 1 to 5 carbon en ^ the beds R ^ fluorine or one Perfluoroalkyl radical with 1 to 5 carbons, η 0 or 1 and X and Y, which are different, mean iodine or fluorine, 2 «1-iodetetrafluoroethylsulfur pontafluoride. 5. 2-Jodtetrafluoräthylschulfelpen fcafluorid. 4 «A method for the preparation of a compound according to claim 1, characterized ₇ that an Olefiu of the formula ———— R Λ. with a mixture of iodine and iodine pentafluoride umaetet _v in dom 109827/1850 the molar ratio of iodine to iodine pentafluoride is at least 1: 1 amounts to" 5ο method geraäss claim 4 »characterized in that a mixture of iodine and iodine pentafluoride is used" which has ^{been heated to 100 to 250 0} C in contact with metallic aluminum, magnesium, thorium, beryllium, calcium or strontium and in which the molar ratio from iodine to iodine pentafluoride 1.8: 1 to 2.5: 1 is _e 109827/1850