DE1618046A1 - Process for the production of new fluoroperhalogenoisopropyl alkyl ethers - Google Patents

Description

Polio A / 10440
U / B

Alled Chemical Corporation, New York, N.Y., USA

Process for the preparation of new fluoroperhalo- - eenieopropyl alkyl ether

The subject of the invention is a process for the production of Fluorieopropyl alkyl ethers of the phonoels

X ₂ IC

in which each of the Beate X, which can be different or different, is a chlorine or fluorine atom and R _{1 is} hydrogen, an alkyl, hydroxyalkyl, carboxyl, carboxyalkyl, carboalkoxy, alogenoarbonyl, halocenoarbonylalkyl, alkyloarboxyalkyl -, sulfoalkyl, alk «nyl, bpoxyalkyl, alkenyloarboxyalkyl, alkali alkanoate, phenyl, halofenphenyl, flulfophenyl

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or Benzoy! group, a group of the formula -N-CH ₂ -CH ₂ , a group of the formula (-CH ₂ -CH ₂ -O-) _n "where η is an integer from 10 to 1000" or a radical of formula

CH ₂ -OC -— CFX ₂ CFX ₂

in which X has the meaning given above and Z is hydrogen or halogen or a group of the formula SOJie in which Me means hydrogen or an alkali metal »is. Da · procedure lat characterized by the fact that nan is an addition product a ferhalofluoroketone and an alkali or superfluoride

the formula

CX ₂ FC ^- ^

in which A is an alkali metal or silver atom Alkyllerungemlttsl of the formula

where R * has the meaning given above and Q chlorine » Bron or iodine or a remainder of the formula 1 "oeOglr" where H * is a Denotes alkyl, alkoxy or aryl group, is or

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^so s

wherein L is an alkylene or phenylene group, or (c)

in which Q is a chlorine, bromine or iodine atom and Z is hydrogen or a halogen atom or a group of the formula 30, Me, in which Me is hydrogen or an alkali metal. in a solvent «preferably acetonitrile, at 20 to 200 ⁰ C converts. The conversion proceeds according to the equation:

X ₂ FC J) A XgFe O-CHgR ¹

The fluoroperhalogen ketone adduct used as starting material can according to the method described in patent application A 53 641 IVb / 12o by the same applicant The addition products mentioned are in the liquid used as solvents in the reaction.

. TOStH 7 2091

like acetonitrile, nitrobenzene, ethylene glycol, dimethyl- » other> Dimethylformamide, tetramethylene sulfone, tetrahydrofuran and dimethyl sulfoxide, soluble. Examples of suitable addition products are the addition compounds of hexafluoroacetone, Monochloropentafluoroacetone, dichloro, trafluoraoetone, TM-fluorotrichloroacetone or 1,1,3,2-tetrafluoroacetone with AgF, CsP, KP or NaP.

To carry out the process according to the invention, the addition product of the fluoroperhalogen ketone and the alkali or silver fluoride is dissolved in a suitable solvent, two times in acetonitrile, and preferably in practically etoichiometric proportions, ie. either in equimolar amounts or using 2 NoI halo ketone adduct per mole of alkyl detergent mixed with the alkyl detergent. The mixture is stirred and, if necessary, heated to increase the rate of the reaction. The duration of the reaction depends on the temperature used. The ·· may be in the range between Räumtemperatur, ie, about 20 to 2 £ TC, up to 200 ⁰ C or, if necessary, also lie * Dl "reaction may be at atmospheric pressure or, if necessary for the DurohfUhrung the reaction is above room temperature, under overpressure. After the reaction has ended, the fluoroalkyl ether formed can be removed by cooling (if necessary), pouring into bis-water to remove the salt formed as a by-product and separating off the salt formed

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organic phaso can be obtained. If necessary, the product can still be washed with water.

Those new compounds that are created by converting the Additlona product from a halogen ketone and a Met * 11 fluoride can be obtained with an alkylaryl compound are sulfonated in their aromatic part by making them with a sulfonating agent, preferably with sulfur trioxide in a halogenated solvent never plurotlchloromethane, implements. For this purpose, the SO can be dissolved in the solvent and the resulting solution dropwise with stirring »for example for 10 to 15 minutes at a temperature of 5 bla 15 ° C so that the sulfonating product can be used. Daa Afonized product can be obtained as sture, preferably However, it is adjusted to pH 8 with alkali hydroxide brought, evaporated to the ^ rookne and GewtSnachtanfalle duroh extraction with an alcohol like XthanoX cleaned.

The invention items made new pre-bindings versatile. Those Verolndunfen in which aina sulfonalure or alkallsulfonate group to an aromatic Ring is bound, make auagazaiohnata superficiallyanactive Means, thereon 0.1 * -ige Luaungen in Waaaar Obarf mohanepensionan in the order of 89 to 30 dya / oa have, opposite Waaaar with aintr CDarflmohanapension of about 72 dyn / o *. Many of the unrelated connections alnd work ane AuarKuoharungamlttal and find sur Varnlohtung

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■ -. ■■■ - 6 - ■ .. "'■ ■

by various insects, which insects are exposed to the fumes of the compound. Compounds which are particularly effective for this purpose have a single Xther grouping and in the radical R- an aromatic ring. Still other compounds are valuable intermediates in the production of other valuable compounds! for example, the compounds made from 2 moles of the perhaloketone adduct and 1 mole of an alkylaryl halide are useful in the preparation of surfactants by sulfonation of the aromatic ring.

Compounds in which R is an alkylene group such as the compound obtained in Example 11 can be epoxidized and the epoxidation product can also be stable Emulsions are polymerized.

Compounds in which R is hydrogen or a low molecular weight Alkyl group is approximately like that obtained according to Example 1 Compound, are effective XUhI and propellant fluids. They are also suitable as a SohKuomi agent when making 4 Polyurethane resin.

The compounds in which R ^{1 is} a single molecular cavboalkoxy group, such as the compound obtained in accordance with Example 10, are not only exceptional features. sur ineektenvertllguns »but also valuable · 2wi« enenproduct ·

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1618048

for the production of the corresponding carboxylic acid (by 'Saponification) and the derived from it · «! Acid chlorides, salts and Amides. In addition, their ester group can be reduced to an alcohol group and these are converted into the acrylate after that Polymerization a product old both bl and waeeerftbweieenden Properties results.

The following examples illustrate the invention. Include here See Examples 1 to 13 for the non-toxic process, Examples 14 to 23 on the further reaction iron «rf charge» · properly established connections to other Reuen connections, their formulas are one of those that can be produced for the invention Products correspond to given forums, and examples 24 and 25 on the use of some of the new compounds as a fumigant. Parts relate aioh to the Oewloht, unless otherwise stated.

The hexafluoroacetone addition product used in the examples and potassium fluoride,

was prepared as follows: 2u about 500 ml of trooken acetonitrile in a 100 ml three-necked flask were 8? g (1.5 NoI) were added dried Kaiiuwfluorid ^{at 150 1 C for 24 hours.} Xn the oemiech were for 1 hour 40 minutes with cooling to a temperature of 25 to

28 ¹ C 225 g (1.35 mol) Hexafluoraotton initiated. 653 g of a clear solution were obtained, of which aliquots were used as required.

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example 1

A. Jfeptafluoroisopropy! Methyl ether :

29.5 β (0.21 mole) methyl iodide and a solution of 110.6 g (0.225 mol) hexafluoroacetone / KP addition product in acetonitrile were placed in one equipped with a magnetic stirrer Pressurized glass bottle was introduced, after which the bottle was tightly closed and its contents were reduced to 905 for 2 hours while stirring.

was heated. Potassium iodide separated during the implementation from the reaction mixture. The reaction vessel was over Left to stand overnight, chilled with ice and opened. being content was in Siswasser. poured and the obtained liquid Phase separated and washed twice with fresh ice water. After distillation, nan received 47.2 g of a 29 to 29 * 5% boiling product. In two of the same analyzes, a middle one was found Yield of £ 57 d. Th. Received. The kernmagnet laugh at resonance spectra for the proton and the fluorine atom of the compound were in agreement with the following structure:

0-CHj

B. Polyethylene made with heptafluoroisopropylmethyl ether

urethane foam;

A rigid polyurethane foam was made as follows

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First, the following Vorgemisoh was made (the Present information relates to the weight of the end product) t

Trade
designate
tion Chemical name Manufacturer use
det as Oew.-ji » M Polyoxypropylene triol Union Car
bide Reagent 42 _# 4o Quadro1 Ν, Η, N *, H ¹ -Tet rakis- (2-
hydroxypropyl) -thylene-
dlamin Wyandotte Catal
tor and 3.97
R # «S8KZ P 22 Dlbutyltin dilaurate Union Car
bid Catal
gate 0.31 L 520 Silicone oil Pores
greetings -
regulator 0.39 - Heptafluorieopropyl
diethyl ether ...... Driving
■ itt ·! 15.9

With this in mind, J7, O3i < Haooonate 4o * O (from ·· Toluylene diisocyanate of the National Aniline Division) first, and the whole thing lasted 15 seconds misused, poured into a mold and turned into a "rigid shell." Soak it up. Di · theruisohe LeltfMhigkelt (K-factor) « measured with a "Pittsburgh Coming Therwal Conduotlvity Sample? Model C5-48, was 0.017 koal / si.h. ^ C (0.14 BTO / ti.sq.ft. of / inoh), from which it was shown that the ether is a useful and effective propellant is

10081172081

-AO-

Example 2

Heptafluorlaoprupoxyacetylbenzene: 62.5 S (0.51 mol) of bromoacetophenone was added over 15 minutes at room temperature and with stirring to a solution of 79 β (0.35 mol) of the addition compound used in Example 1A in 150 ml of dry acetonitrile. After stirring for 20 hours, the solution obtained was filtered and obtained 3.2 g (0 * 28 Hol) potassium bromide (80 £ of theory). The solution was then poured into water, and the weight obtained in the process Oil was after swalamligem what ;! » distilled with fresh water at a pressure of 5 seconds Hg, 39.1 g (36% of the theory) of a liquid of the following formula boiling at 77 to 82%.

0
0-CH ₂ -C

Example 3

Heptafluorleopropylbenaylttthere ß5 # 5 g (0.38 Hol) Bensylbromid were vernisoht with a solution of 119 g (0.53 Hol) addition product of Kexafluoraoeton and Kalluefluorid In 200 ml of acetonitrile, and since "Oenisch was for 3 weeks left · Benson was in Poured dl · gleloh · Yolusaenj water, whereupon the · organic phase separated, which was washed three times with 90 »1 vassar each time. Nan received

. BATH ORIGINAL

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95 S crude product which, after distillation at It, now yielded Hg 79 g of theory) of the product boiling at 50 to 52 °.

Example » · _;

1 _t 3 "Bla" (heptafluorieopropoxymethyD-benzoli) The Oemlsoh was made from 25 g (0.1 mol) 1,3-bis (bromomethyl) benzene and a solution of 0.225 mol adduct of hexafluoraeeton and Xaliu & fluoride in 83 in a Bruck bottle Stirred in 1 acetonitrile for 2 days at room temperature and then heated for 4 hours at 9 ° C. The reaction mixture was cooled and filtered, whereupon 24.2 g (0.2% 10% a.th.) of potassium bromide were obtained was mixed with water and the oil washed three times with 100 nl of water. vacuum distillation at 5 mm Hg obtained gave 3% * (70 * theory) of a C ^ 6 in boiling product of the formula

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1818046

Example 5

1,4 "Bis- (heptafluor isopropoxymethyl) -benzene : Example 4 was repeated!" With the difference that instead of 1,2- ^ je- (bronimefcliyl) -benzene the 1,4-isomer 4 hours at 90% in a pressure bottle with the addition product of hexafluoroacetc · »Kaliumfluorld in acetonitrile was converted. A product of the formula boiling at 66 to 66.5 ° C./5 mm Hg was obtained in a yield of 75%

Example 6

1,2 'bis- (heptafluorlaopropoxymethyl) -beneol "Example 4 was repeated with the difference that instead of 1,3-Bie" (bronmethyl) benzene 1.2 Xsomere 2.5 hours in a Druokflasche at 90 ¹ C was reacted with the addition product of Haxafluormoeton and Kaliumfluororld in acetonitrile to give a product boiling at 51 * 5 to 52K / 5 * m Hg in a yield of 70% of the formula

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Example'/ Hexafluorochloroisopropylbenzylphen Example> tnixäs "riederholt

with the difference that benzyl bromide for 3 hours at

9CK in a pressure bottle with the addition product of potassium fluoride and Pentafluorohloraeeton in aoetonitrile. The product obtained was washed with water and distilled as usual, whereupon a product of the formula was obtained in a yield of 59 lg

received.

Heptafluorlsopropyl ^ fr "brombennrlMthert Example 7 was repeated except" DA9 4-bromobenzyl> hours in a Druolcf lax in Skåe INLT the Addltionaprodukt ouch Hexafl uoraoeton and potassium fluoride was umgeaetzt in Aoetonitril, followed by sodium in 72J <yield a 60 " 5 to 6 liters of C / 6 mm Hg boiling product of the following formula!

Example 9

reaction with poly-cepichlorfaydrin): Bin Oemisoh from 7 »* g of a linear, bifunctional homopolymer of epichlorohydrin with an average molecular weight of 20β0, a hydroxyl number of 5 * and a chlorine content of 38, 20 and from 45 g of a solution of the additive product of Hexafluoraoeton und Kaliumfluorid In Aoetonitrll was stirred for 6 days. «The reaction product was filtered, mixed with water and extracted with Chlorofoiw.« The ChIorofor »extract was washed with water and the solvent was removed · You got a certain amount of product» which was lost through spilling “3.7 g of unified viacose oils · containing 17.5 # fluorine. Duron complete conversion would have been a product of the formula containing 55 $ fluorine

-ICB-CH ₂ -Of _n where η tint is an integer of 20 Die 25 let.

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- 15 -;, ■ ■ .γ - .. ■ - ■: ■

Example 10

Heptafluoroisopropoxy3elgic acid ethyleter; A mixture of 42 g (0.35 mol) of ethyl bromine / acetate and an excessively acidic addition product of hexafluoroacetone and calluefluoride in aoetonitrile was heated to 90 ° C for 8 hours in a pressure bottle with stirring. The reaction egg was cooled and filtered, whereupon 29.6 g (0.24 mol / 96%) of uliurtweid was obtained. To separate the organic product, water was added to the filtrate Washed with water, dried over magnesium sulfate and distilled. 53.5 g (79% of theory) of a product boiling at 80 to 81 ° C./100 mm Hg were obtained

This battery is suitable as an equipment old. Mr Ut iugleloh «in valuable ZMlsohenprodukt for the preparation of various derivatives, the duroh Verseifeo aur Carbonatture and then ttawandl ^ mg of SXure in da · Mureoblorid and de · SXureohlorides in the Astld bsw. the stubborn in a chroaaals were received. .

Babeispiel Ii - ' ^r -

3 »(Heptaf luorisopropoxy)» 1-propent 35 g (0, S08 Hol)

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- Io -.

Were allyl iodide? Heated for hours at 85 to 90 * with 0.20B mol ■ addition product of hexafluorooetone and Kaliunfluorld. The reaction mixture was cooled, washed with water and distilled. 18 g (42 * theory) of a ·· at Atnosphfrendruok at 62-62 "C boiling products 5 ⁹ · was obtained. The presence of the heptafluoriaopropyl group in the compound was evident from the NHR spectrum, which corroborates the following structure

FC 0-CHg-CH ₂ -CH ₂

Analysis:

Ber. P 58.8 * H 2.2 *

Found 5 * »* 2.3

Example 12

Potassium 3- ( heptafluoroisopropoxy) -1-propane sulfonate 27 # 5 8 (0.225 mol) propane sultone were stirred for 18 hours with a solution of 0.225 Hol addition product of hexafluoroethone and potassium fluoride in acetonitrile, a solid being formed. The Geniso was filtered and the solid was cooled. One trhlat 5 * g and after evaporation of the PiItrate sur Trookne a further 14 g, a total of 68 g (89 * 4th th). The use of the following reaction lines

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Example 13

Initially

The addition product of bexafluoraoetone and silver fluoride was prepared as follows: To 40 g trookeneav acetonitrile was added a three-way flask 109 8 (0 * 7% ^ 2) silver fluoride sug * Mtxt, Dusaoli mspidn lsi am Qmlmh% & i 2i to 25% y during 5 Mimtm | 0 »7 ^ MoI) 'Baxaf luor * o # ton #lng« - 621 s · 1ή · ι »klaf« Q löeung de »Addition ··

became · of the addition product wl «follows nit ll-essmund ·· converted 0 «> βοβίββίι au 20 g (0.068U

and 106 g of a solution of 40 g of addition product made of Htxafluorvoaton and silver fluoride in Aoetonltril was for 9 1/2 hours in "in * r Druokf la * oh" to §0 $ "rtsitafc _ff life"? Maoüt * bidihi "K left and" filtered for the purification of eilberorosiiä (1% g "entapraohend 0.0 / 5 mol.). The LSsuüg wunl Se tfurden 3 @ g (O.OTQ MoXj «in ·· oily product» get the naoli

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Oil revealed. The infrared spectrum indicated the presence of the expected Ester group as well as the trifluoromethyl groups in the molecule recognize «that has the following structure:

Example 14

Sulphonation of Heptafluorlaopropylbenzyläthen. 14 g (0.05 dee according to the Voreohrift of Example? Heptafluorlsopropylbenzyläthere produced were 'mixed in a Laboratoriumersaktlonskolben with 50 ml Pluortrichlormethan as Reaktlonsmedium At this Qemieoh was stabilized, a mixture of 4.4 g (0.055 Hol) for 12 minutes at 15 ⁰ C. Sulfur trioxide ("sulfane") in 20 ml of fluorotriohlorate ethane was then added dropwise. The Oemleoh was then stirred for 1.25 hours at room temperature, then poured into water and brought to a pH of 8 with 10% potassium hydroxide solution Trookne evaporated, and a solid was obtained which was extracted with Xthsnol in a Soxhlet extractor. Evaporation to Trookne gave 6.9 g (0.018 mol) of product. Quaternary titration gave a molecular weight of 44o (calculated for the anhydrous potassium sulfonate! 596) A fresh solution of the sulfonate had a surface tension of 29 dyn / om in comparison with the surface tension of water of 72 dy n / em · This shows that the

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bond, the Formet

has considerable surface activity.

Example 15 Sulfonation of 1, 2-Bla "(heptafluoriBopropo3tyiBethyl)" benzene t

9, * g (0.02 mol) 1,2-Bls- {heptafluoriBopropax7Mtbjrl) benzene, which has been prepared according to the procedure of Example 6
"Rar, were recovered from the method given in Example 1, using 0.9 ml (1.8 g, 0.022%) of" sulfane "in fluorine-trihydrate methane as a solvent from ag" ssulf © alert-Han Discoloration in Stbanol 1.9 ß (0.003 Moli 15Ji d.Th,) material of the formula

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Example 16

Sulfonation of 1.3 "Bi8- (heptafluoroisopropo3qflBathTl) benzene. The procedure of Example 15 was repeated using the material obtained in Example 4. The resultant" Kallun salt of the formula -

possessed exceptional surface-active properties} a « A, ΐίί-length aqueous solution exhibited a surface tension from 25 dyn / otn up.

Example 17 Sulphonation of 1,4-BiB- (heptafluorl »opropo3qr» ethyl) -b «tt» olt

The procedure of Example 15 was repeated using the material obtained in Example 5. Am 0.1 * -ige Powerful solution of the preserved potassium salx of the Porael

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had a surface tension of 30 dynes / cm.

2- (H ept ai jLuorXs opropoxy) -thanol: The Oemleoh of 85 nl trooken bic-2- (2-mefchoxyethoxy) ° ethyl ether and 2.38 g (0.063 Hol) sodium borohydride was stirred in a Drelhala flask for 20 minutes until completely dissolved and for a further 20 minutes, while stirring, 27.2 g (0.1 mol) of the heptafluoropropoxyeeeigaKureltthyie® ter * prepared according to Example 10 were added. The exothermic reaction was kept at a temperature of 50 * 5 by cooling again. Denaoh the Geniceh to 9O was ^- C heated, whereupon an exothermic reaction, the temperature of 125 ¹ C aneteigen liefl. The qemieoh was cooled on the room's door, stirred for 18 hours, and then poured into a qeeieoh made of ice and hydrochloric acid. After stirring for 15 one liter, the organic phase located at the bottom was separated off, washed with water and distilled in vacuo. 7.2 g of a product boiling at 709/100 mm Hg were obtained. Analyzes

Ber. V 51M H 2 _s 2j *

def. 56.2 2.1

The NMR spectrum was found to be in agreement with the assumed structure, as was the infrared spectrum, which showed the following bands: 2.9u (hydroxyl group), 7.5 to 8.5μ and 10.1μ (-COO-). The connection is owned by the Wotml

1/20 & 1

? jC OCH ₂ CHgOH

? yC F

and proved to be an effective fumigant for Defense of Panagrellus nematodes.

Example 19

Aorylate des 2-toeptafluoropropoxy) ethanolB; A mixture of 12.5 β (0.10 hol) dea geroKB alcohol prepared in Example 18, 6 g (0.10 mol) methyl acrylate, 0.5 g hydroquinone and 0.1 g 4-toluenesulfonic acid was used for 2 hours heated under reflux for a long time. The azeotrope of methanol and methyl acrylate, boiling at 66k, was then slowly distilled off at a rate of 1 drop per 2 minutes for hours. Then 0.1 g of toluenesulfonic acid was added and the distillation was continued for 1 hour and 23 minutes. A total of 3 # 2 grams of azeotrope was collected. The reaction mixture was then distilled in vacuo, and 9.6 g of a product boiling at 51 ° C / 12 mm Hg were obtained. The infrared spectrum of the compound was in agreement with the assumed structure; it had the following bands: 5> 75 μm ( Carbonyl group), 6.1μ (CC), 7.5 to 8.5μ (CP ^) and ΙΟ, Ιμ (hC-OC-). The compound had the following structure:

BATH ORIGINAL

10S811 / 2091

r '

0-CH ₂ -CH ₂ OC 1 H-CH ₂

P ^ C

8.8 g of the monomeric acrylate produced in this way and 25 g a 1 'oxygenated aqueous solution of sodium auroy sulfate and' 0.05 g of Xallumpersulfate were at room temperature under nitrogen stirred. After 5 minutes the solution became cloudy and the Temperature began to rise as a sign that poly * merisfttlon occurred. If a tea temperature of 35 ^ C was reached, the RealctionBgefKB was cooled from the outside to this temperature To keep open · After 15 minutes the temperature started to sink, followed by 2 1/2 hours at room temperature. was further stirred. The product, 400 g mono milky Polyamreneemleion, was evaporated to dryness, with a rubber-like white polymer was obtained. The polymer (5.9 g) was in an Oemiaoh from 100 al Haxafluorieopropanol and 50 ml of trifluoromethylbenzene dissolved in a Sji solution.

Two Versuoheatüoke white cotton druokatoff were made through Smtauohan in the above-described 2 £ -lge polymer solution iJBprMgniert. To remove excess solution, the Test pieces dried off ^ then practice! Night on the Let air dry and weighed. After that, they were in fixed in an oven at 150Ϊ for 8 minutes (heat set),

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irons and checked. The uptake of impregnant was 5 * 1 and 4.8% by weight. The oil repellency was 70 and 80, the water repellency 70 and 70, from which * goes that the polymer is to achieve both properties suitable

Example 20

HeptafluoroisopropoxyesslgaMure t A mixture of 242 g of ethyl heptafluoroisopropoxyesslgstture prepared according to Example 10 and 430 g of 10% aqueous sodium hydroxide solution was refluxed for one hour at 9551 with stirring. The mixture was then cooled and 1000 ml of water were added. The whole thing was then distilled until 900 ml of distillate was obtained, in which a large part of the ethanol formed during the saponification was located. The reaction mixture was then brought to a pH value of 2 by adding concentrated hydrochloric acid, a heavy oily phase separating out, which was separated off and washed three times with water and then distilled over a column (spinning band column). The unfamiliar product of the formula

' ³ p

1-ί / F

boiled at 87 to B8K / 20 mm Hg. The yield was 166 g. Analysis similar to infrared spectrographic showed the structural formula:

1098 11/209 1

broad barides up to 3μ (hydroxyl group), bands at 5.7μ (Carbonyl group) and 7.5 to 8.5 µ

Example 21

HeptafluorobopiOpoxyacetylchloride: Heptafluoroisopropoxyacetic acid prepared according to Example 20 was added to 68.5 g (0.58 mol) of thionyl chloride in a Lafroratorlum reaction flask over 25 minutes at 25 ^ 122 g (0.5 mol). No temperature increase occurred during the addition. The mixture was then heated to the reflux temperature for 2 hours 20 minutes, the temperature rising from 27 to 91T. The reaction mixture was then distilled. The desired product (61 g) of the formula

P-jC

■ charges e at 105 to 106 ¹ C. The infrared spectrum of the compound such as * bands at 5 # 5μ (carbonyl group), 7.5 to 8.5μ. (CF-j) and 10.1µ (-COC-).

Example 22 H- (Heptafluorl «opropoxyaoetyl) -azlrldini Ee became an implementation

109811/2081

carried out according to the following reaction equation:

-HCl I I

C ₅ P ₇ OCH ₂ COCl + HNCHgCH ₂ -> C ₅ P ₇ OCH ₂ CONCH ₂ CH ₂

A laboratory fluid reaction flask was heated with an electric lamp while the inside of the flask was carefully rinsed with Stloketoff. 150 μl of diethyl ether, 10.1 g of triethyl alcohol and 4.3 g of ethylene oil were then introduced into the flask. ^{The flask was cooled to -30 1} C in a dry ice / aoetone bath, and 26.2 g of heptafluoroisopropoxyacetylohlorld were added over 32 minutes at this tea temperature. Then the Qealaoh was stirred for 1 hour at -30% and sur removal of filtered iriäthylaninhydroohlorid a ätherisohe LBsung of the monomer to obtain · the stored at low Teaperatur was "xm loss · by poly- ■ erlsatlon vemelden xu. The infra-red spectrum revealed the presence of carbonyl groups and CF ^ groups, which solidified the following structure

2wel ProbestUoke will BauBWolldruoketoffes were «it the Soaked in the essential solution of Asiridln described above. Ansohl 1 miserable llefl nan sis dry at room temperature, condi-

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Τ6180Λ6

tionjfft it at 50 # relative humidity, flattened

- * ■ - "- - -" -. "" ■ and checked them. Both samples showed a value for that oil-repellent effect of 80 on, which shows the effectiveness of the Aziridine emerges. It is believed that the Azlridln during drying * conditioning and ironing * on the cloth was polymerized.

Example 23 -

Ow OeBlseli from 9 * 0 8 (0 * 0225 mol) of the according to Example 13 obtained ethyl ethers and 13 ml (10 ^ -iger überereohua) 10 £ -iger Potash lye was heated on RUok for 4 hours. That Reaktlonsgeraiscl * was thereupon with concentrated hydrochloric acid angeeKuert and extracted with XthylXther, with nan the carboxylic acid the fovnel

/ ^w x oh

«C ρ

received.

After evaporation of the ether, 5.2 g of an oily substance were obtained Product. From the infrared spectrum the Presence of the expected bands for the carboxyl group and the trifluoromethyl groups.

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161BQ4S

* 28 ~

0.50 g of the acid were poured into a 600 ml glass jar Water was introduced, and this was done with 10% sodium hydroxide solution brought to pH 9. After that there was so much Water is added, which is then 600 g of a 0.1 liter solution. Has riumealses of the formula

OHft

received «The surface tension of this solution resulted in 28.5 dyn / cRi, ^ oduroh aioh de Salt ale effective otic surfaces

Medium © rWEISο

Example
Baucherverauohe

The PluorisopropylalkylKther Examples>, 7 * δ and 10 were as a fumigant against a number of insects in the adult and larva "st-Ädiuin tested by locked from any Insektersarfc 10 individuals in a Salbenechaehtel of 3.75 om Durcbifleaser with perforated cover» A small amount of suitable insect food was also introduced into every oil. The boxes were placed in larger Qefs, and in each of these larger QefMS were also placed a cotton ball with 0.1 com of the ineecticidal compound before it was sealed "after 24 hours

IQSS11 / 209T

If the small containers were taken out * and after the number of days given in the table below, the mortality was determined. The following results were obtained.

product

example

& be lie X

Il 'F

χ) χ)

100

100

ioo

after ι days

100

12th

100

40

x) The formula of this compound «ran

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Example S3

With the products of Examples 2, 3 and 10, smoking was carried out against ifematodes in a manner similar to that in Example 24. The results obtained are generally shown in Table 12

T & be 11 a II

Product. ^ ffliR

from -

Example R X after O days after i

Il _

90

100 100

! • Ο

10 -GHp-C ^ ρ - 100

BATH ORIGINAL

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Claims (6)

Fa% e afc a na ar tt e h e 1. Fluoroisopropylthier of the formula N
c in which each of the best X, which can be the same or different, signifies a chlorine or fluoride and R denotes hydrogen, an alkyl, hydroxyalkyl, carboxyl, cmrboxyalkyl, carboalkoxy, halocarbonyl, halocarbon, onyliaikyl, alkyicarb » oxyalkyl, sulfoalkyl, alkenyl, Bpoxyaliyl-, Alkenylcarfcoxyalkyl-, Alkalalkanoat-, fhenylr, Halogenpiien ^ I-, or Bönsoylgruppe, a group of the Fora »! a group of the formula C-CH ₂ -CK ₂ -O ^ -, where n is an integer from 10 to 1000, or a remainder of the poreel "' ^: . In which X has the meaning given above and Z is hydrogen or halogen or a group of the »formula SOJN 1st, wherein M is hydrogen or an alkali metal, 1st. 2. A method for producing a fluorine isopropylme thy leathers according to claim 1, in which R is a group other than that of the formula -CO ^ CHgC Hg, characterized in that one is an addition product of a perhalofluoroketone and an alkali »or silver fluoride of the formula OA in which A is an alkali metal or silver atom · with one Alkyl detergents of the general formula In which R has the meaning given in claim 1, but no halocarbonyl, sulfophenyl or halocarbonylalkyl group and Q is chlorine, bromine or iodine or a radical of the formula -OSO ₂ R ⁸ , in which R ^{2 is} an alkyl, alkoxy * or aryl group means 1st or U-OSJ) SI 1/2091 in which L is an alkylene or phenylene group, or c) QCH, in which Q denotes a chlorine, bromine or iodine atom and Z denotes hydrogen or a halogen atom or a group of the formula SOJM, in which M denotes hydrogen or an alkali metal, is, in a liquid solvent at a temperature of 20 to 200 ¹ C and gewUnsehtenfalls then, if the product of the reaction with the Alkyllerungemittel of formula a) (1) a compound of general formula I 1st, in which R is a carboxy ¹ -, carboxyalkyl or carbalkoxy 1st, the product to a compound of general formula I, in which R is a halogeno carbonyl or halocarbonyl alkyl group is »halogenated» or (2) a compound of the general formula I ₉ in which R is a phenyl group 1st, 1st, the product of a compound of the general formula I in which R ^{1 is} a sulfonated sulfonated group, or (3) is a compound of the general formula I in which R ¹ is a group of the general formula II the Z is a hydrogen atom, 1st, the product is sulfonated and optionally converted with an alkali hydroxide to form a compound of the general formula I in which R is a group of the general formula II, in which Z is a group of the form 1 SO ₅ M, in the M has the meaning given in Anapruoh 1, 1st, to form. 1098 11/2091 1518046 3. The method according to claim 2, characterized in » that hexafluoroacetone is used as the perhalofluoroketone. 4. The method according to claim 2 or 3, characterized in that that the alkylating agent is a benzyl halide, ethyl bromoacetate, a bis- (halonethyl) benzene, Propane sultone or ethyl H-bromundecylate used. 5. The method according to any one of claims 2 to 4, characterized characterized in that the addition compound from the perhalofluoroketone is used as the perhalofluoroketone addition product and silver fluoride are used. 6. A process for the preparation of a compound according to claim 1, in which R is a group of the formula -C-MCH ₂ -CH ₂
O is »characterized in that one connects the general formula X ₂ FC OCH ₂ COY 10 9811/2091 161B046 in which X has the meaning given in claim 1 and Y is a halogen atom, reacted with ethyleneimine. 109811/2091