DE1064045B - Process for the production of polytetrafluoroethylated aromatic compounds - Google Patents

Description

Process for the production of polytetrafluoroethylated aromatic Connections Addendum to patent application F15693IVb / 120 (Auslegeschrift 1 058 980) The subject of the main patent application F 15693 IVb / 12 0 is a process for production of aromatic compounds fluorinated in the side chain, which have a tetrafluoroethyl side chain contain, which is characterized in that one tetrafluoroethylene at increased Pressure and elevated temperature in the presence of carbonyl compounds with aromatic compounds Lets connections react. By an excess of the aromatic compound the formation of mono- (tetrafluoroethyl) derivatives is favored.

It has now been found that after that described in the main patent application Process multiple fluoroethylated aromatic compounds can be obtained, if you use tetrafluoroethylene under the same conditions as in the main patent application with mono- (tetrafluoroethyl) derivatives of aromatic compounds.

Several mols of tetrafluoroethylene enter the molecule of the aromatic. The resulting products are usually mixtures represent, the essentially compounds of the general formula R-Ar- (CF2CF2) yH, where z is an integer, if Ar is a benzene nucleus, 1 to 5, y is at least 2, R has the meaning given below and Ar is an aryl radical, in addition to minor Amounts of the isomeric compounds of the general formula R-Ar- (cF2-cF2W, contain, where R = H, alkyl, aryl, OR, RS and y is at least equal to 2 and x in the case that Ar represents a benzene nucleus, at most equal to 4 and the sum of x and y in this Trap is not greater than 6. The reaction takes place at the same time as the concentration of tetrafluoroethylene increases favored.

The compounds mentioned can also be obtained if one on one produced by the reaction of tetrafluoroethylene with aromatic compounds Mixture even more tetrafluoroethylene can act. In this case, the Reaction mixes monofluoroethylated compounds in addition to the di- and polyiluted compounds Get connections. In this way, multiply fluorinated compounds Of course, also in one step from the aromatic starting materials and tetrafluoroethylene can be obtained.

A particularly good implementation can be achieved by the tetrafluoroethylene advantageously diluted with water gas and used to react required pressures and temperatures the aromatic compound in which z. B. Cobalt tetracarbonyl is dissolved, through a pump or lock or the like. Into the reaction chamber gradually introduces. The tetrafluoroethylene can also be used as a mixture with carbon monoxide be used in relatively high concentration. Also through an increase the catalyst concentration increases the formation of these multiple addition products promoted.

The new compounds that can be produced by the process are suitable as fragrances, lubricants and as intermediates, for example for dyes.

They can be converted into the nitro and amino compounds in a known manner convict. The compounds are chemically much more stable than benzyl fluoride, for example.

Example 1 300 g of tetrafinoroethylbenzene (n2D0 = 1.4247), in which the 8th g of cobalt tetracarbonyl were dissolved in an autoclave with 235 g of tetrafluoroethylene mixed and heated after pressing 160 at water gas. The reaction, recognizable on the pressure drop, occurred at 1360 C and 238 at. The pressure was carried out at 1550 C. Repression of carbon dioxide held at 270 atm; the reaction was after 4 hours completed. After cooling and releasing the pressure, 456 g of liquid were obtained with n2.0 = 1.3936 obtained which was fractionally distilled. After a lead of 19th g hydrogenated fluorocarbons and 25 g tetrafluoropropanol, which by the effect of water glass on tetrafluoroethylene emerged as a by-product 204 g of tetrafluoroethylbenzene were recovered. The residue was with Steam distilled and afterwards from the heavy lower layer of the steam distillate drying 130 g of a mixture of approximately equal parts bis- and poly-tetrafluoroethylbenzene obtained from which the bis-tetrafluoroethyl compound by fractional distillation was separated.

Example 2 In a from 600 g of benzene and 279 g of tetrafluoroethylene in Presence of 6.1 g of cobalt tetracarbonyl [Co (CO) 4] 2 at 180 atm pressurized water gas at a temperature of initially 1350 C up to finally increasing to 1870 C Mixture which essentially contains the mono- (tetrafluoroethyl) derivative is at 1700 C a solution of 2 g of cobalt tetracarbonyl in 350 g of benzene within 60 minutes pumped into the autoclave and the reaction at 1500 C to end in a further 2 hours guided. After cooling, letting down the pressure and distilling off the not in reaction trampled benzene, 306 g of a water-white liquid (n2D0 = 1.4127) were obtained, which was fractionally distilled. After the tetrafluoroethylbenzene passing over at 630 C / 50 Torr (Refractive index n2D0 = 1.4247) at 620 C / 13 Torr, 80 g of a fraction with a Refractive index nD20 = 1.3926 obtained, which according to analysis is a bis-tetrafluoroethylbenzene represents that by reaction of mono- (tetrafluoroethyl) benzene with tetrafluoroethylene and is probably a meta derivative.

Analysis: CtoHF8 C H F calculated .......... 43.10%, 2.17% 54.65%; found .......... 43.190 / o, 2.230 / o, 53.95%.

With further distillation of the remaining portions (73 g) goes to 80 to 830 C / 11 Torr a tris-tetrafluoroethylbenzene formed by further reaction with n200 = 1.3855 over, and finally boil up to 1190 C / l2 Torr further higher tetrafluoroethylated Products; Finally, crystals form in the residue.

Example 3 A mixture of 1000 g benzene, 800 g tetrafluoroethylene, 30 g of [Co (CO) 4] 2 became several hours at 135 to 1400 C under a pressure of 160 up to 125 atm of a CO / H2 mixture in a ratio of 7: 1. The received Crude product of 1687 g was freed from excess benzene and yielded after filtration 73 g of a waxy product containing 3 to about 25 parts of tetrafluoroethylene contained. After fractional distillation, the filtrate gave the following compounds: 1. 390 g of tetrafluoroethylbenzene with a boiling point of Bp.10 = 290 C and a refractive index n2D = 1.4250, 2.228 g of octafluorobutylbenzene with a boiling point of bp = 59 ° C and a refractive index Sl2D = 1.3930, 3. 73 g of dodecafluorohexylbenzene with a boiling point of 10 ° C = 85 ° C and from Refractive index n2.0 = 1.3784, 4. 19 g of hexadecafluorooctylbenzene with a boiling point of bp lo = 107 ° C and the refractive index n2D = 1.3692.

21 g of the distillation residue consisted of benzene derivatives with more than 4 tetrafluoroethylene units.

Analyzes: Ad 2: C10 H6 F8 (molecular weight = 278.15) C H F calculated ..... 43.18%, 2.17%, 54.65%; found ...... 43.19%, 2.23%, 53.95%.

To 3: C12H6F12 (molecular weight = 378.17) calculated .......... 38.11 1.60%, 60.2901o; found .......... 38.11 e / 0, 1.63 0 / o, 59.95 0 / o.

To 4: Cl4H6Fl6 (molecular weight = 478.19) calculated .......... 35.166 / o, 1.27%, 63.57%; found .......... 35.30%, 1.33%, 62.80%.

The compounds created by the entry of two or more tetrafluoroethylene molecules obtained contain certain amounts of substances in which several nuclear hydrogen atoms are substituted and dile can only be separated with difficulty by fractional distillation are. The amount of these compounds is higher, the more tetrafluoroethyl groups entered a benzene molecule.

Claims (3)

PATENT CLAIMS: 1. Further development of the manufacturing process of aromatic compounds fluorinated in the side chain by reaction of Tetrafluoroethylene with aromatic compounds at elevated pressure and elevated Temperature in the presence of cobalt carbonyl compounds according to patent application F 15693 IVh / 12o, characterized in that aromatic compounds that already have a Tetrafluoroethylene group bound to the core contain, reacts with tetrafluoroethylene. 2. The method according to claim 1, characterized in that the mono- (ketrafluoroethylated) aromatic compound under the reaction conditions introduces into the reaction vessel containing the submitted tetrafluoroethylene. 3. The method according to claim 1 and 2, characterized in that one one in a crude, in the reaction of tetrafluoroethylene with an aromatic Compound resulting mixture contained mono- (tetrafluoroethylated) aromatic Reacts compound with tetrafluoroethylene.