DE2236777A1 - PRODUCTION OF DIPHENYLAETHERS - Google Patents

Description

Patent attorneys

^Dr Ing.Walter Abitz ^{26 Jul1 1} ^ ²

Dr. Dieter F. M _{orf. '} 164,865

YY-. Hans -A. Browns

HOWARD HALI, & COMPANY 35 Mason Street, Greenwich, Connecticut, V.St.A.

Manufacture of rdpheriyläthern

The invention relates to the preparation of diphenyl ethers which are in particular nitro- and ajiino-substituted.

Various diamino diphenyl ethers are known to be useful Crosslinkers and IT networks for polymers Resins, plastics and elastomers of value, and these compounds As is well known, fdiid by reacting Konouitrochlorbenzol with an alkclinitrophenate using one medium to high boiling point, water soluble - amides aliphatic he liatur, κ. J3. Dimethylacetamide, producible as a solution cruithelium. 3i; (]. Auerlicherv; üi.so thereby form IListisße kte, and the v.lrtEchoftlichstö and arri Leicht:; tor.

jrjre Araid dioeer kind, liiuothylforaornicl, auci- al ;; clOicl, is ] iexi> ^ eeickung LÖKuii ^ KinitttO for serves · I2c.f: litioij (v; .l. UoA-Piitc-Lcclirif t 3 192 26J).

_ Λ - '

2 0 9 8 8 6/1323 ^BAD O ^RIGINAL

The present invention provides a method of making amino and nitro substituted diphenyl ethers using an »aminophenol salt as one of the starting materials available, in which in particular no simultaneous formation of p-dimethylaminonitrobenzene odex · other harmful By-products takes place and in particular further Dimethylformamide can be used as the reaction medium *. V / pus Advantages and Zv; Eck specifications of the invention are entered from the following description.

The production of amino and nitro substituted diphenyl ethers takes place according to the method according to the invention by an alkali metal salt, preferably the potassium salt, of an aminophenol with a halo-nitrobenzene in one of I / inethylformamide formed, liquid Keaküicnsmedium refluxed.

According to a preferred embodiment, a mixture of p-aminophenol, potassium carbonate, p-Ciilornitrobenzol and dimethylformamide is refluxed in an inert atmosphere until the reaction is essentially complete. The resulting product is the 4-amino-4 ^l -nitro-drphenyl ether:

o - /) - i

It was found that in the replacement of the nitrophenol by p-aminophciol the desired KoJidcTisetj.onsroaktion in siedondciü DJ.moth ^ il lormf ^ iic! with gcnügcndex "Geschv / indi gkcib und grosutei].« bin '/ lür · Exclusion of l-; t; bciirca!: tionejü. vcr. runs, so duss DiiautVi.y'IΓυΐ-αι ■■■ amide in very surriedtnsLolleiKli; : '.- V.'oint! Als] {t? {Ik "ti.Oi.!. \ ;. s -..- serves. \; io;: icU g (; r.oigt has. i νΛ d; <r. rp.it p ~ .. '. iiiinop} n.:. iH) .l in Dli; io ί "hy.'lj "oJ * i.iMi: i: i d rjluil parts. ] ^w- (.; dir; i ^; \ 'on a ¹ Veru-O'i ·: iu _lt i ·.; ■ ·>

- 2 - ORIGINAL BATHROOM

209886/1323

^{164 865} 3 2236777

those obtained with p-nitrophenol in dimethylformamide Product is essentially free; this impurity, p-dimethylaminonitrobenzene, is from the hydrogenated product can only be removed with difficulty.

The reaction mixture can then be used to obtain the amino-nitro mixture be worked up, on the other hand, a suitable catalyst can also be added to the reaction mixture, like Pd / carbon catalyst, add them and then hydrogenate them, thereby reducing the liitro- to an aminog.rappe will. The product in this case is 4,4'-diaminodiphenyl ether, also known as 4,4'-oxydianiline:

O ( VWH ₂

Instead of the ρ-aminophenol, one can use the o- or m-aminophenol use, x-zpbei the resulting condensation product the amine group in the corresponding position .aufweißt.

In the same way, instead of p-chloronitrobenzene use other halonitrobenzenes. The halogen atom can be in the p- or o-position and can be chlorine or bromine. In this way, using the basic method according to of the invention, d. H. Reacting an alkali aminophenate with a halonitrobenzene in one consisting of dimethylformamide ßeaktionsmedium a variety of products can be produced.

The following examples serve to further explain the Invention.

Ii Jl, 2-J '- ..' RA- ^ L 2- H

IvI]] (J JUrOIiU = I ₁ -; VO ^ J>'m!>Γ; (° »ϊ>) Hol) p-Amiiiophono.1, ' / Λ ■ /} g

2 O 9 8 ß 6/1 3 2 3

BATH ORIGINAL

(0.515 Hol) anhydrous potassium carbonate, 81.0 g (0.513 mol) p-chloronitrobenzene and 500 ml dimethylformamide were placed under a nitrogen blanket and heated with stirring for 5 hours at 145 to 147 ° C and then cooled and divided into two equal parts. Venn gev. ^r ünscht, one can remove the inorganic salts by filtration, but this is not a requirement.

One half of the solution was concentrated by distilling off dimethylformamide in vacuo, combined with a large amount of water (1000 ml) and filtered. After drying, 56.0 g (97> 5 %) of 4-amino-4'-nitrodiphenyl ether were present.

The second half of the above solution was treated with 6.0 g ^> ~ ° / i> - Pd / C catalyst, the mixture was hydrogenated at 4.2 atmospheres and the hydrogenated solution was filtered, concentrated by distilling off the dimethylformamide in vacuo, with brought together a large amount of water and filtered. The product was diluted with water !? Washed sodium hydroxide solution and water and dried, 43.4 g (87%) of 4,4'-oxydianiline being obtained.

Approximately equinolar amounts of p-aminophenol (10.9 g), p-Kitrochloi'benzol (162.0 g) and potassium carbonate (142.2 g) were added. at 147 to 149 ° C in 1000 ml of dimethyl form amide reflux cbrihaudelt. The reaction was carried out under nitrogen. The cooled solution was filtered to remove inorganic floffe % \ x , mid. in two parts at 0.7 to 4.2 atm over 12 {:; 5 "/ ^ ^; d / C - Ji; italysator hydrogenated. The combination of the filtered solutions and vacuum distillation led to the recovery of 1100 ml of Dinethylform am id (ζuoätfliehe 550 v, \ l D / Ji ' ¹ v / ai'cn ;: ls Uanehfjut admit tat v / ordon). The DHl ^ -Vi CdCr ₁ ·; '. · - ν. ^Γ 1.ιιΐιιιι: · [; in elJ or.cn Vu') J ο betru ;; L) O '/ O ₁ u \) ü ei · läiul iic.c.})]; üi] c.i'f?

209H86 / 1323 BAD ORIGINAL

Ί64.865

Degrees of recovery possible. The residue was combined with a large amount of water, filtered and reprecipitated, 188.6 g (94.3 ° / °) of crude 4,4'-oxydianiline being obtained.

Be i s ρ i el J '

Equimolar amounts of p-aminophenol (54.5 S-) and p-iTitrochlorobenzene (78.3 g) were mixed with 71 »1 B anhydrous potassium carbonate and 350 ml of dimethylformamide, and 6 ßtd. heated at 146 ° C. The mixture was cooled and, without filtering off the inorganic salts, transferred to a hydrogenation container and reduced at 0.7 to 4.2 atmospheres over 6.0 g of 5% I'd / G. After cooling and filtration. Of the catalyst, 4,4'-cteydianiline was isolated in the form of a pink-colored oil by combining the reaction mixture, including the dimethylformic acid, with a large amount of water and filtering. The yield was 84.2 g (84.2 %) ; Ϊ. 1.87 to 189 ° G.

At s. Ρ i el 4

A small excess of colium p-aminoplienate in the reaction start-up mixture leads to a somewhat purer product: A container was filled with 57.3 g (0.524 mol) of p-aminophenol, 87.3 g (0.500 mol) of nitrochlorobenzene, 74, 4 g (0.540 mol) of potassium carbonate and 500 ral Dimethylformamd and charged under nitrogen 6 ßtd. heated at 147 ° C. The oil was filtered off and hydrogenated at 0.7 to 4.2 atmospheres over 6.0 g of 5% rd / C. and c'iaa 4,4 ^f -0; iydianiline isolated in the usual manner, excess iij.i {: oo p-alaiophonol _f was removed by washing the iltorkuohcne with dilute liatron liquor. 92.4 g (92.4%) of a light pink saffron product, mp 188 to 190 ° C., were obtained. The V / i ederaus faliting from 21-butan oil yielded an almost ßca ^J roduct, P. 190 to 191 ° C.

BAD ORIGINAL 2098 86/1323

The use of sodium carbonate of Kaliumcarbonates in place in the above examples, the yield falls from about 90% to about 70% 'I ⁿ the same V / else results in a decrease in the yield of about 90% or greater to about 70%, v / ENU one instead of the ρ-aminophenol, an equivalent amount of p-nitrophenol is used. Furthermore, in the last-mentioned case there is an impurity which is difficult to remove after hydrogenation.

The range of solvents to be used can vary widely will be chosen, and limitations will only arise from considerations of ease of use and practicability result. The reaction can of course be εαιοη with the here preferred or claimed act: .oii & tcJ.lnehnicrn in undorcn, water-miscible, aliphatic amide solvents carry out.

209886/1323 ^ _0R , _Q i _NAL

Claims (2)

Fat e η t a η s ρ r ü c h e 1. Process for the preparation of disubstituted diphenyl- ' ν ■ ethers, characterized in that one Alkaliaiainoplienat with halonitrobenzene in dimethylformamide as the liquid reaction medium to form an amino and nitro-substituted diphenyl ether is refluxed, if desired, then the ether in. known way in the reaction medium to form a diamino diphenyl ether hydrogenated. 2. Verfaliren according to claim 1, characterized in that one works with potassium as the alkali metal. J. Verfaliren according to claim 1 or 2, characterized in that that one uses a halonitrobenzene which has the halogen atom in the o- or p-position to the nitro group. 4 ·. Verfaliren according to one or more of claims ¹ Λ to 3, characterized gekennzeichnet- that one forms the Alkaliaminophenat 'by Kückflussbehandlung of aminophenol with halonitrobenzene in the presence of an alkali metal base in the Heaktionsiaedium in situ. 5 «The method according to claim 4, characterized in that one ends as the alkali metal base potassium carbonate. G. worship according to claim 1, characterized in that one ya cchung with a content approximately ■ equiroola.r.-er amounts of p-amine / phcnoB., P-Chlomitrobenzol and Kaliu ^ icarbonat in MniC'thylforaamid reflux, the anffjl'J ondo riiechunn in Gegermart-eines Kata3.y, ^r : atoro hy-α3 ·: ι.ο: ι · υ, dar. Di.i> ic ⁱ thylfc-: rTicUuu ö dostiJ.lativ v. ^r ioclorgc-ivri ~ int Uno iii.uj ac:,! liücLiitanct cion 4, ^ 1'-Dl.'Jrii kri, '; La.l3 i:.;. i ort. 209 8 06/1 323 BATH ORIGINAL