DE2226039C3 - Process for the production of benzophenone derivatives by catalytic oxidation - Google Patents

Description

R ¹

R " ¹

in the R the same or different alcohols ni with 1 to 4 carbon atoms means / u compounds y. ·. the formula

oxidized.

■ -: · ■ N

R ^;

ν c \ y <

The subject of the patent 21 38 931 is a process for the preparation of basic dyes of the general formula

R ¹

A / λ j

Y V ^ X

R-

R ¹

ir hydrogen. Chlorine, methyl. Methoxy or athoxs. R "is hydrogen or T is chlorine and X is an anion, which is characterized by it. that you have connections the alliiemeincn formula

R ^;

in which, independently of one another, R is hydrogen. \ lk \ ' with 1 to 4 carbon atoms. Hydroxyalkyl mi; 2 ocU-3C-AtOmCn. Cyanoethyl, carbalkoxyalkyl with a total of 2 to 5 carbon atoms. Melhoxyethyl. Ethoxyethy! Alkanoyloxyalkvl with a total of 4 to 11 carbon atoms. Benzyl. Phenylethyl. Phenyl, through methyl. Mc'.ho> .v oflerÄthoxv suhstituierter Plienvl or a resident

A ^;

111 !; .AROUND. I'iillOl. Chi'ir. St. MV. 'llirl (Λ ί!

22nd

039

ierien benzoquinones or phenanthrenequinones substituted by nitro in the presence of oxygen and oxygen-transferring complex-bound heavy metal-containing catalysts dehyuneri. where A ¹ is Λ or a Re-.ι of the formein

R i ^ H;:! R-

'n' "N

R ^! R-

N -CH,

R ^;

Hs has now been found. that the ancestor of the patent 21 38 931 is also very good for production of compounds of the formula!

CO

R 4 s

■ - N ill R

in which R denotes identical or different alkyl radicals having 1 to 4 carbon atoms, from compounds of Formula 11

V-CH ₂ < V- ^N

suitable is.

R radicals are, for example, propyl. Hui \! uru: \ <possibly Methyl or ethyl.

Are quinones, which act as oxidizing agents f .. H. I olrafhior-. Fet avenge lor-. I etrahrom-. DhMiDidkyan- or Tetraeyan-M-bzochmon. 2- \ itro-. ί-7-Dinitio- or ■ o-DinitrophenanthicnehiiKT ;. Ietrachior or i e; rahroffi - !. 2- <~ enzoquinone Be \ o; -zuiii will ^ ri Tetrachkir- Jnü Teirabrom-1.4-ben / nchinon \ crv \ ends.

The quinones can be used as such or in ⁽ -onn der Hydrochinons ^{) 1} aerden. Nitrophenanihrchinone and the Hukgenquinones can be used in the pure form or as the mixtures obtained in the synthesis.

As heavy metals for the Oxidationskataiy.sa'n ·; en are z. B copper. Vanadium. Molybdenum and \ u; preferably To name iron and carbon. The metals lie in the catalysts in complex bond with nitrogen and oxygen atoms of the chelating agents \ or

In detail, for example, are the following bindings called:

Copper complex compounds des

1. 2-Aminoaihanois.

2.! .2-r) iamin (>; i! H. Ms.

3.! .2-diaminopropane:

Kvihaitkomplew erhi'uiiiii ^ en de * ·

4. Λ / omeihins from! .2-Dianiinoiithan

- 2MoI 2-hydroxyl benzaldehyde.

5. A / omethins from i.2-Diaminopii> pan

• 2 moles of 2-hydroxy benzaldehyde.

(1. Azomethines from! .3-Diaminopropane

• 2 moles of 2-! L \ dro. \\ ben / aidehyd.

7. A / ometliins from 1.2-! ) iaminoben / ol

f 2 Mo! 2-Hydroxybenzaldehyde. S. Azomethins from: J-Diamino ^ -ehlorbenzn!

- 2MoI 2-H \ drox \ benzaldehyde. 9. Azomethines from 1.2-Di.nriinoben / o!

- 2 moles of 2-H \ dioxy-3.5-dich! Orbenzaideh \ d. H). A / omethins from I 2-D! Arni! H) -4-chlorobene / o]

- 2 moles of 2-hydro \> - 3 5-dichlorobene / aldehyde \ d.

11. A / .i'methins from 1.2-Diammoalh: in

- 2 moles of 2-Ilydro \> - Smtrobenzalden \ d.

12. \ zomeihins from i.2-Diaminoathan

- 2 moles of 2-H_ \ dro \\ - 3-methoxybene / aldehyde.

13. A / omethins off. ! .2-Diamino; ithan

- ^ - 2 moles of 2-hydroxy-3-athoxybenzakiehyd. ! 4. Azomethines from (i3-aminopropyl) amine

• 2MoI 2-llydroxybenzaldehyde. 15. Azomethine from 1,2-diaminobenzene

- 2 mol 2-1 I \ dro \ y-i-mtrobenza! De!:;. D. Hi. A / omethins from 1,2-diaminoethane

, 2MoI 2-Hydro \ ynaphthaldehyde-l. ! 7. Azomethines from i.2-Diaminopror «-in

- 2 months! 2-hydroxynaphthiuldehyd-l. IS. Azomethines from i.2-Diarnmobenzo!

■ 2 moles of 2-hydroxynaphthalene-1. \ ⁱ ). A / omethines from i.2-diamino-4-chloro-ben / ol Γ mol of 2-hydroxynaphthaldehyde-1.

20. Azomeihins off; .2-diaminobenzene

¹ 2 moles of 3-formyi-4-methyl-5-eyan-2. (I-dih \ dro \ v-pyridine.

21. -V-oineihuii-, r.is ■ .2.4.5-1 etrammoben / ol

4 moi 2-1 hdr;> \ -. benzaldehyde. 22 iTi'ma / ani from (xanessius acid

• 2 Mon! ! ) iazo compound of 4-Chloi-2-amuii '] -. henol - (-> -suifosäii; 'e.

. ': ·. ! eiiaaz.a (14 | aniiulens from i ..j-Diammobeu. ■ ·;

- May.-iidiaidehvd.

2-4. 1 etraa / a.i! 4ianniiien> out ! ^ -D new, - ■ '· ■ MakMidiakkiiyd.

J '

Iron complex compounds of

26. phthalocyanine (fur),

27. phthalocyanine (FeIIl),

28. hexadecachlorophthalocyanines,

29. Phthalocyanine tri (or tetra) sulfonic acid
(y-dialkylaminopropyl) amides,

30. Hematins,

31. the oxo-vanadium complex compound of azomethine from 1,2-diaminoethane

+ 2 moles of 2-hydroxybenzaldehyde or

32. the dioxo-molybdenum complex compound des
Azomethines from 1,2-diaminoethane

+ 2 moles of 2-hydroxybenzaldehyde.

Catalysts 4 to 14, 23, 24, 26 or 27, for example, are used with technical preference.

It can be advantageous to use the catalysts applied to supports. As a carrier material is suitable e.g. B. activated carbon, kieselguhr, aluminum oxide or ceramic materials. The production such catalysts is from the literature, e.g. B. for fuel cells, known.

Advantageously, the new process is carried out so by, that the compounds of formula 11 in solution or suspension in a neutral to acidic pH range at temperatures between about 0 and 150 ° C, preferably 30 to 6O ⁰ C, with about 1O ^-3 one to 10 ~ 'mol of quinone, based on the molar amount of compound II, is dehydrated, the catalysts advantageously being added in one to four times the amount of the quinones. The complex catalysts can be added to the reaction mixture as such or can be formed from the individual components in the reaction mixture.

For the supply and mixing of the oxygen used for the oxidation, normally Pure oxygen or air, with the mixture to be oxidized, are usually suitable for mixing of gas and liquid into consideration, such as those in Houben-W e y 1, Vol. 4/2, pp. 261 to 276. The Working under pressure is of course also possible.

Suitable solvents for the oxidation reaction are, for. B. methanol. Ethanol, propanol, butanol, Isobutanol. Glycol. Methyl glycol, dimethyl glycol. Tetrahydrofuran. Dioxane, ethyl acetate. Chloroform. 1,2-dichloroethane. Carbon tetrachloride. Methylene chloride, Chlorobenzene, dichlorobenzene, benzene, toluene, xylene, acetic acid, propionic acid or lactic acid.

The oxidation can depending on the diphenylmethane derivative can be made in the neutral to acidic pH range, usually the neutral nH range is advantageous.

The diphenylmethanes to be oxidized are expediently in the solutions or suspensions in concentrations between 5 and 60, preferably 20 to 60 percent by weight, based on the weight the solution or suspensions.

Compared to the known preparation of the ketones of the formula I from substituted anilines and phosgene The method according to the invention offers advantages in terms of the yield, the easier feasibility and the low environmental impact.

example 1

A mixture of 508 parts of 4,4'-bisdimethylaminodiphenylmethain, 10 parts of chloranil and 20 parts of complex no. 4 and 1970 parts of methanol are at 50 ° C with vigorous stirring in a closed Apparatus treated with oxygen. Oxygen uptake comes after consumption of 64 parts almost to a standstill. After cooling, the precipitated 4,4-bisdimelhylaminobenzophenone is suctioned off and washed out with methanol. Yield: 459 parts, m.p .: 172-174C.

If complex no. 4 is replaced by other complex compounds in Example I, the following is obtained Exploit:

Example K'.miplex-Ni. Howl in

In a solution of 846 parts of 4,4'-bisdiethylamino · diphenylmcthan. 10 parts of tetrabromohydroquinone, 20 parts of complex no. 6 and 1650 parts of propanol is passed in at 55 ° C with vigorous stirring for 8 hours of air. After cooling down, it becomes crystal! nc precipitate sucked off and washed with a little ice-cold propanol. Yield: 670 g, m.p .: 9, up to 94 ° C. The yield can be improved by working up the filtrate.

Iv.iniplex no. Ai 1 S (I (j 84 7th 79 8th 81 ') 73 10 82 14th 78 23 59 2 B 52 example 1

Claims (1)

Claim: Modification of the process according to patent 21 38 931 for the production of basL · Jier ^ dyes of the Shape! R ¹ R- in which, independently of one another, R is hydrogen. Alkyl with 1 to 4C-Alomen. Hydroxyalkyl with 2 or 3 C-aioms. Cyanathyl. Carbalkoxyalky! with a total of 2 to 5 carbon atoms. Methoxyath \ l. Ethox \ ethy], alkanoyloxyalkyl with a total of 4 to i: C atoms. Benzyl. Phenyla'ihyL Phen \ i. by methyl Meihoxv or Äihoxy suhsiiiuierks Phenyl "or a radical of the formula So, H CH _: R ^{1 is} hydrogen, alkyl has 1 to 4 carbon atoms. Hydroxyalkyl with 2 or 3 carbon atoms. Cyanätlni. Meih'oxyäihyU Älhoxyäthyl or Phenyl. II ² same residues as R. R ^! same residues as R ^:. X hydrogen, chlorine, methyl. Methoxy or Athoxv Y hydrogen. Chlorine. Methyl. Methox} or ethoxy, A phenyl by chlorine. Methyl. Hydroxy methoxy. Ethoxy or the sulfonic acid group is mono- or disubstituted phenyl, a heteroaromatic radical or a radical of the formers N (Ί R ^; R ' R- ¹ R ^{4 is} hydrogen. Chlorine. Methyl. Methoxy or Atho.vy. R ^{5 is} hydrogen or chlorine and X is an anion, by catalytic oxidation in which compounds of the general formula 11 with by fluorine, chlorine. Benzoquinone substituted by bromine or cyano, or phenanthrenequinone substituted by nitro in the presence of oxygen and oxygen (active R ² (II) four-end catalysts containing complex bound heavy metal are dehydrated, where A ' equals A or a remainder of the formulas R ² or formula SO ₁ I. CH, N CU: "ν ν R ¹ R ^! is. thus g e k e π η / e i e h net. that he here compounds of the formula R ^: detergent. Alky! mil I to 4 C-Alomen. Hydroxyalk ;. i! πι '. 2 cider 3C atoms, cyanoyl. Meihoxya'thyi. Ethoxyethyl or phenyl, R- the same radicals ά ie R ir the same radicals as R ^! . X hydrogen. Chlorine. Methyl. Meihoxy or ethoxy, Y hydrogen. Chlorine. Metin i. Meihoxy or crälhoxy. A phenyl, through chlorine. Methyl. Hydroxy, meihoxy, ethoxy or the sulfonic acids uppe mono- or disubstituted phenyl, a heieroaromatic radical or a radical of the formulas