DE1620623A1 - Process for the preparation of dibenzodiazocines - Google Patents

Description

Dr. Walter Befl

Alfred Σ '·; -:.: Τ
DlElt: y :,: ■ "Full Dr. hij: is -. ■ i-jil

Frankfurt a.iü, - Höchst

Adeionstrasse 58 - Tel 312643

Our Ir. 12 459

ΪΗΕ ÜPJOIIE "COMFaKY Kalamazoo, Iviiche, "/ place St.A.

Process for the preparation of dibenzodiazocines

The present invention "relates to a process for the preparation of new 6,1 2-diaryl-di'benzo / ~ b, Ζ / / Λ ', 5 / diazocine, which have the following lOrmel I!

BATH ORIGINAL

909843/17

(O

in which X and Y are hydrogen, halogen, trifluoromethyl, alkyl radicals with I to 4 carbon atoms including hydroxyl groups, Alkoxy groups with 1 to 4 carbon atoms inclusive, and represent acyloxy groups in which the acyl radical an alkane carboxylic acid with 1 to 4 X;: ilenstoff atoms including originates, with at least one of the partners X and Y Is halogen, trifluoromethyl, hydroxy, alkoxy or aeyloxy.

Fluorine, chlorine and bromine are used as halogen substituents and iodine in question.

Examples of alkyl groups are methyl, ethyl 1-, Propyl, isopropyl, butyl, isobutyl group.

909843/1737

BATH ORIGINAL

Examples of alkoxy groups are the methoxy, Ethoxy, propoxy, isopropoxy, butoxy and isobutoxy groups.

Suitable acyloxy groups are the formyloxy, acetoxy, Propionyloxy, butyryloxy and isobutyryloxy groups.

The method according to the invention can be reproduced as follows will :

"(III)

In the above formulas, X ¹ and Y ¹ denote hydrogen, halogen, trifluoromethyl, alkyl groups with 1 to 4 carbon atoms or alkoxy groups with 1 to 4 carbon atoms, where at least one of the parameters X ¹ and Y »denotes halogen, trifluoromethyl or alkoxy.

909843/1737

BATH ORIGINAL

The process according to the invention is characterized in that a 2-aminobenzophenone of the formula II is condensed in the presence of an acid catalyst, for example p-toluenesulfonic acid, to form the corresponding compound of the formula III, which falls under the general formula I. If one of the substituents X or Y in formula I is to be a hydroxyl group, the process is carried out with a starting compound II which has an alkoxy group X ¹ or Y ¹ instead of X - or Y, and the alkoxy group of the ether compound of the formula III thus obtained . is then split off, the desired hydroxyl 'compound of the formula I being obtained. When treating a phenolic compound of the formula I with formic acid or with an alkane carboxylic anhydride (for example acetic anhydride, propionic anhydride, butyric anhydride or isobutyric anhydride), a compound of the formula I is obtained in which one or more substituents are acyloxy groups.

The compounds of the invention obtainable Formula I are active estrogenic agents that prevent fertility in rats, even in amounts of 100% per unit Rat. The estrogenic agents can be administered to birds and mammals, especially in the form of a powder, the is added to the feed, for example with maize

" ⁴ - ^BATH

909843/1737

or soy meal is mixed to help weight gain of animals such as chicks or cattle, to speed up. In higher doses, the compounds can be used for chemosterilization used, especially in birds such as starlings and pigeons, Close to public buildings and airfields, also for the Ghemosterilization of coyotes, rats and mice. To this Purposes, the compounds are mixed with suitable feed in powder form, or, when used for birds, processed into a coating mixture for grains. The compounds can also be administered in the form of hard capsules or they can be combined with solid or liquid pharmaceutical carriers and made into tablets, powder packets or capsules are processed using starch and similar excipients; furthermore can suspend the compounds in suitable solvents or carriers for oral or paranteral administration.

The compounds of formula I can also be used as Find intermediate products use. For example, they can be hydrogenated to form the corresponding secondary Amino compounds that can be reacted with fluosilicic acid to form fluosilicate salts, which Effective moth repellent in dilute aqueous solutions (see U.S. Patents 2,075,359 and 1,915,334).

90984 3/1737

BAD OR1GIN4X

The starting compounds of the process according to the invention, the 2-aminobenzophenones of the formula II, are known and can, for example, by the process of WCLothrop et al., J.Am.Chem. Soc. 65, 363 (1943) and LHSternbach et al., J.Org.Chem. 27, 3781, 3788 (1962). Examples of suitable starting compounds are: 3-bromo-2-aminobenzophenone, 4-bromo-2-aminobenzophenone, 4'-bromo-2-aminobenzophenone, 5-bromo-2-aminobenzophenone, 6-bromo-2-aminobenzophenone, 3.5 dibromo-2-aminobenzophenone, 5-bromo-2 '-fluoro-2-aminobenzophenone, S-BromHHnethoxy ^ -aminobenzophenon, 5-bromo-4' -methyl-2-aminobenzophenone, ^t 2-chloro-2-aminobenzophenone, 3 -Chlor-2-aminobenzophenone, 4-chloro-2-aminobenzophenone, 4'-ChIOr-2-aininobenzophenone ,, 5-chloro-2-aminobenzophenone, 6-chloro-2-aminobenzophenone, 2 ' _f 5-dichloro-2- aminobenzophenone, 3,5-dichloro-2-aminobenzophenone, 4,5 ~ dichloro-2-aminobenzophenone, 4 ', S-dichloro ^ -aminobenzophenone, 5-chloro-2'-fluoro-2-aminobenzophenone, 5-chloro-3 '-fluoro-2-aminobenzophenone, 5-chloro-4'-fluoro-2-aminobenzophenone, 2 ¹ -chloro-5-IEethyl.2-aminobenzophenone, 3'-chloro-4'-methyl-2-aminobenzophenone, 2 · -Chlor-4,5-dimethyl-2-aminobenzophenone, 4 '-chloro-4,5-dimethyl-2-aminobenzophenone, 2 ·, 4' dichloro-4,5-dimethyl-2-amiobenzophenone, 2 ', 5 '-Dichlor-

- 6 -

909843/1737

4 »5-dimethyl-2-aminobenzophenone, 5-chloro-2-methoxy-2-aminobenzophenone, 5-chloro-4'-methoxy-2-aminobenzophenone, 5 '-chloro-2 -methoxy-5-methyl- 2-aminobenzophenone, 5-chloro-2'-methoxy-5'-methyl-2-aminobenzophenone, 5-chloro-2-isopropoxy-2-aminobenzophenone, 5 '-chloro-J-butoxy ^ -aminobenzophenone, 2'- Fluoro-2-aminobenzophenone, 4 ^f- fluoro-2-aminobenzophenone, S-fluoro - ^ - aminobenzophenone, 2 '~ fluoro-5-methyl-2-aminobenzophenone, 2'-trifluoro-methyI-2-aminooenzophenone, 3-TΓifluoΓmethyl aminobenzophenone -2 ^., 5'-Trifluormeth.yl-2-aJminobenzophenon, 4-5frifluormethyl-2-aminobenzophenone, 5-trifluoromethyl-2-aminobenzophenone, 2 ^1, 5-bis (trifluoromethyl) -2-aminobenzophenone _f 2 ^f -Methoxy-2ramino-benzophenone, 2'-ethoxy-2-aminobenzophenone, 4-propoxy-2-aIninQ-benzophenone, 4-butoxy-2-aminobenzophenone, 4-methoxy-2-aminobenzophenone, 4'-methoxy-2-aminobenzophenone , 5-methoxy-2-aminobenzophenone, 2 ', 4-dimethoxy-2-aminobenzophenone, 3> 4-dimethoxy-2-aminobenzophenone _f 3'"4'-dimethoxy-2-aminobenzophenone, 4,4 '^ -trimet hoxy ^ -aminobenzophc-ion, 3 '-Methoxy-2 ·, 5-dimethyl-2-aminobenzophenone, 4' -Methci-y-2 ', 3' -dimethyl-2-aminobenzophenone, 4 '-methoxy-2 ·, 5,1-dimethyl-2-aminobenzophenone, 5-methoxy-2 ', 4'-dimethyl-2-aminobenzophenone, 5-methoxy-2-methyl-2-aminobenzophenone, 5-methoxy-2-butyl-2 -aminobenüophenon _Ψ 4 '-Methoxy-4-

ORIGINAL BATHROOM

9098-3 / 1737

isopropyl-2-aminobenzophenone, 5-bromo-4'-ethoxy-2-aminobenzophenone, 2 ^l -chloro-3'-propoxy-2-aminobenzophenone, 4-fluoro-2'-isobutoxy-2-aminobenzophenone, 2 · iodine -3-ethoxy-2-aminobenzophenone, 3'-iodo-4-butoxy-2-aminobenzophenone, 5-bromo-3'-propoxy-2-aminobenzophenone, 4'-fluoro-2'-ethoxy-2-aminobenzophenone, 2 '-Chlor-4-ethyl-2-aminobenzophenone, 3-iodo-5-butyl-2-aminobenzophenone, 4-bromo-3' -propyl-2-aminobenzophenone, 4-fluoro-3'-isopropyl-2-aminobenzophenoix , 5-ChloΓ-4-isobutyl-2-aminobenzophenone, 5-bromo-3-ethyl-2-aminobenzophenone and the like.

When carrying out the process according to the invention, a certain 2-aminobenzophenone of the formula II heated in solution or suspension with an acidic catalyst. A preferred solvent or suspending agent is high-boiling, essentially anhydrous organic solvents, such as, for example, the xylenes, toluene, 1,3 »5-trimethylbenzene and the same. Lower boiling solvents such as benzene, chloroform, carbon tetrachloride and the like can also be used. Organic and inorganic acids such as e.g. Arylsulfonic acids such as the benzenesulfonic acids, for example benzenesulfonic acid, p-chlorobenzenesulfonic acid, p-bromobenzenesulf acid, p-methoxybenzenesulfonic acid, p-toluene

- θ - ^ÖAD ORIGINAL

909843/1737

sulphonic acid, p-ethylbenzenesulphonic acid, naphthalenesulphonic acids for example 1- and 2-naphthalenesulfonic acids » essentially anhydrous / mineral acids such as hydrogen chloride gas, sulfuric acid, hydrogen bromide gas and the like, with p-toluenesulfonic acid "preferred. The acid catalyst is usually used in an amount of 0.5 Hs 10 wt. #, based on the weight of the starting material II used. The reaction generally takes place at elevated temperatures Temperatures, preferably at the reflux temperature of the Mixtures, the water released during the reaction using a reflux condenser with a water trap is eliminated. The reaction time is usually between 6 hours and 5 (pages. In mixtures of technical grade xylene with a boiling range between 138-149 ° C one is sufficient Response time from 1/2 to 5 days. After the reaction has ended, the product is recovered from the reaction mixture in a conventional manner, for example by evaporation the solvent and purification of the residue by recrystallization, Chromatograph or the like.

The following examples illustrate that according to the invention Procedure, «toneee to, limit.

BAD ORlGiNAL

Example 1; 2,8-dichloro-6,12-diphenyldibenzo / b, f Jβ. , 57 diazocin.

A mixture of 23.17 g (0.1 mol) of 5 * -chloro-2-aminobenzophenone, 0.5 g of p-toluenesulfonic acid and 100 ml of xylene was refluxed for 16 hours using a waterfall. The theoretical amount of water was collected. The reaction mixture was cooled, filtered and the filtrate was washed with saturated sodium carbonate solution and then with water 196-210 ° C. When recrystallizing from ethyl acetate, 13.20 g (62 #) 2,8-dichloro-6,12-diphenyldibenzo / b \ f7 / 1,5.7 diazocine in the form of yellow prisms with a melting point of 216-217 G were obtained.
Analysis; Calculated for Coß ^ iö ^^ 2 ^ 2 ^:

C: 75.08; H: 3.77; Cl: 16.59; N: 6.56. Found:
C: 73.12; H: 3.33; Cl: 16.65; B: 6.82.

-iö - 9ÖS143 / 1737

ff

Example 2: 2,8-: dichloro-6 12 _r-bis- (4-methoxyphenyl) dibenzo ^ b "f7 / Ϊf57diazoc in.

A mixture of 33 t 44 g of 5-chloro-4 ^l -methoxy-2-aminobenzophenone and 3 »34 g of p-toluenesulfonic acid in 335 ml of toluene was refluxed for 65 hours , using a water trap. The mixture was cooled and then 300 ml of ethylene chloride were added. The resulting solution was washed well with water and evaporated to dryness to give a solid which was recrystallized from aqueous acetonitrile ; Yield 26.5 g of 2, 8-pichlor-6 _f 12-bis- (4-methoxyphenyl) -dibenzo ^ b, f7 / ϊ, 57 diazocine, melting point 196-198 C.

An analytically pure sample with a melting point of 196-197 _f 5 ° C was obtained in a further experiment.

Analysis: Calculated for 928 ^H 20 ^C1 2 ^N 2 ° 2 ^:

Cs 69.00; H: 4.14; Cl: 14.55. Found: C: 68.82; H: 4.04; Cl: 14.49. Example 3: 6 _t 12-bis (4-methoxyphenyl) -dibenzo-

A mixture of 12.36 g of 4 ^l -methoxy-2-aminobenzophenone and 1.24 g of p-toluenesulfonic acid in 124 ml of xylene was refluxed for 65 hours using a water trap. The reaction mixture was mixed with methylene chloride and the resulting solution was

BATH

909843/1737

washed each other with aqueous sodium bicarbonate solution, water and brine. The gummy residue which remained after evaporation to dryness was chromatographed on Florisil (anhydrous magnesium silicate, elution with 5 $ acetone-95 $ Skellysolve B-hexane). The combined eluates were evaporated to give a crystalline contaminant which was recrystallized twice from aqueous acetone; in this way it became 5.10 g
6,12-bis (4-methoxyphenyl) -dibenzo ^ b, f "J / J- » 5_7diazocin
obtained from melting point 162-165.5 ° C.

Analysis; Calculated for C ₂₈ H ₂₂ N ₂ O ₂ : C: 80.36; H: 5.30. Found; C: 80.14; H: 5.14-

Example 4: 4,10-bis (trifluoromethyl) -6,12-diphenyldibenzo / b, f // Ϊ, 5_7diazocin.

Following the procedure of Example 1 was
3-trifluoromethyl-2-aminobenzophenone (British patent
956,562) in xylene in the presence of p-toluenesulfonic acid
heated to obtain the above compound.

Example 5: 3,9-bis (trifluoromethyl) -6,12-diphenyl-

dibenzo ^ b, f7 / l, 5_7diazocin.
Following the procedure of Example 1 was
4-trifluoromethyl-2-aminobenzophenone (British patent

- 12 -

909843 / T737
BATH

956.562) heated in xylene in the presence of p-toluenesulfonic acid, whereby the above compound was obtained. Example 6; 2,8-dichloro-6,12-bis (2-fluorophenyl) -

dibenzo / b, f7 / 1,57-diazocine. Subject of the procedure of Example 1 was 5-chloro-2'-fluoro-2-aminobenzophenone /j.0rg.ChemT27, 3781 (1962) 7 in xylene in the presence of p-toluenesulfonic acid heated to obtain the above compound.

Example 7; 2,8-dibromo-6,12-diphenyldibenzo ^ b, f7 / ΐ, 5 / 'diazocin,

Following the procedure of Example 2, 5-bromo-2-aminobenzophenone was obtained /J.Org.Chem.26,4448 (196127 in Toluol heated in the presence of p-chlorobenzenesulfonic acid, wherein the above connection was obtained.

Example 8: 2,4,8,1O-tetrachloro-6,12-diphenyldibenzo- / b, f7 / I, 57d.iazon. .

Following the procedure of Example 1, 3 »5-dichloro-2-aminobenzophenone /j.Org.Chem.26,4448 (1961 ^ 7 was heated in xylene in the presence of p-toluenesulphonic acid, the above compound being obtained. Example 9; 2 , 8-Oichlor-6,12-bis- (4-chlorophenyl) -dibenzo / b, f7 / l, 57diazocin.

Following the procedure of Example 1, 4 ', 5-dichloro-2-aminobenzophenone was obtained ^ J.Org.Chem. 26, '4448 (1961) /

- 15 - ·

909843/1737

BAD ORJGiWAL

heated in xylene to give the above compound.

Example 10; 3,9-dimethoxy-6,12-diphenyldibenzo / b, f7 / 1,5_7 ~

diazocin.

Following the procedure of Example 1, 4-methoxy-2-aminobenzophenone was obtained in xylene in the presence of p-toluene sulfonic acid heated to obtain the above compound.

Example 11: 2,8-Oijod-6,12-bis- (4-ethoxyphenyl) -

dibenzo / b, f7A> 57diazocin.

Following the procedure of Example 1, 5-iodo-4'-ethoxy-2-aminobenzophenone was obtained heated in xylene in the presence of p-toluenesulfonic acid to give the above compound.

Example 12: 3,9-Dipropoxy-6,12-diphenyldibenzo / b, f7 / 1.57-

diazocin.

Following the procedure of Example 1, 4-propoxy-2-aminobenzophenone " in xylene in the presence of p-toluenesulfonic acid heated to obtain the above compound.

Example 15: 2,8-bis (trifluoromethyl) -6,12-bis (2-trifluoro-

methyl-phenyl) -dibenzo / b, f7 / I, 57diazocin. Following the procedure of Example 1, 2 ', 5-bis (trifluoromethyl) -2-aminobenzophenone was obtained heated in xylene in the presence of p-ethylbenzenesulfonic acid, the above Connection received.

- 14 -

909843/1737

BATH ORIGINAL

Example 14: 6,12-bis (3-chloro-4-methylphenyl) -dibenzo-

/ b, f7 / I, 57-aiazocin.

Following the procedure of Example 1, 3'-chloro-4'-methyl-2-aminobenzophenone was obtained heated in xylene in the presence of p-bromobenzenesulfonic acid, using the above compound received.

Example 15: 2 »8-dichloro-6,12-bis- (3-fluorophenyl) -dibenzo-

/ b, f7 / Ϊ, 57diazocin.

Following the procedure of Example 1, 5-chloro-3'-fluoro-2-aminobenzophenone was obtained heated in xylene in the presence of p-toluenesulfonic acid, using the above compound received.

Example 16: 2,8-dibromo-3,9-dimethoxy-6,12-diphenyl-

dibenzo / b, f7 / l »57diazocine.

Following the procedure of Example 1, 5-bromo-4-methoxy-2-aminobenzophenone was obtained heated in xylene in the presence of p-toluenesulfonic acid, whereby the above compound received.

Example 17: 2 _f 8-Diiodo-3,9-dibutyl-6,12-diphenyl-

dibenzo / b, f7 / l, 57dia.zocin.

Following the procedure of Example .1 was 5-iodo-4-butyl-2-aminobenzophenone in xylene in the presence of

- 15 -

90 9 8 437 1 737 BAD

lh

p-toluenesulfonic acid heated, using the above compound received.

Example 18; 4, 10-diisopropyl-6,12-bis (4-methoxyphenyl) -

dibenzo / b, f7 / 1,57diazocin Following the procedure of Example 1 was 3-isopropyl-4'-methoxy-2-aminobenzophenone in xylene in Heated in the presence of p-toluenesulfonic acid to obtain the above compound.

Example 19; 3 »9-difluoro-6,12-bis (2-isobutoxyphenyl) -

dibenzo / b, f7 / Ϊ, 57diazocine. Following the procedure of Example 1 was 4-fluoro-2'-isobutoxy-2-aminobenzophenone in xylene in the presence heated by p-toluenesulfonic acid to obtain the above compound.

Example 20 : 3,9-Diethyl-6,12-bis (2-chlorophenyl) -

dibenzo / b, f7 / Ϊ, 57-diazocine. Following the procedure of Example 1, 2'-chloro-4-ethyl-2-aminobenzophenone was present in xylene heated by p-toluenesulfonic acid, using the above connection e rh ie11.

- 16 -

909843/1737

BATH ORIGINAL

Example 21; 4,10-diiodo-2,8-dibutyl-6,12-diphenyldibenzo / b, f7 / I, 57 <liazocin.

Following the procedure of Example 1 was 3-iodo-5-butyl-2-aminobenzophenone heated in xylene in the presence of p-toluenesulfonic acid, the above Connection received.

Following the procedure of Example 1, other 6,12-diaryldibenzo / b, f7 / l, 57diazocines of the formula II can be prepared by condensing a 2-aminobenzophenone of the formula II with heating in the presence of an acid catalyst such as an arylsulfonic acid. Examples of other ^, ^ - Diaryldibenzo ^ bj ^^ lj ^ äiazocine of the formula III are: 4, lO-dibromo-6,12 * -diphenyl-dibenzo / b, f 7 / Ϊ, 57diazocin, 3,9-dibromo- 6,12-diphenyldibenzo / b, f "] (J. , 57d.iazocin, 6,12-bis (4-bromophenyl) -dibenzo7b, f // Ϊ, 57 ^ i ⁸ " ²¹⁰⁰ ! ¹¹ * 1.7 -Dibromo-6,12-diphenyldibenzo / b, f // l, 5 / diazocin, 2,4,8,10-tetrabromo-6,12-diphenyldibenzo / b, f // l, 5 / diazoc in, 2 , 8-dibromo-6,12-bis (2-fluorophenyl) -dibenzo / b, f / A, 5 / diazocine, 2,8-dibromo-3,9-diethoxy-6,12-diphenyldibenzo / b, f / Ä-, 5 / diazoein, 6,12-bis- (2-chlorophenyl) -dibenzo / b, f7 / l> 57 ⁽ iiazocin, 6,12-bis- (4-chlorophenyl) -dibenzo / b _t tj £ , 5 / diazocin, 2,3,8-, 9-Ietramethyl-6,12-bis- ( Z , 4-dichlorophenyl) dibenzo- / b, f // 1,5 / diazocin, 2,3,8, 9-tetramethyl-6-, 12-bis- (2.5-

- 17 -

909843/1737

BATH ORIGINAL

dichloroplienyl) -dibenzo / b, f7 / 1,5 / diazocin, 2,8-dichloro-6,12-bis- (2-methoxyphenyl) -dibenzo / B, f // l, 57diazocin, 2,8-Mmethyl- 6,12-bis (2-methoxy-4-chlorophenyl) -dibenzo / b, f7 / l, 57diazocin, 2,8-dimethyl-6,12-bis (2-fluorophenyl) -dibenzo / b, f // 1,5 / diazocin, 6,12-bis- (2-trifluoromethylphenyl) -dibenzo / b, f7 / 1,57diazocin, 6,12-bis- (3-trifluoromethylphenyl) -dibenzo / b, I] [I. . , 5_ / diazocin, 3,9-dimethoxy-6,12-diphenyl-dibenzo / b, f / A, 57diazocin, 6,12-ice- (3-methoxyphenyl) -dibenzo / b, f / A> 57diazocin, 6 , 12-bis- (3> 4-dimethoxyphenyl) -dibenzo / b, f // l, 57diazocin, 6., 12-bis- (2-butyl-5-methoxyphenyl) -dibenzo / b, f // l » 5 / diazoc in, 2,8-dibromo-6,12-bis- (4-ethoxyphenyl) -dibenzo / b, f7 / 1,5 ^ dIaZOc in, 6,12-bis- (2-chloro-3-propoxyphenyl ) -dibenzo / b , £] / !, 5 / diazocin, 4,10-diethoxy-6,12-bis- (2-iodophenyl) -rdibenzo / b, f // 3,57-diazocin, 3.9 -Dibutdxy-6,12-bis- (3-oodphenyl) -dibenzo / b, f / A »5 / diazocin, 3,9-diethyl-6,12-bis (2-chlorophenyl) -dibenzo / b, f / A, 57 "-diazocin, 2, e-dichloro ^, 9-diisobutyl-6,12-diphenyldibenzo- / bjf / AjS / diazocin and the like.

Example 22 ; 2,8-dichloro-6,12-bis (4-hydroxyphenyl2-

dibenzo / b, f7A »57 ^ -i ^azoc i ⁿ ^^^ its acetone solvate.
A suspension of 3.0 g of 2,8-dichloro-6,12-bis-

(4-methoxyphenyl) -dibenzo / b, f7A »57diazocin and 3.2 g

- 18 -

9098A3 / 1737

ßAD

anhydrous aluminum chloride in 50 ml of benzene was refluxed for 6 hours. The mixture was poured into 120 ml of a solution obtained by adding ice to 60 ml of 2.5 standard hydrochloric acid. After stirring for 20 minutes, ether was added and the mixture was brought to a pH of about 8 by successive addition of sodium hydroxide and sodium bicarbonate solution. The organic layer was separated, washed with water and brine and evaporated to dryness. The remaining pesticide was chromatographed on Plorisil (elution with first 10%, then 25% acetone, remainder Skellysolve B-hexane). The crude phenol was recrystallized from aqueous acetone, giving 1.49 g of 2,8-dichloro-6,12-bis (4-hyaroxyphenyl) -dibenzo ^ b, f7 / 1,5_7diazocine in the form of an acetone solvate with a melting point of 304- 313 C. Analysis: Calculated for C _o , -H ,, - Cl ₀ N ₀ O ₀ .1 / 2 CUH.O:

C: 67.63} H: 3.92; Cl: 14.52. Found: C: 67.38; H: 4.05; Cl: 14.62. When heating the AcetoneölVats in vacuum 150 C in a finely divided state becomes the unsolvated Connection received.

909843/173 7

BATH ORIGINAL

ίο

Example 251 6,12-bis (4-hydroxyphenyl) -dibenzo / b, f ^ / 1,57-

diazocin.

Following the procedure of Example 22 was
6,12-bis (4-methoxyphenyl) -dibenzo / b, f 7 / Ϊ, 5_7diazocin heated with anhydrous aluminum chloride in benzene; then treated with cold aqueous hydrochloric acid to obtain the above compound.

Example 24: 3,9-dihydroxy-6,12-diphenyldibenzo / b, f7 / Ϊ _f 5-7 ~

diazocin.

Following the procedure of Example 22 was
3,9-dimethoxy-6,12-diphenyldibenzo / b, f J / 1,5> 7diazoc in heated with anhydrous aluminum chloride in benzene; then treated with cold aqueous hydrochloric acid to obtain the above compound.

Example 25; 2,8-Diiodo-6,12-bis- (4-hydroxyphenyl) -

dibenzo / b, f 7 / 1.57 <iia-zocin.

Following the procedure of Example 22 was
2,8-Diiod-6,12-bis (4-ethoxyphenyl) -dibenzo / b, f ~ f (1,57- diazocine was heated with anhydrous aluminum chloride in benzene; it was then treated with cold aqueous hydrochloric acid, whereby received the above connection.

_2o- 909843/1737

BAD ORJGi _WAL

Example 26; 3,9-dihydroxy-6,12-diphenyldibenzo-

/ b, f7 / Ϊ j 57diazocin.

Following the procedure of Example 22, 3,9-dipropoxy-6,12-diphenyldibenzo / b, f7 / Ϊ, 57 ^dia 2ocin was heated with anhydrous aluminum chloride in benzene; then treated with cold aqueous hydrochloric acid to obtain the above compound.

Example 27: 2,8-I) ibromo-3,9-dihydroxy-6,12-diphenyl-

dibenzo / b, f 7 / Ϊ, 57 <liazoc in.

Following the procedure of Example 22, 2,8-dibromo-3,9-dimethoxy-6,12-diphenyldibenzo / b, f7 / 1,5_7 ~ diazocin heated with anhydrous aluminum chloride in benzene; then it was treated with cold aqueous hydrochloric acid, whereby the above compound was obtained.

Example 28; 3,9-dihydroxy-6,12-bis (2-hydroxyphenyl) -

dibenzo / b, f 7 / 1,5_7diazocin.

Following the procedure of Example 22, 3,9-di-methoxy-6,12-bis (2-methoxyphenyl) -dibenzo / b, f7 / 1,57-diazoin was obtained heated with anhydrous aluminum chloride in benzene; then it was treated with cold aqueous hydrochloric acid, whereby the above compound was obtained.

- 21 -

909843/1737

BATH ORIGINAL

Example 29: 2,3,8,9-tetrahydroxy-6,12-bis- (4-hydroxy-

phenyl) -dibenzo / b, f7 / l »57diazocine. Following the procedure of Example 22 2,3,8,9-tetramethoxy-6,12-bis- was f7 / heated (4-methoxyphenyl) dibenzo / b, I, 57 ^di azocine with anhydrous aluminum chloride in benzene; then treated with cold aqueous hydrochloric acid to obtain the above compound.

Example 30: 2,8-Dibromo-6,12-bis (3-hydroxyphenyl) -

dibenzo7b, f7 / Ϊ, 57diazocin. Following the procedure of Example 22 was

2,8-dibromo-6,12-bis (3-propoxyphenyl) -dibenzo / b _f f7 / 1,57-diazocine heated with anhydrous aluminum chloride in benzene; then treated with cold aqueous hydrochloric acid to obtain the above compound.

Example 31 : 4, 10-diisopropyl-6,12-bis (4-hydroxyphenyl) -

dibenzo / b, f7 / Ϊ, 57diazocine.

Following the procedure of Example 22, 4 »10-diisopropyl-6,12-bis- (4-methyphenyl) -dibenzo- / b, f7 / l» 57diazocine heated with anhydrous aluminum chloride in benzene; then was made with cold aqueous hydrochloric acid treated to obtain the above compound.

. _22nd

909843/1737

Following the procedure of Example 22, other phenolic compounds of the formula I can be prepared by cleavage of an alkoxy-substituted compound of the formula III. Examples of phenolic compounds of the formula I which can be prepared by the process of Example 22 are: 6,12-bis- (2-hydroxyphenyl) -dibenzo / b, f7 / 1> 57 ~ diazocine, 6,12-bis- (^ -hydroxyphenyl) -dibenzo / b, i / A » ^ J- diazocin, 6,12-bis- (3,4-dihydroxyphenyl) -dibenzo / b, f // l, 5.7-diazocin, 3,4, 9, 10-Tetrahydroxy-6,12-diphenylibenzo / b, XjJXjb diazocine, 6,12-bis (2,3-dimethyl-4-hyaroxyphenyl) -dibenzo- ■ / b _t f7A »5 / diazocine, 2.8 Dihydroxy-3,9-dimethyl-6,12-bis (2-methylphenyl) -dibenzo / b, ΐ] £ Χ , 5_ / diazocine, 6,12-bis (2,5-dimethyl-4-hydroxyphenyl ) -dibenzo / b, f7 / l, 57aiazocin, 6,12-bis- (5-hydroxy-2-butylρhenyl) -dibenzo / b, ij / 1, § / -diazocin and the like.
Example 32 ; 2,8-dichloro-6,12-bis (4-hydroxyphenyl) -

dibenzo / b, f7 / l »57 diazocinic acetate. A suspension of 1.0 g of 2,8-dichloro-b, 12-bis (4-hyaroxyphenyl) -dibenzo / b, f // l, ^ / diazocinacetone solvate (Example 22) in 13 ml of acetic anhydride was refluxed for 4 hours. The resulting solution was at evaporated to dryness under reduced pressure. The back

- 23 -

.., ■ ' ^BA D ORIGINAL

90 984 3/173 7

Persistent pesticide was extracted twice from aqueous acetone recrystallized, where 2, 8-dichloro-6,12-bis (4-hydroxyphenyl) -dibenzo / b, f7 / Ϊ,! ^ diazocine diacetate obtained from melting point 218-223 ° C. ·.

Analysis: Calculated for ^C 3Q ^H ₂ 0224

C: 66.51; H: 3 *, 71; Cl: 13.05. Found: C: 66.03; H: 3.90; Cl: 13.30. Example 33: 2,8-dichloro-6,12-bis (4-hydroxyphenyl) -

dibenzo / b, f7 / 1,5_7diazocin ~ dibutyrate. Following the procedure of Example 32, 2, ö-dichloro-6,12-bis- (4-hydroxyphenyl) -dibenzene / b, f7 / Ϊ, 5-7-diazocin heated with butyric anhydride to obtain the above compound.

Example 34: 6,12- (4-hydroxyphenyl) -dibenzo / b, f7 / 1,5_7-diazocin-

dipropionate.

Following the procedure of Example 32 was 6,12-bis (4-hydroxyphenyl) dibenzo / b, f7 / Ϊ, 57-iiazocin heated with propionic anhydride to obtain the above compound.

Example 35: 3 »9-dihydroxy-6,12-diphenyldibenzo / b, f7 / 1.57-

diazocine diacetate.

Following the procedure of Example 32, 3,9-dihydroxy-6,12-diphenyldibenzo / b, f J (J., 57 <uazoc in, was treated with acetane hydride to give the above compound.

24 -

909843/1737

BATH ORIGINAL

Example 56: 2,8-Diiodo-6,12-bis (4-hydroxyphenyl) -

dibenzo / b, f7 / Ϊ, 57-diazocin-diisobutyrate. Following the procedure of Example 32 was followed

2,8-Bijod-6,12-bis- (4-hydroxyphenyl) -dibenzo / b, f7 / Ϊ »57-diazocine heated with isobutyric anhydride, whereby-one. received the above connection.

Example 57: 2,8-dibromo-3,9-dihydroxy-6,12-diphenyldi

Following the procedure of Example 32, 2 j 8-dibromo-3,9-dihydroxy-6,12-diphenyldibenzo / S, f7 / 1,57-diazocin heated with acetic anhydride to obtain the above compound.

Example 58 : 3,9-dihydroxy-6,12-bis (2-hydroxyphenyl) -

'fi T r ^ Ci TO Ϊ7 Γ \ J i ^ ι "- / / ι * ^ \ J ^^ C \ T Ci Γ? i ^ \ ft * 1 Y \ ^^" T * f ** * t * T ^ * Cl JCl * f \ / ^ T "^ l ¹ * T *

• vL J- U CiIwU / U · J- / /, Ι - ■ J / ^^ \ x Ju.CL <j L / O J-.Ü Oc LiX QtCv ^ J C 0 <A t / ·

Following the procedure of Example 32, 3,9-dihydroxy-6,12-bis- (2-hydroxyphenyl) -dibenzo / b, f JJl, 5? -Diazocine was heated with acetic anhydride to give the above compound *

Example 59: 2,3,8,9 ^ etraiiydroxy-6,12-bis- (4-hydroxy-

phe nyl,) -d Ib enz ο / b, f 7/1 »5 7 * ~ & iazo c in-hexaac e t at. The operation of Example 32 was followed 2,3,8,9-Ü) etrahydrQXy ~ 6,12-bis- (4-hydroxyphenyl) - 'dibeazo-

BATH ORIGINAL

/ b, f7 / l, 57-d-iaziocin heated with acetic anhydride, whereby one received the above connection.

Example 40: 2,8-dibromo-6,12-bis- {3-hydroxyphenyl) -dibenzo / b, f7 / l> 57- <lia-zocin dipropionate. Following the procedure of Example 32, 2,8-dibromo-6,12-bis (3-hydroxyphenyl) -dibenzo / b, ΐ7 / ΐ »57-diazocine was heated with propionic anhydride to give the above compound.

Example 41: 4,1O-Diisopropyl-6,12-bis- (4-hydroxyphenyl) -

dibenzo / b, ij / ΐ , 57-a.ia-zooin-dibuxyrate. According to the method of Example 32, 4, 10-diisopropyl-6,12-bis (4-hydroxyphenyl) <-dibenzo- / b, f7 / 1,57 "-d-iazocine was heated with buffer anhydride to give the above compound .

Beis-QJel 42 : 6,12-bis (2-hydroxyphenyl) -aibenzo / b, f7 / ϊ * 57 ~

diazocin diisobutyrate.

Following the procedure of Example 32, wurae 6,12-bis (2-hydroxyphenyl) -dibenzo / b, χ7 / Ϊ »57-diazocine heated with isobutyric anhydride to obtain the above compound.

Example 43: 3,9 ~ -diyaroxy * -6,12-diphenyldibenzo / b, f7 / Ϊ, 57 ~ diazocine diformiate.

Following the procedure of Example 32 was

- 26 -

9843/173?

3,9-dihydroxy-o, 12-dipnenyldibenzo / b, f 7 / Ϊ, 57-d-iazoein heated to obtain the above compound.

Example 44 : 6,12-bis (4-hydroxyphenyl) -dibenzo / b, f7 / 1,57-diazocine diforminate ".

was similar to the procedure of Example 32 6,12-bis (4-hydroxyphenyl) -dibenzo / b, f7 / lj57-diazocine heated with formic acid to obtain the above compound.

Following the procedure of Example 32, other esters of phenolic 6,12-biaryldibenzo / b, f7 / 1,57- 'aiazocin of formula I can be prepared by reacting a phenolic compound of Porinel I with an acylating agent such as formic acid or an anhydride of a hydrocarbyl carboxylic acid up to 4 carbon atoms are produced. Examples of such esters are; the diformates, diacetates, dipropionates, dibutyrates and diisobutyrates of 6,12-bis- (3-hydroxyohenyl) -dibenzo / b, f7 / 1,57-diazocin, 6,12-B is- (2 , 3- <ÜEie thyi-4-hydroxyphenyl) -aib enzo / b, ΐ7 / ΐ> 2? ~ Diazocin, ö, I ^ -Bis- (2,5-dimethyl-4-hydroxyphenyl) -dibenzo- / b, 17 / 1,57 ~ iazocin, 6,12-3is- (5-hydroxy-2-butylphenyl ) - ·. dibenzo / b, f 7 / Ϊ157-aiazocin, - 2,6-dihydroxy-5 »9-dim'ethylT- _{; :} o, 12-bis (2-EiethylpAtn? l) -dibenzo ^ b, f7 / lf57-eiazocin; the

- 27 -

9098A3 / 1737

BATH ORIGINAL

Tetraacetates, tetraproprionates, tetrabutyrates, tetraformates and tetraisobutyrates of 6,12-bis- (3,4-dihydroxyphenyl) -dibenzo / b, f J / 1 , 57-d-iazocin, 3 , 4,9, 10-tetrahydroxy-6 , 12-diphenyldibenzoZb, f7 / l »57-cüazocin and the like.

- 28 -

909843/1737

BATH ORIGINAL

Claims (1)

Claims Ι «, Process for the preparation of 6, -12-I) iaryl-dibenzo / b, f7 / T, 5 / diazocines of the general formula in which at least one of the "Su bst i tu ducks X and Y is a Ilalogen / f ^om the 'frifluormethylgruppe, the hydroxy group or an alkyl, alkoxy or acyloxy group having 1 to 4 Koiil ens tof fat autonomous means, characterized in that a -r 2- »AiiiinobenzaphenQn der SOW llllilllfll in which at least one of the; iubstituenten X ¹ and Y ^{1 is} a halogen atom, the trifluoromethyl group, an alkyl or alkoxy group with 1 to 4 carbon atoms, heated in the presence of an acid catalyst, alkoxy groups present optionally by heating with 'Alumiiiiuitcklorld and subsequent treatment with Hydrochloric acid is converted into hydroxyl groups and the hydroxyl groups are optionally acylated with formic acid or the anhydride of a hydrocarboxylic acid with 2 to 4 carbon atoms, 2 «Process according to claim 1, characterized» that the acid catalyst used is a benzosulfonic acid, in particular p-toluenesulfonic acid used, 3. The method according to claim 1 and 2 »characterized in that that 5-chloro ~ 2-aminobenzophenQn or 5-chloro-4'-methoxy-.2-aminobenzophenone used. Pure: The Upjohn Comoany ■ Η Hecytsannalt 3ÖS843 / 1737