DD227434A1 - METHOD FOR PRODUCING NEW HEXAHYDROPHENANTHRIDINES - Google Patents

Abstract

The invention relates to a novel process for the preparation of phenanthridine derivatives, in particular of derivatives of 6,6-pentamethylene-5,6,7,8,9,10-hexahydrophenanthridin. According to the invention, an aniline derivative is reacted with a substituted cyclohexanone in a molar ratio of 1: 2 in the presence of a condensation catalyst at temperatures of 160-190C.

Description

VEB CHEMIEKOMBDiAT BITTERPELD

2633

Process for the preparation of novel heydehydrophenanthridines

Field of application of the invention

The invention relates to a novel process for the preparation of hexahydrophenanthridine derivatives which can be used as intermediates for organic syntheses.

Characteristic of the known technical solution

A number of publications and patents describe various syntheses for the preparation of hydrogenated phenanthridine derivatives. Thus, for example, a series of tetrahydrophenanthridines can be prepared by 1) reaction of 2-diethylaminomethylcyclohexylanone hydrochloride, aniline hydrochloride and zinc chloride in boiling cyclohexanone,

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2) condensation of 2-OHI-methylcyclohexanone, aniline and aniline hydrochloride in boiling alcohol,

3) Reduction and ring closure of various aryliminomethyl eyloheasanones by heating with anhydrous formic acid (J. Chem. Soc. 1948, 1537). Hesahydrophenanthridines are intermediates in octahydrophenanthridine synthesis and can be prepared, for example, from t-nitrostyrene derivatives by reaction with 1,3-butadiene, subsequent reduction, acylation and reaction with phosphorus oxychloride (US Pat. No. 3,243,438, US Pat. No. 3,860,653).

U.S. Patents 3,408,351, 3,336,313, and 3,311 disclose the preparation of octahydrophenanthridine derivatives by reacting 2- (1-cyclohees-enyl-cyanohexanone) with an aldehyde and ammonia or a carboxylic acid amide in the presence of cyclizing Catalysts with the exclusion of oxygen and under pressure "at temperatures of 180 - 425 ⁰ C described.

The known processes for producing hydrogenated phenanthridines are complicated. They require extensive apparatus design, often start from difficult to access intermediates or run over several stages.

Object of the invention

The object of the invention is a new process for the preparation of heso-drophine anthridines, which is characterized by high yields using readily available starting materials.

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Presentation of the invention of the invention:

The object of the invention is to find a technically simple process for the preparation of hexahydrophenanthridines, the apparatus and technical complexity being low and the reaction to the target product being carried out in a one-step process Mol of an aniline derivative of the general formula

I,

in which R is hydrogen, alkyl, alkoxy or halogen and η β is 1 or 2, with 2 mol of a cyclohexanone derivative of the general formula

O ' ²

in which R is hydrogen or alkyl, in the presence of a condensation catalyst at temperatures of 160-190 ⁰ C to compounds of the general formula

2633

III,

1 2

wherein R and R have the above meaning, as condensation catalysts are e.g. Iodine or p-toluenesulphonic acid in embossing. The reaction time is one to two hours. During this time, the water that forms is distilled off. The reaction mixture is worked up by distillation or separated after addition of a suitable solvent to the reaction mixture, the crystallized reaction product. This process is characterized by low apparatus and technical complexity, easy availability of the starting compounds, and implementation as a one-step process. [. Auf] The use of solvents or the excess of one of the components, which is customary in the case of transleading processes, can be carried out in the process according to the invention On the one hand, this significantly increases its economic efficiency, and on the other hand, the formation of undesirable by-products, which otherwise occurs as a result of the self-condensation of the cyclohexanones, is restricted.

In the method according to the invention, the yields of 6,6-pentamethylene-5,6,7,8,9,10-he2: ahydrophenanthridinen be up to 70 %.

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The hexahydrophenanthridines prepared by this process are capable of different reactions on the amino group. Thus, they can be acylated, for example with carboxylic acid anhydrides *, carboxylic acid chlorides or isocyanates, or alkylated with alkyl or aryl halides in the presence of acid-binding agents react with alkyl or aryl halides or strong acids to the corresponding ammonium salts. The compounds prepared by the process described are listed in Table 1.

!Table 1

Compounds of general formula III, which were prepared by the process according to the invention

Fr. R ¹ R ² Kp ( ⁰ C) PpC ⁰ C) Yield (%) 1 H H 175-185 / 1mm 47-50 52 2 2-CH ₃ H 162-165 / Imm 53-55 69 3 3-CH ₃ H 180 / 1mm 78-79 62 4 4-CH ₃ H 155-165 / Imm 11 5 2-C ₂ H ₅ H 175-185 / 1mm 55 6 2-0CH ₃ H 167-169 / Imm 70-71 60 7 3-OCH ₃ H 187-195 / imm 95-97 70 8th 4-OCH ₃ H 155-162 / Imm 97-98 42 9 2-OC ₂ H ₅ H 195-2O2 / 1mm 62 10 3-OC ₂ H ₅ H 190-200 / 1mm 86-87 65 " 11 3-Cl H 185-200 / 1mm 47 12 1,3-CH ₃ H 175-178 / 1mm 11 13 3-OCH ₃ CH ₃ 185-197 / 1mm 103-105 67

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Exemplary embodiments Example 1

Preparation of 6,6-PentajEethylene-5,6,7,8,9,1O-he: xahydrophenanthridine

In a stirred vessel, 279.4 g (3 mol, 273 ml) of aniline and 9 g of iodine (0.036 mol) are heated to 170-175 ⁰ C, with stirring, 588.8 g (6 mol, 622 ml) of cyclohexanone within two Hours under the aniline surface. During this time, the water that forms is distilled off.

After completion of the reaction, the resulting reaction product is distilled in vacuo. At 175 - 185 ⁰ C / 1mm passes over a clear very viscous oil, which results in methanol white crystals with a Pp = 47-50 ⁰ C. The yield is 395 g = 52 %. Analyzes: found: C = 84.88%, 84.84%, H = 9.00 % ₉ 9.19 %

IT «5,38 % ₉ 5,49 % calculated: C » 85,32 % ₉ H = 9,14 % ₉ H = 5,52 %

Example 2

Preparation of 3-methyl-6,6-pentamethylene-5 »6,7» 8,9,1O-hexahydrophenanthridine

Starting from 321.5 g (3 mol) of m-toluidine, 9 g of iodine and 588.8 g of cyclohexanone, the procedure described in Example 1, the 3-methyl-6,6-pentamethylene-5,6,7,8, 9 »10-hexahydrophenanthridine prepared.

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The workup of the crude product is carried out by addition of acetone to the still hot reaction mixture from which then crystallized on cooling the pure 3-methyl-6, G- pentamethylene-5 »6,7,8,9,10-hexahydrophenanthridin. Pp s 78-79 C, Yield: 554 g = 69 % Analyzes:

found: C = 86.01%, 8 ^ 85? S, H = 9.36 %, 9.40%,

5 m 5.10%, 5.18 % calculated: C β 85.34%, H s 9.42%, N = 5.23%

Claims (2)

invention claim 1 ♦ Yerfahren for the preparation of new Hexahydrophenanthridine, characterized in that one mole of an aniline derivative of the general formula (R ¹ ) -ITH (D, in which R is hydrogen, alkyl, alkoxy or halogen and η β is 1 or 2, with 2 moles of a cyclohexanone derivative of the general formula (ID, in which R is hydrogen or alkyl, in the presence of a condensation catalyst at temperatures of 160-190 ⁰ C to compounds of the general formula R * (III) - 9 - 2633 where R and R have the above meaning, implements. 2. A process for the preparation of new hexahydro - phenanthridine according to item 1, characterized in that are preferably used as condensation catalysts iodine or ρ-toluenesulfonic acid.