CS239798B1 - Frame Frames - Google Patents

Abstract

The connection of the frames of a vehicle and its superstructure without interfering with the integrity of the vehicle frame, solving a rigid but detachable connection with prestressing, ensuring that both frames behave as a single unit when transmitting static and dynamic loads arising during the driving of the vehicle or the operation of the technological superstructure. The pins (1) protruding from the superstructure frame (2j carry connecting yokes (3) at their ends, by which the frame (5j of the vehicle is attached to the superstructure frame (2). The mutual displacement of the frames is prevented by the insert (7). The frame connection can be used in agriculture, forestry, and construction.

Description

The invention relates to a process for the preparation of acetals of alpha-hydroxyphenones of the general formula I, in which Ar represents phenyl or naphthyl, optionally substituted with 1 to 2 substituents, such as alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 2 carbon atoms , bromo or phenoxy, R is alkyl of 1 to 3 carbon atoms or together R + R is - (CH ₂ ) wherein n is 2 to 3, R ¹ is hydrogen or alkyl of 1 to 3 carbon atoms.

Said compounds of formula (I) are important intermediates in the production of an important group of arylalkanoic acid compounds. These acids are an active ingredient of non-steroidal drugs with anti-inflammatory, antipyretic, and analgesic effects (see, e.g., Antiinflammatory Agents, Vol.I., Eds. R.A. Sherrer, M.W. Whitehouse, Acad. Press, New York 1974 »Arch Int. Pharmacodyn. Ther. 178, 115 (1969) »Chronioles of Drug Discovery, Chap. 7 pp. 149,

J. Wiley, New York 1981].

Some of these arylalkanoic acids have found utility in large-scale agricultural production in plant protection and as growth regulators (see, e.g., Angew). Chem Int. Ed. 11,

460 (1972), J. Pathol. Bacterial. 85, 361 (1963).

In the prior art has the compounds of formula I are prepared from alpha-halogenfenonů of formula II wherein Ar and R ¹ have the abovementioned meaning and X represents chlorine or bromine by treatment methanoliokého solution of an alkali methoxide in an anhydrous environment, often in an inert atmosphere / see, e.g., European Pat. No. 64 394y Jap. U.S. Pat. C.

144 234 »J. Amer. Chem. Soc. 72 4758 (1950) Tetrahedron Lett. 1981, 4305 »Tetrahedron Lett. 1982, 5427].

These processes have some disadvantages in the technical implementation: working in an anhydrous atmosphere with an inert atmosphere requires complex technological equipment, the use of aggressive substances (alcoholates, sodium) requires special precautions and relatively long reaction times, thus increasing energy consumption and working time.

These known processes are followed in a positive way by the process according to the invention, which removes the disadvantages mentioned. The process for the preparation of the acetals of the alpha-hydroxyphenones of the formula I according to the invention is characterized in that the alpha-halophenone of the formula II is treated with anhydrous hydroxyalkane or dihydroxyalkane having a carbon number of 1 to 3. The molar ratio of the reactants is 1: 2 to 20: 2 to 5, preferably 1: 5 to 15: 2.5: 3.5.

The process according to the invention comprises heating a mixture of a halophenone of the formula II, an alkali metal carbonate and a hydroxy compound with vigorous stirring for a period of 0.2 to 2 hours to a temperature of 20 to 60 ° C, preferably a temperature of 20 to 40 ° C. .

The progress of the reaction can be monitored by chromatographic methods, especially thin layer chromatography on silica gel. After completion of the reaction, the reaction mixture is optionally diluted with a solvent inert to the reactants, the solids are filtered off with suction and, after evaporation of the solvents, a highly pure product of the general formula získá is obtained in almost quantitative yield.

The alkali metal carbonates used in the reaction, preferably sodium carbonate, potassium carbonate, lithium carbonate, sodium or potassium bicarbonate, serve both to generate the corresponding alcoholates and to neutralize the hydrogen halide formed in the reaction.

As hydroxy- or dihydroxyalkanes, preferably methanol, ethanol, propanol, ethylene glycol or 1,3-propanediol are used. Suitable inert solvents for diluting the reaction mixture and washing the solids are dichloromethane, 1,2-dichloroethane, chloroform.

The starting alpha-halophenones of formula (II) are prepared from the corresponding substituted aromatic hydrocarbons, acyl chlorides of formula (III), wherein R ¹ and X are as defined above for C 1 -C 2 and C 2 -C 4 chlorine, preferably 1,2 dichloroethane, tetrachlorethylene, carbon tetrachloride in the presence of an excess of 5 to 20 mol% of a Lewis acid such as aluminum chloride, ferric chloride, zinc at a temperature of 0 to 20 ° C, preferably 0 to 10 ° C.

The one-step process for the preparation of the compounds of formula (I) according to the invention brings about a substantial simplification of the technology, is easy to carry out in large batches and uses inexpensive and safety-free reagents. Furthermore, it brings considerable energy and labor savings, so that its economic advantage is also apparent, the method according to the invention is documented in several exemplary embodiments, which are illustrative only and do not limit the scope of the invention in any way.

He did

To a suspension of 48 g of aluminum chloride in 100 ml of 1,2-dichloroethane, after stirring at room temperature for 15 minutes followed by cooling to 0 ° C over 20-25 minutes, was added a mixture of 47.6 g of 2-chloropropionyl chloride / III, where R ¹ = CH ₃ , X-Cl) and 40.2 g of isobutylbenzene, and finally stirred at 5 to 10 ° C for 4 hours.

Then the reaction mixture was poured onto a mixture of ice and water (300 ml), 100 ml of cono were added. hydrochloric acid, the oil layer separated, the aqueous phase extracted twice with 100 ml of dichloromethane, the combined organics washed with water (30 ml), saturated sodium bicarbonate solution, dried over anhydrous calcium chloride and the solvents distilled off.

Distillation of the residue yielded 61.9 g (92%) of the product of formula II, b.p. 100-105 ° C at 266 Pa, which solidified upon cooling. Melting point: 47-50 ° C; Mp 51-53 ° C.

Example 2

To a mixture of 18 g of bromoproplonafton dissolved in 90 ml of anhydrous methanol was added. with stirring 16.5 g of freshly calcined potash and after stirring for 1 hour at a bath temperature of 40 ° C, the mixture was diluted with 150 ml of dichloroethane, the solids filtered off with suction, washed with dichloroethane (2 x 10 ml) and distilled off the solvents.

After cooling, 16 g (93.2%) of the product of Formula I were obtained, the structure of which was confirmed by NMR spectrum. ⁴ H-NMR / CDCl ^ / O, 91d / 3H, CH ^ /, 3,24s / 3H, OCH ^ / 3,38s / 3H, OCH /, 3,94s / 3H, OCH ₃ /, 4,17q (1H, CH), 7.20d and 7.58-8.20m (5H, nucleus).

Example 3

A mixture of 30.5 g of compound of formula II wherein Ar / CH _{3/2 g} CHCH ₂ C H _4-Cl, 48 g of sodium carbonate and 100 ml of anhydrous methanol was stirred at 25-30 ° C for 1 hour . The progress of the reaction was monitored by thin layer chromatography on silica gel.

The reaction mixture was then diluted with 25 ml of di-chloromethane and treated in a manner analogous to Example 2. 37.1 g of an oily product of formula I were obtained, the structure of which was confirmed by NMR spectrum. ¹ H NMR Spectrum (CDCl ₃ ): 0.87d (6H, CH ₃ ), 0.91d (3H, CH ₃ ), 1.87m (1H, CH), 2.46d (2H, CH ₃ ), 3.20s (3H) OCH3, 3.34s (3H, OCH3), 4.17q (1H, CH), 7.08d and 7.33d (4H, nucleus).

Example 1 a d 4

In the same manner as in Example 1 were 12 g of aluminum chloride, 10 g of isobutylbenzene and 16 g of 2-bromproplonylohloridu produced 21.2 g / 84% / halogenfenonu formula II wherein Ar is 4-isobutylphenyl, R ¹ »CH _3, and X Br, mp 64-66 ° C.

39798

Example 5

To 100 ml of dry dichloroethane was added 15 g of anhydrous zinc chloride and a solution of 15.8 g of 2-methoxynaphthalene and 15.2 g of 2-chloropropionyl chloride in 50 ml of dichloroethane was added dropwise with stirring at 0 ° C. Mixture. was stirred at 0 ° C for 12 h and 12 h at 10 ° C.

After being decanted by pouring onto ice, the organic layer was separated, washed with water, dried over anhydrous calcium chloride, and, after evaporation, the residue was crystallized from methanol. 14.3 g (57.5%) of the halophenone of formula II were obtained, wherein Ar is 6-methoxy-2-naphthyl, R 1 -CH 2 and X-Cl, m.p. Mp 61-64 ° C.

Example 6

In the same manner as in Example 3, it was from a halophenone of formula II wherein Ar =

- 4-tert-butylphenyl, R ¹ = CH / CH / "and X-Br, 10 ml of methanol and 2.2 g of lithium carbonate from j.

produced 2.57 g (92%) of an acetal of formula I wherein Ar 4 -tert. butylphenyl, R 5 CH (cH 4) 2 ^and R 5 CH 2, whose structure was confirmed by NMR spectrum.

NMR (CDCl3): 0.80d (3H, CH3), 0.91d (3H, CH3), 1.35s (9H, CH3), 1.32m (1H,, CH), 2.48m) 1H, CH (3.20s, 3H, OCH3), 3.32s (3H, OCH3), 3.67s (1H, OH), 7.35pd (4H, core).

Example 7

To a mixture of 10 ml of ethylene glycol and 3.45 g of dry sodium carbonate was added with stirring 2.25 g of halophenone of formula II wherein Ar-4-isobutylphenyl, R-CH ₃ and X-Cl and the mixture was stirred at 40 ° C for 4 h. Dilute with 20 ml of dichloromethane, filter, wash the solution quickly with ice water, dry over anhydrous magnesium sulfate and evaporate to dryness.

Yield 2.4 g / 96% / acetal of the formula I where Ar = 4-isobutylphenyl, R = CH ,, R + R = n _{CH2 CH2} oily consistency, whose structure was confirmed by NMR spectrum. 1 H NMR (CDCl 3): 0.87d (6H, CH ₃ ), O, 92d (3H, CH ₃ ), 84m (1H, CH), 2.44d (2H, CH ₂ ), 3.84m (2H), CH ₂ /, 4.14m (2H, CH ₂ ), 4.17q (1H, CH), 7.14d and 7.32d (4H, nucleus).

Example

In the same manner as in Example 3 was 2.7 g halogenfenonu formula II wherein Ar = 4-isobutylphenyl, R ¹ = CH7 and X = Br, 10 ml of ethanol and 2.76 g of potassium carbonate afforded 2.69 g / 96% (o) acetal of formula I, wherein Ar = 4-isobutylphenyl, R = CH3 and R-CH3CH3, the structure of which was confirmed by NMR spectrum. @ ¹ H NMR (CDCl3): 0.88d (6H, CH3), 0.93d (3H, CH3), 84m (1H, CH), 2.24t (3H, CH3), 2.36t) 3H, CH3), 2.44d (2H, CH2 ₎ , 4.1q (1H, CH), 4.36m (2H, CH2 ₎ , 4.48m (2H, CH2 ₎ , 7, 6d and 7 , 28d (4H, kernel).

Example 9

In the same manner as in Example 3, 3 ^l of 24.9 g of halophenone of formula II, where Ar = 6-methoxy-2-naphthyl, R ¹ -CH, and X-cl, 34.5 g of potassium carbonate and 100 ml of methanol, were produced.

27.0 (98%) of an acetal of formula I wherein Ar-6-methoxy-2-naphthyl, RR -CH ₃ as an oil that solidified on standing, mp 54-56 ° C.

Example 10 in the same manner as in Example 3, was from 3.05 g of halophenone II, where Ar = 3-phenoxyphenyl,

R ¹ = CH, and X-Br, 2.76 g of potassium carbonate and 10 ml of methanol produced 2.70 g (94%) of acetyl of formula I, wherein Ar-3-phenoxyphenyl, RR = CH ₃ as a yellow oil.

Its structure was confirmed by NMR spectrum. ¹ H NMR / CDCl ^ / O, 92d / 3H, CH ^ /, 3,22s / 3H, OCH ₃ /, 3,35s / 3H, OCH-j / 4, LLQ / H, C / 6, 20-7.65m (9H, nuclei).

Claims (5)

SUBJECT OF THE INVENTION A process for the preparation of acetals of alpha-hydroxyphenones of the general formula I, in which Ar is phenyl or naphthyl, optionally substituted by 1 to 2 substituents from the group consisting of C 1 -C 4 alkyl, C 1 -C 2 alkoxy, halogen from chloro, bromo, fluorine or phenoxy, R represents alkyl having 1 to 3 carbon atoms or together R + R represents a (-C1) n-group wherein n is 2 to 3, R ¹ represents hydrogen or alkyl having 1 to 3 carbon atoms, from alpha - a halophenone of the formula II wherein Ar and R are as defined above and X is a chlorine or bromine atom, characterized in that the alpha-halophenone of the formula II is treated simultaneously with anhydrous hydroxyalkane or dihydroxyalkane having carbon numbers of 1 to 3 and alkali carbonate metal, wherein the molar ratio of alpha-halophenone, hydroxyalkane and carbonates is 1: 2 to 20: 2 to 5 at 20 to 60 ° C, after which the reaction mixture is optionally diluted in The solid inorganic solids are filtered off and the solvents are evaporated to give the product of formula (I). 2. A process according to claim 1, wherein the hydroxyalkane and dlhydroxyalkanes are methanol, ethanol, propanol, ethylene glycol or 1,3 propanediol. 3. A process according to claim 1, characterized in that it is an alkali metal carbonate. use lithium, sodium or potassium carbonate or sodium or potassium bicarbonate. 4. A process according to any one of claims 1 to 3, wherein the inert solvent is a chlorinated hydrocarbon having 1 to 2 carbon atoms and 2 to 4 chlorine atoms. 5. A process according to any one of claims 1 to 4, wherein the reaction mixture is heated to a temperature of 20 to 40 ° C. 1 drawing OH Ar = CH-R * ¹ 0 0 Ø R Ar-CO-CH-R ⁴ X AND R ⁴ -CH-COO X