DE233631C - - Google Patents

Description

IMPERIAL 7k

PATENT OFFICE.

and oxybenzoic acids.

When treating the homologues of phenol, such as the cresols or xylenols, with Chlorine or other chlorinating agents, like sulfuryl chloride, occurs the chlorine after the previous ones Always include observations in the benzene nucleus.

It has now been found that all or almost all of the chlorine is in the aliphatic side chains occurs when inorganic or organic acid residues are introduced into the hydroxyl group of the phenol in question and these Esters are chlorinated at an elevated temperature, expediently between 150 ° and 180 °. Particularly The carbonic acid and phosphoric acid esters, which are very suitable, have proven to be suitable easily represent from phosgene or phosphorus oxychloride and the corresponding phenols can. Also the introduction of the remainder of the phosphorous acid or the benzenesulfonic acid

ao or another aryl sulfonic acid leads to the same result. The esters obtained are melted and treated with chlorine at elevated temperature until ready for entry of 1, 2 or 3 chlorine atoms calculated weight increase has occurred. You get in this way the esters of substituted benzyl chlorides, benzal chlorides, as intermediates and benzotrichlorides, which as such are used in the industry of dyes, fragrances and pharmaceutical products.

The main value of the present process, however, is that by saponification of these chlorine substitution products smoothly oxybenzyl alcohols, oxybenzaldehydes, and oxybenzoic acids thus obtained from the easily accessible and cheap cresols, xylenols or their nuclear homologues in a simple manner can be produced.

do

Example 1.

242 kg of 0-cresol carbonate (Einhorn and Hollandt, Annalen 301 [1898], p. 115) treated with chlorine at 180 ° C. until a weight gain of 69 kg has occurred. The to-monochloro-o-cresol carbonic acid ester crystallizes on cooling (Melting point 79 °)

CH ₂ . Cl CH ₂ Cl,

! I.

1-0. CO ■ 0-r

50

which can be recrystallized from glacial acetic acid or gasoline. To produce o-oxybenzyl alcohol (saligenin), the ω-Μοηο-chloro-o-cresol carbonic acid ester is boiled with water and excess calcium carbonate at 4 to 5 atmospheres pressure, at the same time the carbonic acid is split off and the chlorine is replaced by the hydroxyl group. The solution filtered off from the calcium carbonate is evaporated somewhat, whereupon o-oxybenzyl alcohol crystallizes out in good yield on cooling. '■ - ■■;

Example 2.
242 kg o-cresol carbonate (unicorn

Hollandt, Annalen 301 [1898], p. 115) treated with chlorine gas at 180 ° until one. Weight gain of 138 kg has occurred. The result is a thick oil which distills under 3O mm of mercury rack at 247 ° C can be and its main amount from (jo-dichloro-o-cresol carbonic acid ester

CH. CL

CHCL

-0-CO-O-,

(Melting point 73 °). With exhaustive saponification, this ester yields salicylaldehyde in very good yield.

Example 3.

242 kg p-cresol carbonate (Bender, reports 19 [1886], p. 2268) are treated with chlorine as described in Example 2. The emerging w-dichloro-p-cresol carbonate solidifies in the cold, shows, recrystallized from alcohol, a melting point of 108 ° and yields p-oxybenzaldehyde on saponification.

Example 4.

242 kg m - Kresolcarbonat (. Patent 81375, Kl 12, melting point 54 ⁰⁾ are treated at about 150 ⁰ C. for as long with chlorine until the weight gain is 207 kg. The resulting oil is u> -trichloro-m-cresol carbonate

, -O-CO-O-

CCl ₃ C (Cl ₃ )

(a not undecomposed ■ distilling oil), because on saponification it yields m-oxybenzoic acid.

Example 5.
368 kg of o-cresol phosphate

po (oc ₆ h \ -ch ₃

^X 0. C ₆ Ht-CH ₃

obtained by prolonged boiling of phosphorus oxychloride (1 mol.) And o-cresol (3 mol.) (Heim, ■ Reports 16 [1883], p. 1767; Rapp, Annalen 224 [1884], p. 173; oil from the boiling point 410 ° at 760 mm pressure) are treated with chlorine at 160 to 180 ° C. up to a weight gain of 207 kg. That on

Oil obtained in this way, which melts at 78 ° C when standing in the cold.

zenden o-oxybenzylidene chloride phosphoric acid ester precipitates in crystalline form, gives a good yield of salicylaldehyde on saponification.

Example 6. ·

In 117 kg of o-cresol phosphorous acid ester

0.C ₆ Hi-CH ₃

P (O -C ₆ H,. CH ₃

^ 0-C ₆ H ₄ -CH ₃

obtained by heating o-cresol with phosphorus trichloride, chlorine is passed in. It First, a crystal separation appears, in that an addition product is initially formed, namely tri-o-cresylphosphite chloride

(CH ₃ -C ₆ H ₄ -O) ₃ PCl ₂

forms. The heat of reaction soon melts these crystals, and chlorine is now passed in at 150 to 180 ° until the weight has increased by 93 kg. A thick oil is formed, which consists mainly of o-oxybenzylidene chloride phosphite chloride (CH Cl ₂ -C ₆ H, O) P Cl ₂ and, with exhaustive saponification, gives good yields of salicylaldehyde.

Example 7.

248 kg o-cresolbenzenesulfonic acid ester (Georgescu, Chem. Centralbl. 1900, I, 543)

CH ₃ -C ₆ H ^ O-SO ₂ -C ₆ H ₅

are treated with chlorine at 150 to 180 °, until a weight gain of 69 kg has occurred. The resulting oil that is used to consists largely of the benzenesulfonic acid ester of o-oxybenzylidene chloride (crystallized from alcohol in needles melting at 73 °) gives good yields with exhaustive saponification of salicylaldehyde.

Example 8.

(Preparation of salicylaldehyde by saponification.) 192 kg of o-oxybenzylidene chloride phosphoric acid ester (melting point 78 °) are dissolved in 2000 liters of alcohol and refluxed for ^x / _{4 hours with a concentrated solution of 160 kg of caustic soda in water.} After the alcohol has been distilled off, the salicylaldehyde sodium compound formed is decomposed with excess sulfuric acid and the salicylaldehyde is distilled off with steam.

According to the method of patent specification 93694, class 12, occurs when exposed to chlorine low temperatures on the acid esters of m-cresol, e.g. B. the benzoic acid ester, a substitution in the core. It has been shown, however, that under the working conditions iao of the present process (elevated temperature) the benzoic acid ester of m-cresol also

Claims (1)

if chlorination takes place in the aliphatic side chain. Example 9. 212 kg benzoyl-m-cresol (Bartolotti, Gazzetta chimica italiana 30, II [igoo], p. 224) are treated with chlorine at 180 ° until one Weight gain of 69 kg has occurred. The ω-dichloro-ni-cresolbenzoic acid ester is formed O - CO C ₆ H ₅ CHCl ₂ , an oil that cannot be distilled without decomposition, even in a vacuum. Will this with water and excess calcium carbonate at 4 to 5 atmospheres pressure boiled, a solution is obtained after filtering off the excess calcium carbonate, from which a mixture of m-oxybenzaldehyde and benzoic acid is precipitated by acids will. This mixture is broken down into its constituents by sodium bisulfite in the usual way disassembled. The benzoic acid proves. prove to be chlorine free. Patent claim: " _o Process for the preparation of oxybenzyl alcohols, oxybenzaldehydes and Oxybenzoic acids, consisting in the fact that the acid esters of the homologues of Phenol treated with chlorine or other chlorinating agents at elevated temperature, expediently at 150 to 180 ° and the phenol esters obtained in this way and chlorinated in the aliphatic side chain allows saponifying agents to act.