CS196471B1 - New p-acylated phenoxyethanoles - Google Patents

Description

The invention relates to novel para-acylated compounds

2-phenoxy ethanols of the formula _HO-CH2-CH2-O of the

(-C (R) 1) wherein R is alkyl and 1 to 9 carbon atoms, phenyl or benzyl. The invention also describes a process for the preparation of these substances which are not known from the literature. The compounds of the present invention could also be obtained by oxidation of a methylene group adjacent to the benzene nucleus from alkyl or alkyl aryl derivatives. The present invention is a continuation of the present invention which solves the preparation of esters of p-acylated 2-phenoxyethanols.

The process for the preparation of the novel p-acylated 2-phenoxyethanol is characterized in that the ester of the general formula R @ ₁ -cooch ₂ ch @ ₂ -o-CR (11)

196 471

Rββ 471 where R has the same meaning as in formula I and R ^ is methyl. In a solvent, the preferred ethyl alcohol is treated with an alkaline solution at the boiling point of the reaction mixture.

This process makes it possible to prepare substances for which the preparation process is not known. The advantage of the process is also the specificity of the reaction and good yields. The prepared compounds can be used as products of further syntheses. The alcoholic group allows the said structures to be bonded to the polymer chain, in particular via acrylic or methacrylic ethers. The introduction of carboxyl groups can find application in the preparation of photopolymers, photosensitizers, or light-degradable polymers.

Example 1

Preparation of 2- (4-propionyl-phenoxy) ethanol

144 g of 2 - [- 4-propionylphenoxy ethanol acetyl ester ea were dissolved in 400 ml of technical ethanol while warm. To the prepared solution ea was added a solution of 90 g of sodium hydroxide in 400 ml of water. The reaction mixture was refluxed for 20 minutes, after which time it no longer contained the starting material. Ethanol ea was evaporated in vacuo and the residue ea was extracted with chloroform. Chloroform e was evaporated in vacuo and the residue was crystallized from 400 ml of carbon tetrachloride after cooling with dry ice. The crystalline substance ea separated and after drying crystallized from 400 ml of ether. The yield was 89 ,? mp 38-39 ° C. ifi / CC1 ₄ / 9max = 740.850, 920, 960, 1045, 1080, 1180, 1230, 1260, 1310, 1350, 1420

1460, 1510, 1610, 1690, 2340, 2940, 3500, 3640 cm &^lt; -1 ^>.

NMR (CDCl ₃ ) = 1.12 (t, 3H, -CH3); 2.65 / s, IH, CH /; 2.83> b, 2H, CH ₂ -C 0 - /; 3,9 '/ m, 4H, _{-0-CH2 -CH2} -0 /; 6.88 (d, 2H, aromatic); 7.90 (d, 2H, aromatic)

Mass Spectrum m / e = 194 (U ⁺ ), 165.121.93

Example 2

Preparation of 2- (4-phenylacetoylphenoxy) ethanol. He used ea in the same manner as in Example 1. Starting from ea acetyleether of 2- (4-phenylacetoyl-phenoxy) ethanol. The product, after evaporation of chloroform e, crystallized from N-heptane. The yield of white crystalline solid, m.p. 97 DEG-98 DEG C., was 82.6%.

IR CC1 _4: CHC1 _3/1: 1 / \) max 740, 910, 980, 1030, 1070, 1170, 1210, 1250, 1305, 1415, 1450, 1505, 1600, 1670, 3010, 3460, 3600 cm ^1st

1 H-NMR (CDCl 3): 2.33 (3.1, 1H, -CH); 3.93 (m, 4H, -O-Cl ₂ -CH ₂ -O-) 4.13 (S, 2H, -CH ₂ -CO-)

6.84 (d, 2H, aromatic), 7.24 (S, 5H, aromatic); 7.96 (d, 2H, aromatic).

Mass Spectrum m / ew 256 / M ⁺ , 165,121,104,93,91,77,76,45

19B 471

Example 3

Preparation of 2- (4-benzoylphenoxy) ethanol.

The same procedure as in Example 1 was used. Starting from aa, 2- (4-benzoylphenoxy) ethanol acetyl ester was used. The product after evaporation of chloroform was crystallized from N-heptane. The yield of white crystalline solid, mp 79-80 ° C, was 91%.

ID / CC1 _4: CHC1 _3/1 1 / p max »740, 840, 920, 935, 1030, 1070, 1150, 1170, 1215, 1250

1280, 1300, 1315, 1415, 1445, 1505, 1600, 1650, 3010, 3460, 3610 cm @ ^-1 .

7.62 / m, 7H, aromatic /

Mass Spectrum m / e 242 (M ⁺ ), 165, 138, 121, 105

Example 4

Preparation of 2- (4-acetylphenoxy) ethanol

The same procedure was used as in Example 1. The yield of white crystalline solid, m.p. 56-57 ° C, was 87%. Similarly prepared 2- (4-octanoylphenoxy) ethanol and 2- (4-decanoylphenoxy) ethanol. They are blots of inaccurate melting point and the NMR and IR spectra confirm that they are the desired substances.

Example 5

Preparation of 2- (4-propionylphenoxy) ethanol without isolation of the starting material.

40 ml of polyphosphoric acid, 0.05 mol (9 g) of phenoxyethyl acetate and 14 ml of proplonic acid were added to the flask. The reaction mixture was homogenized and allowed to stand at room temperature for several days. For the third time, the product did not contain phenoxyethyl acetate. The reaction mixture was poured into water and extracted with ether. Ether aa evaporated to give a pale yellow crystalline substance, 2- [4- (4-propionylphenoxy) ethanol acetyl ester. This was hydrolyzed and worked up as in Example 1. The yield was 91%, mp 38-39 ° C.

Claims (2)

OBJECT OF THE INVENTION 1. The new acylated p-phenoxyethanol of vzcrca guy ₂ CH ₂ O • R wherein R is alkyl of 1 to 9 carbon atoms, phenyl or benzyl. 198 «71 2. A process for the preparation of the novel compounds according to claim 1, characterized in that ea to the ester of the formula R ^ -OOO-Chg-Chg-H -C-R Wherein R is as defined for Formula I and R 1 is methyl, the solvent used in the ethyl alcohol is an alkaline solution at the boiling point of the reaction mixture. Printed by Moravian Printing Works,