DE1936280A1 - Process for the preparation of new aryl esters - Google Patents

Description

Patent attorney "

| ^[ ,. ·. Or.'W. Schalk, Dipl.-Ing. P. Wirfh

- · ■ DipK-lng. G. Dannenberg

SAN J) Q Z AG. 0r. V. Schmiad-Kowarzik '

., '/ β ....' · Dr. P. Weinhold, Dr, D. Gudel

. Basel / Switzerland ₆ Fronkfurt / M., Gr. Eschenheimer Str. 39

.Process for the production of new ary! Esters

The invention relates to a method for production new aryl ester of the formula

R ₁ X

wherein R ₁ u, R ₁ H or

u · R, H,;. · C _1-12 -AlCyI, OH or u .; ^!

. Rg is H, ^_(λ;! C _1-12 -alkyl, halogen, OH or OR ₄

C _1-12 -AIlCyI or -J- ^ JT- R ₂

X-. u. 3C • H, m, ORg or C _1-12 AIlCyI

t 'r ·' · ';' "0 or S mean, which is characterized by '/ _: ·, that one'·:" - ■■ · '■; · antagonism of the formula

. ■ ■ '.:': ■■ '' ^v '.''··. iW · '·.''" ^Vfc · ■ S

$ 00885/1721

■ ·.

ORIGINAL JNSPEGTEO

Ig means H, C _1-12 -AlCyI or OH 3 flooded with H, C _1-12 -AlkJrI, halogen or OH.

909885/17 21

where B,

and R the same as entered above *

Halogen, or OR _e

C _1- ^ -AUCyI and- ■
Έ or methyl mean «
«It« iheffl phenol the 'formula

Ed

(III),

..ι

and X has the meaning given above

have implemented, at least one of the

- ι

Radicals X or X OH, at least two of the

Radical R ^ 'R ₂ and R ₅ radicals and mincte- "ten · one of them" vorssugsweise R. one

must be.

If the compound (II) is an acid halide, then Osisetsung, for example, at temperatures of 50-120 ° ^ preferably 30-100 ° carried out, whereby an inert solvent can be present. Last

This is also the case when the compound II is an ester. In the last-mentioned case, the reaction is preferably carried out at 7Ο-1δθ ° in the presence of an acidic or alkali-acting catalyst.

BATH ORIGINAL.

V '19362B0

The compounds of the formula (II) or (III) are advantageously γ in the molar ratio oa. 1 <1 each other door, Reacted when the phenolic compound is "monovalent is and in the molar ratio oa. 2x1 if this is bivalent * To isolate and purify the aryl esters, the end product can either before or after the Neutralwaseheη in

• ■

an inert solvent, recrystallized from an alcohol be sated.

The new aryl esters are colorless compounds with a defined melting point. These connections are in all organic solvents such as acetone, alcohol »* Dloxan, aromatic and aliphatic hydrocarbons, as well as readily soluble in halogenated hydrocarbons. They have a characteristic UV absorption spectrum and are particularly suitable for protecting colored and uncolored, natural or synthetic, organic Substances against the destructive effects of UV rays from. -Wave range 280-400 nm. In many cases they are suitable also to stabilize these substances against Lieht and * Warmth. -

In question, for example, natural substances are to be protected. or synthetic macromolecular substances, such as _Λ

Rubber, leather, natural or regenerated cellulose

90988S / 1721. /

BATH ORIGINAL

and fiber-forming organic substances «e.g. cellulose derivatives» Polyesters, polyamides, polyacrylonitrile, polyolefins. Polyvinyl chloride, polyvinyl ter. Polyvinyl alcohols, polystyrene. These substances can be in the form of plates, Rods, rather trains, foils, films, ribbons, fibers, Granules, powders and other processing forms, or in the form of solutions, emulsions or dispersions. They are also suitable for light and heat stabilization Vegetable and mineral QeIe, as well as varnishes.

In the examples below, the parts are parts by weight, the percentages are percentages by weight and the temperatures are given in degrees Celsius. The absorption maxima of the compounds mentioned there were measured on solutions of the same in ethyl alcohol which contained 1% dioxane.

Manufacturing examples

example 1

47 parts (0.5 mol) of phenol are in a sulphonation flask presented and melted at 50 °. Then be ii4 parts (0.5 mol) of 3,5-di-tert-butylsalicyic acid chloride

§09883 / 1721

BATH ORIGINAL

• · a tt · ·

slowly admitted. A lively development of hydrochloric acid begins. The reaction mixture becomes slow with stirring heated to 80 °. After about 2 1 /? The esterification is finished hours. The amount of hydrochloric acid developed is 18.2 : Parts. The crude product is recrystallized from methanol, J being 131.6 parts (8l # of theory), 3,5-di-tert.-

butylsalicylic acid phenyl ester is obtained in the form of white crystals soluble in acetone, dioxane, toluene and petrol.

F: 89-90 °, VZ found 172 (theory 172) absorption maximum i 320-330 nm molecular extinction coefficient: 4100

Elemental analysis: ber .: C. 8th H 0 1% found .; 77.25 * 8th .05 * 14, 7β, 90 # , 20 # 14,

Example 2

62 parts (0.5 mol) of resorcinol monomethyl ether are in one Stirring piston presented and 134.4 parts (0.5 mol) of 3,5-di-tert, bufcylsalicylic acid chloride slowly with vigorous stirring admitted. Then the temperature rises to 80 ° and there is a strong evolution of hydrochloric acid gas. After approx. 18.2 parts of salic acid formed in 5 hours »That

90S8.ÖS / 1721

• 'i- ßAD _; OfitGlhfÄt. "

f »ff # rc« 9

Raw product is made from methane ©! urakrigteallisi®rt ₀ Ss 132 parts (74 $ of the theory) of the 3 * 5-: Bi-tez ^s t.-bufeylsalioyleKureOV-netft & tt ^ hegi ^ empty i & form of white crystals are obtained ». Diesel ³ is soluble in acetone, alcohol, "dioxane, toluene, gasoline and chlorinated hydrocarbons"

VZ: 156 (theory 157)

F ί 81-82 · "- i

Absorptionraaxiimßs 310-330 ran)

^; ■■ * ■ ;. - ■■ "■ .-.. ■ '- I

Extinction coefficient: 5500. ]

C H 0

7.85 *

8.40ji 18.0 *

At 8 ρ ie 1 3 "" / _: ",

t5 * l parts (0.5 mol) of p-tert-butylphenol are in one Stirring flask gesehsaolzen And at 100® with stirring 134.4 parts (0.5 mol) of ^ iS-di-tert-butylsalioylic acid ahlorld slowly added «There is a strong evolution of hydrochloric acid gas on * The free after approx. 2 l / s hours The amount of hydrochloric acid gas that has become corresponds to the theoretical amount % expected. The end. Methanol recrystallized crude

Ö09885 / Ί 721

BATH ORIGINAL

product provides 154 parts (80 * of theory) 3,5-di-tert-butylsalicylic acid ^ '- tert-butylphenyl ester in Fora weleeer' Crystals. This is in acetone, alcohol, dioxane, toluene ”; Soluble petrol and chlorinated hydrocarbons.

VZi 146.25 (theory 146.5) "

P ι 100-101 ° · '.- ·.

Absorption maximum: 320-330 pm , '■ · «

Molecular extinction coefficient ι 5500

Elemental analysis ι ber. ι C. K 12th 0 • gef · t 78.50 * 8.95 * 12th .55 * 78.88 * 9.00 * .20 *

. Example 4 ■ ".

The procedure is as in Examples 1-3, with .aber the starting compounds of the formulas (II) and (III) 'are chosen so that the aryl esters A -Λ _Λ ·. /

correspond to the formulas given in the table below: "..

909085/1721

,,,, - ..-, * ßAD ORIGINAL

Example 5

S (O ₁ I mol) · p-chloro-m-cresol are placed in a SuIfler flask and dissolved in 100 ml of toluene. To the

.. · '·. "". This solution is left with. ·. · ■ *

28.28 g * (0.1 mol) 3,5-di-tert.toityl-a-m ^ thQxybenzoylchloride,

Toluene. . . dissolved in 100 ml · "v ~, slowly pour in. It begins.

"A vigorous evolution of hydrochloric acid. While stirring •. The reaction mixture is slowly heated to 80 °. To The esterification is complete in about 2 hours.

The toluene solution of the crude product is then mixed with. Washed out thin soda solution and the toluene stripped off in vacuo. The crude product is a yellowish oil which from 200 ml of methanol is recrystallized.

2 ^, 1 g (87.7 $ of theory) ^ are obtained

benzoic acid ¹ -methyl ^ h '-chloro-phenolester in the form of white, soluble in acetone, dioxane, toluene, gasoline crystals.

P: 97.5-98 °. · · · ■ ']:

Absorption maximum 300 ".. ... '

molecular absorbance efficiency afc

Elemental analysis: _ ■ ". _Λ ^ ₁ ber: ;; "." 71 ^ 03 "7.51 / .. 12.3 ^ 9.12

5 li't. 12.4. 9.0.

Example-6 '''' .. '''"■' ■ . · '. ·

The procedure is as in Example 5, but the Äusgähgsverbiridüngen of the formulas II and III are chosen so that Öäös oils get aryl esters HQ Aen in the table given below correspond to the formulas »... '' ■ ..

6AD 'OfiiGiMAL

O O VO

«I H H

O * vS

in

in CVJ

CVJ lf \ CVJ

■ aj-

CVJ

rH CVJ O CVJ O HI

cvj

rl CVI

r-i Ch ■■ «ί- Φ Ο E. Jt Γ U Ü «Ρ O Bu φ3

σ \

O O O

-, p

» ON ■ si * • ■ =? . eat ϋ O I. O 'ι; . ϋ • ..> Ρ « I 4 »

4109885 / j ^: / 2

BADOaiGlfiAL

Aryl ester

formula A> max

^{; tC} 4 ^H 9

Bh - 85

525 - 79

525

25-166

525

5255

5525 '

BATH ORIGINAL

V-1i93828ö

Ft

Max

70.5-71.5

- 150

-IO6

HS - 119

- 124

72:>

109

0.005 inn Hg

290

500

295

300

290

99 - ιοί

909885/172 *.

295

COPY

0 I.

ORIGINAL INSPECTED

■ .. · Q
* - CH formula 0 OCH F. ■ 96 « X max 290 E. A,
cn / ¹ • ■ ; ch / N-o-c- \ _ .95- 2335 3 / ^tC 4 ^H 9 ^tc 4 ^H 9

ORIGINAL INSPECTED

In this table, Xmax means that of the aryl ester am strongest absorbed wavelength of UV light in, nm and E the molar extinction factor.

The connections A - Q can also contain < ^:

are «if one reacts the phenol of Promel (III) in the form of its alkali metal salt in aqueous-alkaline solution in the presence of a solvent, for example toluene or carbon tetrachloride, with the acid chloride of the formula (II), or if instead of the acid chloride an ester of the formula (III ) mixes with the phenol of the formula (II) and preferably in the presence of a catalyst, for example sodium or boric acid, to 160-180 ⁰

heated. -

Application examples:

a) Polypropylene is mixed in a suitable mixer ("GeIimat") at 180 * - with 0.5% by weight of the compound described in Example 3 and then pressed to 1 mm thick platbon after "200 hours of exposure in the fade -o-mefctsr remain the same mweränderc, ivähi'ancl si © in Abi / a ^ nhaib daa üV-Absor.b- ^ rs already uach 10ö »atiüiiUg · .-." .- r ^ lL ^ ii ^ üüg im Fasla ^ o-in

0 U ·}> ^} > H »i / 1 7 V!
; _:. 8AD ORIGINAL.

to) A commercially available nitrooellulose lacquer is added to 5% of its weight of the compound described in Example 1. With <Jiteem lAok on fir ,. Coatings made from esohen, elm and maple wood prevent these woods from darkening when exposed to light. If the wood is coated with the same lacquer on the same catfish, but without adding the compound mentioned, these woods darken strongly in the light.

o) Polyvinyl chloride is mixed with 0.1 g of the compound described in Example 4 in a suitable mixer.

. mixed at 180 ° and then on a rolling mill to approx. X OMi thick panels processed. These show after 1000 hours exposure with Xenotest no change, while a corresponding additive-free ' Flat: yellow and cracked from the same treatment will" . .- '* ■■ .:

In the examples *), b) and o), instead of the Examples 1, 3 and V available compounds with similar Success Much good Example 2 connection that can be established or dl · compounds defined in the table under A-Q

• ingesetitt «•« den · -_ -. ^ ^: - ■ '<p- ^A ~' .- ''. ■ ■. "

'V ■■■;

\ 5ί, Ί ·· (, 1Α -

8AD ORIGINAL

Claims (5)

Claim I. wherein R ₁ and R ₁ u. R , and R ₂ X and X Y H or C ₁ ^ ₁₂ H, C _1-12 -AlCyI, OH or YR ₂ ^, C _1. ,, - alkyl, halogen, OH 'or Cj; ₁₂ -alkyl or - C "" 0 (page 15a) K,. «■ *., · OR ₆ , or C ₁ 0 or S mean which one thereby marked ^ / 'that one Compound of formula R ₂ -f3 ~ ^COZ R ₁ · "X" 9Ö08Ö5 / 1721 BATH ORIGINAL means H, 0 ^ _ ₁₂ -alkyl or OH η 1 ~ means H, 0 ^ ₁₂ -alkyl, halogen or OH. il -j;) Π: ■. '-' Z R- nVR. and R, the same as given above * Halogen or OR l- ^ ^xmd H or methyl mean «.." with a phenol of the formula HY (Ill) l> R- and X have the meaning given above, where at least one of the radicals X or X is OH, at least two of the radicals R ₁ , R ₂ and R, alkyl radicals and at least one of these, preferably R _{1 is} a tert-butyl radical. must be. ORIGINAL INSPECTED 2) Method according to claim 1, characterized in that one starts from compounds of the formulas (II) and (III) in which Y is oxygen and Z is chlorine * 3) Process according to claims 1 and 2, characterized in that a compound of the formula (II) with 3 »5-di-tert. butylsalicylic acid chloride converts. 4) The use of the compounds of the formula (I) for protecting organic substances against the harmful effects of light. 5) compounds of formula (I). The attorney of law (Dr. V / Schmied-Kowsirzik) It 909 885/1721