DE1593369A1 - Process for the preparation of new fluoranthyl ketones - Google Patents

Description

6 FRANKFURT AM MAIN

OD. (ICNENHEIMII ITI. Ι «0Β.3Θ C. \ §- \)

SANDOZ AG Basel / SWITZERLAND Process for the production of new fluoranthyl ketones

The present invention relates to a process for the preparation of new fluoranthyl ketones of the formula I.

• I

wherein R ₁ H, alkyl, aralkyl, cycloalkyl, halogen R ₂ H, OH, O-alkyl, O-cycloalkyl, O-aryl, O-aralkyl,

COOH, SO ₃ H,

R, H, halogen, OH, alkyl, O-alkyl, O-aralkyl R aromatic or heterocyclic radical n, u and ν 0 or 1
m 0, 1 or 2

and ρ 0, 1, 2 or mean j5, but at least one R ₂ or R, should be present as OH, O-alkyl _# O-cycloalkyl or O-aralkyl, preferably in o-position to the carbonyl group at the Fluoranthene radical or on R _Q , characterized in that a compound of the formula II

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■ · · · .. ·. · ■ '■ BATHROOM

(Ri),

ί — r

II

with a compound of the formula III

converts, where in the formulas II and III FL, FU, Ft ,, R ₀ * n, m * u, ν and ρ have the same meaning as above and X is hydrogen when y-CO is halogen and X -CO is halogen means when Y is hydrogen and where u + ν is at least 1.

The implementation takes place in a known manner according to Friedel-Craft (See Olah: Friedel-Crafts and Related Reactions, Vol. Ill, 1964) e.g. in a solvent such as carbon disulfide, Chlorobenzene, tetrachloroethane or dichloroethane, where 1 mole of the compound of formula II with 1 or 2 moles of the compound of formula III is made to react, depending on the sum of u + ν 1 or 2 1st.

The reaction temperature is kept low at the beginning , for example at 0 ° and increased in the course of the operation to about 120 °.

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Among the compounds of the formula II and III, the CarbonsKureohlorlde are particularly suitable, the duroh treatment of corresponding carboxylic acids can be obtained with thionyl chloride or phosphorus chlorides. The ones described in the examples Acid chlorides were produced with the help of thionyl chloride and used without any special purification.

The new compounds prepared according to the process are suitable, for example, as absorbers for ultraviolet light.

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example 1

36.8 g of 2-methoxy-m-toluic are dissolved in 150 ml of dichloroethane, after which the resulting solution at 0-10 ^c C 27 g of aluminum chloride and then stirring at this temperature the solution of 36 g of fluoranthene in 100 'mL of dichloroethane be admitted. The reaction is carried out at a rising of 20-75 ⁰ C temperature until the development Saiz acid terminated 1st. The solution thus obtained is then decomposed in a mixture of hydrochloric acid and ice, washed several times with water and the solvent is distilled off under reduced pressure. The yield of the crude product is 56 g. It is then recrystallized from toluene. The fluoranthyl-2-oxy-3-methylphenyl ketone thus obtained is a yellow powder. Schmelzpunktt 70-76 ⁰ C. Solubility: soluble in acetone, Dioxaii, toluene, chlorinated hydrocarbons.

Absorption maximum: at 357-372 nyu it has a broad Absorption maximum.

Elemental analysis t calc .: C: 85.6 # Ht 4.97 ## O: 9 »51 #

found: C: 85.6 # Hi 5 * 0 %, 0 : 9 »^%

0.2 # of the fluoranthyl 2-oxy-3-methylphenyl ketone with polystyrene mixed on the Oelimate and then pressed, results a light-resistant polystyrene.

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Example 2

34.1 g of 4-methoxybenzoic acid chloride are dissolved in 150 ml of dichloroethane. 26.6 g of aluminum chloride and then at this temperature under stirring, the solution of 40.4 g Pluoranthen in 100 ml of dichloroethane are introduced at ⁰ C 0-1O into the thus prepared solution. The reaction temperature is maintained between 15-20 ⁰ C. After the evolution of hydrochloric acid has ceased, the product obtained is decomposed in a mixture of hydrochloric acid and ice, washed several times with water and the solvent is distilled off under reduced pressure. The product recrystallized from toluene (fluoranthyl-4-methoxyphenyl ketone) is then obtained in a yield of 48 g, that is 71% of theory. It is then a light yellow amorphous powder.

Melting point 154 to 156 ⁰ C

Solubility «soluble in acetone, toluene, dioxane and

chlorinated hydrocarbons.

Maximum absorption «352-370 myU

Elemental analysis} calc .: C: 85.75 $, Hi 4.8 #, 0: 9

gef.t Ci 86.3 & Ht 4 »7 & 0» 9

ORIGlNAL BATHROOM 909840/1725

Example}

If the 4-methoxybenzoic acid chloride in Example 2 is replaced by the ji-methoxybenzoic acid chloride, _S o, the fluoranthyl-3-methoxy-phenyl ketone is obtained. After recrystallizing it from toluene, a light yellow amorphous powder is obtained.

Yield: 39 g = »6O.5 # of theory Melting point: 107 ° C

Solubility: soluble in acetone, dioxane, toluene and

chlorinated hydrocarbons absorption maximum: 355-375 nJ / U
Elemental analysis: calc .: C: 85.7 # »H: 4.8 #, 0: 9 * 5 #

found: C: 86.1 ^, H: 4.7 #, 0: 9 * 2 $

Example 4

68.2 g of 2-methoxybenzoic acid chloride are dissolved in 200 ml of dichloroethane. Subsequently one carries into the obtained solution 60 g of aluminum chloride at 0-10 ⁰ C, and then added with stirring at this temperature, add the solution of 80.8 g Pluoranthen in 250 ml dichloroethane. The condensation is carried out at a temperature increasing from 10-75 ° C. When the evolution of hydrochloric acid has ended, the solution obtained is decomposed in a mixture of hydrochloric acid and ice, washed several times with water and the dichloroethane is distilled off under reduced pressure. The fluoranthyl 2-oxyphenyl ketone thus obtained

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is freed from impurities by extraction with boiling alcohol. It is obtained as a light yellow powder. Yield: 84 g m 66 % of theory, melting point 102-114 ° C. Solubility, soluble in acetone, dioxane, toluene and

chlorinated hydrocarbons. Absorption maximum 355-570 m Ai

Elemental analysis χ calc .: 85.96 Ct #, H: 4, O77 # * 0: 9> 95 #.

found: Ct 86.5 & H: 4.4 %, 0: 10.0 %

Polyethylene or polypropylene mixed with 0.5% of fluoranthyl-2-oxyphenyl ketone and then pressed or blown produce light-resistant polyethylene or polypropylene.

Example 5

67 g of 2,4-dimethoxy-benzoic acid chloride are dissolved in 150 ml of dichloroethane and, after the addition of 42 g of aluminum chloride condensed to the solution with 59j4 g of fluoranthene at 0-47 °. The work-up of the condensation product is carried out as described in the preceding examples. It puts then a light yellow powder. Raw yield: 104 g

Melting point: l40-l47 ^e C Solubility: soluble in acetone, dioxane, toluene, Chlorobenzene

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Maximum absorption j between 350-360 nyu Elemental analysis j ber.tC: 8l, 95 & Hr 4.952 #, 0:

found tCi 81.7 & Hi 5 # 0 Ji, O: 13 ₅

15.6 *

Example 6

5 β 4-methoxy-2-hydroxybenzoic acid chloride are dissolved in 100 ml of dichloroethane. At 0-10 ⁰ C to wear in the obtained solution 27 g of aluminum chloride and subsequently added at this temperature, a solution of 40 g Pluoranthen in 100 ml of dichloroethane added. Man holding a reaction temperature of a 0-25 ⁰ C. After the hydrochloric acid evolution is complete, the solution is in a Mis ohung from SalzeKure ice and decomposed, washed several times with water and distilling off the dichloroethane. The residue is recrystallized from ethyl acetate. The fluoranthyl-2-oxy-4-methoxyphenyl ketone thus obtained is a light yellow powder.
Yield: 20 g
Melting point: 166 ° C

Solubility: soluble in acetone, dioxane, toluene, chlorobenzene and chlorinated hydrocarbons. Absorption maximum ι between 325-J565 nyu

Elemental analysis: calc. "C: 8l, 56 & H: 4, .847 & Ot 13.58 # OCH,"

8.78 *

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found iC: 8l, 4 £, Ηί4.7 $, 0x13.2 $ OCH,

Soft PVC with 0.2 # fluoranthyl-2-oxy-4-methoxyphenyl ketone mixed and rolled results in light-resistant soft PVC Foils.

Example 7

37 * 5 g of 4-methoxy-2-oxybenzoic acid chloride are dissolved in 100 ml of tetrachloromethane. Bel 0-10 ⁰ C bears 30 g of aluminum chloride in the solution thus obtained and adds subsequently at the same temperature 40 g in 100 ml TetrachlorHthan dissolved fluoranthene added. This is followed by condensation at a temperature increasing from 15 ° C to 110 ° C. After the evolution of hydrochloric acid has ended, the solution is decomposed in a mixture of hydrochloric acid and ice, washed several times and the tetrachloroethane is distilled off. The crude product is recrystallized from dichloroethane. The fluoranthyl-2,4-dioxyphenyl ketone thus obtained is an orange-red powder. Yield: 24 g melting point: 208 ° C

Solubility: soluble in acetone, dioxane, toluene, chlorobenzene and chlorinated hydrocarbons Absorption maximum: 320 - 365 nyu

Elemental analysis: ber.iCi8l, 6 #, Ht 4.17 & 0:14,

found. * Ci8l, 0 #, Hs * 4.00,

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Example 8

17.0 g of 2-methoxybenzoyl chloride in 100 ml of dichloro-Sthan dissolved "C after which 14.6 g of aluminum chloride and anschllessend g In the resulting solution at 0-10 ⁰ 25 with stirring in 100 ml of dichloroethane dissolved mono-tert-12- butylfluoranthene are entered. The condensation is carried out at a temperature of 10-75 ^e C rising. After the evolution of hydrochloric acid has ceased, the solution is decomposed in a mixture of hydrochloric acid and ice, washed several times and the solvent is distilled off.

The 12-tert-butylfluoranthene-2-oxyphenyl ketone thus obtained is a lemon-yellow powder * Ee is recrystallized from isopropanol. Yield J32,2g melting point: 147-150 ⁰ C Solubility soluble in acetone, ethanol, dioxane, toluene

and chlorinated hydrocarbons

Maximum absorption: absorption ^{increasing from 345-365 ny u} Elemental analysis: calc.: C: 85.69 #, Hi 5 »86 #, 0: 8.45 %

found iC: 85.7Ji, H: 6.0 #, 0: 8.6 %

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Example9

If in Example 8 instead of the 2-methoxybenzoic acid chloride 20 g of 2,4-dimethoxybenzoic acid chloride used, so obtained using 14.6 g of aluminum chloride 12-tert-butylfluoranthene-2-oxy-4-methoXy-phenyl ketone, the recrystallized from isopropanol represents an orange-yellow powder.

Yield: IJ g
Melting point »64-69 ° C

Solubility soluble in acetone, alcohol, dioxane,

Toluene and chlorinated hydrocarbons.

Absorption maximum: broad absorption maximum of 310-365 ^m / ^u Elemental analysis: calc.:C:82.33#,H:5.92#,O:11.75# OCH, = 7.597 #

found: C02.6 #, H: 6.2 #, 0: 10.4 %

Example 10

34.1 g of 2-methoxybenzoyl chloride are dissolved in 100 ml of tetrachloroethane, after which was added 29 g of aluminum chloride in the resulting solution at 0-10 ⁰ C and are then added at the same temperature, 47.2 g dissolved in 100 ml of 4-Chlorfluoranthen tetrachloroethane. The condensation is carried out at a temperature increasing ^{from 10 °} C. to HO ^{° C.} let the evolution of salt acid end, so will

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the solution decomposed in a mixture of hydrochloric acid and ice, washed out and the solvent was distilled off under reduced pressure.

The 4-chlorofluoranthene-2 * oxyphenyl ketone thus obtained is

by extraction with boiling alcohol from impurities freed and then represents a lemon yellow powder » Yield: 47 g

Melting point 162 ^e C Solubility soluble in acetone, dioxane, toluene,

Chlorobenzene and chlorinated hydrocarbons

Absorption maximum t of 260-376 m, u a broad maximum. Elemental analysis calc. IC: 77 * 425 #, H:?, 672 #, Ci8,968 #

found: Ci76,O £

The inconsistency in the analysis is due to the presence of 4, ll-dichlorofluoranthyl-2-oxyphenyl ketone. At The corresponding place of 4-chlorofluoranthene can also be used 4-bromofluoranthene can be used. The resulting ketone offers properties similar to those in the example 11 described «

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Example 11

1 g of 2-methoxybenzoic acid chloride are dissolved in 100 ml of tetrachloroethane, after which the solution obtained is at 0> 10 ° C 29 g of aluminum chloride and then 54.2 g of 4 11-dichlorofluorine dissolved in 100 ml of tetrachloroethane at this temperature

anthems added. The condensation is carried out at a ^{temperature increasing from 10 °} C. to HO ^° C. «. When the evolution of hydrochloric acid has ended, the solution is decomposed in a mixture of hydrochloric acid and ice, washed out and the solvent is distilled off in vacuo.

The 4, ll-dichlorofluoranthene-2-oxy-phenyl ketone thus obtained after! ^ crystallization from dichloroethane turns yellow Powder.

Yields 17 g Melting point 180-188 ° C

Solubility: soluble in acetone, dioxane, toluene, chlorobenzene and chlorinated hydrocarbons Absorption maximum from 3 ^ 7-365 nyi an increasing maximum. Elemental analysis: calc.:C:7O,6#,H:3,O9#,O:8,17# Cl * l8,12 #

found iC: 7O, 8 #, H: 3, O #, 0: 7.2 % Cl «l8.3 %

The corresponding 4,11-dibromofluoranthene can also be used in place of 4.11-dichlorofluoranthene. The resulting ketone has properties similar to those in Example 10 described.

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Example 12

40.1 g of 2,4-dimethoxybenzoyl chloride dissolved in 100 ml of tetrachloroethane, after which at 0-10 ⁰ C, 29 g of aluminum chloride and at this temperature 47.2 g in 100 ml of tetrachloroethane dissolved 4-Chlorfluoranthen added subsequently. The condensation is carried out at a temperature rising from 10 ° C to 100 ⁰ C temperature. When the evolution of hydrochloric acid has ended, the solution is decomposed in a mixture of hydrochloric acid and ice, washed several times and the solvent is distilled off. The crude product is recrystallized from alcohol / dioxane in a ratio of 5: 1.

The 4-chlorofluoranthene-2-oxy-4-methoxyphenyl ketone thus obtained is a light yellow powder.
Yield: 26 g
Melting point: 252-26l ° C

Solubility: soluble in acetone, dioxane, toluene,) chlorobenzene and chlorinated hydrocarbons

fabrics

Absorption maximum: from 338-366 m, u a broad absorption maximum

Elemental analysis: calc.: C: 74.52 #, H:] 5> 90 & 0: 12.4 # C1 = »9> 16 #

found iC: 73.3 %

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example

26.0 g of 2-furan carboxylic acid chloride are dissolved in 100 ml of dichloroethane, after which are added to the resulting solution at 0-10 ⁰ C 24g of aluminum chloride and subsequently at this temperature 36 g dissolved in 100 ml of dichloroethane Pluoranthen. The condensation is carried out at a temperature of 10-25 ⁰ C. When the evolution of nitric acid has ended, the solution is decomposed in a mixture of hydrochloric acid and ice, washed out and the solvent is distilled off.

The crude product is recrystallized from alcohol.

The fluoranthyl-2-furanyl ketone thus obtained is a light yellow powder

Yield: 20 g

Melting point: 114-117 ° C

Solubility: soluble in acetone, alcohol, dioxane, toluene

and chlorinated hydrocarbons

Absorption maximum: from 555-373 nyu wide absorption maximum Elemental analysis: calc .: C: 85.12 #, H: 4.0A / 2j £, C: 10,

3 % C: 10,

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Example 14

26.5 g of fluoranthene carboxylic acid-4-chlorld are dissolved in 200 ml of dichloroethane. 13> 6 g of aluminum chloride are added to the solution obtained at 0-10 ° and then 13.8 g of 1,3-dimethoxybenzene are added at this temperature with stirring. The reaction is carried out at 10-25 ⁰ C. When the evolution of hydrochloric acid has ceased, the solution is decomposed in a mixture of hydrochloric acid and ice, washed several times with water and the dichloroethane is distilled off under reduced pressure. The fluoranthyl 2,4-dimethoxyphenyl ketone obtained in this way is a lemon yellow powder «
Yield: 36 g = 98 # of theory, melting point: 14-144 ° C
Solubility: soluble in acetone, dioxane, toluene and

chlorinated hydrocarbons absorption maximum: between 330 and 375 ni / U Elemental analysis: calc.:C:8l,95#,H:4,952#,O:13#O99# OCH, =

16.94 *

found: C: 82,1 & H: 4.9 #, 0: 12.8 % OCHy

15,

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Example 15

26.5 g Pluoranthencarbonsäure-4-chlorld are dissolved in 100 ml of dichloroethane, after which 12.6 g of aluminum chloride are added to the resulting solution at 0-10 ⁰ C. 16.6 g of hydroquinone diethyl ether are then added at this temperature with stirring. The reaction is carried out at a temperature rising from 10 ° to 70 ⁰ C temperature. After the evolution of hydrochloric acid has ceased, the solution is decomposed in a mixture of hydrochloric acid and ice, washed several times and, after the solvent has been distilled off, freed from impurities by extraction with boiling alcohol.

The thus obtained and purified fluoranthyl-2-oxy-5-ethoxyphenyl ketone is a yellow powder.

Yield: 17 * 5 g

Melting point: 99 ° C

Solubility: soluble in acetone, dioxane, toluene, chloro-

rated hydrogen

Maximum absorption: increasing absorption of 350-570 mAx Elemental analysis: calc .: Ci82, l #, H: 4.95 #, O: i; 3, O9 #

found :

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Claims (1)

Claims 1591369 I. Process for the preparation of new fluoranthyl ketones of formula I. (R ₁ Y _n ^ CO-R ₀ (R ₃ ) _p J _v wherein R ₁ H, alkyl, aralkyl, cycloalkyl, halogen R ₂ H, OH, O-alkyl, O-cycloalkyl, O-aryl, O-aralkyl, COOH, SO ₃ H, R ₃ H, halogen, OH, alkyl, O-alkyl, O-aralkyl R aromatic or heterocyclic radical n, u and ν 0 or 1.
m 0, 1 or 2 and ρ are 0, 1, 2 or 3, but at least one R ₂ or R _{3 should be present} as OH, O-alkyl, O-cycloalkyl or O-aralkyl, preferably in the o-position to the carbonyl group on the fluoranthene radical or on R, characterized in that a compound of the formula II ^X v with a compound of the formula III II 9 09840/1725 converts, where in the formulas II and III R ,, Rg, R ,, R, n, m, u, ν and ρ have the same meaning as above and X is hydrogen when y-CO is halogen and X -CO is halogen means when Y is hydrogen and where u + ν is at least 1. II. The use of the manufacturable according to patent claim I. Compound for the absorption of ultraviolet rays. III. Fluoranthyl ketones of the formula I in which R 1 to R 1, R _Q , m, n, p, u and ν have the meanings given in claim I. The patent attorney: 909840/1725 ' ^BAD