DE1908346A1 - Substituted triarylamines - Google Patents

Description

EASTMAN KODAK COMPANY, 343 State Street, Rochester, New York State, United States of America

Substituted triarylamines

Triarylamines are known and are described in a wide variety of literature references * It is also known that unsubstituted Due to their electrophotographic properties, triphenylamines are used as photoconductors for the production of electrophotographic Recording materials for electrophotographic duplicating processes, e.g., xerographic Duplication processes, are suitable. It is also known that a limited class of substituted triphenylamines has similar properties. These substituted triphenylamines are those triphenylamines which are substituted by alkyl, alkoxy or amino radicals.

Surprisingly, it has now been found that in very specific Wisely substituted triarylamines are particularly advantageous electrophotographic Have properties so that they are particularly useful as photoconductors for the production of electrophotographic Recording materials are suitable «

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It has been found that for electrophotographic purposes particularly suitable triarylamines are those in which at least an aryl radical is substituted by at least one group which contains an active hydrogen atom, or a corresponding group Group which can be hydrolyzed in such a way that a group containing an active hydrogen atom can be formed

A group containing an active hydrogen atom is to be understood as meaning a group such as, for example, in the book "Advanced Organic Chemistry" by R.C. Fusoh, pp. 154-157, published by John Wiley ft Sons, 1950. Apart from those described here, an active hydrogen atom containing groups, the new substituted triarylamines can be further substituted by at least one group which can be hydrolyzed to form an active hydrogen atom-containing group. With these groups it is, for example, acyl halide groups, ester groups or amide groups.

The invention thus relates to substituted triarylamines, characterized by one of the following formulas:

I.> xt j \ ν _and

11. ^ N-Ar, £ C "

^Ar 2 ^R 1 ^R 2

where mean:

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and Ar ₂ each represents an optionally substituted phenyl radical;

Ar _{3 is} an optionally substituted phenylene

or naphthylene radical;

• c

Y (a) is a carboxyl radical; ·

(b) an ester residue;

(c) an acyl halide residue;

(d) an amido radical;

(e) an optionally substituted alkylidynoximido radical;

(f) a hydroxyl radical;

(g) an optionally substituted Ätfiynylrest;

(h) a carboxylic acid anhydride residue; (i) a short-chain alkylenecarboxy radical; (j) a short chain alkylene hydroxy radical; (k) a semicarbazono residue, or

(1) an optionally substituted phenylsncarboxyl radical;

X (a) is a carboxyl radical;

(b) an ester residue;

(c) an acyl halide residue;

(d) an amido radical;

(e) a hydrogen atom;

(f) an ethynyl radical;

(g) a methylidynoximido radical; (h) a carboxylic acid anhydride residue | (i) a semicarbazono radical;

(j) a hydroxyl radical;

(k) a short-chain alkylenecarboxyl radical

(1) a short-chain alkylene hydroxyl radical cder

(in) a phenylenecarboxyl radical;

η = 1, 2 or 3;

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R ₁ and R ₂ each represent a short-chain alkyl radical, one

optionally substituted phenyl radical or a hydrogen atom.

Are in the given structural formulas Ar. and Ar, optionally substituted phenyl radicals, these can for example consist of alkylphenyl radicals or halophenyl radicals. The alkyl groups of the alkylphenyl radicals preferably have 1 to 4 carbon atoms. If Ar, has the meaning of a substituted phenylene or naphthylene radical, this means that these radicals can also be substituted by, for example, alkyl radicals and / or halogen atoms'

If Y has the meaning of an ester residue, this can have the have the following structural formula:

- C - OR

* «« ****** where R can have the meaning of a short-chain alkyl radical with 1 to 8 carbon atoms. Y can, however, be a cyclic ester residue, for example a Coumarin residue

If Y has the meaning of an acyl halide radical, this can be, for example, made up of a radical of the following formula:

Il

.- C - halogen

exist.

If Y has the meaning of an amido radical, this can be, for example are represented by the following structural formula:

O
- C - N (R) ₂

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where R is, for example, a short-chain alkyl radical with 1 to 8 Can be carbon atoms or a phenyl radical.

If Y has the meaning of an alkylidynoximido radical, this can be given, for example, by the following structural formula

- C - NOH

• ι

^R 3

reproduce, where R, the meaning of a short-chain alkyl radical, e.g. with 1 to 8 carbon atoms, or can have the meaning of a hydrogen atom.

If Y has the meaning of an ethynyl radical, this can be represented by the following structural formula:

- C = CH -,

where the hydrogen atom of the radical can optionally be substituted, for example by a hydroxyl, aryl or Alkyl radical, in which case hydroxyethynyl radicals, arylethynyl radicals or alkylethynyl radicals are present.

If Y has the meaning of a short-chain alkylene carboxy radical, so it preferably has 2 to 8 carbon atoms.

If Y has the meaning of a short-chain alkylene hydroxy radical, so it preferably has 1 to 8 carbon atoms.

If Y has the meaning of a phenylenecarboxyl radical, this can, for example, have the following structural formula:

The aryl radicals can preferably be 6-10 and the alkyl radicals preferably have 1-8 carbon atoms.

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COOH

wherein D and E can have the meaning of phenyl or short-chain alkyl radicals with 1 to 8 carbon atoms.

X can have the meaning of a hydrogen atom or one of the residues as described for Y

R .. and R ₂ can have the same or different meanings. If R. and R ₂ are alkyl radicals, these preferably have 1 to 8 carbon atoms. If R .. and R ₂ are phenyl radicals, these can optionally be substituted, for example by short-chain alkyl radicals having 1 to 8 carbon atoms and / or halogen atoms.

As already explained, the new substituted triarylamines are particularly advantageous organic photoconductors for the production of electrophotographic recording materials.

The new substituted triarylamines can be synthesized by a wide variety of syntheses. Typical syntheses are presented in will be described in detail in the examples below.

Typical, particularly advantageous substituted triarylmmines of Invention are for example:

Methyl p-diphenyminobenzoate; Ethyl 2, o-diphenyl-4- (p-diphenylaninophenyl) benzbate;

1- (p-Diphenylaminopheny1) -1-hydroxy-3-butyne;

4-hydroxymethyl triphenylamine;

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-τι - (p-Diphenylaninopheny1) ethanol; 3- (p-diphenylaminophenyl) propionic acid; 3-p-diphtnylaminophenyl-1-propanol; 4-hydroxytriphenylamine; 2-Hydroxytriphenylamine | 4-fonyl triphenylajnin oxime; 4-Ac «tyltfiphenylaminoxim; 7-dipynylaainocoumarin; 1- (p-Diphenylaainopheny1) hexano1; 1- (p-Diphtnyluiinophenyl) dodecanol; p-diphenyl ainobenzoic anhydride; 7- (p-Diphenylaminophenyl) -2,4,6-heptatrienoic acid; p-Diphenylaainobnzoic acid-N _t N-diphenylaaid; p-diphenylaainobenzoestture; p * Diphtnylaainob «nzoylchlorid; 4 · (p-Diphtnylaminopheny1) -3-buten-1-yn; p-diphenylaminostyrene; Ethyl p-diphtnylaninocinnanate; Methyl p-diphenylaminocinnanate; p-diphenylaeinocinnanoyl chloride; p-Diphtnylaainocinna ^ inic acid-NN-diphenylaBid; p-Diphtnylaainocinnaic acid ahydride; 3- (p-Dipynylaainophenyl) -2-butenoic acid; Bis (p-diphenylaainobenzal) _{succinic acid 4 * N (} N-bis (p-bronophenyl) aainocinnanic acid; 1- (4-diphenylamino) naphthacrylic acid; 4-formyltriphenylamine seraicarbazone;

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p-diphenylaminocinnamic acid; 4-diphenylaminocinnamaldehyde semicarbazone; p-diphenylaminophenyl vinyl acrylic acid; 7- (p-diphenylaminostyryl) coumarin; p-diphenylaminocinnamyl alcohol; p-diphenylaminophenylvinylacrylaldehyde oxime; O-p-diphenylaminocinnamoyl-p'-diphenylaminobenzaldehyde oxime; p-diphenylaminocinnaraaldehyde oxime; 1,3-bis (p-diphenylaminophenyl) -1-phenylpropen-1-oil; p-Diphenylaminobenzy1-p'-diphenylaminocinnamate and 4-acetyl triphenylamine semicarbazone.

The following examples are intended to illustrate the invention in more detail.

example 1 : p-diphenylaminobenzoic acid

To a solution of 5O ₁ O g (0.174 moles) of 4-Acetyltriphenylamin in tetrahydrofuran was slowly added with stirring 3 equivalents of aqueous potassium chloride Hypo. After stirring for 2 hours, the solution was acidified by adding concentrated hydrochloric acid. The precipitated crystals were filtered off and recrystallized from ethanol. p-Diphenylaminobenzoic acid was obtained in 72% yield (36.0 g). Mp. = 202-204 ⁰ C.

Calculated for C ₁₉ H ₁₅ NO ₂ IC: 78.9; H: 5.2; N: 4.8; Found: C: 78.9; H: 5.2; N: 4.9.

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- 9 Example 2:

ρ-Ν, Ν-diphenylaminocinnamic acid

In 50 ml of dry pyridine, 68.3 g (0.25 moles) of 4-formyltriphenylamine and 26.0 g (0.25 moles) of malonic acid were dissolved. The solution was heated on a steam bath for 5 hours. The reaction product was isolated by pouring the solution into water and acidifying with hydrochloric acid to remove the pyridine. The solid precipitate was filtered off and extracted with ethyl ether in order to remove unreacted starting compounds. The ρ-Ν, Ν-diphenylaminocinnamic acid was obtained in a yield of 33 H (10.5 g).

Mp = 175.7 -. 177.7 ⁰ C.

Calculated for C ₂₁ H ₁₇ NO ₂ : C: 79.9; H: 5.4; N: 4.4;

Found: C: 79.9; Hi 5.6; N: 4.5.

Example 3: Methyl p-diphenylaminobenzoate

An ethanolic solution of 31 g (0.11 moles) of crude 4-carboxytri phenylamine was neutralized with an alcoholic solution of potassium hydroxide. The ethyl alcohol was then evaporated, ifo the residue was dissolved in 50 ml of dimethyl sulfoxide containing 62 g (0.44 mol) of iodomethane. After stirring for 2 hours the reaction product was isolated by pouring into water.

The deposited precipitate was taken up in benzene and washed. The product was then dried and the solvent was evaporated. The benzoate was in one yield obtained from 3 g. It had a melting point of 88.5 to

89.5 ⁰ C. for C ₂₀ H ₁ , 79.17; H: 5.66; N: 4th .62; Calculated 78.9; H: 5.2; N: 4th , 6. found: r ^u 2 * ^L * C:

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- ίο -

Example 4: Ethyl p-diphenylaminocinnamate

A solution of 20.0 g of p-diphenylaminocinnamic acid (0.635 moles), 2.0 g of p-toluenesulfonic acid (0.010 moles), 400 ml of absolute ethanol and 300 ml of toluene was refluxed for 1 1/2 hours. The solvents were then slowly distilled off, after which the residue was taken up in benzene. The benzene solution was then washed with an aqueous potassium carbonate solution and then with distilled water. After drying, the solvent was removed and the residue was recrystallized from 50 ml of ethanol. The compound had a melting point of 70 to 72 ^° C.

Calculated for C ₂₂ H ₁₉ NO ₂ : C: 80.42; H: 6 ₈ 18; N: 4.08; found} C: 80.0; H: 6.0; N: 4.0.

Example 5 p-diphenylaminocinnamoyl chloride

A solution of 47.1 g (0.15 moles) of p-N, N-diphenylaminocinnamic acid 15 ml of oxalyl chloride in 80 ml of dry benzene were added, whereupon the solution was refluxed for 1 hour was heated. The benzene and excess oxalyl chloride were then removed in vacuo. The remaining red oil was recrystallized from dry ethyl ether. The p-diphenylaminocinnamoyl chloride was obtained in a yield of 45 g. It had a melting point of 122-124 ° C.

Calculated for C ₂₁ H ₁₆ ClNO: C: 75.55; H: 5.96; N: 4.2; found: C: 75.8; H: 5.6; N: 3.9.

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Example 6t p-Diphenylaiainocinnamic acid-K ^ N-diphenylamide

A solution of 4.6 g (0.027 moles) of diphenylamine, 9.0 g (0.027 moles) of ρ-Ν, Ν-diphenylinocinnamoyl chloride and 20 ml of triethylamine in 50 ml of toluene mirde heated for 20 minutes and then left to stand overnight. The solution was then filtered off and the precipitate washed with warm ethanol. The reaction product was obtained in a yield of 6 g. It had a melting point 201.5 to 203.5 ⁰ C.

Calculated for C ₂₅ H ₃₂ N ₂ O: Ci 83.04; H: 5.69; Νί 7.18; Found: C: 83.3; H: 5.5; N: 6.8.

Example 7: p-Diphenylaminocinnamic anhydride

A solution of 31.5 g (0.1 mol) of ρ-Ν, Ν-diphenylaminocinnamic acid in 150 ml of acetic anhydride was heated to reflux temperature for 4 hours. The excess acetic anhydride and acetic acid were distilled off, and the residue was recrystallized from p-xylene. The obtained compound had a melting point of 152-156 ⁰ C.

For C ₄₂ H ₃₂ N ₂ O ₃ JC: 82.31; H: 5.27; N: 4.37; found: C: 81.9; H: 5.2; N: 4.6.

Example 8:

3-fp-Piphynylaminophenyl) -2-butenocic acid

6.54 g (0.1 mole) of zinc dust was placed in a flask. A solution of 28.7 g slowly became from a dropping funnel (0.1 mol) of 4-acetyltriphenylamine and 16.7 g (0.1 mol) of ethyl 2-bromoacetate in 75 ml of dry benzene were added dropwise. The reaction

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was introduced through an iodine crystal, whereupon the rate of the reaction taking place was controlled by the rate of addition of the reaction component addition. After the addition was complete, the solution was heated to reflux temperature for a further 1/2 hour and then cooled aqueous sulfuric acid destroyed. The benzene layer was separated, washed with water and dried and the solvent was evaporated. The residue was recrystallized from methanol. The yield of the reaction product was 3 g. The compound had a melting point of 191-192 ⁰ C.

Calculated for C ₂₂ H ₁₉ NO ₂ : C: 79.96; H: 5.81; N: 4.24; found: C: 80.1; H: 5.4; N: 4.4.

Example 9: Bis (p-diphenylaminobenζal) succinic acid

To 0.1 mole of sodium hydride was added 100 ml of benzene containing 27.3 g (0.10 mole) of 4-formyltriphenylamine and 8.71 (0.05 mole) of diethyl succinate. By external cooling was ensured that the temperature of the reaction mixture did not rise by the exothermic reaction vtrlaufende over 35 ⁰ C. After stirring for 2 hours at room temperature, the solution was acidified by adding 100 ml of 6N hydrochloric acid. The solution was then extracted with benzene and the organic phase was washed with water. After the benzene layer had dried, the solvent was removed and the residue was recrystallized from cyclohexene. The yield of the reaction product was 3 g. The reaction product had a ¹ melting point 211-214 ° C.

Calculated for C ₄₂ H ₃₂ N ₂ O ₄ : C: 80.20; H: 5.14; N: 4.46; found: C: 79.9; H: 4.8; N: 4.4.

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Example 10:

4-N, N-Bis f p-bromophenyl ') aminocinnamic acid

A solution of 27.3 g (0.10 moles) of 4-formyltriphenylamine, 37.4 g (0.21 times) of N-bromosuccinimide, and 0.10 g of benzoyl peroxide in 350
ml of carbon tetrachloride was refluxed for 45 minutes. The solution was then cooled, filtered and
freed from this by evaporation of the solvent. The residue was recrystallized from ethanol. 4 ', 4 ⁿ -Dibromo-4-formyltriphenylamine was obtained in this way in a yield of 26.4 g. The compound had a melting point of 156-159 ° G

Calculated for C ₁₉ H ₁₃ Br ₂ NO: C: 52.92; H: 3.04; Br: 37.06;

N: 3.25;

found: . C: 52.6; H: 3.2; Br: 37.4;

N: 3.0.

50 ml of a pyridine solution containing 10.0 g (0.242 moles) of 4x.4 "-dibromo-4-formyltriphenylamine, 8.0 g (0.078 moles) of malonic acid, and 1 ml
Piperidine was heated on the steam bath for 3 hours,
whereupon the reaction mixture was poured into water. The resulting solution was acidified by adding hydrochloric acid, followed by extraction with chloroform. The received
Chloroform solution was washed with water and then dried over magnesium sulfate. The chloroform was evaporated and the residue was recrystallized from ethanol. The yield
of the reaction product was 8.0 g. The connection had one
Melting point from 87 to 89 ⁰ C.

For C ₂₁ H ₁₅ Br ₂ NO ₂ : C: 53.30; H: 3.20; Br: 33.77;

N: 2.96;

Found: C: 53.37; Hi 3.44; Br: 33.7;

No. 3.0.

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Example 11: Ethyl 2,6-diphenyl-4- (p-diphenylaminophenyl) benzoate

A solution of 10.0 g (0.0405 moles) of 2,6-diphenyl-1,4-pyrone and 10.0 g (0.0409 moles) of triphenylamine in 50 ml of phosphorus oxychloride was heated on the steam bath for two hours and then filtered. The precipitate was washed with ethyl ether, filtered off and dissolved in ethanol. The pyrylium cation was in the form of the fluoroborate salt precipitated, filtered off, washed with ethyl ether and dried. There was a total of 18 g of the crude pyrylium salt obtain"

To 11.0 g (0.02 moles) of the crude 2,6-diphenyl-4-p-diphenylaminophenylpyrylium fluoroborate were added 2.6 g (0.02 moles) of ethyl acetoacetate, 4.48 g (0.04 moles) of potassium t -butoxide and 85 ml t-butyl alcohol are added. The resulting solution was refluxed for 3 hours and then cooled. After cooling, the solution was acidified and extracted with benzene. The benzene solution was then dried and placed in a column of neutral aluminum oxide. Evaporation of the filtrate and recrystallization of the residue from ligroin gave 5.0 g of ethyl 2,6-diphenyl-4- (p-diphenylaminophenyl) benzoate. The compound had a melting point of 64-66 ⁰ C.

Calculated for C ₃₉ H ₃₁ NO ₂ : C: 85.83; H: 5.74; Nj 2.57; found: C: 85.7; H: 6.0; N: 2.5.

Example 12;

1- (p-Diphenylaminophenyl) -i-hydroxy-3-butyne

To 10.0 grams (0.153 moles) of zinc dust was added 27.3 grams (0.10 moles) of 4-formyltriphenylamine and 18.0 g (0.15 moles) of 3-bromopropyne, dissolved in 100 ml of dry benzene and 100 ml of dry tetrahydrofuran was added. The reaction was stopped by adding 2.5 ml of iodine to the Zinc initiated. The iodine was added and the solution was refluxed for 2 hours and then cooled. Closing

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100 ml of 10 L sulfuric acid were added. The benzene layer was separated, washed several times with water and dried over magnesium sulphate * The benzene was evaporated and the residue was chromatographed on silica The chromatography column was then eluted with cyclohexane. A right band was eluted, which after evaporation of the solvent led to 18.0 g of reaction product. '

Calculated for C ₂₂ H ₁₉ NO: C: 83.98; Ht 6.28; N: 4.47; found: C: 84.0; H: 6.0; N: 4.6.

Example 13: 4-hydroxymethyl triphenylamine

A dioxane solution of 4-formyltriphenylamine was a Raney nickel catalyst was hydrogenated at 100 ⁰ C in the presence of. The solvent was then distilled off and the residue was recrystallized from acetonitrile. The reaction product had a melting point of 93-94 ⁰ C.

Calculated for C ₁₉ H ₁₇ NO: C: 82.87; H: 6.24; N: 5.09; found: C: 82.8; H: 6.1; N: 5.2.

Example 14:

1- (p-Diphenylaminophenyl) ethanol

56.0 g (0.195 moles) of 4-acetyltriphenylamine were dissolved in ethanol in Presence of a Raney nickel catalyst at a pressure of 2.80 kg / cm hydrogenated · After the hydrogenation, the ethanolic The solution was filtered and the ethanol was evaporated. A light yellow powder remained. By recrystallization from methanol 58.0 g of reaction product with a melting point of 121 ° C. were obtained.

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Calculated for C ₂₀ H ₁₉ NO: C: 84.93; Hi 6.63; Ni 4.84; found: C: 84.5; H: 6.8; N: 5.1.

Example 15: 4-formyl triphenylamine oxime

2.0 g (0.021 moles) potassium acetate and 5.46 g (0.020 moles) 4-formyl triphenylamine were dissolved in 150 ml of ethanol. Then 1.30 g (0.20 moles) of hydroxylamine hydrochloride in 60% aqueous Ethanol was added, whereupon the solution was left to stand overnight * The reaction product was then recrystallized from ethanol. It had a melting point of 168-169 ° C.

Calculated for C ₁₉ H ₁₆ N ₂ O: C: 79.13; H: 5.60; N; 9.72; found: C: 79.0; H: 5.2; N: 9.6.

Example 16; 4-acetyl triphenylamine oxime

This compound was prepared from 4-acetyltriphenylamine by a procedure as described for the preparation of 4-formyltriphenylamine oxime. The compound had a melting point of 140-141 ⁰ C.

k Calculated for C ₂₀ H ₁₃ N ₂ O: C: 79.43; H: 6.01; N: 9.26; found: C: 79.2; H: 6.1; N: 9.2.

Example 17:

1- (p-Diphenylaminophenyl) hexanol

122.5 g (0.5 moles) of triphenylamine were dissolved in 1 liter of nitrobenzene, whereupon the triphenylamine was added at room temperature was acylated by 70.0 g (0.5 mole) of hexanoyl chloride in the presence of 67 g (0.5 mole) of zinc chloride. After 4 hours, the

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The reaction mixture is hydrolyzed by the addition of ice-cold, dilute hydrochloric acid. The organic layer was washed with water, separated, dried and distilled. The reaction product, namely p-Hexanoyltriphenylamin, distilled at a pressure of 0.2 mm Hg at 200-210 ⁰ C. The yield was 88.0 g, corresponding to 51.5 H of theory. The p-hexanoyltriphenylamine was then dissolved in ethanol and hydrogenated at a pressure of 4.20 kg / cm in the presence of a Raney nickel catalyst for 3 hours at room temperature. The solvent was then removed, whereupon the reaction product remained in the form of a thick oil «

Calculated for C ₂₄ H ₂₇ NO: C: 83.42; H: 7.89; N: 4.05; Found: C: 83.1; H: 7.4; N: 4.3.

Example 18: i-Cp-DiphenylaminophenyDdodecanol

p-Dodecanoyl triphenylamine was prepared in a similar manner to p-hexanoyltriphenylamine. The compound distilled at ei nem pressure of 0.18 mm of mercury at 220 - 23O ⁰ C. The compound was obtained in a yield of 62% of theory. A sample of the ketone was then hydrogenated under the same conditions as described in Example 17 for the hydrogenation of p-hexanoyl triphenylamine. The hydrogenation product was then worked up in the same way as described in Example 17.

Calculated for C ₃₀ H ₃₉ NO: C: 83.85; H: 9.17; N: 3.26; found: C: 84.2; H: 9.2; N: 3.4.

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Example 19: p-diphenylaminostyrene

To a 100 ml flask was 20 g (0.069 moles) of 1- (p-diphenylaminophenyl) ethanol and 0.25 g of potassium hydrogen sulfate * The contents of the flask were then distilled in vacuo. p-Diphenylaminostyrene distilled at a pressure of 0.12 mm of mercury at a temperature of 138 ° C.

Calculated for C ₂₀ H ₁₇ N: C: 88.53; H: 6.33; N: 5.16; found: C: 88.2; H: 6.0; N: 5.4.

Example 20: 3- (p-Diphenylaminophenyl) propionic acid

100 g (0.318 moles) of p-diphenylaminocinnamic acid were dissolved in tetrahydrofuran, whereupon the acid was hydrogenated at room temperature in the presence of a palladium / charcoal catalyst. A complete reduction took 1 hour. After filtering the reaction mixture, the solvent was evaporated _B was recrystallized after which the oily residue from acetonitrile. 80 g of reaction product were obtained. It had a melting point of 126 - 128 ⁰ C.

, Calculated for C ₂₁ H ₁₉ NO ₂ : C: 79.21; H: 6.03; N: 4.40; found: C: 78.8; H: 6.4; N: 4.6.

Example 21: 4-biphenylaminocinnamaldehyde oxime

49.0 g (0.2 mole) of triphenylamine and 25.4 g (0.2 moles) of ß-Diäthylaminoacrolein were dissolved in 300 ml of tetrahydrofuran, and the solution was cooled with an ice bath to 10 ⁰ C.

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16.9 g (0.11 mol) of phosphorus oxychloride were added to ^{the solution at such a rate that the temperature remained below 15 °} C. When the addition of the phosphorus oxychloride was complete, the solution was left to stand for 24 hours at room temperature. Then 36 g (0.64 moles) of potassium hydroxide in 100 ml of 50-Ugern aqueous ethanol were added. The resulting solution was stirred at room temperature for 5 hours and then poured into 2 liters of water. The organic reaction product was extracted with chloroform, whereupon the chloroform solution was washed and dried. After evaporation of the solvent, a red oily residue remained. The residue was taken up in cyclohexane and rt chromatography in a column filled with neutral aluminum oxide. The reaction product had a melting point of 132-135 ° C.

Calculated for C ₂₁ H ₁₇ NO: C: 84.26; H: 5.73; N: 4.68; found: Ct 84.0; K: 5.4; N: 5.0.

Equivalent equivalents of sodium acetate and hydroxylamine hydrochloride (0.0435 moles) were dissolved in a small amount of water. An ethanol solution of 13.0 g (0.0435 moles) of p-diphenylaminocinnamaldehyde was added and the solution was heated on a steam bath for several hours. The solution was then concentrated to half its original volume and then cooled to -5 ⁰ C · The reaction product was obtained g in a yield of 2.0. It had an enamel

point of 134 - 136 ⁰ C. C: 80.22; H: 5 .78; N: 8th , 91; Calculated for C, > 1 ^H 18 ^N 2 ° C: 80.0; H: 5 , 5; N: 8th , 7. found:

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Example 22: p-diphenylaminophenyl vinyl acrylic acid

50 g (0.05 moles) of malonic acid and 7.0 g (0.025 moles) of p-diphenylaminocinnamaldehyde were dissolved in 15 ml of pyridine. 2 ml of piperidine were then added as a catalyst and the solution was heated on the steam bath for 4 hours. The pyridine was then removed by pouring the solution into 1 liter of concentrated water containing hydrochloric acid. The chloroform was washed, dried and concentrated to leave a gummy residue. The residue was recrystallized from methanol. The yield of the reaction product was 2.7 g. The reaction product had a melting point of 86-91 ⁰ C.

Example 23: O-p-Diphenylaminocinnamoyl-p'-diphenylaminobenzaldehyde oxime

6.58 g (0.02 moles) of p-diphenylaminocinnamoyl chloride (prepared as described), 5.76 g (0.02 moles) of 4-formyltriphenylamine oxime and 10 ml of triethylamine were dissolved in 100 ml of tetrahydrofuran. The solution was then stirred for 90 minutes and then poured into 600 ml Poured water. The organic reaction product was extracted with chloroform. The chloroform solution was then washed with aqueous Hydrochloric acid and an aqueous base, and then dried. The residue was recrystallized from acetonitrile. The yield of the reaction product was 6.0 g. The melting point of the reaction product was 174-178 ° C.

Calculated for C ₄₀ H ₃₁ N ₃ O ₂ : C: 82.01; H: 5.3-4; N: 7.18; found: C: 82.4; H: 5.6; N: 7.3.

The organic reaction product was extracted with chloroform.

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Example 24:

p-Diphenylaminobenzyl-p'-diphenylaminocinnamate

⁶ »5 S (0.02 moles) of p-diphenylaminocinnamoyl chloride, 5.5 g of 4-hydroxymethyltriphenylamine and 10 ml of triethylamine were dissolved in tetrahydrofuran. After stirring for 90 minutes at room temperature, the solution was poured into water containing hydrochloric acid. The organic reaction product was extracted with chloroform, and the chloroform layer was washed with aqueous hydrochloric acid and aqueous base. After drying, the chloroform was evaporated, leaving a yellow, oily residue. The residue precipitated from ethanol in the form of a gum. The gum was dried to a powder in vacuo. The yield of the reaction product was 2.0 g. The compound had a melting point of 68 70 ⁰ C.

Calculated for C ₄₀ H ₃₂ N ₂ O ₂ : C: 83.8.7; H: 5.64; N: 4.89; found: C: 83.7; H: 6.0; N: 5.1.

Example 25: p-Piphenylaminophenylvinylacrylaldehyde oxime

Equimolar amounts of N-methyl-N-phenylaminovinylacrylaldehyde and triphenylamine were converted to p-diphenylaminophenylacrylaldehyde in the presence of phosphorus oxychloride. To Recrystallization was the reaction product with a like equimolar amount of hydroxylamine hydrochloride reacted in the presence of pyridine at room temperature. Thus became p-diphenylaminophenylvinylacrylaldehyde oxime obtained in good yield.

Example 26: Methyl p-diphenylaminocinnamate

Potassium p-diphenylaminobenzoate was made by neutralization the acid with alcoholic potassium hydroxide. 33.5 g

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Potassium p-diphenylaminobenzoate (0.095 moles) and 40.0 g (0.28 moles) of iodomethane were dissolved in 200 ml of dimethyl sulfoxide. After 45 minutes the solution was poured into 1000 ml of water which had been saturated with sodium chloride. The organic reaction product was then extracted with chloroform. After washing the chloroform solution with an aqueous base, the solution was dried and the chloroform was evaporated off. The residue was recrystallized from 200 ml of methanol. The yield of the reaction product was 20.0 g. The melting point of the reaction product was 108-109 ^° C.

Calculated for C ₂₂ H ₁₉ NO ₂ : C: 80.21; H: 5.84; V: 4.25; Found: C: 80.24; H: 6.0; N: 4.4.

Example 27:

1-f4-Diphenylaminojnaphthacrylic acid

To 150 ml of cold N, N-dimethylformamide, 33.7 g (0.22 moles) of phosphorus oxychloride were slowly added with vigorous stirring. 59.1 g (0.20 mol) of 1-diphenylaminonaphthalene (see reports,, 23, page 2536 ^ ~ * 189O_7) in a mixture of 100 ml of Ν, Ν-dimethylformamide and 200 ml of dichloromethane were then slowly added to the resulting solution . When the addition was complete, the solution was heated on a steam bath for 16 hours. The . Solution was then poured into an ice-water mixture and neutralized with potassium acetate. The aqueous layer was decanted off and the dark oily residue was taken up in chloroform. The chloroform solution was washed with water and dried, after which the chloroform was evaporated. The dark oily residue obtained was then taken up in cyclohexane and passed through a column therein which was filled with neutral aluminum oxide. The yellow filtrate was evaporated and the residue was recrystallized from cyclohexane. In this manner had a melting point of 116 _r 5 28.1 g-diphenylamino-i-naphthaldehyde 4 - obtain 118 ⁰ C.

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Calculated for C ₂₃ H ₁₇ NO: Ci 85.41; Hi 5.31; N: 4.33; found: C: 85.4; H: 5.2; N: 4.3.

23.0 g (0.22 moles) of malonic acid and 21.0 g (0.065 moles) of 4-diphenylamino-1-naphthaldehyde were dissolved in 45 ml of pyridine. 1 ml of piperidine was then added to the solution and the solution was heated on the steam bath for 5 hours. After that, it was poured into water. The resulting solution was acidified by adding concentrated hydrochloric acid and the crude reaction product was filtered off. The reaction product was dissolved in chloroform, and the chloroform solution was washed with dilute hydrochloric acid. After the chloroform solution had been dried, the chloroform was evaporated and the residue was recrystallized from ethanol. The yield of reaction product having a melting point of 247 - 248 g was ⁰ to C 16.

Calculated for C ₂₅ H ₁₉ NO ₂ : Ci 82.16; H: 5.25; N: 3.83; found: Ct 81.9; H: 5.2; N: 3.7.

Example 28: p-Diphenylaminobenzoic acid ° N, N-diphenylamide

0.15 moles of p-diphenylaminobenzoyl chloride was 0.15 moles Diphenylamine heated in toluene and left to stand overnight. The resulting solution was filtered, whereupon the precipitate was washed with ethanol. The reaction product was obtained in good yield.

Example 29:

ρ-Diphenylaainobenzoylchloride

To a solution of 0.15 mol of p-diphenylaminobenzoic acid in

80 ml of dry benzene was added 0.15 moles of oxalyl chloride,

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whereupon the resulting solution is refluxed for 1 hour was heated. The benzene and the residual oxalyl chloride were peeled off in vacuo. The reaction product was recrystallized from dry ethyl ether. The reaction product was in obtain favorable yield.

Example 30i 7-diphenylaminocoumarin

The compound was made by the condensation of diphenylamine and 3-iodoanisole in the presence of potassium carbonate. The 3-methoxytriphenylamine obtained was hydrolyzed with aluminum chloride, whereby 3-hydroxytriphenylamine was obtained. This compound was made by reacting with N, N-dimethylformamide in the presence converted from phosphorus oxychloride to 3-hydroxy-4-formyltriphenylamine. The intermediate obtained was treated with acetic anhydride heated in the presence of sodium acetate, resulting in 7-diphenylaminocoumarin.

Example 31; p-Diphenylaminobenzoic anhydride

The sodium salt of p-diphenylaminobenzoic acid was prepared by treating the acid with potassium hydroxide. This compound was then treated with p-diphenylaminobenzoyl chloride to give the Anhydrides implemented.

Example 32: p-Diphenylaminocinnamy! alcohol

The compound was prepared by reducing p-diphenylaminocinnamaldehyde with lithium aluminum hydride in tetrahydrofuran.

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Example 33:

7- (p-Diphenylaminophenyl) -2,4,6-heptatrienoic acid

5- (N-Methylanilina) -2,4-pentadien-1-al (Th. Zincke, Ann. Volume 338, page 127) was reacted with triphenylamine in the presence of phosphorus oxychloride to form 4-diphenylaminophenylvinylacrylaldehyde. The compound obtained was then reacted with malonic acid in the presence of pyridine and piperidine to give 7- (p-diphenylaminophenyl) -2,4,6-heptatrienoic acid.

Example 34:

1,3-bis (p-diphenylaminophenyl) -1-phenylprop-2-en-1-oil

Made to 10.8 g (0.02 moles) of 4,4'-bis (diphenylamino) chalcone as described in Belgian patent 710 239, in 100 ml of tetrahydrofuran there were 0.02 moles of phenyllithium admitted. After 1 hour, aqueous ammonium chloride was added to the solution. The tetrahydrofuran layer was separated and evaporated. The resulting residue was extracted with chloroform, whereupon the chloroform solution was dried and the chloroform was evaporated. The reaction product was identified by infrared analysis.

Example 35: 4- (p-Diphenylaminophenyl) -3-buten-1-yn

1- (p-Diphenylaminophenyl) -1-hydroxy-3-butyne was prepared according to the method described by S. Ellington and M.C. Whiting in J.C.S. 1950, pages 3650 3656, dehydrated in the manner described by treatment with tosyl chloride and pyridine. The compound was in good yield obtain.

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- 26 Example 36: 4-Hydroxytriphenylamine

To a solution of 100 g (0.363 moles) of p-methoxytriphenylamine in 500 ml of toluene was added 48.3 g (0.363 moles) of anhydrous alurainium chloride. ^{The temperature of the solution was kept below 55 °} C. during the addition of the aluminum chloride. After the addition had ended, the solution was heated on a steam bath for several hours. The solution was then cooled and the toluene decanted. The remaining aluminum complex was hydrolyzed by adding 18% strength aqueous hydrochloric acid. A dark image separated which was separated and partially dissolved in acetonitrile. The Ac © t © ° nitrile was evaporated, leaving an oil that solidified on standing. The solid reaction product was then recrystallized from dichloromethane. There were 73.5 g of reaction product having a melting point of 126 - 128 ⁰ C obtained.

Calculated for C ₁₈ H ₁₅ NO; C: 82.77; H: S ₉ SO; N: 5.36; found; C: 82.6; H; 5, S ^ N: 5.2.

Example 37t 2-hydroxytriphenylamine

Diphenylamine and 2-iodoanisole were found in the method described by CF. Wieland in Ber. £ 3, 699-712 (1910) condensed. The compound had a melting point of 103-105 ⁰ C and was identified as 2-Methoxytriphenylamin.

Calculated for C ₁₉ H ₁₇ NO: C: 82.87; H: 6.23; N: 5.09; found: C: 83.4; H: 6.3; N: 5.2.

By hydrolysis of 2-methoxytriphenylamine with aluminum chloride 2-hydroxytriphenylamine was obtained. The hydrolysis was carried out as described in Example 36. The obtained 2-hydroxytri-

9 0 9 8 A 6 IA Xl 3

- 27-phenylamine had a melting point of 106 - 108 ⁰ C.

Calculated for C ₁₈ H ₁₅ NOi C: 82.77; Hi 5.80; N: 5.36; found: C: 82.4; H: 5.6; N: 5.4.

Example 38: 4-formyl triphenylamine semicarbazone

Equimolar amounts of 4-formyltriphenylamine semicarbazide hydrochloride and sodium acetate were reacted with one another in aqueous ethanol at room temperature. The deposited precipitate was isolated and recrystallized from alcohol. The reaction product was obtained in good yield. It had mp 185-187 ⁰ C.

Example 39: 4-acetyl triphenylamine semicarbazone

The compound was prepared as described in Example 38, with the exception that 4-acetyltriphenylamine was used as a starting point instead of 4-formyltriphenylamine. The reaction product was obtained in good yield. It had a melting point of 177 - 178 ⁰ C.

Example 40: 4-diphenylaminocinnamaldehyde semicarbazone

The compound was prepared as described in Example 39, with the exception, however, that 4-diphenylaminocinnamaldehyde was used as the starting compound instead of 4-formyltriphenylamine. The compound was obtained in good yield «

As already explained, the new substitutes are suitable Triphenylamines are excellent photoconductors in electrophotographic recording materials. In the following, the use

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generation of the new compounds as photoconductors in electrophotographic Recording materials are described in more detail:

First, a coating compound of the following composition was made manufactured:

Organic photoconductor 1.0 g

Polymeric binder 1.0 g

Sensitizer 0.02 g

Methylene chloride 11.7 ml.

This coating compound was then applied to a conventional aluminum support, which was kept at a temperature of about 38 ^° C., to form an electrophotographic recording material. The thickness of the applied layer was measured wet about 0.010 cm.

P-Diphenylaminocinnamic acid was used as the photoconductor and as a sensitizer, 2,4-bis (4-ethylphenyl) -6- (4-styrylstyryl) pyrylium perchlorate. The binder consisted of a copolymer of vinyl meta-bromobenzoate and vinyl acetate. The obtained recording material was then corona discharged in a dark room to a potential of charged about +600 volts. The layer was then covered with a transparent template that was opaque and light transmitting Districts and thereby using a daylight emitting lamp with an intensity of about 75 lux (75 Meter candles) exposed for 12 seconds.

The resulting electrostatic latent image then became conventional Way developed by cascade development by applying a mixture of negative over the surface of the recording material

90.9846 / 1273-

negatively charged black, thermoplastic toner particles on glass beads, which served as supports, was applied. This made a cheap reproduction of the original obtain.

Similar results were obtained using the others described substituted triarylamines, for example p-diphenylaminobenzoic acid, obtain.

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Claims (2)

- 30 patent claims 1) Substituted triarylamines, characterized by one of the following Formulas: and N Ar, cC * I Γ where mean: Ar.j and in each case an optionally substituted phenyl radical; an optionally substituted phenylene or naphthylene radical; (a) a carboxyl radical; (b) an ester residue; (c) an acyl halide residue; (d) an amido radical; (e) an optionally substituted alkylidynoximido radical; (f) a hydroxyl radical; 9 0 9 846/127 3 (g) an optionally substituted ethynyl radical; (h) a carboxylic acid anhydride residue; (i) a short-chain alkylenecarboxy radical; Cj) a short-chain alkylene hydroxy radical; (k) a semicarbazono radical or (1) an optionally substituted phenylenecarboxyl radical; X (a) is a carboxyl radical; (b) an ester residue; (c) an AcXyl halide residue; Cd) an amido radical; Ce) a hydrogen atom; (f) an ethynyl radical; Cg) a methylidynoximido radical; Ch) a carboxylic acid anhydride residue; Ci) a semicarbazono radical; Cj) a hydroxyl radical; Ck) a short-chain alkylenecarboxyl radical; Cl) a short-chain alkylene hydroxyl radical or Cra) a phenylenecarboxyl radical; η = 1, 2 or 3; R and R ₂ each represent a short-chain alkyl radical, an optionally substituted phenyl radical or a hydrogen atom. 2) Substituted triarylamines according to claim 1, consisting of: 909846/1273 Methyl p-diphenylaminobenzoate; * Ethyl 2 _# 6-diphenyl-4- (p-diphenylaminophenyl) benzot; 1- (p-Diphenylaminophenyl) -t-hydroxy-3-butyni 4-hydroxymethyl triphenylamine; 1- (p-diphenylaminophenyl) ethanol; 3- (p-Diphenylaminophenyl) propionic acid i 3-p-diphenylaminopheny1-1-propanol; 4-hydroxytriphenylamine j 2-hydroxytriphenylamine; 4-formyl triphenyl arainoxime; 4-acetyl triphenylamine oxime; 1- (p-diphenyiaminophenyl) hexanol; 1- (p-DiphenyXaminophenyl) dodecanol; 7- (p-Diphenylminophenyl) -2,4,6-hept »trienoic acid; p-diphenylaminobenzoic acid; p-diphenylaminobenzoyl chloride; p-diphenyleminostyroX; Xthyl-p-diphenyläminocinnmnate \ Methyl-p-dipJienylnmiuocinnamet} p-diphenylaminocinnamoyl chloride; p-Diphenylaminocinnainic acid-N ^ N-diphenylitmidi p-diphenylaminocinnovinhydride; 3- (p »diphenylaminophenyl) ~ 2-but # noeflure; Bis (p-diphenylaminobenz * l) amber * tcin5 acidi 4-N, N-bis (p-bromophenyl) aminociiiniunijic acid 1- (4-Diphenyliuiiino) naphth * cryl "aur" i 4-acetyltriphenylamine 5emicarbazone; p-diphenylmainocinninic acid; 7- (p »diphenylaminostyryl) couraarin} 4-acetyltriphonylamine semicarbazone; p-Dipheny! "minopheiiy lviny lacrylaldehydoxime} 0-p" -Diphenylainiiioeinnamoyl-p ^f -diphenylajniiiobenziildehydoxifflj ρ-diphenylaminocinnamaldehydoxime; 1,3-bis (p-diphenylaminophenyl) -1-pheny! Prop-2-en-1-ol; p-Diphenylaminobenzyl-p'-diphenylaminocinnamate or 4-diphenyltminocinnamaldehyde semicarbazone.