DE1959594C3 - Derivatives of 3-carboxyamido-benzenecarboxylic acid alkyl esters and light-sensitive, color photographic emulsions containing them - Google Patents

Description

H, N

(II)

/ - ('OCH, ■ COHN--

where X and R have the same meaning as in the formula ί have made with Ä'.hylhenzolacetat. This mentioned Intermediate product can be obtained by transesterification of methyl 3 - aminobenzoate. Methyl-3-amino-4-lower a! Ko \ yben / oate or methyl 3-3011110-4-halobenzoate with a higher aliphatic alcohol. e.g., n-dodecyl alcohol, isotridecyl alcohol and 2-ethylhexyl alcohol can be obtained.

Of d: n couplers of the above general formula 1 are those where R is a straight chain Alkyl group, in terms of solubility in high boiling points Inferior to solvents, and those. in which R is a branched alkyl group, are very difficult to manufacture since the intermediate of formula 11 is obtained in an oily form and is difficult to crystallize, a large amount of that is still used as a starting material Contains higher alcohol mixed in, and in accordance with the subsequent condensation with ethyl benzoylacetate or isolation of the condensation product becomes very difficult.

It has now surprisingly been found that the new Yellow couplers of the following general form! 111 have excellent solubility in high boiling solvents and are very useful as Are "protected" matchmakers.

The present invention relates to prevention the general formula

where X door is hydrogen, lower alkali or halogen and R is an alkyl radical containing s or more Carbon atoms with possiblyN -cr / weigier COCHCOHV

(Uli

COOCM COOR,
R,

in which X is hydrogen or halogen, Y is hydrogen. lower alkyl, lower alkoxy, aryloxy or halogen, R ₁ tert-butyl or phenyl, R, hydrogen or Cj-C ₁₄ -AlKyI, optionally branched, R ₃ C ₁ -C _ls- alkyl, optionally branched, the sum of the Carbon atoms of the radicals R ₂ and R _{3 is} 8 or more.

The invention also relates to a light-sensitive, Color photographic emulsion, which is characterized in that it is a compound of the foregoing given formula as a Geibkuppler contains.

According to a preferred embodiment, the light-sensitive color photographic emulsion additionally contains nor a common chemical or optical sensitizer.

The preparation of the Cielbkupplei used according to the invention of the above formula 111 to ! ate the condensation of a compound of the formula

H ₂ N - ^ _ ^ (IVi

COOCH COOR,

before in Rj. R, and Y have the same meaning w in formula 111 have, with ethyl pivaloyUicetat or a subsii: uiertcn or unsubstituted AtInlben? .o> [acetal. i) The above compound of the formula IV will result from the fact that 3-aminobenzoic acid or 3-amino- · 4-subsiluicrte-benzoic acid with a 2-lUogenfeu-S. arrester is implemented. The starting materials that Used for the preparation of the new couplers are readily available and at low cost Maintain costs on a technical scale. Except ι item only needs three to three to complete the manufacturing process four steps. Accordingly, according to the briinduiiu used couplings, extremely light Viigiiiiülich and very cheap.

The solubility of the according to the invention ι * agitated couplers in high-boiling solvents luder organic ester solvents. z. B. Dibunl-Iphthulat. Triphenyl phosphate or allyl acetate is remarkably improved in terms of introduction the alkoxycarbonyl group in the a-posi- <· tion of the alkyl group of the carboxylic acid ester, as from the formula 111 can be seen. These couplers can therefore in the form of a stable solution of high con / enti ation isolated / .l and to a foiogialisehen Emulsion added in a sufficient amount - ■ be to a photosensitive. Graphic painterly hcr / .usielicn. that a color image around hrlm density results.

In those compounds of l-'ormellll. in which \ is hydrogen and R ₁ . R- and R-, which have a meaning, and in which the Siibsiuueni Y is hydrogen, a lower alkali lip, a lower alkoxy group. an Ai} lo \ _ \ group oilei sees a haloücnatoin, changes the I ö-liclii.cu according to the following. ') nimiii'.! ■ · ■

lower alk '' \\ Wav-, ΊΜοΓΙ - ■ lower ··
\ lk \! .- ■ \ · \ low - 1 knot

For the compound in which Y stands for a chlorine atom. the solubility of the coupler is, for example, reduced to ₃ to ¹ J of the solubility of that coupler in which Y is a methoi ^ y group.

The solubility of the couplers can, however, be increased in particular by stirring in an alkyl group _{as R 2} or by replacing a straight-chain alkyl group with a branched alkyl group _{as the R 3 radical.} The conversion of the substituent can be effected by using an agent according to the intended purpose. For example, monochloroacetic acid. u-bromopropionic acid. u-bromo-η-butyric acid. <i-bromoisobutyric acid, u-bromo-caprylic acid, or a-bromo-lauric acid used to convert R ₂ , and lauryl alcohol. 2 - ethylhexanol. 2 - octyl alcohol. 7 - /.th> 1 - 2 - methylundecanol - 4 or diisobutylcarbinol are used _{to change R 3} These fatty acids and alcohols are all readily available and commercially available. The α-halogen fatty acid esters can be produced synthetically in good yield and very high purity, so that no admixture of starting material is observed in the crude product if the α-halogen fatty acids are reacted with alcohols in an equivalent molar ratio.

Furthermore, the intermediate of the formula 1 is v \ which by reaction of a substituted or unsubstituted aminobenzoic acid with a ./-Haiogenfeitsäureester in an equivalent molar ratio is available. so pure that no contamination by raw material can be observed in the crude product! will. Therefore, no complicated isolation and cleaning steps are required. In terms of this high purity of the intermediate of formula IV The condensation with i-keio acid esters is smooth before see, and the condensation product obtained can be isolated easily. It is evident from the above explanations that the couplers according to FIG Invention easily m technically simple way under can be produced at low cost Lind that thereby a considerable technical ί orischnii is achieved.

In addition to the advantages set out above, the couplers employed in accordance with the invention possess improved photographic tiuen.sc.Kilun. They can produce a luxh-dense color image and show a reduced formation and desensitization. In addition, a photographic material can be obtained from the emulsion according to the invention, which has a highly transparent color image, since the coupler is well dispersed in view of its good solubility in the high-boiling solvent good spectral absorption properties and are particularly real to light. Warmth and moisture. You don't suffer from one; Discoloration or bleaching, \ etursachi from various chemicals. In particular, couplers with R, .iN tertiary Bunlgn.ppe or Phenylgi type create · .wukrgevwhnlki] eclv.e Faihbilder. It was established that the maximum absorption of each larb image / by Ui'iiien wavelength range is 1 "· ■ η \ er different! When the carbon atoms of the remainder R in.:.: Compound de: I-'onne !! 11 becomes longer at the same time as those slugs, m. Those R _: em W. V. ^ R stollaioin or a short / Kcinge Alk> Igruppi means! Hnspie '-. Wise /.igei' die Kupple! -. Kt follow-up

6 and 7 crumble a maximum absorption at 450 and 460 ΓΠμ respectively. This means that the manufacture of a sensitive, color photographic material is possible, that meets the respective requirements piss if the appropriate length of the carbon chain as R, alkyl group present is selected.

"Typical couplers according to the invention are mentioned below, for example:

(1)

ί— COCHXOHN - f COOCH ₂ COOC ₁₂ H ₂₅ In)

(F. 99 to KHCi

(3)

(4)

(dl

(7)

> - COCHXOHN-

"? - COCH, COHN-, COOCHXOOC ₁₂ H ₂₅ In)
OCH,

COOCH - COOC _{1 (} , H ,, (n)

CH.,

; - COCHXOHN - < COt) CH ₂ COOCH ₂ CHC ₄ H ₄ In)
C ₂ H ₅

COC I1X0HN - ^{/ y}

COCIf, COH N

COC! 1, COlIN CuOCH ₂ C OOCIH, 11 ₁ , ml
CH,

(<X) CH - COOC ₁₂ H ₂₅ InI
CH,

(■ < ) () ( Ί! I I) (If i I in i

(F. 101 to 103 C.

(F. 7! V to 79 C

(F. 9 7 to 9S C

(F. 95 to 97 Cl

'F. 88 to 89 C:

(F. 9 (i to 9 "Cl

OCH.,

- COCHXOHN

(F. 100 to 102 C.

COOCH - COOC ₁₂ H ₂₅ InI CH ₃

(9) HXO

0 <

COCHXOHN - <' ^CH3

CHXH

(F. 65 to 66 C)

COOCHXOOCH CHXHXH - C ₄

CH _:

Cl

COCMXOHN

COOCHXOOC _i: H ₂₅ (n)

oca, c

V- COCHXOHN — f

COOCHXOOC ₁₂ H ₂₅ (n |

(F.vlbk93C)

(F. 99 to 103 C.

Ci

Cl

; ' COCHXOHN— \ ^

COOCHXOOC ₁₂ H ₂₅ In)

iF. 70.5 to 71.5 C)

(13) Ch ₁ -X-XOCHXOHN-. "

^CH - ^3rd

COOCHXOOC; H _{: 5} (n)

C!

COCHCOHN - ^:

^C1 COOCHXOOC _1: H _{; 5}

Cl

■ .— COCHXOHN

COOCHCOOC ₂ H ₅

C, .H ₂₁₁ In) (F "2 to 74 C

(F.? * J to 61 C)

(F. 53 to 55 C.

409 619.326

A light-sensitive, color photographic material is prepared as follows: A yellow coupler of formula III is in a high-boiling solvent with a boiling point of IKO C or above uic Tricresyl phosphate or dibutyl phthalate or a - ' low-boiling solvent! like butyl acetate or: butyl propionate dissolved. Occasionally the coupler may be dissolved in a mixture of these solvents. The resulting solution is mixed with an aqueous gelatin solution containing a surface-active agent; contains. The mixture is emulated in a high-temperature rotary mixer or in a colloid mill and then immediately added to a light-sensitive silver halide photographic emulsion. The photographic emulsion thus obtained is> ^ a carrier such as a film carrier or a barite paper applied and dried to remove most of the low-boiling solvent. Alternatively, the emulsified mixture is charged by cooling to solidify, in noodle shape; extruded and \ >> m low-boiling solvent for example freed by washing them with water. Then they are under Warming is added to the photographic emulsion, which is then processed in the same way as described above is working to be a photosensitive, color photographic Material to receive. The Manufacture of the Photographic. Materials is not on here for example mentioned method is limited. Other modifications can also be practically applicable.

The coupler is preferably used in the photographic emulsion in an amount of 10 to 100 g per mole of the silver halide contained in the emulsion given. The mentioned area is: but not critical. The photographic emulsion used according to the invention may contain any silver such as silver chloride, silver iodide, and silver bromide iodide. the Emulsion can furthermore be caused by a chemical sensitizer, for example a sulfur sensitizer. a natural sensitizer found in the gelatin, a reducing sensitizer or a precious metal salt sensitizer. The photographic emulsion can further contain photographic additives, as are customary can be used, for example antifoggants.

Stabilizers. A η tiveryellowing agent. An anti-diffusion medication. polymeric modifiers or coating auxiliaries. As the optical sensitizer for the photographic emulsion, any of known ones can be used Carhocyanine or merocyanine dyes can be used. When using photographic emulsions spectral sensitivity can be applied in double layers in the same area, the Couplers according to the invention can be contained in only one or in both layers.

The light-sensitive photographic Materials can then undergo exposure or irradiation using X-rays, visible light or! exposed to infrared and then treated with a developing agent that mainly one. P-phenylenediamine series developer contains. After bleaching and fixing, a yellow color image of high density with good results is obtained spectral absorption properties. the one maximum Has absorption at 450 to 465 ma. Such a color image is also excellent Transparency and authenticity to light. Warmth and moisture.

Typical developing agents according to the invention can be used to treat light-sensitive photographic materials, are the sulfates. Sulfites and hydrochlorides of the following Links:

N.N-diethyl-p-phenylenediamine.

N-Ethyl-N -. ^ - methanesulfonamnioäitul-3-me; hyi-4-aminoaniline.

N-ethyl-N-hydroxyüihyl-p-phenylenediamine.
N-ethyl-N-hydroxyethyl-2-methyl-

p-phenylenediamine and
NN-diethyl-2-methyl-p-phenylenediamine.

The yellow couplers used according to the invention were made with known couplers of similar structural formulas compared with regard to the melting point and de: solubility in high-boiling solvents. Solubility is determined by determining the amount (ml) of dibutyl phthalate, du is required. to completely loosen 1 g of the coupler at h0 C. The results are in the table put together.

table

Shape!

Bcnoiiinc

1- I O: amount of dibun ! phth.il.ii (ml

New coupler (61

Cl

COCH ₂ COHN- ^

COOCHCOOC ₁₂ H ₂₅ CH ₃ «8 89

11th

Fortset / imu

l-'ormcl

Known coupler (Japanese patent 55S2 19671

Cl

- COCH ₁ COHN

COOC ₁₂ H ₂₅

New coupler (13) CH,

Cl

CH ₃ - C - COCH ₂ COHN - / '>

CH.,

COOCH ₂ COOC ₁₂ H ₂₅

Known coupler (U.S. Patent 3,265,506)

CH ₃ ^C l

CH ₃ - C - COCH ₂ COHN ~ \ ^ "/

^CH - ¹ NHCOCH, O -

12th

I I (I J MlMIJC l) lhll '\ l

; phih.il.ii null

loo!

72 74 140

0.5

10

New coupler (3)

<f V-COCH ₂ COHN-;

New Coupler (5)

V-COCH ₂ COHN

OCH,

COOCH - COOC _{1 (} , H ₃₃ Ui CH,

Cl

COOCH ₂ COOCi IC "H,., (N) CIi ₃

New Coupler (15)

Cl

V- COCHXOHN%

COOCHCOOC ₂ H ₅

New Coupler (14)

Cl

> ~ cocHCOHN - .:

i
Cl

COOCHXOOC ₁₂ H ₂ S (Ii)

78 79 95 91

- 55

59-61

0.4

continuation

l-onuel

New Coupler (12)
Cl

\\ - COCH ₂ COHN

New coupler (1)

COOCH ₂ COOC ₁₂ H ₂₅ (n)

New Coupler (8)

^ -COCH ₂ COHN —t?

COCH ₂ COOC, jH ₂₅ (n) OCH ₃

COOCH - COOC ₁₂ H ₂₅ (n) CH ₃

New coupler (7)

COOCH-COOC ₄ H ₉ In)

C ₁₁ H ₁₃ (n)

ι- ι egg

70.5-71.5

Needed

Amount of Dibui \ l-

phtlialat ImIl

99-101 0.7

100-102

1.0

96-97

1.0

From Table 1 it can be seen that according to the Invention used new couplers lower melting points and better solubility in high boiling points Solvents have known couplers as the comparatively used. From this it follows found that the new couplers of the invention are very useful as "protected" type couplers.

The present invention will now be further illustrated by means of the following examples.

example 1

20 g of the coupler of the above formula 3 are in a mixture of 20 ml of dibutylphthalal and 60 ml Butyl acetal dissolved at 80 ° C. The resulting solution is treated with 10 ml of an aqueous solution of 10% AIk) I-inaphthalenesulfonal and 200 ml of an aqueous 5 "gelatin solution are mixed. The resulting mixture is treated in a colloid mill. The coupler dispersion obtained becomes 1 kg of a highly sensitive, given photographic gelatin silver iodobromide emulsion, which is then applied to a film support and is dried.

The light-sensitive photographic material thus obtained is exposed to light in the usual manner and then Treated for 10 minutes at 20 C with an Ennviekler solution of the following composition: N.N-diethyl-p-phenylenediamine-

hydrochloride

Sodium sulfite anhydrous

Sodium carbonate (monohydrate) ... potassium bromide

2.5 g 2.0 »82.0 c 2.0 g water up to 1000 ml

The developed film is stopped and fixed in the usual way and then after 10 to 15 Mi has been washed with water for a long time. For 5 minutes with a bleach bath of the following: composition treated:

Potassium ferricyanide 100 g

Potassium bromide 50 g

Water up to 1000 ml

The film is wetted with water for 5 minutes; and then in a fixie for another 5 minutes treated bath of the following composition:

Sodium thiosulphate (pentahydrate) .... 250 g water up to 1000 ml

The film is then washed in water for 20 to 25 minutes and dried. It will be so e brilliant yellow color image with a maximum absorption at 455 μm.

Example 2

10 g of the above coupler eggs Formula 13 are dissolved at 6O ⁰ C in a mixture of 10 ml of tricresyl phosphate and 30 ml of butyl acetate. The solution obtained is mixed with 5 ml of an aqueous solution of 10% alkylnaphthalene sulfonate and 200 ml of an aqueous solution of 5% gelatin. The mixture is treated in a colloid mill. The dispersion obtained is added to 500 g of a gelatin silver iodobromide emulsion, which is then applied to a film support and dried.

The photographic material obtained in this way is exposed to light and for 10 minutes at 20 ° C. with a developer solution treated with the following composition:

Methylaminophenol 3.0 g

Anhydrous sodium sulfite 60.0 g

Hydroquinone 6.0 g

Sodium carbonate anhydrous ... 50.0 g

Potassium bromide 1.0 g

Water up to 1000 ml

After it has been stopped, hardened and washed with water in the usual way, the material is exposed to white light and then ^{treated for 12 minutes at 20 °} C. with a developer solution of the following composition:

Ν, Ν-diethyl-p-phenylenedici.jiin-

hydrochloride

Sodium sulfate anhydrous

Sodium carbonate (monohydrate).
Potassium bromide

treated at 20 ° C with a developer solution of the following composition:

5, Ou
2.0 g
82.0 c
1.0 g
Water up to 1000 ml "

The developed material continues to be stopped, fixed, washed with water and bleached and then Washed with running water for 20 minutes and dried. It will be such a yellow color picture of good transparency with a maximum absorption at 450 ιτίμ obtained.

Example 3

10 g of the above coupler of formula 6 is dissolved at 50 ^c C in 20 ml of dibutyl phthalate. The solution obtained is mixed with 5 ml of an aqueous solution of 10% alkylnaphthalenesulfonal and? 00: nl of an aqueous 5% gelatin solution. The mixture is passed through a colloid mill several times to make a dispersion. The dispersion obtained in this way is added to 500 g of a gel gelatin silver chloride bromide emulsion, which is then applied to a barite paper and dried.

The photographic light-sensitive material thus prepared is exposed to light and then for 10 minutes N-ethyl-N-hydroxyethyl

p-phenylene diamine sulfate

Sodium sulfite anhydrous

Hydroxyamine hydrochloride

Sodium carbonate (monohydrate).
Potassium bromide

40

45 2.5 g
2.0 g
1.0 g
82.0 g
2.0 g
Water up to 1000 mi

The developed material is then treated with a stop solution containing 10 ml of glacial acetic acid, 3.0 g of sodium hydroxide and 1,000 ml of water. Immediately thereafter, it is treated with an acidic hardness fixing solution for 4 minutes. After washing with water for 10 minutes, the material is ^{treated for 8 minutes at 20 °} C with a bleach bath of the following composition:

Ethylenediamine disodium salt

letraacetic acid 40.0 g

Ferric chloride 30.0 g

Sodium carbonate (monohydrate) .. 20.0 g

Potassium bromide 30.0 g

Sodium thiosulphate (pentahydrate) .. 200.0 g

Water up to 1000 ml

The material is rr> for 20 minutes ^; Washed in water and then treated with a Sidbiiir.ieiba-I for 2 minutes and dried. A yellow color image with a maximum absorption at 450 πΐμ is obtained. This picture shows excellent fastness to light and heat ^Q uch N ¹ I storage.

If the coupler of the formula 7 is used in a similar manner in place of ^J - «s coupler of the formula 6, a yellow color image is obtained with a maximum absorption at 460 μm with excellent fastness to light and heat and good storability.

Example 4

2.0 g of the above-mentioned coupler of the formula 12 are dissolved in 5 ml of butyl acetate. The solution obtained is with 1.5 ml of an aqueous solution of 10% alkylnaphthalene sulfonate and 20 ml of an aqueous 5% gelatin solution is mixed and the mixture is treated in a colloid mill.

The coupler dispersion obtained in this way becomes 100 g of a blue-sensitive, highly sensitive gelatin silver bromide iodide emulsion given, which is then applied to a film support and dried.

The photographic material thus obtained is then exposed to light and with the developer solution used in Example 1 treated. It becomes a bright yellow Color image with a »· maximum absorption at 460 ΐτίμ receive.

Claims (3)

Patent claims: 1. Compounds of the general formula
Y R ₁ -COCHCOHN- i X COOCH - COOR ₃
R, in which X is hydrogen or halogen, Y is hydrogen, lower alkyl, lower alkoxy, aryloxy or halogen, R _{1 is} tert-butyl or phenyl. R, hydrogen or C _{1 -C 14} -AJkyK optionally branched. R ₃ C _r C ₁₈ alkyl, optionally branched, the sum of the carbon atoms of the radicals R and R _{3 being} 8 or more. 2. Photosensitive, color photographic emulsion, characterized in that it contains a compound according to claim 1 as a yellow coupler. 3. Light-sensitive, color photographic emulsion according to claim !, characterized marked ·, that it additionally contains a conventional chemical or optical sensitizer. As a coupler for light-sensitive, color photographic Emulsions are known to be water-soluble couplers as well as "protected" type couplers which all in one high-boiling solvents are soluble, which is difficult to mix with water. In general, isi a developed color image obtained by developing a "protected" type coupler, more stable to light, heat, moisture and C.vmicalier than one that is water-soluble Coupler was obtained. The known couplers of the "protected" type are not, however, satisfactory. since their solubility wedge in a high-boiling solvent is so bad that they are easily in the Emulsion layer can crystallize out. With regard to the difficult accessibility or the high The price of the starting materials or the complexity of the synthetic manufacturing process are the most important factors Coupler extremely difficult to access and therefore expensive. It is known on the other side that couplers, made from compounds of the fat series are readily available at low cost im With regard to the mass-produced higher fatty alcohols, higher fatty acids or their Derivatives. However, a number of such couplers have poor solubility in high boiling solvents and tends to crystallize in the emulsion layer Extensive research has therefore been carried out to produce couplers, which have a high solubility in high-boiling solvents and using such substances «Lcr Feltreihc can be produced. For example the coupler of the formula COOK Is chain is made by condensation of an intermediate of the formula COOR