DE921668C - Process for the preparation of optical photographic sensitizers - Google Patents

Description

Issued on the basis of the First Lending Act of July 8, 1949

(WiGBl. P. 175)

FEDERAL REPUBLIC OF GERMANY

ISSUED FEBRUARY 24, 1955

GERMAN PATENT OFFICE

PATENT LETTERING

CLASS 57 b GROUP 802

F 3593 IVa / 57 b

Dr. Oskar Riester, Leverkusen-Wiesdorf and Dr. Fritz Bauer,

Offenbach / M.

have been named as inventors

Farbwerke Hoechst Aktiengesellschaft formerly Master Lucius & Brüning, Frankfurt / M.-Höchst

Process for the production of optical photographic

Sensitizers

Patented in the territory of the Federal Republic of Germany on November 10, 1938 The period from May 8, 1945 up to and including May 7, 1950 is not counted towards the patent term

(Ges. V. July 15, 51)

Patent application published May 20, 1954 Patent issued November 11, 1954

Optical photographic sensitizers of the following general constitution are already known:

(CH-CH) _n =
O = C

R ₂

Ri

X "

These sensitizers have two sensitization maxima, which is unfavorable for many photographic purposes, especially for color photographs, because it causes color distortions will.

The invention relates to the preparation of sensitizing dyes more similar per se Constitution, in which, however, the two sensitization maxima practically become a single maximum coincide so that the disadvantages mentioned do not occur.

It has now been shown that by using the thiohydantoin ring instead of the rhodanine ring to dyes of such sensitizing effect which can occur in the following 70 ways:

^N N '

'. = (CH-CH) _n = C O = C

IS

A "

= (CH-CH) _n =

Here, A and B denote the atom groupings necessary to close the ring, such as

Phenylene, naphthylene, Y = Q, S or Se atoms, Alkyl alkyl

- C -, -CH = CH-,

N-alkyl, N-aralkyl or N-aryl groups, R ₁ = alkyl or aralkyl groups, R ₂ = alkyl, aralkyl, aryl groups, X = any acid radical, for example halogen, R — SO7. Toluenesulfalkyl, ClO ₄ etc., η = the number ο, ι or 2.
The intermediate product

.. = - (CH-CH) _n = C O = C

X = S

R ₂ H ₃ C-C ".

Ri

X "

R ₂

V-CH = I.

X "

arises when you mix the relevant thiohydantoin with aldehydes of the general formula

= (CH-CH) _n = (B. /

R.
or intermediates of the general formula

A '\

COCH, ^no

Γ (Γ TT Γ V \\ "M

condensed.

Dyes of this constitution are also characterized by great intensity and are present especially for the sensitization of halogen silver emulsions, especially for those that are diffusion-resistant Contain dye formers, very suitable.

example 1

By condensing equal proportions of methyl-125 allyl-thiohydantoin and 5, 6-dimethyl-i-ethyl-2-

(co-acetoanilinovinyty-benzthiazole-toluenesulfomethylate of the following constitution H ₃ C- / \ - S,

H ₈ C-. JN

CO —CH,

C ₂ H ₈

CHj-CH ₄ -SO ₁ "

in five times the amount of pyridine at 110 °, the following intermediate is obtained after 4 hours: ¹⁰ CH,

H ₃ CH ₃ C-

^v -S.

, N.

= CH-CH =

C ₂ H ₅

C ₃

This compound is heated ^{at no 0 with dimethyl sulfate.} The resulting addition product

H ₃ C-

H ₈ C

NC ₈ H ₅

= CH-CH = C O = C,

"C- S-CH ₃

is with 1 mole of 5, ö-dimethyl-i-methylbenzthiazole iodoethylate in pyridine after 2 hours at 100 ° to one

CH ₃ SOr

Dye implemented, which is precipitated by adding potassium iodine solution. Its constitution is as follows:

CH ₃

H ₃ CH ₃ C-

—N
C ₂ H ₅

C = CH-CH = C O = C

'C-CH =

C ₃ H ₅

G 5 -CH ₃ N— -CH ₃ C ₂ H

Absorption maximum about 600 τημ, sensitization maximum about 630 ταμ.

Example 2

The intermediate mentioned under 1 is with

50 dimethyl sulfate condensed for 10 minutes at iio °

and with the same amount of 2-methyl-benzselenazole

H ₃ Q / \ s
! \ H ₃ C - \ / - ^{n /} C ₂ H ₅

diethyl sulfate 3 hours at 105 ⁰ in five times
Amount of pyridine converted to a violet dye of the following constitution:

CH,

^N \

C = CH-CH = C \ / ^Se "

C = CH-'C

O = C

N—
C ₂ H ₆

Absorption maximum about 605 ναμ, sensitization maximum about 633 χημ.

Example 3

The condensation product of equal parts of dimethyl thiohydantoin and 4- (co-acetoanilinovinyl) -1 - methyl - quinoline - methyl sulfate as follows Constitution:

H ₈ CN ^ "^ C-CH = CH-N:

XOCH,

CH ₃ SO ₄ -

five times the amount of pyridine is converted into a blue intermediate product of the following constitution:

CH, ■ '

HoC-N

= CH-CH = C

= C, XS

This is heated with the same amount of dimethyl sulfate for 5 minutes at 100 °. The resulting 30 Addition product is briefly rubbed through with absolute ether, the ether is decanted and mixed with the equal amount of 2-methylbenzoxazole diethyl sulfate condensed in five times the amount of pyridine for 2 hours at ι io ° and the dye precipitated as iodide. He has the following constitution:

CH ₃

H ₃ C-

C = XH-CH = X "-CH = C

CH ₃

Absorption maximum 655 m ^, sensitization maximum 705 ναμ.

Example 4

, 0-

^V N—
C ₂ H ₅

Equal amounts of N-ethyl-thiazoline-2-methylene

50 oj-aldehyde and Methylphenylthiohydantoin are dissolved in five times the amount of pyridine and condensed by adding the same amount of piperidine with 2 hours heating at 90 ⁰ the following to give an intermediate structure:

H ₂ C

H ₉ C,

= CH-CH =

\ J = Οχ XS

C ₂ H ₅

The yellow dye is obtained by heating for 10 minutes with the same amount of dimethyl sulfate converted to a body of the following constitution at ioo °:

CH,

H ₂ C
H ₂ C

: = CH - CH = O = C ^ C-S-CH,

C ₂ H ₆

C ₆ H ₅ CH ₃ SOr

This intermediate product is dissolved in pyridine thiazole diethyl sulfate in pyridine to a rotvio- and condensed with the same amount of 2-methyl-4, 5-naphthol-conducting dye of the following constitution:

H ₂ C
H ₂ C

CH ₃

C ₂ H ₅

: = CH - CH =

O = C

"C-CH =

C ₆ H ₅ C ₂ H ₅

C ₃ H ₆ SOr

Absorption maximum 560 ταμ, sensitization maximum 595 ταμ.

Example 5

5 g of ¹ J 3) 3-trimethylindoline-2-methylene-ft) -aldehyde are dissolved with 5 g of methylallylthiohydantoin in 20 ecm of pyridine and by adding 20 ecm of vinegar

CH _3s CH ₃

\ r

IN'

J CH,

acid anhydride and heat to 95 for half an hour to result in an orange-red intermediate Constitution condensed:

CH = C

O = C, ^s cs

^{ι g of this product is heated to 90 0} with 1 ecm diethyl sulfate V2 hour and, after washing with absolute ether, dissolved in 10 ecm pyridine and treated with 2 g 2, 5, 6-trimethylbenzselenazole diethyl sulfate for 2 hours at no ⁰ to give a 110 violet dye Constitution condensed and precipitated as iodide:

C-CH = C ^S N-I

C ₂ H ₆

-CH ₃

CH ₃

Absorption maximum 595 τημ, sensitization maximum 620 ταμ.

Example 6 231 mg of the aldehyde

, = GH-CH = CH-CH = O

N '

C ₂ H ₅
can be represented by cleavage of the polymethm dye

/ \ - S

_x J _x J-CH = CH-CH = CH-NH-C ₆ H ₅

ao and 144 mg dimethylthiohydantoin (can be represented from Aminoacetic acid and methyl mustard oil) are in ι ecm pyridine and 0.5 ecm acetic anhydride slightly warmed. After cooling in a cold mixture, the dye drops from the likely one formula

, = CH — CH = CH-CH = C N-CH,

= C

CH ₃ (obtained in several

the end.

ι g of this dye

small batches) is heated to 100 ° with ι ecm dimethyl sulfate ι hour. The oily product is rubbed with IO ecm ether. The result is a viscous mass (soluble in methanol with a purple-red color). 1 g of 2-methylbenzothiazole diethyl sulfate and 3 ecm of pyridine are then added and the mixture is warmed ^{to no more than 0 for 1 hour.} A few cubic centimeters of methanol and 2 ecm 10% strength aqueous iodine potassium solution are added to the intensely violet liquid. It drops a flaky dye of the likely formula

I = CH-CH = CH-CH = C N — CH "

Co H =

O = C,

j V / —— \ _, Xj [\ _y

CH ₃ C ₂ H ₅

the end.

Absorption maximum in methanol 690 ηιμ, 35 sensitization maximum 720 χημ. (Sensitization maximum determined by bathing a medium-sensitive emulsion in a solution of the dye ι: 500,000.)

Claims (1)

Claim: Process for the production of optical photographic sensitizers, characterized in that that one adducts of acid alkylates, such as halides, alkyl = (CH-CH) _n = C 'O = C. sulfates, toluene sulfalkylates on condensation products of thiohydantoin with heterocyclic nitrogenous bases of the following constitution : R ₂ , N, X " wherein A and B are the atomic groups required to close the ring, such as. B. Phenylene, naphthylene, Y = O, S or Se atoms, alkyl alkyl r rpr_rtj R ₂ N-alkyl, N-aralkyl or N-aryl groups, R ₁ = alkyl and aralkyl groups, R ₂ = alkyl, aralkyl, aryl groups, X = any acid radical, such as halogen, alkyl-S O ^ toluenesulfalkyl, Cl O ₄ , iao η = the number o, 1 or 2, condensed with the quaternary salts of N4ialtiger heterocycles with reactive methyl or methylene groups customary for the synthesis of methine dyes. © 9592 2.55