DE2118553A1 - Azodicarboxamide derivatives and their use - Google Patents

Description

MINNESOTA MINIlTG AND MANUFACTURING COMPANY St. Paul, Minnesota, V.St.A.

"Azodicarboxamide derivatives and their uses" Priority: April 17, 1970, Great Britain, No. 18 564/70

The invention relates to new azodicarboxamide derivatives of the general formula I

0 R ₃

Il »

= N- C-N-R,

(D

in which L., Rp, R ^ and R, each is a hydrogen atom, an aliphatic, alicyclic, aromatic or heterocyclic radical, where R ^ and R _? or R ^, and R ₄ together with the nitrogen atom can form a 5- or 6-membered, optionally substituted ring, and at least one> of the radicals R ,, R ₉ , R ^ or R ₁ , at least one equatorial am- , Sulfonium and / or phosphonium fluids

109S44 / 199S

has, whose positive charge is either salt-like by an anion or by at least one suitable, having a negative charge Substituents in the molecule itself are neutralized in a beta'in-like manner is.

The new compounds can be used, for example, as fog inhibitors in silver halide photographic emulsions. The invention therefore also relates to the application of the new Azodicarboxamide perivate as antifoggants in photographic silver halide emulsions. The maximum amount of a photographic emulsion used to prevent fogging Azodicarbonsäureaaid derivatives to be added can be added in a simple Way to be determined by experiment ^. Generally will however, good results are obtained when 0.1 to 1.5 mmol of the Azodicarboxamide perivate per mole of silver used in the emulsion will. It can be a photographic emulsion for black and white or color photography or for X-ray photography Act. Bromide, iodide or mixtures of halides can be used as the silver halide.

The new azodicarboxamide derivatives are readily soluble in Kasser and can therefore be used in a simple manner in photographic applications Emulsions without the use of organic solvents, which are not only costly but also have undesirable side effects on the emulsion have to be incorporated. In addition, the new compounds are distributed very evenly in the Emulsion. The new azodicarboxylic acid anide derivatives show comparable results or better anti-fog properties and

ϊ y I a a »i I run

also a comparable or better negative contrast (^ f) as well as a comparable or superior size P _1n ,, if they

Iu 3 X

be compared with azodicarboxamide. Often the invention Azodicarboxamide perivate are used in smaller amounts than azodicarboxamide to produce a comparable To achieve veil prevention. Identify an azodicarboxamide derivative according to the invention is added to a silver halide photographic emulsion in such an amount that? a haze formation is prevented, the sensitivity of this emulsion is not reduced to an undesirable extent.

The invention also relates to the use of the inventive Azodicarboxamide perivate as blowing agent in polymers, e.g. plasticizer-containing vinyl chloride homo- or copolymers, because, similar to the azodicarboxamide, the compounds according to the invention produce on decomposition at only moderately increased levels Temperatures a relatively large volume of gaseous decomposition products. How and in what amounts the invention Compounds incorporated into polymers as blowing agents can be determined by a person skilled in the art by means of simple experiments will.

The new azodicarboxamide perivate with at least one quaternary ammonium, siliconium and / or phosphonium grouping must be electronically neutral. The positive charge can therefore be neutralized in the manner of a salt or a beta'in. Example-ie for anions for a salt-like neutralization are residues

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of aryl sulfonates, such as p-toluene sulfonate or alkyl sulfonate, or inorganic ions such as boron tetrafluoride (BF, ") -, iodide, Iodate, chloride, chlorate, perchlorate or nitrate ions.

Examples of azodicarboxamide derivatives according to the invention with a betaine-like structure are compounds of the formulas

CH,

(CE ₇ ) _Ο Ν ^Θ - (CH ₂ ) ₂ -NH-CN = NC-NH- (CH.

₃ ) ₂ i

-SO,

-CH,

-CH,

-CH,

CH,

CH, - S ⁹ - (CH ₀ ), - HH-CH = NC-HH- (

-CH,

J) ₂ -S ^- -CH ₃

-CH,

According to a preferred embodiment, the invention Azodicarboxamide derivatives of the general formula (I) have at least one ammonium, sulfonium and / or phosphonium group of the general formula II

AY ⁺ -R

(II)

. R.

(n)

where the remaining radicals R ₁ , R ₂ , R ₃ and / or R. of the general formula (I) are hydrogen atoms or alkyl radicals and where in the general formula (II) Y is a nitrogen,

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Sulfur or phosphorus atom and R _{5 is} an alkyl radical and A is an aliphatic, alicyclic, aromatic or heterocyclic radical, where Y, R ₅ and R can also form the heterocyclic radical together with A and R is a hydrogen atom, an alkyl radical Radical -AR ^, where R ^ is the radical of the general formula (T) with at least three of the radicals IL, Rp, R ₃ or R. ', which are hydrogen atoms or alkyl radicals, or a polymerizable radical, η is the number 0, 1 or 2 is with the proviso that η has the value 2 if there is a single bond between A and Y and Y is a nitrogen or phosphoxy atom, η has the value 1, -if there is a double bond between A and Y, and Y is a nitrogen or phosphorus atom or there is a single bond between A and Y and Y is a sulfur atom, and η has the value 0 if there is a triple bond between A and Y- and Y is a nitrogen or phosphorus atom or between A and Y is a double bond and Y is a sulfurate is om, and λ is a residue neutralizing the charge on Y.

Examples of such connections are:

r . ''. 0 0

(CH ₃ J ₃ IiOH ₂ -GH ₂ -NH-CN = NC-NH-CH ₂ -CH ₂ -N ⁰ (CH ₃ ) _? 1 2Ζ ^Θ

(CH

) ₃ -N® (CH ₃ ) ₃ 2Ζ ^Θ

■ *, 109844/1998

CH,

e,

O

/ VcH ₂ -NH-CN = NC-NH-CH ₂ - / \

ZT

O

I (CH ₃ ) ₃ l! ® (CH ₂ ) ^ NH-CN = NC-IiH- (CH ₂ ) ₆ -H® (CH ₃ ) A 2 Z *

O

K CH ₃₎ ^ _(CH2) 2-CN-IJH = Ii-C-NH-CH ₂ - CH

J ο

Br ⁶ '? ^H 3

O

⁰ N-CH ₀ -CH ₉ -NH-CN = NC-NH-CH ₀ -CH ₀ -Ii ⁰ (CH ₀ )

CH,

CH ₃

Br *

CH,

^ 0 N-C-N = H-C-Ii

O

-CH ₀ -CHn-ITH-C-IT = NC-KH,

Br

CH,

OO

CH ,,

Br ^e S-Ch ₀ -CH ₀ -NH-CN = NC-NH-CH ₀ -CH ₀ -S Br, 22 ²² I.

CH,

CH,

Br

0

Br *

(CH,), -CH P® QH _{O O} -NH-CN = NC-NH-CH ₉ -CH -P® _O (CH

'7ΐ \

3 ^y 3

In these formulas, Z is a p-toluene sulfonate or a Methosulfate ion and m is an integer.

The quaternary ammonium derivatives of the azodicarboxamides according to the invention can e.g. by condensing an azo

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dicarboxylate with a corresponding Ν, Ν-disubstituted Diamine and subsequent quaternization with a quaternizing agent, like methyl p-toluene sulfonate or with dimethyl sulfate, getting produced. E.g. you can put a solution of 0.1 mol Ν, Ν-dimethyl-ethylenediamine in 100 ml ether on an ice bath cool and stir and add 0.05 mol of diethyl (azodicarboxylate) dropwise offset. A yellow precipitate of NjN'-di-Cäthyl - ^ - diniethylamino ^ azodicarboxamide from F. 193 ° G.

The compounds below can be prepared in an analogous manner will:

N, N '-di (propyl-3-dimethylamino) -azodicarboxamide, mp 189 ° C, from 3-dimethylaminopropylamine; N, N ^! - Di (4-methylpiperazino ^ azodicarboxamide, mp 162 ° C, from 4-methylpiperizine;

N, N'-di- (3-py2 "idylmethyl) -azodicarbonsäureamid, F. 158 ⁰ C, prepared from 3-aminomethylpyridine;

N, N ^l -di (2-pyridylmethyl) -azodicarboxamide, m.p. 140 ⁰ C, from 2-aminomethylpyridine and

N, N'-di- / diethyl-2- (4-morpholino ^ -azodicarbonsäureamid, F. 150 ⁰ C., from 4- (2-aminoethyl) morpholine.

The examples illustrate the invention.

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example 1

A solution of 0.3 mol of p-toluene sulfonic acid methyl ester in 25 ml of chloroform is treated at room temperature with a solution of 0.1 mol of N, N'-di- ^ ethyl-2-dimethylaniino ^ azodicarboxamide in 75 ml of chloroform. A precipitate forms quickly. The reaction has ended after 1 hour. After filtering off and recrystallizing from ethanol, N, N ¹ -di (ethyl-2-trimethylammonium) azodicarboxamide di-p-toluenesulfonate with a melting point of 187 ° C. is obtained.

Example 2

A solution of 0.01 mol of N, N'-di (ethyl-2-dimethylamino) -razodicarboxamide in 40 ml of chloroform is mixed with 0.04 mol of dimethyl sulfate. The reaction is over after 30 minutes. This gives N, E ^l-di- (ethyl-2-trimethylammonium) -azodicarbonsäureamid-di-methosulphate as a yellow precipitate by P. 147 ⁰ C.

N, N'-di (propyl-3-trimethylammonium) azodicarboxamide dimethosulfate is obtained in an analogous manner from P. 163 ° C.

Example3

0.01 mol of N, N ^l -di (3-methylpyridiniuramethyl) -azodicarboxamide is dissolved in 40 ml of dimethylformamide, and 0.04 mol of dimethyl sulfate is added. The solution is left to stand at room temperature for about 15 hours. After adding ether it separates

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an orange-colored oil develops, which, when rubbed with ether and ethanol, turns into buff-colored N, N'-di- (3-methylpyridiniummethyl) -azodicarboxamide dimethosulfate solidified at 167 ° C.

Example4

A solution of 0.1 mol of N, N'-di- (ethyl-2-dimethylamino) -azodicarboxamide in 750 ml of chloroform is mixed with 0.4 mol of p-toluenesulfonic acid methyl ester at room temperature. The solution is stirred for 24 hours at room temperature. The yellow precipitate is filtered off and triturated with chloroform and then with ethanol. N ₁ N'-di- (ethyl-2-trimethylammonium) -azodicarboxamide-di-p-toluene sulfonate with a melting point of 187 ° C. is obtained.

In an analogous manner, N, N'-di- (4-methylpiperazino) -azodicarboxamide is obtained N, N'-di- (4,4'-dimethylpiperaziniura) -azodicarboxamide di-p-toluenesulfonate with a temperature of 228 ° C.

Example 5

A solution of 0.1 mol of N, N'-di- (ethyl-2-dimethylamino) -azodicarbohsaureamid in 750 ml of chloroform, 0.4 mol of dimethyl sulfate is added at room temperature. The solution will be 24 hours touched. The yellow precipitate is triturated with chloroform and then with ethanol. N, N'-di- (ethyl-2-trimethylammonium) azodicarboxamide dimethosulfate is obtained from F. 147 C.

In an analogous manner, one obtains from N, N'-di- (propyl-3 - <- lime thyl-

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amino) -azodicarboxamide K, N'-di ~ (propyl-3-trimethylammonium) -azodiearboxamide-dimethosulfate in front M. 163 ° C.

Be i s ρ i e 1 6

A solution of 0.1 mol of NjN'-di-Cäthyl ^ -dimethylamino ^ azo dicarboxamide in 750 ml of chloroform is mixed with 0.4 mol of propane sultone. The solution is stirred for 24 hours at room temperature. The yellow precipitate is triturated with chloroform and then with ethanol. The compound of the formula is obtained

CH ₀ CH ₀ CH ₀ CH

²² 00 \ ^d

(CH ₃ ) ₂ N® -CH ₂ CH ₂ -HN-CN = NC-NH-CH ₂ CH ₂ N ⁰ CCH ₃ ) ₂

CH ₂ S0 ₃ ^e " ⁰ O ₃ S CH ₂

with a temperature of 225 ° C.

In an analogous manner, N, N'-di- (4-methyl-4-sulfopropylpiperazinium) -azodicarboxamide-betaine are used vom F. 260 C and N, N '-di / 5 ~ (N-dimethyl-N-sulfopylammonium) -pr opyl-7-azodicarboxamide-betaine received from F. 68 C.

^x · 'example?

A solution of 0.1 mol of NjN'-di-Cethyl-S-dimethylaminoJ-azodicarboxamide in 750 ml of chloroform is mixed with 0.4 mol of methyl iodide. The solution is stirred for 24 hours at room temperature. The yellow precipitate is triturated with ethanol. N, N'-di- (ethyl-2-trimethylammonium ') - a;' _J odicarbon-

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acid amide diiodide from Έ. 208 ⁰ C.

Examples

0.01 moles of N, N ^! —Di-Cäthyl-Z-trimethylammoniunO-azodicarboxamide-di-p-toluenesulfonate and 0.02 mol of sodium tetrafluoroborate are dissolved in a small amount of water and ethanol is slowly added until a precipitate is formed. The precipitate is filtered off and triturated with ethanol. N, N ^l -di (ethyl-2-trimethylammonium) -azodicarboxamide di-tetrafluoroborate with a melting point of 148 ° C. is obtained.

Example 9 '

0.01 mol of N, N ^I -di (ethyl-2-trimethylammonium) -azodicarbonsäureaiaid-di-p-toluenesulfonate and 0.02 mol of sodium perchlorate are dissolved in a small amount of water and slowly mixed with ethanol until The precipitate is filtered off and triturated with ethanol, ^{giving N, N 1} -di (ethyl-2-trimethylammonium) azodicarboxamide di-perchlorate with a melting point of 185 ° C.

Example, game 10

0.1 mol of N, N ¹ -di (2-pyridylmethyl-azodicarboxamide is dissolved in about 400 ml of anhydrous, freshly distilled dimethylformamide. 0.4 mol of methyl p-toluenesulfonate is added and the solution is stirred at room temperature for about 15 hours After the addition of ether, an orange color separates

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■ - 12 -

Oil that solidifies when rubbed with ether and then with ethanol. One obtains N, N'-di- (2-methylpyridiniummethyl) -azodicarbonsäureamid-di-p-toluenesulfonate, mp 220 ⁰ C.

In an analogous manner, from N, N '~ di- (3-pyridylmethyl ^ azodicarboxamide N ₁ N'-di- (5-methylpyridiniummethyl) -azodicarboxamide di-p-toluenesulphonate from P. 16? ° C can be prepared.

Example 11

0.01 mol of N, N'-di- (ethyl-2-diinethylaniino ^ azodicarboxamide is in a mixture of 25 ml of chloroform and 25 ml of acetonitrile solved. After adding 0.04 mol of ß-propiolactone the solution was stirred for about 15 hours at room temperature. The precipitate is filtered off and dried. You get N, N'-di- / 2- (N-dimethyl-N-carboxypropylammonium) -ethyl-7-azodicarboxamide-betaine from P. 106 ° C.

Example 12

A solution of 0.4 mol of p-toluenesulfonic acid methyl ester in chloroform is mixed with a solution of 0.1 mol of N, N'-di- / ethyl-2- (4-morpho'lino ^ -azodicarboxamide in 1 liter of chloroform. the solution is stirred for 3 days at 50 ⁰ C. the precipitating from the chloroform solution orange oil is triturated with ether to Pestwerden is obtained a compound of Pormel.

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r O

from P. 154 ⁰ G.

Example 13

It becomes a coarse-grained silver bromoiodide gelatin emulsion produced by ripening under ammoniacal conditions, wherein the silver halide is obtained in cubic crystal form and the mean grain size is about 2.0 μ. The emulsion has an iodine content of about 2 mole percent. This emulsion is then ripened with a sulfur and gold sensitizer. After this digestion treatment, the emulsion is made by adding 4-hydroxy-5-2'-hydroxyethyl-6-methyl-1: 3: 3a: 7-tetraazainden-3-amino-5-methylthio-1: 2: 4-triazole salt stabilized.

The emulsion produced in this way is divided into two parts, A and B. 10 ml of an aqueous solution of 25 mmol of N, N ^l -di (ethyl-2-trimethylammonium) azodicarboxamide di-p-toluenesulfonate are added to portion B (emulsion B). After adding the required auxiliaries, the two emulsions are

/ holds sions on a substrate. Applied from polyester. He / a silver-containing coating layer of 5.0 g / m 2. Each emulsion layer is then coated with a protective gelatin layer which contains a crosslinking agent for gelatin. The coated films are dried, exposed in a sensitometer with a continuous gray wedge and then at a temperature

1C98U / 1995

treated door of 40 ⁰ C in a commercially available standard developer of the type as it is usually used in a modern developer device for X-ray films with a total treatment time of 90 seconds. The rela-

-ities

tive sensitivity / and the haze formation of each developed and treated film was measured. The results are given in the table below.

Emulsion 'haze-relative Em formation sensitivity

A 0.13 2.08

B 0.04 2.10

It can be seen from the results that the azodicarboxamide derivatives of the present invention greatly reduce fogging while at the same time showing only a slight change in sensitivity. It should also be emphasized that the azodicarboxamide derivatives according to the invention are very readily soluble, so that the compounds can be easily and uniformly incorporated into the emulsion.

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Claims (32)

Claims 1. I azodicarboxamide derivatives of the general formula I. R _? 0 OR, IH It I R ₁ -NC-IT = NGN -R ₄ (I) in the R., R _? , R, and R. are each a hydrogen atom, an aliphatic, alicyclic, aromatic or heterocyclic radical, v / obei R. and Rp or R, and R. together with the nitrogen atom a 5- or 6-membered, optionally substituted ring can form, and at least one of the radicals R ₁ , Rpι RZ or R. at least one quaternary ammonium, Has sulfonium and / or phosphonium grouping, the po- either / you 're an anion /
sensitive charge / salty / or by at least one suitable, a negative charge in the molecule itself • · is neutralized like a betaine. 2. azodicarboxamide derivatives according to claim 1, characterized in that that the azodicarboxamide derivatives have at least one ammonium, sulfonium and / or phosphonium grouping of the general formula II -AY ^ -R, - Χ ^θ (II) ^R (n) have and the remaining radicals R., Rp, R, and / or R, in the general formula (I) are hydrogen atoms or alkyl radicals, where in the general formula (II) Y is a nitrogen, sulfur 1098U / 1995 Free or phosphorus atom and Rr- is an alkyl radical and A is an aliphatic p alicyclic, aromatic or heterocyclic. Radical, where Y, - R ₈ - and R together with A can also form the heterocyclic radical / ~ and ~ R a hydrogen atom, an alkyl radical _s a radical '-Jl-Rg where IL- is the radical of the general formula (I5 with at least three of the radicals IL, R ₂ , R ^ or KL is “the hydrogen atoms or alkyl radicals, or a polymerizable radical, η is the number 0 _f 1 or 2 with the proviso that has the value η 2 when standing and between a and Y is a nitrogen Einfaehbindmig Y aiii ψ substance- o'der phosphorus atom, η has the value 1 if there is, and between a and Y is a double bond Y is a nitrogen or Is phosphorus atom or there is a single bond between A and Y and Y is a sulfur atom, and η has the value 0 if there is a triple bond between A and Y and Y is a nitrogen or phosphorus atom or if there is a double bond between A. and Y and Y is a sulfur atom and X ^ is a radical neutralizing the charge of Y « 3. azodicarboxamide derivatives according to claim 1, characterized in that the salt-forming radical is a p-toluenesulfonate or another aryl sulfonate, an alkyl sulfate, Boron tetra / luoride, iodide, chloride, nitrate, iodate, chlorate or perchlorination. 4. azodicarboxamide derivative according to claim 2, characterized in that that R is a disubstituted methyl radical » 5. Azodicarboxamide derivatives according to Änspru'eh 2 109844/1996 "that X, Bortetrafluorid-, perchlorate, chloride or Joiäid-j Kitration characterized Ärylsulfonat a ~ _t Alky! sulphate. 6. Azodiearboxamide berivat of the general formula OO ^ CH ₂ Ch ₂ NH-CNNC-NHCH ₂ CH ₂ ] 2 Z * in which Z is a p-toluenesulfonate or methosulfate ion, 7. Azodicarboxamide derivative of the general formula (CH ₂ ) ₅ 2 Z " in which Z is a p-toluenesulfonate or a methosulfate ion. 8. Azodicarboxamide derivative of the general formula OOH ₂ -NH-CN = NC-NH-CH ₂ -0 2Z ' in the Ζ: j-a p-toluenesulfonate or a methosulf ation, 9. Azodicarboxamide berivat of the general formula S 2 ₆ -NH-CN = NC-NK (CH (CH,), 2Z 10984A / 1998 fei J in which Z is a p-toluene sulfate or methosulfate ion. . . & 10, azodicarboxamide berivat of the general * formula j (GH O O . (CH ₂ ) ₂ -HH-CH = N-8-NH-CH, in which Z is a p-toluenesulfonate or a methosulfate ion. 11. Azodic ^ rboxamide derivative of the formula CH-. ο ο -Ί £ ~ \ -CINC-NHCH ₂ CH ₂ -IT P 12. Azodicarboxamide derivative of the formula (CH ₃ ) ₃ N®-f 0 0 / γ ~ λ CN = NC-NH / Vn ^@ (CH, 3> 3 13. Azodicarboxamide derivative of the general formula Br ^e CH, Il Br ' N-CH ₂ -CH ₂ -NH-CN = Ii-C-NH-CH ₂ -CH ₂ -N ■ (CH ₂ ) CH CH, 109844/1995 in which .in is an integer. 14. Azodicarboxylic acid amide derivative of the formula (CH ₃ ) -] ^X 2'2 0 -N-C-N = N-C-N- Br ^f - (CH ₂ ) ' ₂ -N® (CHj 15. Azodiearboxamide derivative of the formula CH, Γ Br * -CH _n -CH _n -NH-CH = HC " 16. Azodicarboxamide derivative of the formula CH, * S-C1 CH, · C , -CH ₀ -NH-CN = NC-HH-CHp- CH, 17. Azodicarboxamide derivative of the formula O ₍ J ₃ P ^ -CH ₂ -CH ₂ -NH-CN = NC-NH-CH ₂ -CH ₂ -P® (CH ₃ J ₃ Br ' 18. Azodicarboxamide derivative of the formula CH ₀ CH, CH ₀ CH. (CH ₅ ) ₂ Ν ^Φ - (CH ₂ J ₂ -NH-C-KsN-C-NH- ) ₂ ~ Ν SO, CH, 109844/1995 19. Azodicarboxamide berivat of the formula CH ₂ CH ₂ Ii Il _ S & - (CH ₂ ) 2 -NH-CN = NC-NH- (CH ₂ ) ₂ -S ^w -CH ₃
CH ₂ S0 ₃ ^e • ⁰ O ₃ S CH ₂ 20. N, N'-di (methylene-3-methy! Pyridinium) azodicarboxamide dimethosulfate. 21. N ₁ N'-di- (4-, 4'-dimethylpiperaziniunO-azodicarboxamide- ψ li-p-toluenesulfate. 22. N, Ii '- Di (4 - meth.yl-4-sulfopropylpiperazinium) -azodicarboxamide-betaine. 23. N ^ '- Di-Z ^ -CN-dimethyl-N-sulfopropylammonium I-propyl / -azodicarboxamide-betaine. 24. N _f N'-Di- (ethyl-2-trimethylammonium) -azodicarboxamide di-iodide. 25. N, N'-di- (ethyl-2-trimethylammonium) -azodicarboxylic acid di-tetrafluoroborate. 26. N, N ^f -di (ethyl-2-tririethylammonium) -azodicarboxamide di-perchlorate. 27. N, N ^l -di (2-methylpyridiniummethyl) -azodicarboxamide di-p-toluenesulfonate. 28. li, N ^l -di (3 * methylpyridiniummethyl) -azodicarboxamide- 1098A4 / 1995 di-p-toluenesulfonate. 29. N, N '-Di-Zi? - (N-dine thyl-N-carboxypr οpy! Ammonium) -äthyl7-azodicarboxamide-betaln. 30. Use of the azodicarboxamide derivatives according to the claims 1 to 29 as blowing agents in polymers. 31. Use of the azodicarboxamide derivatives according to the claims 1 to 29 as anti-fog agents in silver halide photographic emulsions. 32. Embodiment according to claim Jl, characterized by the use of the azodicarboxamide derivatives in an amount of 0.1 to 1.5 mmol per mol of silver in the silver halide emulsions. 109844/1995