DE2639649A1 - AMINO-NAPHTHALIMIDE SERIES COMPOUNDS - Google Patents

Description

BASF Aktiengesellschaft

Our reference: OZ 32 176 Bg 6700 Ludwigshafen, August 31, 1976

Compounds of the Amino-naphthalimi threes

The invention relates to compounds of the formula I.

RO OR

in which the leftovers

R are identical or different and C.- to C -alkyl or C.- to

C. -Alkoxyethyl mean
R ^{1 is} hydrogen, C ₁ to C ₁₀ alkyl, C ₂ to C ₆ alkenyl, C ₂ to C ₄ alkynyl, C ₁ to Cg alkoxy, C ₁ to Cg alkyl or dialkylamino, Phenoxymethyl, phenyl, tolyl, benzyl or phenylethyl and

2
R branched C, - to C "-alkyl, which is optionally replaced by phenyl,

Hydroxyphenyl, methoxy or Mmethoxyphenyl may be substituted can, are.

383/76 - 2 -

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Residues R Bind, for example, propyl, butyl, methoxyethyl, ethoxyethyl, Propoxyäthyl or Butoxyäthyl and especially methyl or ethyl because of the favorable manufacturing possibilities.

Rests are, for example, methyl, ethyl, n- and iso-propyl, butyl,

-Heptyl,
Pentyl, hexyl, octyl, nonyl or decyl, vinyl, allyl, propenyl, butenyl, styryl, methoxy, ethoxy, n- and iso-propoxy, butoxy, pentoxy, hexoxy, heptyloxy or octoyloxy , Dimethylamino, diethylamino or di-isobutylamino.

2
R radicals are for example

.CH,. ^CH 3 / ^CH 3 / ^CE 3 / ^CH 3 / ^C 2 ^H 5 -CH ⁵ , -CH-C ₀ H _1. , -CH-C ₇ H, CH-CH, -CH

N- PTT ^ 'I \ \

3 ^CH 3 ^C 2 ^H 5

CH, CH ₃ CH ₂ CH, CH ₇ .CH ₇

/ 3 | 3/3 ^ 3/3/3

-CH ₀ -C-CH,, -CH-C-CH-, -CH-C .H-, -CH-CH -CH,

2 \ 3 \ 5 47 έ 4 \

CH _Z CH _x CH ₇

3 3 3

CH CH C ₂ H ₅ CH ₅ CH ₅

-CH-C ₅ H ₁₁ , -CH-C ₆ H ₁₃ , -CH ₂ -CH-C ₄ H ₉ , -CH-C ₇ H ₁₅ , -CH-C ₈ H ₁₇ ,

CH ₅ CH ₅ CH ₅ CH ₅

-CH-C ₆ H ₅ , -CH-CH ₂ -C ₆ H ₅ , -CH-C ₆ H ₄ OH, -CH-CHg-CgH OCH ₅ or

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Compounds can be used to prepare the compounds of the formula I of formula II

with compounds of the formula III

0
xi.ß ¹ III,

in which X is OH, Cl, Br or an acyl radical O-C-R.

Compounds of the formula II are obtained by adding compounds of the formula IV

Shark shark

in which Hai means chlorine or bromine, with compounds of the formula V

ROMe V,

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in which Me means sodium or potassium.

The reaction is expediently carried out in the corresponding alcohols of the formula EOH in the presence of 2-20 %, preferably 5-10%, of a mono- or dialkyl ether of a glycol or polyglycol. Particularly suitable ether groups are C ₁ to C alkoxy radicals, and the glycol chains preferably consist of 2 to 6 ethylene groups.

In a further preferred embodiment, the reaction of the compounds of the formula IV with V in the corresponding alcohols of the formula ROH in the presence of 5-95%, preferably 10-50%, of an inert organic solvent with a boiling point greater than 80 ^° C. is carried out has performed. Such solvents are e.g. B. benzene, toluene, xylenes, trimethylbenzene, mono-, di- or tri-chlorobenzene, or nitrobenzene.

Details of the reactions can be found in the examples, in which details about parts and percentages relate to weight, unless otherwise stated.

The compounds of formula I are suitable as optical brighteners for 2 1/2 acetate, triacetate and especially synthetic linear polyester and polyester-cotton blends. Because of their high

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Temperature stability, they can also be used for mass lightening and for spinning.

The very good lightfastness, the very high parity and in particular the brilliance and the high degree of whiteness in should be emphasized a preferred red-tinged shade of the lightening, as well as the excellent coloring behavior.

Technically preferred are compounds of the general formula I a

I a,

OR OE

in the

B ¹ hydrogen or C., - to C _Q -alkyl,

2
B denotes branched C 1 -C 6 -alkyl and R has the meaning given.

Particularly preferred radicals for R are: CII ₅ , C ₂ H ₅ , C ₄ H ₉ , C ₂ H ₄ OCH ₅ or C.

for B ¹ : H, CH, C ₀ H _1. , C ₂ H ₇ or c £ ^{2 5} 5 25 57 ^ fTT

CH

for B ² : CH (CH,) ,,, CH ⁵ , CH ⁵ , CH C (CH) ,, CH ³ -CH V ⁵⁵ -

CH ₅

CH- (C ₀ Hj-) or CH-CH ₀ -CH (CH,) ,. <- j ρ> * -

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example 1

12 parts of 4 »5-dimethoxy-N-neopentylamino-naphthaliInid, 40 parts of N-methylpyrrolidone and 5» 1 parts of potassium carbonate are presented. Then 6 parts of acetyl chloride are added dropwise at 50 ^° C. with stirring and the mixture is stirred for 5 hours at the same temperature. The mixture is then poured onto ice and filtered off with suction. 13 parts of the compound of the formula are obtained

H ₂ C 0

H ₂ CC-CH ₀ -NC-CH
J * I

H ₃ CO OCH

with a melting point of 228-30 ° C (unicrystallized from isobutanol).

With this product one obtains brilliant brightenings of excellent quality Whiteness and red-tinged nuances * especially on acetate, polyester and polyester / tree full. The very good fastness properties are to be emphasized.

To produce the 4 »5 -?) Iniethoxy-N-neopentylaBiino-naphthalimide, 64 parts of 4,5-dichloro-N-neopentylamino-naphthalimide, 440 parts of methanol, 50 parts of butyl triglycol and 100 parts of 30% sodium methylate solution in methanol are added for 8 hours 65 ⁰ C stirred. After this

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Cooling is filtered off with suction, washed with methanol and dried. Yield: 61 parts (. 98 # of theory). M.p .: 270-72 ⁰ C.

The 4 »5-dichloro-N-neopentylamino-naphthalimide can be obtained by reacting 4» 5-dichloronaphthalic anhydride with neopentylhydrazine. Fp -. 230 to 31 ⁰ C.

Example 2

The implementation and work-up is carried out analogously to Example 1. Instead of acetyl chloride, 7 parts of propionyl chloride are added. 13 »4 parts of the compound of the formula are obtained

H ₃ C 0

H _x CC-OH ₀ -NCC ₀ Hc J / * - I ^ 2

H ₅ C ΟγΝγ, Ο pp .: 225 - 26 ⁰ C (alcohol)

H ₅ CO OCH

Their coloring properties are comparable to those in Example 1 listed compound.

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Example 3

The reaction and work-up are carried out analogously to Example 1. Instead of acetyl chloride, 8 parts of butyric acid chloride are added. 13 parts of the compound of the formula are obtained

H _x C 0

3 \ H

H _x CC-CH ₀ -NCC _x H., 5/2 ι 5 7

Mp .: 203-04 C (isobutanol)

H CO OCH

The coloring properties are those listed in Example 1 Connection comparable.

Example 4

8 parts of 4 »5-dimethoxy-N-neopentylamino-naphthalimide are in 30 parts Formic acid refluxed for 4 hours. The mixture is then poured into water. 8 parts of the compound of the formula are obtained

_{Pp #} . 240 - 42 ° C (isobutanol)

H _x CO OCH _x 3 3

The coloring and coloring properties are comparable to those of the compound from Example 1.

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Example 5

60 parts of 4 »5-dimethoxy-N-isopropylamino-naphthalimide, 200 parts of N-methylpyrrolidone and 25 parts of potassium carbonate are introduced, then one is" at 40 - 50 ⁰ C, 25 parts of acetyl chloride was added dropwise to stirred for 5 hours and "at 50 60 C after. The mixture is then poured onto ice. 68 parts of the compound of the formula are obtained

recrystallized from dimethylformamide

H ₅ CO OCH ₅

The coloring and coloring properties are comparable to those of the compound from Example 1.

To prepare the 4f5-dimethoxy-N-isopropylamino-naphthalimide, 135 parts of 4 »5-dichloro-N-isopropylamino-naphthalimide, 400 parts of methanol and 60 parts of o-dichlorobenzene are initially charged. At reflux temperature, 270 parts of sodium methylate in methanol 30 follow added over 2 hours, then for 7 hours at reflux temperature, stirring is continued. After cooling, it is filtered off with suction, washed with methanol and dried.

Yield: 130 parts (98 % of theory ), pp. = 220-23 ° C. The 4,5-dichloro-N-isopropylamino-naphthalimide can be obtained by reacting 4,5-dichloronaphthalic anhydride with isopropylhydrazine.

Mp .: 190 to 92 ⁰ C.

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Example 6

The reaction and work-up are carried out analogously to Example 5. Instead of acetyl chloride, 25 parts of butyric acid chloride are added. 69 parts of the compound of the formula are obtained

H _x C 0 3 \ Il

CH-N-C-C, H "

/ '37 ο

HC Ck ^ NO .: mp 181-82 C after crystallization from environmental ^ Isotmtanol

H ₂ CO OCH _x

The coloring and colouristic properties are those of the compound from example 1 comparable.

Example 7

5 parts of 4i5-dimethoxy-li-isopropylamino-naphthalimide and 25 parts

Methyl chlorocarbonate is stirred at 60 ° C. for 8 hours.

After cooling, the solid product is filtered off with suction. 5t5 parts are obtained

the compound of the formula

H_C 3

_C 3 \

0 H -N-C-

OH-N-C-OCH,

H CO OCH

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26396A9

Recrystallized from methanol the product "melts at 195-96 ⁰ C.

Their coloring and colouristic properties are those of the Compound from example 1 comparable.

Example 8

10 parts of 4 »5-dimethoxy-N-isopropylamino-naphthalimide, 40 parts of dimethylformamide and 4 parts of potassium carbonate are initially charged. At 80-90 ⁰ C., then 6 parts of dimethylcarbamoyl chloride dropwise added and stirred for 7 hours at this temperature. After cooling, the mixture is poured onto ice and filtered off with suction. 11 parts of the compound of the formula are obtained

HA \ / H
³ CH-NC- / ⁵

H ₅ CO OCH ₅

Fp .: 236-57 ° C. recrystallized from isobutanol

The coloring and colouristic properties are those of the compound from example 1 comparable.

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O.Z. 32 1-76

Example 9

The implementation and work-up is carried out analogously to Example θ. Instead of dimethylcarbamic acid chloride, -u -chloropropionyl chloride is used used. 11 parts of the compound of the formula are obtained

H_C 0
3 \ Il

CH-NCC ₀ H-Cl

Mp .: 203-204 ° C (isobutanol)

Their coloring and colouristic properties are those of the compound from example 1 comparable.

Example 10

12 parts of 4i5-dimetho: ^ - N-isopentylamino-naphthalimide, 40 parts of dimethylformamide and 5 parts of potassium carbonate are initially charged, then 6 parts of acetyl chloride are added dropwise at 50 ^° C. with stirring. The mixture is stirred for a further 4 hours at this temperature and, after cooling, poured onto ice and filtered off with suction. 14 parts of the compound of the formula are obtained

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ς Ο.Ζ. 3?

Mp .: 240 - 41 ° C (ethyl glycol)

The coloring and colouristic properties are those of the compound from example 1 comparable.

To prepare the 4-5-dimethoxy-N-isopentylamino-naphthalimide, 61 parts of 4-5-dichloro-N-isopentylamino-naphthalimide, 240 parts of o-dichlorobenzene and 60 parts of methanol are initially introduced. At 80 ^° C., 72 parts of sodium methylate are added over the course of 2 hours. The mixture is stirred at the reflux temperature for 5 hours. After cooling, 400 parts of methanol are added, suction filtered, washed and dried. Yield: 55 parts (93 # of theory), melting point: 272-75 ° C

The 4, S-dichloro-N-isopentylamino-naphthalimide is obtained by reacting 4,5-dichloronaphthalic anhydride with isopentylhydrazine. Mp .: 218 to 22 ⁰ C.

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Example 11

65 parts of AjS-dimethoxy-N-iBobutylamino-naphthalimide, 300 parts Dimethylformamide and 25 parts of potassium carbonate are presented. At 50 ° C., 25 parts of acetyl chloride are added dropwise with stirring and the mixture is stirred 5 hours at this temperature. After cooling, the mixture is poured into water and filtered off with suction. 71 parts are obtained the compound of the formula

³ CH-NC-CH,
ρ 'ι 3

u ^ iK ^. j, p ^. 281 82 C (dimethylformamide)

H ₂ CO OCH_
5 5

The coloring and colouristic properties are those of Compound from example 1 comparable.

The 4 »5-dimethoxy-N-isobutylamino-naphthalimide is obtained analogously to Example 10 by reacting 4> 5 -dichloro-N-isobutylamino-naphthalimide with sodium methylate. Pp .: 220-21 ⁰ C

The 4 »5-dichloro-N-isobutylamino-naphthalimide is obtained by reaction of 4 »5-Diehlornaphthalic anhydride with isobutylhydrazine. Pp .: 156-60 C.

Leave in accordance with the procedure described in the examples the connections listed in the following table can also be established:

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0.1. J> 2 176

RO OR

example R. I. R ¹ R ² 12th CH ₃ H -CH-CH ₅ 15th η ° 2 ^H 5 It 14th It CH ₂ Cl It 15th Il • A H 16 ti O ₅ H ₁₁ Il 17th It -CH-C ₄ H ₉ It 18th η Cl
-CH-CH ₃ It 19th It -CH = CH ₂ Il

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O.Z. 32 176

example R. R ¹ R ² It 20th OE ₅ -CSCH -CH-CH, It 21 It CH-CH, Il It 22nd I! OE ₃
CH ₂ -CH-CH ₅ Il 23 Il CH ₂ OC ₆ H ₅ It 24 Il CH-CH-C ₆ H ₅ It 25th It 3 6 It 26th ° 2 ^H 5 OE ₃ Il 27 O ₅ E ₇ Il 28 ⁰ A Il 29 C ₂ H ₄ OCH ₅ Il

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example E. E ¹ E ² 50 C ₂ H ₄ OC ₂ H ₅ CH ₅ -CH-CH, 51 C ₂ H ₅ C ₂ H ₅ Il 52 "A. η Il 55 C ₂ H ₄ OCH ₅ Il Il 54 OH, ^C 6 ^H 5 Il 55 Il CH ₂ C ₆ H ₅ It 56 Il ^C 2 ^H 4 ^C 6 ^H 5 Il 57 II ' ^C 6 ^E 4 ^CH 5 η 58 It OC ₂ H ₅ Il 59 π OC ₄ H ₉ Il

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ο.ζ. 52 176

example E. R ¹ I E ² 40 OH ₃ OCH-C ₂ H ₅ f ^H 3
CH-CH 41 ti OCH ₂ -CH-C ₄ H ₉ It 42 It 0C ₀ H-OCH ₃ ,
2 4 3 Il 45 Il 0 - (h ^ -c-ch. It 44 O ₂ E ₅ H 45 OH ₃ yx f / 1 ττ Λ Il 46 It / CH,
K (CH ₂ -CH ⁵ ) ₂ It 47 Il H CH ₃ 48 • I C ₂ H ₅ n

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example E. E ¹ E ² η Il Il 49 OH, • Λ Sun ₂ H ₅ Sun ₅ H ₇ 50 Il Il Il 51 It CH ₂ Cl Il 52 η C ₉ H
| 2 5 η 53 Il OH-CH ₂ 54 ■ ι H 55 Il OH, 56 η C ₂ H ₅ 57 it ° 3 ^Η 7
:

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example R. R ¹ R ² It 58 CH ₃ C ₂ H ₄ Cl f ^H 3
-CH-C ₃ H ₇ ? 2 ^H 5
CH-C ₂ H ₅ 59 ti H / irr ΛΤΤ
Uli-, * \ jtL-r
1 3/3
-CH-CH Il 60 Il CH ₃ It It 61 ti C ₂ H ₅ ti Il 62 η ^C 3 ^E 7 It 63 ti C ₂ H ₄ Cl 64 η H 65 Il CH ₃ 66 ti C ₂ H ₅ 67 It C ₃ H ₇

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example R. S. Il R ¹ H R ² Il 68 CH ₃ Il CH-C ₄ H ₉ -CH-C ₂ H ₅ Il 69 It C ₂ H ₄ Cl CH ₅ -CH ₂ -C-CH
CH ₅ 70 Il CHCl
3 0 C ₂ H ₅ -CH ₂ -C-CH 71 ^C 2 ^H 5 CH ₃ Il 72 V ₉ Il Il 73 CH f 3? ^H 3
CH-CH ₀ -C-CH,
<- ι ί CH, 74 75

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O.Z. 52 176

example E. E ¹ E ² 76 CE ₃ H CH ₅
CH-C ₄ H ₉ 77 η OE ₃ It 78 Il O ₂ H ₅ ? ^Ε 5
OH-O ₄ E ₉ 79 π O ₃ E ₇ Il 80 C ₂ H ₅ OH, It 81 ° Λ η η 82 OE, Il CH ₅ / CH ₅
CH-C ₀ H.-CH
2 4 _Ν
OH,
ΛΙΤΤ 83 Il H ? ^Η 3
CH-C ₅ H ₁₁ 84 Il ? ^Η 3
CH-O ₆ H ₁

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example R. E ¹ E ² 85 CH ₅ OH, CHp-CH-C jHq 86 ti H H 87 ^C 2 ^H 5 OH ₃ It 88 CH ₅ O ₂ E ₅ C ₂ H ₅
CH ₂ -CH-C ₄ H ₉ 89 Il O ₃ H ₇ It 90 It OE ₃ ? ^H 3
flTT Λ | TT
CH-C ₇ H ₁₅ 91
92 Il Il
Il CH,
I 5
CH-C ₆ H ₅ 95 Il O ₂ H ₅ Il

CH,

CH-CH ₂ -C ₆ H ₅

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example a R ¹ E ² 95 OH, C ₂ H ₅ / ΊΤΤ / ΊΤΤ O ΈΓ
2 6 5 96 Il CH ₅ CH-CJS.OH
ο 4 97 Il η -CH-CH ₂ C ₆ H OCH ₅ 98 Il Il -CH-CH ₂ -C ₆ H (OC

The fluorescence of the compounds according to Examples 1 to 98 Dimethylformamide solution is blue-violet in each case.

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Claims (3)

Claims
/ li compounds of the aminonaphthalimide series of the general formula RO OR in which the leftovers R are identical or different and are CL- to C ^ -alkyl or CL- bis Ci, -Alkoxyäthyl mean R is hydrogen, C ₁ to C ₁₀ alkyl, C ₃ to Cg alkenyl, C ₃ to C ^ alkynyl, C ^ to Cg alkoxy, C ₁ to Cg alkyl or dialkylamino, phenoxymethyl, Phenyl, tolyl, benzyl or Phenylethyl and
ρ
R are branched C _{1 -C 1Q} -alkyl which may optionally be substituted by phenyl, hydroxyphenyl, methoxy or dimethoxyphenyl. 2. Compounds according to claim 1 of the formula "Β ¹ O Ji JD I a, OR OR in the B ¹ denotes hydrogen or C ₁ -C 6 -alkyl, B denotes branched C 1 -C 8 -alkyl and R has the meaning given. 809811/0044 - 26 - ORlGlNAL INSPECTED 3. Process for the preparation of compounds according to Claim 1, characterized in that compounds of the formula II R ² -NH II OR OR with compounds of the formula III X-C-R III, Il Λ in which X is OH, Cl, Br or an acyl radical O-C-R, implements. Use of the compounds according to Claim 1 as optical brighteners. BASF Aktiengesellschaft / L · / 651 / 13-11 80981 1/00 A4