CH676240A5 - - Google Patents

Description

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description

The invention relates to new boron complexes of the formula

? VR

(I)

wherein

Y = halogen, ococh3 or 0S03H,

R = H, optionally substituted (e.g. by halogen, hydroxy, nitro, Gi-CU alkoxy) Ci-Cs-alkyl, phenyl or cycloalkyl,

X = H or halogen,

Ri = a substituent and n = 0.1 or 2, and their preparation and use for the preparation of dyes.

If Y is halogen, it is primarily chlorine, bromine or preferably fluorine.

Ri can stand for a large number of substituents which do not adversely affect the course of the manufacturing or further processing process. R 1 is preferably alkyl, alkoxy, -C02-alkyl and -CONH-alkyl, the alkyl and alkoxy radicals preferably containing 1 to 6 carbon atoms. Furthermore Ri can be an acid group such as e.g. -so3m and -co2m mean where M is generally hydrogen, ammonium or an alkali metal atom such as sodium or potassium. Ri can also represent an electronegative group such as nitro, cyano or halogen, especially chlorine or bromine.

Of particular interest are the boron complexes of the formula I in which Y = each F and / or R is hydrogen, Ci-C4-alkyl, c5-c6-cycloalkyl or optionally with Ci-c4-alkyl, Ci-c4-alkoxy, phenoxy or Acetamido substituted phenyl and / or X is hydrogen or bromine and n = 0. For example, c1-c4-AI-kyl represents: methyl, ethyl, n-propyl, n-butyl and the corresponding isomeric radicals.

The boron complexes of the formula I according to the invention are prepared by reacting the compound of the formula in which R, Ri, n and X have the meaning given, with a boron compound which forms the BYY radical, for example Boron trifluoride etherate, preferably boron trifluoride ethyl etherate, BF3 gas or with BCI3, BBr3, H3BO3 / h2so4 or H3BC> 3 / acetic anhydride. At least one mole of the boron compound is used per mole of compound of the formula II. The reaction is preferably carried out in aprotic apolar solvents such as e.g. Benzene, monochlorobenzene, dichlorobenzene, trichlorobenzene or chlorinated hydrocarbons and at elevated temperatures, preferably at 70 - 150 ° C.

The compounds of the formula II are known and can be prepared by known methods. The boron complexes of the formula I obtained in this way are obtained in high yield, the isolation being carried out in a customary manner, e.g. by suction filtering, filtering or centrifuging with subsequent washing and drying.

The boron complexes of the formula I according to the invention are intermediate products and can be used above all for the preparation of dyes, especially disperse dyes and other compounds. The dyes and other compounds are prepared, for example, by the boron complexes of the formula I in an aprotic polar solvent such as dimethyl sulfoxide, N, N-dimethylformamide, N-methylformamide, N-methylacetamide, formamide, acetamide, N- Methyl thyrrolidone, 2-pyrrolidone, N-formylmorpholine, N-formylpiperidine, pyridine or mixtures of these solvents with malononitrile or with compounds of the formula

(ra)

fl? h-r

II II I

II II

(ii)

n • m m n vvv a *

N2-NH2

2nd

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CH 676 240 A5

where R2 is e.g. Ci-c4-alkyl or c5-c6-cycloalkyl which is substituted by phenyl, alkylamine or hydroxy. The reaction is preferably carried out at temperatures of 10-50 ° C.

The dyes obtained by the reaction of the boron complexes of the formula I with malononitrile are new and represent a further subject of the invention. These dyes correspond to the formulas ff W ~ R / \ / \ / \

(Ri) 1- II I II

n -

cm)

^ / \ ^ \ / k "

\ / \

Uh

'cn

(obtained from the boron complexes of the formula I in which X denotes a hydrogen atom) and

NC

(jRi).

3jTHZ

Y Yr

/ \ / s / \

t- il 1 I

V V V v

, cn

(iv)

i.

II

\ / * \

\

cn ita

'cn

(obtained from the boron complexes of the formula I in which X is a halogen atom) in which R is hydrogen, optionally substituted Ci-Cs-alkyl, phenyl or cycloalkyl, Ri is a substituent and n = 0, 1 or 2.

Furthermore, the invention relates to a process for the preparation of compounds of the formula ff W ~ R / \ / \ / \

<Ri) irt J S! (v)

v v v

Ö ÌH-R2

wherein R is a hydrogen atom, an optionally substituted Ci-Cs-alkyl radical, phenyl or cycloalkyl, R2 optionally substituted Ci-C4-alkyl or C5-C6-cycloalkyl, Ri is a substituent and n = 0.1 or 2 by reaction of the boron complexes of the formula I with amines of the formula r2-nh2 in which R2 has the meaning given above.

In the following examples, which explain the invention in more detail without restricting it to this, parts and percentages are, unless stated otherwise, parts by weight and percentages by weight.

Example 1 :

26.5 parts of 1-isopropylaminoanthraquinone are suspended in 250 parts of chlorobenzene, and 18 parts of boron trifluoride-ethyl etherate are added at room temperature. The reaction mixture is stirred at 80 ° C. for 3 hours, clarified by filtration and the filtrate is evaporated. The boron complex of the formula is obtained:

3rd

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CH676240 A5

F ^

A scm f fF <

S \ '\' \

I il l il • • • «

^ \ ^ / • • •

e

The following boron complexes are obtained by the same process:

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CH 676 240 A5

Table 1

î r

• R

^ \ y \ ^ \

• r m •>

I II I il

• • • •

^ / \ / ^ / Ä i

(ii)

BF3- (C2H5) 20

Chlorobenzene y

? Ve. • •. •

^ \ / ^ / \ m '• • ml il il il ». • ». •

^ \ ^ /

8 i

(I)

/ CHs

"C <

ch3 -C2HS

-c2h5

-ch3 -ch3

-h -h

/ "\

- ■ H •

\ /

/ " \ • H •

\ /

> CH3

/ - ^ H3 "<H>

• - ♦

nch3

/ CH3

- ^ ch3

- H • \ /

\

ch3

s \ \ /

\ /

s ~ \ \ /

—Ch3

Br h

Br

H

Br h

Br

H Br

H

Br

Br

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CH 676 240 A5

Table 1 (continued)

E.g.

r x

16

/ ^ \ / ~ ° H3

msss »

Br

ch3n

• - •.

17th

y \ m

\ / chs • - •

ch3 /

chsn

% •

H

18th

\ _r-w

\ / ~ ch3 ch3 /

Br

och3x

19th

\ /

• M

xch3

0CH3x h

20th

_y "~ \

\ /

• = s «

\ h3

Br

21st

- ^ OC2hs

• SS «

H

22

■ s \

- (y-oc2H5

Br

23

# \ - • ^ y-.nhcochs

• Sia h

24th

- ^ y-nhcoch3

• SS «

Br-

Example 25:

3.1 parts of the boron difluoride complex according to Example 1 are introduced at room temperature into a mixture of 100 parts of dimethyl sulfoxide, 4.4 parts of potassium acetate and 6.6 parts of malononitrile. The reaction mixture is stirred for a further 3 h at room temperature and suction filtered. The precipitate is washed with dimethyl sulfoxide and toluene and dried. A blue dye of the formula is obtained:

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CH 676 240 A5

ff P-A

, CH3

S \ / \ ^ \ • • • »

t II I II ■. •, »•

^ / \ ^ \ /

k A

ch3

\ / \

You

'CN

The following dyes are obtained by the same process: Table 2

V

? r *

s \ /% / \

i H i H «. • ». •

\ / \ / ^ / fl

(I)

ff p-R

j ^ \ / \ • '• • •

I II I II \ / \ / \ /

i "

\ / \

ita

CN

(iii)

E.g.

colour

26

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-CH3

—C2HS • - «

/ H N

-" H •

\ -S

/ ch3

/ —N0113

\ H /*

\

ch3

\ / • - *

\ /

-ch3

reddish blue reddish blue reddish blue reddish blue reddish blue reddish blue

Example 32:

If one works analogously to the information according to Example 25 but uses the Bordifiuorid complex of 1-isopropylamino-4-bromoanthraquinone according to Example 2, a green dye of the formula is obtained

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CH 676 240 A5

3p2 ■

! X

NCX ^ .CH3

^ \ ^ ^ I II I I

• v • •. I.

ch3

, CN

i.

Il

\ / \

\

CN

fa

"CN

Example 33:

3.1 parts of the bordifluprid complex according to Example 1 are introduced at room temperature into a mixture of 50 parts of dimethyl sulfoxide and 2 parts of 1-phenyl-4-aminobutane. The mixture is stirred for a further 3 hours at room temperature, diluted with water, the reaction product precipitating. After purification of the crude product with toluene, a compound of the formula is obtained:

ff F "0

/ \ / \ / \

# '• • p

I II II I • • • •

^ / \ / \ ^

• ■

8 ÄH-CH-CHz-CHz — C / • CH3 • = •

which among others represents an intermediate dye.

The following compounds are obtained by the same procedure:

<

, ch3

'ch3

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Table 3

y

? v

S \ / \ s \

I II I II

• v • ». •

^ / N / ^ /

a • * •

a

CD

rz-nh2

ff ï "

y \ s \ f \

II I I II • • • •

\ ^ \ / \ / U UH — R2

(v)

E.g.

r r2

34

35

36

37

38

39

40

41

42

-g2h5 -ch3

<

, ch3

ch3

y '"\

\

och3

/

-ch3

\

/ \

\ / • ss *

\

ch3

✓ \

\ /

• ss *

• - •

•

\ / • ss »

# \ - • —I

/ \

\ /

• ss * • * - •

/ V

\ /

-ch3

oc2h5

-ch (

, ch3

ch3

-ch2ch2ch2n (ch3) 2 -CH2ch2ch2N (ch3) Z

-ch2ch2CH2N (ch3) 2

-CH '

, ch3

ch3

X

, ch3

cha

, ch3

- ° <

ch3 • - •

/ H \ - • H •

, ch3 .-. ^ h3

- <H>

\ h3 -ch2ch20h

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CH 676 240 A5

Claims (13)

Claims 1. Boron complex of the formula Y Y V ? VR / \ / \ / \ (Ri) _4 r, i fi (i) n \ / \ / " ö i where Y = halogen, OCOCHs or oso3h, R = H, optionally substituted Ci-Cs-alkyl, phenyl or cycloalkyl, X = H or halogen, Ri = a substituent and n = 0.1 or 2. 2. Boron complex according to claim 1, wherein Y = per F and R, Ri, n and X have the meaning given in claim 1. 3. Boron complex according to claim 1 or 2, wherein R is hydrogen, Cs-C6-cycloalkyl, Ci-C ^ alkyl or phenyl optionally substituted with Ci-C4-alkyl, Ci-c4-alkoxy, phenoxy or acetamido. 4. Boron complex according to one of claims 1 to 3, wherein Y = F and R has the meaning given in claim 3, X is hydrogen or Br and n = 0. 5. A process for the preparation of a boron complex according to claim 1, characterized in that one mole of the compound of the formula 2 P * f \ / \ (RX) 4- H fi ï (II) n • • • » V \ 'V 8 i in which R is hydrogen, optionally substituted Ci-Cs-alkyl, phenyl or cycloalkyl, X is hydrogen or halogen, Ri is a substituent and n is the number 0, 1 or 2, with at least one mol of the radical BYY reacting boron compound. 6. The method according to claim 5, characterized in that a boron trifluoride etherate is used as the boron compound. 7. Use of the boron complexes according to claim 1 for the preparation of disperse dyes by the boron complexes of the formula I wherein X is halogen in an aprotic polar solvent with malononitrile to give compounds of the formula IV Wz NC \ S \ I V / \ / \ / \ S l 'CN (IV) v V \ n A »" V in NCN converts, wherein R is hydrogen, optionally substituted Ci-Cs-alkyl, phenyl or cycloalkyl, Ri is a substituent and n = 0.1 or 2. 8. Use of the boron complexes according to claim 1 for the preparation of dispersion dyes by the boron complexes of the formula i in an aprotic polar solvent with compounds 10th 5 10th 15 20th 25th 30th 35 40 45 50 55 60 65 CH 676 240 A5 of the formula R2-NH2, in which R2 is optionally substituted Ci-C4-alkyl or Cs-Cß-cycloalkyl to compounds of the formula V. ff P-R / \ / \ / \ ! "J <v> \ / W ö ÌH-R2 where R represents a hydrogen atom, an optionally substituted Ci-Cs-alkyl radical, phenyl or cycloalkyl, R2 optionally substituted Ci-C4-alkyl or C5-C6-cycloalkyl, Ri is a substituent and n = 0.1 or 2. 9. Process for the preparation of a compound of the formula ff W ~ R y \ / \ ^ \ (Rl) —î- H î Û (III) n • • »• n ^ / \ / \ / 4. " Ita ncn wherein R is hydrogen, an optionally substituted Ci-Cs-alkyl radical, phenyl or cycloalkyl, Ri is a substituent and n = 0, 1 or 2, characterized in that a boron complex of the formula I Y Y A- ^ S ✓ ^ ✓ N 5 i s 8th wherein Y = halogen, OCOCH3 or OSO3H, R = H, optionally substituted Ci-Cs-alkyl, phenyl or cycloalkyl, Ri = a substituent and n = 0.1 or 2, means reacted with malononitrile. 10. A compound of formula III, prepared by the process according to claim 9 ff y \ / \ f \ (Ri) —ï- »ï S (III) ^ \ ^ \ / A « ita wherein R is hydrogen, an optionally substituted Ci-Cs-alkyl radical, phenyl or cycloalkyl, Ri is a substituent and n = 0.1 or 2. 11 5 10th 15 20th 25th 30th 35 40 45 50 55 60 65 CH 676 240 A5 11. Process for preparing a compound of formula ip2 Y Ve S \ m * m a * m s} • À e »(IV) V V V ^ cs i »-X. \ / XCN fe wherein R is hydrogen, optionally substituted Ci-Cs-alkyl, phenyl or cycloalkyl, Ri is a substituent and n = 0.1 or 2, characterized in that a boron complex of the formula y y X ? ì- * S \ / ^ / \ î1 i 5 (I) VN / V a ï wherein Y = halogen, OCOCH3 or OSO3H, R = H, optionally substituted Ci-Cs-alkyl, phenyl or cycloalkyl, Ri = a substituent, X = halogen and n = 0.1 or 2, are reacted with malononitrile. 12. A compound of formula IV, prepared by the process according to claim 11 NH2 Y V y ^ (Ri) —ï- 5 ï i ™ (rv) n v • "v" CN V V V v • "\ N 1 I h wherein R is hydrogen, optionally substituted Ci-Cs-alkyl, phenyl or cycloalkyl, Ri is a substituent and n = 0.1 or 2. 13. Process for the preparation of compounds of the formula F1 F "* (Rl) H "î» î (V) n • • • • \ # \ / \ s a Ah-R2 12 5 10th 15 20th 25th 30th 35 40 45 50 55 60 65 CH 676 240 A5 wherein R is a hydrogen atom, an optionally substituted Ci-Cs-alkyl radical, phenyl or cycloalkyl, R2 optionally substituted CHValkyl or Cs-C6-cycloalkyl, Ri is a substituent and n = 0.1 or 2 mean by reacting boron complexes of the formula Y = halogen, OCOCH3 or OSO3H, R = H, optionally substituted Ci-Cs-alkyl, phenyl or cycloalkyl, X = H or halogen, Ri = a substituent and n = 0.1 or 2, with amines of the formula r2-nh2, in which R2 has the meaning given above. (I) wherein 13