Merocyanine derivatives

Abstract

Disclosed are compounds of formula (1) and (2) and/or E/E-, E/Z- or Z/Z geometrical isomer forms thereof; wherein R1-R5, R1-R11 and A are defined as in description. The compounds are used as UV absorbers for protecting household products from photolytic and oxidative degradation, as plastic additives, preferably for food and pharmaceutical packaging applications, for preventing photo-degradation of food by incorporation of the compounds of formula (1) and/or (2) into transparent food containers, for protection of UV-A sensitive drugs from photo-degradation by incorporation of UV absorber in transparent blister foils or transparent pharmacy containers, as additives for photographic and printing applications, as additives for electronic applications and protecting the ingredients in agriculture applications. ##STR00001##

Claims

1. A compound of formula ##STR00082## and/or its E/E-, E/Z- or Z/Z geometrical isomer forms; wherein R.sub.1 and R.sub.2 independently of each other are hydrogen; C.sub.4-C.sub.12alkyl; or hydroxyl-C.sub.3-C.sub.12alkyl; R.sub.3 is a (CO)OR.sub.6 group; or a (CO)NHR.sub.6 group; R.sub.6 is C.sub.1-C.sub.22alkyl, C.sub.2-C.sub.22alkenyl, C.sub.2-C.sub.22alkinyl, C.sub.3-C.sub.22cycloalkyl or C.sub.3-C.sub.22cycloalkenyl, which is optionally substituted by one or more than one OH; R.sub.4 and R.sub.5 are hydrogen; or R.sub.4 and R.sub.5 form a (CH.sub.2).sub.n ring which is optionally interrupted by one or more than one O or by NH; n is a number from 2 to 7; R.sub.7 and R.sub.8 independently of each other are hydrogen; C.sub.1-C.sub.22alkyl, C.sub.2-C.sub.22alkenyl, C.sub.2-C.sub.22alkinyl, which is interrupted by one or more than one O or substituted by one or more than one OH, C.sub.3-C.sub.22cycloalkyl or C.sub.3-C.sub.22cycloalkenyl, wherein said C.sub.3-C.sub.22cycloalkyl or C.sub.3-C.sub.22cycloalkenyl is optionally interrupted by one or more than one O; or R.sub.7 and R.sub.8 together with the nitrogen atom linking them form a (CH.sub.2).sub.n ring which is optionally interrupted by one or more than one O; R.sub.9 and R.sub.10 are hydrogen; or R.sub.9 and R.sub.10 form a (CH.sub.2).sub.n ring which is optionally interrupted by O or by NH; A is O; or NH; R.sub.11 is C.sub.1-C.sub.22alkyl, C.sub.2-C.sub.22alkenyl, C.sub.2-C.sub.22alkinyl, C.sub.3-C.sub.22cycloalkyl or C.sub.3-C.sub.22cycloalkenyl, which is optionally interrupted by one or more than one O; or C.sub.1-C.sub.22alkyl or C.sub.2-C.sub.22alkenyl which is substituted by C.sub.3-C.sub.22cycloalkyl or C.sub.3-C.sub.22cycloalkenyl, wherein said C.sub.3-C.sub.22cycloalkyl or C.sub.3-C.sub.22cycloalkenyl is optionally interrupted by one or more than one O; with the proviso that (I) at least one of R.sub.1, R.sub.2, and R.sub.6 is substituted by hydroxyl; (II) if one of R.sub.1 is hydroxyethyl, R.sub.2 is not hydrogen, methyl or ethyl or hydroxyethyl; and if R.sub.1 is hydrogen, R.sub.2 is not 1-hydroxy-3-methyl-but-2-yl; (III) if R.sub.6 is substituted by one or more than one OH; one of R.sub.1 and R.sub.2 is C.sub.4-C.sub.22alkyl; or R.sub.1 and R.sub.2 together with the linking nitrogen form a piperidyl or morpholinyl radical; and (IV) at least one of R.sub.7 and R.sub.8, or R.sub.11 is interrupted by one or more than one O.

2. The compound according to claim 1, wherein R.sub.1 and R.sub.2 independently of each other are hydrogen; C.sub.4-C.sub.12alkyl; or hydroxyl-C.sub.3-C.sub.12alkyl; R.sub.3 is a (CO)OR.sub.6 group; or a (CO)NHR.sub.6 group; R.sub.6 is C.sub.1-C.sub.22alkyl, C.sub.2-C.sub.22alkenyl, C.sub.2-C.sub.22alkinyl, C.sub.3-C.sub.22cycloalkyl or C.sub.3-C.sub.22cycloalkenyl, which is optionally substituted by one or more than one OH; R.sub.4 and R.sub.5 are hydrogen; or R.sub.4 and R.sub.5 form a (CH.sub.2).sub.n ring which is optionally interrupted by O or by NH; n is a number from 2 to 7; R.sub.7 and R.sub.8 independently of each other are hydrogen; C.sub.1-C.sub.22alkyl, C.sub.2-C.sub.22alkenyl, C.sub.2-C.sub.22alkinyl, which is interrupted by one or more than one O or substituted by one or more than one OH; or R.sub.7 and R.sub.8 together with the nitrogen atom linking them form a (CH.sub.2).sub.n ring which is optionally interrupted by one or more than one O; R.sub.9 and R.sub.10 are hydrogen; or R.sub.9 and R.sub.10 form a (CH.sub.2).sub.n ring which is optionally interrupted by O or by NH; A is O; or NH; R.sub.11 is C.sub.1-C.sub.22alkyl, C.sub.2-C.sub.22alkenyl, C.sub.2-C.sub.22alkinyl, C.sub.3-C.sub.22cycloalkyl or C.sub.3-C.sub.22cycloalkenyl, which is optionally interrupted by one or more than one O; with the proviso that (I) at least one of R.sub.1, R.sub.2, and R.sub.6 is substituted by hydroxyl; (II) if one of R.sub.1 is hydroxyethyl, R.sub.2 is not hydrogen, methyl or ethyl or hydroxyethyl; and if R.sub.1 is hydrogen, R.sub.2 is not 1-hydroxy-3-methyl-but-2-yl; (III) if R.sub.6 is substituted by one or more than one OH; one of R.sub.1 and R.sub.2 is C.sub.4-C.sub.22alkyl; or R.sub.1 and R.sub.2 together with the linking nitrogen form a piperidyl or morpholinyl radical; and (IV) at least one of R.sub.7 and R.sub.8, or R.sub.1 is interrupted by one or more than one O.

3. A compound which corresponds to one of the following formulas ##STR00083## ##STR00084##

4. A compound which is 2-ethoxyethyl(2Z)-cyano{3-[(3-methoxypropyl)amino]cyclohex-2-en-1-ylidene}ethanoate in its E/Z geometrical isomer corresponding to the formula ##STR00085## and/or its E/E geometrical form of formula ##STR00086##

5. A compound of formula ##STR00087## and/or its E/E-, E/Z- or Z/Z geometrical isomer forms; wherein R.sub.1 and R.sub.2 independently of each other are hydrogen; C.sub.1-C.sub.22alkyl, C.sub.2-C.sub.22alkenyl, C.sub.2-C.sub.22alkinyl, which are optionally substituted by at least one hydroxyl; or R.sub.1 and R.sub.2 together with the nitrogen atom linking them form a (CH.sub.2).sub.n ring which is optionally interrupted by O or by NH; R.sub.3 is a (CO)OR.sub.6 group; or a (CO)NHR.sub.6 group; R.sub.6 is C.sub.1-C.sub.12alkyl, which is optionally substituted by one or more than one hydroxyl; R.sub.4 and R.sub.5 are hydrogen; or R.sub.4 and R.sub.5 form a (CH.sub.2).sub.n ring which is optionally interrupted by one or more than one O or by NH; n is a number from 2 to 7; with the proviso that (I) at least one of R.sub.1, R.sub.2, and R.sub.6 is substituted by hydroxyl; (II) if one of R.sub.1 is hydroxyethyl, R.sub.2 is not hydrogen, methyl or ethyl or hydroxyethyl; and if R.sub.1 is hydrogen, R.sub.2 is not 1-hydroxy-3-methyl-but-2-yl; and (III) if R.sub.6 is substituted by one or more than one OH; one of R.sub.1 and R.sub.2 is C.sub.4-C.sub.22alkyl; or R.sub.1 and R.sub.2 together with the linking nitrogen form a piperidyl or morpholinyl radical.

6. The compound of formula (1) according to claim 5, wherein one of R.sub.1 and R.sub.2 is C.sub.4-C.sub.22alkyl; or R.sub.1 and R.sub.2 together with the nitrogen atom linking them form a (CH.sub.2).sub.n-ring which is optionally interrupted by O and/or NH.

7. A compound of formula ##STR00088## and/or its E/E-, E/Z- or Z/Z geometrical isomer forms; wherein R.sub.1 and R.sub.2 respectively together with the linking nitrogen atom to form a piperidyl, radical, or a morpholinyl radical; R.sub.3 is a (CO)OR.sub.6 group; or a (CO)NHR.sub.6 group; R.sub.6 is C.sub.1-C.sub.22alkyl, C.sub.2-C.sub.22alkenyl, C.sub.2-C.sub.22alkinyl, C.sub.3-C.sub.22cycloalkyl or C.sub.3-C.sub.22cycloalkenyl, which is optionally substituted by one or more than one OH; R.sub.4 and R.sub.5 are hydrogen; or R.sub.4 and R.sub.5 form a (CH.sub.2).sub.n ring which is optionally interrupted by one or more than one O or by NH; n is a number from 2 to 7; R.sub.7 and R.sub.8 respectively together with the linking nitrogen atom form a piperidyl radical or a morpholinyl radical; R.sub.9 and R.sub.10 are hydrogen; or R.sub.9 and R.sub.10 form a (CH.sub.2).sub.n ring which is optionally interrupted by O or by NH; A is O; or NH; R.sub.11 is C.sub.1-C.sub.22alkyl, C.sub.2-C.sub.22alkenyl, C.sub.2-C.sub.22alkinyl, C.sub.3-C.sub.22cycloalkyl or C.sub.3-C.sub.22cycloalkenyl, which is optionally interrupted by one or more than one O; or C.sub.1-C.sub.22alkyl or C.sub.2-C.sub.22alkenyl which is substituted by C.sub.3-C.sub.22cycloalkyl or C.sub.3-C.sub.22cycloalkenyl, wherein said C.sub.3-C.sub.22cycloalkyl or C.sub.3-C.sub.22cycloalkenyl is optionally interrupted by one or more than one O; with the proviso that (I) at least one of R.sub.1, R.sub.2, and R.sub.6 is substituted by hydroxyl; (II) if one of R.sub.1 is hydroxyethyl, R.sub.2 is not hydrogen, methyl or ethyl or hydroxyethyl; and if R.sub.1 is hydrogen, R.sub.2 is not 1-hydroxy-3-methyl-but-2-yl; (III) if R.sub.6 is substituted by one or more than one OH; one of R.sub.1 and R.sub.2 is C.sub.4-C.sub.22alkyl; or R.sub.1 and R.sub.2 together with the linking nitrogen form a piperidyl or morpholinyl radical; and (IV) at least one of R.sub.7 and R.sub.8, or R.sub.11 is interrupted by one or more than one O.

8. A compound of formula ##STR00089## and/or its E/E-, E/Z- or Z/Z geometrical isomer forms; wherein R.sub.1 and R.sub.2 independently of each other are hydrogen or C.sub.1-C.sub.22alkyl; or hydroxyl-C.sub.1-C.sub.22alkyl; or R.sub.1 and R.sub.2 together with the nitrogen atom are linked together to form a piperidyl or morpholinyl radical; R.sub.3 is a (CO)OR.sub.6 group; or a (CO)NHR.sub.6 group; R.sub.6 is C.sub.1-C.sub.22alkyl, which may be substituted by one or more than one OH; R.sub.4 and R.sub.5 are hydrogen; or R.sub.4 and R.sub.5 are linked together to form a carbocyclic ring which contains 6 carbon atoms; n is a number from 2 to 7; with the proviso that (I) at least one of R.sub.1, R.sub.2, and R.sub.6 is substituted by hydroxyl; (II) if one of R.sub.1 is hydroxyethyl, R.sub.2 is not hydrogen, methyl or ethyl or hydroxyethyl; and if R.sub.1 is hydrogen, R.sub.2 is not 1-hydroxy-3-methyl-but-2-yl; and (III) if R.sub.6 is substituted by one or more than one OH; one of R.sub.1 and R.sub.2 is C.sub.4-C.sub.22alkyl; or R.sub.1 and R.sub.2 together with the linking nitrogen form a piperidyl or morpholinyl radical.

9. The compound of formula (1) according to claim 8, wherein R.sub.1 and R.sub.2 independently of each other are hydrogen; or hydroxyl-C.sub.1-C.sub.22alkyl; wherein at least one of R.sub.1 and R.sub.2 is hydroxyl-C.sub.1-C.sub.22alkyl; R.sub.3 is a (CO)OR.sub.6 group; or a (CO)NHR.sub.6 group; R.sub.6 is C.sub.1-C.sub.22alkyl; and R.sub.4 and R.sub.5 are hydrogen; or R.sub.4 and R.sub.5 are linked together to form a carbocyclic ring which contains 6 carbon atoms.

10. A compound of formula ##STR00090## and/or its E/E-, E/Z- or Z/Z geometrical isomer forms; wherein R.sub.7 and R.sub.8 independently of each other are hydrogen; C.sub.1-C.sub.22alkyl, C.sub.2-C.sub.22alkenyl, C.sub.2-C.sub.22alkinyl, which is interrupted by one or more than one O or substituted by one or more than one OH, C.sub.3-C.sub.22cycloalkyl or C.sub.3-C.sub.22cycloalkenyl, wherein said C.sub.3-C.sub.22cycloalkyl or C.sub.3-C.sub.22cycloalkenyl is optionally interrupted by one or more than one O; or R.sub.7 and R.sub.8 together with the nitrogen atom form a morpholinyl or piperidyl radical; R.sub.9 and R.sub.10 are hydrogen; or R.sub.9 and R.sub.10 are linked together to form a carbocylic ring which contains 6 carbon atoms; A is O; or NH; R.sub.11 is C.sub.1-C.sub.22alkyl, which is optionally interrupted by one or more than one O; with the proviso that at least one of R.sub.7 and R.sub.8, or R.sub.11 is interrupted by one or more than one O.

Description

EXAMPLES

A. Preparation Examples of Merocyanine UV Absorbers

Example A1

Preparation of the Compound of Formula

(1) ##STR00058##

(2) 55.33 grams of bis-(2-methoxyethyl)amine are reacted with 1,1,3,3-tetramethoxypropane in acetic acid, concentrated and treated with 21.48 grams of ethyl cyanoacetate in the presence of an organic base and a solvent.

(3) The following base/solvent combinations are used:

(4) TABLE-US-00006 Example Base Solvent Example A1.1 DBU (1,8- dimethylformamide diazabicyclo[5.4.0]undec-7-ene) Example A1.2 DBU (1,5- dimethylacetamide diazabicyclo[4.3.0]non-5-ene) Example A1.3 DBN (1,5- 1-methylpyrrolidone diazabicyclo[4.3.0]non-5-ene) Example A1.4 DBN (1,5- dimethylsulfoxide diazabicyclo[4.3.0]non-5-ene) Example A1.5 DBU (1,8- dimethylformamide diazabicyclo[5.4.0]undec-7-ene) Example A1.6 sodium methylate dimethylacetamide Example A1.7 sodium methylate isopropanol Example A1.8 potassium t-butoxide t-butanol

(5) The reaction temperature is between 0 C. and the boiling point of the solvent.

(6) The reaction end point is confirmed by thin layer chromatography or high performance liquid chromatography.

(7) After the reaction, the product (101) is obtained from the reaction mixture through ordinary product isolation by liquid-liquid separation, column chromatography or crystallization by addition of a poor solvent to the reaction mixture.

(8) The desired product (101) is obtained in yields of 66% (36 grams) as a dark brownish oil which crystallized as yellow crystals (Melting point: 76.9 C.).

Example A2

Preparation of the Compound of Formula

(9) ##STR00059##

(10) 55.33 grams of bis-(2-methoxyethyl)amine are condensed with 1,1,3,3-tetramethoxypropane in acetic acid, concentrated and treated with 27.18 grams of 2-methoxyethyl-cyanoacetate in the presence of an organic base and a solvent.

(11) The following base/solvent combinations are used:

(12) TABLE-US-00007 Example Base Solvent Example A2.1 DBU (1,8- dimethylformamide diazabicyclo[5.4.0]undec-7-ene) Example A2.2 DBN (1,5- dimethylacetamide diazabicyclo[4.3.0]non-5-ene) Example A2.3 DBN (1,5- 1-methylpyrrolidone diazabicyclo[4.3.0]non-5-ene) Example A2.4 DBN (1,5- dimethylsulfoxide diazabicyclo[4.3.0]non-5-ene) Example A2.5 DBU (1,8- dimethylformamide diazabicyclo[5.4.0]undec-7-ene) Example A2.6 N-methylmorpholine dimethylacetamide Example A2.7 bis-(2-methoxyethyl)amine 1-methylpyrrolidone Example A2.8 sodium methylate dimethylsulfoxide

(13) After the reaction, the product (102) is obtained from the reaction mixture through silica gel column chromatography (eluent: toluene/acetone).

(14) The desired product (102) is obtained in yields of 75% (45.44 grams) as a yellow powder (melting point: 92.2 C.).

Example A3

Preparation of the Compound of Formula

(15) ##STR00060##

(16) 55.33 grams of bis-(2-methoxyethyl)amine are condensed with 1,1,3,3-tetramethoxypropane in acetic acid, concentrated and treated with 29.85 grams of 2-ethoxyethyl-cyanoacetate in the presence of an organic base and a solvent

(17) The following base/solvent combinations are used:

(18) TABLE-US-00008 Example Base Solvent Example A3.1 DBU (1,8- dimethylformamide diazabicyclo[5.4.0]undec-7-ene) Example A3.2 DBN (1,5- dimethylacetamide diazabicyclo[4.3.0]non-5-ene) Example A3.3 DBN (1,5- 1-methylpyrrolidone diazabicyclo[4.3.0]non-5-ene) Example A3.4 DBN (1,5- dimethylsulfoxide diazabicyclo[4.3.0]non-5-ene) Example A3.5 DBU (1,8- dimethylformamide diazabicyclo[5.4.0]undec-7-ene) Example A3.6 N-methylmorpholine dimethylacetamide Example A3.7 bis-(2-methoxyethyl)amine 1-methylpyrrolidone Example A3.8 sodium methylate dimethylsulfoxide

(19) After the reaction, the product (103) is obtained from the reaction mixture through ordinary product isolation by liquid-liquid separation, column chromatography or crystallization by addition of a poor solvent to the reaction mixture.

(20) The desired product (103) is obtained in yields of 66% (39.99 grams) as beige crystals (melting point: 58.3 C.).

Example A4

Preparation of the Compound of Formula

(21) ##STR00061##

(22) 70.67 grams of piperidine are condensed with 1,1,3,3-tetramethoxypropane in acetic acid, concentrated and treated with 59.72 grams of 2-ethoxyethyl cyanoacetate cyanoacetate in the presence of an organic base and a solvent.

(23) The following base/solvent combinations are used:

(24) TABLE-US-00009 Example Base Solvent Example A4.1 DBU (1,8- dimethylformamide diazabicyclo[5.4.0]undec-7-ene) Example A4.2 DBN (1,5- dimethylacetamide diazabicyclo[4.3.0]non-5-ene) Example A4.3 DBN (1,5- 1-methylpyrrolidone diazabicyclo[4.3.0]non-5-ene) Example A4.4 DBN (1,5- dimethylsulfoxide diazabicyclo[4.3.0]non-5-ene) Example A4.5 DBU (1,8- dimethylformamide diazabicyclo[5.4.0]undec-7-ene) Example A4.6 piperidine dimethylacetamide Example A4.7 piperidine 1-methylpyrrolidone Example A4.8 sodium methylate dimethylsulfoxide

(25) The desired product (104) is obtained in yields of 91% (96.5 grams) as an orange powder.

(26) After silica gel column chromatography (eluent: toluene/acetone) the pure product (104) is obtained yielding dark yellow crystals.

(27) Melting point: 66-67 C.

Example A5a

Preparation of Compound of Formula

(28) ##STR00062##

(29) 132.83 grams of piperidine are condensed with 1,1,3,3-tetramethoxypropane in acetic acid, concentrated and treated with 133.38 grams of 2-(2-methoxyethoxy)-ethyl-cyanoacetate in the presence of an organic base and a solvent.

(30) The following base/solvent combinations are used:

(31) TABLE-US-00010 Example Base Solvent Example A5a.1 DBU (1,8- dimethylformamide diazabicyclo[5.4.0]undec-7-ene Example A5a.2 DBN (1,5- dimethylacetamide diazabicyclo[4.3.0]non-5-ene) Example A5a.3 DBN (1,5- 1-methylpyrrolidone diazabicyclo[4.3.0]non-5-ene) Example A5a.4 DBN (1,5- dimethylsulfoxide diazabicyclo[4.3.0]non-5-ene) Example A5a.5 DBU (1,8- dimethylformamide diazabicyclo[5.4.0]undec-7-ene) Example A5a.6 piperidine dimethylacetamide Example A5a.7 piperidine 1-methylpyrrolidone Example A5a.8 sodium methylate dimethylsulfoxide

(32) The desired product (105) is obtained in yields of 38% (82.4 grams) as an dark oil.

(33) After column chromatography over silica gel and toluene/acetone (9:1) as eluent the product (105) crystallizes from water as orange crystals. Melting point: 43.5-45 C.

Example A5b

Preparation of the Compound of Formula (105)

(34) By using 5 grams of 3-(1-piperidinyl)-2-propenal and 7.39 grams of 2-(2-methoxyethoxy)ethyl-2-cyano acetic acid ester in the presence of a base and optionally a solvent the desired product is obtained in yields of 32% (3.5 grams) as an dark oil.

(35) The following base/solvent combinations are used:

(36) TABLE-US-00011 Example Base Solvent Example A5b.1 piperidine no solvent Example A5b.2 N-methylmorpholine dimethylacetamide Example A5b.3 piperidine 1-methylpyrrolidone Example A5b.4 piperidine dimethylsulfoxide

Example A6

Preparation of the Compound of Formula

(37) ##STR00063##

(38) 2.89 grams of piperidine are condensed with 1,1,3,3-tetramethoxypropane in acetic acid, concentrated and treated with 1.22 grams of 2-cyano-N-(2-hydroxyethyl)acetamide in the presence of an organic base and a solvent.

(39) The following base/solvent combinations are used:

(40) TABLE-US-00012 Example Base Solvent Example A6.1 DBU dimethylformamide (1,8-diazabicyclo[5.4.0]undec-7- ene Example A6.2 DBN dimethylacetamide (1,5-diazabicyclo[4.3.0]non-5-ene) Example A6.3 DBN 1-methylpyrrolidone (1,5-diazabicyclo[4.3.0]non-5-ene) Example A6.4 ethanolamine dimethylsulfoxide Example A6.5 ethanolamine dimethylformamide Example A6.6 piperidine dimethylacetamide Example A6.7 piperidine 1-methylpyrrolidone Example A6.8 sodium methylate dimethylsulfoxide

(41) The reaction end point is confirmed by thin layer chromatography or high performance liquid chromatography.

(42) After the reaction, the product (106) is obtained from the reaction mixture through ordinary product isolation by liquid-liquid separation, column chromatography or crystallization by addition of a poor solvent to the reaction mixture.

(43) The desired product (106) is obtained as a brownish oil which crystallizes in form of yellow crystals (0.24 g, 10%).

(44) Melting point: 139.4-141.0 C.

Example A7

Preparation of Compound of Formula

(45) ##STR00064##

(46) 27.84 grams of piperidine are condensed with 1,1,3,3-tetramethoxypropane in acetic acid, concentrated and treated with 56.77 grams of (2,2-dimethyl-1,3-dioxolan-4-yl)methyl cyanoacetate in the presence of an organic base and a solvent.

(47) The following base/solvent combinations are used:

(48) TABLE-US-00013 Example Base Solvent Example A7.1 DBU dimethylformamide (1,8-diazabicyclo[5.4.0]undec-7- ene Example A7.2 DBN dimethylacetamide (1,5-diazabicyclo[4.3.0]non-5-ene) Example A7.3 DBN 1-methylpyrrolidone (1,5-diazabicyclo[4.3.0]non-5-ene) Example A7.4 DBN dimethylsulfoxide (1,5-diazabicyclo[4.3.0]non-5-ene) Example A7.5 DBU dimethylformamide (1,8-diazabicyclo[5.4.0]undec-7- ene) Example A7.6 piperidine dimethylacetamide Example A7.7 piperidine 1-methylpyrrolidone Example A7.8 piperidine dimethylsulfoxide

(49) 74.74 grams of the compound (107) are obtained yielding yellow crystals.

Example A8

Preparation of Compound of Formula

(50) ##STR00065##

(51) 70 ml of hydro chloride acid (1 N) are added to a solution of 74.74 grams of merocyanine compound (107) in 350 ml of ethanol. The reaction mixture is stirred for 24 hours at 40 C. After adding water the product is extracted several times with ethyl acetate. The combined organic phases are dried with sodium sulphate, filtrated and concentrated under vacuum yielding the crude product as a brown oil.

(52) After crystallization 34.44 grams of the product is yielded as a yellow powder.

(53) Melting point: 101 C.

Example A9

Preparation of the Compound of Formula

(54) ##STR00066##

(55) 236.72 grams of piperidine are condensed with 1,1,3,3-tetramethoxypropane in acetic acid, concentrated and treated with 217.24 grams of 1-(2-hydroxy)pentyl cyanoacetate in the presence of an organic base and a solvent.

(56) The following base/solvent combinations are used:

(57) TABLE-US-00014 Example Base Solvent Example A9.1 DBU dimethylformamide (1,8-diazabicyclo[5.4.0]undec-7- ene) Example A9.2 DBU dimethylacetamide (1,8-diazabicyclo[5.4.0]undec-7- ene) Example A9.3 piperidine 1-methylpyrrolidone Example A9.4 piperidine dimethylsulfoxide Example A9.5 DBU dimethylformamide (1,8-diazabicyclo[5.4.0]undec-7- ene) Example A9.6 DBU dimethylacetamide (1,8-diazabicyclo[5.4.0]undec-7- ene) Example A9.7 DBU 1-methylpyrrolidone (1,8-diazabicyclo[5.4.0]undec-7- ene) Example A9.8 DBU dimethylsulfoxide (1,8-diazabicyclo[5.4.0]undec-7- ene)

(58) 500 grams of the crude product (109) are obtained yielding a dark brown oil.

(59) After column chromatography (silica gel, eluent: toluene/ethyl acetate) and crystallization 53.09 grams (23%) of the desired product (109) are obtained yielding yellow crystals.

(60) Melting point: 130 C.

Example A10

Preparation of Compound of Formula

(61) ##STR00067##

(62) 1.81 grams of morpholine are treated with 1,1,3,3-tetramethoxypropane in acetic acid, concentrated and treated with 1.89 grams of (2,2-dimethyl-1,3-dioxolan-4-yl)methyl cyanoacetate in the presence of an organic base and a solvent.

(63) The following base/solvent combinations are used:

(64) TABLE-US-00015 Example Base Solvent Example A10.1 DBU dimethylformamide (1,8-diazabicyclo[5.4.0]undec-7- ene) Example A10.2 DBU dimethylacetamide (1,8-diazabicyclo[5.4.0]undec-7- ene) Example A10.3 DBN 1-methylpyrrolidone (1,5-diazabicyclo[4.3.0]non-5-ene) Example A10.4 morpholine dimethylsulfoxide Example A10.5 morpholine dimethylformamide Example A10.6 morpholine dimethylacetamide Example A10.7 sodium methylate isopropanol Example A10.8 sodium methylate dimethylsulfoxide

(65) 2.99 grams of the crude product (110) are obtained yielding a dark brown oil. After column chromatography (silica gel, eluent: toluene/acetone) and crystallization 1.17 grams (50%) of the compound (110) are obtained yielding yellowish crystals.

Example A11

Preparation of the Compound of Formula

(66) ##STR00068##

(67) 1 ml of hydro chloride acid (1 N) are added to a solution of 1.17 grams of merocyanine compound (110) in 5 ml of ethanol. The reaction mixture is stirred for 16 hours at room temperature.

(68) The product is filtered off and washed with small amounts of ethanol and water.

(69) After drying under vacuum 0.36 grams of the product (111) is yielded as a yellowish powder.

(70) Melting point: 144.5-146.0 C.

Example A12

Preparation of the Compound of Formula

(71) ##STR00069##

(72) 83.40 grams of morpholine are condensed with 1,1,3,3-tetramethoxypropane in acetic acid and treated with 47.15 grams of 2-ethoxyethyl cyanoacetate in the presence of the organic base and a solvent.

(73) The following base/solvent combinations are used:

(74) TABLE-US-00016 Example Base Solvent Example A12.1 DBU dimethylformamide (1,8-diazabicyclo[5.4.0]undec-7- ene Example A12.2 DBN dimethylacetamide (1,5-diazabicyclo[4.3.0]non-5-ene) Example A12.3 DBN 1-methylpyrrolidone (1,5-diazabicyclo[4.3.0]non-5-ene) Example A12.4 DBN dimethylsulfoxide (1,5-diazabicyclo[4.3.0]non-5-ene) Example A12.5 DBU dimethylformamide (1,8-diazabicyclo[5.4.0]undec-7- ene) Example A12.6 morpholine dimethylacetamide Example A12.7 morpholine 1-methylpyrrolidone Example A12.8 sodium methylate dimethylsulfoxide

(75) 32.58 grams of the compound (112) are obtained yielding yellow crystals.

(76) Melting point: 81.5 C.

Example A13

Preparation of the Compound of Formula

(77) ##STR00070##

(78) By using 113.00 grams of ethyl-2-hydroxyethylaminoacrolein and 102.47 grams of n-butyl cyanoacetate 123.46 grams of the crude product are obtained yielding a brown oil.

(79) After crystallization 23.29 g of the product is obtained yielding yellowish crystals.

(80) Melting point: 78.0 C.

Example A14

Preparation of the Compound of Formula

(81) ##STR00071##

(82) The merocyanine compound (114) is synthesized according to the synthesis of merocyanine (113) yielding the desired product as a brownish oil.

(83) .sup.1H-NMR (CDCl.sub.3):

(84) =7.73 (1H, d), 7.24 (1H, d), 5.5 (1H, t), 4.07-4.33 (5H, m), 3.44-3.55 (2H, m), 3.16-3.26 (2H, m), 1.67 (2H, m), 1.22-1.45 (12H, m), 0.9 (3H, m).

Example A15

Preparation of the Compound of Formula

(85) ##STR00072##

(86) 122.23 grams of 3-[(3-methoxypropyl)amino]-2-cyclohexen-1-one are alkylated with dimethylsulfate or alternatively with diethylsulfate and treated with 75.45 grams of ethyl cyanoacetate in approximately equimolar proportions in the presence of a base and optionally a solvent.

(87) The following base/solvent combinations are used:

(88) TABLE-US-00017 Example Base Solvent Example A15.1 DBU dimethylacetamide (1,8-diazabicyclo[5.4.0]undec-7- ene) Example A15.2 triethylamine isopropanol Example A15.3 3-methoxypropylamine isopropanol Example A15.4 3-methoxypropylamine tert-amylalcohol Example A15.5 3-methoxypropylamine toluene Example A15.6 3-methoxypropylamine dimethylformamide Example A15.7 3-methoxypropylamine no solvent Example A15.8 N-morpholine isopropanol

(89) Completion of the alkylation reaction can be monitored for example by TLC, GC or HPLC methods.

(90) 162.30 grams of the product (115) are obtained yielding a brown oil.

(91) After crystallization the product is obtained yielding yellowish crystals.

(92) Melting point: 92.7 C.

Example A16

Preparation of the Compound of Formula

(93) ##STR00073##

(94) 101.00 grams of 3-[(3-methoxypropyl)amino]-2-cyclohexen-1-one are alkylated with dimethylsulfate or alternative with diethylsulfate and treated with 86.00 grams of 2-cyano-N-(3-methoxy-propyl)-acetamide in approximately equimolar proportions in the presence of a base and optionally a solvent.

(95) The following base/solvent combinations are used:

(96) TABLE-US-00018 Example Base Solvent Example A16.1 DBU dimethylacetamide (1,8-diazabicyclo[5.4.0]undec-7- ene) Example A16.2 triethylamine isopropanol Example A16.3 3-methoxypropylamine isopropanol Example A16.4 3-methoxypropylamine tert-amyl alcohol Example A16.5 3-methoxypropylamine toluene Example A16.6 3-methoxypropylamine dimethylformamide Example A16.7 3-methoxypropylamine no solvent

(97) The crude product (116) is obtained yielding a dark brown oil.

(98) After silica gel column chromatography (eluent: toluene/methanol 99:1) 81.8 grams of the product are obtained yielding yellowish crystals.

(99) Melting point: 84.7-85.3 C.

Example A17

Preparation of the Compound of Formula

(100) ##STR00074##

(101) 111.0 grams of 3-[(2-ethylhexyl)amino]-2-cyclohexen-1-one are alkylated with dimethylsulfate or alternatively with diethylsulfate and are then treated with 64.10 grams of 2-cyano-N-(2-hydroxy-ethyl)-acetamide in the presence of a base and optionally a solvent.

(102) The following base/solvent combinations are used:

(103) TABLE-US-00019 Example. Base Solvent Example A17.1 DBU dimethylacetamide (1,8-diazabicyclo[5.4.0]undec-7- ene) Example A17.2 triethylamine isopropanol Example A17.3 ethanolamine isopropanol Example A17.4 2-ethylhexylamine tert-amyl alcohol Example A17.5 ethanolamine toluene Example A17.6 ethanolamine dimethylformamide Example A17.7 ethanolamine no solvent

(104) The reaction temperature is between 60 to 120 C.

(105) The crude product is obtained yielding brownish crystals.

(106) After recrystallization 97 grams of the product were obtained yielding yellowish crystals.

(107) Melting point: 117-119 C.

Example A18

Preparation of the Compound of Formula

(108) ##STR00075##

(109) 100.56 grams of 3-[(2-hydroxypropyl)amino]-2-cyclohexen-1-one are alkylated with dimethylsulfate or alternatively with diethylsulfate and treated with 84.70 grams of isobutyl cyanoacetate in the presence of a base and optionally a solvent.

(110) The following base/solvent combinations are used:

(111) TABLE-US-00020 Example Base Solvent Example A18.1 DBU dimethylacetamide (1,8-diazabicyclo[5.4.0]undec-7- ene) Example A18.2 triethylamine isopropanol Example A18.3 1-amino-2-propanol isopropanol Example A18.4 N-methylmorpholine tert-amyl alcohol Example A18.5 1-amino-2-propanol toluene Example A18.6 1-amino-2-propanol dimethylformamide Example A18.7 1-amino-2-propanol no solvent

(112) 15.97 grams of the crude product (118) is obtained yielding a dark brown oil.

(113) After silica gel chromatography (eluent: hexane/ethyl acetate) 45.67 grams of the product (118) are obtained yielding yellowish crystals. Melting point: 106.7 C.

Example A19

Preparation of the Compound of Formula

(114) ##STR00076##

(115) 13.09 grams of 3-[(3-methoxypropyl)amino]-2-cyclohexen-1-one are alkylated with dimethylsulfate or alternatively with diethylsulfate and treated with 10.12 grams of isobutyl cyanoacetate in the presence of a base and optionally a solvent.

(116) The following base/solvent combinations are used:

(117) TABLE-US-00021 Example Base Solvent Example A19.1 DBU dimethylacetamide (1,8-diazabicyclo[5.4.0]undec-7- ene) Example A19.2 triethylamine isopropanol Example A19.3 3-methoxypropylamine isopropanol Example A19.4 N-methylmorpholine tert-amyl alcohol Example A19.5 3-methoxypropylamine toluene Example A19.6 3-methoxypropylamine dimethylformamide Example A19.7 3-methoxypropylamine no solvent

(118) 15.97 grams of the crude product (119) are obtained yielding a dark brown oil.

(119) After silica gel chromatography (eluent: toluene/acetone) 13.46 grams of the product (119) are obtained yielding yellowish crystals. Melting point: 96.3 C.

Example A20

Preparation of the Compound of Formula

(120) ##STR00077##

(121) 222.62 grams of dipropylamine are condensed with 1,1,3,3-tetramethoxypropane in acetic acid and treated with 200.13 grams of (2,2-dimethyl-1,3-dioxolan-4-yl)methyl cyanoacetate in the presence of an organic base and a solvent as described on page 4 in US2003/0181483A1.

(122) The following Base/solvent combinations are used:

(123) TABLE-US-00022 Example Base Solvent Example A20.1 DBU dimethylformamide (1,8-diazabicyclo[5.4.0]undec-7- ene Example A20.2 DBN dimethylacetamide (1,5-diazabicyclo[4.3.0]non-5- ene) Example A20.3 DBN 1-methylpyrrolidone (1,5-diazabicyclo[4.3.0]non-5- ene) Example A20.4 DBN dimethylsulfoxide (1,5-diazabicyclo[4.3.0]non-5- ene) Example A20.5 DBU dimethylformamide (1,8-diazabicyclo[5.4.0]undec-7- ene) Example A20.6 dipropylamine dimethylacetamide Example A20.7 sodium methylate 1,2-dimethoxyethane Example A20.8 N-methylmorpholine dimethylsulfoxide

(124) 327 grams of the crude product (120) are obtained yielding a brown oil.

Example A21

Preparation of the Compound of Formula

(125) ##STR00078##

(126) 317 ml of hydro chloride acid (1 N) are added to a solution of 327 grams of crude merocyanine (120) in 990 ml of ethanol.

(127) The reaction mixture is stirred for 16 hours at room temperature.

(128) After removal of ethanol in vacuum the reaction mass was taken up in water and the product is extracted several times with ethyl acetate.

(129) The collected organic phases are concentrated in vacuum.

(130) After silica gel column chromatography (eluent: toluene/ethyl acetate) and crystallization 70 grams of the desired product (121) are obtained yielding yellowish crystals.

(131) Melting point: 73 C.

Example A22

Preparation of the Compound of Formula

(132) ##STR00079##

(133) 66.43 grams of dibutylamine are condensed with 1,1,3,3-tetramethoxypropane in acetic acid and treated with 46.81 grams of (2,2-dimethyl-1,3-dioxolan-4-yl)methyl cyanoacetate in the presence of an organic base and a solvent.

(134) The following Base/solvent combinations are used:

(135) TABLE-US-00023 Example Base Solvent Example A22.1 DBU dimethylformamide (1,8-diazabicyclo[5.4.0]undec-7- ene Example A22.2 DBN dimethylacetamide (1,5-diazabicyclo[4.3.0]non-5-ene) Example A22.3 DBN 1-methylpyrrolidone (1,5-diazabicyclo[4.3.0]non-5-ene) Example A22.4 DBN dimethylsulfoxide (1,5-diazabicyclo[4.3.0]non-5-ene) Example A22.5 DBU dimethylformamide (1,8-diazabicyclo[5.4.0]undec-7- ene) Example A22.6 dibutylamine dimethylacetamide Example A22.7 N-methylmorpholine 1-methylpyrrolidone Example A22.8 sodium methylate dimethylsulfoxide

(136) 82.49 grams of the crude product (122) are obtained yielding a black oil.

Example A23

Preparation of the Compound of Formula

(137) ##STR00080##

(138) 80 ml of hydro chloride acid (1 N) are added to a solution of 82.5 grams of crude merocyanine (122) in 250 ml of ethanol. The reaction mixture is stirred for 16 hours at room temperature.

(139) After removal of ethanol in vacuum the reaction mass is taken up in water and the product (122) is extracted several times with ethyl acetate.

(140) The collected organic phases are concentrated in vacuum.

(141) After silica gel column chromatography (eluent: toluene/acetone) 37.85 grams of the desired product are obtained yielding a brownish oil.

(142) HPLC (210 nm): 99.3 A-%. .sup.1H-NMR (CDCl.sub.3): =7.8 (1H, d), 7.2 (1H, d), 5.6 (1H, t), 4.27 (2H, m), 3.98 (1H, m), 3.5-3.7 (2H, m), 3.25-3.33 (4H, m), 3.00 (2H, s), 1.61 (4H, m), 1.35 (4H, m), 0.96 (6H, m).

Example A24

Preparation of the Compound of Formula

(143) ##STR00081##

(144) 148.4 grams of 3-[(3-methoxypropyl)amino]-2-cyclohexen-1-one are alkylated with dimethylsulfate or alternatively with diethylsulfate and treated with 130.00 grams of 2-ethoxyethyl cyanoacetate in the presence of an organic base and a solvent.

(145) The following base/solvent combinations are used:

(146) TABLE-US-00024 Example Base Solvent Example A24.1 DBU dimethylacetamide (1,8-diazabicyclo[5.4.0]undec-7- ene) Example A24.2 triethylamine isopropanol Example A24.3 3-methoxypropylamine isopropanol Example A24.4 N-methylmorpholine tert-amyl alcohol Example A24.5 3-methoxypropylamine toluene Example A24.6 3-methoxypropylamine dimethylformamide Example A24.7 3-methoxypropylamine no solvent

(147) After column chromatography (silica gel, eluent: toluene/ethyl acetate) and crystallization 134.96 grams of the desired product (124) are obtained yielding yellow crystals.

(148) Melting point: 90-91.5 C.

(149) UV Shielding Properties

(150) The UV shielding properties of the merocyanine derivatives are investigated by measuring their UV spectra in ethanol. In the following table the investigated absorption maxima (.sub.max) together with the corresponding A.sup.1%.sub.1cm values are listed.

(151) TABLE-US-00025 Absorption maximum Comp. No. .sub.max A.sup.1%.sub.1 cm (101) 380 2283 (102) 380 2046 (103) 380 1965 (104) 381 2568 (105) 381 2252 (106) 380 2530 (108) 381 2467 (111) 380 2414 (113) 381 2235 (115) 385 2207 (116) 385 1644 (117) 386 1618 (118) 385 2083 (119) 385 2036 (121) 381 2230 (124) 385 1947

(152) All merocyanine compounds according to the present invention possess extraordinary high shielding properties in the UV region as indicated by A.sup.1%.sub.1cm values above 1500.