Claims
- 1. A process for the manufacture of 2,5-bis-(benzoxazolyl)-thiophene compounds of the formula ##STR54## wherein R.sub.1 ' represents hydrogen, halogen, alkyl of 1 to 12 carbon atoms, haloalkyl, hydroxyalkyl, cyanoalkyl or phenylalkyl, each containing 1 to 4 carbon atoms in the alkyl moiety, alkyl of 1 to 4 carbon atoms which is substituted by a group of the formula
- --COOY or --CONY.sub.1 Y.sub.2
- in which Y represents hydrogen, an alkali metal, alkaline earth metal or ammonium salt, alkyl of 1 to 18 carbon atoms, alkenyl of 2 to 4 carbon atoms, hydroxyalkyl, cyanoalkyl or phenylalkyl, each containing 1 to 4 carbon atoms in the alkyl moiety, alkoxyalkyl of altogether 2 to 8 carbon atoms, phenyl or phenyl which is substituted by alkyl of 1 to 12 carbon atoms, and each of Y.sub.1 and Y.sub.2 independently represents hydrogen, alkyl of 1 to 8 carbon atoms, hydroxyalkyl, cyanoalkyl or phenylalkyl each containing 1 to 4 carbon atoms in the alkyl moiety; alkenyl of 3 or 4 carbon atoms, cyclohexyl, alkoxy of 1 to 4 carbon atoms, phenyl, phenoxy, cyano, alkylsulphonyl of 1 to 4 carbon atoms, the sulpho group or an alkali metal salt thereof, or the group of the formula
- --COOY or --CONY.sub.1 Y.sub.2
- in which Y, Y.sub.1 and Y.sub.2 are as defined above,
- R.sub.2 ' represents hydrogen, alkyl of 1 to 4 carbon atoms or chlorine,
- R.sub.3 ' represents hydrogen or methyl, and each of
- R.sub.4 ' and R.sub.5 ' independently represents hydrogen, alkyl of 1 to 4 carbon atoms, or together they represent the trimethylene or tetramethylene radical
- which process comprises reacting in an inert solvent at a temperature of -5.degree. C. to 100.degree. C. in the presence of a base or an acid a sulfide of the formula ##STR55## wherein R.sub.1 ', R.sub.2 ' and R.sub.3 ' are as defined above, with a compound of the formula ##STR56## wherein R.sub.4 ' and R.sub.5 ' are as defined above or an acetal, ketal, imine, oxime, hydrozone, sulfate, bisulfite or hydrate functional derivative thereof.
- 2. A process according to claim 1 for the manufacture of 2,5-bis-(benzoxazolyl)-thiophene compounds of the formula ##STR57## wherein R.sub.1 ' represents hydrogen halogen, alkyl of 1 to 12 carbon atoms, haloalkyl, hydroxyalkyl, cyanoalkyl or phenylalkyl, each containing 1 to 4 carbon atoms which is substituted by a group of the formula
- --COOY or --CONY.sub.1 Y.sub.2 ,
- in which Y represents hydrogen, a salt forming cation, alkyl of 1 to 18 carbon atoms, alkynyl of 2 to 4 carbon atoms, hydroxyalkyl, cyanoalkyl or phenylalkyl, each containing 1 to 4 carbon atoms in the alkyl moiety, alkoxyalkyl of altogether 2 to 8 carbon atoms, phenyl or phenyl which is substituted by alkyl of 1 to 12 carbon atoms, and each of y.sub.1 and Y.sub.2 independently represents hydrogen, alkyl of 1 to 8 carbon atoms, hydroxyalkyl, cyanoalkyl or phenylalkyl, each containing 1 to 4 carbon atoms in the alkyl moiety; alkenyl of 3 or 4 carbon atoms, cyclohexyl, alkoxy of 1 to 4 carbon atoms, phenyl, phenoxy, cyano, alkylsulphonyl of 1 to 4 carbon atoms, the sulpho group or an alkali metal salt thereof, or a group of the formula
- --COOY or --CONY.sub.1 Y.sub.2
- in which Y, Y.sub.1 and Y.sub.2 are as defined above,
- R.sub.2 ' represents hydrogen, alkyl of 1 or 4 carbon atoms, alkoxy of 1 to 4 carbon atoms or chloride and
- R.sub.3 ' represents hydrogen or methyl,
- which process comprises reacting a sulphide of the formula ##STR58## wherein R.sub.1 ', R.sub.2 ' and R.sub.3 ' are as defined above, with glyoxal, trimeric glyoxal hydrate, polymeric glyoxal, glyoxal bisulfite, glyoxal sulphate or with an acetal, hemiacetal, mono- or bisaldimine, mono- or bisaldoxine or hydrazone of glyoxal.
- 3. A process according to claim 1 for the manufacture of 2,5-bis-(benzoxazolyl)-thiophene compounds of the formula ##STR59## wherein R.sub.1 " represents hydrogen, chlorine, alkyl or 1 to 12 carbon atoms, cyanoalkyl or phenylalkyl, each containing 1 to 4 carbon atoms in the alkyl moiety, carboxyalkyl of 2 to 5 carbon atoms, carbalkoxyalkyl of 3 to 9 carbon atoms, phenyl, cyclohexyl, alkoxy of 1 to 4 carbon atoms, alkylsulphonyl of 1 to 4 carbon atoms, a group of the formula --COOY',
- in which Y' represents hydrogen, alkyl of 1 to 18 carbon atoms, alkoxyalkyl of altogether 2 to 6 carbon atoms, phenylalkyl containing 1 to 4 carbon atoms in the alkyl moiety, alkenyl containing 3 or 4 carbon atoms or an alkali metal or ammonium ion, or a group of the formula --CONY.sub.1 'Y.sub.2 '
- in which Y.sub.1 ' represents hydrogen, alkyl of 1 to 8 carbon atoms or hydroxyalkyl of 1 to 4 carbon atoms and Y.sub.2 ' represents a hydrogen or alkyl of 1 to 4 carbon atoms,
- R.sub.2 " represents hydrogen, alkyl of 1 to 4 carbon atoms or alkoxy of 1 to 4 carbon atoms, and
- each of
- R.sub.4 " and R.sub.5 " represents hydrogen, alkyl of 1 to 4 carbon atoms or together they represent the tetramethylene radical, which process comprises reacting a sulphide of the formula ##STR60## wherein R".sub.1 and R".sub.2 have the given meanings, with a compound of the formula ##STR61## wherein R".sub.4 and R".sub.5 are as defined above, or with said functional derivative thereof.
- 4. A process according to claim 1 for the manufacture of 2,5-bis-(benzoxazolyl)-thiophene compounds of the formula ##STR62## wherein R.sub.1 " represents hydrogen, alkyl of 1 to 12 carbon atoms, cyclohexyl, carboxalkyl of 2 to 5 carbon atoms, carbalkoxyalkyl of 3 to 9 carbon atoms, phenylalkyl containing 1 to 4 carbon atoms in the alkyl moiety, phenyl, carboxyl, carbalkoxy of 2 to 5 carbon atoms or alkylsulphonyl of 1 to 4 carbon atoms, R.sub.4 '" and R.sub.5 '" independently represent hydrogen or alkyl of 1 to 4 carbon atoms, and R.sub.2 " is hydrogen, alkyl of 1 to 4 carbon atoms or alkoxy of 1 to 4 carbon atoms, which process comprises reacting a sulphide of the formula ##STR63## wherein R.sub.1 '" and R.sub.2 '" have the given meanings, with an .alpha.,.beta.-dicarbonyl compound of the formula ##STR64## wherein R.sub.4 '" and R.sub.5 '" have the given meanings, or with said functional derivative thereof.
- 5. A process according to claim 3 for the manufacture of 2,5-bis-(benzoxazolyl)-thiophene compounds of the formula ##STR65## wherein R.sub.1 '" represents hydrogen, alkyl of 1 to 12 carbon atoms, cyclohexyl, carboxyalkyl of 2 to 5 carbon atoms, carbalkoxyalkyl of 3 to 9 carbon atoms, phenylalkyl containing 1 to 4 carbon atoms in the alkyl moiety, phenyl, carboxyl, carbalkoxy of 2 to 5 carbon atoms or alkylsulphonyl of 1 to 4 carbon atoms, and each of
- R.sub.4 '" and R.sub.5 '" independently represents hydrogen or alkyl of 1 to 4 carbon atoms,
- which process comprises reacting a mulphide of the formula ##STR66## wherein R'".sub.1 has the given meaning, with an .alpha.,.beta.-dicarbonyl compound of the formula ##STR67## wherein R'".sub.4 and R'".sub.6 have the given meanings, or with said functional derivative thereof.
- 6. A process according to claim 1 for the manufacture of 2,5-bis-(benzoxazolyl)-thiophene compounds of the formula ##STR68## wherein R.sub.1 '" represents hydrogen, alkyl of 1 to 12 carbon atoms, cyclohexyl, carboxyalkyl of 2 to 5 carbon atoms, carbalkoxyalkyl of 3 to 9 carbon atoms, phenylalkyl containing 1 to 4 carbon atoms in the alkyl moiety, phenyl, carboxyl, carbalkoxy of 2 to 5 carbon atoms or alkylsulphonyl of 1 to 4 carbon atoms, and R.sub.2 is hydrogen, alkyl of 1 to 4 carbon atoms or alkoxy of 1 to 4 carbon atoms, which process comprises reacting a sulphide of the formula ##STR69## wherein R.sub.1 '" and R.sub.2 '" have the meanings, with glyoxal, trimeric or polymeric glyoxal, glyoxal bisulphite or glyoxal bisaldimes.
- 7. A process according to claim 1 wherein the reaction is carried out at a temperature between 0.degree. C. to 50.degree. C.
- 8. A process according to claim 6 for the manufacture of 2,5-bis-(benzoxazolyl)-thiophene compounds of the formula ##STR70## wherein R.sub.1.sup.IV represents hydrogen, alkyl of 1 to 4 carbon atoms, chlorine, alkylsulphenyl of 1 to 4 carbon atoms, carboxyl, carbalkoxy of 2 to 5 carbon atoms, benzyl or .alpha.,.alpha.-dimethylbenzyl, which process comprises reacting a sulphide of the formula ##STR71## wherein R.sub.1.sup.IV has the given meaning, with glyoxal.
- 9. A process according to claim 8 for the manufacture of 2,5-bis-(benzoxazolyl)-thiophene compounds of the formula ##STR72## wherein R.sub.1.sup.V represents hydrogen, alkyl of 1 to 4 carbon atoms, benzyl, .alpha.,.alpha.-dimethylbenzyl or chlorine, which process comprises reacting a mulphide of the formula ##STR73## wherein R.sub.1.sup.V has the given meaning, with glyoxal.
- 10. A process according to claim 1 wherein the base is an alcoholate or hydroxide of an alkali metal.
Priority Claims (2)
Number |
Date |
Country |
Kind |
5892/77 |
May 1975 |
CHX |
|
8574/76 |
Jul 1976 |
CHX |
|
Parent Case Info
This is a continuation of application Ser. No. 965,719, filed Dec. 1, 1978, now abandoned, which is a continuation of Ser. No. 810,814, filed June 28, 1977, now abandoned.
US Referenced Citations (4)
Foreign Referenced Citations (1)
Number |
Date |
Country |
940770 |
Nov 1963 |
GBX |
Non-Patent Literature Citations (6)
Entry |
Elderfield, "Heterocyclic Compounds", vol. 5, (Wiley & Sons), 1957, p. 438. |
Wynberg et al., J. Amer. Chem. Soc. 87,1739-1741, (1965). |
Johnson et al., J. Amer. Chem. Soc. 72,514, (1950). |
Hinsberg, Berrehtre 43,901-906 (1910) and 45,2413-2418 (1912). |
Brown et al., J. Chem. Soc. 1948, 2147. |
Johnson et al., Org. Reactions 6, p. 1 (1951). |
Continuations (2)
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Number |
Date |
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Parent |
965719 |
Dec 1978 |
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Parent |
810814 |
Jun 1977 |
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