Title: Process for preparing phthalide and naphthalide indicator dyes

Do you think this is a good invention? Vote now:

Votes so far: For:(0) Against:(0)
Claims: What is claimed is:

1. A process which comprises the steps of:

1. reacting in substantially equimolar proportions in an inert organic liquid solvent at a temperature between about 20.degree.C. and 120.degree.C. in the presence of an acid catalyst selected from toluene-p-sulfonic acid, sulfuric acid, trifluoroacetic acid and trichloroacetic acid, (a) a compound selected from ##SPC33##

wherein R.sup.1 is selected from hydrogen, alkoxy containing 1 to 3 carbon atoms and alkyl containing 1 to 3 carbon atoms; R.sup.2 is selected from hydrogen, hydroxy, carboxy, sulfonamido, sulfamoyl, o-hydroxyphenyl, bis-trifluoromethylcarbinol, methoxy, alkyl containing 1 to 16 carbon atoms; R.sup.3 is selected from hydrogen, alkoxy containing 1 to 18 carbon atoms and alkyl containing 1 to 3 carbon atoms; R.sup.4 is selected from hydrogen, hydroxy and carboxy; R.sup.5 is selected from hydrogen and alkoxy containing 1 to 18 carbon atoms; R.sup.6 is selected from hydrogen, phenyl, alkyl containing 1 to 3 carbon atoms, and alkoxy containing 1 to 18 carbon atoms; R.sup.7 is selected from hydrogen, phenyl, o-hydroxyphenyl and alkyl containing 1 to 3 carbon atoms and R.sup.8 is selected from hydrogen, cyano, carboxy, halo, trifluoromethyl, sulfonyl and alkoxy containing 1 to 18 carbon atoms with (b) an aldehydic acid selected from phthalaldehydic acid, unsubstituted or substituted in one of the 4- or 7-positions with carboxy and naphthalaldehydic acid, unsubstituted, to form the corresponding adduct having the formula: ##SPC34##

wherein A is a radical selected from p-hydroxyphenyl, p-hydroxynaphthyl, pyrr-2-yl and indol-3-yl corresponding to said (i), (ii) and (iii) and (iv), respectively, and X represents the carbon atoms necessary to complete a ring-closing moiety selected from phthalide, unsubstituted or substituted in the 4- or 7-position with carboxy, and naphthalide, unsubstituted; and

2. reacting said adduct with a quinone selected from chloranil, o-chloranil and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone in a molar ratio of about 1.1 to 1.5 moles of quinone per 1.0 mole of adduct in an inert organic liquid solvent at a temperature between about 20.degree.C. and 200.degree.C. to form the corresponding oxidation product selected from ##SPC35##

wherein A and X have the same meaning given above, and ##SPC36##

wherein A' is selected from ##SPC37##

wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 and X have the same meaning given above and mixtures of (I) and (II), said (I) being produced under anhydrous conditions and said (II) and said mixtures of (i) and (II) being produced in the presence of moisture.

2. A process as defined in claim 1 which includes the additional step of:

3. reacting said oxidation product with a compound (c) selected from (i), (ii), (iii) and (iv) as defined in (a) above in substantially equimolar proportions in an inert organic liquid solvent at a temperature between about 20.degree.C. and 120.degree.C. in the presence of an acid catalyst selected from toluene-p-sulfonic acid, sulfuric acid, trifluoroacetic acid, trichloroacetic acid and a Lewis acid to form the corresponding 3,3-disubstituted phthalide or naphthalide, ##SPC38##

wherein A and B each is a radical selected from p-hydroxyphenyl, p-hydroxynaphthyl, pyrr-2-yl, and indol-3-yl corresponding to said (i), (ii), (iii) and (iv), respectively, and X represents the carbon atoms necessary to complete a ring-closing moiety selected from phthalide, unsubstituted or substituted in the 4- or 7-position with carboxy and naphthalide, unsubstituted.

3. A process as defined in claim 2 wherein said step (1) is conducted in the presence of toluene-p-sulfonic acid.

4. A process as defined in claim 2 wherein said step (2) is conducted under substantially anhydrous conditions.

5. A process as defined in claim 4 wherein said quinone is o-chloranil.

6. A process as defined in claim 2 wherein said compound (a) is (iv).

7. A process as defined in claim 6 wherein said indole compound (a) is 7-carboxyindole.

8. A process as defined in claim 7 wherein said aldehydic acid is naphthalaldehydic acid.

9. A process as defined in claim 8 wherein said compound (c) is (iv).

10. A process as defined in claim 9 wherein said indole compound (c) is 7-hexadecylsulfonamidoindole.

11. A process as defined in claim 9 wherein said indole compound (c) is 2-ortho-hydroxyphenyl indole.

12. A process as defined in claim 9 wherein said indole compound (c) is 7-carboxyindole.

13. A process as defined in claim 9 wherein said indole compound (c) is 5-bromo-7-octadecylsulfamoyl indole.

14. A process as defined in claim 2 wherein said compound (a) is (i).

15. A process as defined in claim 14 wherein said phenol compound (a) is 2,6-diisopropylphenol.

16. A process as defined in claim 15 wherein said compound (c) is (ii).

17. A process as defined in claim 16 wherein said 1-naphthol compound (c) is 2-hexadecyl-1-naphthol and said aldehydic acid is naphthalaldehydic acid.

18. A process as defined in 14 wherein said compound (c) is (i).

19. A process as defined in claim 18 wherein said phenol compound (a) is o-cresol, said phenol compound (c) is o-cresol and said aldehydic acid is 7-carboxy-phthalaldehydic acid.

20. A process as defined in claim 2 wherein said compound (a) is (ii).

21. A process as defined in claim 20 wherein said compound (c) is (ii).

22. A process as defined in claim 21 wherein said aldehydic acid is naphthalaldehydic acid.

23. A process as defined in claim 22 wherein said 1-naphthol compound (a) is 2-carboxy-1-naphthol and said 1-naphthol compound (c) is 2-carboxy-1-naphthol.

24. A process as defined in claim 1 wherein said oxidation product formed in step (2) is ##SPC39##

wherein A and X have the same meaning given above.

25. A process as defined in claim 1 wherein said oxidation product formed in step (2) is ##SPC40##

wherein A' is selected from ##SPC41##

wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 and X have the same meaning given above.

26. A process as defined in claim 1 wherein said quinone is 2,3-dichloro-5,6-dicyano-1,4-benzoquinone.

27. A process as defined in claim 1 wherein said quinone is o-chloranil.

28. A process as defined in claim 1 wherein said step (1) is conducted in the presence of toluene-p-sulfonic acid.

29. A process as defined in claim 1 wherein said compound (a) is (i).

30. A process as defined in claim 1 wherein said compound (a) is (ii).

31. A process as defined in claim 1 wherein said compound (a) is (iv).

Other info:

Inventors: Borror, Alan L. (Lexington, MA, US)

Application Number: 446716
Filing Date: 1974-02-28
Publication_date: 1976-01-06
Assignee: Polaroid Corporation (Cambridge, MA)
Primary Class(es): 548/456 503/220, 546/108, 546/167, 548/302.1, 548/427, 548/440, 548/441, 548/463, 548/518, 548/519, 548/521, 548/522, 548/525, 549/281, 549/307, 549/308, 549/309,
Other Classes:
US Patent Ref:

3491116

Jan, 1970

Lin

260/326.

Other Refs:
Primary Examiner: Gotts, Lewis
Assistant Examiner: Williams, S. P.
Attorney: Campbell; Sybil A.