Patent GB-819654-A (GB)
Title: New quinone derivatives and a process for their preparation
Inventor: HENBEST HAROLD BERNARD
Filed: 1956-02-15
Abstract: The invention comprises aminovinyl quinones of the general formula #f[-CR=CH.NR1R2]n where #f is a quinone residue which may be unsubstituted or substituted in the quinone ring by one or more electronegative groups or atoms, R is hydrogen or an alkyl group containing up to 5 carbon atoms, R1 is an alkyl or hydroxyalkyl group, R2 is an alkyl, hydroxyalkyl, aralkyl or aryl group or R1 and R2 together with the nitrogen atom form a saturated heterocyclic ring and n is either 1 or 2, the groups R1 and R2 being unsubstituted or substituted by groups other than strongly electronegative groups. The preferred compounds are those where all the carbon atoms in the quinone ring are substituted by chloro and/or methoxy groups, R is hydrogen, R1 methyl, ethyl or hydroxyethyl, R2 methyl, ethyl, hydroxyethyl or phenyl or together with R1 and the nitrogen form a morpholine ring.  The compounds may be prepared by treating a quinone having at least one position reactive to a nucleophillic reagent with an aldehyde of the formula R.CH2CHO and a secondary amine of the formula HN.R1R2 where R, R1 and R2 are as above. The reaction may be carried out in an inert non-acidic solvent, e.g. benzene, ether, dioxan or light petroleum, at room temperature or slightly above.  In the examples, tetrachloro-p-benzoquinone and acetaldehyde are treated with (1) diethylamine to give the blue 2,3,5-trichloro - 6 - diethylaminovinyl - p - benzoquinone, (2) dimethylamine to give the blue 2,3,5 - trichloro - 6 - dimethylaminovinyl - p - benzoquinone, (3) morpholine to give the blue 2,3,5 - trichloro - 6 - morpholinovinyl - p - benzoquinone, (4) diethanolamine to give the blue 2,3,5 - trichloro - 6 - di - (hydroxyethyl) aminovinyl - p - benzoquinone, (5) methylaniline to give the blue 2,3,5-trichloro-6-methylanilinovinyl-p-benzoquinone, (7) as (1) but using double the amount of diethylamine to give 2,5-dichloro - 3,6 - bis - diethylaminovinyl - p - benzoquinone, (6) 3,5 - dichloro - 2,6 - dimethoxy - p - benzoquinone is treated with acetaldehyde and diethylamine to give 3,5-dichloro - 2 - methoxy - 6 - diethylaminovinyl-p - benzoquinone; 2,3 - dichloro - naphthaquinone is treated with acetaldehyde, and (8) dimethylamine to give the red 2-chloro-3-(21-dimethylaminovinyl) - 1,4 - naphthaquinone, and (9) diethylamine to give the red 2-chloro-3-(21-diethylaminovinyl)-1,4-naphthaquinone.ALSO:The invention comprises aminovinyl quinones of the general formula #f[-CR=CH.NR1R2]n where #f is a quinone residue which may be unsubstituted or substituted in the quinone ring by one or more electronegative groups or atoms, R is hydrogen or an alkyl group containing up to 5 carbon atoms, R1 is an alkyl or hydroxyalkyl group, R2 is an alkyl, hydroxyalkyl, aralkyl or aryl group or R1 and R2 together with the nitrogen atom form a saturated heterocyclic ring and n is either 1 or 2, the groups R1 and R2 being unsubstituted or substituted by groups other than strongly electronegative groups. The compounds are said to find application as dyes and the preferred compounds are those where all the carbon atoms in the quinone ring are substituted by chloro and/or methoxy groups, R is hydrogen, R1 methyl, ethyl or hydroxyethyl, R2 methyl, ethyl, hydroxyethyl or phenyl or together with R1 and the nitrogen form a morpholine ring. The compounds may be prepared by treating a quinone having at least one position reactive to a nucleophillic reagent with an aldehyde of the formula R.CH2CHO and a second amine of the formula HN.R1R2, where R, R1 and R2 are as above. The reaction may be carried out in an inert non-acidic solvent, e.g. benzene, ether, dioxan or light petroleum, at room temperature or slightly above.  In the examples tetrachloro-p-benzoquinone and acetaldehyde are treated with (1) diethylamine to give the blue 2,3,5-trichloro - 6 - diethylaminovinyl - p - benzo - quinone, (2) dimethylamine to give the blue 2,3,5 - trichloro - 6 - dimethylaminovinyl - p - benzoquinone, (3) morpholine to give the blue 2,3,5 - trichloro - 6 - morpholinovinyl - p - benzoquinone, (4) diethanolamine to give the blue 2,3,5 - trichloro - 6 - di - (hydroxyethyl) aminovinyl-p-benzoquinone, (5) methylaniline to give the blue 2,3,5-trichloro-6-methylanilinovinyl-p-benzoquinone, (7) as (1) but using double the amount of diethylamine to give 2,5 - dichloro - 3,6 - bis - diethylamino - vinyl-p-benzoquinone, (6) 3,5 - dichloro - 2,6 - dimeth - oxy-p-benzoquinone is treated with acetaldehyde and diethylamine to give 3,5-dichloro-2-methoxy - 6 - diethylaminovinyl - p - benzo - quinone; 2,3 - dichloro - naphthaquinone is treated with acetaldehyde and (8) dimethylamine to give the red 2-chloro-3-(21-dimethylaminovinyl) - 1,4 - naphthaquinone and (9) diethylamine to give the red 2-chloro-3-(21-diethylaminovinyl)-1,4-naphthaquinone.