GB2075496A - Novel naphtholic compounds and their preparation - Google Patents

Novel naphtholic compounds and their preparation Download PDF

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GB2075496A
GB2075496A GB8108287A GB8108287A GB2075496A GB 2075496 A GB2075496 A GB 2075496A GB 8108287 A GB8108287 A GB 8108287A GB 8108287 A GB8108287 A GB 8108287A GB 2075496 A GB2075496 A GB 2075496A
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compound
absent
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ring system
aromatic ring
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3M Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C50/00—Quinones
    • C07C50/26—Quinones containing groups having oxygen atoms singly bound to carbon atoms
    • C07C50/32—Quinones containing groups having oxygen atoms singly bound to carbon atoms the quinoid structure being part of a condensed ring system having two rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/06—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by conversion of non-aromatic six-membered rings or of such rings formed in situ into aromatic six-membered rings, e.g. by dehydrogenation
    • C07C37/07—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by conversion of non-aromatic six-membered rings or of such rings formed in situ into aromatic six-membered rings, e.g. by dehydrogenation with simultaneous reduction of C=O group in that ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
    • C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
    • C07C39/14—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings with at least one hydroxy group on a condensed ring system containing two rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
    • C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
    • C07C39/17—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings containing other rings in addition to the six-membered aromatic rings, e.g. cyclohexylphenol
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/26—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/23—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C46/00—Preparation of quinones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C46/00—Preparation of quinones
    • C07C46/02—Preparation of quinones by oxidation giving rise to quinoid structures
    • C07C46/06—Preparation of quinones by oxidation giving rise to quinoid structures of at least one hydroxy group on a six-membered aromatic ring

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)

Abstract

Compounds suitable for use as dye-forming developers in photographic systems which yield coloured dyes upon oxidation, the compounds having the general formula: <IMAGE> in which: one of R<1> and R<2> represent OH, -NR<3>R<4> in which R<3> and R<4> represent alkyl or the necessary atoms to complete a heterocyclic ring system, or -OR<5> in which R<5> represents an alkyl, aryl or alkaryl group having 8 to 12 carbon atoms, and either R<6> is absent and the other of R<1> and R<2> represents an aromatic ring system linked via a carbon atom in an aromatic ring, or when said one of R<1> and R<2> above is -NR<3>R<4> or -OR<5> said other of R<1> and R<2> can additionally represent hydrogen, or, the other of R<1> and R<2> is hydrogen and R<6> represents the necessary atoms to form an aromatic ring system fused to the naphthol nucleus in the 5 and 6 positions, with the proviso that when R<2> is OH, R<1> is not <IMAGE>

Description

SPECIFICATION Novel naphtholic compounds and their preparation This invention relates to novel naphtholic compounds and to their preparation. In particular the invention relates to a group of naphtholic compounds which are suitable for use as dye-forming developing agents in photographic systems.
Our copending P.C.T. Patent Application No. which claims priority from British Patent Application No. 8008984 discloses developer solutions, a photographic process and photographic elements in which dye-forming developing agents are present so that during processing of the exposed silver halide they undergo a reaction involving oxidation to produce a dye which amplifies the silver image.
Accordingly, it is possible to reduce the silver content of photographic films and obtain the same optical density by utilizing the dye-forming developing agents. By a suitable choice of dye-forming developing agents a wide range of coloured images may be obtained upon processing.
It is an object of the present invention to provide compounds which have utility as dye-forming developing agents.
Therefore according to the present invention there is provided a compound of the general formula:
in which: one of R' and R2 represent OH, -NR2R4 in which R3 and R4 represent alkyl or the necessary atoms to complete a heterocyclic ring system, or -OR5 in which R5 represents an alkyl, aryl or alkaryl group having 8 to 12 carbon atoms, and either R5 is absent and the other of R1 and R2 represents an aromatic ring system linked via a carbon atom in an aromatic ring, or when said one of R1 and R2 above is -NR3R4 orOR5 said other of R1 and R2 can additionally represent hydrogen, or The other of R1 and R2 is hydrogen and R6 represents the necessary atoms to form an aromatic ring system fused to the naphthol nucleus in the 5 and 6 positions, with the proviso that when R2 is OH, R1 is not
The compounds of the invention produce coloured dyes upon oxidation including blue, yellow and orange-red dyes depending upon the particular substituents. The compounds of the invention are suitable for use as dye-forming developing agents in the invention disclosed in the above-mentioned copending Patent Application.
In the general formula (1) one of R1 and R2 represents OH, -NR3R4, in which R3 and R4 independently represent alkyl groups, preferably lower alkyl groups having up to 5 carbon atoms, or R3 and R4 may represent the necessary atoms to complete a heterocyclic ring system, e.g. pyrrolyl, pyridyl and morpholine rings. Alternatively, one of R1 and R2 representOR5 in which R5 represents an alkyl group, generally having up to 1 5 carbon atoms, e.g. octyl and dodecyl, an aryl group, e.g. phenyl which may be substituted, or multiple aromatic rings, e.g. naphthyl, or R5 may represent an alkaryl group having 8 to 12 carbon atoms.
When R6 is absent the other of R1 and R2 may represent an aromatic ring system linked via a carbon atom in an aromatic ring. Examples of such substituents include phenyl groups which may be substituted and multiple ring systems, e.g. naphthyl. Other suitable substituents include the necessary group to form a dimer compound, i.e. the substituent comprises the necessary atoms to provide a nucleus which is the same as the nucleus to which it is attached. Alternatively, when R6 is absent and one of R1 and R2 is -NR3R4 or -OR5, the other of R1 and R2 may be hydrogen.
The substituent R6 may be present when the other of R1 and R2 is hydrogen, in which case R6 represents the necessary atoms to form an aromatic ring system fused to the naphthol nucleus.
Examples of such compounds including polynuclear hydroquinones.
There are various modes of preparation for the compounds of the invention in accordance with general formula (1) depending upon the particular substituents.
Compounds of formula (1) in which R1 is H, R2 is -OR5 and R6 is absent may be prepared according to the following reaction scheme:
HCI gas is used to promote the ketone formation from 1 ,4-dihydroxynaphthalene. Attack from an alcohol and elimination of water gives 4-OR5-1 -naphthol. Any alcohol or 1 ,4-naphthohydroquinone can be used provided there is no substituent at the position ortho to the OH.
The bis-a-naphthols, in which R' represents a nucleus identical to the nucleus to which it is attached and R6 is absent, may be prepared according to the following reaction scheme:
The 4-R2-1 -naphthol is first oxidized to Russig's Blue derivative by ferric chloride. The bis-cY- naphthol is obtained by adding zinc dust to a stirred and hot suspension of the dye in acetic acid until the mixture becomes colourless. The colourless solution is then poured over water and the precipitate filtered, washed with water and dried.
The naphthol derivatives, in which R2 is -NR3R4 and R6 is absent may be prepared according to the following reaction schemes:
The compounds are obtained either by reaction of the 4-amino group with Hal-R3 in the presence of an acid acceptor or condensing an amino group with a diketone.
Compounds in which R' is aryl, R2 is OH and R6 is absent may be prepared according to the following reaction scheme:
The dyes are first prepared either by reacting 1 ,4-naphthoquinone with a diazonium salt or with substituted benzenes or naphthalenes in glacial acid in the presence of concentrated sulphuric acid.
Compounds are obtained by reducing the dyes with zinc dust and acetic acid.
Compounds in which R1 is OH, R2 is aryl and R6 is absent may be prepared by the following reaction scheme:
The compounds are prepared in a similar manner to those in which R1 is aryl by adding concentrated H2SO4 to a mixture of 1 ,2-naphthoquinone and aromatic compound.
The polynuclear hydroquinones, in which R6 is a fused ring system, may be prepared according to the following reaction schemes:
The compounds are made by reduction of the corresponding quinones with Zn/HOAc which in turn are obtained by refluxing an activated vinylbenzene or naphthalene with an excess of benzoquinone in acetic acid.
The following Table 1 reports compounds of general formula (1) in accordance with the invention together with their mode of preparation.
TABLE 1
No. Compound Preparation 1 4-octyloxy-1-naphthol saturating a solution of 1,4-dihydroxy- naphthalene and n-octanol in ether with HCI gas 4 2 4-dodecyloxy-1-naphthol see Example 1 3 1,1 '-dihydroxy-4,4'-didodecyloxy- see Example 2 2,2'-binaphthyl 4 4-(2,5-dimethylpyrrolyl)-1- refluxing a mixture of 4-amino-1-naphthol naphthol and acetonylacetone 5 2-(2,4-dimethoxyphenyl)-1,4- see Example 3 dihydroxynaphthalene 6 N{1-(4-hydroxy)naphthyll-- refluxing a mixture of 4-amino-1-naphthol pyridone hydrochloride and dehydroacetic acid 7 N41-(44iydroxy)naphthylj- refluxing a mixture of 4-amino-1-naphthol pyridone hydrochloride and chelidonic acid 8 1,4-dihydroxychrysene reducing chrysoquinone (obtained by refluxing 1-vinyinaphthalene and benzoquinone in glacial HOAc) with zinc 9 1,4-d ihydroxybenzophenanthrene reducing the corresponding quinone (obtained by refluxing 2-vinyl naphthalene and benzoquinone in glacial HOAc) with Zn 10 1,4-dihydroxy-6-methoxy- reducing the 6-methoxy-1,4 phenanthrene naphthalene quinone- (obtained by refluxing p-methoxy styrene and benzoquinone in HOAc) with Zn 11 1,4-dihydroxy-10-methoxy- reducing 10-methoxy-1 ,4-phenanthrene naphthalene quinone (obtained by refluxing a-methoxy styrene and benzoquinone in HOAc) with-Zn 12 2-(4-dimethylaminophenyl)-1,4- reducing the dye contained from reduction d ihydroxynaphthalene of 1,4-naphthoquinone with N,N-d imethyl- aminobenzene diazonium salt 13 2-(2,4 < 5-trimethoxyphenyl)-1,4- by adding H2SO4 to a stirred solution of dihydroxynaphthalene 1 14-naphthoqu none and 1 2,4-trimethoxy- benzene in HOAc glacial 14 2-(2-hydroxy-4-methoxyphenyl)- reducing the dye obtained by adding 1,4-dihydroxynaphthalene H2 804 to a stirred solution of 1,4-naphtho quinone ans m-methoxyphenyl in glacial acetic acid 15 2-[1-(4hydroxy)naphthyl]-1,4- reducing the dye obtained by adding dihydroxynaphthalene H2SO4 to a stirred solution of 1,4-naphtho quinone and a-naphthol in glacial acetic acid TABLE 1 (Continued)
No. Compound Preparation 16 4-[1-(4-hydroxy)-naphthyl]-1,2 adding H2SO4 to a stirred solution of dihydroxynaphthalene glacial HOAc and glacial HOAc 17 4-(2,4-dimethoxyphenyl)-1,2 adding H S04 to a stirred solution of dihydroxynaphthalene 1,2-naphthoquinone 1 ,3-d imethoxy- benzene in HOAc 18 4-(2,4.5-tri methoxyphenyl)-1,2- adding H2SO4 to a solution of 1,2 dihydroxynaphthalene naphthoquinone and 1,2,4-trimethoxy benzene in acetic acid 19 4-(p-dimethylaminophenyl)-1,2- adding H2SO4 to a solution of 1,2 dihydroxynaphthalene naphthoquinone and N,N-d iethy t- aniline in acetic acid 20 1,1'-dihydroxy-4,4'-di[N-(2,5- reducing the blue dye obtained by dimethyl)-pyrroly]-2,2'-dinaphthyl oxidation of compound 4 with ferric chloride 1,11,1 '-dihydroxy-4,4'-di-diethyl- reducing the blue dye obtained by amino-2,2 '-dinaphthy I oxidation of 4-diethylarnfn-o#i - naphthol with ferric chloride 22 1,1'-dihydroxy-4,4-di[N-(2,6- reducing the blue dye obtained by dimethyl)-dihydromorpholinyl]- oxidation of compound 7 with 2,2'-dinaphthyl ferric chloride 23 4-diethylamino-1-naphthol ref fluxing an acetone solution of 4 amino-1-naphthol and excess bromo ethane in the presence of sodium carbonate The following Table 2 reports the characteristics of certain of the compounds recorded in Table 1 together with the colour of the dyes obtained on oxidation by silver chloride.It will be noted that the compounds of the invention provide dyes ranging from blue to yellow to orange-red upon oxidation which are suitable for use in amplifying the silver image in photographic elements.
TABLE 2
Data Colour of dye upon oxidation Compound IR v (cam'') extinction No. melting point (m.p.) coefficient A max 1 blue 2 m.p 94 to 95iC blue 20322 643 3 m.p.66to67C blue 4 blue 5 yellow 2595 428 8 3280 (OH) yellow 1610, 1405, 1275 2595 434 12 13 3390, 3310 (OH) 1590, 1505, 1267, 1030 - yellow 14 yellow 15 yellow 16 yellow 17 r yellow The invention will now be illustrated by the following Examples.
EXAMPLE 1 Compound No. 2- 4-n-dodecyloxy-1 -naphthol A mixture of 8 g of 1 ,4-dihydroxynaphthalene and 27 g of n-dodecanol in 200 ml dry ether was stirred at room temperature and saturated with a stream of hydrogen chloride gas for 3 hours. The solution was filtered and evaporated. Residue recrystallized from petroleum ether gave colourless crystals.
Yield 8g (49%) Melting point 94 to 950C
C % H % Calculated 80.49 9.75 Found 80.76 10.4 EXAMPLE 2 Compound No. 3 - 1,1 '-dihydroxy-4,4'-didodecyloxy-2,2'-dinaphthyl.
A) 4,4'-didodcyloxy-o-dinaphthoquinone An excess ferric chloride solution was added to a stirred solution of 10 g of 4-dodecyloxy-1 naphthol in 50 ml methanol. The precipitated blue dye was filtered, washed repeatedly with distilled water, cold methanol. Recrystallization from ether gave blue leaflets.
Yield 8.4 g (84%) Melting point 83 to 850C B) 1,1 '-dihydroxy-4,4'-didodecyloxy-2,2'-dinaphthyl To a stirred suspension of 4 g of 4,4'-didodecyloxy-o-dinaphthoquinone in 50 ml glacial acetic acid at 400C was added zinc powder until the colour discharged. The colourless solution was filtered, poured over a large excess of water. The precipitate was filtered, washed repeatedly with water and dried. The compound tends to turn bluish upon contact with air.
Yield 3.5 g (87%) Melting point 66 to 670C EXAMPLE 3 Compound No. 5 - 2-(2,4-dimethoxyphenyl)- 1 ,4-dihydroxynaphthalene.
A) 2-(2.4-dimethoxyphenyl)-l ,4-naphthoquinone A mixture of 1.6 g of 1,4-naphthoquinone and 1.5 g of m-dimethoxybenzene in 200 ml glacial acetic acid containing 1 ml concentrated H2SO4 was stirred at room temperature overnight. The dark green precipitate was filtered, washed with aqueous methanol and dried. Recrystallization from methanol gave orange-red crystals.
Yield 1.3 g (44%)
C % H % Calculated 73,47 4 75 Found 75.1 4.95 B) 2-(2,4-dimethoxyphenyl)- 1 ,4-naphthalenediol.
To a solution of 2.94 g of 2-(2,4-dimethoxyphenyl)-1 ,4-naphthoquinone in hot acetic acid was added zinc dust portionwise until the colour discharged. The solution was filtered and filtrate poured over water. The white powder that precipitated was filtered, washed with water and dried.
Recrystallization from chloroform gave colourless crystals.
Yield 2.5 g (85%)
C % H % Calculated 72.97 5,4 Found 73.25 5.32

Claims (14)

1. A compound of the general formula:
in which: one of R' and R2 represent OH, -NR3R4 in which R3 and R4 represent alkyl or the necessary atoms to complete a heterocyclic ring system, or -OR5 in which R5 represents an alkyl, aryl or aikaryl group having 8 to 12 carbon atoms, and either R6 is absent and the other of R1 and R2 represents an aromatic ring system linked via a carbon atom in an aromatic ring, or when said one of R' and R2 above is -NR3R4 Or ~OR5 said other of R1 and R2 can additionally represent hydrogen, or the other of R' and R2 is hydrogen and R6 represents the necessary atoms to form an aromatic ring system fused to the naphthol nucleus in the 5 and 6 positions, with the proviso that when R2 is OH, R1 is not
2. A compound as claimed in Claim 1 in which R' is hydrogen and R6 is absent.
3. A compound as claimed in Claim 2 in which R2 is alkoxy containing up to 12 carbon atoms.
4. A compound as claimed in Claim 2 in which R2 is -NR3R4.
5. A compound as claimed in Claim 1 in which R1 is phenyl or naphthyl each of which may be substituted, R2 is OH and R6 is absent.
6. A compound as claimed in Claim 1 in which R' is OH, R2 is phenyl or naphthyl each of which may be substituted and R6 is absent.
7. A compound as claimed in Claim 1 in which R' comprises the necessary atoms to form a bis compound and R6 is absent.
8. A compound as claimed in Claim 1 in which R6 comprises a benzene or naphthalene ring fused to the naphthol nucleus.
9. A compound as claimed in Claim 1 having the structure of any one of Compounds 1 to 23 reported in Table 1 herein.
10. A compound as claimed in Claim 1 substantially as herein described with reference to any one of the Examples.
11. A method of preparing a compound as claimed in Claim 1 in which R1 = H, R2 = --OR5 and R6 is absent which comprises the following reaction:
12. A method of preparing a compound as claimed in Claim 7 which comprises the following reaction:
1 3. A method of preparing a compound as claimed in Claim 4 which comprises one of the following reactions:
14. A method of preparing a compound as claimed in Claim 5 which comprises the following reaction:
1 5. A method of preparing a compound as claimed in Claim 6 which comprises the following reaction:
1 6. A method of preparing a compound as claimed in Claim 7 which comprises reducing the corresponding quinones in the presence of zinc and acetic acid.
1 7. A method of preparing a compound as claimed in Claim 1 substantially as herein described with reference to any one of the Examples.
GB8108287A 1980-03-17 1981-03-17 Novel naphtholic compounds and their preparation Expired GB2075496B (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4535056A (en) * 1984-03-15 1985-08-13 Minnesota Mining And Manufacturing Company Yellow color formers for use in color photothermographic system
US4699868A (en) * 1984-03-02 1987-10-13 Minnesota Mining And Manufacturing Company Photographic tanning developer formulation
US4835177A (en) * 1987-06-11 1989-05-30 Merck & Co., Inc. Aminoalkyl naphthalenediols as host resistance enhancers against viral infection
WO1990011988A1 (en) * 1989-04-04 1990-10-18 Sloan-Kettering Institute For Cancer Research Substituted 1-phenylnaphthalenes

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4699868A (en) * 1984-03-02 1987-10-13 Minnesota Mining And Manufacturing Company Photographic tanning developer formulation
US4535056A (en) * 1984-03-15 1985-08-13 Minnesota Mining And Manufacturing Company Yellow color formers for use in color photothermographic system
US4835177A (en) * 1987-06-11 1989-05-30 Merck & Co., Inc. Aminoalkyl naphthalenediols as host resistance enhancers against viral infection
WO1990011988A1 (en) * 1989-04-04 1990-10-18 Sloan-Kettering Institute For Cancer Research Substituted 1-phenylnaphthalenes
US5112869A (en) * 1989-04-04 1992-05-12 Sloan-Kettering Institute For Cancer Research Substituted 1-phenylnaphthalenes

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PCNP Patent ceased through non-payment of renewal fee

Effective date: 19940317