GB1590914A - 3,3-di-substituted phthalides and their use as colour-formers - Google Patents

3,3-di-substituted phthalides and their use as colour-formers Download PDF

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GB1590914A
GB1590914A GB1677779A GB1677779A GB1590914A GB 1590914 A GB1590914 A GB 1590914A GB 1677779 A GB1677779 A GB 1677779A GB 1677779 A GB1677779 A GB 1677779A GB 1590914 A GB1590914 A GB 1590914A
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carbon atoms
alkyl
dimethylaminophthalide
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STWB Inc
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Sterling Drug Inc
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D207/33—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D207/337—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
    • B41M5/132—Chemical colour-forming components; Additives or binders therefor
    • B41M5/136—Organic colour formers, e.g. leuco dyes
    • B41M5/145—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
    • C07D209/18—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D209/20—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals substituted additionally by nitrogen atoms, e.g. tryptophane
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
    • C07D307/88—Benzo [c] furans; Hydrogenated benzo [c] furans with one oxygen atom directly attached in position 1 or 3
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/24—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D455/00—Heterocyclic compounds containing quinolizine ring systems, e.g. emetine alkaloids, protoberberine; Alkylenedioxy derivatives of dibenzo [a, g] quinolizines, e.g. berberine
    • C07D455/03—Heterocyclic compounds containing quinolizine ring systems, e.g. emetine alkaloids, protoberberine; Alkylenedioxy derivatives of dibenzo [a, g] quinolizines, e.g. berberine containing quinolizine ring systems directly condensed with at least one six-membered carbocyclic ring, e.g. protoberberine; Alkylenedioxy derivatives of dibenzo [a, g] quinolizines, e.g. berberine
    • C07D455/04—Heterocyclic compounds containing quinolizine ring systems, e.g. emetine alkaloids, protoberberine; Alkylenedioxy derivatives of dibenzo [a, g] quinolizines, e.g. berberine containing quinolizine ring systems directly condensed with at least one six-membered carbocyclic ring, e.g. protoberberine; Alkylenedioxy derivatives of dibenzo [a, g] quinolizines, e.g. berberine containing a quinolizine ring system condensed with only one six-membered carbocyclic ring, e.g. julolidine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/06—Peri-condensed systems

Description

PATENT SPECIFICATION ( 11) 1 590 914
d 4 ( 21) Application No 16777/79 ( 22) Filed 13 Sept 1977 r S ( 62)-Divided out of No1590913 ( 1 ( 31) Convention Application No 726482 ( 32) Filed 24 Sept 1976 ( 31) Convention Application No 793544 l ( 32) Filed 4 May 1977 in _I ( 33) United States of America (US) ( 44) Complete Specification published 10 June 1981 ( 51) INT CL 3 C 09 B 57/00 B 41 M 5/12 ( 52) Index at acceptance C 4 P 100 DIX ( 54) 3,3-DI-SUBSTITUTED PHTHALIDES AND THEIR USE AS COLOR-FORMERS ( 71) We, STERLING DRUG INC, a Corporation organised and existing under the laws of the State of Delaware, United States of America, of 90 Park Avenue, New York, State of New York, United States of America, do hereby, declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the 5
following statement:-
The invention relates to 3,3-di-substituted phthalides:
In the complete specification of our co-pending Application for Letters Patent
No 38133/77 (Serial No 1,590,913), out of which the present Application is divided, there are disclosed 10 3-Y-3-Z-5-X-6-N(R)2 phthalides having the formula Formula I (wherein each R independently represents hydrogen, non-tertiary alkyl of one to four carbon atoms, benzyl or benzyl substituted in the benzene ring by one or two 15 of halo or alkyl of one to three carbon atoms; X represents hydrogen or halo; Y represents a mono-valent radical having one of the formulas (A) (B) (C) (D) (E) (F) or; and N (G) (H) Z represents a monovalent radical having one of the formulae (A), (B) or (G) above in which RI represents hydrogen, non-tertiary alkoxy of one to four carbon atoms, dialkylamino or N-alkylbenzylamino in which alkyl is non-tertiary alkyl of one to four carbon atoms; R 2 represents hydrogen, alkyl of one to three carbon atoms or 5 non-tertiary alkoxy of one to four carbon atoms; R 3 represents hydrogen, alkyl of one to three carbon atoms, non-tertiary alkoxy of one to four carbon atoms, halo or dialkylamino in which alkyl is non-tertiary alkyl of one to four carbon atoms; R 4 represents one or two of hydrogen, alkyl of one to three carbon atoms, alkoxy of one to three carbon atoms, halo or nitro; R 5 represents hydrogen, nontertiary alkyl 10 of one to eight carbon atoms, alkenyl of two to four carbon atoms, benzyl of benzyl substituted in the benzene ring by one or two of halo or alkyl of one to three carbon atoms; R" represents hydrogen, alkyl of one to three carbon atoms or phenyl; and R 7 and R 8 represent hydrogen or alkyl of one to three carbon atoms) and a process for the preparation of these compounds 15 Certain classes of compounds of Formula I are novel and it is to one such class of compounds that the present invention relates.
Accordingly, the present invention provides 3 ( 2 R 3 ' 4 R' phenyl) 3 ( 2 R 3 -3 R 2 ' 4 RI" phenyl) 5 X 6 -N -(R)2 phthalides, which are particularly useful as colorless precursors in the art of carbonless duplicating, 20 and which have the formula l Formula IV / I 9 R p./u Ra wherein each R independently represents non-tertiary alkyl of one to four carbon atoms; R' represents hydrogen, non-tertiary alkoxy of one to four carbon atoms, N-alkylbenzylamino in which alkyl is non-tertiary alkyl of one to four carbon atoms 25 or, when R 3 is other than dialkylamino, dialkylamino in which alkyl is non-tertiary alkyl of one to four carbon atoms; RI'" represents dialkylamino in which alkyl is non-tertiary alkyl of one to four carbon atoms, R 2 ' represents hydrogen or alkyl of one to three carbon atoms; R 3 represents hydrogen, alkyl of one to three carbon atoms, non-tertiary alkoxy of one to four carbon atoms, halo or dialkylamino in 30 which alkyl is non-tertiary alkyl of one to four carbon atoms; R 3 ' represents hydrogen, alkyl of one to three carbon atoms, non-tertiary alkoxy of one to four carbon atoms or halo; X represents hydrogen or halo; and with the proviso that R 2 ', R 3, R 3 ' and X cannot all be hydrogen at the same time.
As used herein, the term "non-tertiary alkyl of one to eight carbon atoms" 35 means saturated monovalent aliphatic radicals, including branched chain radicals, for example, methyl, ethyl, propyl, isopropyl, butyl, amyl, I-methylbutyl, 3methylbutyl, hexyl, isohexyl, heptyl, isoheptyl, octyl, isooctyl and 2ethylhexyl.
When the terms "alkyl of one to three carbon atoms", "alkoxy of one to three carbon atoms" and "non-tertiary alkoxy of one to four carbon atoms" are used 40 herein, there is meant saturated, acyclic group which may be straight or branched as exemplified by methyl, ethyl, propyl, isopropyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, and isobutoxy.
1,590,914 3 1,590,914 3 As used herein, the term "alkenyl of two to four carbon atoms" means a monovalent aliphatic radical possessing a single double bond, for example, ethenyl (or vinyl), 2-propenyl (or allyl), 1-methylethenyl (or isopropenyl), 2methyl-2propenyl, 2-methyl-1-propenyl, 2-butenyl and 3-butenyl.
When the term "halo" is used herein, there are included chloro, fluoro, 5 bromo and iodo The preferred halo substituent is chloro because the other halogens offer no particular advantages over chloro and because of the relatively low cost and ease of preparation of the required chloro intermediates However, the other above-named halo substituents are also satisfactory.
The term "N-alkylbenzylamino" as used herein, means an amino radical 10 substituted by an alkyl substituent and a benzyl substituent in which the benzene ring may be unsubstituted or substituted by one or two of halo or alkyl of one to three carbon atoms.
The novel compounds represented by Formula IV above are essentially colorless in the depicted form When the compounds of Formula IV are contacted 15 with an acidic medium for example, silica gel or one of the types regularly employed in pressure-sensitive carbonless duplicating systems, for example, silton clay of phenolic resins, they develop a colored image of good to excellent tinctorial strength The development of color on contact with silica gel, silton clay or a phenolic resin demonstrates that these compounds are highly suitable for use as 20 colorless precursors, that is, color-forming substances in pressuresensitive carbonless duplicating systems For such application, the compounds may be incorporated in any of the commercially accepted systems known in the carbonless duplicating art A typical technique for such application is as follows Solutions of the colorless precursor compounds in suitable aromatic solvents are 25 microencapsulated by well-known procedures The microcapsules are coated on the reverse side of a transfer sheet with the aid of a suitable binder and the coatedtransfer sheet is then assembled in a manifold with the microcapsule coated side in contact with a receiving sheet coated with an electron accepting substance, for example, silton clay or a phenolic resin Application of pressure to the manifold 30 such as that exerted by a stylus, typewriter or other form of writing or printing causes the capsules on the reverse side to rupture The solution of the color former released from the ruptured microcapsules flows to the receiving sheet and on contact with the acidic medium thereon forms a bluish-green to reddishpurple colored image of good tinctorial strength It is, of course, obvious that variants of 35 this mode of application can be utilized For example, the receiving sheet in a manifold can alternatively be coated with the subject compounds and the acidic developing agent can be contained in microcapsules applied to the reverse side of the top sheet in the manifold.
It has also been found that when the compounds of Formula IV are intimately 40 mixed with an acidic developer of the type generally employed in thermal papers, that is, papers which produce a colored image when contacted with a heated stylus or heated type, for example, bisphenol A, heating of the mixture produces a colored image of varying shades from yellow to purple depending on the particular compound of the invention employed The ability of the compounds of Formula IV 45 to form a deep color when heated in admixture with an acidic developer such as bisphenol A, makes them useful in thermal paper marking systems, either where an original or a duplicate copy is prepared by contacting the thermal paper with a heated stylus or heated type in any of the methods generally known in the art.
In view of the utility of the novel compounds represented by Formula IV as 50 described above, another aspect of this invention resides in pressuresensitive carbonless duplicating systems and thermal paper marking systems containing as a color-forming substance a compound of Formula IV.
As stated above, the compounds of Formula IV may be prepared by the process disclosed in our aforementioned co-pending Application No 38133/77 55 Serial No 1,590,913.
In this process one condenses a 3-N-(R)2 4 X-benzoic acid with an aldehyde of the formula Y-CHO in the presence of an acid condensing agent under dehydrating conditions to produce a 3-Y-5-X-6 IN(R)2 phthalide having the formula 60 4 1,590,914 4 j+Formula II wherein R, X and Y have the same respective meanings indicated in Formula I.
One then condenses said phthalide of Formula II with a compound of the formula Z-H in the presence of an alkaline or an acid condensing agent to produce a 5 2 (a-Y-a-Z)methyl -4 X-R-N(R)2 benzoic acid of the formula 0, j Cool.
g Xcoo Formula III wherein R, X, Y and Z have the same respective meanings indicated in Formula I.
One then oxidizes said benzoic acid to produce a 3-Y-3-Z-5-X-6-N(R)2 phthalide of Formula I 10 The aformentioned co-pending Application No 38133/77 Serial No 1,590,914 claims the compounds of Formula III per se, the aforementioned process for their preparation from the compounds of Formula III and the process for their oxidation to compounds of Formula I.
Further novel compounds of Formula I are described and claimed in our co 15 pending Application for Letters Patent No 16778/79 (Serial No 1,590,915) which is also divided out of the aforementioned Application No 38133/77 Serial No.
1,590,914.
The molecular structures of the compounds of this invention were assigned on the basis of the modes of synthesis and study of their infrared, nuclear magnetic 20 resonance, and mass spectra and elemental analysis.
The following examples will further illustrate the invention without, however, limiting it thereto All melting points are uncorrected.
Example 1
A A mixture of 600 ml of water, 10 8 g of flake potassium hydroxide, 36 0 g of 25 3-( 4-dimethylaminophenyl)-6-dimethylaminophthalide prepared as in Example 1, part A of our aforementioned co-pending Application No 38133/77 Serial No.
1,590,914 and 20 0 g of N,N-diethyl-m-toluidine was heated with stirring in a stainless steel autoclave at 120 C for approximately seven hours and at 160 C for approximately six hours The resulting mixture was cooled to ambient temperature 30 and filtered to remove the insolubles The obtained aqueous solution of the potassium salt of 2 l 2 methyl 4,4 ' bis(dimethylamino) benzhydryll 5 dimethylaminobenzoic acid (Formula III: R=CH 3; X=H; Y= 4-(CH 3)2 NC 6 H 4; Z= 4(CH 3)2 N-2-CH 3 C 6 H 3) was utilized directly in the oxidation of the next part of this example 35
B The p H of the benzoic acid-potassium salt solution obtained in part A directly above was adjusted to 9 5 by the addition of sodium bicarbonate, the solution was heated at 80 C for approximately seven hours under an atmosphere of oxygen at 60-65 psi The resulting mixture was cooled to room temperature; the solid which separated was collected by filtration and dried at room temperature The solid was 40 dissolved in toluene, treated with decolorizing charcoal and filtered The toluene solution was extracted with 300 ml of 3 N hydrochloric acid and separated The aqueous acid layer was adjusted to p H 5 by the addition of sodium acetate The solid which separated was collected by filtration, washed with water and dried in vacuo at 60 C to obtain 16 5 g of 3 ( 4 dimethylaminophenyl) 3 ( 4 45 diethylamino 2 methylphenyl) 6 dimethylaminophthalide (Formula IV: R=CH 3; X=H; R"=N(CH 3)2; R 3 '=H; R"'=N(C 2 Hs)2; R 3 =CH 3; R 2 '=H); a solid melting at 183-184 C.
The nuclear magnetic resonance spectrum was in accord with the assigned structure Analysis by mass spectrum showed a m/e peak at 457 (M+) The infrared spectral analysis had a maximum at 1763 (C=O; s) cm- 5 A toluene solution of the product spotted on silica gel, an acidic clay or a phenolic resin develops a grape-colored image.
Example 2
A Following a procedure similar to that described in Example 1, part A of our aforementioned co-pending Application No 38133/77 Serial No 1,590,914, 36 0 g 10 of 3-( 4-dimethylaminophenyl)-6-dimethylaminophthalide prepared as described in Example 1, part A of our aforementioned co-pending Application No 38133/77 Serial No 1,590,914 and 23 0 g of 3-ethoxy-N,N-diethylaniline were interacted to obtain a solution of the potassium salt of 2 l 4 ' diethylamino 2 ' ethoxy ( 4 dimethylamino) benzhydryll 5 dimethylaminobenzoic acid (Formula III: R=CH 3; 15 X=H; Y= 4-(CH 3)2 NC 6 H 4; Z= 4-(C 2 H,)2 N-2 C 2 HO 50-C 6 H 3) which was used without isolation in the next step.
B Proceeding in a manner similar to that described in Example 1, part C of our aforementioned co-pending Application No 38133/77 Serial No 1,590,914, the potassium salt solution of 2 l 4 ' diethylamino 2 ' ethoxy ( 4 20 dimethylamino) benzhydryll 5 dimethylaminobenzoic acid from A was oxidized to obtain 6 8 g of 3 ( 4 diethylamino 2 ethoxyphenyl) 3 ( 4 dimethylaminophenyl) 6 dimethylaminophthalide (Formula IV: R=CH 3; X=H; R 1 '=N(CH 3)2; R 3 '=H; R"=N(C 2 H,)2; R 3 =C 2 H^O; R 2 '=H), a solid melting over the range 93-99 C 25 The infrared spectral analysis showed a maximum at 1755 (C=O; b, s) cm-L.
The nuclear magnetic resonance spectrum was in accord with the assigned structure Mass spectral analysis showed a m/e peak at 487 (M+).
A toluene solution of the product spotted on silica gel, an acidic clay or a phenolic resin develops a deep blue-colored image 30 Example 3
A Employing a procedure similar to that described in Example 1, part A of our aforementioned co-pending, Application No 38133/77 Serial No 1,590,914, for interacting 8 2 g of p-anisaldehyde and 11 6 g of 3-dimethylaminobenzoic acid utilizing acetic anhydride alone as the reaction medium there was obtained 9 4 g of 35 3 ( 4 methoxyphenyl) 6 dimethylaminophthalide (Formula II: R=CH 3; X=H; Y= 4-CH 3 OC 6 H 4) as a white solid melting at 169-170 C.
The infrared spectral analysis showed a maximum at 1755 (C=O; s) cm-L The nuclear magnetic resonance spectrum was concordant with the assigned structure.
A toluene solution of the product spotted on an acid clay develops a blue 40 colored image.
B Employing a procedure similar to that described in Example 1, part B of our aforementioned co-pending Application No 38133/77 Serial No 1,590,914, 3( 4methoxyphenyl)-6-dimethylaminophthalide, prepared as described in part A above, was interacted with N,N,N',N'-tetramethyl-m-phenylenediamine to obtain 45 the potassium salt of 2 l 2,4 bis(dimethylamino) 4 ' methoxybenzhydryll 5 dimethylaminobenzoic acid (Formula III: R=CH 3; X=H; Y= 4-CH 3 OC 6 H 4; Z= 2,4l(CH 3)2 Nl 2-C 6 H 3) which was employed in the oxidation step without prior isolation from its alkaline aqueous preparation medium.
C Proceeding in a manner similar to that described in Example 1, part C, of our 50 aforementioned co-pending Application No 38133/77 Serial No 1,590,914, for oxidizing the potassium salt of 2-l 2,4-bis(dimethylamino)-4 'methoxybenzhydryll-5dimethylaminobenzoic acid, there was obtained 10 4 g of 3 l 2,4 bis(dimethylamino)phenyll 3 ( 4 methoxyphenyl) 6 dimethylaminophthalide (Formula IV: R=CH 3; X=H; R 1 '=CH 30; R 3 '=H; R"=R 3 N(CH 3)2; R 2 '=H) an 55 orange-tan colored solid which melted at 90-94 C.
The infrared spectrum showed a maximum at 1762 (C=O; s) cm-' The nuclear magnetic resonance spectrum was consistent with the assigned structure.
A toluene solution of the product spotted on phenolic resin develops a blackcolored image 60 Example 4
A Proceeding in a manner similar to Example 1, part A of our aforementioned co-pending Application No 38133/77 Serial No 1,590,914, 11 6 g of 3 1,590,914 dimethylaminobenzoic acid and 8 2 g of o-anisaldehyde were interacted using acetic anhydride alone as the reaction medium to obtain 11 7 g of 3 ( 2 methoxyphenyl) 6 dimethylaminophthalide (Formula II: R=CH 3; X=H; Y= 2CH 3 OC 6 H 4) as an orange solid melting at 165-166 5 C.
A significant infrared maximum appeared at 1760 (C=O; s) cm-' The nuclear 5 magnetic resonance spectra was concordant with the assigned structure.
A toluene solution of the product spotted on an acid clay develops a pale yellow-colored image.
B Following the procedure described in Example 1, part B, of our aforementioned co-pending Application No 38133/77 Serial No 1,590,914, 3( 2 10 methoxyphenyl)-6-dimethylaminophthalide from A is interacted with N,N,N', N'tetrabutyl-m-phenylene diamine to obtain 2 l 2,4 bis(dibutylamino) ( 2 'methoxybenzhydryll 5 dimethylaminobenzoic acid (Formula III: R=CH 3; X=H; Y= 2-CH 3 OC 6 H 4; Z= 2,4-l(C 4 Hg)2 Nl 2-C 6 H 3).
C Employing a procedure similar to that described in Example 1, part C of our 15 aforementioned co-pending Application No 38133/77 Serial No 1,590,914, 2 l 2,4 bis(dibutylamino) ( 2 ' methoxyphenyl)benzhydryll 5 dimethylaminobenzoic acid from B is oxidized to obtain 3 l 2,4 bis(dibutylamino)phenyll 3 ( 2 methoxyphenyl) 6 dimethylaminophthalide (Formula IV: R=CH 3; X=H; R'=H; R 3 '=CH 30; R"=R 3 =N(C 4 Hg)2 R 2 '=H) 20 Example 5
A Following a procedure similar to that described in Example 1, part A, of our aforementioned co-pending Application No 38133/77 Serial No 1,590,914, 11 6 g.
of 3-dimethylaminobenzoic acid and 9 0 g of 4-ethox benzaldehyde were interacted in acetic anhydride to obtain 2 6 g of 3 ( 4 ethoxyphenyl) 6 25 dimethylaminophthalide (Formula II: R=CH 3; X=H; Y= 4-C 2 H 5 OC 6 H 4) as a white solid melting at 115 5-118 C.
Infrared spectral analysis showed a maximum at 1750 (C=O; s) cm- The nuclear magnetic resonance analysis was in accord with the assigned structure A toluene solution of the product spotted on an acid clay develops a greencolored 30 image.
B Employing a procedure similar to that described in Example 1, part B of our aforementioned co-pending Application No 38133/77 Serial No 1,590,914, 3( 4ethoxyphenyl)-6-dimethylaminophthalide from A is interacted with N,Ndimethylm-toluidine to obtain 2 ( 4 dimethylamino 2 methyl 4 ' ethoxybenzhydryl) 35 dimethylaminobenzoic acid (Formula III: R=CH 3; X=H; Y= 4-C 2 Hs OC 6 H 4; Z= 4(CH 3)2 N-2-CH 3 C 6 H 3).
C Proceeding in a manner similar to that described in Example 1, part C of our aforementioned co-pending Application No 38133/77 Serial No 1,590,914, 2 ( 4 dimethylamino 2 methyl 4 ' ethoxybenzhydryl) 5 dimethylaminobenzoic 40 acid from part B above is oxidized to obtain 3 ( 4 dimethylamino 2 methylphenyl) 3 ( 4 ethoxyphenyl) 6 dimethylaminophthalide (Formula IV:
R=CH 3; X=H; RI'=C 2 H 1 O; R 3 '=H; RI"=N(CH 3)2; R 3 =CH 3; R 2 '=H).
Example 6
A Employing a procedure similar to that described in Example 1, part A of our 45 aforementioned co-pending Application No 38133/77 Serial No 1,590,914, for interacting 11 6 g of 3-dimethylaminobenzoic acid and 12 4 g of 89 percent 3ethoxy-4-methoxybenzaldehyde in acetic anhydride, there was obtained 3 ( 3 ethoxy 4 methoxyphenyl) 6 dimethylaminophthalide (Formula II: R=CH 3; X=H; Y= 3-C 2 H 50-4-CH 3 O-C 6 H 3) a solid which had an infrared spectrum 50 maximum at 1760 (C=O; s) cm-'.
B Proceeding in a manner similar to that described in Example 1, part B of our aforementioned co-pending Application No 38133/77 Serial No 1,590,914, 3( 3ethoxy-4-methoxyphenyl)-6-dimethylaminophthalide from A is interacted with N,N,N',N'-tetra-sec-butyl-m phenylenediamine to obtain 2 l 2,4 bis(di sec 55 butylamino) 3 ' ethoxy 4 ' methoxybenzhydryll 5 dimethylaminobenzoic acid (Formula III: R=CH 3; X=H; Y= 3-C 2 H 50-4-CH 3 OC 6 H 3; Z= 2,4-l(s-C 4 Hg)2 Nl 2 C 6 H 3).
C Following the procedure described in Example I, part C of our aforementioned co-pending Application No 38133/77 Serial No 1,590,914, 2 l 2,4 bis(di sec butylamino) 3 ' ethoxy 4 ' methoxybenzhydryll 5 dimethylaminobenzoic 60 acid from B is oxidized to obtain 3 l 2,4 bis(di sec butylamino)phenyll 3 ( 3 ethoxy 4 methoxyphenyl) 6 dimethylaminophthalide (Formula IV: R=CH 3; X=H; R'"=CH 30; R 2 '=C 2 H 5 O; R 3 =H; R' '=R 3 '=N(s-C 4 Hg)2).
1,590,914 Example 7
A Proceeding in a manner similar to Example 1, part A of our aforementioned co-pending Application No 38133/77 Serial No 1,590,914, 11 6 g of 3dimethylaminobenzoic acid and 10 0 g of 2,4-dimethoxybenzaldehyde were interacted in acetic anhydride to obtain 14 0 g of 2 ( 2,4 dimethoxyphenyl) 6 5 dimethylaminophthalide (Formula II: R=CH 3; X=H; Y= 2,4-(CH 3 a O)2 C 6 H 3) as a yellow-colored solid melting at 123-125 C.
A significant infrared maximum appeared at 1750 (C=O; s) cm-,.
A toluene solution of the product spotted on an acid clay develops a bluecolored image 10 B Proceeding in a manner similar to that described in Example 1, part B of our aforementioned co-pending Application No 38133/77 Serial No 1,590,914, 25 1 g.
of 3 ( 2,4 dimethoxyphenyl) 6 dimethylaminophthalide prepared as described in part A aboye and 13 4 g of N,N,N',N' tetramethyl m phenylenediamine were interacted to obtain the potassium salt of 2 l 2,4 15 dimethoxy 2 ',4 ' bis(dimethylamino)benzhydryll 5 dimethylaminobenzoic acid (Formula III: R=CH 3; X=H; Y= 2,4-(CH 30)2 C 6 H 3; Z= 2,4 l(CH 3)2 Nl 2 C 6 H 3) which was employed in the oxidation step without prior isolation from its aqueous preparation medium.
C Following the procedure described in Example 1, part C of our 20 aforementioned co-pending Application No 38133/77 Serial No 1,590,914, for oxidizing the potassium salt of 2 l 2,4 dimethoxy 2 ',4 ' bis(dimethylamino)benzhydryll 5 dimethylaminobenzoic acid there was obtained 9 0 g of 3 ( 2,4 dimethoxyphenyl) -3 l 2,4 bis(dimethylamino) phenyll 6 dimethylaminophthalide (Formula IV: R=CH 3; X=H; R 1 '=R 3 =CH 30; 25 R"=R 3 =N(CH 3)2; R 2 '=H; a reddish-brown-colored solid which melted over the range 153-160 C.
A significant infrared maximum appeared at 1760 (C=O; s) cm-' The nuclear magnetic resonance spectrum was consistent with the assigned structure.
A toluene solution of the product spotted on a phenolic resin develops a 30 reddish-brown-colored image.
Example 8
Proceeding in a manner similar to that described in Example 26 part E of the aforementioned co-pending Application No 38133/77 Serial No 1,590,914,0 3 g of 3 ( 2,4 dimethoxyphenyl) 6 dimethylaminophthalide, prepared in a manner 35 similar to Example 7, part A above, was interacted with 3 0 ml of N,Ndimethylaniline in the presence of 0 3 g of anhydrous ferric chloride to obtain significant amounts of 2 l( 2,4 dimethoxy 4 ' dimethylamino)benzhydryll 5 dimethylaminobenzoic acid (Formula III: R=CH 3; X=H; Y= 2,4-(CH 3 O)2 C 6 H 3; Z= 4(CH 3)2 NC 6 H 4) and 3( 4dimethylaminophenyl) 3 ( 2,4 dimethoxyphenyl) 6 40 dimethylaminophthalide (Formula IV: R=CH 3; X=H; R'=R 3 '=CH 30; R 1 '=N(CH 3)2; R 2 '=R 3 =H).
Example 9
A Following the procedure described in Example 26, part A, of the aforementioned co-pending Application No 38133/77 Serial No 1,590,914, 9 9 g of 45 3 ( 4 methoxyphenyl) 6 dimethylaminophthalide, prepared as described in Example 3, part A above, and 89 0 ml of N,N dimethylaniline were interacted in the presence of 9 5 g of anhydrous zinc chloride at room temperature to obtain 13.7 g of 2 ( 4 dimethylamino 4 ' methoxybenzhydryl) 5 dimethylaminobenzoic acid as an off-white colored solid melting at 185190 C 50 B A stirred mixture of 8 1 g of 2 ( 4 dimethylamino 4 ' methoxybenzhydryl) 5 dimethylaminobenzoic acid from part A above, 40 0 ml.
of water, 1 6 g of 50 percent aqueous sodium hydroxide and 2 7 ml of isopropyl alcohol was maintained at a temperature in the range of 85-96 C while 20 3 g of ten percent aqueous hydrogen peroxide was added over a period of approximately 55 six hours The reaction was set aside at ambient temperature overnight The solid was collected by filtration, washed free of alkali with water dried in vacuo to obtain 5.5 g of 3 ( 4 dimethylaminophenyl) 3 ( 4 methoxyphenyl) 6dimethylaminophthalide (Formula IV: R"'=N(CH 3)2; R 1 "=CH 30; R 3 =R 3 '=R 2 '=H) a yellow-colored solid which melted at 156-161 C 60 A significant infrared maximum appeared at 1754 (C=O; s) cm- The nuclear magnetic resonance spectrum was consistent with the assigned structure.
A toluene solution of the product spotted on an acid clay or an acidic resin develops a green-colored image.
1,590,914 Example 10
A Employing a procedure similar to that described in Example 26, part A of our aforementioned co-pending Application No 38133/77 Serial No 1,590,914, 5 4 g of 3 ( 4 dimethylaminophenyl) 5 dimethylaminophthalide, prepared as described in Example 1, part A of our aforementioned co-pending Application No 5 38133/77 Serial No 1,590,914, and 57 g of N,N-diethyl-m-toluidine were interacted in the presence of anhydrous zinc chloride at 100 to 110 C to obtain 4 5 g of 2 l( 2 methyl 4 diethylamino 4 ' dimethylamino)benzhydryll 5 dimethylaminobenzoic acid (Formula III: R=CH 3; X=H; Y= 4-(CH 3)2 NC 6 H 4; Z= 2CH 3-4-(C 2 Hs)NC 6 H 4) as a brownish pink colored solid which melted over the range 10 105-115 C.
A significant infrared maximum appeared at 1700 (C=O; s) cm-' The nuclear magnetic resonance spectrum was in accord with the assigned structure.
B Proceeding in a manner similar to that described in Example 9, part B above, 3 7 g of 2 l( 2methyl 4 diethylamino 4 ' dimethylamino)benzhydryll 5 15 dimethylaminobenzoic acid from part A above was oxidized to obtain 1 8 g of 3 ( 2 methyl 4 diethylaminophenyl) 3 ( 4 dimethylaminophenyl) 6dimethylaminophthalide (Formula IV: R=CH 3; X=H; R 1 '=N(CH 3)2; R 3 '=H; RI'=N(C 2 Hs)2; R 3 =CH 3, R 2 '=H) as a brown solid which melted at 190195 C.
A significant infrared maximum appeared at 1760 (C=O; s) cm-' The nuclear 20 magnetic resonance spectrum was in accord with the assigned structure.
A toluene solution of the product when spotted on silica gel or a phenolic resin develops a purple-colored image.
Example 11
A Following a procedure similar to that described in Example 1, part A, of our 25 aforementioned Application No 38133/77 Serial No 1,590,914, 36 6 g of 2chloro4-dimethylaminobenzaldehyde and 33 0 g of 4-dimethylaminobenzoic acid were interacted in acetic anhydride to obtain 52 1 g of 3 ( 2 chloro 4 dimethylaminophenyl) 6 dimethylaminophthalide (Formula I: R=CH 3; X=Z=H; Y= 2-CI-4-(CH 3)2 NC 6 H 3) as a red crystalline solid which melted at 159-160 C 30 A significant infrared maximum appeared at 1770 (C=O; s) cm-'.
B Employing a procedure similar to that described in Example 26, part A of our aforementioned co-pending Application No 38133/77 Serial No 1,590,914, 6 5 g; of 3 ( 2 chloro 4 dimethylaminophenyl) 6 dimethylphthalide from part A above and 30 0 ml of N,N-dimethylaniline were interacted in the presence of 5 3 g 35 of anhydrous zinc chloride to obtain 8 0 g of 2 l 2 chloro 4,4 ' dimethylamino)benzhydryll 5 dimethylaminobenzoic acid (Formula III: R=CH 3; X=H Y= 2 C 1-4-(CH 3)2 NC 8 H 3; Z= 4-(CH 3)2 NC 6 H 4) as a pink powder which melted over the range 180-190 C.
The infrared spectrum showed a maximum at 1610 (C=O; s, b) cm-' The 40 nuclear magnetic resonance was concordant with the assigned structure.
C Proceeding in a manner similar to that described in Example 9, part B above, 5.4 g of 2 l 2 chloro 4,4 ' bis(dimethylamino)benzhydryll 5 dimethylaminobenzoic acid was oxidized to obtain 2 9 g, of 3 ( 2 chloro 4 dimethylaminophenyl) 3 ( 4 dimethylaminophenyl) 6 dimethylaminophthalide 45(Formula IV: R=CH 3; X=H; R'=N(CH 3)2; R 3 '=CI; R'"=N(CH 3)2; R 2 '=R 3 =H) a pale bluish-gray-colored solid which melted at 233-234 C.
A significant infrared maximum appeared at 1760 (CO); S cm The nuclear magnetic resonance spectrum was concordant with the assigned structure.
A toluene solution of the product spotted on silica gel develops a bluish 50 purple-colored image.
Example 12
A Employing a procedure similar to that described in Example 26, part A of our aforementioned co-pending Application No 38133/77 Serial No 1590914, 7 0 g of 3 ( 2,4 dimethoxyphenyl) 6 dimethylaminophthalide, prepared as described 55 in Example 7, part A above and 31 0 ml of N,N dimethylaniline were interacted in the presence of zinc chloride at room temperature to obtain 10 9 g of 2 ( 2,4 dimethoxy 4 ' dimethylaminobenzhydryl) 5 dimethylaminobenzoic acid (Formula III: R=CH 3; X=H; Y= 2,4-(CH 3 O)2 C 6 H 3); Z= 4-(CH 3)2 NC 6 H 4), a white solid which melted over the range 105-135 C 60 The infrared spectrum had a significant maximum at 1696 (C=O; s) cm-' The nuclear magnetic resonance spectrum was consistent with the assigned structure.
B Following a procedure similar to that described in Example 9, part B above, 6.5 g of 2 ( 2,4 dimethoxy 4 ' dimethylaminobenzhydryl) 5 1,590,914 dimethylaminobenzoic acid was oxidized to obtain 2 2 g of 3 ( 2,4 dimethoxyphenyl) 3 ( 4 dimnethylaminophenyl 6 dimethylaminophthalide (Formula IV: R=CH 3; X=H; R'=R 3 'CH 3 O; R 1 '=N(CH 3)2; R 2 '=R 3 =H), a pale yellow-colored solid which melted at 191 5-193 5 C.
A significant infrared maximum appeared at 1758 (C=O; s) cm-' The nuclear 5 magnetic resonance spectrum was in accord with the assigned structure.
A toluene solution of the product spotted on a phenolic resin develops a light blue-colored image.
Example 13
A Proceeding in a manner similar to that described in Example 26, part A of our 10 aforementioned co-pending Application No 38133/77 Serial No 1,590,914,9 9 g of 3 ( 2 methoxyphenyl) 6 dimethylaminophthalide, prepared as described in Example 4, part A above and 49 0 ml of N,N-dimethylaniline were interacted in the presence of zinc chloride at room temperature to obtain 14 3 g of 2 ( 2 methoxy 4 ' dimethylaminobenzhydryl) 5 dimethylaminobenzoic acid (Formula 15 III: R=CH 3; X=H; Y= 2-(CH 3 OC O H 4; Z= 4-(CH 3)2 NC 6 H 4), a light yellow solid which melted over the range 229-234 C.
The infrared spectrum had a significant maximum at 1690 (C=O; s) cm-' The nuclear magnetic resonance spectrum was consistent with the assigned sturcture.
B Employing a procedure similar to that described in Example 9, part B above, 20 6.1 g of 2 ( 2 methoxy 4 ' dimethylaminobenzhydryl) 5 dimethylaminobenzoic acid was oxidized with hydrogen peroxide to obtain 1 05 g.
of 3 ( 2 methoxyphenyl) 3 ( 4 dimethylaminophenyl) 6 dimethylaminophthalide (Formula IV: R=CH 3; X=H; R 3 '=CH 30; R'=H; R'"=N(CH 3)2; R 2 '-R 3 =H, light yellow-colored solid which melted at 215-216 C 25 A significant infrared maximum appeared at 1750 (C=O; s) cm- The nuclear magnetic resonance spectrum was consistent with the assigned structure; A toluene solution of the product spotted on silica gel develops a light bluecolored image and spotted on a phenolic resin develops a light greencolored image 30 It is contemplated that by following a procedure selected from those described in Example 1, part B, Example 2, part B, Example 5, part A, or Example 26, part A of our aforementioned co-pending Application No 38133/77 Serial No 1,590, 914, for interacting approximately molar equivalent quantities of the appropriate 3Y-5-X-6-N(R)2 phthalide and Z-H in the presence of the indicated 35 condensing agent, the compounds of Examples 14 and 15 are obtained.
Example 14
3 ( 2 Methylphenyl 3 ( 3 isopropyl 4 diethylaminophenyl) 6 lN methyl N ( 4 methylbenzyl)laminophthalide using 2 l 3 isopropyl 4 diethylamino 2 ' methyl)benzhydryll 5 IN methyl N ( 4 40 methylbenzyl)aminolbenzoic acid.
Example 15
3 ( 2 Fluorophenyl) 3 l 3 propoxy 4 (N sec butylbenzylamino)phenyll 6 (N ethyl N methyl)aminophthalide using 2 l( 2 'fluoro 3 propoxy -4 N sec butylbenzylamino)benzhydryll 5 (N 45 ethyl N methyl)aminobenzoic acid.

Claims (3)

WHAT WE CLAIM IS:-
1 A compound of the Formula IV (herein) wherein each R independently represents non-tertiary alkyl of one to four carbon atoms: RW' represents hydrogen, non-tertiary alkoxy of one to four carbon atoms, N-alkylbenzylamino in which 50 alkyl is non-tertiary alkyl of one to four carbon atoms or, when R 3 is other than dialkylamino, dialkylamino in which alkyl is non-tertiary alkyl of one to four carbon atoms; RI" represents dialkylamino in which alkyl is non-tertiary alkyl of one to four carbon atoms; R
2 ' represents hydrogen or alkyl of one to three carbon atoms; R 3 represents hydrogen, alkyl of one to three carbon atoms, nontertiary 55 alkoxy of one to four carbon atoms, halo or dialkylamino in which alkyl is nontertiary alkyl of one to four carbon atoms; R 3 ' represents hydrogen, alkyl of one to three carbon atoms, non-tertiary alkoxy of one to four carbon atoms or halo; X represents hydrogen or halo; and with the proviso that R 2 ', R 3, R 3 ' and X cannot all be hydrogen at the same time 60 1,590,914 1,590,914 10 2 3 ( 4 Dimethylaminophenyl) 3 ( 2 methyl 4 diethylaminophenyl) 6 dimethylaminophthalide.
3.3 ( 4 Dimethylaminophenyl) 3 ( 2 ethoxy 4 diethylaminophenyl) 6 dimethylaminophthalide.
4 3 ( 4 Dimethylaminophenyl) 3 ( 4 methoxyphenyl) 6 5 dimethylaminophthalide.
3 l 2,4 Bis(dimethylamino)phenyll 3 ( 4 methoxyphenyl) 6 dimethylaminophthalide.
6 A compound according to claim 1, wherein R 3 when alkoxy has I to 3 carbon atoms 10 7 A compound according to claim 1, wherein R 3 is non-tertiary alkoxy of 4 carbon atoms.
8 A compound according to claim 1, substantially as herein described with reference to the Examples.
9 A pressure-sensitive carbonless duplicating system or thermal paper 15 marking system containing as a color-forming substance a compound according to any one of the preceding claims.
A pressure-sensitive carbonless duplicating system or thermal paper marking system as claimed in claim 9 substantially as herein described with reference to the Examples 20 LANGNER PARRY Chartered Patent Agents, High Holborn House, 52-54 High Holborn, London, WCIV 6 RR Agents for the Applicants Printed for Her Majesty's Stationery Office, by the Courier Press, Leamington Spa, 1981 Published by The Patent Office, 25 Southampton Buildings, London, WC 2 A l AY, from which copies may be obtained.
GB1677779A 1976-09-24 1977-09-13 3,3-di-substituted phthalides and their use as colour-formers Expired GB1590914A (en)

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US4189171A (en) * 1977-03-01 1980-02-19 Sterling Drug Inc. Marking systems containing 3-aryl-3-heterylphthalides and 3,3-bis(heteryl)phthalides
US4275206A (en) * 1979-03-05 1981-06-23 Appleton Papers Inc. Lactone compounds containing an indolizine radical
US4920220A (en) * 1987-11-12 1990-04-24 Ciba-Geigy Corporation Chromogenic 1-heterocyclic substituted 2,4-benzoxazines
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