GB1590915A - 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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GB1590915A
GB1590915A GB1677879A GB1677879A GB1590915A GB 1590915 A GB1590915 A GB 1590915A GB 1677879 A GB1677879 A GB 1677879A GB 1677879 A GB1677879 A GB 1677879A GB 1590915 A GB1590915 A GB 1590915A
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indolyl
halo
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STWB 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Indole Compounds (AREA)
  • Color Printing (AREA)
  • Furan Compounds (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Heterocyclic Compounds Containing Sulfur Atoms (AREA)
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  • Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Description

PATENT SPECIFICATION
( 21) Application No 16778/79 ( 22) Filed 13 Sept 1977 ( 62) Divided out of No 1590913 ( 31) Convention Application No 726482 ( 32) Filed 24 Sept 1976 ( 31) Convention Application No 793544 ( 32) Filed 4 May 1977 in ( 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 ( 11) 1 590 915 ( 19) g ' ( 54) 3,3-DI-SUBSTITUTED PHTHALIDES AND THEIR USE AS COLOUR-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
following statement:-
The invention relates to 3,3 di substituted phthalides.
In the complete specification of our copending Application for Letters Patent
No 38133/77 (Serial No 1,590,913, out of which the present Application is divided there are disclosed 3Y 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 of halo or alkyl of one to three carbon atoms; X represents hydrogen or halo; Y represents a monovalent radical having one of the formulas q'153 44 \ (A) (B c (A) "'= -'"-I / (D) 0 Pt 4 Cr I 'y 11,1 \N:L 1 1 , (E) (F) Cor K 3 and (H) (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, Rs represents hydrogen, nontertiary alkyl 10 of one to eight carbon atoms, alkenyl of two to four carbon atoms, benzyl or benzyl substituted in the benzene ring by one or two of halo or alkyl of one to three carbon atoms, R 6 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 " 3 R 2 " 4 R" phenyl) 3 ( 1 R 5 2 5/6 R 4 3 indolyl) -5 -X 6 -N -(R)2 phthalides of the formula 20 At P Formula V 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 or, when at least one of R 2 " and R 3 " are other than hydrogen, dialkylamino in 25 which alkyl is non-tertiary alkyl of one to four carbon atoms; R 2 " and R 3 " each represent hydrogen, non-tertiary alkoxy of one to four carbon atoms or halo; 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 of one to eight carbon atoms, alkenyl of two to four carbon atoms, benzyl or benzyl 30 substituted in the benzene ring by one or two of halo or alkyl of one to three carbon atoms; R 6 represents hydrogen, alkyl of one to three carbon atoms or phenyl; and X represents hydrogen or halo.
As used herein, the term "non-tertiary alkyl of one to eight carbon atoms" means saturated monovalent aliphatic radicals, including branched chain radicals, 35 for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl, I me'hylbutyl, 3 methylbutyl, hexyl, isohexyl, heptyl, isoheptyl, octyl, isooctyl and 2 ethylhexyl.
1,590,915 3 1,590,915 3 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 herein, there is meant saturated, acyclic groups which may be straight or branched as exemplified by methyl, ethyl, propyl, isopropyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec butoxy, and isobutoxy 5 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), 2 methyl 2 propenyl, 2 methyl 1 propenyl, 2 butenyl and 3 butenyl.
When the term "halo" is used herein, there are included chloro, fluoro, bromo 10 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 15 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 V above are essentially colorless in the depicted form When the compounds of formula V are contacted 20 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 or 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 25 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 30 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 coated transfer 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 35 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 40 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 V are intimately 45 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 V 50 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 V as 55 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 V.
As stated above, the compounds of formula IV may be prepared by the process disclosed in our aforementioned copending Application No 38133/77 (Serial No 60 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 N (R)2 phthalide having the formula 65 1,590,915 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 2 (a Y a Z)methyl 4 X 5 N(R)2 benzoic acid of the formula 5 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.
The aforementioned copending Applicaton No 38133/77 (Serial No 10 1,590,913), claims the compounds of formula III per se, the aforementioned process for their preparation from the compounds of formula II and the process for their oxidation to compounds of formula I.
Further novel compounds of formula I are described and claimed in our copending Application for Letters Patent No 16777/79 (Serial No 1,590,914) , 15 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 resonance, and mass spectra and elemental analysis 20 The following examples will further illustrate the invention without, however, limiting it thereto All melting points are uncorrected.
Example I
A Employing a procedure similar to that described in Example 1, part A of our aforementioned copending Application No 38133/77 (Serial No 1,590,914), for 25 interacting 7 2 g of 4 (N ethylbenzylamino)benzaldehyde and 5 2 g of 3 dimethylaminobenzoic acid, there was obtained 7 5 g of 3 l 4 (Nethylbenzylamino)phenyll 6 dimethylaminophthalide (formula II: R=CH,; X=H; Y=(C 6 H 5 CH 2)(C 2 Hs)NC 6 H 4) as a viscous oil.
The infrared spectral analysis showed a maximum at 1760 (C=O; s) cm-' The 30 nuclear magnetic resonance spectrum was consistent with the assigned structure.
A toluene solution of the product spotted on silica gel develops a greencolored image.
B Following a procedure similar to that described in Example 2, part A of our aforementioned copending Application No 38133/77 (Serial No 1,590,913), 4 0 g 35 of 3 l 4 (N ethylbenzylamino)phenyll 6 dimethylaminophthalide and 1 6 g of I ethyl 2 methyl indole were interacted to obtain 2 la l 4 (N ethylbenzylamino)phenyll a (I ethyl 2 methyl 3 indolyl)lmethyl 5 dimethylaminobenzoic acid (formula III: R=CH 3; X=H; Y=(C 6 H 5 CH 2)(C 6 Hs)2 NC 6 H 4; Z=l C 2 Hs 2 CH 3 3 indolyl) which was not 40 isolated but used in part D below.
C Similar results were obtained when the acetic acid reaction medium was replaced with monochlorobenzene and aluminum chloride or trifluoroacetic acid.
D Proceeding in a manner similar to that described in Example 2, part B of our aforementioned copending Application No 38133/77 (Serial No 1,590,913), 2 {a l 4 (N ethylbenzylamino)phenylla ( 1 ethyl 2 methyl 3 indolyl)}methyl 5 dimethylaminobenzoic acid from B above was oxidized to obtain 2 0 g of 3 l 4 (N ethylbenzylamino)phenyll 3 (I ethyl 2 methyl 3 indolyl) 6 dimethylaminophthalide (formula V: R=CH 3; X=H; 5 R'=N(C 2 H)(CH 2 C 6 Hs); R 2 "=R 3 '"=H; R 5 =C 2 Hs; R 6 =CH 3; R 4 =H) as a pink solid melting over the range 66-95 C with decomposition.
Significant infrared maximum appeared at 1760 (C=O; s) cm-1.
A toluene solu;-m I of the product spotted on an acidic resin develops a deep blue-colored image 10 Example 2
A Proceeding in a manner similar to Example 1, part A of our aforementioned copending Application No 38133/77 (Serial No 1,590,913), 18 3 g of 4dimethylamino 2 chlorobenzaldehyde and 16 5 g of 3 dimethylaminobenzoic acid were interacted to obtain 20 5 g of 3 ( 4 dimethylamino 2 chlorophenyl) 15 6 dimethylaminophthalide (formula II: R=CH 3; X=H; Y= 2 Cl 4(CH 3)2 NC 6 H 3) a red-colored solid melting at 159 5-160 5 C.
A toluene solution of the product spotted on an acid clay develops a pale green-colored image.
B Following the procedure described in Example 1, part B of our aforementioned 20 copending Application No 38133/77 (Serial No 1,590,913), but substituting triethylamine for potassium hydroxide as the condensing agent, 3 ( 4dimethvlamino 2 chlorophenyl) 6 dimethylaminophthalide from A is interacted with 5 nitro I ( 4 chlorobenzyl) 2 methylindole to obtain 2 fa l 5 nitro 1 ( 4 chlorobenzyl) 2 methyl 3 indolyll a ( 2 chloro 25 4 dimethylaminophenyl)lmethyl 5 dimethylaminobenzoic acid (formula III:
R=CH 3; X=H; Y= 2 Cl 4 -(CH 3)2 NC 6 H 3; Z= 5 NO 2 I ( 4 Ci C 6 H 4 CH 2) 2 CH 3 3 indolyl).
C Employing a procedure similar to that described in Example 1, part C of our aforementioned copending Application No 38133/77 (Serial No 1,590,913), 2 30 {a l 5 nitro 1 ( 4 chlorobenzyl) 2 Mnethyl 3 indolyll - a (:2 chloro 4 dimethylaminophenyl}methyl 5 dimethylaminbbenzoic acid from B is oxidized to obtain3 l 5 nitro I ( 4 chlorobgnzylj 2 methyl 3 indolyll 3 72 chloro' 4 dimethylaminophenyl) 6 -3 dimethylaminophthalide (formula V: R=CH 3; X=H; R"=N(CH 3)2; R 3 "= 4 C 1 C 6 H 4 CH 2; R 6 =CH 3; R 4 = 5 35 NO 2).
Example 3
A Employing a procedure similar to that described in Example 1, part A of our aforementioned copending Application No 38133/77 (Serial No 1,590,913), for interacting 8 2 g of p anisaldehyde and 11 6 g of 3 dimethylaminobenzoic acid 40 utilizing acetic anhydride alone as the reaction medium there was obtained 9 4 g of 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-' The nuclear magnetic resonance spectrum was concordant with the assigned structure 45 A toluene solution of the product spotted on an acid clay develops a bluecolored image.
B Proceeding in a manner similar to that described in Example 1, part B of our aforementioned copending Application No 38133/77 (Serial No 1,590,913), but substituting lithium carbonate for potassium hydroxide as the condensing agent, 50 3 ( 4 methoxyphenyl) 6 dimethylaminophthalide from A is interacted with I butyl 2 methylindole to obtain 2 la ( 1 butyl 2 methyl 3 indolyl) a ( 4 methoxyphenyl)lmethyl 5 dimethylaminobenzoic acid (formula III:
R=CH 3; X=H; Y= 4 CH 3 OC 6 H 4; Z= 1 C 4 H 9 2 CH 3 3 indolyl).
C Following the procedure described in Example 1, part C of our 55 aforementioned copending Application No 38133/77 (Serial No 1,590,913), 2 la ( 1 butyl 2 methyl 3 indolyl) a ( 4 methoxyphenyl)lmethyl 5 dimethylaminobenzoic acid from B is oxidized to obtain 3 ( 1 butyl 2 methyl 3 indolyl) 3 ( 4 methoxyphenyl) 6 dimethylaminophthalide (formula V:
R=CH 3; X=H; R"=CH 3 O; R 2 "=R 3 "=H; R 9 =C 4 Hg; R 6 =CH 3; R 4 =H) 60 Example 4
A Employing a procedure similar to that described in Example 1, part A of our 1,590,915 aforementioned Application No 38133/77 (Serial No 1,590,913), for interacting 11.6 g of 3 dimethylaminobenzoic acid and 10 6 g of 3,4 dimethoxybenzaldehyde in acetic anhydride there was obtained 0 75 g of 3 ( 3,4 dimethoxyphenyl) 6 dimethylaminophthalide (formula II: R=CH 3; X=H; Y= 3, 4 (CH 3 O)2 C 6 H 3) a light yellow-colored solid melting at 148-150 C 5 A significant infrared maximum appeared at 1765 (C=O; s) cm-'.
A toluene solution of the product spotted on an acid clay develops a pale yellow-colored image.
B Proceeding in a manner similar to that described in Example 1, part B of our aforementioned copending Application No 38133/77 (Serial No 1,590,913), but 10 substituting quinuclidine for potassium hydroxide as the condensing agent, 3 ( 3,4 dimethoxyphenyl) 6 dimethylaminophthalide from A is interacted with I octyl 2 methylindole to obtain 2 la ( 1 octyl 2 methyl 3 indolyl) a ( 3,4 dimethoxyphenyl)lmethyl 5 dimethylaminobenzoic acid (formula III:
R=CH 3; X=H; Y= 3,4 (CH 3 O)2 C 6 H 3; Z=lC 8 H 172 CH 3 3 indolyl) 15 C Following the procedure described in Example 2, part B of our aforementioned copending Application No 38133/77 (Serial No 1,590,913), 2 la ( 1 octyl 2 methyl 3 indolyl) a ( 3,4 dimethoxyphenyl)lmethyl 5 dimethylaminobenzoic acid from B is oxidized to obtain 3 ( 1 octyl 2 methyl 3 indolyl) 3 ( 3,4 dimethoxyphenyl) 6 dimethylaminophthalide (formula V: 20 R=CH 3; X=H; R"=R 2 "=CH 3 O; R 3 "=H; R 5 =C 8 H,7; R 6 =CH 3; R 4 =H).
Example 5
A Proceeding in a manner similar to Example 1, part A of our aforementioned copending Application No 38133/77 (Serial No 1,590,913), 11 6 g of 3dimethylaminobenzoic acid and 10 0 g of 2,4 dimethoxybenzaldehyde were 25 interacted in acetic anhydride to obtain 14 0 g of 2 ( 2,4 di methoxyphenyl 6 dimethylaminophthalide (formula II: R=CH 3; X=H; Y= 2,4 (CHO 30)2 C 6 H 3) as a yellow-colored solid melting at 123-125 C.
A significant infared maximum appeared at 1750 (C=O; s) cm-'.
A toluene solution of the product spotted on an acid clay develops a blue 30 colored image.
B Following the procedure described in Example 1, part B of our aforementioned copending Application No 38133/77 (Serial No 1,590,913), but substituting tetraethylammonium hydroxide for potassium hydroxide as the condensing agent, 3 ( 2,4 dimethoxyphenyl) 6 dimethylaminophthalide from A is interacted 35 with 5 iodo 1 ( 1 methylhexyl)indole to obtain 2 {a l 5 iodo I ( 1 methylhexyl) 3 indolyll a ( 2,4 dimethoxyphenyl))methyl 5 dimethylaminobenzoic acid (formula III: R=CH 3; X=H; Y= 2,4 (CH 3 O)2 C 6 H 3; Z= 5 I I l 1 CH 3 (C 6 H 12)l3 indolyl.
C Employing a procedure similar to that described in Example 2, part B of our 40 aforementioned copending Application No 38133/77 (Serial No 1,590,913), 2 {a l 5 iodo I ( 1 methylhexyl) 3 indolyl) a ( 2,4 dimethoxyphenyl)}methyl 5 dimethylaminobenzoic acid from B is oxidized to obtain 3 l 5 iodo I ( 1 methylhexyl) 3 indolyll 3 ( 2,4dimethoxyphenyl) 6 dimethylaminophthalide (formula V: R=CH 3; X=H; 45 R"=R 3 "=CH 30; R 2 "=H; R 5 =l CH 3 (C 6 H 12); R 6 =H; R 4 = 5 I).
D Employing a procedure similar to that described in Example 1, part B of our aforementioned copending Application No 38133/77 (Serial No 1,590,913), 25 1 g of' 3 ( 2,4 dimethoxyphenyl) 6 dimethylaminophthalide prepared as described in part A above, and 15 5 g of I ethyl 2 methylindole were 50 interacted to obtain the potassium salt of 2 la -( 2,4 dimethoxyphenyl) a ( 1 ethyl 2 methyl 3 indolyl)lmethyl 5 dimethylaminobenzoic acid (formula III:
R=CH 3; X=H; Y= 2,4 (CH 3 O)2 C 6 H 3; Z=l C 2 Hs 2 CH 3 3 indolyl) which was used in the oxidation step without prior isolation from its aqueous preparation medium 55 E Proceeding in a manner similar to that described in Example 1, part C of our aforementioned copending Application No 38133/77 (Serial No 1,590,913), for oxidizing the potassium salt of 2 la ( 2,4 dimethoxyphenyl) a ( 1 ethyl 2 methyl 3 indolyl)lmethyl 5 dimethylaminobenzoic acid, there was obtained 1 6 g of 3 ( 2,4 dimethoxyphenyl) 3 ( 1 ethyl 2 methyl 3 60 indolyl) 6 dimethylaminophthalide (formula V: R=CH 3; X=H; R"=R 3 "=CH 3; R 2 "=H; R 5 =C 2 H 5; R 6 =CH 3; R 4 =H), an off-white solid which melted at 215-217 C.
1,590,915 A significant infrared maximum appeared at 1764 (C=O; s) cm-' The nuclear magnetic resonance spectrum was in accord with the assigned structure.
A toluene solution of the product spotted on silica gel develops a grapecolored image.
Example 6 5
A Following the procedure described above in Example 26, part A of our aforementioned copending Application No 38133/77 (Serial No 1,590,913), 14 2 g of 3 ( 4 methoxyphenyl) 6 dimethylaminophthalide prepared as described in Example 3, part A above and 35 0 ml of I ethyl 2 methylindole were interacted in the presence of anhydrous zinc chloride at a temperature in the range of 90 to 10 C to obtain 15 5 g of 2la ( 4 methoxyphenyl) a ( 1 ethyl 2 methyl 3 indolyl)lmethyl 5 dimethylaminobenzoic acid (formula III: R=CH 3; X=H; Y= 4 CH 3 OC 6 H 4; Z=l C 2 H 5 2 CH 3 3 indolyl), a light gray-colored solid which melted over the range 115-126 C.
The infrared spectrum had a significant maximum at 1683 (C=O; s) cm-' The 15 nuclear magnetic resonance spectrum was consistent with the assigned structure.
B Proceeding in a manner similar to that described in Example 1, part C of our aforementioned copending Application No 38133/77 (Serial No 1,590,913) 2 la ( 4 methoxyphenyl) a ( 1 ethyl 2 methyl 3 indolyl)lmethyl 5 dimethylaminobenzoic acid is oxidized to obtain 3 ( 4 methoxyphenyl) 3 ( 1 20 ethyl 2 methyl 3 indolyl) 6 dimethylaminophthalide (formula V: R=CH 3; X=H; R 1 '=CH 3 O; R 2 "=R 3 "=H; R 5 =C 2 H 5; R 6 =CH 3; R 4 =H).
Example 7
A Employing a procedure similar to that described in Example 1, part A of our aforementioned copending Application No 38133/77 (Serial No 1,590,913), 13 3 g 25 of 2 butoxy 4 diethylaminobenzaldehyde and 9 7 g of m dimethyl aminobenzoic acid were refluxed in acetic anhydride to obtain 3 ( 2 butoxy 4 diethylaminophenyl) 6 dimethylaminophthalide (formula I: R=CH 3; X=Z=H; Y= 2 C 4 H 90 4 (C 2 H 5)2 NC 6 H 3) as a tarry residue.
The infrared spectrum had a significant maximum which appeared at 1760 30 (C=O; s) cm-' The nuclear magnetic resonance spectrum was in accord with the assigned structure.
B Proceeding in a manner similar to Example 26, part A of our aforementioned copending Application No 38133/77 (Serial No 1,590,913), 3 ( 2 butoxy 4 diethylaminophenyl) 6 dimethylaminophthalide from part A above is interacted 35 with I octyl 2 ethylindole to obtain 2 la ( 2 butoxy 4diethylaminophenyl) a ( 1 octyl 2 ethyl 3 indolyl)lmethyl 5dimethylaminobenzoic acid (formula III: R=CH 3; X=H; Y= 2 C 4 H 90 4(C 2 H 5)2 NC 6 H 3; Z=l C 8 H 17 2 C 2 H 5 3 indolyl).
C Following the procedure described in Example 2, part B of our aforementioned 40 copending Application No 38133/77 (Serial No 1,590,913), 2 la ( 2 butoxy 4 diethylaminophenyl) a ( 1 octyl 2 ethyl 3 indolyl)lmethyl 5 dimethylaminobenzoic acid from B above is oxidized to obtain 3 ( 2 butoxy -4 diethylaminophenyl) 3 ( 1 octyl 2 ethyl 3 indolyl) 6 dimethylaminophthalide (formula V: R=CH 3; X=H; R"'=N(C 2 H 5)2; R 3 "=C 4 H 90; 45 R 2 "=H; R 5 =C 8 H 17; R 6 =C 2 Hs; R 4 =H).
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 copending Application No 38133/77 (Serial No 1,590, 913), for interacting approximately molar equivalent quantities of the appropriate 3 50 Y 5 X 6 N(R)2 phthalide and Z-H in the presence of the indicated condensing agent, the compounds of Examples 8 and 9 are obtained.
Example 8
3 l 1 ( 4 bromobenzyl) 2 isopropyl 3 indolyll 3 ( 2,3dimethoxyphenyl) 6 diethylaminophthalide using 2 {a l 1 ( 4 55 bromobenzyl) 2 isopropyl 3 indolyll a ( 2,3 dimethoxyphenyl)}methyl 5 diethylaminobenzoic acid.
Example 9
3 ( 2,3,4 trimethoxyphenyl) 3 ( 1 isoamyl 3 indolyl) 6 (N ethyl N butylamino)phthalide using 2 la ( 2,3,4 trimethoxyphenyl) a 60 ( 1 isoamyl 3 indolyl)lmethyl 5 (N ethyl N butylamino)benzoic acid.
1,590,915

Claims (8)

WHAT WE CLAIM IS:-
1 A compound of the formula V (herein) 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, or when at least one of R 2 5 and R 3 " are other than hydrogen, dialkylamino in which alkyl is nontertiary alkyl of one to four carbon atoms; R 2 " and R 3 " each represent hydrogen, alkoxy of one to three carbon atoms or halo; 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; Rs represents hydrogen, non-tertiary alkyl of one to eight carbon atoms, alkenyl of 10 two to four carbon atoms, benzyl or benzyl substituted in the benzene ring by one or two of halo or alkyl of one to three carbon atoms; RW represents hydrogen, alkyl of one to three carbon atoms or phenyl; and X represents hydrogen or halo.
2
3 l( 4 N ethylbenzylamino)phenyll 3 (I ethyl 2 methyl 3 indolyl) 6 dimethylaminophthalide 15 3 3 ( 2,4 dimethoxyphenyl) 3 ( 1 ethyl 2 methyl 3 indolyl) -6 dimethylaminophthalide.
4 A compound according to Claim 1, wherein Rs is not alkenyl of 2 to 4 carbon atoms.
5 A compound according to Claim 1, wherein Rs is alkenyl of 2 to 4 carbon 20 atoms.
6 A compound according to Claim 1, and substantially as herein described with reference to the Examples.
7 A pressure-sensitive car bonless duplicating system or thermal paper marking system containing as a color-forming substance a compound according to 25 any one of the preceding claims.
8 A pressure-sensitive carbonless duplicating system or thermal paper marking system as claimed in Claim 7 and substantially as herein described with reference to the Examples.
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.
1,590,915 R
GB1677879A 1976-09-24 1977-09-13 3,3-di-substituted phthalides and their use as colour formers Expired GB1590915A (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
EP2981523B1 (en) * 2013-04-02 2021-05-19 Syngenta Participations AG Insecticidal compounds
JP2024143725A (en) * 2023-03-30 2024-10-11 富士フイルム株式会社 On-press development type lithographic printing plate precursor, method for producing a lithographic printing plate, and lithographic printing method
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NL7710326A (en) 1978-03-29

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