US2915415A - Leucauramine derivate of benzoyl leuco methylene blue and transfer sheet coated therewith - Google Patents

Leucauramine derivate of benzoyl leuco methylene blue and transfer sheet coated therewith Download PDF

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Publication number
US2915415A
US2915415A US739982A US73998258A US2915415A US 2915415 A US2915415 A US 2915415A US 739982 A US739982 A US 739982A US 73998258 A US73998258 A US 73998258A US 2915415 A US2915415 A US 2915415A
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Prior art keywords
leucauramine
transfer sheet
methylene blue
derivate
sheet coated
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Expired - Lifetime
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US739982A
Inventor
Francis Frederick George
Neale David John
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Caribonum Ltd
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Caribonum Ltd
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Priority claimed from GB1933757A external-priority patent/GB817564A/en
Application filed by Caribonum Ltd filed Critical Caribonum Ltd
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B11/00—Diaryl- or thriarylmethane dyes
    • C09B11/02—Diaryl- or thriarylmethane dyes derived from diarylmethanes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/914—Transfer or decalcomania

Definitions

  • the present invention relates to improvements in colouring materials and is concerned, in particular, with colouring materials of the kind which can be readily produced by subjecting a colourless material to a chemical reaction.
  • a recent development which is an improvement over conventional carbon and other colour transfer sheet materials consists in the use of one or more colourless materials which, when transferred by the action of writing from ka colourless transfer sheet to a copy sheet having a suitable acid character, is or are readily converted into a coloured material in the form of a copy or record of the written matter.
  • One notable advantage of this development is that colour is only produced by the actual process of writing and the transfer sheet material is substantially colourless.
  • One object of the present invention is to provide an improved colourless material of this kind, which can be carried in a coating on a colourless transfer sheet material and which, when transferred to an acid copy sheet or otherwise subjected to slightly acid oxidising conditions, is converted into a substantially light-fast coloured material.
  • the present invention consists in l0-(4-N-leucauraminebenzoyl)3,7-bis-(dimethy1amino)-phenothiazine, of the formula:
  • the present invention also consists in a transfer sheet material which carries a colourless coating which includes -(4Nleucaurarninebenzoyl)3,7bis(dimethyl amino)phenothiazine.
  • One general method of preparing leucauramine derivatives comprises the intercondensation of a primary amine 2,915,415 Patented (Dec. 1, 1959 ice ,Y
  • R can be any appropriate radical capable of forming a primary amine.
  • the colourless compound of the invention can be made by condensing Michlers hydrol with 10-(4aminobenzoyl) 3,7 bis-(dimethylamino) phenothiazine, which is the para-amino derivative of benzoyl-leuco-methylene blue.
  • a further aspect of the present invention comprises a method of preparing the afore-mentioned colourless compound by the intercondensation of Michler ⁇ s hydrol with 10-(4-amino-benzoyl) 3,7 bis-(dimethylamino) phenothiazine, of the formula:
  • One notable advantage of the compound of the invention is that it is in effect an addition compound of leucauramine and beuzoyl-leuco-methylene blue and both of these substances, and many of their derivatives, are colourless materials which turn blue in the presence of a weak acid.
  • Benzoyl-leuco-methylene blue and its amine derivative do not however develop colour immediately, but only after a time, and it is thought that this colour development is due to slow oxidation in the presence of weak acids.
  • the compound of the invention can be considered to have a combination of the properties of these two substances and also has the further advantage that the blue derivative which it produces in the presence of an acid substance is substantially unaffected by light, so that copies of written matter produced by means of transfer sheet material according to the invention have excellent light-fastness and are substantially permanent.
  • the compound of this invention namely, l0- (4-N-leucauramine-benzoyl)3,7bis (dimethyll amino)- phenothiazine, is substantially colourless in the commercially pure state, whether in solution or not.
  • a transfer sheet material which carries a colourless coating which includes l0-(4-N-leucauramine-benzoyl) 3,7-bis-(Adimethybamino)-phenothiazine 3.
  • a method of preparing 10-(4N-leueauramnebenzoyl)-3,7-bis-(dimethylamino)phenothiazine,v which comprises intercondensing Michlers hydrol and p-aminobenzoyl-leucomethylene blue by adding Michlers hydrol to a water-containing methylated spirit solution of p-amino-benzoyl-leuco-methylene blue, reducing the pH to about 6.0 and reuxing the mixture.

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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)
  • Color Printing (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)

Description

Dec. 1, 1959 F, G, FR cls ETAL 2,915,415
LEUCA MINE IV BENZO L CO-METH NE B AND NS SHEET CO HEREWIT Filed June 5, 1958 l t L Wala.
LEUCAURAMINE DERIVATE F BENZOYLy LEUCO METHYLENE BLUE AND TRANS- 1 FER SHEET COATED THEREWITH Frederick George Francis, Old Southgate, London, and David John Neale, Woodford, England, assignors to Caribonum Limited, London, England, a British cont- Pally Application June 5, 1958, Serial No. 739,982
Claims priority, application Great Britain June 19, 1957 4 Claims. (Cl. 117-36) The present invention relates to improvements in colouring materials and is concerned, in particular, with colouring materials of the kind which can be readily produced by subjecting a colourless material to a chemical reaction.
A recent development which is an improvement over conventional carbon and other colour transfer sheet materials consists in the use of one or more colourless materials which, when transferred by the action of writing from ka colourless transfer sheet to a copy sheet having a suitable acid character, is or are readily converted into a coloured material in the form of a copy or record of the written matter. One notable advantage of this development is that colour is only produced by the actual process of writing and the transfer sheet material is substantially colourless.
One object of the present invention is to provide an improved colourless material of this kind, which can be carried in a coating on a colourless transfer sheet material and which, when transferred to an acid copy sheet or otherwise subjected to slightly acid oxidising conditions, is converted into a substantially light-fast coloured material.
The present invention consists in l0-(4-N-leucauraminebenzoyl)3,7-bis-(dimethy1amino)-phenothiazine, of the formula:
, s (GHmN more):
Ilm (onattNon-@Ntonm An alternative name for this compound is 4(3,7bis dimethylamino thiodiphenylaminoformyl) phenyl -leucauramine.
The present invention also consists in a transfer sheet material which carries a colourless coating which includes -(4Nleucaurarninebenzoyl)3,7bis(dimethyl amino)phenothiazine.
One general method of preparing leucauramine derivatives comprises the intercondensation of a primary amine 2,915,415 Patented (Dec. 1, 1959 ice ,Y
, 2 with Michlefs hydrol, 4,4'bis(dimethytamino) diphem ylcarbinol, by a reaction which can be `represented as:
where R can be any appropriate radical capable of forming a primary amine. The colourless compound of the invention can be made by condensing Michlers hydrol with 10-(4aminobenzoyl) 3,7 bis-(dimethylamino) phenothiazine, which is the para-amino derivative of benzoyl-leuco-methylene blue.
A further aspect of the present invention comprises a method of preparing the afore-mentioned colourless compound by the intercondensation of Michler`s hydrol with 10-(4-amino-benzoyl) 3,7 bis-(dimethylamino) phenothiazine, of the formula:
s www@ -Nwns), N
One notable advantage of the compound of the invention is that it is in effect an addition compound of leucauramine and beuzoyl-leuco-methylene blue and both of these substances, and many of their derivatives, are colourless materials which turn blue in the presence of a weak acid. Benzoyl-leuco-methylene blue and its amine derivative do not however develop colour immediately, but only after a time, and it is thought that this colour development is due to slow oxidation in the presence of weak acids. The compound of the invention can be considered to have a combination of the properties of these two substances and also has the further advantage that the blue derivative which it produces in the presence of an acid substance is substantially unaffected by light, so that copies of written matter produced by means of transfer sheet material according to the invention have excellent light-fastness and are substantially permanent. Moreover, the compound of this invention, namely, l0- (4-N-leucauramine-benzoyl)3,7bis (dimethyll amino)- phenothiazine, is substantially colourless in the commercially pure state, whether in solution or not.
In order that the invention may be readily understood, the following example is given.
To a hot solution of 4.6 grams of p-amino-benzoylleuco-methylene blue in 200 rnl. of 64 O.P. methylated spirit diluted with 13 ml. of water is added 3.2 grams E I 2,915,415 i l A u y .f
of Michlers'hydrol. After reducingl the pH to about' 6.0 with 5 N hydrochloric acid, the mixture is reuxed for two hours, cooled to about 2 C. and allowed to stand over-night at this temperature. The crystalline precipitate is filtered off, and washed with a little methylated spirit. The dried product may be recrystallised from Warm benzene, after addition of petroleum ether, to give pale yellow crystals melting at 249 C.
We claim:
2. A transfer sheet material, which carries a colourless coating which includes l0-(4-N-leucauramine-benzoyl) 3,7-bis-(Adimethybamino)-phenothiazine 3. A colourless composition Vof matter for use as transferable coatingapplied to transfer sheet material, which composition includes 10(4N-leucauraminebenzoyl)-3,7bis(dimethylamino)phenothiazine.
4. A method of preparing 10-(4N-leueauramnebenzoyl)-3,7-bis-(dimethylamino)phenothiazine,v which comprises intercondensing Michlers hydrol and p-aminobenzoyl-leucomethylene blue by adding Michlers hydrol to a water-containing methylated spirit solution of p-amino-benzoyl-leuco-methylene blue, reducing the pH to about 6.0 and reuxing the mixture.
References Cited in the lc of this patent UNITED STATES PATENTS Adams Mar.' vs, 1957

Claims (1)

  1. 2. A TRANSFER SHEET MATERIAL, WHICH CARRIES A COLOURLESS COATING WHICH INCLUDES 10-(4-N-LEUCAURAMINE-BENZOYL)3,7-BIS-(DIMETHYL-AMINO)-PHENOTHIAZINE.
US739982A 1957-06-19 1958-06-05 Leucauramine derivate of benzoyl leuco methylene blue and transfer sheet coated therewith Expired - Lifetime US2915415A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB1933757A GB817564A (en) 1957-06-19 10-(4-n-leucauramine-benzoyl)-3,7-bis-(dimethylamino)-phenothiazine

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3034917A (en) * 1958-08-26 1962-05-15 Caribonum Ltd Transfer sheet coated with stabilized colorless leucauramine derivative
US3447944A (en) * 1965-12-06 1969-06-03 Sterling Drug Inc Thermographic copying system
US3873340A (en) * 1972-07-27 1975-03-25 Hodogaya Chemical Co Ltd Pressure-sensitive copying paper containing phenoxazine compounds
US3900217A (en) * 1970-06-13 1975-08-19 Fuji Photo Film Co Ltd Pressure-sensitive copying paper
US4124227A (en) * 1976-05-31 1978-11-07 Moore Business Forms, Inc. Oxime ethers of Michler's hydrol, method of producing same and pressure-sensitive recording systems containing such compounds
US4132436A (en) * 1976-02-04 1979-01-02 Fuji Photo Film Co., Ltd. Recording material

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2646367A (en) * 1951-06-28 1953-07-21 Ncr Co Transfer paper
US2712507A (en) * 1953-06-30 1955-07-05 Ncr Co Pressure sensitive record material
US2783228A (en) * 1955-06-27 1957-02-26 Ncr Co Nitro derivatives of benzoyl leuco methylene blue
US2783227A (en) * 1955-06-27 1957-02-26 Ncr Co Naphthoyl leuco methylene blue
US2784186A (en) * 1957-03-05 Halo derivatives of benzoyl leuco

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2784186A (en) * 1957-03-05 Halo derivatives of benzoyl leuco
US2646367A (en) * 1951-06-28 1953-07-21 Ncr Co Transfer paper
US2712507A (en) * 1953-06-30 1955-07-05 Ncr Co Pressure sensitive record material
US2783228A (en) * 1955-06-27 1957-02-26 Ncr Co Nitro derivatives of benzoyl leuco methylene blue
US2783227A (en) * 1955-06-27 1957-02-26 Ncr Co Naphthoyl leuco methylene blue

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3034917A (en) * 1958-08-26 1962-05-15 Caribonum Ltd Transfer sheet coated with stabilized colorless leucauramine derivative
US3447944A (en) * 1965-12-06 1969-06-03 Sterling Drug Inc Thermographic copying system
US3900217A (en) * 1970-06-13 1975-08-19 Fuji Photo Film Co Ltd Pressure-sensitive copying paper
US3873340A (en) * 1972-07-27 1975-03-25 Hodogaya Chemical Co Ltd Pressure-sensitive copying paper containing phenoxazine compounds
US4132436A (en) * 1976-02-04 1979-01-02 Fuji Photo Film Co., Ltd. Recording material
US4124227A (en) * 1976-05-31 1978-11-07 Moore Business Forms, Inc. Oxime ethers of Michler's hydrol, method of producing same and pressure-sensitive recording systems containing such compounds

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