US2783228A - Nitro derivatives of benzoyl leuco methylene blue - Google Patents

Nitro derivatives of benzoyl leuco methylene blue Download PDF

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Publication number
US2783228A
US2783228A US518333A US51833355A US2783228A US 2783228 A US2783228 A US 2783228A US 518333 A US518333 A US 518333A US 51833355 A US51833355 A US 51833355A US 2783228 A US2783228 A US 2783228A
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United States
Prior art keywords
color
blue
methylene blue
nitro derivatives
leuco methylene
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Expired - Lifetime
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US518333A
Inventor
Clyde S Adams
Marjorie J Cormack
Frazier Mary Lou
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
NCR Voyix Corp
National Cash Register Co
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NCR Corp
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Filing date
Publication date
Priority to NL208242D priority Critical patent/NL208242A/xx
Priority to NL94595D priority patent/NL94595C/xx
Application filed by NCR Corp filed Critical NCR Corp
Priority to US518333A priority patent/US2783228A/en
Application granted granted Critical
Publication of US2783228A publication Critical patent/US2783228A/en
Anticipated expiration legal-status Critical
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/124Duplicating 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
    • B41M5/132Chemical colour-forming components; Additives or binders therefor
    • B41M5/136Organic colour formers, e.g. leuco dyes

Definitions

  • This invention relates to the light-stable leucomethylene blue derivative 10 (nitrobenzoyl) -"3,7 bis(dimethylamino)phenothiazine, having the structure S (ormmgsgmcmn 10 N and in which R is taken from the group consisting of 4-nitro and 3-nitro.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Color Printing (AREA)

Description

United States Patent O NITRO DERIVATIVES or BENZOYL LEUCO METHYLENE BLUE Clyde S. Adams, Yellow Springs, Marjorie J. Cormack,
Dayton, and Mary Lou Frazier, Springfield, Ohio, assignors to The National Cash Register Company, Dayton, Ohio, a corporation of Maryland No Drawing. Application June 27, 1955, Serial No. 518,333
3 Claims. (Cl. 260-243) This inventionrelates to the light-stable leucomethylene blue derivative 10 (nitrobenzoyl) -"3,7 bis(dimethylamino)phenothiazine, having the structure S (ormmgsgmcmn 10 N and in which R is taken from the group consisting of 4-nitro and 3-nitro.
The known unnitrated leuco compound IO-benzoyl- 3,7-bis(dimethylamino)phenothiazine, also known as benzoyl leucomethylene blue, normally is substantially colorless and has been used as a color reactant which turns to a blue-green color on prolonged contact with acid clay-like materials such as attapulgite and halloysite. It is used in conjunction with other, faster-reacting, colorless color reactants, which also are turned to the colored form on contact with such acid clay-like materials.
The present primary use of these color-reactant materials is their incorporation in transfer coatings on the rear surfaces of manifold sheets. These manifold sheets are placed over paper sensitized with attapulgite or halloysite, and an impression, by printing or writing, is made, transferring the color reactants to the sensitized surface of the under sheets, thus making an impression in color thereon. A typical manifold sheet, of the type described, is disclosed in United States Patent No. 2,646,367, which issued on the application of Chester Davis and Ned A. Thacker on July 21, 1953. In that patent, there is disclosed a base web of paper having a coating made of wax and an oil, the oil having dissolved therein the fastreacting colorless color reactant crystal violet lactone, more specifically described as 3,3-bis(p-dimethylaminophenyl)-6-dimethylamino-phthalide, which turns to a dark blue color upon coming into contact with attapulgite r halloysite, and the slower-reacting compound benzoyl leucomethylene blue, before mentioned. The crystal violet lactone color fades on prolonged exposure to light, and, as it gradually fades away, the slower-reacting benzoyl leucomethylene blue develops color, so that the printing or writing is not lost.
One drawback to the use of benzoyl leucomethylene blue is that it gradually decomposes to the colored form on exposure to light. Thus, a manifold sheet with the coated side exposed to light gradually assumes an undesirable blue-green color.
Therefore, it is the object of this invention to provide 2,783,228 Patented Feb. 26, 19 57 double salt of leucomethylene blue, having the structure To 100 grams (0.202'mole) of the zinc chloride double salt of leucomethylene blue are added 225 grams (3.5 moles) of pyridine and 75 grams (0.404 mole) of pulverized p-nitrobenzoyl chloride. The reaction mixture is reone half hour.
fiuxed gently with stirring for two hours in a three-necked, round-bottom flask fitted. with a mechanical stirrer, a reflux condenser, and a thermometer. The reaction mixture then is poured into one liter of water and stirred for The dark blue-green precipitate which forms is filtered off and washed with water. This washed blue-green precipitate is transferred to a beaker and stirred for one half hour with 40'grams of sodium hydroxide dissolved in one liter of Water. The precipitate is filtered The resulting dark benzene solution then is treated with fullers earth and filtered. The resulting orange-red filtrate is concentrated to 800 milliliters and precipitated with petroleum ether.
The resulting product, 10-(4-nitrobenzoyl)-3,7-bis(dimethylamino phenothiazine, is a crystalline material of a light orange-yellow color having the structure The 10 (3 nitrobenzoyl) 3,7 bis(dimethylamino) phenothiazine, having the structure is made by the same process except that m-nitrobenzoyl chloride is used instead of p-nitrobenzoyl chloride. This derivative also is a crystalline material of a light orangeyellow color.
The light orange-yellow color of these nitro derivatives of benzoyl leucomethylene blue is unimportant in making the described manifold paper, as it is used in such small quantities and in such thin films that the coating appears as a creamy off-color white. However, in contact with attapulgite or halloysite, they become intensely blue-green in color.
3 4 What is claimed is: 3. The substantially light-stable leucomethylene blue 1. 10 nitrobenzoyl 3,7 bis(dimethylamino)phenderivative of the formula 10-(3-nitrobenzoyl)-3,7-bis thiazine, having the structure (dimethylamiuo)phenothiazine, having the structure S S (mom-, a menu; 5 (cHmN 5 mom),
g g) \o i? in :5 R is taken from the group consisting of 44mm References Cited in the file of this patent an -n1trc 2. The substantially light-stable leucomethylene blue FO I PATENTS derivative of the formula 10-(4-uitrobenzoyl)-3,7-bis 113,721 Germany Sept. 28, 1900 (dimethylamino)phenothiazine, having the stmcture 512,300 Belgium July 15, 1952 s 725,275 Great Britaiu Mar. 2, 1955 (fllmflgfigmflflm

Claims (1)

1. 10 -NITROBENZOYL -3,7-BIS(DIMETHYLAMINO)PHENOTHIAZINE, HAVING THE STRUCTURE
US518333A 1955-06-27 1955-06-27 Nitro derivatives of benzoyl leuco methylene blue Expired - Lifetime US2783228A (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
NL208242D NL208242A (en) 1955-06-27
NL94595D NL94595C (en) 1955-06-27
US518333A US2783228A (en) 1955-06-27 1955-06-27 Nitro derivatives of benzoyl leuco methylene blue

Applications Claiming Priority (1)

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US518333A US2783228A (en) 1955-06-27 1955-06-27 Nitro derivatives of benzoyl leuco methylene blue

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US2783228A true US2783228A (en) 1957-02-26

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2915415A (en) * 1957-06-19 1959-12-01 Caribonum Ltd Leucauramine derivate of benzoyl leuco methylene blue and transfer sheet coated therewith
US3427180A (en) * 1965-03-31 1969-02-11 Ncr Co Pressure-sensitive record system and compositions
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
US4563415A (en) * 1983-04-05 1986-01-07 Minnesota Mining And Manufacturing Company Thermographic system using naphthoylated leuco phenazine dyes
US4647525A (en) * 1984-10-01 1987-03-03 Minnesota Mining And Manufacturing Company Stabilized leuco phenazine dyes and their use in an imaging system
US4889932A (en) * 1984-10-01 1989-12-26 Minnesota Mining And Manufacturing Company Stabilized leuco phenazine dyes and their use in an imaging system

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE512300A (en) * 1951-06-23
DE113721C (en) * 1899-06-01 1900-09-28 Process for the preparation of acidyl derivatives of leukothionine dyes

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE113721C (en) * 1899-06-01 1900-09-28 Process for the preparation of acidyl derivatives of leukothionine dyes
BE512300A (en) * 1951-06-23

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2915415A (en) * 1957-06-19 1959-12-01 Caribonum Ltd Leucauramine derivate of benzoyl leuco methylene blue and transfer sheet coated therewith
US3427180A (en) * 1965-03-31 1969-02-11 Ncr Co Pressure-sensitive record system and compositions
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
US4563415A (en) * 1983-04-05 1986-01-07 Minnesota Mining And Manufacturing Company Thermographic system using naphthoylated leuco phenazine dyes
US4647525A (en) * 1984-10-01 1987-03-03 Minnesota Mining And Manufacturing Company Stabilized leuco phenazine dyes and their use in an imaging system
US4889932A (en) * 1984-10-01 1989-12-26 Minnesota Mining And Manufacturing Company Stabilized leuco phenazine dyes and their use in an imaging system

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Publication number Publication date
NL94595C (en)
NL208242A (en)

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