US2783227A - Naphthoyl leuco methylene blue - Google Patents

Naphthoyl leuco methylene blue Download PDF

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Publication number
US2783227A
US2783227A US518332A US51833255A US2783227A US 2783227 A US2783227 A US 2783227A US 518332 A US518332 A US 518332A US 51833255 A US51833255 A US 51833255A US 2783227 A US2783227 A US 2783227A
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United States
Prior art keywords
naphthoyl
blue
methylene blue
leuco methylene
bis
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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US518332A
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 NL208241D priority Critical patent/NL208241A/xx
Priority to NL94594D priority patent/NL94594C/xx
Application filed by NCR Corp filed Critical NCR Corp
Priority to US518332A priority patent/US2783227A/en
Application granted granted Critical
Publication of US2783227A publication Critical patent/US2783227A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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

Definitions

  • the known leucomethylene blue compound IO-benzoyl- 3,7-bis(dimethylamino)phenothiazine has been used as a color reactant in connection with manifold sheets such as those described in the United States Patent No. 2,646,367, which issued on the application of Chester Davis and Ned A. Thacker on July 21, 1953.
  • a manifold sheet having a colorless transfer coating on one side, the coating being made of wax and an oil having dissolved in it the colorless color reactant crystal violet lactone, which is 3,3-bis- (p-dimethylaminophenyl)-6-dimethylaminophthalide, and the beforementioned benzoyl leucomethylene blue.
  • the benzoyl leucomethylene blue has one characteristic in its disfavor, and that is that it slowly decomposes to the blue-green color on exposure to light, which means that, if the transfer coating is exposed to light for a long time, it turns to an undesirable blue-green color.
  • the manufacture of l0-(2-naphthoyl)-3,7-bis (dimethylamino)phenothiazine may be started with the commercially available zinc chloride double salt of leucomethylene blue, having the structure
  • To 35 grams (0.0706 mole) of the zinc chloride double salt of leucomethylene blue is added 97 grams (1.25 moles) of pyridine in a three-necked, round-bottom flask fitted with a mechanical stirrer, a thermometer, and a reflux condenser.
  • To the above mixture is added slowly 25 grams (0.131 mole) of 2-naphthoyl chloride while 2,783,227 Patented Feb. 26, 1957 2 stirring.
  • the reaction mixture is refluxed gently for one hour.
  • the resultant hot reaction mixture then is poured into one liter of cold water andmechanically stirred for one half hour.
  • the brown semi-solid precipitate which forms is washed with water and thereafter stirred with 17.5 grams of sodium hydroxide dissolved in one half liter of water for one half hour.
  • the alkaline solution then is decanted ofi, and the semi-solid residue is washed with water and extracted with 2.2 liters of hot benzene.
  • the dark benzene solution then is treated with fullers earth and filtered.
  • the resultant amber filtrate is concentrated to 400 milliliters and precipitated with petroleum ether.
  • the resulting final product, l0-(2-naphthoyl)-3,7-bis- (dimethylamino)phenothiazine, is a light yellow crystalline material having the following structure:
  • IO-(I-naphthoyl)-3,7-bis(dimethylamino)phenothiazine having the i in which R is taken from the group consisting of l-naphthoyl and 2-naphthoyl.
  • the substantially light-stable leucomethylene blue derivative 10 (2-naphthoyl) 3,7 bis(dimethylamino)- phenothiazine having the following structure:

Description

United States. Patent v g 7 2,783,227 NAPHTHOYL LEUCO METHYLENE BLUE 3 Claims. (Cl. 260-243) This invention relates to the substantially light-stable leucomethylene blue derivative -naphthoyl-3,7-bis (dimethylamino)phenothiazine, having the structure where R is taken from the group consisting of l-naphthoyl and 2-naphthoyl.
The known leucomethylene blue compound IO-benzoyl- 3,7-bis(dimethylamino)phenothiazine has been used as a color reactant in connection with manifold sheets such as those described in the 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 manifold sheet having a colorless transfer coating on one side, the coating being made of wax and an oil having dissolved in it the colorless color reactant crystal violet lactone, which is 3,3-bis- (p-dimethylaminophenyl)-6-dimethylaminophthalide, and the beforementioned benzoyl leucomethylene blue. If such a manifold sheet is placed with the transfer coating in contact with the surface of a copy sheet sensitized with particles of attapulgite, halloysite, or equivalent acid claylike material, and an impression is made by printing or writing on the top side of the manifold sheet, the color reactants will be transferred with the oil onto the sensitized surface of the copy sheet. The crystal violet lactone will immediately turn dark blue when coming into contact with the sensitizing clay-like material, thus manifesting whatever was printed or written on the top sheet. After prolonged exposure to light, this dark blue color will fade, but the benzoyl leucomethylene blue will be developing a blue-green color, so that the printed or Written matter will not be lost.
The benzoyl leucomethylene blue has one characteristic in its disfavor, and that is that it slowly decomposes to the blue-green color on exposure to light, which means that, if the transfer coating is exposed to light for a long time, it turns to an undesirable blue-green color.
Therefore, it is the object of this invention to provide more light-stable naphthoylated derivatives of leucomethylene blue.
The manufacture of l0-(2-naphthoyl)-3,7-bis (dimethylamino)phenothiazine may be started with the commercially available zinc chloride double salt of leucomethylene blue, having the structure To 35 grams (0.0706 mole) of the zinc chloride double salt of leucomethylene blue is added 97 grams (1.25 moles) of pyridine in a three-necked, round-bottom flask fitted with a mechanical stirrer, a thermometer, and a reflux condenser. To the above mixture is added slowly 25 grams (0.131 mole) of 2-naphthoyl chloride while 2,783,227 Patented Feb. 26, 1957 2 stirring. The reaction mixture is refluxed gently for one hour. The resultant hot reaction mixture then is poured into one liter of cold water andmechanically stirred for one half hour. The brown semi-solid precipitate which forms is washed with water and thereafter stirred with 17.5 grams of sodium hydroxide dissolved in one half liter of water for one half hour. The alkaline solution then is decanted ofi, and the semi-solid residue is washed with water and extracted with 2.2 liters of hot benzene. The dark benzene solution then is treated with fullers earth and filtered. The resultant amber filtrate is concentrated to 400 milliliters and precipitated with petroleum ether.
The resulting final product, l0-(2-naphthoyl)-3,7-bis- (dimethylamino)phenothiazine, is a light yellow crystalline material having the following structure:
S Ha)zN s mom).
In making the l-naphthoyl derivative, IO-(I-naphthoyl)-3,7-bis(dimethylamino)phenothiazine, having the i in which R is taken from the group consisting of l-naphthoyl and 2-naphthoyl.
2. The substantially light-stable leucomethylene blue derivative 10 (2-naphthoyl) 3,7 bis(dimethylamino)- phenothiazine, having the following structure:
3 3. The substantially light-stable leucomethylene blue derivative lO-(l-naphthoyl) 3,7 bis(dimethylamino)- phenothiazine, having the following structure:
S 113,721 an 1 6 \NC $12,300 7 i 5 3 5 125,275
FQREIGN PATENTS Germany Sept. 28, 1900 Belgium July 15, 1952 Great Britain Mar. 2, 1955

Claims (1)

1. 10-NAPHTHOYL-3,7-BIS(DIMETHYLAMINO) PHENOTHIAZINE, HAVING THE STRUCTURE
US518332A 1955-06-27 1955-06-27 Naphthoyl leuco methylene blue Expired - Lifetime US2783227A (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
NL208241D NL208241A (en) 1955-06-27
NL94594D NL94594C (en) 1955-06-27
US518332A US2783227A (en) 1955-06-27 1955-06-27 Naphthoyl leuco methylene blue

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US518332A US2783227A (en) 1955-06-27 1955-06-27 Naphthoyl leuco methylene blue

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US2783227A true US2783227A (en) 1957-02-26

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NL (2) NL208241A (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2909520A (en) * 1959-10-20 Process for making acylated
US2915415A (en) * 1957-06-19 1959-12-01 Caribonum Ltd Leucauramine derivate of benzoyl leuco methylene blue and transfer sheet coated therewith
US3873340A (en) * 1972-07-27 1975-03-25 Hodogaya Chemical Co Ltd Pressure-sensitive copying paper containing phenoxazine compounds
US4237281A (en) * 1978-10-13 1980-12-02 Ciba-Geigy Aktiengesellschaft Dyestuffs containing amino or imino groups
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
US2909520A (en) * 1959-10-20 Process for making acylated
US2915415A (en) * 1957-06-19 1959-12-01 Caribonum Ltd Leucauramine derivate of benzoyl leuco methylene blue and transfer sheet coated therewith
US3873340A (en) * 1972-07-27 1975-03-25 Hodogaya Chemical Co Ltd Pressure-sensitive copying paper containing phenoxazine compounds
US4237281A (en) * 1978-10-13 1980-12-02 Ciba-Geigy Aktiengesellschaft Dyestuffs containing amino or imino groups
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
NL94594C (en)
NL208241A (en)

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