US2783228A - Nitro derivatives of benzoyl leuco methylene blue - Google Patents
Nitro derivatives of benzoyl leuco methylene blue Download PDFInfo
- 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
- Authority
- US
- United States
- Prior art keywords
- color
- blue
- methylene blue
- nitro derivatives
- leuco methylene
- Prior art date
- 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
Links
- 150000002828 nitro derivatives Chemical class 0.000 title description 3
- 229960000907 methylthioninium chloride Drugs 0.000 title 1
- -1 10 -NITROBENZOYL -3,7-BIS(DIMETHYLAMINO)PHENOTHIAZINE Chemical compound 0.000 claims description 4
- ZKURGBYDCVNWKH-UHFFFAOYSA-N [3,7-bis(dimethylamino)phenothiazin-10-yl]-phenylmethanone Chemical compound C12=CC=C(N(C)C)C=C2SC2=CC(N(C)C)=CC=C2N1C(=O)C1=CC=CC=C1 ZKURGBYDCVNWKH-UHFFFAOYSA-N 0.000 description 5
- QTWZICCBKBYHDM-UHFFFAOYSA-N leucomethylene blue Chemical class C1=C(N(C)C)C=C2SC3=CC(N(C)C)=CC=C3NC2=C1 QTWZICCBKBYHDM-UHFFFAOYSA-N 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 4
- 229960000892 attapulgite Drugs 0.000 description 4
- 229910052621 halloysite Inorganic materials 0.000 description 4
- 229910052625 palygorskite Inorganic materials 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- LIZLYZVAYZQVPG-UHFFFAOYSA-N (3-bromo-2-fluorophenyl)methanol Chemical compound OCC1=CC=CC(Br)=C1F LIZLYZVAYZQVPG-UHFFFAOYSA-N 0.000 description 2
- SKDHHIUENRGTHK-UHFFFAOYSA-N 4-nitrobenzoyl chloride Chemical compound [O-][N+](=O)C1=CC=C(C(Cl)=O)C=C1 SKDHHIUENRGTHK-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000002178 crystalline material Substances 0.000 description 2
- CEZVAZTZKUQHGY-UHFFFAOYSA-N n,n-dimethyl-10h-phenothiazin-1-amine Chemical compound S1C2=CC=CC=C2NC2=C1C=CC=C2N(C)C CEZVAZTZKUQHGY-UHFFFAOYSA-N 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- AGIJRRREJXSQJR-UHFFFAOYSA-N 2h-thiazine Chemical compound N1SC=CC=C1 AGIJRRREJXSQJR-UHFFFAOYSA-N 0.000 description 1
- DDCCHUHICUGJCF-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazine Chemical compound S1C2=CC(N(C)C)=CC=C2N=C2C1C=C(N(C)C)C=C2 DDCCHUHICUGJCF-UHFFFAOYSA-N 0.000 description 1
- NXTNASSYJUXJDV-UHFFFAOYSA-N 3-nitrobenzoyl chloride Chemical compound [O-][N+](=O)C1=CC=CC(C(Cl)=O)=C1 NXTNASSYJUXJDV-UHFFFAOYSA-N 0.000 description 1
- IPAJDLMMTVZVPP-UHFFFAOYSA-N Crystal violet lactone Chemical compound C1=CC(N(C)C)=CC=C1C1(C=2C=CC(=CC=2)N(C)C)C2=CC=C(N(C)C)C=C2C(=O)O1 IPAJDLMMTVZVPP-UHFFFAOYSA-N 0.000 description 1
- 235000012745 brilliant blue FCF Nutrition 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910000286 fullers earth Inorganic materials 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- XMVJITFPVVRMHC-UHFFFAOYSA-N roxarsone Chemical group OC1=CC=C([As](O)(O)=O)C=C1[N+]([O-])=O XMVJITFPVVRMHC-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
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
- 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.
Landscapes
- 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
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL94595D NL94595C (en) | 1955-06-27 | ||
| NL208242D NL208242A (en) | 1955-06-27 | ||
| US518333A US2783228A (en) | 1955-06-27 | 1955-06-27 | Nitro derivatives of benzoyl leuco methylene blue |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US518333A US2783228A (en) | 1955-06-27 | 1955-06-27 | Nitro derivatives of benzoyl leuco methylene blue |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2783228A true US2783228A (en) | 1957-02-26 |
Family
ID=24063475
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US518333A Expired - Lifetime US2783228A (en) | 1955-06-27 | 1955-06-27 | Nitro derivatives of benzoyl leuco methylene blue |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US2783228A (en) |
| NL (2) | NL208242A (en) |
Cited By (7)
| 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)
| 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 |
-
0
- NL NL94595D patent/NL94595C/xx active
- NL NL208242D patent/NL208242A/xx unknown
-
1955
- 1955-06-27 US US518333A patent/US2783228A/en not_active Expired - Lifetime
Patent Citations (2)
| 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)
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| NL94595C (en) | |
| NL208242A (en) |
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