USRE27306E - Phthalide compounds and their preparation - Google Patents
Phthalide compounds and their preparation Download PDFInfo
- Publication number
- USRE27306E USRE27306E US27306DE USRE27306E US RE27306 E USRE27306 E US RE27306E US 27306D E US27306D E US 27306DE US RE27306 E USRE27306 E US RE27306E
- Authority
- US
- United States
- Prior art keywords
- phthalide
- acid
- bis
- amino
- preparation
- 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
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- 238000002360 preparation method Methods 0.000 title description 2
- 125000005506 phthalide group Chemical class 0.000 title 1
- VTFNZBODTQTEIP-UHFFFAOYSA-N 3,3-bis[4-(dimethylamino)phenyl]-5-nitro-2-benzofuran-1-one Chemical compound C1=CC(N(C)C)=CC=C1C1(C=2C=CC(=CC=2)N(C)C)C2=CC([N+]([O-])=O)=CC=C2C(=O)O1 VTFNZBODTQTEIP-UHFFFAOYSA-N 0.000 claims abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 17
- -1 phthalide compound Chemical class 0.000 description 9
- 150000001412 amines Chemical class 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- WNZQDUSMALZDQF-UHFFFAOYSA-N 2-benzofuran-1(3H)-one Chemical class C1=CC=C2C(=O)OCC2=C1 WNZQDUSMALZDQF-UHFFFAOYSA-N 0.000 description 6
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 238000007792 addition Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000002252 acyl group Chemical group 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 3
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 2
- JEXCBTXFJQTLFP-UHFFFAOYSA-N 3-nitro-3h-2-benzofuran-1-one Chemical compound C1=CC=C2C([N+](=O)[O-])OC(=O)C2=C1 JEXCBTXFJQTLFP-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000000981 basic dye Substances 0.000 description 2
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000000802 nitrating effect Effects 0.000 description 2
- 238000006396 nitration reaction Methods 0.000 description 2
- 150000002828 nitro derivatives Chemical class 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- HDECRAPHCDXMIJ-UHFFFAOYSA-N 2-methylbenzenesulfonyl chloride Chemical compound CC1=CC=CC=C1S(Cl)(=O)=O HDECRAPHCDXMIJ-UHFFFAOYSA-N 0.000 description 1
- OEIOKPQWHXSUCH-UHFFFAOYSA-N 3-amino-3h-2-benzofuran-1-one Chemical class C1=CC=C2C(N)OC(=O)C2=C1 OEIOKPQWHXSUCH-UHFFFAOYSA-N 0.000 description 1
- YVIYCJBOJWNEDS-UHFFFAOYSA-N 4-aminonaphthalene-1-sulfonic acid;sodium Chemical compound [Na].C1=CC=C2C(N)=CC=C(S(O)(=O)=O)C2=C1 YVIYCJBOJWNEDS-UHFFFAOYSA-N 0.000 description 1
- MXGKRZOFDLMYOO-UHFFFAOYSA-N 5-amino-3,3-bis[4-(dimethylamino)phenyl]-2-benzofuran-1-one Chemical compound C1=CC(N(C)C)=CC=C1C1(C=2C=CC(=CC=2)N(C)C)C2=CC(N)=CC=C2C(=O)O1 MXGKRZOFDLMYOO-UHFFFAOYSA-N 0.000 description 1
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000002168 alkylating agent Substances 0.000 description 1
- 229940100198 alkylating agent Drugs 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- CSKNSYBAZOQPLR-UHFFFAOYSA-N benzenesulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=CC=C1 CSKNSYBAZOQPLR-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 150000008050 dialkyl sulfates Chemical class 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N p-toluenesulfonic acid Substances CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 229910003446 platinum oxide Inorganic materials 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
Classifications
-
- 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
- C07D307/885—3,3-Diphenylphthalides
-
- 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
- C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
- C09B11/10—Amino derivatives of triarylmethanes
- C09B11/24—Phthaleins containing amino groups ; Phthalanes; Fluoranes; Phthalides; Rhodamine dyes; Phthaleins having heterocyclic aryl rings; Lactone or lactame forms of triarylmethane dyes
Definitions
- the present invention relates to the production of nitro and amino derivatives of 3,3-bis-(4-dialkylaminophenyl)- phthalides and alkyl, acyl and sulfonyl derivatives of the amino derivatives.
- the amino derivatives and the alk'yl derivatives thereof are reactive with acidic clays to form a color so as to be useful in copying papers of known construction.
- the acyl and sulfonyl derivatives form basic dyes and are also useful in pressure sensitive copying papers.
- amino derivatives of the present invention are formed from 3,3-bis-(4- dialkylaminophenyl) -phthalide which are known compounds, the preferred production thereof being described in Japanese Patent S.N. [37/ 18,902] 37/18,092 published November 16, 1962.
- 3,3-bis-(4-dialkylaminophenyl)-phthalide can be reacted with an acid mixture of sulfuric acid and [nitrous] nitric acid, preferably containing sulfuric acid in an excess of at least 3:1, to convert the phthalide compound to its nitro derivative, especially in the 5 position, which, in turn, can be reduced to the corresponding amine under neutral or acidic conditions.
- the nitration reaction is desirably conducted at low temperature, e.g., in the range of from -20 to 50 C., preferably from 0 to 30 C.
- the reduction of the nitro phthalide is preferably accomplished in solution in hydrochloric acid, acetic acid or mixtures thereof, preferred reducing agents being [ferrous oxide] iron [and] illustrated by zinc metal powder.
- preferred reducing agents being [ferrous oxide] iron [and] illustrated by zinc metal powder.
- the reduction may be accomplished in diverse ways, as for example, with hydrogen gas using appropriate catalysts such as palladium or charcoal, platinum oxide, or nickel.
- Other metals which may be used for reduction are aluminum, tin, and magnesium.
- Alkyl derivatives of the amino phthalide compounds are effected through the use of an alkylating agent, such as dialkyl sulfates or p-toluene-sulfonic acid alkyl esters, preferably in the presence of an alkaline compound such as alkaline wth metal hydroxides, or carbonates, e.g., barium hydroxide, calcium hydroxide, calcium carbonate, etc., formamide, and nitrogen-containing heterocyclic compounds, such as pyridine or picoline.
- an alkylating agent such as dialkyl sulfates or p-toluene-sulfonic acid alkyl esters
- an alkaline compound such as alkaline wth metal hydroxides, or carbonates, e.g., barium hydroxide, calcium hydroxide, calcium carbonate, etc., formamide, and nitrogen-containing heterocyclic compounds, such as pyridine or picoline.
- the alkylation is preferably carried out in organic solvent medium, suitable solvents being chlorobenzene, dichlorobenzene, trichlorobenzene, nitrobenzene, dioxane, forrnamide, dimethyl formamide, etc.
- suitable solvents being chlorobenzene, dichlorobenzene, trichlorobenzene, nitrobenzene, dioxane, forrnamide, dimethyl formamide, etc.
- Some of the solvents can also function as the alkaline compound, especially pyridine and picoline.
- the amino compounds are convertible to an acyl or sulfonyl derivative in which form it is useful as a basic dye or in pressure-sensitive coloring systems by reaction with an acid anhydride or acid chloride, e.g., by reaction with acetic anhydride, benzoylchloride, cyanylchloride, benzene sulfonylchloride and toluene sulfonylchloride.
- the amino compounds may also be converted into useful azo dyes by coupling the conventionally [diasotized] ice diazotized amino compound with a conventional coupler such as fl-naphthol, sodium naphthionic acid or Schefiers acid.
- a conventional coupler such as fl-naphthol, sodium naphthionic acid or Schefiers acid.
- Example 1 3 grams of 3,3-bis (4-dimethylaminopherlyl)-phthalide are dissolved in 50 ml. of industrial grade concentrated sulfuric acid (98%), the temperature being maintained below 50 C. during dissolution. A liquid mixture (5.5 ml.) of sulfuric acid (specific gravity 1.80) and [nitrous] nitric acid (specific gravity 1.45) having a ratio of sulfuric acid to [nitrous] nitric acid of 5:1 is gradually added to the solution of phthalide compound in sulfuric acid and the mixture so-produced is maintained at a temperature in the range of from 030 C. for one hour.
- reaction product is then diluted by the addition of 300 ml. of ice water and precipitated by neutralization with sodium hydroxide.
- the precipitate is filtered, dried and recrystallized with methanol to provide an approximately quantitative yield of 5-nitro-3,3-bis-(4-dimethylaminophenyl)-phthalide in the form of yellow crystals melting in the range of l68l70 C.
- Example 2 4 grams of the product of Example 1 are dissolved in 50 ml. industrial grade concentrated hydrochloric acid and the nitro derivative is reduced to the corresponding amine by the addition of powdered [ferrous oxide] reducing agent in an amount of 5% in excess of the theoretical equivalent amount. The temperature is maintained at 60 C. for one hour and the reaction product is then diluted by the addition of ice water in a volume equal to the volume of the solution which is diluted. Sodium acetate is then added to a pH of 4 with cooling to provide a blue precipitate essentially free of ferric hydroxide contamination.
- Example 3 Repeating Example 2 using zinc or tin metal powder provides essentially the same results.
- Example 4 The phthalide compound of Example 1 can also be reduced to the corresponding amine by dissolving 4 grams thereof in 50 ml. of an acid mixture of 32% hydrochloric acid (20 ml.) and glacial acetic acid (30 ml.). A catalyst constituted by 0.2 gram of palladium deposited upon 2 grams of activated charcoal is added to the solution which is then refluxed while a stream of hydrogen gas is passed therethrough for 3 hours. After filtering and recrystallizing as in Example 2, essentially pure crystals of S-amino- 3,3-bis(4-dimethylaminophenyl)-phthalide is obtained.
- Example 5 1 gram of 5-amino-3,3-bis-(4-dimethylaminophenyl)- phthalide is mixed with 3 grams of acetic anhydride, heated to -l40 C., and then permitted to cool. The product is poured into an aqueous solution of sodium carbonate to precipitate white crystals of 5-[acetylamine-] acetylamino-3,3-bis-(4dimethylaminophenyl) phthalide having a melting point of 214 C. upon recrystallization in ethanol.
- Example 6 [Example 5 is repeated using benzoyl chloride to provide white crystals of 5-benzoylamino 3,3 bis- (4-dimethylamino phen'yl) -phthalide.
- Example 7 Example 8 Example 7 is repeated using 0.015 mol of p-toluene ulfonic acid methyl ester in place of the dimethyl sulfate If Example 7. Approximately the same results (a yield 1f crude product of about 80%) are obtained.
- a method of nitrating 3,3-bis-(4 dialkylaminohenyD-phthalide comprising reaching said phthalide comound with a mixture of sulfuric acid and nitrous acid]
- a method as recited in claim 4 in which said hthal-ide compound in solution in sulfuric acid is added 3 a mixture containing nitrous acid and an excess of ulfuri-c acid while maintaining a temperature of from 30 0.]
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
1. 5-NITRO-3,3-BIS-(4-DIMETHYLAMINOPHENYL)-PHTHALIDE.
Description
United States Patent 27,306 PHTHALIDE COMPOUNDS AND THEIR PREPARATION Ryohei Oda, Kyoto, Hiroshi Fujii, Amagasaki, and Hiroyuki Moriga and Taiji Higaki, Nishiuomiya, Japan (all Kanzaki Paper Mfg. Co., Ltd., 4 Ginza Higashi 4, Chuo-ku, Tokyo, Japan) No Drawing. Original No. 3,244,730, dated Apr. 5, 1966, Ser. No. 295,820, July 17, 1963. Application for reissue Aug. 5, 1966, Ser. No. 574,260
Int. Cl. C07d /38 US. Cl. 260-3434 3 Claims Matter enclosed in heavy brackets II] appears in the original patent but forms no part of this reissue specification; matter printed in italics indicates the additions made by reissue.
The present invention relates to the production of nitro and amino derivatives of 3,3-bis-(4-dialkylaminophenyl)- phthalides and alkyl, acyl and sulfonyl derivatives of the amino derivatives. The amino derivatives and the alk'yl derivatives thereof are reactive with acidic clays to form a color so as to be useful in copying papers of known construction. The acyl and sulfonyl derivatives form basic dyes and are also useful in pressure sensitive copying papers.
The amino derivatives of the present invention are formed from 3,3-bis-(4- dialkylaminophenyl) -phthalide which are known compounds, the preferred production thereof being described in Japanese Patent S.N. [37/ 18,902] 37/18,092 published November 16, 1962.
In accordance with the present invention, it has been found that 3,3-bis-(4-dialkylaminophenyl)-phthalide can be reacted with an acid mixture of sulfuric acid and [nitrous] nitric acid, preferably containing sulfuric acid in an excess of at least 3:1, to convert the phthalide compound to its nitro derivative, especially in the 5 position, which, in turn, can be reduced to the corresponding amine under neutral or acidic conditions.
The nitration reaction is desirably conducted at low temperature, e.g., in the range of from -20 to 50 C., preferably from 0 to 30 C.
The reduction of the nitro phthalide is preferably accomplished in solution in hydrochloric acid, acetic acid or mixtures thereof, preferred reducing agents being [ferrous oxide] iron [and] illustrated by zinc metal powder. However, the reduction may be accomplished in diverse ways, as for example, with hydrogen gas using appropriate catalysts such as palladium or charcoal, platinum oxide, or nickel. Other metals which may be used for reduction are aluminum, tin, and magnesium.
Alkyl derivatives of the amino phthalide compounds are effected through the use of an alkylating agent, such as dialkyl sulfates or p-toluene-sulfonic acid alkyl esters, preferably in the presence of an alkaline compound such as alkaline wth metal hydroxides, or carbonates, e.g., barium hydroxide, calcium hydroxide, calcium carbonate, etc., formamide, and nitrogen-containing heterocyclic compounds, such as pyridine or picoline. The alkylation is preferably carried out in organic solvent medium, suitable solvents being chlorobenzene, dichlorobenzene, trichlorobenzene, nitrobenzene, dioxane, forrnamide, dimethyl formamide, etc. Some of the solvents can also function as the alkaline compound, especially pyridine and picoline.
The amino compounds are convertible to an acyl or sulfonyl derivative in which form it is useful as a basic dye or in pressure-sensitive coloring systems by reaction with an acid anhydride or acid chloride, e.g., by reaction with acetic anhydride, benzoylchloride, cyanylchloride, benzene sulfonylchloride and toluene sulfonylchloride.
The amino compounds may also be converted into useful azo dyes by coupling the conventionally [diasotized] ice diazotized amino compound with a conventional coupler such as fl-naphthol, sodium naphthionic acid or Schefiers acid.
The invention is illustrated in the following examples.
Example 1 3 grams of 3,3-bis (4-dimethylaminopherlyl)-phthalide are dissolved in 50 ml. of industrial grade concentrated sulfuric acid (98%), the temperature being maintained below 50 C. during dissolution. A liquid mixture (5.5 ml.) of sulfuric acid (specific gravity 1.80) and [nitrous] nitric acid (specific gravity 1.45) having a ratio of sulfuric acid to [nitrous] nitric acid of 5:1 is gradually added to the solution of phthalide compound in sulfuric acid and the mixture so-produced is maintained at a temperature in the range of from 030 C. for one hour.
The reaction product is then diluted by the addition of 300 ml. of ice water and precipitated by neutralization with sodium hydroxide. The precipitate is filtered, dried and recrystallized with methanol to provide an approximately quantitative yield of 5-nitro-3,3-bis-(4-dimethylaminophenyl)-phthalide in the form of yellow crystals melting in the range of l68l70 C.
Example 2 4 grams of the product of Example 1 are dissolved in 50 ml. industrial grade concentrated hydrochloric acid and the nitro derivative is reduced to the corresponding amine by the addition of powdered [ferrous oxide] reducing agent in an amount of 5% in excess of the theoretical equivalent amount. The temperature is maintained at 60 C. for one hour and the reaction product is then diluted by the addition of ice water in a volume equal to the volume of the solution which is diluted. Sodium acetate is then added to a pH of 4 with cooling to provide a blue precipitate essentially free of ferric hydroxide contamination. By filtration and repeated recrystallization in ethanol, there is obtained white crystals of 5-amino-3,3-bis-(4dimethylaminophenyl)-phtha1ide having a melting point of 221 C. The crude blue precipitate is obtained in a yield of about 86 Example 3 Repeating Example 2 using zinc or tin metal powder provides essentially the same results.
Example 4 The phthalide compound of Example 1 can also be reduced to the corresponding amine by dissolving 4 grams thereof in 50 ml. of an acid mixture of 32% hydrochloric acid (20 ml.) and glacial acetic acid (30 ml.). A catalyst constituted by 0.2 gram of palladium deposited upon 2 grams of activated charcoal is added to the solution which is then refluxed while a stream of hydrogen gas is passed therethrough for 3 hours. After filtering and recrystallizing as in Example 2, essentially pure crystals of S-amino- 3,3-bis(4-dimethylaminophenyl)-phthalide is obtained.
Example 5 1 gram of 5-amino-3,3-bis-(4-dimethylaminophenyl)- phthalide is mixed with 3 grams of acetic anhydride, heated to -l40 C., and then permitted to cool. The product is poured into an aqueous solution of sodium carbonate to precipitate white crystals of 5-[acetylamine-] acetylamino-3,3-bis-(4dimethylaminophenyl) phthalide having a melting point of 214 C. upon recrystallization in ethanol.
Example 6 [Example 5 is repeated using benzoyl chloride to provide white crystals of 5-benzoylamino 3,3 bis- (4-dimethylamino phen'yl) -phthalide.
Example 7 Example 8 Example 7 is repeated using 0.015 mol of p-toluene ulfonic acid methyl ester in place of the dimethyl sulfate If Example 7. Approximately the same results (a yield 1f crude product of about 80%) are obtained.
The invention is defined in the claims which follow.
We claim:
1. 5-nitro-3,3-'bis- 4-dimethylaminophenyl -phtha1ide.
2. 5-acetylamin0-3,3 bis (4 dimethylaminophenyl)- hthalide.
3. 5-benzoylamino-3,3 bis-(4 dimethylaminophenyl)- hthalide.
[4. A method of nitrating 3,3-bis-(4 dialkylaminohenyD-phthalide comprising reaching said phthalide comound with a mixture of sulfuric acid and nitrous acid] [5. A method as recited in claim 4 in which said hthal-ide compound in solution in sulfuric acid is added 3 a mixture containing nitrous acid and an excess of ulfuri-c acid while maintaining a temperature of from 30 0.]
4 [6. A method of producing amine derivatives of 3,3- bis-(dialkylaminophenyl) phthah'des comprising nitrating 3,3-bis-(4-dialkylaminophenylyphthalide with a mixture of sulfuric acid and nitrous acid and reducing the nitro phthalide produced by said nitration] References Cited The following references, cited by the Examiner, are of record in the patented file of this patent or the original patent.
UNITED STATES PATENTS 2,066,533 1/1937 Lazier 260-3433 2,079,325 5/1937 Larchar 260--343.3
2,088,633 8/1937 Bousquet et al. 260343.3
2,105,664 1/1938 Lazier 260---343.3
' FOREIGN PATENTS 3,823,795 11/1963 Japan.
OTHER REFERENCES Noller: Chemistry of Organic Compounds (1958), QD-253 N65, pp. 439, 45657.
ALEX MAZEL, Primary Examiner J. A. NARCAVAGE, Assistant Examiner US. Cl. X.R.
Claims (1)
1. 5-NITRO-3,3-BIS-(4-DIMETHYLAMINOPHENYL)-PHTHALIDE.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US57426066A | 1966-08-05 | 1966-08-05 |
Publications (1)
Publication Number | Publication Date |
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USRE27306E true USRE27306E (en) | 1972-03-14 |
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ID=24295349
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US27306D Expired USRE27306E (en) | 1966-08-05 | 1966-08-05 | Phthalide compounds and their preparation |
Country Status (1)
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US (1) | USRE27306E (en) |
-
1966
- 1966-08-05 US US27306D patent/USRE27306E/en not_active Expired
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