Classifications

• • 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
  • C09B57/00—Other synthetic dyes of known constitution
  • C09B57/04—Isoindoline dyes
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
  • C07B59/00—Introduction of isotopes of elements into organic compounds ; Labelled organic compounds per se
  • C07B59/002—Heterocyclic compounds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
  • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
  • C07D209/44—Iso-indoles; Hydrogenated iso-indoles
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
  • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
  • C07D209/44—Iso-indoles; Hydrogenated iso-indoles
  • C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
  • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
  • C07D209/44—Iso-indoles; Hydrogenated iso-indoles
  • C07D209/50—Iso-indoles; Hydrogenated iso-indoles with oxygen and nitrogen atoms in positions 1 and 3
• • 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
  • C09B61/00—Dyes of natural origin prepared from natural sources, e.g. vegetable sources
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
  • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
  • C07B2200/05—Isotopically modified compounds, e.g. labelled

Definitions

• the present invention relates to an isoindoline compound, a composition containing the isoindoline compound, and a method for producing the isoindoline compound.
• KII (3-iminoisoindolin-1-one) is an important intermediate that can be used in the synthesis of Y173 (isoindoline yellow pigment), while DII (1,3-diiminoisoindoline) can be used to synthesize Y139 and It is an important intermediate for making existing pigments such as Y185 (isoindoline yellow pigment), nonmetallic phthalocyanine, and metal phthalocyanine.
• KII and DII are not only important for the production of existing pigments, but also for the synthesis of new isoindoline pigments and dyes, as well as bioactive isoindolines with properties such as anticancer, antioxidant, and antibacterial agents.
• phthalonitrile is harmful to the human body and has a negative impact on the environment.
• the only source of phthalonitrile is petroleum resources.
• the purpose of the present invention is to provide bio-derived isoindoline compounds (KII, DII, etc.) that can be obtained using a safe, clean, and carbon-neutral approach.
• bio-derived isoindoline compounds KII, DII, etc.
• the present inventor used bio-derived furan and bio-derived maleic anhydride as raw materials, obtained a DA intermediate through a Diels-Alder (DA) reaction, and obtained a DA intermediate using bio-derived furan and bio-derived maleic anhydride as raw materials.
• the intermediate is subjected to dehydration and ring-opening reaction, and in the final step, some or all of the oxygen atoms are exchanged with nitrogen, resulting in Bio-KII or Bio-DII containing 14 C radioactive carbon atoms.
• a and B each independently represent an oxygen atom or NH.
• R 1 to R 4 each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, , represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a phenyl group which may be substituted with an alkyl group.
• R 2 and R 3 may be closed to form a 5- to 8-membered ring.
• R 1 to R 4 have the same meanings as R 1 to R 4 above.
• [6] A composition containing the compound represented by the formula (I) according to any one of [1] to [5]. [7] The composition according to [6], which is used as a pigment composition. [8] The composition according to [6], which contains at least two kinds of compounds represented by the formula (I). [9] A method for producing an isoindoline compound represented by the following formula (I) containing 14 C radioactive carbon atoms, comprising: (In the above formula (I), A and B each independently represent an oxygen atom or NH.
• R 1 to R 4 each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, , represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a phenyl group which may be substituted with an alkyl group. Note that R 2 and R 3 may be closed to form a 5- to 8-membered ring.
• a compound represented by the following formula (PA) is obtained from a compound represented by the following formula (DA), (In formula (DA), R 1 to R 4 have the same meanings as R 1 to R 4 above.) (In formula (PA), R 1 to R 4 have the same meanings as R 1 to R 4 above.)
• a method for producing an isoindoline compound which comprises obtaining an isoindoline compound represented by the formula (I) from a compound represented by the formula (PA).
• the compound represented by the formula (PA) is mixed with hydrochloric acid, sulfuric acid, methanesulfonic acid, p - formed by using any acid selected from the group of toluenesulfonic acid, acetic acid, acetic anhydride, triflic acid, phosphoric acid, phosphoric anhydride, polyphosphoric acid, pyrophosphoric acid, nitric acid, or mixtures of these acids
• hydrochloric acid sulfuric acid, methanesulfonic acid
• p - formed by using any acid selected from the group of toluenesulfonic acid, acetic acid, acetic anhydride, triflic acid, phosphoric acid, phosphoric anhydride, polyphosphoric acid, pyrophosphoric acid, nitric acid, or mixtures of these acids
• the method for producing an isoindoline compound according to [9] which comprises reacting under acidic conditions.
• bio-derived isoindoline compounds (KII, DII, etc.) that can be obtained using a safe, clean, and carbon-neutral approach.
• FIG. 3 is a diagram showing the GC/MS measurement results of Example 1.
• FIG. 3 is a diagram showing the HPLC measurement results of Example 2.
• the isoindoline compounds of the present invention contain 14 C radioactive carbon atoms.
• the isoindoline compound of the present invention is represented by the following formula (I).
• a and B independently represent an oxygen atom or NH.
• R 1 to R 4 are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a phenyl group which may be substituted with an alkyl group. represents a group. Note that R 2 and R 3 may be closed to form a 5- to 8-membered ring.
• the isoindoline compound of the present invention is produced using bio-derived furan and bio-derived maleic anhydride, it contains bio (biomass) components derived from bio-based raw materials.
• bio (biomass) components derived from bio-based raw materials The presence of biocomponents in the isoindoline compound of the present invention can be confirmed, for example, by measuring 14 C radioactive carbon atoms.
• biomass degree is generally used.
• carbon in petroleum-derived compounds and compositions does not contain 14 C (radioactive carbon 14, half-life 5730 years), so the concentration of 14 C can be measured by accelerator mass spectrometry. This makes it possible to confirm whether the generated compound or composition is a petroleum-derived compound or a bio-derived compound.
• a sample to be measured is burned to generate carbon dioxide, and the carbon dioxide purified in a vacuum line is reduced with hydrogen using iron as a catalyst to generate graphite.
• this graphite was attached to a 14 C-AMS dedicated device (manufactured by NEC Corporation) based on a tandem accelerator, and the 14 C count, the 13 C concentration ( 13 C/ 12 C), and the 14 C concentration ( 14 It is obtained by measuring C/ 12 C) and calculating the ratio of the 14 C concentration of the sample carbon to the standard modern carbon from this measured value.
• oxalic acid HOxII
• NIST National Institute of Standards
• pMC percent modern carbon
• pMC percent modern carbon
• the pMC (percent modern carbon) in the isoindoline compound of the present invention represented by formula (I) is preferably 1% or more, more preferably 50% or more, and even more preferably 75% or more. It is preferably 90% or more, more preferably 99% or more.
• containing a radioactive carbon atom 14 C not only has the meaning in the segregation approach, but also includes the meaning in the mass balance approach and the book and claim approach (Reference: Enabling Circular Economy for Chemical with the Mass Balance Approach, the Ellen MacAthur Foundation network).
• R 2 and R 3 may be closed to form a 5- to 8-membered ring, as described above.
• the ring structure can be a functional ether, alcohol, or carboxyl functional group.
• the term "functional group” means that the ring structure may have an -OH group, -COOH group, or -O- group.
• it means that a compound represented by the following formula (v), the following formula (vi), or the following formula (vii) may be used.
• Preferred embodiments of the isoindoline compound represented by formula (I) include, for example, an isoindoline compound represented by (I-1) below and an isoindoline compound represented by (I-2) below.
• R 1 to R 4 have the same meanings as R 1 to R 4 above.
• isoindoline compound represented by formula (I-1) for example, KII represented by the following (I-1-1), isoindoline compound represented by formula (I-2)
• I-1-1 isoindoline compound represented by formula (I-2)
• DII represented by (I-2-1) below.
• the isoindoline compounds of the invention of formula (I) containing 14 C radioactive carbon atoms, ie containing biocomponents, can be obtained by the method described below.
• a compound represented by the following formula (PA) is obtained from a compound represented by the following formula (DA),
• R 1 to R 4 have the same meanings as R 1 to R 4 above.
• R 1 to R 4 have the same meanings as R 1 to R 4 above.
• the isoindoline compound represented by the above formula (I) can be obtained from the compound represented by the above formula (PA).
• the reaction is carried out under acidic conditions.
• acidic conditions may be any conditions as long as they allow the reaction to proceed suitably; for example, hydrochloric acid, sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid, acetic acid, acetic anhydride, triflic acid, phosphoric acid, anhydrous It is formed by using any acid selected from the group of phosphoric acid, polyphosphoric acid, pyrophosphoric acid, nitric acid, or mixtures of these acids.
• a preferred embodiment of the method for producing an isoindoline compound represented by formula (I) is a method for producing an isoindoline compound represented by formula (I-1) above, and a method for producing an isoindoline compound represented by formula (I-2) above. Examples include methods for producing isoindoline compounds. Each manufacturing method will be explained in detail below.
• the isoindoline compound represented by the formula (I-1) of the present invention can be obtained from the compound represented by the following formula (DA) through the compound represented by the following formula (PA). A specific reaction route for this production method is shown below.
• R 1 to R 4 have the same meanings as R 1 to R 4 above.
• Compound (PA) can be produced by subjecting compound (DA) to a ring-opening dehydration reaction.
• Any reaction solvent may be used as long as it allows the reaction to proceed suitably, and examples thereof include water, acetonitrile, toluene, xylene, alkylbenzene, mixed solvents of each, and non-solvent.
• the reaction temperature may be any temperature as long as it allows the reaction to proceed suitably, but is preferably from 20 to 150°C, more preferably from 30 to 120°C, and even more preferably from 40 to 100°C.
• the lower limit is preferably 20°C or higher, preferably 25°C or higher, preferably 30°C or higher, preferably 35°C or higher, and preferably 40°C or higher.
• the upper limit is preferably 150°C or less, preferably 140°C or less, preferably 130°C or less, preferably 120°C or less, preferably 110°C or less, and preferably 100°C or less.
• the above reaction is carried out under acidic conditions.
• acidic conditions may be any as long as they allow the reaction to proceed suitably, but include hydrochloric acid, sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid, acetic acid, acetic anhydride, triflic acid, phosphoric acid, phosphoric anhydride, It is formed by using any acid selected from the group of polyphosphoric acid, pyrophosphoric acid, nitric acid, or mixtures of these acids. Among these, it is preferable to use acids containing sulfur or phosphorus. This is because these acids may have a ⁇ + or ⁇ ⁇ configuration, as represented by the following formula (p).
• X represents -OH, -ONa, -OK, or a methyl group.
• Y represents a sulfur atom or a phosphorus atom, and Z represents a hydrogen atom, -COCH 3 , -COH, or -(PO 2 ) n represents OH.
• the amount of the acid is preferably 0.1 to 3000 mol%, preferably 0.5 to 2500 mol%, preferably 1 to 2000 mol%, and preferably 5 to 1500 mol% based on the compound represented by formula (DA). , preferably 10 to 1000 mol%, preferably 20 to 500 mol%, preferably 50 to 500 mol%, preferably 70 to 500 mol%, preferably 100 to 500 mol%, preferably 150 to 500 mol%, preferably 200 to 500 mol%, 250 to 500 mol% is preferable, and 300 to 500 mol% is preferable.
• the lower limit is preferably at least 0.1 mol%, preferably at least 0.5 mol%, preferably at least 1 mol%, preferably at least 5 mol%, preferably at least 10 mol%, preferably at least 20 mol%, preferably at least 50 mol%, and 70 mol%. % or more, preferably 100 mol% or more, preferably 150 mol% or more, preferably 200 mol% or more, preferably 250 mol% or more, and preferably 300 mol% or more.
• the upper limit is preferably 3000 mol% or less, preferably 2500 mol% or less, preferably 2000 mol% or less, preferably 1500 mol% or less, preferably 1000 mol% or less, and preferably 500 mol% or less. Any combination of these upper and lower limits can be used.
• reaction B As shown in reaction A above, after the reaction is carried out under acidic conditions, in reaction B, amination is carried out in the presence of molybdenum ammonium as a catalyst and urea or NH 3 as an amine source. In reaction B, when oxygen atoms in the compound represented by the above compound (PA) are replaced with nitrogen atoms, it is not necessary to add any additives as long as 1 to 2 oxygen atoms are replaced.
• PA oxygen atoms in the compound represented by the above compound (PA) are replaced with nitrogen atoms, it is not necessary to add any additives as long as 1 to 2 oxygen atoms are replaced.
• R 1 to R 4 have the same meanings as R 1 to R 4 above.
• Reaction A is as described in ⁇ Reaction A>> in the section ⁇ Method for producing isoindoline compound represented by (I-1)> above.
• Reaction C After reacting under acidic conditions as shown in Reaction A above, in Reaction C, amination is carried out in the presence of molybdenum ammonium as a catalyst and urea or NH 3 as an amine source.
• molybdenum ammonium as a catalyst
• urea or NH 3 as an amine source.
• reaction C when replacing the oxygen atom in the compound represented by the above compound (PA) with a nitrogen atom, it is not necessary to add any additive as long as 1 to 2 oxygen atoms are replaced.
• a compound represented by the following formula (q) in order to prevent side reactions such as oligomerization and polymerization.
• M f+ represents NH 4 + , Li + , Na + , K + , Mg 2+ , Ca 2+ , or Al 3+ .
• reaction D the isoindoline compound represented by formula (I-2) is produced by providing aqueous ammonia and sodium hydroxide to the reactant obtained through reaction C.
• a composition containing the compound represented by formula (I) is obtained, but by purification by a known and commonly used method, the compound represented by formula (I) (e.g. It is also possible to extract only the compound represented by formula (I-1) or the compound represented by formula (I-2).
• the compound represented by the above formula (DA) used to produce the isoindoline compound represented by (I) of the present invention is obtained by reacting a compound represented by the following formula (FR) with maleic anhydride. It can be obtained by
• R 1 to R 4 have the same meanings as R 1 to R 4 above.
• the maleic anhydride is derived from biomass.
• the compound represented by the above formula (FR) is preferably derived from biomass. It is more preferable that both the above maleic anhydride and the compound represented by the above formula (FR) are derived from biomass.
• the biomass degree of the raw material used in the above production method is preferably 1% or more, more preferably 50% or more, more preferably 75% or more, more preferably 90% or more, and even more preferably 99% or more. Furthermore, if biomass raw materials can be obtained using the mass balance method or the book and claim method, it becomes easier to achieve a biomass content of 1% to 100%. This patent covers biomass content including biomass raw materials using the mass balance method and book-and-claim method.
• Biomass-derived maleic anhydride can be obtained by dehydrating and cyclizing maleic acid obtained by oxidizing FF or HMF obtained by the method described in, for example, Japanese Patent No. 5791838 or Japanese Patent No. 6328990, Alternatively, it can be obtained by direct oxidation.
• a biomass-derived compound represented by the formula (FR) for example, decarbonylation, reduction reaction, and dehydration reaction are performed on FF and HMF obtained by the methods described in the above-mentioned Patent No. 5791838 and the above-mentioned Patent No. 6328990. It can be obtained by appropriately combining the above methods.
• Compound (DA) can be produced by subjecting compound (FR) and maleic anhydride to a Diels-Alder reaction.
• the above reaction may be carried out using a reaction solvent or without a solvent. Any reaction solvent may be used as long as it allows the reaction to proceed suitably, but chloroform, dioxane, ethyl acetate, alkylbenzene, toluene, xylene, and diethyl ether are preferred.
• the reaction temperature may be any temperature as long as it allows the reaction to proceed suitably, but is preferably -10 to 100°C, more preferably 0 to 80°C, even more preferably 10 to 70°C, and even more preferably 15 to 50°C. is particularly preferred.
• the lower limit is preferably -10°C or higher, more preferably 0°C or higher, even more preferably 10°C or higher, and particularly preferably 15°C or higher.
• the upper limit is preferably 100°C or less, more preferably 80°C or less, even more preferably 70°C or less, and particularly preferably 50°C or less.
• the reaction pressure may be any pressure that allows the reaction to proceed suitably, but is preferably 0.1 to 5 MPa, more preferably 0.1 to 3 MPa, even more preferably 0.1 to 1 MPa, and even more preferably 0.1 to 0. .5 MPa is particularly preferred.
• the lower limit is preferably 0.1 MPa or more, preferably 0.2 MPa or more, preferably 0.3 MPa or more, and preferably 0.4 MPa or more.
• the upper limit is preferably 5 MPa or less, preferably 3 MPa or less, preferably 1 MPa or less, preferably 0.9 MPa or less, preferably 0.8 MPa or less, preferably 0.7 MPa or less, preferably 0.6 MPa or less, and 0.5 MPa or less. The following are preferred.
• composition containing isoindoline compound The present invention may be a composition containing one or more isoindoline compounds of the present invention represented by formula (I).
• Preferred embodiments of the composition of the present invention include, for example, a composition containing an isoindoline compound represented by the following formula (I-1), a composition containing an isoindoline compound represented by the following formula (I-2), and a composition containing an isoindoline compound represented by the following formula (I-2).
• Examples include compositions containing an isoindoline compound represented by the following formula (I-3).
• R 1 to R 4 have the same meanings as R 1 to R 4 above.
• isoindoline compound represented by the above formula (I-1) or the isoindoline compound represented by the above formula (I-2) is subjected to an isomerization reaction as shown in the following formula (s),
• the isoindoline compound represented by the following formula (i) or the following formula (ii) or the isomerization reaction as shown by the following formula (t) is used to form a compound represented by the following formula (iii) or the following formula (iv).
• isoindoline compounds are generated.
• R 1 to R 4 have the same meanings as R 1 to R 4 above.
• the composition of the present invention includes, for example, a composition containing an isoindoline compound represented by the above formula (I-1) and an isoindoline compound represented by the above formula (i) or the above formula (ii). It may be a composition containing an isoindoline compound represented by the above formula (I-2) and an isoindoline compound represented by the above formula (iii) or (iv).
• a pigment composition can be produced using the above composition.
• the isoindoline compound of the present invention represented by formula (I) and containing 14 C radioactive carbon atoms obtained by the above method is an important intermediate for making pigments.
• various excellent pigments such as Y173, Y139, and Y185 can be produced.
• the isoindoline compound of the present invention can also be used to produce various excellent bioactive isoindolines having properties such as anticancer agents, antioxidants, and antibacterial agents.
• the isoindoline compound of the present invention contains carbon derived from biomass, and contributes to reducing environmental load by being carbon neutral.
• the isoindoline compound of the present invention is obtained by the above production method, the number and position of various types of functional groups can be controlled by changing the type of furan or changing to another type of diene. be able to.
• the isoindoline compound of the present invention is applicable to a variety of uses. For example, a pigment is produced using the isoindoline compound of the present invention and a composition containing the isoindoline compound, and if necessary, other resins, rubbers, additives, pigments and the like are used.
• dyes, etc. it is adjusted and used in coating materials for cosmetics, pharmaceuticals, or agricultural chemicals, printing markers, stationery, writing instruments, printing inks, inkjet inks, metal inks, paints, plastic colorants, color toners, color filters, etc.
• Example 1 Bio KII 14 g of acetic anhydride was added to 74 g of methanesulfonic acid, and 5 g of DA intermediate was slowly added while cooling in an ice bath. The reaction mixture was stirred at room temperature for 2 hours and then heated at 80° C. for 4 hours. The reaction mixture was extracted with toluene (3 x 50 mL). The combined toluene was washed with brine, sodium bicarbonate and evaporated under reduced pressure. The obtained needle white was mixed with 5.3 g of urea and 0.02 g of molybdenum in 10 mL of alkylbenzene. The reaction mixture was heated at 150°C for 2 hours.
• Example 2 Bio DII 14 g of acetic anhydride was added to 74 g of methanesulfonic acid, and 5 g of DA intermediate was slowly added while cooling in an ice bath. The reaction mixture was stirred at room temperature for 2 hours and then heated at 80° C. for 4 hours. The reaction mixture was extracted with toluene (3 x 50 mL). The combined toluene was washed with brine, sodium bicarbonate and evaporated under reduced pressure. The obtained needle white was mixed with 13 g of urea, 6 g of ammonium nitrate, and 0.03 g of molybdenum in 10 mL of alkylbenzene. After heating the reaction mixture at 165° C.
• the alkylbenzene was removed by vacuum distillation. After adding 30 mL of methanol and distilling for 15 minutes, the mixture was cooled to room temperature and filtered. The obtained solid was dispersed in 10 mL of water, and 3 g of ammonia water and 4.4 mL of 25% caustic soda were added. The solution was cooled in an ice bath, and the precipitated solid was filtered and washed with water. By drying the obtained solid under reduced pressure, 2.9 g of a 100% pure compound containing radioactive carbon C14 in its molecule was obtained.

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• 2023
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