CN105504105A - Oxime ester photoinitiator and preparation method thereof - Google Patents
Oxime ester photoinitiator and preparation method thereof Download PDFInfo
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- CN105504105A CN105504105A CN201511035287.2A CN201511035287A CN105504105A CN 105504105 A CN105504105 A CN 105504105A CN 201511035287 A CN201511035287 A CN 201511035287A CN 105504105 A CN105504105 A CN 105504105A
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- Prior art keywords
- described step
- diphenyl sulfide
- substituted
- carbazole
- oxime ester
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- -1 Oxime ester Chemical class 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical group C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 claims abstract description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract 4
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims abstract 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract 2
- 229910052799 carbon Inorganic materials 0.000 claims abstract 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract 2
- 229910052760 oxygen Inorganic materials 0.000 claims abstract 2
- 239000001301 oxygen Substances 0.000 claims abstract 2
- 239000000126 substance Substances 0.000 claims abstract 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 44
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 31
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 29
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 22
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 14
- 230000000977 initiatory effect Effects 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 239000012043 crude product Substances 0.000 claims description 12
- 150000005826 halohydrocarbons Chemical class 0.000 claims description 12
- 238000002425 crystallisation Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- 230000008025 crystallization Effects 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 8
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 8
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 claims description 7
- 150000007530 organic bases Chemical class 0.000 claims description 7
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 6
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 6
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 6
- 238000010009 beating Methods 0.000 claims description 6
- 238000001953 recrystallisation Methods 0.000 claims description 6
- 238000010025 steaming Methods 0.000 claims description 6
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 claims description 4
- JQJPBYFTQAANLE-UHFFFAOYSA-N Butyl nitrite Chemical compound CCCCON=O JQJPBYFTQAANLE-UHFFFAOYSA-N 0.000 claims description 4
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 150000002191 fatty alcohols Chemical class 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- OWFXIOWLTKNBAP-UHFFFAOYSA-N isoamyl nitrite Chemical compound CC(C)CCON=O OWFXIOWLTKNBAP-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- KAOQVXHBVNKNHA-UHFFFAOYSA-N propyl nitrite Chemical compound CCCON=O KAOQVXHBVNKNHA-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical class C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims 15
- 150000001716 carbazoles Chemical group 0.000 claims 6
- 229910052736 halogen Inorganic materials 0.000 claims 2
- 239000005864 Sulphur Substances 0.000 claims 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 229910052717 sulfur Inorganic materials 0.000 abstract 1
- 239000011593 sulfur Substances 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 14
- 238000000967 suction filtration Methods 0.000 description 14
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 10
- 239000007787 solid Substances 0.000 description 9
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 230000006837 decompression Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- CDIIZULDSLKBKV-UHFFFAOYSA-N 4-chlorobutanoyl chloride Chemical compound ClCCCC(Cl)=O CDIIZULDSLKBKV-UHFFFAOYSA-N 0.000 description 3
- FIFUQYYQPAGBFT-UHFFFAOYSA-N C1(CCCC1)CC(C)=NO.C1(=CC=CC=C1)SC1=CC=CC=C1 Chemical compound C1(CCCC1)CC(C)=NO.C1(=CC=CC=C1)SC1=CC=CC=C1 FIFUQYYQPAGBFT-UHFFFAOYSA-N 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 229920001084 poly(chloroprene) Polymers 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- LSZLUAGBZHUXBP-UHFFFAOYSA-N C1(CCCC1)CC(C)=O.C1(=CC=CC=C1)SC1=CC=CC=C1 Chemical compound C1(CCCC1)CC(C)=O.C1(=CC=CC=C1)SC1=CC=CC=C1 LSZLUAGBZHUXBP-UHFFFAOYSA-N 0.000 description 1
- 0 CCC(C(*)=O)=N*C(*)=C Chemical compound CCC(C(*)=O)=N*C(*)=C 0.000 description 1
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 description 1
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- OKHSVCZDYHBEKX-UHFFFAOYSA-N formyl chloride toluene Chemical compound C(=O)Cl.CC1=CC=CC=C1 OKHSVCZDYHBEKX-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- 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
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
- C07D295/12—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms
- C07D295/125—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
- C07D295/13—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses an oxime ester photoinitiator and a preparation method thereof. The chemical structure of the oxime ester photoinitiator is shown in the description, wherein the structure of R1 is shown in the description, n is an integer ranging from 0 to 5, m is an integer ranging from 1 to 6, R2 represents methyl or phenyl or substituted phenyl or benzyl or substituted benzyl, R3 represents a diphenyl sulfide group or a substituted diphenyl sulfide group or a carbazole group or a substituted carbazole group, and Y is one of carbon, nitrogen, oxygen and sulfur. The preparation method of the oxime ester photoinitiator is high in yield, low in cost, good in safety, friendly to environment and suitable for industrial production.
Description
Technical field
The invention belongs to field of new, particularly relate to a kind of light trigger for unsaturated polyester light initiation polymerization and preparation method thereof.
Background technology
Oxime ester lightlike initiating agent preparation process of the prior art can produce environmentally harmful refuse, and meanwhile, productive rate is low, is not suitable for suitability for industrialized production.
Summary of the invention
In order to solve the problem, the object of the present invention is to provide that a kind of yield is high, cost is low, security is good, environmentally friendly, and be applicable to the preparation method of the oxime ester lightlike initiating agent of suitability for industrialized production.
In order to achieve the above object, the preparation method of light trigger oxime ester class provided by the invention comprises the following step carried out in order:
(1) using aryl thing as raw material, using halohydrocarbon as solvent, under the effect of Zr catalyst, carry out condensation with 4-chlorobutanoylchloride, temperature of reaction is-10 DEG C ~ 40 DEG C, adds acid and process after reaction terminates, and filter, crystallization, drying obtains intermediate one;
(2) using tetrahydrofuran (THF) as solvent, or tetrahydrofuran (THF) and water are as solvent, in presence of an acid, above-mentioned intermediate one reacted with nitrous acid ester at the temperature of 0 ~ 40 DEG C and makes crude product, finally crude product organic solvent making beating purifying being obtained intermediate two.
(3) using halohydrocarbon as solvent, under the existence of organic bases, react with Benzoyl chloride, temperature of reaction is at-10 ~ 40 DEG C, and after reaction terminates, washing, steaming desolventizes and obtains crude product.Crude product adds organic solvent recrystallization and obtains intermediate three.
(4) with saturated alcohol or tetrahydrofuran (THF) for solvent, react with morpholine and make crude product, organic solvent recrystallization obtains product.
Synthetic route of the present invention is as follows:
Following route can be not limited to the present invention as example of the present invention:
In described step (1), halohydrocarbon is at least one in methylene dichloride, chloroform, tetracol phenixin, 1,2-ethylene dichloride, chlorobenzene, and the amount ratio of halohydrocarbon and diphenyl sulfide is 2 ~ 20ml:1g.
In the described step (1) described in step (1), 4-chlorobutanoylchloride consumption is 1-5 times of diphenyl sulfide molar weight.
In described step (1), Zr catalyst consumption is 0.1-5 times of diphenyl sulfide molar weight.
Acid in described step (1) is selected from least one in hydrochloric acid, sulfuric acid, nitric acid, acetic acid or butyric acid, and the consumption of acid is 2-10 times of diphenyl sulfide molar weight.
The organic solvent that in described step (1), crystallization is used is selected from least one in methyl alcohol, ethanol, ethyl acetate, ether, toluene, isopropyl ether and methyl tertiary butyl ether.
In described step (2), nitrous acid ester is selected from least one in propyl nitrite, butyl nitrite, Isopentyl nitrite, and the consumption of nitrous acid ester is 1 ~ 5 times of intermediate one molar weight.
In described step (2), making beating organic solvent used is selected from least one in normal hexane, normal heptane, hexanaphthene, toluene, sherwood oil.
In described step (3), halohydrocarbon is at least one in methylene dichloride, chloroform, tetracol phenixin, 1,2-ethylene dichloride, chlorobenzene, and the amount ratio of halohydrocarbon and intermediate two is 2 ~ 20ml:1g.
At least one in organic bases dimethylamine in described step (3), diethylamine, triethylamine, pyridine, the consumption of organic bases is 1 ~ 5 times of intermediate two molar weight.
In described step (3), the consumption of Benzoyl chloride is 1 ~ 5 times of intermediate two molar weight.
In described step (3), recrystallization organic solvent is selected from least one in methyl alcohol, ethanol, propyl alcohol, ethyl acetate, ether, toluene, isopropyl ether and methyl tertiary butyl ether.
In described step (4), in saturated fatty alcohol ROH, R is the alkyl of carbonatoms 1 to 5, and the amount ratio of saturated fatty alcohol roh or tetrahydrofuran (THF) and intermediate three is 3 ~ 25ml: 1g.
In described step (4), the consumption of morpholine is 1.0-10 times of the molar weight of intermediate three.
In described step (4), crystallization organic solvent is selected from least one in methyl alcohol, ethanol, propyl alcohol, ethyl acetate, ether, toluene, isopropyl ether and methyl tertiary butyl ether.
The preparation method of light trigger oxime ester class provided by the invention is using diphenyl sulfide as raw material, under the effect of Zr catalyst, carry out condensation with 4-chlorobutanoylchloride obtain intermediate one, the latter's acid exists down and nitrous acid ester is obtained by reacting intermediate two, then under the existence of organic bases, react with Benzoyl chloride and obtain intermediate three, last and morpholine is obtained by reacting the finished product.Because the reaction times of this preparation method is short, reaction conditions is gentle, so security is good, and operating process is simple, and the product purity obtained is high, and does not use environmentally harmful solvent, and production cost is low, is therefore suitable for suitability for industrialized production.
Embodiment
Below in conjunction with specific embodiment, the preparation method to light trigger oxime ester class provided by the invention is described in detail.
Embodiment 1:
A. intermediate one
preparation
111.8g diphenyl sulfide (0.6mol), 1mol Zr catalyst and 600ml methylene dichloride is added in the four-hole bottle that electric mixer and thermometer are housed; pass into nitrogen protection; the temperature of this reaction solution is down to-5 ~ 0 DEG C; then drip 110.0g4-chlorobutanoylchloride (0.78mol) and the mixing solutions of the methylene dichloride of 150g, be warming up to 15 DEG C after dropwising and continue stirring 2 hours.After completion of the reaction, reaction solution is poured in the dilute sulphuric acid of 2000ml1mol/L, separate lower floor's organic phase.Aqueous phase 300ml dichloromethane extraction.Merge organic phase, wash once with 500ml saturated sodium bicarbonate solution, then wash three times to neutral with 500ml, add 200g anhydrous magnesium sulfate drying, steam methylene dichloride.Residual solid adds 500ml petroleum ether and stirring suction filtration, adds 500ml methyl alcohol in gained crude product, and crystallisation by cooling after backflow, obtain white solid intermediate one, dry to obtain product 157.0g, yield 90%, purity is greater than 98%.
B. intermediate two
preparation
93.0g intermediate one (0.32mol), 1000g tetrahydrofuran (THF), 500g concentrated hydrochloric acid and 59.4g butyl nitrite (0.58mol) is added, stirring at normal temperature 5 hours in the four-hole bottle that electric mixer and thermometer are housed.Add 2500ml water after completion of the reaction to stir, standing stay-over demixion, obtains clear yellow viscous liquid, and ethylene dichloride extracts, and adds 120g anhydrous magnesium sulfate drying.Suction filtration, steaming desolventizes, and obtains oily dope, pours in 400ml toluene and pulls an oar, suction filtration, obtains white solid powder shape diphenyl sulfide cyclopentyl acetoxime.Dry, obtain product 67.5g, yield 66%, purity is greater than 98%.
C. intermediate three
preparation
95.9g intermediate two (0.30mol), 1000ml methylene dichloride, 32.9g diethylamine (0.45mol) is added in the four-hole bottle that electric mixer and thermometer are housed, stir, be cooled to the mixing solutions that-5 DEG C start to drip 54.8g Benzoyl chloride (0.39mol) and 50g methylene dichloride.Dropwise rear continuation stirring 2 hours, drip 1500ml cold water, layering, once use 500ml saturated sodium bicarbonate solution, the hydrochloric acid of 500ml water, 1000ml0.5N, 500ml washing, use 300g anhydrous magnesium sulfate drying, suction filtration, filtrate steaming removal solvent, obtains viscous liquid.Add proper amount of methanol wherein, can separate out white solid intermediate three, filter, dry to obtain product 94.1g, yield 74%, purity is greater than 98%.
D. product
preparation
In the four-hole bottle that electric mixer and thermometer are housed, add 84.8g intermediate three (0.2mol), 850ml methyl alcohol, be stirred to entirely molten, drip 87.1g morpholine (1.0mol), continue to be stirred to reaction after dropwising complete.After decompression steams partial solvent, reaction solution is poured in 4000ml water, suction filtration, add ethanol in proper amount crystallization, dry, obtain 90.1g product, HPLC purity 98.6%, yield 95%.
Embodiment 2:
A.1-the preparation of diphenyl sulfide based-4-neoprene ketone
111.8g diphenyl sulfide (0.6mol), 2mol Zr catalyst and 500ml chloroform is added in the four-hole bottle that electric mixer and thermometer are housed; pass into nitrogen protection; the temperature of this reaction solution is down to 0 ~ 5 DEG C; then drip 126.9g4-chlorobutanoylchloride (0.9mol) and the mixing solutions of the chloroform of 200g, be warming up to 15 DEG C after dropwising and continue stirring 2 hours.After completion of the reaction, reaction solution is poured in the dilute hydrochloric acid of 2000ml2mol/L, separate lower floor's organic phase.Aqueous phase 300ml chloroform extraction.Merge organic phase, wash once with 500ml saturated sodium bicarbonate solution, then wash three times to neutral with 500ml, add 200g anhydrous magnesium sulfate drying, steam chloroform.Residual solid adds 500ml petroleum ether and stirring suction filtration, adds 500ml ethanol in gained crude product, and crystallisation by cooling after backflow, obtain white solid intermediate one, dry to obtain product 153.5g, yield 88%, purity is greater than 98%.
B.1-the preparation of diphenyl sulfide based-4-neoprene diketone-2-oxime
93.0g diphenyl sulfide cyclopentyl acetone (0.32mol), 1000g tetrahydrofuran (THF), 500g concentrated hydrochloric acid and 75.0g butyl nitrite (0.64mol) is added, stirring at normal temperature 5 hours in the four-hole bottle that electric mixer and thermometer are housed.Add 2500ml water after completion of the reaction to stir, standing stay-over demixion, obtains clear yellow viscous liquid, and ethylene dichloride extracts, and adds 120g anhydrous magnesium sulfate drying.Suction filtration, steaming desolventizes, and obtains oily dope, pours in 400ml normal hexane and pulls an oar, suction filtration, obtains white solid powder shape diphenyl sulfide cyclopentyl acetoxime.Dry, obtain product 72.7g, yield 71%, purity is greater than 98%.
C.1-the preparation of diphenyl sulfide based-4-neoprene diketone-2-oxime-O-ester
95.9g diphenyl sulfide cyclopentyl acetoxime (0.30mol), 1200ml chloroform, 39.5g triethylamine (0.39mol) is added in the four-hole bottle that electric mixer and thermometer are housed, stir, be cooled to the mixing solutions that 0 DEG C starts to drip 50.6g Benzoyl chloride (0.36mol) and 50g chloroform.Dropwise rear continuation stirring 2 hours, drip 1500ml cold water, layering, once use 500ml saturated sodium bicarbonate solution, the hydrochloric acid of 500ml water, 1000ml0.5N, 500ml washing, use 300g anhydrous magnesium sulfate drying, suction filtration, filtrate steaming removal solvent, obtains viscous liquid.Add ethanol in proper amount wherein, can separate out white solid 1-diphenyl sulfide-1-cyclopentyl third oxime ester class, filter, dry to obtain intermediate three 99.2g, yield 78%, purity is greater than 98%.
D. the preparation of product
In the four-hole bottle that electric mixer and thermometer are housed, add 42.4g intermediate three (0.1mol), 500ml ethanol, be stirred to entirely molten, drip 87.1g morpholine (1.0mol), continue to be stirred to reaction after dropwising complete.After decompression steams partial solvent, reaction solution is poured in 3000ml water, suction filtration, add appropriate ethyl acetate crystallization, dry, obtain 45.6g product, HPLC purity 99.0%, yield 96%.
Embodiment 3:
A. intermediate one
preparation
100.5gN-ethyl carbazole (0.51mol), 300ml methylene dichloride is added in the four-hole bottle that electric mixer and thermometer are housed, the temperature of this reaction solution is down to-10 ~ 0 DEG C, add 1mol Zr catalyst, then drip 102.0g o-methyl-benzene formyl chloride (0.66mol) and the mixing solutions of 100ml methylene dichloride, dropwise rear insulated and stirred 1 hour.Add 74.5g chloroacetyl chloride (0.66mol) and the mixing solutions of 50ml methylene dichloride afterwards, continue stirring reaction 30 minutes.After completion of the reaction, reaction solution is poured in the dilute hydrochloric acid of 1500ml1mol/L, stir separatory after 1 hour, wash with water to neutrality.Decompression steams solvent, and add the making beating of 1000ml ethanol, suction filtration, it is 98.0% that drying obtains 165.0g intermediate one, HPLC purity, and yield is 83%.
B. intermediate two
preparation
25.0g oxammonium hydrochloride (0.36mol), 47.1g Potassium ethanoate (0.48mol), 300ml water is added in the four-hole bottle that electric mixer and thermometer are housed, be stirred to and dissolve completely, add 1200ml ethanol again, 93.6g intermediate one (0.24mol), reflux is to reacting complete.Poured into by reaction solution in 4000ml cold water, suction filtration, solid adds the making beating of 300ml ethanol, suction filtration, and dry, obtain 87.4g1-(6-o-methyl-benzene formyl radical-N-ethyl carbazole-3-base)-acetophenone oxime, HPLC purity is 98.2%, and yield is 90%.
C. intermediate three
preparation
81.0g intermediate two (0.2mol) is added in the four-hole bottle that electric mixer and thermometer are housed, 1000ml tetrahydrofuran (THF), be stirred to entirely molten, drip the dimethylamine agueous solution (2.0mol) of 300g30%, continue to be stirred to reaction after dropwising complete.After decompression steams partial solvent, reaction solution is poured in 5000ml water, suction filtration, dry, obtain 78.6g intermediate three, HPLC purity 98.0%, yield 95%.
D. product
preparation
300ml methylene dichloride is added in the four-hole bottle that electric mixer, thermometer, water trap are housed, 95.1g intermediate three (0.23mol), 27.6g acetic acid (0.46mol) and 21.3g boric acid (0.34mol), reflux water-dividing, after completion of the reaction, successively with sodium hydrogen carbonate solution, be washed to neutrality, add anhydrous sodium sulfate drying, filter.Filtrate steams solvent, and gained semisolid adds the crystallization of 150ml ethyl acetate and obtains 74.4g white solid product, and HPLC purity is 98.6%, and yield is 71%.
Claims (9)
1. an oxime ester lightlike initiating agent, its chemical structure is:
Wherein R
1structure is
wherein n is the integer of 0 ~ 5, and m is the integer of 1 ~ 6, R
2for methyl, phenyl, substituted-phenyl, benzyl or substituted benzyl, R
3for diphenyl sulfide group, substituted diphenyl sulfide group, carbazole group or substituted carbazole group, Y is the one in carbon, nitrogen, oxygen, sulphur.
2. an oxime ester lightlike initiating agent preparation method, is characterized in that: comprise the following step carried out in order:
(1) with diphenyl sulfide, substituted diphenyl sulfide, carbazole or substituted carbazole for raw material, using halohydrocarbon as solvent, condensation is carried out with halogen acyl halide under the effect of Zr catalyst, temperature of reaction is-10 DEG C ~ 40 DEG C, add acid after reaction terminates to process, filter, crystallization, drying obtains intermediate one
(2) using tetrahydrofuran (THF) as solvent, or tetrahydrofuran (THF) and water are as solvent, in presence of an acid, above-mentioned intermediate one reacted with nitrous acid ester at the temperature of 0 ~ 40 DEG C and makes crude product, finally crude product organic solvent making beating purifying being obtained intermediate two
(3) using halohydrocarbon as solvent, under the existence of organic bases, react with Benzoyl chloride, temperature of reaction is at-10 ~ 40 DEG C, and after reaction terminates, washing, steaming desolventizes and obtains crude product.Crude product adds organic solvent recrystallization and obtains intermediate three
(4) using saturated fatty alcohol roh or tetrahydrofuran (THF) as solvent, reacted with nitrogenous compound at 0 ~ 150 DEG C and make crude product by above-mentioned intermediate two, organic solvent recrystallization obtains product
3. a kind of oxime ester lightlike initiating agent preparation method according to claim 2, is characterized in that: in described step (1), halohydrocarbon is methylene dichloride, chloroform, tetracol phenixin, 1,2-ethylene dichloride, at least one in chlorobenzene, said halohydrocarbon and diphenyl sulfide, substituted diphenyl sulfide, the amount ratio of carbazole or substituted carbazole is 2 ~ 20ml:1g, and preferably, in described step (1), halogen acyl halide consumption is diphenyl sulfide, substituted diphenyl sulfide, doubly, preferably, in described step (1), Zr catalyst consumption is diphenyl sulfide to the 1-5 of carbazole or substituted carbazole molar weight, substituted diphenyl sulfide, doubly, preferably, the acid in described step (1) is selected from hydrochloric acid to the 0.1-5 of carbazole or substituted carbazole molar weight, sulfuric acid, nitric acid, at least one in acetic acid or butyric acid, the consumption of acid is diphenyl sulfide, substituted diphenyl sulfide, doubly, preferably, the organic solvent that in described step (1), crystallization is used is selected from methyl alcohol to the 2-10 of carbazole or substituted carbazole molar weight, ethanol, ethyl acetate, ether, toluene, at least one in isopropyl ether and methyl tertiary butyl ether.
4. a kind of oxime ester lightlike initiating agent preparation method according to claim 2, it is characterized in that: in described step (2), nitrous acid ester is selected from least one in propyl nitrite, butyl nitrite, Isopentyl nitrite, the consumption of nitrous acid ester is that 1 ~ 5 times of intermediate one molar weight is preferred, and in described step (2), making beating organic solvent used is selected from least one in normal hexane, normal heptane, hexanaphthene, toluene, sherwood oil.
5. a kind of oxime ester lightlike initiating agent preparation method according to claim 2, it is characterized in that: in described step (3), halohydrocarbon is methylene dichloride, chloroform, tetracol phenixin, 1, at least one in 2-ethylene dichloride, chlorobenzene, the amount ratio of halohydrocarbon and intermediate two is 2 ~ 20ml:1g.
6. a kind of oxime ester lightlike initiating agent preparation method according to claim 2, it is characterized in that: the organic bases dimethylamine in described step (3), diethylamine, triethylamine, at least one in pyridine, the consumption of organic bases is 1 ~ 5 times of intermediate two molar weight, preferably, in described step (3), the consumption of Benzoyl chloride is 1 ~ 5 times of intermediate two molar weight, preferably, in described step (3), recrystallization organic solvent is selected from methyl alcohol, ethanol, propyl alcohol, ethyl acetate, ether, toluene, at least one in isopropyl ether and methyl tertiary butyl ether.
7. a kind of oxime ester lightlike initiating agent preparation method according to claim 2, it is characterized in that: in described step (4), in saturated fatty alcohol ROH, R is the alkyl of carbonatoms 1 to 5, and the amount ratio of saturated fatty alcohol roh or tetrahydrofuran (THF) and intermediate three is 3 ~ 25ml: 1g.
8. a kind of oxime ester lightlike initiating agent preparation method according to claim 2, is characterized in that: in described step (4), the consumption of nitrogenous compound is 1.0-10 times of the molar weight of intermediate three.
9. a kind of oxime ester lightlike initiating agent preparation method according to claim 2, is characterized in that: in described step (4), crystallization organic solvent is selected from least one in methyl alcohol, ethanol, propyl alcohol, ethyl acetate, ether, toluene, isopropyl ether and methyl tertiary butyl ether.
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| CN109666088A (en) * | 2017-10-16 | 2019-04-23 | 北京英力科技发展有限公司 | A kind of diketone oxime ester compound and its manufacturing method and application |
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