CN105646578B - A kind of light trigger is double（2,4,6 trimethylbenzoyls）The preparation method of phenyl phosphine oxide - Google Patents
A kind of light trigger is double（2,4,6 trimethylbenzoyls）The preparation method of phenyl phosphine oxide Download PDFInfo
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- CN105646578B CN105646578B CN201610148918.XA CN201610148918A CN105646578B CN 105646578 B CN105646578 B CN 105646578B CN 201610148918 A CN201610148918 A CN 201610148918A CN 105646578 B CN105646578 B CN 105646578B
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- WKGDNXBDNLZSKC-UHFFFAOYSA-N oxido(phenyl)phosphanium Chemical compound O=[PH2]c1ccccc1 WKGDNXBDNLZSKC-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 claims abstract description 18
- -1 trimethylbenzene acyl chloride Chemical class 0.000 claims abstract description 17
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052786 argon Inorganic materials 0.000 claims abstract description 7
- 239000007789 gas Substances 0.000 claims abstract description 7
- VZEGPPPCKHRYGO-UHFFFAOYSA-N diethoxyphosphorylbenzene Chemical compound CCOP(=O)(OCC)C1=CC=CC=C1 VZEGPPPCKHRYGO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 69
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 11
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical class [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 10
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 8
- 239000012074 organic phase Substances 0.000 claims description 7
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-Me3C6H3 Natural products CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 238000001953 recrystallisation Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- SCHRRICRQNJJKN-UHFFFAOYSA-N P.[O] Chemical compound P.[O] SCHRRICRQNJJKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000013517 stratification Methods 0.000 claims description 2
- 238000005292 vacuum distillation Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 15
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 9
- 229910052708 sodium Inorganic materials 0.000 abstract description 9
- 239000011734 sodium Substances 0.000 abstract description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 abstract description 6
- 230000003647 oxidation Effects 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 5
- 229910052700 potassium Inorganic materials 0.000 abstract description 5
- 239000011591 potassium Substances 0.000 abstract description 5
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- FYGHSUNMUKGBRK-UHFFFAOYSA-N trimethylbenzene Natural products CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 abstract 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- SXNICUVVDOTUPD-UHFFFAOYSA-N CC1=CC(C)=CC(C)=C1C(=O)P(=O)C1=CC=CC=C1 Chemical class CC1=CC(C)=CC(C)=C1C(=O)P(=O)C1=CC=CC=C1 SXNICUVVDOTUPD-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- IBDMRHDXAQZJAP-UHFFFAOYSA-N dichlorophosphorylbenzene Chemical compound ClP(Cl)(=O)C1=CC=CC=C1 IBDMRHDXAQZJAP-UHFFFAOYSA-N 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 150000001263 acyl chlorides Chemical class 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- IMDXZWRLUZPMDH-UHFFFAOYSA-N dichlorophenylphosphine Chemical compound ClP(Cl)C1=CC=CC=C1 IMDXZWRLUZPMDH-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-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
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 238000006136 alcoholysis reaction Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 150000003003 phosphines Chemical class 0.000 description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- HIKRJHFHGKZKRI-UHFFFAOYSA-N 2,4,6-trimethylbenzaldehyde Chemical class CC1=CC(C)=C(C=O)C(C)=C1 HIKRJHFHGKZKRI-UHFFFAOYSA-N 0.000 description 1
- ICSNLGPSRYBMBD-UHFFFAOYSA-N 2-aminopyridine Chemical compound NC1=CC=CC=N1 ICSNLGPSRYBMBD-UHFFFAOYSA-N 0.000 description 1
- PEJJTUMTZBUFGS-UHFFFAOYSA-N C1(=CC=CC=C1)P.[Na] Chemical compound C1(=CC=CC=C1)P.[Na] PEJJTUMTZBUFGS-UHFFFAOYSA-N 0.000 description 1
- XVZXOLOFWKSDSR-UHFFFAOYSA-N Cc1cc(C)c([C]=O)c(C)c1 Chemical group Cc1cc(C)c([C]=O)c(C)c1 XVZXOLOFWKSDSR-UHFFFAOYSA-N 0.000 description 1
- 206010019233 Headaches Diseases 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 206010028813 Nausea Diseases 0.000 description 1
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N acetaldehyde dimethyl acetal Natural products COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 231100000869 headache Toxicity 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- PDZGAEAUKGKKDE-UHFFFAOYSA-N lithium;naphthalene Chemical compound [Li].C1=CC=CC2=CC=CC=C21 PDZGAEAUKGKKDE-UHFFFAOYSA-N 0.000 description 1
- ZGEZPSPEVXDOMG-UHFFFAOYSA-N lithium;phosphane Chemical class [Li].P ZGEZPSPEVXDOMG-UHFFFAOYSA-N 0.000 description 1
- 230000008693 nausea Effects 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- XDNIBIHCBXESNN-UHFFFAOYSA-N phosphane;toluene Chemical compound P.CC1=CC=CC=C1 XDNIBIHCBXESNN-UHFFFAOYSA-N 0.000 description 1
- 125000001476 phosphono group Chemical group [H]OP(*)(=O)O[H] 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
- C07F9/5337—Phosphine oxides or thioxides containing the structure -C(=X)-P(=X) or NC-P(=X) (X = O, S, Se)
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Abstract
The invention discloses a kind of light trigger double (2; 4; 6 trimethylbenzoyls) phenyl phosphine oxide preparation method; phenyl-phosphonic acid diethylester reaction generation Phenylphosphine at a temperature of 60 DEG C 70 DEG C, in argon gas with excessive red aluminum solution; Phenylphosphine and 2; 4; 6 trimethylbenzene acyl chloride reactions obtain 2,4,6 trimethylbenzoyldiphenyl toluene solutions; without separation; 2,4,6 trimethylbenzoyldiphenyls are by hydrogen peroxide oxidation into 2 pairs (2; 4,6 trimethylbenzoyls) phenyl phosphine oxide.The technique does not use the metallic sodium or potassium of danger, and technique is advanced, simple to operate, safe, and product yield is high, quality better, easily large-scale production.
Description
Technical field
The present invention relates to a kind of double (2,4, the 6- trimethylbenzoyl) phenyl phosphine oxides of light trigger, and in particular to phenyl
Diethyl phosphonate and the red aluminum solution of excess react at a temperature of 70 DEG C~80 DEG C, in inert gas, after the completion of reaction, remove
The red aluminum of amount obtains the toluene solution of Phenylphosphine；It is anti-with 2,4,6- tri-methyl chlorides in the presence of alkali compounds again
Should, obtained intermediate obtains double (2,4,6- trimethylbenzoyl) phenyl phosphine oxides, belonging to by hydrogen peroxide oxidation again
Work synthesizes field.
Background technology
Double (2,4,6- trimethylbenzoyl) phenyl phosphine oxides are double acyl group oxides, and the light trigger produces after decomposing
Four activated centres of two benzoyl free radicals and a phosphono diradical, its photochemical speed is fast, because in coating, oil
The fields such as ink, adhesive, resist, welding compound obtain extensive use, therefore develop a kind of advanced technique, reaction safety, production
The preparation method of easily controllable (2,4,6- trimethylbenzoyls) phenyl phosphine oxide of process is very necessary.
It is the method for several production (2,4,6- trimethylbenzoyls) phenyl phosphine oxides improved in recent years below：
1, using phenylphosphonic dichloride as initiation material, react to form phosphine lithium salts intermediate with lithium under the catalysis of naphthalene lithium, then with
Acyl chloride reaction, last oxidized and obtain (2,4,6- trimethylbenzoyl) phenyl phosphine oxide (WO 00/32612), this method is anti-
Answer condition harsh, be not suitable for industrialized production.
2, with tertiary amine (such as triethylamine) for acid binding agent, aryl phosphine directly with after acyl chloride reaction, it is then oxidized and obtain (2,4,6-
Trimethylbenzoyl) phenyl phosphine oxide (US 4,737,593), this method reaction selectivity is poor, and impurity is more, and yield is low (general
Below 40%), be not suitable for industrialized production.
3, it is oxidized again after aryl phosphine and acyl chloride reaction to obtain double (2,4,6- trimethylbenzenes in the presence of active lithium reagent
Formoxyl) phenyl phosphine oxide (US 6,020,528, US 5,723,512), lithium metal is expensive, it is difficult to realizes industrialization.
4, phenylphosphonic dichloride obtains benzene with lithium metal, sodium or nak response in a solvent, in the presence of catalyst (activator)
Base phosphine metal compound, then with 2, the reaction of 4,6- tri-methyl chlorides, obtain intermediate, object is obtained by hydrogen peroxide oxidation
(CN99813713.8, CN200480022027.5), because phenylphosphonic dichloride is easy during the course of the reaction with lithium metal, sodium or potassium
Form the poly- phosphine compound of ring and cannot get independent Phenylphosphine sodium, so yield is relatively low, and fire has occurred using potassium, sodium.
5, after phenylphosphonic dichloride and metallic sodium or nak response, add the tert-butyl alcohol and protonated, then again with 2,
4,6- tri-methyl chlorides are reacted, and double (2,4,6- trimethylbenzoyl) phenyl phosphine oxides are obtained by hydrogen peroxide oxidation
(CN200480020599.X), this method needs to use extremely active metallic sodium or potassium, will to consersion unit and each raw material
Ask higher, the security of course of reaction is relatively low, and easily initiation fire, the yield of the technique are also relatively low in alcoholysis or hydrolytic process.
6, phenylphosphonic dichloride and organic solvent are added in the reactor, under nitrogen protection, agitation and dropping water inlet ,-
Hydrolysis two hours in 10-100 DEG C of temperature range, generation Phenylphosphine and byproduct phenyl-phosphonic acid, the Phenylphosphine 2,4 of generation,
6- trimethylbenzenes acyl chlorides is raw material, sends out double (2,4, the 6- trimethylbenzoyl) Phenylphosphines of class reaction generation under nitrogen protection,
Again double (2,4,6- trimethylbenzoyls) phenyl phosphine oxides (CN102942593 B) of object are obtained through hydrogen peroxide oxidation.The party
It is more difficult that method isolates Phenylphosphine, phenyl-phosphonic acid.
7, in toluene, Phenylphosphine that sodium is prepared with dichlorophenyl phosphine reaction under nitrogen protection, then with hydrogen peroxide
Phenyl phosphine oxide is made, phenyl phosphine oxide, 2,4,6- trimethylbenzaldehydes are raw material, in the presence of a catalyst, are aoxidized with phenyl
Phosphine condensation reaction, then through peroxidization (CN103980310 B).But this method need use extremely active metallic sodium or
Potassium, higher to consersion unit and each ingredient requirement, the security of course of reaction is relatively low, easily triggers fire in alcoholysis or hydrolytic process
Calamity, yield are also relatively low.
The content of the invention
It is an object of the invention to provide one kind that a kind of raw material process is advanced, reaction safety, course of reaction is easily controllable
The preparation method of double (2,4,6- trimethylbenzoyls) phenyl phosphine oxides of light trigger.
To reach above-mentioned purpose, the technical solution adopted by the present invention is：A kind of double (the 2,4,6- trimethylbenzene first of light trigger
Acyl group) phenyl phosphine oxide preparation technology, comprise the following steps that：
A. under argon gas protection, into the reactor equipped with organic solvent, red aluminum solution is added, is dripped after being cooled to 0-5 DEG C
Add phenyl-phosphonic acid diethylester, after dripping, be warming up to 60-80 DEG C of reaction 10-12 hour, obtain containing excessive red aluminum solution, phenyl
The organic solution of phosphine, distillation obtain the organic solution containing Phenylphosphine；
In the step, phenyl-phosphonic acid diethylester, the ratio between the amount of material of red aluminum are 1:2-5.
Described organic solvent is any of benzene, toluene or dimethylbenzene, preferably toluene.
B. under argon gas protection, by alkali compounds dissolving in organic solvent, be added dropwise that step A obtains containing Phenylphosphine
Organic solvent, 40-60 DEG C is warming up to after dripping, room temperature is down to after reacting 2-3h, then be added dropwise 2,4,6- trimethylbenzene acyl chlorides, risen
Temperature reacts 3-5h, after the completion of reaction, adds hydrochloric acid solution washing, stand to 50~80 DEG C (preferable reaction temperature is 60-65 DEG C)
Separate organic phase, as 2, the big toluene solution crude product of 4,6- trimethylbenzoy-dipheny phosphines；
Organic solvent described in the step is any of benzene, toluene or dimethylbenzene, preferably toluene, and described is organic
Alkali is any of sodium tert-butoxide, caustic alcohol, sodium methoxide, triethylamine, DMA, pyridine, is more preferably
Sodium tert-butoxide.
C. without separation, the big toluene solution crude product temperature of 2,4,6- trimethylbenzoy-dipheny phosphines is down to 25
Below DEG C, it is 30% hydrogen peroxide that mass concentration, which is slowly added dropwise, controls temperature in reactor to react 2-8h at 20-80 DEG C, reaction is completed
Afterwards, the NaHSO that mass concentration is 5% is added3Solution is washed, and standing separates organic phase, and organic phase uses aqueous slkali, water washing with this,
Vacuum distillation recovered solvent toluene obtains crude product, and double (2,4,6- trimethylbenzoyl) phenyl phosphine oxides are obtained with solvent recrystallization；
In the step, described recrystallization solvent is that any of n-hexane, normal heptane, petroleum ether (are preferably positive heptan
Alkane)；Described aqueous slkali is that any of sodium hydroxide solution, sodium bicarbonate solution, sodium carbonate liquor (are preferably hydroxide
Sodium solution).
Double (2,4,6- trimethylbenzoyl) phenyl phosphine oxides provided by the invention are prepared compared with prior art, are had
Advantages below：
1, phenyl dichloro phosphorus is replaced using phenyl-phosphonic acid diethylester, because phenyl dichloro phosphorus has combustibility, meets moisture
Toxic chlorinated hydrogen is solved, also with offending stink, suction people, which knows from experience, to be made one to feel headache, nausea.
2, double (2,4,6- trimethylbenzoyl) the phosphine oxide preparation methods of phenyl provided by the invention, use red aluminum solution
Instead of lithium aluminium hydride reduction, diethyl phosphonate is reduced into Phenylphosphine, and without using active metallic sodium or potassium, therefore course of reaction is not easy
Ignition calamity.
3, good reaction selectivity, product yield is high, environment-friendly；Significantly improve double (2,4,6- trimethylbenzoyls)
Phenyl phosphine oxide, yield reach more than 90%, and purity reaches 99.3%, are adapted to large-scale production.
Embodiment
The essence of the present invention is explained further with reference to specific embodiment.
Embodiment 1
A. under argon gas protection, 10.0L toluene and 9.6L (34.5mol) red aluminum solution, drop are added in 50L reactor
Diethyl phosphonate 2.46Kg (11.45mol) is added dropwise to 0-5 DEG C in temperature, keeps system temperature at 0-5 DEG C, after being added dropwise, heating
To 70-80 DEG C of 10-12h of heating, reaction finishes, and obtains the toluene solution containing excessive red aluminum, Phenylphosphine, and distillation obtains containing Phenylphosphine
The toluene solution 10.1L of (11.40mol).
B. under argon gas protection, take 2.22Kg sodium tert-butoxides (23.0mol) to be dispersed in 5L toluene, be added to 50L
Reactor in, the anhydrous toluene solution of Phenylphosphine made from step A is slowly added dropwise, drop finishes, and is warming up to 50 DEG C of reaction 2-3h, drop
To room temperature, 2,4,6- trimethylbenzene acyl chlorides 4.20Kg (23.0mol) are added dropwise, about 2-3h is dripped off, and interior temperature is no more than 65 DEG C, after dripping off
Dropping tank is cleaned with 1-2L toluene, and is put into reactor.60~65 DEG C of reacting liquid temperature is controlled, after being added dropwise to complete, is continued anti-
Should about 3-5h.After the completion of reaction, the hydrochloric acid solution for adding 6.5L5% is washed, and is stirred 1-2h, stratification, is obtained organic phase, as 2,
4,6- trimethylbenzoy-dipheny phosphine toluene solutions.Without separation, reactor reacting liquid temperature is down to less than 25 DEG C,
30% hydrogen peroxide 3.25kg is slowly added dropwise, about 1-3h is dripped off, and controls temperature in reactor to react 2-4h at 45~55 DEG C, reaction is completed
Afterwards, 5% NaHSO is added3Solution is washed, and standing separates organic phase, is respectively washed twice with 2% sodium hydroxide, water successively, and decompression is steamed
Recycling design toluene is evaporated, normal heptane recrystallization is added, obtains 2,4,6- trimethylbenzoy-dipheny phosphine oxygen, it is light yellow solid
Body, content 99.3%, yield 92.3%.
Embodiment 2：
Organic base sodium tert-butoxide changes sodium methoxide, other same examples one, its target compound yield 87.2% into.
Embodiment 3：
Organic base sodium tert-butoxide changes caustic alcohol, other same examples one, its target compound yield 86.4% into.
Embodiment 4：
Organic base sodium tert-butoxide changes triethylamine, other same examples one, its target compound yield 42.3% into.
Embodiment 5：
Organic base sodium tert-butoxide changes DMA, other same examples one, its target compound yield 52.6% into.
Embodiment 6：
Organic base sodium tert-butoxide changes pyridine amine, other same examples one, its target compound yield 60.2% into.
Claims (1)
1. a kind of light trigger is double（2,4,6- trimethylbenzoyls）The preparation method of phenyl phosphine oxide, it is characterised in that the system
Preparation Method comprises the following steps：
A. under argon gas protection, 10.0L toluene and 9.6L red aluminum solution are added in 50L reactor, is cooled to 0-5 DEG C, drop
Add phenyl-phosphonic acid diethylester 2.46Kg, keep system temperature at 0-5 DEG C, after being added dropwise, be warming up to 70-80 DEG C of reaction of heating
10-12h, reaction finish, and obtain the toluene solution containing excessive red aluminum, Phenylphosphine, and distillation obtains the toluene solution containing Phenylphosphine
10.1L；
B. under argon gas protection, take 2.22Kg sodium tert-butoxides to be dispersed in 5L toluene, be added in 50L reactor, delay
Slow that the toluene solution containing Phenylphosphine made from step A is added dropwise, drop finishes, and is warming up to 50 DEG C of reaction 2-3h, is down to room temperature, is added dropwise 2,4,
6- trimethylbenzene acyl chlorides 4.20Kg, 2-3h are dripped off, and interior temperature is no more than 65 DEG C, cleans dropping tank with 1-2L toluene after dripping off, and put
Enter in reactor；60~65 DEG C of reacting liquid temperature is controlled, after being added dropwise to complete, continues to react 3-5h；After the completion of reaction, 6.5L is added
5% hydrochloric acid solution is washed, and is stirred 1-2h, stratification, is obtained organic phase, as 2,4,6- trimethylbenzoy-dipheny phosphine first
Benzole soln；Without separation, reactor reacting liquid temperature is down to less than 25 DEG C, 30% hydrogen peroxide 3.25kg, 1-3h drop is slowly added dropwise
It is complete, control temperature in reactor to react 2-4h at 45~55 DEG C, after the completion of reaction, add 5% NaHSO3Solution is washed, and standing separates
Organic phase, respectively washed twice with 2% sodium hydroxide, water successively, vacuum distillation recovered solvent toluene, add normal heptane recrystallization,
Obtain 2,4,6- trimethylbenzoy-dipheny phosphine oxygen, light yellow solid, content 99.3%, yield 92.3%.
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| CN111087425B (en) * | 2020-01-10 | 2022-04-19 | 天津大学 | Large-particle-size phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide crystal form and crystallization method thereof |
| CN112159429B (en) * | 2020-10-29 | 2022-06-21 | 天津久日新材料股份有限公司 | Preparation method of bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide |
| CN112538093B (en) * | 2020-12-18 | 2022-07-22 | 河南荣峰光电科技有限公司 | Preparation method of photoinitiator |
| CN112547122A (en) * | 2020-12-18 | 2021-03-26 | 商河知济新材料技术中心 | Use of tert-butoxide and pyridinium salts in the preparation of a photoinitiator |
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| CN104558031A (en) * | 2014-12-09 | 2015-04-29 | 天津久联科技有限公司 | Preparation method of phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide |
| CN105131036A (en) * | 2015-07-24 | 2015-12-09 | 张家港吉慕特化工科技有限公司 | Preparation process of photo-initiator bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide |
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| CN104558031A (en) * | 2014-12-09 | 2015-04-29 | 天津久联科技有限公司 | Preparation method of phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide |
| CN105131036A (en) * | 2015-07-24 | 2015-12-09 | 张家港吉慕特化工科技有限公司 | Preparation process of photo-initiator bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide |
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