CA2030179A1 - Process for the preparation of pure cyclic phosphoric acid diaryl esters - Google Patents
Process for the preparation of pure cyclic phosphoric acid diaryl estersInfo
- Publication number
- CA2030179A1 CA2030179A1 CA 2030179 CA2030179A CA2030179A1 CA 2030179 A1 CA2030179 A1 CA 2030179A1 CA 2030179 CA2030179 CA 2030179 CA 2030179 A CA2030179 A CA 2030179A CA 2030179 A1 CA2030179 A1 CA 2030179A1
- Authority
- CA
- Canada
- Prior art keywords
- pohal3
- glacial acetic
- phosphoric acid
- acetic acid
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 238000000034 method Methods 0.000 title claims abstract description 22
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910000147 aluminium phosphate Inorganic materials 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229960000583 acetic acid Drugs 0.000 claims abstract description 22
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 20
- 229910001868 water Inorganic materials 0.000 claims abstract description 14
- 239000011541 reaction mixture Substances 0.000 claims abstract description 11
- 239000013078 crystal Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 22
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 16
- -1 cyclic phos-phonic acid diaryl ester Chemical class 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 125000004122 cyclic group Chemical group 0.000 claims description 9
- 229910019213 POCl3 Inorganic materials 0.000 claims description 8
- IMHDGJOMLMDPJN-UHFFFAOYSA-N biphenyl-2,2'-diol Chemical group OC1=CC=CC=C1C1=CC=CC=C1O IMHDGJOMLMDPJN-UHFFFAOYSA-N 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 229910019201 POBr3 Inorganic materials 0.000 claims description 3
- UXCDUFKZSUBXGM-UHFFFAOYSA-N phosphoric tribromide Chemical compound BrP(Br)(Br)=O UXCDUFKZSUBXGM-UHFFFAOYSA-N 0.000 claims description 3
- 125000001118 alkylidene group Chemical group 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 150000005840 aryl radicals Chemical class 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 238000007865 diluting Methods 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 229910001510 metal chloride Inorganic materials 0.000 claims description 2
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- ZMBHCYHQLYEYDV-UHFFFAOYSA-N trioctylphosphine oxide Chemical compound CCCCCCCCP(=O)(CCCCCCCC)CCCCCCCC ZMBHCYHQLYEYDV-UHFFFAOYSA-N 0.000 claims description 2
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 claims description 2
- 150000002903 organophosphorus compounds Chemical class 0.000 claims 1
- 229940116254 phosphonic acid Drugs 0.000 claims 1
- 239000002253 acid Substances 0.000 description 9
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- PPTXVXKCQZKFBN-UHFFFAOYSA-N (S)-(-)-1,1'-Bi-2-naphthol Chemical group C1=CC=C2C(C3=C4C=CC=CC4=CC=C3O)=C(O)C=CC2=C1 PPTXVXKCQZKFBN-UHFFFAOYSA-N 0.000 description 4
- RMRHEPZUTYXELS-UHFFFAOYSA-N 6-hydroxybenzo[d][1,3,2]benzodioxaphosphepine 6-oxide Chemical compound O1P(O)(=O)OC2=CC=CC=C2C2=CC=CC=C21 RMRHEPZUTYXELS-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 2
- 238000004679 31P NMR spectroscopy Methods 0.000 description 2
- OSPXRUHPRVZMJN-UHFFFAOYSA-N 6-chlorobenzo[d][1,3,2]benzodioxaphosphepine 6-oxide Chemical compound O1P(Cl)(=O)OC2=CC=CC=C2C2=CC=CC=C21 OSPXRUHPRVZMJN-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- MDNWOSOZYLHTCG-UHFFFAOYSA-N Dichlorophen Chemical compound OC1=CC=C(Cl)C=C1CC1=CC(Cl)=CC=C1O MDNWOSOZYLHTCG-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-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
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- LRDIEHDJWYRVPT-UHFFFAOYSA-N 4-amino-5-hydroxynaphthalene-1-sulfonic acid Chemical compound C1=CC(O)=C2C(N)=CC=C(S(O)(=O)=O)C2=C1 LRDIEHDJWYRVPT-UHFFFAOYSA-N 0.000 description 1
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- FQUNFJULCYSSOP-UHFFFAOYSA-N bisoctrizole Chemical compound N1=C2C=CC=CC2=NN1C1=CC(C(C)(C)CC(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2N=C3C=CC=CC3=N2)O)=C1O FQUNFJULCYSSOP-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000005406 washing 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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65744—Esters of oxyacids of phosphorus condensed with carbocyclic or heterocyclic rings or ring systems
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
Abstract of the disclosure:
Process for the preparation of pure cyclic phosphoric acid diaryl esters To prepare pure cyclic phosphoric acid diaryl esters from POHal3 and a bis-phenol derivative or a dihydroxy-dinaphthyl derivative, POHal3 is employed in a stoichio-metric excess of 0 to 500 mol% and the reaction is carried out in the presence of a catalyst at temperatures from 50 to 180°C over a period of 1 to 24 hours. After the reaction, excess POHal3 is removed and the reaction mixture is diluted with 0.1 to 10 g of glacial acetic acid per g. The reaction mixture diluted with glacial acetic acid is hydrolyzed with 1 to 4 moles of water, calculated on the number of moles of POHal3 reacted, and the cyclic phosphoric acid diaryl esters deposited in the form of crystals are filtered off.
Process for the preparation of pure cyclic phosphoric acid diaryl esters To prepare pure cyclic phosphoric acid diaryl esters from POHal3 and a bis-phenol derivative or a dihydroxy-dinaphthyl derivative, POHal3 is employed in a stoichio-metric excess of 0 to 500 mol% and the reaction is carried out in the presence of a catalyst at temperatures from 50 to 180°C over a period of 1 to 24 hours. After the reaction, excess POHal3 is removed and the reaction mixture is diluted with 0.1 to 10 g of glacial acetic acid per g. The reaction mixture diluted with glacial acetic acid is hydrolyzed with 1 to 4 moles of water, calculated on the number of moles of POHal3 reacted, and the cyclic phosphoric acid diaryl esters deposited in the form of crystals are filtered off.
Description
2 ~
Process for the preparation of pure cyclic phosphoric acid diaryl e~ter~
The present invention xelates to a process for the -_ preparation of pure cyclic phosphoric acid diaryl esters.
S Cyclic phosphoric acid diaryl esters are being incor-porated to an increasing extent into plastics as stabilizers and additives for improving the clarity of thermoplastics and into photographic ystems as color stabilizers.
The cyclic phosphoric acid diaryl esters used for this purpose must be employed in a pure, colorless state.
...
According to DE-C-2,212,660 or EP-s-68,326, cyclic binaphthyl-phosphoric acid esters or bisphenol-phosphoric acid esters can be prepared by the action of POC13 on the corresponding binaphthyl-Z,2'-diols or bisphenyl-2,2'-diols in the presence of basic substances, in particular pyridine, in stoichiometric amounts as an acid-binding agent. The cyclic phosphoric acid diaryl ester is then isolated in the pure form by further purification steps.
. ' .
A disadvantage here i8 the large amount of acid-binding agents to be employed, which leads to undesirable ef-fluents during reprocessing.
,' ' The ob~ect was therefore to provide a process for the preparation of pure cyclic phosphoric acid diaryl esters which operates with high yield~ and in a simple, eco-nomical manner and with which no undesirable effluents b are obtained.
A ~imple process has now been found for the preparation . of pure cyclic phosphoric acid diaryl esters from POHal3 and a bis-phenol derivative of the formula I
-- .
,~
: .~.
' ,.: , ' , .', , .. ., , .' , ':.. ' .; .''~ . -: . . .- : : -,. :.
-:: .: . - - ;
: . , : : -,~:...... , . ~ .
~, .
,.:
., .
2 ~ . 7S,3.
-- 2 _ Rl R~H
~ H
; in which Rl to R4 can be alkyl having 1 to 18 carbon atoms, an aryl radical having 6 to 10 carbon atom~, arylalkyl having 1 to 3 carbon atom~ in the chain, halogen or H, and in which A is a direct C-C bond or an alkylidene group of the formula . I
. R, - C - R_ o in which R5 and R~ can be alkyl having 1 to 12 carbon atoms, an optionally substituted cyclic sys~em having a total of 5 to 12 carbon atoms or H, or from a dihydroxy-dinaphthyl derivative of the formula II
l2 ll R ~ 3H
¦ II
. R
' . in which R~ to R4, R7 and R3 can be alkyl having 1 to 18 carbon atoms, halogen or H, which comprises a) employing POHal3 in a stoichiometric excess of O to . 500 mol~, :
b) carrying out the reaction in the presence of a ~. ' .
: .: , . .
- ,.~ . . ~ . , :.
.. - - . ., .:
, . ' ~
..
- . .
:, :
203~7~
cataly~t at temperatures of 50 to 180C over a period of 1 to 24 hours, :
c) removing excess POHal3 after the reaction, d) diluting the reaction mixture with 0.1 to 10 g of glacial acetic acid per g, e) hydrolyzing the reaction mixture diluted with glacial acetic acid with 1 to 4 mol of water, calculated on the number of moles of POHal3 reacted, and 10 f) filtering off the cyclic phosphoric acid diaryl ester deposited as crystals, of the formula III
,. ~ .
;.
R~o R ~ III
J ~'1 "'~
. in which A, R1~ R2, R3, R~, R5 and R8 have the meaning given in the case of formula I, ::
or the cyclic pho~phoric acid diaryl ester of the `:: formula IV
Rz ~1 \p ~ IV
7 ~a : in which R1~ R2, R3, R4, R~ and RA have the meaning given .~ in the case of formula II. ~ -, . ~
:.
Qj~
., .
. . :' .~
:,,:~::: .. : :,, :''' -': .' :,', "' :' ' ' ' , . .. , . '' '':'.' . . ... ' - 4 ~
: ~he proce~s according to the invention can further~ore optionally also be de~igned such that aa) POC13 or POBr3 is employed as the POHal3;
bb) nitrogen bases, such as 4-dimethylaminopyridine or N,N-dimethylformamide, organopho~phorus compounds, such as trioctylphosphine oxide or triphenylphos-phine oxide, or metal chlorides, such a~ aluminum chloride or magnesium chloride, are employed as the catalyst;
..
cc) the hydrolysis is carried out at a temperature of 10 to 140C, in particular 60 to 120C;
dd) after removal of the glacial acetic acid, the cyclic phosphoric acid diaryl ester is treated at temper-atures of 40 to 120C, in particular at 100C, preferably under reduced pressure, to remove the residual glacial acetic acid;
ee) the glacial acetic acid removed i8 worked up by : distillation;
.: ff) the reaction is carried out under an increased pressure of up to 3 bar;
.:
: gg) 2,2'-dihydroxy-1,1'-dinaphthyl (CAS No. ~602-09-5]) is reacted with POCl3;
~; hh) 2,2'-dihydroxybiphenyl (CAS No. ~1806-27-7]) is reacted with POCl3;
.: , .
ii) after removal of the glacial acetic acid, the cyclic ~. phosphoric acid diaryl ester is washed with an organic solvent, such as acetone, hexane or . methanol.
..
Using the process according to the invention it is now ~ ' ... .~... ... ........ ,...... . . ~
. - . . . . - - ,. .- ~. .
.,, ~ . -. . ~ . .
:- .
.. . . . . . . .
..... . .
203~ 7~
possible to avoid the disadvantages of known proce~ses, such as, for example, the removal of by-products by extraction by means of large amounts of solvents, the occurrence of caking, losses in yield and the low product S purity.
The use of acetic acid in the hydrolysis has proved to be particularly advantageous here, ~ince the starting materials are very readily soluble but the products are in general relatively sparingly soluble in this solvent and are thus obtained directly in a crystalline form which can easily be filtered.
The use of acetic acid in the hydrolysis has proved to be particularly appropriate in the case of 2,2'-biphenyl-~` ylenephosphoryl chloride (CAS No. ~52258-06-7]), because the end product crystallizes in a high yield and a high purity, even though tarry by-products, in particular oxidation products of the phenol, are entrained into the process with the raw material.
: ':
This finding is all the more surprising since it was known that ~P ~
reacts by itself, that is to say without addition of ~ water, to form .'.: .
Process for the preparation of pure cyclic phosphoric acid diaryl e~ter~
The present invention xelates to a process for the -_ preparation of pure cyclic phosphoric acid diaryl esters.
S Cyclic phosphoric acid diaryl esters are being incor-porated to an increasing extent into plastics as stabilizers and additives for improving the clarity of thermoplastics and into photographic ystems as color stabilizers.
The cyclic phosphoric acid diaryl esters used for this purpose must be employed in a pure, colorless state.
...
According to DE-C-2,212,660 or EP-s-68,326, cyclic binaphthyl-phosphoric acid esters or bisphenol-phosphoric acid esters can be prepared by the action of POC13 on the corresponding binaphthyl-Z,2'-diols or bisphenyl-2,2'-diols in the presence of basic substances, in particular pyridine, in stoichiometric amounts as an acid-binding agent. The cyclic phosphoric acid diaryl ester is then isolated in the pure form by further purification steps.
. ' .
A disadvantage here i8 the large amount of acid-binding agents to be employed, which leads to undesirable ef-fluents during reprocessing.
,' ' The ob~ect was therefore to provide a process for the preparation of pure cyclic phosphoric acid diaryl esters which operates with high yield~ and in a simple, eco-nomical manner and with which no undesirable effluents b are obtained.
A ~imple process has now been found for the preparation . of pure cyclic phosphoric acid diaryl esters from POHal3 and a bis-phenol derivative of the formula I
-- .
,~
: .~.
' ,.: , ' , .', , .. ., , .' , ':.. ' .; .''~ . -: . . .- : : -,. :.
-:: .: . - - ;
: . , : : -,~:...... , . ~ .
~, .
,.:
., .
2 ~ . 7S,3.
-- 2 _ Rl R~H
~ H
; in which Rl to R4 can be alkyl having 1 to 18 carbon atoms, an aryl radical having 6 to 10 carbon atom~, arylalkyl having 1 to 3 carbon atom~ in the chain, halogen or H, and in which A is a direct C-C bond or an alkylidene group of the formula . I
. R, - C - R_ o in which R5 and R~ can be alkyl having 1 to 12 carbon atoms, an optionally substituted cyclic sys~em having a total of 5 to 12 carbon atoms or H, or from a dihydroxy-dinaphthyl derivative of the formula II
l2 ll R ~ 3H
¦ II
. R
' . in which R~ to R4, R7 and R3 can be alkyl having 1 to 18 carbon atoms, halogen or H, which comprises a) employing POHal3 in a stoichiometric excess of O to . 500 mol~, :
b) carrying out the reaction in the presence of a ~. ' .
: .: , . .
- ,.~ . . ~ . , :.
.. - - . ., .:
, . ' ~
..
- . .
:, :
203~7~
cataly~t at temperatures of 50 to 180C over a period of 1 to 24 hours, :
c) removing excess POHal3 after the reaction, d) diluting the reaction mixture with 0.1 to 10 g of glacial acetic acid per g, e) hydrolyzing the reaction mixture diluted with glacial acetic acid with 1 to 4 mol of water, calculated on the number of moles of POHal3 reacted, and 10 f) filtering off the cyclic phosphoric acid diaryl ester deposited as crystals, of the formula III
,. ~ .
;.
R~o R ~ III
J ~'1 "'~
. in which A, R1~ R2, R3, R~, R5 and R8 have the meaning given in the case of formula I, ::
or the cyclic pho~phoric acid diaryl ester of the `:: formula IV
Rz ~1 \p ~ IV
7 ~a : in which R1~ R2, R3, R4, R~ and RA have the meaning given .~ in the case of formula II. ~ -, . ~
:.
Qj~
., .
. . :' .~
:,,:~::: .. : :,, :''' -': .' :,', "' :' ' ' ' , . .. , . '' '':'.' . . ... ' - 4 ~
: ~he proce~s according to the invention can further~ore optionally also be de~igned such that aa) POC13 or POBr3 is employed as the POHal3;
bb) nitrogen bases, such as 4-dimethylaminopyridine or N,N-dimethylformamide, organopho~phorus compounds, such as trioctylphosphine oxide or triphenylphos-phine oxide, or metal chlorides, such a~ aluminum chloride or magnesium chloride, are employed as the catalyst;
..
cc) the hydrolysis is carried out at a temperature of 10 to 140C, in particular 60 to 120C;
dd) after removal of the glacial acetic acid, the cyclic phosphoric acid diaryl ester is treated at temper-atures of 40 to 120C, in particular at 100C, preferably under reduced pressure, to remove the residual glacial acetic acid;
ee) the glacial acetic acid removed i8 worked up by : distillation;
.: ff) the reaction is carried out under an increased pressure of up to 3 bar;
.:
: gg) 2,2'-dihydroxy-1,1'-dinaphthyl (CAS No. ~602-09-5]) is reacted with POCl3;
~; hh) 2,2'-dihydroxybiphenyl (CAS No. ~1806-27-7]) is reacted with POCl3;
.: , .
ii) after removal of the glacial acetic acid, the cyclic ~. phosphoric acid diaryl ester is washed with an organic solvent, such as acetone, hexane or . methanol.
..
Using the process according to the invention it is now ~ ' ... .~... ... ........ ,...... . . ~
. - . . . . - - ,. .- ~. .
.,, ~ . -. . ~ . .
:- .
.. . . . . . . .
..... . .
203~ 7~
possible to avoid the disadvantages of known proce~ses, such as, for example, the removal of by-products by extraction by means of large amounts of solvents, the occurrence of caking, losses in yield and the low product S purity.
The use of acetic acid in the hydrolysis has proved to be particularly advantageous here, ~ince the starting materials are very readily soluble but the products are in general relatively sparingly soluble in this solvent and are thus obtained directly in a crystalline form which can easily be filtered.
The use of acetic acid in the hydrolysis has proved to be particularly appropriate in the case of 2,2'-biphenyl-~` ylenephosphoryl chloride (CAS No. ~52258-06-7]), because the end product crystallizes in a high yield and a high purity, even though tarry by-products, in particular oxidation products of the phenol, are entrained into the process with the raw material.
: ':
This finding is all the more surprising since it was known that ~P ~
reacts by itself, that is to say without addition of ~ water, to form .'.: .
3 ~ - OH
and acetyl chloride, cf. HOUBEN-HEYLs "Methoden der Organischen Chemie~ (Nethods of Organic Chemistry), E2, (1982), page 503.
: J
.
::.. ~: .. : : :. -. ~, ... . .. .
,.. : .:,. - . - . .: .
. ::.,:: :. ~ - - , - 6 2030~ 7y The registration numbers (CAS No.) quoted in Chemical Ab~tracts are also given for the individual components for unambiguous characterization.
.
The cyclic phosphoric acid diaryl esters according to the invention can be converted in a solvent, such as water, methanol or dioxane, into the corresponding alkali metal salts using alkali metal ~alts, in particular NaOH or ; Na2CO3, or into the ammonium salt by gaseous ammonia if the corresponding salts have to be employed during further processing.
Only small amount~ of catalyst are employed according to the invention. According to the prior art, stoichio-metrically large amounts of acid-binding substances, such as, for example, pyridine, in inert solvents are used.
During the hydrolysis, the pyridine ~alt of the cyclic phosphoric diaryl ester is formed first, and then has to be neutralized by a corresponding foreign acid and in this way leads to an undesirable salt loading in the effluent.
The proces~ according to the invention is illustrated further by the examples.
Comparison Example 1 (~Phosphorus and Sulfur~, Gordon and Breach Science Publishers, Inc., USA, Volume 8 (1980) page 144) ,'.
i- 25 A solution of 30 g (0.16 mol) of 2,2'-dihydroxybiphenyl (CAS No. ~1806-27-7~ in 200 ml of anhydrous ether is added dropwise to a solution of 35 g (0.23 mol) of POC13 and 26 g (0.33 mol) of pyridine in 200 ml of anhydrous ether. After the pyridine hydrochloride has been filtered - 30 off, the solvent is removed in vacuo and the residue is ; recrystallized from ligroin (100 - 125C).
; Yield of 2,2'-biphenylylenephosphoryl chloride: 90 % of ;~ theory.
,~
: . ~
.. :
~;'' ~., '""'1 '" ' ' ~'.'.' ~" ' ' ' 1.
2 ~ 7 ~
200 ml of concentrated hydrochloric acid are added in - portions to a ~olution of 10 g of 2,2~-biphenylylenephos-phoryl chloride (CAS No. [52258-06-7]) in 200 ml of water, while stirring. ~he 2,2~-biphenylyenephosphoric S acid (CAS No. [35227-84-0]) which has precipitated i~
filtered off, washed with concentrated hydrochloric acid and dried in vacuo over ROH.
; Yield: 80 S of theory; melting point: 262 to 263C, with decomposition. -. .
Comparison Example 2 '~ ~
0.5 ml of N,N-dimethylformamide i8 added to 93.1 g of 2,2~-dihydroxybiphenyl (CAS No. tl806-27-7]) and 153.3 g of POCl3 and the mixture i8 kept at the boiling point under reflux for 10 hours. Unreacted POC13 i8 removed under a water pump vacuum and the crystalline residue is taken up in 200 ml of toluene.
, The solution i8 added dropwise to 1 1 of half-- concentrated HCl, while stirring vigorously. An oil, s which solidifies on heating and blocks the stirrer, is deposited at the phase boundary. 111 g of brown-colored ; product (2,2'-biphenylylenephosphoric acid (CAS No.
[35227-84-0]) i8 obtained by co~minution of the solid, ; filtration, washing and drying.
Yields 89.4 % of theory; melting point: 262C, with decomposition.
.''', Example 3 i ' 1464 g of 2,2'-dihydroxybiphenyl (CAS No. [1806-27-7]) and 2412 g of POC13 are kept at the boiling point under ~i reflux for 10 hours with 0.5 g of N,N'-dimethylformamide.
; 30 After the unreacted POCl3 has been stripped off under a water pump vacuum, 1000 ml of glacial acetic acid are ` added to the reaction mixture at 80-C and 200 m} of water are added dropwi~e at a tempera~ure of 80-C in the course of 40 minute~, while stirring. Crystalline 2,2~-biphenyl-ylenephosphoric acid (CAS No. [35227-84-0]) precipitates . ., ., .
~ A ., .
- 8 - 2 ~30~ ~9 out, HCl being evolved. After cooling to room temper-ature, the crystal slurry~ is filtered off with suction, washed with 2 x 200 ml of acetone and dried. 1864 g of crystals are obtained.
Yield: 95.5 3 of theory; melting point: 273C (without decomposition).
31P-NMR (D20) 5.6 ppm j:
Example 4 r 268 g of 2,2'-dihydroxy-1,1'-dinaphthyl ~CAS No. [602-09-5]), 550 g of POC13 and 0.5 g of N,N-dimethylformamide are reacted in accordance with Example 3.
500 ml of glacial acetic acid are added to the reaction mixture and 25 ml of H2O are added dropwise at a temper-ature of 75C in the course of 15 minutes, while stirring.
234 g of colorless crystals are obtained (binaphthylyl-enephosphoric acid (CAS No. t35193-63-6]) are obtained.
Yield: 72 % of theory; melting point: 202C.
, 31p_NNR (CDCl3) 10-8 ppm-Example 5 ~,......................................................................... .
138 g of 3,3~,5,5~-tetra-tert.-butyl-2,2~-biphenyldiol (CAS No. t6390-69-8]), 130 g of POCl3 and 1 g of tri-,- octylphosphine oxide are reacted in accordance with ; Example 3. 150 ml of glacial acetic acid are added to thereaction mixture and 8.5 ml of H2O are added at a temper-ature of 130C under pressure in the course of 10 min-utes, while stirring.
131 g of colorless crystals (cyclic phosphoric acid diaryl ester) are obtained.
Yield: 82.4 % of theory; melting point: 160 to 170C.
3lP-NMR (CDCl3)-l-l ppm-; Example 6 ,.
~,...
100 g of 2,2'-methylene-bis(4-chlorophenol) (Cas No.
~" ~
' .
. ~ . ,, . " ,. , ... , , ., . , . , ., . .. , . .. .... ..... .... ~ .. .... . .. .. .. . ... . . .. . . .. .
g 2~3~-~7~
[97-23-4]), 171 g of POC13 and 0.1 g of N,N-dimethyl-formamide are reacted in accordance with Example 3~
180 ml of glacial acetic acid are added to the reaction mixture. 9 ml of H20 are added dropwi~e to the suspension, S formed on ~tirring, at a temperature of 70-C in the course of 10 minutes. The product i8 filtered off with suction and then ~uspended in n-hexane. After filtration with suction and drying, 84 g of product are obtained (cyclic phosphoric acid diaryl ester).
; 10 Yield: 75.0 ~ of theory; decomposition point: 290-C.
3lP-NMR (C5D~) 13.6 ppm-~, Example 7 100 g of 2,2'-methylene-bis(4-methyl-6-tert.-butyl-phenol) (CAS No. ~119-47-1], 135 g of POC13 and 0.2 g of lS N,N-dimethylformamide are reacted in accordance with Example 3.
k: 60 ml of glacial acetic acid are added to the reaction mixture and 6.5 ml of H2O are added dropwise at a temp-erature of 60-C in the course of 10 minutes, while ;; 20 ~tirring.
34 g of colorless crystals are obtained (cyclic pho~-' phoric acid diaryl ester).
Yield: 33 % of theory; melting point: 297 to 301C.
3lP-NMR (C~D5) 12.1 ppm-Example 8 '' 123 g of 2,2'-methylene-bis(4,6-di-tert.-butylphenol) (CAS No. tl4362-12-0]), 210 g of POBr3 and O.S g of N,N-dimethylformamide are reacted in accorance with E~ample 3.
150 ml of glacial acetic acid are added to the reaction mixture and 8.5 ml of H2O are added dropwise at a temper-ature of 60-C in the course of 10 minutes, while stirring.
48 g of colorless crystals are obtained (cyclic phos-`~ 35 phoric acid diaryl ester (CAS No. ~106396-29-6]).
:, ~, . . .
r lO- 20~79 Yield: 34 % of theory; melting point: 272 to 275C.
31P-NMR ( C61)6 ) 1 1 . 4 ppm .
.;. ':
': .
,.
:;;~
,.................................... .
..
;
~:
..
,', '~:
.,; , .. . .
~. ;j ,.. .
i:
.
;~
:
, .
,, .
.~.". ~.
, .:
, .. . . , , . -.. .: . . .. . . . .
. .
and acetyl chloride, cf. HOUBEN-HEYLs "Methoden der Organischen Chemie~ (Nethods of Organic Chemistry), E2, (1982), page 503.
: J
.
::.. ~: .. : : :. -. ~, ... . .. .
,.. : .:,. - . - . .: .
. ::.,:: :. ~ - - , - 6 2030~ 7y The registration numbers (CAS No.) quoted in Chemical Ab~tracts are also given for the individual components for unambiguous characterization.
.
The cyclic phosphoric acid diaryl esters according to the invention can be converted in a solvent, such as water, methanol or dioxane, into the corresponding alkali metal salts using alkali metal ~alts, in particular NaOH or ; Na2CO3, or into the ammonium salt by gaseous ammonia if the corresponding salts have to be employed during further processing.
Only small amount~ of catalyst are employed according to the invention. According to the prior art, stoichio-metrically large amounts of acid-binding substances, such as, for example, pyridine, in inert solvents are used.
During the hydrolysis, the pyridine ~alt of the cyclic phosphoric diaryl ester is formed first, and then has to be neutralized by a corresponding foreign acid and in this way leads to an undesirable salt loading in the effluent.
The proces~ according to the invention is illustrated further by the examples.
Comparison Example 1 (~Phosphorus and Sulfur~, Gordon and Breach Science Publishers, Inc., USA, Volume 8 (1980) page 144) ,'.
i- 25 A solution of 30 g (0.16 mol) of 2,2'-dihydroxybiphenyl (CAS No. ~1806-27-7~ in 200 ml of anhydrous ether is added dropwise to a solution of 35 g (0.23 mol) of POC13 and 26 g (0.33 mol) of pyridine in 200 ml of anhydrous ether. After the pyridine hydrochloride has been filtered - 30 off, the solvent is removed in vacuo and the residue is ; recrystallized from ligroin (100 - 125C).
; Yield of 2,2'-biphenylylenephosphoryl chloride: 90 % of ;~ theory.
,~
: . ~
.. :
~;'' ~., '""'1 '" ' ' ~'.'.' ~" ' ' ' 1.
2 ~ 7 ~
200 ml of concentrated hydrochloric acid are added in - portions to a ~olution of 10 g of 2,2~-biphenylylenephos-phoryl chloride (CAS No. [52258-06-7]) in 200 ml of water, while stirring. ~he 2,2~-biphenylyenephosphoric S acid (CAS No. [35227-84-0]) which has precipitated i~
filtered off, washed with concentrated hydrochloric acid and dried in vacuo over ROH.
; Yield: 80 S of theory; melting point: 262 to 263C, with decomposition. -. .
Comparison Example 2 '~ ~
0.5 ml of N,N-dimethylformamide i8 added to 93.1 g of 2,2~-dihydroxybiphenyl (CAS No. tl806-27-7]) and 153.3 g of POCl3 and the mixture i8 kept at the boiling point under reflux for 10 hours. Unreacted POC13 i8 removed under a water pump vacuum and the crystalline residue is taken up in 200 ml of toluene.
, The solution i8 added dropwise to 1 1 of half-- concentrated HCl, while stirring vigorously. An oil, s which solidifies on heating and blocks the stirrer, is deposited at the phase boundary. 111 g of brown-colored ; product (2,2'-biphenylylenephosphoric acid (CAS No.
[35227-84-0]) i8 obtained by co~minution of the solid, ; filtration, washing and drying.
Yields 89.4 % of theory; melting point: 262C, with decomposition.
.''', Example 3 i ' 1464 g of 2,2'-dihydroxybiphenyl (CAS No. [1806-27-7]) and 2412 g of POC13 are kept at the boiling point under ~i reflux for 10 hours with 0.5 g of N,N'-dimethylformamide.
; 30 After the unreacted POCl3 has been stripped off under a water pump vacuum, 1000 ml of glacial acetic acid are ` added to the reaction mixture at 80-C and 200 m} of water are added dropwi~e at a tempera~ure of 80-C in the course of 40 minute~, while stirring. Crystalline 2,2~-biphenyl-ylenephosphoric acid (CAS No. [35227-84-0]) precipitates . ., ., .
~ A ., .
- 8 - 2 ~30~ ~9 out, HCl being evolved. After cooling to room temper-ature, the crystal slurry~ is filtered off with suction, washed with 2 x 200 ml of acetone and dried. 1864 g of crystals are obtained.
Yield: 95.5 3 of theory; melting point: 273C (without decomposition).
31P-NMR (D20) 5.6 ppm j:
Example 4 r 268 g of 2,2'-dihydroxy-1,1'-dinaphthyl ~CAS No. [602-09-5]), 550 g of POC13 and 0.5 g of N,N-dimethylformamide are reacted in accordance with Example 3.
500 ml of glacial acetic acid are added to the reaction mixture and 25 ml of H2O are added dropwise at a temper-ature of 75C in the course of 15 minutes, while stirring.
234 g of colorless crystals are obtained (binaphthylyl-enephosphoric acid (CAS No. t35193-63-6]) are obtained.
Yield: 72 % of theory; melting point: 202C.
, 31p_NNR (CDCl3) 10-8 ppm-Example 5 ~,......................................................................... .
138 g of 3,3~,5,5~-tetra-tert.-butyl-2,2~-biphenyldiol (CAS No. t6390-69-8]), 130 g of POCl3 and 1 g of tri-,- octylphosphine oxide are reacted in accordance with ; Example 3. 150 ml of glacial acetic acid are added to thereaction mixture and 8.5 ml of H2O are added at a temper-ature of 130C under pressure in the course of 10 min-utes, while stirring.
131 g of colorless crystals (cyclic phosphoric acid diaryl ester) are obtained.
Yield: 82.4 % of theory; melting point: 160 to 170C.
3lP-NMR (CDCl3)-l-l ppm-; Example 6 ,.
~,...
100 g of 2,2'-methylene-bis(4-chlorophenol) (Cas No.
~" ~
' .
. ~ . ,, . " ,. , ... , , ., . , . , ., . .. , . .. .... ..... .... ~ .. .... . .. .. .. . ... . . .. . . .. .
g 2~3~-~7~
[97-23-4]), 171 g of POC13 and 0.1 g of N,N-dimethyl-formamide are reacted in accordance with Example 3~
180 ml of glacial acetic acid are added to the reaction mixture. 9 ml of H20 are added dropwi~e to the suspension, S formed on ~tirring, at a temperature of 70-C in the course of 10 minutes. The product i8 filtered off with suction and then ~uspended in n-hexane. After filtration with suction and drying, 84 g of product are obtained (cyclic phosphoric acid diaryl ester).
; 10 Yield: 75.0 ~ of theory; decomposition point: 290-C.
3lP-NMR (C5D~) 13.6 ppm-~, Example 7 100 g of 2,2'-methylene-bis(4-methyl-6-tert.-butyl-phenol) (CAS No. ~119-47-1], 135 g of POC13 and 0.2 g of lS N,N-dimethylformamide are reacted in accordance with Example 3.
k: 60 ml of glacial acetic acid are added to the reaction mixture and 6.5 ml of H2O are added dropwise at a temp-erature of 60-C in the course of 10 minutes, while ;; 20 ~tirring.
34 g of colorless crystals are obtained (cyclic pho~-' phoric acid diaryl ester).
Yield: 33 % of theory; melting point: 297 to 301C.
3lP-NMR (C~D5) 12.1 ppm-Example 8 '' 123 g of 2,2'-methylene-bis(4,6-di-tert.-butylphenol) (CAS No. tl4362-12-0]), 210 g of POBr3 and O.S g of N,N-dimethylformamide are reacted in accorance with E~ample 3.
150 ml of glacial acetic acid are added to the reaction mixture and 8.5 ml of H2O are added dropwise at a temper-ature of 60-C in the course of 10 minutes, while stirring.
48 g of colorless crystals are obtained (cyclic phos-`~ 35 phoric acid diaryl ester (CAS No. ~106396-29-6]).
:, ~, . . .
r lO- 20~79 Yield: 34 % of theory; melting point: 272 to 275C.
31P-NMR ( C61)6 ) 1 1 . 4 ppm .
.;. ':
': .
,.
:;;~
,.................................... .
..
;
~:
..
,', '~:
.,; , .. . .
~. ;j ,.. .
i:
.
;~
:
, .
,, .
.~.". ~.
, .:
, .. . . , , . -.. .: . . .. . . . .
. .
Claims (14)
1. A process for the preparation of a pure cyclic phos-phonic acid diaryl ester from POHal3 and a bis-phenol derivative of the formula I
in which R1 to R4 can be alkyl having 1 to 18 carbon atoms, an aryl radical having 6 to 10 carbon atoms, arylalkyl having 1 to 3 carbon atoms in the chain, halogen or H, and in which A is a direct C-C bond or an alkylidene group of the formula in which R5 and R6 can be alkyl having 1 to 12 carbon atoms, a substituted cyclic system having a total of 5 to 12 carbon atoms or H, or a dihydroxy-dinaphthyl derivative of the formula II
in which R1 to R4, R7 and R8 can be alkyl having 1 to 18 carbon atoms, halogen or H, which comprises a) employing POHal3 in a stoichiometric excess of 0 to 500 mol%, b) carrying out the reaction in the presence of a catalyst at temperatures of 50 to 180°C over a period of 1 to 24 hours, c) removing excess POHal3 after the reaction, d) diluting the reaction mixture with 0.1 to 10 g of glacial acetic acid per g, e) hydrolyzing the reaction mixture diluted with glacial acetic acid with 1 to 4 mol of water, calculated on the number of moles of POHal3 reacted, and f) filtering off the cyclic phosphoric acid diaryl ester deposited as crystals, of the formula III
III
in which A, R1, R2, R3, R4, R5 and R6 have the meaning given in the case of formula I, or the cyclic phosphoric acid diaryl ester of the formula IV
IV
in which R1, R2, R3, R4, R7 and R8 have the meaning given in the case of formula II.
in which R1 to R4 can be alkyl having 1 to 18 carbon atoms, an aryl radical having 6 to 10 carbon atoms, arylalkyl having 1 to 3 carbon atoms in the chain, halogen or H, and in which A is a direct C-C bond or an alkylidene group of the formula in which R5 and R6 can be alkyl having 1 to 12 carbon atoms, a substituted cyclic system having a total of 5 to 12 carbon atoms or H, or a dihydroxy-dinaphthyl derivative of the formula II
in which R1 to R4, R7 and R8 can be alkyl having 1 to 18 carbon atoms, halogen or H, which comprises a) employing POHal3 in a stoichiometric excess of 0 to 500 mol%, b) carrying out the reaction in the presence of a catalyst at temperatures of 50 to 180°C over a period of 1 to 24 hours, c) removing excess POHal3 after the reaction, d) diluting the reaction mixture with 0.1 to 10 g of glacial acetic acid per g, e) hydrolyzing the reaction mixture diluted with glacial acetic acid with 1 to 4 mol of water, calculated on the number of moles of POHal3 reacted, and f) filtering off the cyclic phosphoric acid diaryl ester deposited as crystals, of the formula III
III
in which A, R1, R2, R3, R4, R5 and R6 have the meaning given in the case of formula I, or the cyclic phosphoric acid diaryl ester of the formula IV
IV
in which R1, R2, R3, R4, R7 and R8 have the meaning given in the case of formula II.
2. The process as claimed in claim 1, wherein POCl3 is employed as the POHal3.
3. The process as claimed in claim 1, wherein POBr3 is employed as the POHal3.
4. The process as claimed in claim 1, wherein a nitrogen base chosen from the group comprising 4-dimethylamino-pyridine and N,N-dimethylformamide is employed as the catalyst.
5. The process as claimed in claim 1, wherein an organo-phosphorus compound chosen from the group comprising trioctylphosphine oxide and triphenylphosphine oxide is employed as the catalyst.
6. The process as claimed in claim 1, wherein a metal chloride chosen from the group comprising aluminum chloride and magnesium chloride is employed as the catalyst.
7. The process as claimed in claim 1, wherein the hydrol-ysis is carried out at a temperature of 10 to 140°C.
8. The process as claimed in claim 7, wherein the hydrol-ysis is carried out at 60 to 120°C.
9. The process as claimed in claim 1, wherein, after removal of the glacial acetic acid, the cyclic phosphoric acid diaryl ester is treated at temperatures of 40 to 120°C under reduced pressure to remove the residual glacial acetic acid.
10. The process as claimed in claim 9, wherein the glacial acetic acid removed is worked up by distillation.
11. The process as claimed in claim 1, wherein the reaction is carried out under an increased pressure of up to 3 bar.
12. The process as claimed in claim 1, wherein 2,2'-dihydrosy-1,1-dinaphthyl is reacted with POCl3.
13. The process as claimed in claim 1, wherein 2,2'-dihydroxybiphenyl is reacted with POCl3.
14. The process as claimed in claim 1, wherein, after removal of the glacial acetic acid, the cyclic phosphoric acid diaryl ester is washed with an organic solvent chosen from the group comprising acetone, hexane and methanol.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19893940765 DE3940765A1 (en) | 1989-12-09 | 1989-12-09 | METHOD FOR PRODUCING PURE CYCLIC PHOSPHORSAEUREDIARYLESTER |
| DEP3940765.9 | 1989-12-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2030179A1 true CA2030179A1 (en) | 1991-06-10 |
Family
ID=6395155
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2030179 Abandoned CA2030179A1 (en) | 1989-12-09 | 1990-11-16 | Process for the preparation of pure cyclic phosphoric acid diaryl esters |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0432505A3 (en) |
| JP (1) | JPH03181493A (en) |
| CA (1) | CA2030179A1 (en) |
| DE (1) | DE3940765A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101948486A (en) * | 2010-08-20 | 2011-01-19 | 洛阳市中达化工有限公司 | Synthesis method of 2,2'-methylene-bis(4,6-dibert-butylphenol) phosphate |
| CN102807583A (en) * | 2011-06-02 | 2012-12-05 | 中国石油化工股份有限公司 | Synthesis methods of organophosphate ester and organophosphate salt |
| CN106892943A (en) * | 2017-03-07 | 2017-06-27 | 山东省化工研究院 | A kind of compound in triazine class, preparation method and applications |
| CN113896745A (en) * | 2020-07-06 | 2022-01-07 | 华东理工大学 | Continuous preparation method of substituted diaryl phosphate compound |
| US11306194B2 (en) | 2018-02-13 | 2022-04-19 | Adeka Corporation | Nucleating agent, polyolefin-based resin composition containing same, and molded article thereof |
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| US20190284217A1 (en) * | 2016-10-26 | 2019-09-19 | Adeka Corporation | Novel compound, composition including same, olefin-based resin composition, molded article thereof, and method for improving impact resistance of molded article |
| CN112707935A (en) * | 2020-12-26 | 2021-04-27 | 山西省化工研究所（有限公司） | Preparation method of environment-friendly aromatic phosphate nucleating agent |
| CN113735907A (en) * | 2021-09-26 | 2021-12-03 | 上海交通大学 | High-yield preparation method of organic phosphate nucleating agent |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT951631B (en) * | 1971-03-18 | 1973-07-10 | Richardson Merrell Spa | USEFUL COMPOUNDS FOR THE SEPARATION OF GEOMETRIC AND STRUCTURAL OPTICAL ISOMERS AND RELATED SYNTHESIS PROCEDURE |
| US3812220A (en) * | 1972-05-15 | 1974-05-21 | Ashland Oil Inc | Phosphate esters of hindered phenols |
| GB8625149D0 (en) * | 1986-10-21 | 1986-11-26 | Kodak Ltd | Stabilisation of dye images |
-
1989
- 1989-12-09 DE DE19893940765 patent/DE3940765A1/en not_active Withdrawn
-
1990
- 1990-11-15 EP EP19900121855 patent/EP0432505A3/en not_active Withdrawn
- 1990-11-16 CA CA 2030179 patent/CA2030179A1/en not_active Abandoned
- 1990-11-30 JP JP33083290A patent/JPH03181493A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101948486A (en) * | 2010-08-20 | 2011-01-19 | 洛阳市中达化工有限公司 | Synthesis method of 2,2'-methylene-bis(4,6-dibert-butylphenol) phosphate |
| CN102807583A (en) * | 2011-06-02 | 2012-12-05 | 中国石油化工股份有限公司 | Synthesis methods of organophosphate ester and organophosphate salt |
| CN102807583B (en) * | 2011-06-02 | 2014-12-03 | 中国石油化工股份有限公司 | Synthesis methods of organophosphate ester and organophosphate salt |
| CN106892943A (en) * | 2017-03-07 | 2017-06-27 | 山东省化工研究院 | A kind of compound in triazine class, preparation method and applications |
| US11306194B2 (en) | 2018-02-13 | 2022-04-19 | Adeka Corporation | Nucleating agent, polyolefin-based resin composition containing same, and molded article thereof |
| CN113896745A (en) * | 2020-07-06 | 2022-01-07 | 华东理工大学 | Continuous preparation method of substituted diaryl phosphate compound |
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| Publication number | Publication date |
|---|---|
| EP0432505A2 (en) | 1991-06-19 |
| JPH03181493A (en) | 1991-08-07 |
| EP0432505A3 (en) | 1991-08-14 |
| DE3940765A1 (en) | 1991-06-13 |
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