WO2010121774A1 - Process for the production of cyanic acid c,c'-[2-(6-oxido-6h-dibenz[c,e][1,2]oxa-phosphorin-6-yl)-1,4-phenylene] ester - Google Patents
Process for the production of cyanic acid c,c'-[2-(6-oxido-6h-dibenz[c,e][1,2]oxa-phosphorin-6-yl)-1,4-phenylene] ester Download PDFInfo
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- WO2010121774A1 WO2010121774A1 PCT/EP2010/002395 EP2010002395W WO2010121774A1 WO 2010121774 A1 WO2010121774 A1 WO 2010121774A1 EP 2010002395 W EP2010002395 W EP 2010002395W WO 2010121774 A1 WO2010121774 A1 WO 2010121774A1
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- WIPO (PCT)
- Prior art keywords
- mol
- benzenediol
- solvent
- iii
- acetone
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 24
- XLJMAIOERFSOGZ-UHFFFAOYSA-N cyanic acid Chemical compound OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 150000002148 esters Chemical class 0.000 title claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 38
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000002904 solvent Substances 0.000 claims abstract description 18
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims abstract description 14
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims abstract description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 9
- QPJDMGCKMHUXFD-UHFFFAOYSA-N cyanogen chloride Chemical compound ClC#N QPJDMGCKMHUXFD-UHFFFAOYSA-N 0.000 claims abstract description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 5
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims abstract description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims abstract description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims abstract description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims abstract description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims abstract description 3
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 claims description 9
- 239000000725 suspension Substances 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 229960004337 hydroquinone Drugs 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- -1 acetonithle Chemical compound 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 abstract description 6
- 238000010626 work up procedure Methods 0.000 abstract description 2
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- 239000000047 product Substances 0.000 description 15
- 238000001914 filtration Methods 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N 1,4-Benzenediol Natural products OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- ZZTSQZQUWBFTAT-UHFFFAOYSA-N diethylcyanamide Chemical compound CCN(CC)C#N ZZTSQZQUWBFTAT-UHFFFAOYSA-N 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 0 *Oc(cc1P2(Oc(cccc3)c3-c3ccccc23)=O)ccc1O* Chemical compound *Oc(cc1P2(Oc(cccc3)c3-c3ccccc23)=O)ccc1O* 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- ATDGTVJJHBUTRL-UHFFFAOYSA-N cyanogen bromide Chemical compound BrC#N ATDGTVJJHBUTRL-UHFFFAOYSA-N 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C07F9/657163—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 the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657172—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 the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
Definitions
- the present invention relates to a process for the production of cyanic acid C C-[2-(6-oxido-6/ ⁇ klibenz[c,e][1 ,2]oxaphosphorin-6-yl)-1 ,4-phenylene] ester of formula
- R is -C ⁇ N.
- JP 2008-088079 A requires the use of dichloromethane and several aqueous washing steps and it has been found that the product obtained contains significant amounts of residual halogenide and diethylcyanamide as a byproduct.
- the halogenide content is particularly disadvantageous in applications such as molding compounds for electronic components.
- R is -C ⁇ N
- the solvent used throughout the process is selected from the group consisting of acetone, butanone and tetrahydrofuran.
- the solvent is acetone.
- the temperature of the reaction mixture in steps (ii) and (iii) is preferably between -5 0 C and -12 0 C.
- step (iii) of the process of the invention is exothermic, the temperature of the reaction mixture should be controlled by appropriate cooling and the rate of addition of triethylamine has to be limited and the reaction mixture agitated in order to avoid temperature excursions which may lead to unwanted side reactions.
- the triethylammonium chloride precipitate may be separated of by any method known in the art, in particular by filtration or centhfugation. In order to avoid product loss by inclusion or adsorption the triethylammonium chloride is advantageously washed with cold fresh solvent after filtration or centrifugation.
- the triethylammonium chloride is obtained in solid form, the triethylamine required in step (iii) can be easily recovered and recycled, e.g. by adding a strong base such as sodium hydroxide and distilling off the triethylamine from the chloride of the strong base (e.g., sodium chloride) formed. This will also substantially reduce the amount of waste produced in the process of the invention.
- a strong base such as sodium hydroxide
- the product solution obtained after separating off the triethylammonium chloride is concentrated by evaporating an amount of solvent that is sufficient to achieve a product concentration of at least 40 wt.% in the remaining solution.
- the evaporation may be carried out at ambient or reduced pressure.
- acetone is used as solvent the final product concentration can be as high as 45-50 wt.% or more.
- the crystallization of the product is advantageously induced by the addition of seed crystals of the desired product and carried out at a temperature of 0-15 0 C, for example about 10 0 C.
- the crystallized product is separated from the mother liquor, which again can be achieved by any method known in the art, such as filtration or centrifugation, and eventually dried.
- the purity of the product may be further improved by washing with cold fresh solvent.
- the process of the invention requires only one non-halogenated solvent and avoids any contact of the product or starting materials with water. This reduces the amount of waste generated and allows recycling of the solvent and recovery of the triethylamine from the triethylammonium chloride byproduct.
- the product is obtained as a white crystalline solid with extremely low halogenide content.
- the precipitated triethylammonium chloride was filtered off and the filter cake was washed with acetone.
- the combined filtrates were concentrated by evaporation of the solvent until a 45-50 wt.% solution of the title compound in acetone was obtained.
- the solution was transferred into a crystallization flask and cooled to 10 0 C. Upon addition of some seed crystals the product began to crystallize. The crystals were separated by filtration and washed with cold acetone. Yield: 690 g, (1.84 mol, 75%) of a white crystalline solid.
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- 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Cyanic acid C, C'-[2-(6-oxido-6H-dibenz[c,e][1,2]oxaphosphorin-6-yl)-1,4-phenylene] ester of formula (I) wherein R is -C≡N, is prepared by reacting the corresponding benzenediol (I, R = H) with cyanogen chloride and triethylamine in a solvent selected from acetone, butanone, butyl acetate, ethyl acetate, methyl acetate, isopropyl alcohol, toluene, diethyl ether, diethyl carbonate, acetonitrile, tetrahydrofuran, and any mixture of any of the foregoing. The process of the invention does not require a halogenated solvent or an aqueous work-up step and provides a pure, crystalline product having extremely low halogen content.
Description
Process for the production of cyanic acid C,C'-[2-(6-ox\do-6H-(i\benz[c,e]^,2]oxa- phosphorin-6-yl)-1 ,4-phenylene] ester
The present invention relates to a process for the production of cyanic acid C C-[2-(6-oxido-6/τklibenz[c,e][1 ,2]oxaphosphorin-6-yl)-1 ,4-phenylene] ester of formula
The above ester of cyanic acid is a flameproofing agent, in particular for epoxy resins (JP 2008-088079 A). It has been prepared by reacting the corresponding hydro- quinone compound 2-(6-oxido-6Λk.ibenz[c,e][1 ,2]oxaphosphorin-6-yl)-1 ,4-benzenediol (I, R = H), which is commercially available from Sanko Co., Ltd., Japan, with cyanogen bromide and triethylamine in acetone at 0-5 0C (JP 2008-088079 A). The work-up described in JP 2008-088079 A requires the use of dichloromethane and several aqueous washing steps and it has been found that the product obtained contains significant amounts of residual halogenide and diethylcyanamide as a byproduct. The halogenide content is particularly disadvantageous in applications such as molding compounds for electronic components.
It was an object of the present invention to provide an improved process for the production of cyanic acid CC-[2-(6<>xido-6/τklibenz[c,e][1 ,2]oxaphosphorin-6-yl)- 1 ,4-phenylene] ester that does without halogenated solvents and aqueous washing steps and affords a pure product containing only negligible traces of halogenide.
This object has been achieved by the process of claim 1.
It has been found that pure cyanic acid C, C-[2-(6-oxido-6/y-dibenz[c, e][1 ,2]oxaphos- phorin-6-yl)-1 ,4-phenylene] ester of formula
wherein R is -C≡N, can be prepared in a process comprising the steps of
(i) preparing a suspension of 2-(6-oxido-6/τkϋbenz[c,6?][1 ,2]oxaphosphorin-6-yl)- 1 ,4-benzenediol (I, R = H) in a solvent selected from the group consisting of acetone, butanone, butyl acetate, ethyl acetate, methyl acetate, isopropyl alcohol, toluene, diethyl ether, diethyl carbonate, acetonitrile, tetrahydrofuran, and any mixture of any of the foregoing,
(ii) adding at least two mol, based on one mol of benzenediol (I, R = H)1 of cyanogen chloride at a temperature below 0 CC to the suspension obtained in step (i), (iii) slowly adding at least two mol, based on one mol of benzenediol (I1 R = H), of triethylamine at a temperature below 0 0C, (iv) separating off the solid triethylammonium chloride formed during step (iii),
(v) evaporating the solvent until a concentrated solution containing at least 40 wt.% of the desired product (I, R = -C≡N) is obtained, (vi) cooling the concentrated solution obtained in step (v) to induce crystallization of the product, and (vii) separating off and drying the crystallized product.
In a preferred embodiment the solvent used throughout the process is selected from the group consisting of acetone, butanone and tetrahydrofuran.
Most preferably the solvent is acetone.
The concentration of the benzenediol starting material (I, R = H) in the suspension of step (i) is not critical, it may be for example in the range of 10-15 wt.%.
The cyanogen chloride in step (ii) is advantageously used in a slight excess, preferably in an amount of 2.0 to 2.5 mol per mol of benzenediol starting material (I1 R = H). More preferably, cyanogen chloride is used in an amount of 2.1 to 2.3 mol per mol of benzenediol.
Likewise, the triethylamine in step (iii) is used in a slight excess, preferably in an amount of 2.0 to 2.2 mol per mol of benzenediol starting material (I, R = H). More preferably, triethylamine is used in an amount of 2.05 to 2.15 mol per mol of benzenediol.
The temperature of the reaction mixture in steps (ii) and (iii) is preferably between -5 0C and -12 0C.
Since in particular step (iii) of the process of the invention is exothermic, the temperature of the reaction mixture should be controlled by appropriate cooling and the rate of addition of triethylamine has to be limited and the reaction mixture agitated in order to avoid temperature excursions which may lead to unwanted side reactions.
The triethylammonium chloride precipitate may be separated of by any method known in the art, in particular by filtration or centhfugation. In order to avoid product loss by inclusion or adsorption the triethylammonium chloride is advantageously washed with cold fresh solvent after filtration or centrifugation.
Since the triethylammonium chloride is obtained in solid form, the triethylamine required in step (iii) can be easily recovered and recycled, e.g. by adding a strong base such as sodium hydroxide and distilling off the triethylamine from the chloride of the strong base (e.g., sodium chloride) formed. This will also substantially reduce the amount of waste produced in the process of the invention.
The product solution obtained after separating off the triethylammonium chloride is concentrated by evaporating an amount of solvent that is sufficient to achieve a product concentration of at least 40 wt.% in the remaining solution. The evaporation may be carried out at ambient or reduced pressure. When acetone is used as solvent the final product concentration can be as high as 45-50 wt.% or more.
The crystallization of the product is advantageously induced by the addition of seed crystals of the desired product and carried out at a temperature of 0-15 0C, for example about 10 0C.
In the final step (vi) the crystallized product is separated from the mother liquor, which again can be achieved by any method known in the art, such as filtration or centrifugation, and eventually dried. The purity of the product may be further improved by washing with cold fresh solvent.
The process of the invention requires only one non-halogenated solvent and avoids any contact of the product or starting materials with water. This reduces the amount of waste generated and allows recycling of the solvent and recovery of the triethylamine from the triethylammonium chloride byproduct. The product is obtained as a white crystalline solid with extremely low halogenide content.
Example 1
2-(6-Oxido-6/τklibenz[c, e][1 ,2]oxaphosphorin-6-yl)-1 ,4-benzenediol (800 g, 2.46 mol) was suspended in dry acetone (6000 g) at -6 0C. Gaseous cyanogen chloride (346.6 g, 5.52 mol) was added to this suspension at -9 0C. At this temperature triethylamine (527 g, 5.18 mol) was added over a period of 2 h under vigorous stirring. The reaction mixture was stirred for another 45 min at -9 0C before the suspension formed was allowed to warm to -6 0C. The precipitated triethylammonium chloride was filtered off and the filter cake was washed with acetone. The combined filtrates were concentrated by evaporation of the solvent until a 45-50 wt.% solution of the title compound in acetone was obtained. The solution was transferred into a crystallization flask and cooled to 10 0C. Upon addition of some seed crystals the product began to crystallize. The crystals were separated by filtration and washed with cold acetone. Yield: 690 g, (1.84 mol, 75%) of a white crystalline solid.
1H NMR (DMSO-de): δ = 8.40 (dd, 1 H), 8.33 (dd, 1 H), 8.03-7.77 (m, 5H)1 7.66-7.61 (m, 1 H), 7.56-7.52 (dd, 1 H), 7.43-7.38 (m, 2H). Chlorine: <10 ppm Diethylcyanamide: <7000 ppm Monohydroxy compound: <1 %
Gel time: >40 min @ 150 0C, determined using a GELNORM® Gel Timer (Gel Instru- mente AG, Thalwil, Switzerland)
Claims
1. Process for the production of cyanic acid C,C-'[2-(Q-ox\do-6H-d\benz[c,e]^ ,2]oxa- phosphorin-6-yl)-1 ,4-phenylene] ester of formula
wherein R is -C≡N, comprising the steps of
(i) preparing a suspension of 2-(6-oxido-6/^-dibenz[c,e][1 ,2]oxaphosphorin-6- yl)-1 ,4-benzenediol (I, R = H) in a solvent selected from the group consisting of acetone, butanone, butyl acetate, ethyl acetate, methyl acetate, isopropyl alcohol, toluene, diethyl ether, diethyl carbonate, acetonithle, tetrahydro- furan, and any mixture of any of the foregoing,
(ϋ) adding at least two mol, based on one mol of benzenediol (I1 R = H), of cyanogen chloride at a temperature below 0 0C to the suspension obtained in step (i),
(iϋ) slowly adding at least two mol, based on one mol of benzenediol (I1 R = H), of thethylamine at a temperature below 0 0C, (iv) separating off the solid triethylammonium chloride formed during step (iii),
(V) evaporating the solvent until a concentrated solution containing at least 40 wt.% of the desired product (I, R = -C=N) is obtained,
(vi) cooling the concentrated solution obtained in step (v) to induce crystallization of the product, and
(vii) separating off and drying the crystallized product.
2. The process of claim 1 , wherein the solvent is selected from the group consisting of acetone, butanone and tetrahydrofuran.
3. The process of claim 2, wherein the solvent is acetone.
4. The process of any of claims 1 to 3, wherein in step (ii) the cyanogen chloride is added in an amount of 2.0 to 2.5 mol per mol of benzenediol (I1 R = H).
5. The process of claim 4, wherein in step (ii) the cyanogen chloride is added in an amount of 2.1 to 2.3 mol per mol of benzenediol (I1 R = H).
6. The process of any of claims 1 to 5, wherein in step (iii) the thethylamine is added in an amount of 2.0 to 2.2 mol per mol of benzenediol (I1 R = H).
7. The process of claim 6, wherein in step (iii) the triethylamine is added in an amount of 2.05 to 2.15 mol per mol of benzenediol (I, R = H).
8. The process of any of claims 1 to 7, wherein steps (ii) and (iii) are conducted at a temperature between -5 0C and -20 0C.
9. The process of any of claims 1 to 8, wherein the crystallization in step (vi) is induced by the addition of seed crystals at a temperature of 0-15 0C.
10. The process of any of claims 1 to 9, wherein the triethylammonium chloride obtained in step (iv) is treated with a strong base to recover the triethylamine which is then isolated by distillation.
1 1. The process of claim 10, wherein the strong base is sodium hydroxide.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP09005760.5 | 2009-04-24 | ||
| EP09005760 | 2009-04-24 |
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| Publication Number | Publication Date |
|---|---|
| WO2010121774A1 true WO2010121774A1 (en) | 2010-10-28 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2010/002395 WO2010121774A1 (en) | 2009-04-24 | 2010-04-20 | Process for the production of cyanic acid c,c'-[2-(6-oxido-6h-dibenz[c,e][1,2]oxa-phosphorin-6-yl)-1,4-phenylene] ester |
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| Country | Link |
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| WO (1) | WO2010121774A1 (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008088079A (en) * | 2006-09-29 | 2008-04-17 | Fushimi Pharm Co Ltd | Cyclic phosphinate compound comprising cyanato group and method for preparing the same |
-
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- 2010-04-20 WO PCT/EP2010/002395 patent/WO2010121774A1/en active Application Filing
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008088079A (en) * | 2006-09-29 | 2008-04-17 | Fushimi Pharm Co Ltd | Cyclic phosphinate compound comprising cyanato group and method for preparing the same |
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