WO2010049083A1 - Process for the production of organic dithiopyrophosphates - Google Patents
Process for the production of organic dithiopyrophosphates Download PDFInfo
- Publication number
- WO2010049083A1 WO2010049083A1 PCT/EP2009/007532 EP2009007532W WO2010049083A1 WO 2010049083 A1 WO2010049083 A1 WO 2010049083A1 EP 2009007532 W EP2009007532 W EP 2009007532W WO 2010049083 A1 WO2010049083 A1 WO 2010049083A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- methylpyridine
- steps
- water
- chloride
- base
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 claims abstract description 58
- WQYSXVGEZYESBR-UHFFFAOYSA-N thiophosphoryl chloride Chemical compound ClP(Cl)(Cl)=S WQYSXVGEZYESBR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000000185 1,3-diols Chemical class 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 6
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims abstract description 4
- 125000005997 bromomethyl group Chemical group 0.000 claims abstract description 4
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 claims abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000002585 base Substances 0.000 claims description 9
- LAUKEERIEDZFQE-UHFFFAOYSA-N 2-chloro-2-sulfanylidene-1,3,2$l^{5}-dioxaphosphinane Chemical compound ClP1(=S)OCCCO1 LAUKEERIEDZFQE-UHFFFAOYSA-N 0.000 claims description 7
- CIFZCCWGXMYJEU-UHFFFAOYSA-N dithiodiphosphoric acid Chemical compound OP(O)(=S)OP(O)(O)=S CIFZCCWGXMYJEU-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 239000008346 aqueous phase Substances 0.000 claims description 4
- 239000012074 organic phase Substances 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- 238000011084 recovery Methods 0.000 claims description 3
- 229910001854 alkali hydroxide Inorganic materials 0.000 claims description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- 239000012458 free base Substances 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 238000005580 one pot reaction Methods 0.000 claims description 2
- PFUKZFFEUQXNRF-UHFFFAOYSA-N 3-methylpyridin-1-ium;chloride Chemical compound [Cl-].CC1=CC=C[NH+]=C1 PFUKZFFEUQXNRF-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 238000010626 work up procedure Methods 0.000 description 2
- 0 *C(C(*)(*)C(*)(*)O1)OP1(OP1(OC(*)(*)C(*)(*)C(*)O1)=S)=S Chemical compound *C(C(*)(*)C(*)(*)O1)OP1(OP1(OC(*)(*)C(*)(*)C(*)O1)=S)=S 0.000 description 1
- ITQTTZVARXURQS-UHFFFAOYSA-O 3-methylpyridin-1-ium Chemical compound CC1=CC=C[NH+]=C1 ITQTTZVARXURQS-UHFFFAOYSA-O 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 238000010268 HPLC based assay Methods 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229940000425 combination drug Drugs 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 150000007530 organic bases Chemical group 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004753 textile Substances 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
- C07F9/657109—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 esters of oxyacids of phosphorus in which one or more exocyclic oxygen atoms have been replaced by (a) sulfur atom(s)
- C07F9/657136—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 esters of oxyacids of phosphorus in which one or more exocyclic oxygen atoms have been replaced by (a) sulfur atom(s) the molecule containing more than one cyclic phosphorus atom
-
- 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
- C07F9/657109—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 esters of oxyacids of phosphorus in which one or more exocyclic oxygen atoms have been replaced by (a) sulfur atom(s)
-
- 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
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/5398—Phosphorus bound to sulfur
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/06—Organic materials
- C09K21/12—Organic materials containing phosphorus
Definitions
- the invention relates to an improved process for the production of organic dithiopyrophosphates of formula
- R 1 , R 2 , R 3 , R 4 and R 5 independently are hydrogen, C1-4 alkyl, chloromethyl or bromomethyl.
- Compounds of formula I are known as flame retardants for polymers, in particular for textile applications, see e.g. NL 7508884 A.
- R 1 , R 2 , R 3 , R 4 and R 5 are as defined above, and
- C1-4 alkyl is to be understood to mean any linear or branched alkyl group having one to four carbon atoms, in particular methyl, ethyl, propyl, iso- propyl, butyl, isobutyl, sec-butyl and /e/f-butyl.
- 3-methylpyridine may be used alone or in a mixture with another solvent. In a preferred embodiment of the process of the invention, 3-methylpyridine is used as the sole solvent in both steps.
- 3-methylpyridine alone or in combina- tion with other bases.
- 3-methylpyridine is used as the sole base in both steps.
- both reaction steps are conducted as a one-pot reaction without isolating the 2-chloro-2-thioxo-1 ,3,2-dioxaphosphorinane intermediate (III).
- step (i) the thiophosphoryl chloride is slowly added to a solution of the 1 ,3-diol (II) in 3-methylpyridine and in step (ii) the water is slowly added to the reaction mixture obtained in step (i).
- steps (i) and (ii), at least in part, take place simultaneously in that the hydrolysis of the 2-chloro-2-thioxo-1 ,3,2-dioxaphosphorinane intermediate (III) commences before the whole 1 ,3-diol starting material (II) is reacted.
- the addition of water may be started after one half, one third, or even less of the thiophosphoryl chloride has been added.
- R 1 , R 4 and R 5 in formulas I, Il and III are hydrogen atoms at each occurrence and both R 2 and R 3 are methyl groups.
- Steps (i) and (ii) are advantageously conducted at reaction temperatures between -10 0 C and 100 0 C, preferably between 20 0 C and 100 0 C or between 40 0 C and 80 0 C. If both steps are conducted separately, the temperature in the first step is preferably between 20 0 C and 50 0 C, and in the second step between 50 0 C and 60 0 C. If thiophosphoryl chloride and water are added simultaneously or in overlapping periods of time, the reaction is preferably started at 20 0 C to 50 0 C and completed at 50 0 C to 60 0 C. Since the reaction is exothermic, the reaction temperature increase can — at least in part — be achieved by utilizing the heat of reaction.
- Both reaction steps can be conducted in relatively concentrated solutions, preferably using between 5 mol and 10 mol of 3-methylpyridine per mol of 1 ,3-diol (II) or thio- phosphoryl chloride. Since 3 mol of 3-methylpyridine per mol of thiophosphoryl chloride are required as base to bind the hydrogen chloride formed in steps (i) (2 mol of HCI) and (ii) (1 mol of HCI), the remaining amount of between 2 mol and 7 mol of 3-methylpyridine that can serve as solvent is remarkably small.
- the 3-methylpyridinium chloride is obtained in solid or liquid (i.e., melt or concentrated solution) form.
- the work-up of the reaction mixture obtained after step (ii) can be performed in a simple manner by adding an amount of water sufficient to dissolve the 3-methyl- pyhdinium chloride formed in reaction steps (i) and (ii) and isolating the dithiopyro- phosphate (I) by filtration.
- the 3-methylpyridinium chloride is obtained in liquid form the work-up can be further simplified by filtering off the product before addition of water.
- the dithiopyrophosphate is advantageously washed with water to remove residual 3-methylpridine and 3-methylpyridinium chloride. It has been found that the washing process can be facilitated by addition of a surfactant to the washing water.
- Preferred surfactants are nonionic surfactants such as triethanolamine polyglycol ethers. Suitable compounds are commercially available, e.g. under the brand name Stokomin ® (Bozzetto GmbH, Krefeld, Germany).
- the 3-methylpyridine is recovered from the filtrate and recycled.
- the recovery is conducted as follows: Water and an alkali hydroxide, most preferably sodium hydroxide, are added to the filtrate to liberate the 3-methylpyridine free base from the 3-methylpyridinium chloride formed in reaction steps (i) and (ii), whereby an aqueous phase containing dissolved alkali chloride and an organic phase comprising 3-methylpyridine and some dissolved water are formed.
- the aqueous phase is separated off and essentially pure 3-methylpyridine is obtained by rectification of the organic phase, where the recovered 3-methylpyridine is separated from the dissolved water that accumulates (as such or as azeotropic mixture with 3-methylpyridine) in the head of the rectification column.
- This recovery and recycling process is particularly easy when 3-methylpyridine is used as sole solvent.
- a 1 L stirred reactor was charged with 3-methylpyridine (600 g, 6.44 mol) and 2,2-di- methyl-1 ,3-propanediol (104.5 g, 1 mol). The mixture was warmed to 45 0 C and thio- phosphoryl chloride (PSCb, 98%, 172.9 g, 1 mol) was added over 4 h while the temperature was not allowed to exceed 50 0 C. After another 30 min, water (9.5 g, 0.53 mol) was added dropwise at 45-50 °C. The mixture was then warmed to 60 0 C and kept at that temperature for 15 h. Water (160 g) was then added to dissolve the 3-methylpyri- dinium chloride formed in the reaction.
- PSCb thio- phosphoryl chloride
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Pyridine Compounds (AREA)
Abstract
Organic dithiopyrophosphates of formula wherein R1, R2, R3, R4 and R5 independently are hydrogen, C1-4 alkyl, chloromethyl or bromomethyl, are prepared in a two-step process from the corresponding 1,3-diols and thiophosphoryl chloride, using 3-methylpyridine both as solvent and as base.
Description
Process for the production of organic dithiopyrophosphates
The invention relates to an improved process for the production of organic dithiopyrophosphates of formula
Compounds of formula I are known as flame retardants for polymers, in particular for textile applications, see e.g. NL 7508884 A.
Known processes for the production of the organic dithiopyrophosphates of formula I involve the reaction of a 1 ,3-diol with thiophosphoryl chloride (PSCb) to give a 2-chloro-2-thioxo-1 ,3,2-dioxaphosphorinane intermediate which is isolated and then reacted with an oxide, hydroxide, carbonate or hydrogencarbonate of an alkali or alkaline earth metal (most preferably calcium oxide) in the presence of a tertiary organic base (CH 625 806) or with water (NL 7508884 A). The prior art processes require different solvents or solvent mixtures for the two reaction steps and isolation of the intermediate 2-chloro-2-thioxo-1 ,3,2-dioxaphosphorinane. Moreover, when calcium oxide is used in the second step this results in the formation of calcium chloride which has to separated and disposed of.
It is an object of the present invention to provide a simplified process for the production of the organic dithiopyrophosphates of formula I that does not require different solvents and does not result in the formation of inorganic salts as byproducts.
According to the invention, this object has been accomplished by the process defined in claim 1. Applicants have found that organic dithiopyrophosphates of formula
(I),
wherein R1, R2, R3, R4 and R5 independently are hydrogen,
alkyl, chloromethyl or bromomethyl, can be produced by a process comprising the steps of
(i) reacting a 1 ,3-diol of formula
wherein R1, R2, R3, R4 and R5 are as defined above, and
(ii) partially hydrolyzing the 2-chloro-2-thioxo-1 ,3,2-dioxaphosphorinane (III) with water in the presence of a base to obtain the corresponding dithiopyrophosphate (I), wherein 3-methylpyridine is used both as an organic solvent and as a base in steps (i) and (ii).
Here and hereinbelow, C1-4 alkyl is to be understood to mean any linear or branched alkyl group having one to four carbon atoms, in particular methyl, ethyl, propyl, iso- propyl, butyl, isobutyl, sec-butyl and /e/f-butyl.
As a solvent, 3-methylpyridine may be used alone or in a mixture with another solvent. In a preferred embodiment of the process of the invention, 3-methylpyridine is used as the sole solvent in both steps.
It is also within the scope of the invention to use 3-methylpyridine alone or in combina- tion with other bases. In a preferred embodiment, 3-methylpyridine is used as the sole base in both steps.
In a particularly preferred embodiment, both reaction steps are conducted as a one-pot reaction without isolating the 2-chloro-2-thioxo-1 ,3,2-dioxaphosphorinane intermediate (III).
In an even more preferred embodiment, in step (i) the thiophosphoryl chloride is slowly added to a solution of the 1 ,3-diol (II) in 3-methylpyridine and in step (ii) the water is slowly added to the reaction mixture obtained in step (i). Surprisingly it has been found that it is possible to shorten the process of the invention by starting the addition of water before the addition of thiophosphoryl chloride is completed. Thus it is possible to have steps (i) and (ii), at least in part, take place simultaneously in that the hydrolysis of the 2-chloro-2-thioxo-1 ,3,2-dioxaphosphorinane intermediate (III) commences before the whole 1 ,3-diol starting material (II) is reacted. The addition of water may be started after one half, one third, or even less of the thiophosphoryl chloride has been added.
In an especially preferred embodiment, R1, R4 and R5 in formulas I, Il and III are hydrogen atoms at each occurrence and both R2 and R3 are methyl groups.
Steps (i) and (ii) are advantageously conducted at reaction temperatures between -10 0C and 100 0C, preferably between 20 0C and 100 0C or between 40 0C and 80 0C. If both steps are conducted separately, the temperature in the first step is preferably between 20 0C and 50 0C, and in the second step between 50 0C and 60 0C. If thiophosphoryl chloride and water are added simultaneously or in overlapping periods of time, the reaction is preferably started at 20 0C to 50 0C and completed at 50 0C to 60 0C. Since the reaction is exothermic, the reaction temperature increase can — at least in part — be achieved by utilizing the heat of reaction.
Both reaction steps can be conducted in relatively concentrated solutions, preferably using between 5 mol and 10 mol of 3-methylpyridine per mol of 1 ,3-diol (II) or thio- phosphoryl chloride. Since 3 mol of 3-methylpyridine per mol of thiophosphoryl chloride are required as base to bind the hydrogen chloride formed in steps (i) (2 mol of HCI) and (ii) (1 mol of HCI), the remaining amount of between 2 mol and 7 mol of 3-methylpyridine that can serve as solvent is remarkably small. Depending on the temperature, in particular the temperature in step (ii), and the amount of 3-methylpyridine used as solvent, the 3-methylpyridinium chloride is obtained in solid or liquid (i.e., melt or concentrated solution) form.
The work-up of the reaction mixture obtained after step (ii) can be performed in a simple manner by adding an amount of water sufficient to dissolve the 3-methyl- pyhdinium chloride formed in reaction steps (i) and (ii) and isolating the dithiopyro- phosphate (I) by filtration. In case the 3-methylpyridinium chloride is obtained in liquid form the work-up can be further simplified by filtering off the product before addition of water.
After filtration the dithiopyrophosphate is advantageously washed with water to remove residual 3-methylpridine and 3-methylpyridinium chloride. It has been found that the washing process can be facilitated by addition of a surfactant to the washing water. Preferred surfactants are nonionic surfactants such as triethanolamine polyglycol ethers. Suitable compounds are commercially available, e.g. under the brand name Stokomin® (Bozzetto GmbH, Krefeld, Germany).
In a preferred embodiment the 3-methylpyridine is recovered from the filtrate and recycled.
More preferably, the recovery is conducted as follows: Water and an alkali hydroxide, most preferably sodium hydroxide, are added to the filtrate to liberate the 3-methylpyridine free base from the 3-methylpyridinium chloride formed in reaction steps (i) and (ii), whereby an aqueous phase containing dissolved alkali chloride and an organic phase comprising 3-methylpyridine and some dissolved water are formed. The aqueous phase is separated off and essentially pure 3-methylpyridine is obtained by rectification of the organic phase, where the recovered 3-methylpyridine is separated from the dissolved water that accumulates (as such or as azeotropic mixture with 3-methylpyridine) in the head of the rectification column. This recovery and recycling process is particularly easy when 3-methylpyridine is used as sole solvent.
The following non-limiting example illustrates the process of the invention.
Example 1 2,2'-Oxybis-(5,5-dimethyl-1 ,3,2-dioxaphosphohnane)-2,2'-disulfide
(I, R1 = R4 = R5 = H, R2 = R3 = CH3)
A 1 L stirred reactor was charged with 3-methylpyridine (600 g, 6.44 mol) and 2,2-di- methyl-1 ,3-propanediol (104.5 g, 1 mol). The mixture was warmed to 45 0C and thio- phosphoryl chloride (PSCb, 98%, 172.9 g, 1 mol) was added over 4 h while the temperature was not allowed to exceed 50 0C. After another 30 min, water (9.5 g, 0.53 mol) was added dropwise at 45-50 °C. The mixture was then warmed to 60 0C and kept at that temperature for 15 h. Water (160 g) was then added to dissolve the 3-methylpyri-
dinium chloride formed in the reaction. The product was isolated by filtration, washed with water several times and sucked dry. To facilitate the removal of residual 3-methyl- pyridine, 0.015 wt.% Stokomin® Ml 07 surfactant (triethanolamine tris-alkylpolyglycol ether) was added to the washing water. Yield: 75%.
Example 2
2,2'-Oxybis-(5,5-dimethyl-1 ,3)2-dioxaphosphorinane)-2,2'-disulfide (I, Ri = R4 = R5 = H, R2 = R3 = CH3)
A 1 L stirred reactor was charged with 3-methylpyridine (600 g, 6.44 mol) and 2,2-di- methyl-1 ,3-propanediol (105.2 g, =1 mol). The mixture was warmed to 50 0C and thio- phosphoryl chloride (PSCb, 167.5 g, =1 mol) was added over 3 h while the tempera- ture was not allowed to exceed 50 0C. One hour after the start of the thiophosphoryl chloride addition the continuous addition of water (9.2 g, 0.51 mol) over a period of 5.5 h was started and after completion of the thiophosphoryl chloride addition the temperature was increased to 60 CC within 1 h. After completion of the water addition, stirring was continued overnight (ca. 16 h) at 60 0C. Water (18O g) was then added within about 2 min to dissolve the 3-methylpyridinium chloride formed in the reaction. The product was isolated by filtration and washed with the filtrate. Yield: 222 g moist product, content (HPLC assay): 66.1 %, corresponding to 84.6% yield.
Claims
1. A process for the production of an organic dithiopyrophosphate of formula
(i) reacting a 1 ,3-diol of formula
wherein R1, R2, R3, R4 and R5 are as defined above, in an organic solvent with thiophosphoryl chloride in the presence of a base, to obtain a 2-chloro-2-thioxo-1 ,3,2-dioxaphosphohnane of formula
wherein R1, R2, R3, R4 and R5 are as defined above, and (ii) partially hydrolyzing the 2-chloro-2-thioxo-1 ,3,2-dioxaphosphorinane (III) with water in the presence of a base to obtain the corresponding dithiopyrophosphate (I), characterized in that 3-methylpyhdine is used both as an organic solvent and as a base in steps (i) and (ii).
2. The process of claim 1 , wherein in steps (i) and (ii) 3-methylpyridine is used as the sole solvent.
3. The process of claim 1 or 2, wherein in steps (i) and (ii) 3-methylpyridine is used as the sole base.
4. The process of any of claims 1 to 3, wherein steps (i) and (ii) are conducted as a one-pot reaction without isolating the 2-chloro-2-thioxo-1 ,3,2-dioxaphosphorinane intermediate (III).
5. The process of claim 4, wherein in step (i) the thiophosphoryl chloride is slowly added to a solution of the 1 ,3-diol (II) in 3-methylpyridine and in step (ii) the water is slowly added to the reaction mixture obtained in step (i).
6. The process of claim 5, wherein the addition of water is started before the addition of thiophosphoryl chloride is completed.
7. The process of any of claims 1 to 6, wherein R1, R4 and R5 at each occurrence are hydrogen atoms and R2 and R3 are methyl groups.
8. The process of any of claims 1 to 7, wherein, after isolating the dithiopyro- phosphate (I) by filtration, the 3-methylpyridine is recovered from the filtrate and recycled.
9. The process of claim 8, wherein the 3-methylpyridine recovery comprises the steps of adding water and an alkali hydroxide to the filtrate to liberate the 3-methylpyridine free base from the 3-methylpyhdinium chloride formed in reaction steps (i) and (ii), thus forming an aqueous phase containing dissolved alkali chloride and an organic phase containing 3-methylpyridine and dissolved water; separating off the aqueous phase; and rectification of said organic phase to obtain essentially pure 3-methylpyridine.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EA201100660A EA017760B1 (en) | 2008-10-29 | 2009-10-21 | Process for the production of organic dithiopyrophosphates |
| CN200980141484.9A CN102186870B (en) | 2008-10-29 | 2009-10-21 | Process for the production of organic dithiopyrophosphates |
| US13/126,422 US8324418B2 (en) | 2008-10-29 | 2009-10-21 | Process for he production of organic dithiopyrophosphates |
| EP09740274A EP2350103A1 (en) | 2008-10-29 | 2009-10-21 | Process for the production of organic dithiopyrophosphates |
| HK11114054.1A HK1159639A1 (en) | 2008-10-29 | 2011-12-29 | Process for the production of organic dithiopyrophosphates |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP08018859.2 | 2008-10-29 | ||
| EP08018859 | 2008-10-29 | ||
| EP09008812.1 | 2009-07-06 | ||
| EP09008812 | 2009-07-06 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2010049083A1 true WO2010049083A1 (en) | 2010-05-06 |
Family
ID=41278296
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2009/007532 WO2010049083A1 (en) | 2008-10-29 | 2009-10-21 | Process for the production of organic dithiopyrophosphates |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US8324418B2 (en) |
| EP (1) | EP2350103A1 (en) |
| KR (1) | KR20110091699A (en) |
| CN (1) | CN102186870B (en) |
| EA (1) | EA017760B1 (en) |
| HK (1) | HK1159639A1 (en) |
| TW (1) | TWI427082B (en) |
| WO (1) | WO2010049083A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107674096A (en) * | 2017-10-31 | 2018-02-09 | 南通江山农药化工股份有限公司 | Uninanned platform technique and its equipment of the organic disulfide for pyrophosphate fire retardant |
| CN109705390A (en) * | 2018-12-29 | 2019-05-03 | 南京师范大学 | A kind of Halogen ring-type pyrophosphate is preparing the application in flame retarded rigid polyurethane foams plastics |
| CN109503662A (en) * | 2019-01-14 | 2019-03-22 | 马鞍山昂扬新材料科技有限公司 | The preparation method of viscose rayon combustion inhibitor special |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL7508884A (en) * | 1974-07-30 | 1976-02-03 | Sandoz Ag | PROCESS FOR PREPARING POLYMER MATERIALS. |
| CH603674A5 (en) * | 1975-05-16 | 1978-08-31 | Sandoz Ag | Derivs of bis (2-(oxo or thiono)-1,3,2-dioxaphosphorinanyl)oxide |
| US5948930A (en) * | 1997-09-11 | 1999-09-07 | Bayer Corporation | Process for preparing O-alkyl, O-alkylphosphorochloridothioates |
-
2009
- 2009-10-21 US US13/126,422 patent/US8324418B2/en not_active Expired - Fee Related
- 2009-10-21 CN CN200980141484.9A patent/CN102186870B/en not_active Expired - Fee Related
- 2009-10-21 EA EA201100660A patent/EA017760B1/en not_active IP Right Cessation
- 2009-10-21 WO PCT/EP2009/007532 patent/WO2010049083A1/en active Application Filing
- 2009-10-21 EP EP09740274A patent/EP2350103A1/en not_active Withdrawn
- 2009-10-21 KR KR1020117012142A patent/KR20110091699A/en active IP Right Grant
- 2009-10-23 TW TW098135900A patent/TWI427082B/en not_active IP Right Cessation
-
2011
- 2011-12-29 HK HK11114054.1A patent/HK1159639A1/en not_active IP Right Cessation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL7508884A (en) * | 1974-07-30 | 1976-02-03 | Sandoz Ag | PROCESS FOR PREPARING POLYMER MATERIALS. |
| CH603674A5 (en) * | 1975-05-16 | 1978-08-31 | Sandoz Ag | Derivs of bis (2-(oxo or thiono)-1,3,2-dioxaphosphorinanyl)oxide |
| US5948930A (en) * | 1997-09-11 | 1999-09-07 | Bayer Corporation | Process for preparing O-alkyl, O-alkylphosphorochloridothioates |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2350103A1 (en) | 2011-08-03 |
| US20110207955A1 (en) | 2011-08-25 |
| US8324418B2 (en) | 2012-12-04 |
| TWI427082B (en) | 2014-02-21 |
| HK1159639A1 (en) | 2012-08-03 |
| CN102186870B (en) | 2014-03-19 |
| EA201100660A1 (en) | 2011-12-30 |
| CN102186870A (en) | 2011-09-14 |
| TW201016719A (en) | 2010-05-01 |
| KR20110091699A (en) | 2011-08-12 |
| EA017760B1 (en) | 2013-02-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2010042887A2 (en) | Methods for preparing oxazolidinones and compositions containing them | |
| JP2007530687A5 (en) | ||
| JP2024023340A (en) | Preparation method for glufosinate ammonium | |
| US8324418B2 (en) | Process for he production of organic dithiopyrophosphates | |
| JPH03372B2 (en) | ||
| KR100976762B1 (en) | Improved method for preparation of adefovir dipivoxil | |
| JP3287845B2 (en) | Method for improving the synthesis of 2,6-dichloro-5-fluoronicotinic acid and 2,6-dichloro-5-fluoronicotinoyl chloride | |
| JP4228571B2 (en) | Method for producing aromatic aldehyde | |
| CN106674281B (en) | A kind of Rosuvastatin midbody compound, preparation method and its usage | |
| RU2260010C2 (en) | Method for preparing n-phosphonomethylglycine and intermediate substance for its preparing | |
| CN113387844B (en) | Preparation method of dialkyl azodicarbonate | |
| CN102612512A (en) | Process for the preparation of substituted phenylalanines | |
| US20210198172A1 (en) | Process for preparing an alkoxymethyl alkynyl ether compound having a terminal triple bond | |
| JPH0421674A (en) | Production of 2-chloro-5-(aminomethyl)thiazole | |
| US2996531A (en) | Preparation of alkylcarbamoylmethyl dimethylphosphorodithioates | |
| US4703123A (en) | Process for producing 2,3,5,6-tetrachloropyridine | |
| JPH0419216B2 (en) | ||
| JPH02196757A (en) | Preparation of 2-chlorobenzylamine | |
| KR100281844B1 (en) | Method for producing bisstyryl fluorescent brightener | |
| KR20000017154A (en) | Improved process for the production of an N-acyl derivative of O,S-dialkyl phosphoroamidothioate | |
| JPH0687820A (en) | Method of preparing n-alkylsulfonamide | |
| JP2659587B2 (en) | 4-aziridinyl pyrimidine derivatives and their production | |
| US4804764A (en) | Process for producing 2,3,5,6-tetrachloropyridine | |
| EP0090202B1 (en) | Process for preparing p.chlorophenoxyacetyl-piperonylpiperazine | |
| CA1233823A (en) | Process for the production of 4-substituted acetoacetic acid derivatives |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| WWE | Wipo information: entry into national phase |
Ref document number: 200980141484.9 Country of ref document: CN |
|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 09740274 Country of ref document: EP Kind code of ref document: A1 |
|
| DPE1 | Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101) | ||
| REEP | Request for entry into the european phase |
Ref document number: 2009740274 Country of ref document: EP |
|
| WWE | Wipo information: entry into national phase |
Ref document number: 2009740274 Country of ref document: EP |
|
| WWE | Wipo information: entry into national phase |
Ref document number: 13126422 Country of ref document: US |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| WWE | Wipo information: entry into national phase |
Ref document number: 201100660 Country of ref document: EA |
|
| WWE | Wipo information: entry into national phase |
Ref document number: 3919/DELNP/2011 Country of ref document: IN |
|
| ENP | Entry into the national phase |
Ref document number: 20117012142 Country of ref document: KR Kind code of ref document: A |