CA2040603A1 - Process for the preparation of 1-halogen-1-oxophospholenes - Google Patents
Process for the preparation of 1-halogen-1-oxophospholenesInfo
- Publication number
- CA2040603A1 CA2040603A1 CA002040603A CA2040603A CA2040603A1 CA 2040603 A1 CA2040603 A1 CA 2040603A1 CA 002040603 A CA002040603 A CA 002040603A CA 2040603 A CA2040603 A CA 2040603A CA 2040603 A1 CA2040603 A1 CA 2040603A1
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- Prior art keywords
- alkyl
- bromine
- chlorine
- reaction
- process according
- Prior art date
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- Abandoned
Links
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 15
- 239000011574 phosphorus Substances 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 10
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 23
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 23
- 229910052794 bromium Inorganic materials 0.000 claims description 23
- 229910052801 chlorine Inorganic materials 0.000 claims description 23
- 239000000460 chlorine Substances 0.000 claims description 23
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 14
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 125000006526 (C1-C2) alkyl group Chemical group 0.000 claims description 3
- 125000006705 (C5-C7) cycloalkyl group Chemical group 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 229910000064 phosphane Inorganic materials 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 150000003002 phosphanes Chemical class 0.000 claims description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims 4
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims 3
- 238000011065 in-situ storage Methods 0.000 claims 2
- 239000005922 Phosphane Substances 0.000 claims 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 238000002955 isolation Methods 0.000 claims 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 abstract description 3
- 150000002148 esters Chemical class 0.000 abstract description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 12
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000004821 distillation Methods 0.000 description 5
- NGGOLKYHIKQDQB-UHFFFAOYSA-N 1-chloro-4-methyl-2,3-dihydro-1$l^{5}-phosphole 1-oxide Chemical class CC1=CP(Cl)(=O)CC1 NGGOLKYHIKQDQB-UHFFFAOYSA-N 0.000 description 4
- HCSDJECSMANTCX-UHFFFAOYSA-N dichloro(methoxy)phosphane Chemical compound COP(Cl)Cl HCSDJECSMANTCX-UHFFFAOYSA-N 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000012267 brine Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001350 alkyl halides Chemical class 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 2
- CVWUIWZKLYGDNJ-UHFFFAOYSA-N tripentyl phosphite Chemical compound CCCCCOP(OCCCCC)OCCCCC CVWUIWZKLYGDNJ-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- SQCZQTSHSZLZIQ-UHFFFAOYSA-N 1-chloropentane Chemical compound CCCCCCl SQCZQTSHSZLZIQ-UHFFFAOYSA-N 0.000 description 1
- AGIJRRREJXSQJR-UHFFFAOYSA-N 2h-thiazine Chemical compound N1SC=CC=C1 AGIJRRREJXSQJR-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- PHSPJQZRQAJPPF-UHFFFAOYSA-N N-alpha-Methylhistamine Chemical compound CNCCC1=CN=CN1 PHSPJQZRQAJPPF-UHFFFAOYSA-N 0.000 description 1
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- YGZSVWMBUCGDCV-UHFFFAOYSA-N chloro(methyl)silane Chemical class C[SiH2]Cl YGZSVWMBUCGDCV-UHFFFAOYSA-N 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000011067 equilibration Methods 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- XTTGYFREQJCEML-UHFFFAOYSA-N tributyl phosphite Chemical compound CCCCOP(OCCCC)OCCCC XTTGYFREQJCEML-UHFFFAOYSA-N 0.000 description 1
- SJHCUXCOGGKFAI-UHFFFAOYSA-N tripropan-2-yl phosphite Chemical compound CC(C)OP(OC(C)C)OC(C)C SJHCUXCOGGKFAI-UHFFFAOYSA-N 0.000 description 1
- ILLOBGFGKYTZRO-UHFFFAOYSA-N tris(2-ethylhexyl) phosphite Chemical compound CCCCC(CC)COP(OCC(CC)CCCC)OCC(CC)CCCC ILLOBGFGKYTZRO-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 System
- 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
- C07F9/6568—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 atoms as the only ring hetero atoms
- C07F9/65681—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 atoms as the only ring hetero atoms the ring phosphorus atom being part of a (thio)phosphinic acid or ester thereof
Abstract
ABSTRACT OF THE DISCLOSURE
This invention relates to a process for the preparation of 1-halogen-1-oxophospholenes by the reaction of phosphorous acid monoalkyl ester dihalides with 1,3-dienes which is carried out continuously in a single stage under pressure and at elevated temperatures, using phosphorus trihalides as solvents.
Le A 27 569
This invention relates to a process for the preparation of 1-halogen-1-oxophospholenes by the reaction of phosphorous acid monoalkyl ester dihalides with 1,3-dienes which is carried out continuously in a single stage under pressure and at elevated temperatures, using phosphorus trihalides as solvents.
Le A 27 569
Description
2 ~ J.
A ~ROCESS FOR THE PREPARATION OF l-HALOGEN-l-OXOPHOSPHOLENES
BACKGROUND OF THE INVENTION
~ his invention relates to a process for the preparation of l-halogen-l-oxophospholenes by the continuous reaction of alkoxydihalogen phosphanes with 1,3-dienes.
l-Halogen-l-oxophospholenes corresponding to the following general foni,~la ~ x , ~ or ~ O
in which the groups R2, R3, R4 and R5 denote, independent-ly of one another, hydrogen, chlorine, bromine or (Cl-C4)-alkyl groups optionally substituted with chlorine or bromine and X stands for chlorine or bromine are important starting compounds, e.g. for substances used as flame-retarding compounds in halogen-free synthetic resin systems, as carbodiimidisation catalysts or as fungicides.
The increasing demand for l-halogen-1-oxophosphol-.
enes has made it essential to prepare these compounds in ~e A 27 569 industrial quantities. The methods of synthesis hitherto known have, however, various disadvantages so that large quantities could hitherto not be produced or only under very disadvantageous conditions.
Thus DE-PS 1 191 204, for example, describes the direct addition of phosphorus trihalides to 1,3-dienes to produce trihalogenphospholenes which are then converted into l-halogen-l-oxophospholenes by a reaction with oxygen-donor substances such as water, alcohols, ketones, orthocarbonyl compounds, etc. This process is, however, very unsatisfactory on account of the rlaction times, which extend over several days, the number of stages required and the poor yields.
Another process uses phosphorous acid monoester dichlorides as starting materials which are added to 1,3-dienes in an autoclave and then split up into l-halogen-l-oxophospholenes and alkyl halides or alkylene dihalides [B.A. Arbusov, A.O. Vizel, Y.Y. Samitov and Y.F. Tarenko, Izv, Akad. Nauk, SSSR, Ser. Khim (1967) (3), 648; N.A.
Razumova, L.J. Zubtsova and A.A. Petrov, Zh. Obsh. Khim.
40 (12), 2554, (1969)~. The reaction times may be reduced within certain limits by the addition of phosphorus trihalides tN.N. Bliznyuk, Z.N. Kvasha and A.F. Kolomiets, Zh. Obschch. Khim. 37, 1811 (1967)] but even then, economically acceptable short reaction times are not obtained.
The problem therefore arose of providing a process by which large quantities of l-halogen-l-oxophospholenes could be produced economically without the above-described disadvantages o~ the known processes, such as long reaction times, low yields and polymerisation of the diene components, ~nd which w~uld be simple to handle.
This problem has been solved by the process according to the inYention.
Le A 27 569 2 DESC~IPTION OF THE PREFERRED EMBODIMENTS
This invention relates to a process for the preparation of l-halogen-l-oxophospholenes by the reaction of phosphorous acid monoalkyl ester dihalides with 1,3-dienes which is carried out continuously in a single stageunder pressure and at elevated temperatures, using phosphorus trihalides as solvents.
The reaction is illustrated by the following reaction scheme:
~ ~ R OPX2 3 ~ ~ ~ Rl-X
R3 1 as solvent R3 H R2 in which R2, R3, R4 and R5 may denote, independently of one another, hydrogen or (Cl-C4)-alkyl, preferably (Cl-C2)-alkyl, optionally substituted with chlorine and/or bromine, and the gr_up R1 is a ~Cl-C10)-alkyl group, preferably a (Cl-C5)-alkyl group, optionally substituted with chlorine and/or bromine and X may stand for chlorine or bromine.
Particularly preferred is the continuous reaction Df phosphorus trihalides, trialkylphosphites and 1,3-dienes or phosphorus trihalides, 1,2-epoxides and 1,3-dienes -in excess phosphorus trihalide. In this reaction, the intermediate products (alkoxydihalogenphosphanes) formed from the reaction of phosphorus trihalides with trialkylphosphites or epoxides need not be icolated.
The phosphorus trihalide is preferably used in an excess of from 75 to 125%.
Le A ~7 569 3 ~ $s The intermediate products talkoxydihalogenphos-phanes~ are formed in accordance with the following reaction scheme:
2 PX3 ~ p(oP~l) 3 PX3 ~, 3 RlOPX2 as solvent or PX3 1 ~C - C\ PX3 ~ R1OPX2, Rl = X-C -C
R6 o R9 as solvent R6 R9 in which X ctands for chlorine or bromine, Rl stands for a (Cl-C10)-alkyl group, preferably a (Cl-C5)-alkyl group, optionally substituted with chlorine and/or bromine and R6, R7, R8 and R9 denote, independently of one another, hydrogen, chlorine, bromine or (Cl-C~)-alkyl, preferably (C1-C2)-alkyl, optionally substituted with chlorine and/or 10 bromine, or they denote (C5-C7)-cycloalkyl or phenyl.
Most of the isomerically pure l-halogen-l-oxophos-pholenes are in crystalline form at room temperature, which normally renders them difficult to handle. Under the conditions of synthesis according to the invention, 15 however, these compounds are always obtained as an isomeric mixture of l-halogen-l-oxophospholene-3 and l-halogen-1-oxophospholene-2, in most cases in liquid form.
The phosphorus trihalides used for the process 20 according to the invention may be phosphorus trichloride or phosphorus tribromide.
The alkyl dihalogenphosphanes to be used according to the invention are ~ompounds corresponding to the general formula RlC)PX2 25 in which the group denoted by Rl is a (Cl-C10)-alkyl Le A 27_569 4 L ~L~
group, preferably a (Cl-C5~-alkyl group, optionally substituted with chlorine and/or bromine, and X may stand for chlorine or bromine. These compounds may be prepared by known methods, e.g. from phosphorus trihalides and 5 alcohols with removal of the resulting hydrogen chloride in a vacuum. Other known processes for their preparation are given in Houben-Weyl, Methoden der Organischen Chemie, Volume 12/2, pages 12 et seq and Supplementary Volume E 1, pages 352 et seq.
The following are examples of the trialkylphos-phites of the general formula i' P(ORl)3, wherein Rl has the meaning indicated above used for the 15 special embodiment of the process according to the invention: ~rimethylphosphite, triethylphosphite, tri-isopropylphosphite, tributylphosphite, tripentylphosphite, tris-(2-ethyl-hexyl)-phosphite and tri-2-chloroethyl-phosphite, the low boiling methyl and ethyl derivatives 20 being preferred. An important criterion for the choice for the trialkylphosphites is the suitability for technical utilization of the alkyl halides obtained as by-products of the reaction with phosphorus trihalide. When methoxy-dichlorophosphane prepared from phosphorus trichloride and25 methanol or by equilibration of phosphorus trichloride with trimethylphosphite is used, chloromethane is obtained as by-product in addition to l-chloro-l-oxophospholene and may be used, for example, in the Rochow synthesis of methylchlorosilanes.
3D The 1,2-epoxides to be used in the special embodiment of the process according to the invention may be compounds corresponding to the following formula ~e ~ 27 5~9 5 2 ~ ~ f ~
~6 ~ R9 wherein R6, R7, R8 and R9 denot2, independently of one another, hydrogen, chlorine, bromine, (Cl-C4)-alXyl, preferably (Cl-C2~-alkyl, optionally substituted with chlorine and/or bromine, or (C5-C7)-cycloalkyl or phenyl.
Ethylene oxide, propylene oxide and epichlorohydrin are preferred.
The 1,3-dienes used may in principle be any 1,3-dienes corresponding to the following general formula R4 ~H
R3~
in which R2, R3, R4 and R5 may denote, independently of one another, hydrogen, chlorine, bromine or (Cl-C4)-alkyl, preferably (C1-C2)-alkyl, optionally substituted with chlorine and/or bromine. The following are examples of particularly suitable 1,3-dienes: Butadiene, isoprene, chloroprene and l-methyl-butadiene. Butadiene and isoprene are particularly preferred.
Polymerisation inhibitors which are coluble in the reaction mixture, e.g. phen~thiazine, hydroquinone, p-tert.-butylpyrocatechol, etc. may be added to the reaotion mixture in quantities of up to 1% by weiqht (Houben-Weyl, Methoden der Orqanischen Chemie, Volume 14/1, pages 26 et seq).
~ç A 2? _569 6 2 ~ 3 ~' The process according to the invention is prefer-ably carried out in a temperature range of from 50 to 180~C, most preferably from 100 to 150~C.
The reaction times depend on the temperatures employed. At the preferred temperature range, they are generally from 15 minutes to 2 hours, in particular from 30 minutes to 1 hour.
The process according to the invention may, for example, be carried out as follows:
The starting materials are introduced by dosing pumps into a ~ixing vessel which is equipped for cooling and also serves as receiver !for a pressure resistant dosing pump used for conveying the reaction mixture into a heatable pressure coil. A valve attached to the end of the pressure coil maintains the required pressure inside the coil. This pressure is equal to the vapour pressure of the volatile components at the given reaction temperature.
Discharge of the reaction products also takes place through the above-mentioned valve.
The l-halogen-l-oxophospholene is freed by known methods, e.g. distillation at low pressure, from the phosphorus trihalide used as solvent and the halogen or dihalogenalkane produced as by-product.
Further purification oP the l-halogen-1-oxophos-2j pholene may also be carried out by distillation at reduced pressure.
The invention will now be described in more detail with the aid of the following Examples.
Le A 27 569 7 EXAMPLES
Example l Continuous preparation of an isomeric mixture of 1-chloro-3-methyl-1-oxophospholenes 275 g (4 mol) of isoprene, gl7 g (6,67 mol) of phosphorus trichloride and 165 g (1.33 mol) of trimethyl-phosphite are measured per hour into a water cooled mixing vessel. The tempe ature in the mixing vessel is 18~C.
A pressure resistant pump delivers the homogeneous reaction mixture (1.2 l/hour) into a reaction coil of 700 ml capacity situated in an oil bath heated to 130~C.
The average dwe~l time is 35 minutes. The pressure inside the reaction coil is 15 bar. As the reaction mixture leaves the reaction coil, the pressure in the mixture is released and the mixture cools and is collected in a crude product container by way of a pressure retaining valve.
Most of the chloromethane escapes at this stage and is condensed in a brine condenser and collected in another container also cooled with brine. The yields are deter-mined by measuring the hourly rates of throughput. The crude product is heated to 80~C at normal pressure to drive out any remaining chloromethane. Excess phosphorus trichloride is drawn off at 20 mbar up to a sump tempera-ture of 70~C and is condensed in a brine condenser.
Distillation of the residue (110 - 120~C at 3 mbar) yields 568 g (94.4% of the theoretical yield) of 1-chloro-3-methyl-l-oxophospholene. The isomeric mixture is composed of 58% of 1-chloro-3-methyl-1-oxophospholene-3 and 42% of l-chloro-3-methyl-1-oxophospholene-2. The yield of chloromethane is 196 g (97% of theoretical yield).
Ex~
The same procedure is carried out in Example 2 as in Example 1. Methoxydichlorophosphane is in this case used as starting material which has previously been prepared in a separate apparatus by a known method from phosphor~s trichloride and methanol and already contains Le A 27 569 8 3~
the excess phosphorus trichloride required as solvent for the subsequent reaction.
The following are introduced per hour into the cooled mixing vessel:
S 275 g (4 mol) of isoprene and 1082 g of the previously prepared methoxydichlorophosphane/phosphorus trichloride mixture containing 4 mol of methoxydichloro-phosphane.
Reaction and working up are carried out as described in Example 1.
539 g (89.5% of theoretical yield) of 1-chloro-3-methyl-l-oxophospholene purified by distillation are obtained per hour.
Example 3 The following are reacted per hour under conditions analogous to those of Example 1:
275 g (4 mol) of isoprene, 917 g (6.67 mol) of phosphorus trichloride and 221 g (1.33 mol) of triethylphosphite.
The pressure maintained during the continuous process is 10 bar.
The quantity of reaction mixture collected per hour is used for determining the yield.
After the product has been worked up by distilla-tion, 500 g (83.0% of the theoretical amount) of an isomeric mixture of 1-chloro-3-methyl-1-oxophospholene are obtained. It consists of 21.8% of 1-chloro-3-methyl-1-oxophospholene-3 and 78.2% of 1-chloro-3-methyl-1-oxophospholene-2.
238 g (92.2% of the theoretical amount) of ethyl chloride are obtained.
~xam~le 4 The following are continuously reacted per hour under the conditions described in Example 1:
275 g (4 mol) of isoprene, 917 g (6.67 mol) of phosphorus trichloride and 388 g (1.33 mol) of tri-n-pentylphosphite.
Le A 2? 569 9 The pressure in the reaction coil i~ 3 bar.
The quantitv of reaction mixture collected per hour for distillative working up is used for ~etermining the yield. The following are obtained:
358 g ~84% of theoretical amount) of n-pentyl chloride and 495 g ~.2% o~ theoretical amount) of an isomeric mixture of 18.1% of 1-chloro-3-methyl-1-oxophos-pholene-3 and 81.9% of 1-chloro~3-methyl-1-oxophos-pholene-2.
Example 5 The procedure is the same as in Example 1.
But~diene, phosphorus trichloride and trimethylphosphite i are put into the process.
The following were put through per hour:
216 g (4 mol) of butadiene, 917 g (6.67 mol) of phosphorus trichloride and 165 g (1.33 mol) of trimethylphosphite.
Determination of the yield is based on the quantity of reaction mixture obtained per hour, which after distillative working up of provides 494 g (90. 5~) of an isomeric mixture of 56% of 1-chloro-1-oxophospholene-3 and 44% of 1-chloro-1-oxophospholene-2.
It is undexstood that the specification and examples are illustrative but not limitative of the present invention and that other embodiments within the spirit and scope of the invention will suggest themselves to those skilled in the art.
e A 27 ~69 10
A ~ROCESS FOR THE PREPARATION OF l-HALOGEN-l-OXOPHOSPHOLENES
BACKGROUND OF THE INVENTION
~ his invention relates to a process for the preparation of l-halogen-l-oxophospholenes by the continuous reaction of alkoxydihalogen phosphanes with 1,3-dienes.
l-Halogen-l-oxophospholenes corresponding to the following general foni,~la ~ x , ~ or ~ O
in which the groups R2, R3, R4 and R5 denote, independent-ly of one another, hydrogen, chlorine, bromine or (Cl-C4)-alkyl groups optionally substituted with chlorine or bromine and X stands for chlorine or bromine are important starting compounds, e.g. for substances used as flame-retarding compounds in halogen-free synthetic resin systems, as carbodiimidisation catalysts or as fungicides.
The increasing demand for l-halogen-1-oxophosphol-.
enes has made it essential to prepare these compounds in ~e A 27 569 industrial quantities. The methods of synthesis hitherto known have, however, various disadvantages so that large quantities could hitherto not be produced or only under very disadvantageous conditions.
Thus DE-PS 1 191 204, for example, describes the direct addition of phosphorus trihalides to 1,3-dienes to produce trihalogenphospholenes which are then converted into l-halogen-l-oxophospholenes by a reaction with oxygen-donor substances such as water, alcohols, ketones, orthocarbonyl compounds, etc. This process is, however, very unsatisfactory on account of the rlaction times, which extend over several days, the number of stages required and the poor yields.
Another process uses phosphorous acid monoester dichlorides as starting materials which are added to 1,3-dienes in an autoclave and then split up into l-halogen-l-oxophospholenes and alkyl halides or alkylene dihalides [B.A. Arbusov, A.O. Vizel, Y.Y. Samitov and Y.F. Tarenko, Izv, Akad. Nauk, SSSR, Ser. Khim (1967) (3), 648; N.A.
Razumova, L.J. Zubtsova and A.A. Petrov, Zh. Obsh. Khim.
40 (12), 2554, (1969)~. The reaction times may be reduced within certain limits by the addition of phosphorus trihalides tN.N. Bliznyuk, Z.N. Kvasha and A.F. Kolomiets, Zh. Obschch. Khim. 37, 1811 (1967)] but even then, economically acceptable short reaction times are not obtained.
The problem therefore arose of providing a process by which large quantities of l-halogen-l-oxophospholenes could be produced economically without the above-described disadvantages o~ the known processes, such as long reaction times, low yields and polymerisation of the diene components, ~nd which w~uld be simple to handle.
This problem has been solved by the process according to the inYention.
Le A 27 569 2 DESC~IPTION OF THE PREFERRED EMBODIMENTS
This invention relates to a process for the preparation of l-halogen-l-oxophospholenes by the reaction of phosphorous acid monoalkyl ester dihalides with 1,3-dienes which is carried out continuously in a single stageunder pressure and at elevated temperatures, using phosphorus trihalides as solvents.
The reaction is illustrated by the following reaction scheme:
~ ~ R OPX2 3 ~ ~ ~ Rl-X
R3 1 as solvent R3 H R2 in which R2, R3, R4 and R5 may denote, independently of one another, hydrogen or (Cl-C4)-alkyl, preferably (Cl-C2)-alkyl, optionally substituted with chlorine and/or bromine, and the gr_up R1 is a ~Cl-C10)-alkyl group, preferably a (Cl-C5)-alkyl group, optionally substituted with chlorine and/or bromine and X may stand for chlorine or bromine.
Particularly preferred is the continuous reaction Df phosphorus trihalides, trialkylphosphites and 1,3-dienes or phosphorus trihalides, 1,2-epoxides and 1,3-dienes -in excess phosphorus trihalide. In this reaction, the intermediate products (alkoxydihalogenphosphanes) formed from the reaction of phosphorus trihalides with trialkylphosphites or epoxides need not be icolated.
The phosphorus trihalide is preferably used in an excess of from 75 to 125%.
Le A ~7 569 3 ~ $s The intermediate products talkoxydihalogenphos-phanes~ are formed in accordance with the following reaction scheme:
2 PX3 ~ p(oP~l) 3 PX3 ~, 3 RlOPX2 as solvent or PX3 1 ~C - C\ PX3 ~ R1OPX2, Rl = X-C -C
R6 o R9 as solvent R6 R9 in which X ctands for chlorine or bromine, Rl stands for a (Cl-C10)-alkyl group, preferably a (Cl-C5)-alkyl group, optionally substituted with chlorine and/or bromine and R6, R7, R8 and R9 denote, independently of one another, hydrogen, chlorine, bromine or (Cl-C~)-alkyl, preferably (C1-C2)-alkyl, optionally substituted with chlorine and/or 10 bromine, or they denote (C5-C7)-cycloalkyl or phenyl.
Most of the isomerically pure l-halogen-l-oxophos-pholenes are in crystalline form at room temperature, which normally renders them difficult to handle. Under the conditions of synthesis according to the invention, 15 however, these compounds are always obtained as an isomeric mixture of l-halogen-l-oxophospholene-3 and l-halogen-1-oxophospholene-2, in most cases in liquid form.
The phosphorus trihalides used for the process 20 according to the invention may be phosphorus trichloride or phosphorus tribromide.
The alkyl dihalogenphosphanes to be used according to the invention are ~ompounds corresponding to the general formula RlC)PX2 25 in which the group denoted by Rl is a (Cl-C10)-alkyl Le A 27_569 4 L ~L~
group, preferably a (Cl-C5~-alkyl group, optionally substituted with chlorine and/or bromine, and X may stand for chlorine or bromine. These compounds may be prepared by known methods, e.g. from phosphorus trihalides and 5 alcohols with removal of the resulting hydrogen chloride in a vacuum. Other known processes for their preparation are given in Houben-Weyl, Methoden der Organischen Chemie, Volume 12/2, pages 12 et seq and Supplementary Volume E 1, pages 352 et seq.
The following are examples of the trialkylphos-phites of the general formula i' P(ORl)3, wherein Rl has the meaning indicated above used for the 15 special embodiment of the process according to the invention: ~rimethylphosphite, triethylphosphite, tri-isopropylphosphite, tributylphosphite, tripentylphosphite, tris-(2-ethyl-hexyl)-phosphite and tri-2-chloroethyl-phosphite, the low boiling methyl and ethyl derivatives 20 being preferred. An important criterion for the choice for the trialkylphosphites is the suitability for technical utilization of the alkyl halides obtained as by-products of the reaction with phosphorus trihalide. When methoxy-dichlorophosphane prepared from phosphorus trichloride and25 methanol or by equilibration of phosphorus trichloride with trimethylphosphite is used, chloromethane is obtained as by-product in addition to l-chloro-l-oxophospholene and may be used, for example, in the Rochow synthesis of methylchlorosilanes.
3D The 1,2-epoxides to be used in the special embodiment of the process according to the invention may be compounds corresponding to the following formula ~e ~ 27 5~9 5 2 ~ ~ f ~
~6 ~ R9 wherein R6, R7, R8 and R9 denot2, independently of one another, hydrogen, chlorine, bromine, (Cl-C4)-alXyl, preferably (Cl-C2~-alkyl, optionally substituted with chlorine and/or bromine, or (C5-C7)-cycloalkyl or phenyl.
Ethylene oxide, propylene oxide and epichlorohydrin are preferred.
The 1,3-dienes used may in principle be any 1,3-dienes corresponding to the following general formula R4 ~H
R3~
in which R2, R3, R4 and R5 may denote, independently of one another, hydrogen, chlorine, bromine or (Cl-C4)-alkyl, preferably (C1-C2)-alkyl, optionally substituted with chlorine and/or bromine. The following are examples of particularly suitable 1,3-dienes: Butadiene, isoprene, chloroprene and l-methyl-butadiene. Butadiene and isoprene are particularly preferred.
Polymerisation inhibitors which are coluble in the reaction mixture, e.g. phen~thiazine, hydroquinone, p-tert.-butylpyrocatechol, etc. may be added to the reaotion mixture in quantities of up to 1% by weiqht (Houben-Weyl, Methoden der Orqanischen Chemie, Volume 14/1, pages 26 et seq).
~ç A 2? _569 6 2 ~ 3 ~' The process according to the invention is prefer-ably carried out in a temperature range of from 50 to 180~C, most preferably from 100 to 150~C.
The reaction times depend on the temperatures employed. At the preferred temperature range, they are generally from 15 minutes to 2 hours, in particular from 30 minutes to 1 hour.
The process according to the invention may, for example, be carried out as follows:
The starting materials are introduced by dosing pumps into a ~ixing vessel which is equipped for cooling and also serves as receiver !for a pressure resistant dosing pump used for conveying the reaction mixture into a heatable pressure coil. A valve attached to the end of the pressure coil maintains the required pressure inside the coil. This pressure is equal to the vapour pressure of the volatile components at the given reaction temperature.
Discharge of the reaction products also takes place through the above-mentioned valve.
The l-halogen-l-oxophospholene is freed by known methods, e.g. distillation at low pressure, from the phosphorus trihalide used as solvent and the halogen or dihalogenalkane produced as by-product.
Further purification oP the l-halogen-1-oxophos-2j pholene may also be carried out by distillation at reduced pressure.
The invention will now be described in more detail with the aid of the following Examples.
Le A 27 569 7 EXAMPLES
Example l Continuous preparation of an isomeric mixture of 1-chloro-3-methyl-1-oxophospholenes 275 g (4 mol) of isoprene, gl7 g (6,67 mol) of phosphorus trichloride and 165 g (1.33 mol) of trimethyl-phosphite are measured per hour into a water cooled mixing vessel. The tempe ature in the mixing vessel is 18~C.
A pressure resistant pump delivers the homogeneous reaction mixture (1.2 l/hour) into a reaction coil of 700 ml capacity situated in an oil bath heated to 130~C.
The average dwe~l time is 35 minutes. The pressure inside the reaction coil is 15 bar. As the reaction mixture leaves the reaction coil, the pressure in the mixture is released and the mixture cools and is collected in a crude product container by way of a pressure retaining valve.
Most of the chloromethane escapes at this stage and is condensed in a brine condenser and collected in another container also cooled with brine. The yields are deter-mined by measuring the hourly rates of throughput. The crude product is heated to 80~C at normal pressure to drive out any remaining chloromethane. Excess phosphorus trichloride is drawn off at 20 mbar up to a sump tempera-ture of 70~C and is condensed in a brine condenser.
Distillation of the residue (110 - 120~C at 3 mbar) yields 568 g (94.4% of the theoretical yield) of 1-chloro-3-methyl-l-oxophospholene. The isomeric mixture is composed of 58% of 1-chloro-3-methyl-1-oxophospholene-3 and 42% of l-chloro-3-methyl-1-oxophospholene-2. The yield of chloromethane is 196 g (97% of theoretical yield).
Ex~
The same procedure is carried out in Example 2 as in Example 1. Methoxydichlorophosphane is in this case used as starting material which has previously been prepared in a separate apparatus by a known method from phosphor~s trichloride and methanol and already contains Le A 27 569 8 3~
the excess phosphorus trichloride required as solvent for the subsequent reaction.
The following are introduced per hour into the cooled mixing vessel:
S 275 g (4 mol) of isoprene and 1082 g of the previously prepared methoxydichlorophosphane/phosphorus trichloride mixture containing 4 mol of methoxydichloro-phosphane.
Reaction and working up are carried out as described in Example 1.
539 g (89.5% of theoretical yield) of 1-chloro-3-methyl-l-oxophospholene purified by distillation are obtained per hour.
Example 3 The following are reacted per hour under conditions analogous to those of Example 1:
275 g (4 mol) of isoprene, 917 g (6.67 mol) of phosphorus trichloride and 221 g (1.33 mol) of triethylphosphite.
The pressure maintained during the continuous process is 10 bar.
The quantity of reaction mixture collected per hour is used for determining the yield.
After the product has been worked up by distilla-tion, 500 g (83.0% of the theoretical amount) of an isomeric mixture of 1-chloro-3-methyl-1-oxophospholene are obtained. It consists of 21.8% of 1-chloro-3-methyl-1-oxophospholene-3 and 78.2% of 1-chloro-3-methyl-1-oxophospholene-2.
238 g (92.2% of the theoretical amount) of ethyl chloride are obtained.
~xam~le 4 The following are continuously reacted per hour under the conditions described in Example 1:
275 g (4 mol) of isoprene, 917 g (6.67 mol) of phosphorus trichloride and 388 g (1.33 mol) of tri-n-pentylphosphite.
Le A 2? 569 9 The pressure in the reaction coil i~ 3 bar.
The quantitv of reaction mixture collected per hour for distillative working up is used for ~etermining the yield. The following are obtained:
358 g ~84% of theoretical amount) of n-pentyl chloride and 495 g ~.2% o~ theoretical amount) of an isomeric mixture of 18.1% of 1-chloro-3-methyl-1-oxophos-pholene-3 and 81.9% of 1-chloro~3-methyl-1-oxophos-pholene-2.
Example 5 The procedure is the same as in Example 1.
But~diene, phosphorus trichloride and trimethylphosphite i are put into the process.
The following were put through per hour:
216 g (4 mol) of butadiene, 917 g (6.67 mol) of phosphorus trichloride and 165 g (1.33 mol) of trimethylphosphite.
Determination of the yield is based on the quantity of reaction mixture obtained per hour, which after distillative working up of provides 494 g (90. 5~) of an isomeric mixture of 56% of 1-chloro-1-oxophospholene-3 and 44% of 1-chloro-1-oxophospholene-2.
It is undexstood that the specification and examples are illustrative but not limitative of the present invention and that other embodiments within the spirit and scope of the invention will suggest themselves to those skilled in the art.
e A 27 ~69 10
Claims (6)
1. A process for the preparation of 1-halogen-l-oxophospholenes corresponding to the formula wherein X stands for chlorine or bromine and R2, R3, R4 and R5 denote, independently of one another, hydrogen (C1-C4)-alkyl, or (C1-C4)-alkyl substituted with chlorine and/or bromine by the reaction of alkoxydihalogen phosphanes corresponding to the formula in which the group denoted by R1 is a (C1-C10)-alkyl or (C1-C10)-alkyl substituted with chlorine and/or bromine, and X stands for chlorine or bromine, with 1,3-dienes corresponding to the formula in which R2, R3, R4 and R5 have the same meanings as indicated above, Le A 27 569 11 characterized in that the reaction is carried out continuously in a single stage under pressure at an elevated temperature, using phosphorus trihalides as solvent.
2. A process according to Claim 1, characterized in that the alkyl dihalogenphosphane R1O-PX2 to be used is produced in situ without isolation from trialkyl phosphite corresponding to the formula (R1O)3P
wherein R1 stands for (C1-C10)-alkyl, or (C1-C10)-alkyl substituted with chlorine and/or bromine, and the phosphorus trihalide is used as a solvent.
wherein R1 stands for (C1-C10)-alkyl, or (C1-C10)-alkyl substituted with chlorine and/or bromine, and the phosphorus trihalide is used as a solvent.
3. A process according to Claim 1, characterized in that the alkoxydihalogen phosphane R1O-PX2 to be used is produced in situ, without being isolated, from a 1,2-epoxide corresponding to the formula wherein R6, R7, R8 and R9 denote, independently of one another, hydrogen, chlorine, bromine, (C1-C4)-alkyl, (C1-C4)-alkyl substituted with chlorine and/or bromine, (C5-C7)-cycloalkyl or phenyl, and the phsophorus trihalide is used as a solvent.
4. A process according to Claim 1, characterized in that the reaction is carried out at temperatures from 50°
to 180°C, preferably from 100° to 150°C.
Le A 27 569 12
to 180°C, preferably from 100° to 150°C.
Le A 27 569 12
5. A process according to claim 1 wherein R2, R3, R4 and R5 independently of one another denote (C1-C2)-alkyl.
6. A process according to claim 1 wherein R1 denotes (C1-C5)-alkyl.
Le A 27 569 13
Le A 27 569 13
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4012489A DE4012489A1 (en) | 1990-04-19 | 1990-04-19 | METHOD FOR PRODUCING 1-HALOGEN-1-OXOPHOSPHOLENES |
| DEP4012489.4 | 1990-04-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2040603A1 true CA2040603A1 (en) | 1991-10-20 |
Family
ID=6404666
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002040603A Abandoned CA2040603A1 (en) | 1990-04-19 | 1991-04-16 | Process for the preparation of 1-halogen-1-oxophospholenes |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0452755B1 (en) |
| JP (1) | JPH04234894A (en) |
| CA (1) | CA2040603A1 (en) |
| DE (2) | DE4012489A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6509401B1 (en) | 1997-08-29 | 2003-01-21 | Clariant Gmbh | Synergistic flame retardant combination of salts of 1-hydroxy-dihydrophosphole oxides and/or 1-hydroxyphospholane oxides and nitrogen compounds for use in polymers |
| WO2017083471A1 (en) | 2015-11-13 | 2017-05-18 | Icl-Ip America Inc. | Reactive flame retardants for polyurethane and polyisocyanurate foams |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8925362D0 (en) * | 1989-11-09 | 1989-12-28 | Ici Plc | Anthanthrone derivatives |
| DE19608011A1 (en) | 1996-03-04 | 1997-09-11 | Hoechst Ag | Salts of 1-hydroxy-dihydrophospholoxides and 1-hydroxy-phospholanoxides and their use as flame retardants |
| DE19708726A1 (en) | 1997-03-04 | 1998-09-10 | Hoechst Ag | Flame-retardant polymer molding compounds |
| DE19708724A1 (en) | 1997-03-04 | 1998-09-10 | Hoechst Ag | Aluminum salts of alkyl-1-alkoxyethylphosphinic acids |
| DE19708725A1 (en) | 1997-03-04 | 1998-09-10 | Hoechst Ag | Aluminum salts of alkyl hydroxymethylphosphinic acids |
| DE19720977A1 (en) | 1997-05-20 | 1998-11-26 | Hoechst Ag | Process for the preparation of aluminum salts of cyclic phosphinic acids |
| DE19734246A1 (en) | 1997-08-07 | 1999-02-11 | Hoechst Ag | Process for the preparation of aluminum salts of cyclic phosphinic acids |
| DE19903709A1 (en) | 1999-01-30 | 2000-08-10 | Clariant Gmbh | Flame retardant combination for thermoplastic polymers II |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1956187A1 (en) * | 1969-11-07 | 1971-05-13 | Vnii Fitopatologii | Organophosphorus fungicides |
| DE2919754A1 (en) * | 1979-05-16 | 1980-11-27 | Hoechst Ag | METHOD FOR PRODUCING 1-HALOGEN-1-OXODELTA HIGH 3 -PHOSPHOLENES |
-
1990
- 1990-04-19 DE DE4012489A patent/DE4012489A1/en not_active Withdrawn
-
1991
- 1991-04-06 EP EP91105457A patent/EP0452755B1/en not_active Expired - Lifetime
- 1991-04-06 DE DE59107830T patent/DE59107830D1/en not_active Expired - Fee Related
- 1991-04-15 JP JP3108351A patent/JPH04234894A/en active Pending
- 1991-04-16 CA CA002040603A patent/CA2040603A1/en not_active Abandoned
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6509401B1 (en) | 1997-08-29 | 2003-01-21 | Clariant Gmbh | Synergistic flame retardant combination of salts of 1-hydroxy-dihydrophosphole oxides and/or 1-hydroxyphospholane oxides and nitrogen compounds for use in polymers |
| WO2017083471A1 (en) | 2015-11-13 | 2017-05-18 | Icl-Ip America Inc. | Reactive flame retardants for polyurethane and polyisocyanurate foams |
| WO2017083468A1 (en) | 2015-11-13 | 2017-05-18 | Icl-Ip America Inc. | Reactive flame reardants for polyurethane and polyisocyanurate foams |
Also Published As
| Publication number | Publication date |
|---|---|
| DE4012489A1 (en) | 1991-10-24 |
| DE59107830D1 (en) | 1996-06-27 |
| EP0452755B1 (en) | 1996-05-22 |
| EP0452755A1 (en) | 1991-10-23 |
| JPH04234894A (en) | 1992-08-24 |
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