- Synthesis of dichlorophenylphosphine via a Friedel-Crafts reaction in [Et4N]Br-XAlCl3 ionic liquids
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The Friedel-Crafts reaction of phosphorus trichloride and benzene in [Et4N]Br-XAlCl3 ([Et4N]Br = tetraethylammonium bromide) ionic liquids (ILs) was investigated for the clean synthesis of dichlorophenylphosphine (DCPP). A simple product isolation procedure was achieved, and the effects of IL's composition, reaction time, and quantity on this reaction were studied. The [Et4N]Br-XAlCl3 ILs gave this reaction a green character. From the isolation experiments, it was found that (a) because of the formation of the complex of DCPP and AlCl3, the catalytic activity of the [Et3NH]Cl-XAlCl3 ([Et 3NH]Cl = triethylhydrogenamonium chloride) was reduced; (b) with the addition of quaternary ammonium to the IL's residue, additional DCPP could be recovered. Copyright Taylor & Francis Inc.
- Wu, Yu-Yong,Wang, Li-Sheng,Wang, Zhong-Wei
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- AlCl3-catalyzed C-H p hosphination of benzene: A mechanistic study
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The characteristics of the reaction for the preparation of dichlorophenylphosphine (DCPP) via benzene and PCl3 in the presence of AlCl3 were studied. Some unique characteristics were observed when a catalytic amount of AlCl3 was used. Namely, more than one mole of DCPP was obtained per mole AlCl3, the reaction solution was layered, and DCPP could be directly separated. Our mechanistic study showed that benzene reacted with PCl3 to form DCPP-AlCl3, and DCPP-AlCl3 dissociated into DCPP and AlCl3, continuing to catalyze this reaction. This resulted in the high catalytic efficiency of AlCl3. The layering of the reaction solution was caused by the immiscibility of DCPP-AlCl3 with the raw materials, greatly facilitating the dissociation process of DCPP-AlCl3. The formation of diphenylphosphorus chloride (DPC) was due to a continuous Friedel-Crafts reaction between DCPP and benzene. DPC cooperated with AlCl3 to form the stable coordination compound DPC-AlCl3 that did not dissociate and was responsible for the deactivation of AlCl3.
- Duan, Haodong,Gao, Jun,Guo, Ge,Han, Yuxi,Leng, Kangwei,Li, Xinjin,Wang, Zhongwei,Xu, Xiaolei,Yu, Qing
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- METHODS FOR PREPARING ARYLPHOSPHINE-BORANE COMPLEXES
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A method for preparing phosphine-borane complexes from aryldihalophosphine includes mixing sodium borohydride, a solvent having at least 50 vol % glycol ethers, and the aryldihalophosphine to obtain a solution. The solution is maintained at a reaction temperature for a duration of time to obtain the phosphine-borane complexes. The solvent may include 1,2-dimethoxyethane and tetrahydrofuran. A ratio of tetrahydrofuran to 1,2-dimethoxyethane in the solvent may be from 0.1:1.0 to 2.5:1.0.
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- Ionic liquid modified silica gel loaded aluminum chloride catalyst (by machine translation)
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The ionic liquid modified silica gel loaded aluminum chloride catalyst is prepared by mixing and stirring ionic liquid and silica gel, heating to, stirring the ionic liquid modified silica gel obtained in step a, stirring 100 - 150 °C under stirring, removing 1 - 2h ethanol under stirring, heating the mixture under reduced pressure to, and carrying out reaction to obtain yellow powder b 5 - 10h 120 - 160 °C 1 - 2hIn the process of preparing the phenyldiphosphine chloride, very high yield (above 90%) can be achieved, the catalyst removal system is simple in post-treatment, and the catalyst can be removed only through filtration, and the catalyst can be reused after being dried. (by machine translation)
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Paragraph 0034-0047
(2020/10/04)
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- Method for preparing alkyl phosphine hahalide and reactor for method
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The invention relates to a method for preparing compounds as shown in a formula (I) and a formula (II) which are shown in the description and a reactor specially used for implementing the method. In the formula (I) and the formula (II), X represents halogen, and R represents an alkyl group. The method comprises the step of enabling yellow phosphorus to react with the compound as shown in a formula(III) in a reactor under a condition that no catalyst exists. The method is characterized in that a material on the surface, which is in contact with reaction space, in the reactor is nickel-based alloy used as anti-corrosion alloy, or the reactor is totally formed by the nickel-based alloy used as the anti-corrosion alloy along the whole reaction wall thickness direction. According to the methoddisclosed by the invention, the nickel-based alloy used as the anti-corrosion alloy is adopted as the material of the reactor and accessories of the reactor, an improved anti-corrosion effect betterthan that of an existing reactor and accessories thereof can be realized, and the cost is acceptable, so that the method can be realized in an industrial scale.
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Paragraph 0119; 0120; 0127; 0128; 0129; 0130
(2019/01/06)
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- Semiconducting Material Comprising a Phosphine Oxide Matrix and Metal Salt
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The present invention is directed to a semiconducting material comprising: i) a compound according to formula (I) wherein R1, R2 and R3 are independently selected from C1-C30-alkyl, C3-C30 cycloalkyl, C2-C30-heteroalkyl, C6-C30-aryl, C2-C30-heteroaryl, C1-C30-alkoxy, C3-C30-cycloalkyloxy, C6-C30 aryloxy, and from structural unit having general formula E-A-, wherein—A is a C6-C30 phenylene spacer unit, and—E is an electron transporting unit that is selected from C10-C60 aryl and C6-C60 heteroaryl comprising up to 6 heteroatoms independently selected from O, S, P, Si and B and that comprises a conjugated system of at least 10 delocalized electrons, and—at least one group selected from R1, R2 and R3 has the general formula E-A-; and ii) at least one complex of a monovalent metal having formula (II) wherein—M+ is a positive metal ion bearing a single elementary charge, and each of A1, A2, A3 and A4 is independently selected from H, substituted or unsubstituted C6-C20 aryl and substituted or unsubstituted C2-C20 heteroaryl, wherein a heteroaryl ring of at least 5 ring-forming atoms of the substituted or unsubstituted C2-C20 heteroaryl comprises at least one hetero atom selected from O, S and N.
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- Preparation method for catalytically compounding benzyl phosphonate by using basic ionic liquid
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The invention belongs to the technical field of organic synthesis and relates to a preparation method for benzyl phosphonate as a key intermediate of an acyl phosphine oxide type photoinitiator. According to the method, benzene, phosphorus trichloride and alkyl alcohol are taken as main raw materials and are compounded into benzyl phosphonate through two-step reaction. The preparation method is characterized in that a target product is generated through the low-temperature reaction of the dichlorophenyl phosphine and alcohol under the condition of a gemini basic ionic liquid catalyst in the second step reaction, the reaction temperature is controlled within -10 DEG C to 10 DEG C, the dichlorophenyl phosphine is dropwise added and then the mixture reacts for 0.5-7 hours under a stirring condition after the temperature is increased to 30-50 DEG C. The preparation method has the advantages of low cost, simple and convenient after-treatment, high yield, and the like, and is suitable for industrial production.
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Paragraph 0037; 0038; 0039; 0059; 0060
(2018/01/12)
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- Phosphor material containing heteratomic parent nucleus-o-fluorene ring structure and organic light emitting diode
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The invention provides a phosphor material containing a heteratomic parent nucleus-o-fluorene ring structure and an organic light emitting diode and belongs to the technical field of organic photoelectric materials. The technical problems in the prior art that the organic photoelectric material has low luminous efficiency, high driving voltage and other poor luminous properties are solved. The experimental results prove that the organic light emitting diode (OLED) prepared by adopting the phosphor material containing the heteratomic parent nucleus-o-fluorene ring structure disclosed by the invention has the highest luminous efficiency up to 18.8cd/A and the driving voltage of 3.2V. The phosphor material is an excellent OLED material.
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Paragraph 0036; 0037
(2017/09/26)
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- Method for producing dichlorophenylphosphine
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The invention relates to a method for producing dichlorophenylphosphine.According to the technical scheme, chlorobenzene, simple-substance phosphorus and phosphorus chloride are adopted as raw materials and subjected to a reaction in a tubular reactor, and the dichlorophenylphosphine is obtained, wherein the reaction equation of the dichlorophenylphosphine is P4+6C6H5Cl+2PCl=6C6H5PCl.The method has the advantages that due to the fact that the main reaction is performed in the tubular reactor, no catalyzer is needed, the materials can directly reach reaction conditions proportionally to be subjected to a rapid reaction, the production cycle is shortened, and generation of a large number of by-products is avoided; meanwhile, potential safety hazards brought by a high-temperature and high-pressure reaction by means of an autoclave in the prior art are avoided; no waste gas or waste residues or waste water is generated in the production process, operation is easy, products are easy to separate, and the product purity is high; the adopted raw material cost is low, the yield is high, and the produced dichlorophenylphosphine has the large cost advantage and environment-friendly advantage compared with dichlorophenylphosphine prepared through an existing technology.
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Paragraph 0023
(2016/12/12)
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- Lewis acid ionic liquid immobilized on chitosan for synthesis of dichlorophenylphosphine
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Lewis acid ionic liquid immobilized on chitosan as a new catalyst was prepared via the synthesis of l-trimethoxy-silylpropyl-3- methylindazoliumchloride-AlCl3, l-trimethoxy-silylpropyl-3- methylindazolium-chloride-InCl3 and l-trimethoxy-silylpropyl-3- methylindazolium-chloride-FeCl3 and then grafting them to chitosan respectively. Their catalytic activities were investigated in the synthesis of dichlorophenylphosphine. The results showed when the three catalysts' amounts were 0.0225, 0.0195 and 0.015 g respectively, the substrate of benzene could be completely transformed into dichlorophenylphosphine on the conditions of the phosphorus trichloride 0.22 g, the molar ratio of phosphorus trichloride to benzene 1.8 : 1, the reaction temperature 75 °C and the reaction time 120 min. Moreover, the molar ratios of ionic liquid moiety to benzene were merely 0.285, 0.187 and 0.172 % respectively, which were much lower than that of the corresponding pure ionic liquids to benzene. The catalyst can be reused for many times with fine catalytic efficiency. In addition, the new catalyst using chitosan with the higher deacetylation degree as carrier could improve catalytic activity and reusability. Copyright
- Qiu, Xian-Hua,Xie, Yu,Wang, Xiao-Ying,Cao, Qian-Yong,Tang, Xing-Hua,Hu, Jin-Gang,Hong, Xiao-Wei,Yan, Si-Feng
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p. 1673 - 1678
(2013/06/26)
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- A new method for the synthesis of dichlorophosphines
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A new method for the synthesis of alkyldichlorophosphines by chlorination of alkylphosphines with phosphorus pentachloride under mild conditions is described.
- Tavtorkin, Alexander N.,Toloraya, Sofia A.,Nifant'Ev, Eduard E.,Nifant'Ev, Ilya E.
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supporting information; experimental part
p. 824 - 825
(2011/03/18)
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- 2,3-Diphosphino-1,4-diphosphonium ions
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Salts of the first crystallographically characterized chlorophosphinophosphonium ions have been prepared, and their reaction with Ph3P results in reductive coupling of the chlorophosphine centers to give the first acyclic 2,3-diphosphino-1,4-diphosphonium ions, representing a key framework in the development of catena-phosphorus chemistry. These new salts of general formula [R3P-PR′-PR′-PR3][OTf] 2 are also obtained in a one-pot diastereoselective reaction of a dichlorophosphine, a tertiary phosphine, and trimethylsilyltrifluoromethanesulfonate. The structural and spectroscopic features of the new dications complement those of the known diphosphonium and 2-phosphino-1,3-diphosphonium dications. Quantitative ligand exchange reactions are observed when derivatives of [Ph3P-PR′-PR′-PPh 3][OTf]2 are combined with Me3P, demonstrating the coordinative nature of the phosphine-phosphonium P-P bonds and implicating a bonding model involving the diphosphenium dication acceptor. The observed solid state structures have been interpreted in the context of computational studies.
- Carpenter, Yuen-Ying,Dyker, C. Adam,Burford, Neil,Lumsden, Michael D.,Decken, Andreas
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experimental part
p. 15732 - 15741
(2009/03/12)
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- Green synthesis of dichlorophenylphosphine sulfide using chloroaluminate ionic liquids as a catalyst
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Triethylhydrogenammonium chloride-XAlCl3 Ionic Liquids (ILs) were used as a catalyst for the clean synthesis of dichlorophenylphosphine sulfide. Two synthesis routes were investigated; one of them was a reaction of sulfur and Dichlorophenylphosphine (DCPP), and another was a one-pot reaction of benzene, phosphorus, chloride, and sulfur. Effects of the ILs composition and reaction time and the quantity of the ILs on the reactions were studied. A simple product isolation procedure was achieved. The ILs showed reusable and low-consumption characters in the reaction of sulfur and DCPP. Thus the triethylhydrogenammonium chloride-XAlCl3 ILs gave this reaction a green character. Copyright Taylor & Francis Group, LLC.
- Wang, Li-Sheng,Kang, Hui-Bao,Wang, Zhong-Wei,Wang, Chong-Gang
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p. 227 - 236
(2007/10/03)
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- A direct and new convenient oxidation: Synthesis of substituted arylphosphonates from aromatics
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An easy synthesis of aryl phosphonates by oxidation from aryldichlorophosphines with iodine in good yields is described. Aryldichlorophosphines are obtained by reaction of phosphorous trichloride with some aromatics in presence of various Lewis acids. BiCl3 and Bi(OTf)3 are used for the first time and bismuth trichloride is, for the first time in the case of anisole or thioanisole phosphonylation, used as a true regenerable Lewis acid catalyst in a reaction of direct phosphonylation of aromatics.
- Simeon, Fabrice,Jaffres, Paul-Alain,Villemin, Didier
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p. 10111 - 10118
(2007/10/03)
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- 31P-NMR Study of Intermediates in Preparation of Phenyldichlorophosphine
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Phenyldichlorophosphine was prepared via the AlCl3-PCl3 complex method, wherein benzene was caused to react with phosphorus trichloride (PCl3) in the presence of aluminum chloride (AlCl3) followed by the separation of AlCl3 with tris(2-chloroethyl)-phosphate.The intermediates and mechanism of the reaction were investigated by 31P nuclear magnetic resonance (NMR) spectroscopy.The results revealed three kinds of intermediates in NMR time scale in the reaction.A reaction mechanism was proposed. - Keywords: Phenyldichlorophosphine; 31P nuclear magnetic resonance; intermediate; mechanism.
- Wu, T. R.,Chen, W. Y.,Chiu, Y. S.,Chang, T. C.
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p. 197 - 204
(2007/10/03)
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- Studies on chiral thiophosphoric acids and their derivatives 16. - The asymmetric cyclization of L-(+)-prolinol with (thio)phosphoro(-no)dichloridates
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The cyclizations of L-(+)-prolinol 5 with (thio)phosphoro(-no)dichloridates 6 give 1,2,3-azaphosphaoxabicyclo[3.3.0]octanes 7 consisting of unequal amounts of diastereoisomers, eight pairs of which have been successfully resolved by silica gel column chromatography or recrystallization. The influences of reaction temperature, solvent and substrate concentration upon the asymmetric induction have also been investigated.
- He, Zheng-Jie,Wang, You-Ming,Tang, Chu-Chi
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- INVESTIGATION OF THE REACTION BETWEEN BENZENE, PHOSPHORUS TRICHLORIDE, AND ALUMINUM CHLORIDE BY MEANS OF 31P NMR SPECTROSCOPY
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Reaction between C6H6, PCl3, and AlCl3 at 60-160 deg C and reactant ratios of (1-3): 1:1 was studied by means 31P NMR spectroscopy.Reaction starts at 60-70 deg C with the formation of the salt +AlCl4-.The subsequent transformation of this salt at 130-140 deg C includes two alternative processes: a) the direct replacement of P-chloro by aryl; b) intramolecular interaction and disproportionation with the subsequent formation of phosphinophosphonium salts +Al2Cl7- and +AlCl7-.Both courses lead to the formation of the salt +AlCl4-.The structures of the intermediates were proved by model reactions of phenylphosphonous dichloride and diphenylphosphinous chloride with aluminum chloride.By the reactions of the salt +AlCl4- with halobenzenes we proved that the process goes predominantly by course (b).The highest yield of diarylphosphinous chlorides was obtained with optimum proportions of the reactants of 2:1:1.
- Tarasova, R. I.,Zykova, T. V.,Shagvaleev, F. Sh.,Sitdikova, T. Sh.,Moskva, V. V.
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p. 2346 - 2349
(2007/10/02)
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- INTERACTION OF DISULFIDES AND SULFENYLCHLORIDES WITH C-N,N-DIALKYLAMINOSUBSTITUTED PHOSPHAALKENES
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Interaction of dialkyl disulfides with C-N,N-dimethylaminomethylene-P-phenylphosphine 1a results in the complete cleavage of the P=C double bond and formation of S,S-dialkylphenyldithiophosphonites.Ethyl sulfenylchloride undergoes dehydrochlorination by 1a, while phenyl sulfenylchloride cleaves the P=C bond in C-N,N-dialkylaminosubstituted phosphaalkenes with the predominant formation of either PhP(SPh)2 6 or PhP(SPh)Cl 7 depending on the phosphaalkene used and reaction conditions. Key words: C-(N,N-dialkylamino) substituted phosphaalkenes; disulfides; sulfenylchlorides.
- Ionkin, A. S.,Nikolaeva, N. V.,Nekhoroshkov, V. M.,Efremov, Yu. Ya.,Arbuzov, B. A.
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p. 361 - 365
(2007/10/02)
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- METHOD FOR PREPARATION OF PHENYLDICHLOROPHOSPINE
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Red phosphorus is arylated by chlorobenzene in phosphorus trichloride only in the presence of catalysts.The effect of various substances on the reaction rate is studied.Best results were obtained when Pd(II), Cu(I), and sulfur chlorides and sulfur compounds were used.
- Petrov, K. A.,Kryukova, L. Yu.,Treshchalina, L. V.
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p. 2336 - 2338
(2007/10/02)
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- Process for making chlorophosphines and thiophosphinic acid chlorides, and 9-chloro-9-thioxo-9-phosphabicyclononanes
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Chlorophosphines or thiophosphinic acid chlorides of the general formulae RPCl2, R2 PCl or R2 P(=S)Cl are made from feed materials selected from hydrogen-functional primary or secondary phosphines or secondary phosphine sulfides, where R stands for identical or different, linear or branched, substituted or unsubstituted alkyl radicals having from 1-16 carbon atoms, aryl radicals, aralkyl radicals or alkylaryl radicals having from 6-9 carbon atoms or cycloalkyl radicals having from 5-10 carbon atoms. To this end, the feed materials are reacted with phosphorus pentachloride, or with chlorine gas in the presence of phosphorus trichloride at temperatures within the range -78° to +145° C. It is possible for two radicals R to be linked together by one or two substituted or unsubstituted hydrocarbon chains having from 1-4 carbon atoms.
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- Process for the preparation of phenyl- and thienyl-chlorophosphane derivatives
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Organic chlorophosphanes of the formula II STR1 in which R1 =an aromatic or heterocyclic radical and R2 =an aliphatic radical or Cl are prepared by reacting organic phosphorus oxychlorides of the formula I STR2 in which R1 and R2 have the meaning mentioned above with triphenylphosphane (C6 H5)3 P at an elevated temperature. The organic chlorophosphanes II are, in the main, intermediates in various specialized fields, such as the pharmaceuticals, plant protection, dyestuffs and polymers sectors.
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- Process for preparing chlorophenylphosphanes
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Chlorophenylphosphanes of the formula in which n=1 or 2, are prepared by reacting triphenylphosphane, (C6 H5)3 P, with phosphorus trichloride, PCl3, at temperatures between about 320° and 700° C.; in the temperature range between about 320° and 500° C. the reaction is preferably carried out under elevated pressure, in particular under autogenous pressure, while in the temperature range between about 500° and 700° C. atmospheric pressure is preferably used. The composition of the final product can be controlled by the choice of the molar ratio of the starting materials. The final products dichlorophenylphosphane and chlorodiphenylphosphane are mainly intermediates in various fields, such as, for example, the crop protection and the polymer sectors.
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- Process for preparing chlorodiphenylphosphane
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Chlorodiphenylphosphane is prepared by reacting dichlorophenylphosphane with triphenylphosphane at temperatures between about 300° and 700° C. In the temperature range from about 300° to 500° C., this reaction is preferably carried out under elevated pressure, in particular under the autogenous pressure which becomes established in a sealed system, while atmospheric pressure is preferably used in the temperature range from about 500° to 700° C. The reaction product chlorodiphenylphosphane is in the main an intermediate in various fields, such as, for example, the polymer sector.
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