[go: up one dir, main page]

US3356774A - Process for the manufacture of omicron, omicron-dialkylthiono-phosphoric acid chlorides - Google Patents

Process for the manufacture of omicron, omicron-dialkylthiono-phosphoric acid chlorides Download PDF

Info

Publication number
US3356774A
US3356774A US392611A US39261164A US3356774A US 3356774 A US3356774 A US 3356774A US 392611 A US392611 A US 392611A US 39261164 A US39261164 A US 39261164A US 3356774 A US3356774 A US 3356774A
Authority
US
United States
Prior art keywords
chlorine
omicron
reaction
alcohol
acid chloride
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US392611A
Other languages
English (en)
Inventor
Niermann Hermann
Cremer Joseph
Harnich Heinz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Knapsack AG
Knapsack Griesheim AG
Original Assignee
Knapsack AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Knapsack AG filed Critical Knapsack AG
Application granted granted Critical
Publication of US3356774A publication Critical patent/US3356774A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
    • C07F9/165—Esters of thiophosphoric acids
    • C07F9/20—Esters of thiophosphoric acids containing P-halide groups

Definitions

  • R stands for an alkyl radical having 1 to 6 carbon atoms.
  • 0,0-diethylthionophosphoric acid chloride can be prepared by a two step process wherein, in a first process step, phosphorus pentasulfide is caused to react with ethanol according to the following equation:
  • the 0,0-diethylthionophosphoric acid chloride prepared in conventional manner is obtained with a maximum yield of 70%, related to the amount of 0,0-diethyldithiophosphoric acid obtained in the first process step.
  • the present invention obviates the above disadvantages by providing a process wherein the work-up of resulting by-products and special cooling of the reaction mixture may be omitted. Furthermore, the process is carried out in a single step with the use of a readily available and commercially cheap starting product.
  • ROl OR 51 in which R stands for an alkyl radical having 1 to 6 carbon atoms is basically carried out according to the following reaction equation:
  • the process of the present invention comprises introducing a stream of chlorine gas into a P S -suspension in an inert solvent at a temperature within the range of about 0 to 150 C. and adding dropwise concurrently therewith an alcohol having 1 to 6 carbon atoms, allowing the reaction to proceed to completion, expelling the solvent, and isolating 0,0-dialkylthionophosphoric acid chloride from the reaction mixture by subjecting it to distillation.
  • the yield of 0,0-dialkylthionophosphoric acid chlorides is influenced by the proportion of alcohol and chlorine added per unit of time to the phosphorus pentasulfide suspension.
  • Maximum yields are obtained by adding the chlorine gas to the phosphorus pentasulfide suspension in an inert solvent in such a way that about half of the calculated chlorine quantity has been introduced thereinto once the total amount of alcohol has been added. In other words, chlorine and alcohol are introduced at a feed rate or speed of approximately 1:2. The balance chlorine portion is then introduced continuously at a constant feed rate into the suspension. Introduction of the chlorine gas either after the addition of the total amount of alcohol or at a feed rate the same as the alcohol will result in reduced yields.
  • the yields are a function of the temperature used in the process of the present invention, i.e. that by maintaining a reaction temperature of about 70 to C. within the interesting range of about 0 to C. is most advantageous.
  • a further feature of the present invention resides in the use of an inert solvent for making the necessary phosphorus pentasulfide suspension.
  • the inert solvents useful for this include e.g. toluene, xylene, carbon tetrachloride, petroleum ether (B.P.: 6595 C.) or the like as well as the 0,0-dialkylthionophosphoric acid chloride obtained as the reaction product.
  • the alcohols useful for use in carrying out the process of the present invention include e.g. methanol, ethanol, propanol, iso-propanol, n-butanol, iso-butanol, amyl alcohol, hexyl alcohol and the isomers thereof.
  • the process of the present invention is generally carried out by charging an appropriate reaction vessel with approximately equal parts by weight of phosphorus pentasulfide and inert solvent, stirring the material in the vessel so as to obtain a suspension, gradually admixing the suspension with a suitable alcohol and chlorine gas, the chlorine gas being introduced in such a way that about half of the calculated chlorine quantity has undergone reaction once the total amount of alcohol has been added to the suspension.
  • the chlorine balance portion is introduced subsequent to the alcohol addition while maintaining the initial rate of flow.
  • the reaction temperature is maintained e.g. at 70 C. by slight heating or slight cooling as the case may be.
  • reaction mixture is first freed from the inert solvent, and 0,0-dialkylthionophosphoric acid chloride is then distilled off, preferably under reduced pressure.
  • temperature in the sump portion of the reaction vessel may increase to about 150 C.
  • the remaining 3 liquid sump phase solidifies on cooling and consists substantially of elementary sulfur.
  • the yields can be further improved by introducing into the reaction mixture diluted chlorine gas, i.e. chlorine gas in admixture with an inert gas, e.g. carbon dioxide and argon, preferably nitrogen, in a ratio by volume of about 1:05 to 1:3.
  • diluted chlorine gas i.e. chlorine gas in admixture with an inert gas, e.g. carbon dioxide and argon, preferably nitrogen, in a ratio by volume of about 1:05 to 1:3.
  • the process of the present invention taken as a whole offers a series of characteristic advantages over customary methods. Firstly, it enables the desired process product to be prepared in a single process step, the necessary feed product being readily available and relatively cheap. Secondly, the reaction of the phosphorus pentasulfide with alcohol and chlorine gas is but slightly exothermal and therefore requires no cooling. steps in the absence of any danger of explosion. Furthermore, any expensive work-up or destruction of by-products is obviated because the sulfur obtained as the distillation residue is useful for further application.
  • dialkylthionophosphoric acid chloride prepared by the process of the present invention is obtained in yields of more than'90%, related to the dialkyldithiophosphoric acid formed as an intermediary product, i.e. in yields considerably higher than those obtained by conventional methods.
  • Example 1 1.11 kg. phosphorus pentasulfide were suspended while stirring in 1 liter toluene which had beenplaced into a 4-liter four-necked flask, and the suspension was admixed within 100 minutes with 1,285 liters ethanol and 532 grams, i.e. the half of the necessary chlorine gas. Once the alcohol had been added, a further 532 grams chlorine gas were caused to react with the phosphorus pentasulflde which had meanwhile dissolved. During the whole reaction time, the temperature was maintained at 70 C. by slight heating or slight cooling. After the chlorine had been added, the toluene was expelled from the reaction mixture and diethylthionophosphoric acid chloride was distilled off at 68 C. and under a pressure of 8 mm. mercury. The remaining liquid distillation residue was first heated at a sump temperature of 150 C., then cooled and the residue which consisted substantially of elementary sulfur was allowed to solidify.
  • Example 2 In a manner analogous to that described in Example 1, 222 grams phosphorus pentasulfide were suspended while stirring in 194 cc. toluene placed in a 1-liter four-necked round flask, and the suspension was admixed in the course of 100 minutes with 187 cc. methanol. During the methanol addition, 107 grams chlorine gas were introduced followed by the introduction of a further 107 grams chlorine gas during a further 100 minutes period of time. During the reaction, the reaction temperature was at about 70 C. After the necessary amount of chlorine gas had been introduced, the toluene was expelled from the reaction mixture and dimethylthionophosphoric acid chloride was distilled off under a pressure of 16 mm.
  • Example 3 and dibutylthionophosphoric acid chloride was distilled off at a pressure of 5 mm. mercury at a boiling temperature of 107 C. 293 grams dibutylthionophosphoric acid chloride were obtained. This corresponded to a yield of 60% related to the amount of phosphorus pentasulfide used.
  • Example 4 The apparatus was a 20-1iter glass flask provided with a stirring means and 4 inlet sockets, of which each socket was intended respectively to serve as methanol supply, gas admission, reflux condenser and temperature determination.
  • the reflux condenser had an internal width of mm. and was packed over a length of 1 meter with saddle-shaped packing material.
  • the gas admission line was a T-piece serving to supply chlorine and nitrogen.
  • the glass flask was placed in a metal trough having joints for supplying cooling water and hot steam. 5.55 kg. P 5 were suspended while stirring in 7.8 liters CCL; in the flask and 4.45 liters CH OH were added. At the start of the reaction, the flask had to be cooled with some water.
  • the reaction material was maintained at a temperature of 40 to 50 C. and a mixture of 350 l./hr. C1 and 350 l./hr. N was introduced thereinto.
  • the chlorine was used in a proportion corresponding to a molar ratio of P2S5:Cl2 1I2.5.
  • R stands for an alkyl radical having 1 to 6 carbon atoms
  • R stands for an alkyl radical having 1 to 6 carbon atoms
  • the inert solvent is at least one member selected from the group consisting of toluene, xylene, carbon tetrachloride, a pctroleum ether having a boiling point of 65 to 95 C., and the 0,0-dialkylthionophosphoric acid chloride obtained as the final product.
  • inert gas is at least one member selected from the group consisting of nitrogen, carbon dioxide and argon.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
US392611A 1963-09-13 1964-08-27 Process for the manufacture of omicron, omicron-dialkylthiono-phosphoric acid chlorides Expired - Lifetime US3356774A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEK50811A DE1191369B (de) 1963-09-13 1963-09-13 Verfahren zur Herstellung von O, O-Dialkyl-thionophosphorsaeurechloriden
DEK53557A DE1211170B (de) 1963-09-13 1964-07-24 Verfahren zur Herstellung von O, O-Dialkylthionophosphorsaeurechloriden

Publications (1)

Publication Number Publication Date
US3356774A true US3356774A (en) 1967-12-05

Family

ID=25983798

Family Applications (1)

Application Number Title Priority Date Filing Date
US392611A Expired - Lifetime US3356774A (en) 1963-09-13 1964-08-27 Process for the manufacture of omicron, omicron-dialkylthiono-phosphoric acid chlorides

Country Status (6)

Country Link
US (1) US3356774A (de)
CH (1) CH437260A (de)
DE (2) DE1191369B (de)
DK (1) DK114129B (de)
GB (1) GB1043096A (de)
NL (1) NL153206B (de)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3502750A (en) * 1965-10-12 1970-03-24 Rhone Poulenc Sa Process for the preparation of dialkyl phosphorochloridothioates
US4159289A (en) * 1978-03-02 1979-06-26 Ethyl Corporation Process for preparing dialkyl phosphorochloridothioates
US4185053A (en) * 1977-10-03 1980-01-22 Stauffer Chemical Company Process for manufacturing substantially pure dialkyl phosphorochloridothionate
US4247490A (en) * 1979-09-10 1981-01-27 Ethyl Corporation Process for the purification of dialkylphosphorochloridothioates
US4292139A (en) * 1979-09-11 1981-09-29 Ethyl Corporation Method for inhibiting deposit formation in distillation units associated with separation and purification of alkyl phosphorochloridothioates
EP0048172A1 (de) * 1980-09-17 1982-03-24 Stauffer Chemical Company Verfahren zur Herstellung von Dialkyl-Phosphorochloridothionaten
US5278331A (en) * 1990-10-09 1994-01-11 Ethyl Corporation Waste treatment in dialkyl phosphorochloridothioate production

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1191369B (de) * 1963-09-13 1965-04-22 Knapsack Ag Verfahren zur Herstellung von O, O-Dialkyl-thionophosphorsaeurechloriden
DE2538310C3 (de) * 1975-08-28 1980-08-28 Hoechst Ag, 6000 Frankfurt Verfahren zur Herstellung von O.O-Dialkylthionophosphorsäurechloriden

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1211170B (de) * 1963-09-13 1966-02-24 Knapsack Ag Verfahren zur Herstellung von O, O-Dialkylthionophosphorsaeurechloriden

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1211170B (de) * 1963-09-13 1966-02-24 Knapsack Ag Verfahren zur Herstellung von O, O-Dialkylthionophosphorsaeurechloriden

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3502750A (en) * 1965-10-12 1970-03-24 Rhone Poulenc Sa Process for the preparation of dialkyl phosphorochloridothioates
US4185053A (en) * 1977-10-03 1980-01-22 Stauffer Chemical Company Process for manufacturing substantially pure dialkyl phosphorochloridothionate
US4159289A (en) * 1978-03-02 1979-06-26 Ethyl Corporation Process for preparing dialkyl phosphorochloridothioates
EP0005310A1 (de) * 1978-03-02 1979-11-14 Ethyl Corporation Verfahren zur Herstellung von O,O-Dialkylphosphothionsäurechloriden, Verwendung der so hergestellten Verbindungen als Zwischenstoffe und Verwendung einiger der Endprodukte als Insektizide
US4247490A (en) * 1979-09-10 1981-01-27 Ethyl Corporation Process for the purification of dialkylphosphorochloridothioates
US4292139A (en) * 1979-09-11 1981-09-29 Ethyl Corporation Method for inhibiting deposit formation in distillation units associated with separation and purification of alkyl phosphorochloridothioates
EP0048172A1 (de) * 1980-09-17 1982-03-24 Stauffer Chemical Company Verfahren zur Herstellung von Dialkyl-Phosphorochloridothionaten
US4332747A (en) * 1980-09-17 1982-06-01 Stauffer Chemical Company Process for producing dialkyl phosphorochloridothionates
US5278331A (en) * 1990-10-09 1994-01-11 Ethyl Corporation Waste treatment in dialkyl phosphorochloridothioate production

Also Published As

Publication number Publication date
DE1211170B (de) 1966-02-24
NL153206B (nl) 1977-05-16
NL6410551A (de) 1965-03-15
DE1191369B (de) 1965-04-22
GB1043096A (en) 1966-09-21
CH437260A (de) 1967-06-15
DK114129B (da) 1969-06-02

Similar Documents

Publication Publication Date Title
US4064163A (en) Process for the manufacture of aliphatic phosphonic acids
US3356774A (en) Process for the manufacture of omicron, omicron-dialkylthiono-phosphoric acid chlorides
US3760001A (en) Production of trialkylphosphines
US2685602A (en) Alkene phosphonous dichlorides and methods of making the same
US3848064A (en) Production of sulfur tetrafluoride from sulfur chlorides and fluorine
US4354983A (en) Process for the purification of O,O-dialkylthionophosphoric acid chlorides
JPS5949233B2 (ja) Ｏ，ｏ−ジアルキルチオノ燐酸クロリドの製造法
US2662095A (en) Dimethyl-phosphoric acid amide and its production
US3574735A (en) Process for the manufacture of unsaturated phosphonic acid dichlorides
US3104259A (en) Method of preparing phosphinic chlorides
US6143923A (en) Process for manufacturing 1-hydroxyalkylidene-1,1-diphosphonic acid (HADP)
US3389179A (en) Preparation of alkylamines by the ammonolysis of alkyl halides
US3781389A (en) Process for the production of substituted thionophosphoryl chlorides
US4185053A (en) Process for manufacturing substantially pure dialkyl phosphorochloridothionate
US3031509A (en) Preparation of dialkyl phosphines
US2082568A (en) Vinylethinyl derivatives and processes for producing same
US3458569A (en) Process for producing methylphosphonodichloridothioate
US2974159A (en) Production of primary-2-hydroxy-ethylphosphite
US4296047A (en) Continuous preparation of phosphoric acid alkyl ester dichlorides
US2575317A (en) Process for the production of phosphorus sulfochloride
US3179696A (en) Preparation of methane phosphonyl dichloride via phosgenation
US3279885A (en) Process of preparing ammonium dicyanamide
US3931294A (en) Production of 2-phenyl-ethylene phosphonic acid
US3035081A (en) Process for preparing dialkyl alkylphosphonothionates
US3590104A (en) Process for preparing 0,0-dialkyl-0-phenyl phosphorothioates