The method of obtaining dialkylamino esters alkylphosphonic acids

 

(57) Abstract:

Use: production of organophosphorus substances. The inventive method comprises the interaction of dichlorohydrin alkylphosphonic acid with the alcohol used as solvent in alkanovykh, chloralkali or cycloalkane hydrocarbons with a boiling point of 70 to 120 degrees. With that taken in the amount of 300-600 ml per g/mol source dichlorohydrin. When conducting the interaction of the resulting hydrogen chloride is removed from the reaction zone pairs solvent through a top-down refrigerator, solvent after condensation and patrascanu return to the reaction zone until the termination of the allocation of hydrogen chloride in the gas phase of gazorazdelitel, the resulting mass is neutralized to pH 7.5 to 8.0. 3 table.

The invention relates to the production of organophosphorus substances, namely full esters alkylphosphonic acids of the General formula:

< / BR>
where R is alkyl WITH1-C4halogenated

R', R" is alkyl (C4-C8.

These esters are used as extractants of rare earth elements, softeners, low-temperature polymer compositions, flame retardants.

Known methods the floor is with excess alcohol in the presence of hydrogen chloride acceptors without them.

In the presence of acceptor outputs of secondary esters while high(75-80%) /1, 2/, however, in the industry this method is difficult to use due to the formation of a voluminous precipitation, which require the creation of an independent technology of their processing.

Upon receipt of the diesters alkylphosphonic acids without acceptor reaction occurs mainly at low temperatures and permanently remove the released hydrogen chloride or vacuum /3, 4/, or by Stripping with dry inert gas (nitrogen, air) /5/. The yield of the target product named means does not exceed 75%

The yield of the target product depends on the intensity of removal of hydrogen chloride.

In the second case, /7/ the reaction is carried out in a solution of dichloroethane at 30-40oWith simultaneous removal of hydrogen chloride from dry air. The yield of the target product 73

The disadvantage of these methods is the length of the synthesis process (5-6 hours) due to low velocity of the esterification reaction, which is carried out at low temperatures; high energy process and the difficulty of maintaining a low temperature exothermal process that leads to the creation of additional circulation Comte is imesa, mainly hydrogen chloride, the solubility of which in the reaction mass at low temperatures high enough; the formation of large quantities of wastewater at the stage of synthesis (4 m3/t and a relatively low yield (73) of the target product in the second case.

Closest to the proposed to the technical essence and the achieved result is a method of obtaining diapir by the interaction of dichlorohydrin alkylphosphonic acid with 2-ethylhexanol in a molar ratio of 1: 2,2, respectively, and a residual pressure of 100 mm RT.article in the boiling solvent, benzene or methylene chloride, as described in /7/ (pages 4-5) and taken as a prototype. In order to avoid entrainment of the solvent process is carried out under reflux. The best way of diapir 88,4 is achieved by conducting the reaction in boiling methylene chloride, benzene yield of 76.2

The disadvantage of this method, taken as a prototype, is a relatively low output diapir in the arbitrary choice of the solvent, as in the case of benzene, and the use of low-boiling methylene chloride, the use of which in the conditions of industrial production, as noted by the authors, the /7/ is associated with a number of difficulties that avny the entrainment of the solvent and leads to waste of raw materials and deterioration of the ecological characteristics of the process.

The aim of the present invention is to increase the yield of the target product and to improve the environmental performance of the process of obtaining dialkylamino esters alkylphosphonic acids.

This objective is achieved in that the solvent used alcamovia, chloralkali and cycloalkane hydrocarbons, better non-polar, with a boiling point of 70 to 120oWith, for example hexane, carbon tetrachloride, cyclohexane, in the amount of 300-600, better 400-500 ml/g-mol source dichlorohydrin, and the interaction of dichlorohydrin alkylphosphonic acid with the alcohol is carried out at the boiling temperature of the solvent, and removing hydrogen chloride from the reaction zone carry pairs of solvent, which together with the hydrogen chloride is directed through a top-down refrigerator. Condensed in descending fridge solvent with hydrogen chloride sent to patristical. The solvent of gazorazdelitel return to the reaction zone and hydrogen chloride comes to recycling. The return of the solvent in the reaction zone is carried out until the termination of allocation of hydrogen chloride in the gas phase of gazorazdelitel. The resulting reaction mass is neutralized water sastopamiem solvent under reflux prototype /7/ does not allow for quick and maximum removal of hydrogen chloride from the reaction zone. In the result of phlegmaria solvent at the reflux up to 30-40 hydrogen chloride is returned to the reaction zone, that is the cause of adverse reactions and reduce the yield of the target product.

We found that as the solvent, it is advisable to use alcamovia, chloralkali and cycloalkane hydrocarbons, better non-polar, with a boiling point of 70 to 120oC.

The use of solvents with higher boiling point makes it difficult to remove them from the finished product, and with temperatures below associated with the loss of solvent.

The amount of solvent used in the synthesis, is 300-600, better 400-500 ml/g-mol of dichlorohydrin.

In table 1 and 2 shows the data justifying the choice of solvent and its amount.

Output dialkylamide ether of the proposed method 90-96 Consumption, 20-Noah alkali is 40-50 ml/g-mol source dichlorohydrin. The time of synthesis is reduced in 1,5-2 times in comparison with known methods.

The proposed method of obtaining esters alkylphosphonic acids is as follows.

In a reactor equipped with a stirrer, thermometer, addition funnel, del the hydride alkylphosphonic acid and the solvent. The temperature in the reactor is brought to the boiling point of the solvent and dose of alcohol (solvent or without) through the bubbler under the layer of liquid in the reactor. During the dosing intensive boiling solvent and removing pairs of solvent hydrogen chloride. Solvent vapours together with hydrogen chloride pass through the reflux condenser and a downward fridge, chilled water or brine, and come in patristical, where hydrogen chloride sent for recycling, and the solvent return (continuously) in the reaction zone. The temperature of the solvent after the downward fridge if necessary, may be different. The return of the solvent in the reaction zone is carried out until the termination of allocation of hydrogen chloride in the gas phase of gazorazdelitel that determines the end time of the synthesis reaction full of air. This time is about 2.5-4 hours.

The reaction mass after cooling, neutralize with controlled pH 7.5 to 8.0 20 th water solution of caustic soda in the amount of 40-50 ml/g-mol source dichlorohydrin. The resulting mixture was separated with a separating funnel, the organic layer washed twice with water 100-200 ml/g-mol source dichlorohydrin and after separation from the organization who s not less than 95 diapir alkylphosphonic acid.

The research results are confirmed by the following examples.

Example 1. To 133 g (1 g-mol) of dichlorohydrin methylphosphonic acid in 300 ml of hexane with stirring and boiling point of hexane under dosed liquid layer in the reactor 286 g (2.2 g-mol) of 2-ethylhexanol in 100 ml of hexane. Hydrogen chloride from the reaction zone to remove pairs of hexane. Pair with hexane hydrogen chloride pass down the fridge, where hexane is condensed and a temperature of 25oC is fed together with hydrogen chloride in patristical. Fasoracetam serves as a separating funnel, the top of which is removed in the system of trapping hydrogen chloride, and from the bottom through the water seal is continuously returned to the reactor hexane.

2 hours after the termination of allocation of hydrogen chloride in the gas phase of gazorazdelitel that is identified by any of the acid indicator, distillate solvent cease. The reaction mass is then cooled to 20-25oWith and neutralize 20% sodium hydroxide under controlled pH 7.5 to 8.0.

After separation in a separating funnel allocate 750 ml organic layer and 60 ml of water-salt layer. The organic layer is washed twice with water (200 ml) and washed from organic the product in the amount of 305 g containing diapir di(2-ethylhexyl)-methylphosphonate(gachsaran) to 95.3

The output diapir 90,8 source dichlorohydrin. The quantity of wastewater to 0.47 l/g-mol of dichlorohydrin or 1.5 m3/t of product.

The elemental composition of the finished product:

Found: P 9,18; 9,24 FROM 64.2; AND 63.9 N 11,78; 11,90

Calculated: 9,67 63,72 11,64

Example 2. Differs from example 1 in that the solvent used carbon tetrachloride. The product is obtained from 66.5 g (0.5 g-mol) of dichlorohydrin in 250 ml of carbon tetrachloride and 143 grams (1.1 g-mol) of 2-ethylhexanol. The synthesis time of 2.1 hours. To neutralize the acidic impurities to a pH of 7.8 went 24 20 ml aqueous caustic soda.

Received 155 g of the product with the content of the basic substance 96,1 Output diapir on dichlorohydrin br93.1 Total wastewater 1.42 m3/t of product.

The elemental composition of the finished product:

Found: P 9,60; 9,66 WITH 64,0; 64,1 N 11,77; 11,80

Calculated: 9,67 63,72 11,64

Example 3. Carried out analogously to example 1. As initial reagents take 40 g (0.3 g-mol) of dichlorohydrin in 100 ml of cyclohexane and 49 g (0.66 g-mol) of n-butanol in 50 ml of cyclohexane. The reaction time is 4 hours. Received 60,2 product content dibutylamino ether 96 Output 92,5 Amounts of wastewater 1.4 m3/so

The elemental composition of the finished product:

Found: P 14,82; 14,97 With 51,73; 51,96 N. 10,2 shall Madrid ethylphosphonic acid and n-butanol. The output diapir 93,6 Amounts of wastewater 1.4 m3/so

The elemental composition of the finished product:

Found: P 13,76 WITH 54,38 N 10,96

Calculated: 13,94 54,03 10,43

Example 5. Carried out analogously to example 2. As initial reagents using the acid chloride chloroethylphosphonic acid, in the amount of 0.5 g-mol) in 250 ml of carbon tetrachloride and hexyl alcohol 1.1 g-mole. The reaction time of 2.0 hours. The output diapir 95.6% of the Amount of wastewater 1.45 m3/so

The elemental composition of the finished product:

Found: P 9,94 With 53,01 N 9,72 CL 11,70

Calculated: accounted for 10.39 52,76 9,38 11,89

Example 6 is carried out analogously to example 2. As initial reagents using a 0.3 g-mole of acid chloride isobutyrophenone acid in 150 ml of carbon tetrachloride and 0.66 g-mole of 2-ethylhexanol. The reaction time is 4 hours. The output diapir of 91.3 amounts of wastewater 1,40 m3/so

The elemental composition of the finished product:

Found: P 8,40; 8,46 WITH 66,22; 66,20, N 12,20; 12,27

Calculated: 8,56 to 66.30 of $ 11.97

Comparative analysis revealed that the proposed method is compared with the prototype allows to increase the output of diesters 8-12 compared to the base to reduce the synthesis of diesters 1.5-2.5 times, to reduce the consumption of sodium hydroxide in 2.5-3.0 times, to reduce the quantities of the BR>
< / BR>
where R is alkyl, C1WITH4, halogen;

R' and R" is alkyl WITH4WITH8,

the interaction of dichlorohydrin alkylphosphonic acid with the alcohol in the solvent at the temperature of its boiling point, characterized in that, to increase the yield of the target product in the solvent used alcamovia, chloroalkane or cycloalkane hydrocarbons with a boiling point of 70 to 120oWith that taken in the amount of 300 to 600 ml per 1 g/mol source dichlorohydrin, when conducting the interaction of the resulting hydrogen chloride is removed from the reaction zone pairs solvent through a top-down refrigerator, solvent after condensation and patrascanu return to the reaction zone until the end of the excretion of hydrogen chloride in the gas phase of gazorazdelitel, the resulting reaction mass is neutralized to 7.5 to 8.0.

 

Same patents:

The invention relates to the chemistry of phosphorus - organic compounds, and in particular to a new method of obtaining S-triphenylcarbinol esters of dealkylation and tetrathiofulvalene acids of General formula (I)

(RX)SGePh3where R is lower alkyl; X Is 0, S

The invention relates to new phosphorylated to Surinam General formula

R-- OCH2-COOH,

(I) where R is a saturated or unsaturated aliphatic hydrocarbon residue with a straight or branched chain, containing 6-30 carbon atoms which may be substituted with halogen, -OR, - SR1or-NR1R2group, where R1and R2lowest alkali

The invention relates to organic chemistry and can be used to obtain phosphonates, which can be used to reduce the Flammability of polymer materials

The invention relates to the chemistry of organophosphorus compounds, namely substituted carbamoylphosphate General formula I,

Pwhere R = CH3Cl, which can find application in agricultural practice as growth regulators for cotton

The invention relates to chemistry fosforsodyerzhascikh heterocyclic compounds, and in particular to methods for obtaining compounds of formula

H3C -N(C2H5)2which is an effective postregulation some crops

The invention relates to the chemistry of organophosphorus compounds, namely to a new method of obtaining S-trialkylsilyl - ash and stanilova esters of 4-methoxyphenylacetic or triiodobenzoic acids of General formula I 4-MeOC6Hwhere R, R1is lower alkyl; E is Si, Sn; X Is O, S

FIELD: organic chemistry, in particular improved method for production of phosphorinated and chlorinated methacrylates.

SUBSTANCE: invention relates to method for production of compounds having general formula , wherein R is lower alkyl and R1 is lower alkoxyl, phenoxyl, or group of formula . Claimed method includes reaction of pentavalent phosphorous acid chloroanhydride with glycydil methacrylate at 20-50°C in presence of titanium tetrachloride as catalyst in amount of 0.02-0.05 % calculated as reagent mass.

EFFECT: one-step method for production of phosphorous and chlorine containing methacrylates with improved water resistance.

2 tbl, 7 ex

FIELD: chemistry of organophosphorus compounds.

SUBSTANCE: invention relates to compounds with the bond C-P, namely to phosphorus-boron-containing methacrylate that can be used as inhibitor of combustion of polyvinyl alcohol-base film materials. Invention describes phosphorus-boron-containing methacrylate of the following formula: wherein n = 4-8. Polyvinyl alcohol films modified with indicated phosphorus-boron-containing methacrylate shows the enhanced refractoriness, rupture strength up to 206 kgf/cm2, water absorption up to 240% and relative elongation up to 12%.

EFFECT: valuable properties of substance.

1 tbl, 2 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to the improved method for preparing N-phosphonomethylglycine. Method involves interaction of derivative of hexahydrotriazine of the formula (II):

wherein X represents CN, COOZ, CH2OY and others; Z and Y represent hydrogen atom and others with triacylphosphite of the formula: P(OCOR3)3 (III) wherein R3 means (C1-C18)-alkyl or aryl that can be substituted. The prepared product is hydrolyzed and (if X represents CH2OY) oxidized. The proposed method is a simple in realization, economy and provides high degree of the end product purity.

EFFECT: improved preparing method.

19 cl, 11 ex

FIELD: organic chemistry, chemical technology, medicine.

SUBSTANCE: invention relates to acyclic nucleoside phosphonate derivatives of the formula (1): wherein means a simple or double bond; R1 means hydrogen atom; R2 and R3 mean hydrogen atom or (C1-C7)-alkyl; R7 and R8 mean hydrogen atom or (C1-C4)-alkyl; R4 and R5 mean hydrogen atom or (C1-C4)-alkyl possibly substituted with one or more halogen atoms, or -(CH2)m-OC(=O)-R6 wherein m means a whole number from 1 to 5; R6 means (C1-C7)-alkyl or 3-6-membered heterocycle comprising 1 or 2 heteroatoms taken among the group consisting of nitrogen (N) and oxygen (O) atoms; Y means -O-, -CH(Z)-, =C(Z)-, -N(Z)- wherein Z means hydrogen atom, hydroxy-group or halogen atom, or (C1-C7)-alkyl; Q (see the claim invention); its pharmaceutically acceptable salts or stereoisomers. Also, invention proposes methods for preparing compounds of the formula (1) and their using in treatment of hepatitis B or preparing a medicinal agent designated for this aim.

EFFECT: improved preparing method, valuable medicinal properties of compounds and agent.

16 cl, 10 tbl, 87 ex

FIELD: chemistry of organophosphorus compounds.

SUBSTANCE: invention relates to the improved method for synthesis phosphorus-chlorine-containing methacrylates that can be used in synthesis of polymeric, among them, uncolored, optically transparent and composition materials with reduced inflammability. Invention describes a method for synthesis of phosphorus-chlorine-containing methacrylates of the general formula:

wherein R means lower alkyl, chloroalkyl, alkoxyl, phenoxyl or group of the formula:

R1 means lower alkoxyl, phenoxyl or group of the formula:

Method involves interaction of phosphoric pentavalent acid chloroanhydrides with methacrylic acid glycidyl ester at heating in the presence of hexamethylenephosphorotriamide or dimethylformamide as a catalyst wherein catalyst is taken in the amount 0.3-0.6% of reagents mass, and process is carried out at rise of temperature from 40°C to 80°C in the presence of compound chosen from the group: alkyl- or alkoxy-substituted phenols taken in the amount 0.03-0.3% of reagents mass. Method provides decreasing water absorption of (co)polymerization products of synthesized phosphorus-chlorine-containing methacrylates and reducing retention time of surface stickiness of fiber glass synthesized on their basis and at retention the level of other properties, among them transparence and colorless.

EFFECT: improved method of synthesis, improved and valuable properties of compounds.

2 tbl, 10 ex

FIELD: organic chemistry, biochemistry, medicine.

SUBSTANCE: invention relates to phosphonic acid compounds used as inhibitors of serine proteinase of the general formula (I): wherein R1 is chosen from group comprising piperidinyl, pyrrolidinyl and 1,3,8-triazaspiro[4,5]dec-8-yl (wherein heterocyclic ring as added to nitrogen atom in ring) and -N(R7R80 wherein this heterocyclic ring is substituted optionally with one or two substitutes chosen independently from group comprising the following compounds: (a) C1-C8)-alkyl substituted optionally at terminal carbon atom with a substitute chosen from group comprising aryl, heteroaryl; c) phenyl and naphthalenyl; i) benzothiazolyl; R7 is chosen from group comprising hydrogen atom and (C1-C8)-alkyl; R8 is chosen from group comprising: (aa) (C1-C8)-alkyl; (ab) cycloalkyl; (ac) cycloalkenyl, and (ad) heterocyclyl (wherein R8 is added to carbon atom in ring) wherein (ab) cycloalkyl; (ac) cycloalkenyl, and (ad) heterocyclyl (wherein heterocyclyl (ad) comprises at least one cyclic nitrogen atom) substitutes and cycloalkyl moiety (aa) of a substitute is substituted optionally with substitutes chosen independently from group comprising: (ba) (C1-C8)-alkyl substituted at terminal carbon atom with a substitute chosen from group comprising amino-group (with two substitutes chosen independently from group comprising hydrogen atom and (C1-C8)-alkyl); (bb) (C1-C8)-alkoxy-group substituted at terminal carbon atom with a substitute chosen from group comprising carboxyl; (bc) carbonyl substituted with a substitute chosen from group comprising (C1-C8)-alkyl, aryl, aryl-(C2-C8)-alkenyl; (bd) aryl; (be) heteroaryl; (bf) amino-group substituted with two substitutes chosen independently from group comprising hydrogen atom and (C1-C8)-alkyl; (bh) halogen atom; (bi) hydroxy-group; (bk) heterocyclyl wherein (bd) is aryl substitute, and heteroaryl moiety (bc) comprise a substitute (halogen atom)1-3; R4 is chosen from group comprising aryl and heteroaryl wherein heteroaryl comprises halogen atom as a substitute; R2 and R3 are bound with benzene ring and represent hydrogen atom, and R2 and R3 form in common optionally at least one ring condensed with benzene ring forming polycyclic system wherein this polycyclic system is chosen from group comprising (C9-C14)-benzocondensed cycloalkenyl, (C9-C14)-benzocondensed phenyl; R5 is chosen from group comprising hydrogen atom and (C1-C8)-alkyl; R6 is chosen from group comprising (C1-C8)-alkyl and hydroxy-group; Y is absent, and X represents a single substitute that is added by a double bond and represents oxygen atom (O), and Z is chosen from group comprising a bond, hydrogen atom, and its salts. Also, invention relates to a method for synthesis of these compounds, to their composition inhibiting serine proteinase and to a method for its preparing. Proposed invention describes a method for treatment of inflammatory or serine proteinase-mediated disorder.

EFFECT: valuable biochemical and medicinal properties of compounds.

64 cl, 5 tbl, 38 ex

FIELD: organic chemistry, medicine, biochemistry.

SUBSTANCE: invention describes compound of the formula (I): wherein R1 means hydrogen atom (H); R2 means -SH, -S-C(O)-R8, -P(O)(OR5)2, -P(O)(OR5)R6, -P(O)(OR5)-R7-C(O)-R8, -P(O)(OR5)-R7-N(R5)-S(O)2-R9 or -P(O)(OR5)-R7-N(R5)-C(S)-N(R6)2; R3 means tetrazole, -C(O)OR6, -C(O)O-R7-OC(O)R5; R4 means optionally substituted aryl, or R4 means N-heterocyclyl. Also, invention describes compounds of the formula (II): and (III): wherein X means -CH2- or -O-, and pharmaceutical compositions comprising indicated compounds. Proposed compounds possess inhibitory effect on activity of plasma carboxypeptidase B and used as anti-thrombosis agents.

EFFECT: valuable medicinal and biochemical properties of compounds.

34 cl, 19 ex

FIELD: chemistry.

SUBSTANCE: invention concerns process of production of diisopropyl {[1-(hydroxymethyl)-cyclopropyl]oxy}methylphosphonate represented by the formula , which is the key intermediate compound in synthesis of antiviral nucleoside analogue. The invention also concerns new intermediate compounds of formulae and , and their production of compound (2) obtained under this invention, which is an antiviral nucleoside analogue (especially against hepatitis B virus) represented by the formula .

EFFECT: high purity grade and high output.

4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to protection of metals from corrosion using lacquer coating. This engineering problem can be solved by using calcium hydroxyethylidenediphosphonate with formula CH3(OH)C(PO3)2Ca2 as an anti-corrosion pigment, with higher anti-corrosion activity as compared to the prototype - protonated zinc hydroxyethylidenediphosphonate and a control specimen - zinc tetraoxychromate.

EFFECT: low-toxic high performance anti-corrosion pigment.

1 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention refers to method of production of C-phosphorylated alkylamidines serving as parent compounds of biologically active compounds for medicine and agriculture, of formula: where R1=C3-C4alkyl or isoalkyl; R2=CH3, C6H5; R3=C2-C4-alkyl or isoalkyl; R4=H, CH3, C3H7, C6H5, COOC2H5. Method includes in production of sodium derivatives of C-phosphorylated alkylamidines resulted from reaction of C-phosphorylated acetamidine with sodium. Produced sodium derivative is alkylated with alkylhalogenide in dioxane medium at mole ratio sodium:C-phosphorylated acetamidine:alkylhalogenide (1:1:1÷1.1), respectvely at temperature 20÷50°C.

EFFECT: production of new C-phosphorylated alkylamidines with high yield exceeding 78%.

1 cl, 9 ex

Up!