The method of obtaining 1,3-dichloromethane

 

(57) Abstract:

The invention relates to a method for producing 1,3-dichloromethane, which is used in the production of thermo - and hemostatic polymers, insecticides and pharmaceuticals. The method is carried out by catalytic chlorination of adamantane with gloriously agents, in particular chloroform or methylene chloride. As the catalyst used two salt or trivalent iron. The process is conducted in the presence of titanium metal in the form of powder, chips or plate and a polymer selected from such compounds as polybutadiene, polyisoprene or styrene-butadiene rubber, taken in an amount of 2-10 g of polymer per 1 g-atom of iron. The molar ratio of [Fe] : [Ti] : [Ad] : [CH2CL2or l3] = 1: 0,1-10: 500-1000: 500-1000. The process is carried out in 3-5 hours at 150-200oC. Technical result improved economic and environmental performance of the process, the simplification stage of separation of the catalyst. table 1.

The invention relates to the field of organic chemistry, in particular to a method for producing 1,3-dichloromethane.

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1,3-dichloromethan finds wide application in the production of thermo - and hemostasis. - M. : Nauka, 1989. S. 264 [1] ; Fort, R. C. Adamantane, The Chemistry of Diamond Molecules. N. Y. : Dekker, 1976, 385 p. [2] ).

Synthesis of 1,3-dichloropentane (2) was carried out by chlorination adamantane (1) chlorosulfonic acid (Lerman B. M. , H. Aref'eva I. , Kuziev A. R. , Tolstikov, A. Izv. THE USSR ACADEMY OF SCIENCES. Ser. chem. N 4, 894 (1971) [3] ). The reaction proceeds at low temperature (-5oC) and for (2) with high output required a large excess of ClSO2OH (molar ratio) [AdH] : [ClSO2OH] = 1: 8-10).

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The disadvantages of this method are as follows:

1. High consumption of highly reactive reagent - chlorosulfonic acid.

2. The necessity of using low temperatures (-5oC) when the duration of the reaction 60 hours.

3. The complexity of the selection of target products from dilute solutions chlorosulfonic acid, because Stripping them of course deeper chlorination is excluded.

4. The formation of large quantities of waste.

One of the well known methods of producing chlorinated adamantane (including 1,3-dichloromethane) is chlorination using carbon tetrachloride (CCl4under the action of acid catalysts, preferably AlC which the output chloroadamantane, presents 1-chloroadamantane (3) and 1,3-dichloropentane (2), 84%, CCl4is gloriouse the agent and the environment [5] .

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This method has the following disadvantages:

1. The reaction proceeds selectivity with the formation of a mixture of 1-chloro-(3)- and 1,3-dichloropentane (2).

2. The process is performed with a large excess of catalyst is AlCl3used in equimolar amounts relative to adamantane.

3. High consumption of AlCl3creates a number of difficulties, since it greatly complicated the process of isolation and purification of the target product. The reaction produces a significant amount of inorganic waste (AlCl36H2O, Al(OH)3, HCl) and wastewater processing which requires much labor to energy consumption.

1,3-Dichloromethan (2) was obtained by chlorination of adamantane using CCl4under the action of Rh-containing catalyst: Rh(PPh3)3Cl, [Rh(CO)2Cl] 2Ph4(CO)12if 200oC for 5 hours at a molar ratio [AdH] : [Rh] : [CCl4] = 1: 0,01: 3 (RF patent 2126784. Dzhemilev, U. M. , R. Khusnutdinov I. , Sidneva N. A. , Latypov Century. N. "A method of obtaining a 1-chloroadamantane" [6] ).

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This method has the population.

2. The high cost of rhodium salts.

3. Low yield of 1,3-dichloropentane (2) (~ 10%), because the main product of the reaction is 1-chloroadamantane (3).

When used in the chlorination reaction of adamantane with CCl4Co-containing catalyst (patent RF 2125551. Dzhemilev, U. M. , R. Khusnutdinov I. , Sidneva N. A. , Latypov Century. N. "A method of obtaining a mixture of 1-chloro - 1,3-dichloropentane" [7] ) mainly formed 1,3-dichloromethan (2) (the ratio of 1,3-dichloropentane (2) 1-chloroadamantane (3) is 69: 31)

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The main disadvantage of this method is neselektivno process: the output of 1,3-dichloromethane does not exceed 69%.

When used for chlorination adamantane catalyst obtained by the application of FeCl36H2O on K-10 montmorillonite (montmorillonite is an aluminosilicate, the General formula of this type of mineral: (OH)4Si8Al4O28nH2O) followed by dehydration (azeotropic distillation with CCl4) (K. Bergmann, C. T. O Konski. , J. Phys. Chem. , 67, N 10, 2169 (1963) [8] ) there is an increase in the selectivity of the reaction of 1,3-dichloropentane (2) to 98% (S. Chalais, Cornelis A., U. Kolodziejski, P. Laszlo, A. Mathy, P. Metra, Heiv. Chim. Acta, V. 68, 1196 (1985) [9] )

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Such withdrawal 1,3-dichloropentane (2) is achieved at is hours (the molar ratio of [AdH] : [FeCl3] : [CCl4] = 1: 3.36: 105).

The similarity of the three characteristics (source reagent, catalyst, final product) the prototype was taken method of chlorination adamantane using CCl4under the action of FeCl3/10 K [9] .

The prototype has the following disadvantages:

1. High consumption of catalyst FeCl3/10 K and gloriouse reagent used in the three-fold and 100-fold excess of the reagent, respectively.

2. FeCl3is a solid substance, which creates difficulties with its dosage and adding to the reactor, part of the technological operations carried out manually.

3. High consumption of FeCl3/K 10 creates difficulties associated with the isolation and purification of the target product. Because of the formation of a large number of inorganic wastes whose disposal is difficult, the process is environmentally hazardous.

4. The formation of large quantities of wastewater, because the selection of target products of the reaction mass is treated with water (formation of crystalline FeCl36H2O accompanied by the release of a large amount of heat). When the hydrolysis FeCl3allocated free of HCl, which promotes corrosion of the equipment. It is necessary to provide ( and expensive due to the large consumption of catalyst, reagent (CCl4), the waste, the availability of additional technological stage of decomposition of the reaction mass and the inability to reuse FeCl3and CCl4that are either hydrolyzed or polluted water.

The authors propose a method of obtaining 1,3-dichloropentane (2) free from the above disadvantages.

The method consists of chlorination adamantane using chloroform or methylene chloride under the action of the three-component catalyst containing salt (or complexes) of iron (II) or (III) metallic titanium (in the form of powder, chips, plates), and polymers (rubbers include polybutadiene, polyisoprene, butadiene-styrene rubber) in a molar ratio of [Fe] : [Ti] = 1: 0.1 - 10, preferably = 1: 1 and 2-10 grams of polymer per 1 g-atom of iron.

For the preparation of the catalyst used two salt or trivalent iron - FeCl3, FeBr2, Fe(C17H35CO2)3(iron stearate), Fe(C15H31CO2)3(iron palmitate), Fe(acac)3, Fe(naphthenate)3, Fe(OAc)2, Fe(C7H15CO2)3, Fe(C6H5CO2)3.

Complex catalyst promotes razloga adveritising by heating a solution of salts of iron and titanium powder, chips) in chloroform or methylene chloride, as well as polybutadiene or polyisoprene) in a sealed ampoule or steel mikroavtobus at a temperature of 200oC for 0.5-1 hour.

Thus obtained catalyst has a high activity in the chlorination adamantane, which for 3 hours at 200oC is transformed into 1,3-dichloromethan (2) with a quantitative yield.

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The optimal molar ratio of Fe: Ti: AdH: CHCl3(CH2Cl2) is= 1: (0.1-10): (500-1000): (500-10000) and 2-10 grams of polymer per 1 g-atom of iron.

Significant differences of the proposed method from the prototype:

1. For catalysis of the chlorination reaction of adamantane with CHCl3(or CH2Cl2used new two-component catalysts containing compounds of iron (II) or (III), metallic titanium and polymer.

2. If in the known method of chlorination catalyst (FeCl3) is used in a threefold excess to adamantane, offer only 0.005-0.01 moles relative to 1 pray substrate.

The advantages of the proposed method are as follows:

1. Moderate consumption of the catalyst 0.005-0.01 moles relative to 1 pray adamantane.

4. Reducing waste.

5. Unreacted CHCl3without additional purification may be returned in the response.

6. Reduce the cost and environmental safety of the process.

The proposed method is illustrated by examples.

Example 1. The method of preparing the active form of the catalyst.

In steel mikroavtobus (V = 17 ml) or in a glass ampoule (V = 20 ml) were placed 1 mmol salts of iron, 0.1-10 mmol of titanium, 2-10 grams of polymer (polybutadiene or polyisoprene) per 1 g-atom of iron and also 500-1000 mmol CHCl3(or CH2Cl2). Autoclave (ampoule) tightly closed and heated for 0.5-1 hour at 200oC. Then the autoclave (ampoule) was cooled to 20oC, was opened. The catalyst used for chlorination of adamantane.

Example 2.

In steel mikroavtobus (V = 17 ml) or glass vial (20 ml) to a pre-prepared active form of the catalyst was added to 500 mmol adamantane, 150 mmol CHCl3hermetically closed, the contents were heated for 3 hours at 200oC.

J. mass was filtered through a layer of Al2O3(2 Gy). Unreacted CHCl3drove away, the residue was recrystallize from methanol, isolated 1,3-dichloromethan in the form of white crystals wereopl. 130-131oC (lit. data 130-132oC [9] ); Exit 98%.

Other examples of the method are given in table. 1.

The method of obtaining 1,3-dichloromethane by catalytic chlorination of adamantane with gloriously agents at 150-200oC for 3-5 h, characterized in that as glorieuses agent is chloroform or methylene chloride, and the process is conducted in the presence of a catalyst consisting of salts of two or trivalent iron, of titanium metal in the form of powder, chips or plate and a polymer selected from such compounds as polybutadiene, polyisoprene or styrene-butadiene rubber, taken in an amount of 2-10 g of polymer per 1 g-atom of iron, when the molar ratio of [Fe] : [Ti] : [Ad] : [CH2CL2or l3] = 1: 0,1-10: 500-1000: 500-1000.

 

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FIELD: organic chemistry, chemical technology.

SUBSTANCE: method involves the alkylation reaction of adamantine or mixture of alkyladamantanes with the general number of carbon atoms 11-20 in methylene chloride solution medium at temperature 15-25°C in the presence of catalytic system representing an equimolar mixture of aluminum halide and halide-containing promoter of the general formula: AlX3 x CpHrXz wherein X means Cl, Br; p = 0; r = 0; z = 2, or P = 1; z = 4, either p = 1; r = 2; z = 2. The conversion of adamantine is 78-94%. Invention provides the development of the improved technological procedure for preparing the end substances with the enhanced importance.

EFFECT: improved preparing method.

7 tbl, 16 ex

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4 ex

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EFFECT: improved method of synthesis.

3 ex

FIELD: organic synthesis.

SUBSTANCE: invention relates to improved method of preparing title compounds depicted by general formula: , wherein R1 = R2 = H : R = N(CH3)2, OCH3, C(CH3)3; R1 = H, R2 = CH3 : R = N(CH3)2, C(CH3)3; R1 = R2 = CH3 : R = N(CH3)2, which are intermediates in synthesis of biologically active products, via reaction of 1,3-dehydroadamantane or homologues thereof with benzene derivatives selected from series: N,N-dimethylaniline, anisole, and tert-butylbenzene at molar ratio of reactants1:(5-6), respectively, in a benzene derivative at 120-130°C for 5-6 h.

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6 ex

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SUBSTANCE: invention relates to chemistry of adamantine derivatives, namely, to a novel method for synthesis of (adamant-1-ylmethylene)-containing aromatic compounds of the general formula (I): , wherein R1 = R2 = R3 = R4 means hydrogen atom (H) (1); R1 means -CH3; R2 = R3 = R4 means H (2); R1 = R3 = R4 means H; R2 means -CH3 (3); R1 = R2 = R4 means H; R3 means -CH3 (4); R1 = R2 means H; R2 = R4 means -CH3 (5); R1 = R3 = R4 means -CH3; R2 means H (6); Ad means 1-adamantyl that are intermediate products for synthesis of biologically active substances. Method involves adding aromatic compounds to adamantine derivative wherein 1,3-dehydroadamantane is used as a adamantine derivative, and the following compounds are used as aromatic compounds: toluene, o-, m-, p-xylene, mesitylene, durene in the mole ratio of reagent = 1:(2-4) in the parent aromatic compound medium, at their boiling point (110-197°C) for 60 min. Invention provides simplifying method for synthesis of abovementioned compounds and their synthesis with higher yields.

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6 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for synthesis of adamantyl-containing aromatic compounds of the general formula: , wherein R1 = R2 = R3 = R4 means hydrogen atom (H); R5 means Ad (1); R1 means -CH3; R2 = R3 = R5 means H; R4 means Ad (2); R1 means -C2H5; R2 = R3 = R5 means H; R4 means Ad (3); R1 means i-C3H7; R2 = R3 = R5 means H; R4 means Ad (4); R1 = R2 means -CH3; R3 = R5 means H; R4 means Ad (5); R1 = R3 means -CH3; R2 = R5 means H; R4 means Ad (6); R1 = R4 means -CH3; R2 = R3 means H; R5 means Ad (7) that are intermediate products for synthesis of biologically active substances. Method involves adding aromatic compounds to a adamantine derivative wherein 1,3-dehydroadamantane is used as a adamantine derivative, and compounds chosen from the following order: benzene, toluene, ethylbenzene, isopropylbenzene (cumene), o-, m-, p-xylene are used as aromatic compounds in the mole ratio of reagents = 1:(2-4) in diethyl ether medium, at temperature 30-35°C, or in the parent aromatic compound medium at their boiling point (80-110°C) for 30 min, in the presence of catalytic amounts of sulfuric acid. Method provides preparing the claimed compounds with the high yield.

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7 ex

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