1,3,5,7-tetraalkyladamantanes as novel adamantane derivatives, method for synthesis of 1,3,5,7-tetraalkyladamantane and modification of polyalkyladamantane mixtures

FIELD: chemistry.

SUBSTANCE: invention relates to a method for synthesis for 1,3,5,7-tetraalkyladamantane of general formula where R1=R2=R3=R4=Et; R1=R2=R3=R4=n-Pr; R1=R4=Me, R3=R4=Et; R1=R2=Me, R3=R4=n-Pr; R1=R2=R3=n-Pr, as well as polyalkyladamantane mixtures in the presence of electrophilic catalysts, characterised by that adamantane, 1,3-dimethyladamantane or a mixture of polyalkyladamantanes with a total of 11-20 carbon atoms is alkylated with CnH2n olefins, where n=2 or 3, in the presence of a catalyst system with gross formula AlX3·CkHalr, where X=CI, Hal=Br, k=0, r=2, or X=Br, Hal=CI, k=1, r=4, and the process is carried out in a CH2X2 (X=Cl, Br) solution at 15 - 25°C for 2-3 hours in molar ratio [adamantane]:[catalyst] = (15-10):1. The invention also relates to novel compounds EFFECT: high output and selectivity of desired compounds.

2 cl, 32 ex, 6 tbl

 

The invention relates to the field of organic chemistry, namely tetraalkylammonium with alkyl groups at tertiary carbon atoms adamantanol kernel, specifically to 1,3,5,7-tetraalkylammonium General formula:

the method of obtaining 1,3,5,7-tetraalkylammonium General formula

and kodifikatsii mixtures of polyacyladipate with the total number of carbon atoms 11-20 obtaining more valuable mixtures with a high content of ethyl and various groups.

Based on extensive data, published scientific and patent literature, 1,3,5,7-tetraalkylammonium promising as components of industrial fluids comprehensive source of compounds for obtaining heat-resistant polymers, dendrimers and biologically active compounds. The invention can be used for the production of valuable heat-resistant non-toxic lubricants or their components, friction systems, cable oils, transmission fluids, additives for lubricating oils, as starting compounds for the synthesis of polymers and dendrimers, as well as for the synthesis of biologically active compounds of a new generation [Ehimare, Adamantanes, Moscow, Nauka, 1989]. Prospects for the use of alkyladamantanes as a valuable chemical and heat-resistant liquid is nd with good viscosity properties shown in numerous patents, alkyladamantanes with alkyl groups at the nodal positions have a high chemical durability and polyacyladipate with the total number of carbon atoms in the molecule 22-30 high coefficient of friction and good lubricating characteristics, is recommended as components of the hydraulic transmission fluid with improved adhesion factor (R..Moore, US. Patent 3646234, C.A. 1971, 75, 109956; I.N.Duling; D.S.Gates; R..Moore; F.P.Glazier; US. Patent 3648531, C.A. 1972, 76, 143219; I.N.Duling; D.S.Gates; R..Moore; F.P.Glazier; R..Moore, US. Patent 40043927, C.A. 1977, 87, 18887080). The dehydrogenation 1,3,5,7-tetraalkylammonium opens the possibility for the synthesis of a new group of unsaturated adamantanes - high strength and chemically resistant polymers. [Aphroden; See, USP, 1982, 480] and promising new dendrimers (Polym News. 1992, 17, 301; Macromolecules, 1994, 27, 7011). 1,3,5,7-Tetraalkylammonium also promising for the synthesis of a new series of 2-functional derivatives 1,3,5,7-tetraalkylammonium of interest for the synthesis of biologically active compounds of a new generation, because of adamantane compounds with a functional group at the 2-position possess biological activity [..Nagasawa; J.A.Elberling; F.N.Shirota, J. Med. Chem, 1973, 16, 823; 1975, 18, 826].

The present invention is devoted to receiving new 1,3,5,7-tetraalkylammonium and application of a new way to get known is s 1,3,5,7-tetraalkylammonium and modification of mixtures of alkyladamantanes order to obtain more valuable products. These new substances, their properties, method of production known 1,3,5,7-tetraalkylammonium and modification of polyacyladipate not described in literature.

The described method of synthesis of methyladipate containing a methyl group at the nodal positions adamantanol polyhedra (1,3-dimethyl, 1,3,5-trimethyl - 1,3,5,7-tetramethylguanidine)by isomerization of the corresponding perhydroanthracene compounds. The drawbacks of this method are low selectivity and applicability only to get methyladenine (Ehiri, Adamantanes, Moscow, Nauka, 1989).

Described is an example of retrieving 1,3,5-trimethyl-7-atinadamente by isomerization Dihydrocodeine under the action of aluminum chloride. The disadvantage of this method is the low availability of the source of the hydrocarbon and the inapplicability of the method for the synthesis of other polyacyladipate (J. Org. Chem. 1966, 31, 2014).

A known method of producing adamantanes with alkyl groups at the nodal positions of methyladenine or dimethyladamantane, consisting in the capacity of methylene groups in the tertiary carbon atom through a sequence of stages, synthesized, carbonylation, recovery, again synthesized with the formation of bromide containing one methylene group compared with the initially formed bromide, etc. Using ecostrategy, get alkyladamantanes normal structure with different length alkyl groups (J. of General chemistry, 1964, 34, 579). The disadvantages of this method are the multistage process, the low yields of the target products, the applicability to get only mono and dialkylamines of adamantanes.

Described is a method of obtaining alkyladamantanes by interaction alkyllithium connections adamantanecarbonyl acids (Petrochemicals, 1969, 3, 323). The disadvantages of this method are the low selectivity because as byproducts derived alcohols and olefins, the need to work in an inert atmosphere under strict absence of moisture and the applicability of the method for the synthesis of exclusively monoalkylamines.

You know getting alkyladamantanes in the interaction of adamantane with olefins in the presence of a proton or lisovich acids. However, this method has a low selectivity and low efficiency. The reactions take place with a low conversion of adamantane and lead to a motley mixture containing alkyl and alkenylamine and polyallylamine products, and obtain in this way tetraalkylammonium, including tetraethylammonium and tetrapropylammonium not. In addition, in reactions with olefins produces by-products not adamantanol nature, resulting by oligomere the emission source of olefins. For example, the described method of alkylation adamantane ethylene in the environment of hexane in the presence of bromide or aluminum chloride at -10°C (Dokl. Academy Of Sciences, 1970, 191, 831). The drawbacks of this method: neselektivno and inefficiency of reactions leading to the formation of more than 20 alkyladamantanes with different length and different structure of alkyl radicals, conducting the reaction at low temperature. When the molar ratio [AdH]:[lr3]=1:4 for 8 hours target product, 1-atinadamente, is formed with an exit 0.063 wt.% per lr3and in the reaction with ll3when the ratio [AdH]:[ll3]=1:2 output 1-atinadamente is 0.0024 wt.% per ll3. This method is chosen as a prototype.

The reaction of adamantane with propylene lead to the formation of a mixture of 16 products, although in this case the selectivity of the formation of 1-propylalanine is slightly higher and amounts to ~17 wt.% on proreagirovshim adamantane (Dokl. Academy Of Sciences, 1970, 191, 831).

A known method of producing alkyladamantanes alkylation alkyladamantanes Heptene under the action of 20-fold excess of 96%sulfuric acid (L.Vodika, J.Burkhard, J.Jonku. Collection of Chech. Chem. Comm. 1980, 45, 835). It alkyladamantanes with one (AdC7H15Ad, m=17, and AdC14H29, m=24) and two adamantanamine cycles (AdC14H28Ad, m=34) with an overall yield of 20%. Summarywhat of alkyladamantanes with the number of carbon atoms in the molecule m=24 and 34 is only 6%, and the main reaction products are oligomers of Heptene. The disadvantages of this method are the low outputs of alkyladamantanes and especially higher alkyladamantanes, large quantities of by-products, non-catalytic nature of the process, the use of inaccessible adamantanol and a large excess of aggressive concentrated sulphuric acid.

A known method of producing polyacyladipate by reacting adamantane with olefins in the presence of solid alumoxane catalysts (alumina, activated with sulfuric acid, silica-alumina and zeolite-containing catalyst) at a temperature of 190-290°C. the result is a complex mixture of products with a high content of alkenylamine (in some cases they are the main products (I.e. Bagriy, Adamantanes, Moscow, Nauka, 1989, 160). The drawbacks of this method: neselektivno reactions, a high content of unsaturated derivatives of adamantane, inefficiency reactions, low conversion of adamantane, the inapplicability of the method for the synthesis of 1,3,5,7-tetraethyl - and tetrapropylammonium.

Described method of thermal alkylation adamantane ethylene. At 300°C, a pressure of 30 ATM and duration of the reaction more than 80 hours to obtain a viscous oil (10 wt.%) BP. 141-197°C at 20 mm and Tsam <-60°C. According to mass spectrometry, oil identifiziert is but presumably as a mixture of 1,3,5,7-Tetra-, 1,3,5-tri - and 1,3-diethyl-adamantanes with a predominance of the latter (Autodialing, V.V. Vikulin. Petrochemicals, 1974, 822). At 300°C the content of the proposed 1,3,5,7-tetramethylguanidine in a mixture of 2-3 wt.% 120 hours Method has no prospects of obtaining 1,3,5,7-tetratetracontane, the structure of which has not been, and if this substance and is formed, the method for obtaining a highly selective and inefficient, requires strict conditions and for a very long time.

Describes how to obtain 1,3-dimethyl-5,7-diethylaminopentane by reacting 1-bromo-3,5 - dimethyladamantane and ethylene under the action of bromide of aluminum at -30°C in the presence of a solvent containing a tertiary carbon atom (R..Moore, US. Patent 3655782, 1972). The yield of the target product is 85%. The disadvantages of this method are the use of inaccessible 1-bromo-3,5-dimethyladamantane, conducting the reaction under cooling, which requires additional energy consumption.

The present invention is to obtain new individual 1,3,5,7-tetraalkylammonium with one or two adamantanamine nuclei, creating a new way to get 1,3,5,7-tetraalkylammonium and modification of mixtures of alkyladamantanes order to obtain more valuable products. Received 1,3,5,7-tetraalkylammonium must possess a number of valuable properties, such as high the boiling point, good lubricating characteristics possessed by polyacyladipate, high chemical inertness, due to the absence of reactive tertiary CH bonds, which opens the possibility to use them as a valuable chemical-resistant lubricants or their components, and other industrial fluids wide range of purposes. The dehydrogenation of alkyl groups 1,3,5,7-tetraalkylammonium should lead to valuable monomers - adamantanes with 4 unsaturated groups and dendrimers - symmetric molecules with adamantanone a polyhedron in the center. Carbonylation 1,3,5,7-tetraalkylammonium opens perspectives for the synthesis of a new group, 2-functional tetraalkylammonium interest as biologically active compounds.

The problem is solved by getting a new individual 1,3,5,7 - tetraalkylammonium with various groups with one or two adamantylidene nuclei, creating a new way of getting 1,3,5,7-tetraalkylammonium and modification of mixtures of polyacyladipate by alkylation adamantane or 1,3-dimethyladamantane, or polyacyladipate with the total number of carbon atoms 11-20-olefins of General formula CnH2nwhere n=2, 3, namely, that as the catalyst systems containing equimolar mixture of the aluminium halide is Oia and haloesters promoter of the General formula: l 3·klrwhere X=Cl, Hal=Br, k=0, r=2 or X=Br, Hal=Cl, k=1, r=4, and the process is carried out in a solution dihalomethane General formula: CH2X2(X=Cl, Br) at 15-25°C for 2-3 hours at a molar ratio [adamantane]:[catalyst]=(15-10):1 for individual 1,3,5,7 - tetraalkylammonium, and in the case of mixtures of polyacyladipate with a ratio of 1.2-1.5 mmol of catalyst per 1 g of the original mixture of polyacyladipate.

The claimed catalysts were previously used for the synthesis of polyalkylated of adamantanes and saturated hydrocarbons (Isegrim, Lavanish, Switch, Imerisia, Aeeseap, Ugulava. RF patent №2277080).

The proposed method in the reactions of adamantane with ethylene and propylene conversion of adamantane 98-100%. The selectivity of the formation of 1,3,5,7 - tetramethylguanidine, 78-100%. In the reaction of adamantane with propylene is formed a mixture of 1,3,5,7 - tetrapropylammonium with one adamantanone the core (R1=R2=n-WG) and two 1,3,5 - tri-n-propylalanine groups n WG3Ad), the United three methylene units through the tertiary carbon atoms of each group (R1=n-RG, R2=(CH2)3dr3in the ratio of [AdPr4]:[(WG3Ad)2With3H6]=3.7:1.

The reaction of obtaining 1,3,5,7-tetraalkylammonium in the presence of these catalysts occurs according to the scheme, including education is under the action of the electrophile from adamantane (or its homologue) of substituted-cation which is attached to the olefin with the formation of new cation, then turning in alkyladamantanes cation. The development of this chain reaction and repetition of the above stages leads to 1,3,5,7-tetraalkylammonium. The formation of the product containing two adamantly fragment (dr3)2With3H6includes education Tris-propylpiperidine and its alkylation Tris-propylaminoethyl-cation:

The reaction is carried out as follows: in a round bottom flask, equipped with a crane for carrying out the reaction in an atmosphere of olefin, at a temperature of 15-25°C and stirring with a magnetic stirrer, to prepare a catalyst by mixing equimolar amounts VG2with aluminium chloride or polyhalomethanes with aluminum bromide in solution dihalomethane. In the resulting solution of catalyst in the atmosphere of the olefin is injected adamantane and continue to stir the reaction mixture at the same temperature for 2-3 hours. The reaction mixture is treated with water, extracted with ether, the ether extracts washed with water until neutral and dried with Na2SO4. After removal of the solvent, the products produce by distillation in vacuum. The conversion of adamantane in reactions with propylene are 98-100%. In the reaction of adamantane with propylene is formed a mixture of 1,,5,7 - tetraalkylammonium with one adamantanone the core (R 1=R2=n-WG) and two 1,3,5 - tri-n-propylalanine groups n WG3Ad), the United three methylene units through the tertiary carbon atoms of each group (R1=n-RG, R2=(CH2)3dr3in the ratio of [AdPr4]:[(WG3Ad)2With3H6]=3:1. Both compounds are new. The structure of the new products proved by data of elemental analysis, NMR spectra and mass spectral.

The proposed method was applied to obtain from adamantane and ethylene 1,3,5,7-tetratetracontane, the formation of which has been previously assumed, but has not been rigorously proven (Autodialing, V.V. Vikulin. Petrochemicals, 1974, 822) to obtain 1,3-dimethyladamantane and ethylene previously described 1,3-dimethyl-5,7-diethylaminopentane and receipt of 1,3-dimethyladamantane and propylene previously registered 1,3-dimethyl-5,7-di-n-propylalanine. The synthesis is carried out on the above-described method. The conversion of 1,3-dimethyladamantane and outputs 1,3-dimethyl-5,7-dialkylamino also be 95-100% and 78-100%, respectively.

The advantages of the proposed method of synthesis of 1,3,5,7-tetratetracontane before method described in (Petrochemicals, 1974, 822)are in high output (170 wt.% compared to 3% wt.% based on adamantane), high selectivity (70-98% compared with 8%), the reaction conditions (15-25°C for 2 -3 hours instead of 300°C is for 120 h).

Structure of 1,3-dimethyl-5,7-diethylaminopentane and 1,3-dimethyl-5,7-di-n-propylalanine confirmed by the data of elemental analysis and mass spectra.

The advantage of obtaining 1,3-dimethyl-5,7-diethylaminopentane on the proposed method consist in the use of available 1,3-dimethyladamantane instead of 1-bromo-3,5-dimethyladamantane and conducting the reaction at room temperature instead of -30°C.

The proposed catalysts allow to modify the composition of volatile alkyladamantanes by alkylation their ethylene or propylene, transforming the original mix is more valuable polyacyladipate. Modifying the mixture of alkyladamantanes AdCnwith n=1-10, preferably monoalkylamines, turns into another mixture, significantly enriched polyalkylbenzene the adamantanes. Modification of alkyladamantanes AdCnethylene leads to a mixture enriched with atinadamente, and propylene - propylalanine. Thus, the original alkyladamantanes make more thermally and chemically stable liquid with high viscosity. The change in the composition of mixtures of polyacyladipate composition AdC1- AdC10after their modification by olefins were evaluated by mass spectral, change intensities of characteristic fragment ions.

So, comparing the intensities of the fragment ions m/z 135 (basically the ions monoalkylamines) and m/z 177 (ions, characteristic of propylalanine) showed that after alkylation fraction alkyladamantanes AdCn(n=1-10) propylene in the presence of CCL4·lr3(or CH2·ll3in CH2Cl2at room temperature the formed volatile fraction of alkyladamantanes the ion intensity of m/z 135 reduced by almost 2 times, and ions of m/z 177 increased 3.2 times compared to the original mixture of alkyladamantanes. In the presence of a catalyst VG2·lCl3in CH2Cl2the ion intensity of m/z 135 in the volatile fraction reduced to 1.8 times, and the ions m/z 177 increased 3.9 times. The study by the method of mass spectrometry direct input of volatile ingredients faction, formed after the reaction AdCn(n=1-10) with propylene, showed that it consists of alkyladamantanes two types of AdCn: (with m to 24, where m is the total number of carbon atoms in the molecule) and Ad2Cn(m 32). Modification of alkyladamantanes AdCn(n=1-10) under the action of ethylene also causes a reduction of the intensity of the ions of m/z 135 in the volatile fraction of 1.5-1.65 times and increase the intensity of ions m/z 164 (typical for atinadamente) 2.25-2.50. Ions with m/z 164 are after modification alkyladamantanes AdCn(n=1-10) ethylene 45-50% of the total ion current. A detailed study of the composition-modified ethylene polyacyladipate by GLC-MS displays the, that atinadamente be not less than 76% of all products.

Table 1 shows the elemental analysis data of new tetraalkylammonium 1,3,5,7-AdR4(R=n-Pr), (Pr3Ad)2C3H6. Table 2 shows the NMR and mass spectra of new products. For (Pr3Ad)2C3H6given spectra13With NMR and mass spectra. Proton spectra for (WG3Ad)2With3H6due to the large overlap is not informative.

The structure of 1,3,5,7-Tetraethylenepentamine, 1,3-dimethyl-5,7-diethylaminopentane, 1,3-dimethyl-5,7-dipropylamino proved by elemental analysis data (table 3) and NMR and mass spectra (table 4). In tables 5 and 6 show the data of mass-spectral study of the modification of polyacyladipate and propylene, and ethylene.

Example 1. In a dry round bottom flask, equipped with a crane for carrying out the reaction in an atmosphere of olefin, at a temperature of 20-25°C and stirring with a magnetic stirrer to prepare a catalyst by mixing 0.517 g (3.23 mmole) VG2and 0.431 g (3.23 mmole) ll3in 4 ml of CH2Br2. To the catalyst in an atmosphere of ethylene add 4.39 (at 32.28 mmole) adamantane. The reaction mixture is stirred at 20°C for 2 hours, then treated with water, extracted with ether, the ether extracts washed with water until neutral and dried with Na2SO4. Anal is C GC - MS showed that the reaction mixture consists of a Number2, 'adet3and AdFt4(here and further Ad - adamantly balance, regardless of the number of deputies). Small amounts are present isomers'adet5; adamantane in the mixture is missing. The GLC has the following ratio of ingredients (weight%): 'adet488%, 'adet32%, 'adet24%, mixture of isomers'adet55%.

Example 2. The catalyst obtained by mixing 0.465 g (2.91 mmole) VG2and 0.388 g (2.91 mmole) ll3at 15°C in 3.5 ml of CH2VG2in the atmosphere of ethylene add 3.95 (29.05 mmole) adamantane. The reaction mixture was stirred at 15°C for 2.5 hours, then treated with water, extracted with ether. The ether extracts are washed with water until neutral, dried with Na2SO4. The GLC has the following ratio of ingredients (weight%): 'adet486%, 'adet33%, 'adet25%, mixture of isomers'adet33%. Conversion AdH=100%.

Example 3. The catalyst obtained by mixing 0.511 g (3.20 mmole) VG2and 0.427 g (3.20 mmole) ll3at 0°C in 4 ml of CH2VG2in the atmosphere of ethylene add 4.34 (31.86 mmole) adamantane. The reaction mixture was stirred at 0°C for 2 hours, then treated with water, extracted with ether. The ether extracts are washed with water until neutral and dried with Na2SO 4. The GLC has the following ratio of ingredients (weight%): 'adet469%, 'adet315%, 'adet214%. The conversion of adamantane was 98%.

Example 4. In the atmosphere of ethylene of 4.08 g (30 mmol) of adamantane, 0.48 g (3 mmole) VG2and 0.4 g (3 mmole) ll3at 20°C in 4 ml of CH2Br2after 3 hours will receive the following products (wt.%): 'adet478%, 'adet34%, 'adet27.7%, mixture of isomers'adet5and Number67%. Adamantane in the reaction mixture is missing.

Example 5. In the atmosphere of ethylene of 2.28 g (16.7 mmole) adamantane, 0.18 g (0.11 mmole) VG2and 0.15 g (1.11 mmole) ll3at 20°C in 0.5 ml of CH2VG2after 3 hours will receive the following products (wt.%): 'adet474%, 'adet314% and Number212%. Adamantane in the reaction mixture is missing

Example 6. In the atmosphere of ethylene from 2.4 g (17.6 mmole) adamantane, 0.14 g (0.88 mmole) VG2and 0.12 g (0.9 mmole) ll3at 20°C in 0.6 ml of CH2VG2after 3 hours will receive the following products (wt.%): 'adet449%, 'adet326% and Number225%. Adamantane in the reaction mixture is missing.

Example 7. The catalyst obtained by mixing 0.56 g (3.50 mmole) VG2and 0. 47 g (3.52 mmole) ll3at 20°C in 6 ml of CH2VG2in the atmosphere of ethylene was added 4.8 g (35.2 mmole) adamantane, stirred at 20°C for 3.5 hours. After standard processing, you receive the following products (wt.%): AdEtsub> 478%, 'adet35% and'adet29%other products 6%. Adamantane in the reaction mixture is missing.

Example 8. The catalyst obtained by mixing 0.517 g (3.23 mmole) VG2and 0.431 g (3.23 mmole) ll3at 20-25°C in 4 ml of CH2Cl2in an atmosphere of ethylene, add 4.39 (32.22 mmole) adamantane. The reaction mixture is stirred at 20°C for 2 hours, then treated with water, extracted with ether. The ether extracts are washed with water until neutral and dried with Na2SO4. Adamantane in the mixture is missing. The GLC has the following ratio of ingredients (weight%): 'adet486%, 'adet37%, 'adet26%, mixture of isomers'adet5~ 1%.

Example 9. When using as a catalyst of aluminum chloride in the absence of bromine from 0.92 g (6.75 mmole) adamantane, 0.18 g (1.35 mmole) ll3at 20°C in 0.5 ml of CH2Cl2after 2 hours get a reaction mixture containing (wt.%): AdH 0.22 g (conversion of 70%), 'adet 0.27 g, 'adet20.37 g, 'adet30.38 g, 'adet40.29, the Total yield of alkyl products on the original AdH 142 wt.%, content'adet4in a mixture of alkyl products 22%.

Example 10. In the atmosphere of ethylene at 20-25°C 0.869 g (6.38 mmole) adamantane and 0.17 g (1.27 mmole) ll3in 0.5 ml of CH2Cl2after 12 hours receive a mixture containing (wt.%): 'adet20.092 g, 'adet30.46 g, 'adet20.89 is. The total yield of alkyladamantanes per adamantane 166 wt.%, content'adet4in a mixture of alkyl products 62%.

Example 11. Mix 0.51 g (3.74 mmole) adamantane with 0.1 g ll3(0.75 mmole) in 0.5 ml of hexane in an atmosphere of ethylene at 20-25°C for 3 hours. Conversion of adamantane is equal to 0.

Example 12. At 20-25°C in an atmosphere of ethylene for 3 hours mix 27.95 g (205.2 mmole) adamantane with 5.87 g (20 mmol) of catalyst VG2·lCl3formed when the mixture of 3.20 g VG2with 2.67 g ll3in 25 ml of CH2VG2. The reaction mixture carefully (dropwise) hydrolyzing with water, extracted with ether. The ether extracts are washed with water until neutral, dried with Na2SO4separate the organic layer from the desiccant by filtration and the solvent is distilled off in vacuum. After removal of the solvent receive 46.64 g products (167 wt.% from the original adamantane). Distilled product in vacuum. After several distillations get 24.54 g (88 wt.% from the original adamantane) analytically pure 1,3,5,7-tetratetracontane BP. 139°C at 1-2 mm Pradhan contains 6.5 g'adet4mixed with'adet3and Number2. The data of elemental analysis of the product BP. 139°C at 1-2 mm are shown in table 1, and its spectra in table 2.

Example 13. At 20°C is stirred with a magnetic stirrer 0.0859 g (0.56 mmole) CCL4and 0.15 g 0.56 mmole) lr 3in 0.5 ml of CH2Cl2. To the resulting catalyst in an atmosphere of ethylene was added 0.76 g (5.50 mmole) adamantane and stirred the reaction mixture at 20°C for 2 hours. Then the reaction mixture is carefully hydrolyzing with water, extracted with ether. The ether extracts are washed with water until neutral, dried with Na2SO4separate the organic layer from the desiccant by filtration. According to GC the mixture (wt.%): 'adet495% and Number25% at complete conversion of adamantane.

Example 14. At 20°C is stirred with a magnetic stirrer 0.0859 g (0.56 mmole) CCL4and 0.15 g (0.56 mmole) lr3in 1 ml of CH2VG2. To the resulting catalyst in an atmosphere of ethylene was added 1.17 g (8.6 mmole) of adamantane and stirred the reaction mixture at 20°C for 3 hours. After hydrolysis of the reaction mixture, extraction with ether, washing the ether layer with water and drying it to the mixture (wt.%): 'adet473% and Number315%, 'adet27%, the highest alkyladamantanes 5%, while the conversion of adamantane 99%.

Example 15. At 20°C is stirred with a magnetic stirrer 0.11 g (0.72 mmole) CCl4and 0.20 g (0.72 mmole) lr3in 0.7 ml of CH2Cl2. To the resulting catalyst in an atmosphere of ethylene was added 0.99 g (7.15 mmole) adamantane and stirred the reaction mixture at 20°C for 1 hour. After hydrolysis of the reaction mixture, ek the traction ether, wash the ether layer with water and drying it to the mixture (wt.%): 'adet448% and Number327%, 'adet217%, Number 8%, the conversion of adamantane 89%.

Example 16. The catalyst obtained from 0.16 g (1.02 mmole) VG2and 1.39 g (1.04 mmole) ll3in 0.5 ml of CH2VG2at 20°C in an atmosphere of propylene with stirring was added 1.42 g (10.42 mmole) adamantane and continue mixing at 20°C for 3 hours. After hydrolysis of the reaction mixture, extraction with ether, washing the ether layer with water and drying it to obtain a mixture of products: (weight%): AdPr475%, AdPr312% and AdPr29%, other products 4%. Adamantane in the reaction mixture is missing.

Example 17. To 0.11 g (0.375 mmole)catalyst VG2·lCl3obtained from 0.375 mmole VG2and 0.375 mmole ll3in a solution of 0.5 ml of CH2Cl2at 20°C in an atmosphere of propylene with stirring was added 0.51 g (3.74 mmole) adamantane and continue mixing at 20°C for 3 hours. After hydrolysis of the reaction mixture, extraction with ether, washing the ether layer with water and drying it is produced volatile products, containing 88% AdPr4(0.31 g, 27 mol.% from AdH) and 18% dr3(0.067 g, 6.8 mol.% from d).

Example 18. To 0.22 g (0.75 mmole) of catalyst VG2·ll3derived from 0.75 mmole VG2and 0.75 mmole ll3in solution 1 ml of CH2Cl2at 20°C, atmosphere propylene under stirring was added 1.02 g (7.48 mmole) adamantane and continue mixing at 20°C for 1 hour. After hydrolysis of the reaction mixture, extraction with ether, washing the ether layer with water and drying it is derived (wt.%): AdH - 0.082 g (conversion of 92%), AdPr 0.28 g, AdPr2G, AdPr3G, AdPr40.22, Total output propylalanine in the calculation of the original adamantane 124 wt.%, the content of AdPr4in a mixture of products of alkyl-17.5%.

Example 19. The catalyst obtained from 0.24 g (1.5 mmole) VG2and 0.20 g (1.5 mmole) ll3in 2 ml of CH2Cl2at 20°C in an atmosphere of propylene with stirring was added 2 g (14.8 mmole) adamantane and continue mixing at 20°C for 2 hours. After hydrolysis of the reaction mixture, extraction with ether, washing the ether layer with water, drying the solution, removal of the solvent and distillation of the residue in vacuum at temperatures up to 190°C at 1-2 mm obtain 1.65 g of the volatile fraction containing (wt.%): 70% AdPr4(1.16 g, 26 mol.% from theory) and 30% AdPr3. The weight of non-volatile residue, representing (Pr3Ad)2C3H6in mixture with a small amount of AdPr4,0.92,

Example 20. To 0.11 g (0.375 mmole) of catalyst VG2·ll3in 0.5 l of CH2Cl2at 20°C in an atmosphere of propylene with stirring was added 0.51 g (3.75 mmole) adamantane and continue mixing at 20°C for 1 hour. After hydrolysis of the reaction mixture, extraction with ether, washing the ether the Loya water and drying receive the mixture, containing (wt.%): AdH 0.042 g (conversion of 92%), AdPr 0.135 g, AdPr20.185 g, AdPr30.188 g, AdPr40.11, Total output propylalanine in the calculation of the original AdH 121 wt.%, the content of AdPr4in a mixture of alkyl products 18% (10 mol.% from theory).

Example 21. To 1.45 g (4.93 mmole) of catalyst VG2·lCl3in 8 ml of CH2Cl2at 20°C in an atmosphere of propylene with stirring add 6.715 g (49.4 mmole) adamantane and continue mixing at 20°C for 2 hours. After hydrolysis of the reaction mixture, extraction with ether, washing the ether layer with water, drying the solution and removal of the solvent is collected in a vacuum at temperatures up to 190°C at 1 mm volatile fraction, which consists of 5.51 g (18.12 mmole) AdPr4, 2.46 g (8.63 mmole) dr3, 0.22 g (1.0 mmole) AdPr2, 0.10 g AdPr (0.56 mmole). The residue (6.81 g) is a volatile ingredients very viscous liquid, which, according to mass spectrometry direct input, is a blend of 40% AdPr4and 60% (AdPr3)2C3H6. After several distillations selected 2.18 g of analytically pure 1,3,5,7-AdPr4with so Kip. 188-190°C at 1 mm and 4.09 g vysokoletuchih balance (AdPr3)2C3H6. The molar ratio of [AdPr4]:[(AdPr3)2]=3.7:1. The data of elemental analysis of the products AdPr4and (AdPr3)2in table 1, and the spectra in the tables is 2. Products no adamantane compounds with unsaturated groups and products are not adamantanol nature.

Example 22. To 0.598 g (1.42 mmole) of catalyst CCL4·lr3obtained from 0.219 g (1.42 mmole) CCl4and 0.379 g (1.42 mmole) lr3in 2 ml of CH2Cl2at 20°C in an atmosphere of propylene with stirring was added 1.93 g (14.12 mmole) adamantane and continue mixing at 20°C for 2 hours. After hydrolysis of the reaction mixture, extraction with ether, washing the ether layer with water and drying it to obtain a mixture of propylalanine containing 72% AdPr4.

Example 23. At 20°C in an atmosphere of ethylene with stirring add 0.739 g (4.5 mmole) of 1,3-dimethyladamantane to the catalyst VG2·ll3obtained from 0.072 g (0.45 mmole) VG2and 0.06 g (0.045 mmole) lCl3in 0.5 ml of CH2Cl2and continue mixing at 20°C for 2 hours. After hydrolysis of the reaction mixture, extraction with ether, washing the ether layer with water and drying it to obtain 0.99 g of 1,3-dimethyl-5,7-diethylaminopentane (yield quantitative).

Example 24. In the atmosphere of ethylene from 1.35 g (8.22 mmole) of 1,3-dimethyladamantane, g (0.82 mmole) CCL4and 0.22 g (0.82 mmole) lr3in 1 ml of CH2Cl2at 20°C after 2 h obtain 1.32 g of 1,3-dimethyl-5,7-diethylamine as the sole product.

Example 25. At 20°C in the atmosphere is tilana under stirring add 3.93 g (23.92 mmole) of 1,3-dimethyladamantane to the catalyst, obtained from 0.38 g (2.4 mmole) VG2and 0.32 g (2.4 mmole) ll34 ml) and continue stirring at 20°C for 2 hours. After hydrolysis of the reaction mixture, extraction with ether, washing the ether layer with water and drying it to obtain 4.78 g of 1,3-dimethyl-5,7-diethylaminopentane (yield 91% of theory). After removal of the solvent and Pradhana collected fraction with BP. 93°C at 2 mm elemental analysis Data for 1,3-dimethyl-5,7-diethylaminopentane are shown in table 3, and mass spectra in table 4.

Example 26. At 20°C in an atmosphere of propylene with stirring add 0.616 g (3.75 mmole) of 1,3-dimethyladamantane to the catalyst obtained from 06 g (0.375 mmole) VG2and 0.05 g (0.375 mmole) ll3in 0.5 ml of CH2Cl2and continue mixing at 20°C for 2 hours. After hydrolysis of the reaction mixture, extraction with ether, washing the ether layer with water and drying obtain 0.88 g of 1,3-dimethyl-5,7-dipropylamine (yield 95% of theory).

Example 27. At 20°C in an atmosphere of propylene with stirring was added 1.64 g (10.0 mmole) of 1,3-dimethyladamantane to the catalyst obtained from 0.015 g (1.0 mmole) CCl4and 0.26 g (1 mmole) lr3in 1.5 ml of CH2Cl2and continue stirring for 2 hours. After hydrolysis of the reaction mixture, extraction with ether, washing the ether layer with water and drying it to obtain 2.23 g of 1,3-dimethyl-5,7-dipr is Piedmontese (yield 90% of theory). After removal of the solvent and Pradhana collected fraction with BP. 115°C at 2 mm elemental analysis Data for 1,3-dimethyl-5,7-diethylaminopentane are shown in table 3, and mass spectra in table 4.

Example 28. At 20°C in an atmosphere of propylene with stirring was added 0.82 g (5.0 mmole) of 1,3-dimethyladamantane to the catalyst obtained from 0.0775 g (0.5 mmole) CCL4and g (0.5 mmole) lr3in 1 ml of CH2VG2and continue stirring for 2 hours. After hydrolysis of the reaction mixture, extraction with ether, washing the ether layer with water and drying it to obtain 0.93 g of 1,3-dimethyl-5,7-dipropylamine (yield 75% of theory).

Example 29. Modification of polyacyladipate by alkylation with propylene

Fraction of alkyladamantanes AdCn(n=1-10, where n is the total number of carbon atoms in alkyl groups), preferably monoalkylamines, BP. 100°C at 1-2 mm was synthesized from adamantane and n-octane in the presence of CH3l·ll3according to the method described in the patent (Isegrim, Lavanish, Switch, Imerisia, Aeeseap, Ugulava. RF patent №22770808). A mixture of alkyladamantanes contained AdC1-C315%, d4-C649% and AdC7-C1035%. Mass spectral determined the percentage of the ion current of ions with m/z 135, and the current of ions with m/z 177 to the total ion current (table ). At 20°C in an atmosphere of propylene with stirring was added 1.5 g of this mixture of alkyladamantanes to the catalyst obtained from 0.348 g (2.28 mmole) CCl4and 0.61 g (2.28 mmole) lr3in 1.1 ml of CH2Cl2and continue stirring for 2 hours. After hydrolysis of the reaction mixture, extraction with ether, washing the ether layer with water and drying it to obtain 0.36 g (24 wt.% from the initial mixture AdAlk) the volatile fraction of polyacyladipate AdCn(n=1-10), and 1.16 g nonvolatile fraction (77% of the initial mixture AdCn). Volatile fraction according to GZH - MS differs considerably from the original mixture of high content polyallylamine products and high content of alkyladamantanes containing various groups. As follows from table 5, formed in the volatile fraction of the intensity of the total ion current of ions m/z 135, characteristic of monoalkylamines, reduced in comparison with the corresponding value in the original mixture from 33% to 17%, at the same time, the intensity of the total ion current of ions m/z 177, characteristic for propylalanine, increased from 2.3% to 7.4%.

The study by the method of mass spectrometry direct input of volatile ingredients faction, formed after the reaction AdCn(m=1-10) with propylene, showed that it consists of alkyladamantanes two types of AdCn(m to 24) and Ad2Cn(up to 32 m, where m is the total number is about carbon atoms in the molecule).

Example 30. Modification of polyacyladipate by alkylation with propylene

At 20°C in an atmosphere of propylene with stirring, add 2 g of a mixture of polyacyladipate AdCn(n=1-10) to the catalyst obtained from 0.48 g (3.0 mmole) VG2and 0.4 g (3.0 mmole) ll3in 2 ml of CH2Cl2and continue stirring for 2 hours. After hydrolysis of the reaction mixture, extraction with ether, washing the ether layer with water and drying it to obtain 0.60 g of the volatile fraction of polyacyladipate AdCn(n=1-10), 30 wt.% from the initial volatile fraction of polyacyladipate AdCn(n=1-10). It is shown that the intensity of the ion current m/z 135 reduced to 18%and the ion current of ions m/z 177 increased to 9% compared with the corresponding values in the original mixture (table 5).

Example 31. Modification of polyacyladipate by alkylation with ethylene

At 20-25°C in an atmosphere of ethylene for 2 hours, stirred for 1.75 g of a mixture of polyacyladipate AdCn(n=1-10) with a catalyst derived from 0.39 g (2.58 mmole) CCl4and 0.69 g (2.59 mmole) lr3in 1.1 ml of CH2Cl2. After hydrolysis of the reaction mixture, extraction with ether, washing the ether layer with water and drying obtain 1.99 g of the volatile fraction (113 wt.% from the initial mixture AdAlk). Analysis of the mixture by GLC-MS showed that it consists mainly of solvent floor is alkyladamantanes (table 6).

Example 32. Modification of polyacyladipate by alkylation with ethylene

At 20-25°C in an atmosphere of ethylene for 2 hours, stirred for 1.5 g of a mixture of AdCn(n=1-10) with a catalyst derived from 0.36 g (2.28 mmole) VG2and 0.30 g (2.28 mmole) ll3in 1.5 ml of CH2Cl2. After hydrolysis of the reaction mixture, extraction with ether, washing the ether layer with water and drying obtain 1.80 g (120 wt.% from the original mixture) polyacyladipate AdCn(n=1-10), qualitatively similar to the mixture of polyacyladipate obtained in experiment 31 (table 5).

Table 1
The data of elemental analysis of new products: 1,3,5,7-Pr4Ad and
(WG3Ad)2With3H6
ConnectionBrutto-formulaMol. weight%%H
FoundCalculatedFoundCalculated
Pr4AdWith22H40304.54At 86.4886.76 13.1113.24
(WG3Ad)2With3H6C41H72564.9887.0087.1513.0012.85

Table 2
The NMR and mass spectra of new products: 1,3,5,7-Pr4Ad and (WG3Ad)2With3H6
ConnectionRangeSpectral characteristics and classification
13C-NMR, δ:
MS, m/z (IRel):
15.20 (13,16,19,22CH3); 16.00 (15,12,18,21CH2); 34.38 (1,3,5,7C); 47.11 (11,14,17,20CH2); 49.37 (2,4,6,8,9,10CH2)
304 (M+, 0,5), 261 (M-Pr, 100), 219 (5), 218 (2), 178 (6), 177 (37), 151 (4), 149 (5), 137 (2), 136 (2), 135 (13), 123 (6), 121 (8), 109 (4), 107 (5), 95 (4), 93 (12), 79 (12), 55 (23)
13C-NMR:15.08(26,29,32,35,38CH3); 15.89(25,28,31,34,37,40CH2); 31.53 (12CH2); 34.21 (3,5,7,16,18,21C); 35.85 (1,14C); 45,33 (11,13CH2 ); 46,63 (24,27,30,33,36CH2); 46,84 (2,6,8,15,20CH2); 47,00 (4,9,10,17,222,23CH2),
MS (15eV):564 (M+, 0,1), 563 (M-H, 0,6), 522 (M-42, 5), 521 (M-43, 11), 479 (M-42-43), 303 (Pr3AdC3H6+,2), 289 (Pr3AdC2H4+, 1), 275 (Pr3AdCH2+, 4), 261 (Pr3Ad+, 100), 259 (5), 247 (5), 233 (16), 219 (37), 205 (10), 191 (9), 177 (11), 163 (7), 151 (7), 149 (6), 135 (7), 109 (4), 107 (5)

Table 3
Elemental analysis data of 1.3.5,7-tetraethylsilane-
on, 1,3-dimethyl-5,7-diethylaminopentane and 1,3-dimethyl-5,7-di-n-propylalanine
ConnectionBrutto-formulaMol. weight%%H
FoundCalculatedFoundCalculated
Et4AdC18H32248.4487.2387.0212.8012.98
Me2'adet 2C16H28220.3886.9787.1913.0312.81
Me2AdPr2C18H32248.4486.8887.0213.1512.98

Table 4
The NMR and mass spectra of 1.3.5,7-Tetraethylenepentamine, 1,3-dimethyl-5,7-
diethylaminopentane and 1,3-dimethyl-5,7-di-n-propylalanine
ConnectionRangeSpectral characteristics and classification
1H-NMR, δ:0,79 (t., 12H,12,14,16,18CH3); 0,93 (q., 8H,11,13,15,17CH2); 1,15 (quintet, 12H,2,4,6,8,9,10CH2),
13C-NMR, δ:7,26(12,14,16,18CH3); 34,17(11,13,15,17CH2); 36,12(1,3,5,7S): 45,98(2,4,6,8,9,10CH2)
MS, m/z (IRel):248 (M+/sup> , 0,9), 219 (M-Et, 100), 163 (10), 150(10), 135(10), 133 (20), 123 (4), 121 (8) 119 (3), 107 (7), 105 (3), 95 (3), 91 (5), 81 (4), 79 (9), 55 (13)
MS, m/z (IRel):220 (M+, 5), 205 (M-IU, 13), 191 (M-Et, 100), 163 (3), 149 (12), 136 (11), 135 (48), 123 (7), 122 (8), 121 (47), 109 (4), 107 (5), 95 (4), 93 (12), 91 (10), 55 (23)
MS, m/z (IRel):248 (M+, 0,8), 233 (M-IU, 3), 205 (M-Pr, 100), 163 (3), 150 (3), 149 (24), 135 (7), 123 (3), 121 (20), 109 (4), 108 (2), 107 (24), 105 (6), 95 (6), 93 (9), 91 (8), 55 (15)

Table 5
Modification of a mixture of alkyladamantanes propylene. The initial mixture of alkyladamantanes (dn(n=1-10))
The total ion current (original mix)298209708
The total ion current of the ion m/z 13598419501
The total ion current of the ion m/z 1776820223
A mixture of alkyladamantanes after the reaction with propylene (experience 29)
The total ion current (original mix)60136435
The total ion current of the ion is m/z 135 10228902
The total ion current of the ion m/z 1774436428
A mixture of alkyladamantanes after the reaction with propylene (experience 30)
The total ion current (original mix)70168499
The total ion current of the ion m/z 13512630330
The total ion current of the ion m/z 1776315165
The content of ions m/z 135 (ion current):
33% (original mix)
17% (example 28)
18% (example 29)
The content of ions m/z 177 (ion current):
2.99% (original mix)
7.38% (example 29)
9.0% (example 30)

/tr>
Table 6
Modification of a mixture of alkyladamantanes (AdCn(n=1-10), ethylene (PR which measures 31, 32)
The initial mixture of alkyladamantanes (AdCn(n=1-10))
The total ion current (original mix)298209708
The total ion current of the ion m/z 13598419501
The total ion current of the ion m/z 16479250607
A mixture of alkyladamantanes after reaction with ethylene (example 31)
The total ion current (original mix)5964194
The total ion current of the ion m/z 1351192839
The total ion current of the ion m/z 16426838873
A mixture of alkyladamantanes after reaction with ethylene (example 32)
The total ion current (original mix)8946291
The total ion current of the ion m/z 1351968184
The total ion current of the ion m/z 1644473145
The content of ions m/z 135 (ion current):
33% (original mix)
20% (example 31)
22% (experiment 32)
The content of ions m/z 164 (ion current):
26.6% (original mix)
45% (example 31)
50% (example 32)

Transcript by GLC-MS 76% of mixture components (AdCn(n=1-10)), obtained after modifying the initial mixture (AdCn(n=1-10)), ethylene in the presence of a catalyst CCL4·2lr3shows that the resulting products are atinadamente. Below is a scan of the component (t), its content in the mixture, it Brutto-formula and the mass spectrum of the component in the mixture formed of polyacyladipate AdCn(n=1-10) (example 31).

(1) t=11.26, 1.67%, 'adet2Me: 206, M+(3); 191, M+- CH3(8); 177, M+- C2H5(100); 135, Ad+(20);

(2) t=13.32, at 11.93%, 'adet3: 22, M+(2); 191, M+- C2H5(100); 163, M+C2H5-C2H4(0.6); 149, Ad+CH3, 135, Ad+(20);

(3) t=13.41, 1.72%, 'adet2Pr: 219, M+- CH3(4); 205, M+- C2H5(69); 191, M+- C3H7(100); 149, Ad+CH3(10), 135, Ad+(20);

(4) t - 15.20, 16.01%, 'adet3Me: 234, M+(1); 205, M+- C2H5(100); 177, M+- C2H5-C2H4(0.7); 149, Ad+CH3(16), 135, Ad+(21);

(5) t=16.43, 2.62%, 'adet2Pr2: 219, M+- C2H5(100); 205, M+- C3H7(82); 163, M-C3H7-C3H6(11); 149, Ad+CH3(18), 135, Ad+(28);

(6) t=16.94, 31.23%, 'adet2Pr2: 219, M+- C2H5(100); 205, M+- C3H7(82); 163, M+- C3H7-C3H6(11); 149, Ad+CH3(18), 135, Ad+(28);

(7) t=18.06, 6.77%, 'adet3Pr: 262, M+(1); 234, M+- C2H4(18); 233, M+- C2H5(100); 220, M+- C3H6(11); 219, M+- C3H7(51); 191, M+- C3H7-C2H4(3); 177, M+- C2H5-2C2H4(7); 163, M+- C3H7-C3H6(11); 149, Ad+CH3(18), 135, Ad+(28);

(8) t=19.35, 4.25%, 'adet3Bu: 276, M+(0.5); 247, M+- C2H5(100); 219, M+- C4H9(68); 191, M+- C 4H9-C2H4(11); 163, M+- C4H9-2C2H4(8); 149, Ad+CH3(20), 135, Ad+(3).

As follows from the experiments, the aluminum chloride in the absence of bromine significantly less active than the catalyst VG2·ll3(examples 9, 10), conducting the reaction in hexane instead of methylene chloride leads to complete inhibition of alkylation (example 11), the reaction goes well in the chloride and bromide, methylene (examples 1 and 17). The increase in temperature from 15 to 25°C does not affect the result. Conversely, lowering the temperature to 0°C leads to a decrease in the selectivity of education tetraalkylammonium product (examples 2 and 3). The increase in reaction time over 3 hours does not improve the selectivity of the formation of the target product and therefore impractical (op. 4 and 7). The increase in the ratio [AdH]:[VG2·ll3]= from 15 to 20 reduces the selectivity of the formation of tetraalkylammonium from 74% to 49% (examples 5 and 6). The increase in the number of solvent practically does not increase the output, and therefore, it is impractical (examples 1 and 7).

The present invention has the following advantages over known methods of making alkyladamantanes of adamantane and olefins:

1) you can not synthesize previously described individual tetraalkylammonium, not containing t is lichnye carbon atoms in adamantinoma core, from adamantane and propylene. Based on known data, new tetraalkylammonium promising as components of industrial fluids wide destination and source connections to obtain heat-resistant polymers, dendrimers and biologically active compounds;

2) allows to synthesize tetraalkylammonium, not containing tertiary carbon atoms in adamantinoma the core of adamantane or 1,3-dimethyladamantane and olefins (ethylene and propylene) according to the method that has advantages over previously described: the conversion of adamantane close to quantitative vs. 40% and below in the previously described methods, the selectivity of the formation of the target product is 75-100% against 23% in the previously described method of obtaining 1,3,5,7-tetratetracontane, the reaction was performed at room temperature instead of 300°C (in case of receipt of 1,3,5,7-tetramethylguanidine) or -10 or -30°C (in the case of obtaining 1,3-dimethyl-5,7-diethyl(or dipropyl)adamantane, the reaction time is 2-3 hours instead of 90-120 hour (in case of receipt of 1,3,5,7-tetramethylguanidine);

3) the proposed method allows you to modify the mixture of polyacyladipate (m=11-20, where m is the total number of carbon atoms in the molecule), mainly monoalkylamines, under the action of ethylene or propylene, enriching it more valuable polyalkylbenzene products and higher homologues;

4) JV the property based on the use of available industrial catalysts;

5) the reaction of obtaining tetraalkylammonium and modification of alkyladamantanes under the action of olefins occur in catalytic mode;

6) the products are not connected not adamantanol nature and adamantanes with unsaturated groups in contrast to the known reactions of adamantanes with olefins in the presence of acid systems;

7) the reaction is conducted at atmospheric pressure of the olefin in the absence of proton acids.

1. 1,3,5,7-tetraalkylammonium General formula

2. The method of obtaining 1,3,5,7-tetraalkylammonium General formula
,
where R1-R2=R3=R4=Et;
R1=R2=R3=R4=n-Pr;
R1=R2=Me, R3=R4=Et;
R1=R2=Me, R3=R4= n-Pr;

as well as mixtures of polyacyladipate in the presence of electrophilic catalysts, characterized in that the adamantane, 1,3-dimethyladamantane or a mixture of polyacyladipate with the total number of carbon atoms 11-20 alkylate With olefinsnH2nwhere n=2 or 3, in the presence of a catalytic system gross formula l3·tolrwhere X=Cl, Hal=Br, k=0, r=2, or X=Br, Hal=Cl, k=l, r=4, and the process is carried out in a solution of CH2X2(X=Cl, Br) at 15-25°C for 2-3 h at a molar ratio [adamantane]:[catalyst]=(15-10):1.



 

Same patents:

FIELD: production of monomers used for production of high-molecular compounds, alkylation of benzene by lower olefins in alkylator.

SUBSTANCE: proposed method is carried out in three stages: at the first stage, liquid hydrocabons, viz.: dehydrated benzene, polyalkylbenzenes and return benzene are mixed; at the second stage, ethylene and other olefins are introduced in liquid hydrocarbon mixture and at the third stage, aluminum chloride-based catalytic complex is introduced; at all three stages, flow moves in alkylator in turbulent mode; alkylator is provided with turbulization aids. Alkylator includes vertical cylindrical hollow housing with component inlet branch pipes fitted from below; components are delivered also through comb; branch pipes for discharge of reaction mass and gaseous products are mounted in the upper position. Housing is made from contraction tube, diffuser and cylindrical members interconnected coaxially. Initial component inlet branch pipes are located along housing axis; olefin and catalytic complex inlet branch pipes are located at distance from liquid hydrocarbon inlet branch pipes no less than two turbulization sections.

EFFECT: increased yield of alkyl benzene due to continuous process in small-sized equipment.

3 cl, 1 dwg, 3 ex

FIELD: industrial organic synthesis.

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EFFECT: increased degree of benzene conversion.

2 ex

FIELD: catalyst preparation methods.

SUBSTANCE: immobilized ionic liquid is prepared by anion-assisted immobilization of ionic liquid, for which purpose a carrier is treated with anion source, for instance with inorganic halide to produce ionic liquid or applying it onto carrier. Alternatively, ionic liquid may be immobilized because of cation covalently linked to carrier, e.g. through silyl groups, or incorporated into carrier via synthesis of carrier in presence of acceptable base. Immobilized ionic liquid are meant for use as catalysts, e.g. in Friedel-Krafts reaction.

EFFECT: optimized preparation procedures.

18 cl, 10 ex

FIELD: petrochemical processes.

SUBSTANCE: process comprises continuous-mode alkylation of benzene (20-25%) with α-olefins, in particular C8-C14 fraction (70-80%), in presence of catalyst complex (1.5-2%) at elevated temperature. Alkylate is neutralized and washed to remove catalyst complex, after which rectified to isolate desired product. Before alkylation, benzene and α-olefins are combined and azeotropically dried. Rectification is carried out at least in two steps and bottom temperature in any step is the same as boiling temperature of α-olefins and pressure in each subsequent step is below pressure of preceding step. Plant for alkylation of benzene with α-olefins is also disclosed.

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The invention relates to the field of petrochemicals, in particular the production of monoalkylbenzenes interaction of benzene with olefins in the presence of aluminum chloride recycle of polyalkylbenzenes

The invention relates to a technology for production of alkyl benzenes in the presence of a catalyst in the form of an ORGANOMETALLIC complex of aluminium chloride and can be used in the washing of the catalyst, the decomposition of chlorinated organic compounds and neutralizing alkylates

FIELD: chemistry.

SUBSTANCE: invention relates to pyrrole derivatives of formula (I): , where R1 denotes hydrogen; R2 denotes adamantine which is unsubstituted or substituted with a hydroxy group or halogen; R3 denotes trifluoromethyl, pyrazole, triazole, piperidine, pyrrolidine, hydroxymethylpiperidine, benzylpiperazine, hydroxypyrrolidine, tert-butylpyrrolidine, hydroxyethylpiperazine, hydroxypiperidine or thiomorpholyl group; R4 denotes cyclopropyl, tert-butyl, -CH(CH3)2CH2OH, methyl, -CF3 or -(CH2)nCF3 group, where n equals 1 or 2; R5 denotes hydrogen or lower alkyl which is unsubstituted or substituted with a halogen, as well as pharmaceutically acceptable salts thereof.

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17 cl, 99 ex, 1 tbl

FIELD: chemistry.

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7 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.

EFFECT: improved method of synthesis.

7 ex

FIELD: organic chemistry, chemical technology.

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.

EFFECT: improved methods of synthesis.

6 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.

EFFECT: expanded synthetic possibilities.

6 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to chemistry of adamantine derivatives, namely to a method for synthesis of 1-dialkylamino-4-oxoadamantanes of the general formula: wherein R means Method involves substitution of bromine atom in 1-bromo-4-oxoadamantane for dialkylamino-group in interaction with dialkylamine chosen from the following order: piperidine, morpholine or piperazine in the mole ratio of reagents = 1:((3-4), at temperature 190-220°C for 7-8 h. Invention provides synthesis of semifinished products used in synthesis of biologically active substances.

EFFECT: improved method of synthesis.

3 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to chemistry of adamantanes, namely to a method for synthesis of 1-aryl-4-oxoadamantanes of the general formula: wherein R means -CH3, -OH, -N(CH3)2, -OCH3. Method involves interaction of 1-bromo-4-oxoadamantane with benzene derivative chosen from the following order: toluene, phenol, dimethylaniline or anisole in the mole ratio of reagents = 1:(506), at temperature 100-180°C in the presence Lewis acids AlCl3, FeBr3, ZnCl2 for 5-8 h. Method provides synthesis of novel compounds that are semifinished substances in synthesis of biologically active compounds.

EFFECT: improved method of synthesis.

4 ex

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

The invention relates to the field of organic chemistry, in particular to a method for monochloramine derivatives of adamantane and diamantane, which are used in the production of thermo - and hemostatic polymers that serve as the raw material for the synthesis of medicines and are used in the synthesis of other derivatives adamantanone (amines, alcohols, acids)

The invention relates to a method for producing 1,3-dichloromethane, which is used in the production of thermo - and hemostatic polymers, insecticides and medicines

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

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to chemistry of adamantanes, namely to a method for synthesis of 1-aryl-4-oxoadamantanes of the general formula: wherein R means -CH3, -OH, -N(CH3)2, -OCH3. Method involves interaction of 1-bromo-4-oxoadamantane with benzene derivative chosen from the following order: toluene, phenol, dimethylaniline or anisole in the mole ratio of reagents = 1:(506), at temperature 100-180°C in the presence Lewis acids AlCl3, FeBr3, ZnCl2 for 5-8 h. Method provides synthesis of novel compounds that are semifinished substances in synthesis of biologically active compounds.

EFFECT: improved method of synthesis.

4 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to chemistry of adamantine derivatives, namely to a method for synthesis of 1-dialkylamino-4-oxoadamantanes of the general formula: wherein R means Method involves substitution of bromine atom in 1-bromo-4-oxoadamantane for dialkylamino-group in interaction with dialkylamine chosen from the following order: piperidine, morpholine or piperazine in the mole ratio of reagents = 1:((3-4), at temperature 190-220°C for 7-8 h. Invention provides synthesis of semifinished products used in synthesis of biologically active substances.

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.

EFFECT: expanded synthetic possibilities.

6 ex

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