Method of obtaining alkyl ethers of 1- and 2-naphthalenecarboxylic acids

FIELD: chemistry.

SUBSTANCE: invention relates to the field of organic chemistry, in particular to a method of obtaining alkylethers of 1- and 2-naphthalenecarboxylic acids, which are used in the synthesis of herbicides, plant growth hormones, dyes, photomaterials and polymers. The method of obtaining compounds of formula (1a-b) or (2a-b) in which R=CH3, C2H5, n-C3H7, consists in the fact that naphthalene is subjected to interaction with CCl4 and alcohol (methanol, ethanol, n-propanol) in the presence of metallic iron, activated HCl, and acetylacetone with the molar ratio of [Fe0(met.)]:[acetylacetone]:[naphthalene]:[CCl4]:[alcohol]=5-50:5:100:100-1000:100-1000, at a temperature of 130°C for 4-12 h in the argon atmosphere.

EFFECT: total output of alkyl ethers of 1- and 2-naphthalenecarboxylic acids reaches 75%.

1 tbl, 21 ex

 

The present invention relates to the field of organic synthesis, in particular to a method for alilovic esters of 1 - and 2-naphthaleneboronic acids.

Naphthaleneboronic acid are widely used in organic synthesis. They are used in the synthesis of herbicides, growth hormones of plants, dyes, photographic materials and polymers [1. Sikkenga D. L., Kullmann D. E., Behrens P. K., Zeitlin M. A., Hoover S. C. U.S. Pat. 2128641, (1999). The Russian Federation]. Derivatives naphthaleneboronic acids are used in medicine and cosmetology [2. Odra R. Pat. 2385708, (2010). The Russian Federation].

In the literature there are various methods of obtaining naphthaleneboronic acids.

So, 1-naphthaleneboronic acid (1) synthesize prolonged heating cinemediapromo acid (C6H5SSSS(COOH)NHCOC6H5with 24% hydrochloric acid in a sealed tube at 120°C [3. Erlenmeyer jr. That Is, Matter O. // Ann. 1904. No. 337. P. 271]. In [4. Price S., Chapin E. C. // J. Am. Chem. Soc. 1941. No. 63. P. 1857; 5. 1942. No. 64. P. 2227] present an unusual method to obtain 1-naphthaleneboronic acid (1), based on the condensation of benzene, furan-2-carboxylic acid in the presence of AlCl3first, when cooled, and then heated to 60°C (12-18 h). Output (1) is 10-13%.

The most common are methods of obtaining naphthaleneboronic acids from the corresponding halogen derivatives of Naftali is A.

2-Naphthaleneboronic acid (2) was synthesized by cyanidation 2-bromonaphthalene (3) with KCN in the presence of a catalyst CuCN, Cu° in aqueous ethylene glycol for 31 h (yield 14%) [6. Loevenich J., A. Loeser // Ber. 1927. No. 60. P. 320] or into a Grignard reagent and processing ethereal solution of the latter with carbon dioxide at -20°C (yield 42%) [7. J. Salkind // Ber. 1934. No. 67. R. 1031].

Recently a new method of synthesis of 1-St 2-naphthaleneboronic acids (1, 2) interaction 1-iodine-(4) and 2-bromonaphthalene (3) malononitrile in the presence of a copper-containing catalyst [8. Yang D., Yang N., Fu H. // Chem. Commun. 2011. Vol.47. No. 8. P. 2348-2350]. Output 1-naphthaleneboronic acid (1) this method is -50%, 2-naphthalenethiol (2) - 44%.

Disadvantages:

1. The use of highly toxic malononitrile;

2. A significant duration of reaction 36-48 h;

3. The need to work under pressure. The carboxylation of 1-bromonaphthalene (5) using carbon dioxide in the presence of palladium catalyst and diethylzinc (C2H5)2Zn leads to the formation of 1-naphthaleneboronic acid (1) with a yield of 72% [9. Romo M, Francisco R // ER 2311788 (2011); 10. Correa, A., Martin R. // J. Am. Chem. Soc. 2009. Vol.131. No. 44. P. 15974-15975].

Disadvantages:

1. The use of expensive palladium catalysis is ora;

2. The use of equipment operating under pressure;

3. The fire hazards of the process due to the use of 2-fold excess snowspeeders on the air diethylzinc.

1-Natalymartynova acid (1) obtained by carboxylation of 1-iodonaphthalene (4) with lithium formate under the action of a palladium catalyst in the medium of acetic anhydride. Output 1-naphthaleneboronic acid (1) when using homogeneous and supported catalysts are approximately equal and are 82-89% [11. Cacchi, S., Cotet, S. L., G. Fabrizi, G. Forte, Goggiamani A., Martin L., Martinez, S., Molins E., Moreno-Manas, M., F. Petrucci, A. Roig, A. Vallribera // Tetrahedron. 2007. Vol.63. No. 11. P. 2519-2523; 12. Cacchi, S., G. Fabrizi, Coggiamani A. // Org. Lett. 2003. Vol.5. No. 23. P. 4269-4272].

The disadvantages of the methods:

1.Use as solvent of acetic anhydride, a precursor;

2. The use of expensive palladium catalyst;

3. The necessity of using a large number of auxiliary reagents ((CH3)2NC(O)H, HCOOLi, LiCl, Et(Pri)2and others), are not part of the final product.

1-Naphthaleneboronic acid (1) can be obtained by carbonyliron 1-chloronaphthalene (6) for 20 min in water under the action of iodide of Nickel at 180°C [13. Pat. 2424(1952). Japan // S. A. 1954. Vol.48. No. 2105].

The literature describes a number of catalytic methods for the synthesis of 1-St 2-naftalina nowych acids (1,2) carbonyliron halogensubstituted of haftasonu under the action of complexes With, Rh, Pd, Mo and Ni. So, carbonyliron 1-chloronaphthalene (6) under the action of catalyst Co2(CO)8in various conditions was obtained 1-natalymartynova sikota (1). In [14. Boyar B. N., Hard I.e., Lanina S. A. // Journal of applied chemistry. 2005. So 78. Vol.11. C. 1844-1848] exit acid (1) in the presence of propylene epoxide is 92%, while in [15. Francalanci F., E. Bencini, A. Gardano, Vincenti M., Foa M. // J. Were Obtained. Chem. 1986. No. 301. P. 27-30] when using dimethylsulfate and CA(Oh)2does not exceed 20%. Similar reaction of 1-bromonaphthalene (5) with and MeI received a 1-naphthaleneboronic acid (1) with a yield of 44% [16. Miura M, Akase F, Nomura M // J.Org. Chem. 1987. No. 52. P. 2623-2625].

The disadvantages of the methods:

1. The need to use toxic catalyst octacarbonyl cobalt;

1. A significant duration of reaction (20 h);

3. Low selectivity of the process;

4. As the oxidant used flammable propylene epoxide.

In [17. Mizuno T., Alper N. // J. Mol. Catal. A: Chem. 1997. Vol.123. No. 1. P. 21-24] for the carbonylation of 1-iodonaphthalene (4) to obtain 1-naphthaleneboronic acid (1) proposed to use a complex of rhodium with triphenylphosphine.

Disadvantages of the method:

1. The process is carried out under a pressure of 41 bar;

2. The use of expensive and hard-to-reach registeruser katal the congestion;

3. High temperature 210°C, a significant duration of reaction (16 h).

1-Naphthaleneboronic acid (1) obtained by carboxylation of 1-iodonaphthalene (4) under the action of catalyst - cyanide Nickel for 16 hours Exit acid (1) is 60% [18. Amer I., Alper N. // J. Org. Chem. 1988. No.. 53. P. 5147-5148].

Disadvantages of the method:

1. A significant duration of reaction 16 h;

2. The use as catalyst of toxic cyanide Nickel;

3. The necessity of using an excess of NaOH, which complicates the selection of the final product.

1-Naphthaleneboronic acid (1) with a yield of 67% can be obtained from 1-bromonaphthalene (5) in the presence of catalysts based on molybdenum and palladium [19. Wu X., M. Larhed // Org. Lett. 2005. Vol.7. No. 15. P. 3327-3329].

The series of works dedicated to carbonyliron halogensubstituted naftalina with carbon monoxide under the action of palladium complexes. In [20. Pri-Bar, I., O. Buchman // J. Org. Chem. 1988. Vol.53. No. 3. P. 624-626] implemented carbonylation of 1-(5) and 2-bromonaphthalene (3) with the formation of 1-(1) and 2-naphthaleneboronic acid (2) with the release of ~80% in the presence of PdCl2-PPh3.

Reaction of 1-iodonaphthalene (4) and 1-bromonaphthalene (5) with carbon monoxide in the presence of palladium catalysts results 1-naphthaleneboronic acid (1) with the Odom 80% [21. Grushin, V. V., Alper N. // Organometallics. 1993. Vol.12. No. 10. P. 3846-3850], 35% [22. Klobayashi So, Sakakura T., Tanaka M. // Tetrahedron Lett. 1987. Vol.28. No. 24. P. 2721-2722] and 55% [23. Calo V., Giannoccaro P., A. Nacci, A. Monopoli // J. Organometal.Chem. 2002. Vol.645. No. 1-2. P. 152-157].

The disadvantages of the methods:

1. The use of expensive palladium catalysts;

2. The need to work under pressure;

3. A significant duration of reaction (115 h);

4. The reference compound is inaccessible 1-iodonaphthalene

(4);

5. Low selectivity of the process.

In the literature there is a series of works to obtain 1-naphthaleneboronic acid (1) through the Grignard reagent. So, in [24. Fieser L. F., Holmes N. L., Newman, M. S. //J. Am. Chem. Soc. 1936. No. 58. P. 1055] described the synthesis of 1-naphthaleneboronic acid (1) with the release of 90% of 1-bromonaphthalene (5) via Grignard reagent, followed by carboxylation, or processing 1-bromonaphthalene (5) butyllithium in debutalbum ether at room temperature, followed by addition of solid CO2(exit to 91%) [25. Gilman N., Moore F. W. //J. Am. Chem. Soc. 1940. No. 62. P. 1843; 26. Gilman H., Swiss J. //J. Am. Chem. Soc. 1940. No. 62. P. 1847].

1-Naphthaleneboronic acid (1) is synthetized from naphthylacetamide (5A) (previously obtained from magnesium and 1-bromonaphthalene (5)) and barium carbonate, which generates CO2in the medium of anhydrous tetrahydrofuran [27. Andres N. // J. Label Compd. Radiopharm.1989. Vol.27. No. 11. P. 1307-1315].

When receiving 1-naphthaleneboronic acid (1) from 1-naphthylacetamide (5A) and carbon dioxide output (1) was higher and amounted to 68% [28. Gilman N., John N. St Century., Schulse F. // Org. Syn. 1931. Vol.2. No. 11. P. 80; 1943. Vol.2. No. 2. P. 425].

Similarly, but with a lower output is the reaction involving 1-chloronaphthalene (6) under the action of magnesium and CO2[29. Brown, C. Sikkel J., Carvalho C, Sargent, M. V. // J. Chem. Soc, Perkin Trans. 1982. No. 1. P. 3007-3010].

The disadvantages of the methods:

1. The need to use at the stage of synthesis of Grignard reagents anhydrous ether solvents (THF, diethyl ether);

2. The use of equipment operating under pressure;

3. A multi-stage process;

4. The use of sulfuric acid;

5. The use of toxic barium carbonate;

6. The source reagents are 1-chloro (6) or 1-bromonaphthalene (5) and metallic magnesium;

7. Low output 1-naphthaleneboronic acid (34%).

In some works naphthaleneboronic acid obtained by the oxidation of alkylnaphthalenes.

So, 1-methylnaphthalene (9) oxidizes 1-naphthaleneboronic acid (1) diluted nitric acid for 4-5 days. Harder oxidized 2-methylnaphthalene (10), which pravr is transformed into a 2-naphthaleneboronic acid (2) by boiling with concentrated nitric acid. 2-Naphthaleneboronic acid (2) can be obtained by treatment of 2-(1-butenyl)-naphthalene (11) by permanganate barium in acetone at room temperature and subsequent treatment with bichromate of sodium in boiling acetic acid [30. Chemistry and technology of naphthalene compounds of series / edited by A. I. Korolev. - M.: the Chemical literature, 1963, S. 478-481].

1-Natalymartynova acid (1) with a yield of 71% is formed by the oxidation of 1-methylnaphthalene (9) bromide / bromate in the water. [31. Patil R. D., S. Bhadra, S. Adimurthy, Ranu B C // Synth. Commun. 2010. Vol.40. No. 19. P. 2922-2929.]:

Disadvantages of the method:

1. The formation of large amounts of waste due to the use of an excess of sulfuric acid (1-methylnaphthalene (9) : H2SO4=1:1.5) and inorganic reagents NaBr-NaBrO3.

In [32. Ranu Century, Brandra S., Adak L. // Tetrahedron Lett. 2008. Vol.49. No. 16. P. 2588-2591] 1-naphthaleneboronic acid (1) was obtained by oxidation of 1-ethylnaphthalene (10) tert-butyl hydroperoxide under the influence of indium catalyst.

Disadvantages of the method:

1. The use of inflammable, toxic tertbutyl-hydroperoxide;

2. The need to use scarce reagents: 1-ethylnaphthalene (10) and chloride India.

When the photo-oxidation of 1-methylnaphthalene (9) and 1-(11) and 2-hydroxymethylcytosine (12) with oxygen in the presence of CBr4and PPh3obrazuyutsa-(1) and 2-naphthaleneboronic acid (2) with the yield up to 88% [33. Sugai T., Itoh A. // Tetrahedron Lett. 2007., Vol.48. No. 52. P. 9096-9099].

The analogous reaction in the environment of H2O-HBr and MeCN results in 1-(1) and 2-naphthaleneboronic acid (2) with higher outputs 81 and 94%, respectively [34. Hirashima, S. - i., Hashimoto, S., Masaki Y, Itoh A. // Tetrahedron. 2006. Vol.62. No. 33. P. 7887-7891].

The disadvantages of the methods:

1. The use of Hydrobromic acid;

2. The source connections are difficult and expensive reagents.

1-(1) and 2-Naphthaleneboronic acid (2) can be obtained from 1-(13) and 2-nitronaphthalene (14), respectively, under the action of the strain Rhodococcus sp AJ270. Output 1-naphthaleneboronic acid (1) is 80%, 2-naphthalenethiol (2) - 69% [35. Meth-Cohn, O., Wang, M.-X. III. Chem. Soc. Perkin Trans. 1997. No. l. p.1099-1104].

In [36. Kay F. W., Morton A. // J. Chem. Soc. 1914. No. 105. P. 1565; 37. Kamm O., Mc Clugage H. B. // J. Am. Chem. Soc. 1916. No. 38. P. 419] 1-naphthaleneboronic acid (1) obtained by oxidation of 1-naphthylethylene (16) or by saponification of 1-naphthonitrile (13).

Frequent literary example of getting naphthaleneboronic acid is the oxidation of the corresponding aldehydes.

So, 1-naphthaldehyde (17) is oxidized to 1-naphthaleneboronic acid (1) with bichromate of sodium in boiling acetic acid or during curing in air [30. IMIA and technology of naphthalene compounds of series / edited by A. I. Korolev. M: Chemical literature, 1963, S. 481,479].

1-(1) and 2-Naphthaleneboronic acid (2) with yields of 70% obtained by the oxidation of 1(17)- and 2-naphthaldehyde (18), respectively [38. Shirini F., Zolfigol, M. A., Torabi S. // Synth. Commun. 2006. Vol.36. No. 19. P. 2833-2840].

1-Naphthaleneboronic acid (1) from 1-naphthaldehyde (17) can also be obtained by the reaction of Cannizaro [39. Yoshizawa, K., Toyota, S., Toda F. // Tetrahedron Lett. 2001. Vol.42. No. 45. P. 7983-7985], oxidation using trisodiumcitrate sodium (Angeli''s salt) Na2N2O3[40. Torun L., Mohammad T., Morrison H. // Tethrahedron Lett. 1999. No. 40. P. 5279-5282] and the oxidation of the excess of hydrogen peroxide in the presence SeO2[41. Brzaszcz M., K. Kloc, Marosah M, Mlochowski J. // Synth. Commun. 2000. Vol.30. No. 24. P. 4425-4434].

The disadvantages of the methods:

1. Use as the source remote connection 1-naftalinimidnymi (17);

2. Use as a catalyst expensive and toxic selenium dioxide;

3. The need for the use of oxidants (Na2N2O3H2O2) and base (KOH).

Of particular interest is the synthesis naphthaleneboronic acids directly from the available naphthalene (19).

For example, naphthalene (19) is heated for several hours with formaldehyde and hydrochloric acid and the resulting 1-chloromethylation (20) onslaut to acid (1) manganese dioxide in 10% H2 4at 90-95°C [42. The Switzerland. Pat. 256515 (1949)].

In [43. Nemoto, K., Yoshida N., Egusa N., Morohashi, N., Hattori T. // J. Org. Chem. 2010. Vol.47. No. 8. P. 7855-7862] describes the carboxylation of naphthalene (19) in the presence of system Ph3SiCl/AlBr3with the formation of a mixture of 1-naphthaleneboronic (1) and 2-naphthaleneboronic acids (2).

Disadvantages:

1. The use of reagents and catalyst in stoichiometric ratio;

2. Work under high pressure carbon dioxide 3 MPa;

3. The use of toxic reagents disulphide and triphenylsilane.

Together 1- (1) and 2- (2) naphthaleneboronic acid were obtained by carboxylation of naphthalene (19) with carbon monoxide in the presence of a catalyst based on palladium in various environments. If the environment is potassium persulfate and triperoxonane acid, the total output naphthaleneboronic acids (1, 2) is 6% [44. Lu W., Yamaoka Y., Taniguchi Y., Kitamura T., Takaki, K., Fujiwara Y. // J. Were Obtained. Chem. 1999. Vol.580. No. 2. P. 290-294], in the environment of t-BuOH/CH3COOH/CH2CHCH2Cl turned out less than 1% [45. Fujiwara Y., Kawata I., Sugimoto H., Taniguchi H. // J. Were Obtained. Chem. 1983. Vol.256. No. 2. P. 35-36], and in the acetic acid medium total output acids (1, 2) is 90% [46. Sakakibara T., Odaira Y. // J. Org. Chem. 1976. Vol.41. No. 11. P. 2049-2052].

The disadvantages of the methods:

1. The use of expensive catalysts is based on the palladium and silver;

2. A significant duration of response to 72 h;

3. The use of a large excess of aggressive reagents: acetic acid, potassium persulfate and triperoxonane acid.

The authors propose a method of obtaining alilovic esters naphthaleneboronic acid that does not have the above drawbacks.

The method consists in the interaction of naphthalene (19) with carbon tetrachloride and alcohols (methanol, ethanol, n-propanol) in the presence of metallic iron (activated HCl) and acetylacetone (ligand), at a temperature of 130°C for 4-12 h at a molar ratio [Fe0]:[acetylacetone]:[naphthalene]:[CCl4]:[alcohol]=5-50:5:100:100-1000:100-1000 obtaining alilovic esters of 1 - and 2-naphthaleneboronic acids. At a temperature of 130°C the total output alilovic esters of 1 - and 2-naphthaleneboronic acid reaches 75%. It should be noted that when the magnification ratio of the catalyst to the naphthalene to [50]:[100] increases the conversion of initial naphthalene to 100%, the yield of esters 1-naphthaleneboronic acid up to 70%, but the reaction is less selective due to the formation of dialkylated esters 1,5 - and 2,6-naphthalenesulphonic acids (3A-b, 4A-b). The synthesis is carried out in an argon atmosphere.

In the absence of catalyst, acetylacetone, CCl4or alcohol (or any component), the reaction fails.

Significant differences of the proposed method from the prototype.

To obtain alilovic esters of 1-(1A-C) and 2-naphthaleneboronic acids (2A-C) of naphthalene (19) use of metallic iron acetylacetone-CCl4-ROH.

The advantages of the proposed method

1. Using available reagents: naphthalene, CCl4and aliphatic alcohols;

2. Low consumption of catalyst;

3. The lack of aggressive oxidizers;

4. Reduce the cost and simplify the technology as a whole by reducing energy and labor costs;

5. High yield of esters 1-naphthaleneboronic acid up to 70%.

The proposed method is illustrated by examples:

EXAMPLE 1. Getting propyl esters of 1 - and 2-naphthaleneboronic acids (1B, 2B).

The reaction was carried out in glass vials of 10 ml, placed in mikroavtobus stainless steel with a volume of 17 ml) with constant stirring and regulated heating.

In a vial in a stream of argon was loaded 2.2 mg (5 mmol) of Fe0(met.) (activated HCl), 0.004 ml (5 mmol) of acetylacetone, 102 mg (100 mmol) of naphthalene, 0.77 ml (1000 mmol) of carbon tetrachloride and 0.6 ml (1000 mmol) of n-propyl alcohol. Sealed ampoule was placed in an autoclave, the autoclave was tightly closed and heated at 130°C for 6 h with constant stirring. After the reaction, the autoclave was cooled to whom atoi temperature, the ampoule was opened, the reaction mass is neutralized and filtered through a paper filter. The solvent is kept off, the residue was distilled under vacuum. The conversion of initial naphthalene (19) was 66%, the output propyl ester 1-naphthaleneboronic acid (1B) - 41%, 2-naphthaleneboronic (26) - 25%.

The compounds proved by NMR, mass spectrometry.

Propyl ester 1-naphthaleneboronic acid (1B)

An NMR spectrum13With (δ, M. D.): 10.44 (CH3), 21.90 (CH2CH3), 66.70 (CH2With2H5), 125.24 (3), 126.51 (6), 126.59 (7), 127.19 (8), 128.51 (5), 130.04 (2), 130.28 (1), 132.50 (9), 133.19 (4), 133.88 (10), 168.95 (soo). An NMR spectrum1H (CDCl3, δ, M. D.): 0.98 t (3H, CH3J 1.8 Hz), 1.6 m (2H, CH2CH2CH3J 3.7 Hz), 4.1 t (2H, CH2CH2CH3J 1.5 Hz), 8.6 (1H, With2N J 0,4 Hz), 7.6 l, d (1H, WITH3N J 7 Hz, 9 Hz), 8.2 (1H, WITH4N J 7 Hz), 7.8 (1H, With5N J 8 Hz), 7.5 m (1H, WITH6N J 8 Hz), 7.5 m (1H, WITH7N J 8 Hz), 7.88 (1H, WITH9N J 8 Hz).

Mass spectrum, m/z (IRel(%)): 214.10 [M]+(70), 172(100), 156(21), 155(96), 128(13), 127(58), 115(4).

Propyl ester 2-naphthaleneboronic acid (2V)

An NMR spectrum13With (δ, M. D.): 10.52 (CH3), 22.17 (CH2CH3), 66.63 (CH2With2H5), 125.24 (6), 125.84 (C3), 127.19 (4), 127.47 (10), 127.74 (7) 128.51 ( 5), 129.31 (1), 131.36 (C8), 132.50 (9), 135.47 (2), 167.59 (soo). An NMR spectrum1H (CDCl3, δ, M. D.): 1.08 t (3H, CH3J 3 Hz), 2.03 m (2H, CH2CH2CH3J of 1.05 Hz), 4.3 tons (2H, CH2CH2CH3J 2 Hz), 7.68 d (H,3N J 8 Hz), 8.2 (H, C4N J 7 Hz), 7.8 (1H, WITH5N J 8 Hz), 7.5 m (1H, WITH6N J 8 Hz), 7.5 m (1H, With7N J 8 Hz), 8.04 (1H, With8N J 8 Hz),8.6(1H,WITH1N).

Mass spectrum, m/z (IRel(%)): 214.10 [M]+(47), 207 (29), 205 (5), 173 (15), 172(95), 163 (10), 155(100).

EXAMPLE 2-5. Getting propyl esters of 1 - and 2-naphthaleneboronic acids (1B, 2B).

Analogously to example 1, except the number of recovered catalyst: [Fe0]:[acetylacetone]:[naphthalene]:[CCL4]:[n-propanol]=10:5:100:1000:1000 (example 2) the conversion of initial naphthalene (19) was 68% yield propyl ester 1-naphthaleneboronic acid (1B) - 48%, 2-naphthaleneboronic (2B) - 20%; when the ratio [Fe0]:[acetylacetone]:[naphthalene]:[CCl4]:[n-propanol]=20:5:100:1000:1000 (example 3) - conversion of naphthalene (19) was 93%, the output propyl ester 1-naphthaleneboronic acid (1B) - 56%, 2-naphthaleneboronic (2B) - 17%, the yield of 1,5-DIPROPYLENE ether 1,5-naphthaleneboronic acid (3b) - 13%, 2,6-DIPROPYLENE ether 2,6-naphthaleneboronic acid (4B) - 7%; the ratio of reactants [Fe0]:[acetylacetone]:[naphthalene]:[CCl4]:[n-propanol]=30: 5:100:1000:1000 (example 4) the conversion was 96%,the output propyl ester 1-naphthaleneboronic acid (1B) - 63%, 2-naphthaleneboronic (2B) - 12%, the yield of 1,5-DIPROPYLENE ether 1,5-naphthaleneboronic acid (3V) - 15%, 2,6-DIPROPYLENE ether 2,6-naphthaleneboronic acid (4B) - 6%; at a molar ratio of reagents [Fe0]:[acetylacetone]:[naphthalene]:[CCl4]: [alcohol]=50:5:100:1000:1000 (example 5) the conversion of initial naphthalene (19) was 100%, the output propyl ester 1-naphthaleneboronic acid (1B) - 70%, the yield of 1,5-DIPROPYLENE ether 1,5-naphthaleneboronic acid (3b) - 22%, 2,6-DIPROPYLENE ether 2,6-naphthaleneboronic acid (4B) - 8%.

DIPROPYLENE ether 1,5-naphthaleneboronic acid (3V)

An NMR spectrum13With (δ, M. D.): 10.56 (CH3), 22.02 (CH2CH3), 67.11 (CH2O), 125.86 (C4), 125.86 (C8), 126.17 (3), 126.17 (7), at 132.15 (2), at 132.15 (6), 133.19 (9), 133.19 (10), 140.24 (1), 140.24 (5), 167.59 (soo). An NMR spectrum1H (CDCl3, δ, M. D.): 0.98 t (3H, CH3J 5.8 Hz), 1.6 m (2H, CH2CH2CH3J 1.7 Hz), 4.1 t (2H, CH2CH2CH3J 4 Hz), 9.1 (2H, WITH2,6N J 9 Hz), 7.6 l, d (1H, WITH3N J Hz, 9 Hz), 8.28 (2H, WITH4,8N J Hz), 7.6 m (1H, WITH7H, J Hz).

Mass spectrum, m/z (IRel(%)): 300.10 [M]+(64), 258 (28), 241 (85), 221 (18), 216 (100), 199 (61), 150 (13), 126 (19), 143 (9).

DIPROPYLENE ether 2,6-naphthaleneboronic acid (4V)

An NMR spectrum13With (δ, M. D.): 10.67 (CH3), 22.16 (CH2CH3), 66.88 (CH2O), 127.67 (the 3), 127.67 (7), 130.47 (4), 130.47 (8), 131.68 (1), 131.68 (5), 134.03 (9), 134.03 (10), 140.24 (2), 140.24 (6), 167.59 (soo). An NMR spectrum1H (CDCl3, δ, M. D.): 1.08 t (3H, CH3J 5.2 Hz), 1.8 m (2H, CH2CH2CH3J 2 Hz), 4.4 tons (2H, CH2CH2CH3J 4 Hz), 8.6 (2H, WITH1,5H), 8.2 (2H, WITH3,7N J 8 Hz), 8.20 (2H, WITH4,8N J 7 Hz).

Mass spectrum, m/z (IRel(%)): 300.10 [M]+(43), 281 (19), 258 (21), 241 (79), 216 (100), 207 (47), 199 (48), 171 (27), 126 (16), 115 (24).

EXAMPLES 6-9. Getting propyl esters of 1 - and 2-naphthaleneboronic acids (1B, 2B).

Analogously to example 1, except for the duration of the reaction: 4 hours (example 6) conversion of initial naphthalene (19) was 23%, the output propyl ester 1-naphthaleneboronic acid (1B) - 11%, 2-naphthaleneboronic acid (2B) - 12%; 8 hours (example 7) - conversion (19) - 60%, the output propyl ester 1-naphthaleneboronic acid (1B) - 35%, 2-naphthaleneboronic acid (2B) - 25%; for 10 hours (example 8) the conversion of naphthalene (19) amounted to 71%, the output propyl ester 1-naphthaleneboronic acid (1B) - 39%, 2-naphthaleneboronic acid (2B) - 32%; 12 hours (example 9) conversion of 44%, the output propyl ester 1-naphthaleneboronic acid (1B) - 23%, 2-naphthaleneboronic acid (2B) - 17%.

EXAMPLES 10-14. Getting propyl esters of 1 - and 2-naphthaleneboronic acids (1B, 2B).

Analogously to example 1, except soo is wearing catalyst and reagents: [Fe 0]:[acetylacetone]:[naphthalene]:[CCl4]:[n-propanol]=5:5:100:100:100 (example 10) - conversion of the initial naphthalene (19) was 30%, the output propyl ester 1-naphthaleneboronic acid (1B) - 30%; when the ratio [Fe0]: [acetylacetone]:[naphthalene]:[CCl4]:[n-propanol]=5:5:100:300:300 (example 11) - conversion was 50%, the output propyl ester 1-naphthaleneboronic acid (1B) - 35%, 2-naphthaleneboronic acid (2B) - 15%; when the ratio [Fe0]: [acetylacetone]: [naphthalene]: [CCl4]:[n-propanol]=5:5:100:1000:500 (example 12) - conversion of naphthalene (19) was 40%, the output propyl ester 1-naphthaleneboronic acid (1B) - 26%, 2-naphthaleneboronic acid (2B) - 13%; when the ratio [Fe0]:[acetylacetone]:[naphthalene]:[CCl4]: [n-propanol]=5:5:100:500:500 (example 13) - conversion of naphthalene (19) was 75%, the output propyl ester 1-naphthaleneboronic acid (1B) - 45%, 2-naphthaleneboronic acid (2B) - 23%, the yield of 1,5-DIPROPYLENE ether 1,5-naphthaleneboronic acid was 7%; the ratio [Fe0]:[acetylacetone]:[naphthalene]:[CCl4]:[n-propanol]=5:5:100:500:1000 (example 14) - conversion of the initial naphthalene (19) was 46%, the output propyl ester 1-naphthaleneboronic acid (1B) - 26%, 2-naphthaleneboronic acid (2B) - 15%), and the yield of 2,6-dipropionyl ether 2,6-naphthaleneboronic acid was 5%.

EXAMPLE 15. Obtaining the ethyl ester of 1 - and 2-naphthaleneboronic the slot (16,26).

The reaction was carried out in glass vials of 10 ml, placed in mikroavtobus stainless steel with a volume of 17 ml) with constant stirring and regulated heating.

In a vial in a stream of argon was loaded 2.2 mg (5 mmol) of Fe0(met.) (activated HCl), of 0.004 ml (5 mmol) of acetylacetone, 102 mg (100 mmol) of naphthalene, of 0.77 ml (1000 mmol) of carbon tetrachloride and 0.47 ml (1000 mmol) of ethyl alcohol. Sealed ampoule was placed in an autoclave, the autoclave was tightly closed and heated at 130°C for 6 h with constant stirring. After the reaction, the autoclave was cooled to room temperature, the ampoule was opened, the reaction mass is neutralized and filtered through a paper filter. The solvent is kept off, the residue was distilled under vacuum. The conversion of initial naphthalene (19) was 30%, the yield of ethyl ether 1-naphthaleneboronic acid (16) - 16%, 2-naphthaleneboronic (26)- 14%.

The compounds proved by NMR, mass spectrometry.

Ethyl ester of 1-naphthaleneboronic acid (16)

TKip165-166°C/10 Torr (Cf. lit. [30]: TKip310°C. an NMR Spectrum13With (δ, M. D.): 14.40 (CH3), 61.04 (CH2O), 125.27(C3), 126.17 (6), 126.60 (7), 127.44 (8), 128.16 (5). 129.33(C1), 130.11 (2), 131.37 (9), 133.23 (4), 133.85 (10), 167.59 (C=O). An NMR spectrum1H (CDC13, δ, M. D.): 1.40 m(3H, CH3J 7.6 Hz), 4.4 kV (2H, CH2CH3J 3.7 Hz), 8.97 (1H, WITH2N J 9 Hz), 7.63 d, d (1H, WITH3N J 7 Hz, 9 Hz), 8.21 (1H, WITH4N J 7 Hz), 8 d (1H, 7.75N J 8 Hz), 7.5 m (1H, WITH6N J 8 Hz), 7.5 m (1H, WITH7N J 8 Hz), 7.87 (1H, WITH8N J 8 Hz).

Mass spectrum, m/z (IRel(%)): 200.10 [M]+(71), 172 (15), 156 (17), 155 (100), 127 (68), 126(13).

Ethyl ester of 2-naphthaleneboronic acid (26)

Tthe Plava31-33°C (Cf. lit. [30]: Tthe Plava32°C. an NMR Spectrum13With (δ, M. D.): 14.40 (CH3), 61.10 (CH3CH2), 124.50 (6), 125.27(C3), 126.60 (10), 127.44 (4), 127.76 (7), 128.16 (5), 128.55 (1), 130.96 (8), 131.37 (9), 133.85 (2), 167.59 (C=O). An NMR spectrum1H (CDCl3, δ, M. D.): 1.37 m (3H, CH3J 7.6 Hz), 4.4 kV (2H, CH2CH3J 3.8 Hz), 7.63 (1H, WITH3N J 7 Hz), 8.2 (1H, With4N J 7 Hz), 7.8 (1H, WITH5N J 8 Hz), 7.5 m (1H, WITH6N J 8 Hz), 7.4 m (1H, With7N J 8 Hz), 7.8 m (1H, WITH8N J 8 Hz), 8.5 (1H, WITH1N)

Mass spectrum, m/z (IRel(%)): 200.10 [M]+(65), 186 (46), 156 (16), 155 (100), 126(14), 44 (24).

EXAMPLES 16-17. Obtaining the ethyl ester of 1 - and 2-naphthaleneboronic acids (16,26).

Analogously to example 15 with the exception of the quantity of withdrawn catalyst: [Fe0]: [acetylacetone]:[naphthalene]:[CCL4]:[ethanol]=10:5:100:1000:1000 (example 16) - conversion of the initial naphthalene (19) was 48%, the yield of ethyl ether 1-naphthaleneboronic acid (16) - 38%, 2-naphthalene is arbonboy (26) - 10%; when the ratio [Fe0]:[acetylacetone]:[naphthalene]:[CCl4]:[ethanol]=50:5:100:1000:1000 (example 17) - conversion of 90%, the yield of ethyl ether 1-naphthaleneboronic acid (16) - 65%, 2-naphthaleneboronic (26) - 6%. The output of 1,5-diethyl ether 1,5-naphthaleneboronic acid (36) - 14%, 2,6-diethyl ether 2,6-naphthaleneboronic acid (46) - 5%. Diethyl ether 1,5-naphthaleneboronic acid (36)

An NMR spectrum13With (δ, M. D.): 14.37 (CH3), 61.22 (CH2O), 126.17 (4), 126.17 (8), 126.60 (3), 126.60 (7), 131.37 (2), 131.37 (6), 133.23 (9), 133.23 (10), 133.85 (1), 133.85 (5), 167.57 (soo). An NMR spectrum1H (CDCl3, δ, M. D.): 1.40 m (3H, CH3J 15.3 Hz), 4.3 kV (2H, CH2CH3J 4.3 Hz), 9.1 (2H, WITH2,6N J 9 Hz), 7.6 l, d (1H, WITH3N J 7 Hz, 9 Hz), 7,65 m (1H, WITH7N, 8 Hz), 8.28 (2H, WITH4,8N J 7 Hz).

Diethyl ether 2,6-naphthaleneboronic acid (46)

An NMR spectrum13With (δ, M. D.): 14.34 (CH3), 61.25 (CH2O), 130.56 (4), 130.56 (8), 127.66 (3), 127.66 (7), 133.23 (2), 133.23 (6), 133.85 (9), 133.85 (10), 130.96 (1), 130.96 (5), 167,59 (soo). An NMR spectrum1H (CDCl3, δ, M. D.): 1.35 m (3H, CH3J 15.3 Hz), 4.4 kV (2H, CH2CH3J 7.6 Hz), 8.6 (2H, WITH1,5H), 8.71 (2H, WITH3,7N J 8 Hz), 7.95 (1H, WITH4N J 8 Hz), 7.98 (1H, WITH8N J 8 Hz).

EXAMPLE 18. Obtaining methyl ester and 2-naphthaleneboronic acids (1A, 16).

In a vial in a stream of argon was loaded 2.2 mg (5 mmol) of Fe0(met.) (activated HCl), of 0.004 ml (5 mmol) of acetylacetone, 102 mg (100 mmol) of naphthalene, of 0.77 ml (1000 mmol) of carbon tetrachloride and 0.32 ml (1000 mmol) of methyl alcohol. Sealed ampoule was placed in an autoclave, the autoclave was tightly closed and heated at 130°C for 6 h with constant stirring. After the reaction, the autoclave was cooled to room temperature, the ampoule was opened, the reaction mass is neutralized and filtered through a paper filter. The solvent is kept off, the residue was distilled under vacuum. The conversion of initial naphthalene (19) amounted to 34%, the yield of methyl ester 1-naphthaleneboronic acid (1A) - 23%, 2-naphthaleneboronic (2A) - 10%.

The compounds proved by NMR, mass spectrometry.

Methyl ether 1-naphthaleneboronic acid (1A)

TKip155-157°C/10 Torr (Cf. lit. [30]: TKip165°C/17 Torr). An NMR spectrum13With (δ, M. D.): 52.19 (CH3), 126.27 (6), 125.34 (3), 126.39 (7), 127.19 (8), 128.36 (5), 128.77 (1), 130.44 (2), 132.59 (9), 132.69 (4), 133.47 (10), 167.32(soo). An NMR spectrum1H (CDC13, δ, M. D.): 3.99 (3H, CH3), 8.7 (1H, WITH2N J 9 Hz), 7.69 d, d (1H, WITH3N J 7 Hz, 9 Hz), 8.23 (1H, WITH4N J 7 Hz), 8.00 (1H, C5H J 8 Hz), 7.5 m (1H, WITH6N J 7 Hz), 7.58 m (1H, WITH7N J 7 Hz), 7.9 the (1H, With8N J 8 Hz).

Mass spectrum, m/z (IRel(%)): 186.17 [M]+(69), 155 (100), 127 (81), 126 (15), 77(10), 75(5).

Methyl ester 2-naphthaleneboronic acid (16)

Tthe Plava76-78°C (Cf. lit. [30]: Tthe Plava77°C. an NMR Spectrum13With (δ, M. D.): 52.28 (CH3), 125.34 (6), 125.43 (3), 126.80 (10), 127.19 (4), 127.88 (7), 128.68 (5), 129.40 (1), 131.16 (8), 132.59 (9), 135.57 (2), 167.90 (soo).

An NMR spectrum1H (CDCl3, δ, M. D.): 3.93 (3H, CH3), 7.7 (1H, WITH3N J 7 Hz), 8.19 (1H, With4N J 7 Hz), 7.83 (1H, With5N J 8 Hz), 7.48 m (1H, C6H J 7 Hz), 7.4 m (1H, C7H J 7 Hz), 7.8 (1H, WITH8N J 8 Hz), 8.6 (1H, WITH1N).

Mass spectrum, m/z (1Rel(%)): 186.17 [M]+(69), 155 (100), 127 (80), 126 (15), 40(16).

EXAMPLES 19-21. Obtaining the methyl esters of 1 - and 2-naphthaleneboronic acids (1A, 2A).

Analogously to example 18 except the quantity of withdrawn catalyst: [Fe0]:[acetylacetone]:[naphthalene]:[CCl4]:[methanol]=10:5:100:1000:1000 (example 19) - conversion of the initial naphthalene (19) was 36%, the yield of methyl ester 1-naphthaleneboronic acid (1A) - 27%, 2-naphthaleneboronic (2A) - 11%; when the ratio [Fe0]: [acetylacetone]:[naphthalene]:[CCl4]:[methanol]=20:5:100:1000:1000 (example 20) - conversion of 48%, the yield of methyl ester 1-naphthaleneboronic acid (1A) - 36%, 2-naphthaleneboronic (2A) - 12%; when the ratio [Fe0]:[acetylacetone]:[naphthas is Lin]:[CCl 4]: [methanol]=50:5:100:1000:1000 (example 21) - conversion of naphthalene (19) was 50%, the yield of methyl ester 1-naphthaleneboronic acid (1A) - 36%, 2-naphthaleneboronic (2A) - 14%.

Other examples of the method are given in table 1.

Table 1 - Results of the experiments on the synthesis alilovic esters naphthaleneboronic acids by the reaction of naphthalene with ROH and CCL4under the action of iron metal
No.The molar ratio of [Fe0]:[L]:[C10H8]: [CCl4]:[ROH]AlcoholConditionsConversion, %The output of the ether, %The output diapir, %
1-naphthalene carboxylic acid2-naphthalene carboxylic acid1,5-naphthalene dicarboxylic acid2,6-naphthalene dicarboxylic acid
5:5:100:1000:1000D130°, 6 h664125 --
10:5:100:1000:1000D130°, 6 h604417--
20:5:100:1000:1000D130°, 6 h935617137
30:5:100:1000:1000D130°, 6 h966312156
50:5:100:1000:1000D130°, 6 h10070-228
5:5:100:1000:1000D130° C, 4 h23 1112--
5:5:100:1000:1000D130° C, 8 h683929--
5:5:100:1000:1000D130° C, 10 h713932--
5:5:100:1000:1000D130°,12 h442317--
5:5:100:100:100D130°, 6 h3030---
5:5:100:300:300D130°, h 503515--
5:5:100:500:500D130°, 6 h7545237-
5:5:100:500:1000D130°, 6 h462615-5
5:5:100:1000:500D130°, 6 h402613--
5:5:100:1000:1000EtOH130°, 6 h301614--
10:5:100:1000:1000 EtOH130°, 6 h483810--
50:5:100:1000:1000EtOH130°, 6 h90656145
5:5:100:1000:1000MeOH130°, 6 h34239--
10:5:100:1000:1000MeOH130°, 6 h362711--
20:5:100:1000:1000MeOH130°, 6 h483612--
50:5:100:1000:1000MeOH130°, 6 h503614--

The method of obtaining alilovic esters of 1 - and 2-naphthaleneboronic acid formula

R=CH3C2H5n-C3H7,
characterized in that the naphthalene is subjected to interaction with CCl4and alcohol (methanol, ethanol, n-propanol) in the presence of metallic iron, activated Hcl, and acetylacetone at a molar ratio of [Fe0(met.)]:[acetylacetone]:[naphthalene]:[CCl4]:[alcohol]=5-50:5:100:100-1000:100-1000, at a temperature of 130°C for 4-12 h in argon atmosphere.



 

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1 cl, 1 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to a method of producing methyl ethers of organic acids and can be used in analytical chemistry. The disclosed method involves methylation of trace amounts of an organic acid, where synthesis of diazomethane and methylation take place in a single sealed reactor consisting of two parts, where in one part of the reactor diazomethane is obtained by adding a given volume of chloroform to a mixture of potassium hydroxide in ethanol and hydrazine hydrate, and methylation takes place in the other part of the reactor containing the organic acid solution, and into which gaseous diazomethane is fed from the first part. The given volume of chloroform is added gradually in portions of not more than 0.1 ml per minute until a light-yellow isopropanol solution is obtained and then held for not less than 10 minutes. Excess diazomethane and other volatile impurities are removed from the solution through their fast evaporation by holding the solution in a vacuum.

EFFECT: design of a method of methylating trace amounts of organic acids for their determination in a solution through gas-liquid chromatography, which enables calibration of analytical devices with high accuracy.

1 cl, 1 dwg, 3 ex

FIELD: chemistry.

SUBSTANCE: invention concerns organic chemistry, particularly method of obtaining 6-hydroxyspiro[3,4]octane-6-alkylcarboxylates (1), R=C2H5, n-C4H9, where methylenecyclobutane undergoes interaction with triethylaluminum (AlEt3) in the presence of zirconacene dichloride catalyst Cp2ZrCl2 at molar ratio of methylenecyclobutane:AlEt3:Cp2ZrCl2=10:(12-16):(0.5-0.9), in argon atmosphere at room temperature and atmospheric pressure in hexane for 4 hours, with further addition of copper bromide catalyst (CuBr) in amount of 10-14 molar % in respect of methylenecyclobutane, and dialkyl ether of oxalic acid thrice exceeding amount of AlEt3, to reaction mass at -15°C, followed by stirring of reaction mass at room temperature with further acid hydrolysis of reaction mass.

EFFECT: 6-hydroxyspiro[3,4]octane-6-alkylcarboxylates applicable in fine organic synthesis and production of paint coating materials and bioactive substances, with total 76-95% output of end product after reaction mass hydrolysis.

1 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention concerns organic chemistry, particularly method of obtaining spiro[3,4]oct-6-ylformiate. Method (1) involves interaction of methylenecyclobutane with triethylaluminium (AlEt3) in the presence of zirconocene dichloride catalyst (Cp2ZrCl2) at molar ratio of methylenecyclobutane: AlEt3:Cp2ZrCl2=10:(11-15):(0.5-0.7) in argon atmosphere at room temperature and atmospheric pressure in hexane for 7 hours, with further addition of copper chloride catalyst (CuCl) in amount equimolar to Cp2ZrCl2, and alkylformiate of the general formula HCO2R (where R=Et, n-Pr, n-Bu) thrice exceeding amount of AlEt3, to reaction mass at -15°C, further stirring at room temperature for 8-10 hours, and acid hydrolysis of reaction mass. Total output of end product after acid hydrolysis of reaction mass reaches 73-89%.

EFFECT: possible application in fine organic synthesis and production of paint coating materials and bioactive substances.

1 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: raw material composition based on fatty acids or esters of fatty acids, obtained by hydrolysis of oil from seeds or by re-etherification of oil from seeds with C1-8-alkanol, contains more than 70 wt % of unsaturated fatty oleic acid, and less than 1.5 milliequivalents of admixture(s), poisoning methathesis catalyst, per kilogram of composition, after purification with adsorbent. Admixture contains one or more organic hydroperoxides. Method of olefin methathesis lies in contacting of raw composition, obtained from seed oil and containing one or more unsaturated fatty acids or esters of unsaturated fatty acids, with lower olefin in presence of catalyst based on phosphororganic transition metal complex. Used raw material composition contains less than 25 milliequivalents of admixture(s), poisoning methathesis catalyst, per kilogram of raw material composition, able to inhibit methathesis catalyst. As a result of reaction olefin with shortened chain and unsaturated acid or unsaturated ester with shortened chain is obtained. Method of obtaining complex polyether polyepoxide lies in carrying out the following stages. At the first stage raw material compositiojn, obtained from seed oil, containing one or more unsaturated fatty acids or esters of fatty acids, contacts with lower olefin in presence of olefin methathesis catalyst. Used raw material composition contains less than 25 milliequivalents of admixture(s), poisoning methathesis catalyst, per kilogram of composition. At the second stage (re)etherification of obtained unsaturated acid with shortened chain or unsaturated ester with shortened chain with polyol is carried out. At the third stage epoxidation of obtained complex polyether polyolefin is carried out with epoxidising agent optionally in presence of catalyst. Method of obtaining α,ω-oxoacid, complex α,ω-oxyester and/or α,ω-diol with shortened chain lies in carrying out the following stages. At the first stage raw material composition, obtained from seed oil, containing one or more unsaturated fatty acids or esters of fatty acids contacts with lower olefin in presence of olefin methathesis catalyst. Used raw material composition contains less than 25 milliequivalents of admixture(s), poisoning methathesis catalyst, per kilogram of composition. At the second stage hydroformilation is carried out with hydrating of obtained unsaturated acid or ester with shortened chain in presence of hydroformiolation/hydration catalyst.

EFFECT: increase of catalyst serviceability and obtaining chemical compounds with high productivity.

25 cl, 3 tbl, 12 ex

FIELD: chemistry.

SUBSTANCE: invention refers to advanced process of diacerein production with aloe-emodin and it mono-, di - and triacetylate derivatives within 0 to 5 parts per million containing water-organic solution of weak-base diacerein salt is extracted with solvent miscible or practically immiscible with water. Method allows for product containing diacerein and up to 5 parts per million of aloe-emodin, i.e. enables product with low aloe-emodin content, and is characterised with simplicity of implementation.

EFFECT: product with low aloe-emodin content and simplicity of implementation.

10 cl, 6 ex

FIELD: chemistry.

SUBSTANCE: method involves catalytic telomerisation of butadiene with diethylamine in the presence of a catalyst based on cationic complexes of palladium (II) of general formula [(acac)Pd(L)2]BF4 (where acac is an acetylacetonate ligand, L=PPh3, P'Pr3, P"Bu3 P(p-Tol)3 or (L)2=diphosphine ligands, selected from bis(diphenylphosphino)methane(dppm), bis(diphenylphosphino)propane(dppp), bis(diphenylphosphino)butane(dppb), bis(diphenylphosphino)ferrocene(dppf)). The process is carried out in a substrate medium, specifically diethylamine and butadiene, at temperature of 50-90°C. The method enables to obtain N,N-diethylocta-2,7-diene-1-amine with selectivity of 99.9% from the overall mixture of reaction products with high process output which reaches 4180 g of product per 1 g Pd. The catalysts used are more readily available compared to those previously used for the process.

EFFECT: improved method.

1 tbl, 1 ex

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