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Method of producing 1-bromo-3-alkylborolanes. RU patent 2507208.

Method of producing 1-bromo-3-alkylborolanes. RU patent 2507208.
IPC classes for russian patent Method of producing 1-bromo-3-alkylborolanes. RU patent 2507208. (RU 2507208):

C07F5/02 - Boron compounds
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FIELD: chemistry.

SUBSTANCE: present invention relates to production of organoboron compounds. The method is carried out by reacting α-olefins with triethylaluminium in the presence of a zirconocene dichloride catalyst in an atmosphere of argon at temperature of -20°C for 6 hours, followed by cooling the reaction mass to -60°C. Boron bromide is then added in double the amount relative to AlEt3 in a medium of hexane and mixed at temperature of -20°C for 30-60 minutes. Tetrahydrofuran is then added to the reaction mass cooled to -60°C immediately before rectification.

EFFECT: invention enables to obtain organoboron compounds which can be used as components of catalyst systems in oligomerisation and polymerisation of olefin, diene and acetylene hydrocarbons, as well as in fine organic and organometallic syntheses.

1 tbl, 1 ex

 

The invention relates to the field of synthesis, particularly to a method of obtaining 1-bromo-3- of the General formula (1):

where R=n-C 4 H 9 , h-C 6 H 13 , h-8 C H 17

The proposed connection can find application as components of catalytic systems for the processes of oligo - and olefin polymerization, diene and acetylene hydrocarbons, as well as in fine organic and synthesis [1. .-Xian Chen. Cocatalysts foz metal-catalyzed polymerization: activators, activation processes, and structure-activity relationships // Chem. Rev. 2000, 100, 1391-1434].

Known method [2. H.C.Brown, M.Zaidlewicz. Hydroboration representative of acyclic α tensor and dienes with monochloroborane etherate // JACS, 1976, 98(16), 4917-4925] obtain Cl-substituted (2) reaction of cyclic 1,4- using according to the scheme:

A well-known method can not be obtained 1-bromo-3- (1).

Known method [3. R.Koster, ..Grassberger. Halogen-organoborane durch katalytische Komproportionierung von Trigalogenboranen und Organoboranen // Liebing Ann. Chem., 1968, 719, 169] 1-chloro-3- (3) reaction α tensor and with number of boron chloride in the presence of reagent at a temperature of 100-110 C scheme:

A well-known method can not be obtained 1-bromo-3- (1).

Known method [4. RF patent №2440356] 1-fluoro-3- (4) reaction α-olefins with in the presence of a catalyst Cp 2 ZrCl 2 with the subsequent addition BF 3 ·Et 2 O according to the scheme:

R=n-Bu (a); h-Hex (b); h-Oct (c)

The reaction is carried out at a molar ratio of α-olefin:AlEl 3 :2 Cp ZrCl 2 =10:(20-30):(0.3-0.7); BF 3-Et 2 O add in number in relation to AlEt 3 .

Known process can get 1-bromo-3- (1).

Thus, in the literature there are no data on the synthesis of 1-bromo-3- (1).

A new method of production of 1-bromo-3- (1).

The essence of the method lies in the interaction in the atmosphere of inert gas α-olefin (Gex-1-ene, Oct-1-ene, Oct-1-ene) with (AlEt 3 ) in the presence of a catalyst (2 Cp ZrCl 2 ), taken in the molar ratio of α-olefin:AlEt 3 :2 Cp ZrCl 2 =10:(10÷14):(0.3 to 0.7), preferably 10:12:0.5, at room temperature (about 20 C) for 6 h, with the subsequent cooling of the reaction mass to -60 C, the addition of boron bromide (BBr 3 ) the twofold compared to AlEt number 3, stirring at a temperature ~20 C during 30-60 min, preferably 45 minutes Then the reaction mass is cooled to -60 C and added THF. The target product is allocated by distillation in vacuum. Output 1-bromo-3- (1) is 65-82%. The reaction proceeds according to the scheme:

R=i-Bu (a); i-Hex (b); i-Oct ()

1-Bromo-3- (1) are formed only with the participation of α olefins , catalyst and boron bromide. In the presence of other boron derivatives (e.g., Et 2 BBr, C 6 F 5 BBr 2 ), other compounds (e.g., Et 2 AlCl, EtAlCl 2 , i-Bu 3 Al), other unsaturated compounds (for example, , ) or other catalysts (for example, Cp 2 TiCl 2 , Pd(acac) 2 , NiCl 2 , Ni(acac) 2 , CoCl 2 ) target products (1) are not formed.

Conduct the reactions in the presence of zirconium catalyst Cp 2 ZrCl 2 more 7 mol.% in relation to the α does not significantly increase the output of target products (1). Using the catalyst Cp 2 ZrCl 2 less than 3 mol.% in relation to the α reduces output (1), that is connected, probably, with a decrease of catalytically active centers in the reaction mass. The reaction was carried out at room temperature (about 20 C). At higher temperatures (for example, 40 C) not observed increase the output of target products, and at a lower temperature (for example, 0 C) reduced rate of the reaction. Adding boron bromide and tetrahydrofuran carried out at a temperature of 60 degrees C. Lowering the temperature, for example, to -80°C does not affect the output of target products, however, insufficient cooling (for example, -20 C) leads to a decrease in the output of target products.

Significant differences between the proposed method:

The proposed method allows to obtain 1-bromo-3-. To do this, as the parent compounds used α-olefins, , catalyst and boron bromide. Due to the fact that the reaction proceeds with strong heating, boron bromide BBr 3 type cooling up to 60 degrees C by distillation of the reaction mass add THF. Without adding THF substituted not formed, and instead formed 1,4-. In the known method as the parent compounds are applied α-olefins, , catalyst and boron TRIFLUORIDE, added at a temperature of 0 C [2]. A well-known method can not be obtained 1-bromo-3-.

The method is illustrated by the following examples:

EXAMPLE 1. The glass reactor mounted on a magnetic stirrer in argon atmosphere is placed 1.12 g (10 mmol) Oct-1-ene, 1.92 ml (12 mmol) 92%AlEt 3 , 0.15 g (0.5 mmol) Cp 2 ZrCl 2 and mix 6 hours at room temperature, then add 10 ml of hexane, cool reaction mass is up to -60 C, slowly adds these dropwise 6 g (24 mmol) boron bromide and stirred for 45 min at room temperature. Then again cooled reaction mass is up to -60 C, add 2 ml of THF, the temperature is brought up to room temperature. The solvent was evaporated and the reaction mass is distilled in vacuum. Get 1-bromo-3- (16) with the release of 75%.

1-Bromo-3- (1B): BP. 80 C/6 Torr. NMR-spectrum of the 1 H (d, ppm, CDCl 3 ): 0.46 (DD, 1H, C(2)H a , 3 J=10.S Hz, 2 J=18.5 Hz), 0.81 (m, 1H, C(5) (H (a ), 0.93 (t, 3H, C(11)N 3 , 3 J=7.5 Hz), 1.08-1.15 (m, 1H, C(4)H (a ), 1.3-1.4 (m, 11N, (5 N b, (6)N 2, (7)2(8)N 2, (9)N 2(10)N 2 ), 1.53 (DD, 1H, C(2)H b , 3 J=6.9, 2 J=18.5), 1.7 (m, 1H, C(3)H)1.95 (m, 1H, C(4)H (b ). NMR-spectrum of 13 (d, ppm, CDCl 3 ): 14.22 (C(11)), 23.32 (C(10)), 27.41 (C(5)), 29.3 (C(7)), 30.99 (C(8)), 32.99 (C(9)), 34.18 (C(4)), 35.15 (C(2)), 38.91 (C(6)), 41.98 (C(3)). NMR-spectrum of 11 B (d, ppm, CDCl 3 ): 91.9 (W ½ =0.246 kHz).

1-Bromo-3- (1a): BP. 85 C/16 Torr. NMR-spectrum of the 1 H (d, ppm, CDCl 3 ): 0.46 (DD, 1H, C(2)H (a , V=12.0, 2 J=17.9 Hz), 0.73-0.95 (m, 4H, C(5) (H (a , C(9)N 3 ), 1.11 (m, 1H, C(4)H (a ) 1.21-1.5 (m, 7H, (5)H b, (6)N 2 , C(7) 2 , C(8)N 2 ), 1.59 (DD, 1H, C(2)H b , 3 J=6.0 Hz, 2 J=17.9 Hz), 1.75 (m, 1H, s(3) (H), 1.92 (m, 1H, C(4)H (b ). NMR-spectrum of 13 C (d, ppm, CDCl 3 ): 14.23 (C(9)), 23.11 (C(8)), 27.19 (C(5)), 32.34 (C(7)), 33.45 (C(4)), 35.51 (C(2)), 37.63 (C(6)), 41.52 (C(3)). NMR-spectrum of 11 B (d, ppm, CDCl 3 ): 92.46 (W ½ =0.235 kHz).

1-Bromo-3- (1B): BP. 94 C/4 Torr. NMR-spectrum of the 1 H (d, ppm, CDCl 3 ): 0.47 (DD, 1H, C(2)H a , 3 J=11.3 Hz, 2 J=17.4 Hz, 0.75 (m, 1H, S(5) (H (a ), 0.83 (t, 3H, C(13)N 3 , 3 J=7.2 Hz), 1.09 (m, 1H, C(4)H (a ), 1.2-1.49 (m, 15N, (5)H b, (6)N 2, (7)2(8)N 2, (9)N 2(10)N 2, (11), N 2(12)N 2 ), 1.62 (DD, 1H, C(2)H b J J=7.2 Hz, 2 J=17.4 Hz), 1.77 (m, 1H, s(3) (H), 1.89-1.93 (m, 1H, WITH(4)N (b ). NMR-spectrum of 13 (d, ppm, CDCl 3 ). 14.15 (C(13)), 22.74 (C(12)), 27.17 (C(5)), 29.44 (C(9)), 29.76 (C(7)), 30.08 (C(8)), 31.99 (C(10, 11)), 33.41 (C(4)), 35.50 (C(2)), 37.91 (C(6)), 41.48 (C(3)). NMR-spectrum of 11 B (d, ppm, CDCl 3 ): 93.72 (W ½ =0.275 kHz).

Other examples confirming the method given in the table.

#

Source α-olefin

The molar ratio of α-olefin:AlEt 3 :2 Cp ZrCl 2 :BBr 3 , mmol

The total response time, min

Exit (1),%

1 2 3 4 5 1

Oct-1-ene

10:12:0.5:24

6 hours and 45 minutes

75 2 -«-

10:14:0.5:28

6 hours and 45 minutes

79 3 -«-

10:10:0.5:20

6 hours and 45 minutes

70 4 -«-

10:12:0.7:24

6 hours and 45 minutes

79 5 -«-

10:12:0.3:24

6 hours and 45 minutes

65 6 -«-

10:12:0.5:24

7 h 00 min

81 7 -«-

10:12:0.5:24

6 h 30 min

68 8

Gex-1-ene

10:12:0.5:24

6 hours and 45 minutes

82 9

Oct-1-ene

10:12:0.5:24

6 hours and 45 minutes

72

The reaction was carried out at room temperature (about 20 C).

A method of obtaining a 1-bromo-3- of the General formula (1)

where R=n-C 4 H 9 , h-C 6 H 13 , h-8 C H 17

interaction α-olefins (Gex-1-ene, Oct-1-ene, Oct-1-ene) with AlEt 3 in the presence of a catalyst Cp 2 ZrCl 2

in hexane at a molar ratio of α-olefin:AlEt 3 :2 Cp ZrCl 2 =10:(10÷14):(0.3 to 0.7) in the inert atmosphere at temperature of ~20 C for 6 hours, with the subsequent interaction with boron, characterized in that in the capacity of halogenide boron use BBr 3 , taken in the doubles against the AlEt 3 number, add BBr 3 is carried out at a temperature of -60 C in the environment of aliphatic solvent (hexane), further stirring the reaction mass is carried out at a temperature of ~20 C during 30-60 min, immediately before rectifying the cooled down to -60 C type THF.

 

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