RU2654806C2 - METHOD OF OBTAINING COMPLEXES OF 1-CHLORO-2-ALKYL (PHENYL) BORIRENES WITH SMe2 - Google Patents
METHOD OF OBTAINING COMPLEXES OF 1-CHLORO-2-ALKYL (PHENYL) BORIRENES WITH SMe2 Download PDFInfo
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- RU2654806C2 RU2654806C2 RU2016104994A RU2016104994A RU2654806C2 RU 2654806 C2 RU2654806 C2 RU 2654806C2 RU 2016104994 A RU2016104994 A RU 2016104994A RU 2016104994 A RU2016104994 A RU 2016104994A RU 2654806 C2 RU2654806 C2 RU 2654806C2
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- chloro
- acetylene
- phenyl
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- 238000000034 method Methods 0.000 title claims abstract description 18
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 title abstract description 7
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical class [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 title 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 14
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 239000012298 atmosphere Substances 0.000 claims abstract description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- -1 acetylene hydrocarbons Chemical class 0.000 abstract description 10
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 230000003993 interaction Effects 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 3
- MKNXBRLZBFVUPV-UHFFFAOYSA-L cyclopenta-1,3-diene;dichlorotitanium Chemical compound Cl[Ti]Cl.C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 MKNXBRLZBFVUPV-UHFFFAOYSA-L 0.000 abstract description 3
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 abstract description 3
- 150000001336 alkenes Chemical class 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 150000001993 dienes Chemical class 0.000 abstract description 2
- 229930195733 hydrocarbon Natural products 0.000 abstract description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 2
- 125000002524 organometallic group Chemical group 0.000 abstract description 2
- 229910015844 BCl3 Inorganic materials 0.000 abstract 2
- 230000000694 effects Effects 0.000 abstract 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 2-octanone Chemical compound CCCCCCC(C)=O ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 0.000 description 6
- NUJGJRNETVAIRJ-UHFFFAOYSA-N octanal Chemical compound CCCCCCCC=O NUJGJRNETVAIRJ-UHFFFAOYSA-N 0.000 description 6
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 5
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 210000005069 ears Anatomy 0.000 description 4
- 150000000475 acetylene derivatives Chemical class 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- YRJSKCCBXWXREJ-UHFFFAOYSA-N C1(=CC=CC=C1)[Si](C1=CC=CC=C1)(C1=CC=CC=C1)B Chemical compound C1(=CC=CC=C1)[Si](C1=CC=CC=C1)(C1=CC=CC=C1)B YRJSKCCBXWXREJ-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000006303 photolysis reaction Methods 0.000 description 2
- 230000015843 photosynthesis, light reaction Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
- OIJTZPGWOYZZSN-UHFFFAOYSA-N 1$l^{2}-borirene Chemical class [B]1C=C1 OIJTZPGWOYZZSN-UHFFFAOYSA-N 0.000 description 1
- GSYXKQFFKNRDQE-UHFFFAOYSA-N 1-tert-butylborirene Chemical class C(C)(C)(C)B1C=C1 GSYXKQFFKNRDQE-UHFFFAOYSA-N 0.000 description 1
- GLVKGYRREXOCIB-UHFFFAOYSA-N Bornylene Natural products CC1CCC(C(C)(C)C)C=C1 GLVKGYRREXOCIB-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910007926 ZrCl Inorganic materials 0.000 description 1
- QQIRAVWVGBTHMJ-UHFFFAOYSA-N [dimethyl-(trimethylsilylamino)silyl]methane;lithium Chemical compound [Li].C[Si](C)(C)N[Si](C)(C)C QQIRAVWVGBTHMJ-UHFFFAOYSA-N 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- ZDWYFWIBTZJGOR-UHFFFAOYSA-N bis(trimethylsilyl)acetylene Chemical group C[Si](C)(C)C#C[Si](C)(C)C ZDWYFWIBTZJGOR-UHFFFAOYSA-N 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical class B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- GINAGCMIRYVIQT-UHFFFAOYSA-N ethynyl(trimethyl)stannane Chemical group C[Sn](C)(C)C#C GINAGCMIRYVIQT-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 description 1
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 1
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000005556 structure-activity relationship Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Предлагаемое изобретение относится к области борорганического синтеза, конкретно к способу получения комплексов 1-хлор-2-алкил(фенил)бориренов с SMe2 общей формулы (1):The present invention relates to the field of organoboron synthesis, specifically to a method for producing complexes of 1-chloro-2-alkyl (phenyl) borirenes with SMe 2 of the general formula (1):
Предлагаемые соединения могут найти применение в качестве компонентов каталитических систем в процессах олиго- и полимеризации олефиновых, диеновых и ацетиленовых углеводородов, а также в тонком органическом и металлорганическом синтезах ([1], Е. You-Xian Chen. Cocotalyct for metal-catalyzed polymerization: activators, activation processes, and structure-activity relationships // Chem. Rev., 2000, 100, 1391-1434).The proposed compounds can be used as components of catalytic systems in the processes of oligo- and polymerization of olefin, diene and acetylene hydrocarbons, as well as in fine organic and organometallic syntheses ([1], E. You-Xian Chen. Cocotalyct for metal-catalyzed polymerization: activators, activation processes, and structure-activity relationships // Chem. Rev., 2000, 100, 1391-1434).
Известен способ ([2], Pues С, Berndt A. 1-tert-Butylborirenes // An-gew. Chem. Int. Ed. Engl., 1984, 23, 4, 313-314) получения 1-трет-бутилбориренов общей формулы (2) взаимодействием триметилстаннилацетиленов с 1,2-бис(трет-бутил)-1,2-дихлорбораном по схеме:A known method ([2], Pues C, Berndt A. 1-tert-Butylborirenes // An-gew. Chem. Int. Ed. Engl., 1984, 23, 4, 313-314) for the preparation of 1-tert-butylboriene total formula (2) the interaction of trimethylstannylacetylene with 1,2-bis (tert-butyl) -1,2-dichloroborane according to the scheme:
Известным способом не могут быть получены комплексы 1-хлор-2-алкил(фенил)бориренов с SMe2 (1).In a known manner, complexes of 1-chloro-2-alkyl (phenyl) borirenes with SMe 2 (1) cannot be obtained.
Известен способ ([3], Eisch J.J., Shafii В., Boleslawski М.Р. Di-π-methane-like photorearrangements of α,β-unsaturated organoboranes in the synthesis of borirenes and boracarbenoid intermediates // Pure & Appl. Chem., 1991, 63, 3, 365-368) получения 1,2,3-триарилбориренов общей формулы (3) фотооблучением (300 нм) диарил(арилэтинил)боранов в тетрагидрофуране по схеме:The known method ([3], Eisch JJ, Shafii B., Boleslawski M. P. Di-π-methane-like photorearrangements of α, β-unsaturated organoboranes in the synthesis of borirenes and boracarbenoid intermediates // Pure & Appl. Chem. , 1991, 63, 3, 365-368) for the preparation of 1,2,3-triarylborienes of the general formula (3) by photoirradiation (300 nm) of diaryl (arylethynyl) boranes in tetrahydrofuran according to the scheme:
Известным способом не могут быть получены комплексы 1-хлор-2-алкил(фенил)бориренов с SMe2 (1).In a known manner, complexes of 1-chloro-2-alkyl (phenyl) borirenes with SMe 2 (1) cannot be obtained.
Известен способ ([4] Habben С, Meller A. Synthese und eigenschaf-ten von 1-[bis(trimethylsilyl)amino]borirenen // Chem. Ber., 1984, 117, 2531-2537) получения 1-[бис(триметилсилил)амино]бориренов общей формулы (6) взаимодействием натрия с 3-[бис(триметилсил)амино]-3H-1,2,3-дитиаборолами (5), полученными взаимодействием ацетиленов с 3,5-дибром-1,2,4,3,5-тритиадибороланом (4) и последующим взаимодействием литийгексаметилдисилазаном в гексане, по схеме:A known method ([4] Habben C, Meller A. Synthese und eigenschaf-ten von 1- [bis (trimethylsilyl) amino] borirenen // Chem. Ber., 1984, 117, 2531-2537) to obtain 1- [bis (trimethylsilyl ) amino] borirenes of the general formula (6) by the interaction of sodium with 3- [bis (trimethylsil) amino] -3H-1,2,3-dithiaborols (5) obtained by the interaction of acetylenes with 3,5-dibromo-1,2,4 , 3,5-tritiadiborolan (4) and the subsequent interaction of lithiumhexamethyldisilazane in hexane, according to the scheme:
Известным способом не могут быть получены комплексы 1-хлор-2-алкил(фенил)бориренов с SMe2 (1).In a known manner, complexes of 1-chloro-2-alkyl (phenyl) borirenes with SMe 2 (1) cannot be obtained.
Известен способ ([5], Pachaly В., West R. Photochemical generation of triphenylsilylboranediyl (С6Н5)3SiВ: from organosilylboranes // Angew. Chem. Int. Ed., 1984, 23, 6, 454-455) получения 1-трифенилсилил-2,3-бис(триметилсилил)борирена (9) реакцией бис(триметилсилил)ацетилена с трифенилсилилбориленом (8), полученным фотохимическим облучением трифенилсилилборана (7)A known method ([5], Pachaly B., West R. Photochemical generation of triphenylsilylboranediyl (C 6 H 5 ) 3 SiB: from organosilylboranes // Angew. Chem. Int. Ed., 1984, 23, 6, 454-455) for producing 1-triphenylsilyl-2,3-bis (trimethylsilyl) borylene (9) by reacting bis (trimethylsilyl) acetylene with triphenylsilyl borylene (8) obtained by photochemical irradiation of triphenylsilylborane (7)
Известным способом не могут быть получены комплексы 1-хлор-2-алкил(фенил)бориренов с SMe2 (1).In a known manner, complexes of 1-chloro-2-alkyl (phenyl) borirenes with SMe 2 (1) cannot be obtained.
Известен способ ([6], Braunschweig Н., Herbst Т., Rais D., Seeler F. Synthesis of borirenes by photochemical borylene transfer from [(OC)5M=BN(SiMe3)2] (M=Cr, Mo) to alkynes // Angew. Chem. Int. Ed., 2005, 44, 7461-7463) получения бориренов общей формулы (10) фотолизом раствора (OC)5M=B-N(SiMe3)2 (М=Cr, Мо) в присутствии ацетилена в течение 2-4 часов при комнатной температуре по схеме:The known method ([6], Braunschweig N., Herbst T., Rais D., Seeler F. Synthesis of borirenes by photochemical borylene transfer from [(OC) 5 M = BN (SiMe 3 ) 2 ] (M = Cr, Mo ) to alkynes // Angew. Chem. Int. Ed., 2005, 44, 7461-7463) for the preparation of borirenes of the general formula (10) by photolysis of a solution (OC) 5 M = BN (SiMe 3 ) 2 (M = Cr, Mo) in the presence of acetylene for 2-4 hours at room temperature according to the scheme:
Известным способом не могут быть получены комплексы 1-хлор-2-алкил(фенил)бориренов с SMe2 (1).In a known manner, complexes of 1-chloro-2-alkyl (phenyl) borirenes with SMe 2 (1) cannot be obtained.
Таким образом, в литературе отсутствуют сведения по синтезу 1-хлор-2-алкил(фенил)бориренов (1).Thus, in the literature there is no information on the synthesis of 1-chloro-2-alkyl (phenyl) borirenes (1).
Предлагается новый способ получения комплексов 1-хлор-2-алкил(фенил)бориренов с SMe2 (1).A new method is proposed for preparing complexes of 1-chloro-2-alkyl (phenyl) borirenes with SMe 2 (1).
Сущность способа заключается во взаимодействии в атмосфере инертного газа ацетилена (окт-1-ин, или дец-1-ин, или фенилацетилен) с BCl3-SMe2 в присутствии Mg (порошок) и катализатора титанацендихлорида (Cp2TiCl2) в ТГФ, взятыми в мольном соотношении ацетилен: BCl3⋅SMe2 : Mg : Cp2TiCl2 = 10 : (15÷25) : (20÷40) : (1.8÷2.2), предпочтительно 10:20:30:2.0. Реакцию проводят при охлаждении реакционной массы до 0°С в течение 1 ч с последующим нагреванием до комнатной температуры (~20-22°С) и перемешиванием в течение 12-16 ч, предпочтительно 14 ч. Выход комплексов 1-хлор-2-алкил(фенил)бориренов с SMe2 (1) составляет 58-90%. Реакция протекает по схеме:The essence of the method consists in the interaction in an atmosphere of an inert gas of acetylene (oct-1-in, or dec-1-in, or phenylacetylene) with BCl 3 -SMe 2 in the presence of Mg (powder) and a catalyst titanacenedichloride (Cp 2 TiCl 2 ) in THF taken in the molar ratio of acetylene: BCl 3 ⋅SMe 2 : Mg: Cp 2 TiCl 2 = 10: (15 ÷ 25): (20 ÷ 40): (1.8 ÷ 2.2), preferably 10: 20: 30: 2.0. The reaction is carried out by cooling the reaction mass to 0 ° C for 1 h, followed by warming to room temperature (~ 20-22 ° C) and stirring for 12-16 h, preferably 14 h. Yield of 1-chloro-2-alkyl complexes (phenyl) borirenes with SMe 2 (1) is 58-90%. The reaction proceeds according to the scheme:
Комплексы 1-хлор-2-алкил(фенил)бориренов с SMe2 (1) образуются только лишь с участием ацетиленов, диметилсульфидного комплекса треххлористого бора (BCl3⋅SMe2), порошка магния, катализатора титанацендихлорида и растворителя ТГФ. В присутствии других соединений бора (PhBCl2, BF3⋅ТГФ, BF3⋅SMe2, ВВr3, BI3 или BF3⋅Et2O), других непредельных соединений (например, α-олефины, аллены) или другого катализатора (например, Cp2ZrCl2, Pd(acac)2, NiCl2, Ni(acac)2, СоСl2) целевые продукты (1) не образуются.The complexes of 1-chloro-2-alkyl (phenyl) borirerenes with SMe 2 (1) are formed only with the participation of acetylenes, a dimethyl sulfide complex of boron trichloride (BCl 3 ⋅SMe 2 ), magnesium powder, a catalyst of titanocene dichloride, and a THF solvent. In the presence of other boron compounds (PhBCl 2 , BF 3 ⋅ THF, BF 3 ⋅ SME 2 , BBr 3 , BI 3 or BF 3 ⋅ Et 2 O), other unsaturated compounds (e.g. α-olefins, allens) or another catalyst ( for example, Cp 2 ZrCl 2 , Pd (acac) 2 , NiCl 2 , Ni (acac) 2 , CoCl 2 ) the target products (1) are not formed.
Проведение указанной реакции в присутствии титанового катализатора Cp2TiCl2 больше 2.2 мол % по отношению к ацетилену не приводит к существенному увеличению выхода целевых продуктов (1). Использование катализатора Cp2TiCl2 менее 1.8 мол % по отношению к ацетилену снижает выход комплексов бориренов (1), что связано, возможно, со снижением каталитически активных центров в реакционной массе. Изменение соотношений исходных реагентов в сторону уменьшения содержания BCl3⋅SMe2 по отношению к исходному ацетилену приводит к снижению выхода комплексов бориренов (1).Carrying out this reaction in the presence of a titanium catalyst Cp 2 TiCl 2 more than 2.2 mol% with respect to acetylene does not lead to a significant increase in the yield of the target products (1). The use of the catalyst Cp 2 TiCl 2 less than 1.8 mol% with respect to acetylene reduces the yield of boriene complexes (1), which is possibly associated with a decrease in catalytically active centers in the reaction mass. A change in the ratios of the starting reagents towards a decrease in the content of BCl 3 ⋅SMe 2 with respect to the starting acetylene leads to a decrease in the yield of borirene complexes (1).
Существенные отличия предлагаемого способаSignificant differences of the proposed method
В предлагаемом способе в качестве исходных соединений используются ацетилены, BCl3⋅SMe2, катализатор титанацендихлорид. Предлагаемый способ позволяет получать комплексы 1-хлор-2-алкил(фенил)бориренов с SMe2 (1). Известный способ [6] основан на фотолизе раствора (OC)5M=B-N(SiMe3)2 (М=Cr, Мо) в присутствии ацетилена. Известным способом не могут быть получены комплексы 1-хлор-2-алкил(фенил)бориренов с SMe2 (1).In the proposed method, acetylenes, BCl 3 ⋅SMe 2 , and a titanocen dichloride catalyst are used as starting compounds. The proposed method allows to obtain complexes of 1-chloro-2-alkyl (phenyl) borirenes with SMe 2 (1). The known method [6] is based on the photolysis of a solution (OC) 5 M = BN (SiMe 3 ) 2 (M = Cr, Mo) in the presence of acetylene. In a known manner, complexes of 1-chloro-2-alkyl (phenyl) borirenes with SMe 2 (1) cannot be obtained.
Способ поясняется следующими примерами.The method is illustrated by the following examples.
ПРИМЕР 1. В стеклянный реактор в атмосфере аргона при перемешивании последовательно загружают при 0°С 3 мл ТГФ, 0.055 г (0.5 ммоль) окт-1-ина, 0.036 г (1.5 ммоль) порошка Mg, 0.025 г (0.1 ммоль) Ср2TiCl2 и насыпают 0.179 г (1.0 ммоль) BCl3⋅SMe2 и перемешивают в течение 1 часа. Далее реакционную массу нагревают до комнатной температуры и перемешивают 14 ч. Получают комплекс 1-хлор-2-гексилборирена с SMe2 (1a). Выход целевого продукта (1а) определяли по общему выходу продуктов окисления (85%). При окислении 1а перекисью водорода в щелочной среде образуются октаналь (2а) и октан-2-он (3а) в соотношении 1:1 по схеме:EXAMPLE 1. In a glass reactor in an argon atmosphere, with stirring, 3 ml of THF, 0.055 g (0.5 mmol) oct-1-in, 0.036 g (1.5 mmol) of Mg powder, 0.025 g (0.1 mmol) of Cr 2 are successively charged at 0 ° C. TiCl 2 and pour 0.179 g (1.0 mmol) of BCl 3 ⋅SMe 2 and stirred for 1 hour. Next, the reaction mass is warmed to room temperature and stirred for 14 hours. A complex of 1-chloro-2-hexylborirene with SMe 2 (1a) is obtained. The yield of the target product (1a) was determined by the total yield of oxidation products (85%). During the oxidation of 1a with hydrogen peroxide in an alkaline medium, octanal (2a) and octan-2-one (3a) are formed in a 1: 1 ratio according to the scheme:
Октаналь (11): Спектр ЯМР 1Н (δ, м.д., CDCl3): 0.89 т (J 7.1 Гц, 3Н), 1.21-1.36 м (8Н, С4Н2, С5Н2, С6Н2, С7Н2), 1.55-1.60 м (2Н, С3Н2), 2.34-2.45 м (2Н, С2Н2), 9.60 с (1Н, С1Н). Спектр ЯМР 13С (δ, м.д., CDCl3): 14.20 (С8), 22.22 (С3), 22.72 (С7), 29.16 (С5), 29.27 (С4), 31.77 (С6), 44.04 (С2), 203.02 (С1).Octanal (11): 1 H NMR Spectrum (δ, ppm, CDCl 3 ): 0.89 t (J 7.1 Hz, 3H), 1.21-1.36 m (8H, C 4 H 2 , C 5 H 2 , C 6 Н 2 , С 7 Н 2 ), 1.55-1.60 m (2Н, С 3 Н 2 ), 2.34-2.45 m (2Н, С 2 Н 2 ), 9.60 s (1Н, С 1 Н). 13 C NMR spectrum (δ, ppm, CDCl 3 ): 14.20 (C 8 ), 22.22 (C 3 ), 22.72 (C 7 ), 29.16 (C 5 ), 29.27 (C 4 ), 31.77 (C 6 ), 44.04 (C 2 ), 203.02 (C 1 ).
Октан-2-он (12): Спектр ЯМР 1Н (δ, м.д., CDCl3): 0.90 т (J 7.2 Гц, 3Н), 1.20-1.31 м (6Н, С5Н2, С6Н2, С7Н2), 1.52-1.63 м (2Н, С4Н2), 2.15 с (3Н, С7Н3), 2.44 м (2Н, С3Н2). Спектр ЯМР 13С (δ, м.д., CDCl3): 14.31 (С8), 22.86 (С7), 24.10 (С4), 29.41 (С1), 29.57 (С5), 32.03 (С6), 44.06 (С3), 206.05 (С2).Octan-2-one (12): 1 H NMR Spectrum (δ, ppm, CDCl 3 ): 0.90 t (J 7.2 Hz, 3H), 1.20-1.31 m (6H, C 5 H 2 , C 6 N 2 , С 7 Н 2 ), 1.52-1.63 m (2Н, С 4 Н 2 ), 2.15 s (3Н, С 7 Н 3 ), 2.44 m (2Н, С 3 Н 2 ). 13 C NMR spectrum (δ, ppm, CDCl 3 ): 14.31 (C 8 ), 22.86 (C 7 ), 24.10 (C 4 ), 29.41 (C 1 ), 29.57 (C 5 ), 32.03 (C 6 ), 44.06 (C 3 ), 206.05 (C 2 ).
Комплекс 1-хлор-2-гексилборирена с SMe2 (1a) идентифицировали методом ЯМР 13С и 1Н из реакционной массы без выделения. Для этого реакционную массу отфильтровывали, растворитель упаривали в вакууме при комнатной температуре, остаток растворяли в CDCl3 и анализировали.The complex of 1-chloro-2-hexylborirene with SMe 2 (1a) was identified by 13 C and 1 H NMR from the reaction mass without isolation. For this, the reaction mass was filtered, the solvent was evaporated in vacuo at room temperature, the residue was dissolved in CDCl 3 and analyzed.
1-Хлор-2-гексилборирен SМе2 (1а): Спектр ЯМР 1Н (δ, м.д., CDCl3): 0.6-0.75 уш.м (3Н, С9Н3), 0.96-1.00 м (6Н, С6Н2, С7Н2, С8Н2), 1.39-1.42 м (2Н, С5Н2), 1.19 уш.с (6Н, SMe2), 2.39 м (2Н, С4Н2), 6.60 уш.с (1Н, С3Н). Спектр ЯМР 13С (δ, м.д., CDCl3): 13.89 (С9), 18.90 уш.с (SMe2), 22.45 (С8), 29.25, 30.63 (С5-6), 31.26 (С7), 35.00 уш. сигнал (С4), 128.76, 129.01 (С3), 139.74, 140.00 (С2). Спектр ЯМР 11В (δ, м.д., CDCl3): 1.89, 2.46.1-Chloro-2-hexylboronene SME 2 (1a): 1 H NMR spectrum (δ, ppm, CDCl 3 ): 0.6-0.75 br.m (3H, С 9 Н 3 ), 0.96-1.00 m (6Н , С 6 Н 2 , С 7 Н 2 , С 8 Н 2 ), 1.39-1.42 m (2Н, С 5 Н 2 ), 1.19 br.s (6Н, SMe 2 ), 2.39 m (2Н, С 4 Н 2 ), 6.60 br.s. (1Н, С 3 Н). 13 C NMR spectrum (δ, ppm, CDCl 3 ): 13.89 (C 9 ), 18.90 br s (SMe 2 ), 22.45 (C 8 ), 29.25, 30.63 (C 5-6 ), 31.26 (C 7 ), 35.00 ears. signal (C 4 ), 128.76, 129.01 (C 3 ), 139.74, 140.00 (C 2 ). 11 V NMR Spectrum (δ, ppm, CDCl 3 ): 1.89, 2.46.
ПРИМЕР 2. Аналогично пр. 1, но вместо окт-1-ина использовали дец-1-ин. Выход (16) 87%.EXAMPLE 2. Similarly, pr. 1, but instead of oct-1-in used dec-1-in. Yield (16) 87%.
1-Хлор-2-октилборирен ⋅ SМе2 (1б): Спектр ЯМР 1Н (δ, м.д., CDCl3): 0.88-0.93 уш.м (3Н, С11Н3), 1.15-1.14 м (10Н, С6Н2, С7Н2, С8Н2, С9Н2, С10Н2), 1.35 уш.с (6Н, SMe2), 1.68 м (2Н, С5Н2), 2.51 м (2Н, С4Н2), 6.60 уш.с (1Н, С3Н). Спектр ЯМР 13С (δ, м.д., CDCl3): 13.99 (С11), 19.10 (SMe2), 22.58 (С8), 29.16, 29.36, 29.39, 29.75 (С5-8), 31.80 (С9), 35.5 уш. сигнал (С4), 128.11 (С3), 139.92 (С2). Спектр ЯМР 11В (δ, м.д., CDCl3): 2.54.1-Chloro-2-octylboronene ⋅ SMe 2 (1b): 1 H NMR spectrum (δ, ppm, CDCl 3 ): 0.88-0.93 br.m (3H, С 11 Н 3 ), 1.15-1.14 m ( 10Н, С 6 Н 2 , С 7 Н 2 , С 8 Н 2 , С 9 Н 2 , С 10 Н 2 ), 1.35 br.s (6Н, SMe 2 ), 1.68 m (2Н, С 5 Н 2 ), 2.51 m (2H, C 4 H 2 ), 6.60 br.s (1H, C 3 H). 13 C NMR spectrum (δ, ppm, CDCl 3 ): 13.99 (C 11 ), 19.10 (SMe 2 ), 22.58 (C 8 ), 29.16, 29.36, 29.39, 29.75 (C 5-8 ), 31.80 ( C 9 ), 35.5 ears. signal (C 4 ), 128.11 (C 3 ), 139.92 (C 2 ). 11 V NMR Spectrum (δ, ppm, CDCl 3 ): 2.54.
ПРИМЕР 3. Аналогично примеру 1, но вместо окт-1-ина использовали фенилацетилен. Выход (1в) 75%.EXAMPLE 3. Analogously to example 1, but phenylacetylene was used instead of oct-1-in. Yield (1c) 75%.
1-Хлор-2-фенилборирен ⋅ SМе2 (1в): Спектр ЯМР 1Н (δ, м.д., CDCl3): 1.30 уш.с (6Н, SMe2), 7.00-7.20 м (6Н, В-С3Н, СНаром). Спектр ЯМР 13С (δ, м.д., CDCl3): 18.70 уш. сигнал (SMe2), 126.30-128.10 уш. сигнал (С3, Ph), 141.68 уш. сигнал (С2), 144.10 (С4). Спектр ЯМР 11В (δ, м.д., CDCl3): 2.30.1-Chloro-2-phenylboronylene ⋅ SMe 2 (1c): 1 H NMR spectrum (δ, ppm, CDCl 3 ): 1.30 br.s (6H, SMe 2 ), 7.00-7.20 m (6H, B- C 3 H, CH arom ). 13 C NMR Spectrum (δ, ppm, CDCl 3 ): 18.70 br. signal (SMe 2 ), 126.30-128.10 ears. signal (C 3 , Ph), 141.68 ears. signal (C 2 ), 144.10 (C 4 ). 11 V NMR Spectrum (δ, ppm, CDCl 3 ): 2.30.
Другие примеры, подтверждающие способ, приведены в табл.1.Other examples confirming the method are given in table 1.
Реакции проводили сначала при охлаждении до 0°С в течение 1 ч, затем при комнатной температуре (~20-22°С) 12-16 ч.The reaction was carried out first with cooling to 0 ° C for 1 h, then at room temperature (~ 20-22 ° C) 12-16 h.
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| BERNDT A. et al, 1-tert-Butylborirenes, Angew. Chem. Int. Ed., 1984, v. 23, p. 313-314. * |
| BERNDT A. et al, 1-tert-Butylborirenes, Angew. Chem. Int. Ed., 1984, v. 23, p. 313-314. BRAUNSCHWEIG H. et at, Electronic and Structural Effect of Stepwise Borylation and Quaternization on Borirene Aromaticity, J. Am. Chem. Soc., 2013, v. 135, p. 1903-1911. * |
| BRAUNSCHWEIG H. et at, Electronic and Structural Effect of Stepwise Borylation and Quaternization on Borirene Aromaticity, J. Am. Chem. Soc., 2013, v. 135, p. 1903-1911. * |
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