CN104610334A - Synthesis method of vinyl carborane derivative - Google Patents

Synthesis method of vinyl carborane derivative Download PDF

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Publication number
CN104610334A
CN104610334A CN201510056765.1A CN201510056765A CN104610334A CN 104610334 A CN104610334 A CN 104610334A CN 201510056765 A CN201510056765 A CN 201510056765A CN 104610334 A CN104610334 A CN 104610334A
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carborane
alkylhalide group
thiazolinyl
synthetic method
reaction
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陆居有
吕剑
杜咏梅
薛云娜
李娇毅
万洪
张建伟
孙道安
王志轩
李春迎
李凤仙
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Xian Modern Chemistry Research Institute
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Xian Modern Chemistry Research Institute
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00Compounds containing elements of Groups 3 or 13 of the Periodic System
    • C07F5/02Boron compounds
    • C07F5/05Cyclic compounds having at least one ring containing boron but no carbon in the ring

Abstract

The invention provides a synthesis method of a vinyl carborane derivative. The synthesis method is suitable for preparing vinyl carborane and comprises the synthesis step of carrying out cross coupling reaction on raw materials including 1-halogenoalkyl-1, 2- carborane and allylmagnesium halide in an anhydrous ether solvent in the coexistence of an inert atmosphere, a catalyst and a ligand to obtain vinyl carborane. The synthesis method provided by the invention is mild in condition, short in step, high in yield and capable of overcoming the defect of low product yield caused by rigorous reaction condition and long synthesis step in the prior art. Meanwhile, the synthesis method is simple in process, easy to implement and suitable for large-scale production.

Description

A kind of synthetic method of thiazolinyl carborane derivative
Technical field
The present invention relates to a kind of preparation method of carborane, particularly relate to a kind of synthetic method of thiazolinyl carborane derivative.
Background technology
Carborane derivative is high due to combustion heat value, receives the concern of aviation and rocket worker always.Thiazolinyl carborane is the excellent burning ratemodifier of double-basis and composite modified double base propellant, in nitro-cotton/triglycol dinitrate/aluminium powder/ammonium perchlorate's propelling agent, such as add 1-pseudoallyl-2-third-(2-oxygen) the base carborane (IPCA) of 12%, combustion speed doubles left and right, reaches 101.6 mm/second (140 kilograms per centimeter 2).In addition, IPCA is high boiling liquid, can also play plastification, to Propellant Processing Characteristics and mechanical property useful.
Document Kabalka G W, Hondrogiannis G.Directive effects in the hydroboration of1-alkenyl derivatives of o-carborane with representative hydroborating agents.Journal of Organometallic Chemistry, 1997, 327-337 discloses a kind of 1-(3-butenyl)-1, the synthetic method of 2-carborane, the method is with 1, 2-carborane is raw material, first obtained 1-t-Butyldimethylsilyl-1 under n-Butyl Lithium effect, 2-carborane, 1-t-Butyldimethylsilyl-2-alkene butyl-1 is obtained with allyl bromide 98 generation nucleophilic substitution reaction after the latter's lithiumation, 2-carborane, finally deprotection base synthesis 1-(3-butenyl)-1 in tetrabutyl ammonium fluoride solution, 2-carborane.Because strong basicity lithium reagent activity is very high, reaction need be carried out at low temperatures, causes reaction conditions harsher; This route comprises 3 step reactions, and step is long, and target product total recovery is 38.5%.
Summary of the invention
In order to solve shortcomings and deficiencies of the prior art, the invention provides a kind of mild condition, step is short, the synthetic method of thiazolinyl carborane derivative that productive rate is high.
The synthetic method of thiazolinyl carborane derivative provided by the invention, the structural formula of thiazolinyl carborane derivative is as follows:
Wherein n=1,2 or 3.
The present invention is two-step reaction, and its synthetic route is as follows:
Wherein n=1,2 or 3; X=Cl or Br.
The method, comprises the following steps for raw material with 1-alkylhalide group-1,2-carborane and allylic halogenated magnesium:
By 1-alkylhalide group-1 in inert atmosphere, 2-carborane, catalyzer, part and anhydrous ether kind solvent add dry reaction container, stir the lower mixing solutions dripping allylic halogenated magnesium and anhydrous ether kind solvent, temperature of reaction is 10 DEG C ~ 100 DEG C, reaction times is 1h ~ 48h, obtain crude product through cancellation, extraction, drying, vacuum concentration successively, then obtain thiazolinyl carborane derivative through underpressure distillation.Wherein rare gas element is helium, nitrogen or argon gas, catalyzer is cuprous salt or cupric salt, part be carbon part, nitrogen ligand, Phosphine ligands, containing the bitooth ligand of two kinds of ligating atoms or polydentate ligand, anhydrous ether kind solvent is anhydrous diethyl ether, anhydrous tetrahydro furan, anhydrous dioxane or dry ethylene glycol dimethyl ether, 1-alkylhalide group-1,2-carborane and catalyst molar ratio are 1 ~ 20:1,1-alkylhalide group-1,2-carborane and part mol ratio are 1 ~ 20:1,1-alkylhalide group-1,2-carborane and allylic halogenated magnesium mol ratio are 1:1 ~ 10.
Rare gas element preferred nitrogen of the present invention, the preferred copper halide of catalyzer, cuprous halide, neutralized verdigris, copper sulfate, acetylacetone copper or trifluoroacetic acid copper, part triphenylphosphine, tricyclohexyl phosphine, tri-butyl phosphine, N-Methyl pyrrolidone, 1,10-phenanthroline, bicycloheptadiene, three (2-pyridylmethyl) amine, R-(+)-1,1'-dinaphthalene-2, the two diphenyl phosphine, 4 of 2'-, two (diphenylphosphine)-9 of 5-, 9-dimethyl xanthene or two (diphenylphosphine) ethane of 1,2-.
1-alkylhalide group-1 of the present invention, 2-carborane and catalyst molar ratio preferably 5 ~ 20:1,1-alkylhalide group-1,2-carborane and part mol ratio preferably 5 ~ 20:1,1-alkylhalide group-1,2-carborane and allylic halogenated preferred 1:1 ~ 3 of magnesium mol ratio, temperature of reaction preferably 25 DEG C ~ 40 DEG C, reaction times preferred 6h ~ 12h.
1-alkylhalide group-1,2-carborane of the present invention preferred 1-brooethyl-1,2-carborane, 1-bromotrifluoromethane-1,2-carborane or 1-chloropropyl 1,2-carborane, allylic halogenated magnesium is allylic bromination magnesium or allylmgcl, the preferred anhydrous tetrahydro furan of anhydrous ether kind solvent.
Advantage of the present invention: (a) reaction conditions of the present invention is gentle, and without the need to low temperature environment, in documents, synthetic method needs cold condition, and especially three-step reaction temperature is-76 DEG C; B () step of the present invention is short, be 1 step reaction, and the synthetic route that documents provides is 3 step reactions; C () product yield of the present invention improves, can reach 96.5%, the product yield of documents synthetic method is 38.5%.
Embodiment
Below in conjunction with specific embodiment, the present invention is described further.
The synthesis of embodiment 1:1-(4-pentenyl)-1,2-carborane
By 2.51g (10mmol) 1-bromotrifluoromethane-1 under nitrogen atmosphere, 2-carborane, 0.05g (0.5mmol) cuprous chloride, 0.05g (0.5mmol) N-Methyl pyrrolidone and 20mL anhydrous tetrahydro furan add in 100mL four-hole boiling flask, 10mmol allylic bromination magnesium and anhydrous tetrahydro furan mixing solutions is added under stirring, temperature of reaction is 25 DEG C, stopped reaction after 8h, saturated ammonium chloride solution is added in system, extracted with diethyl ether 30mL × 3 time, merge organic phase, anhydrous magnesium sulfate drying, steaming desolventizes, obtain 2.20g crude product, underpressure distillation obtains colourless liquid 1-(4-pentenyl)-1, 2-carborane 1.72g, purity 98.5%, yield 80.9%.
Structural Identification: 1-(4-pentenyl)-1,2-carborane
Ultimate analysis: molecular formula C 7h 20b 10, theoretical value: C 39.62, H 9.43; Measured value: C 39.70, H 9.36.
Infrared (KBr, cm -1): 3065,2979,2957,2935,2866,2594,1459,1440,993,917,723.
1h NMR (deuterochloroform, δ/ppm): δ 5.74-5.66 (m, 1H), 5.03-5.02 (m, 1H), 5.00-4.99 (m, 1H), 3.54 (s, 1H), 2.21-2.17 (m, 2H), 2.05-2.01 (m, 2H), 1.60-1.54 (m, 2H).
Said structure analytical data confirms that the material obtained by this synthetic method is 1-(4-pentenyl)-1,2-carborane really.
Embodiment 2 ~ 8
Embodiment 2 ~ 8 is according to method identical in embodiment 1 synthesis 1-(4-pentenyl)-1,2-carborane, difference is the catalyzer that embodiment 1 adopts is cuprous chloride, and the catalyzer in embodiment 2 ~ 8 is respectively cupric chloride, cuprous bromide, cuprous iodide, neutralized verdigris, copper sulfate, acetylacetone copper, trifluoroacetic acid copper.The experimental result of embodiment 2 ~ 8 is as shown in table 1.
Table 1 catalysts and solvents is on the impact of cross-coupling reaction
Embodiment Catalyzer Solvent Productive rate (%)
2 Cupric chloride Anhydrous diethyl ether 70.2
3 Cuprous bromide Anhydrous tetrahydro furan 66.5
4 Cuprous iodide Anhydrous dioxane 75.5
5 Neutralized verdigris Dry ethylene glycol dimethyl ether 80.3
6 Copper sulfate Anhydrous tetrahydro furan 83.5
7 Acetylacetone copper Anhydrous tetrahydro furan 78.6
8 Trifluoroacetic acid copper Anhydrous tetrahydro furan 85.4
Embodiment 9 ~ 17
Embodiment 9 ~ 17 is according to method identical in embodiment 1 synthesis 1-(4-pentenyl)-1,2-carborane, difference is the part that embodiment 1 adopts is N-Methyl pyrrolidone, part in embodiment 9 ~ 17 is respectively triphenylphosphine, tricyclohexyl phosphine, tri-butyl phosphine, 1,10-phenanthroline, bicycloheptadiene, three (2-pyridylmethyl) amine, R-(+)-1,1'-dinaphthalene-2, the two diphenyl phosphine, 4 of 2'-, two (diphenylphosphine)-9 of 5-, 9-dimethyl xanthene, 1,2-two (diphenylphosphine) ethane.The experimental result of embodiment 9 ~ 17 is as shown in table 2.
Table 2 part and temperature of reaction are on the impact of linked reaction
Embodiment Part Temperature of reaction (DEG C) Productive rate (%)
9 Triphenylphosphine 10 75.5
10 Tricyclohexyl phosphine 20 76.5
11 Tri-butyl phosphine 30 65.3
12 1,10-phenanthroline 40 70.3
13 Bicycloheptadiene 60 85.6
14 Three (2-pyridylmethyl) amine 80 88.5
15 The two diphenyl phosphine of R-(+)-1,1'-dinaphthalene-2,2'- 100 75.4
16 4,5-two (diphenylphosphine)-9,9-dimethyl xanthene 40 79.8
17 Two (diphenylphosphine) ethane of 1,2- 40 83.3
Embodiment 18 ~ 23
Embodiment 18 ~ 23 is according to method identical in embodiment 1 synthesis 1-(4-pentenyl)-1,2-carborane, difference is catalyzer and 1-bromotrifluoromethane-1 in embodiment 1, the mol ratio of 2-carborane is 0.05:1, and catalyzer in embodiment 18 ~ 23 and 1-bromotrifluoromethane-1,2-carborane mol ratio are respectively 0.1:1,0.2:1,0.4:1,0.6:1,0.8:1,1:1.The experimental result of embodiment 18 ~ 23 is as shown in table 3.
Table 3 catalyst ratio is on the impact of linked reaction
Embodiment Catalyst ratio Productive rate (%)
18 0.1:1 85.5
19 0.2:1 86.5
20 0.4:1 85.3
21 0.6:1 80.3
22 0.8:1 83.6
23 1:1 88.9
Embodiment 24 ~ 29
Embodiment 24 ~ 29 is according to method identical in embodiment 1 synthesis 1-(4-pentenyl)-1,2-carborane, difference is part and 1-bromotrifluoromethane-1 in embodiment 1, the mol ratio of 2-carborane is 0.05:1, and part in embodiment 24 ~ 29 and 1-bromotrifluoromethane-1,2-carborane mol ratio are respectively 0.1:1,0.2:1,0.4:1,0.6:1,0.8:1,1:1.The experimental result of embodiment 24 ~ 29 is as shown in table 4.
Table 4 part ratio is on the impact of linked reaction
Embodiment Part ratio Productive rate (%)
24 0.1:1 75.5
25 0.2:1 76.5
26 0.4:1 75.3
27 0.6:1 70.3
28 0.8:1 73.6
29 1:1 78.9
Embodiment 30 ~ 34
Embodiment 30 ~ 34 is according to method identical in embodiment 1 synthesis 1-(4-pentenyl)-1,2-carborane, difference is allylic bromination magnesium and 1-bromotrifluoromethane-1 in embodiment 1, the mol ratio of 2-carborane is 1:1, and allylic bromination magnesium in embodiment 30 ~ 34 and 1-bromotrifluoromethane-1,2-carborane mol ratio are respectively 2:1,4:1,6:1,8:1,10:1.The experimental result of embodiment 30 ~ 34 is as shown in table 5.
Table 5 allylic bromination magnesium ratio is on the impact of linked reaction
Embodiment Allylic bromination magnesium ratio Productive rate (%)
30 2:1 78.5
31 4:1 77.5
32 6:1 78.3
33 8:1 80.3
34 10:1 83.6
Embodiment 35 ~ 39
Embodiment 35 ~ 39 is according to method identical in embodiment 1 synthesis 1-(4-pentenyl)-1,2-carborane, and difference is the reaction times of embodiment 1 is 8h, and the reaction times in embodiment 35 ~ 39 is respectively 1,4,12,24,48.The experimental result of embodiment 35 ~ 39 is as shown in table 6.
Table 6 reaction times is on the impact of linked reaction
Embodiment Reaction times (h) Productive rate (%)
35 1 68.5
36 4 70.5
37 12 78.3
38 24 80.3
39 48 79.6
Embodiment 40 ~ 42
Embodiment 40 ~ 42 is according to method identical in embodiment 1 synthesis 1-(4-pentenyl)-1,2-carborane, difference is embodiment 1 1-alkylhalide group-1,2-used carborane is 1-bromotrifluoromethane-1,2-carborane, allylic halogenated magnesium is allylic bromination magnesium, and 1-alkylhalide group-1, the 2-carborane in embodiment 40 ~ 41 is respectively 1-brooethyl-1,2-carborane, 1-chloropropyl-1,2-carborane, the allylic halogenated magnesium of embodiment 42 is allylmgcl.The experimental result of embodiment 40 ~ 42 is as shown in table 7.
Table 71-alkylhalide group-1,2-carborane is on the impact of linked reaction
Embodiment 1-alkylhalide group-1,2-carborane Allylic halogenated magnesium Productive rate (%)
40 1-brooethyl-1,2-carborane Allylic bromination magnesium 62.5
41 1-chloropropyl-1,2-carborane Allylic bromination magnesium 65.5
42 1-bromotrifluoromethane-1,2-carborane Allylmgcl 78.5
Structural Identification: 1-(3-butenyl)-1,2-carborane
Ultimate analysis: molecular formula C 6h 18b 10, theoretical value: C 36.36, H 9.09; Measured value: C 36.40, H 9.10.
Infrared (KBr, cm -1): 3068,2974,2953,2930,2864,2592,1459,1447,991,918,723.
1h NMR (deuterochloroform, δ/ppm): δ 5.74-5.69 (m, 1H), 5.01-4.98 (m, 1H), 4.97-4.95 (m, 1H), 3.52 (s, 1H), 2.59-2.53 (m, 2H), 2.29-2.25 (m, 2H).
Said structure analytical data confirms that the material obtained by this synthetic method is 1-(3-butenyl)-1,2-carborane really.
Structural Identification: 1-(5-hexenyl)-1,2-carborane
Ultimate analysis: molecular formula C 8h 22b 10, theoretical value: C 42.47, H 9.73; Measured value: C 42.40, H 9.78.
Infrared (KBr, cm -1): 3066,2976,2958,2933,2868,2595,1460,1444,996,915,722.
1h NMR (deuterochloroform, δ/ppm): δ 5.75-5.68 (m, 1H), 5.05-5.03 (m, 1H), 5.01-4.97 (m, 1H), 3.56 (s, 1H), 2.22-2.19 (m, 2H), 2.02-2.00 (m, 2H), 1.62-1.55 (m, 2H), 1.33-1.30 (m, 2H).
Said structure analytical data confirms that the material obtained by this synthetic method is 1-(5-hexenyl)-1,2-carborane really.

Claims (6)

1. a synthetic method for thiazolinyl carborane derivative, the structural formula of thiazolinyl carborane derivative is as follows:
Wherein n=1,2 or 3;
With 1-alkylhalide group-1,2-carborane and allylic halogenated magnesium for raw material, comprise the following steps:
With 1-alkylhalide group-1, 2-carborane and allylic halogenated magnesium are raw material, at inert atmosphere, under catalyzer and part exist jointly, there is cross-coupling reaction in anhydrous ether kind solvent and obtain carborane radical alkene derivatives, wherein catalyzer is cuprous salt or cupric salt, part is carbon part, nitrogen ligand, Phosphine ligands, containing bitooth ligand or the polydentate ligand of two kinds of ligating atoms, 1-alkylhalide group-1, 2-carborane and catalyst molar ratio are 1 ~ 20:1, 1-alkylhalide group-1, 2-carborane and part mol ratio are 1 ~ 20:1, 1-alkylhalide group-1, 2-carborane and allylic halogenated magnesium mol ratio are 1:1 ~ 10, temperature of reaction is 10 DEG C ~ 100 DEG C, reaction times is 1h ~ 48h.
2. the synthetic method of thiazolinyl carborane derivative according to claim 1, it is characterized in that described 1-alkylhalide group-1,2-carborane is 1-brooethyl-1,2-carborane, 1-bromotrifluoromethane-1,2-carborane or 1-chloropropyl-1,2-carborane, allylic halogenated magnesium is allylic bromination magnesium or allylmgcl.
3. the synthetic method of thiazolinyl carborane derivative according to claim 1, is characterized in that described catalyzer is copper halide, cuprous halide, neutralized verdigris, copper sulfate, acetylacetone copper or trifluoroacetic acid copper; Described part is triphenylphosphine, tricyclohexyl phosphine, tri-butyl phosphine, N-Methyl pyrrolidone, 1,10-phenanthroline, bicycloheptadiene, three (2-pyridylmethyl) amine, R-(+)-1,1'-dinaphthalene-2, the two diphenyl phosphine, 4 of 2'-, two (diphenylphosphine)-9 of 5-, 9-dimethyl xanthene or two (diphenylphosphine) ethane of 1,2-.
4. the synthetic method of thiazolinyl carborane derivative according to claim 1, is characterized in that described rare gas element is helium, nitrogen or argon gas; Described anhydrous ether kind solvent is anhydrous diethyl ether, anhydrous tetrahydro furan, anhydrous dioxane or dry ethylene glycol dimethyl ether.
5. the synthetic method of thiazolinyl carborane derivative according to claim 1, it is characterized in that 1-alkylhalide group-1,2-carborane and catalyst molar ratio are 5 ~ 20:1,1-alkylhalide group-1,2-carborane and part mol ratio are 5 ~ 20:1,1-alkylhalide group-1,2-carborane and alkyl halide magnesium mol ratio are 1:1 ~ 3.
6. the synthetic method of thiazolinyl carborane derivative according to claim 1, it is characterized in that temperature of reaction is 25 DEG C ~ 40 DEG C, the reaction times is 6h ~ 12h.
CN201510056765.1A 2015-02-03 2015-02-03 Synthesis method of vinyl carborane derivative Pending CN104610334A (en)

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CN110437269A (en) * 2019-09-17 2019-11-12 西安近代化学研究所 A kind of B (4,5) alkyl replaces the synthetic method of caborane compounds
CN111303194A (en) * 2020-04-07 2020-06-19 西安近代化学研究所 Synthesis method of B (4,5) alkenyl substituted carborane derivative

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CN110437269A (en) * 2019-09-17 2019-11-12 西安近代化学研究所 A kind of B (4,5) alkyl replaces the synthetic method of caborane compounds
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CN111303194A (en) * 2020-04-07 2020-06-19 西安近代化学研究所 Synthesis method of B (4,5) alkenyl substituted carborane derivative

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Application publication date: 20150513