CN104610328A - Synthesis method of alkyl carborane derivative - Google Patents

Synthesis method of alkyl carborane derivative Download PDF

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Publication number
CN104610328A
CN104610328A CN201510056801.4A CN201510056801A CN104610328A CN 104610328 A CN104610328 A CN 104610328A CN 201510056801 A CN201510056801 A CN 201510056801A CN 104610328 A CN104610328 A CN 104610328A
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carborane
alkyl
alkylhalide group
reaction
synthetic method
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陆居有
吕剑
薛云娜
李娇毅
杜咏梅
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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    • 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
    • C07F5/05—Cyclic compounds having at least one ring containing boron but no carbon in the ring

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Abstract

The invention provides a synthesis method of an alkyl carborane derivative. The synthesis method is suitable for preparing alkyl carborane and comprises the synthesis steps 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 alkyl 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 product purification difficulty caused by rigorous reaction condition, long synthesis step, low product yield and complex system in the prior art. Meanwhile, the system method is simple in process, easy to implement and suitable for large-scale production.

Description

A kind of synthetic method of alkyl 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 alkyl carborane derivative.
Background technology
Alkyl carborane is polyhedron closed form cage structure, there is good thermostability and chemical stability, due to Boron contents and combustion heat value higher, good with solid propellant each component consistency, compositepropellent and double-basis compositepropellent can be made to obtain high combustion the speed even good ballisticperformances of superelevation combustion speed as high burningrate catalyst; In addition, be liquid under this compounds normal temperature, they except mainly plaing except adjustment of combustion rate effect, also have the function of softening agent concurrently in solid propellant.
The principal item of alkyl carborane derivative has 1-sec.-propyl-1,2-carborane, 1-normal-butyl-1,2-carborane and 1-n-hexyl-1,2-carborane (NHC), and under normal temperature, they are all liquid.They are added in the compositepropellents such as hydroxy-terminated polybutadienes (being called for short fourth hydroxyl), carboxy terminated polybutadiene (being called for short fourth carboxylic) and urethane, addition is 10 ~ 13%, play softening agent on the one hand, the combustion speed of propelling agent can be made again simultaneously to improve two to three times.Wherein most study and with practical value be NHC, " pallas pit viper " antitank rocket launcher of United States Army development adopts NHC to make its propelling agent reach the fast performance of high combustion as burning ratemodifier exactly; In addition in the substituting fourth hydroxyl conditioner formulations of " soldier " anti-ballistic system especial manufacture, also be adopt NHC as burning ratemodifier, its add-on is 13.10%, except having held concurrently except softening agent effect, propelling agent can also be made to obtain the height combustion speed of 144.78 mm/second and the high specific impulse of 245 seconds.1-n-hexyl-1,2-carborane has excellent Comprehensive performance due to it in high burning rate propellant formula, has become a carborane burning ratemodifier kind of producing in a large number and applying.
Document c, Benakki R, Teixidor F, Casab ó J.Dimethoxyethane as a Solvent forthe Synthesis of C-Monosubstituted o-Carborane Derivatives.Inorg.Chem.1995,34,3844-3845 discloses a kind of preparation method of 1-normal-butyl-1,2-carborane.The method comprise 2 steps reaction, first with 1,2-carborane be raw material, dry ethylene glycol dimethyl ether for solvent, react with highly basic n-Butyl Lithium under 0 DEG C of condition obtain carborane list lithium salts; And then, under-15 DEG C of conditions, carborane list lithium salts and n-butyl chloride generation substitution reaction obtain 1-normal-butyl-1,2-carborane.Because strong basicity n-Butyl Lithium activity is very high, carborane list lithium salts is further converted to the two lithium salts of carborane, and the latter and halohydrocarbons reaction generate two alkyl and replace carborane, cause target product yield to reduce, the more complicated difficulty also increasing aftertreatment of system; Severe reaction conditions, needs low temperature environment; This route steps is long, and target product total recovery is 67.2%.
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 alkyl carborane derivative that productive rate is high.
The synthetic method of alkyl carborane derivative provided by the invention, the structural formula of alkyl carborane derivative is as follows:
Wherein n=1,2 or 3; R is straight chained alkyl, branched-chain alkyl or cycloalkyl.
The present invention is two-step reaction, and its synthetic route is as follows:
Wherein n=1,2 or 3; X=Cl or Br; R is straight chained alkyl, branched-chain alkyl or cycloalkyl.
The method, comprises the following steps for raw material with 1-alkylhalide group-1,2-carborane and alkyl halide 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 alkyl halide 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 alkyl 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 alkyl halide 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 preferred 1:1 ~ 3 of alkyl halide 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, alkyl halide magnesium preferred alkyl magnesium bromide or alkylmagnesium chloride, 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 the 2nd step temperature of reaction is-15 DEG C; B () step of the present invention is short, be 1 step reaction, and the synthetic route that documents provides is 2 step reactions; C () product yield of the present invention improves, can reach 96.5%, the product yield of documents synthetic method is 67.2%; D () reaction system of the present invention composition is single, aftertreatment is simple, and owing to there is monosubstituted and disubstituted alkyl carborane simultaneously in documents, system is complicated, purifying products difficulty.
Embodiment
Below in conjunction with specific embodiment, the present invention is described further.
The synthesis of embodiment 1:1-n-hexyl-1,2-carborane (NHC)
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 normal-butyl magnesium bromide 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 2.25g crude product, underpressure distillation obtains colourless liquid 1-n-hexyl-1, 2-carborane 2.15g, purity 98.0%, yield 94.5%.
Structural Identification:
Ultimate analysis: molecular formula C 8h 24b 10, theoretical value: C 42.10, H 10.52; Measured value: C 42.53, H 10.77.
Infrared (KBr, cm -1): 3066,2957,2931,2860,2593,1465,1379,723.
1h NMR (deuterochloroform, δ/ppm): δ 3.55 (s, 1H), 2.18 (t, 2H, J=8.5Hz, cluster-CH 2-), 1.46-1.43 (m, 2H ,-CH 2-), 1.27-1.25 (m, 6H ,-CH 2cH 2cH 2-), 0.88 (t, 3H, J=6.8Hz ,-CH 3).
Said structure analytical data confirms that the material obtained by this synthetic method is 1-n-hexyl-1,2-carborane really.
Embodiment 2 ~ 8
Embodiment 2 ~ 8 is according to method identical in embodiment 1 synthesis 1-n-hexyl-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 93.5
3 Cuprous bromide Anhydrous tetrahydro furan 92.0
4 Cuprous iodide Anhydrous dioxane 91.8
5 Neutralized verdigris Dry ethylene glycol dimethyl ether 90.9
6 Copper sulfate Anhydrous tetrahydro furan 89.4
7 Acetylacetone copper Anhydrous tetrahydro furan 91.2
8 Trifluoroacetic acid copper Anhydrous tetrahydro furan 91.5
Embodiment 9 ~ 17
Embodiment 9 ~ 17 is according to method identical in embodiment 1 synthesis 1-n-hexyl-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 85.5
10 Tricyclohexyl phosphine 20 96.5
11 Tri-butyl phosphine 30 95.3
12 1,10-phenanthroline 40 90.3
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 85.4
16 4,5-two (diphenylphosphine)-9,9-dimethyl xanthene 40 89.8
17 Two (diphenylphosphine) ethane of 1,2- 40 93.3
Embodiment 18 ~ 23
Embodiment 18 ~ 23 is according to method identical in embodiment 1 synthesis 1-n-hexyl-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 95.5
19 0.2:1 94.5
20 0.4:1 93.3
21 0.6:1 90.3
22 0.8:1 93.6
23 1:1 92.9
Embodiment 24 ~ 29
Embodiment 24 ~ 29 is according to method identical in embodiment 1 synthesis 1-n-hexyl-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 92.5
25 0.2:1 93.5
26 0.4:1 91.3
27 0.6:1 90.3
28 0.8:1 93.6
29 1:1 92.9
Embodiment 30 ~ 34
Embodiment 30 ~ 34 is according to method identical in embodiment 1 synthesis 1-n-hexyl-1,2-carborane, difference is normal-butyl magnesium bromide 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 normal-butyl magnesium bromide ratio is on the impact of linked reaction
Embodiment Allylic bromination magnesium ratio Productive rate (%)
30 2:1 95.5
31 4:1 95.8
32 6:1 95.2
33 8:1 95.5
34 10:1 96.0
Embodiment 35 ~ 39
Embodiment 35 ~ 39 is according to method identical in embodiment 1 synthesis 1-n-hexyl-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 95.5
36 4 94.8
37 12 95.3
38 24 95.2
39 48 93.6
Embodiment 40 ~ 41
Embodiment 40 ~ 41 is according to method identical in embodiment 1 synthesis 1-n-hexyl-1,2-carborane, difference is embodiment 1 1-alkylhalide group-1 used, 2-carborane is 1-bromotrifluoromethane-1,2-carborane, 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 experimental result of embodiment 40 ~ 41 is as shown in table 7.
Table 7 1-alkylhalide group-1,2-carborane is on the impact of linked reaction
Embodiment 1-alkylhalide group-1,2-carborane Productive rate (%)
40 1-brooethyl-1,2-carborane 81.5
41 1-chloropropyl-1,2-carborane 85.5
Embodiment 42 ~ 52
Embodiment 42 ~ 52 is according to method identical in embodiment 1 synthesis 1-n-hexyl-1,2-carborane, difference is the alkyl halide magnesium that embodiment 1 adopts is normal-butyl magnesium bromide, and the alkyl halide magnesium in embodiment 42 ~ 52 is respectively ethylmagnesium bromide, n-propyl magnesium bromide, normal-butyl magnesium bromide, n-pentyl magnesium bromide, n-hexyl magnesium bromide, n-heptyl magnesium bromide, n-octyl magnesium bromide, isopropyl magnesium bromide, cyclohexyl magnesium bromide, n-butylmagnesium chloride magnesium or n-pentyl magnesium chloride.The experimental result of embodiment 42 ~ 52 is as shown in table 8.
Table 8 alkyl halide magnesium is on the impact of linked reaction
Embodiment Alkyl halide magnesium Productive rate (%)
42 Ethylmagnesium bromide 95.5
43 N-propyl magnesium bromide 94.5
44 Normal-butyl magnesium bromide 96.3
45 N-pentyl magnesium bromide 93.3
46 N-hexyl magnesium bromide 92.6
47 N-heptyl magnesium bromide 93.0
48 N-octyl magnesium bromide 94.0
49 Isopropyl magnesium bromide 94.0
50 Cyclohexyl magnesium bromide 89.5
51 N-butylmagnesium chloride magnesium 92.0
52 N-pentyl magnesium chloride 91.5

Claims (6)

1. a synthetic method for alkyl carborane derivative, the structural formula of alkyl carborane derivative is as follows:
Wherein n=1,2 or 3; R is straight chained alkyl, branched-chain alkyl or cycloalkyl;
With 1-alkylhalide group-1,2-carborane and alkyl halide magnesium for raw material, comprise the following steps:
With 1-alkylhalide group-1, 2-carborane and alkyl halide 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 alkyl carborane derivative, 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 alkyl halide 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 alkyl carborane derivative according to claim 1, 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; Alkyl halide magnesium is alkyl bromination magnesium or alkylmagnesium chloride.
3. the synthetic method of alkyl 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 alkyl 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 alkyl 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 alkyl 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.
CN201510056801.4A 2015-02-03 2015-02-03 Synthesis method of alkyl carborane derivative Pending CN104610328A (en)

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Application publication date: 20150513