CN102584878B - A kind of ionic liquid containing divalent boron cluster negative ion and preparation method thereof - Google Patents

A kind of ionic liquid containing divalent boron cluster negative ion and preparation method thereof Download PDF

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CN102584878B
CN102584878B CN201210014812.2A CN201210014812A CN102584878B CN 102584878 B CN102584878 B CN 102584878B CN 201210014812 A CN201210014812 A CN 201210014812A CN 102584878 B CN102584878 B CN 102584878B
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boron cluster
cluster ion
dissolved
ion liquid
acetonitrile
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CN102584878A (en
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赵国英
周娜
孙剑
李海方
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Institute of Process Engineering of CAS
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Abstract

The present invention relates to a kind of containing dianion [closo-B 12cl 12] 2-boron cluster ion liquid and preparation method thereof, belong to new chemical material and preparing technical field thereof.The ionic liquid that the present invention relates to belongs to the one of boron cluster ion liquid, and we for raw material, prepare the Novel boron cluster ion liquid containing different cationic structural with sodium borohydride, iodine, N-alkyl imidazole, quaternary ammonium salt, quaternary alkylphosphonium salt and N-Fixanol etc.Such boron cluster ion liquid has been applied to the field of ionic liquid as the weak coordination melting salt of one novel " green ", " cleaning ", compensate for the shortcoming of traditional weak coordinated ionic liquid in catalyzed reaction.With other boron cluster ion liquid phase ratios, the boron cluster ion liquid that the present invention relates to has high thermostability and chemical stability, overcome the shortcoming that fusing point is high simultaneously, realize the designability of boron cluster ion liquid fusing point first, urge the application of functionalization boron cluster ion liquid in catalyzed reaction.

Description

A kind of ionic liquid containing divalent boron cluster negative ion and preparation method thereof
Technical field:
The invention belongs to field of ionic liquid, specifically relate to a kind of ionic liquid and preparation method thereof, especially a kind of containing dianion [closo-B 12cl 12] 2-the preparation method of boron cluster ion liquid and such ionic liquid.
Background technology:
Ionic liquid, is also referred to as " room temperature molten salt ", and referring to the complete compound be made up of ion be in a liquid state under the condition of room temperature or a little higher than room temperature, is novel " green solvent " that the class emerged in recent years receives much concern.Compared with traditional molecular solvent, it is wide that ionic liquid has liquid state range, good chemistry and thermostability, the series of advantages such as vapour pressure is lower, it also has adjustable physical and chemical performance in addition, for some specifically reaction can design ionic liquid targetedly and, to carry out catalysis, thus show huge potentiality and application prospect in the Green Process of current chemical, be regarded as solvent the most rising in Green Chemistry and cleaning procedure.
Wherein, boron cluster ion liquid is a kind of ionic liquid with extremely weak Coordinate property, and except the special property of ionic liquid, its negatively charged ion also has weak nucleophilic, character such as reduction inertia and electric charge dispersion etc.; Simultaneously by carrying out modified with functional group to positively charged ion, a kind of boron cluster ion liquid of functionalization can be formed.Traditional weakly coordinating anion, such as BF 4 -, PF 6 -and CF 3sO 3 -, easily decompose the hydrofluoric acid generating and there is highly corrosive, make it in catalyzed reaction, receive serious restriction.Boron cluster anions has been applied to the field of ionic liquid as the negatively charged ion of one novel " green ", " cleaning ", compensate for the shortcoming of traditional weak coordinated ionic liquid.2000, Reed prepared first containing carborane anion (CB 11h 12 -, CB 11h 6cl 6 -, and CB 11h 6br 6 -) ionic liquid, and propose weak coordination boron cluster ion liquid first.Go deep into along with to the research of boron cluster ion liquid, a large amount of ionic liquid containing boron cluster anions is produced out.2008, the people such as Larsen were to [nido-C 2b 9h 12] -[closo-CB 11h 12] -make and comparing, and point out that the former has lower fusing point; In the same year, the people such as Gabel have prepared containing [closo-B 12h 11nR 3] -ionic liquid at room temperature, and find the positive ions such as the proton that potassium, lithium are even non-solvated also can with [closo-B 12h 11nR 3] -generate low melting point ion solid.2009, Clara existing some boron cluster ion liquid of systematic research on the basis of previous work.
Containing divalent boron cluster negative ion [closo-B 12cl 12] 2-ionic liquid belong to the one of boron cluster ion liquid, this anionoid is combined with the positively charged ion such as imidazoles, quaternary ammonium, quaternary phosphonium and pyridine by respectively, and generating Novel boron cluster ion liquid belongs to reported first, and its preparation method is also that the present invention mentions first.[closo-B in the present invention 12cl 12] 2-derivative not only may be used for stable active positively charged ion and strong electrophilic reagent, can also be used to prepare diproton super acid H 2b 12c 12with strong methylating reagent Me 2b 12cl 12.In addition, the boron cluster ion liquid in the present invention overcomes the high shortcoming of fusing point that self structure high degree of symmetry brings, and by methods involving, the fusing point of such boron cluster ion liquid can change a lot thereupon, thus, realize its fusing point designability.
Summary of the invention:
Technical problem to be solved by this invention is: provide a kind of containing dianion [closo-B 12cl 12] 2-novel boron cluster ion liquid and preparation method thereof.Boron cluster ion liquid in the present invention overcomes the high shortcoming of fusing point, and by methods involving, the fusing point of such boron cluster ion liquid can change a lot thereupon, thus, realize its fusing point designability.In addition, the invention provides one above-mentioned containing dianion [closo-B 12cl 12] 2-the preparation method of boron cluster ion liquid.
Technical scheme of the present invention is:
The invention provides a class boron cluster ion liquid, its structural formula is as follows: negatively charged ion is divalence, and structure is [closo-B 12cl 12] 2- positively charged ion is 1. [R 1r 2mim] +, wherein R 1=C nh 2n+1, n=0 ~ 16/C nh 2noH, n=2 ~ 6; R 2=CH 3; 2. [N aaam] +, wherein a=C nh 2n+1, n=1 ~ 4; M=C nh 2n+1, n=2 ~ 16/C nh 2noH, n=2 ~ 6; 3. [P pppm] +, wherein p=phenyl; M=C nh 2n+1, n=2 ~ 16/C nh 2noH, n=2 ~ 6; 4. [PyR] +, wherein, R=C nh 2n+1, n=1 ~ 16; Boron cluster ion liquid structure after combination is formula I, formula II, shown in formula III and formula IV:
Imidazolium
formula I
Wherein R 1=R 2=CH 3; R 3=C nh 2n+1, n=0 ~ 16/C nh 2noH, n=2 ~ 6;
Ammonium
formula II
Wherein R 1=R 2=R 3=C nh 2n+1, n=1 ~ 4; R 4=C nh 2n+1, n=2 ~ 16/C nh 2noH, n=2 ~ 6;
Phosphonium
formula III
Wherein R 1=C nh 2n+1, n=2 ~ 16/C nh 2noH, n=2 ~ 6;
Pyridinium
formula IV
Wherein, R=C nh 2n+1, n=1 ~ 16;
Provided by the invention containing dianion [closo-B 12cl 12] 2-the preparation method of boron cluster ion liquid is one of following any two kinds of methods:
Method one, comprises the following steps:
1., under the condition of argon shield, by NaBH 4be dissolved in diglyme, while vigorous stirring, be warming up to 100 DEG C; Now, elemental iodine be dissolved in diglyme and dropwise instill in reaction flask in 6h; After dropwising, reaction system is 100 DEG C in temperature, stirs 12h under argon shield, and impelling reacts completely generates Na [B 3h 8].
2., next day, oil bath is warming up to 185 DEG C, reaction system refluxes stopped reaction after 24h under argon shield, and underpressure distillation, except desolventizing diglyme, obtains product Na 2[B 12h 12] and associated byproducts NaBH 4, NaI.
3., by upper step except residual solid after desolventizing is dissolved in water, then carefully drip concentrated hydrochloric acid wherein, the solution storage after acidifying is in refrigerator overnight, and temperature is+6 DEG C, and the boric acid of generation is crossed and filtered.
4., add triethylamine in the filtrate of upwards step removing boric acid, after the turbid solution that obtains stirs 12h, to filter and by the dissolution of solid that obtains in water, filtered while hot after 50 DEG C of stirred in water bath 2h, temperature 50-60 DEG C, removing soluble impurity boric acid etc., product [NEt 3h] 2[B 12h 12] after filtration, vacuum 80 DEG C of dry 12h obtain.
5., [the NEt will obtained 3h] 2[B 12h 12] being dissolved in the cesium hydroxide also adding 3 equivalents in water wherein, the solid filtering of generation, boiling water recrystallization, vacuum 80 DEG C of dry 8h obtain product C s 2[B 12h 12].
6., under argon shield, by Cs 2[B 12h 12] be dissolved in acetonitrile, then slowly drip SO wherein 2c l2; After dropwising, be warming up to 65 DEG C of backflow 24h, stopped reaction, distillation removing solvent acetonitrile, generate white powder and utilize boiling water recrystallization to remove soluble impurity, obtained product C s 2[B 12cl 12].
7., by Cs 2[B 12cl 12] be dissolved in acetonitrile, Cs in molar ratio 2[B 12cl 12]: substance A=1: substance A to be dissolved in acetonitrile and to join in reaction flask by 2, and stirring at room temperature 12h, filters insoluble impurity CsCl, to revolve after steaming removing solvent acetonitrile residual solid powder through washing, vacuum 100 DEG C of dry 12h, obtained [R 1r 2mim] 2[B 12cl 12], [P pppm] 2[B 12cl 12] and [PyR] 2[B 12cl 12].
Wherein substance A is 1. [R 1r 2mim] Cl, wherein R 1=C nh 2n+1, n=0 ~ 16/C nh 2noH, n=2 ~ 6; R 2=CH 3; 2. [P pppm] Br, wherein p=phenyl; M=C nh 2n+1, n=2 ~ 16/C nh 2noH, n=2 ~ 6; 3. [PyR] Br, wherein, R=C nh 2n+1, n=1 ~ 16;
Method two, comprises the following steps:
Step 1.-6. with method one, obtained Cs 2[B 12cl 12].
7., substance B being dissolved in volume ratio is in the mixed solvent of 1: 1 acetonitrile and water, then dropwise joins Cs 2[B 12cl 12] acetonitrile solution in, stirring at room temperature 12h, revolve steam removing solvent acetonitrile, the pressed powder obtained is dissolved in acetonitrile again, after filtration, revolves steamings, washing, vacuum 70 DEG C of dry 12h, obtain [N a aam] 2[B 12cl 12].Its mol ratio is Cs 2[B 12cl 12]: substance B=1: 2;
Wherein substance B is [N aaam] Br, wherein a=C nh 2n+1, n=1 ~ 4; M=C nh 2n+1, n=2 ~ 16/C nh 2noH, n=2 ~ 6;
The general formula of this reaction is:
The invention has the beneficial effects as follows:
Provided by the invention containing dianion [closo-B 12cl 12] 2-boron cluster ion liquid and preparation thereof compared with prior art have following unusual effect:
(1) the present invention is to provide a kind of novel extremely weak coordinated ionic liquid, develop the new variety of ionic liquid.
(2) provided by the invention containing dianion [closo-B 12cl 12] 2-boron cluster ion liquid overcomes the high shortcoming of fusing point that this type of ionic liquid brings because of self structure high degree of symmetry, and by methods involving, the fusing point of such boron cluster ion liquid can change a lot thereupon, thus, realize its fusing point designability.
(3) with other boron cluster ion liquid phase ratios, the invention provides boron cluster ion liquid, its dianion [closo-B 12cl 12] 2-have icosahedron structure, this makes such ionic liquid have higher thermostability and chemical stability.
Therefore, this invention exploits a kind of novel extremely weak coordinated ionic liquid, and to some extent solve containing dianion [closo-B 12cl 12] 2-the shortcoming that boron cluster ion liquid fusing point is high, achieves the designability of boron cluster ion liquid fusing point.
Accompanying drawing explanation
Fig. 1, Fig. 2, Fig. 3, Fig. 4 are respectively the nucleus magnetic hydrogen spectrum of the ionic liquid containing divalent boron cluster negative ion of preparation in embodiment 1,2,3,4.Fig. 5, Fig. 6, Fig. 7, Fig. 8 are respectively the electrospray ionization mass spectrum containing the ionic liquid of divalent boron cluster negative ion prepared in embodiment 1,2,3,4, and (upper figure is positive mass spectrum figure, and figure below is ion mass spectrum figure
Embodiment
Describe the present invention further below in conjunction with example, specific examples does not limit the claims in the present invention.
Embodiment 1:
synthesis and characterization:
(1) under argon shield condition, by 9.79g NaBH 4(0.26mol) be dissolved in 40ml diglyme, 100 DEG C are warming up to while vigorous stirring, then being dissolved in by 20.56g elemental iodine (0.081mol) in 35ml diglyme and dropwise instilling in reaction flask in 6h, the hydrogen produced in reaction process and diborane overflow from the bubbler that silicone oil is housed; After dropwising, reaction system is 100 DEG C in temperature, stirs 12h under argon shield, and impelling reacts completely generates Na [B 3h 8].
(2) next day, oil bath is warming up to 185 DEG C, refluxes under argon shield 24h, stopped reaction, underpressure distillation except after desolventizing diglyme white powder material (comprise product Na 2[B 12h 12] and impurity Na [BH 4], NaI).
(3) upper step being obtained white powder is dissolved in the 60ml aqueous solution, then carefully 28ml concentrated hydrochloric acid is dripped wherein, reaction process generates with hydrogen, settled solution after acidifying is stored in refrigerator overnight, temperature is+6 DEG C, can be observed clear crystal boric acid (1.5g) next day to suspend in the solution, filtered and obtain settled solution.
(4) upwards walk in the settled solution obtained and add 40ml triethylamine (PH=9-10), now a large amount of white precipitate generates, and after turbid solution stirring at room temperature 14h, filters to obtain white powder 8g; This white powder to be dissolved in the 25ml aqueous solution and to stir 2h at 50 DEG C, filtered while hot (50-60 DEG C) removing soluble impurity, product [NEt 3h] 2[B 12h 12] vacuum 80 DEG C of dry 12h.
(5) in a large beaker, to [the NEt be dissolved in the 100ml aqueous solution 3h] 2[B 12h 12] 10g adds the CsOH of 3 equivalents, the precipitation of generation is after filtration, boiling water recrystallization, vacuum 80 DEG C of dry 8h obtain product C s 2[B 12h 12].
(6) under argon shield, by 5.0g Cs 2[B 12h 12] (0.012mol) be dissolved in 150ml acetonitrile (heavily steam), then slowly drips 150ml SO wherein 2cl 2(1.85mol), turbid solution becomes clarification very soon, and be warming up to 65 DEG C of backflow 24h stopped reaction after dropwising, distillation removing solvent acetonitrile, the white powder obtained uses boiling water recrystallization removing soluble impurity to obtain product C s 2[B 12cl 12] 8g.
(7) by 59mg [C 2mim] Cl (0.4mmol) is dissolved in 5ml acetonitrile, and then joined another and dissolved 164mgCs 2[B 12cl 12] (0.2mmol) 10ml acetonitrile in, reaction becomes muddy by clarification at once, filters after stirring at room temperature 12h, and mother liquor revolves and steams removing solvent acetonitrile, and the white powder obtained is through washing (3 × 2.5cm 3), vacuum 100 DEG C of dry 12h, obtain 149mg white powder [C 2mim] 2[B 12cl 12], productive rate 96%. 1h NMR (600MHz, DMSO-d 6): 9.255 (s, 1H), 7.812 (s, 1H), 7.724 (s, 1H), 4.214 (q, J=7.6Hz, 2H), 3.861 (s, 3H), 1.420 (t, J=6.8Hz, 3H); Ultimate analysis (calculated value %): C=18.92 (18.54), H=2.903 (2.85), N=7.15 (7.21), Cl=54.95 (54.72); ESI (m/z +/-): Cation 111.0883, Anion 277.3695; Mp=265 DEG C, TGA=480 DEG C.
Embodiment 2:
synthesis and characterization:
Step (1)-(6), with embodiment 1, obtain Cs 2[B 12cl 12].
(7) by 146mg [N 11116] Br (0.4mmol) be dissolved in volume ratio be 1: 1 acetonitrile and water mixed solvent 10ml in, then it is dropwise joined and is dissolved with 164mg Cs 2[B 12cl 12] (0.2mmol) 10ml acetonitrile in, revolve after stirring at room temperature 12h and steam removing solvent acetonitrile, pressed powder is dissolved in 15ml acetonitrile, after filtering out insoluble impurity CsCl, mother liquor revolves and steams removing solvent acetonitrile, and the white powder obtained is through washing (3 × 2.5cm 3), vacuum 70 DEG C of dry 12h obtain 215mg [N 11116] 2[B 12cl 12], productive rate 96%. 1hNMR (600MHz, DMSO-d 6): 3.033 (s, 9H), 3.255 (t, J=8.3Hz, 2H), 1.665 (q, 2H), 1.294-1.240 (m, 26H), 0.857 (t, J=6.2Hz, 3H); Ultimate analysis (calculated value %): C=41.33 (40.60), H=7.458 (7.53), N=2.83 (2.49), Cl=37.79 (37.84); ESI (m/z +/-): Cation 284.3228, Anion 277.3697; Mp=104 DEG C, TGA=390 DEG C.
Embodiment 3:
synthesis and characterization:
Step (1)-(6), with embodiment 1, obtain Cs 2[B 12cl 12].
(7) by 148mg [P ppp2] Br (0.4mmol) is dissolved in 5ml acetonitrile, then joined another and be dissolved with 164mg Cs 2[B 12cl 12] (0.2mmol) 10ml acetonitrile in, reaction solution becomes muddy by clarification immediately, filters after stirring at room temperature 12h, and mother liquor revolves and steams removing solvent acetonitrile and obtain pale yellow powder, through washing (3 × 2.5cm 3), vacuum 100 DEG C of dry 12h, obtain 209mg [P ppp2] 2[B 12cl 12], productive rate 92%. 1h NMR (600MHz, DMSO-d 6): 7.801-7.788 (m, 15H), 3.624 (q, J=7.6Hz, 2H), 1.225 (t, J=7.6Hz, 3H); Ultimate analysis (calculated value %): C=42.47 (42.22), H=3.644 (3.54), Cl=37.12 (37.39); ESI (m/z +/-): Cation 291.1216, Anion 277.3693; Mp=293 DEG C, TGA=494 DEG C.
Embodiment 4:
synthesis and characterization:
Step (1)-(6), with embodiment 1, obtain Cs 2[B 12cl 12].
(7) 86mg [PyB] Br (0.4mmol) is dissolved in 5ml acetonitrile, is then joined another and dissolve 164mg Cs 2[B 12cl 12] (0.2mmol) 10ml acetonitrile in, reaction solution becomes muddy by clarification at once, filters after stirring at room temperature 12h, and mother liquor revolves and steams removing solvent acetonitrile and obtain pale yellow powder, through washing (3 × 2.5cm 3), vacuum 100 DEG C of dry 12h, obtain 149mg [P ppp2] 2[B 12cl 12], productive rate 90%. 1hNMR (600MHz, DMSO-d 6): 9.103 (d, J=5.5Hz, 2H), 8.611 (t, J=6.8Hz, 1H), 8.168 (t, J=7.6Hz, 2H), 4.608 (t, J=7.6Hz, 2H), 1.902 (q, 2H), 1.286 (s, 2H), 0.916 (t, J=7.6Hz, 3H); Ultimate analysis (calculated value %): C=26.48 (26.12), H=3.396 (3.41), N=3.40 (3.39), Cl=51.26

Claims (3)

1. containing dianion [closo-B 12cl 12] 2-boron cluster ion liquid, its structure is shown below:
2. prepare a method for boron cluster ion liquid, the structure of wherein said ionic liquid is concrete synthetic route is as follows:
3. method according to claim 2, is characterized in that, the concrete synthesis step of described ionic liquid is as follows:
1., under the condition of argon shield, by NaBH 4be dissolved in diglyme, while vigorous stirring, be warming up to 100 DEG C; Now, elemental iodine be dissolved in diglyme and dropwise instilled in reaction flask in 6 hours; After dropwising, reaction system is 100 DEG C in temperature, stirs 12h under argon shield, and impelling reacts completely generates Na [B 3h 8];
2., next day, oil bath is warming up to 185 DEG C, stopped reaction after reaction system refluxes 24 hours under argon shield, underpressure distillation, except desolventizing diglyme, obtains product Na 2[B 12h 12] and associated byproducts NaBH 4, NaI;
3., by upper step except residual solid after desolventizing is dissolved in water, then carefully drip concentrated hydrochloric acid wherein, the solution storage after acidifying is in refrigerator overnight, and temperature is+6 DEG C, and the boric acid of generation is crossed and filtered;
4., add triethylamine in the filtrate of upwards step removing boric acid, after the turbid solution that obtains stirs 12h, to filter and by the dissolution of solid that obtains in water, filtered while hot after 50 DEG C of stirred in water bath 2h, temperature is 50-60 DEG C, removing soluble impurity boric acid etc., product [NEt 3h] 2[B 12h 12] after filtration, vacuum 80 DEG C of dry 12h obtain;
5., [the NEt will obtained 3h] 2[B 12h 12] being dissolved in the cesium hydroxide also adding 3 equivalents in water wherein, the solid filtering of generation, boiling water recrystallization, vacuum 80 DEG C of dry 8h obtain product C s 2[B 12h 12];
6., under argon shield, by Cs 2[B 12h 12] be dissolved in acetonitrile, then slowly drip SO wherein 2cl 2; After dropwising, be warming up to 65 DEG C of backflows 24 hours, stopped reaction, distillation removing solvent acetonitrile, generate white powder and utilize boiling water recrystallization to remove soluble impurity, obtained product C s 2[B 12cl 12];
7., by Cs 2[B 12cl 12] be dissolved in acetonitrile and material being dissolved in volume ratio is in the mixed solvent of 1:1 acetonitrile and water, then with cs 2[B 12cl 12the mol ratio of]=2:1 will dropwise join Cs 2[B 12cl 12] acetonitrile solution in, stirring at room temperature 12h, revolve and steam removing solvent acetonitrile, the pressed powder obtained is dissolved in acetonitrile again, after filtration, revolves and to steam and after washing, vacuum-drying dewaters 12h at 70 DEG C, obtained
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