CN102558206A - Process for synthetizing n-hexyl carborane - Google Patents

Abstract

The invention discloses a process for synthetizing an n-hexyl carborane. A constitutional formula of the process for synthetizing an n-hexyl carborane is presented in (I). The process for synthetizing an n-hexyl carborane comprises the steps of firstly adding tetraethylammonium dodecahydrododecaborates and a tetrahydrothiophene solvent into a reaction flask at a temperature between 0 DEG C and 10 DEG C, adding a pre-made mixture solution of the concentrated sulfuric acid and the tetrahydrothiophene into a reaction flask at a temperature between 5 DEG C and 15 DEG C, maintaining the reaction for 2 to 10 hours, adjusting the PH value of the reaction solution by triethylamine to be within a range between 7 and 10, filtering, distillating the tetrahydrothiophene in the filtering solution to dryness to obtain dodecahydrodecaborane tetrahydrothiophene complex which is an intermediate of the acquired dried solid, and secondly adding the dodecahydrodecaborane tetrahydrothiophene complex obtained in the first step, toluene and 1-octynoate into the reaction flask to maintain the reaction for 1 hour to six hours at a temperature between 90 DEG C and 120 DEG C to obtain the distillated toluene, adjusting the PH value of the obtained solution to a range between 7 and 10 by using pyridine, performing extraction, washing and distillation to obtain the n-hexyl carborane.

Description

The compound method of n-hexyl carborane

Technical field

The present invention relates to a kind of compound method of n-hexyl carborane.

Background technology

Carborane class superelevation burning ratemodifier has combustion heat value height, low, the good stability of toxicity, advantages such as flameholding, and compatible with the propelling agent component, particularly can make compositepropellent and double-base propellent obtain high combustion speed even superelevation combustion speed (50-1000mm/s).Earlier 1970s needs the high SP that fires speed owing to development is antitank with missile killer, and carborane is paid attention to by people as the excellent specific property of high burning ratemodifier.

U.S. Pat 4150057 discloses a kind of method for preparing the n-hexyl carborane, and this method is a raw material with the two tetraethyl ammoniums of decahydro ten boric acid, and synthetic route is as follows.

(Et ₄N) ₂B ₁₀H ₁₀+LiCl→Li ₂B ₁₀H ₁₀+Et ₄NCl

Li ₂B ₁₀H ₁₀+2HCl+2(CH ₃) ₂S→B ₁₀H ₁₂[(CH ₃) ₂S] ₂+LiCl

This method is three steps, is respectively: 1) decahydro ten boric acid ammonium salts and lithium chloride carry out IX and obtain decahydro ten boric acid lithium salts; 2) reaction of decahydro ten boric acid lithium salts and dimethyl sulphide obtains the two dimethyl sulphide ether complexes of ten dihydros, ten boron; 3) two dimethyl sulphide ether complexes of ten dihydros, ten boron and octyne-1 reaction obtain the n-hexyl carborane, and overall yield of reaction is 32.3%.But the reactions step of this method is more.

Summary of the invention

The technical problem that the present invention will solve is the deficiency that overcomes prior art, provides a kind of reactions step less n-hexyl carborane compound method.

Reactions step of the present invention was two steps, and its synthetic route is following:

For solving the problems of the technologies described above, the compound method of n-hexyl carborane of the present invention, its structure shown in (I),

With the two tetraethyl ammoniums of decahydro ten boric acid is raw material, may further comprise the steps:

1) the two tetraethyl ammoniums of decahydro ten boric acid are joined in the reaction flask with THTP, 0 ℃～10 ℃ of temperature, the adding mass concentration is 98% the vitriol oil and the mixing solutions of THTP; In temperature is 5 ℃～15 ℃, reaction 2～10h, and using triethylamine to transfer the reaction solution pH value is 7～10; Filter; Steam the THTP that removes in the filtrating, get the two THTP complex compounds of midbody ten dihydros ten boron behind the gained solid drying, wherein the mol ratio of the two tetraethyl ammoniums of sulfuric acid and decahydro ten boric acid is 2: 1～6: 1; 98% (quality) vitriol oil in the mixing solutions of 98% (quality) vitriol oil and THTP and the mol ratio of THTP are 1: 1～3: 1;

2) the two THTP complex compounds of ten dihydros, ten boron, 1-octyne and the toluene that step 1) are obtained join in the reaction flask; 90～120 ℃ of temperature, reaction 1～6h steams toluene; After gained liquid uses pyridine to regulate PH to be 7～10, through extraction, wash and distill the n-hexyl carborane; Wherein the mol ratio of two THTP complex compounds of ten dihydros, ten boron and 1-octyne is 1: 1～1: 5.

Preferred method of the present invention may further comprise the steps:

1) the two tetraethyl ammoniums of 5.7g decahydro ten boric acid are joined in the reaction flask with the 30mL THTP, 5 ℃ of temperature, adding 16.7g mass concentration is 98% the vitriol oil and the mixing solutions of 9mL THTP; After dripping, be 10 ℃ of reaction 7h down, the reaction solution pH value transferred to 8 with triethylamine in temperature; Filter; With the THTP evaporate to dryness in the filtrating, get the two THTP complex compound 3.6g of midbody ten dihydros ten boron behind the gained solid drying, yield 86.3%.The mol ratio of the vitriol oil and THTP is 2: 1 in the mixing solutions of wherein preparing in advance, and the mol ratio of the two tetraethyl ammoniums of vitriol oil consumption and decahydro ten boric acid is 4: 1;

2) the two THTP complex compounds of 3.6g ten dihydros ten boron, 15mL toluene and the 1.9g1-octyne that step 1) are obtained join in the reaction flask; 110 ℃ of temperature, reaction 2h steams toluene; In the gained thick liquid, add pyridine pH value is transferred to 8; Through extract, wash, distill the n-hexyl carborane, 1.1g, yield 40.2%.Wherein, the two THTP complex compounds of ten dihydros, ten boron are 1: 2 with the ratio of 1-octyne.

Advantage of the present invention:

The step of the compound method of n-hexyl carborane of the present invention is less, and its reactions step was two steps, and the method for preparing the n-hexyl carborane in the documents is a three-step reaction; And the preparation of the midbody decahydro ten boric acid lithium salts in the method for documents, storage and use operation are complicated.

Embodiment

Below in conjunction with specific embodiment the present invention is done further detailed description.

Synthesizing of embodiment 1 n-hexyl carborane

1) the two tetraethyl ammoniums of 5.7g (15mmol) decahydro ten boric acid being joined in the reaction flask with 30mL (340mmol) THTP, is 5 ℃ in temperature, is in the mixing solutions adding reaction flask of 98% the vitriol oil and 9mL (102mmol) THTP with 16.7g (167mmol) mass concentration; After dripping; In temperature is 10 ℃ of reaction 7h down, and reaction finishes, and using the pH value of triethylamine conditioned reaction system is 8; Filter; The steaming of THTP in the filtrating is removed, get the two THTP complex compound 3.6g of ten dihydros, ten boron behind the gained solid drying, yield 86.3%.

2) the two THTP complex compound 3.6g (12mmol) of ten dihydros, ten boron, 15mL (140mmol) toluene and 1.9g (17mmol) the 1-octyne that step 1) are obtained join in the reaction flask, 110 ℃ of heat temperature raising to temperature, reaction 2h; Toluene is steamed, add pyridine, the pH value that makes gained liquid is 8; Divide with the 12mL pentane to extract this liquid four times, sodium hydroxide solution and the 12mL moisture with 12mL 15% washs for three times successively, and Skellysolve A is steamed; Gained liquid distills under vacuum tightness 27Pa; Receive 104～105 ℃ of cuts, get n-hexyl carborane 1.1g, yield 40.2%.

Structure is identified:

Ultimate analysis (B ₁₀C ₈H ₂₄):

Calculated value (%): C 42.05, and H 10.59, and B 47.36;

Measured value (%): C 41.97, and H 10.53, and B 47.24.

Infrared (KBr, cm ^-1), v:3066,2957,2931,2859,2594,1465,1379,1116,1069,1019,723;

Nucleus magnetic hydrogen spectrum (CDCl ₃, 500MHz), δ: 0.879 (T, J=7Hz, 3H) 1.220-1.262 (m, 6H), 1.412-1.515 (m, 2H), 2.132-2.193 (m, 2H), 3.555 (S, 1H);

Appraising datum confirms that the material that obtains as stated above is the n-hexyl carborane really.

Synthesizing of embodiment 2 n-hexyl carboranes

1) the two tetraethyl ammoniums of 6.3g (16.7mmol) decahydro ten boric acid are joined in the reaction flask with 33mL (374mmol) exsiccant THTP, stirring is cooled to 0 ℃, is that the mixing solutions of 98% vitriol oil and 9mL (102mmol) THTP is added dropwise in the reaction flask with 10.2g (102mmol) mass concentration; After dripping; In temperature is 5 ℃ of reaction 2h down, and reaction finishes, and with triethylamine the reaction solution pH value is transferred to 7; Filter; The steaming of THTP in the filtrating is removed, get the two THTP complex compound 3.7g of ten dihydros, ten boron behind the gained solid drying, yield 80.7%.

2) just the two THTP complex compounds of 2.8g (9mmol) ten dihydros ten boron that obtain of step 1), 12mL (112mmol) toluene join in the reaction flask with 1.4g (13mmol) 1-octyne, are heated to 90 ℃, react 2h; Toluene is steamed, the pH value of gained thick liquid is transferred to 8, divide with the 10mL pentane to extract this liquid three times with pyridine; Sodium hydroxide solution and 9mL moisture with 10mL 15% washs for three times successively; Skellysolve A is steamed, and gained liquid distills under 27Pa, receives 104～105 ℃ of cuts; Get n-hexyl carborane 0.8g, yield 40.2%.

Synthesizing of embodiment 3 n-hexyl carboranes

1) the two tetraethyl ammoniums of 5.4g (14mmol) decahydro ten boric acid being joined in the reaction flask with 28mL (317mmol) exsiccant THTP, stir and be cooled to 15 ℃, is in the mixing solutions adding reaction flask of 98% the vitriol oil and 9mL (102mmol) THTP with 30.6g (306mmol) mass concentration; After adding; In temperature is 0 ℃ of reaction 10h down, and reaction finishes, and with triethylamine the reaction solution pH value is transferred to 7; Filter; The steaming of THTP in the filtrating is removed, get the two THTP complex compound 3.2g of ten dihydros, ten boron behind the gained solid drying, yield 81.4%.

2) the two THTP complex compounds of the 2.4g that step 1) is obtained (8mmol) ten dihydros ten boron, 9.6mL (90mmol) toluene and 1.1g (10mmol) 1-octyne join in the reaction flask, are heated to 120 ℃, reaction 6h; Toluene is steamed, the pH value of gained thick liquid is transferred to 10, divide with the 9mL pentane to extract this liquid three times with pyridine; Sodium hydroxide solution and 9mL moisture with 9mL 15% washs for three times successively; Skellysolve A is steamed, and gained liquid distills under 27Pa, receives 104～105 ℃ of cuts; Get n-hexyl carborane 0.7g, yield 39.2%.

Claims (2)

1. the compound method of a n-hexyl carborane, its structural formula shown in (I),

With the two tetraethyl ammoniums of decahydro ten boric acid is raw material, may further comprise the steps:

1) the two tetraethyl ammoniums of decahydro ten boric acid are joined in the reaction flask with THTP, 0 ℃～10 ℃ of temperature, the adding mass concentration is 98% the vitriol oil and the mixing solutions of THTP; In temperature is 5 ℃～15 ℃, reaction 2～10h, and using triethylamine to transfer the reaction solution pH value is 7～10; Filter; Steam the THTP that removes in the filtrating, get the two THTP complex compounds of midbody ten dihydros ten boron behind the gained solid drying, wherein the mol ratio of the two tetraethyl ammoniums of sulfuric acid and decahydro ten boric acid is 2: 1～6: 1; 98% (quality) vitriol oil in the mixing solutions of 98% (quality) vitriol oil and THTP and the mol ratio of THTP are 1: 1～3: 1;

2) the two THTP complex compounds of ten dihydros, ten boron, 1-octyne and the toluene that step 1) are obtained join in the reaction flask; 90～120 ℃ of temperature, reaction 1～6h steams toluene; After gained liquid uses pyridine to regulate PH to be 7～10, through extraction, wash and distill the n-hexyl carborane; Wherein the mol ratio of two THTP complex compounds of ten dihydros, ten boron and 1-octyne is 1: 1～1: 5.

2. the compound method of n-hexyl carborane according to claim 1 may further comprise the steps:

1) the two tetraethyl ammoniums of 5.7g decahydro ten boric acid are joined in the reaction flask with the 30mL THTP, 5 ℃ of temperature, adding 16.7g mass concentration is 98% the vitriol oil and the mixing solutions of 9mL THTP; After dripping, be 10 ℃ of reaction 7h down, the reaction solution pH value transferred to 8 with triethylamine in temperature; Filter; With the THTP evaporate to dryness in the filtrating, get the two THTP complex compound 3.6g of midbody ten dihydros ten boron behind the gained solid drying, yield 86.3%.The mol ratio of the vitriol oil and THTP is 2: 1 in the mixing solutions of wherein preparing in advance, and the mol ratio of the two tetraethyl ammoniums of vitriol oil consumption and decahydro ten boric acid is 4: 1;

2) the two THTP complex compounds of 3.6g ten dihydros ten boron, 15mL toluene and the 1.9g1-octyne that step 1) are obtained join in the reaction flask; 110 ℃ of temperature, reaction 2h steams toluene; In the gained thick liquid, add pyridine pH value is transferred to 8; Through extract, wash, distill the n-hexyl carborane, 1.1g, yield 40.2%.Wherein, the two THTP complex compounds of ten dihydros, ten boron are 1: 2 with the ratio of 1-octyne.