CN116253754A - Method for synthesizing high-abundance boron 10 isotope biboronate - Google Patents
Method for synthesizing high-abundance boron 10 isotope biboronate Download PDFInfo
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- CN116253754A CN116253754A CN202310056065.7A CN202310056065A CN116253754A CN 116253754 A CN116253754 A CN 116253754A CN 202310056065 A CN202310056065 A CN 202310056065A CN 116253754 A CN116253754 A CN 116253754A
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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 System
- C07F5/02—Boron compounds
- C07F5/022—Boron compounds without C-boron linkages
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- C—CHEMISTRY; METALLURGY
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- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B59/00—Introduction of isotopes of elements into organic compounds ; Labelled organic compounds per se
- C07B59/004—Acyclic, carbocyclic or heterocyclic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen, sulfur, selenium or tellurium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
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- C07B2200/05—Isotopically modified compounds, e.g. labelled
Abstract
The invention relates to a method for synthesizing biboronate of high-abundance boron 10 isotope, which comprises the following steps: multi-functional (N) 1 ,N 2 -dimethyl o-phenylenediamine) fluoroborane preparation: n (N) 1 ,N 2 Reacting dimethyl o-phenylenediamine, a hydrocarbon solvent A, high-abundance boron 10 isotope boron trifluoride solution and alkali to obtain the boron trifluoride; second floor (N) 1 ,N 2 -dimethyl o-phenylenediamine) chloroborane preparation: (N) 1 ,N 2 -dimethyl o-phenylenediamine) fluoroborane, hydrocarbon solvent B and chlorosilane are reacted to obtain the catalyst; coupling: hydrocarbon solvent C, metallic sodium, (N) 1 ,N 2 After the reaction of the hydrocarbon solution of the-dimethyl o-phenylenediamine) chloroborane, the N containing high-abundance boron 10 isotope is obtained by washing and drying 1 ,N 2 -a dimethyl o-phenylenediamine diboron compound; esterification: hydrocarbon solvent E, N 1 ,N 2 And (3) reacting the dimethyl o-phenylenediamine diboron compound, glycol and hydrogen chloride hydrocarbon solution, washing and drying to obtain the high-abundance boron 10 isotope diboron ester. The invention has mild reaction condition and high conversion rate.
Description
Technical Field
The invention relates to the field of organic compound synthesis, in particular to a method for synthesizing high-abundance boron 10 isotope biboronate.
Background
Due to the widespread use of boron 10 in the nuclear and medical industries, the natural abundance is only 19.8% 10 B (B)Effective separation is one of the most interesting issues for global manufacturers and scientists. In various cases 10 Of the enrichment methods of B, chemical exchange distillation is the most studied method, and is produced in large quantities to date 10 B the only practical method. While BF 3 As a lewis acid having excellent electron accepting ability, a raw material for separating high-abundance boron 10 isotopes is generally selected.
BF 3 The application range of the method is difficult to expand because the transformation mode is single. Diboron reagent, in particular bis (pinacolato) diboron ester (B) 2 pin 2 ) Is a tool molecule mainly used for the boride of halides and the boride of alkanes, halides and unsaturated substrates. According to statistics, B 2 pin 2 About 1.55 ten thousand chemical reactions are involved, and about 1.53 ten thousand organoboron compounds containing Bpin units. Undoubtedly, if a synthesis is developed 10 B 2 pin 2 Other methods commonly used for boron 10 diboron compounds will be largely abundant 10 The application of the compound B in various fields.
For natural abundance boric acid esters, the prior art mostly uses boron tribromide (BBr 3 ) Or boron trichloride (BCl) 3 ) As a raw material, BBr with high abundance of boron 10 isotopes cannot be obtained due to separation technology 3 And BCl 3 . The current source of high abundance boron 10 isotopes is mainly boron trifluoride (BF 3 ) The compound is not easy to be further converted because of larger B-F alkali bond energy. There is no method for BF 3 Report of conversion of the compound to the biboronate.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for synthesizing high-abundance boron 10 isotope biboronate with mild reaction conditions and high conversion rate.
In order to solve the problems, the method for synthesizing the biboronate of the high-abundance boron 10 isotope comprises the following steps:
⑴（N 1 ,N 2 -dimethyl o-phenylenediamine) fluoroborane preparation:
in the reactionAdding N into the device A 1 ,N 2 Dropwise adding boron 10 isotope boron trifluoride solution and alkali into dimethyl o-phenylenediamine and hydrocarbon solvent A at 0-25 ℃ until NMR detection reaction is finished, thereby obtaining (N) 1 ,N 2 -dimethyl o-phenylenediamine) fluoroborane;
the N is 1 ,N 2 -the ratio of dimethyl o-phenylenediamine to the hydrocarbon solvent a is 1g: 1-15 ml; the N is 1 ,N 2 -the molar ratio of dimethyl o-phenylenediamine to the boron trifluoride solution of high abundance boron 10 isotope is 1.0:1.0 to 10.0 equivalents; the N is 1 ,N 2 -the molar ratio of dimethyl-o-phenylenediamine to the base is 1.0:1.0 to 5.0 equivalents;
⑵（N 1 ,N 2 -dimethyl o-phenylenediamine) chloroborane preparation:
adding said (N) to reactor B 1 ,N 2 -dimethyl o-phenylenediamine) fluoroborane and a hydrocarbon solvent B, dropwise adding chlorosilane at room temperature, and reacting at 0-120 ℃ until the NMR detection reaction is finished; concentrating under vacuum after the reaction is finished to obtain (N) 1 ,N 2 -dimethyl o-phenylenediamine) chloroborane;
said (N) 1 ,N 2 -dimethyl o-phenylenediamine) fluoroborane to hydrocarbon solvent B in a ratio of 1g: 1-20 ml; the N is 1 ,N 2 -the molar ratio of dimethyl-o-phenylenediamine to said chlorosilane is 1.0:0.6 to 5.0 equivalents;
coupling:
adding hydrocarbon solvent C and metallic sodium into a reactor C, stirring and refluxing until the metallic sodium is completely melted, and dripping (N) at 85-120 DEG C 1 ,N 2 -dimethyl o-phenylenediamine) chloroborane, and keeping the temperature unchanged until the NMR detection reaction is finished; after the reaction is finished, the temperature of the system is reduced to 20-50 ℃, and a solid crude product is obtained by filtering and drying filtrate; washing the solid crude product with normal hexane at 0-50 ℃, filtering again, and drying to obtain N containing high-abundance boron 10 isotope 1 ,N 2 -a dimethyl o-phenylenediamine diboron compound;
the dosage of the hydrocarbon solvent C is1-10 milliliters of sodium per millimole; said (N) 1 ,N 2 In hydrocarbon solutions of-dimethyl-o-phenylenediamine) chloroboranes (N 1 ,N 2 -dimethyl o-phenylenediamine) chloroborane to said sodium metal in a molar ratio of 1.0:1.0 to 6.0 equivalents; the ratio of n-hexane to the crude product was 1g: 1-5 ml;
esterification:
adding hydrocarbon solvent E and N into a reactor D 1 ,N 2 -dimethyl o-phenylenediamine diboron compound, firstly adding glycol at 10-30 ℃, then dropwise adding hydrocarbon solution of hydrogen chloride at-78-30 ℃, and after the completion of the dropwise adding, raising the temperature to 25-120 ℃ and keeping the temperature unchanged until the end of the NMR detection reaction; cooling the system to 15-25 ℃ after the reaction is finished, filtering by diatomite, and concentrating until no fraction exists to obtain a solid; washing the solid at 0-50 ℃ by using normal hexane to obtain the biboronate of the high-abundance boron 10 isotope;
the N is 1 ,N 2 -the ratio of dimethyl o-phenylenediamine diboron compound to the hydrocarbon solvent E is 1g: 1-30 ml; the N is 1 ,N 2 -the molar ratio of dimethyl o-phenylenediamine diboron compound to the diol is 1.0:1.0 to 3.0 equivalents; the N is 1 ,N 2 -the molar ratio of dimethyl o-phenylenediamine diboron compound to the hydrocarbon solution of hydrogen chloride is 1.0:4.0 to 10.0 equivalents; the N is 1 ,N 2 -the ratio of dimethyl o-phenylenediamine diboron compound to the n-hexane is 1g: 1-10 ml.
The boron 10 isotope boron trifluoride solution with high abundance in the step (A) refers to one of boron trifluoride ethers, ketones and amine compounds, or is boron trifluoride compound with natural abundance.
The hydrocarbon solvent A in the step (A) refers to one of n-heptane, n-hexane or cyclohexane.
The alkali in the step (A) refers to one of triethylamine, N-diisopropylethylamine, pyridine compounds, carbonate compounds and alkyl lithium reagents.
N in the step (A) 1 ,N 2 The structure of the-dimethyl-phthalimido group is shown as a formula (I), and the compound can also be adoptedReplacing with a structure as shown in any one of the formulas (II) - (VI):
the hydrocarbon solvent B in the step II and the hydrocarbon solvent C in the step III refer to one of n-heptane, n-hexane, cyclohexane, toluene or xylene.
The chlorosilane in the step II refers to one of tetrachlorosilane, monomethyl trichlorosilane, dimethyl dichlorosilane or trimethyl chlorosilane.
Said (N) 1 ,N 2 -dimethyl o-phenylenediamine) chloroborane using a one pot process:
adding N to reactor E 1 .N 2 Dropwise adding boron 10 isotope boron trifluoride solution, alkali and chlorosilane into dimethyl o-phenylenediamine and N-hexane at room temperature, and reacting at 0-120 ℃ until the NMR detection reaction is finished to obtain (N) 1 ,N 2 -dimethyl o-phenylenediamine) chloroborane; the N is 1 ,N 2 -the ratio of dimethyl o-phenylenediamine to n-hexane is 1g: 1-20 ml; the N is 1 .N 2 -the molar ratio of dimethyl o-phenylenediamine to the boron trifluoride solution of high abundance boron 10 isotope is 1.0:1.0 to 10.0 equivalents; the N is 1 ,N 2 -the molar ratio of dimethyl-o-phenylenediamine to chlorosilane is 1.0:0.6 to 5.0 equivalents; the N is 1 ,N 2 -the molar ratio of dimethyl-o-phenylenediamine to the base is 1.0:1.0 to 5.0 equivalents.
In the step III (N) 1 ,N 2 By a hydrocarbon solution of-dimethyl-o-phenylenediamine) chloroborane is meant 1g (N 1 ,N 2 -dimethyl o-phenylenediamine) chloroborane is dissolved by 1-10 ml hydrocarbon solvent D to prepare the catalyst; the hydrocarbon solvent D refers to toluene or xylene.
The hydrocarbon solvent E in the step refers to one of n-heptane, toluene or xylene.
The hydrocarbon solution of hydrogen chloride in the step refers to hydrogen chloride diethyl ether solution or hydrogen chloride 1, 4-dioxane solution.
The diol in the step has a structure shown in any one of the formulas (VII) -II:
compared with the prior art, the invention has the following advantages:
1. the invention uses 10 BF 3 Compounds, N 1 ,N 2 Dimethyl-o-phenylenediamine, chlorosilane, metallic sodium and diol as starting materials, can be synthesized by a one-step process or a two-step process (N) 1 ,N 2 -dimethyl o-phenylenediamine) chloroborane, and then preparing various diboron 10 biboronates under mild conditions through coupling and ester formation synthesis, thereby laying a foundation for large-scale production.
2. N used in the present invention 1 ,N 2 The dimethyl o-phenylenediamine compound can be equivalently recovered after the esterification step, so that the cost is saved.
3. The product of each step is continuously thrown into the next step in the form of a solution, the operation is simple and easy, the reaction yield and purity of each step are relatively high, and the total yield can reach 35% -60%.
4. The method has mild reaction conditions and high conversion rate, can be amplified to kilogram level, and provides feasible synthesis conditions for large-scale production of the high-abundance boron 10 isotope diboronate. In addition, the invention is also applicable to the synthesis of high isotope boron 11 biboronate.
Detailed Description
A method of synthesizing a high abundance boron 10 isotope of a biboronate comprising the steps of:
⑴（N 1 ,N 2 -dimethyl o-phenylenediamine) fluoroborane preparation:
adding N in the reactor A 1 ,N 2 Dropwise adding boron 10 isotope boron trifluoride solution and alkali into dimethyl o-phenylenediamine and hydrocarbon solvent A at 0-25 ℃ until NMR detection reaction is finished, thereby obtaining (N) 1 ,N 2 -dimethyl-o-phenylenediamine) fluoroborane。
Wherein: n (N) 1 ,N 2 The ratio of dimethyl o-phenylenediamine to hydrocarbon solvent A is 1g: 1-15 ml, preferably 3-15 ml; n (N) 1 ,N 2 The molar ratio of dimethyl o-phenylenediamine to boron trifluoride solution with high abundance of boron 10 isotope is 1.0:1.0 to 10.0 equivalents, preferably 1.0:1.0 to 5.0 equivalents; n (N) 1 ,N 2 -the molar ratio of dimethyl-o-phenylenediamine to base is 1.0:1.0 to 5.0 equivalents, preferably 1.0:2.0 to 3.0 equivalents.
The high-abundance boron 10 isotope boron trifluoride solution refers to one of boron trifluoride ethers, ketones and amine compounds, or is boron trifluoride compound with natural abundance.
The hydrocarbon solvent A refers to one of n-heptane, n-hexane or cyclohexane, preferably n-hexane.
The base is one of triethylamine, N-diisopropylethylamine, pyridine compounds, carbonate compounds and alkyl lithium reagent.
N 1 ,N 2 The structure of the dimethylphthalamide group is shown in formula (I), and the structure shown in any one of formulas (II) -VI) can be used for replacing the structure shown in the formula (II) -VI:
⑵（N 1 ,N 2 -dimethyl o-phenylenediamine) chloroborane preparation:
adding (N) in reactor B 1 ,N 2 -dimethyl o-phenylenediamine) fluoroborane and a hydrocarbon solvent B, dropwise adding chlorosilane at room temperature, and reacting at 0-120 ℃ until the NMR detection reaction is finished; concentrating under vacuum after the reaction is finished to obtain (N) 1 ,N 2 -dimethyl o-phenylenediamine) chloroborane.
Wherein: (N) 1 ,N 2 -dimethyl o-phenylenediamine) fluoroborane to hydrocarbon solvent B in a ratio of 1g: 1-20 ml, preferably 5-20 ml; n (N) 1 ,N 2 -the molar ratio of dimethyl-o-phenylenediamine to chlorosilane is 1.0:0.6 to 5.0 equivalents, preferably 1.0:1.0 to 4.0 equivalents.
The hydrocarbon solvent B refers to one of n-heptane, n-hexane, cyclohexane, toluene or xylene, preferably toluene.
The chlorosilane is one of tetrachlorosilane, monomethyl trichlorosilane, dimethyl dichlorosilane or trimethyl chlorosilane.
Coupling:
adding hydrocarbon solvent C and metallic sodium into a reactor C, stirring and refluxing until the metallic sodium is completely melted, and dripping (N) at 85-120 DEG C 1 ,N 2 -dimethyl o-phenylenediamine) chloroborane, and keeping the temperature unchanged until the NMR detection reaction is finished; after the reaction is finished, the temperature of the system is reduced to 20-50 ℃, and a solid crude product is obtained by filtering and drying filtrate; washing the solid crude product with normal hexane at 0-50 ℃, and filtering and drying again to obtain N containing high-abundance boron 10 isotope 1 ,N 2 -a dimethyl o-phenylenediamine diboron compound.
Wherein: the dosage of the hydrocarbon solvent C is 1-10 milliliters per millimole of sodium; (N) 1 ,N 2 In hydrocarbon solutions of-dimethyl-o-phenylenediamine) chloroboranes (N 1 ,N 2 -dimethyl o-phenylenediamine) chloroborane to sodium metal in a molar ratio of 1.0:1.0 to 6.0 equivalents, preferably 1.0:2.0 to 3.0 equivalents; the ratio of n-hexane to crude product was 1g: 1-5 ml.
The hydrocarbon solvent C is one of n-heptane, n-hexane, cyclohexane, toluene or xylene, preferably toluene.
（N 1 ,N 2 By a hydrocarbon solution of-dimethyl-o-phenylenediamine) chloroborane is meant 1g (N 1 ,N 2 -dimethyl o-phenylenediamine) chloroborane is dissolved by 1-10 ml hydrocarbon solvent D to prepare the catalyst; hydrocarbon solvent D refers to toluene or xylene.
Esterification:
into the reactor D is added hydrocarbon solvent E, N 1 ,N 2 -dimethyl o-phenylenediamine diboron compound, firstly adding glycol at 10-30 ℃, then dropwise adding hydrocarbon solution of hydrogen chloride at-78-30 ℃, and after the completion of the dropwise adding, raising the temperature to 25-120 ℃ and keeping the temperature unchanged until the end of the NMR detection reaction; cooling the system to 15 after the reaction is finishedFiltering at 25 ℃ through diatomite, and concentrating until no fraction exists to obtain a solid; washing the solid at 0-50 ℃ by using normal hexane to obtain the high-abundance boron 10 isotope diboronate.
Wherein: n (N) 1 ,N 2 The ratio of the dimethyl o-phenylenediamine diboron compound to the hydrocarbon solvent E is 1g: 1-30 ml, preferably 10-30 ml; n (N) 1 ,N 2 -the molar ratio of dimethyl o-phenylenediamine diboron compound to diol is 1.0:1.0 to 3.0 equivalents, preferably 1.0:2.0 to 3.0 equivalents; n (N) 1 ,N 2 -the molar ratio of dimethyl o-phenylenediamine diboron compound to hydrogen chloride hydrocarbon solution is 1.0:4.0 to 10.0 equivalents; n (N) 1 ,N 2 The ratio of dimethyl o-phenylenediamine diboron compound to n-hexane is 1g:1 to 10ml, preferably 1 to 5ml.
The hydrocarbon solvent E is one of n-heptane, toluene or xylene, preferably toluene.
The hydrocarbon solution of hydrogen chloride refers to an ether solution of hydrogen chloride or a solution of hydrogen chloride 1, 4-dioxane.
The diol has a structure as shown in any one of the formulas (VII) - (ii):
in the method (N) 1 ,N 2 Dimethyl o-phenylenediamine) chloroborane can also be prepared using a one-pot process:
adding N to reactor E 1 .N 2 Dropwise adding boron 10 isotope boron trifluoride solution, alkali and chlorosilane into dimethyl o-phenylenediamine and N-hexane at room temperature, and reacting at 0-120 ℃ until the NMR detection reaction is finished to obtain (N) 1 ,N 2 -dimethyl o-phenylenediamine) chloroborane.
Wherein: n (N) 1 ,N 2 The ratio of dimethyl-o-phenylenediamine to n-hexane is 1g: 1-20 ml, preferably 5-20 ml; n (N) 1 .N 2 The molar ratio of dimethyl o-phenylenediamine to boron trifluoride solution with high abundance of boron 10 isotope is 1.0:1.0 to 10.0 equivalents, preferably 1.0:1.0 to 5.0 equivalents; n (N) 1 ,N 2 -twoThe molar ratio of methyl o-phenylenediamine to chlorosilane is 1.0:0.6 to 5.0 equivalents, preferably 1.0:1.0 to 4.0 equivalents; n (N) 1 ,N 2 -the molar ratio of dimethyl-o-phenylenediamine to base is 1.0:1.0 to 5.0 equivalents, preferably 1.0:2.0 to 3.0 equivalents.
Example 1
Synthesis of high abundance boron 10's pinacol ester of biboronic acid 10 B 2 pin 2 The method of (1):
the method comprises the following steps:
(N) of high abundance boron 10 1 ,N 2 -dimethyl o-phenylenediamine) chloroborane preparation:
adding N-hexane solvent (300 mL) and N to reactor E 1 ,N 2 Dimethyl o-phenylenediamine (27.2 g,200 mmol), dropwise adding boron trifluoride diethyl etherate (28.0 g,200 mmol) with high abundance of boron 10 isotope at 0-25 ℃, N, N-diisopropylethylamine (51.7 g, 400 mmol) and tetrachlorosilane (35.8 g,200 mmol), and reacting at 90 ℃ until the NMR detection reaction is finished; after the reaction, filtering, and vacuum drying the filtrate to obtain the product (N) of high-abundance boron 10 1 ,N 2 -dimethyl o-phenylenediamine) chloroborane in 82% yield to be put into the next step.
N of high abundance boron 10 1 ,N 2 -preparation of a dimethyl o-phenylenediamine diboron compound:
toluene (150 mL) and metallic sodium (11.5 g, 500 mmol) were added to a reactor C, and stirred and refluxed until the metallic sodium was completely melted, and the mixture (N) obtained in the above step was added dropwise at 110 ℃to the reactor C 1 ,N 2 -a solution of dimethylbenzenediamido) chloroborane in toluene (150 mL), after which the addition is completed, and the temperature is raised to 120 ℃ until the end of the NMR detection reaction; after the reaction is finished, the system is cooled to 25 ℃, filtered, and the filtrate is dried in vacuum to obtain a crude product; then washing the crude product with N-hexane at 0deg.C, filtering again, drying to obtain solid N with high abundance of boron 10 isotope 1 ,N 2 -dimethyl o-phenylenediamine diboron compound, and the process for preparing the sameThe rate is 76%, and the process is ready for the next step.
Preparation of pinacol borate of high abundance boron 10:
adding toluene solvent (150 mL) to the reactor D, N obtained in the above step 1 ,N 2 Dimethylphthalenediamine diboron compound (14.4 g, 50 mmol), pinacol (11.8 g, 100 mmol) was added at 25℃and hydrogen chloride diethyl ether solvent (500 mol) was added dropwise at 0℃and the temperature was raised to 80℃and kept unchanged until the end of the NMR detection reaction; after the reaction, the system is cooled to 25 ℃, diatomite is filtered, the mixture is concentrated to no fraction after the filtration, and the solid is washed by using normal hexane (6 mL) at 0 ℃ to obtain the biboronate with high abundance of boron 10 isotope, and the yield is 88%.
The second method is as follows:
(N) of high abundance boron 10 1 ,N 2 -dimethyl o-phenylenediamine) fluoroborane preparation:
adding N-hexane solvent (20 mL) and N to reactor A 1 ,N 2 Dimethyl o-phenylenediamine (1.36 g,10 mmol), boron trifluoride diethyl etherate (4.2 g, 30 mmol) added with high abundance of boron 10 isotope and N, N-diisopropylethylamine (2.59 g,20 mmol) are dripped at 0 ℃ to 25 ℃ and reacted until the NMR detection reaction is finished; reaction 5 h, filtering, and vacuum drying the filtrate to give a material (N) with high abundance of boron 10 1 ,N 2 -dimethyl o-phenylenediamine) fluoroborane in 71% yield to be put into the next step.
(N) of high abundance boron 10 1 ,N 2 -dimethyl o-phenylenediamine) chloroborane preparation:
toluene (15 mL) and (N) obtained in the above step were charged into a reactor B 1 ,N 2 Dimethylphthalenyl diamine) fluoroborane (7.1 mmol) was added dropwise to tetrachlorosilane (12 g,7.1 mmol) at room temperature, and the mixture was reacted at 90℃until the NMR detection reaction was completed; after the reaction, the system is concentrated in vacuum, and the obtained concentrated substance is (N) of high abundance boron 10 1 ,N 2 -dimethyl o-phenylenediamine) chloroborane in 93% yield to be taken in the next step.
N of high abundance boron 10 1 ,N 2 -preparation of a dimethyl o-phenylenediamine diboron compound:
toluene (8 mL) and metallic sodium (184 mg, 8 mmol) were added to reactor C, stirred and refluxed until the metallic sodium was completely melted, and the mixture (N) obtained in the above step was added dropwise at 110 ℃to the reactor C 1 ,N 2 -a solution of dimethylbenzenediamido) chloroborane in toluene (8 mL), after which the addition is completed, and the temperature is raised to 120 ℃ until the end of the NMR detection reaction; after the reaction, the system is cooled to 25 ℃, filtered, and the filtrate is dried in vacuum to obtain a crude product, then the crude product is washed by normal hexane at 0 ℃, filtered and dried again, and the obtained solid is N of high abundance boron 10 isotope 1 ,N 2 -dimethyl o-phenylenediamine diboron compound in 72% yield to be put into the next step.
Preparation of pinacol borate of high abundance boron 10:
toluene solvent (7 mL) was added to the reactor D, and N obtained in the above step was added 1 ,N 2 Dimethylphthalenediamine diboron compound (662 mg, 2.3 mmol), diol is added at 25℃and hydrogen chloride diethyl ether solvent (23 mol) is added dropwise at 0℃and the temperature is raised to 80℃after the addition, keeping the temperature unchanged until the end of the NMR detection reaction; after the reaction, the system is cooled to 25 ℃, diatomite is filtered, the mixture is concentrated to no fraction after the filtration, and the solid is washed by using normal hexane (6 mL) at 0 ℃ to obtain the biboronate with high abundance of boron 10 isotope, and the yield is 87%.
Example 2
Synthesis of bis (3, 4-diethylhexyl-3, 4-diol) diborane B for high abundance boron 10 2 Epin 2 The method of (1):
(N) of high abundance boron 10 1 ,N 2 -dimethyl o-phenylenediamine) chloroborane preparation:
n-heptane solvent (20 mL) and N were added to reactor E 1 ,N 2 Dimethyl o-phenylenediamine (1.36 g,10 mmol), boron trifluoride diethyl etherate (1.4 g,10 mmol) added with an abundance of boron 10 isotope and N, N-diisopropylethylamine (2.58 g,20 mmol) and tetrachlorosilane (1.79 g,10 mmol) were added dropwise at 0℃to 25℃and reacted at 90℃until the NMR detection reaction was completed; after the reaction, adding N-hexane solvent (5 mL) into the system, filtering, vacuum drying the filtrate to obtain the product (N) of high-abundance boron 10 1 ,N 2 -dimethyl o-phenylenediamine) chloroborane in 80% yield to be put into the next step.
N of high abundance boron 10 1 ,N 2 -preparation of a dimethyl o-phenylenediamine diboron compound:
xylene (8 mL), metallic sodium (575 mg, 25 mmol) were added to reactor C and stirred and refluxed until metallic sodium was completely melted, and the (N) produced in the above step was added dropwise at 110 ℃to the reactor C 1 ,N 2 -a solution of dimethylbenzenediamido) chloroborane in xylene (8 mL), after which the addition is completed, and the temperature is raised to 120 ℃ until the end of the NMR detection reaction; after the reaction, the system is cooled to 25 ℃, filtered, and the filtrate is dried in vacuum to obtain a crude product, then the crude product is washed by normal hexane at 0 ℃, filtered and dried again, and the obtained solid is N of high abundance boron 10 isotope 1 ,N 2 -dimethyl o-phenylenediamine diboron compound in 76% yield to be put into the next step.
⑶ 10 B 2 Epin 2 Is prepared from the following steps:
adding toluene solvent (8 mL) to the reactor D to obtain N 1 ,N 2 Dimethyl o-phenylenediamine diboron compound (720 mg, 2.5 mmol), 3, 4-diethyl-3, 4-diol (1.74 g,10 mmol) was added at 25 ℃, and hydrogen chloride diethyl ether solvent (15 mol) was added dropwise at 0 ℃ after the addition, the temperature was raised to 80 ℃ and the temperature was kept unchanged until the end of the NMR detection reaction; after the reaction is finished, the system is cooled to 25 ℃, diatomite is filtered, and column chromatography is carried out to obtain 10 B 2 Epin 2 Yield 76%.
Example 3
Synthesis of Di (neopentyl glycol) diborane B for high abundance boron 10 2 neop 2 The method of (1):
(N) of high abundance boron 10 1 ,N 2 -dimethyl o-phenylenediamine) chloroborane preparation:
adding cyclohexane solvent (20 mL) and N to reactor E 1 ,N 2 Dimethyl o-phenylenediamine (1.36 g,10 mmol), boron trifluoride diethyl etherate (1.4 g,10 mmol) added with an abundance of boron 10 isotope and N, N-diisopropylethylamine (2.58 g,20 mmol) and tetrachlorosilane (1.79 g,10 mmol) were added dropwise at 0℃to 25℃and reacted at 90℃until the NMR detection reaction was completed; after the reaction, adding N-hexane solvent (5 mL) into the system, filtering, vacuum drying the filtrate to obtain the product (N) of high-abundance boron 10 1 ,N 2 -dimethyl o-phenylenediamine) chloroborane in 74% yield to be put into the next step.
N of high abundance boron 10 1 ,N 2 -preparation of a dimethyl o-phenylenediamine diboron compound:
toluene (8 mL) and metallic sodium (575 mg, 25 mmol) were added to reactor C and stirred and refluxed until the metallic sodium was completely melted, and the (N) obtained in the above step was added dropwise at 110 ℃to the reactor C 1 ,N 2 -a solution of dimethylbenzenediamido) chloroborane in toluene (8 mL), after which the addition is completed, and the temperature is raised to 120 ℃ until the end of the NMR detection reaction; after the reaction, the system is cooled to 25 ℃, filtered, and the filtrate is dried in vacuum to obtain a crude product, then the crude product is washed by normal hexane at 0 ℃, filtered and dried again, and the obtained solid is N of high abundance boron 10 isotope 1 ,N 2 -dimethyl o-phenylenediamine diboron compound in 76% yield to be put into the next step.
⑶ 10 B 2 neop 2 Is prepared from the following steps:
adding toluene solvent (8 mL) to the reactor D to obtain N 1 ,N 2 Dimethylphthalenediamine diboron compound (720 mg, 2.5 mmol), neopentyl glycol (520 mg, 5 mmol) was added at 25℃and dissolved in ethyl hydrogen chloride dropwise at 0℃Agent (25 mol), after the dripping, the temperature is raised to 80 ℃ and kept unchanged until the NMR detection reaction is finished; after the reaction, the system was cooled to 25 ℃, filtered through celite, concentrated to no fraction, and the solid was washed with n-hexane (0.5 mL) at 0 ℃ to give 10 B 2 neop 2 The yield was 81%.
Example 4
Synthesis of high abundance boron 10 pyrocatechol bisborate B 2 cat 2 The method of (1):
(N) of high abundance boron 10 1 ,N 2 -dimethyl o-phenylenediamine) chloroborane preparation:
toluene solvent (20 mL) and N were added to reactor E 1 ,N 2 Dimethyl o-phenylenediamine (1.36 g,10 mmol), boron trifluoride diethyl etherate (1.4 g,10 mmol) added with an abundance of boron 10 isotope and N, N-diisopropylethylamine (2.58 g,20 mmol) and tetrachlorosilane (1.79 g,10 mmol) were added dropwise at 0℃to 25℃and reacted at 90℃until the NMR detection reaction was completed; after the reaction, adding N-hexane solvent (5 mL) into the system, filtering, vacuum drying the filtrate to obtain the product (N) of high-abundance boron 10 1 ,N 2 -dimethyl o-phenylenediamine) chloroborane in 82% yield to be put into the next step.
N of high abundance boron 10 1 ,N 2 -preparation of a dimethyl o-phenylenediamine diboron compound:
toluene (8 mL) and metallic sodium (575 mg, 25 mmol) were added to reactor C and stirred and refluxed until the metallic sodium was completely melted, and the (N) obtained in the above step was added dropwise at 110 ℃to the reactor C 1 ,N 2 -a solution of dimethylbenzenediamido) chloroborane in toluene (8 mL), after which the addition is completed, and the temperature is raised to 120 ℃ until the end of the NMR detection reaction; after the reaction, the system is cooled to 25 ℃, filtered, and the filtrate is dried in vacuum to obtain a crude product, then the crude product is washed by normal hexane at 0 ℃, filtered and dried again, and the obtained solid is N of high abundance boron 10 isotope 1 ,N 2 -dimethyl o-phenylenediamine diboron compound in 76% yield to be put into the next step.
⑶ 10 B 2 cat 2 Is prepared from the following steps:
adding toluene solvent (8 mL) to the reactor D to obtain N 1 ,N 2 Dimethylphthalenediamine diboron compound (720 mg, 2.5 mmol), catechol (550 mg, 5 mmol) was added at 25℃and hydrogen chloride diethyl ether solvent (37.5 mol) was added dropwise at 0℃and the temperature was raised to 80℃and kept unchanged until the NMR detection reaction was completed; after the reaction, the system is cooled to 25 ℃, diatomite is filtered, the mixture is concentrated to no fraction after the filtration, and acetonitrile and normal hexane are used for washing the solid at 0 ℃ to obtain 10 B 2 cat 2 The yield was 71%.
Example 5
Synthesis of high abundance boron 10's pinacol ester of biboronic acid 10 B 2 pin 2 The method of (1):
n-heptane solvent (7 mL), N, was added to reactor D 1 ,N 2 -dimethyl o-phenylenediamine diboron compound (662 mg, 2.3 mmol), pinacol is added at 25 ℃, and hydrogen chloride diethyl ether solvent (23 mol) is added dropwise at 0 ℃, the temperature is raised to 80 ℃ after the addition, and the temperature is kept unchanged until the NMR detection reaction is finished; after the reaction, the system is cooled to 25 ℃, diatomite is filtered, the mixture is concentrated to no fraction after the filtration, and the solid is washed by using normal hexane (6 mL) at 0 ℃ to obtain the biboronate with high abundance of boron 10 isotope, and the yield is 87%.
Example 6
Synthesis of high abundance boron 10's pinacol ester of biboronic acid 10 B 2 pin 2 The method of (1):
toluene solvent (7 mL), N was added to reactor D 1 ,N 2 -dimethylphthalenesDiamine diboron compound (662 mg, 2.3 mmol), pinacol (4.6 mmol) was added at 25 ℃,1, 4-dioxane solvent (23 mol) was added dropwise at 0 ℃, the temperature was raised to 80 ℃ after the addition, and the temperature was kept unchanged until the end of the NMR detection reaction; after the reaction, the system is cooled to 25 ℃, diatomite is filtered, the mixture is concentrated to no fraction after the filtration, and the solid is washed by using normal hexane (6 mL) at 0 ℃ to obtain the biboronate with high abundance of boron 10 isotope, and the yield is 84%.
Example 7
Preparation of chiral dippinane diol diborate for synthesizing high abundance boron 10 10 B 2 pai 2 The method of (1):
toluene solvent (7 mL), N was added to reactor D 1 ,N 2 Dimethylparaben diamine diboron compound (662 mg, 2.3 mmol), bippinanediol (4.6 mmol) is added at 25℃and hydrogen chloride diethyl ether solvent (23 mol) is added dropwise at 0℃after the addition, the temperature is raised to 80℃and the temperature is kept unchanged until the NMR detection reaction is completed; after the reaction, the system is cooled to 25 ℃, diatomite is filtered, the mixture is concentrated to no fraction after the filtration, and the solid is washed by using normal hexane (6 mL) at 0 ℃ to obtain the biboronate with high abundance of boron 10 isotope, and the yield is 31%.
Example 8
Preparation of bis (2, 4-dimethyl-2, 4-diol) diborane with high abundance of boron 10:
toluene solvent (2 mL), N was added to reactor D 1 ,N 2 -dimethyl o-phenylenediamine diboron compound (87 mg, 0.3 mmol), 2, 4-dimethyl-2, 4-diol is added at 25 ℃, hydrogen chloride diethyl ether solvent (3 mol) is added dropwise at 0 ℃, the temperature is raised to 80 ℃ after the addition, and the temperature is kept unchanged until the GC-MS detection reaction is finished; after the reaction, the system is cooled to 25 ℃, filtered, concentrated to no fraction after filtration, and used at 0 DEG CHexane (2 mL) washed the solid to give di (2, 4-dimethyl-2, 4-diol) diborane in 42% yield with high abundance of boron 10 isotopes.
Example 9
(N) of high abundance boron 10 1 ,N 2 -dimethyl o-phenylenediamine) fluoroborane preparation:
n-heptane solvent (20 mL) and N were added to reactor A 1 ,N 2 Dimethyl o-phenylenediamine (1.36 g,10 mmol), boron trifluoride diethyl etherate (4.2 g, 30 mmol) added with high abundance of boron 10 isotope and N, N-diisopropylethylamine (2.59 g,20 mmol) are dripped at 0 ℃ to 25 ℃ and reacted until the NMR detection reaction is finished; reaction 5 h, adding N-hexane solvent (5 mL) to the system, filtering, and vacuum drying the filtrate to obtain a material (N) of high abundance boron 10 1 ,N 2 -dimethyl o-phenylenediamine) fluoroborane in a yield of 70%.
Example 10
(N) of high abundance boron 10 1 ,N 2 -dimethyl o-phenylenediamine) fluoroborane preparation:
adding cyclohexane solvent (20 mL) and N to reactor A 1 ,N 2 Dimethyl o-phenylenediamine (1.36 g,10 mmol), boron trifluoride diethyl etherate (4.2 g, 30 mmol) added with high abundance of boron 10 isotope and N, N-diisopropylethylamine (2.59 g,20 mmol) are dripped at 0 ℃ to 25 ℃ and reacted until the NMR detection reaction is finished; reaction 5 h, adding N-hexane solvent (5 mL) to the system, filtering, and vacuum drying the filtrate to obtain a material (N) of high abundance boron 10 1 ,N 2 -dimethyl o-phenylenediamine) fluoroborane in 64% yield.
Example 11
(N) of high abundance boron 10 1 ,N 2 -dimethylphthalenesDiamine) preparation of fluoroborane:
adding cyclohexane solvent (20 mL) and N to reactor A 1 ,N 2 Dimethyl o-phenylenediamine (1.36 g,10 mmol), boron trifluoride diethyl etherate (4.2 g, 30 mmol) added with an abundance of boron 10 isotope and triethylamine (2.03 g,20 mmol) are dripped at 0-25 ℃ and reacted until the NMR detection reaction is finished at 90 ℃; reaction 5 h, adding N-hexane solvent (5 mL) to the system, filtering, and vacuum drying the filtrate to obtain a material (N) of high abundance boron 10 1 ,N 2 -dimethyl o-phenylenediamine) fluoroborane in 68% yield.
Example 12
(N) of high abundance boron 10 1 ,N 2 -dimethyl o-phenylenediamine) fluoroborane preparation:
adding cyclohexane solvent (20 mL) and N to reactor A 1 ,N 2 Dimethyl o-phenylenediamine (1.36 g,10 mmol), boron trifluoride diethyl etherate (4.2 g, 30 mmol) added with an abundance of boron 10 isotope and pyridine (1.59 g,20 mmol) are dripped at 0-25 ℃, and the reaction is completed at 90 ℃ until the NMR detection reaction is completed; reaction 5 h, adding N-hexane solvent (5 mL) to the system, filtering, and vacuum drying the filtrate to obtain a material (N) of high abundance boron 10 1 ,N 2 -dimethyl o-phenylenediamine) fluoroborane in 41% yield.
Example 13
(N) of high abundance boron 10 1 ,N 2 -dimethyl o-phenylenediamine) chloroborane preparation:
adding n-hexane solvent (2 mL) and to reactor EN 1 ,N 2 Dimethyl o-phenylenediamine (136 mg,1 mmol), dropwise adding boron trifluoride diethyl etherate (140 mg,1 mmol) with an abundance of boron 10 isotope at 0-25 ℃, N, N-diisopropylethylamine (259 mg, 2 mmol) and monomethyl trichlorosilane (449 mg, 3 mmol), and reacting at 90 ℃ until the NMR detection reaction is finished; after the reaction, filtering, and vacuum drying the filtrate to obtain the product (N) of high-abundance boron 10 1 ,N 2 -dimethyl o-phenylenediamine) chloroborane in a yield of 70%.
Example 14
(N) of high abundance boron 10 1 ,N 2 -dimethyl o-phenylenediamine) chloroborane preparation:
adding N-hexane solvent (2 mL) and N to reactor E 1 ,N 2 -dimethyl o-phenylenediamine (136 mg,1 mmol), dropwise adding boron trifluoride diethyl etherate (140 mg,1 mmol) with an abundance of boron 10 isotope at 0 ℃ to 25 ℃, N-diisopropylethylamine (259 mg, 2 mmol) and dimethyl dichlorosilane (388 mg, 3 mmol), after the dropwise addition, reacting at 90 ℃ until the NMR detection reaction is completed; after the reaction, filtering, and vacuum drying the filtrate to obtain the product (N) of high-abundance boron 10 1 ,N 2 -dimethyl o-phenylenediamine) chloroborane in 55% yield.
Example 15
(N) of high abundance boron 10 1 ,N 2 -dimethyl o-phenylenediamine) chloroborane preparation:
adding N-hexane solvent (2 mL) and N to reactor E 1 ,N 2 Dimethyl-o-phenylenediamine (136 mg,1 mmol), dropwise adding boron trifluoride diethyl etherate (140 mg,1 mmol), N, N-diisopropylethylamine (259 mg, 2 mmol) and trimethylchlorosilane (326 mg, 3 mmol) with an abundance of boron 10 isotope at 0℃to 25℃and, after the dropwise addition, at 90℃The reaction is finished until the NMR detection reaction is finished; after the reaction, filtering, and vacuum drying the filtrate to obtain the product (N) of high-abundance boron 10 1 ,N 2 -dimethyl o-phenylenediamine) chloroborane in 37% yield.
Example 16
(N) of high abundance boron 10 1 ,N 2 -dimethyl o-phenylenediamine) chloroborane preparation:
adding N-hexane solvent (2 mL) and N to reactor E 1 ,N 2 -dimethyl o-phenylenediamine (136 mg,1 mmol), dropwise adding boron trifluoride dimethyl ether (113 mg,1 mmol) with an abundance of boron 10 isotope at 0-25 ℃, N-diisopropylethylamine (259 mg, 2 mmol) and tetrachlorosilane (169 mg,1 mmol), and reacting at 90 ℃ until the NMR detection reaction is finished; after the reaction, filtering, and vacuum drying the filtrate to obtain the product (N) of high-abundance boron 10 1 ,N 2 -dimethyl o-phenylenediamine) chloroborane in 86% yield.
Example 17
(N) of high abundance boron 10 1 ,N 2 -dimethyl o-phenylenediamine) chloroborane preparation:
adding N-hexane solvent (2 mL) and N to reactor E 1 ,N 2 Dimethyl o-phenylenediamine (136 mg,1 mmol), dropwise adding boron trifluoride acetone complex (1 mmol) with high abundance of boron 10 isotope at 0-25 ℃, N, N-diisopropylethylamine (259 mg, 2 mmol) and tetrachlorosilane (169 mg,1 mmol), and reacting at 90 ℃ until the NMR detection reaction is finished; after the reaction, filtering, and vacuum drying the filtrate to obtain the product (N) of high-abundance boron 10 1 ,N 2 -dimethyl o-phenylenediamine) chloroborane in 80% yield.
Example 18
Synthetic natureAbundance of pinacol ester of biboron B 2 pin 2 The method of (1):
(N) of natural abundance 1 ,N 2 -dimethyl o-phenylenediamine) chloroborane preparation:
adding N-hexane solvent (30 mL) and N to reactor E 1 ,N 2 Dimethyl o-phenylenediamine (2.72 g,20 mmol), boron trifluoride diethyl etherate (2.82 g,20 mmol) in natural abundance, N, N-diisopropylethylamine (5.17 g, 40 mmol) and tetrachlorosilane (3.58 g,20 mmol) were added dropwise at 0℃to 25℃and reacted at 90℃until the NMR detection reaction ended; after the reaction, filtering, and vacuum drying the filtrate to obtain natural abundance (N) 1 ,N 2 -dimethyl o-phenylenediamine) chloroborane in 84% yield to be taken in the next step.
N of natural abundance 1 ,N 2 -preparation of a dimethyl o-phenylenediamine diboron compound:
toluene (15 mL) and metallic sodium (1.15 g, 50 mmol) were added to a reactor C, and stirred and refluxed until the metallic sodium was completely melted, and the mixture (N) obtained in the above step was added dropwise at 110 ℃to the reactor C 1 ,N 2 -a solution of dimethylbenzenediamido) chloroborane in toluene (15, mL) and, after addition, raising the temperature to 120 ℃ until the end of the NMR detection reaction; after the reaction, the system is cooled to 25 ℃, filtered, and the filtrate is dried in vacuum, then the solid is washed by normal hexane at 0 ℃, filtered and dried again, and the obtained solid is N with natural abundance 1 ,N 2 -dimethyl o-phenylenediamine diboron compound in 74% yield to be put into the next step.
Preparation of natural abundance boronic acid pinacol ester:
the xylene solvent (15, mL) was added to the reactor D, and N was obtained in the above step 1 ,N 2 Dimethylphthalenediamine diboron compound (1.45 g, 5 mmol), pinacol (1.18 g,10 mmol) was added at 25℃and hydrogen chloride diethyl ether solvent (50 mol) was added dropwise at 0℃and the temperature was raised to 80Maintaining the temperature unchanged until the NMR detection reaction is finished; after the reaction, the system was cooled to 25 ℃, filtered through celite, concentrated to no fraction after filtration, and solid B was washed with n-hexane (1 mL) at 0 ℃ to give the naturally abundant bisborate in 87% yield.
It should be understood that the technical solution of the present invention is not limited to the above specific embodiments, and all technical modifications made according to the technical solution of the present invention without departing from the spirit of the present invention and the scope of the claims are within the scope of the present invention.
Claims (12)
1. A method of synthesizing a high abundance boron 10 isotope of a biboronate comprising the steps of:
⑴（N 1 ,N 2 -dimethyl o-phenylenediamine) fluoroborane preparation:
adding N in the reactor A 1 ,N 2 Dropwise adding boron 10 isotope boron trifluoride solution and alkali into dimethyl o-phenylenediamine and hydrocarbon solvent A at 0-25 ℃ until NMR detection reaction is finished, thereby obtaining (N) 1 ,N 2 -dimethyl o-phenylenediamine) fluoroborane;
the N is 1 ,N 2 -the ratio of dimethyl o-phenylenediamine to the hydrocarbon solvent a is 1g: 1-15 ml; the N is 1 ,N 2 -the molar ratio of dimethyl o-phenylenediamine to the boron trifluoride solution of high abundance boron 10 isotope is 1.0:1.0 to 10.0 equivalents; the N is 1 ,N 2 -the molar ratio of dimethyl-o-phenylenediamine to the base is 1.0:1.0 to 5.0 equivalents;
⑵（N 1 ,N 2 -dimethyl o-phenylenediamine) chloroborane preparation:
adding said (N) to reactor B 1 ,N 2 -dimethyl o-phenylenediamine) fluoroborane and a hydrocarbon solvent B, dropwise adding chlorosilane at room temperature, and reacting at 0-120 ℃ until the NMR detection reaction is finished; concentrating under vacuum after the reaction is finished to obtain (N) 1 ,N 2 -dimethyl o-phenylenediamine) chloroborane;
said (N) 1 ,N 2 -dimethyl o-phenylenediamine) fluoroborane to hydrocarbon solvent B in a ratio of 1g: 1-20 ml; the N is 1 ,N 2 -the molar ratio of dimethyl-o-phenylenediamine to said chlorosilane is 1.0:0.6 to 5.0 equivalents;
coupling:
adding hydrocarbon solvent C and metallic sodium into a reactor C, stirring and refluxing until the metallic sodium is completely melted, and dripping (N) at 85-120 DEG C 1 ,N 2 -dimethyl o-phenylenediamine) chloroborane, and keeping the temperature unchanged until the NMR detection reaction is finished; after the reaction is finished, the temperature of the system is reduced to 20-50 ℃, and a solid crude product is obtained by filtering and drying filtrate; washing the solid crude product with normal hexane at 0-50 ℃, filtering again, and drying to obtain N containing high-abundance boron 10 isotope 1 ,N 2 -a dimethyl o-phenylenediamine diboron compound;
the dosage of the hydrocarbon solvent C is 1-10 ml per millimole of sodium; said (N) 1 ,N 2 In hydrocarbon solutions of-dimethyl-o-phenylenediamine) chloroboranes (N 1 ,N 2 -dimethyl o-phenylenediamine) chloroborane to said sodium metal in a molar ratio of 1.0:1.0 to 6.0 equivalents; the ratio of n-hexane to the crude product was 1g: 1-5 ml;
esterification:
adding hydrocarbon solvent E and N into a reactor D 1 ,N 2 -dimethyl o-phenylenediamine diboron compound, firstly adding glycol at 10-30 ℃, then dropwise adding hydrocarbon solution of hydrogen chloride at-78-30 ℃, and after the completion of the dropwise adding, raising the temperature to 25-120 ℃ and keeping the temperature unchanged until the end of the NMR detection reaction; cooling the system to 15-25 ℃ after the reaction is finished, filtering by diatomite, and concentrating until no fraction exists to obtain a solid; washing the solid at 0-50 ℃ by using normal hexane to obtain the biboronate of the high-abundance boron 10 isotope;
the N is 1 ,N 2 -the ratio of dimethyl o-phenylenediamine diboron compound to the hydrocarbon solvent E is 1g: 1-30 ml; the N is 1 ,N 2 -the molar ratio of dimethyl o-phenylenediamine diboron compound to the diol is 1.0:1.0 to 3.0 equivalents; the N is 1 ,N 2 -the molar ratio of dimethyl o-phenylenediamine diboron compound to the hydrocarbon solution of hydrogen chloride is 1.0:4.0 to 10.0 equivalents; the N is 1 ,N 2 -the ratio of dimethyl o-phenylenediamine diboron compound to the n-hexane is 1g: 1-10 ml.
2. A method of synthesizing a high abundance boron 10 isotope biboronate according to claim 1 wherein: the boron 10 isotope boron trifluoride solution with high abundance in the step (A) refers to one of boron trifluoride ethers, ketones and amine compounds, or is boron trifluoride compound with natural abundance.
3. A method of synthesizing a high abundance boron 10 isotope biboronate according to claim 1 wherein: the hydrocarbon solvent A in the step (A) refers to one of n-heptane, n-hexane or cyclohexane.
4. A method of synthesizing a high abundance boron 10 isotope biboronate according to claim 1 wherein: the alkali in the step (A) refers to one of triethylamine, N-diisopropylethylamine, pyridine compounds, carbonate compounds and alkyl lithium reagents.
5. A method of synthesizing a high abundance boron 10 isotope biboronate according to claim 1 wherein: n in the step (A) 1 ,N 2 The structure of the dimethylphthalamide group is shown in formula (I), and the structure shown in any one of formulas (II) -VI) can be used for replacing the structure shown in the formula (II) -VI:
6. a method of synthesizing a high abundance boron 10 isotope biboronate according to claim 1 wherein: the hydrocarbon solvent B in the step II and the hydrocarbon solvent C in the step III refer to one of n-heptane, n-hexane, cyclohexane, toluene or xylene.
7. A method of synthesizing a high abundance boron 10 isotope biboronate according to claim 1 wherein: the chlorosilane in the step II refers to one of tetrachlorosilane, monomethyl trichlorosilane, dimethyl dichlorosilane or trimethyl chlorosilane.
8. A method of synthesizing a high abundance boron 10 isotope biboronate according to claim 1 wherein: said (N) 1 ,N 2 -dimethyl o-phenylenediamine) chloroborane using a one pot process:
adding N to reactor E 1 .N 2 Dropwise adding boron 10 isotope boron trifluoride solution, alkali and chlorosilane into dimethyl o-phenylenediamine and N-hexane at room temperature, and reacting at 0-120 ℃ until the NMR detection reaction is finished to obtain (N) 1 ,N 2 -dimethyl o-phenylenediamine) chloroborane; the N is 1 ,N 2 -the ratio of dimethyl o-phenylenediamine to n-hexane is 1g: 1-20 ml; the N is 1 .N 2 -the molar ratio of dimethyl o-phenylenediamine to the boron trifluoride solution of high abundance boron 10 isotope is 1.0:1.0 to 10.0 equivalents; the N is 1 ,N 2 -the molar ratio of dimethyl-o-phenylenediamine to chlorosilane is 1.0:0.6 to 5.0 equivalents; the N is 1 ,N 2 -the molar ratio of dimethyl-o-phenylenediamine to the base is 1.0:1.0 to 5.0 equivalents.
9. A method of synthesizing a high abundance boron 10 isotope biboronate according to claim 1 wherein: in the step III (N) 1 ,N 2 By a hydrocarbon solution of-dimethyl-o-phenylenediamine) chloroborane is meant 1g (N 1 ,N 2 -dimethyl o-phenylenediamine) chloroborane is dissolved by 1-10 ml hydrocarbon solvent D to prepare the catalyst; the hydrocarbon solvent D refers to toluene or xylene.
10. A method of synthesizing a high abundance boron 10 isotope biboronate according to claim 1 wherein: the hydrocarbon solvent E in the step refers to one of n-heptane, toluene or xylene.
11. A method of synthesizing a high abundance boron 10 isotope biboronate according to claim 1 wherein: the hydrocarbon solution of hydrogen chloride in the step refers to hydrogen chloride diethyl ether solution or hydrogen chloride 1, 4-dioxane solution.
12. A method of synthesizing a high abundance boron 10 isotope biboronate according to claim 1 wherein: the diol in the step has a structure shown in any one of the formulas (VII) -II:
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