[ CAS No. 429-42-5 ] {[proInfo.proName]}

Name: 429-42-5|Tetrabutylammoniumtetrafluoroborate|98%
Brand: Ambeed
SKU: A353681
Rating: 92 (25 reviews)

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Cat. No.: {[proInfo.prAm]}

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Quality Control of [ 429-42-5 ]

COA NMR CNMR HPLC LC-MS

Related Doc. of [ 429-42-5 ]

SDS Specification

Alternatived Products of [ 429-42-5 ]

Product Details of [ 429-42-5 ]

CAS No. :	429-42-5	MDL No. :	MFCD00011634
Formula :	C₁₆H₃₆BF₄N	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	NNZZSJSQYOFZAM-UHFFFAOYSA-N
M.W :	329.27	Pubchem ID :	67932
Synonyms :	Tetra-n-butylammonium tetrafluoroborate	Chemical Name :	Tetrabutylammoniumtetrafluoroborate

Calculated chemistry of [ 429-42-5 ]

Physicochemical Properties

Num. heavy atoms :	22
Num. arom. heavy atoms :	0
Fraction Csp3 :	1.0
Num. rotatable bonds :	12
Num. H-bond acceptors :	4.0
Num. H-bond donors :	0.0
Molar Refractivity :	91.59
TPSA :	0.0 Å²

Pharmacokinetics

GI absorption :	Low
BBB permeant :	No
P-gp substrate :	Yes
CYP1A2 inhibitor :	No
CYP2C19 inhibitor :	No
CYP2C9 inhibitor :	No
CYP2D6 inhibitor :	No
CYP3A4 inhibitor :	No
Log Kp (skin permeation) :	-6.27 cm/s

Lipophilicity

Log Po/w (iLOGP) :	0.0
Log Po/w (XLOGP3) :	2.87
Log Po/w (WLOGP) :	7.98
Log Po/w (MLOGP) :	1.25
Log Po/w (SILICOS-IT) :	2.29
Consensus Log Po/w :	2.88

Druglikeness

Lipinski :	0.0
Ghose :	None
Veber :	1.0
Egan :	1.0
Muegge :	1.0
Bioavailability Score :	0.55

Water Solubility

Log S (ESOL) :	-2.9
Solubility :	0.417 mg/ml ; 0.00127 mol/l
Class :	Soluble
Log S (Ali) :	-2.53
Solubility :	0.973 mg/ml ; 0.00296 mol/l
Class :	Soluble
Log S (SILICOS-IT) :	-6.35
Solubility :	0.000148 mg/ml ; 0.000000449 mol/l
Class :	Poorly soluble

Medicinal Chemistry

PAINS :	0.0 alert
Brenk :	2.0 alert
Leadlikeness :	1.0
Synthetic accessibility :	2.09

Safety of [ 429-42-5 ]

Signal Word:	Danger	Class:	9
Precautionary Statements:	P261-P264-P270-P271-P280-P302+P352-P304+P340-P305+P351+P338-P310-P330-P362+P364-P403+P233-P501	UN#:	3077
Hazard Statements:	H302-H315-H318-H335-H410	Packing Group:	Ⅲ
GHS Pictogram:

Application In Synthesis of [ 429-42-5 ]

* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

Upstream synthesis route of [ 429-42-5 ]
Downstream synthetic route of [ 429-42-5 ]

[ 429-42-5 ] Synthesis Path-Upstream 1~2

1
[ 429-42-5 ]
[ 1619-62-1 ]

Reference： [1] Bulletin of the Chemical Society of Japan, 1989, vol. 62, # 7, p. 2219 - 2228

2
[ 429-42-5 ]
[ 429-41-4 ]

Reference： [1] Zeitschrift fuer Naturforschung, B: Chemical Sciences, 1990, vol. 45, # 4, p. 469 - 475

[ 429-42-5 ] Synthesis Path-Downstream 1~22

1
[ 429-42-5 ]
[ 311-89-7 ]

Yield	Reaction Conditions	Operation in experiment
	With hydrogen fluoride electrochemical reaction; Yield given;

Reference： [1]Dimitrov. A.; Radeck, W.; Ruediger, St.; Bechstein, O. [Journal of Fluorine Chemistry, 1993, vol. 60, # 1, p. 57 - 60]

2
[ 429-42-5 ]
tetra-n-butylammonium (2-cyanophenyl)-trifluoroboronate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
56%		A flask with 2.00 g of 2-bromobenzonitrile (11.0 mmol) capped with a septum was flushed with argon and 30 mL of dry degassed THF was added. The solution was cooled to -94C and 10 mL of 1.60 M n-butyllithium solution in hexane (16.0 mmol, 1.50 eq.) was slowly added within 10 min. The obtained solution was stirred for 20 min at this temperature. 33.0 ml of 1.50 M solution of zinc chloride (22.0 mmol, 2.00 eq.) were added to the reaction mixture and stirred for 20 min. The solution consisting of 7.20 g (22.0 mol, 2.00 eq.) <strong>[429-42-5]tetra-n-butylammonium tetrafluoroborate</strong> in 20 mL THF was slowly added and the reaction mixture was stirred for 1 hour at -94C. The reaction was allowed to warm up to room temperature overnight. Then it was opened to the air, and the solvent was removed in vacuo. The residue was washed with diethyl ether and extracted three times with 50 mL of warm dry acetone. The obtained solution was concentrated to about 50 mL and 400 mL of diethyl ether was added. The precipitate was filtered off, washed with ether and dried. 2.50 g (56%) of tetra-n-butylammonium (2-cyanophenyl)-trifluoroboronate as a white crystalline solid was obtained. Assay: 1H NMR >98%.

Reference： [1]Patent: EP1764365,2007,A1 .Location in patent: Page/Page column 9

3
[ 120967-70-6 ]
[ 429-42-5 ]
4(CH₃(CH₂)3)4N⁽¹⁺⁾*(C₆H₄O₂)Rh(C₈H₁₂)^(1-)*3BF₄^(1-)=((CH₃(CH₂)3)4N)(C₆H₄O₂)Rh(C₈H₁₂)*3(CH₃(CH₂)3)4NBF₄ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
61%	With potassium tert-butylate; In tetrahydrofuran; at 20℃; for 4h;	1+BF4- (0.1 g, 0.24 mmol) and Bu4N+BF4-(0.21 g, 0.75 mmol) were dissolved in THF (5 mL) in a 20 mL-one neck Schlenk flask and the solution was mixed with 3 eq. KtBuO (0.082 g, 0.74 mmol) and stirred at r.t. for 4 h. After reaction, in comparison to the synthetic procedure for K+3-, there was no precipitate. The solvent was evaporated and the resulting yellow solid was washed five times with diethyl ether (15 mL, five times). After drying in vacuum, the solid was dissolved in THF and the diethyl ether was added carefully on the layer of THF. After a few days yellow crystals were collected and the isolated yield was 61% (0.23 g, 0.15 mmol). 1H NMR (DMSO-d6): δ 4.90(s, benzoquinone ring, 4H), 3.48(br, COD, 4H), 3.17(t, J=7.8 Hz, Bu, 32H), 2.19 (m, COD, 4H), 1.97 (m, COD, 4H), 1.57(brm, Bu, 32H), 1.32 (m, Bu, 32H), 0.94 (t, J=7.2 Hz, Bu, 48H) ppm. Elemental Anal. Calcd. for C78H160O2N4Rh1B3F12: C, 60.46; H, 10.41; N, 3.62. Found; C, 59.23; H, 10.52; N, 3.52.

Reference： [1]Patent: US2007/117981,2007,A1 .Location in patent: Page/Page column 7

4
[ 429-42-5 ]
[ 3375-31-3 ]
[ 75-05-8 ]
[ 21797-13-7 ]

Reference： [1]Journal of the American Chemical Society,2007,vol. 129,p. 2246 - 2247

5
[ 90590-75-3 ]
[ 1633-22-3 ]
[ 429-42-5 ]
[ 90614-02-1 ]

Yield	Reaction Conditions	Operation in experiment
100%	In acetone; trifluoroacetic acid a mixt. of Ru-compd. (0.154 mmol) and (2(2))(1,4)cyclophane (1.57 mmol)in dry acetone was boiled under reflux while adding degassed F3CCO2H; the mixt. was boiled under reflux for 35 min; after cooling the mixt. wasconcd. and N(C4H9)4BF4 was added; the soln. was then filtered and ether was added to the filtrate, the yellow powder was pptd.;

Reference： [1]Swann, R. Thomas; Hanson, A. W.; Boekelheide, V. [Journal of the American Chemical Society, 1986, vol. 108, # 12, p. 3324 - 3334]

6
[ 41203-22-9 ]
[ 429-42-5 ]
manganese(ll) chloride [ No CAS ]
[ 375393-71-8 ]

Reference： [1]Inorganic Chemistry,2001,vol. 40,p. 5722 - 5726

7
[Ni₅(3,6-bis(2-pyridyl)-1,2,4,5-tetrazine)5(CH₃CN)10][SbF₆]10 [ No CAS ]
[ 429-42-5 ]
[ 3109-63-5 ]
[Ni₄(3,6-bis(2-pyridyl)-1,2,4,5-tetrazine)4(CH₃CN)8][BF₄][PF₆][SbF₆]6 [ No CAS ]

Reference： [1]Journal of the American Chemical Society,2005,vol. 127,p. 12909 - 12923

8
[ 1643-19-2 ]
[ 429-42-5 ]

Yield	Reaction Conditions	Operation in experiment
96%	With potassium tetrafluoroborate; In dichloromethane; water; at 20℃; for 24h;	Example 12: Synthesis of [(n-Bu4)Nj [BF4JK[BF4] (3.12 g, 24.78 mmol) was dissolved in 15 ml of H20. [(n-Bu)4N]Br (8.05 g, 24.98 mmol) was dissolved in 25 ml of CH2C12 and added to the aqueous solution of K[BF4]. After stirring for 24 hours at ambient temperature the phases were separated. The organic phase waswashed three times with 10 ml of water dried over anhydrous Mg2SO4 and filtered. The filtrate was concentrated on a rotary evaporator to obtain a white solid. The obtained solid was dried at 90C in vacuo for 15 hours. The yield of [(n-Bu4)N][BF4] was 7.83 g (96 %, 23.8 mmol).AnalyticsMp: 153CC/H/N Analysis calc. % (found): C 58.36 (58.48), H 11.02 (10.84),N 4.25 (4.13)‘H NMR (25C, CD3CN, 300.13 MHz, delta in ppm): 0.96 (t, 12H, CH3, 3J(1H-1H) = 7.3 Hz), 1.35 (m, 8H, CH3-CH2, 1.61 (m, 8H, CH2-CH2N), 3.11 (m, 8H, NCH2) 13C NMR(25 C, CD3CN, 250.13 MHz, delta in ppm): 14.42 (s, 4C, CH3), 20.94 (m, 4C, CH3-CH2), 24.95 (m, 4C, CH2-CH2N), 59.93 (m, 4C, NCH2)“B NMR (25C, CD3CN, 96.29 MHz, delta in ppm): -1.18 (s, 1B, BF4) ‘9F NMR(25C, CD3CN, 300.13 MHz, delta inppm): -151.61 (4F, BF4)IR (ATR, 32 scans, v in cm1): 2960 (m), 2935 (w), 2875 (w), 1486 (m), 1468 (w), 1382 (w),1285 (w), 1152 (w), 1093 (m), 1047 (s), 1034 (s), 881 (w), 800 (w), 739 (w) RAMAN (460 mW, 150 scans cnf1): 2964 (7), 2933 (10), 2876 (10), 2746 (1), 1453 (4),1327(2), 1153(1), 1137 (2), 911 (2), 880 (1), 766 (1), 256 (2), 79(1)
96%	With potassium tetrafluoroborate; In dichloromethane; water; at 20℃; for 24h;	K[BF4] (3.12 g, 24.78 mmol) was dissolved in 15 ml of H20. [(n-Bu)4N]Br (8.05 g, 24.98mmol) was dissolved in 25 ml ofCH2Cb and added to the aqueous solution ofK[BF4]. Afterstirring for 24 hours at ambient temperature the phases were separated. The organic phase was washed three times with 10 ml of water dried over anhydrous Mg2S04 and filtered. Thefiltrate was concentrated on a rotary evaporator to obtain a white solid. The obtained solidwas dried at 90C in vacuo for 15 hours. The yield of [(n-BU4)N][BF4] was 7.83 g (96 %, 23.8mmol).AnalyticsMp: 153CC/H/N Analysis calc. % (found): C 58.36 (58.48), H 11.02 (1 0.84), N 4.25 ( 4.13)1H NMR (25C, CD3CN, 300.13 MHz, delta in ppm): 0.96 (t, 12H, CH3, 3JCH-1H) = 7.3 Hz),10 1.35 (m, 8H, CH3-CHz, 1.61 (m, 8H, CHz-CHzN), 3.11 (m, 8H, NCHz)13C NMR (25 C, CD3CN, 250.13 MHz, delta in ppm): 14.42 (s, 4C, CH3), 20.94 (m, 4C,CH3-CH2), 24.95 (m, 4C, CH2-CH2N), 59.93 (m, 4C, NCH2)11B NMR (25C, CD3CN, 96.29 MHz, delta in ppm): -1.18 (s, 1B, BF4)19F NMR (25C, CD3CN, 300.13 MHz, delta in ppm): -151.61 (4F, BF4)15 IR (ATR, 32 scans, v in cm-1): 2960 (m), 2935 (w), 2875 (w), 1486 (m), 1468 (w), 1382 (w),1285 (w), 1152 (w), 1093 (m), 1047 (s), 1034 (s), 881 (w), 800 (w), 739 (w)RAMAN (460 mW, 150 scans cm-1): 2964 (7), 2933 (10), 2876 (10), 2746 (1), 1453 (4),1327(2), 1153(1), 1137 (2), 911 (2), 880 (1), 766 (1), 256 (2), 79 (1)
96%	With potassium tetrafluoroborate; In dichloromethane; water; at 20℃; for 24h;	A solution of [(n-Bu4)N]Br (8.05 g, 24.98 mmol) in 50 ml of CH2C12 was added to a solution of K[BF4] (3.12 g, 24.78 mmol) in 30 ml of H20. After stirring for 24 h at ambient temperature the phases were separated. The organic phase was washed three times with 10 ml of water, dried over anhydrous Mg2S04 and filtered. The filtrate was concentrated on a rotary evaporator to obtain a white solid. The obtained solid was dried at 90C in vacuo for 15 hours. The yield of [(n-Bu4)N][BF4] was 7.83 g (96%, 23.8 mmol). DSC (10 Kmin" ): m.p. = 153C C/H/N Analysis calc. % (found): C 58.36 (58.48), H 11.02 (10.84), N 4.25 (4.13) 1H NMR (25C, CD3CN, 300.13 MHz, delta in ppm): 0.96 (t, 12H, CH3), 1.35 (m, 8H, CH3- CH2, 1.61 (m, 8H, CH2-CH2N), 3.11 (m, 8H, NCH2) 13C NMR (25 C, CD3CN, 75.47 MHz, delta in ppm): 14.4 (s, 4C, CH3), 20.9 (m, 4C, CH3- CH2), 25.0 (m, 4C, CH2-CH2N), 59.9 (m, 4C, NCH2) UB NMR (25C, CD3CN, 96.29 MHz, delta in ppm): -1.2 (s, IB, BF ) 19F NMR (25C, CD3CN, 282.40 MHz, delta in ppm): -151.6 (s, 4F, BF4) IR (ATR, 32 scans, v in cm"1): 2960 (m), 2935 (w), 2875 (w), 1486 (m), 1468 (w), 1382 (w), 1285 (w), 1152 (w), 1093 (m), 1047 (s), 1034 (s), 881 (w), 800 (w), 739 (w) RAMAN (460 mW, 150 scans, v in cm"1): 2964 (7), 2933 (10), 2876 (10), 2746 (1), 1453 (4), 1327(2), 1153(1), 1137 (2), 911 (2), 880 (1), 766 (1), 256 (2), 79 (1)

With sodium tetrafluoroborate; In water;

General procedure: A short column with 0.2 m length and 0.02 m diameter was loaded with 20 g of activated resin. This column was then washed with deionised distilled water. It was then treated with 100 ml of unimolar salt solution containing desired anion. The column was again washed 3-4 times with 100 ml portions of deionised distilled water. 100 ml of 0.1 M aqueous solution of tetrabutylammonium bromide was then introduced in the column. Few drops of eluent were tested with silver nitrate solution and the absence of bromide ions was confirmed by nonappearance of yellowish white precipitates. Water from the eluent was removed under vacuum (15 mm/Hg) at 60-70 C temperature. Finally compounds were dried in a vacuum desiccator for 72 h. The ion-exchange cycle for IL synthesis is shown in Fig. 1.

Reference： [1]Patent: WO2014/29833,2014,A1 .Location in patent: Page/Page column 11; 12
[2]Patent: WO2014/29834,2014,A1 .Location in patent: Page/Page column 9; 10
[3]Patent: WO2016/162400,2016,A1 .Location in patent: Page/Page column 30-31
[4]European Journal of Organic Chemistry,2012,p. 3566 - 3569
[5]Journal of Organic Chemistry,2011,vol. 76,p. 391 - 395
[6]Thermochimica Acta,2013,vol. 556,p. 23 - 29

9
[Bu₄N][trans-C₄H₉CF=CFBF₃] [ No CAS ]
[ 1081842-01-4 ]
[ 1361257-53-5 ]
[ 429-42-5 ]

Yield	Reaction Conditions	Operation in experiment
76%	With chlorine; In acetonitrile; at 0 - 20℃;Inert atmosphere;	A solution of [Bu4N][trans-C4H9CF55CFBF3] (399 mg,0.93 mmol) in MeCN (5 mL) was cooled to ~0 C under anatmosphere of dry argon. Chlorine (1.2 mmol) in argon wasbubbled during 15 min through the stirred solution and a whitesuspension was formed. Residual chlorine was removed bybubbling of argon during 45 min at ~0 C. The suspension wasstirred at ~20 C for additional 10 min and then centrifuged. Thecolorless mother liquor contained trans-C4H9CF55CFCl (majorproduct), [Bu4N][BF4], and [Bu4N][C4H9CFCl-CFClBF3] (resonancesat -110 (m, 1F, F2), -137 (m, 1F, F1), and -147 (q(1:1:1:1), 1J(F, B) = 39 Hz, 3F, BF3) ppm (19F NMR) (minor). Thevolatiles were distilled off. The residue was suspended in benzene(2 mL) and the volatiles were distilled off again. The combineddistillates were washed with water (3x10 mL) and dried withMgSO4. NMR spectroscopy showed resonances of trans-C4H9CF55CFCl (0.71 mmol, 76% yield), besides traces of cis-C4H9CF55CFCl and trans-C3H7CHClCF55CFCl.

Reference： [1]Journal of Fluorine Chemistry,2012,vol. 135,p. 114 - 128

10
[ 38932-80-8 ]
potassium (trans-1,2-difluorohex-1-en-1-yl)trifluoroborate [ No CAS ]
[ 1361257-64-8 ]
[ 429-42-5 ]

Yield	Reaction Conditions	Operation in experiment
0.32 mmol; 0.7 mmol	In tetrahydrofuran; water; at 20℃; for 0.5h;	K[trans-C4H9CF55CFBF3] (159 mg, 0.70 mmol) was reacted with [Bu4N][Br3] (365 mg, 0.76 mmol) in aq THF (1:1, v/v) (4 mL) as described above and yielded a solution of trans-C4H9CF55CFBr (0.32 mmol) and [Bu4N][BF4] (0.70 mmol) (19F NMR).

Reference： [1]Journal of Fluorine Chemistry,2012,vol. 135,p. 114 - 128

11
[ 7677-24-9 ]
[ 429-42-5 ]
[ 1569490-54-5 ]

Yield	Reaction Conditions	Operation in experiment
90%	With phosphorus pentachloride; at 20℃; for 3h;Inert atmosphere;	Example 8 was repeated with the difference:1. PC15 (30 mg, 6 mol %, the mol % being based onthe combined molar amount of [(n-Hu)4N] [HF4] and PC15)were used instead of FeC13.1Afterthe stirring for 3 han’‘Band ‘9F NMR spectrawere measured. In accordance to ‘9F NMR and ‘H NMR theproduct contained 100% of compound of formula (1).1 After removing the solvent the obtained white solidsubstance was dried at 50 C. in vacuo to yield 0.680 g (90%,1.66 mmol) of compound of formula (1).C/H/N Analysis calc. % (found): C, 65.14 (64.44); H, 10.36 (10.41); N, 15.99 (16.20).1‘H NMR (25 C., CDC13, 300.13 MHz, delta in ppm): 1.00 (t, 12H, CH3), 1.41 (m, 8H, CH3-CH2), 1.60 (m, 8H, CH2-CH2N), 3.12 (m, 8H, NCH2)“H NMR (25 C., CDC13, 300.13 MHz, delta in ppm): -17.6 (d, 1H, HF(CN)3, ‘J(”H-’9F)=45 Hz) ‘3C NMR (25 C., CDC13, 300.13 MHz, delta in ppm): 13.3 (s, 4C, CH3), 19.4 (t, 4C, CH2-CH3), 23.6 (s, 4C, N-CH2---CH2), 58.7 (t, 4C, NCH2), 127.2 (dq, 3C, HF(CN)3, ‘J(’3C-’9F)=38 Hz, ‘J(’3C-”H)=75 Hz) ‘9F NMR (25 C., CDC13, 300.13 MHz, delta in ppm): -210.9 (q, iF, HF(CN)3, ‘J(”H-’9F)=45 Hz)IR (ATR, 32 scans, v in cm’): 2964 (m), 2935 (m),2876 (m), 2214 (w), 1474 (m), 1381 (m), 1171 (w), 1040 (m), 960 (w), 938 (,), 903 (s), 803 (w), 736 (m), 536 (w); [(n-Hu)4N][HF4] (0.491 g, 1.49 mmol), prepared according to Preparation Description A, FeC13 (20 mg, 7 mol %, the mol % being based on the combined molar amount of [(n-Hu)4N][HF4] and FeC13) and (CH3)3SiCN (1.58 g, 1.59 mmol) were stirred under argon atmosphere at ambient temperature for 3 h.After the stirring at ambient temperature for 3 h an11H and ‘9F NMR spectra were measured. In accordance to‘9F NMR and “H NMR the product contained 100% of compound of formula (4). Afterremoving the solvent the obtained light yellow solid substance was dried at 50 C. in vacuo to yield 0.400 g (69%, 1.17 mmol) of compound of formula (4).
83%		[(n-Bu)4N][BF4] (1.17 g, 3.55 mmol), prepared according to example 12, and (CH3)3SiCN (1.23 g, 12.44 mmol) were filled under argon atmosphere with a residual oxygen content of below 5 ppm and with a residual water content of below 1 ppm into a teflon tube. The teflon tube was closed using a teflon lid and place in an autoclave. The autoclave wasplaced inside a muffle furnace which was heated to 150C in 30 mm. This temperature was held for 13 h.After cooling to ambient temperature the reaction mixture was mixed with water and aqueous hydrogen peroxide (0.5 ml, 5 mmol, 30 wt%). After stirring at 60C for an hour the solution was cooled to ambient temperature. The product was extracted with dichloromethane threetimes. The organic phase was separated and dried with Mg504 and filtered. The filtrate was evaporated on a rotary evaporator. The yield of the yellow crystalline product was 0.95 g (76%, 2.71 mmol). Only one boron and one fluorine species, the one of the desired product, is visible in 11B NMR and in the 19F NMR respectively. AnalyticsMp: 60CC/H/N Analysis caic. % (found): C 65.14 (64.90), H 10.36 (10.15), N 15.99 (15.87)‘H NMR (25C, CD3CN, 300.13 MHz, delta in ppm): 0.97 (t, 12H, CH3, 3J(1H-1H) = 7.2 Hz),1.36 (m, 8H, CH3-CH2, 3J(1H-1H) = 7.6 Hz), 1.59 (m, 8H, CH2-CH2N), 3.08 (m, 8H,NCH2)‘3C NMR(25C, CD3CN, 250.13 MHz, delta in ppm): 13.78 (s, 4C, CH3), 20.30 (m, 4C, CH3-CH2), 24.29 (m, 4C, CH2-CH2N), 59.33 (m, 4C, NCH2), 127.83 (3C, CN)“B NMR (25C, CD3CN, 96.29 MHz, delta in ppm): -17.87 (d, 1B, BF(CN)3, 1J(13C-11B =44.02 Hz)‘9FNMR(25C, CD3CN, 300.13 MHz, delta in ppm): -211.73 (q, iF, 1J(11B-19F)=44.96Hz, 2J(10B-19F) = 34.74 Hz)IR (ATR, 32 scans, v in cm1): 2964 (m), 2935 (m), 2876 (m), 2214 (w), 1474 (m), 1408(w), 1382 (w), 1361(w), 1350 (w), 1322 (w), 1311 (w), 1285(w), 1244 (w), 1171 (w), 1130(w), 1110 (w), 1080 (w), 1040 (m), 991 (w), 959 (m), 938 (m), 926 (m), 903 (s), 821 (w),803 (w), 736 (m), 668 (w), 592 (w), 532 (w)RAMAN (500 mW, 400 scans cm1): 2971 (5), 2941 (7), 2878 (6), 2219 (10), 1452 (3), 1324 (2), 1113 (2), 1062 (1), 910 (1), 883 (1), 594 (1), 264 (1), 224 (1), 130 (2);_Example 1 was repeated with the differences:1. [(n-Bu)4N][BF4] (17.957 g, 54.5 mmol) and (CH3)3SiCN (21.1 g, 213 mmol) were used.2. The temperature was 140C instead of 150C, which was held for 20 h instead of 13 h.3. 5 ml of the aqueous hydrogen peroxide were used instead of 0.5 ml.A light yellow crystalline product was obtained (15.847 g, 83%, 45.2 mmol).
76%		Example 1: Synthesis of [(n-Bu)4N] [BF(CN)3] [0063] [(n-Bu)4N][BF4] (1.17 g, 3.55 mmol), prepared according to example 12, and (CH3)3SiCN (1.23 g, 12.44 mmol) were filled under argon atmosphere with a residual oxygen content of below 5 ppm and with a residual water content of below 1 ppm into a teflon tube. The teflon tube was closed using a teflon lid and place in an autoclave. The autoclave was placed inside a muffle furnace which was heated to 150C in 30 min. This temperature was held for 13 h. After cooling to ambient temperature the reaction mixture was mixed with water and aqueous hydrogen peroxide (0.5 ml, 5 mmol, 30 wt%). After stirring at 60C for an hour the solution was cooled to ambient temperature. The product was extracted with dichloromethane three times. The organic phase was separated and dried with MgSO4 and filtered. The filtrate was evaporated on a rotary evaporator. The yield of the yellow crystalline product was 0.95 g (76%, 2.71 mmol). Only one boron and one fluorine species, the one of the desired product, is visible in 11B NMR and in the 19F NMR respectively. Analytics Mp: 60C [0064] C/H/N Analysis calc. % (found): C 65.14 (64.90), H 10.36 (10.15), N 15.99 (15.87) 1H NMR (25C, CD3CN, 300.13 MHz, delta in ppm): 0.97 (t, 12H, CH3, 3J(1H-1H) = 7.2 Hz), 1.36 (m, 8H, CH3-CH2, 3J(1H-1H) = 7.6 Hz), 1.59 (m, 8H, CH2-CH2N), 3.08 (m, 8H, NCH2) 13C NMR (25C, CD3CN, 250.13 MHz, delta in ppm): 13.78 (s, 4C, CH3), 20.30 (m, 4C, CH3-CH2), 24.29 (m, 4C, CH2-CH2N), 59.33 (m, 4C, NCH2), 127.83 (3C, CN) 11B NMR (25C, CD3CN, 96.29 MHz, delta in ppm): -17.87 (d, 1B, BF(CN)3, 1J(13C-11B = 44.02 Hz) 19F NMR (25C, CD3CN, 300.13 MHz, delta in ppm): -211.73 (q, 1F, I1J(11B-19F) = 44.96 Hz, 2J(10B-19F) = 34.74 Hz) IR (ATR, 32 scans, ν in cm-1): 2964 (m), 2935 (m), 2876 (m), 2214 (w), 1474 (m), 1408(w), 1382 (w), 1361(w), 1350 (w), 1322 (w), 1311 (w), 1285(w), 1244 (w), 1171 (w), 1130 (w), 1110 (w), 1080 (w), 1040 (m), 991 (w), 959 (m), 938 (m), 926 (m), 903 (s), 821 (w), 803 (w), 736 (m), 668 (w), 592 (w), 532 (w) RAMAN (500 mW, 400 scans cm-1): 2971 (5), 2941 (7), 2878 (6), 2219 (10), 1452 (3), 1324 (2), 1113 (2), 1062 (1), 910 (1), 883 (1), 594 (1), 264 (1), 224 (1), 130 (2)

Reference： [1]Patent: US2016/229874,2016,A1 .Location in patent: Paragraph 0378-0386; 0393; 0394; 0395; 0396; 0397-0402
[2]European Journal of Inorganic Chemistry,2016,vol. 2016,p. 1175 - 1183
[3]Patent: WO2014/29833,2014,A1 .Location in patent: Page/Page column 6; 7; 10
[4]Patent: EP2772495,2014,A1 .Location in patent: Paragraph 0063-0064

12
[ 7677-24-9 ]
[ 429-42-5 ]
[ 261356-48-3 ]

Yield	Reaction Conditions	Operation in experiment
95%		[(n-Bu)4N][BF4] (1.03 g, 3.13 mmol), prepared according to example 2, and (CH3) 3SiCN(1.87 g, 18.85 mmol) were filled under argon atmosphere with a residual oxygen content ofbelow 5 ppm and with a residual water content of below 1 ppm into a teflon tube of anautoclave. The autoclave was placed inside a muffle furnace and heated to 200C within 30 minutes. Thetemperature was held for 15 hours.After cooling to ambient temperatures the black oily reaction mixture was mixed with water(10 ml) and aqueous H20 2 (1 ml, 10 mmol, 30 wt%). After stirring at 60C for an hour and5 cooling to ambient temperature the suspension was filtered. The brown solid was washed twotimes with water. The crude product was dissolved in 10 ml ofCH3CN and 0.5 g activatedcharcoal was added. After stirring for 15 minutes at 50C the suspension was filtered and newactivated charcoal was added. This procedure was repeated four times. The orange solutionwere evaporated on a rotary evaporator to obtain the product with a yield of 836 mg (75%,10 2.34 mmol).Only one boron species, the one of the desired product, and no fluorine species is visible in11B NMR and in the 19F NMR respectively. Analytics15 Mp: 79CC/H/N Analysis calc.% (found): C 67.22 (66.18), H 10.15 (9.85), N 19.60 (19.99)1H NMR (25C, CD3CN, 300.13 MHz, delta in ppm): 0.96 (t, 12H, CH3•3JCH-1H) = 7.3 Hz),1.35 (m, 8H, CH3-CH2•3JCH-1H) = 7.5 Hz), 1.59 (m, 8H, CHz-CH2N), 3.07 (m, 8H, NCH2)13C NMR (25 C, CD3CN, 250.13 MHz, delta in ppm): 14.40 (s, 4C, CH3), 20.94 (m, 4C,20 CH3-CH2), 24.93 (m, 4C, CHz-CH2N), 59.98 (m, 4C, NCH2), 123.85 (q, 4C, CN, 1JC 1B-13C)= 71.0 Hz)11B NMR (25C, CD3CN, 96.29 MHz, delta in ppm): -38.63 (s, 1B, B(CN)4,1J( 13C-11B =71.0 Hz)IR (ATR, 32 scans, v in cm-1): 2963 (s), 2935 (m), 2876 (m), 2221 (w), 1705 (w), 1591 (w),25 1474 (m), 1456 (w), 1409 (w), 1381 (w), 1360 (w), 1324 (w), 1244 (w), 1169 (w), 1110 (w),1060 (w), 1035 (w), 991 (w), 967 (w), 931 (s), 885 (m), 842 (w), 824 (w), 802 (w), 736 (m),534 (w)30Cyanid content was 81 ppm.Si content was 163 ppm. Example 4: Synthesis of [(n-Bu)4N] [B(CN)4]Example 1 was repeated with the following differences:1. [(n-Bu)4N][BF4] (2.14 g, 6.50 mmol), prepared according to example 2, and (CH3)3SiCN(3.87 g, 39.00 mmol) were used.2. After the 15 hours at 200C the reaction mixture was cooled to ambient temperature and20 the excess (CH3 )3SiCN was removed in vacuo. The brown solid was dissolved in 20 mlof ethyl acetate and 4 g activated carbon was added. The suspension was stirred at 50Cfor 10 minutes. The suspension was filtered off to obtain an orange solution. Theactivated carbon residue on the filter was 5 times extracted, each time with 10 ml ethylacetate, by suspending the activated carbon in the ethyl acetate, stirring for 10 minutes at25 50C and filtering.The orange solution and the five ethyl acetate extracts were combined and the ethylacetate was removed under reduced pressure. The obtained solid was dried in vacuo toyield 2.20 g (95%, 6.16 mmol) of [(n-Bu4)N][B(CN)4].
79%	With gallium(III) trichloride; at 20℃; for 3h;Inert atmosphere;	Example 8 was repeated with the difference:1. GaC13 (30 mg, 5 mol %, the mol % being based on the combined molar amount of [(n-Bu)4N] [BF4] and GaC13) were used instead of FeC13.2. The reaction mixture was refluxed instead of stirring at ambient temperature.Afterthe stirring for 3 han’‘B and ‘9F NMR spectrawere measured. In accordance to ‘B the reaction mixturecontained 100% of compound of formula (5). After removing the solvent the obtained light yellowsolid substance was dried at 500 C. in vacuo to yield 0.425 g(79%, 1.19 mmol) of compound of formula (5). C/H/N Analysis calc. % (found): C, 67.22 (66.43); H, 10.15 (9.96); N, 19.60 (19.00).‘H NMR (25 C., CDC13, 300.13 MHz, delta in ppm): 1.03 (t, 12H, CH3), 1.44 (m, 8H, CH3-CH2), 1.62 (m, 8H, CH2-CH2N), 3.12 (m, 8H, NCH2); [(n-Hu)4N][HF4] (0.491 g, 1.49 mmol), prepared according to Preparation Description A, FeC13 (20 mg, 7 mol %, the mol % being based on the combined molar amount of [(n-Hu)4N][HF4] and FeC13) and (CH3)3SiCN (1.58 g, 1.59 mmol) were stirred under argon atmosphere at ambient temperature for 3 h.After the stirring at ambient temperature for 3 h an11H and ‘9F NMR spectra were measured. In accordance to‘9F NMR and “H NMR the product contained 100% of compound of formula (4). Afterremoving the solvent the obtained light yellow solid substance was dried at 50 C. in vacuo to yield 0.400 g (69%, 1.17 mmol) of compound of formula (4).

Reference： [1]Patent: WO2014/29834,2014,A1 .Location in patent: Page/Page column 8; 9; 11
[2]European Journal of Inorganic Chemistry,2016,vol. 2016,p. 1175 - 1183
[3]Patent: US2016/229874,2016,A1 .Location in patent: Paragraph 0378-0386; 0430; 0431; 0432; 0433; 0434-0439

13
[ 1643-19-2 ]
[ 14075-53-7 ]
[ 429-42-5 ]

Yield	Reaction Conditions	Operation in experiment
96%	In dichloromethane; water; at 20℃; for 24h;	Example 12: Synthesis of [(n-Bu4)N][BF4] [0084] K[BF4] (3.12 g, 24.78 mmol) was dissolved in 15 ml of H2O. [(n-Bu)4N]Br (8.05 g, 24.98 mmol) was dissolved in 25 ml of CH2Cl2 and added to the aqueous solution of K[BF4]. After stirring for 24 hours at ambient temperature the phases were separated. The organic phase was washed three times with 10 ml of water dried over anhydrous Mg2SO4 and filtered. The filtrate was concentrated on a rotary evaporator to obtain a white solid. The obtained solid was dried at 90C in vacuo for 15 hours. The yield of [(n-Bu4)N][BF4] was 7.83 g (96 %, 23.8 mmol). Analytics Mp: 153C [0085] C/H/N Analysis calc. % (found): C 58.36 (58.48), H 11.02 (10.84), N 4.25 (4.13) 1H NMR (25C, CD3CN, 300.13 MHz, delta in ppm): 0.96 (t, 12H, CH3, 3J(1H-1H) = 7.3 Hz), 1.35 (m, 8H, CH3-CH2, 1.61 (m, 8H, CH2-CH2N), 3.11 (m, 8H, NCH2) 13C NMR (25C, CD3CN, 250.13 MHz, delta in ppm): 14.42 (s, 4C, CH3), 20.94 (m, 4C, CH3-CH2), 24.95 (m, 4C, CH2-CH2N), 59.93 (m, 4C, NCH2) 11B NMR (25C, CD3CN, 96.29 MHz, delta in ppm): -1.18 (s, 1B, BF4) 19F NMR (25C, CD3CN, 300.13 MHz, delta in ppm): -151.61 (4F, BF4) IR (ATR, 32 scans, nu in cm-1): 2960 (m), 2935 (w), 2875 (w), 1486 (m), 1468 (w), 1382 (w), 1285 (w), 1152 (w), 1093 (m), 1047 (s), 1034 (s), 881 (w), 800 (w), 739 (w) RAMAN (460 mW, 150 scans cm-1): 2964 (7), 2933 (10), 2876 (10), 2746 (1), 1453 (4), 1327(2), 1153(1), 1137 (2), 911 (2), 880 (1), 766 (1), 256 (2), 79 (1)
96%	In dichloromethane; water; at 20℃; for 24h;	A solution of [(n-Bu4)N]Br (8.05 g, 24.98 mmol) in50 ml of CH2C12 was added to the solution of K[BF4] (3.12 g,24.78 mmol) in 30 ml of H20. After stirring for 24 h at ambient temperature the phases were separated. The organic phase was washed three times with 10 ml of water, dried over anhydrous Mg2 SO4 and filtered. The filtrate was concentrated on a rotary evaporator to obtain a white solid. The obtained solid was dried at 90 C. in vacuo for 15 hours. The yield of [(n-Bu4)N] [HF4] was 7.83 g (96%, 23.8 mmol).DSC (10 Kmin?): m.p.=153 C.10345] C/H/N Analysis calc. % (found): C, 58.36 (58.48);H, 11.02 (10.84); N, 4.25 (4.13).?H NMR (25 C., CD3CN, 300.13 MHz, delta in ppm): 0.96 (t, 12H, CH3), 1.35 (m, 8H, CH3-CH2, 1.61 (m, 8H, CH2-CH2N), 3.11 (m, 8H, NCH2)13C NMR (25 C., CD3CN, 250.13 MHz, delta in ppm): 14.42 (s, 4C, CH3), 20.94 (m, 4C, CH3-CH2), 24.95 (m, 4C, CH2-CH2N), 59.93 (m, 4C, NCH2)?B NMR (25 C., CD3CN, 96.29 MHz, delta in ppm): -1.18 (s, 1H, HF4)?9F NMR (25 C., CD3CN, 300.13 MHz, delta in ppm): -151.61 (s, 4F, HF4)IR (ATR, 32 scans, v in cm?): 2960 (m), 2935 (w),2875 (w), 1486 (m), 1468 (w), 1382 (w), 1285 (w), 1152 (w), 1093 (m), 1047 (s), 1034 (s), 881 (w), 800 (w), 739 (w)RAMAN (460 mW, 150 scans, v in cm?): 2964(7),2933 (10), 2876(10), 2746(1), 1453 (4), 1327(2), 1153(1),1137 (2), 911 (2), 880 (1), 766 (1), 256 (2), 79(1)

Reference： [1]Patent: EP2772495,2014,A1 .Location in patent: Paragraph 0084-0085
[2]Chemistry - A European Journal,2016,vol. 22,p. 4175 - 4188
[3]European Journal of Inorganic Chemistry,2016,vol. 2016,p. 1175 - 1183
[4]Patent: US2016/229874,2016,A1 .Location in patent: Paragraph 0342; 0343; 0344; 0345; 0346; 0347; 0348-0351

14
[ 13755-29-8 ]
[ 1643-19-2 ]
[ 429-42-5 ]

Yield	Reaction Conditions	Operation in experiment
96%	In dichloromethane; water;	As the high melting point intermediate Q + Y -, an ammonium salt ionic liquid represented by the general formula (2) and having R1 = R2 = R3 = R4 = n-butyl group was synthesized (hereinafter, cation Q + in this ionic liquid is abbreviated as [N4444] ). That is, [N4444] [Br] purchased from Tokyo Kasei was anion-exchanged to [N4444] [BF4] by double decomposition extraction method. Specifically, an aqueous solution of [N4444] [Br] and an aqueous solution of NaBF 4 were mixed according to the above-described formula (8), further dichloromethane was added and stirred. In addition, NaBF 4 was used in a material amount ratio of 1.5 equivalents with respect to [N 4444] [Br]. Dichloromethane was used in an amount of 1 part by weight with respect to [N4444] [Br]. When the mixture was allowed to stand, it was separated into two layers of an aqueous layer and an organic layer, so the organic layer was separated and the solvent was distilled off to obtain [N4444] [BF4]. The obtained [N4444] [BF4] was recrystallized three times under the conditions of Table 3.

Reference： [1]Patent: JP2017/200889,2017,A .Location in patent: Paragraph 0117
[2]RSC Advances,2015,vol. 5,p. 25287 - 25294
[3]Journal of Materials Chemistry C,2017,vol. 5,p. 9370 - 9375

15
[ 109-73-9 ]
[ 429-42-5 ]

Yield	Reaction Conditions	Operation in experiment
50%	With tetrafluoroboric acid diethyl ether; In diethyl ether;	Butylamine (200 mg, 2.7 mmol) was dissolve in 1 mL diethylether, and 442 mg (2.7 mmol) of tetrafluoroboric acid diethyl ether complex, HBF4.Et2O, was added to the solution leading to the formation of a white solid salt in a quantitative yield. The product was then filtered off and recrystallized two times from ethylacetate. The product was then dried under high vacuum and stored at -20 C. Yield: 50% of a white solid. 1H NMR (300 MHz, DMSO) δ 7.58 (s, 3H), 2.84-2.71 (m, 2H), 1.56-1.43 (m, 2H), 1.39-1.25 (m, 2H), 0.89 (t, J=7.3 Hz, 3H). 13C-NMR (300 MHz, DMSO-d6) δ=38.64, 29.09, 19.08, 13.49. EA: C: 29.61% (calc.: 29.85%), H: 7.27% (calc.: 7.51%), N: 8.60% (calc.: 8.70%).

Reference： [1]Patent: US2015/87788,2015,A1 .Location in patent: Paragraph 0069

16
[ 7677-24-9 ]
[ 429-42-5 ]
C₁₆H₃₆N⁽¹⁺⁾*CBF₃N^(1-) [ No CAS ]
tetra-n-butylammonium dicyanido(difluorido)borate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
82%Spectr.; 69%	at 20℃; for 100h;Inert atmosphere;	Example 8 was repeated with the differences: 1. That no FeC13 was added to the reaction mixture.2. The reaction mixture was stirred for 100 h instead of 3 h. After stirring at ambient temperature for 100 h an‘B and ‘9F NMR spectra were measured. In accordance to ‘9F and “B NMR the productcontained about 82% of compound of formula (3) and 18% ofcompound of formula (4).1NMR data are the same as stated here:‘H NMR (25 C., CDC13, 300.13 MHz, delta in ppm): 0.98 (t, 12H, CH3), 1.41 (m, 8H, CH3-CH2), 1.61 (m, 8H, CH2-CH2N), 3.16 (m, 8H, NCH2)“B NMR (25 C., CDC13, 300.13 MHz, delta in ppm): -3.6 (q, 1B, BF3(CN), ‘J(”B-’9F)=28 Hz)13C NMR (25 C., CDC13, 300.13 MHz, delta in ppm): 13.4 (s, 4C, CH3), 19.5 (t, 4C, CH2-CH3), 23.7 (s, 4C, N-CH2--CH2), 58.5 (t, 4C, NCH2)‘9F NMR (25 C., CDC13, 300.13 MHz, delta in ppm): -137.0 (q, 3F, BF3(CN), ‘J(”B-’9F)=28 Hz)1IR (ATR, 32 scans, v in cm’): 2964 (m), 2937 (m),2877 (m), 2206 (w), 1474 (m), 1383 (m), 1261 (w), 1106(s), 1058 (s), 990 (m), 952 (s), 881 (m), 799 (m), 738 (m),681 (m), 532 (w)and as in example 8.; [(n-Hu)4N][HF4] (0.491 g, 1.49 mmol), prepared according to Preparation Description A, FeC13 (20 mg, 7 mol %, the mol % being based on the combined molar amount of [(n-Hu)4N][HF4] and FeC13) and (CH3)3SiCN (1.58 g, 1.59 mmol) were stirred under argon atmosphere at ambient temperature for 3 h.After the stirring at ambient temperature for 3 h an11H and ‘9F NMR spectra were measured. In accordance to‘9F NMR and “H NMR the product contained 100% of compound of formula (4). Afterremoving the solvent the obtained light yellow solid substance was dried at 50 C. in vacuo to yield 0.400 g (69%, 1.17 mmol) of compound of formula (4).
82%Spectr.; 18%Spectr.	at 20℃; for 100h;Inert atmosphere;	[(n-Bu)4N][BF ] (0.491 g, 1.49 mmol), prepared according to Preparation Description A, and (CH3)3SiCN (1.58 g, 1.59 mmol) were stirred under argon atmosphere at ambient temperature for 100 h. After the stirring at ambient temperature for 100 h an nB and 19F NMR spectra were measured. In accordance to 19F and nB NMR the product contained about 82% of compound of formula (4) and 18% of compound of formula (5). [(n-Bu)4N][BF3(CN)] [(n-Bu)4N][BF2(CN)2] (5) 1H NMR (25C, CDCls, 300.13 MHz, delta in ppm): 0.98 (t, 12H, CH3), 1.41 (m, 8H, CH3-CH2), 1.61 (m, 8H, CH2-CH2N), 3.16 (m, 8H, NCH2) nB NMR (25C, CDCI3, 300.13 MHz, delta in ppm): -3.6 (q, IB, BF3(CN), ^("B-^F) = 28 Hz), -7.2 (q, IB, BF2(CN)2, ^("B-^F) = 42 Hz) 13C NMR (25C, CDCI3, 300.13 MHz, delta in ppm): 13.4 (s, 4C, CH3), 19.5 (t, 4C, CH2-CH3), 23.7 (s, 4C, N-CH2-CH2), 58.5 (t, 4C, NCH2) 19F NMR (25C, CDC13, 300.13 MHz, delta in ppm): -137.0 (q, 3F, BF3(CN), ^("B-^F) = 28 Hz), -153.1 (q, 2F, BF2(CN)2, ^("B-^F) = 42 Hz) IR (ATR, 32 scans, v in cm"1): 2964 (m), 2937 (m), 2877 (m), 2206 (w), 1474 (m), 1383 (m), 1261 (w), 1106 (s), 1058 (s), 990 (m), 952 (s), 881 (m), 799 (m), 738 (m), 681 (m), 532 (w)

Reference： [1]European Journal of Inorganic Chemistry,2016,vol. 2016,p. 1175 - 1183
[2]Patent: US2016/229874,2016,A1 .Location in patent: Paragraph 0378-0386; 0457; 0458; 0459; 0460; 0461-0468
[3]Patent: WO2016/162400,2016,A1 .Location in patent: Page/Page column 33-34

17
[ 7677-24-9 ]
[ 429-42-5 ]
tetra-n-butylammonium dicyanido(difluorido)borate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
87.2%	With chloro-trimethyl-silane; In 1,2-dimethoxyethane; at 76℃; for 7h;Inert atmosphere;	General procedure: Reaction Step In a 100 mL glass three-necked flask, 5.00 g (45.5 mmol; 1.0 eq.) Of sodium tetrafluoroborate (Wako Pure Chemical Industries, Ltd.), 14.91 g (150.3 mmol; 3.3 eq.) Of trimethylsilyl cyanide (manufactured by Tokyo Chemical Industry Co., Ltd.) were charged, and then a thermometer, a Dimroth, a gas inlet tube were attached, and a reaction apparatus with a septum was assembled. 50 mL of 1,2-dimethoxyethane as a reaction solvent was charged from a septum using a syringe and stirred with a stirrer piece under nitrogen flow. Next, 0.6 mL (4.6 mmol; 0.1 eq.) Of Lewis acid catalyst, trimethylsilyl chloride, was similarly charged from a septum using a syringe. At this time, 1.1 parts by mass of a Lewis acid catalyst was used per 100 parts by mass of the reaction solvent. The flask was placed in an oil bath at 100 C. to initiate the reaction. After a while, raw material tetrafluoroboric acid sodium dissolved and gas evolution was seen. Gas generation stopped within about 10 minutes. The reaction was carried out for 7 hours, and the temperature in the system at this time was 75 C. (reflux). The reaction mixture was an orange solution, and the obtained cyanoborate compound(Cyanoborate compound in the reaction mixture)Was confirmed by 11 B-NMR, the tricyanofluoro form was found to be 100 mol%.Purification processThe solvent was distilled off from the reaction mixture under reduced pressure to obtain an orange solid. 50 mL of ultrapure water was added thereto for dissolution, and 5 mL of 30% by mass hydrogen peroxide water was further added thereto. Then, while stirring, 5.8 g (54.7 mmol) of anhydrous sodium carbonate was added slowly.At this time, the color of the solution changed from orange to colorless and slight bubbles were observed. Analysis of a 50-fold diluted solution with Quantofix test paper (peroxide, cyanide ion) showed that only 100 mg / L of peroxide was detected, and cyanide ions were not detected. Thereafter, 1.7 g (10.8 mmol) of sodium thiosulfate was added to decompose the residual peroxide. This liquid was similarly analyzed by Quantofix test paper to confirm that peroxide was completely decomposed. Further, the aqueous solution was extracted four times with 30 mL of ethyl acetate, and the obtained ethyl acetate solution was washed with a saturated aqueous solution of sodium chloride. Ethyl acetate was distilled off with an evaporator to obtain a white solid.Vacuum drying (80 C., 20 hours) was performed to obtain 5.05 g of white tricyanofluoroborate. The yield was 84.7%
69%	With iron(III) chloride; at 20℃; for 3h;Inert atmosphere;	[(n-Hu)4N][HF4] (0.491 g, 1.49 mmol), prepared according to Preparation Description A, FeC13 (20 mg, 7 mol %, the mol % being based on the combined molar amount of [(n-Hu)4N][HF4] and FeC13) and (CH3)3SiCN (1.58 g, 1.59 mmol) were stirred under argon atmosphere at ambient temperature for 3 h.After the stirring at ambient temperature for 3 h an11H and ‘9F NMR spectra were measured. In accordance to‘9F NMR and “H NMR the product contained 100% of compound of formula (4). Afterremoving the solvent the obtained light yellow solid substance was dried at 50 C. in vacuo to yield 0.400 g (69%, 1.17 mmol) of compound of formula (4). C/H/N Analysis calc. % (found): C, 62.97 (62.58); H, 10.57 (10.65); N, 12.24 (12.35).‘H NMR (25 C., CDC13, 300.13 MHz, delta in ppm): 0.99 (t, 12H, CH3), 1.41 (m, 8H, CH3-CH2), 1.61 (m, 8H, CH2-CH2N), 3.13 (m, 8H, NCH2)“H NMR (25 C., CDC13, 300.13 MHz, delta in ppm): -7.2 (q, 1H, HF2(CN)2, ‘J(”H-’9F)=42 Hz) ‘3C NMR (25 C., CDC13, 300.13 MHz, delta in ppm): 13.3 (s, 4C, CH3), 19.4 (t, 4C, CH2-CH3), 23.6 (s, 4C, N-CH2--CH2), 58.6 (t, 4C, NCH2)‘9F NMR (25 C., CDC13, 300.13 MHz, delta in ppm): -153.1 (q, 2F, HF2(CN)2, ‘0.1(”H-’9F)=42 Hz) IR (ATR, 32 scans, v in cm’): 2966 (m), 2939 (m),2878 (m), 2210 (m), 1474 (m), 1383 (m), 1242 (w), 1170(w), 1006(m), 1050(s), 1007(s), 939(m), 880 (s), 797 (m),737 (m), 632 (w), 550 (w)

Reference： [1]Patent: JP2017/222591,2017,A .Location in patent: Paragraph 0111-0112; 0119-0120
[2]European Journal of Inorganic Chemistry,2016,vol. 2016,p. 1175 - 1183
[3]Patent: US2016/229874,2016,A1 .Location in patent: Paragraph 0378; 0379; 0380; 0381; 0382; 0383; 0384-0386

18
[ 405-31-2 ]
[ 429-42-5 ]
BF₄^(1-)*C₁₈H₁₂F₃S₃⁽¹⁺⁾ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With trifluorormethanesulfonic acid; In dichloromethane; at -78℃;Electrochemical reaction;	General procedure: The anodic oxidation was carried out in an H-type divided cell (4G glassfilter) equipped with a carbon felt anode (Nippon Carbon JF-20-P7, ca. 320 mg, dried at 250 oC/1mm Hg for 2 h before use) and a platinum plate cathode (20 mm x 20 mm). In the anodic chamberwas placed a solution of ArSSAr (1a, Ar = p-FC6H4, 253.9 mg, 1.0 mmol) in 0.3 MBu4NBF4/CH2Cl2 (8.0 mL). In the cathodic chamber were placed 0.3 M Bu4NBF4/CH2Cl2 (8.0 mL)and trifluoromethanesulfonic acid (TfOH) (60 μL, d = 1.7 g/mL, ca. 0.68 mmol). The constantcurrent electrolysis (8 mA) was carried out at -78 oC with magnetic stirring until 0.67 F/mol ofelectricity was consumed. Then, N-allylbenzamide (2a, 80.6 mg, 0.50 mmol in CH2Cl2 (1 mL x 2))was added to the resulting solution of ArS(ArSSAr)+ (ca. 0.67 mmol) by the cannula transfer, andstirred at -78 oC for 30 min. The temperature was gradually increased from -78 oC to rt for 30 min.Then, Et3N (1.0 mL) was added to quench the reaction. The solvent was removed under reducedpressure and the residue was quickly filtered through a short column of silica gel to removeBu4NBF4. The silica gel was washed with ether, and the crude material was purified by flashchromatography (hexane/AcOEt = 3:2) to obtain the product 3aa (123.3 mg, 86%)

Reference： [1]Heterocycles,2018,vol. 96,p. 1373 - 1382

19
[ 1142-19-4 ]
[ 429-42-5 ]
BF₄^(1-)*C₁₈H₁₂Cl₃S₃⁽¹⁺⁾ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With trifluorormethanesulfonic acid; In dichloromethane; at -78℃;Electrochemical reaction;	General procedure: The anodic oxidation was carried out in an H-type divided cell (4G glassfilter) equipped with a carbon felt anode (Nippon Carbon JF-20-P7, ca. 320 mg, dried at 250 oC/1mm Hg for 2 h before use) and a platinum plate cathode (20 mm x 20 mm). In the anodic chamberwas placed a solution of ArSSAr (1a, Ar = p-FC6H4, 253.9 mg, 1.0 mmol) in 0.3 MBu4NBF4/CH2Cl2 (8.0 mL). In the cathodic chamber were placed 0.3 M Bu4NBF4/CH2Cl2 (8.0 mL)and trifluoromethanesulfonic acid (TfOH) (60 μL, d = 1.7 g/mL, ca. 0.68 mmol). The constantcurrent electrolysis (8 mA) was carried out at -78 oC with magnetic stirring until 0.67 F/mol ofelectricity was consumed. Then, N-allylbenzamide (2a, 80.6 mg, 0.50 mmol in CH2Cl2 (1 mL x 2))was added to the resulting solution of ArS(ArSSAr)+ (ca. 0.67 mmol) by the cannula transfer, andstirred at -78 oC for 30 min. The temperature was gradually increased from -78 oC to rt for 30 min.Then, Et3N (1.0 mL) was added to quench the reaction. The solvent was removed under reducedpressure and the residue was quickly filtered through a short column of silica gel to removeBu4NBF4. The silica gel was washed with ether, and the crude material was purified by flashchromatography (hexane/AcOEt = 3:2) to obtain the product 3aa (123.3 mg, 86%)

Reference： [1]Heterocycles,2018,vol. 96,p. 1373 - 1382

20
[ 103-19-5 ]
[ 429-42-5 ]
BF₄^(1-)*C₂₁H₂₁S₃⁽¹⁺⁾ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With trifluorormethanesulfonic acid; In dichloromethane; at -78℃;Electrochemical reaction;	General procedure: The anodic oxidation was carried out in an H-type divided cell (4G glassfilter) equipped with a carbon felt anode (Nippon Carbon JF-20-P7, ca. 320 mg, dried at 250 oC/1mm Hg for 2 h before use) and a platinum plate cathode (20 mm x 20 mm). In the anodic chamberwas placed a solution of ArSSAr (1a, Ar = p-FC6H4, 253.9 mg, 1.0 mmol) in 0.3 MBu4NBF4/CH2Cl2 (8.0 mL). In the cathodic chamber were placed 0.3 M Bu4NBF4/CH2Cl2 (8.0 mL)and trifluoromethanesulfonic acid (TfOH) (60 μL, d = 1.7 g/mL, ca. 0.68 mmol). The constantcurrent electrolysis (8 mA) was carried out at -78 oC with magnetic stirring until 0.67 F/mol ofelectricity was consumed. Then, N-allylbenzamide (2a, 80.6 mg, 0.50 mmol in CH2Cl2 (1 mL x 2))was added to the resulting solution of ArS(ArSSAr)+ (ca. 0.67 mmol) by the cannula transfer, andstirred at -78 oC for 30 min. The temperature was gradually increased from -78 oC to rt for 30 min.Then, Et3N (1.0 mL) was added to quench the reaction. The solvent was removed under reducedpressure and the residue was quickly filtered through a short column of silica gel to removeBu4NBF4. The silica gel was washed with ether, and the crude material was purified by flashchromatography (hexane/AcOEt = 3:2) to obtain the product 3aa (123.3 mg, 86%)

Reference： [1]Heterocycles,2018,vol. 96,p. 1373 - 1382

21
[ 14024-63-6 ]
2,6-bis(3,4-diethyl-5-carboxy-1H-pyrrol-2yl)pyridine [ No CAS ]
[ 429-42-5 ]
[ 7732-18-5 ]
[ 68-12-2 ]
8C₂₃H₂₅N₃O₄^(2-)*2C₁₆H₃₆N⁽¹⁺⁾*8C₃H₇NO*2HO^(1-)*8Zn⁽²⁺⁾*2H₂O [ No CAS ]

Reference： [1]Journal of the American Chemical Society,2019

22
[ 429-42-5 ]
methyl 3<SUP>1</SUP>-pyridiniopyropheophorbide-a chloride [ No CAS ]
methyl 3<SUP>1</SUP>-pyridiniopyropheophorbide-a tetrafluoroborate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
92%	In dichloromethane; water; at 20℃; for 0.5h;	General procedure: Chloride salt 2a-Cl was dissolved in H2O (3 mL), to which aCH2Cl2 solution (3 mL) of Bu4NX or NaX (1.34.1equiv.) wasadded and stirred at room temperature under air atmosphere for0.5 h. The separated organic phase was washed with H2O threetimes, dried over Na2SO4, and filtered off. After evaporation,the residue was purified by FCC with CH2Cl2 and CH3OH andprecipitation from CH2Cl2 and hexane to give 2a-X as blackpowder.

Reference： [1]Bulletin of the Chemical Society of Japan,2020,vol. 93,p. 467 - 476

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