[ CAS No. 2343-89-7 ] {[proInfo.proName]}

Name: 2343-89-7|Methyl 2-fluoroacrylate|97% (stabilized with BHT)
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SKU: A272348
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3d Animation Molecule Structure of 2343-89-7

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Quality Control of [ 2343-89-7 ]

COA NMR CNMR HPLC LC-MS

Related Doc. of [ 2343-89-7 ]

SDS Specification

Alternatived Products of [ 2343-89-7 ]

Product Details of [ 2343-89-7 ]

CAS No. :	2343-89-7	MDL No. :	MFCD04039286
Formula :	C₄H₅FO₂	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	ZTZJVAOTIOAZGZ-UHFFFAOYSA-N
M.W :	104.08	Pubchem ID :	2782524
Synonyms :

Calculated chemistry of [ 2343-89-7 ] Expand+

Physicochemical Properties

Num. heavy atoms :	7
Num. arom. heavy atoms :	0
Fraction Csp3 :	0.25
Num. rotatable bonds :	2
Num. H-bond acceptors :	3.0
Num. H-bond donors :	0.0
Molar Refractivity :	22.2
TPSA :	26.3 Å²

Pharmacokinetics

GI absorption :	High
BBB permeant :	Yes
P-gp substrate :	No
CYP1A2 inhibitor :	No
CYP2C19 inhibitor :	No
CYP2C9 inhibitor :	No
CYP2D6 inhibitor :	No
CYP3A4 inhibitor :	No
Log Kp (skin permeation) :	-6.21 cm/s

Lipophilicity

Log Po/w (iLOGP) :	1.67
Log Po/w (XLOGP3) :	1.02
Log Po/w (WLOGP) :	1.06
Log Po/w (MLOGP) :	0.59
Log Po/w (SILICOS-IT) :	0.56
Consensus Log Po/w :	0.98

Druglikeness

Lipinski :	0.0
Ghose :	None
Veber :	0.0
Egan :	0.0
Muegge :	2.0
Bioavailability Score :	0.55

Water Solubility

Log S (ESOL) :	-1.0
Solubility :	10.5 mg/ml ; 0.101 mol/l
Class :	Very soluble
Log S (Ali) :	-1.16
Solubility :	7.17 mg/ml ; 0.0689 mol/l
Class :	Very soluble
Log S (SILICOS-IT) :	-0.61
Solubility :	25.5 mg/ml ; 0.245 mol/l
Class :	Soluble

Medicinal Chemistry

PAINS :	0.0 alert
Brenk :	1.0 alert
Leadlikeness :	1.0
Synthetic accessibility :	1.22

Safety of [ 2343-89-7 ]

Signal Word:	Danger	Class:	3,6.1
Precautionary Statements:	P273-P260-P210-P370+P378-P391-P301+P310+P330	UN#:	1992
Hazard Statements:	H301-H372-H411-H225	Packing Group:	Ⅱ
GHS Pictogram:

Application In Synthesis of [ 2343-89-7 ]

* 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 [ 2343-89-7 ]
Downstream synthetic route of [ 2343-89-7 ]

[ 2343-89-7 ] Synthesis Path-Upstream 1~2

1
[ 67-56-1 ]
[ 420-25-7 ]
[ 201230-82-2 ]
[ 430-99-9 ]
[ 2343-89-7 ]

Yield	Reaction Conditions	Operation in experiment
70.9%	at 100℃; for 13 h; Autoclave	8.98 g (71.87 mmol) of 1-bromo-1-fluoroethene, 8.01 g (79.2 mmol) of triethylamine, 51.5 mg (0.072 mmol) of dichloro[bis(diphenylphosphinophenyl)ether]palladium (II), and 36 mE of non-dried methanol were placed in a 1 50-mE stainless autoclave, and 1.0 MPaG carbon monoxide was introduced thereto, followed by stirring at 100° C. for 13 hours. After completion of the reaction, the autoclave was cooled, and the unreacted gas was purged. The autoclave was opened, and 186 mg (1.0 mmol) of hexafluorobenzenewas added as an internal standard substance, followed by stirring. The mixture was then allowed to stand for a short period of time to precipitate the salt. The supernatant was diluted with deuterated chloroform, and subjected to quantification based on 19F-NMR integral values. The diluted supernatant was found to contain 50.93 mmol (yield: 70.9percent) of 2-fluoroacrylic acid methyl ester, 10.13 mmol (yield:14.1percent) of 2-fluoroacrylic acid, and 8.12 mmol (recovery:11.3percent) of unreacted 1 -bromo-1 -fluoroethene. The conversion was 87.5percent, and the selectivity was 81.0percent.

Reference： [1] Patent: US2016/318842, 2016, A1, . Location in patent: Paragraph 0149; 0150

2
[ 2343-89-7 ]
[ 430-99-9 ]

Reference： [1] Organic and Biomolecular Chemistry, 2015, vol. 13, # 3, p. 717 - 728

[ 2343-89-7 ] Synthesis Path-Downstream 1~105

1
[ 2365-93-7 ]
[ 2343-89-7 ]

Yield	Reaction Conditions	Operation in experiment
85%	With 10H-phenothiazine; sulfuric acid; zinc In water at 82 - 86℃; for 0.333333h;	5 Example 5: Preparation of methyl 2-fluoroacrylate Zinc (6g, 0.092 mol), water (20g, 1.11 mol), con. H2S04 (0.2g, 0.002 mol) and phenothiazine (0.5g, 0.0025 mol) were added sequentially in a reaction vessel. Thereaction mixture was heated to 82°C to 86°C and methyl 3-bromo-2-chloro-2- fluoropropanoate (15 g, 0.068 mol) was added to the reaction mass slowly over a period of 20 minutes. An azeotropic mixture was distilled off at 55°C and 550 mbar simultaneously. Then, 10 ml saturated calcium chloride solution was added to the azeotropic mixture and the organic layer was separated and dried to give methyl 2- fluoroacrylate as a clear colorless liquid.Yield(%): 85Purity (%): 94
82%	With hydrogen sulfide; sodium N-nitroso-N-phenylhydroxylaminate; zinc In water at 100℃;
80%	With zinc

With sulfuric acid; zinc

Reference： [1]Current Patent Assignee: SRF LIMITED - WO2017/13683, 2017, A1 Location in patent: Page/Page column 9; 10
[2]Boguslavskaya, L. S.; Chuvatkin, N.; Morozova, T. V.; Panteleeva, I. Yu.; Kartashov, A. V.; Sineokov, A. P. [Journal of Organic Chemistry USSR (English Translation), 1987, p. 1060 - 1064][Zhurnal Organicheskoi Khimii, 1987, vol. 23, # 6, p. 1173 - 1177]
[3]Boguslavskaya, L. S.; Chuvatkin, N. N. [Journal of Fluorine Chemistry, 1991, vol. 54, # 1-3, p. 138]
[4]Current Patent Assignee: AKZO NOBEL NV - GB590015, 1947, A Current Patent Assignee: AKZO NOBEL NV - US2454663, 1946, A

2
[ 55900-27-1 ]
[ 2343-89-7 ]

Yield	Reaction Conditions	Operation in experiment
95%	With 2,6-di-tert-butyl-4-methyl-phenol; sodium phosphate In 1-methyl-pyrrolidin-2-one at 150℃;	2 2. Preparation of methyl 2-fluoroacrylateAn amount of di-tert-butylhydroxytoluene (BHT) of 4 g (0.02 mol), 500 g of N-methylpyrrolidine (NMP) and 360 g (2.2 mol) of tribasic sodium phosphate are introduced into a sulfonation pan and the mixture is heated to 150° C. An amount of di-tert-butylhydroxytoluene (BHT) of 51 mg (2.2*10-4 mol) is introduced into the distillation receiver of the vertical recovery bend. A vacuum of 300 mbar is applied and the metered addition of a total of 287 g (98%, 2.0 mol) of methyl 3-chloro-2-fluoropropionate is begun. The metered addition is continued in the degree in which the methyl 2-fluoroacrylate is distilled over. When no more distillate stream passes over, the vacuum is lowered to 150 mbar. When no more product passes over even here, the pressure is raised by addition of nitrogen. The distillation bottoms are cooled and discharged via the bottom valve. The product is obtained after distillation as a colorless liquid (205 g, 95%, 1.87 mol, 93.5% yield).
	With dimethyl amine In diethyl ether; benzene

Reference： [1]Current Patent Assignee: LANXESS AG - US2012/283468, 2012, A1 Location in patent: Page/Page column 5
[2]Elkik,E. et al. [Comptes Rendus des Seances de l'Academie des Sciences, Serie C: Sciences Chimiques, 1976, vol. 282, p. 1129 - 1131]

3
[ 2343-89-7 ]
[ 99953-33-0 ]

Yield	Reaction Conditions	Operation in experiment
39%	With bromine trifluoride; bromine In 1,1,2-Trichloro-1,2,2-trifluoroethane at 10 - 20℃;

Reference： [1]Boguslavskaya, L. S.; Chuvatkin, N. N.; Kartashov, A. V.; Ternovskoi, L. A. [Journal of Organic Chemistry USSR (English Translation), 1987, vol. 23, p. 230 - 236][Zhurnal Organicheskoi Khimii, 1987, vol. 23, # 2, p. 262 - 269]

4
[ 380-26-7 ]
[ 2343-89-7 ]
[ 292638-85-8 ]

Yield	Reaction Conditions	Operation in experiment
74%	With thiourea; zinc In diphenylether at 95℃;

Reference： [1]Majumdar, Ramendra N.; Harwood, H. James [Synthetic Communications, 1981, vol. 11, # 11, p. 901 - 908]

5
[ 85345-88-6 ]
[ 2343-89-7 ]

Yield	Reaction Conditions	Operation in experiment
97%	With potassium phtalimide at -78 - 150℃;

Reference： [1]Tolman, Vladimir; Spronglova, Pavla [Collection of Czechoslovak Chemical Communications, 1983, vol. 48, # 1, p. 319 - 326]

6
[ 885264-31-3 ]
[ 2343-89-7 ]
C₁₈H₂₃FN₄O₄S [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With triethylamine; lithium bromide In tetrahydrofuran at 20℃; for 17h;	1.1e Step 1e. Into a mixture of the crude compound from step 1c (0.75 mmol at most) in THF (5 mL) was added commercially available methyl 2-fluoroacrylate (156 mg, 1.5 mmol), lithium bromide (130 mg, 1.5 mmol), and Et3N (0.21 mL, 1.5 mmol). The resulted mixture was stirred at room temperature for 17 hours before being partitioned (EtOAc-water). The organics were washed with water, brine, dried (Na2SO4), and evaporated. The residue was chromatographed (silica, hexanes-EtOAc) to give the desired compound (201 mg, 64.8% two steps).ESIMS m/z=411.08 [M+H]+.13C NMR (CDCl3) 171.7, 168.9, 168.0, 143.4, 140.0, 131.1, 120.2, 105.9, 102.6, 82.9, 69.5, 68.1, 58.4, 52.9, 41.3, 28.1.

Reference： [1]Current Patent Assignee: ENANTA PHARMACEUTICALS INC - US2009/4140, 2009, A1 Location in patent: Page/Page column 22

7
[ 2343-89-7 ]
[ 5675-31-0 ]

Yield	Reaction Conditions	Operation in experiment
70%	Stage #1: methyl 2-fluoroprop-2-enoate With aluminum (III) chloride; lithium aluminium tetrahydride In diethyl ether at 0℃; for 1h; Stage #2: With water; sodium sulfate In diethyl ether at 0℃;
46%	With aluminum (III) chloride; lithium aluminium tetrahydride In diethyl ether at -5℃; for 3.5h;	a To a mixture of lithium aluminium hydride (131.2 g, 3.46 mol) in diethyl ether (3 L) was carefully added A1C13 (63.0 mL, 1.15 mol) at -5 °C. The mixture was stirred at -5 °C for 30 min, then methyl 2-fluoroprop-2-enoate (240 g, 2.31 mol) was added dropwise at -5 °C. The mixture was stirred at -5 °C for other 3.5 h. Wet sodium sulfate was added at 0 °C and the mixture was filtered. The filtrate was isolated by atmospheric distillation at 50 °C affording the title compound (163.0 g, 46 %) as colourless liquid in ether. 1H NMR (400 MHz, CDC13): 4.63 (dd, J1 = 2.8 Hz, J2 = 17.2 Hz, 1H), 4.53 (dd, J1 = 2.8 Hz, J2 = 51.6 Hz, 1H), 4.08 (dd, J1 = 3.2 Hz, J2 = 10.8 Hz, 1H), 3.30 (m, 1H).
46%	With aluminum (III) chloride; lithium aluminium tetrahydride In diethyl ether at -5℃; for 3.5h;	a) 2-fluoroprop-2-en-l-ol To a mixture of LiAlEL (131.2 g, 3.46 mol) in diethyl ether (3 L) was carefully added AlCh (63.0 mL, 1.15 mol) at -5 °C. The mixture was stirred at -5 °C for 30 min, then methyl 2- fluoroprop-2-enoate (240 g, 2.31 mol) was added dropwise at -5 °C. The mixture was stirred at - 5 °C for other 3.5 h. Wet sodium sulfate was added at 0 °C and the mixture was filtered. The filtrate was isolated by atmospheric distillation at 50 °C affording the title compound (163.0 g, 46 %) as colourless liquid in ether. NMR (400 MHz, CDCL): 4.63 (1H, dd, 7=17.2, 2.8 Hz), 4.53 (1H, dd, .7=51.6, 2.8 Hz), 4.08 (1H, dd, 7=10.8, 3.2 Hz), 3.30 (1H, m).

82 %Spectr.	With aluminum (III) chloride; lithium aluminium tetrahydride In diethyl ether at -5℃; for 1h;
	Stage #1: methyl 2-fluoroprop-2-enoate With aluminum (III) chloride; lithium aluminium tetrahydride In diethyl ether at 0℃; for 1h; Inert atmosphere; Stage #2: With water; sodium hydroxide In diethyl ether at 0℃; Inert atmosphere;
	With aluminum (III) chloride; lithium aluminium tetrahydride In diethyl ether at -5℃; for 1h;	40.II Step II: A suspension of LiAlH4 (6.6 g, 0.17 mol) in Et2O (150 mL) was treated carefully with AlCl3 (7.6 g, 0.057 mol) at -5° C. The resulting mixture was stirred for 30 minutes at -5° C., and methyl 2-fluoroacrylate (12 g, 0.114 mmol) was added dropwise. The mixture was stirred at -5° C. for additional 1 hour. Thereafter, an excess of wet Na2SO4 was added to decompose excess of AlCl3. Solid phase was separated by filtration and Et2O was carefully removed at atmospheric pressure to give 7.4 g of 40% solution of 2-fluoroprop-2-en-1-ol in Et2O which was further diluted with CH2Cl2 (20 mL). To this solution, DIPEA (6.33 mL, 0.036 mol) was added. The resulting solution was cooled to -30° C., and MsCl (2.42 mL, 0.031 mol) was added dropwise. The reaction mixture was allowed to warm to room temperature, and stirred for additional 1 hour. The mixture was washed with water, 10% solution of citric acid, brine, dried over Na2SO4, and evaporated under reduced pressure to give 2-fluoroallyl methanesulfonate (AR2) (3.77 g, 0.024 mol, 93%). The product is relatively unstable and has to be used immediately in the next step.
	With aluminum (III) chloride; lithium aluminium tetrahydride In diethyl ether at -5℃; for 1h;	40.II Step 2 A suspension of LiAlH4 (6.6 g, 0.17 mol) in Et20 (150 mL) was treated carefully with AICI3 (7.6 g, 0.057 mol) at -5 °C. The resulting mixture was stirred for 30 minutes at -5 °C, and methyl 2-fluoroacrylate (12 g, 0.114 mmol) was added dropwise. The mixture was stirred at -5 °C for additional 1 hour. Thereafter, an excess of wet Na2S04 was added to decompose excess of AICI3. Solid phase was separated by filtration and Et20 was carefully removed at atmospheric pressure to give 7.4 g of 40% solution of 2-fluoroprop-2-en-l-ol in Et20 which was further diluted with CH2C12 (20 mL). To this solution, DIPEA (6.33 mL, 0.036 mol) was added. The resulting solution was cooled to -30 °C, and MsCl (2.42 mL, 0.031 mol) was added dropwise. The reaction mixture was allowed to warm to room temperature, and stirred for additional 1 hour. The mixture was washed with water, 10% solution of citric acid, brine, dried over Na2S04, and evaporated under reduced pressure to give 2-fluoroallyl methanesulfonate (AR2) (3.77 g, 0.024 mol, 93%). The product is relatively unstable and has to be used immediately in the next step.
	With aluminum (III) chloride; lithium aluminium tetrahydride In diethyl ether at -10℃; for 1h; Inert atmosphere; Sealed tube;
	With aluminum (III) chloride; lithium aluminium tetrahydride In diethyl ether at 0℃; for 1h; Inert atmosphere;
	With aluminum (III) chloride; lithium aluminium tetrahydride In diethyl ether at -5℃; for 1h;

Reference： [1]Hatano, Manabu; Mizuno, Tomokazu; Izumiseki, Atsuto; Usami, Ryota; Asai, Takafumi; Akakura, Matsujiro; Ishihara, Kazuaki [Angewandte Chemie - International Edition, 2011, vol. 50, # 51, p. 12189 - 12192]
[2]Current Patent Assignee: ROCHE HOLDING AG - WO2019/238633, 2019, A1 Location in patent: Page/Page column 131
[3]Current Patent Assignee: ROCHE HOLDING AG - WO2021/228795, 2021, A1 Location in patent: Page/Page column 74
[4]Tkachenko, Anton N.; Radchenko, Dmytro S.; Mykhailiuk, Pavel K.; Grygorenko, Oleksandr O.; Komarov, Igor V. [Organic Letters, 2009, vol. 11, # 24, p. 5674 - 5676]
[5]King, Sandra M.; Ma, Xiaoshen; Herzon, Seth B. [Journal of the American Chemical Society, 2014, vol. 136, # 19, p. 6884 - 6887]
[6]Current Patent Assignee: ROCHE HOLDING AG - US2014/343032, 2014, A1 Location in patent: Paragraph 1001
[7]Current Patent Assignee: ROCHE HOLDING AG - WO2014/184328, 2014, A1 Location in patent: Page/Page column 140
[8]Schwarz, Kevin J.; Pearson, Colin M.; Cintron-Rosado, Gabriel A.; Liu, Peng; Snaddon, Thomas N. [Angewandte Chemie - International Edition, 2018, vol. 57, # 26, p. 7800 - 7803][Angew. Chem., 2018, # 130, p. 7926 - 7929,4]
[9]Lu, Yanhui; Goldstein, Elizabeth L.; Stoltz, Brian M. [Organic Letters, 2018, vol. 20, # 18, p. 5657 - 5660]
[10]Current Patent Assignee: JOHNSON & JOHNSON INC; AMPSON SCIENT ERLANAN INFINITELY - WO2021/18237, 2021, A1 Location in patent: Page/Page column 98-99

8
[ 2343-89-7 ]
[ 93102-05-7 ]
[ 1279669-60-1 ]

Yield	Reaction Conditions	Operation in experiment
95%	With trifluoroacetic acid In dichloromethane at 0 - 20℃; for 4h;	N-Benzyl-3-fluoro-β-proline methyl ester (5). A solution of TFA (0.4 mL) in dry CH2Cl2 (10 mL) was slowly added to a stirred solution of N-benzyl-N-(methoxymethyl)-N-trimethylsilylmethylamine (2) (12.0 g, 0.050 mol) and methyl 2-fluoroacrylate (4) (5.0 g, 0.048 mol) in dry CH2Cl2 (150 mL) at 0 °C. CAUTION: exothermic reaction. The reaction mixture was stirred for an additional 4 h at room temperature. An excess of aq saturated NaHCO3 solution was added. The organic phase was washed with 100 mL of brine, dried over Na2SO4 and evaporated under vacuum. The residue was purified by flash column chromatography using hexane/EtOAc = 2/1 mixture as eluent to give the pure product 5 (10.5 g, 95% yield) as a colourless oil. Rf = 0.5. 1H NMR (500 MHz; CDCl3; Me4Si), δ: 2.23-2.33 (1H, m, 4-CHH), 2.44-2.54 (1H, m, 4-CHH), 2.69 (1H, q, J = 8.0 Hz, NCHH), 2.95-3.03 (3H, m, NCHH + NCH2), 3.71 (1H, d, J = 13.5 Hz, PhCHH), 3.74 (1H, d, J = 13.5 Hz, PhCHH), 3.83 (3H, s, OCH3), 7.28-7.36 (5H, m, Ph). 13C NMR (125 MHz; CDCl3; Me4Si), δ: 37.11 (d, 2JCF = 23.8 Hz, 4-CH2), 52.77 (s, OCH3), 52.98 (s, PhCH2N), 59.70 (s, 5-CH2), 63.40 (d, 2JCF = 23.8 Hz, 2-CH2), 99.80 (d, 1JCF = 191.3 Hz, 3-CF), 127.21 (s, CH, Ph), 128.37 (s, CH, Ph), 128.70 (s, CH, Ph), 139.53 (s, quat-C, Ph), 171.42 (d, 2JCF = 27.5 Hz, CO2Me). 19F NMR (477 MHz; CDCl3; Me4Si), δ: -149.28 (quint, 3JFH = 28.6 Hz, F). GC-MS: 237 (M+). Anal. calcd for C13H16FNO2: C, 65.81; H, 6.80; N, 5.90. Found: C, 65.51; H, 6.43; N, 5.95.
80%	With trifluoroacetic acid In dichloromethane at 20℃; for 4h; Inert atmosphere;
	With trifluoroacetic acid In dichloromethane at 0 - 20℃; for 16h; Inert atmosphere;	2.1 1002421 step 1 : A 0.3 M solution of methyl 2-fluoroacrylate (4.37 g, 41.99 mmol) and DCM (140 mL) was stirred under nitrogen and cooled to 0 °C. The reaction mixture was then treated with N- benzyl-l-methoxy-N-((trimethylsilyl)methyl)methanamine (10.47 g, 44.09 mmol) followed by TFA (1.56 mL, 20.99 mmol). The reaction mixture was warmed to RT and stirred for 16 h. The reaction mixture was then concentrated in vacuo. The crude product was purified by Si02 Biotage chromatography (hexanes/acetone) to afford 4.24 g (42.6%) of methyl l-benzyl-3- fluoropyrrolidine-3-carboxylate (72a): 1H NMR (400 MHz, DMSO-de) δ = 7.35-7.23 (m, 5H), 3.72 (s, 3H), 3.63 (s, 2H), 2.97-2.80 (m, 3H), 2.54-2.48 (m, 1H), 2.43-2.30 (m, 1H), 2.18-2.04 (m, 1H).

With trifluoroacetic acid In dichloromethane at 0℃;

Reference： [1]Location in patent: experimental part Yarmolchuk, Vladimir S.; Mykhailiuk, Pavel K.; Komarov, Igor V. [Tetrahedron Letters, 2011, vol. 52, # 12, p. 1300 - 1302]
[2]Current Patent Assignee: SHENZHEN DONGYANGGUANG INDUSTRIAL DEVELOPMENT CO LTD - WO2015/62486, 2015, A1 Location in patent: Paragraph 00185
[3]Current Patent Assignee: ROCHE HOLDING AG; PFIZER INC - WO2013/20062, 2013, A1 Location in patent: Paragraph 00242
[4]Tang, Lin; Wu, Weibin; Zhang, Cunlong; Shi, Zhichao; Chen, Dawei; Zhai, Xin; Jiang, Yuyang [Bioorganic Chemistry, 2021, vol. 114]

9
methyl α-bromo-α-fluoropropionate [ No CAS ]
[ 2343-89-7 ]

Yield	Reaction Conditions	Operation in experiment
	With 10H-phenothiazine; potassium carbonate In N,N-dimethyl-formamide at 70℃; for 5h;	13; 14 Example 13To 5 mL of N,N-dimethylformamide, 1.00 g (gas chromatographic purity: 84.1%, 4.55 mmol, 1.00 eq) of methyl 2-bromo-2-fluoropropionate of the following formula, 82.0 mg (0.539 mmol, 0.12 eq) of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 750 mg (5.43 mmol, 1.19 eq) of potassium carbonate and 10.0 mg (0.0502 mmol, 0.01 eq) of phenothiazine were added. The resulting reaction liquid was stirred for 5 hours at 70° C. The conversion rate of the reaction terminated liquid was determined by 19F-NMR to be 100%. The amount of methyl 2-fluoroacrylate of the following formula contained in the reaction terminated liquid was determined by 19F-NMR (quantification according to internal standard method) to be 444 mg (4.27 mmol); and the yield of the methyl 2-fluoroacrylate was 94%. The amount of methyl 2,2-difluoropropionate (estimated structure) generated as a by-product was determined by 19F-NMR to be methyl 2-fluoroacrylate:methyl 2,2-difluoropropionate=1:0.01.Example 14Produced was 854 g of a N,N-dimethylformamide solution containing methyl 2-fluoroacrylate of the following formula in a similar manner with reference to Examples 9 to 13 (content amount of methyl 2-fluoroacrylate: 89.8 g (863 mmol) as determined by 19F-NMR (quantification according to internal standard method), amount of methyl 2,2-difluoropropionate (estimated structure) generated as by-product: methyl 2-fluoroacrylate:methyl 2,2-difluoropropionate=1:0.08 as determined by 19F-NMR, gas chromatographic purity: 10.6%). This N,N-dimethylformamide solution was subjected to fractional distillation (theoretical plate number: 30, boiling point: 29 to 31° C., reduced pressure level: 9.1 kPa, reflux ratio: 60:1 to 20:1), thereby yielding 66.6 g of a main fraction of methyl 2-fluoroacrylate. The amount of the methyl 2-fluoroacrylate contained in the main fraction was determined by 19F-NMR (quantification according to internal standard method) to be 60.2 g (578 mmol). The recovery rate of the main fraction on a purity basis was 67%. The gas chromatographic purity of the main fraction was 97.3%. In the main fraction, there was contained 2.7% of methyl 2,2-difluoropropionate. As the water content of the main fraction was high (0.9%), the main fraction was dehydrated by a molecular sieve 4A (the molecular sieve was used in an amount of 560 mg per 1.00 g of the main fraction; and the main fraction was left together with the molecular sieve for 2 days). (The water content of the dehydrated main fraction was 0.0%.) Herein, the fractional distillation was conducted in the presence of 2,6-di-tert-butyl-4-methylphenol (BHT). More specifically, 1.90 g (8.63 mmol, 0.01 eq) of 2,6-di-tert-butyl-4-methylphenol (BHT) was added in advance to each of the bottom and top of the distillation column and the isolating distillation fraction. (The total amount of 2,6-di-tert-butyl-4-methylphenol (BHT) additionally used was 0.03 eq.) The 1H-NMR and 19F-NMR data of the methyl 2-fluoroacrylate are indicated below. 1H-NMR [reference material: (CH3)4Si, deuterated solvent: CDCl3] δ ppm; 3.85 (s, 3H), 5.36 (dd, 13.2 Hz, 3.2 Hz, 1H), 5.69 (dd, 3.2 Hz, 44.0 Hz, 1H). 19F-NMR [reference material: C6F6, deuterated solvent: CDCl3] δ ppm; 44.67 (dd, 42.7 Hz, 13.7Hz, 1F). The 1H-NMR and 19F-NMR data and mass chromatography (MS) data of the methyl 2,2-difluoropropionate (estimated structure) are also indicated below. 1H-NMR [reference material: (CH3)4Si, deuterated solvent: CDCl3] δ ppm; 1.81 (t, 18.8 Hz, 3H), 3.88 (s, 3H). 19F-NMR [reference material: C6F6, deuterated solvent: CDCl3] δ ppm; 62.90 (q, 18.3 Hz, 2F).

Reference： [1]Current Patent Assignee: CENTRAL GLASS CO LTD - US2012/59187, 2012, A1 Location in patent: Page/Page column 10-11

10
[ 2343-89-7 ]
[ 76862-09-4 ]
[ 1417912-31-2 ]

Yield	Reaction Conditions	Operation in experiment
85%	With tetrakis(acetonitrile)copper(I)tetrafluoroborate; (S)-TF-Biphamphos; triethylamine In dichloromethane at 20℃; Inert atmosphere; enantioselective reaction;

Reference： [1]Yan, Dingce; Li, Qinghua; Wang, Chunjiang [Chinese Journal of Chemistry, 2012, vol. 30, # 11, p. 2714 - 2720]

11
[ 2343-89-7 ]
[ 66646-88-6 ]
[ 1417912-37-8 ]

Yield	Reaction Conditions	Operation in experiment
79%	With tetrakis(acetonitrile)copper(I)tetrafluoroborate; (S)-TF-Biphamphos; triethylamine In dichloromethane at 20℃; Inert atmosphere; enantioselective reaction;

Reference： [1]Yan, Dingce; Li, Qinghua; Wang, Chunjiang [Chinese Journal of Chemistry, 2012, vol. 30, # 11, p. 2714 - 2720]

12
[ 2343-89-7 ]
[ 355425-48-8 ]
[ 1417912-40-3 ]

Yield	Reaction Conditions	Operation in experiment
75%	With tetrakis(acetonitrile)copper(I)tetrafluoroborate; (S)-TF-Biphamphos; triethylamine In dichloromethane at 20℃; Inert atmosphere; enantioselective reaction;

Reference： [1]Yan, Dingce; Li, Qinghua; Wang, Chunjiang [Chinese Journal of Chemistry, 2012, vol. 30, # 11, p. 2714 - 2720]

13
[ 2343-89-7 ]
methyl 2-(1-naphthalenemethyleneamino)acetate [ No CAS ]
[ 1417912-41-4 ]

Yield	Reaction Conditions	Operation in experiment
78%	With tetrakis(acetonitrile)copper(I)tetrafluoroborate; (S)-TF-Biphamphos; triethylamine In dichloromethane at 20℃; Inert atmosphere; enantioselective reaction;

Reference： [1]Yan, Dingce; Li, Qinghua; Wang, Chunjiang [Chinese Journal of Chemistry, 2012, vol. 30, # 11, p. 2714 - 2720]

14
[ 2343-89-7 ]
[ 38053-91-7 ]
[ 1449662-36-5 ]

Yield	Reaction Conditions	Operation in experiment
	In toluene at 150℃; Inert atmosphere; Sealed tube;	A9.1 Step 1 Preparation of methyl 1-fluoro-4-((trimethylsilyl)oxy)cyclohex-3-enecarboxylate General procedure: Step 1 Preparation of methyl 1-fluoro-4-((trimethylsilyl)oxy)cyclohex-3-enecarboxylate The title compound was prepared following the procedure described in general procedure Step 1, using methyl 2-fluoroacrylate as reactant and taken to the next step without further purification. Step 1 Preparation of Cyclohexenyloxytrimethylsilane In a pressure vessel, a solution of acrylate (1 eq), 449 (buta-1,3-dien-2-yloxy)trimethylsilane (1.1 eq) in 260 toluene was flushed with nitrogen, sealed and heated at 150° C. for 1-3 days. The reaction mixture was cooled to RT and concentrated in vacuo to give crude 450 product which was used for the next step without purification.

Reference： [1]Current Patent Assignee: GLAXOSMITHKLINE PLC - US2013/210787, 2013, A1 Location in patent: Paragraph 0322; 0370; 0371

15
[ 50-00-0 ]
[ 453-18-9 ]
[ 2343-89-7 ]

Yield	Reaction Conditions	Operation in experiment
79.3%	Stage #1: methyl fluoroacetate With Dimethyl oxalate; sodium methylate In dimethyl sulfoxide at 15 - 25℃; for 1h; Inert atmosphere; Stage #2: formaldehyd With 2,6-di-tert-butyl-4-methyl-phenol In dimethyl sulfoxide at 20 - 35℃; for 1h; Inert atmosphere;	5.a; 5.b synthesis of Methyl 2-Fluoroacrylate methyl fluoroacetate was added 184.2g (2.0mol) to 3000mL reaction flask, oxalic acid dimethyl ester 272.0g (2.3mol) and dimethylsulfoxide 1473.6g (18.7mol), was substituted twice with nitrogen, with stirring at room temperature dissolution, until a clear reaction mixture was dissolved, solid sodium methoxide was added in 140.5g (2.6mol), the control temperature of 15 to 25 ° C, after 1 hour addition was complete, the reaction solution was concentrated under reduced pressure started, the vacuum degree ≥0.095Mpa, the reaction liquid temperature 35 ° C, after two hours and concentrated, in the control sample, the methanol content of 11.0%, a fluorine content of 0.3% methyl acetate, after passing the reaction, acetic acid was added to quench the reaction solution was added a polymerization inhibitor of 2,6-di-t butyl-p-cresol, 0.1g, was then portionwise added paraformaldehyde 72g (2.4mol), the control temperature of 20 to 35 degrees Celsius, after completion of the addition, stirred for 1 hour incubation, samples in the control, 0.15% intermediate enol salt, 2-fluoro-methacrylate content 10.4%, crude yield 85.4%. b, PurificationAfter the crude reaction solution obtained above, and water was added 460.5g (25.6mol), stir at room temperature after the start distillation under reduced pressure, the reaction solution was slowly warmed to control the degree of vacuum 0.098 MPa, total reflux started, until the vapor temperature was stabilized, start the crude product was detected receiving phase temperature of 25 to 40 ° C fractions, the receiving tank with coolant to cool the back reception using two recovery tank, the reaction solution was slowly warmed to a temperature of 75 ° C, stop receiving collected 280.0g of crude product received content of 62% (GC), the crude product was washed with a saturated aqueous sodium chloride was added 280.0g once, the organic layer was layered to give 170g, continue after washed twice, to give the product 160g, was added anhydrous sodium sulfate 20g, and dried to give 165 g product, total yield 79.3%, GC purity 99.4%.
58%	Stage #1: methyl fluoroacetate With Dimethyl oxalate; sodium methylate In methanol; pentane at 20 - 25℃; for 24.25h; Stage #2: formaldehyd In pentane at 5 - 10℃; for 5h;	2 Example 2: Claisen condensation with 30% NaOMe solution in pentane Example 2: Claisen condensation with 30% NaOMe solution in pentane Step A Dimethyl oxalate (28.2 g, 1.1 equiv.) was suspended in pentane (100 mL) at 20-25°C followed by addition of methyl fluoroacetate (20.0 g). The mixture was stirred for 15 min at 20-25°C (two clear phases) and 30% NaOMe solution in methanol (48.9 g, 1.25 equiv.) was added dropwise. The resulting turbid solution was stirred for 24 h at 20- 25°C (crystallization observed after 2 h at 20-25°C). Step B The suspension was cooled to 0°C, the Claisen salt was filtered off and washed with pentane (3x 40 mL). Step C The wet salt and pentane (120 mL) was charged to the reactor and the suspension was cooled to 5-10°C. Paraformaldehyde (4.0 g, 1 .2 equiv.) was added in 10 portions and the suspension was stirred at 5-10°C for additional 5 h. Step D The reaction mixture was quenched with water (1 15 mL) and the aqueous phase extracted once with pentane (2x 60 mL). Combined organic phase was analyzed by quantitative GC. With this reaction 93% conversion of methyl fluoroacetate was reached. The yield was 66% prior to distillation. Methyl fluoroacrylate was isolated in a yield of 58% after distillation.

Reference： [1]Current Patent Assignee: WATERSTONE PHARMACEUTICALS - CN104478715, 2016, B Location in patent: Paragraph 0081; 0082; 0083; 0084; 0085
[2]Current Patent Assignee: THERMO FISHER SCIENTIFIC INC - WO2014/1365, 2014, A1 Location in patent: Page/Page column 7-8

16
[ 2343-89-7 ]
[ 133407-38-2 ]
[ 1461698-11-2 ]

Yield	Reaction Conditions	Operation in experiment
92%	With trifluoroacetic acid In dichloromethane at 0 - 20℃; for 5h; Inert atmosphere;	4.5. Methyl 3-fluoro-1-[(1R)-1-phenylethyl]pyrrolidine-3-carboxylate (13) A solution of TFA (1.8 g, 0.015 mol, 0.1 equiv) in dry CH2Cl2(150 mL) was slowly added to a stirred solution of (R)-12 (40.0 g,0.159 mol, 1.03 equiv) and methyl 2-fluoroacrylate 3 (16.0 g,0.153 mol, 1 equiv) in dry CH2Cl2 (250 mL) at 0 C. (CAUTION:exothermic reaction) The reaction mixture was stirred for an additional5 h at room temperature. The reaction mixture was neutralizedby adding a saturated aqueous solution of NaHCO3. The organic phase was washed with saturated solution of NaCl(2503 mL), separated and dried over anhydrous Na2SO4. Thesolvent was removed under reduced pressure on a rotary evaporator.The residue was purified by column chromatography usinghexane/EtOAc3/1 mixture as eluent to give the pure product 13(35.3 g, 0.14 mol, 92% yield) as a colorless oil. Rf0.5.1HNMR(500MHz; CDCl3,Me4Si; 2 diastereoisomers are present)d: 1.37e1.40 (m, 3H, CHCH3), 2.12e2.28 (m, 1H), 2.33e2.51 (m, 2H),2.68e2.79 (m,1H), 2.83e3.02 (m, 1H), 3.05e3.12 (m, 1H), 3.28e3.37(m, 1H), 3.76e3.79 (m, 3H, OCH3), 7.20e7.33 (m, 5H, C6H5).13C NMR (125 MHz; CDCl3; Me4Si; 2 diastereoisomers arepresent), d: 23.0 (CH3), 36.9, 51.6, 52.8, 62.6, 65.0, 99.9 (m,JCF193 Hz, CF), 127.0 (s, C6H5), 127.2 (s, C6H5), 128.4 (s, C6H5), 144.7(s, C6H5), 171.4 (s, C]O).19F NMR (477 MHz; CDCl3; C6F6; 2 diastereoisomers are present)d: 148.2 (147.6) (m, J26 Hz).Anal. Calcd for C14H18FNO2: C, 66.91; H, 7.22; N, 5.57. Found: C,66.84; H, 7.35; N, 5.42.LCeMS: 252 (M).[a]D20 17.03 (c 0.702 g/100 mL, MeOH).

Reference： [1]Yarmolchuk, Vladimir S.; Mykhalchuk, Vladimir L.; Mykhailiuk, Pavel K. [Tetrahedron, 2014, vol. 70, # 18, p. 3011 - 3017]

17
[ 2343-89-7 ]
[ 430-99-9 ]

Reference： [1]Organic and Biomolecular Chemistry,2015,vol. 13,p. 717 - 728

18
[ 504-29-0 ]
[ 2343-89-7 ]
C₈H₇FN₂O [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With triethylamine In toluene at 0 - 110℃; for 3h;	Synthesis of Intermediate I1.5 To a stirred solution of pyridine-2-amine (5 g, 53.19 mmol) and methyl 2-fluoroprop-2- enoate in toluene (20 ml.) was added trimethylamine (159.57 mmol) dropwise at 0°C. The reaction was heated to 1 10°C and stirred at this temperature for 3 h until completion of reaction was monitored by TLC. The reaction mixture was quenched with ice cold water and filtered through celite (rinsed with 200 ml. EtOAc). Then, the mixture was extracted with ethyl acetate (3x100 ml_), the organic phases were dried over Na2S04 and concentrated to afford 4.6 g of crude 11.4. The product was used in the next step without purification. H-NMR (CDCIs, 400 MHz) (ppm): 8.58 (s, 1 H), 8.38 (m, 1 H), 8.28 (m, 1 H), 7.78 (m, 1 H), 7.12 (m, 1 H), 5.82 (m, 1 H), 5.21 (m, 1 H).

Reference： [1]Current Patent Assignee: BASF SE - WO2015/40162, 2015, A1 Location in patent: Page/Page column 142

19
[ 67-56-1 ]
[ 420-25-7 ]
[ 201230-82-2 ]
[ 2343-89-7 ]

Yield	Reaction Conditions	Operation in experiment
90.7%	With bis-triphenylphosphine-palladium(II) chloride; lithium carbonate; triethylamine at 90℃; for 6h; Autoclave;	1 Example 1 Example 1 [0058] 0.87 g (6.96 mmol) of 1-bromo-1-fluoroethene, 0.89 g (8.8 mmol) of triethylamine, 0.168 g (0.24 mmol) of dichlorobis(triphenylphosphine)palladium(II), 0.060 g (0.80 mmol) of lithium carbonate, and 10 mL of methanol were placed in a 50-mL stainless-steel autoclave. Carbon monoxide (1.0 MPaG) was introduced thereinto, followed by stirring at 90°C for 6 hours. After the completion of the reaction, the autoclave was cooled, and the unreacted gas was purged. Subsequently, the autoclave was opened, and 186 mg (1.0 mmol) of hexafluorobenzene was added as an internal standard, followed by stirring. The reaction mixture was allowed to stand for a while, thereby precipitating a salt. The supernatant was diluted with deuterochloroform, followed by quantification based on an 19F-NMR integrated value, which revealed that 2-fluoroacrylic acid methyl ester (MFA) was present in an amount of 6.31 mmol (yield: 90.7%), and unreacted 1-bromo-1-fluoroethene was present in an amount of 0.19 mmol (recovery: 3.0%). The conversion was 97%. NMR analysis detected four unknown components, and the selectivity of MFA was 94.5%. The table below shows the results.
90.1%	With dichloro[4,5-bis(diphenylphosphino)-9,9’-dimethylxanthene]palladium(II); triethylamine at 100℃; for 8h; Autoclave;	2 8.88 g (71.07 mmol) of 1-bromo-1-fluoroethene,8.01 g (79.2 mmol) of triethylamine, 54.4 mg (0.072 mmol) of dichloro[4,5-bis(diphenylphosphino)-9,9’-dimethylxan- thene]palladium(II), and 36 mL of methanol dried beforehand were placed in a 150-mL stainless autoclave, and 1.0 MPaG carbon monoxide was introduced thereto, followed by stirring at 100° C. for 8 hours. After completion of the reaction, the autoclave was cooled, and the unreacted gas was purged. The autoclave was opened, and 186 mg (1.0 mmol) of hexafluorobenzene was added as an internal standard substance, followed by stirring. The mixture was then allowed to stand for a short period of time to precipitate the salt. The supernatant was diluted with deuterated chloroform, and subjected to quantification based on ‘9F-NMR integral values. The diluted supernatant was found to contain 64.03 mmol (yield: 90.1%) of 2-fluoroacrylic acid methyl ester and 5.83 mmol (recovery: 8.2%) of unreacted 1 -bromo- 1 -fluoroethene. The conversion was 91.0%, and the selectivity was 99.0%.
71.8 g	With bis-triphenylphosphine-palladium(II) chloride; tributyl-amine; lithium carbonate at 90℃; for 6h; Autoclave;	2 Production Example 2 In the case ofIn an autoclave, 20.0 g of 1-bromo-1-fluoroethene, 32.6 g of tributylamine, 10.0 g of dichlorobis (triphenylphosphine) palladium (II)0.56 g of lithium carbonate, 1.2 g of lithium carbonate and 15.4 g of methanol were charged, 1.0 MPaG of carbon monoxide was introduced, and the mixture was stirred at 90 ° C. for 6 hours.Unreacted gas was purged and the reaction product solution in the autoclaveWere taken out. The amount was 71.8 g.As a result of analyzing this reaction product solution,2-fluoroacrylic acid methyl ester is reacted with15.5 g, ionic liquidContaining 41.8 g of tributylamine hydrobromide.

Reference： [1]Current Patent Assignee: DAIKIN INDUSTRIES LIMITED - EP2891646, 2015, A1 Location in patent: Paragraph 0058
[2]Current Patent Assignee: DAIKIN INDUSTRIES LIMITED - US2016/318842, 2016, A1 Location in patent: Paragraph 0129; 0130
[3]Current Patent Assignee: DAIKIN INDUSTRIES LIMITED - JP2017/36231, 2017, A Location in patent: Paragraph 0067

20
[ 67-56-1 ]
[ 2317-91-1 ]
[ 201230-82-2 ]
[ 2343-89-7 ]

Yield	Reaction Conditions	Operation in experiment
91.8%	With dichloro[ferrocene-1,1'-diylbis(diisopropylphosphine-P)]palladium(II); triethylamine at 100℃; for 8h; Autoclave;	4 Example 4 A 50 mL stainless steel autoclave was charged with 1-chloro-1-fluoroethene 2.02 g (25.10 mmol), triethylamine 2.76 g (27.3 mmol) , Dichloro [1,1-bis (diisopropylphosphino) ferrocene] palladium (II) 74.0 mg (0.124 mmol) , And 12.5 mL of previously dehydrated methanol were charged, 0.7 MPaG of carbon monoxide was introduced, and the mixture was stirred at 100 ° C. for 8 hours. After completion of the reaction, after cooling the autoclave, unreacted gas was purged and unplugged, and an internal standard 186 mg (1.0 mmol) of hexafluorobenzene was added as a sub-substance and stirred Standing for a while to precipitate salt. The supernatant was diluted with deuterochloroform and 19 F-NMR As a result of quantitative determination by integral value, 2-fluoroacrylic acid methyl ester was found to be 23.0 Mmol (yield 91.8%) and unreacted 1-chloro-1-fluoroethene 1.33 m Mol (recovery rate 5.3%). The conversion was 91.8% and the selectivity was 100%.
77.4%	With bis(tri-t-butylphosphine)palladium⁽⁰⁾ at 100℃; for 18h; Autoclave;	13 Example 13 Example 13 [0070] 0.92 g (11.4 mmol) of 1-chloro-1-fluoroethene, 1.38 g (13.7 mmol) of triethylamine, 0.40 g (0.62 mmol) of bis(tri-t-butylphosphine)palladium(0), and 6.2 mL of methanol were placed in a 50-mL stainless-steel autoclave. Carbon monoxide (0.7 MPaG) was introduced thereinto, followed by stirring at 100°C for 18 hours. After the completion of the reaction, the autoclave was cooled, and the unreacted gas was purged. Subsequently, the autoclave was opened, and 186 mg (1.0 mmol) of hexafluorobenzene was added as an internal standard, followed by stirring. The reaction mixture was allowed to stand for a while, thereby precipitating a salt. The supernatant was diluted with deuterochloroform, followed by quantification based on an 19F-NMR integrated value, which revealed that 2-fluoroacrylic acid methyl ester (MFA) was present in an amount of 8.82 mmol (yield: 77.4%), and unreacted 1-chloro-1-fluoroethene was present in an amount of 1.89 mmol (recovery: 16.6%). The conversion was 81.3%.
	With 1,4-bis(dicyclohexylphosphino)butane bis(tetrafluoroborate); palladium(II) acetylacetonate; triethylamine at 90℃; for 24h; Autoclave;	1; 2; 3; 4; 5; 6; 8; 9; 11; 12; 13; 15; 16; 18 Example 12 1-Chloro-1-fluoroethene (6.04 g), triethylamine (8.35 g), bis(acetylacetonato)palladium (II) (11.4 mg), 1,4-bis(dicyclohexylphosphino)butane bis(tetrafluoroborate) (23.5 mg), and methanol (33 g) were placed in an autoclave. Carbon monoxide (0.75 MPaG) was introduced thereinto, followed by stirring at 90° C. for 24 hours.The unreacted gas was purged; and the reaction liquid in the autoclave was quantified based on 19F-NMR integral values, which revealed that the amount of 2-fluoroacrylic acid methyl ester was 7.26 g (yield: 93%, selectivity: 94%), the yield of 2-fluoroacrylate was 4.6%, and the remaining percentage of unreacted 1-chloro-1-fluoroethene was 1.4%.

Reference： [1]Current Patent Assignee: DAIKIN INDUSTRIES LIMITED - JP2015/143199, 2015, A Location in patent: Paragraph 0052
[2]Current Patent Assignee: DAIKIN INDUSTRIES LIMITED - EP2891646, 2015, A1 Location in patent: Paragraph 0070
[3]Current Patent Assignee: DAIKIN INDUSTRIES LIMITED - US2021/269383, 2021, A1 Location in patent: Paragraph 0289-0306; 0309-0312; 0315-0320; 0322-0325; 0328-0

21
[ 2343-89-7 ]
[ 677728-84-6 ]
methyl 3-(3,5-difluorophenyl)-5-fluoro-4,5-dihydro-1,2-oxazole-5-carboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
91%	With sodium hydrogencarbonate In isopropyl alcohol at 40℃; for 1h;	A.8 Preparation of methyl 3-(3,5-difluorophenyl)-5-fluoro-4,5-dihydro-1,2-oxazole-5-carboxylate 1.000 g (5.22 mmol) of 3,5-difluoro-N-hydroxybenzenecarboximidoyl chloride is dissolved in 23 ml of isopropanol, then 1086.6 mg (10.44 mmol) of methyl 2-fluoroacrylate are added thereto, and then the mixture is admixed with 2.192 g (26.10 mmol) of sodium hydrogencarbonate. The mixture is left to stir at 40° C. for 1 h, taken up in water and extracted with ethyl acetate to obtain 1.230 g (91%) of the above compound in solid form. 1H NMR [CDCl3]: δ=3.65 (dd, 1H); 3.96 (s, 3H); 4.12 (dd, 1H); 6.96 (t, 1H); 7.22 (d, 2H).

Reference： [1]Current Patent Assignee: BAYER AG - US2015/245615, 2015, A1 Location in patent: Paragraph 0179; 0180

22
[ 2343-89-7 ]
[ 13329-40-3 ]
(Z)-methyl 3-(4-acetylphenyl)-2-fluoroacrylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
70%	With palladium(II) trifluoroacetate; silver carbonate In 1,4-dioxane at 90℃; for 4h; stereospecific reaction;

Reference： [1]Rousée, Kevin; Bouillon, Jean-Philippe; Couve-Bonnaire, Samuel; Pannecoucke, Xavier [Organic Letters, 2016, vol. 18, # 3, p. 540 - 543]

23
[ 2343-89-7 ]
[ 3058-39-7 ]
[ 126976-32-7 ]

Yield	Reaction Conditions	Operation in experiment
90%	With palladium(II) trifluoroacetate; silver carbonate In 1,4-dioxane at 90℃; for 4h; stereospecific reaction;
	With palladium(II) trifluoroacetate; silver carbonate In 1,4-dioxane at 90℃; for 4h; Sealed tube; Inert atmosphere;

Reference： [1]Rousée, Kevin; Bouillon, Jean-Philippe; Couve-Bonnaire, Samuel; Pannecoucke, Xavier [Organic Letters, 2016, vol. 18, # 3, p. 540 - 543]
[2]Huang, Xin; David, Emilie; Jubault, Philippe; Besset, Tatiana; Couve-Bonnaire, Samuel [Journal of Organic Chemistry, 2020, vol. 85, # 21, p. 14055 - 14067]

24
[ 2343-89-7 ]
[ 766-85-8 ]
(Z)-methyl 2-fluoro-3-(3-methoxyphenyl)acrylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
99%	With palladium(II) trifluoroacetate; silver carbonate In 1,4-dioxane at 90℃; for 4h; stereospecific reaction;

Reference： [1]Rousée, Kevin; Bouillon, Jean-Philippe; Couve-Bonnaire, Samuel; Pannecoucke, Xavier [Organic Letters, 2016, vol. 18, # 3, p. 540 - 543]

25
[ 2343-89-7 ]
[ 69113-59-3 ]
methyl Z-3-(3-cyanophenyl)-2-fluoroprop-2-enoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
74%	With palladium(II) trifluoroacetate; silver carbonate In 1,4-dioxane at 90℃; for 4h; stereospecific reaction;
	With palladium(II) trifluoroacetate; silver carbonate In 1,4-dioxane at 90℃; for 4h; Sealed tube; Inert atmosphere;

26
[ 645-00-1 ]
[ 2343-89-7 ]
(Z)-methyl 2-fluoro-3-(3-nitrophenyl)acrylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
80%	With palladium(II) trifluoroacetate; silver carbonate In 1,4-dioxane at 90℃; for 4h; stereospecific reaction;

Reference： [1]Rousée, Kevin; Bouillon, Jean-Philippe; Couve-Bonnaire, Samuel; Pannecoucke, Xavier [Organic Letters, 2016, vol. 18, # 3, p. 540 - 543]

27
[ 2343-89-7 ]
[ 529-28-2 ]
methyl (2Z)-2-fluoro-3-(2-methoxyphenyl)acrylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
72%	With palladium(II) trifluoroacetate; silver carbonate In 1,4-dioxane at 90℃; for 4h; stereospecific reaction;

Reference： [1]Rousée, Kevin; Bouillon, Jean-Philippe; Couve-Bonnaire, Samuel; Pannecoucke, Xavier [Organic Letters, 2016, vol. 18, # 3, p. 540 - 543]

28
[ 2343-89-7 ]
[ 2113-51-1 ]
(Z)-methyl 3-([1,1'-biphenyl]-2-yl)-2-fluoroacrylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
59%	With palladium(II) trifluoroacetate; silver carbonate In 1,4-dioxane at 90℃; for 4h; stereospecific reaction;

Reference： [1]Rousée, Kevin; Bouillon, Jean-Philippe; Couve-Bonnaire, Samuel; Pannecoucke, Xavier [Organic Letters, 2016, vol. 18, # 3, p. 540 - 543]

29
[ 615-37-2 ]
[ 2343-89-7 ]
(Z)-methyl 2-fluoro-3-(2-methylphenyl)acrylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
99%	With palladium(II) trifluoroacetate; silver carbonate In 1,4-dioxane at 90℃; for 4h; stereospecific reaction;

Reference： [1]Rousée, Kevin; Bouillon, Jean-Philippe; Couve-Bonnaire, Samuel; Pannecoucke, Xavier [Organic Letters, 2016, vol. 18, # 3, p. 540 - 543]

30
[ 2343-89-7 ]
[ 610-97-9 ]
(Z)-methyl 2-(2-fluoro-3-methoxy-3-oxoprop-1-en-1-yl)benzoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
99%	With palladium(II) trifluoroacetate; silver carbonate In 1,4-dioxane at 90℃; for 4h; stereospecific reaction;

Reference： [1]Rousée, Kevin; Bouillon, Jean-Philippe; Couve-Bonnaire, Samuel; Pannecoucke, Xavier [Organic Letters, 2016, vol. 18, # 3, p. 540 - 543]

31
[ 2343-89-7 ]
[ 612-55-5 ]
[ 1075204-23-7 ]

Yield	Reaction Conditions	Operation in experiment
99%	With palladium(II) trifluoroacetate; silver carbonate In 1,4-dioxane at 90℃; for 4h; stereospecific reaction;

Reference： [1]Rousée, Kevin; Bouillon, Jean-Philippe; Couve-Bonnaire, Samuel; Pannecoucke, Xavier [Organic Letters, 2016, vol. 18, # 3, p. 540 - 543]

32
[ 591-50-4 ]
[ 2343-89-7 ]
methyl (Z)-2-fluoro-3-phenylpropenoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
99%	With palladium(II) trifluoroacetate; silver carbonate In 1,4-dioxane at 90℃; for 4h; stereospecific reaction;
	With palladium(II) trifluoroacetate; silver carbonate In 1,4-dioxane at 90℃; for 4h; Sealed tube; Inert atmosphere;

33
[ 2343-89-7 ]
[ 4028-63-1 ]
(Z)-methyl 2-fluoro-3-(2,4,6-trimethylphenyl)acrylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
84%	With palladium(II) trifluoroacetate; silver carbonate In 1,4-dioxane at 90℃; for 4h; stereospecific reaction;

Reference： [1]Rousée, Kevin; Bouillon, Jean-Philippe; Couve-Bonnaire, Samuel; Pannecoucke, Xavier [Organic Letters, 2016, vol. 18, # 3, p. 540 - 543]

34
[ 2343-89-7 ]
[ 328-73-4 ]
(Z)-methyl 3-(3,5-bis(trifluoromethyl)phenyl)-2-fluoroacrylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
72%	With palladium(II) trifluoroacetate; silver carbonate In 1,4-dioxane at 90℃; for 4h; stereospecific reaction;

Reference： [1]Rousée, Kevin; Bouillon, Jean-Philippe; Couve-Bonnaire, Samuel; Pannecoucke, Xavier [Organic Letters, 2016, vol. 18, # 3, p. 540 - 543]

35
[ 10486-61-0 ]
[ 2343-89-7 ]
(Z)-methyl 2-fluoro-3-(thiophen-3-yl)acrylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
60%	With palladium(II) trifluoroacetate; silver carbonate In 1,4-dioxane at 90℃; for 4h; stereospecific reaction;

Reference： [1]Rousée, Kevin; Bouillon, Jean-Philippe; Couve-Bonnaire, Samuel; Pannecoucke, Xavier [Organic Letters, 2016, vol. 18, # 3, p. 540 - 543]

36
[ 2689-65-8 ]
[ 2343-89-7 ]
(Z)-methyl 2-fluoro-3-(5-formylfuran-2-yl)acrylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
56%	With palladium(II) trifluoroacetate; silver carbonate In 1,4-dioxane at 90℃; stereospecific reaction;

Reference： [1]Rousée, Kevin; Bouillon, Jean-Philippe; Couve-Bonnaire, Samuel; Pannecoucke, Xavier [Organic Letters, 2016, vol. 18, # 3, p. 540 - 543]

37
[ 2343-89-7 ]
[ 80360-14-1 ]
(Z)-methyl 2-fluoro-3-(1-(phenylsulfonyl)-1H-indol-3-yl)acrylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
56%	With palladium(II) trifluoroacetate; silver carbonate In 1,4-dioxane at 90℃; stereospecific reaction;

Reference： [1]Rousée, Kevin; Bouillon, Jean-Philippe; Couve-Bonnaire, Samuel; Pannecoucke, Xavier [Organic Letters, 2016, vol. 18, # 3, p. 540 - 543]

38
[ 108-86-1 ]
[ 2343-89-7 ]
methyl (Z)-2-fluoro-3-phenylpropenoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
34%	With palladium(II) trifluoroacetate; triphenylphosphine; silver carbonate In 1,4-dioxane at 90℃; for 16h;

Reference： [1]Rousée, Kevin; Bouillon, Jean-Philippe; Couve-Bonnaire, Samuel; Pannecoucke, Xavier [Organic Letters, 2016, vol. 18, # 3, p. 540 - 543]

39
[ 2343-89-7 ]
[ 696-62-8 ]
[ 113128-33-9 ]

Yield	Reaction Conditions	Operation in experiment
84%	With palladium(II) trifluoroacetate; silver carbonate In 1,4-dioxane at 90℃; for 4h; stereospecific reaction;
	With palladium(II) trifluoroacetate; silver carbonate In 1,4-dioxane at 90℃; for 4h; Sealed tube; Inert atmosphere;

40
[ 2343-89-7 ]
[ 589-87-7 ]
(Z)-methyl 3-(4-bromophenyl)-2-fluoroacrylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
89%	With palladium(II) trifluoroacetate; silver carbonate In 1,4-dioxane at 90℃; for 4h; chemoselective reaction;

Reference： [1]Rousée, Kevin; Bouillon, Jean-Philippe; Couve-Bonnaire, Samuel; Pannecoucke, Xavier [Organic Letters, 2016, vol. 18, # 3, p. 540 - 543]

41
[ 2343-89-7 ]
[ 352-34-1 ]
(Z)-methyl 3-(4-fluorophenyl)-2-fluoroacrylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
99%	With palladium(II) trifluoroacetate; silver carbonate In 1,4-dioxane at 90℃; for 4h; stereospecific reaction;

Reference： [1]Rousée, Kevin; Bouillon, Jean-Philippe; Couve-Bonnaire, Samuel; Pannecoucke, Xavier [Organic Letters, 2016, vol. 18, # 3, p. 540 - 543]

42
[ 2343-89-7 ]
[ 455-13-0 ]
[ 126976-31-6 ]

Yield	Reaction Conditions	Operation in experiment
99%	With palladium(II) trifluoroacetate; silver carbonate In 1,4-dioxane at 90℃; for 4h; stereospecific reaction;

Reference： [1]Rousée, Kevin; Bouillon, Jean-Philippe; Couve-Bonnaire, Samuel; Pannecoucke, Xavier [Organic Letters, 2016, vol. 18, # 3, p. 540 - 543]

43
[ 2343-89-7 ]
[ 2393-23-9 ]
2-fluoro-N-(4-methoxybenzyl)acrylamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
64%	Stage #1: 4-methoxy-benzylamine With sodium hexamethyldisilazane In tetrahydrofuran at 0 - 20℃; for 0.5h; Inert atmosphere; Stage #2: methyl 2-fluoroprop-2-enoate In tetrahydrofuran at 0 - 20℃; Inert atmosphere;	4.2.1 General procedure for the synthesis of N-substituted -fluoroacrylamides (2a-i) General procedure: A solution of 2.0 M NaHMDS in THF (7.5 mL, 15.0 mmol) was added to the solution of RNH2 (1.2 equiv) in THF (25 mL) at 0 °C under Ar atmosphere. The reaction solution was then stirred for 30 min at room temperature, after that, methyl 2-fluoroacrylate (0.91 mL, 10.0 mmol) was added dropwise at 0 °C. The resulting solution was then warmed to room temperature and stirred for overnight. After quenched with saturated NH4Cl aqueous solution, the mixture was extracted with EtOAc (2×100 mL), and the combined organic layers were washed with brine (20mL) and dried over NaSO4. After filtration and concentration, the residue was purified by column chromatography, and the isolated yields were shown in Table 1. 4.2.1.1 2-Fluoro-N-(4-methoxybenzyl)-acrylamide (2a) Eluent solvent: petroleum ether/ethyl acetate=2/1. White solid, mp 94-95 °C. IR (neat): ν 3258, 2916, 2848, 1640, 1541, 1514, 1371, 1323, 1251, 1177, 988, 827 cm-1. 1H NMR (400 MHz, CDCl3): δ 7.25 (d, J=7.5Hz, 2H, ArH), 6.88 (d, J=7.5Hz, 2H, ArH), 6.51 (brs, 1H, NH), 5.72 (dd, J=47.8, 1.6Hz, 1H, CH2=CF), 5.13 (dd, J=15.3, 1.6Hz, 1H, CH2=CF), 4.46 (d, J=5.6Hz, 2H, CH2Ar), 3.80 (d, J=0.5Hz, 3H, OCH3). 13C NMR (150 MHz, CDCl3): δ 159.3 (d, J=28.8Hz), 159.2, 156.2 (d, J=267.8Hz), 129.3, 114.1, 99.1 (d, J=15.5Hz), 55.2, 42.9. 19F NMR (376 MHz, CDCl3): δ -121.6 (ddd, JH-F(trans)=47.8Hz, JH-F(cis)=15.3Hz, J=1.9Hz). HRMS (ESI) m/z: calcd for C11H13FNO2+ [M+H]+ 210.0925, found: 210.0926

Reference： [1]Li, Yang; Li, Kai; Wu, Yue; Ma, Qiaoning; Lei, Xinsheng [Tetrahedron, 2016, vol. 72, # 32, p. 4845 - 4853]

44
[ 2343-89-7 ]
[ 100-46-9 ]
2-fluoro-N-benzylacrylamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
54%	Stage #1: benzylamine With sodium hexamethyldisilazane In tetrahydrofuran at 0 - 20℃; for 0.5h; Inert atmosphere; Stage #2: methyl 2-fluoroprop-2-enoate In tetrahydrofuran at 0 - 20℃; Inert atmosphere;	4.2.1 General procedure for the synthesis of N-substituted -fluoroacrylamides (2a-i) General procedure: A solution of 2.0 M NaHMDS in THF (7.5 mL, 15.0 mmol) was added to the solution of RNH2 (1.2 equiv) in THF (25 mL) at 0 °C under Ar atmosphere. The reaction solution was then stirred for 30 min at room temperature, after that, methyl 2-fluoroacrylate (0.91 mL, 10.0 mmol) was added dropwise at 0 °C. The resulting solution was then warmed to room temperature and stirred for overnight. After quenched with saturated NH4Cl aqueous solution, the mixture was extracted with EtOAc (2×100 mL), and the combined organic layers were washed with brine (20mL) and dried over NaSO4. After filtration and concentration, the residue was purified by column chromatography, and the isolated yields were shown in Table 1.

Reference： [1]Li, Yang; Li, Kai; Wu, Yue; Ma, Qiaoning; Lei, Xinsheng [Tetrahedron, 2016, vol. 72, # 32, p. 4845 - 4853]

45
[ 2343-89-7 ]
[ 3300-51-4 ]
2-fluoro-N-(4-(trifluoromethyl)benzyl)acrylamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
56%	Stage #1: p-Trifluoromethylbenzylamine With sodium hexamethyldisilazane In tetrahydrofuran at 0 - 20℃; for 0.5h; Inert atmosphere; Stage #2: methyl 2-fluoroprop-2-enoate In tetrahydrofuran at 0 - 20℃; Inert atmosphere;	4.2.1 General procedure for the synthesis of N-substituted -fluoroacrylamides (2a-i) General procedure: A solution of 2.0 M NaHMDS in THF (7.5 mL, 15.0 mmol) was added to the solution of RNH2 (1.2 equiv) in THF (25 mL) at 0 °C under Ar atmosphere. The reaction solution was then stirred for 30 min at room temperature, after that, methyl 2-fluoroacrylate (0.91 mL, 10.0 mmol) was added dropwise at 0 °C. The resulting solution was then warmed to room temperature and stirred for overnight. After quenched with saturated NH4Cl aqueous solution, the mixture was extracted with EtOAc (2×100 mL), and the combined organic layers were washed with brine (20mL) and dried over NaSO4. After filtration and concentration, the residue was purified by column chromatography, and the isolated yields were shown in Table 1.

Reference： [1]Li, Yang; Li, Kai; Wu, Yue; Ma, Qiaoning; Lei, Xinsheng [Tetrahedron, 2016, vol. 72, # 32, p. 4845 - 4853]

46
[ 2343-89-7 ]
[ 3959-07-7 ]
2-fluoro-N-(4-bromobenzyl)acrylamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
55%	Stage #1: 4-Bromobenzylamine With sodium hexamethyldisilazane In tetrahydrofuran at 0 - 20℃; for 0.5h; Inert atmosphere; Stage #2: methyl 2-fluoroprop-2-enoate In tetrahydrofuran at 0 - 20℃; Inert atmosphere;	4.2.1 General procedure for the synthesis of N-substituted -fluoroacrylamides (2a-i) General procedure: A solution of 2.0 M NaHMDS in THF (7.5 mL, 15.0 mmol) was added to the solution of RNH2 (1.2 equiv) in THF (25 mL) at 0 °C under Ar atmosphere. The reaction solution was then stirred for 30 min at room temperature, after that, methyl 2-fluoroacrylate (0.91 mL, 10.0 mmol) was added dropwise at 0 °C. The resulting solution was then warmed to room temperature and stirred for overnight. After quenched with saturated NH4Cl aqueous solution, the mixture was extracted with EtOAc (2×100 mL), and the combined organic layers were washed with brine (20mL) and dried over NaSO4. After filtration and concentration, the residue was purified by column chromatography, and the isolated yields were shown in Table 1.

Reference： [1]Li, Yang; Li, Kai; Wu, Yue; Ma, Qiaoning; Lei, Xinsheng [Tetrahedron, 2016, vol. 72, # 32, p. 4845 - 4853]

47
[ 2343-89-7 ]
[ 62-53-3 ]
2-fluoro-N-phenylacrylamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
75%	Stage #1: aniline With sodium hexamethyldisilazane In tetrahydrofuran at 0 - 20℃; for 0.5h; Inert atmosphere; Stage #2: methyl 2-fluoroprop-2-enoate In tetrahydrofuran at 0 - 20℃; Inert atmosphere;	4.2.1 General procedure for the synthesis of N-substituted -fluoroacrylamides (2a-i) General procedure: A solution of 2.0 M NaHMDS in THF (7.5 mL, 15.0 mmol) was added to the solution of RNH2 (1.2 equiv) in THF (25 mL) at 0 °C under Ar atmosphere. The reaction solution was then stirred for 30 min at room temperature, after that, methyl 2-fluoroacrylate (0.91 mL, 10.0 mmol) was added dropwise at 0 °C. The resulting solution was then warmed to room temperature and stirred for overnight. After quenched with saturated NH4Cl aqueous solution, the mixture was extracted with EtOAc (2×100 mL), and the combined organic layers were washed with brine (20mL) and dried over NaSO4. After filtration and concentration, the residue was purified by column chromatography, and the isolated yields were shown in Table 1.

Reference： [1]Li, Yang; Li, Kai; Wu, Yue; Ma, Qiaoning; Lei, Xinsheng [Tetrahedron, 2016, vol. 72, # 32, p. 4845 - 4853]

48
[ 2343-89-7 ]
[ 104-94-9 ]
2-fluoro-N-(4-methoxyphenyl)acrylamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
70%	Stage #1: 4-methoxy-aniline With sodium hexamethyldisilazane In tetrahydrofuran at 0 - 20℃; for 0.5h; Inert atmosphere; Stage #2: methyl 2-fluoroprop-2-enoate In tetrahydrofuran at 0 - 20℃; Inert atmosphere;	4.2.1 General procedure for the synthesis of N-substituted -fluoroacrylamides (2a-i) General procedure: A solution of 2.0 M NaHMDS in THF (7.5 mL, 15.0 mmol) was added to the solution of RNH2 (1.2 equiv) in THF (25 mL) at 0 °C under Ar atmosphere. The reaction solution was then stirred for 30 min at room temperature, after that, methyl 2-fluoroacrylate (0.91 mL, 10.0 mmol) was added dropwise at 0 °C. The resulting solution was then warmed to room temperature and stirred for overnight. After quenched with saturated NH4Cl aqueous solution, the mixture was extracted with EtOAc (2×100 mL), and the combined organic layers were washed with brine (20mL) and dried over NaSO4. After filtration and concentration, the residue was purified by column chromatography, and the isolated yields were shown in Table 1.

Reference： [1]Li, Yang; Li, Kai; Wu, Yue; Ma, Qiaoning; Lei, Xinsheng [Tetrahedron, 2016, vol. 72, # 32, p. 4845 - 4853]

49
[ 455-14-1 ]
[ 2343-89-7 ]
2-fluoro-N-(4-trifluoromethylphenyl)acrylamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
85%	Stage #1: 4-trifluoromethylphenylamine With sodium hexamethyldisilazane In tetrahydrofuran at 0 - 20℃; for 0.5h; Inert atmosphere; Stage #2: methyl 2-fluoroprop-2-enoate In tetrahydrofuran at 0 - 20℃; Inert atmosphere;	4.2.1 General procedure for the synthesis of N-substituted -fluoroacrylamides (2a-i) General procedure: A solution of 2.0 M NaHMDS in THF (7.5 mL, 15.0 mmol) was added to the solution of RNH2 (1.2 equiv) in THF (25 mL) at 0 °C under Ar atmosphere. The reaction solution was then stirred for 30 min at room temperature, after that, methyl 2-fluoroacrylate (0.91 mL, 10.0 mmol) was added dropwise at 0 °C. The resulting solution was then warmed to room temperature and stirred for overnight. After quenched with saturated NH4Cl aqueous solution, the mixture was extracted with EtOAc (2×100 mL), and the combined organic layers were washed with brine (20mL) and dried over NaSO4. After filtration and concentration, the residue was purified by column chromatography, and the isolated yields were shown in Table 1.

Reference： [1]Li, Yang; Li, Kai; Wu, Yue; Ma, Qiaoning; Lei, Xinsheng [Tetrahedron, 2016, vol. 72, # 32, p. 4845 - 4853]

50
[ 2343-89-7 ]
[ 591-19-5 ]
2-fluoro-N-(3-bromophenyl)acrylamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
75%	Stage #1: m-Bromoaniline With sodium hexamethyldisilazane In tetrahydrofuran at 0 - 20℃; for 0.5h; Inert atmosphere; Stage #2: methyl 2-fluoroprop-2-enoate In tetrahydrofuran at 0 - 20℃; Inert atmosphere;	4.2.1 General procedure for the synthesis of N-substituted -fluoroacrylamides (2a-i) General procedure: A solution of 2.0 M NaHMDS in THF (7.5 mL, 15.0 mmol) was added to the solution of RNH2 (1.2 equiv) in THF (25 mL) at 0 °C under Ar atmosphere. The reaction solution was then stirred for 30 min at room temperature, after that, methyl 2-fluoroacrylate (0.91 mL, 10.0 mmol) was added dropwise at 0 °C. The resulting solution was then warmed to room temperature and stirred for overnight. After quenched with saturated NH4Cl aqueous solution, the mixture was extracted with EtOAc (2×100 mL), and the combined organic layers were washed with brine (20mL) and dried over NaSO4. After filtration and concentration, the residue was purified by column chromatography, and the isolated yields were shown in Table 1.

Reference： [1]Li, Yang; Li, Kai; Wu, Yue; Ma, Qiaoning; Lei, Xinsheng [Tetrahedron, 2016, vol. 72, # 32, p. 4845 - 4853]

51
[ 2343-89-7 ]
[ 95-53-4 ]
2-fluoro-N-(o-tolyl)acrylamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
67%	Stage #1: <i>o</i>-toluidine With sodium hexamethyldisilazane In tetrahydrofuran at 0 - 20℃; for 0.5h; Inert atmosphere; Stage #2: methyl 2-fluoroprop-2-enoate In tetrahydrofuran at 0 - 20℃; Inert atmosphere;	4.2.1 General procedure for the synthesis of N-substituted -fluoroacrylamides (2a-i) General procedure: A solution of 2.0 M NaHMDS in THF (7.5 mL, 15.0 mmol) was added to the solution of RNH2 (1.2 equiv) in THF (25 mL) at 0 °C under Ar atmosphere. The reaction solution was then stirred for 30 min at room temperature, after that, methyl 2-fluoroacrylate (0.91 mL, 10.0 mmol) was added dropwise at 0 °C. The resulting solution was then warmed to room temperature and stirred for overnight. After quenched with saturated NH4Cl aqueous solution, the mixture was extracted with EtOAc (2×100 mL), and the combined organic layers were washed with brine (20mL) and dried over NaSO4. After filtration and concentration, the residue was purified by column chromatography, and the isolated yields were shown in Table 1.

Reference： [1]Li, Yang; Li, Kai; Wu, Yue; Ma, Qiaoning; Lei, Xinsheng [Tetrahedron, 2016, vol. 72, # 32, p. 4845 - 4853]

52
methyl α-bromo-α-fluoropropionate [ No CAS ]
[ 2343-89-7 ]
[ 38650-84-9 ]

Yield	Reaction Conditions	Operation in experiment
1: 73% 2: 23%	With 2,6-di-tert-butyl-4-methyl-phenol; hydrogen fluoride; 1,8-diazabicyclo[5.4.0]undec-7-ene In toluene at 50℃; for 48h; Cooling with ice;	1 [example 1] To 1,3-dimethyl-2-imidazolidinone (DMI) 140mL (0.519L /mol), 1,8- diazabicyclo [5.4.0] undec-7-ene (DBU) · 3 hydrogen fluoride 97 .6g(460mmol, 1.70eq), DBU24.7g (162mmol, 0.600eq) and 2,6-di-tert-butyl-4-methylphenol 250mg (1.13mmol, 0.00419eq) were added and the mixture was stirred underice-cooling (molar ratio of the organic base and hydrogen fluoride is 1: 2.2,fluoride ion 5.10eq). To this homogeneous solution, α- halogeno -α- fluoroesters (material substrate) 50.0g (270mmol, 1.00eq) represented by thefollowing formula was added under ice-cooling,and the mixture was stirred for 2 days at 50 . Conversion rate by 19 F NMR analysis of the reaction-completionsolution was 87%, and Production ratio of α, α- difluoro esters (the desiredproduct), hydrolysis body of α, α- difluoro esters (the desired producthydrolysis body) and α- fluoro -α, β- unsaturated ester (by-product)represented by the following formulae was 73: 4: 23.

Reference： [1]Current Patent Assignee: CENTRAL GLASS CO LTD - JP5659658, 2015, B2 Location in patent: Paragraph 0088-0090; 0101-0103; 0107-0109; 0113-0115

53
methyl α-bromo-α-fluoropropionate [ No CAS ]
[ 2343-89-7 ]
[ 373-96-6 ]
[ 38650-84-9 ]

Yield	Reaction Conditions	Operation in experiment
18%; 5%; 70%	With 2,6-di-tert-butyl-4-methyl-phenol; hydrogen fluoride; 1,8-diazabicyclo[5.4.0]undec-7-ene; In acetonitrile; at 50℃; for 72h;Cooling with ice;	In acetonitrile 50.0mL (0.463L / mol), 1,8- diazabicyclo [5.4.0] undec-7-ene (DBU) · 3hydrogen fluoride 31.7g (149mmol, 1.38eq), DBU10 .1g (66.3mmol, 0.614eq) and2,6-di--tert--butyl-4-methyl phenol 100mg (454mumol, 0.00420eq) was added, andthe mixture was stirred under ice-cold (organic base and hydrogen fluoridemolar ratio of 1: 2.1, fluoride ion 4.14eq). To this homogeneous solution, thefollowing formula The in indicated by alpha-halogeno -alpha- fluoro esters 20.0g (108mmol, 1.00eq) was added under ice-cooling,and the mixture was stirred for 3 days at 50 C. The conversion rate of F-NMRanalysis of the completion of the reaction solution is 70%, the following formula In indicated by alpha, alpha-difluoro esters (the desired product), alpha, alpha- hydrolysis minute dismantling ofdifluoro esters (the desired product hydrolysis minute dismantling) and alpha-fluoro -alpha, beta- unsaturated ester (byproduct) the production ratio of 77: 5: 18 aand the internal standard method (internal standard alpha, alpha,alpha-trifluoro toluene) was quantified by, contains the target compound can57.2Mmol, yield 53% Met

Reference： [1]Patent: JP5659658,2015,B2 .Location in patent: Paragraph 0098-0100; 0104-0106; 0120-0122

54
Gly-Ni-(S)-2-[N-(N-benzylpropyl)amino]benzophenone [ No CAS ]
[ 2343-89-7 ]
C₃₁H₃₀FN₃NiO₅ [ No CAS ]
C₃₁H₃₀FN₃NiO₅ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: Gly-Ni-(S)-2-[N-(N-benzylpropyl)amino]benzophenone With diisopropylamine In methanol for 250h; Stage #2: methyl 2-fluoroprop-2-enoate In methanol	1 Condensation of Ni-BPB-Gly and ethy 2-fluoroacrylate The i-Pr2NH 1 mL (7.2 mmol) was added at room temperature to a suspension of 15 mL of Ni-BPB-Gly MeOH 3 g (6 mmol). After stirring the reaction mixture for 30 minutes and treated with ethyl acrylate, 3.7 mL (30 mmol) 2-fluoro. TLC in the progress of the reaction SiO2 (AcOEt: CHCl3 (2: 3)) was our monitoring. The reaction was completed in about 250 hours. Then, the mixture was neutralized by the addition of 42 mL of 2% AcOH aqueous solution concentration was mixed with 25 mL MeOH. The mixture of Ni-BPB-4-F-GluOMe diastereomers of precipitated complexes are generated. The precipitate was filtered off, washed with water (3 × 30 mL). It was suspended in CCl4 and the resulting solid complexes, and concentrated in vacuo to dryness. The procedure was repeated three times to remove water from the mixture. Was purified by column chromatography to the complexes (2 SiO2,3 × 20 cm, AcOEt / CHCl3, 3). The main fractions 2.66 g (4.4 mmol, 74%) is Ni-BPB-(2S, 4R)-4-F-GluOMe and Ni-BPB-(2S, 4S)-4-F-GluOMe the mixture is 1.5 / 1 It was contained in a proportion melting point: 191 to 193 . [Α] D25 +2477 (c 0.5, CHCl3).

Reference： [1]Current Patent Assignee: LIFE HEALTHCARE GROUP HOLDINGS (PTY) LTD; RUSSIAN ACADEMY OF SCIENCES - KR101495924, 2015, B1 Location in patent: Paragraph 0882; 0883

55
[ 67-56-1 ]
[ 420-25-7 ]
[ 201230-82-2 ]
[ 430-99-9 ]
[ 2343-89-7 ]

Yield	Reaction Conditions	Operation in experiment
14.1%; 70.9%	With dichloro[bis(2-(diphenylphosphino)phenyl)ether]palladium(ll); triethylamine; at 100℃; under 7500.75 Torr; for 13h;Autoclave;	8.98 g (71.87 mmol) of 1-bromo-1-fluoroethene, 8.01 g (79.2 mmol) of triethylamine, 51.5 mg (0.072 mmol) of dichloro[bis(diphenylphosphinophenyl)ether]palladium (II), and 36 mE of non-dried methanol were placed in a 1 50-mE stainless autoclave, and 1.0 MPaG carbon monoxide was introduced thereto, followed by stirring at 100° C. for 13 hours. After completion of the reaction, the autoclave was cooled, and the unreacted gas was purged. The autoclave was opened, and 186 mg (1.0 mmol) of hexafluorobenzenewas added as an internal standard substance, followed by stirring. The mixture was then allowed to stand for a short period of time to precipitate the salt. The supernatant was diluted with deuterated chloroform, and subjected to quantification based on 19F-NMR integral values. The diluted supernatant was found to contain 50.93 mmol (yield: 70.9percent) of 2-fluoroacrylic acid methyl ester, 10.13 mmol (yield:14.1percent) of 2-fluoroacrylic acid, and 8.12 mmol (recovery:11.3percent) of unreacted 1 -bromo-1 -fluoroethene. The conversion was 87.5percent, and the selectivity was 81.0percent.

Reference： [1]Patent: US2016/318842,2016,A1 .Location in patent: Paragraph 0149; 0150

56
[ 50-00-0 ]
C₆H₆FO₅^(1-)*Na⁽¹⁺⁾ [ No CAS ]
[ 2343-89-7 ]

Yield	Reaction Conditions	Operation in experiment
93%	In 1-methyl-pyrrolidin-2-one; lithium hydroxide monohydrate at 20℃; for 24h;	B-1; B-2; B-3; B-4; B-5; B-6; B-7; B-10; B-11; 1 Example B-2 1155 g of NMP and 1 g of water were added to 431 g of the solution of Example A-1 in a three-necked eggplant flask, and then 30 g of paraformaldehyde was divided into 30 portions and then added at room temperature for 24 hours. The reaction was aged to obtain the desired compound (1) (ie, 2-fluoroacrylic acid methyl ester) having a structure corresponding to the substrate in a yield of 93%.
19 g	Stage #1: C₆H₆FO₅^(1-)*Na⁽¹⁺⁾ In dimethyl sulfoxide for 0.333333h; Molecular sieve; Stage #2: formalin In dimethyl sulfoxide at 40℃; for 1.5h; Molecular sieve;	2 Preparation of alpha-fluoroacrylic acid methyl ester In a dry two-necked flask (500 mL), add 40 mm glass tube, suction joint, thermometer, magnet.Add 2-fluoro-3-oxo-succinate sodium(40 g) and dimethylsulfoxide (300 mL) (dried over 4A molecular sieves)Stir for 20 minFollowed by addition of paraformaldehyde (6 g). After the temperature of the reaction solution was raised to 40 ° C, the reaction was completed after about 1.5 hours. Connect the vacuum distillation unit to perform the vacuum distillation operation [25mmHg / 60 (external bath temperature)]. To obtain crude α-fluoroacrylic acid methyl ester. The crude product was washed with 60 mL of saturated brine solution. The upper organic phase was dried over anhydrous sodium sulfate.Filtered to give 19 g of alpha-fluoroacrylic acid methyl ester,Purity> 98%.

Reference： [1]Current Patent Assignee: DAIKIN INDUSTRIES LIMITED - WO2022/54894, 2022, A1 Location in patent: Paragraph 0125; 0133-0139; 0142-0144
[2]Current Patent Assignee: TIANJIN TERRABAY PHARMACEUTICALS TECHNOLOGY - CN102731304, 2016, B Location in patent: Paragraph 0036; 0037

57
C₁₄H₁₅FO₆ [ No CAS ]
[ 2343-89-7 ]

Yield	Reaction Conditions	Operation in experiment
81.2%	With 4-methoxy-phenol at 170℃; for 9h;	12 450 g of 1,3-dimethylimidazolidinone,420 mg of 4-methoxyphenol,253.5 g of the compound of the formula (3) [R1 = Me, R2 = p-methylbenzoyl]Into the reactor,Heated to 170 ° C,Reaction 9h,Distillation to obtain a mixture,After the mixture was distilled,71.9 g was obtainedΑ-fluoroacrylic acid methyl ester,The product was analyzed by IR, 1H-NMR, 13C-NMR,Is α-fluoroacrylic acid methyl ester, content: 99.5%Yield: 81.2%.

Reference： [1]Current Patent Assignee: QUZHOU FURUIKAI CHEMICAL TECH - CN105777545, 2016, A Location in patent: Paragraph 0073; 0074

58
C₁₃H₁₃FO₆ [ No CAS ]
[ 2343-89-7 ]

Yield	Reaction Conditions	Operation in experiment
83.9%	With 10H-phenothiazine In sulfolane at 180℃; for 6h;	11 598 g of sulfolane,240 mg phenothiazine,213.3 g of the compound of the formula (3) [R1 = Me, R2 = benzoyl]Into the reactor,Heated to 180 ° C,Reaction for about 6h,And the mixture was distilled to obtain a mixed solution. After the mixture was distilled,To give 65.6 g of alpha-fluoroacrylic acid methyl ester,The product was analyzed by IR, 1H-NMR, 13C-NMR,Is α-fluoroacrylic acid methyl ester, content: 99.2%Yield:83.9%.

Reference： [1]Current Patent Assignee: QUZHOU FURUIKAI CHEMICAL TECH - CN105777545, 2016, A Location in patent: Paragraph 0071; 0072

59
C₁₃H₁₅FO₇S [ No CAS ]
[ 2343-89-7 ]

Yield	Reaction Conditions	Operation in experiment
73.8%	With 2,6-di-tert-butyl-4-methyl-phenol In sulfolane at 140℃; for 17h;	14 A mixture of 468 g of sulfolane,30 mg of BHT,234.1 g of the compound [3] (R1 = Me, R2 = Ts) was added to the reaction vessel,Heated to 140 ° C,Reaction for about 17 h,Distillation to obtain a mixture,After the mixture is distilled,To give 53.7 g of alpha-fluoroacrylic acid methyl ester,The product was analyzed by IR, 1H-NMR, 13C-NMR, α-fluoroacrylic acid methyl ester, content: 99.5%Yield: 73.8%.

Reference： [1]Current Patent Assignee: QUZHOU FURUIKAI CHEMICAL TECH - CN105777545, 2016, A Location in patent: Paragraph 0077; 0078

60
C₁₄H₂₅FO₅ [ No CAS ]
[ 2343-89-7 ]

Yield	Reaction Conditions	Operation in experiment
81.2%	With 10H-phenothiazine at 170℃; for 15h;	16 760 g of 1,3-dimethylimidazolidinone,480 mg phenothiazine,190 g of the compound of the formula (3) [R1 = Me, R2 = n-octyl]Into the reactor,Heated to 170 ° C,Reaction for about 15 h,Distillation to obtain a mixture,After the mixture was distilled,To obtain 54.9 g of alpha-fluoroacrylic acid methyl ester,The product was analyzed by IR, 1H-NMR, 13C-NMR, α-fluoroacrylic acid methyl ester, content: 99.4% Yield: 81.2%.

Reference： [1]Current Patent Assignee: QUZHOU FURUIKAI CHEMICAL TECH - CN105777545, 2016, A Location in patent: Paragraph 0081; 0082

61
[ 922-69-0 ]
[ 75-43-4 ]
[ 2343-89-7 ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: 1,1-dimethoxyethylene; Dichlorofluoromethane With tetrabutylammomium bromide; potassium hydroxide In hexane; water at 5 - 10℃; Stage #2: With 2,6-di-tert-butyl-4-methyl-phenol at 0 - 145℃;	8.iii In a 300 ml flaks, 20 g of 1,1-dimethoxyethene, 0.1 g of tetrabutylammonium bromide, 80 g of a 48% aqueous potassium hydroxide solution and 40 g of hexane were mixed, cooled to 5° C. and stirred, and 32 g of dichlorofluoromethane was continuously fed thereto so that the reaction temperature would not exceed 10° C. After completion of feeding of dichlorofluoromethane, disappearance of 1,1-dim ethoxyethene was confirmed by gas chromatography, and then 40 g of distilled water was added to separate the reaction mixture into two layers. The content of 1-chloro-1-fluoro-2,2-dimethoxycyclopropane contained in the crude liquid was 29 g by 1H-NMR (quantitative determination by internal standard method). The yield was 83.6%. (0104) 1H-NMR and 19F-NMR data of 1-chloro-1-fluoro-2,2-dimethoxycyclopropane are shown below. (0105) 1H-NMR (400 MHz, CDCl3), δ ppm; 1.51 (dd, 1H), 1.74 (dd, 1H), 3.47 (s, 3H), 3.49 (s, 3H). (0106) 19F-NMR (400 MHz, CDCl3), δ ppm; -147.35 (dd, 1F). (0107) Further, the content of 2-fluoro-3,3,3-trimethoxy-1-propene was 1.7 g by 1H-NMR (quantitative determination by internal standard method). The yield was 5.0%. (0108) 1H-NMR and 19F-NMR data of 2-fluoro-3,3,3-trimethoxy-1-propene are shown below. (0109) 1H-NMR (400 MHz, CDCl3), δ ppm; 3.22 (s, 9H), 5.22 (dd, 1H), 6.92 (dd, 1H). (0110) 19F-NMR (400 MHz, CDCl3), δ ppm; -126.09 (dd, 1F). In a 100 ml three-necked flask connected with a receiver (cooled to 0° C., 0.5 g of 2,6-di-tert-butyl-4-methylphenol (BHT) as a polymerization inhibitor initially added) for reaction distillation, 0.5 g of 2,6-di-tert-butyl-4-methylphenol (BHT) and 100 ml of 1,2,4-trichlorobenzene are put, and the pressure is reduced to a degree of vacuum of 360 torr. The flask is heated to 145° C., dropwise addition of 45 g of the organic layer crude liquid prepared in Example 7 is started, and dropwise addition is continued at a rate to maintain the internal temperature of 145° C. Formed methyl a-fluoroacrylate is collected in the receiver. The content of methyl a-fluoroacrylate contained in the crude liquid collected in the receiver is 10 g by 1H-NMR (quantitative determination by internal standard method). The yield is 94.6%.

Reference： [1]Current Patent Assignee: AGC INC - US2017/57902, 2017, A1 Location in patent: Paragraph 0103-0111

62
1-chloro-1-fluoro-2,2-dimethoxycyclopropane [ No CAS ]
[ 2343-89-7 ]

Yield	Reaction Conditions	Operation in experiment
89.5%	With 2,6-di-tert-butyl-4-methyl-phenol; methoxybenzene at 120 - 130℃;	8 Example 8 Preparation of 2-fluoroacrylic acid methyl ester with 1-chloro-1-fluoro-2,2-dimethoxycyclopropane 100 g of anisole,1 g BHT was added to a 250 ml four-necked flask,Vacuum to 500mmHg,And with a receiving device, the receiving device also contains 1 g of BHT. Stirring up to 120 ° C,1 g of 1-chloro-1-fluoro-2,2-dimethoxycyclopropane was slowly added dropwise,Temperature control at 120 -130 ,There is a gas to be steamed,By condensation (-20 - 10 ),100 g of a liquid was obtained.In the vacuum of 2.2kP distillation,Oil bath 30 ,Internal temperature 14 ,The top temperature of 12 ° C liquid is distilled off,When the top temperature rises to 14 ° C,Stop the distillation.To obtain 60g product,GC 99%.Yield 89.5%.
12.3 g	With 2,6-di-tert-butyl-4-methyl-phenol at 145℃;	6 [Example 6] Production Example of Compound (F¹)-Containing Composition In a three-necked flask (inner volume 100 mL) connected to a receiver cooled to 0° C. (initially added with 0.5 g of 2,6-di-tert-butyl-4-methylphenol as polymerization inhibitor (hereinafter to be also indicated as BHT)) were charged BHT (0.5 g) and 1,2,4-trichlorobenzene (100 mL). The inner pressure of 360 Torr and the inner temperature at 145° C. were maintained, and dropwise addition of purified product (20 g) of Example 2 was started to perform the thermal decomposition reaction of compound (A1) and the generated fraction was collected in the receiver to give compound (F1). (0112) The content of compound (F1) in the fraction was 12.3 g, and the fraction (compound (F1)-containing composition) contained 99.3 mol % of compound (F1), 0.01 mol % of compound (P1), and 0.02 mol % of compound (Q1). The fraction contained a trace amount of hexane.

Reference： [1]Current Patent Assignee: SHANGHAI XINFU MEDICINE TECH - CN106397206, 2017, A Location in patent: Paragraph 0070; 0071; 0072; 0073; 0074; 0075; 0076-0081
[2]Current Patent Assignee: AGC INC - US2019/263746, 2019, A1 Location in patent: Paragraph 0111-0112

63
dimethyl 2-fluoro-2-chloromethylmalonate [ No CAS ]
[ 2343-89-7 ]

Yield	Reaction Conditions	Operation in experiment
92%	With 2,6-di-tert-butyl-4-methyl-phenol; sodium carbonate In 1-methyl-pyrrolidin-2-one at 150℃; for 4h;	7 Example 7 Example 7 Preparation of methyl 2-fluoroacrylate from dimethyl 2-fluoro-2-chloromethylmalonate (Inventive) Into a mixture of 100 g of N-methylpyrrolidone, 70 g of sodium carbonate and 5 g of 2,6-di-tert-butyl-4-methylphenol were metered, at 300 mbar and 150° C., 50 g of the product from example 3 within about 4 hours. 27 g of a colorless liquid having a purity of 88% were obtained (about 93% of theory). For further purification, the product was fractionally distilled under reduced pressure with addition of 2,6-di-tert-butyl-4-methylphenol in a distillation yield of about 92% of theory.

Reference： [1]Current Patent Assignee: LANXESS AG - US2017/197905, 2017, A1 Location in patent: Paragraph 0081

64
dimethyl 2-fluoro-2-chlorosulfinyloxymethylmalonate [ No CAS ]
[ 2343-89-7 ]

Yield	Reaction Conditions	Operation in experiment
	With 2,6-di-tert-butyl-4-methyl-phenol; sodium carbonate In 1-methyl-pyrrolidin-2-one at 130℃; for 4h;	9 Example 9 Example 9 Preparation of methyl 2-fluoroacrylate from dimethyl 2-fluoro-2-chlorosulfinyloxymethylmalonate (Inventive) Into a mixture of 40 g of N-methylpyrrolidone, 32 g of sodium carbonate and 1.4 g of 2,6-di-tert-butyl-4-methylphenol were metered, at 300 mbar and 130° C., 48.6 g of the product from example 5 within about 4 hours. The distillate obtained was washed with water at 0° C. 14.8 g of a colorless liquid having a purity of nearly 88% were obtained (about 82% of theory).

Reference： [1]Current Patent Assignee: LANXESS AG - US2017/197905, 2017, A1 Location in patent: Paragraph 0083

65
[ 107843-23-2 ]
[ 2343-89-7 ]

Yield	Reaction Conditions	Operation in experiment
70%	With sulfolane; potassium fluoride; 2,6-di-tert-butyl-4-methyl-phenol at 90 - 105℃; for 1.25h;	1 Example 1 To a 100 mL recovery flask, 2.91 g (50 mmol) of potassium fluoride, 55.1 mg (0.250 mmol) of dibutylhydroxytoluene (BHT)45.0 g (250 mmol) of dimethyl 2-fluoro-2-hydroxymethylmalonate,And 11.5 mL (14.5 g) of sulfolane were charged,And mixed. The mixture was heated under atmospheric pressure at 90 ° C. for 15 minutes, subsequently under reduced pressure and 105 ° C. for 1 hour, and distilled simultaneously with the reaction to obtain methyl-2-fluoroacrylate as a mixture with methanol.The yield was 18.2 g (26.8 g as a mixture with methanol), and the yield was 70%.The mixture contained dimethoxymethane. The ratio of the mass of dimethoxymethane to the mass of methyl-2-fluoroacrylate calculated by gas chromatography under the following conditions was 0.16% (w / w).
24 g	With 2,6-di-tert-butyl-4-methyl-phenol; sodium carbonate In 1-methyl-pyrrolidin-2-one at 150℃;	8 Example 8 Example 8 Preparation of methyl 2-fluoroacrylate from dimethyl 2-fluoro-2-hydroxymethylmalonate (Inventive) A mixture, prepared at room temperature, of 50 g of N-methylpyrrolidone, 30 g of sodium carbonate, 2.5 g of 2,6-di-tert-butyl-4-methylphenol and 50 g of the product from example 1 was heated gradually to 150° C. at a reduced pressure of 300 mbar. The distillate obtained was washed at 0° C. with a 20% by weight aqueous sodium chloride solution to free it of methanol. 24 g of a colorless liquid having a purity of 96% were obtained (about 82% of theory). For further purification, the product was fractionally distilled under reduced pressure with addition of 2,6-di-tert-butyl-4-methylphenol in a distillation yield of about 92% of theory.

Reference： [1]Current Patent Assignee: DAIKIN INDUSTRIES LIMITED - JP6237223, 2017, B2 Location in patent: Paragraph 0029
[2]Current Patent Assignee: LANXESS AG - US2017/197905, 2017, A1 Location in patent: Paragraph 0082

66
[ 67-56-1 ]
[ 430-99-9 ]
[ 2343-89-7 ]

Yield	Reaction Conditions	Operation in experiment
93%	With thionyl chloride; at 5 - 35℃; for 2h;	8.64 g (0.096 mol) of <strong>[430-99-9]2-fluoroacrylic acid</strong> was mixed in a 100 ml three-necked flask at 5-10 ° C,And 13.1 g (0.11 mol) of thionyl chloride were added, the temperature was raised to 30 ° C, 6.4 g (0.2 mol) of methanol was added dropwise,Insulation 30-35 reaction 2h,The system was neutralized by adding aqueous NaHCO3 solution,20 g (0.23 mol) of methyl t-butyl ether was added for extraction,The organic phase was distilled to give methyl 2-fluoroacrylate. Yield 93percent.

Reference： [1]Patent: CN107417524,2017,A .Location in patent: Paragraph 0078; 0079; 0080; 0081; 0082; 0083; 0084-0087

67
[ 2343-89-7 ]
[ 71999-74-1 ]
[ 942189-96-0 ]

Reference： [1]Organic Letters,2018,vol. 20,p. 337 - 340

68
[ 2343-89-7 ]
[ 689-67-8 ]
[ 73183-34-3 ]
C₂₃H₄₀BFO₅ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With 1,3-bis(2,6-diisopropylphenylimidazol)-2-ylidene copper(I) dibenzoylmethanate In toluene at 20℃; for 18h; Schlenk technique; Inert atmosphere;

Reference： [1]Rasson, Corentin; Stouse, Adrien; Boreux, Arnaud; Cirriez, Virginie; Riant, Olivier [Chemistry - A European Journal, 2018, vol. 24, # 37, p. 9234 - 9237]

69
[ 2343-89-7 ]
[ 1466-76-8 ]
(Z)-methyl 2-fluoro-3-(2,6-dimethoxyphenyl)acrylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
98%	With palladium(II) trifluoroacetate; silver carbonate In 1,4-dioxane; dimethyl sulfoxide at 120℃; for 12h; Sealed tube; diastereoselective reaction;

Reference： [1]Bouazzaoui, Ouafa; Rousée, Kevin; Mulengi, Joseph Kajima; Pannecoucke, Xavier; Bouillon, Jean-Philippe; Couve-Bonnaire, Samuel [European Journal of Organic Chemistry, 2018, vol. 2018, # 27, p. 3705 - 3715]

70
[ 2343-89-7 ]
[ 91-52-1 ]
(Z)-methyl 2-fluoro-3-(2,4-dimethoxyphenyl)acrylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
86%	With palladium(II) trifluoroacetate; silver carbonate In 1,4-dioxane; dimethyl sulfoxide at 120℃; for 12h; Sealed tube; diastereoselective reaction;

71
[ 2343-89-7 ]
[ 134-11-2 ]
(Z)-methyl 2-fluoro-3-(2-ethoxyphenyl)acrylate [ No CAS ]

Reference： [1]European Journal of Organic Chemistry,2018,vol. 2018,p. 3705 - 3715

72
[ 2343-89-7 ]
[ 14389-86-7 ]
(Z)-methyl 2-fluoro-3-(2-benzyloxyphenyl)acrylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
65%	With palladium(II) trifluoroacetate; silver carbonate In 1,4-dioxane; dimethyl sulfoxide at 120℃; for 12h; Sealed tube; diastereoselective reaction;

73
[ 2343-89-7 ]
[ 480-63-7 ]
(Z)-methyl 2-fluoro-3-(2,4,6-trimethylphenyl)acrylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
89%	With palladium(II) trifluoroacetate; silver carbonate In 1,4-dioxane; dimethyl sulfoxide at 120℃; for 12h; Sealed tube; diastereoselective reaction;

74
[ 2343-89-7 ]
[ 385-00-2 ]
(Z)-methyl 2-fluoro-3-(2,6-difluorophenyl)acrylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
82%	With palladium(II) trifluoroacetate; silver carbonate In 1,4-dioxane; dimethyl sulfoxide at 120℃; for 12h; Sealed tube; diastereoselective reaction;

75
[ 2343-89-7 ]
[ 2252-37-1 ]
(Z)-methyl 2-fluoro-3-(2-bromo-6-fluorophenyl)acrylate [ No CAS ]

Reference： [1]European Journal of Organic Chemistry,2018,vol. 2018,p. 3705 - 3715

76
[ 2343-89-7 ]
[ 50-30-6 ]
(Z)-methyl 2-fluoro-3-(2,6-dichlorophenyl)acrylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
62%	With palladium(II) trifluoroacetate; silver carbonate In 1,4-dioxane; dimethyl sulfoxide at 140℃; for 6h; Sealed tube; diastereoselective reaction;

77
[ 2343-89-7 ]
[ 50-43-1 ]
(Z)-methyl 2-fluoro-3-(2,4,6-trichlorophenyl)acrylate [ No CAS ]

Reference： [1]European Journal of Organic Chemistry,2018,vol. 2018,p. 3705 - 3715

78
[ 2343-89-7 ]
[ 6280-88-2 ]
(Z)-methyl 2-fluoro-3-(4-chloro-2-nitrophenyl)acrylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
60%	With palladium(II) trifluoroacetate; silver carbonate In 1,4-dioxane; dimethyl sulfoxide at 120℃; for 12h; Sealed tube; diastereoselective reaction;

79
[ 2343-89-7 ]
[ 33844-21-2 ]
(Z)-methyl 2-fluoro-3-(4-methoxy-2-nitrophenyl)acrylate [ No CAS ]

Reference： [1]European Journal of Organic Chemistry,2018,vol. 2018,p. 3705 - 3715

80
[ 2343-89-7 ]
[ 4731-65-1 ]
methyl 2-fluoro-3-(2-methoxyphenyl)acrylate [ No CAS ]

Reference： [1]European Journal of Organic Chemistry,2018,vol. 2018,p. 3705 - 3715

81
[ 2343-89-7 ]
(1r,3r,5R,7S)-2-((4-iodophenyl)(4-methoxyphenyl)methylene)adamantane [ No CAS ]
C₂₈H₂₉FO₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With palladium(II) trifluoroacetate; silver carbonate In 1,4-dioxane at 90℃; Inert atmosphere;	17.I [00335] Compound 36: (Z)-3-(4-(((lr,3r,5R,7S)-adamantan-2-ylidi hydroxyphenyl)methyl)phenyl)-2-fluoroacrylic acid [00336] (lr,3r,5R,7S)-2-((4-iodophenyl)(4-methoxyphenyl)methylene)adamantane was reacted with methyl 2-fluoroacrylate following the general Heck reaction using Pd(TFA)2 as catalyst and Ag2C03 as base. The reaction mixture was extracted with ethyl acetate and washed with brine. The organic extracts were combined, dried over anhydrous Na2S04, and concentrated in vacuo. The crude product was dissolved in methanol. A 2M NaOH solution (2 mL) was added dropwise. After stirring for 10 min, the mixture was extracted with ethyl acetate. The organic layers were collected and concentrated in vacuo. Demethylation with BBr3 and further purification by flash column chromatography gave compound 36 as a white powder. 1H NMR (500 MHz, acetone-de) δ 7.61 (d, J = 8.2 Hz, 2H), 7.20 (d, J = 8.2 Hz, 2H), 6.98 (d, J = 8.5 Hz, 2H), 6.78 (d, J = 8.5 Hz, 2H), 6.50 (d, J = 16.0 Hz, 1H), 2.81 (s, 1H), 2.76 (s, 1H), 1.99 (s, 2H), 1.88 (d, J = 13.1Hz, 10H). LRMS (ESI) for C26H24F03 (M-H+), found 403.3.

Reference： [1]Current Patent Assignee: UNIVERSITY OF ILLINOIS (SYSTEM) - WO2018/175965, 2018, A1 Location in patent: Paragraph 00335; 00336

82
[ 5281-20-9 ]
[ 2343-89-7 ]
(±)-methyl 1-fluoro-2,2-dimethylcyclopropane-1-carboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
86%	With iodosylbenzene In dichloromethane at 20℃; for 1h; Green chemistry;

Reference： [1]Allouche, Emmanuelle M. D.; Charette, André B. [Chemical Science, 2019, vol. 10, # 13, p. 3802 - 3806]

83
[ 2343-89-7 ]
[ 312-94-7 ]
(Z)-methyl 2-fluoro-4-oxo-4-(2-(trifluoromethyl)phenyl)but-2-enoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
81%	With fac-tris(2-phenylpyridinato-N,C₂')iridium(III); 2,6-di-tert-butyl-4-methylpyridine In chloroform at 23℃; for 16h; Irradiation; Sealed tube; diastereoselective reaction;

Reference： [1]Lei, Zhen; Banerjee, Arghya; Kusevska, Elena; Rizzo, Eric; Liu, Peng; Ngai, Ming-Yu [Angewandte Chemie - International Edition, 2019, vol. 58, # 22, p. 7318 - 7323][Angew. Chem., 2019, vol. 131, # 22, p. 7396 - 7401,6]

84
[ 2343-89-7 ]
lithium 2-fluoroacrylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With water; lithium hydroxide In methanol at 20℃; for 2h;	75 (R)-(l-((((7-(2-fluoroacryloyl)-7-azabicyclo[2.2. l]heptan-l-yl)methoxy)carbonyl)amino)-2-(4- fluorophenyl)ethyl)boronic acid To a stirred solution of methyl 2-fluoroacrylate (lg, 9.61 mmol) in MeOththO = 10: 1 (10 mL), LiOH (460.16 mg, 19.22 mmol) was added at rt. The reaction mixture was stirred for 2 h. After completion of the reaction, the mixture was concentrated under reduced pressure to get crude product lithium 2-fluoroacrylate (1.05 g). The crude product was directly used to next step without purification.

Reference： [1]Current Patent Assignee: SANOFI - WO2019/99582, 2019, A1 Location in patent: Paragraph 0525

85
[ 2343-89-7 ]
[ 2684-60-8 ]
(±)-methyl (S)-3-fluoro-5,5-dimethyl-4,5-dihydro-3H-pyrazole-3-carboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
62%	In dichloromethane at 20℃; for 2h;

Reference： [1]Allouche, Emmanuelle M. D.; Benoit, Guillaume; Charette, André B.; Rullière, Pauline [Angewandte Chemie - International Edition, 2018, vol. 57, # 20, p. 5777 - 5782][Angew. Chem., 2018, vol. 58, p. 2921 - 2936,16]

86
[ 2343-89-7 ]
2-nitro-1-phenylethanone O-methyloxime [ No CAS ]
5-fluoro-3-(methoxyiminophenylmethyl)-4,5-dihydroisoxazole-5-carboxylic acid methyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
62%	With phenyl isocyanate; triethylamine In tetrahydrofuran at 20℃; for 24h;	General procedure for cycloaddition reactions of nitrile oxides with alkenes [5-(4-Chloro-phenyl)-4,5-dihydro-isoxazol-3-yl]-phenyl-methanone O-methyl-oxime (3a) General procedure: To a 50 mL round-bottomed flask were added 2-nitro-1-phenyl-ethanone O-methyl-oxime 1a (1.5 mmol, 1.0 equiv.), 4-chlorostyrene 2 (249 mg, 1.8 mmol, 1.2 equiv.) and THF (6 mL). After the reaction mixture was cooled to 0 °C, phenyl isocyanate (429 mg, 3.6 mmol, 2.4 equiv.) was added dropwise followed by triethylamine (15 mg, 0.15 mmol, 0.10 equiv.). The resulting mixture was warmed to room temperature and stirred for 24 h. The reaction mixture was quenched by saturated NH4Claq and the aqueous layer was extracted with AcOEt (20 mL x 2). The combined organic layer was washed with brine, dried over Na2SO4 and evaporated under reduced pressure. The precipitated solid was washed with DCM and removed by filtration. The filtrate was evaporated under reduced pressure and the residue was purified by silica gel column chromatography (n-hexane/AcOEt) to afford the title compound as a pale yellow oil (454 mg, 96%), Z/E = 93:7. Z- and E-isomers were inseparable. Z/E ratio was determined by analysis of 1H NMR by the relative integration of the methyls resonance at δ 4.02 (Z-isomer, major) and δ 3.93 (E-isomer, minor).

Reference： [1]Umemoto, Nao; Imayoshi, Ayumi; Tsubaki, Kazunori [Tetrahedron Letters, 2020, vol. 61, # 33]

87
[ 4447-55-6 ]
[ 2343-89-7 ]

Yield	Reaction Conditions	Operation in experiment
46.9%	With sodium fluoride at 30℃; for 3h;	1.2-3.2 (2) Raise the temperature in the reactor to 35°C, add 20 g of NaF into the reactor, and react for 3 hours while stirring, at this time, the mother liquor of methyl 2-fluoroacrylate is obtained;(3) Put the mother liquor of methyl 2-fluoroacrylate at -100 for 12h24h;(4) Hot filtration of the mother liquor of methyl 2-fluoroacrylate at 50°C to obtain a filtrate of methyl 2-fluoroacrylate;(5) Recrystallize the filtrate of methyl 2-fluoroacrylate in a salt bath at 0°C, filter and collect the crude product of methyl 2-fluoroacrylate;(6) The crude product of methyl 2-fluoroacrylate is rectified, and the fraction is collected at a temperature of 90° C. to obtain a product of methyl 2-fluoroacrylate. At this time, its purity measured by GC was 98%, and the calculated yield was 46.9%.
	With 2,6-di-tert-butyl-4-methyl-phenol; triethylamine In dichloromethane at 37℃; for 87h;	8 Example 8: Synthesis of MFA using Example 7 and thethylamine as base A solution of example 7 of the difluoro compound methyl 2,3- difluoropropionate (0.5 g, 4.0 mmol, 1 eq), thethylamine (0.49 g, 0.67 ml_, 4.8 mmol, 1.2 eq), and BHT (4.9 mg, 0.02 mmol, 0.0055 eq) in DCM (20 mL) was stirred at 37 °C for 87 hours. The reaction was stopped, worked up and the solvent was removed under atmospheric distillation. The desired product MFA (Retention time 3.5 min by GC-FID, Method B) was found besides starting material Methyl 2,3-difluoropropionate (Retention time 4.3 min by GC-FID, Method B) and BHT (Retention time 12.2 minutes by GC-FID, Method B). The resulting MFA was compared to a reference standard of MFA.

Reference： [1]Current Patent Assignee: LUOYANG SUNLAND CHEM SCI TECH - CN111116362, 2020, A Location in patent: Paragraph 0061; 0063-0068; 0070-0075; 0077-0081
[2]Current Patent Assignee: VIFOR PHARMA LTD - WO2021/191876, 2021, A1 Location in patent: Paragraph 00118

88
[ 67-56-1 ]
[ 75-38-7 ]
[ 201230-82-2 ]
[ 2343-89-7 ]

Yield	Reaction Conditions	Operation in experiment
5%	Stage #1: methanol With bis-triphenylphosphine-palladium(II) chloride; triethylamine; triphenylphosphine; lithium iodide In 1,4-dioxane at -78 - 30℃; for 1.5h; Autoclave; Sealed tube; Inert atmosphere; Stage #2: Vinylidene fluoride; carbon monoxide In 1,4-dioxane at 90℃; for 24h; Autoclave; Sealed tube;	1-7 In a 50 ml autoclave, Pd2Cl2 (PPh3) 2 (350 mg, 0.5 mmol, 5 mol%), PPh3 (524 mg, 2 mmol, 20 mol%), Et3N (1.01 g, 10 mmol, 1 equivalent), LiI (1.34 g). 10 mmol, 1 eq), methanol (320 mg, 10 mmol, 1 eq) and 1,4-dioxane (10 ml) were added, the autoclave was sealed and stirred at -78 ° C. for 0.5 hours. Then, after replacing with nitrogen gas (N2) three times, the mixture was stirred at 30 ° C. for 1 hour. Then, compound 1 (vinylidene fluoride) (about 1 g, 0.4 MPa) and CO (0.4 MPa) were added, and the mixture was stirred at 90 ° C. for 24 hours.After completion of the reaction, the mixture was left at room temperature for 0.5 hours and then stirred at -78 ° C. for 0.5 hours. Then, after replacing with nitrogen gas (N2) three times, the mixture was stirred at 30 ° C. for 1 hour. Then, the autoclave was opened, CF3C6H5 (0.73 g, 5 mmol, 0.5 eq) was added, and the mixture was stirred for about 10 minutes.The obtained reaction solution was diluted with CDCl3 and measured by 19F-NMR, and the yield was calculated. The yield of the target product (Compound 2) was 5%.

Reference： [1]Current Patent Assignee: OSAKA UNIVERSITY; DAIKIN INDUSTRIES LIMITED - JP2015/160846, 2015, A Location in patent: Paragraph 0069-0076

89
[ 2343-89-7 ]
[ 32783-20-3 ]
C₁₄H₁₉FO₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
52%	With chloro-trimethyl-silane; [4,4′-bis(1,1-dimethylethyl)-2,2′-bipyridine-N1,N1′]bis{3,5-difluoro-2-[5-(trifluoromethyl)-2-pyridinyl-κN]phenyl-κC}iridium(III) hexafluorophosphate; Diethyl 2,6-dimethyl-4-phenyl-1,4-dihydropyridine-3,5-dicarboxylate In N,N-dimethyl-formamide for 16h; Irradiation; Inert atmosphere;

Reference： [1]Dixon, Darren J.; Leitch, Jamie A.; Rogova, Tatiana; Rossolini, Thomas [ACS Catalysis, 2020, vol. 10, # 19, p. 11430 - 11437]

90
[ 88070-48-8 ]
[ 2343-89-7 ]
methyl (2Z)-2-fluoro-3-[2-(methylcarbamoyl)phenyl]prop-2-enoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
55%	With silver hexafluoroantimonate; dichloro[1,3-di(ethoxycarbonyl)-2,4,5-trimethylcyclopentadienyl]rhodium(III) dimer; acetic acid; silver carbonate In <i>tert</i>-butyl alcohol at 40℃; for 24h; Inert atmosphere;	Rh-Catalyzed Reaction of N-Methylbenzamide (1a) with Methyl 2-Trifluoromethylacrylate (2) (entry 7 in Table 1) General procedure: A mixture of N-methylbenzamide (1a) (0.5mmol, 68 mg), methyl 2-(Trifluoromethyl)acrylate (2) (0.5 mmol, 77 mg), [CpERhCl2]2 (0.01 mmol, 9mg), AgSbF6 (0.2 mmol, 69 mg), AcOH (1 mmol, 60 mg), Ag2CO3 (1 mmol, 276 mg) and1-methylnaphthalene (ca. 20 mg) as internal standard was stirred in tBuOH (3 mL) under Ar at 40 °Cfor 24 h. Then the resulting mixture was diluted by dichloromethane (15 mL). The organic layer was washed by 1 N HCl (15 mL), water (15 mL), and brine (15 mL) and dried over Na2SO4. After removal of the solvents under vacuum, product 3a (139 mg, 97%) was purified by gel permeation chromatography using EtOAc as eluant.

Reference： [1]Yoshimoto, Risa; Morisaka, Hideaki; Usuki, Yoshinosuke; Shibata, Yu; Tanaka, Ken; Satoh, Tetsuya [Chemistry Letters, 2020, vol. 49, # 12, p. 1481 - 1483]

91
[ 2343-89-7 ]
[ 163229-48-9 ]
C₁₉H₂₂FNO₆ [ No CAS ]

Reference： [1]Chemical Science,2022,vol. 13,p. 2296 - 2302
[2]Journal of Organic Chemistry,2021,vol. 86,p. 1730 - 1747

92
[ 17422-33-2 ]
[ 2343-89-7 ]
methyl 3-(6-chloro-1H-indol-1-yl)-2-fluoropropanoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
51%	With caesium carbonate In N,N-dimethyl-formamide at 20℃;	B.3 B.3. Synthesis of methyl 3-(6-chloro-1 H-indol-1 -yl)-2-fluoropropanoate XI-3 To a solution of 6-chloroindole (1.06 g, 6.99 mmol) and CS2CO3 (2.73 g, 8.39 mmol) in DMF (10 ml_), was added methyl 2-fluoroacrylate (0.8 g, 7.69 mmol) dropwise. Subsequently, the mixture was stirred at room temperature overnight. The reaction was quenched with H O (50 ml_) and extracted with Et 1 H NMR (600 MHz, CDCh) d 7.52 (d, J = 8.4 Hz, 1 H), 7.37 - 7.31 (m, 1 H), 7.12 - 7.07 (m, 2H), 6.51 (dd, J = 3.2, 0.9 Hz, 1 H), 5.20 (ddd, J = 48.3, 6.3, 3.0 Hz, 1 H), 4.66 - 4.47 (m, 2H), 3.76 (s, 3H).

Reference： [1]Current Patent Assignee: UCB - WO2020/254289, 2020, A1 Location in patent: Page/Page column 57

93
[ 2343-89-7 ]
[ 55052-27-2 ]
methyl 3-(6-chloro-1H-pyrrolo[2,3-b]pyridin-1-yl)-2-fluoropropanoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
76%	With caesium carbonate In N,N-dimethyl-formamide at 20℃;	B.4 B.4. Synthesis of methyl 3-(6-chloro-1 H-pyrrolo[2,3-b]pyridin-1 -yl)-2- fluoropropanoate XI-4 To a solution of 6-chloro-1 H-pyrrolo[2,3-b]pyridine (1.07 g, 6.99 mmol) and CS2CO3 (2.73 g, 8.39 mmol) in DMF (10 ml_) was added methyl 2-fluoroacrylate (0.8 g, 7.69 mmol) dropwise. The mixture was stirred at room temperature overnight, quenched with H2O (50 ml_) and extracted with Et21 H NMR (600 MHz, CDC ) d 7.84 (d, J = 8.1 Hz, 1 H), 7.24 (dd, J = 3.6, 1.4 Hz, 1 H), 7.09 (d, J = 8.1 Hz, 1 H), 6.49 (d, J = 3.6 Hz, 1 H), 5.28 (ddd, J = 48.4, 6.6, 3.4 Hz, 1 H), 4.91 - 4.54 (m, 2H), 3.78 (s, 3H).

Reference： [1]Current Patent Assignee: UCB - WO2020/254289, 2020, A1 Location in patent: Page/Page column 58

94
[ 2343-89-7 ]
[ 161173-98-4 ]
methyl (Z)-5-(3-bromophenyl)-2-fluoropent-2-enoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
76%	With [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro-(3-phenyl-1H-inden-1-ylidene)(tricyclohexylphosphine)ruthenium(II) In dichloromethane at 80℃; for 15h; Inert atmosphere; Sealed tube; diastereoselective reaction;

Reference： [1]Nouaille, Augustin; Pannecoucke, Xavier; Poisson, Thomas; Couve-Bonnaire, Samuel [Advanced Synthesis and Catalysis, 2021, vol. 363, # 8, p. 2140 - 2147]

95
[ 2343-89-7 ]
[ 63667-83-4 ]
methyl (Z)-2-fluoro-5-(2-methoxyphenyl)pent-2-enoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
87%	With [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro-(3-phenyl-1H-inden-1-ylidene)(tricyclohexylphosphine)ruthenium(II) In dichloromethane at 80℃; for 15h; Inert atmosphere; Sealed tube; diastereoselective reaction;

Reference： [1]Nouaille, Augustin; Pannecoucke, Xavier; Poisson, Thomas; Couve-Bonnaire, Samuel [Advanced Synthesis and Catalysis, 2021, vol. 363, # 8, p. 2140 - 2147]

96
[ 872-05-9 ]
[ 2343-89-7 ]
methyl (Z)-2-fluoroundeca-2-enoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
87%	With [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro-(3-phenyl-1H-inden-1-ylidene)(tricyclohexylphosphine)ruthenium(II) In dichloromethane at 80℃; for 15h; Inert atmosphere; Sealed tube; diastereoselective reaction;

Reference： [1]Nouaille, Augustin; Pannecoucke, Xavier; Poisson, Thomas; Couve-Bonnaire, Samuel [Advanced Synthesis and Catalysis, 2021, vol. 363, # 8, p. 2140 - 2147]

97
[ 2343-89-7 ]
[ 112-88-9 ]
methyl (Z)-2-fluorononadec-2-enoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
98%	With [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro-(3-phenyl-1H-inden-1-ylidene)(tricyclohexylphosphine)ruthenium(II) In dichloromethane at 80℃; for 15h; Inert atmosphere; Sealed tube; diastereoselective reaction;

Reference： [1]Nouaille, Augustin; Pannecoucke, Xavier; Poisson, Thomas; Couve-Bonnaire, Samuel [Advanced Synthesis and Catalysis, 2021, vol. 363, # 8, p. 2140 - 2147]

98
[ 50-00-0 ]
[ 344-14-9 ]
[ 2343-89-7 ]

Yield	Reaction Conditions	Operation in experiment
	With 10H-phenothiazine; caesium carbonate In sulfolane at 120℃;	1 Sulfolane (125g), DMFM (1 OOg), phenothiazine (1.37g), and cesium carbonate (21.7g) were charged into a jacketed reactor with mechanical stirring set to 250 rpm. Paraformaldehyde (22g) was dosed to the reaction mixture. After the exotherm finished, the reactor jacket temperature was ramped to 120°C and vacuum was applied slowly to 200 mbar (20 kPa). The temperature and pressure were held at the set points, while the decarboxylation reaction proceeded. Product was collected via a condenser (at -20°C) into a round bottom flask in a dry ice and acetone bath. Once distillate was no longer being collected (about 1 hour), the temperature was cooled to 30°C and the vacuum released. Distillate was analyzed with GC-MS and GC-FID for identification and quantification, respectively. The receiver flask contained 81.6g total, 64.3g of which was quantified as MFA, resulting in a distillate of 79% pure MFA and a crude yield of 92.7% (Table 1 Condition 20).The distillate comprised of the reaction products, methanol and MFA, and minor amounts of solvent. Crude product identification and quantitation was accomplished by GC-MS and GC-FID, respectively. Acetonitrile was utilized as a diluent for analyses. Only three significant signals were detected in the crude product: MeOH (32g/mol), MFA (104.1g/mol), and solvent. NMR further confirmed the product identities. Guantification of theoretical yield was achieved through a 5-point GC-FID calibration curve for each identified component Characterization: HNMR, GC-MS, b.p Boiling point: 91 °C at 1 bar MS: m/z Calculated for C4H5FO2: 104.1 , found [M]+ 104.1 1H NMR (500 MHz, CDCIs), d 5.69 (1 H, dd, JH-F = 43.25), 5.3 (1 H, dd, J = 13), 3.854 (3H, s).

Reference： [1]Current Patent Assignee: VIFOR PHARMA LTD - WO2021/97012, 2021, A1 Location in patent: Paragraph 0073-0078

99
[ 67-56-1 ]
[ 115781-23-2 ]
[ 2343-89-7 ]
C₄H₅F₃O [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
96%	With potassium hydroxide In water; N,N-dimethyl-formamide at 120℃; for 2h;	1-3 [Example 1] 0.77 g (1.3 M, N, N-dimethylformamide solution) of 1,1,2,3-tetrafluoro-1-propen (compound (1) in which X1, X2, X3 and Y are all fluorine atoms): Moisture 0.22 g of methanol (water content 400 ppm) was added to (amount 300 ppm), 0.01 g of a 48% potassium hydroxide aqueous solution was added thereto, and the mixture was stirred at 120 ° C. for 2 hours. By GC analysis, a conversion rate of 35%, CH2 = CF-CF2OCH3 in a yield of 5%, and CH2 = CF-COOCH3 in a yield of 30% were obtained. Moreover, when GC-MS analysis was carried out, two new peaks were confirmed. One was confirmed to match the peak and fragment with pure CH2 = CF-COOCH3. The other was the parent fragment 126, and 95, 81, 31 and the like were confirmed as other fragments, and it was confirmed that the reaction was carried out via the intermediate CH2 = CF-CF2OCH3. When this solution was further reacted for 12 hours, a conversion rate of 100%, CH2 = CF-CF2OCH3 in a yield of 4%, and CH2 = CF-COOCH3 in a yield of 96% were obtained.

Reference： [1]Current Patent Assignee: AGC INC - JP2021/95363, 2021, A Location in patent: Paragraph 0076-0078

100
[ 4538-50-5 ]
[ 2343-89-7 ]

Yield	Reaction Conditions	Operation in experiment
	With HO₄S^(1-)K⁽¹⁺⁾13FH In 1,2-dichloro-ethane at 0 - 20℃;	4 Example 4: Synthesis of MFA precursor using Methyl Acrylate-Epoxide Route (KHSO₄- 13HF, in DCE) The first step, synthesis of methyl oxirane-2-carboxylate, was reported with 80% yield (B Ochiai and T Hirano, 2014). Methyl oxirane-2-carboxylate (102 mg, 1 mmol) was dissolved in 2 mL of DCE and cooled to 0 °C. KHSO4-13HF (435 mg, 1.1 mmol) was added to the solution dropwise while stirring. The reaction was stirred at room temperature overnight. Both starting material and epoxide opening product were observed. The GC retention time of epoxide opening product matched the retention time of desired product, methyl 2-fluoro-3-hydroxypropanoate. In addition, impurities at higher retention time were observed, which are possible products from epoxide polymerization.

Reference： [1]Current Patent Assignee: VIFOR PHARMA LTD - WO2021/191876, 2021, A1 Location in patent: Paragraph 00110

101
[ 922-67-8 ]
[ 2343-89-7 ]

Yield	Reaction Conditions	Operation in experiment
	With DMPU-HF; gold In 1,2-dichloro-ethane at 55℃; for 3h;	1; 2 Example 1: Synthesis of MFA using Methyl Propiolate Route (DMPU-HF) Methyl propiolate (472.5 mg, 5.62 mmol), 999.38 mg DMPU-HF, 72.11 mg Au catalyst and 2.5 mL dichloroethane (DCE) were added into a reaction vessel fitted with a stirrer. The reaction temperature was held at 55 °C for 3 hours. After completion of the reaction, a conversion of approximately 90% was observed by HPLC; the product peak had the same retention time as MFA. The regio-selectivity of this reaction will need to be confirmed using 1H NMR analysis. (0119) [00104] The DMPU reagent cannot be removed through aqueous workup. Distillation can be used to separate the MFA product from the DCE solvent, but is challenging because the boiling point of MFA (91 °C) and DCE (84°C) are close. (OE Okoromoba, et al. 2014, at S7 (supporting information))

Reference： [1]Current Patent Assignee: VIFOR PHARMA LTD - WO2021/191876, 2021, A1 Location in patent: Paragraph 00103-00106

102
[ 2343-89-7 ]
[ 99365-40-9 ]
methyl 2-fluoro-3-(2-oxo-1,3-dihydroindol-6-yl)prop-2-enoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
37%	With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II) dichloromethane adduct; triethylamine In N,N-dimethyl-formamide at 110℃; for 2h; Sealed tube; Inert atmosphere;	47.1 Example 47: (Z)-2-fluoro-N-(3-fluoro-2-methylphenyl)-3-(2-oxoindolin-6-yl)acrylamide Step 1: Into a 40-mL sealed tube purged and maintained with an inert atmosphere of nitrogen, was placed DMF (20.0 mL), 6-bromo-1,3-dihydroindol-2-one (1.0 g, 4.72 mmol, 1.0 eq), methyl 2-fluoroacrylate (0.59 g, 5.66 mmol, 1.20 eq), Pd(dppf)Cl2.CH2Cl2 (77.0 mg, 0.094 mmol, 0.02 eq), Et3N (1.3 mL, 9.43 mmol, 2.0 eq). The resulting solution was stirred for 2 h at 110 °C. The resulting mixture was concentrated. The residue was applied onto a silica gel column with (25/75). This resulted in 420 mg (37%) of methyl 2-fluoro-3-(2-oxo-1,3-dihydroindol-6-yl)prop-2- enoate as
37%	With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II) dichloromethane adduct; triethylamine In N,N-dimethyl-formamide at 110℃; for 2h; Sealed tube; Inert atmosphere;	47.1 Example 47: (Z)-2-fluoro-N-(3-fluoro-2-methylphenyl)-3-(2-oxoindolin-6-yl)acrylamide Step 1: Into a 40-mL sealed tube purged and maintained with an inert atmosphere of nitrogen, was placed DMF (20.0 mL), 6-bromo-1,3-dihydroindol-2-one (1.0 g, 4.72 mmol, 1.0 eq), methyl 2-fluoroacrylate (0.59 g, 5.66 mmol, 1.20 eq), Pd(dppf)Cl2.CH2Cl2 (77.0 mg, 0.094 mmol, 0.02 eq), Et3N (1.3 mL, 9.43 mmol, 2.0 eq). The resulting solution was stirred for 2 h at 110 °C. The resulting mixture was concentrated. The residue was applied onto a silica gel column with (25/75). This resulted in 420 mg (37%) of methyl 2-fluoro-3-(2-oxo-1,3-dihydroindol-6-yl)prop-2- enoate as

Reference： [1]Current Patent Assignee: NRG THERAPEUTICS - WO2022/49376, 2022, A1 Location in patent: Page/Page column 93
[2]Current Patent Assignee: NRG THERAPEUTICS - WO2022/49376, 2022, A1 Location in patent: Page/Page column 93

103
[ 50-00-0 ]
C₆H₆FO₅^(1-)*K⁽¹⁺⁾ [ No CAS ]
[ 2343-89-7 ]

Yield	Reaction Conditions	Operation in experiment
89%	In 1-methyl-pyrrolidin-2-one; lithium hydroxide monohydrate at 20℃; for 24h;	B-9 Example B-9 In a three-necked eggplant flask, 408 g of NMP and 1 g of water were added to 408 g of the solution of Example A-4, and 30 g of paraformaldehyde was added in three portions. The reaction was aged at room temperature for 24 hours to give the desired compound (1) (ie, 2-fluoroacrylic acid methyl ester) having a structure corresponding to the substrate in a yield of 88%.

Reference： [1]Current Patent Assignee: DAIKIN INDUSTRIES LIMITED - WO2022/54894, 2022, A1 Location in patent: Paragraph 0125; 0141

104
[ 2343-89-7 ]
1-(4-(trifluoromethyl)phenyl)-1,2,3,4-tetrahydroquinolin-3-amine [ No CAS ]
2-fluoro-N-(1-(4-(trifluoromethyl)phenyl)-1,2,3,4-tetrahydroquinolin-3-yl)acrylamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
43%	With tris(methyl)aluminum In toluene at 100℃; for 3h; Sealed tube;	A.10 Example 10: Synthesis of 2-fluoro-N-(1-(4-(trifluoromethyl)phenyl)-1,2,3,4- tetrahydroquinolin-3-yl)acrylamide (Cpd. No.039) A solution of 1-(4-(trifluoromethyl)phenyl)-1,2,3,4-tetrahydroquinolin-3-amine (Int-1) (200 mg, 0.68 mmol) in toluene (5.0 mL) was treated with methyl 2-fluoroacrylate (108 mg, 1.03 mmol) and Me3Al (2M in toluene, 1.02 mL, 2.05 mmol) at RT (sealed tube). The reaction mixture was stirred at 100°C for 3 h. Progress of the reaction was monitored by TLC. TLC mobile phase: 10% MeOH in DCM, RF: 0.51, TLC detection: UV. The reaction mixture was cooled to RT, diluted with EtOAc (10 mL) and water (10 mL). The organic layer was separated, washed with brine (10 mL), dried over Na2SO4 and concentrated under reduced pressure to afford crude product (250 mg, LC/MS 46%) which was purified by normal phase column chromatography using a 24 g column and a gradient of 40% EtOAc in pet ether as an eluent to afford 2-fluoro-N-(1-(4-(trifluoromethyl)phenyl)- 1,2,3,4-tetrahydroquinolin-3-yl)acrylamide (Cpd. No.039) as a pale yellow solid (109 mg, 43%). (LC/MS; m/z 365.2 [M+H]+)
43%	With tris(methyl)aluminum In toluene at 100℃; for 3h; Sealed tube;	A.10 Example 10: Synthesis of 2-fluoro-N-(1-(4-(trifluoromethyl)phenyl)-1,2,3,4- tetrahydroquinolin-3-yl)acrylamide (Cpd. No.039) A solution of 1-(4-(trifluoromethyl)phenyl)-1,2,3,4-tetrahydroquinolin-3-amine (Int-1) (200 mg, 0.68 mmol) in toluene (5.0 mL) was treated with methyl 2-fluoroacrylate (108 mg, 1.03 mmol) and Me3Al (2M in toluene, 1.02 mL, 2.05 mmol) at RT (sealed tube). The reaction mixture was stirred at 100°C for 3 h. Progress of the reaction was monitored by TLC. TLC mobile phase: 10% MeOH in DCM, RF: 0.51, TLC detection: UV. The reaction mixture was cooled to RT, diluted with EtOAc (10 mL) and water (10 mL). The organic layer was separated, washed with brine (10 mL), dried over Na2SO4 and concentrated under reduced pressure to afford crude product (250 mg, LC/MS 46%) which was purified by normal phase column chromatography using a 24 g column and a gradient of 40% EtOAc in pet ether as an eluent to afford 2-fluoro-N-(1-(4-(trifluoromethyl)phenyl)- 1,2,3,4-tetrahydroquinolin-3-yl)acrylamide (Cpd. No.039) as a pale yellow solid (109 mg, 43%). (LC/MS; m/z 365.2 [M+H]+)

Reference： [1]Current Patent Assignee: SPRINGWORKS THERAPEUTICS, INC; FLANDERS INSTITUTE FOR BIOTECHNOLOGY; KATHOLIEKE UNIVERSITEIT LEUVEN - WO2022/72741, 2022, A1 Location in patent: Page/Page column 206
[2]Current Patent Assignee: SPRINGWORKS THERAPEUTICS, INC; FLANDERS INSTITUTE FOR BIOTECHNOLOGY; KATHOLIEKE UNIVERSITEIT LEUVEN - WO2022/72741, 2022, A1 Location in patent: Page/Page column 206

105
[ 2343-89-7 ]
[ 201230-82-2 ]
methyl (2R)-2-fluoro-2-methyl-3-oxopropanoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With dicarbonylacetylacetonato rhodium (I); hydrogen; C₇₇H₇₇NO₄P₂ In toluene at 80℃; for 24h; enantioselective reaction;

Reference： [1]Wen, Jialin; Zhang, Dequan; Zhang, Xumu [Chemical Science, 2022]

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• 1,4-Addition of an Amine to a Conjugated Enone • 1,4-Addition of an Amine to a Conjugated Enone • 1,4-Additions of Organometallic Reagents • Acid-Catalyzed Equilibration of Alkenes • Acid-Catalyzed Rearrangement of Alkenes • Acyl Group Substitution • Addition of a Hydrogen Halide to an Internal Alkyne • Addition of Hydrogen Halides Forms Geminal Dihaloalkanes • Addition of Radicals to Alkenes • Alcohols Convert Acyl Chlorides into Esters • Alcoholysis of Anhydrides • Aldol Condensation • Alkene Hydration • Alkenes React with Ozone to Produce Carbonyl Compounds • Alkyl Halide Occurrence • Alkylation of Enolate Ions • Allylic Deprotonation • Allylic Halides Undergo SN1 Reactions • Allylic Substitution • Amines Convert Esters into Amides • An Alkane are Prepared from an Haloalkane • Base-Catalyzed Hydration of α,β -Unsaturated Aldehydes and Ketones • Baylis-Hillman Reaction • Bouveault-Blanc Reduction • Brown Hydroboration • Carbene Addition to Double Bonds • Catalytic Hydrogenation • Catalytic Hydrogenation of Alkenes • Claisen Condensations Produce β-Dicarbonyl Compounds • Claisen Condensations Produce β-Dicarbonyl Compounds • Complex Metal Hydride Reductions • Conjugated Enone Takes Part in 1,4-Additions • Convert Esters into Aldehydes Using a Milder Reducing Agent • Decarboxylation of 3-Ketoacids Yields Ketones • Deprotection of Cbz-Amino Acids • Deprotonation of a Carbonyl Compound at the α -Carbon • Dimerization, Oligomerization of Alkenes • Dissolving-Metal Reduction of an Alkyne • Electrocyclic Reactions • Electrophilic Addition of Halogen to Alkynes • Electrophilic Addition of HX to Alkenes • Elimination from Dihaloalkanes to Give Haloalkenes • Enamine Formation • Enamines Can Be Used to Prepare Alkylated Aldehydes • Enol-Keto Equilibration • Epoxidation • Epoxidation by Peroxycarboxylic Acids • Ester Cleavage • Ester Hydrolysis • Ether Synthesis by Oxymercuration-Demercuration • Exclusive 1,4-Addition of a Lithium Organocuprate • Friedel-Crafts Alkylation of Benzene with Haloalkanes • Friedel-Crafts Alkylation Using Alkenes • Friedel-Crafts Alkylations of Benzene Using Alkenes • Grignard Reagents Transform Esters into Alcohols • Halogen and Alcohols Add to Alkenes by Electrophilic Attack • Halogen and Alcohols Add to Alkenes by Electrophilic Attack • Halogenation • Halogenation of Alkenes • Halogenation-double Dehydrohalogenation • Hantzsch Pyridine Synthesis • Heat of Combustion • Heck Reaction • Hydroboration-Oxidation • Hydrogen Bromide Add to Alkenes in Anti-Markovnikov Fashion • Hydrogenation • Hydrogenation by Palladium on Carbon Gives the Saturated Carbonyl Compound • Hydrogenation with Lindlar Catalyst • Hydrogenation with Lindlar Catalyst • Hydroxylation • Isomerization of β, γ -Unsaturated Carbonyl Compounds • Ketones Undergo Mixed Claisen Reactions to Form β-Dicarbonyl Compounds • Lithium Organocuprate may Add to the α ,β -Unsaturated Carbonyl Function in 1,4-Fashion • Michael Addition • Osmium Tetroxide Reacts with Alkenes to Give Vicinal Diols • Oxidation of Alcohols to Carbonyl Compounds • Oxidative Cleavage of Double Bonds • Oxymercuration-Demercuration • Paternò-Büchi Reaction • Pauson-Khand Cyclopentenone Synthesis • Polymerization of Alkenes • Preparation of Alkenes • Preparation of Alkenes by Dehydration of Alcohols • Preparation of Alkenes by Dehydration of Alcohols • Prins Reaction • Radical Addition of a Thiol to an Alkene • Radical Addition of HBr to Terminal Alkynes • Radical Addition of HBr to Terminal Alkynes • Radical Allylic Substitution • Reactions of Alkenes • Reactions of Amines • Reactions with Organometallic Reagents • Reduction of an Ester to an Alcohol • Reduction of an Ester to an Aldehyde • Reductive Amination • Sharpless Asymmetric Amino Hydroxylation • Sharpless Asymmetric Dihydroxylation • Specialized Acylation Reagents-Carbodiimides and Related Reagents • Specialized Acylation Reagents-Vilsmeier Reagent • The Cycloaddition of Dienes to Alkenes Gives Cyclohexenes • The Heck Reaction • The Wittig Reaction • Transesterification • Vicinal Anti Dihydroxylation of Alkenes • Wacker Oxidation • Woodward Cis-Dihydroxylation

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[ 2343-89-7 ]

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Precautionary Statements-General
Code	Phrase
P101	If medical advice is needed,have product container or label at hand.
P102	Keep out of reach of children.
P103	Read label before use
Prevention
Code	Phrase
P201	Obtain special instructions before use.
P202	Do not handle until all safety precautions have been read and understood.
P210	Keep away from heat/sparks/open flames/hot surfaces. - No smoking.
P211	Do not spray on an open flame or other ignition source.
P220	Keep/Store away from clothing/combustible materials.
P221	Take any precaution to avoid mixing with combustibles
P222	Do not allow contact with air.
P223	Keep away from any possible contact with water, because of violent reaction and possible flash fire.
P230	Keep wetted
P231	Handle under inert gas.
P232	Protect from moisture.
P233	Keep container tightly closed.
P234	Keep only in original container.
P235	Keep cool
P240	Ground/bond container and receiving equipment.
P241	Use explosion-proof electrical/ventilating/lighting/equipment.
P242	Use only non-sparking tools.
P243	Take precautionary measures against static discharge.
P244	Keep reduction valves free from grease and oil.
P250	Do not subject to grinding/shock/friction.
P251	Pressurized container: Do not pierce or burn, even after use.
P260	Do not breathe dust/fume/gas/mist/vapours/spray.
P261	Avoid breathing dust/fume/gas/mist/vapours/spray.
P262	Do not get in eyes, on skin, or on clothing.
P263	Avoid contact during pregnancy/while nursing.
P264	Wash hands thoroughly after handling.
P265	Wash skin thouroughly after handling.
P270	Do not eat, drink or smoke when using this product.
P271	Use only outdoors or in a well-ventilated area.
P272	Contaminated work clothing should not be allowed out of the workplace.
P273	Avoid release to the environment.
P280	Wear protective gloves/protective clothing/eye protection/face protection.
P281	Use personal protective equipment as required.
P282	Wear cold insulating gloves/face shield/eye protection.
P283	Wear fire/flame resistant/retardant clothing.
P284	Wear respiratory protection.
P285	In case of inadequate ventilation wear respiratory protection.
P231 + P232	Handle under inert gas. Protect from moisture.
P235 + P410	Keep cool. Protect from sunlight.
Response
Code	Phrase
P301	IF SWALLOWED:
P304	IF INHALED:
P305	IF IN EYES:
P306	IF ON CLOTHING:
P307	IF exposed:
P308	IF exposed or concerned:
P309	IF exposed or if you feel unwell:
P310	Immediately call a POISON CENTER or doctor/physician.
P311	Call a POISON CENTER or doctor/physician.
P312	Call a POISON CENTER or doctor/physician if you feel unwell.
P313	Get medical advice/attention.
P314	Get medical advice/attention if you feel unwell.
P315	Get immediate medical advice/attention.
P320
P302 + P352	IF ON SKIN: wash with plenty of soap and water.
P321
P322
P330	Rinse mouth.
P331	Do NOT induce vomiting.
P332	IF SKIN irritation occurs:
P333	If skin irritation or rash occurs:
P334	Immerse in cool water/wrap n wet bandages.
P335	Brush off loose particles from skin.
P336	Thaw frosted parts with lukewarm water. Do not rub affected area.
P337	If eye irritation persists:
P338	Remove contact lenses, if present and easy to do. Continue rinsing.
P340	Remove victim to fresh air and keep at rest in a position comfortable for breathing.
P341	If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing.
P342	If experiencing respiratory symptoms:
P350	Gently wash with plenty of soap and water.
P351	Rinse cautiously with water for several minutes.
P352	Wash with plenty of soap and water.
P353	Rinse skin with water/shower.
P360	Rinse immediately contaminated clothing and skin with plenty of water before removing clothes.
P361	Remove/Take off immediately all contaminated clothing.
P362	Take off contaminated clothing and wash before reuse.
P363	Wash contaminated clothing before reuse.
P370	In case of fire:
P371	In case of major fire and large quantities:
P372	Explosion risk in case of fire.
P373	DO NOT fight fire when fire reaches explosives.
P374	Fight fire with normal precautions from a reasonable distance.
P376	Stop leak if safe to do so. Oxidising gases (section 2.4) 1
P377	Leaking gas fire: Do not extinguish, unless leak can be stopped safely.
P378
P380	Evacuate area.
P381	Eliminate all ignition sources if safe to do so.
P390	Absorb spillage to prevent material damage.
P391	Collect spillage. Hazardous to the aquatic environment
P301 + P310	IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician.
P301 + P312	IF SWALLOWED: call a POISON CENTER or doctor/physician IF you feel unwell.
P301 + P330 + P331	IF SWALLOWED: Rinse mouth. Do NOT induce vomiting.
P302 + P334	IF ON SKIN: Immerse in cool water/wrap in wet bandages.
P302 + P350	IF ON SKIN: Gently wash with plenty of soap and water.
P303 + P361 + P353	IF ON SKIN (or hair): Remove/Take off Immediately all contaminated clothing. Rinse SKIN with water/shower.
P304 + P312	IF INHALED: Call a POISON CENTER or doctor/physician if you feel unwell.
P304 + P340	IF INHALED: Remove victim to fresh air and Keep at rest in a position comfortable for breathing.
P304 + P341	IF INHALED: If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing.
P305 + P351 + P338	IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing.
P306 + P360	IF ON CLOTHING: Rinse Immediately contaminated CLOTHING and SKIN with plenty of water before removing clothes.
P307 + P311	IF exposed: call a POISON CENTER or doctor/physician.
P308 + P313	IF exposed or concerned: Get medical advice/attention.
P309 + P311	IF exposed or if you feel unwell: call a POISON CENTER or doctor/physician.
P332 + P313	IF SKIN irritation occurs: Get medical advice/attention.
P333 + P313	IF SKIN irritation or rash occurs: Get medical advice/attention.
P335 + P334	Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages.
P337 + P313	IF eye irritation persists: Get medical advice/attention.
P342 + P311	IF experiencing respiratory symptoms: call a POISON CENTER or doctor/physician.
P370 + P376	In case of fire: Stop leak if safe to Do so.
P370 + P378	In case of fire:
P370 + P380	In case of fire: Evacuate area.
P370 + P380 + P375	In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion.
P371 + P380 + P375	In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion.
Storage
Code	Phrase
P401
P402	Store in a dry place.
P403	Store in a well-ventilated place.
P404	Store in a closed container.
P405	Store locked up.
P406	Store in corrosive resistant/ container with a resistant inner liner.
P407	Maintain air gap between stacks/pallets.
P410	Protect from sunlight.
P411
P412	Do not expose to temperatures exceeding 50 oC/ 122 oF.
P413
P420	Store away from other materials.
P422
P402 + P404	Store in a dry place. Store in a closed container.
P403 + P233	Store in a well-ventilated place. Keep container tightly closed.
P403 + P235	Store in a well-ventilated place. Keep cool.
P410 + P403	Protect from sunlight. Store in a well-ventilated place.
P410 + P412	Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF.
P411 + P235	Keep cool.
Disposal
Code	Phrase
P501	Dispose of contents/container to ...
P502	Refer to manufacturer/supplier for information on recovery/recycling

Physical hazards
Code	Phrase
H200	Unstable explosive
H201	Explosive; mass explosion hazard
H202	Explosive; severe projection hazard
H203	Explosive; fire, blast or projection hazard
H204	Fire or projection hazard
H205	May mass explode in fire
H220	Extremely flammable gas
H221	Flammable gas
H222	Extremely flammable aerosol
H223	Flammable aerosol
H224	Extremely flammable liquid and vapour
H225	Highly flammable liquid and vapour
H226	Flammable liquid and vapour
H227	Combustible liquid
H228	Flammable solid
H229	Pressurized container: may burst if heated
H230	May react explosively even in the absence of air
H231	May react explosively even in the absence of air at elevated pressure and/or temperature
H240	Heating may cause an explosion
H241	Heating may cause a fire or explosion
H242	Heating may cause a fire
H250	Catches fire spontaneously if exposed to air
H251	Self-heating; may catch fire
H252	Self-heating in large quantities; may catch fire
H260	In contact with water releases flammable gases which may ignite spontaneously
H261	In contact with water releases flammable gas
H270	May cause or intensify fire; oxidizer
H271	May cause fire or explosion; strong oxidizer
H272	May intensify fire; oxidizer
H280	Contains gas under pressure; may explode if heated
H281	Contains refrigerated gas; may cause cryogenic burns or injury
H290	May be corrosive to metals
Health hazards
Code	Phrase
H300	Fatal if swallowed
H301	Toxic if swallowed
H302	Harmful if swallowed
H303	May be harmful if swallowed
H304	May be fatal if swallowed and enters airways
H305	May be harmful if swallowed and enters airways
H310	Fatal in contact with skin
H311	Toxic in contact with skin
H312	Harmful in contact with skin
H313	May be harmful in contact with skin
H314	Causes severe skin burns and eye damage
H315	Causes skin irritation
H316	Causes mild skin irritation
H317	May cause an allergic skin reaction
H318	Causes serious eye damage
H319	Causes serious eye irritation
H320	Causes eye irritation
H330	Fatal if inhaled
H331	Toxic if inhaled
H332	Harmful if inhaled
H333	May be harmful if inhaled
H334	May cause allergy or asthma symptoms or breathing difficulties if inhaled
H335	May cause respiratory irritation
H336	May cause drowsiness or dizziness
H340	May cause genetic defects
H341	Suspected of causing genetic defects
H350	May cause cancer
H351	Suspected of causing cancer
H360	May damage fertility or the unborn child
H361	Suspected of damaging fertility or the unborn child
H361d	Suspected of damaging the unborn child
H362	May cause harm to breast-fed children
H370	Causes damage to organs
H371	May cause damage to organs
H372	Causes damage to organs through prolonged or repeated exposure
H373	May cause damage to organs through prolonged or repeated exposure
Environmental hazards
Code	Phrase
H400	Very toxic to aquatic life
H401	Toxic to aquatic life
H402	Harmful to aquatic life
H410	Very toxic to aquatic life with long-lasting effects
H411	Toxic to aquatic life with long-lasting effects
H412	Harmful to aquatic life with long-lasting effects
H413	May cause long-lasting harmful effects to aquatic life
H420	Harms public health and the environment by destroying ozone in the upper atmosphere

[ CAS No. 2343-89-7 ] {[proInfo.proName]}

Quality Control of [ 2343-89-7 ]

Related Doc. of [ 2343-89-7 ]

Product Details of [ 2343-89-7 ]

Calculated chemistry of [ 2343-89-7 ] Expand+

Physicochemical Properties

Pharmacokinetics

Lipophilicity

Druglikeness

Water Solubility

Medicinal Chemistry

Safety of [ 2343-89-7 ]

Application In Synthesis of [ 2343-89-7 ]

[ 2343-89-7 ] Synthesis Path-Upstream 1~2

[ 2343-89-7 ] Synthesis Path-Downstream 1~105

Technical Information

Related Functional Groups of [ 2343-89-7 ]

Fluorinated Building Blocks

Alkenes

Aliphatic Chain Hydrocarbons

Esters

Precautionary Statements-General

Prevention

Response

Storage

Disposal

Physical hazards

Health hazards

Environmental hazards

Inquiry

Related Functional Groups of
[ 2343-89-7 ]