Name: 53774-20-2|2-Methylbut-3-enoic acid|95%
Brand: Ambeed
SKU: A332937
Price: 8.0 USD
Availability: InStock
Rating: 90 (26 reviews)

1
[ 106-98-9 ]
[ 1822-71-5 ]
[ 53774-20-2 ]

Yield	Reaction Conditions	Operation in experiment
	With pentane

Reference： [1]Morton; Holden [Journal of the American Chemical Society, 1947, vol. 69, p. 1677,1679]

2
(E/Z)-crotyl bromide [ No CAS ]
[ 22037-73-6 ]
[ 53774-20-2 ]

Yield	Reaction Conditions	Operation in experiment
	With diethyl ether; magnesium

Reference： [1]Roberts; Young [Journal of the American Chemical Society, 1945, vol. 67, p. 150] Lane; Roberts; Young [Journal of the American Chemical Society, 1944, vol. 66, p. 543]

3
[ 107-01-7 ]
[ 1822-71-5 ]
[ 53774-20-2 ]

Yield	Reaction Conditions	Operation in experiment
	With pentane

Reference： [1]Morton; Holden [Journal of the American Chemical Society, 1947, vol. 69, p. 1677,1679]

4
(E/Z)-crotyl bromide [ No CAS ]
[ 124-38-9 ]
[ 53774-20-2 ]

Yield	Reaction Conditions	Operation in experiment
58%	Stage #1: (E/Z)-crotyl bromide With lithium chloride; zinc In tetrahydrofuran for 2h; Stage #2: carbon dioxide With hydrogenchloride for 24h;
	(i) Mg, (ii) /BRN= 1900390/; Multistep reaction;
	Stage #1: (E/Z)-crotyl bromide; carbon dioxide With indium; cesium fluoride In N,N-dimethyl-formamide at 60℃; for 14h; Autoclave; Stage #2: With hydrogenchloride; water In ethyl acetate; N,N-dimethyl-formamide regioselective reaction;

Reference： [1]Vellalath, Sreekumar; Romo, Daniel [Israel Journal of Chemistry, 2017, vol. 57, # 3, p. 335 - 339]
[2]Rossi,R.; Ingrosso,G. [Gazzetta Chimica Italiana, 1968, vol. 98, p. 866 - 883]
[3]Miao, Bukeyan; Ma, Shengming [Chemical Communications, 2014, vol. 50, # 25, p. 3285 - 3287]

5
[ 563-52-0 ]
[ 124-38-9 ]
[ 53774-20-2 ]

Yield	Reaction Conditions	Operation in experiment
70%	Stage #1: 2-chloro-3-butene With iodine; magnesium In tetrahydrofuran Inert atmosphere; Reflux; Stage #2: carbon dioxide In tetrahydrofuran at -78℃; for 1h; Inert atmosphere;
	(i) Mg, (ii) /BRN= 1900390/; Multistep reaction;
	With magnesium Multistep reaction;

	Stage #1: 2-chloro-3-butene With magnesium In tetrahydrofuran Heating; Stage #2: carbon dioxide In tetrahydrofuran at -78 - 10℃; Further stages.;
19 %Spectr.	Stage #1: 2-chloro-3-butene; carbon dioxide With indium; lithium iodide In N,N-dimethyl-formamide at 60℃; for 14h; Autoclave; Stage #2: With hydrogenchloride; water In ethyl acetate; N,N-dimethyl-formamide regioselective reaction;

Reference： [1]Location in patent: experimental part O'Connor, Patrick D.; Bin Kim; Brimble, Margaret A. [European Journal of Organic Chemistry, 2009, # 26, p. 4405 - 4411]
[2]Rossi,R.; Ingrosso,G. [Gazzetta Chimica Italiana, 1968, vol. 98, p. 866 - 883]
[3]Bloodworth; Curtis; Spencer; Tallant [Tetrahedron, 1993, vol. 49, # 13, p. 2729 - 2750]
[4]Andreana, Peter R; McLellan, Jason S; Chen, Yongchen; Wang, Peng George [Organic letters, 2002, vol. 4, # 22, p. 3875 - 3878]
[5]Miao, Bukeyan; Ma, Shengming [Chemical Communications, 2014, vol. 50, # 25, p. 3285 - 3287]

6
[ 53774-20-2 ]
[ 4516-90-9 ]

Yield	Reaction Conditions	Operation in experiment
84%	With lithium aluminium tetrahydride
75%	With lithium aluminium tetrahydride In diethyl ether Heating;
	With lithium aluminium tetrahydride

Reference： [1]Bloodworth; Curtis; Spencer; Tallant [Tetrahedron, 1993, vol. 49, # 13, p. 2729 - 2750]
[2]Grandguillot; Rouessac [Tetrahedron, 1991, vol. 47, # 28, p. 5133 - 5148]
[3]Pearce,G.T. et al. [Journal of Organic Chemistry, 1976, vol. 41, # 17, p. 2797 - 2803]

7
[ 53774-20-2 ]
[ 24560-24-5 ]

Yield	Reaction Conditions	Operation in experiment
	With thionyl chloride
	With oxalyl dichloride at 0 - 20℃; for 57h;
	With oxalyl dichloride In chloroform at 0 - 20℃; for 3h;

	With 1-chloro-1-(dimethylamino)-2-methyl-1-propene In dichloromethane at 20℃; for 1h;
	With oxalyl dichloride; N,N-dimethyl-formamide In dichloromethane at 0 - 20℃; for 2h; Inert atmosphere;

Reference： [1]Rossi,R.; Ingrosso,G. [Gazzetta Chimica Italiana, 1968, vol. 98, p. 866 - 883]
[2]Rajendra, G.; Miller, Marvin J. [Journal of Organic Chemistry, 1987, vol. 52, # 20, p. 4471 - 4477]
[3]Yevglevskis, Maksims; Lee, Guat L.; Threadgill, Michael D.; Woodman, Timothy J.; Lloyd, Matthew D. [Chemical Communications, 2014, vol. 50, # 91, p. 14164 - 14166]
[4]Yang, Wu; Wang, Yufeng; Lai, Amy; Clark, Charles G.; Corte, James R.; Fang, Tianan; Gilligan, Paul J.; Jeon, Yoon; Pabbisetty, Kumar B.; Rampulla, Richard A.; Mathur, Arvind; Kaspady, Mahammed; Neithnadka, Premsai Rai; Arumugam, Arunachalam; Raju, Sivashankaran; Rossi, Karen A.; Myers, Joseph E.; Sheriff, Steven; Lou, Zhen; Zheng, Joanna J.; Chacko, Silvi A.; Bozarth, Jeffrey M.; Wu, Yiming; Crain, Earl J.; Wong, Pancras C.; Seiffert, Dietmar A.; Luettgen, Joseph M.; Lam, Patrick Y. S.; Wexler, Ruth R.; Ewing, William R. [Journal of Medicinal Chemistry, 2020, vol. 63, # 13, p. 7226 - 7242]
[5]Chen, Shiru; Cheng, Yingjie; Deng, Guo-Jun; Huang, Huawen; Ji, Xiaochen; Qu, Zhonghua [Advanced Synthesis and Catalysis, 2022, vol. 364, # 9, p. 1573 - 1579]

8
[ 53774-20-2 ]
[ 59014-11-8 ]

Yield	Reaction Conditions	Operation in experiment
18.5%	With (R)-1-phenyl-ethyl-amine In acetone Inert atmosphere; Reflux;	(S)-2-Methyl-3-butenoic acid ((S)-4; Method A) To a stirring solution of (±)-2-methyl-3-butenoic acid ((±)-4, 20.0 g, 0.200 mol) in acetone (200 mL) was added (R)-1-phenylethylamine (24.2 g, 0.200 mol) dropwise. The mixture washeated under reux to dissolve a precipitated salt. After coolingto room temperature, the precipitated salt was ltered. The resultingsalt was puried by recrystallization (1.0 g of salt/4.5 mLof acetone, twice). The obtained salt (9.07 g) was dissolved intodil. HCl (3 ; 90 mL), and the solution was extracted with Et2O.The organic layer was washed with brine, dried (Na2SO4) andconcentrated under reduced pressure to give (S)-4 (3.69 g, 18.5%yield): []D23 = +23.0 (c 1.50, CHCl3); NMR H (300 MHz, CDCl3):1.30 (3H, d, J = 7.2 Hz), 3.19 (1H, quint, J = 7.2 Hz), 5.14 (1H, dt,J = 10.2, 1.2 Hz), 5.18 (1H, dt, J = 17.1, 1.2 Hz), 5.93 (1H, ddd, J = 17.1,10.2, 7.2 Hz), 10.18 (1H, br); NMR C (125 MHz, CDCl3): 16.5, 43.5,116.6, 136.5, 181.2. The enantiomeric purity of (S)-4 was determinedby chiral GC analysis to be 54% e.e. Chiral GC: conditions:column, Chiramix (Tamogami et al. 2001) (0.25mmID × 30mL,0.25 μm df); temperature, 75 °C to 180 °C (0.7 °C/min); carrier N2(0.7 mL/min); tR (S)-4: 31.0 min (77.0%), (R)-4: 32.1 min (23.0%).
	With (-)-α-methylbenzylamine

Reference： [1]Masuda, Yui; Ogura, Yusuke; Ohkubo, Yasutaka; Takikawa, Hirosato; Watanabe, Hidenori [Bioscience, Biotechnology and Biochemistry, 2021, vol. 85, # 6, p. 1390 - 1394]
[2]Rossi,R. et al. [Gazzetta Chimica Italiana, 1968, vol. 98, p. 1391 - 1399]

9
[ 80-59-1 ]
[ 53774-20-2 ]

Yield	Reaction Conditions	Operation in experiment
83%	With n-butyllithium; diisopropylamine In tetrahydrofuran; hexane at -78 - 20℃; for 1h; Inert atmosphere;
82.9%	With lithium diisopropyl amide In tetrahydrofuran; hexane for 1h; Ambient temperature;
	With n-butyllithium; diisopropylamine In tetrahydrofuran; hexane at -78 - 24℃; for 1h;

Reference： [1]Combettes, Lorraine E.; Schuler, Marie; Patel, Rakesh; Bonillo, Baltasar; Odell, Barbara; Thompson, Amber L.; Claridge, Tim D. W.; Gouverneur, Véronique [Chemistry - A European Journal, 2012, vol. 18, # 41, p. 13126 - 13132]
[2]Rajendra, G.; Miller, Marvin J. [Journal of Organic Chemistry, 1987, vol. 52, # 20, p. 4471 - 4477]
[3]Deng, Ruohan; Engle, Keary M.; Fu, Yue; Gao, Yang; Li, Zi-Qi; Liu, Peng; Tran, Van T. [Angewandte Chemie - International Edition, 2020, vol. 59, # 51, p. 23306 - 23312][Angew. Chem., 2020, vol. 132, # 51, p. 23506 - 23512,7]

10
[ 53774-20-2 ]
[ 16644-98-7 ]
(3S,5S)-5-((E)-Hex-1-enyl)-3-methyl-dihydro-furan-2-one [ No CAS ]
(3R,5S)-5-((E)-Hex-1-enyl)-3-methyl-dihydro-furan-2-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With N,N-diethyl-N-isopropylamine; tetrabutyl-ammonium chloride In N,N-dimethyl-formamide at 80℃; for 20h; Yield given. Yields of byproduct given;

Reference： [1]Larock, Richard C.; Leuck, David J.; Harrison, L. Wayne [Tetrahedron Letters, 1988, vol. 29, # 49, p. 6399 - 6402]

11
[ 53774-20-2 ]
[ 3240-34-4 ]
dihydro-3-methyl-4-acetoxy-2(3H)-furanone [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
51%	With tetrafluoroboric acid In acetic acid for 1h; Ambient temperature;

Reference： [1]Tiecco, Marcello; Testaferri, Lorenzo; Tingoli, Marco; Bartoli, Donatella [Tetrahedron, 1990, vol. 46, # 20, p. 7139 - 7150]

12
[ 53774-20-2 ]
[ 588-72-7 ]
(3S,5S)-3-Methyl-5-((E)-styryl)-dihydro-furan-2-one [ No CAS ]
(3R,5S)-3-Methyl-5-((E)-styryl)-dihydro-furan-2-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With N,N-diethyl-N-isopropylamine; tetrabutyl-ammonium chloride In N,N-dimethyl-formamide at 80℃; for 20h; Yield given. Yields of byproduct given;

Reference： [1]Larock, Richard C.; Leuck, David J.; Harrison, L. Wayne [Tetrahedron Letters, 1988, vol. 29, # 49, p. 6399 - 6402]

13
[ 53774-20-2 ]
4-Bromomethyl-3-methyl-oxetan-2-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
42%	With bromine; sodium hydrogencarbonate at 0℃;

Reference： [1]Black, T. Howard; Huang, Jianhua [Tetrahedron Letters, 1993, vol. 34, # 9, p. 1411 - 1412]

14
[ 53774-20-2 ]
[ 64-19-7 ]
cis-dihydro-3-methyl-4-acetoxy-2(3H)-furanone [ No CAS ]
trans-dihydro-3-methyl-4-acetoxy-2(3H)-furanone [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
1: 37% 2: 37%	With ammonium persulfate; trifluorormethanesulfonic acid at 70℃;

Reference： [1]Tiecco, Marcello; Testaferri, Lorenzo; Tingoli, Marco [Tetrahedron, 1993, vol. 49, # 24, p. 5351 - 5358]

15
[ 53774-20-2 ]
[ 106-99-0 ]
(3E,6E)-2-Methyl-octa-3,6-dienoic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
68%	at 120℃; for 14h;

Reference： [1]Salerno, Giuseppe; Gigliott, Francesco; Chiusoli, Gian Paolo [Journal of Organometallic Chemistry, 1986, vol. 314, p. 231 - 240]

16
[ 124-38-9 ]
[ 106-99-0 ]
[ 53774-20-2 ]

Yield	Reaction Conditions	Operation in experiment
70%	With isopropylmagnesium bromide In diethyl ether Ambient temperature;

Reference： [1]Sato, Fumie; Iijima, Satoshi; Sato, Masao [Journal of the Chemical Society. Chemical communications, 1981, # 4, p. 180 - 181]

17
[ 124-38-9 ]
[ 591-97-9 ]
[ 53774-20-2 ]

Yield	Reaction Conditions	Operation in experiment
	With magnesium 1.) -70 deg C, THF; 2.) -70 deg C, 0.5 h, then allowed to warm up to 0 deg C; Yield given. Multistep reaction;
49 %Spectr.	Stage #1: carbon dioxide; 1-chloro-2-butene With indium; lithium iodide In N,N-dimethyl-formamide at 60℃; for 14h; Autoclave; Stage #2: With hydrogenchloride; water In ethyl acetate; N,N-dimethyl-formamide regioselective reaction;

Reference： [1]Oppolzer, Wolfgang; Kuendig, Ernest Peter; Bishop, Paul M.; Perret, Celia [Tetrahedron Letters, 1982, vol. 23, # 38, p. 3901 - 3904]
[2]Miao, Bukeyan; Ma, Shengming [Chemical Communications, 2014, vol. 50, # 25, p. 3285 - 3287]

18
(E)-1-Bromo-2-butene [ No CAS ]
[ 124-38-9 ]
[ 1617-32-9 ]
[ 53774-20-2 ]

Yield	Reaction Conditions	Operation in experiment
1: 28 % Spectr. 2: 72 % Spectr.	With tetraethylammonium perchlorate; magnesium In N,N-dimethyl-formamide at -10℃; electrochemical reaction;

Reference： [1]Tokuda, Masao; Kabuki, Takashi; Katoh, Yoshitaka; Suginome, Hiroshi [Tetrahedron Letters, 1995, vol. 36, # 19, p. 3345 - 3348]

19
[ 53774-20-2 ]
[ 3282-30-2 ]
C₁₀H₁₆O₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With triethylamine In tetrahydrofuran at -78℃; for 1h;

Reference： [1]Dobarro, Alicia; Velasco, Dolores [Tetrahedron, 1996, vol. 52, # 43, p. 13733 - 13738] Dobarro, Alicia; Velasco, Dolores [Tetrahedron, 1996, vol. 52, # 42, p. 13525 - 13530]

20
[ 53774-20-2 ]
[ 543-27-1 ]
C₁₀H₁₆O₄ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With 4-methyl-morpholine In tetrahydrofuran at -78℃; for 1h;
	With 4-methyl-morpholine In tetrahydrofuran for 0.0833333h;

Reference： [1]Dobarro, Alicia; Velasco, Dolores [Tetrahedron, 1996, vol. 52, # 43, p. 13733 - 13738] Dobarro, Alicia; Velasco, Dolores [Tetrahedron, 1996, vol. 52, # 42, p. 13525 - 13530]
[2]Padwa, Albert; Wang, Qiu [Journal of Organic Chemistry, 2006, vol. 71, # 8, p. 3210 - 3220]

21
[ 75-77-4 ]
[ 53774-20-2 ]
(E)-2-Methyl-4-trimethylsilanyl-but-2-enoic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
51%	With n-butyllithium; potassium <i>tert</i>-butylate In tetrahydrofuran; hexane at -75℃;

Reference： [1]Moret, Eticnne; Franzini, Livia; Schlosser, Manfred [Chemische Berichte, 1997, vol. 130, # 3, p. 335 - 339]

22
[ 53774-20-2 ]
[ 22122-36-7 ]

Yield	Reaction Conditions	Operation in experiment
	With bromine; triethylamine 1.) CH₂Cl₂, 1 h, 2.) CHCl₃, reflux, 4 h; Yield given. Multistep reaction;
	Multi-step reaction with 2 steps 1: 42 percent / Br₂, NaHCO₃ / 0 °C 2: 59 percent / AgNO₃ / acetic acid / Heating

Reference： [1]Roehrig, Susanne; Hennig, Lothar; Findeisen, Matthias; Welzel, Peter; Mueller, Dietrich [Tetrahedron, 1998, vol. 54, # 14, p. 3439 - 3456]
[2]Black, T. Howard; Huang, Jianhua [Tetrahedron Letters, 1993, vol. 34, # 9, p. 1411 - 1412]

23
[ 80-59-1 ]
[ 591-51-5 ]
[ 53774-20-2 ]
[ 19731-91-0 ]

Yield	Reaction Conditions	Operation in experiment
43%	In tetrahydrofuran at -30℃; for 5h;

Reference： [1]Aurell, Maria Jose; Domingo, Luis Ramon; Mestres, Ramon; Munos, Elena; Zaragoza, Ramon Jose [Tetrahedron, 1999, vol. 55, # 3, p. 815 - 830]

Yield	Reaction Conditions	Operation in experiment
68%	With water In diethyl ether Ambient temperature;

25
[ 53774-20-2 ]
[ 107-18-6 ]
2-methyl-but-3-enoic acid allyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
75%	With toluene-4-sulfonic acid In chloroform for 16h; Heating;

Reference： [1]Andreana, Peter R; McLellan, Jason S; Chen, Yongchen; Wang, Peng George [Organic letters, 2002, vol. 4, # 22, p. 3875 - 3878]

26
[ 53774-20-2 ]
[ 513-42-8 ]
2-methyl-but-3-enoic acid 2-methyl-allyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
72%	With toluene-4-sulfonic acid In chloroform for 16h; Heating;

Reference： [1]Andreana, Peter R; McLellan, Jason S; Chen, Yongchen; Wang, Peng George [Organic letters, 2002, vol. 4, # 22, p. 3875 - 3878]

27
[ 124-38-9 ]
[ 17486-12-3 ]
[ 53774-20-2 ]

Yield	Reaction Conditions	Operation in experiment
42%	With methylaluminum dichloride In hexane at 20℃; for 3h;

Reference： [1]Hattori, Tetsutaro; Suzuki, Yutaka; Miyano, Sotaro [Chemistry Letters, 2003, vol. 32, # 5, p. 454 - 455]

28
[ 124-38-9 ]
[ 34584-84-4 ]
[ 53774-20-2 ]

Yield	Reaction Conditions	Operation in experiment
43%	With methylaluminum dichloride In hexane at 20℃; for 3h;

Reference： [1]Hattori, Tetsutaro; Suzuki, Yutaka; Miyano, Sotaro [Chemistry Letters, 2003, vol. 32, # 5, p. 454 - 455]

29
[ 16529-56-9 ]
[ 53774-20-2 ]

Yield	Reaction Conditions	Operation in experiment
100 % Chromat.	With potassium phosphate buffer; Escherichia coli SS₁₀₀₁ cells In water at 35℃; for 1h;
	With water at 35℃; for 1h; Enzymatic reaction; potassium phosphate buffer;	18 EXAMPLE; 18 Hydrolysis of 2-Methyl-3-Butenitrile to 2-Methyl-3-Butenoic acid by E. coli SS1001 Cells A 5.0 mL suspension of 0.500 g (wet cell paste) E. COLI SS1001 cells (ATCC PTA-1177) in 50 mM potassium phosphate buffer (pH 7.0) was added to a mixture of 4.91 mL of 50 mM potassium phosphate buffer (PH 7.0) and 81.8 mg of 2-methyl-3-butenenitrile (101 mM final concentration), and the resulting suspension stirred at 35 C. Samples (0.100 mL) were mixed with 0.900 mL of 60 mM N-ethylacetamide (HPLC external standard) in 1: 1 ACETONITRILE : methanol, the resulting mixture was mixed, centrifuged, and the supernatant analyzed by HPLC for 2-METHYL- 3-butenenitrile and 2-methyl-3-butenoic acid. After 1 H, the conversion of 2-methyl-3-butenenitrile was 100 %, and 2-methyl-3-butenoic acid was the only product produced over the course of the reaction.

Reference： [1]Hann, Eugenia C.; Sigmund, Amy E.; Fager, Susan K.; Cooling, Frederick B.; Gavagan, John E.; Bramucci, Michael G.; Chauhan, Sarita; Payne, Mark S.; DiCosimo, Robert [Tetrahedron, 2004, vol. 60, # 3, p. 577 - 581]
[2]Current Patent Assignee: DUPONT DE NEMOURS INC - WO2004/101513, 2004, A2 Location in patent: Page 32-33

30
[ 53774-20-2 ]
[ 125763-07-7 ]
(3R,4R)-4-Bromomethyl-3-methyl-oxetan-2-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With N-Bromosuccinimide; diphenyl diselenide In acetonitrile at -30℃; for 5h; Title compound not separated from byproducts;
	With bromine; sodium hydrogencarbonate In diethyl ether

Reference： [1]Mellegaard, Shelli R.; Tunge, Jon A. [Journal of Organic Chemistry, 2004, vol. 69, # 25, p. 8979 - 8981]
[2]Vellalath, Sreekumar; Romo, Daniel [Israel Journal of Chemistry, 2017, vol. 57, # 3, p. 335 - 339]

31
acetic acid 1-ethoxythiocarbonylsulfanyl-3-methyl-butyl ester [ No CAS ]
[ 53774-20-2 ]
5-acetoxy-3-ethoxythiocarbonylsulfanyl-2,7-dimethyl-octanoic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
81%	With dilauryl peroxide In 1,2-dichloro-ethane Heating;

Reference： [1]Bagal, Sharanjeet K.; Tournier, Lucie; Zard, Samir Z. [Synlett, 2006, # 10, p. 1485 - 1490]

32
[ 4894-61-5 ]
[ 124-38-9 ]
[ 53774-20-2 ]

Yield	Reaction Conditions	Operation in experiment
55%	Stage #1: trans-but-2-enyl chloride With iodine; magnesium In tetrahydrofuran at 20℃; for 0.5h; Inert atmosphere; Reflux; Stage #2: carbon dioxide With sulfuric acid In tetrahydrofuran at -78℃; for 0.5h;
51%	Stage #1: trans-but-2-enyl chloride With magnesium In tetrahydrofuran for 3h; Heating; Stage #2: carbon dioxide In tetrahydrofuran Further stages.;

Reference： [1]Yevglevskis, Maksims; Lee, Guat L.; Threadgill, Michael D.; Woodman, Timothy J.; Lloyd, Matthew D. [Chemical Communications, 2014, vol. 50, # 91, p. 14164 - 14166]
[2]Yang, Sung-Hyun; Caprio, Vittorio [Synlett, 2007, # 8, p. 1219 - 1222]

33
[ 53774-20-2 ]
[ 100-51-6 ]
[ 37526-85-5 ]

Yield	Reaction Conditions	Operation in experiment
98%	With dmap; dicyclohexyl-carbodiimide at 20℃; for 12h;
98%	With dmap; dicyclohexyl-carbodiimide In dichloromethane at 20℃; for 4h;	116.116B To a solution of 2-methylbut-3-enoic acid (2 g, 18.98 mmol) in CH2C12 (38.0 ml) was added phenylmethanol (1.966 ml, 18.98 mmol), DCC (3.92 g, 18.98 mmol) and DMAP (0.232 g, 1.898 mmol) (slight exotherm). The reaction was stirred at rt for four hours. The reaction was filtered off solid, rinsed with hexane, concentrated. Purification by normal phase chromatography gave 3.55 g (98%) of 116B as a colorless oil
95%	With dmap; dicyclohexyl-carbodiimide In dichloromethane at 20℃; for 16h;	2.1 To a solution of 2-methylbut-3-enoic acid (1.0 g, 9.99 mmol) in dichloromethane (1 mL) was added benzyl alcohol (1.1 g, 9.99 mmol), N,N-dicyclohexylcarbodiimide (2.1 g, 9.99 mmol) and dimethylaminopyridine (122 mg, 1.00 mmol). After stirring at 20 °C for 16 hours, the reaction mixture was filtered. The filtrate was concentrated under reduced pressure. The residue was purified by column chromatography (silica gel, 100 - 200 mesh, 0 - 5% ethyl acetate in petroleum ether) to afford benzyl 2-methylbut-3-enoate (1.8 g, 95%) as colorless oil.

	With dmap; dicyclohexyl-carbodiimide In dichloromethane at 0 - 20℃; Inert atmosphere;
	With dmap; dicyclohexyl-carbodiimide In dichloromethane at 20℃;	Intermediate 13. Benzyl 2-methylbut-3-enoate: To a solution of 2-methylbut- 3-enoic acid (9.5 g, 95 mmol) in DCM (80 mL) was added phenylmethanol (10.26 g, 95 mmol), N^-methanediylidenedicyclohexanamine (19.58 g, 95 mmol) and DMAP (1.159 g, 9.49 mmol) (exothermic reaction) and the resulting mixture was stirred at rt over weekend. The reaction mixture was filtered through a pad of CELITE to remove the solids and the filtrate was collected and concentrated. The filtrate was then concentrated and subjected to silica gel chromatography to yield the desired product as colorless oil.
	With dmap; dicyclohexyl-carbodiimide In dichloromethane at 20℃;	[00354] Intermediate 17. Benzyl 2-methylbut-3-enoate: To a solution of 2-methylbut- 3-enoic acid (9.5 g, 95 mmol) in DCM (80 mL) was added phenylmethanol (10.26 g, 95 mmol), N^-methanediylidenedicyclohexanamine (19.58 g, 95 mmol) and DMAP (1.159 g, 9.49 mmol) (exothermic reaction) and the reaction was stirred at rt over weekend. The reaction mixture was filtered through a pad of CELITE to remove the solids and the filtrate was concentrated. The residue was purified by silica gel chromatography to yield the desired product as a colorless oil.
186.2 mg	With dmap; dicyclohexyl-carbodiimide In dichloromethane at 20℃; Cooling with ice;

Reference： [1]Yang, Sung-Hyun; Caprio, Vittorio [Synlett, 2007, # 8, p. 1219 - 1222]
[2]Current Patent Assignee: BRISTOL-MYERS SQUIBB CO - WO2011/100401, 2011, A1 Location in patent: Page/Page column 248
[3]Current Patent Assignee: TENAYA THERAPEUTICS INC - WO2021/127643, 2021, A1 Location in patent: Paragraph 00233-00234
[4]Location in patent: experimental part Den Hartog, Tim; Macia, Beatriz; Minnaard, Adriaan J.; Feringa, Ben L. [Advanced Synthesis and Catalysis, 2010, vol. 352, # 6, p. 999 - 1013]
[5]Current Patent Assignee: BRISTOL-MYERS SQUIBB CO - WO2013/22814, 2013, A1 Location in patent: Paragraph 00314
[6]Current Patent Assignee: BRISTOL-MYERS SQUIBB CO - WO2013/22818, 2013, A1 Location in patent: Paragraph 00354
[7]Miao, Bukeyan; Ma, Shengming [Chemical Communications, 2014, vol. 50, # 25, p. 3285 - 3287]

34
[ 53774-20-2 ]
furan-2-yl-(2-methyl-but-3-enoyl)-carbamic acid <i>tert</i>-butyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: 4-methylmorpholine / tetrahydrofuran / 0.08 h 2: 0.69 g / n-BuLi / tetrahydrofuran; hexane / 0.17 h / 0 °C

Reference： [1]Padwa, Albert; Wang, Qiu [Journal of Organic Chemistry, 2006, vol. 71, # 8, p. 3210 - 3220]

35
[ 53774-20-2 ]
tert-butyl 4-methyl-3-oxo-10-oxa-2-azatricyclo[5.2.10^1,5]dec-8-ene-2-carboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 1: 4-methylmorpholine / tetrahydrofuran / 0.08 h 2: 0.69 g / n-BuLi / tetrahydrofuran; hexane / 0.17 h / 0 °C 3: 96 percent / 12 h / 25 °C

Reference： [1]Padwa, Albert; Wang, Qiu [Journal of Organic Chemistry, 2006, vol. 71, # 8, p. 3210 - 3220]

36
[ 53774-20-2 ]
tert-butyl 4-methyl-3-oxo-10-oxa-2-azatricyclo[5.2.10^1,5]dec-8-ene-2-carboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 1: 4-methylmorpholine / tetrahydrofuran / 0.08 h 2: 0.69 g / n-BuLi / tetrahydrofuran; hexane / 0.17 h / 0 °C 3: 12 h / 25 °C

Reference： [1]Padwa, Albert; Wang, Qiu [Journal of Organic Chemistry, 2006, vol. 71, # 8, p. 3210 - 3220]

37
[ 53774-20-2 ]
[ 343268-71-3 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: 72 percent / p-TsOH / CHCl₃ / 16 h / Heating 2: 75 percent / Ti(OiPr)4 / RuCl₂(=CHPh)(PCy₃)(1,3-Mes-2-imidazolidin-2-yl) / 7.5 h / Heating

Reference： [1]Andreana, Peter R; McLellan, Jason S; Chen, Yongchen; Wang, Peng George [Organic letters, 2002, vol. 4, # 22, p. 3875 - 3878]

38
[ 53774-20-2 ]
3-methyl-3,6-dihydro-pyran-2-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: 75 percent / p-TsOH / CHCl₃ / 16 h / Heating 2: 83 percent / Ti(OiPr)4 / RuCl₂(=CHPh)(PCy₃)(1,3-Mes-2-imidazolidin-2-yl) / 7.5 h / Heating

Reference： [1]Andreana, Peter R; McLellan, Jason S; Chen, Yongchen; Wang, Peng George [Organic letters, 2002, vol. 4, # 22, p. 3875 - 3878]

39
[ 53774-20-2 ]
(4R,5S,2'R)-3-(2'-methyl-3'-butenoyl)-4-methyl-5-phenyl-2-oxazolidinone [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: N-methylmorpholine / tetrahydrofuran / 1 h / -78 °C 2: 1.) n-BuLi, 2.) N-methylmorpholine / 1.) THF, -78 deg C, 2.) THF, a) -78 deg C, 1 h, b) RT, 4 h
	Multi-step reaction with 2 steps 1: N-methylmorpholine / tetrahydrofuran / 1 h / -78 °C 2: 1.) n-BuLi / 1.) THF, -78 deg C, 30 min, 2.) THF, a) -78 deg C, 1 h, b) from -78 deg C to RT, 4 h

Reference： [1]Dobarro, Alicia; Velasco, Dolores [Tetrahedron, 1996, vol. 52, # 43, p. 13733 - 13738]
[2]Dobarro, Alicia; Velasco, Dolores [Tetrahedron, 1996, vol. 52, # 42, p. 13525 - 13530]

40
[ 53774-20-2 ]
(4R,5S,2'S)-3-(2'-methyl-3'-butenoyl)-4-methyl-5-phenyl-2-oxazolidinone [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: N-methylmorpholine / tetrahydrofuran / 1 h / -78 °C 2: 1.) n-BuLi, 2.) N-methylmorpholine / 1.) THF, -78 deg C, 2.) THF, a) -78 deg C, 1 h, b) RT, 4 h
	Multi-step reaction with 2 steps 1: N-methylmorpholine / tetrahydrofuran / 1 h / -78 °C 2: 1.) n-BuLi / 1.) THF, -78 deg C, 30 min, 2.) THF, a) -78 deg C, 1 h, b) from -78 deg C to RT, 4 h

Reference： [1]Dobarro, Alicia; Velasco, Dolores [Tetrahedron, 1996, vol. 52, # 43, p. 13733 - 13738]
[2]Dobarro, Alicia; Velasco, Dolores [Tetrahedron, 1996, vol. 52, # 42, p. 13525 - 13530]

41
[ 53774-20-2 ]
(S)-4-Benzyl-3-((R)-2-methyl-but-3-enoyl)-oxazolidin-2-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: Et₃N / tetrahydrofuran / 1 h / -78 °C 2: 1.) n-BuLi, 2.) Et₃N / 1.) THF, -78 deg C, 2.) THF, a) -78 deg C, 1 h, b) RT, 4 h
	Multi-step reaction with 2 steps 1: Et₃N / tetrahydrofuran / 1 h / -78 °C 2: 1.) n-BuLi / 1.) THF, -78 deg C, 30 min, 2.) THF, a) -78 deg C, 1 h, b) from -78 deg C to RT, 4 h
	Multi-step reaction with 2 steps 1: N-methylmorpholine / tetrahydrofuran / 1 h / -78 °C 2: 1.) n-BuLi / 1.) THF, -78 deg C, 30 min, 2.) THF, a) -78 deg C, 1 h, b) from -78 deg C to RT, 4 h

Multi-step reaction with 2 steps 1: N-methylmorpholine / tetrahydrofuran / 1 h / -78 °C 2: 1.) n-BuLi, 2.) N-methylmorpholine / 1.) THF, -78 deg C, 2.) THF, a) -78 deg C, 1 h, b) RT, 4 h

Reference： [1]Dobarro, Alicia; Velasco, Dolores [Tetrahedron, 1996, vol. 52, # 43, p. 13733 - 13738]
[2]Dobarro, Alicia; Velasco, Dolores [Tetrahedron, 1996, vol. 52, # 42, p. 13525 - 13530]
[3]Dobarro, Alicia; Velasco, Dolores [Tetrahedron, 1996, vol. 52, # 42, p. 13525 - 13530]
[4]Dobarro, Alicia; Velasco, Dolores [Tetrahedron, 1996, vol. 52, # 43, p. 13733 - 13738]

42
[ 53774-20-2 ]
(S)-4-Benzyl-3-((S)-2-methyl-but-3-enoyl)-oxazolidin-2-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: Et₃N / tetrahydrofuran / 1 h / -78 °C 2: 1.) n-BuLi, 2.) Et₃N / 1.) THF, -78 deg C, 2.) THF, a) -78 deg C, 1 h, b) RT, 4 h
	Multi-step reaction with 2 steps 1: Et₃N / tetrahydrofuran / 1 h / -78 °C 2: 1.) n-BuLi / 1.) THF, -78 deg C, 30 min, 2.) THF, a) -78 deg C, 1 h, b) from -78 deg C to RT, 4 h
	Multi-step reaction with 2 steps 1: N-methylmorpholine / tetrahydrofuran / 1 h / -78 °C 2: 1.) n-BuLi / 1.) THF, -78 deg C, 30 min, 2.) THF, a) -78 deg C, 1 h, b) from -78 deg C to RT, 4 h

Multi-step reaction with 2 steps 1: N-methylmorpholine / tetrahydrofuran / 1 h / -78 °C 2: 1.) n-BuLi, 2.) N-methylmorpholine / 1.) THF, -78 deg C, 2.) THF, a) -78 deg C, 1 h, b) RT, 4 h

Reference： [1]Dobarro, Alicia; Velasco, Dolores [Tetrahedron, 1996, vol. 52, # 43, p. 13733 - 13738]
[2]Dobarro, Alicia; Velasco, Dolores [Tetrahedron, 1996, vol. 52, # 42, p. 13525 - 13530]
[3]Dobarro, Alicia; Velasco, Dolores [Tetrahedron, 1996, vol. 52, # 42, p. 13525 - 13530]
[4]Dobarro, Alicia; Velasco, Dolores [Tetrahedron, 1996, vol. 52, # 43, p. 13733 - 13738]

43
[ 53774-20-2 ]
[ 184292-93-1 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: Et₃N / tetrahydrofuran / 1 h / -78 °C 2: 1.) n-BuLi, 2.) Et₃N / 1.) THF, -78 deg C, 2.) THF, a) -78 deg C, 1 h, b) RT, 4 h
	Multi-step reaction with 2 steps 1: Et₃N / tetrahydrofuran / 1 h / -78 °C 2: 1.) n-BuLi / 1.) THF, -78 deg C, 30 min, 2.) THF, a) -78 deg C, 1 h, b) from -78 deg C to RT, 4 h
	Multi-step reaction with 2 steps 1: N-methylmorpholine / tetrahydrofuran / 1 h / -78 °C 2: 1.) n-BuLi, 2.) Et₃N / 1.) THF, -78 deg C, 2.) THF, a) -78 deg C, 1 h, b) RT, 4 h

Reference： [1]Dobarro, Alicia; Velasco, Dolores [Tetrahedron, 1996, vol. 52, # 43, p. 13733 - 13738]
[2]Dobarro, Alicia; Velasco, Dolores [Tetrahedron, 1996, vol. 52, # 42, p. 13525 - 13530]
[3]Dobarro, Alicia; Velasco, Dolores [Tetrahedron, 1996, vol. 52, # 43, p. 13733 - 13738]

44
[ 53774-20-2 ]
[ 110080-01-8 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: oxalyl chloride / 57 h / 0 - 20 °C 2: NH₂OH*HCl, KOH / tetrahydrofuran; methanol / 2.25 h / 0 - 20 °C

Reference： [1]Rajendra, G.; Miller, Marvin J. [Journal of Organic Chemistry, 1987, vol. 52, # 20, p. 4471 - 4477]

45
[ 53774-20-2 ]
[ 110080-02-9 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 1: oxalyl chloride / 57 h / 0 - 20 °C 2: NH₂OH*HCl, KOH / tetrahydrofuran; methanol / 2.25 h / 0 - 20 °C 3: pyridine / tetrahydrofuran / 0.5 h / 0 °C

Reference： [1]Rajendra, G.; Miller, Marvin J. [Journal of Organic Chemistry, 1987, vol. 52, # 20, p. 4471 - 4477]

46
[ 53774-20-2 ]
[ 129085-01-4 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 6 steps 1: 75 percent / LiAlH₄ / diethyl ether / Heating 2: 1) NaH / 1) DME, reflux, overnight, 2) reflux, 24 h 3: 1) AgBF₄, 2) aq. Na₂CO₃ / 1) CH₂Cl₂, -60 deg C, then rt, overnight, 2) CH₂Cl₂, 3 h, reflux 4: hydrazine hydrate / ethanol / 2 h / Heating 5: t-BuOK / dimethylsulfoxide / Ambient temperature 6: H₂ / Raney nickel / ethanol / 60 h / 2250.2 Torr

Reference： [1]Grandguillot; Rouessac [Tetrahedron, 1991, vol. 47, # 28, p. 5133 - 5148]

47
[ 53774-20-2 ]
[ 129085-01-4 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 6 steps 1: 75 percent / LiAlH₄ / diethyl ether / Heating 2: 1) NaH / 1) DME, reflux, overnight, 2) reflux, 24 h 3: 1) AgBF₄, 2) aq. Na₂CO₃ / 1) CH₂Cl₂, -60 deg C, then rt, overnight, 2) CH₂Cl₂, 3 h, reflux 4: hydrazine hydrate / ethanol / 2 h / Heating 5: t-BuOK / dimethylsulfoxide / Ambient temperature 6: H₂ / Raney nickel / ethanol / 60 h / 2250.2 Torr

Reference： [1]Grandguillot; Rouessac [Tetrahedron, 1991, vol. 47, # 28, p. 5133 - 5148]

48
[ 53774-20-2 ]
(Z)-2-<2-<2-(p-Methoxyphenoxy)ethyl>-2-methylcyclobutane>propan-1-ol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 6 steps 1: 75 percent / LiAlH₄ / diethyl ether / Heating 2: 1) NaH / 1) DME, reflux, overnight, 2) reflux, 24 h 3: 1) ZnCl₂, 2) aq. Na₂CO₃ / 1) CH₂Cl₂, rt, overnight, 2) CH₂Cl₂, reflux 4: hydrazine hydrate / ethanol / 2 h / Heating 5: t-BuOK / dimethylsulfoxide / Ambient temperature 6: H₂ / Raney nickel / ethanol / 60 h / 2250.2 Torr

Reference： [1]Grandguillot; Rouessac [Tetrahedron, 1991, vol. 47, # 28, p. 5133 - 5148]

49
[ 53774-20-2 ]
(E)-2-<2-<2-(p-Methoxyphenoxy)ethyl>-2-methylcyclobutane>propan-1-ol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 6 steps 1: 75 percent / LiAlH₄ / diethyl ether / Heating 2: 1) NaH / 1) DME, reflux, overnight, 2) reflux, 24 h 3: 1) ZnCl₂, 2) aq. Na₂CO₃ / 1) CH₂Cl₂, rt, overnight, 2) CH₂Cl₂, reflux 4: hydrazine hydrate / ethanol / 2 h / Heating 5: t-BuOK / dimethylsulfoxide / Ambient temperature 6: H₂ / Raney nickel / ethanol / 60 h / 2250.2 Torr

Reference： [1]Grandguillot; Rouessac [Tetrahedron, 1991, vol. 47, # 28, p. 5133 - 5148]

50
[ 53774-20-2 ]
[ 82638-92-4 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 2: Ph₃P-Br₂-Et₃N 3: 79 percent / CCl₄ / 120 h / 30 °C

Reference： [1]Dondoni, Alessandro [Journal of Organic Chemistry, 1982, vol. 47, # 20, p. 3998 - 4000]

51
[ 53774-20-2 ]
[ 82638-95-7 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 2: Ph₃P-Br₂-Et₃N 3: 24 percent / CCl₄ / 35 h / Ambient temperature

Reference： [1]Dondoni, Alessandro [Journal of Organic Chemistry, 1982, vol. 47, # 20, p. 3998 - 4000]

52
[ 53774-20-2 ]
[ 82638-93-5 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 2: Ph₃P-Br₂-Et₃N 3: 45 percent / CCl₄ / 35 h / Ambient temperature

Reference： [1]Dondoni, Alessandro [Journal of Organic Chemistry, 1982, vol. 47, # 20, p. 3998 - 4000]

53
[ 53774-20-2 ]
(-)(R)-2-Methyl-1-isopropylamino-butan [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 4 steps 1: SOCl₂ 2: diethyl ether 3: LiAlH₄ / diethyl ether 4: H₂ / Pd-CaCO₃ / methanol / 760 Torr

Reference： [1]Rossi,R.; Ingrosso,G. [Gazzetta Chimica Italiana, 1968, vol. 98, p. 866 - 883]

54
[ 7204-29-7 ]
[ 53774-20-2 ]

Yield	Reaction Conditions	Operation in experiment
		1 2M3BA=2-Methyl-3-butenoic acid 2M3BA=2-Methyl-3-butenoic acid CrX=Mixture of Crotyl acetate, 3-Acetoxybutene-1, 3-Iodobutene-1, cis- and trans-crotyl iodides 3PA=cis+trans-3-pentenoic acid

Reference： [1]Current Patent Assignee: DUPONT DE NEMOURS INC; KONINKLIJKE DSM N.V. - US6015923, 2000, A

55
[ 106-99-0 ]
[ 542-28-9 ]
[ 53774-20-2 ]

Yield	Reaction Conditions	Operation in experiment
4.1%		1 Example 1 After 1 hour the butadiene (BD) conversion was 78.3%, the yield of cis- and trans-3-pentenoic acid (3PA) was 90.9%, the yield of 2-methyl-3-butenoic acid (2M3BA) was 4.2% and the yield of valerolactone (VL) was 5.0%. After 5 hours the BD conversion was 98.2%, the yield of 3PA was 74%, the yield of 2M3BA was 4.1% and the yield of valerolactone was 15.6%.

Reference： [1]Current Patent Assignee: KOCH INDUSTRIES, INC. - US5962732, 1999, A

56
[ 1617-32-9 ]
[ 106-99-0 ]
[ 542-28-9 ]
[ 53774-20-2 ]

Yield	Reaction Conditions	Operation in experiment
3.2%		2 Example 2 After 1 hour the butadiene conversion was 52.3% and the 3PA yield was 92.1%, the yield of 2M3BA was 3.2% and the yield of VL was 0.9%.

Reference： [1]Current Patent Assignee: KOCH INDUSTRIES, INC. - US5962732, 1999, A

57
[ 53774-20-2 ]
[ 762-72-1 ]
[ 1432497-06-7 ]

Yield	Reaction Conditions	Operation in experiment
59%	With Hoveyda-Grubbs catalyst second generation; p-benzoquinone In dichloromethane Reflux; Inert atmosphere;
	In dichloromethane for 24h; Heating;

Reference： [1]Combettes, Lorraine E.; Schuler, Marie; Patel, Rakesh; Bonillo, Baltasar; Odell, Barbara; Thompson, Amber L.; Claridge, Tim D. W.; Gouverneur, Véronique [Chemistry - A European Journal, 2012, vol. 18, # 41, p. 13126 - 13132]
[2]Tredwell, Matthew; Luft, Jennifer A. R.; Schuler, Marie; Tenza, Kenny; Houk, Kendall N.; Gouverneur, Veronique [Angewandte Chemie - International Edition, 2008, vol. 47, # 2, p. 357 - 360]

58
[ 1271-19-8 ]
[ 927-77-5 ]
[ 106-99-0 ]
[ 53774-20-2 ]

Yield	Reaction Conditions	Operation in experiment
85%	With hydrogenchloride; air; carbon dioxide In diethyl ether Addn. of n-PrMgBr (Et2O) to stirred Et2O suspn. of Cp2TiCl2 and C4H6 (Ar, 0°C) over 5 min, stirring (30 min) at room temp. Bubbling of CO2 through soln. (1 h, room temp.), hydrolysis with aq. HCl, passing of air into react. mixt. for 15 min.; Filtn. gives Cp2TiCl2 in 93% yield recovery. Addn. of aq. NaOH to filtrate, sepn. of org. layer, discarding; extn. of aq. layer with ether, discarding, addn. of concd. HCl, extn. with ether, drying, concn. in vac. Purifn. by trap-to-trap distn.;

Reference： [1]Gao, Yuan; Iijima, Satoshi; Urabe, Hirokazu; Sato, Fumie [Inorganica Chimica Acta, 1994, vol. 222, p. 145 - 154]

59
[ 12087-70-6 ]
[ 1271-19-8 ]
[ 53774-20-2 ]

Yield	Reaction Conditions	Operation in experiment
1: 85% 2: 82%	With hydrogenchloride; air; carbon dioxide In diethyl ether Passing of gaseous CO2 through Et2O soln. of Ti-compd. (Ar) for 1 h, hydrolysis with aq. HCl and then bubbling of air into react. mixt. for 15 min.; Collecting of pptd. crystals of Cp2TiCl2 by filtn., addn. of aq. NaOH, sepn. of org. layer and discarding. Extn. of aq. layer with ether, discarding, addn. of concd. HCl, extn. with ether, drying, concn. in vac. Purifn. by trap-to-trap distn., (1)H NMR.;

Reference： [1]Gao, Yuan; Iijima, Satoshi; Urabe, Hirokazu; Sato, Fumie [Inorganica Chimica Acta, 1994, vol. 222, p. 145 - 154]

60
[ 69079-28-3 ]
[ 53774-20-2 ]

Yield	Reaction Conditions	Operation in experiment
91%	With sodium hydroxide; dihydrogen peroxide In methanol; water at 20℃; for 0.0833333h;

Reference： [1]Location in patent: experimental part Grellepois, Fabienne; Portella, Charles [Synthesis, 2008, # 21, p. 3443 - 3446]

61
[ 53774-20-2 ]
C₅H₇FO [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With pyridine; trifluoro-[1,3,5]triazine In dichloromethane at 0℃; for 2h; Inert atmosphere;

Reference： [1]Location in patent: experimental part O'Connor, Patrick D.; Bin Kim; Brimble, Margaret A. [European Journal of Organic Chemistry, 2009, # 26, p. 4405 - 4411]

62
[ 53774-20-2 ]
[ 1193511-13-5 ]
[ 1193511-19-1 ]

Yield	Reaction Conditions	Operation in experiment
54%	With Hoveyda-Grubbs catalyst second generation In dichloromethane for 72h; Inert atmosphere; Reflux;

Reference： [1]Wilkinson, Susan C.; Lozano, Oscar; Schuler, Marie; Pacheco, Maria C.; Gouverneur, Veronique; Salmon, Roger [Angewandte Chemie - International Edition, 2009, vol. 48, # 38, p. 7083 - 7086][Angewandte Chemie, 2009, vol. 121, # 38, p. 7217 - 7220]

63
[ 53774-20-2 ]
[ 24400-84-8 ]
[ 1193511-17-9 ]

Yield	Reaction Conditions	Operation in experiment
47%	With Hoveyda-Grubbs catalyst second generation In dichloromethane for 72h; Inert atmosphere; Reflux;

Reference： [1]Wilkinson, Susan C.; Lozano, Oscar; Schuler, Marie; Pacheco, Maria C.; Gouverneur, Veronique; Salmon, Roger [Angewandte Chemie - International Edition, 2009, vol. 48, # 38, p. 7083 - 7086][Angewandte Chemie, 2009, vol. 121, # 38, p. 7217 - 7220]

64
[ 124-38-9 ]
[ 106-99-0 ]
[ 5204-64-8 ]
[ 53774-20-2 ]

Yield	Reaction Conditions	Operation in experiment
3%	Stage #1: carbon dioxide; buta-1,3-diene With triethylaluminum In N,N-dimethyl-formamide; toluene at 20℃; for 39h; Stage #2: With hydrogenchloride In water; N,N-dimethyl-formamide; toluene Cooling;

Reference： [1]Takaya, Jun; Sasano, Kota; Iwasawa, Nobuharu [Organic Letters, 2011, vol. 13, # 7, p. 1698 - 1701]

65
[ 124-38-9 ]
[ 106-99-0 ]
[ 5204-64-8 ]
[ 53774-20-2 ]
[ 13201-46-2 ]

Yield	Reaction Conditions	Operation in experiment
3%	Stage #1: carbon dioxide; buta-1,3-diene With triethylaluminum In tetrahydrofuran; toluene at 20℃; for 40h; Stage #2: With hydrogenchloride In tetrahydrofuran; water; toluene Cooling;
3%	Stage #1: carbon dioxide; buta-1,3-diene With triethylaluminum In N,N-dimethyl-formamide; toluene at 20℃; for 72h; Stage #2: With hydrogenchloride In water; N,N-dimethyl-formamide; toluene Cooling;

Reference： [1]Takaya, Jun; Sasano, Kota; Iwasawa, Nobuharu [Organic Letters, 2011, vol. 13, # 7, p. 1698 - 1701]
[2]Takaya, Jun; Sasano, Kota; Iwasawa, Nobuharu [Organic Letters, 2011, vol. 13, # 7, p. 1698 - 1701]

66
[ 53774-20-2 ]
[ 20626-49-7 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1.1: pivaloyl chloride; 4-methyl-morpholine / tetrahydrofuran / 2 h / -78 - 0 °C 1.2: 2.58 h / -78 °C 2.1: lithium hydroxide; dihydrogen peroxide / tetrahydrofuran; water / 0.5 h / 0 °C
	Multi-step reaction with 2 steps 1.1: 4-methyl-morpholine; pivaloyl chloride / tetrahydrofuran / -78 - 0 °C 1.2: 2 h / -78 °C 2.1: dihydrogen peroxide; lithium hydroxide / water; tetrahydrofuran / 0.5 h / 0 °C
	Multi-step reaction with 2 steps 1.1: 4-methyl-morpholine; pivaloyl chloride / tetrahydrofuran / 2 h / -78 - 0 °C 1.2: 2.5 h / -78 °C 2.1: hydrogenchloride / tetrahydrofuran; water; chloroform / 0 °C / pH 3

	Multi-step reaction with 2 steps 1.1: 4-methyl-morpholine; pivaloyl chloride / tetrahydrofuran / -78 - 0 °C 1.2: 1.58 h / -78 °C 2.1: dihydrogen peroxide; lithium hydroxide / tetrahydrofuran; water / 0.5 h / 0 °C
	Multi-step reaction with 2 steps 1.1: 4-methyl-morpholine; pivaloyl chloride / tetrahydrofuran / 2 h / -78 - 0 °C 1.2: 2.58 h / -78 °C 2.1: dihydrogen peroxide; lithium hydroxide / tetrahydrofuran; water / 0.5 h / 0 °C
	Stage #1: 2-methylbut-3-enoic acid With (<i>S</i>)-1-phenyl-ethylamine In acetone at 80℃; for 0.666667h; Stage #2: With hydrogenchloride In water at 20 - 30℃; for 0.666667h;	B.2; B.3 Step 2 : Preparation of (R)-2-methylbut-3-enoic acid (S)-1-phenyl-ethane salt (SM-2-4) Compound SM-2-2 (48g, 48mmol) was dissolved in acetone (100 mL) was added Compound SM-2-3 (67mL, 52mmol), refluxed for 40min 80C , natural cooling after crystallization.After suction filtration, the filter cake was added 50mL of acetone, dissolved by heating, crystallization at room temperature, suction-filtered to give the target molecule SM-2-4 (20.5g, 19%, dr≈2/1).Compound SM-2-4 (22g, 99mmol) was dissolved in 1N hydrochloric acid solution (135mL) was stirred at rt 40min, after-treatment to give SM-2 (9.8g, 98%)
	Multi-step reaction with 2 steps 1.1: 4-methyl-morpholine; pivaloyl chloride / tetrahydrofuran / 2 h / -78 - 0 °C 1.2: 2 h / -78 °C / Inert atmosphere 2.1: dihydrogen peroxide; lithium hydroxide / tetrahydrofuran; water / 1.25 h / -1.5 - 1 °C

Reference： [1]Current Patent Assignee: BRISTOL-MYERS SQUIBB CO - WO2013/22814, 2013, A1
[2]Current Patent Assignee: BRISTOL-MYERS SQUIBB CO - WO2013/22818, 2013, A1
[3]Current Patent Assignee: BRISTOL-MYERS SQUIBB CO - WO2015/116882, 2015, A1
[4]Current Patent Assignee: BRISTOL-MYERS SQUIBB CO - WO2016/205482, 2016, A1
[5]Current Patent Assignee: BRISTOL-MYERS SQUIBB CO - WO2015/116886, 2015, A1
[6]Current Patent Assignee: SICHUAN KELUN PHARMACEUTICAL COMPANY LIMITED - CN109721613, 2019, A Location in patent: Paragraph 0212; 0213; 0216-0220
[7]Corte, James R.; Pinto, Donald J. P.; Fang, Tianan; Osuna, Honey; Yang, Wu; Wang, Yufeng; Lai, Amy; Clark, Charles G.; Sun, Jung-Hui; Rampulla, Richard; Mathur, Arvind; Kaspady, Mahammed; Neithnadka, Premsai Rai; Li, Yi-Xin Cindy; Rossi, Karen A.; Myers, Joseph E.; Sheriff, Steven; Lou, Zhen; Harper, Timothy W.; Huang, Christine; Zheng, Joanna J.; Bozarth, Jeffrey M.; Wu, Yiming; Wong, Pancras C.; Crain, Earl J.; Seiffert, Dietmar A.; Luettgen, Joseph M.; Lam, Patrick Y. S.; Wexler, Ruth R.; Ewing, William R. [Journal of Medicinal Chemistry, 2020, vol. 63, # 2, p. 784 - 803]

67
[ 53774-20-2 ]
[ 1422387-22-1 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 4 steps 1.1: pivaloyl chloride; 4-methyl-morpholine / tetrahydrofuran / 2 h / -78 - 0 °C 1.2: 2.58 h / -78 °C 2.1: lithium hydroxide; dihydrogen peroxide / tetrahydrofuran; water / 0.5 h / 0 °C 3.1: 2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphosphinane-2,4,6-trioxide; pyridine / ethyl acetate / -10 - 20 °C / Inert atmosphere 4.1: toluene-4-sulfonic acid / dichloromethane / 1 h / Inert atmosphere; Reflux 4.2: 4 h / Inert atmosphere; Reflux
	Multi-step reaction with 4 steps 1.1: 4-methyl-morpholine; pivaloyl chloride / tetrahydrofuran / -78 - 0 °C 1.2: 2 h / -78 °C 2.1: dihydrogen peroxide; lithium hydroxide / water; tetrahydrofuran / 0.5 h / 0 °C 3.1: 2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphosphinane-2,4,6-trioxide; pyridine / ethyl acetate / -10 - 20 °C 4.1: toluene-4-sulfonic acid / dichloromethane / 1 h / Inert atmosphere; Reflux 4.2: 4 h / Inert atmosphere; Reflux
	Multi-step reaction with 4 steps 1.1: 4-methyl-morpholine; pivaloyl chloride / tetrahydrofuran / 2 h / -78 - 0 °C 1.2: 2 h / -78 °C / Inert atmosphere 2.1: dihydrogen peroxide; lithium hydroxide / tetrahydrofuran; water / 1.25 h / -1.5 - 1 °C 3.1: pyridine; 2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphosphinane-2,4,6-trioxide / ethyl acetate / -10 - 20 °C 4.1: toluene-4-sulfonic acid; tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride / dichloromethane / 5 h / 40 °C / Inert atmosphere

Reference： [1]Current Patent Assignee: BRISTOL-MYERS SQUIBB CO - WO2013/22814, 2013, A1
[2]Current Patent Assignee: BRISTOL-MYERS SQUIBB CO - WO2013/22818, 2013, A1
[3]Corte, James R.; Pinto, Donald J. P.; Fang, Tianan; Osuna, Honey; Yang, Wu; Wang, Yufeng; Lai, Amy; Clark, Charles G.; Sun, Jung-Hui; Rampulla, Richard; Mathur, Arvind; Kaspady, Mahammed; Neithnadka, Premsai Rai; Li, Yi-Xin Cindy; Rossi, Karen A.; Myers, Joseph E.; Sheriff, Steven; Lou, Zhen; Harper, Timothy W.; Huang, Christine; Zheng, Joanna J.; Bozarth, Jeffrey M.; Wu, Yiming; Wong, Pancras C.; Crain, Earl J.; Seiffert, Dietmar A.; Luettgen, Joseph M.; Lam, Patrick Y. S.; Wexler, Ruth R.; Ewing, William R. [Journal of Medicinal Chemistry, 2020, vol. 63, # 2, p. 784 - 803]

68
[ 53774-20-2 ]
[ 1422387-18-5 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 5 steps 1.1: pivaloyl chloride; 4-methyl-morpholine / tetrahydrofuran / 2 h / -78 - 0 °C 1.2: 2.58 h / -78 °C 2.1: lithium hydroxide; dihydrogen peroxide / tetrahydrofuran; water / 0.5 h / 0 °C 3.1: 2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphosphinane-2,4,6-trioxide; pyridine / ethyl acetate / -10 - 20 °C / Inert atmosphere 4.1: toluene-4-sulfonic acid / dichloromethane / 1 h / Inert atmosphere; Reflux 4.2: 4 h / Inert atmosphere; Reflux 5.1: palladium 10% on activated carbon; hydrogen / methanol / 20 h / 2585.81 Torr / Inert atmosphere
	Multi-step reaction with 5 steps 1.1: 4-methyl-morpholine; pivaloyl chloride / tetrahydrofuran / -78 - 0 °C 1.2: 2 h / -78 °C 2.1: dihydrogen peroxide; lithium hydroxide / water; tetrahydrofuran / 0.5 h / 0 °C 3.1: 2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphosphinane-2,4,6-trioxide; pyridine / ethyl acetate / -10 - 20 °C 4.1: toluene-4-sulfonic acid / dichloromethane / 1 h / Inert atmosphere; Reflux 4.2: 4 h / Inert atmosphere; Reflux 5.1: hydrogen; palladium 10% on activated carbon / methanol / 20 h / 2585.81 Torr / Inert atmosphere
	Multi-step reaction with 5 steps 1.1: 4-methyl-morpholine; pivaloyl chloride / tetrahydrofuran / 2 h / -78 - 0 °C 1.2: 2 h / -78 °C / Inert atmosphere 2.1: dihydrogen peroxide; lithium hydroxide / tetrahydrofuran; water / 1.25 h / -1.5 - 1 °C 3.1: pyridine; 2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphosphinane-2,4,6-trioxide / ethyl acetate / -10 - 20 °C 4.1: toluene-4-sulfonic acid; tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride / dichloromethane / 5 h / 40 °C / Inert atmosphere 5.1: hydrogen; palladium 10% on activated carbon / methanol; tetrahydrofuran / 22 h / 20 °C / 2844.39 Torr

Reference： [1]Current Patent Assignee: BRISTOL-MYERS SQUIBB CO - WO2013/22814, 2013, A1
[2]Current Patent Assignee: BRISTOL-MYERS SQUIBB CO - WO2013/22818, 2013, A1
[3]Corte, James R.; Pinto, Donald J. P.; Fang, Tianan; Osuna, Honey; Yang, Wu; Wang, Yufeng; Lai, Amy; Clark, Charles G.; Sun, Jung-Hui; Rampulla, Richard; Mathur, Arvind; Kaspady, Mahammed; Neithnadka, Premsai Rai; Li, Yi-Xin Cindy; Rossi, Karen A.; Myers, Joseph E.; Sheriff, Steven; Lou, Zhen; Harper, Timothy W.; Huang, Christine; Zheng, Joanna J.; Bozarth, Jeffrey M.; Wu, Yiming; Wong, Pancras C.; Crain, Earl J.; Seiffert, Dietmar A.; Luettgen, Joseph M.; Lam, Patrick Y. S.; Wexler, Ruth R.; Ewing, William R. [Journal of Medicinal Chemistry, 2020, vol. 63, # 2, p. 784 - 803]

69
[ 53774-20-2 ]
methyl N-[(10R,14S)-14-amino-10-methyl-9-oxo-8,16-diazatricyclo[13.3.1.0^2,7]-nonadeca-1⁽¹⁹⁾,2⁽⁷⁾,3,5,15,17-hexaen-5-yl]carbamate bis-trifluoroacetic acid salt [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 6 steps 1.1: pivaloyl chloride; 4-methyl-morpholine / tetrahydrofuran / 2 h / -78 - 0 °C 1.2: 2.58 h / -78 °C 2.1: lithium hydroxide; dihydrogen peroxide / tetrahydrofuran; water / 0.5 h / 0 °C 3.1: 2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphosphinane-2,4,6-trioxide; pyridine / ethyl acetate / -10 - 20 °C / Inert atmosphere 4.1: toluene-4-sulfonic acid / dichloromethane / 1 h / Inert atmosphere; Reflux 4.2: 4 h / Inert atmosphere; Reflux 5.1: palladium 10% on activated carbon; hydrogen / methanol / 20 h / 2585.81 Torr / Inert atmosphere 6.1: dichloromethane / 1 h / 20 °C
	Multi-step reaction with 6 steps 1.1: 4-methyl-morpholine; pivaloyl chloride / tetrahydrofuran / -78 - 0 °C 1.2: 2 h / -78 °C 2.1: dihydrogen peroxide; lithium hydroxide / water; tetrahydrofuran / 0.5 h / 0 °C 3.1: 2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphosphinane-2,4,6-trioxide; pyridine / ethyl acetate / -10 - 20 °C 4.1: toluene-4-sulfonic acid / dichloromethane / 1 h / Inert atmosphere; Reflux 4.2: 4 h / Inert atmosphere; Reflux 5.1: hydrogen; palladium 10% on activated carbon / methanol / 20 h / 2585.81 Torr / Inert atmosphere 6.1: dichloromethane / 1 h / 20 °C
	Multi-step reaction with 6 steps 1.1: 4-methyl-morpholine; pivaloyl chloride / tetrahydrofuran / 2 h / -78 - 0 °C 1.2: 2 h / -78 °C / Inert atmosphere 2.1: dihydrogen peroxide; lithium hydroxide / tetrahydrofuran; water / 1.25 h / -1.5 - 1 °C 3.1: pyridine; 2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphosphinane-2,4,6-trioxide / ethyl acetate / -10 - 20 °C 4.1: toluene-4-sulfonic acid; tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride / dichloromethane / 5 h / 40 °C / Inert atmosphere 5.1: hydrogen; palladium 10% on activated carbon / methanol; tetrahydrofuran / 22 h / 20 °C / 2844.39 Torr 6.1: dichloromethane / 1 h / 20 °C

Reference： [1]Current Patent Assignee: BRISTOL-MYERS SQUIBB CO - WO2013/22814, 2013, A1
[2]Current Patent Assignee: BRISTOL-MYERS SQUIBB CO - WO2013/22818, 2013, A1
[3]Corte, James R.; Pinto, Donald J. P.; Fang, Tianan; Osuna, Honey; Yang, Wu; Wang, Yufeng; Lai, Amy; Clark, Charles G.; Sun, Jung-Hui; Rampulla, Richard; Mathur, Arvind; Kaspady, Mahammed; Neithnadka, Premsai Rai; Li, Yi-Xin Cindy; Rossi, Karen A.; Myers, Joseph E.; Sheriff, Steven; Lou, Zhen; Harper, Timothy W.; Huang, Christine; Zheng, Joanna J.; Bozarth, Jeffrey M.; Wu, Yiming; Wong, Pancras C.; Crain, Earl J.; Seiffert, Dietmar A.; Luettgen, Joseph M.; Lam, Patrick Y. S.; Wexler, Ruth R.; Ewing, William R. [Journal of Medicinal Chemistry, 2020, vol. 63, # 2, p. 784 - 803]

70
[ 53774-20-2 ]
(R)-4-(phenylmethyl)-2-oxazolidinone [ No CAS ]
(4R)-4-benzyl-3-[(2R)-2-methylbut-3-enoyl]-1,3-oxazolidin-2-one [ No CAS ]
(4R)-4-benzyl-3-[(2S)-2-methylbut-3-enoyl]-1,3-oxazolidin-2-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
1: 55% 2: 38%	Stage #1: 2-methylbut-3-enoic acid With 4-methyl-morpholine; pivaloyl chloride In tetrahydrofuran at -78 - 0℃; for 2h; Stage #2: (R)-4-(phenylmethyl)-2-oxazolidinone With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 2.58333h;	Intermediate 35A. (R)-4-Benzyl-3-((R)-2-methylbut-3-enoyl)oxazolidin-2- one: To the solution of 2-methylbut-3-enoic acid (5.59 g, 55.9 mmol) and N- methylmorpholine (6.14 ml, 55.9 mmol) in THF (62 mL) at 0 °C was added pivaloyl chloride (6.87 ml, 55.9 mmol) dropwise. The reaction mixture was cooled down to -78 °C, and stirred for ~2 h. In a separate flask: To the solution of (R)-4-benzyloxazolidin-2- one (8.25 g, 46.6 mmol) in THF (126 mL) at -78 °C was added N-butyllithium (2.5 M in hexane) (20.49 mL, 51.2 mmol) dropwise. After 35 min, this reaction was transferred via cannula to the first reaction. The reaction mixture was stirred at -78 °C for 2 h, then the cold bath was removed, and the reaction was quenched with saturated NH4C1. The reaction was diluted with water and extracted with EtOAc (3x). The combined organic layers were washed with brine, dried over Na2S04, filtered, and concentrated to give a yellow oil (15 g). Purification by silica gel chromatography afforded the desired product (6.59 g, 55%) as a colorless oil. MS (ESI) m/z: 282.1 (M+Na)+. 1H NMR (500 MHz, CDCls) δ 7.36 - 7.19 (m, 5H), 6.03 - 5.93 (m, 1H), 5.23 - 5.10 (m, 2H), 4.69 - 4.63 (m, 1H), 4.51 - 4.43 (m, 1H), 4.23 - 4.15 (m, 2H), 3.29 (dd, J = 13.5, 3.3 Hz, 1H), 2.79 (dd, J = 13.5, 9.6 Hz, 1H), 1.35 (d, J = 6.9 Hz, 3H) ppm. The other diastereomer (R)-4-benzyl- 3-((S)-2-methylbut-3-enoyl)oxazolidin-2-one (4.6 g, 38%) also obtained as a white solid. MS (ESI) m/z: 260.1 (M+H)+.
1: 55% 2: 38%	Stage #1: 2-methylbut-3-enoic acid With 4-methyl-morpholine; pivaloyl chloride In tetrahydrofuran at -78 - 0℃; Stage #2: (R)-4-(phenylmethyl)-2-oxazolidinone With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 2h;	[00417] Intermediate 45A. (R)-4-Benzyl-3-((R)-2-methylbut-3-enoyl)oxazolidin-2- one: To the solution of 2-methylbut-3 -enoic acid (5.59 g, 55.9 mmol) and N- methylmorpholine (6.14 ml, 55.9 mmol) in THF (62 mL) at 0 °C was added pivaloyl chloride (6.87 ml, 55.9 mmol) dropwise. The reaction mixture was cooled down to -78 °C, and stirred for ~2 h. In a separate flask: To the solution of (R)-4-benzyloxazolidin-2- one (8.25 g, 46.6 mmol) in THF (126 mL) at -78 °C was added dropwise N-butyllithium (2.5 M in hexane) (20.49 mL, 51.2 mmol). After 35 min, this reaction was transferred via cannula to the first reaction. The reaction mixture was stirred at -78 °C for 2 h, then the cold bath was removed, and the reaction was quenched with saturated NH4CI. The reaction was diluted with water and extracted with EtOAc (3x). The combined organic layers were washed with brine, dried over Na2S04, filtered, and concentrated to give a yellow oil (15 g). Purification by silica gel chromatography afforded the desired product (6.59 g, 55%) as a colorless oil. MS(ESI) m/z: 282.1 (M+Na)+. 1H NMR (500 MHz, CDCI3) δ 7.36 - 7.19 (m, 5H), 6.03 - 5.93 (m, 1H), 5.23 - 5.10 (m, 2H), 4.69 - 4.63 (m, 1H), 4.51 - 4.43 (m, 1H), 4.23 - 4.15 (m, 2H), 3.29 (dd, J = 13.5, 3.3 Hz, 1H), 2.79 (dd, J = 13.5, 9.6 Hz, 1H), 1.35 (d, J = 6.9 Hz, 3H) ppm. The other diastereomer (R)-4-benzyl- 3-((S)-2-methylbut-3-enoyl)oxazolidin-2-one (4.6 g, 38%) also obtained as a white solid. MS(ESI) m/z: 260.1 (M+H)+.
1: 55% 2: 38%	Stage #1: 2-methylbut-3-enoic acid With 4-methyl-morpholine; pivaloyl chloride In tetrahydrofuran at -78 - 0℃; for 2h; Stage #2: (R)-4-(phenylmethyl)-2-oxazolidinone With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 2.58333h;	2A 2A. Preparation of (R)-4-benzyl-3 -((R)-2-methylbut-3 -enoyl)oxazolidin-2-one To the solution of 2-methylbut-3-enoic acid (5.59 g, 55.9 mmol) and NMM (6.14mL, 55.9 mmol) in THF (62 mL) at 0 °C was added pivaloyl chloride (6.87 mL, 55.9mmol) dropwise. The reaction mixture was cooled down to -78 °C, and stirred for 2 h.In a separate flask: To the solution of (R)-4-benzyloxazolidin-2-one (8.25 g, 46.6 mmol)in THF (126 mL) at -78 °C was added 2.5 M nBuLi in hexane (20.49 mL, 51.2 mmol)dropwise. After 35 mm, this reaction was transferred via cannula to the first reaction. The reaction mixture was stirred at -78 °C for 2 h, then the cold bath was removed, and the reaction was quenched with sat NH4C1. The reaction was diluted with water and extracted with EtOAc (3x). The combined organic layers were washed with brine, driedover Na2SO4, filtered, and concentrated to give a yellow oil (15 g). Purification by silica gel chromatography afforded (R)-4-benzyl-3 -((R)-2-methylbut-3 -enoyl)oxazolidin-2-one (6.59 g, 55%) as a colorless oil. MS(ESI) m/z: 282.1 (M+Na). ‘H NMR (500 MHz, CDC13) ö 7.36 - 7.19 (m, 5H), 6.03 - 5.93 (m, 1H), 5.23 - 5.10 (m, 2H), 4.69 - 4.63 (m, 1H), 4.51 -4.43 (m, 1H), 4.23-4.15 (m, 2H), 3.29 (dd, J 13.5, 3.3 Hz, 1H), 2.79 (dd, J= 13.5, 9.6 Hz, 1H), 1.35 (d, J= 6.9 Hz, 3H) ppm. The other diastereomer (R)-4-benzyl-3-((S)-2-methylbut-3-enoyl)oxazolidin-2-one (4.6 g, 38%) was also obtained as a white solid. MS(ESI) m/z: 260.1 (M+H).

1: 55% 2: 38%	Stage #1: 2-methylbut-3-enoic acid With 4-methyl-morpholine; pivaloyl chloride In tetrahydrofuran at -78 - 0℃; for 2h; Stage #2: (R)-4-(phenylmethyl)-2-oxazolidinone With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 2.5h;	6A 6A. Preparation of (R)-4-benzyl-3-((R)-2-methylbut-3-enoyl)oxazolidin-2-one To the solution of 2-methylbut-3-enoic acid (5.59 g, 55.9 mmol) and NMM (6.14 ml, 55.9 mmol) in THF (62 mL) at 0 °C was added pivaloyl chloride (6.87 ml, 55.9 mmol) dropwise. The reaction mixture was cooled to -78 °C, and stirred for ~2 h. In a separate flask: To the solution of (R)-4-benzyloxazolidin-2-one (8.25 g, 46.6 mmol) in THF (126 mL) at -78 °C was added 2.5 M nBuLi in hexane (20.49 mL, 51.2 mmol) dropwise. After 35 min, this reaction was transferred via cannula to the first reaction. The reaction mixture was stirred at -78 °C for 2 h, then the cold bath was removed, and the reaction was quenched with sat NH4C1. The reaction was diluted with water and extracted with EtOAc (3x). The combined organic layers were washed with brine, dried over Na2S04, filtered, and concentrated to give a yellow oil (15 g). Purification by silica gel chromatography afforded (R)-4-benzyl-3-((R)-2-methylbut-3-enoyl)oxazolidin-2-one (6.59 g, 55%) as a colorless oil. MS(ESI) m/z: 282.1 (M+Na)+. XH NMR (500 MHz, CDCI3) δ 7.36 - 7.19 (m, 5H), 6.03 - 5.93 (m, 1H), 5.23 - 5.10 (m, 2H), 4.69 - 4.63 (m, 1H), 4.51 - 4.43 (m, 1H), 4.23 - 4.15 (m, 2H), 3.29 (dd, J = 13.5, 3.3 Hz, 1H), 2.79 (dd, J = 13.5, 9.6 Hz, 1H), 1.35 (d, J = 6.9 Hz, 3H) ppm. The other diastereomer (R)-4-benzyl- 3-((S)-2-methylbut-3-enoyl)oxazolidin-2-one (4.6 g, 38%) also was obtained as a white solid. MS(ESI) m/z: 260.1 (M+H)+.
1: 55% 2: 38%	Stage #1: 2-methylbut-3-enoic acid With 4-methyl-morpholine; pivaloyl chloride In tetrahydrofuran at -78 - 0℃; Stage #2: (R)-4-(phenylmethyl)-2-oxazolidinone With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1.58333h;	1A 1 A. Preparation of (R)-4-Benzyl-3 -((R)-2-methylbut-3 -enoyl)oxazolidin-2-one To the solution of 2-methylbut-3-enoic acid (5.59 g, 55.9 mmol) and NMM (6.14ml, 55.9 mmol) in THF (62 ml) at 0 °C was added pivaloyl chloride (6.87 ml, 55.9 mmol) dropwise. The reaction mixture was cooled to -78 °C, and stirred for 2 h. In aseparate flask: To a solution of (R)-4-benzyloxazolidin-2-one (8.25 g, 46.6 mmol) in THF (126 ml) at -78 °C was added 2.5 M n-BuLi in hexane (20.49 ml, 51.2 mmol) dropwise. After 35 mm, this reaction was transferred via cannula to the first reaction. The reaction mixture was stirred at -78 °C for 2 h, then the cold bath was removed, and the reaction was quenched with sat NH4C1. The reaction was diluted with water andextracted with EtOAc (3 x). The combined organic layers were washed with brine, dried over Na2SO4, filtered, and concentrated to give a yellow oil (15 g). Purification by silica gel chromatography afforded(R)-4-b enzyl-3 -((R)-2-methylbut-3 -enoyl)oxazolidin-2-one (6.59 g, 55%) as a colorless oil. MS (ESI) m/z: 282.1 (M+Na)t ‘HNMR (500 IVIFIz, CDC13) ö 7.36-7.19 (m,5H), 6.03 - 5.93 (m, 1H), 5.23 - 5.10 (m, 2H), 4.69 -4.63 (m, 1H), 4.51 -4.43 (m, 1H),4.23 -4.15 (m, 2H), 3.29 (dd, J 13.5, 3.3 Hz, 1H), 2.79 (dd, J 13.5, 9.6 Hz, 1H),1.35 (d, J 6.9 Hz, 3H) ppm. The other diastereomer(R)-4-b enzyl-3 -((S)-2-methylbut-3 -enoyl)oxazolidin-2-one (4.6 g, 38%) also obtainedas a white solid. MS (ESI) m/z: 260.1 (M+H)+
1: 50% 2: 43%	Stage #1: 2-methylbut-3-enoic acid With 4-methyl-morpholine; pivaloyl chloride In tetrahydrofuran at -78 - 0℃; for 2h; Stage #2: (R)-4-(phenylmethyl)-2-oxazolidinone With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 2h; Inert atmosphere;

Reference： [1]Current Patent Assignee: BRISTOL-MYERS SQUIBB CO - WO2013/22814, 2013, A1 Location in patent: Paragraph 00359
[2]Current Patent Assignee: BRISTOL-MYERS SQUIBB CO - WO2013/22818, 2013, A1 Location in patent: Paragraph 00417
[3]Current Patent Assignee: BRISTOL-MYERS SQUIBB CO - WO2015/116886, 2015, A1 Location in patent: Page/Page column 148; 149
[4]Current Patent Assignee: BRISTOL-MYERS SQUIBB CO - WO2015/116882, 2015, A1 Location in patent: Page/Page column 80; 81
[5]Current Patent Assignee: BRISTOL-MYERS SQUIBB CO - WO2016/205482, 2016, A1 Location in patent: Page/Page column 86
[6]Corte, James R.; Pinto, Donald J. P.; Fang, Tianan; Osuna, Honey; Yang, Wu; Wang, Yufeng; Lai, Amy; Clark, Charles G.; Sun, Jung-Hui; Rampulla, Richard; Mathur, Arvind; Kaspady, Mahammed; Neithnadka, Premsai Rai; Li, Yi-Xin Cindy; Rossi, Karen A.; Myers, Joseph E.; Sheriff, Steven; Lou, Zhen; Harper, Timothy W.; Huang, Christine; Zheng, Joanna J.; Bozarth, Jeffrey M.; Wu, Yiming; Wong, Pancras C.; Crain, Earl J.; Seiffert, Dietmar A.; Luettgen, Joseph M.; Lam, Patrick Y. S.; Wexler, Ruth R.; Ewing, William R. [Journal of Medicinal Chemistry, 2020, vol. 63, # 2, p. 784 - 803]

71
[ 53774-20-2 ]
[ 1422387-07-2 ]
[ 1422387-08-3 ]

Yield	Reaction Conditions	Operation in experiment
83%	With 2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphosphinane-2,4,6-trioxide; N-ethyl-N,N-diisopropylamine In ethyl acetate at -10 - 20℃; Inert atmosphere;	11.11G 11G. tert-Butyl N-[(lS)-l-(2-fluoro-5-{4-[(methoxycarbonyl)amino]-2-(2- methylbut-3-enamido)phenyl}pyridin-3-yl)but-3-en-l-yl]carbamate: To a solution of 2- methylbut-3-enoic acid (0.216 mL, 2.091 mmol) and 1 IF (0.900 g, 2.091 mmol) in EtOAc (59.7 mL) was added DIEA (1.095 mL, 6.27 mmol) and the reaction was allowed to cool to -10 °C under argon. To this mixture was added 1-propanephosphonic acid cyclic anhydride in EtOAc (2.464 mL, 4.18 mmol) and the reaction was allowed to stir for 5 min, and then warmed to 0 °C while stirring under argon. The reaction was then slowly allowed to warm to rt and stirred at rt overnight. After overnight stirring, the reaction mixture was concentrated and purified by silica gel chromatography to give 11G (887 mg, 83%) as a white solid. MS (ESI) m/z: 513.1 (M+H)+.
83%	With 2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphosphinane-2,4,6-trioxide; N-ethyl-N,N-diisopropylamine In ethyl acetate at -10 - 20℃; Inert atmosphere;	1.1G [00440] 1G. Methyl (4-(5-((lS)-l-((fert-butoxycarbonyl)amino)but-3-en-l-yl)-6- fluoropyridin-3-yl)-3-((2-methylbut-3-enoyl)amino)phenyl)carbamate: To a solution of 2-methylbut-3-enoic acid (0.216 mL, 2.091 mmol) and IF (0.900 g, 2.091 mmol) in EtOAc (59.7 mL) was added DIEA (1.095 mL, 6.27 mmol) and the reaction was allowed to cool to -10 °C under argon. To this mixture was then added T3P (2.464 mL, 4.18 mmol) and the reaction was allowed to stir for 5 min at the same temperature and then allowed to warm to 0 °C followed by to rt slowly while stirring under argon at rt. After overnight stirring, the reaction mixture was concentrated and purified by silica gel chromatography to give 1G (887 mg, 83%) as a white solid. MS(ESI) m/z: 513.1 (M+H)+.
83%	With 2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphosphinane-2,4,6-trioxide; N-ethyl-N,N-diisopropylamine In ethyl acetate at -10 - 20℃; Inert atmosphere;

Reference： [1]Current Patent Assignee: BRISTOL-MYERS SQUIBB CO - WO2013/22814, 2013, A1 Location in patent: Paragraph 00432
[2]Current Patent Assignee: BRISTOL-MYERS SQUIBB CO - WO2013/22818, 2013, A1 Location in patent: Paragraph 00440
[3]Yang, Wu; Wang, Yufeng; Lai, Amy; Clark, Charles G.; Corte, James R.; Fang, Tianan; Gilligan, Paul J.; Jeon, Yoon; Pabbisetty, Kumar B.; Rampulla, Richard A.; Mathur, Arvind; Kaspady, Mahammed; Neithnadka, Premsai Rai; Arumugam, Arunachalam; Raju, Sivashankaran; Rossi, Karen A.; Myers, Joseph E.; Sheriff, Steven; Lou, Zhen; Zheng, Joanna J.; Chacko, Silvi A.; Bozarth, Jeffrey M.; Wu, Yiming; Crain, Earl J.; Wong, Pancras C.; Seiffert, Dietmar A.; Luettgen, Joseph M.; Lam, Patrick Y. S.; Wexler, Ruth R.; Ewing, William R. [Journal of Medicinal Chemistry, 2020, vol. 63, # 13, p. 7226 - 7242]

72
[ 53774-20-2 ]
[ 1329171-26-7 ]
methyl N-(4-{2-[(1S)-1-[(tert-butoxy)carbonyl]amino}but-3-en-1-yl]pyridin-4-yl}-3-(2-methylbut-3-enamido)phenyl)carbamate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
72%	With 2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphosphinane-2,4,6-trioxide; N-ethyl-N,N-diisopropylamine In ethyl acetate at -10 - 0℃; for 7h;	12.12I 121. Methyl N-(4- {2- [( 1 S)- 1 - { [(tert-butoxy)carbonyl] amino } but-3 -en- 1 - yl]pyridin-4-yl}-3-(2-methylbut-3-enamido)phenyl)carbamate: To a cooled solution (-10 °C) of 2-methylbut-3-enoic acid (0.456 mL, 4.41 mmol) and 12H (1.82 g, 4.41 mmol) in EtOAc (126 mL) and DIEA (2.312 mL, 13.24 mmol) was added dropwise a solution of 1- propanephosphonic acid cyclic anhydride in EtOAc (5.20 mL, 8.82 mmol). After 5 min, the reaction was allowed to warm to 0 °C. After 7 h, the reaction was stopped and concentrated. Purification by normal phase chromatography gave 121 (1.57 g, 72%) as a mixture of diastereomers and as a yellow solid. MS (ESI) m/z: 495.1 (M+H)+.
72%	With 2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphosphinane-2,4,6-trioxide; N-ethyl-N,N-diisopropylamine In ethyl acetate at -10 - 0℃; for 7h;	2.2I [00452] 21. Methyl N-(4-{2-[(lS)-l-[(tert-butoxy)carbonyl]amino}but-3-en-l- yl]pyridin-4-yl}-3-(2-methylbut-3-enamido)phenyl)carbamate (Diastereomers): To a cooled solution (-10 °C) of 2-methylbut-3-enoic acid (0.456 mL, 4.41 mmol) and 2H (1.82 g, 4.41 mmol) in EtOAc (126 mL) and DIEA (2.312 mL, 13.24 mmol) was added dropwise a solution of 1-propanephosphonic acid cyclic anhydride in EtOAc (5.20 mL, 8.82 mmol). After 5 min, the reaction was allowed to warm to 0 °C. After 7 h, the reaction was stopped and concentrated. Purification by normal phase chromatography gave 21 (1.57 g, 72%>) as a mixture of diastereomers and as a yellow solid. MS(ESI) m/z: 495.1 (M+H)+.

Reference： [1]Current Patent Assignee: BRISTOL-MYERS SQUIBB CO - WO2013/22814, 2013, A1 Location in patent: Paragraph 00444
[2]Current Patent Assignee: BRISTOL-MYERS SQUIBB CO - WO2013/22818, 2013, A1 Location in patent: Paragraph 00452

73
[ 53774-20-2 ]
[ 1422387-82-3 ]
[ 1422387-83-4 ]

Yield	Reaction Conditions	Operation in experiment
83%	With 2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphosphinane-2,4,6-trioxide; N-ethyl-N,N-diisopropylamine In ethyl acetate at -10 - 20℃; for 49h; Inert atmosphere;	27.27J 27J. Methyl N-(4-{2-[(lS)-l-[(tert-butoxy)carbonyl]amino}but-3-en-l-yl]- 6-methoxypyridin-4-yl}-3-(2-methylbut-3-enamido)phenyl)carbamate: DIPEA (3.02 mL, 17.29 mmol) was added to a solution of 2-methylbut-3-enoic acid (0.865 g, 8.64 mmol) and 271 (2.55 g, 5.76 mmol) in EtOAc (57.6 ml) at -10 °C under argon. Next, 1- propanephosphonic acid cyclic anhydride (6.79 ml, 11.53 mmol; 50% solution in EtOAc) was added dropwise and the reaction stirred for 1 h under set conditions and then allowed to come to rt. After 48 hours, the reaction was diluted with EtOAc, washed with saturated NaHC03, brine, dried over Na2S04, filtered, and concentrated. Purification by normal phase chromatography gave the desired product (2.52 g, 83%) as a white solid. MS (ESI) m/z: 525.1 (M+H)+.
83%	Stage #1: 2-methylbut-3-enoic acid; methyl N-(3-amino-4-{2-[(1S)-1-[(tert-butoxy)carbonyl]amino}but-3-en-1-yl]-6-methoxypyridin-4-yl}phenyl)carbamate With N-ethyl-N,N-diisopropylamine In ethyl acetate at -10℃; Inert atmosphere; Stage #2: With 2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphosphinane-2,4,6-trioxide In ethyl acetate at -10 - 20℃; for 49h; Inert atmosphere;	5.5J methyl N-(4-{2-[(1S)-1-[(tert-butoxy)carbonyl]amino}but-3-en-1-yl]-6-methoxypyridin-4-yl}-3-(2-methylbut-3-enamido)phenyl)carbamate DIPEA (3.02 mL, 17.29 mmol) was added to a solution of 2-methylbut-3-enoic acid (0.865 g, 8.64 mmol) and 5I (2.55 g, 5.76 mmol) in EtOAc (57.6 ml) at -10 °C under argon. Next, 1-propanephosphonic acid cyclic anhydride (6.79 ml, 11.53 mmol; 50% solution inEtOAc) was added dropwise and the reaction stirred for 1 h under set conditions and then allowed to come to rt. After 48 hours, the reaction was diluted withEtOAc, washed with sat. aq. 5 NaHCO3,brine, dried over Na2SO4, filtered, and concentrated. Purification by normalphase chromatography gave 5J (2.52 g, 83%) as a white solid.

Reference： [1]Current Patent Assignee: BRISTOL-MYERS SQUIBB CO - WO2013/22814, 2013, A1 Location in patent: Paragraph 00511
[2]Current Patent Assignee: BRISTOL-MYERS SQUIBB CO - JP2015/528022, 2015, A Location in patent: Paragraph 0350

74
[ 53774-20-2 ]
[ 1329171-26-7 ]
[ 1422387-23-2 ]

Yield	Reaction Conditions	Operation in experiment
81%	With 2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphosphinane-2,4,6-trioxide; N-ethyl-N,N-diisopropylamine In ethyl acetate at -78 - 20℃; Inert atmosphere;	21.21A [00467] 21A. Methyl (3-(but-3-enoylamino)-4-(2-((lS)-l-((tert- butoxycarbonyl)amino)but-3-en-l-yl)pyridin-4-yl)phenyl)carbamate: To a solution of but-3-enoic acid (0.412 mL, 4.85 mmol) in EtOAc (100 mL) was added DIEA (2.54 mL, 14.55 mmol) and 2G (2 g, 4.85 mmol) and the reaction mixture was allowed to cooled to -78 °C under argon. To this mixture was then added T3P (5.71 mL, 9.70 mmol) and the reaction was allowed to stir for 15 min at the same temperature and the reaction temperature was gradually warmed to rt and stirred at rt for overnight. After stirring for overnight at rt, the reaction mixture was concentrated to yield dark brown oil which was purified using silica gel chromatography to yield the desired product (1.88 g, 81%) as a white solid. MS(ESI) m/z: 481.2 (M+H)+.

Reference： [1]Current Patent Assignee: BRISTOL-MYERS SQUIBB CO - WO2013/22818, 2013, A1 Location in patent: Paragraph 00467

75
[ 53774-20-2 ]
[ 1422388-52-0 ]
[ 1422387-37-8 ]

Yield	Reaction Conditions	Operation in experiment
38%	Stage #1: 2-methylbut-3-enoic acid With 4-methyl-morpholine; isobutyl chloroformate In tetrahydrofuran at 0℃; for 3h; Inert atmosphere; Stage #2: methyl N-(3-amino-4-(6-((1S)-1-((tert-butoxycarbonyl)amino)but-3-en-1-yl)-2-oxo-1,2-dihydropyridin-4-yl)phenyl)carbamate In N,N-dimethyl-formamide at 20℃; for 72h;	29.29I [00505] 291. Methyl (4-(6-((lS)-l-((tert-butoxycarbonyl)amino)but-3-en-l-yl)-2-oxo- l,2-dihydropyridin-4-yl)-3-((2-methylbut-3-enoyl)amino)phenyl)carbamate: Isobutyl chloro formate (0.956 g, 7.00 mmol) was added to 2-methylbut-3-enoic acid (0.701 g, 7.00 mmol) and 4-methylmorpholine (0.770 mL, 7.00 mmol) in THF (33.3 mL) at 0 °C under a nitrogen atmosphere and stirred for 3 h. The resulting solids were filtered off and the filtrate was used directly for next step. To a round bottom flask containing the mixed anhydride, 29H (0.200 g, 0.467 mmol) and 4-methylmorpholine (0.770 ml, 7.00 mmol) in DMF (6 mL) was added portionwise (1 mL) every ten minutes over 1 h. The reaction mixture was then stirred at rt. After 3 d, the reaction mixture was partitioned between EtOAc and 1.0 NaOH (20 mL). The organic layer was washed with 1.0 N NaOH, H20, 1.0 N HC1 solution, H20, and brine. The organic layer was dried, filtered and concentrated. The crude product was again dissolved in THF (20 mL) and treated with NaOH (10 mL, 10.00 mmol). After stirring for 1 h, the reaction mixture was concentrated and purified using reverse phase HPLC to give the desired product (0.09 g, 38%). MS(ESI) m/z: 511.4 (M+H)+.

Reference： [1]Current Patent Assignee: BRISTOL-MYERS SQUIBB CO - WO2013/22818, 2013, A1 Location in patent: Paragraph 00505

76
[ 124-38-9 ]
[ 75851-67-1 ]
[ 53774-20-2 ]

Yield	Reaction Conditions	Operation in experiment
62%	Stage #1: carbon dioxide; 4,4,5,5-tetramethyl-2-(1-methyl-2-propenyl)-1,3,2-dioxaborolane With chloro[1,3-bis(2,6-di-i-propylphenyl)imidazol-2-ylidene]copper(I); potassium <i>tert</i>-butylate In tetrahydrofuran at 70℃; for 16h; Inert atmosphere; Sealed tube; Stage #2: With hydrogenchloride In tetrahydrofuran Inert atmosphere; Sealed tube; regioselective reaction;

Reference： [1]Duong, Hung A.; Huleatt, Paul B.; Tan, Qian-Wen; Shuying, Eileen Lau [Organic Letters, 2013, vol. 15, # 15, p. 4034 - 4037]

77
[ 124-38-9 ]
[ 69611-02-5 ]
[ 53774-20-2 ]

Yield	Reaction Conditions	Operation in experiment
79%	Stage #1: carbon dioxide; (E)-2-(but-2-enyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane With chloro[1,3-bis(2,6-di-i-propylphenyl)imidazol-2-ylidene]copper(I); potassium <i>tert</i>-butylate In tetrahydrofuran at 70℃; for 16h; Inert atmosphere; Sealed tube; Stage #2: With hydrogenchloride In tetrahydrofuran Inert atmosphere; Sealed tube; regioselective reaction;

Reference： [1]Duong, Hung A.; Huleatt, Paul B.; Tan, Qian-Wen; Shuying, Eileen Lau [Organic Letters, 2013, vol. 15, # 15, p. 4034 - 4037]

78
[ 53774-20-2 ]
C₂₆H₃₅N₅O₄ [ No CAS ]
C₃₁H₄₁N₅O₅ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
259 mg	With benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In acetonitrile at 20℃; for 16h; Inert atmosphere;	20 To 19a (390 mg, 0.67 mmol) in anhydrous dichloromethane (7 ml.) at 0°C and under an atmosphere of nitrogen, was added trimethylsilyl trifluoromethanesulfonate (182 μΙ_, 1.01 mmol). The reaction mixture was stirred at 0°C for 1 hour before quenching with a saturated aqueous solution of sodium hydrogen carbonate and extracting with ethyl actate (2 x). The organic layers were dried over sodium sulfate, filtered and concentrated in vacuo to afford a white solid. The solid was dissolved in anhydrous acetonitrile (4 mL) and 2-methyl-but-3-enoic acid (81 mg, 0.81 mmol), /V-(3-dimethylaminopropyl)-/V'-ethylcarbodiimide hydrochloride (184 mg, 0.94 mmol) and 1-hydroxybenzotriazole monohydrate (103 mg, 0.67 mmol) were added. The reaction was stirred at RT for 16 h and concentrated in vacuo. The residue was purified by silica gel chromatography using /'so-hexanes/ethyl acetate 1 :1 then 1 :3 to give the title compound (259 mg, 69 %) as a clear viscous oil

Reference： [1]Current Patent Assignee: CYPRALIS LTD - WO2013/185103, 2013, A1 Location in patent: Page/Page column 108; 109

79
[ 14660-45-8 ]
[ 75851-67-1 ]
[ 53774-20-2 ]

Yield	Reaction Conditions	Operation in experiment
62%	With chloro[1,3-bis(2,6-di-i-propylphenyl)imidazol-2-ylidene]copper(I) In tetrahydrofuran at 70℃; for 16h; Inert atmosphere; Sealed tube;	Carboxylation of Allylboronic Pinacol Esters with PMC; GeneralProcedure (Scheme 1) General procedure: In a glovebox, Cu(IPr)Cl (9 mg, 0.02 mmol, 5 mol%) and PMC(45 mg, 0.39 mmol, 1.1 equiv) were charged to a glass reactiontube. A solution of 1 (0.36 mmol) in THF (1 mL) was added, the tube was sealed, taken out of the glovebox, and heated at 70 °C for16 h. After cooling to r.t., H2O (2 mL) was added and the reaction mixture was acidified with aqueous HCl (1 M), and saturated with sodium chloride. After extraction with Et2O (3 × 3 mL), the organic phase was dried over anhydrous sodium sulfate and concentrated under vacuo. The product was purified by silica gel column chromatography.

Reference： [1]Duong, Hung A.; Nguyen, Tuan Minh; Rosman, Nurul Zubaidah Binte; Tan, Lionel Jia Liang [Synthesis, 2014, vol. 46, # 14, p. 1881 - 1885]

80
[ 53774-20-2 ]
(S)-tert-butyl (1-(4-(4-amino-1-(difluoromethyl)-1H-pyrazol-5-yl)pyridin-2-yl)but-3-en-1-yl)carbamate [ No CAS ]
tert-butyl ((1S)-1-(4-(1-(difluoromethyl)-4-(2-methylbut-3-enamido)-1H-pyrazol-5-yl)pyridin-2-yl)but-3-en-1-yl)carbamate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
74%	With pyridine; 2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphosphinane-2,4,6-trioxide In water; ethyl acetate at 20℃; for 20.5h; Inert atmosphere;	135A 13 5A. Preparation of tert-butyl ((15)-i -(4-( 1 -(difluoromethyl)-4-(2-methylbut-3 - enamido)- 1 H-pyrazol-5 -yl)pyridin-2-yl)but-3 -en-i -yl)carbamate To a N2 flushed, 3-necked, 250 mL RBF was added a solution of (S)-tert-butyl (1- (4-(4-amino- 1 -(difluoromethyl)- 1H-pyrazol-5 -yl)pyridin-2-yl)but-3 -en-i -yl)carbamate (1.8 g, 4.74 mmol), prepared as described in Intermediate 30C, and EtOAc (20 mL). The solution was cooled to -10 °C and (±)-2-methylbut-3-enoic acid (0.475 g, 4.74 mmol), pyridine (0.767 mL, 9.49 mmol), and T3P (4.24 mL, 7.12 mmol) were added. Thecooling bath was removed and the solution was allowed to warm to rt and then stir over a period of 20 h. Water (15 mL) and EtOAc (15 mL) were added and the mixture was stirred for 30 mm. The organic phase was separated and the aqueous layer was extracted with EtOAc (30 mL). The combined organic extracts were washed with brine (50 mL), dried over Na2SO4, filtered and concentrated. Purification by normal phasechromatography eluting with a gradient of hexanes/EtOAc gave racemic tert-butyl ((iS)1 -(4-( 1 -(difluoromethyl)-4-(2-methylbut-3 -enamido)- 1 H-pyrazol-5 -yl)pyridin-2-yl)but-3 - en-i-yl)carbamate (1.7 g, 3.50 mmol, 74% yield). MS(ESI) m/z: 462.4 [M+H].

Reference： [1]Current Patent Assignee: BRISTOL-MYERS SQUIBB CO - WO2015/116886, 2015, A1 Location in patent: Page/Page column 373

81
[ 578-66-5 ]
[ 53774-20-2 ]
2-methyl-N-(quinolin-8-yl)but-3-enamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
66%	With dmap; N-[3-(N,N-dimethylamino)-propyl]-N'-ethyl-carbodiimide hydrochloride In dichloromethane at 20℃; for 16h;
43%	With N-[(dimethylamino)-3-oxo-1H-1,2,3-triazolo[4,5-b]pyridin-1-yl-methylene]-N-methylmethanaminium hexafluorophosphate In dichloromethane at 21 - 24℃; for 16h;
	With pyridine; O-(7-azabenzotriazol-1-yl)-n,n,n',n'-tetramethyluronium hexafluoro-phosphate In dichloromethane at 20℃; for 16h;

	With pyridine; N-[(dimethylamino)-3-oxo-1H-1,2,3-triazolo[4,5-b]pyridin-1-yl-methylene]-N-methylmethanaminium hexafluorophosphate In dichloromethane at 20℃;
	With pyridine; N-[(dimethylamino)-3-oxo-1H-1,2,3-triazolo[4,5-b]pyridin-1-yl-methylene]-N-methylmethanaminium hexafluorophosphate In dichloromethane at 20℃;
	With N-[(dimethylamino)-3-oxo-1H-1,2,3-triazolo[4,5-b]pyridin-1-yl-methylene]-N-methylmethanaminium hexafluorophosphate In dichloromethane at 20℃;
	With dmap; N-[3-(N,N-dimethylamino)-propyl]-N'-ethyl-carbodiimide hydrochloride In dichloromethane at 20℃;

Reference： [1]Yang, Tao; Jiang, Yi; Luo, Yixin; Lim, Joel Jun Han; Lan, Yu; Koh, Ming Joo [Journal of the American Chemical Society, 2020, vol. 142, # 51, p. 21410 - 21419]
[2]Gurak, John A.; Yang, Kin S.; Liu, Zhen; Engle, Keary M. [Journal of the American Chemical Society, 2016, vol. 138, # 18, p. 5805 - 5808]
[3]Shi, Peng; Wang, Jie; Gan, Zixu; Zhang, Jingyu; Zeng, Runsheng; Zhao, Yingsheng [Chemical Communications, 2019, vol. 55, # 71, p. 10523 - 10526]
[4]Zheng, Kewang; Xiao, Guanlin; Guo, Tao; Ding, Yalan; Wang, Chengdong; Loh, Teck-Peng; Wu, Xiaojin [Organic Letters, 2020, vol. 22, # 2, p. 694 - 699]
[5]Lu, Ming-Zhu; Loh, Teck-Peng; Luo, Haiqing; Hu, Zhengsong; Shao, Changdong; Kan, Yuhe [Organic Letters, 2020, vol. 22, # 22, p. 9022 - 9028]
[6]Guo, Li-Yun; Li, Lin; Li, Qing; Li, Yang; Liu, Yu-Tao; Ni, Yu-Qing; Pan, Fei [Advanced Synthesis and Catalysis, 2022, vol. 364, # 6, p. 1109 - 1116]
[7]Gao, Fan; Jia, Wan-Yuan; Li, Ming; Li, Yuke; Liang, Yong-Min; Qiu, Yi-Feng; Quan, Zheng-Jun; Sun, Guo-Qing; Wang, Xi-Cun; Zhao, Guo-Xiao [Organic Letters, 2022, vol. 24, # 14, p. 2738 - 2743]

82
[ 53774-20-2 ]
ethyl 2-(4-(2-amino-4-nitrophenyl)pyridin-2-yl)pent-4-enoate [ No CAS ]
ethyl 2-(4-(2-(2-methylbut-3-enamido)-4-nitrophenyl)pyridin-2-yl)pent-4-enoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With 2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphosphinane-2,4,6-trioxide; N-ethyl-N,N-diisopropylamine In ethyl acetate at 20℃;	15.D STEP D: ethyl 2-(4-(2-(2-methylbut-3 -enamido)-4-nitrophenyl)pyridin-2-yl)pent-4-enoate To a stirred solution of ethyl 2-(4-(2-amino-4-nitrophenyl)pyridin-2-yl)pent-4-enoate (1.6 g, 4.69 mmol) in ethyl acetate (18.03 ml) was added 2-methyl-3-butenoic acid (0.700 ml, 6.09 mmol),T3P (5.58 ml, 9.37 mmol) and DIPEA (2.456 ml, 14.06 mmol) at RT. The reaction mixture was stirred at RT overnight. The reaction mixture was diluted with EtOAc and the organi layer was washed with sat. NaHCO3, dired over MgSO4, filtered and concentrated. The cmde product was purified by flash column chromatography on silica gel (EtOAc/Hex = i/i) to give the title compound. LC/MS = 423.91 [M+i]

Reference： [1]Current Patent Assignee: MERCK & CO INC - WO2017/74833, 2017, A1 Location in patent: Page/Page column 61; 62

83
[ 53774-20-2 ]
C₃₁H₄₃N₅O₆ [ No CAS ]
C₃₁H₄₁N₅O₅ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
69%	Stage #1: C₃₁H₄₃N₅O₆ With trimethylsilyl trifluoromethanesulfonate In dichloromethane at 0℃; for 1h; Inert atmosphere; Stage #2: 2-methylbut-3-enoic acid With benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In acetonitrile at 20℃; for 16h;	20 To 19a (390 mg, 0.67 mmol) in anhydrous dichloromethane (7 mL) at 0° C. and under an atmosphere of nitrogen, was added trimethylsilyl trifluoromethanesulfonate (182 μL, 1.01 mmol). The reaction mixture was stirred at 0° C. for 1 hour before quenching with a saturated aqueous solution of sodium hydrogen carbonate and extracting with ethyl actate (2×). The organic layers were dried over sodium sulfate, filtered and concentrated in vacuo to afford a white solid. The solid was dissolved in anhydrous acetonitrile (4 mL) and 2-methyl-but-3-enoic acid (81 mg, 0.81 mmol), N-(3-dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride (184 mg, 0.94 mmol) and 1-hydroxybenzotriazole monohydrate (103 mg, 0.67 mmol) were added. The reaction was stirred at RT for 16 h and concentrated in vacuo. The residue was purified by silica gel chromatography using iso-hexanes/ethyl acetate 1:1 then 1:3 to give the title compound (259 mg, 69%) as a clear viscous oil.

Reference： [1]Current Patent Assignee: CYPRALIS LTD - US2017/190737, 2017, A1 Location in patent: Paragraph 0313

84
[ 53774-20-2 ]
[ 20781-20-8 ]
N-(2,4-dimethoxybenzyl)-2-methylbut-3-enamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
80%	Stage #1: 2-methylbut-3-enoic acid; 2,4-Dimethoxybenzylamine With N-[(dimethylamino)-3-oxo-1H-1,2,3-triazolo[4,5-b]pyridin-1-yl-methylene]-N-methylmethanaminium hexafluorophosphate In dichloromethane at 20℃; for 0.05h; Stage #2: With pyridine In dichloromethane at 20℃; for 12h;

Reference： [1]Derosa, Joseph; Kleinmans, Roman; Tran, Van T.; Karunananda, Malkanthi K.; Wisniewski, Steven R.; Eastgate, Martin D.; Engle, Keary M. [Journal of the American Chemical Society, 2018, vol. 140, # 51, p. 17878 - 17883]

85
[ 53774-20-2 ]
[ 32231-50-8 ]
[ 1730-91-2 ]

Reference： [1]Chemistry - A European Journal,2019,vol. 25,p. 5071 - 5076

86
[ 13201-46-2 ]
[ 53774-20-2 ]

Yield	Reaction Conditions	Operation in experiment
96%	With n-butyllithium; diisopropylamine In tetrahydrofuran; hexane at -78 - 30℃; for 2h;	B.1 Step 1 Preparation of 2-methylbut-3-enoic acid (SM-2-2): At -78 deg.] C solution of diisopropylamine (194mL, 1.38mol) was dissolved in tetrahydrofuran (750mL), was added n-butyllithium (500mL, 2.5M in hexanes, 1.25mol), -78 deg.] C maintaining the reaction 1h, was then added SM-2-1 (50.0g, 499mmol) in tetrahydrofuran (250 mL) was stirred at rt for 2h.After handled SM-2-2 (48g, 96%).

Reference： [1]Current Patent Assignee: SICHUAN KELUN PHARMACEUTICAL COMPANY LIMITED - CN109721613, 2019, A Location in patent: Paragraph 0212-0215

87
[ 563-52-0 ]
[ 124-38-9 ]
[ 5204-64-8 ]
[ 53774-20-2 ]

Yield	Reaction Conditions	Operation in experiment
	With tetraethylammonium chloride; magnesium In acetonitrile at 0℃; Electrochemical reaction; Overall yield = 48 percentChromat.; regioselective reaction;

Reference： [1]Wu, La-Xia; Zhao, Ying-Guo; Guan, Ye-Bin; Wang, Hui; Lan, Yang-Chun; Wang, Huan; Lu, Jia-Xing [RSC Advances, 2019, vol. 9, # 56, p. 32628 - 32633]

88
[ 53774-20-2 ]
[ 39657-45-9 ]
1-(2-isoxazolidinyl)-2-methyl-3-buten-1-one [ No CAS ]

Reference： [1]Organic and biomolecular chemistry,2020,vol. 18,p. 1563 - 1566

Type	HazMat fee for 500 gram (Estimated)
Excepted Quantity	USD 0.00
Limited Quantity	USD 15-60
Inaccessible (Haz class 6.1), Domestic	USD 80+
Inaccessible (Haz class 6.1), International	USD 150+
Accessible (Haz class 3, 4, 5 or 8), Domestic	USD 100+
Accessible (Haz class 3, 4, 5 or 8), International	USD 200+

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CAS No. :	53774-20-2	MDL No. :	MFCD00042650
Formula :	C₅H₈O₂	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	GQWNPIKWYPQUPI-UHFFFAOYSA-N
M.W :	100.12	Pubchem ID :	143088
Synonyms :

Num. heavy atoms :	7
Num. arom. heavy atoms :	0
Fraction Csp3 :	0.4
Num. rotatable bonds :	2
Num. H-bond acceptors :	2.0
Num. H-bond donors :	1.0
Molar Refractivity :	27.45
TPSA :	37.3 Å²

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) :	-6.12 cm/s

[ CAS No. 53774-20-2 ] {[proInfo.proName]}

Quality Control of [ 53774-20-2 ]

Related Doc. of [ 53774-20-2 ]

Product Details of [ 53774-20-2 ]

Calculated chemistry of [ 53774-20-2 ]

Physicochemical Properties

Pharmacokinetics

Lipophilicity

Druglikeness

Water Solubility

Medicinal Chemistry

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Application In Synthesis of [ 53774-20-2 ]

[ 53774-20-2 ] Synthesis Path-Downstream 1~88

Related Functional Groups of
[ 53774-20-2 ]

Carboxylic Acids

Precautionary Statements-General

Prevention

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Log Po/w (iLOGP) :	1.22
Log Po/w (XLOGP3) :	1.11
Log Po/w (WLOGP) :	0.89
Log Po/w (MLOGP) :	0.79
Log Po/w (SILICOS-IT) :	0.34
Consensus Log Po/w :	0.87

Lipinski :	0.0
Ghose :	None
Veber :	0.0
Egan :	0.0
Muegge :	1.0
Bioavailability Score :	0.56

Log S (ESOL) :	-1.03
Solubility :	9.39 mg/ml ; 0.0938 mol/l
Class :	Very soluble
Log S (Ali) :	-1.49
Solubility :	3.27 mg/ml ; 0.0326 mol/l
Class :	Very soluble
Log S (SILICOS-IT) :	-0.06
Solubility :	87.8 mg/ml ; 0.877 mol/l
Class :	Soluble

PAINS :	0.0 alert
Brenk :	1.0 alert
Leadlikeness :	1.0
Synthetic accessibility :	2.05

Signal Word:	Danger	Class:	8
Precautionary Statements:	P210-P234-P260-P264-P280-P301+P330+P331+P310-P303+P361+P353+P310+P363-P304+P340+P310-P305+P351+P338+P310-P370+P378-P390-P403+P235-P405-P406-P501	UN#:	3265
Hazard Statements:	H227-H290-H314	Packing Group:	Ⅱ
GHS Pictogram:

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

[ CAS No. 53774-20-2 ] {[proInfo.proName]}

Quality Control of [ 53774-20-2 ]

Related Doc. of [ 53774-20-2 ]

Product Details of [ 53774-20-2 ]

Calculated chemistry of [ 53774-20-2 ]

Physicochemical Properties

Pharmacokinetics

Lipophilicity

Druglikeness

Water Solubility

Medicinal Chemistry

Safety of [ 53774-20-2 ]

Application In Synthesis of [ 53774-20-2 ]

[ 53774-20-2 ] Synthesis Path-Downstream 1~88

Related Functional Groups of [ 53774-20-2 ]

Carboxylic Acids

Precautionary Statements-General

Prevention

Response

Storage

Disposal

Physical hazards

Health hazards

Environmental hazards

Inquiry

Related Functional Groups of
[ 53774-20-2 ]