33797-51-2|N,N-Dimethylmethyleneiminium iodide| Ambeed

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1
[ 69097-20-7 ]
[ 33797-51-2 ]
[ 108010-12-4 ]

Yield	Reaction Conditions	Operation in experiment
76%	In diethyl ether for 5h; Ambient temperature;

Reference： [1]Oesterle, Thomas; Simchen, Gerhard [Liebigs Annalen der Chemie, 1987, p. 693 - 700]

2
[ 63846-76-4 ]
[ 33797-51-2 ]
[ 77256-53-2 ]

Reference： [1]Journal of Organic Chemistry,1981,vol. 46,p. 2363 - 2373

3
[ 274-56-6 ]
[ 33797-51-2 ]
3-dimethylaminomethylpyrazolo<1,5-a>pyridine [ No CAS ]

Reference： [1]Heterocycles,1994,vol. 38,p. 1881 - 1888

4
[ 33797-51-2 ]
[ 81971-99-5 ]
3-[(4Z,10Z,15Z,19Z)-8-Dimethylaminomethyl-18-(2-methoxycarbonyl-ethyl)-3,7,12,17-tetramethyl-22,24-dihydro-porphin-2-yl]-propionic acid methyl ester [ No CAS ]
3,8-bis<(dimethylamino)methyl>-13,17-bis<2-(methoxycarbonyl)ethyl>-2,7,12,18-tetramethylporphin [ No CAS ]

Reference： [1]Chemische Berichte,1995,vol. 128,p. 173 - 182

5
[ 4264-35-1 ]
[ 119219-77-1 ]
[ 33797-51-2 ]
methyl (1RS,5RS,13SR)-13-[(dimethylamino)methyl]-2-methyl-7-oxo-2,5,6,7-tetrahydro-1,5-methano-1H-azonino[4,3-b]indole-4(E)-acrylate [ No CAS ]

Reference： [1]Journal of Organic Chemistry,1997,vol. 62,p. 3597 - 3609

6
[ 2985-39-9 ]
[ 33797-51-2 ]
[ 20593-63-9 ]

Reference： [1]Heterocycles,1997,vol. 46,p. 65 - 70
[2]Organic Letters,2019,vol. 21,p. 6135 - 6139

7
[ 4630-82-4 ]
[ 33797-51-2 ]
methyl 1-(N,N-dimethylaminomethyl)cyclohexane-1-carboxylate hydrochloride [ No CAS ]

Reference： [1]Journal of the Chemical Society. Perkin Transactions 2 (2001),1997,p. 2787 - 2793

8
[ 33797-51-2 ]
[ 147503-82-0 ]
ethyl 3-N,N-dimethylaminomethyl-1H-pyrrolo<2,3-c>pyridine-5-carboxylate [ No CAS ]

Reference： [1]Bioorganic and Medicinal Chemistry,1999,vol. 7,p. 921 - 932

9
[ 39741-91-8 ]
[ 33797-51-2 ]
[ 74-88-4 ]

Yield	Reaction Conditions	Operation in experiment
	In [D₃]acetonitrile at 65℃;

Reference： [1]Fletcher, Michelle O.; Zhang, Li; Vu, Quyen; Dolbier Jr., William R. [Journal of the Chemical Society. Perkin Transactions 2 (2001), 1999, # 6, p. 1187 - 1192]

10
[ 33797-51-2 ]
[ 123-08-0 ]
[ 116546-04-4 ]

Yield	Reaction Conditions	Operation in experiment
75%	With potassium carbonate In dichloromethane
70%	With potassium carbonate In dichloromethane for 16h; Reflux;	5.1.1.58. 5-[3-(N,N-dimethylaminomethyl)-4-hydroxybenzylidene]-3-(4-methoxyphenyl)-1,3-oxazolidin-2,4-dione (12c) To a mixture of p-hydroxybenzaldehyde (1.0 g, 8.2 mmol), N,N-dimethylmethylene ammonium iodide (1.6 g, 1.0 equiv) in dichloromethane (30 mL) was added anhydrous potassium carbonate (1.7 g, 1.5 equiv). The mixture was stirred under reflux for 16 h. After cooling, the mixture was extracted with chloroform, and the organic layers was washed with brine and dried over anhydrous magnesium sulfate. After filtration, the solvent was removed in vacuo, and the residue was purified by silica gel column chromatography, eluted with chloroform/methanol (v/v = 30/1) to give 3-(N,N-dimethylaminomethyl)-4-hydroxybenzaldehyde (1.0 g, 70%); 1H NMR (400 MHz, CDCl3) δ 2.37 (s, 6H), 3.73 (s, 2H), 6.91 (d, J = 8.3 Hz, 1H), 7.54-7.55 (m, 1H), 7.70 (dd, J = 2.1, 8.3 Hz, 1H), 8.00-9.50 (brs, 1H), 9.81 (s, 1H).

Reference： [1]Zanaletti, Riccardo; Freccero, Mauro [Chemical Communications, 2002, # 17, p. 1908 - 1909]
[2]Location in patent: experimental part Harada, Koichiro; Kubo, Hideki; Abe, Jun; Haneta, Mari; Conception, Arnel; Inoue, Shinichi; Okada, Satoshi; Nishioka, Kazuhiko [Bioorganic and Medicinal Chemistry, 2012, vol. 20, # 10, p. 3242 - 3254]

11
[ 91229-91-3 ]
[ 33797-51-2 ]
[ 695188-71-7 ]

Yield	Reaction Conditions	Operation in experiment
74%	In tetrahydrofuran at -78℃;

Reference： [1]Ardá, Ana; Jiménez, Carlos; Rodríguez, Jaime [Tetrahedron Letters, 2004, vol. 45, # 16, p. 3241 - 3243]

12
[ 638-66-4 ]
[ 33797-51-2 ]
[ 852525-43-0 ]

Yield	Reaction Conditions	Operation in experiment
82%	In dichloromethane at 20℃;

Reference： [1]Mizutani, Hirotake; Watanabe, Masayuki; Honda, Toshio [Synlett, 2005, # 5, p. 793 - 796]

13
[ 33797-51-2 ]
[ 426825-75-4 ]
[ 959918-06-0 ]

Yield	Reaction Conditions	Operation in experiment
45%	In tetrahydrofuran for 24h; Heating / reflux;	INTERMEDIATE 13; 3-r(Dimethylamino)methyl1-6-iodoimidazo[l,2-(a;]pyridine; A stirred solution of 6-iodoimidazo[l,2-α]pyridine (2.0 g, 8.2 mmol) and Eschenmoser's salt (5.0 g, 2.7 mmol) in THF (50 mL) was heated to reflux for 24 h. The reaction mixture was then diluted with EtOAc (50 mL), washed with water (3 x 20 mL), dried (MgSO4), filtered and concentrated in vacuo. The residual solid was triturated from Et2O, collected by filtration and dried to give the title compound (1.1 g, 45%) as a brown powder. δH (DMSO-d6) 8.67 (IH, m), 7.45 (IH, s), 7.43-7.41 (2H, m), 3.72 (2H, s), 2.14 (6H, s). LCMS (ES+) 302.2 (M+H)+.

Reference： [1]Current Patent Assignee: UCB - WO2007/141504, 2007, A1 Location in patent: Page/Page column 52

14
[ 942195-86-0 ]
[ 33797-51-2 ]
[ 1015174-89-6 ]

Yield	Reaction Conditions	Operation in experiment
90%	Stage #1: 4-hydroxy-N N,2-trimethyl-1-[(4-methylphenyl)sulfonyl]-1H-benzimidazole-6-carboxamide; eschenmoser's salt In dichloromethane at 20 - 40℃; for 15h; Stage #2: With sodium hydrogencarbonate In dichloromethane; water	8.5 To a solution of 4-hydroxy-λ/,λ/,2-trimethyl-1-[(4-methylphenyl)sulfonyl]-1 H-benzimidazole-6-25 carboxamide (1.00 g, 2.68 mmol, Step 4) in dichloromethane (50 mL) was added/V,λ/-dimethylmethyleneiminium iodide (545 mg, 2.95 mmol) at room temperature and the mixture was stirred at 4O0C for 15 hours. The reaction was quenched by saturated sodium hydrogencarbonate aqueous solution. The mixture was extracted with dichloromethane. The organic layer was dried over sodium sulfate and concentrated in vacuo to afford the title compound as a yellow amorphous (1.04 g,30 90%).1H NMR (CDCI3, 270 MHz) δ: 7.78 (d, J = 8.6 Hz, 2H), 7.35 (s, 1 H), 7.32-7.24 (m, 2H), 3.83-3.56 (br, 2H),3.17 (s, 3H), 2.87 (s, 3H), 2.77 (s, 3H), 2.40 (s, 3H), 2.36 (s, 6H) ppm. (OH was not observed)MS (ESI) m/z: 431 (M+H)+, 429 (M-H)".
90%	Stage #1: 4-hydroxy-N N,2-trimethyl-1-[(4-methylphenyl)sulfonyl]-1H-benzimidazole-6-carboxamide; eschenmoser's salt In dichloromethane at 40℃; for 15h; Stage #2: With sodium hydrogencarbonate In dichloromethane; water at 20℃;	1.6 4-hydroxy-λ/,λ/,2-trimethyl-1-[(4-methylphenyl)sulfonyl]-1 /-/-benzimidazole-6- carboxamide (15 g, 40 mmol, STEP 5) and λ/,λ/-dimethylmethyleneiminium iodide (8.9 g, 48 mmol) in dichloromethane (200 ml_) was stirred at 40 0C for 15 hours. The reaction mixture was cooled to room temperature, and quenched with saturated sodium hydrogen carbonate aqueous solution (200 ml_). The mixture was extracted with dichloromethane (200 ml_ x 2). The combined organic layer was dried over magnesium sulfate and concentrated in vacuum. The residue was purified by column chromatography on amino gel (hexane : ethyl acetate gradient elution from 1 : 1 to ethyl acetate only) to afford the title compound as a white amorphous (15.5 g, 90%). 1H NMR (CDCI3, 270 MHz) δ: 7.79-7.76 (d, J = 8.1 Hz, 2H), 7.35-7.30 (m, 3H), 3.90-3.50 (br. s, 2H), 3.17 (s, 3H), 2.86 (s, 3H), 2.77 (s, 3H), 2.40 (s, 3H), 2.35 (s, 6H) ppm (-OH was not observed). MS (ESI) m/z: 431 (M+H)+, 429 (M-H)".

Reference： [1]Current Patent Assignee: RAQUALIA PHARMA INC. - WO2008/35195, 2008, A1 Location in patent: Page/Page column 45
[2]Current Patent Assignee: RAQUALIA PHARMA INC. - WO2008/114123, 2008, A1 Location in patent: Page/Page column 51-52

15
[ 33797-51-2 ]
[ 186663-74-1 ]
tert-butyl-3-((dimethylamino)methyl)-2-hydroxyphenylcarbamate [ No CAS ]

Reference： [1]Tetrahedron,2007,vol. 63,p. 9997 - 10002

16
[ 33797-51-2 ]
[ 177485-39-1 ]
3-Dimethylaminomethyl-5-ethoxycarbonylimidazo[1,2-a]pyridine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With sodium hydrogencarbonate; sodium thiosulfate; In dichloromethane; acetonitrile;	REFERENCE EXAMPLE 20 3-Dimethylaminomethyl-<strong>[177485-39-1]5-ethoxycarbonylimidazo[1,2-a]pyridine</strong> To a solution of 1.90 g (10.0 mmol) of <strong>[177485-39-1]5-ethoxycarbonylimidazo[1,2-a]pyridine</strong> in 40 ml of acetonitrile was added 2.41 g (13.0 mmol) of N,N-dimethylmethyleneammonium iodide. The mixture was heated for two hours under reflux. The solvent was distilled off. To the residue was added methylene chloride. The mixture was washed with an aqueous solution of sodium thiosulfate and an aqueous solution of sodium hydrogencarbonate, successively, dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by column chromatography (eluent: ethyl acetate) to afford 1.496 g of the desired compound (60.6%, a pale yellow solid). This product was recrystallized from ethyl acetate to afford the desired compound (colorless crystals), m.p.117.0-118.0 C. Elemental Analysis Calcd for C13 H17 N3 O2: Calcd.: C, 63.14; H, 6.93; N, 16.99 Found: C, 63.09; H, 6.68; N, 16.94 NMR(200 MHz,CDCl3)delta: 1.45(3H,t,J=7.2 Hz), 1.96(6H,s), 3.72(2H,s), 4.45(2H,q,J=7.2 Hz), 7.20(1H,dd,J=8.8, 7.0 Hz), 7.28(1H,dd,J=7.0, 1.6 Hz), 7.59(1H,s), 7.78(1H,dd,J=8.8, 1.6 Hz). IR(KBr): 1718, 1714, 1626.

Reference： [1]Patent: US5958942,1999,A

17
[ 1006-94-6 ]
ethyl acetate n-hexane [ No CAS ]
[ 33797-51-2 ]
[ 2436-17-1 ]

Yield	Reaction Conditions	Operation in experiment
	With potassium cyanide; sodium hydrogencarbonate; methyl iodide In methanol; dichloromethane; water; N,N-dimethyl-formamide	5-Methoxy-3-indoleacetonitrile (5c). 5-Methoxy-3-indoleacetonitrile (5c). A solution of N,N-dimethylmethylene ammonium iodide (3.25 g, 17.5 mmol) and 5-methoxyindole, 5a (1.47 g, 10 mmol) in CH2 Cl2 (100 mL) was stirred at room temperature for 6 hours with exclusion of moisture. A saturated aqueous solution of NaHCO3 was added to the ice-cooled reaction mixture with stirring. The layers were separated, the organic phase was washed with water, dried (Na2 SO4) and evaporated in vacuo. The crude 5b was dissolved in methanol (50 mL); 2.5 mL of DMF and 2.5 mL of water were added, followed by KCN (5.2 g, 80 mmol) and MeI (14.2 g, 100 mmol). The reaction mixture was warmed at 50° C. for 3 hours, then it was poured into ice-water and extracted with CH2 Cl2. The extracts were washed with brine, dried (Na2 SO4) and concentrated in vacuo. The residue was re-crystalized from ethyl acetate-hexane (1.02 g, yield: 55%, starting from 5a), oil. 1 H NMR: 3.71(s, 2H, CH2), 3.88(s, 3H, OCH3), 6.97-7.73(m, 4Harom), 8.41(br s, 1H, NHindole).

Reference： [1]Current Patent Assignee: INST FARMACOLOGICO LOMBARDO IF; ISTITUTO FARMACOLOGICO LOMBARDO IFLO - US5552428, 1996, A

18
[ 33797-51-2 ]
[ 5586-88-9 ]
[ 944819-25-4 ]

Yield	Reaction Conditions	Operation in experiment
43%	With acetic acid at 125℃; for 1h;	92.1 Step 1 1-(4-Chloro-phenyl)-propan-2-one (8.6 g, 51 mmol) and Eschenmoser's salt (12.3 g, 66.3 mmol) were dissolved in glacial acetic acid and heated in a closed pressure tube at 125° C. under nitrogen for 1 h. After cooling to room temperature, the solution was concentrated. The residue was dissolved in EtOAc, washed with saturated NaHCO3 aqueous solution, dried (MgSO4), concentrated, and chromatographed (SiO2, 39:1-19:1 hexane/EtOAc) to give 3-(4-chloro-phenyl)-but-3-en-2-one as yellow oil (3.92 g, 43%).

Reference： [1]Current Patent Assignee: MERCK & CO INC - US2007/197628, 2007, A1 Location in patent: Page/Page column 163-164

19
[ 1271-86-9 ]
[ 33797-51-2 ]
[ 32717-10-5 ]

Yield	Reaction Conditions	Operation in experiment
52%		Preparation of 1 , 2-bis- (dimethylaminomethyl) ferrocenen-Butyllithium (Aldrich, 2.5 molar in hexane, 24 ml, 54 mmol) is added to a solution of (dimethylaminomethyl ) ferrocene (Aldrich, 13.13 g, 10.69 ml, 48.97 mmol) in diethyl ether (80 ml) under nitrogen at a temperature of 25C and the reaction mixture stirred for 4 hours. The resulting red solution is then cooled to approximately -700C in a dry ice/acetone bath and Eschenmosers salt (ICH2NMe2) (Aldrich, 10 g, 54 mmol) is added. The reaction is allowed to warm to room temperature and stirred overnight .The resultant solution is quenched with excess aqueous sodium hydroxide and the resulting product extracted with diethyl ether (3 x 80 ml) dried over anhydrous magnesium sulfate, filtered over celite, and volatiles removed in vacuo to yield the crude title compound as a light orange crystalline solid. The crude product is recrystallised from light petrol with cooling to -17C and the recrystallised product washed with cold petrol to yield the title compound as a light orange solid (13.2 g, 74%). The compound can be further purified by sublimation to give 8.5 g (52%) of the Part (I) title compound (mpt 74C) .1H NMR(250 MHz; CDCl3 ) : 54.23 (brd, 2H) ; 4.11-4.10 (t, IH) ; 4.04(s, 5H) ; 3.43, 3.38, 3.23, 3.18 (AB quartet, 2H) ; 2.22(s, 6H) . <n="94"/>13C NMR (63 MHz; CDCl3 ): 583.81 ; 70.40; 69.25; 66.84; 57.35; 45.23.Elemental analysis: Found: C 63.7%; H 8.9%; N 9.5% Calculated: C 64.0%; H 8.1%; N 9.4%
52%		n-Butyllithium (Aldrich, 2.5 molar in 82 hexane, 24 ml, 54 mmol) is added to a solution of 83 <strong>[1271-86-9](dimethylaminomethyl)ferrocene</strong> (Aldrich, 13.13 g, 10.69 ml, 48.97 mmol) in 31 diethyl ether (80 ml) under nitrogen at a temperature of 25 C. and the reaction mixture stirred for 4 hours. The resulting red solution is then cooled to approximately -70 C. in a dry ice/acetone bath and Eschenmosers salt (ICH2NMe2) (Aldrich, 10 g, 54 mmol) is added. The reaction is allowed to warm to room temperature and stirred overnight. (0510) The resultant solution is quenched with excess aqueous sodium hydroxide and the resulting product extracted with diethyl ether (3×80 ml) dried over anhydrous magnesium sulfate, filtered over celite, and volatiles removed in vacuo to yield the crude title compound as a light orange crystalline solid. The crude product is recrystallised from light petrol with cooling to -17 C. and the recrystallised product washed with cold petrol to yield the 84 title compound as a light orange solid (13.2 g, 74%). The compound can be further purified by sublimation to give 8.5 g (52%) of the title compound (mpt 74 C.). (0511) 1H NMR (250 MHz; CDCl3): δ4.23 (brd, 2H); 4.11-4.10 (t, 1H); 4.04 (s, 5H); 3.43, 3.38, 3.23, 3.18 (AB quartet, 2H); 2.22 (s, 6H). (0512) 13C NMR (63 MHz; CDCl3): δ83.81; 70.40; 69.25; 66.84; 57.35; 45.23. (0513) Elemental analysis: Found: C, 63.7%; H, 8.9%; N, 9.5%. (0514) Calculated: C, 64.0%; H, 8.1%; N, 9.4%.

Reference： [1]Patent: WO2008/65448,2008,A1 .Location in patent: Page/Page column 92-93
[2]Patent: US9802185,2017,B2 .Location in patent: Page/Page column 46

20
[ 387-43-9 ]
[ 33797-51-2 ]
[ 101909-46-0 ]

Yield	Reaction Conditions	Operation in experiment
55%	In dichloromethane; at 20℃;	To a solution of 3-nitropropionic acid (1.Og, 8.4mmol) and triazole base 1 (2.4g, 10.5mmol) in acetonitrile (2OmL) at O0C was added N-methylmorpholine (0.92mL,8.4mmol), followed by l-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride(2.42g, 12.6mmol) and the reaction mixture stirred for Ih. The reaction mixture was allowed to self warm to room temperature and stirred overnight. The reaction mixture was diluted with ethyl acetate and washed with water, sat. NaHCO3(aq), and brine. The organic phase was dried over MgSO4, evaporated and the residue triturated with diethyl ether to give amide 9 (2.1g, 85percent) as a white solid.

Reference： [1]Patent: WO2008/40974,2008,A1 .Location in patent: Page/Page column 29

21
[ 33797-51-2 ]
[ 42865-77-0 ]
[ 1029135-22-5 ]

Yield	Reaction Conditions	Operation in experiment
	In acetonitrile at 80℃;

Reference： [1]Gracias, Vijaya; Ji, Zhiqin; Akritopoulou-Zanze, Irini; Abad-Zapatero, Cele; Huth, Jeffrey R.; Song, Danying; Hajduk, Philip J.; Johnson, Eric F.; Glaser, Keith B.; Marcotte, Patrick A.; Pease, Lori; Soni, Nirupama B.; Stewart, Kent D.; Davidsen, Steven K.; Michaelides, Michael R.; Djuric, Stevan W. [Bioorganic and Medicinal Chemistry Letters, 2008, vol. 18, # 8, p. 2691 - 2695]

22
[ 19685-09-7 ]
[ 33797-51-2 ]
[ 119413-54-6 ]

Yield	Reaction Conditions	Operation in experiment
		Example 2; 10-hydroxy-camptothecin (0.1 g) , N,N-dimethylmethyleneiminium iodide (about 0.06 g) , dichloromethane (about 1.3 g) , and isopropanol (about 0.8 g) were charged into a suitable reactor. The resulting mixture was stirred for 5-10 minutes. Then triethylamine (0.002-0.03 g) was added, and the resulting mixture was stirred at room temperature . After the reaction was complete, the mixture of hydrochloride acid (37%, 0.003-0.045 g) and isopropanol (about 0.14 g) was added to the resulting mixture. The resulting mixture was stirred over 4 hours, and then the solid was filtered, washed with dichloromethane <n="9"/>(about 1 g) and dried under vacuum to give about 0.11 g of topotecan HCl .

Reference： [1]Patent: WO2008/127606,2008,A1 .Location in patent: Page/Page column 7-8

23
[ 1068601-61-5 ]
[ 33797-51-2 ]
[ 1068601-63-7 ]

Yield	Reaction Conditions	Operation in experiment
2.16 g	In methanol at 23 - 65℃; Inert atmosphere;

Reference： [1]Kummer, David A.; Chain, William J.; Morales, Marvin R.; Quiroga, Olga; Myers, Andrew G. [Journal of the American Chemical Society, 2008, vol. 130, # 40, p. 13231 - 13233]

24
[ 33797-51-2 ]
[ 105-56-6 ]
[ 7085-85-0 ]

Yield	Reaction Conditions	Operation in experiment
	With methanesulfonic acid; sulfuric acid In chloroform-d1 at 20 - 70℃; for 3h; screw-capped test-tube;	Eschenmoser's (iodide) salt was employed as a commercially available iminium salt. When this salt was mixed into deuterated chloroform, the salt was observed to be scarcely soluble at room temperature. However, when MeSO3H and H2SO4 were added, the colour changed becoming dark brown and the solubility increased. After heating in the presence of added ethyl cyanoacetate on an equimolar basis at a temperature of 70° C. for a period of time of 3 hours, the reaction produced monomeric cyanoacrylate, as evidenced by direct 1N NMR analysis.
	Stage #1: eschenmoser's salt With methanesulfonic acid; sulfuric acid In chloroform-d1 Stage #2: ethyl 2-cyanoacetate In chloroform-d1 at 70℃; for 3h;	For comparative purposes, Eschenmoser's iodide salt-a non-protonated iminium salt-was employed as a commercially available iminium salt, and was placed in deuterated chloroform and observed to be scarcely soluble. When MeSO3H and H2SO4 were added the solubility was observed to increase. After heating in the presence of ethyl cyanoacetate on an equimolar basis at a temperature of 70° C. for a period of time of 3 hours, the reaction produced monomeric cyanoacrylate in low yield.

Reference： [1]Current Patent Assignee: HENKEL AG & CO. KGAA - US7569719, 2009, B1 Location in patent: Page/Page column 11-12
[2]Current Patent Assignee: HENKEL AG & CO. KGAA - US7718821, 2010, B1 Location in patent: Page/Page column 7

25
[ 399-52-0 ]
[ 33797-51-2 ]
[ 343-90-8 ]

Reference： [1]Journal of Medicinal Chemistry,2008,vol. 51,p. 6980 - 7004

26
[ 33797-51-2 ]
[ 58414-52-1 ]
[ 1206786-43-7 ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: thiophen-3-yl-acetic acid methyl ester With lithium hexamethyldisilazane In tetrahydrofuran at -78℃; for 0.5h; Stage #2: eschenmoser's salt In tetrahydrofuran at -78 - 0℃;	42 Preparation of methyl 3-(dimethylamino)-2-(thiophen-3-yl)propanoate (E42) Example 42 Preparation of methyl 3-(dimethylamino)-2-(thiophen-3-yl)propanoate (E42) To methyl 2-(thiophen-3-yl)acetate (E41) in THF cooled to -78° C. was added LiHMDS, and the solution stirred at -78° C. for 30 min. Then N,N-Dimethylmethyleneiminium iodide was added directly and the solution was allowed to warm to 0° C. The mixture was poured into NaHCO3 (sat), extracted with EtOAc, dried (Na2SO4), filtered, and evaporated. Column chromatography (SiO2, 5% MeOH/CH2Cl2) gave pure methyl 3-(dimethylamino)-2-(thiophen-3-yl)propanoate (E42).
	Stage #1: thiophen-3-yl-acetic acid methyl ester With lithium hexamethyldisilazane In tetrahydrofuran at -78℃; for 0.5h; Stage #2: eschenmoser's salt In tetrahydrofuran at -78 - 0℃;	42 Example 42. Preparation of methyl 3-(dimethylamino)-2-(thiophen-3-yl)propanoate (E42). To methyl 2-(thiophen-3-yl)acetate (E41) in THF cooled to -78 °C was added LiHMDS, and the solution stirred at -78 °C for 30 minutes. Then N,N- dimethylmethyleneiminium iodide (Eschenmoser’s salt) was added directly and the solution was allowed to warm to 0 °C. The mixture was poured into NaHC03 (sat. aq.), extracted with EtOAc, dried over Na2S04, filtered, and the solvent evaporated. Column chromatography (Si02, 5% MeOH/CH2Cl2) gave pure methyl 3-(dimethylamino)-2-(thiophen-3-yl)propanoate (E42).

Reference： [1]Current Patent Assignee: AERIE PHARMACEUTICALS INC - US2010/22585, 2010, A1 Location in patent: Page/Page column 14
[2]Current Patent Assignee: AERIE PHARMACEUTICALS INC - WO2019/178324, 2019, A1 Location in patent: Paragraph 00221

27
[ 27200-79-9 ]
[ 33797-51-2 ]
[ 173960-56-0 ]

Reference： [1]Synthesis,2010,p. 1883 - 1890

28
[ 33797-51-2 ]
[ 93247-78-0 ]
[ 312915-01-8 ]

Yield	Reaction Conditions	Operation in experiment
		lH-Indole-7-carboxylic acid, methyl ester (0.091 mol), Eschenmoser's salt (0.1 mol) in acetic acid (300 ml) were heated at 650C for 2 hours. The precipitate was filtered off, dissolved in DCM and potassium carbonate 10percent. Potassium carbonate (solid) was added and the mixture was stirred at room temperature for 1 hour and then extracted. The organic layer was separated, dried over MgSO4, filtered and the solvent was evaporated, yielding 1Og of intermediate 5.

Reference： [1]Patent: WO2010/89327,2010,A2 .Location in patent: Page/Page column 42

29
5-[hydroxy-(4-methoxy-phenyl)-methylene]-2,2-dimethyl-[1,3]dioxane-4,6-dione [ No CAS ]
[ 33797-51-2 ]
[ 69716-28-5 ]
[ 75-31-0 ]
[ 1325731-25-6 ]

Reference： [1]Organic Letters,2011,vol. 13,p. 4732 - 4735

30
[ 86497-40-7 ]
[ 33797-51-2 ]
[ 91342-74-4 ]

Yield	Reaction Conditions	Operation in experiment
46%		Step 7[00134] 3-[(Dimethylamino)methyl1-5-methylhexan-2-one: To a stirred solution of trimethyl(5-methylhex-2-en-2-yloxy)silane (118 g, 633 mmol, 1.00 equiv) in anhydrous acetonitrile (800 mL) was added N-methyl-N- methylenemethanaminium iodide (128.8 g, 696.3 mmol, 1.10 equiv) in several batches and the resultant mixture was stirred at 20C overnight. Then the solution was concentrated under vacuum to remove the solvent. The residue was dissolved in 400 mL 1 Nu HCl (aq.) and extracted with ieri-butyl methyl ether. Then the water phase was basiced with 2 Nu aq. NaOH and extracted with ieri-butyl methyl ether. The organic phase was dried and concentrated under vacuum. The liquid was purified by distilling (80C/0.5 mmHg) to provide 50 g (46%) of 3- [(dimethylamino)methyl]-5-methylhexan-2-one as a colorless oil. 'H-NMR (300 MHz, -DMSO) 0.92 (d, 3H), 0.98 (d, 3H), 1.11-1.23 (m, IH), 1.23-1.38 (m, IH), 1.54-1.70 (m, IH), 2.30 (s, 3H), 3.01 (s, 9H), 3.10-3.32 (m, 2H), 3.81-3.88 (m, IH).
46%	In acetonitrile; at 20℃;	[0199] 3-[(Dimethylamino)methyl]-5-methylhexan-2-one: To a stuffed solution of trimethyl(5-methylhex-2-en-2-yloxy)silane (118 g, 633 mmol, 1.00 equiv) in anhydrous acetonitrile (800 mL) was added N-methyl-N-methylenemethanaminium iodide (128.8 g, 696.3 mmol, 1.10 equiv) in several batches and the resultant mixture was stirred at 20C overnight. Then the solution was concentrated under vacuum to remove the solvent. The residue was dissolved in 400 mL 1 N HC1 (aq.) and extracted with tert-butyl methyl ether. Then the water phase was basiced with 2 N aq. NaOH and extracted with tert-butyl methyl ether. The organic phase was dried and concentrated under vacuum. The liquid was purified by distilling (80C/0.5 mmHg) to provide 50 g (46%) of 3-[(dimethylamino)methyl]-5-methylhexan-2-one as a colorless oil. ?H-NMR (300 MHz, d6-DMSO) cY0.92 (d, 3H), 0.98 (d, 3H), 1.11-1.23 (m, 1H), 1.23-1.38 (m, 1H), 1.54-1.70 (m, 1H), 2.30 (s, 3H), 3.01 (s, 9H), 3.10-3.32 (m, 2H), 3.8 1-3.88 (m, 1H).
46%	In acetonitrile; at 20℃;	To a stilTed solution of trimethyl(5-methylhex-2-en-2-yloxy)silane (118 g, 633 mmol, 1.00 equiv) in anhydrous acetonitrile (800 mL) was added N-methyl-N-methylenemethanaminium iodide (128.8 g, 696.3 mmol, 1.10 equiv) in several batches and the resultant mixture was stirred at 20C overnight. Then the solution was concentrated under vacuum to remove the solvent. The residue was dissolved in 400 mL 1 N HC1 (aq.) and extracted with tert-butyl methyl ether. Then the water phase was basiced with 2 N aq. NaOH and extracted with tert-butyl methyl ether. The organic phase was dried and concentrated under vacuum. The liquid was purified by distilling (80C/0.5 mmHg) to provide 50 g (46%) of 3-[(dimethylamino)methyl]-5-methylhexan-2-one as a colorless oil. ?H-NMR (300 MHz, d6-DMSO) c50.92 (d, 3H), 0.98 (d, 3H), 1.11-1.23 (m, 1H), 1.23-1.38 (m, 1H), 1.54-1.70 (m, 1H), 2.30 (s, 3H), 3.01 (s, 9H), 3.10-3.32 (m, 2H), 3.81-3.88 (m, 1H).

46%

In acetonitrile; at 20℃;

To a stirred solution of trimethyl(5-methylhex-2-en-2-yloxy)silane (118 g, 633 mmol, 1.00 equiv) in anhydrous acetonitrile (800 mL) was added N-methyl-N-methylenemethanaminium iodide (128.8 g, 696.3 mmol, 1.10 equiv) in several batches and the resultant mixture was stirred at 20 C. overnight. Then the solution was concentrated under vacuum to remove the solvent. The residue was dissolved in 400 mL 1 N HCl (aq.) and extracted with tert-butyl methyl ether. Then the water phase was basiced with 2 N aq. NaOH and extracted with tert-butyl methyl ether. The organic phase was dried and concentrated under vacuum. The liquid was purified by distilling (80 C./0.5 mmHg) to provide 50 g (46%) of 3-[(dimethylamino)methyl]-5-methylhexan-2-one as a colorless oil. 1H-NMR (300 MHz, d6-DMSO) delta0.92 (d, 3H), 0.98 (d, 3H), 1.11-1.23 (m, 1H), 1.23-1.38 (m, 1H), 1.54-1.70 (m, 1H), 2.30 (s, 3H), 3.01 (s, 9H), 3.10-3.32 (m, 2H), 3.81-3.88 (m, 1H).

Reference： [1]Patent: WO2011/153157,2011,A2 .Location in patent: Page/Page column 44
[2]Patent: WO2015/77520,2015,A1 .Location in patent: Paragraph 0199
[3]Patent: WO2015/77521,2015,A1 .Location in patent: Paragraph 00167
[4]Patent: US2018/169087,2018,A1 .Location in patent: Paragraph 0228; 0229

31
[ 21573-31-9 ]
[ 33797-51-2 ]
2-methylene-oct-7-enal [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
75%	With triethylamine In dichloromethane Inert atmosphere;

Reference： [1]Hayashi, Ryuji; Ma, Zhi-Xiong; Hsung, Richard P. [Organic Letters, 2012, vol. 14, # 1, p. 252 - 255]

32
[ 1908-61-8 ]
[ 33797-51-2 ]
[ 138303-98-7 ]

Yield	Reaction Conditions	Operation in experiment
55%	Stage #1: 4-bromo[2.2]paracyclophane With n-butyllithium In diethyl ether; hexane at 20℃; for 2h; Inert atmosphere; Stage #2: eschenmoser's salt In diethyl ether; hexane at 20℃; for 1h; Inert atmosphere; Stage #3: With hydrogenchloride In diethyl ether Inert atmosphere;

Reference： [1]Location in patent: experimental part Dunina, Valery V.; Turubanova, Eugeniya I.; Gorunova, Olga N.; Livantsov, Michail V.; Lyssenko, Konstantin A.; Antonov, Dmitrii Yu.; Grishin, Yuri K. [Polyhedron, 2012, vol. 31, # 1, p. 413 - 421]

33
[ 16695-54-8 ]
[ 33797-51-2 ]
[ 69716-28-5 ]
[ 1353748-65-8 ]

Reference： [1]ACS Combinatorial Science,2012,vol. 14,p. 85 - 88

34
[ 16695-54-8 ]
[ 33797-51-2 ]
[ 14337-43-0 ]
[ 1325731-22-3 ]

Yield	Reaction Conditions	Operation in experiment
	With potassium hydrogencarbonate In N,N-dimethyl-formamide at 125℃; for 0.5h; Microwave irradiation;

Reference： [1]Location in patent: scheme or table Knapp, John M.; Zhu, Jie S.; Wood, Alex B.; Kurth, Mark J. [ACS Combinatorial Science, 2012, vol. 14, # 2, p. 85 - 88]

35
[ 705-87-3 ]
[ 33797-51-2 ]
[ 69716-28-5 ]
[ 1353748-64-7 ]

Reference： [1]ACS Combinatorial Science,2012,vol. 14,p. 85 - 88

36
[ 1001-24-7 ]
[ 33797-51-2 ]
[ 69716-28-5 ]
[ 1353748-62-5 ]

Reference： [1]ACS Combinatorial Science,2012,vol. 14,p. 85 - 88

37
[ 89601-01-4 ]
[ 33797-51-2 ]
[ 69716-28-5 ]
[ 1353748-67-0 ]

Reference： [1]ACS Combinatorial Science,2012,vol. 14,p. 85 - 88

38
[ 24309-97-5 ]
[ 33797-51-2 ]
[ 69716-28-5 ]
[ 1353748-66-9 ]

Reference： [1]ACS Combinatorial Science,2012,vol. 14,p. 85 - 88

39
[ 882-36-0 ]
[ 33797-51-2 ]
[ 69716-28-5 ]
[ 1353748-68-1 ]

Reference： [1]ACS Combinatorial Science,2012,vol. 14,p. 85 - 88

40
[ 58102-45-7 ]
[ 33797-51-2 ]
[ 69716-28-5 ]
[ 1353748-69-2 ]

Reference： [1]ACS Combinatorial Science,2012,vol. 14,p. 85 - 88

41
[ 25233-52-7 ]
[ 33797-51-2 ]
[ 69716-28-5 ]
[ 1353748-63-6 ]

Reference： [1]ACS Combinatorial Science,2012,vol. 14,p. 85 - 88

42
[ 10075-50-0 ]
[ 33797-51-2 ]
[ 830-93-3 ]

Yield	Reaction Conditions	Operation in experiment
	With acetic acid In methanol at 25℃; for 4h; Inert atmosphere;

Reference： [1]Soto, Sara; Vaz, Esther; Dell'Aversana, Carmela; Alvarez, Rosana; Altucci, Lucia; De Lera, Angel R. [Organic and Biomolecular Chemistry, 2012, vol. 10, # 10, p. 2101 - 2112]

43
[ 102-54-5 ]
[ 33797-51-2 ]
1,1′-bis(N,N′-dimethylaminomethyl)ferrocene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
55%	Stage #1: ferrocene With n-butyllithium; N,N,N,N,-tetramethylethylenediamine In hexane; pentane at 20℃; for 22h; Inert atmosphere; Stage #2: eschenmoser's salt In diethyl ether; hexane; pentane at 20℃; for 18.17h; Reflux; Inert atmosphere;	5 Synthesis of Fc(NMe₂)₂ Example 5. Synthesis and Characterization of FcN2 Synthesis of Fc(NMe2)2 The solution of n-BuLi (2.5 M, 7.2 mL, 18.0 mmol) in hexane was added into the mixture of Fc (1.62 g, 8.7 mmol) and TMEDA (2.68 mL, 18.0 mmol) in 80 mL dry pentane. After stirred at room temperature for 4 h, orange precipitate was observed. The dark orange solution was stirred at room temperature for another 18 h, 80 mL of dry ether was added to dilute the reaction mixture. Solid Eschenmoser's salt was added in one portion, the mixture was stirred at room temperature for another 18 h and heated up under reflux for 10 min. 2 mL H2O was added to quench the reaction, and then, the organic phase was washed with 50 mL H2O and 50 mL brine, dried with Na2SO4. The product was purified by flash column chromatography with neutral alumina (ethyl acetate:MeOH=10:1). The pure product was obtained as an orange oil (1.44 g, 55% yield). 1H NMR (CDCl3, 500 MHz, ppm): δ 2.18 (s, 12H), 3.27 (s, 4H), 4.08 (s, 4H), 4.11 (s, 4H).
35%	Stage #1: ferrocene With n-butyllithium; N,N,N,N,-tetramethylethylenediamine In hexane at 20℃; for 13h; Inert atmosphere; Schlenk technique; Stage #2: eschenmoser's salt In tetrahydrofuran at 20℃; for 24h; Reflux; Inert atmosphere; Schlenk technique;

Reference： [1]Current Patent Assignee: UTAH STATE UNIVERSITY - US2018/72669, 2018, A1 Location in patent: Paragraph 0221; 0242; 0243
[2]Salas, Paloma F.; Herrmann, Christoph; Cawthray, Jacqueline F.; Nimphius, Corinna; Kenkel, Alexander; Chen, Jessie; De Kock, Carmen; Smith, Peter J.; Patrick, Brian O.; Adam, Michael J.; Orvig, Chris [Journal of Medicinal Chemistry, 2013, vol. 56, # 4, p. 1596 - 1613]

44
[ 934172-61-9 ]
[ 33797-51-2 ]
[ 1449369-08-7 ]

Yield	Reaction Conditions	Operation in experiment
112 mg	In N,N-dimethyl-formamide; acetonitrile at 90℃;	211.2 Step 21 1.2: To a solution of ethyl 2-(3-methyl-1H-pyrazol-1-yl)acetate (94mg) and DMF (1.5mL) in MeCN (3mL) was added Ν,Ν-dimethylmethyleneiminium iodide (390mg). The reaction mixture was stirred at 90°C overnight. After cooling down, the reaction mixture was diluted with DCM and washed with sat. NaHCO3 and water. The aq. layers were extracted with DCM, the combined org. layers were dried (MgSO4), filtered off and evaporated in vacuo to afford ethyl 2-(4-((dimethylamino)methyl)-3-methyl-1H-pyrazol-1-yl)acetate (112mg, brown oil). LC-MS (B): tR = 0.39min; [M+H]+: 226.23.
112 mg	In N,N-dimethyl-formamide; acetonitrile at 90℃;	211.2 Step 211.2: To a solution of ethyl 2-(3-methyl-1H-pyrazol-1-yl)acetate (94 mg) and DMF (1.5 mL) in MeCN (3 mL) was added N,N-dimethylmethyleneiminium iodide (390 mg). The reaction mixture was stirred at 90° C. overnight. After cooling down, the reaction mixture was diluted with DCM and washed with sat. NaHCO3 and water. The aq. layers were extracted with DCM, the combined org. layers were dried (MgSO4), filtered off and evaporated in vacuo to afford ethyl 2-(4-((dimethylamino)methyl)-3-methyl-1H-pyrazol-1-yl)acetate (112 mg, brown oil). LC-MS (B): tR=0.39 min; [M+H]+: 226.23.

Reference： [1]Current Patent Assignee: IDORSIA PHARMACEUTICALS LTD - WO2013/114332, 2013, A1 Location in patent: Page/Page column 131; 132
[2]Current Patent Assignee: IDORSIA PHARMACEUTICALS LTD - US2014/371204, 2014, A1 Location in patent: Paragraph 0918

45
[ 33797-51-2 ]
[ 38647-11-9 ]
[ 1596799-19-7 ]

Yield	Reaction Conditions	Operation in experiment
62%	Stage #1: l-triptonide With lithium hexamethyldisilazane In tetrahydrofuran at -78℃; for 0.5h; Inert atmosphere; Stage #2: eschenmoser's salt In tetrahydrofuran at -78℃; for 1h; Inert atmosphere;

Reference： [1]Xu, Hongtao; Tang, Huanyu; Feng, Huijin; Li, Yuanchao [ChemMedChem, 2014, vol. 9, # 2, p. 290 - 295]

46
[ 67-56-1 ]
[ 922490-90-2 ]
[ 33797-51-2 ]
[ 3070-71-1 ]

Reference： [1]Organic and Biomolecular Chemistry,2014,vol. 12,p. 5400 - 5406

47
[ 67-56-1 ]
[ 3709-27-1 ]
[ 33797-51-2 ]
[ 3070-71-1 ]

Reference： [1]Organic and Biomolecular Chemistry,2014,vol. 12,p. 5400 - 5406

48
[ 7126-39-8 ]
[ 33797-51-2 ]
C₈H₁₂N₂O [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
87%	In acetonitrile; at 60℃;	General procedure: A sample of the heterocycle was dissolvedin CH2Cl2 or CH3CN (as shown in Tables 1 and 2, 0.15?0.2 M).Dimethylmethylideneammonium iodide (Eschenmoser?s salt, 2 equiv.) was added in a singleportion. The reaction mixture was stirred at room temperature or at 60 °C until TLC analysisindicated the complete consumption of the starting material (20 min?26 h). The reactionmixture was diluted with CH2Cl2 or EtOAc (for CH3CN as reaction medium) and saturatedaqueous NaHCO3. The phases were separated, and the aqueous layer was extracted once. TheS3organic layer was dried (Na2SO4), and the solvent was evaporated. The crude product wasused without further purification in the next step.

Reference： [1]Synlett,2015,vol. 26,p. 484 - 488

49
trimethyl-(5-methylhex-2-en-2-yloxy)silane [ No CAS ]
[ 33797-51-2 ]
[ 91342-74-4 ]

Yield	Reaction Conditions	Operation in experiment
46%	In acetonitrile; at 20℃;	3- j(Dimethylamino)methyll-5-methylhexan-2-one: To a stirred solution of trimethyl(5-methylhex-2-en-2-yloxy)silane (118 g, 633 mmol, 1.00 equiv) in anhydrous acetonitrile (800 mL) was added N-methyl-Nmethylenemethanaminium iodide (128.8 g, 696.3 mmol, 1.10 equiv) in several batches and the resultant mixture was stirred at 20C overnight. Then the solution was concentrated under vacuum to remove the solvent. The residue was dissolved in 400 mL 1 N HC1 (aq.) and extracted with tert-butyl methyl ether. Then the water phase was basiced with 2 N aq. NaOH and extracted with tert-butyl methyl ether. The organic phase was dried and concentrated under vacuum. The liquid was purified by distilling (80C/0.5 mmHg) to provide 50 g (46%) of 3- [(dimethylamino)methyl]-5-methylhexan-2-one as a colorless oil. ?H-NMR (300 MHz, d6-DMSO) NO.92 (d, 3H), 0.98 (d, 3H), 1.11-1.23 (m, 1H), 1.23-1.38 (m, 1H), 1.54-1.70 (m, 1H), 2.30 (s, 3H), 3.01 (s, 9H), 3.10-3.32 (m, 2H), 3.81-3.88 (m,

Reference： [1]Patent: WO2015/112707,2015,A1 .Location in patent: Paragraph 00193

50
[ 1293-65-8 ]
[ 33797-51-2 ]
[ 259827-20-8 ]

Yield	Reaction Conditions	Operation in experiment
87.5%		Under a nitrogen atmosphere,2.0370 g (5.924 mmol) of <strong>[1293-65-8]1,1'-<strong>[1293-65-8]dibromoferrocene</strong></strong> was dissolved in THF (50 ml)Under cooling at -78 C.,4.0 ml (6.516 mmol) of n-butyllithium (1.6 M, n-hexane solution) was added and the mixture was stirred for 20 minutes.ThenN, N-dimethylmethylene ammonium iodide2.2 g (11.848 mmol) was added, then the mixture was allowed to stand at room temperature and stirred for 16 hours.An ammonium chloride aqueous solution (100 ml) and chloroform (150 ml) were added to the reaction solution, and the mixture was separated. The aqueous phase was further extracted twice with 50 ml of chloroform.The obtained organic phase (250 ml) was washed with saturated brine,After drying over sodium sulfate, concentration under reduced pressure gave a crude product. This was purified by silica gel column chromatography to obtain 1.6692 g (5.1835 mmol, yield 87.5%) of 1-bromo-1 '- ((dimethylamino) methyl) ferrocene as an intermediate.

Reference： [1]Patent: JP2018/203652,2018,A .Location in patent: Paragraph 0055; 0056; 0057

51
[ 25714-71-0 ]
[ 33797-51-2 ]
[ 250209-01-9 ]

Yield	Reaction Conditions	Operation in experiment
96%	With n-butyllithium; N-ethyl-N,N-diisopropylamine In tetrahydrofuran at 20℃; for 14.5h;	1.1; 1.1; 2.1; 3.1; 4.1; 5.1; 6.1 (1) Preparation of 2-methylene-4-hydroxybutanal 1.5 L of tetrahydrofuran was added to a 3 L flask, stirring was started, the rotation speed was set to 800 rpm, the temperature was lowered to -10 ° C, and then 3 mol of n-butyllithium and 2.5 mol of diisopropylamine were added thereto.After 2.5 hours of reaction,Add 1 mol of 4-hydroxybutanal and stir for 2.5 h.1.5 mol of (N,N-dimethyl)methylene iodide was added, followed by reaction at room temperature for 12 h.At the end of the reaction, 0.5 L of water was added to the system, and the mixture was extracted three times with dichloromethane, 0.5 L each time. The organic phase was combined, and dichloromethane was recovered under reduced pressure. The mother liquid was distilled off at 1 kPa with a packed column of theoretical number of 20 The reaction solution after removing the solvent,The reflux ratio was 2:1, and the fraction at the top of the column was collected at 38-39 ° C.Obtaining 2-methylene-4-hydroxybutanal,The content of 2-methylene-4-hydroxybutanal was analyzed by gas chromatography to be 97.2%, and the yield was 96%.

Reference： [1]Current Patent Assignee: WANHUA CHEMICAL GROUP CO LTD - CN110143875, 2019, A Location in patent: Paragraph 0049-0051; 0056-0058; 0063-0065; 0070-0094

52
[ 5166-53-0 ]
[ 33797-51-2 ]
[ 91342-74-4 ]

Yield	Reaction Conditions	Operation in experiment
67%		Step 1: using 5-methyl-3-hexen-2-one (1 mol) and tetramethyldisiloxane (0.8 mol) as raw materials.The addition reaction is carried out under the condition of a copper hydride triphenylphosphine complex (0.8% mol) as a catalyst.The reaction solvent is 1.5 L of toluene, the reaction temperature is 90 C, and the reaction time is 2 hours to obtain Intermediate 6;Step 2: Adding N,N-dimethylmethylene iodide (1.5 mol) to the intermediate 6 obtained in the first stepAnd an anhydrous zinc chloride (5% mol) catalyst to carry out Mannich reaction,The reaction temperature is 90 C, and the reaction time is 3 hours.That is, a crude 3-[(dimethylamino)methyl]-5-methyl-2-hexanone is obtained;Step 3: Purifying the crude 3-[(dimethylamino)methyl]-5-methyl-2-hexanone obtained in the second step by distillation,That is, 3-[(dimethylamino)methyl]-5-methyl-2-hexanone is obtained as a fine product.The final product was 115g;The purity of the final 3-[(dimethylamino)methyl]-5-methyl-2-hexanone was 99.6%, and the yield was 67%.

Reference： [1]Patent: CN110143889,2019,A .Location in patent: Paragraph 0056-0109

53
[ 33797-51-2 ]
[ 344340-40-5 ]
2-(6-chloro-9H-purin-9-yl)-1-phenylprop-2-en-1-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
49%	With triethylamine In dichloromethane at 40℃; for 48h;

Reference： [1]Huang, Ke-Xin; Xie, Ming-Sheng; Sang, Ji-Wei; Qu, Gui-Rong; Guo, Hai-Ming [Organic Letters, 2021, vol. 23, # 1, p. 81 - 86]

CAS No. :	33797-51-2	MDL No. :	MFCD00011810
Formula :	C₃H₈IN	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	VVDUZZGYBOWDSQ-UHFFFAOYSA-M
M.W :	185.01	Pubchem ID :	2724133
Synonyms :

Signal Word:	Warning	Class:	N/A
Precautionary Statements:	P261-P301+P312-P302+P352-P304+P340-P305+P351+P338	UN#:	N/A
Hazard Statements:	H302-H315-H319-H335	Packing Group:	N/A
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.
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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.
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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:
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P372	Explosion risk in case of fire.
P373	DO NOT fight fire when fire reaches explosives.
P374	Fight fire with normal precautions from a reasonable distance.
P376	Stop leak if safe to do so. Oxidising gases (section 2.4) 1
P377	Leaking gas fire: Do not extinguish, unless leak can be stopped safely.
P378
P380	Evacuate area.
P381	Eliminate all ignition sources if safe to do so.
P390	Absorb spillage to prevent material damage.
P391	Collect spillage. Hazardous to the aquatic environment
P301 + P310	IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician.
P301 + P312	IF SWALLOWED: call a POISON CENTER or doctor/physician IF you feel unwell.
P301 + P330 + P331	IF SWALLOWED: Rinse mouth. Do NOT induce vomiting.
P302 + P334	IF ON SKIN: Immerse in cool water/wrap in wet bandages.
P302 + P350	IF ON SKIN: Gently wash with plenty of soap and water.
P303 + P361 + P353	IF ON SKIN (or hair): Remove/Take off Immediately all contaminated clothing. Rinse SKIN with water/shower.
P304 + P312	IF INHALED: Call a POISON CENTER or doctor/physician if you feel unwell.
P304 + P340	IF INHALED: Remove victim to fresh air and Keep at rest in a position comfortable for breathing.
P304 + P341	IF INHALED: If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing.
P305 + P351 + P338	IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing.
P306 + P360	IF ON CLOTHING: Rinse Immediately contaminated CLOTHING and SKIN with plenty of water before removing clothes.
P307 + P311	IF exposed: call a POISON CENTER or doctor/physician.
P308 + P313	IF exposed or concerned: Get medical advice/attention.
P309 + P311	IF exposed or if you feel unwell: call a POISON CENTER or doctor/physician.
P332 + P313	IF SKIN irritation occurs: Get medical advice/attention.
P333 + P313	IF SKIN irritation or rash occurs: Get medical advice/attention.
P335 + P334	Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages.
P337 + P313	IF eye irritation persists: Get medical advice/attention.
P342 + P311	IF experiencing respiratory symptoms: call a POISON CENTER or doctor/physician.
P370 + P376	In case of fire: Stop leak if safe to Do so.
P370 + P378	In case of fire:
P370 + P380	In case of fire: Evacuate area.
P370 + P380 + P375	In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion.
P371 + P380 + P375	In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion.
Storage
Code	Phrase
P401
P402	Store in a dry place.
P403	Store in a well-ventilated place.
P404	Store in a closed container.
P405	Store locked up.
P406	Store in corrosive resistant/ container with a resistant inner liner.
P407	Maintain air gap between stacks/pallets.
P410	Protect from sunlight.
P411
P412	Do not expose to temperatures exceeding 50 oC/ 122 oF.
P413
P420	Store away from other materials.
P422
P402 + P404	Store in a dry place. Store in a closed container.
P403 + P233	Store in a well-ventilated place. Keep container tightly closed.
P403 + P235	Store in a well-ventilated place. Keep cool.
P410 + P403	Protect from sunlight. Store in a well-ventilated place.
P410 + P412	Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF.
P411 + P235	Keep cool.
Disposal
Code	Phrase
P501	Dispose of contents/container to ...
P502	Refer to manufacturer/supplier for information on recovery/recycling

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

[ CAS No. 33797-51-2 ] {[proInfo.proName]}

Quality Control of [ 33797-51-2 ]

Related Doc. of [ 33797-51-2 ]

Product Details of [ 33797-51-2 ]

Safety of [ 33797-51-2 ]

Application In Synthesis of [ 33797-51-2 ]

[ 33797-51-2 ] Synthesis Path-Upstream 1~4

[ 33797-51-2 ] Synthesis Path-Downstream 1~53

Precautionary Statements-General

Prevention

Response

Storage

Disposal

Physical hazards

Health hazards

Environmental hazards

Inquiry