[ CAS No. 936850-09-8 ] {[proInfo.proName]}

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Quality Control of [ 936850-09-8 ]

COA NMR CNMR HPLC LC-MS

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SDS Specification

Alternatived Products of [ 936850-09-8 ]

Product Details of [ 936850-09-8 ]

CAS No. :	936850-09-8	MDL No. :	MFCD17016128
Formula :	C₁₀H₁₆N₂O₂	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	-
M.W :	196.25	Pubchem ID :	-
Synonyms :

Safety of [ 936850-09-8 ]

Signal Word:	Warning	Class:	N/A
Precautionary Statements:	P280-P305+P351+P338	UN#:	N/A
Hazard Statements:	H302	Packing Group:	N/A
GHS Pictogram:

Application In Synthesis of [ 936850-09-8 ]

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

Upstream synthesis route of [ 936850-09-8 ]
Downstream synthetic route of [ 936850-09-8 ]

[ 936850-09-8 ] Synthesis Path-Upstream 1~1

1
[ 936850-09-8 ]
[ 887591-62-0 ]

Reference： [1] Arkivoc, 2018, vol. 2018, # 4, p. 195 - 214

[ 936850-09-8 ] Synthesis Path-Downstream 1~3

1
[ 142253-54-1 ]
[ 74-88-4 ]
[ 936850-09-8 ]

Yield	Reaction Conditions	Operation in experiment
89%		Step 1 In a 100 mL 2-neck round-bottomed flask, <strong>[142253-54-1]tert-butyl 3-cyanoazetidine-1-carboxylate</strong> (1.5 g, 8.2 mmol) was dissolved in THF (30 mL). The colorless solution was cooled to -76 C. and lithium bis(trimethylsilyl)amide (1.0M solution in THF, 9.0 mL, 9.0 mmol) was added dropwise over 25 min. The yellow solution was stirred at -76 C. for 30 min then iodomethane (0.78 mL, 12.5 mmol) was slowly added. The reaction mixture was stirred at -76 C. for 30 min and then warmed to room temperature over 1 h. The reaction mixture was quenched with 10 mL of saturated NH4Cl and diluted with 10 mL of water then extracted with ~100 ml EtOAc (2*). The combined organic layers were washed with ~10 mL water and ~10 mL brine then dried over sodium sulfate, filtered and concentrated. The residue was chromatographed over 40 g silica gel with EtOAc/hexanes, (gradient: 0-30% EtOAc). All fractions containing product were combined and concentrated to afford 1.44 g (89%) of 3-cyano-3-methyl-azetidine-1-carboxylic acid tert-butyl ester as a yellow solid.
69%		To a solution of <strong>[142253-54-1]tert-butyl 3-cyanoazetidine-1-carboxylate</strong> (22) (50 mg, 0.275 mmol, 1 equiv.) in THF (1.0 mL) was added LiHMDS (1M in THF, 0.302 mL, 0.302mmol, 1.1 equiv.) at -78 oC and stirred for 30 min. at the same temperature. Methyl iodide (25.7 muL, 0.411mmol, 1.5 equiv.) was added via syringe and stirred at -78 oC for 45 min. followed by stirring at rt for 1 h. Theresulting mixture was quenched with NH4Cl (1 mL) and extracted with ethyl acetate (3 x 2 mL). The combinedorganic extracts were washed with brine (2 mL), dried over Na2SO4, and concentrated. The crude material waspurified by flash chromatography (silica gel, 5-40% EtOAc in hexanes) to give the desired product 26 (37.4 mg,69%, caution: product can be lost through sublimation under high vacuum.). Physical State: yellow crystallinesolid (mp 57 oC); Rf = 0.53 (3:7 EtOAc/hexanes, vis. KMnO4); 1H NMR (500 MHz, CDCl3): delta 4.29 (d, J 8.6 Hz, 2H),3.80 (d, J 8.6 Hz, 2H), 1.67 (s, 3H), 1.45 (s, 9H); 13C NMR (126 MHz, CDCl3): delta 155.7, 122.2, 80.7, 59.3 (br, 2C),28.3 (3C), 26.0, 23.5; HRMS (ESI-TOF): calc?d for C10H16N2NaO2 [M+Na+] 219.1109; found 219.1087.
32%		PREPARATION S: 3-cyano-3-methylazetidine, TFA salt[0438] STEP A: tert-butyl 3-cyano-3-methylazetidine-l-carboxylate[0439] To an oven-dried 25 mL round bottom flask equipped for stirring was added diisopropylamine (1.318 mL, 9.33 mmol) under nitrogen. THF (10 mL) was added and the colorless solution was cooled to 00C. n-BuLi in hexanes (1.6N, 5.83 mL, 9.33 mmol) was added dropwise and the solution was stirred at 00C for 30 min. The solution was cooled to -78C and a solution of tert-butyi 3-cyanoazetidine-l-carboxylate (1 g, 5.49 mmol) in THF (3 mL) was added and the solution was stirred at -78C for 30 min. Iodomethane (0.445 mL, 7.13 mmol) was added dropwise at -78C. The reaction mixture was stirred for 30 min; it was then allowed to slowly warm up to 25C and was stirred for 16 h. The reaction mixture was quenched at 00C with aqueous ammonium chloride (5 mL) and was extracted with DCM (3 times). The extracts were dried over Na2SO4. Purification by silica column chromatography (MeOH/DCM, 0-5%) afforded the title compound as a yellow oil (0.35 g, 32%). 1H NMR (500 MHz, CDCl3) delta 1.45 (s, 9 H) 1.67 (s, 3 H) 3.80 (d, J=8.30 Hz, 2 H) 4.29 (d, J=8.79 Hz, 2 H).

Step 2: To a stirred solution of 8004A (50.0 g, 0.274 mol) in THF (500 mL) at -78 C is added a LiHMDS solution in THF (1 M; 330 mL, 0.330 mol, 1 .2 eq). The mixture is stirred for 30 min, then methyliodide (122g, 0.860 mol, 3.1 eq) is added and the mixture is stirred at RT for 60 min. The reaction mixture is neutralized at 0 C by adding a saturated aqueous NH4CI solution (500 ml_) and the aqueous layer is extracted with EtOAc (3 x 250 ml_). The organic layers are combined, washed with brine, dried over Na2S04, filtered and concentrated. The crude residue is purified by silica gel flash chromatography (eluent: petroleum ether / EtOAc, 10% to 15%) to afford intermediate 8004B.

Reference： [1]Patent: US2011/230462,2011,A1 .Location in patent: Page/Page column 89-90
[2]Arkivoc,2018,vol. 2018,p. 195 - 214
[3]Patent: WO2010/144486,2010,A1 .Location in patent: Page/Page column 97-98
[4]Patent: WO2013/152065,2013,A2 .Location in patent: Page/Page column 27; 28

2
[ 936850-09-8 ]
[ 936850-33-8 ]

Yield	Reaction Conditions	Operation in experiment
92%	Stage #1: tert-butyl 3-cyano-3-methylazetidine-1-carboxylate With 2,2,2-trifluoroethanol at 150℃; for 4h; Microwave irradiation; Inert atmosphere; Stage #2: With hydrogenchloride In diethyl ether at 0℃;	95.2 Step 2 A 20 mL microwave vial was charged with 3-cyano-3-methyl-azetidine-1-carboxylic acid tert-butyl ester (0.75 g, 3.82 mmol) and 2,2,2-trifluoroethanol (15.0 mL, 206 mmol). The vial was flushed with Argon and closed. The colorless solution was heated at 150° C. for 4 h under microwave irradiation. The reaction mixture was cooled to 0° C. and hydrogen chloride (1.0M solution in diethyl ether, 4.6 mL, 4.6 mmol) was added dropwise. The light yellow solution was concentrated and the residue was triturated with diethyl ether to afford 466 mg (92%) of 3-cyano-3-methyl-azetidine hydrochloride as a light yellow powder.
	With hydrogenchloride In 1,4-dioxane at 0 - 20℃; for 6h;	2.A.3 Preparation of intermediate 8004 Step 3: To a stirred solution of 8004B (30.0 g, 0.153 mol) in 1 ,4-dioxane (150 ml_) at 0 °C is added a HCI solution in dioxane (4M; 150 ml_, 0.60 mol, 3.9 eq) and the mixture is stirred at RT for 6 h. All volatiles are removed under reduced pressure. The crude residue is triturated in hexanes and collected by Buchner filtration to afford 8004 as the hydrochloride salt which is used without further purification.

Reference： [1]Current Patent Assignee: ROCHE HOLDING AG - US2011/230462, 2011, A1 Location in patent: Page/Page column 90
[2]Current Patent Assignee: C.H. Boehringer Sohn AG & Co. KG - WO2013/152065, 2013, A2 Location in patent: Page/Page column 28

3
[ 936850-09-8 ]
[ 887591-62-0 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium hydroxide; In methanol; water; for 4.0h;Reflux;	[Note: Since cyanoazetidine 26 is volatile, acombined procedure designed to maximize the yield is provided here. However, if azetidine 26 is already inhand, follow just the NaOH hydrolysis step.] To a solution of tert-butyl 3-cyanoazetidine-1-carboxylate (22)(150 mg, 0.823 mmol, 1 equiv.) in dry THF (3 mL) was added LiHMDS (1M in THF, 0.905 mL, 0.905 mmol, 1.1equiv.) at ?78 oC and stirred for 30 min. at the same temperature. Methyl iodide (77 muL, 1.23 mmol, 1.5 equiv.)was added via syringe and stirred at ?78 oC for 45 min. followed by stirring at rt for 1 h. The resulting mixturewas quenched with NH4Cl (2 mL) and extracted with ethyl acetate (3 x 2 mL). The combined organic extractswere washed with brine (3 mL), dried over Na2SO4, and concentrated. Compound 26 was used in the next stepwithout further purification. A solution of NaOH (115 mg, 4.12 mmol, 5 equiv.) in H2O (3 mL) was slowly addedto a solution of tert-butyl 3-cyano-3-methylazetidine-1-carboxylate (26) in MeOH (3 mL) and then refluxeduntil judged complete by TLC (ca. 4 h). The reaction mixture was cooled to rt and the MeOH was removed in vacuo. The mixture was neutralized with 10 percent aq. citric acid (3 mL) and extracted with CH2Cl2 (3 x 10 mL). Thecombined organic layers were washed with brine (50 mL), dried over Na2SO4, and concentrated to give thedesired product 27 (107.5 mg, 61percent for 2 steps). Physical State: white crystalline solid (mp 135?136 oC); 1HNMR (500 MHz, CDCl3): [mixture of rotamers] delta 6.71 (br s, 1H, COOH minor rotamer), 5.91 (br s, 1H, COOHmajor rotamer), 4.25 (d, J 8.5 Hz, 2H, major), 4.19 (d, J 8.4 Hz, 2H, minor), 3.69 (d, J 8.5 Hz, 2H, minor), 3.68 (d,J 8.6 Hz, 2H, major), 1.55 (s, 3H), 1.44 (s, 9H); 13C NMR (126 MHz, CDCl3): [mixture of rotamers] delta 179.3(major), 178.5 (minor), 156.6 (minor), 156.5 (major), 80.3 (minor), 80.1 (major), 58.5 (br, major + minor, 2 x2C), 39.1 (minor), 38.7 (major), 28.5 (major, 3C), 28.5 (minor, 3C), 23.1 (minor), 22.6 (major); HRMS (ESI-TOF):calc?d for C10H16NO4 [M-H] 214.1079; found 214.1080.

Reference： [1]Arkivoc,2018,vol. 2018,p. 195 - 214

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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.
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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.
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Code	Phrase
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P304	IF INHALED:
P305	IF IN EYES:
P306	IF ON CLOTHING:
P307	IF exposed:
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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.
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P337	If eye irritation persists:
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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.
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P376	Stop leak if safe to do so. Oxidising gases (section 2.4) 1
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P378
P380	Evacuate area.
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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.
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P413
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H200	Unstable explosive
H201	Explosive; mass explosion hazard
H202	Explosive; severe projection hazard
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H204	Fire or projection hazard
H205	May mass explode in fire
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H222	Extremely flammable aerosol
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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
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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
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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
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H331	Toxic if inhaled
H332	Harmful if inhaled
H333	May be harmful if inhaled
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H361d	Suspected of damaging the unborn child
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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. 936850-09-8 ] {[proInfo.proName]}

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Application In Synthesis of [ 936850-09-8 ]

[ 936850-09-8 ] Synthesis Path-Upstream 1~1

[ 936850-09-8 ] Synthesis Path-Downstream 1~3

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