[ CAS No. 317358-61-5 ] {[proInfo.proName]}

Name: 317358-61-5|tert-Butyl 3-bromobenzyl(methyl)carbamate|95%
Brand: Ambeed
SKU: A533816
Rating: 91 (25 reviews)

,{[proInfo.pro_purity]}

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

DV 2D 3D

3d Animation Molecule Structure of 317358-61-5

Structure of 317358-61-5 * Storage: {[proInfo.prStorage]}

Cart0 Add to My Favorites Add to My Favorites Bulk Inquiry Inquiry Add To Cart

Search after Editing

* Storage: {[proInfo.prStorage]}

For Research Only 110K+ Compounds Competitive Price 1-2 Day Shipping

Quality Control of [ 317358-61-5 ]

COA NMR CNMR HPLC LC-MS

Related Doc. of [ 317358-61-5 ]

SDS Specification

Alternatived Products of [ 317358-61-5 ]

Product Details of [ 317358-61-5 ]

CAS No. :	317358-61-5	MDL No. :	MFCD09701230
Formula :	C₁₃H₁₈BrNO₂	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	DJNHISMHPSMPBN-UHFFFAOYSA-N
M.W :	300.19	Pubchem ID :	20738487
Synonyms :

Safety of [ 317358-61-5 ]

Signal Word:	Warning	Class:
Precautionary Statements:	P261-P280-P301+P312-P302+P352-P305+P351+P338	UN#:
Hazard Statements:	H302-H315-H319-H335	Packing Group:
GHS Pictogram:

Application In Synthesis of [ 317358-61-5 ]

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

Upstream synthesis route of [ 317358-61-5 ]
Downstream synthetic route of [ 317358-61-5 ]

[ 317358-61-5 ] Synthesis Path-Upstream 1~1

1
[ 317358-61-5 ]
[ 67344-77-8 ]

Reference： [1] Patent: US2004/39038, 2004, A1,

[ 317358-61-5 ] Synthesis Path-Downstream 1~22

1
[ 171663-13-1 ]
[ 74-88-4 ]
[ 317358-61-5 ]

Yield	Reaction Conditions	Operation in experiment
100%		b-tert-Butyl (3-bromobenzyl)methylcarbamate5.4 g (134 mmol) of 60% sodium hydride are added to a solution of 32 g (111 mmol) of <strong>[171663-13-1]tert-butyl (3-bromobenzyl)carbamate</strong> in 450 mL of dimethylformamide. The reaction medium is stirred at room temperature for 30 minutes and 21 mL (335 mmol) of iodomethane are then added. The reaction medium is stirred at room temperature for 20 hours and then hydrolyzed in water and extracted with ethyl acetate. The organic phases are combined, washed with saturated sodium chloride solution and dried over sodium sulfate. The solvent is evaporated off and 36.2 g (100%) of tert-butyl (3-bromobenzyl)methylcarbamate are obtained in the form of an orange-colored oil.
100%		5.4 g (0.134 mol, 1.2 eq.) of 60% sodium hydride are added to a solution of 32.0 g (0.111 mol, 1 eq.) of <strong>[171663-13-1]tert-butyl (3-bromobenzyl)carbamate</strong> in 450 ml of dimethylformamide. The reaction medium is stirred at ambient temperature for 30 minutes and then 20.9 ml (0.335 mol, 3 eq.) of iodomethane are added. The reaction medium is stirred at ambient temperature for 20 hours, then hydrolysed in water and extracted with ethyl acetate. The organic phases are combined, washed with a saturated sodium chloride solution and dried over sodium sulphate. The solvent is evaporated and 36.23 g of tert-butyl (3-bromobenzyl)(methyl)carbamate are obtained in the form of an orange oil. Yield = 100%
92%	With sodium hydride; In DMF (N,N-dimethyl-formamide);	19 g (475 mmol) of sodium hydride (60% in oil) are added portionwise to a solution of 128 g (447 mmol) of tert-butyl (3-bromobenzyl) carbamate in 800 ml of DMF, and the reaction medium is stirred until the evolution of gas has ceased. 29.3 ml (470 mmol) of methyl iodide are added dropwise and stirring is continued for 18 hours. The reaction medium is poured into ice-cold water and extracted with ethyl acetate. The organic phase is separated out by settling of the phases, dried over magnesium sulphate and evaporated. 152.5 g of ter-butyl (3-bromobenzyl) -N-methylcarbamate are obtained in a yield of 92%

In N,N-dimethyl-formamide;

(b) tert-butyl (3-bromobenzyl)-N-methylcarbamate 128 g (447 mmol) of <strong>[171663-13-1]tert-butyl (3-bromobenzyl)carbamate</strong> and 800 ml of DMF are introduced into a round-bottomed flask and under a nitrogen stream. 19 g (475 mmol) of sodium hydride (60% in oil) are added in small quantities and the mixture is stirred until the gas emission ceases. 29.3 ml (470 mmol) of methyl iodide are then added and the mixture is stirred overnight. The reaction medium is poured into ice-cold water, extracted with ethyl acetate, the organic phase decanted off, dried over magnesium sulphate and evaporated off. 152.5 g (92%) of the expected product are recovered.

Reference： [1]Patent: US2009/12129,2009,A1 .Location in patent: Page/Page column 21
[2]Patent: WO2006/18325,2006,A1 .Location in patent: Page/Page column 29
[3]Patent: WO2004/48351,2004,A2 .Location in patent: Page 31-32
[4]Patent: US2003/134885,2003,A1

2
[ 317358-61-5 ]
[ 87199-17-5 ]
[ 398149-88-7 ]

Yield	Reaction Conditions	Operation in experiment
60%	With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In water; toluene; at 90℃; for 24h;	307 ml (615 mmol) of aqueous potassium carbonate solution (2M) are added dropwise to a mixture of 61.5 g (205 mmol) of ter-butyl (3-bromobenzyl) -N- methylcarbamate, 46 g (307 mmol) of 4-formylbenzeneboronic acid and 500 ml of toluene. The reaction medium is then degassed with argon and 7 g (6. 2 mmol) of tetrakis (triphenylphosphine) palladium (0) are added. After heating at 90C for 24 hours, the reaction medium is poured into water and extracted with ethyl acetate. The organic phase is separated out by settling of the phases, dried over magnesium sulphate and evaporated. The residue obtained is purified by chromatography on a column of silica eluted with a mixture of heptane and ethyl acetate (70/30). After evaporating off the solvents, 67 g of tert-butyl (4'-formylbiphenyl-3-ylmethyl) methylcarbamate are collected in a yield of 60%

Reference： [1]Patent: WO2004/48351,2004,A2 .Location in patent: Page 32

3
[ 317358-61-5 ]
[ 71597-85-8 ]
[ 706780-09-8 ]

Yield	Reaction Conditions	Operation in experiment
68%	With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; water; at 80℃; for 12h;	41.6 ml (83.2 mmol) of aqueous 2M potassium carbonate solution are added dropwise to a solution of 10 g (33 mmol) of tert-butyl (3-bromobenzyl)-N- methylcarbamate and 8.3 g (60 mmol) of 4-hydroxy- benzeneboronic acid in 100 ml of ethylene glycol dimethyl ether. The reaction medium is degassed and 1.9 g (1.7 mmol) of tetrakis (triphenylphosphino)- palladium are added. After heating for 12 hours at 80C, the reaction medium is cooled, diluted with water and extracted with ethyl acetate. The organic phase is dried over sodium sulphate, filtered and concentrated under vacuum. The residue obtained is purified by chromatography on a column of silica eluted with an 80/20 heptane/ethyl acetate mixture. 7 g of tert-butyl (4'-HYDROXYBIPHENYL-3-YLMETHYL) methylcarbamate are obtained in the form of a beige-coloured solid, in a yield of 68%. Melting point: 174C.

Reference： [1]Patent: WO2004/52840,2004,A1 .Location in patent: Page 54-55

4
aqueous potassium carbonate [ No CAS ]
tetrakis(triphenylphosphine)-palladium⁽⁰⁾ chloride [ No CAS ]
[ 317358-61-5 ]
[ 87199-17-5 ]
argon [ No CAS ]
[ 398149-88-7 ]

Yield	Reaction Conditions	Operation in experiment
	In toluene;	(c) tert-butyl (4'-formylbiphenyl-3-ylmethyl)methylcarbamate 61.5 g (205 mmol) of <strong>[317358-61-5]tert-butyl (3-bromobenzyl)-N-methylcarbamate</strong>, 40 g (260 mmol) of 4-formylbenzeneboronic acid and 800 ml of toluene are introduced into a three-necked flask and under argon. 205 ml of an aqueous potassium carbonate solution (2 M) are added dropwise, the reaction medium is degassed with argon and 7 g of tetrakis(triphenylphosphine)-palladium(0) chloride are added and the mixture is heated at 90 C. for 24 hours. The reaction medium is poured into water, extracted with dichloromethane, the organic phase decanted off, dried over magnesium sulphate and evaporated off. The residue obtained is purified by chromatography on a silica column eluted with a heptane and ethyl acetate (70-30) mixture. After evaporation of the solvents, 38 g (57%) of the expected product are recovered.

Reference： [1]Patent: US2003/134885,2003,A1

5
[ 317358-61-5 ]
[ 73183-34-3 ]
[ 817618-31-8 ]

Yield	Reaction Conditions	Operation in experiment
83%	With potassium acetate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In N,N-dimethyl-formamide;	In a manner analogous to Example 1c, by reaction of 33.0 g (0.11 mol, 1 eq.) of <strong>[317358-61-5]tert-butyl (3-bromobenzyl)(methyl)carbamate</strong>, of 29.3 g (0.115 mol, 1.05 eq.) of bis(pinacolato)diboron and of 32.3 g (0.33 mol, 3 eq.) of potassium acetate in 500 ml of dimethylformamide in the presence of 3.6 g (4 mol%) of [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(ll) (PdCI2dppf), 31.56 g of tert-butyl methyl[3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzyl]carbamate are obtained, after chromatography on silica gel (heptane/ethyl acetate 90/10), in the form of a green oil. Yield = 83%
60%	With tris-(dibenzylideneacetone)dipalladium(0); potassium acetate; XPhos; In 1,4-dioxane; at 100℃; for 48h;	tert-Butyl 3-bromobenzyl(methyl)carbamate (Preparation 15b, 678 mg, 2.26 mmol) was treated with 4,4,4?,4?,5,5,5?,5?-octamethyl-2,2?-bi-1 ,3,2-dioxaborolane (860 mg, 3.40 mmol), potassium acetate (665 mg, 6.78 mmol), dicyclohexyl(2,4,6-triisopropylbiphenyl-2-yl)phosphine (108 mg, 0.23 mmol) and tris(dibenzylideneacetone)dipalladium(0) (103 mg, 0.11 mmol) in dioxane (7 mL) at 100C for 48 hours. The residue was purified by flash chromatography (hexanes to diethyl ether) to yield the title compound (570 mg, 60%) as a colourless oil.LRMS (mz): 348 (M÷1).1H-NMR oe (300 MHz, CDCI3): 1.36 (s, 12 H), 1.59 (s, 9 H), 2.85 (br. s., 3 H), 4.44 (br. s., 2 H), 7.32 - 7.44 (m, 2 H), 7.60 - 7.81 (m, 2 H).
	With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; potassium acetate; In 1,4-dioxane; at 80℃; for 3h;	The compound BB-2-3 (6.34 g, 24.99 mmol, 1.50 eq), the compound BB-13-2 (5.00 g, 16.66 mmol, 1.00 eq), potassium acetate (3.27 g, 33.32 mmol, 2.00 eq) and Pd(dppf)Cl2.CH2Cl2 (1.36 g, 1.67 mmol, 0.10 eq) were added into a dried reaction flask, and dioxane (100.00 mL) was added. The reaction temperature was raised to 80C and the reaction was stirred for 3 hours. After completion of the reaction, the reaction solution was filtered through diatomaceous earth. The filtrate was collected and evaporated to dryness by rotary evaporation to give a crude product. The crude product was purified by column chromatography (PE/EA=5/1) to give the target compound BB-13. 1H NMR (400 MHz, CDCl3-d) delta 7.73-7.68(m, 2 H), 7.37-7.33(m, 2 H), 4.42(br. s., 2 H), 2.85-2.76(m, 3 H), 1.49(s, 9 H), 1.35(s, 12 H). MS m/z: 291.9 [M+H]+

Reference： [1]Patent: WO2006/18325,2006,A1 .Location in patent: Page/Page column 29
[2]Patent: WO2017/220431,2017,A1 .Location in patent: Page/Page column 48
[3]Patent: EP3643308,2020,A1 .Location in patent: Paragraph 0168; 0169; 0171

6
[ 171663-13-1 ]
[ 317358-61-5 ]

Yield	Reaction Conditions	Operation in experiment
		(b) tert-Butyl (3-bromo benzyl)-N-methylcarbamate In a manner similar to that of Example 1(b), starting with 85 g (297 mmol) of tert-butyl (3-bromo benzyl)carbamate, 92.5 g (100%) of the expected product are obtained.

Reference： [1]Patent: US2004/39038,2004,A1

7
[ 317358-61-5 ]
[ 67344-77-8 ]

Yield	Reaction Conditions	Operation in experiment
	In methanol; dichloromethane;	(c) (3-Bromo benzyl)methylamine 20.2 g (67 mmol) of tert-butyl (3-bromo-benzyl)-N-methylcarbamate are introduced into 100 ml of dichloromethane in a round-bottomed flask under a stream of nitrogen, and 26 ml (335 mmol) of trifluoroacetic acid are added. The reaction medium is stirred at room temperature for 8 hours and hydrolyzed with saturated potassium carbonate solution. The mixture is extracted with dichloromethane and the organic phase is separated out after settling of the phases has taken place, washed with water, dried over magnesium sulfate and evaporated. The residue obtained is purified by chromatography on a column of silica eluded with a mixture of dichloromethane and methanol (50/50). After evaporation of the solvents, 9 g (67percent) of the expected product are collected.

Reference： [1]Patent: US2004/39038,2004,A1

8
[ 317358-61-5 ]
3-methyl-4-formylbenzene-boronic acid [ No CAS ]
[ 398151-58-1 ]

Yield	Reaction Conditions	Operation in experiment
		(a) tert-Butyl (4'-formyl-3'-methylbiphenyl-3-ylmethyl)-N-methylcarbamate In a manner similar to that of Example 1(e), by reacting 1.1 g (3.5 mmol) of <strong>[317358-61-5]tert-butyl (3-bromo-benzyl)-N-methylcarbamate</strong> obtained in Example 79(b) with 750 mg (4.6 mmol) of 3-methyl-4-formylbenzene-boronic acid, and after purification by chromatography on a column of silica eluted with a heptane/ethyl acetate mixture (7/3), 1 g (87%) of the expected product is obtained in the form of a yellow oil.

Reference： [1]Patent: US2004/39038,2004,A1

9
[ 706780-09-8 ]
[ 74-88-4 ]
[ 317358-61-5 ]

Yield	Reaction Conditions	Operation in experiment
92%		19 g (475 mmol) of sodium hydride (60% in oil) are added portionwise to a solution of 128 g (447 mmol) of tert-butyl (3-bromobenzyl) carbamate in 800 ml of DMF, and the reaction medium is stirred until the evolution of gas has ceased. 29.3 ml (470 mmol) of methyl iodide are added dropwise and stirring is continued for 18 hours. The reaction medium is poured into ice-cold water and extracted with ethyl acetate. The organic phase is separated out after settling has taken place, dried over magnesium sulphate and evaporated. 152.5 g of tert-butyl (3-bromobenzyl)-N- methylcarbamate are obtained in a yield of 92%.

Reference： [1]Patent: WO2004/52840,2004,A1 .Location in patent: Page 53-54

10
[ 24424-99-5 ]
[ 67344-77-8 ]
[ 317358-61-5 ]

Yield	Reaction Conditions	Operation in experiment
96%	With triethylamine; In dichloromethane; at 20℃; for 16h;	Step 1: tert-Butyl 3-bromobenzyl(methyl)carbamate[00171] BOC20 (1.309 g, 1.378 mL, 5.998 mmol) was added to a stirred solution of l-(3- bromophenyl)-N-methyl-methanamine (1 g, 4.998 mmol) and Ets (606.9 mg, 836.0 mu^, 5.998 mmol) in DCM (20 mL) at ambient temperature and the reaction stirred for 16 hours. The reaction mixture was washed with 0.5M HC1 (x 1), water (x 2) and brine (x 1). The combined organic extractcs were dried (MgS04), filtered and concentrated in vacuo. The residue was purified by column chromatography (ISCO Companion.(TM)., 40 g column, eluting with 0 to 50percent EtO Ac/Petroleum Ether) to give the sub-title product as a colourless oil (1.44 g, 96percent Yield). XH NMR (400.0 MHz, DMSO) d 1.38 - 1.43 (2 x br s, 9H), 2.77 (s, 3H), 4.37 (s, 2H), 7.23 (d, 1H), 7.33 (t, 1H), 7.41 (s, 1H) and 7.48 (d, 1H) ppm; MS (ES+) 302.1.

Reference： [1]Patent: WO2011/143399,2011,A1 .Location in patent: Page/Page column 67-68

11
[ 317358-61-5 ]
[ 1232423-98-1 ]
[ 1350351-57-3 ]