31140-40-6

Usage

Chemical Properties

White crystalline powder

InChI:InChI=1/C9H7ClO4/c1-13-8(11)6-2-4-7(5-3-6)14-9(10)12/h2-5H,1H3

Synthetic route

phosgene (75-44-5) + methyl 4-hydroxylbenzoate (99-76-3) → methyl 4-[(chlorocarbonyl)oxy]benzoate (31140-40-6)

Conditions	Yield
With quinoline; benzene
In benzene
With pyridine In toluene
With quinoline; toluene

methyl 4-[(chlorocarbonyl)oxy]benzoate (31140-40-6) + 1,2-(2,3-dihydro-1H-azirino)-<60>fullerene (156286-12-3) → C69H7NO4

Conditions	Yield
With pyridine In various solvent(s) at 70℃; for 1h;	78%

1-cyanopyrazolidine (909015-28-7) + methyl 4-[(chlorocarbonyl)oxy]benzoate (31140-40-6) → 4-[(methyloxy)carbonyl]phenyl 2-cyanopyrazolidine-1-carboxylate

Conditions	Yield
In dichloromethane at 20℃;	45.2%

bis(tetrabutylammonium)-closo-dodecahydroxy-dodecaborate + methyl 4-[(chlorocarbonyl)oxy]benzoate (31140-40-6) → 2C16H36N(1+)*C108H84B12O60(2-)

Conditions	Yield
With pyridine In acetonitrile at 0 - 20℃; Inert atmosphere;	32%

closo-B12(OH)12(2-) + methyl 4-[(chlorocarbonyl)oxy]benzoate (31140-40-6) → B12(OCO2C6H4COOCH3)12(2-)

Conditions	Yield
With pyridine In acetonitrile B12(OH)12(2-), chloroformate, pyridine, acetonitrile (excess), 96 h, room temp.; filtered, the solvent was removed under vac., the residue was pptd. fromCH2Cl2 with diethyl ether, benchtop flash column chromy. using gradient of CH2Cl2 and CH3CN over neutral alumina;	32%

C14H22N2S8 (1191406-61-7) + methyl 4-[(chlorocarbonyl)oxy]benzoate (31140-40-6) → C30H40N4O2S16 (1191406-63-9)

Conditions	Yield
With pyridine In tetrahydrofuran at 20℃; Inert atmosphere;	30%

methyl 4-[(chlorocarbonyl)oxy]benzoate (31140-40-6) + 1,4-diazabicyclo[3.2.2]nonane (283-38-5) → 1,4-diaza-bicyclo[3.2.2]nonane-4-carboxylic acid 4-methoxycarbonyl-phenyl ester

Conditions	Yield
	25%

1-cyanohexahydropyridazine (909015-29-8) + methyl 4-[(chlorocarbonyl)oxy]benzoate (31140-40-6) → 4'-[(methyloxy)carbonyl]phebyl 2-cyanotetrahydropyridazine-1-carboxylate

Conditions	Yield
In dichloromethane at 20℃;	1%

methyl 4-[(chlorocarbonyl)oxy]benzoate (31140-40-6) + 2-(Diethylamino)ethanol (100-37-8) → carbonic acid-(2-diethylamino-ethyl ester)-(4-methoxycarbonyl-phenyl ester)

Conditions	Yield
With benzene
With benzene

methyl 4-[(chlorocarbonyl)oxy]benzoate (31140-40-6) + 2-(Diethylamino)ethanol (100-37-8) → carbonic acid-(2-diethylamino-ethyl ester)-(4-methoxycarbonyl-phenyl ester) + dimethyl 4,4′-(carbonylbis(oxy))dibenzoate (74721-70-3)

Conditions	Yield
With benzene

methyl 4-[(chlorocarbonyl)oxy]benzoate (31140-40-6) + N,N-bis(2-chloroethyl)benzene-1,4-diamine hydrochloride (945-68-6) → 4-{4-[Bis-(2-chloro-ethyl)-amino]-phenylcarbamoyloxy}-benzoic acid methyl ester (27885-39-8)

Conditions	Yield
With pyridine

2-biphenyl-4-yl-propan-2-ol (34352-74-4) + methyl 4-[(chlorocarbonyl)oxy]benzoate (31140-40-6) → methyl 4-[({[2-(biphenyl-4-yl)propan-2-yl]oxy}carbonyl)oxy]benzoate (31140-37-1)

Conditions	Yield
With pyridine In dichloromethane

methyl 4-[(chlorocarbonyl)oxy]benzoate (31140-40-6) + 4-amino-phenol (123-30-8) → 4-(4-Hydroxy-phenylcarbamoyloxy)-benzoic acid methyl ester (41920-47-2)

methyl 4-[(chlorocarbonyl)oxy]benzoate (31140-40-6) → methyl 4-(2-(diethylamino)ethoxy)benzoate (3483-96-3)

Conditions	Yield
Multi-step reaction with 2 steps 1: benzene 2: durch zweimalige Destillation unter vermindertem Druck View Scheme
Multi-step reaction with 2 steps 1: benzene 2: durch zweimalige Destillation unter vermindertem Druck View Scheme
Multi-step reaction with 2 steps 1: benzene 2: durch zweimalige Destillation unter vermindertem Druck View Scheme

methyl 4-[(chlorocarbonyl)oxy]benzoate (31140-40-6) → p-Carboxyphenyl-N-p-(bis-2-chlorethylamino)-phenylcarbamat (27885-40-1)

Conditions	Yield
Multi-step reaction with 2 steps 1: Py 2: aq. HCl, AcOH View Scheme

methyl 4-[(chlorocarbonyl)oxy]benzoate (31140-40-6) → C15H12Cl2NO6P (41920-50-7)

Conditions	Yield
Multi-step reaction with 2 steps 2: POCl3, Et3N View Scheme

methyl 4-[(chlorocarbonyl)oxy]benzoate (31140-40-6) → C16H13Cl2N2O7P

methyl 4-[(chlorocarbonyl)oxy]benzoate (31140-40-6) + 4-(dicyanomethylene)-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran (96042-30-7) + 1-(1-ethylpropyl)piperazine → 4-(1-Ethylpropyl)piperazine-1-carboxylic Acid 4-methoxycarbonylphenyl Ester Hydrochloride Salt (485798-59-2)

Conditions	Yield
In hydrogenchloride; ethyl acetate	670 mg (90%)

1,2,3,4-tetrahydro-2-amino-isoquinoline (4836-98-0) + methyl 4-[(chlorocarbonyl)oxy]benzoate (31140-40-6) → 4-(3,4-Dihydro-1H-isoquinolin-2-ylcarbamoyloxy)-benzoic Acid Methyl Ester

Conditions	Yield
With N-ethyl-N,N-diisopropylamine In n-heptane; dichloromethane; ethyl acetate

methyl 4-[(chlorocarbonyl)oxy]benzoate (31140-40-6) + 8-[3-(N-glycyl-N-methylamino)-2,6-dichlorobenzyloxy]-2-methylquinoline (167834-66-4) → 8-[2,6-dichloro-3-[N-[(4-methoxycarbonylphenoxycarbonyl)glycyl]-N-methylamino]benzyloxy]-2-methylquinoline

Conditions	Yield
With triethylamine In tetrahydrofuran; water; ethyl acetate

(3R,4R)-3-(([tert-butyl(dimethyl)silyl]oxy)methyl)-4-(2-furyl)pyrrolidine (915390-18-0) + methyl 4-[(chlorocarbonyl)oxy]benzoate (31140-40-6) → 4-(methoxycarbonyl)phenyl (3R,4R)-3-(([tert-butyl(dimethyl)silyl]oxy)methyl)-4-(2-furyl)pyrrolidine-1-carboxylate (915390-19-1)

Conditions	Yield
With sodium hydrogencarbonate In tetrahydrofuran; water at 20℃; for 3h;

3-[(3S,4R)-4-(([tert-butyl(dimethyl)silyl]oxy)methyl)pyrrolidin-3-yl]pyridine (915390-20-4) + methyl 4-[(chlorocarbonyl)oxy]benzoate (31140-40-6) → 4-(methoxycarbonyl)phenyl (3R,4S)-3-(([tert-butyl(dimethyl)silyl]oxy)methyl)-4-pyridin-3-ylpyrrolidine-1-carboxylate (915390-21-5)

Conditions	Yield
With N-ethyl-N,N-diisopropylamine In tetrahydrofuran at 20℃; for 3h;

tert-butyl [(1R)-1-(1-naphthyl)ethyl]([(3R,4S)-4-phenylpyrrolidin-3-yl]methyl)carbamate (915389-64-9) + methyl 4-[(chlorocarbonyl)oxy]benzoate (31140-40-6) → 4-(methoxycarbonyl)phenyl (3R,4S)-3-(((tert-butoxycarbonyl)[(1R)-1-(1-naphthyl)ethyl]amino)methyl)-4-phenylpyrrolidine-1-carboxylate

Conditions	Yield
With pyridine In tetrahydrofuran at 20℃; for 168h;

methyl 4-[(chlorocarbonyl)oxy]benzoate (31140-40-6) + (3R,4S)-3-(([tert-butyl(dimethyl)silyl]oxy)methyl)-4-phenylpyrrolidine (300853-88-7) → 4-(methoxycarbonyl)phenyl (3R,4S)-3-(([tert-butyl(dimethyl)silyl]oxy)methyl)-4-phenylpyrrolidine-1-carboxylate (915390-15-7)

Conditions	Yield
With pyridine In tetrahydrofuran at 0 - 20℃; for 3h;

tert-butyl [(1R)-1-(1-naphthyl)ethyl][(4-phenylpiperidin-3-yl)methyl]carbamate (1027702-60-8) + methyl 4-[(chlorocarbonyl)oxy]benzoate (31140-40-6) → 4-(methoxycarbonyl)phenyl 3-({(tert-butoxycarbonyl)[(1R)-1-(1-naphthyl)ethyl]amino}methyl)-4-phenylpiperidine-1-carboxylate (1027702-74-4)

Conditions	Yield
With sodium hydrogencarbonate In tetrahydrofuran; water at 20℃;

tert-butyl [(1R)-1-(1-naphthyl)ethyl][(4-phenylpiperidin-3-yl)methyl]carbamate (1027702-60-8) + methyl 4-[(chlorocarbonyl)oxy]benzoate (31140-40-6) → 4-(methoxycarbonyl)phenyl 4-({(tert-butoxycarbonyl)[(1R)-1-(1-naphthyl)ethyl]amino}methyl)-3-phenylpiperidine-1-carboxylate (1027704-67-1)

Conditions	Yield
With triethylamine In tetrahydrofuran at 20℃; for 1h;

tert-butyl {[4-(3-fluorophenyl)piperidin-3-yl]methyl}[(1R)-1-(1-naphthyl)ethyl]carbamate (1027702-88-0) + methyl 4-[(chlorocarbonyl)oxy]benzoate (31140-40-6) → 4-({[3-({(tert-butoxycarbonyl)[(1R)-1-(1-naphthyl)ethyl]amino}methyl)-4-(3-fluorophenyl)piperidin-1-yl]carbonyl}oxy)benzoic acid (1027702-95-9)

Conditions	Yield
Stage #1: tert-butyl {[4-(3-fluorophenyl)piperidin-3-yl]methyl}[(1R)-1-(1-naphthyl)ethyl]carbamate; methyl 4-[(chlorocarbonyl)oxy]benzoate With triethylamine In tetrahydrofuran at 20℃; for 2h; Stage #2: With sodium hydroxide; water In tetrahydrofuran; isopropyl alcohol at 20℃; for 48h; Stage #3: With hydrogenchloride In tetrahydrofuran; water; isopropyl alcohol

tert-butyl {[4-(2-fluorophenyl)piperidin-3-yl]methyl}[(1R)-1-(1-naphthyl)ethyl]carbamate + methyl 4-[(chlorocarbonyl)oxy]benzoate (31140-40-6) → 4-({[3-({(tert-butoxycarbonyl)[(1R)-1-(1-naphthyl)ethyl]amino}methyl)-4-(2-fluorophenyl)piperidin-1-yl]carbonyl}oxy)benzoic acid (1027703-64-5)

Conditions	Yield
Stage #1: tert-butyl {[4-(2-fluorophenyl)piperidin-3-yl]methyl}[(1R)-1-(1-naphthyl)ethyl]carbamate; methyl 4-[(chlorocarbonyl)oxy]benzoate With sodium hydrogencarbonate In tetrahydrofuran; water at 20℃; for 1h; Stage #2: With sodium hydroxide; water In tetrahydrofuran; methanol at 20℃; Stage #3: With hydrogenchloride In tetrahydrofuran; methanol; water

Upstream product

• 75-44-5 phosgene 
• 99-76-3 methyl 4-hydroxylbenzoate 

Downstream Products

• 74721-70-3 dimethyl 4,4′-(carbonylbis(oxy))dibenzoate 
• 27885-39-8 4-{4-[Bis-(2-chloro-ethyl)-amino]-phenylcarbamoyloxy}-benzoic acid methyl ester 
• 31140-37-1 methyl 4-[({[2-(biphenyl-4-yl)propan-2-yl]oxy}carbonyl)oxy]benzoate 
• 41920-47-2 4-(4-Hydroxy-phenylcarbamoyloxy)-benzoic acid methyl ester 
• 41920-50-7 C₁₅H₁₂Cl₂NO₆P 
• 485798-59-2 4-(1-Ethylpropyl)piperazine-1-carboxylic Acid 4-methoxycarbonylphenyl Ester Hydrochloride Salt 
• 915390-19-1 4-(methoxycarbonyl)phenyl (3R,4R)-3-(([tert-butyl(dimethyl)silyl]oxy)methyl)-4-(2-furyl)pyrrolidine-1-carboxylate 
• 915390-21-5 4-(methoxycarbonyl)phenyl (3R,4S)-3-(([tert-butyl(dimethyl)silyl]oxy)methyl)-4-pyridin-3-ylpyrrolidine-1-carboxylate 
• 915390-15-7 4-(methoxycarbonyl)phenyl (3R,4S)-3-(([tert-butyl(dimethyl)silyl]oxy)methyl)-4-phenylpyrrolidine-1-carboxylate 
• 1027702-74-4 4-(methoxycarbonyl)phenyl 3-({(tert-butoxycarbonyl)[(1R)-1-(1-naphthyl)ethyl]amino}methyl)-4-phenylpiperidine-1-carboxylate 
• 1027704-67-1 4-(methoxycarbonyl)phenyl 4-({(tert-butoxycarbonyl)[(1R)-1-(1-naphthyl)ethyl]amino}methyl)-3-phenylpiperidine-1-carboxylate 
• 1027702-95-9 4-({[3-({(tert-butoxycarbonyl)[(1R)-1-(1-naphthyl)ethyl]amino}methyl)-4-(3-fluorophenyl)piperidin-1-yl]carbonyl}oxy)benzoic acid 
• 1027703-64-5 4-({[3-({(tert-butoxycarbonyl)[(1R)-1-(1-naphthyl)ethyl]amino}methyl)-4-(2-fluorophenyl)piperidin-1-yl]carbonyl}oxy)benzoic acid 
• 1027682-85-4 4-(methoxycarbonyl)phenyl 3-({[(1R)-1-(1-naphthyl)ethyl]amino}methyl)-4-phenylpiperidine-1-carboxylate 

Relevant academic research and scientific papers

N alpha - alpha , alpha -dimethyl-3,5-dialkoxybenzylcarbonyl amino acid 3,4-dihydro-3-hydroxy-4-oxo-1,2,3-benzotriazin-3-yl and pentafluorophenyl esters

This invention provides Ddz-amino acid pentafluorophenyl esters and Ddz-amino acid 3,4-dihydro-3-hydroxy-4-oxo-1,2,3-benzotriazine (ODhbt) esters and their side-chain protected derivatives. Preferred esters and derivatives are crystalline solids. The invention also provides ( alpha , alpha -Dimethyl-3,5-dimethoxybenzyl)-p-methoxycarbonylphenylcarbonate, an improved reagent for the introduction of the Ddz group. Pfp and ODhbt esters of this invention have favorable coupling to racemization ratios and are particularly suited for automated solid-phase peptide synthesis. The invention relates in addition to methods of making the esters of this invention and to methods of using these esters in peptide synthesis.

1-Aziridine carboxylic acid derivatives with immunostimulant activity

2-Substituted-1-aziridine-carboxylic acid esters exhibiting immuno-stimulant activity and of the formula STR1 wherein X is a carbamoyl or alkoxycarbonyl radical, and R1 is an aliphatic hydrocarbon radical optionally substituted by halogen, alkoxy, amino, carbamoyloxy, cycloalkyl, hydroxyl, an imido or heterocyclic radical, cycloalkyl; or aryl, aralkyl, aryloxyalkyl or arylthioalkyl wherein the aryl moiety is optionally substituted by halogen, alkyl, alkoxy, hydroxyl, amino, nitro, cyano, acyl, carbalkoxy, thioalkyl, alkylsulphonyl, phenyl or trifluoromethyl. Counterparts where X is --CN and R1 is as above, except for ethyl, are also new.