38345-66-3

Usage

Uses

Reducing reagent in organic synthesis.

Purification Methods

Purify the hydrochloride by dissolving 1.5g in 13.5 mL of 5N HCl, heat to boiling and evaporate in a vacuum. Recrystallise the hydrochloride three times from MeOH/EtOAc giving m 189-190o, []D -33.7o (c 1, H2O) {enantiomer has +34.2o}. The hydrochloride in the minimum volume of water is basified with aqueous 5N NaOH and extracted with Et2O. The extract is dried (K2CO3) and evaporated, leaving a residue which is stored in a desiccator over solid KOH as a low melting solid. It can be recovered using these procedures from asymmetric reductions with LAH, and re-used. [Pohland & Sullivan J Am Chem Soc 77 3400 1955, Sullivan et al. J Org Chem 28 2483 1963, Beilstein 13 IV 2221.]

InChI:InChI=1/C19H25NO/c1-16(15-20(2)3)19(21,18-12-8-5-9-13-18)14-17-10-6-4-7-11-17/h4-13,16,21H,14-15H2,1-3H3/t16-,19-/m1/s1

Synthetic route

(2RS,3SR)-4-dimethylamino-3-methyl-1,2-diphenyl-butan-2-ol (126-04-5, 38345-66-3, 52079-40-0, 52079-41-1, 63957-11-9, 72541-03-8) → (2S,3R)-(+)-4-Dimethylamino-1,2-diphenyl-3-methyl-2-butanol (38345-66-3)

Conditions	Yield
With camphor-10-sulfonic acid

dimethyl amine (124-40-3) + p-toluenesulfonyl chloride (98-59-9) → (2S,3R)-(+)-4-Dimethylamino-1,2-diphenyl-3-methyl-2-butanol (38345-66-3)

Conditions	Yield
In dimethyl sulfoxide for 48h; Ambient temperature;

formaldehyd (50-00-0) + threo-(+)-4-Amino-1,2-diphenyl-3-methyl-2-butanol-maleat → (2S,3R)-(+)-4-Dimethylamino-1,2-diphenyl-3-methyl-2-butanol (38345-66-3)

Conditions	Yield
With formic acid

lithium aluminium tetrahydride (16853-85-3) + benzoylferrocene (1272-44-2) + (2S,3R)-(+)-4-Dimethylamino-1,2-diphenyl-3-methyl-2-butanol (38345-66-3) → (R)-phenylhydroxymethylferrocene

Conditions	Yield
With hydrogenchloride; ammonium chloride In diethyl ether (Ar); soln. of Chirald in Et2O stirred at 0°C, added to soln. of LiAlH4 in ether, cooled to -70°C; dropwise addn. of ethereal soln. of Fe-complex at -70°C; treatment with wet ether and aq. NH4Cl;; ethereal ext. treated with 1 N HCl; crystn. (hexane);	90%

lithium aluminium tetrahydride (16853-85-3) + benzoylruthenocene + (2S,3R)-(+)-4-Dimethylamino-1,2-diphenyl-3-methyl-2-butanol (38345-66-3) → (C5H5)Ru(C5H4CH(OH)C6H5)

Conditions	Yield
With hydrogenchloride; ammonium chloride In diethyl ether (Ar); soln. of Chirald in Et2O stirred at 0°C added to soln. of LiAlH4 in ether cooled to -70°C; dropwise addn. of ethereal soln. of Ru-complex at -50°C; treatment with wet ether and aq. NH4Cl;; ethereal ext. treated with 1 N HCl; crystn. (hexane);	90%

(2S,3R)-(+)-4-Dimethylamino-1,2-diphenyl-3-methyl-2-butanol (38345-66-3) + binaphthol chlorophosphite (137156-22-0, 171878-71-0, 155613-52-8) → (1'S,2'R)-2-(1'-benzyl-3'-dimethylamino-2'-methyl-1'-phenyl-propoxy)dinaphtho[2,1-d:1',2'-f](1,3,2) dioxaphosphepine (479253-09-3)

Conditions	Yield
With triethylamine In toluene	89%

(2S,3R)-(+)-4-Dimethylamino-1,2-diphenyl-3-methyl-2-butanol (38345-66-3) + [(R)-1,1'-binaphthyl-2,2'-diyl]chlorophosphite → (Rax)-(1'S,2'R)-2-(1'-benzyl-3'-dimethylamino-2'-methyl-1'-phenyl-propoxy)dinaphtho[2,1-d:1',2'-f](1,3,2) dioxaphosphepine

Conditions	Yield
With triethylamine In toluene	87%

(2S,3R)-(+)-4-Dimethylamino-1,2-diphenyl-3-methyl-2-butanol (38345-66-3) + 1-dodecylbromide (143-15-7) → (+)-(2R,3S)-N-(3-hydroxy-2-methyl-3,4-diphenylbutyl)-N,N-dimethyldodecan-1-ammonium bromide (1356938-68-5)

Conditions	Yield
In acetonitrile for 240h; Reflux;	65%

(2S,3R)-(+)-4-Dimethylamino-1,2-diphenyl-3-methyl-2-butanol (38345-66-3) + benzyl chloride (100-44-7) → (2R,3S)-(+)N-benzyl-N,N-dimethyl-N-(3,4-diphenyl-3-hydroxy-2-methylbutyl) ammonium chloride

Conditions	Yield
In ethanol for 18h; Heating;	28%

methyl 2-oxo-2-phenylacetate (15206-55-0) + (2S,3R)-(+)-4-Dimethylamino-1,2-diphenyl-3-methyl-2-butanol (38345-66-3) + lithium tetrabutylaluminate (14263-32-2) → α-butyl-α-hydroxy phenyl methyl ester (75844-45-0, 97690-16-9)

Conditions	Yield
With hydrogenchloride In hexane at 0℃; for 2h; asymmetric alkylation; various solvent;
With hydrogenchloride Multistep reaction;

diazoacetic acid ethyl ester (623-73-4) + dimethylmonochlorosilane (1066-35-9) + (2S,3R)-(+)-4-Dimethylamino-1,2-diphenyl-3-methyl-2-butanol (38345-66-3) → [((1S,2R)-1-Benzyl-3-dimethylamino-2-methyl-1-phenyl-propoxy)-dimethyl-silanyl]-acetic acid ethyl ester

Conditions	Yield
With dirhodium tetraacetate; triethylamine 1.) CH2Cl2, room temperature, 2.) CH2Cl2, room temperature, 2 h; Yield given. Multistep reaction;

(2S,3R)-(+)-4-Dimethylamino-1,2-diphenyl-3-methyl-2-butanol (38345-66-3) → 2-[((1S,2R)-1-Benzyl-3-dimethylamino-2-methyl-1-phenyl-propoxy)-dimethyl-silanyl]-propionic acid ethyl ester

Conditions	Yield
Multi-step reaction with 2 steps 1: 1.) Rh2(OAc)4, 2.) NEt3 / 1.) CH2Cl2, room temperature, 2.) CH2Cl2, room temperature, 2 h 2: hexamethyldisilazane, n-BuLi / hexane; tetrahydrofuran / 1.) -50 deg C, 2 h, 2.) -80 deg C, 2 h View Scheme

lithium aluminium tetrahydride (16853-85-3) + 1,1’-dibenzoylferrocene (12180-80-2, 32983-90-7) + (2S,3R)-(+)-4-Dimethylamino-1,2-diphenyl-3-methyl-2-butanol (38345-66-3) → (+/-), meso-1,1'-bis(α-hydroxybenzyl)ferrocene

Conditions	Yield
With ammonium chloride In diethyl ether (Ar); soln. of Chirald in Et2O stirred at 0°C added to soln. of LiAlH4 in ether cooled to -70°C; dropwise addn. of ethereal soln. of Fe-complex at -20°C; treatment with wet ether and aq. NH4Cl;; rapid chromy. (Al2O3, ether); crystn. (heptane);	>99

lithium aluminium tetrahydride (16853-85-3) + 1,1'-dibenzoylruthenocene + (2S,3R)-(+)-4-Dimethylamino-1,2-diphenyl-3-methyl-2-butanol (38345-66-3) → (C5H4CH(OH)C6H5)Ru(C5H4CH(OH)C6H5)

Conditions	Yield
With hydrogenchloride; ammonium chloride In diethyl ether (Ar); soln. of Chirald in Et2O stirred at 0°C added to soln. of LiAlH4 in ether cooled to -70°C; dropwise addn. of ethereal soln. of Ru-complex at -20°C; treatment with wet ether and aq. NH4Cl; ethereal ext. treated with HCl;; crystn. (heptane or hexane);	>99

(2RS)-3,3,3-trifluoro-2-methylpropanoic acid (381-97-5) + (2S,3R)-(+)-4-Dimethylamino-1,2-diphenyl-3-methyl-2-butanol (38345-66-3) → C4H5F3O2*C19H25NO + C4H5F3O2*C19H25NO

Conditions	Yield
In isopropyl alcohol at 20 - 70℃;	A n/a B n/a

Upstream product

• 50-00-0 formaldehyd 
• 91-03-2 3-dimethylamino-2-methyl-1-phenyl-propan-1-one 
• 6921-34-2 benzylmagnesium chloride 
• 124-40-3 dimethyl amine 
• 98-59-9 p-toluenesulfonyl chloride 
• 126-04-5 (2RS,3SR)-4-dimethylamino-3-methyl-1,2-diphenyl-butan-2-ol 

Downstream Products

• 75844-45-0 α-butyl-α-hydroxy phenyl methyl ester 
• 72541-03-8 (2R,3S)-(-)-4-dimethylamino-1,2-diphenyl-3-methyl-2-butanol 
• 24274-73-5 (E)-1,2-diphenyl-2-butene 
• 52016-49-6 dimethyl-(2-methyl-3,4-diphenyl-but-2-enyl)-amine 
• 1356938-68-5 (+)-(2R,3S)-N-(3-hydroxy-2-methyl-3,4-diphenylbutyl)-N,N-dimethyldodecan-1-ammonium bromide 
• 479253-09-3 (1'S,2'R)-2-(1'-benzyl-3'-dimethylamino-2'-methyl-1'-phenyl-propoxy)dinaphtho[2,1-d:1',2'-f](1,3,2) dioxaphosphepine 

Relevant academic research and scientific papers

Haptens and tracers for immunoassays for propoxyphene

Disclosed is a substantially optically pure hapten, useful in an immunoassay for dextropropoxyphene and/or nordextropropoxyphene. The hapten corresponds to a specified structural formula (IX). Also disclosed is an immunogen derived from the hapten as well as an antibody raised in response to an immunogen derived from the hapten. Also disclosed is a fluorescent tracer derived from a substantially optically pure compound corresponding to the hapten, the tracer being useful in an immunoassay for dextropropoxyphene and/or nordextropropoxyphene. Also disclosed is an improved immunoassay for determining dextropropoxyphene and/or nordextropropoxyphene in a biological sample involving a step of contacting the sample with antibodies raised in response to the immunogen. Also disclosed is a fluorescence polarization immunoassay (FPIA) for determining dextropropoxyphene and/or nordextropropoxyphene involving a step of contacting the sample with antibodies raised in response to the immunogen, and/or involving a step of contacting the sample with a fluorescent tracer.