138-55-6

Basic information

• Product Name: (4S)-2,6,6-trimethyl-4-[(2R,3R,4S,5S,6R)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxy-cyclohexene-1-carbaldehyde
• Synonyms: (4S)-2,6,6-trimethyl-4-[(2R,3R,4S,5S,6R)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxy-cyclohexene-1-carbaldehyde;Picrocrocin;(R)-4-(β-D-glucopyranosiloxy)-2,6,6-trimethyl-1-cyclohexene-1-carbaldehyde;(R)-4-(β-D-Glucopyranosyloxy)-2,6,6-trimethyl-1-cyclohexene-1-carbaldehyde;Saffron-bitter;Picrocrocine;1-Cyclohexene-1-carboxaldehyde,4-(b-D-glucopyranosyloxy)-2,6,6-triMethyl-,(4R)-;Safranbitter
• CAS NO: 138-55-6
• Molecular Formula: C₁₆H₂₆O₇
• Molecular Weight: 330.37
• Mol File: 138-55-6.mol
• Article Data: 1

Chemical Properties

• Melting Point: 196℃ (ethyl acetate )
• Boiling Point: 520.4°Cat760mmHg
• Flash Point: 187.1°C
• Appearance: /
• Density: 1.31±0.1 g/cm3 (20 ºC 760 Torr)
• Vapor Pressure: 5.27E-13mmHg at 25°C
• Refractive Index: 1.561
• PKA: 12.91±0.70(Predicted)
• CAS DataBase Reference: (4S)-2,6,6-trimethyl-4-[(2R,3R,4S,5S,6R)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxy-cyclohexene-1-carbaldehyde(CAS DataBase Reference)
• NIST Chemistry Reference: (4S)-2,6,6-trimethyl-4-[(2R,3R,4S,5S,6R)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxy-cyclohexene-1-carbaldehyde(138-55-6)
• EPA Substance Registry System: (4S)-2,6,6-trimethyl-4-[(2R,3R,4S,5S,6R)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxy-cyclohexene-1-carbaldehyde(138-55-6)

Safety Data

• Hazardous Substances Data: 138-55-6(Hazardous Substances Data)

Usage

Description

Picrocrocin, composing of safranal and glycoside, is one major compounds of saffron (Crocus sativus L. stigma), responsible for the bitter taste of saffron and a molecular marker of this spice, whose taste cannot be imitated from other spices or seasonings, and it can serve to identify true saffron. Saffron possesses various therapeutic activities such as antihypertensive, anticonvulsant, antitussive, antigenototoxic, anticancer, cytotoxic effects, anxiolytic, antioxidant, antidepressant, anti-inflammatory, and relaxant activity. As major bioactive compounds of saffron, picrocrocin also has some valuable medicinal properties similar as saffron, especially anticancer effect.

Antitumor activity

Picrocrocin as component of saffron displays same antitumor activity that have great potential for the prevention and treatment of various cancers through affecting cellular DNA and RNA synthesis and free radical scavenging activities of cancer. The experiments results for studying the effect of picrocrocin on proliferation of human tumoral cells (HeLa cell) in vitro showed that picrocrocin have a dose dependent inhibition of cell growth, and doses of picrocrocin inducing 50% inhibition of HeLa cell growth are 3 mM, in which picrocrocin have minor cytotoxicity for normal cells. Thus, picrocrocin can inhibit the growth of cancer cell. Other study results have showed that picrocrocin with highly bioaccessible could be transported quickly and reduced the proliferation of human adenocarcinoma and hepatocarcinoma cells.

Uses

Picrocrocin is a secondary metabolite of Saffron and has been found to be the taste component of saffron.

Definition

ChEBI: A beta-D-glucoside of beta-cyclocitral; the precursor of safranal. It is the compound most responsible for the bitter taste of saffron.

InChI:InChI=1/C16H26O7/c1-8-4-9(5-16(2,3)10(8)6-17)22-15-14(21)13(20)12(19)11(7-18)23-15/h6,9,11-15,18-21H,4-5,7H2,1-3H3/t9-,11-,12-,13+,14-,15-/m1/s1

Synthetic route

(4R)-4-(β-D-Glucopyranosyloxy)-2,6,6-trimethyl-1-cyclohexen-1-methanol (76686-29-8) → (R)-4-(β-D-glucopyranosyl)-2,6,6-trimethyl-1-cyclohexene-1-carboxaldehyde (138-55-6)

Conditions	Yield
With sodium acetate; pyridinium chlorochromate In dimethyl sulfoxide for 16h; Ambient temperature;	10%

(3R)-3-Hydroxy-β-cyclogeranylacetat (76686-27-6) → (R)-4-(β-D-glucopyranosyl)-2,6,6-trimethyl-1-cyclohexene-1-carboxaldehyde (138-55-6)

Conditions	Yield
Multi-step reaction with 3 steps 1: 23 percent / Ag2O, CaSO4 / benzene / 18 h / Heating 2: 83.5 percent / Na / methanol / 18 h / Heating 3: 10 percent / Pyridiniumchlorochromat, Natriumacetat / dimethylsulfoxide / 16 h / Ambient temperature View Scheme

Isopropenyl (IPM)-Aether des (3R)-3-Hydroxy-β-cyclocitral → (R)-4-(β-D-glucopyranosyl)-2,6,6-trimethyl-1-cyclohexene-1-carboxaldehyde (138-55-6)

Conditions	Yield
Multi-step reaction with 5 steps 1: 23.5 g / NaBH4 / propan-2-ol / 1.) 0-5 deg C 2.) rt, 3 h 2: Et3N / diethyl ether / 1.) 0-5 deg C 2.) rt, 5 h 3: 23 percent / Ag2O, CaSO4 / benzene / 18 h / Heating 4: 83.5 percent / Na / methanol / 18 h / Heating 5: 10 percent / Pyridiniumchlorochromat, Natriumacetat / dimethylsulfoxide / 16 h / Ambient temperature View Scheme

(4R)-4-(β-D-Glucopyranosyloxy)-2,6,6-trimethyl-1-cyclohexen-1-methanol-pentaacetat (76686-28-7) → (R)-4-(β-D-glucopyranosyl)-2,6,6-trimethyl-1-cyclohexene-1-carboxaldehyde (138-55-6)

Conditions	Yield
Multi-step reaction with 2 steps 1: 83.5 percent / Na / methanol / 18 h / Heating 2: 10 percent / Pyridiniumchlorochromat, Natriumacetat / dimethylsulfoxide / 16 h / Ambient temperature View Scheme

[(R)-4-(1-Methoxy-1-methyl-ethoxy)-2,6,6-trimethyl-cyclohex-1-enyl]-methanol (76686-26-5) → (R)-4-(β-D-glucopyranosyl)-2,6,6-trimethyl-1-cyclohexene-1-carboxaldehyde (138-55-6)

Conditions	Yield
Multi-step reaction with 4 steps 1: Et3N / diethyl ether / 1.) 0-5 deg C 2.) rt, 5 h 2: 23 percent / Ag2O, CaSO4 / benzene / 18 h / Heating 3: 83.5 percent / Na / methanol / 18 h / Heating 4: 10 percent / Pyridiniumchlorochromat, Natriumacetat / dimethylsulfoxide / 16 h / Ambient temperature View Scheme

Upstream product

• 76686-27-6 (3R)-3-Hydroxy-β-cyclogeranylacetat 
• 76686-28-7 (4R)-4-(β-D-Glucopyranosyloxy)-2,6,6-trimethyl-1-cyclohexen-1-methanol-pentaacetat 
• 76686-26-5 [(R)-4-(1-Methoxy-1-methyl-ethoxy)-2,6,6-trimethyl-cyclohex-1-enyl]-methanol 
• 76686-29-8 (4R)-4-(β-D-Glucopyranosyloxy)-2,6,6-trimethyl-1-cyclohexen-1-methanol 

Relevant articles and documents

Synthesis of optically active natural carotenoids and structurally related compounds. VI. Synthesis of picrocrocin

-