554-35-8

Basic information

• Product Name: LINAMARIN
• Synonyms: Phaseolunatin =Linamarin;2-(alpha-D-Glucopyranosyloxy)-2-methylpropanenitrile;Linamarine;Phaseolunatine;2-(b-D-Glucopyranosyloxy)-2-methyl-propanenitrile;2-(D-GLUCOPYRANOSYLOXY)-2-METHYL-PROPANENITRILE,PHASEOLUNATIN=LINAMARIN;α-Hydroxyisobutyronitrile β-D-glucopyranoside;α-Hydroxyisobutyronitrile β-D-glucose, 2-(β-D-Glucopyranosyloxy)-2-methylpropionitrile, Linamarin
• CAS NO: 554-35-8
• Molecular Formula: C₁₀H₁₇NO₆
• Molecular Weight: 247.25
• Product Categories: Carbohydrates & Derivatives
• Mol File: 554-35-8.mol
• Article Data: 3

Chemical Properties

• Melting Point: 142-143°C
• Boiling Point: 390.28°C (rough estimate)
• Flash Point: 240°C
• Appearance: /
• Density: 1.2868 (rough estimate)
• Vapor Pressure: 6.02E-11mmHg at 25°C
• Refractive Index: 1.4610 (estimate)
• Storage Temp.: 2-8°C
• Solubility: Soluble in DMSO, Methanol, and Ethanol
• PKA: 12.73±0.70(Predicted)
• Stability: Acid Sensitive
• CAS DataBase Reference: LINAMARIN(CAS DataBase Reference)
• NIST Chemistry Reference: LINAMARIN(554-35-8)
• EPA Substance Registry System: LINAMARIN(554-35-8)

Safety Data

• Hazard Codes: Xn
• Statements: 20/22-36/37/38
• Safety Statements: 26-36
• WGK Germany: 3
• RTECS: TZ4850000
• Hazardous Substances Data: 554-35-8(Hazardous Substances Data)

Usage

Description

Linamarin is a glucoside of acetone cyanohydrin found in the leaves and roots of cassava, lima beans, and flax. It is thought to function in the transport of nitrogen from plant leaves to roots in young plants but also serves as a plant defense mechanism. Linamarin is converted to toxic hydrocyanic acid or prussic acid when it comes into contact with linamarase, an enzyme that is released when the cells of cassava roots are ruptured.

Chemical Properties

White Crystalline Solid

Uses

Different sources of media describe the Uses of 554-35-8 differently. You can refer to the following data:
1. Can be found in the seed skins and embryos of flax
2. Can be found in the seed skins and embryos of flax.

References

1) Jensen?et al.?(2011),?Convergent evolution in biosynthesis if cyanogenic defense compounds in plants; Nat. Commun.,?2?273 2) Rivadeneyra?et al. (2013),?Neurotoxic effect of linamarin in rats associated with cassava (Manihot esculenta Crantz) consumption; Food Chem. Toxicol.,?59?230 3) Kimani?et al. (2014),?Memory deficits associated with sublethal cyanide poisoning relative to cyanate toxicity in rodents; Metab. Brain Dis.,?29?105

InChI:InChI=1/C10H17NO6/c1-10(2,4-11)17-9-8(15)7(14)6(13)5(3-12)16-9/h5-9,12-15H,3H2,1-2H3/t5-,6-,7+,8-,9+/m1/s1

Synthetic route

2-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyloxy)isobutyronitrile (66432-53-9) → linamarin (554-35-8)

Conditions	Yield
With potassium carbonate In methanol for 0.25h;	80%

Isobutyronitrile (78-82-0) → linamarin (554-35-8)

Conditions	Yield
With culture nutrient solution; Turnera angustifolia Miller shoots In water for 72h; hydroxylation; illumination;	6.8%

linustatin (72229-40-4) → β-D-glucose (492-61-5) + linamarin (554-35-8)

Conditions	Yield
With β-glucosidase (EC No. 3.2.1.21) In water at 37℃; for 2h;	A 40.1 mg B 51.7 mg

neolinustatin (72229-42-6) → β-D-glucose (492-61-5) + linamarin (554-35-8) + β-gentiobiose (5996-00-9)

Conditions	Yield
With hydrogenchloride for 1h; Product distribution; Ambient temperature;

O-(2,3,4,6-Tetra-O-acetyl-α-D-glucopyranosyl)trichloroacetimidate (74808-10-9) → linamarin (554-35-8)

Conditions	Yield
Multi-step reaction with 3 steps 1: 31 percent / BF3*Et2O / CH2Cl2 / 1.) -50 deg C, 15 min,2.) -50 deg C to room temperature, 3 h 2: 1.) COCl)2, DMSO, 2.) Et3N / 1.) CH2Cl2, -78 deg C, 10 min, 2.) -78 deg C, 15 min 3: 80 percent / K2CO3 / methanol / 0.25 h View Scheme

2-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyloxy)isobutyramide (207512-69-4) → linamarin (554-35-8)

Conditions	Yield
Multi-step reaction with 2 steps 1: 1.) COCl)2, DMSO, 2.) Et3N / 1.) CH2Cl2, -78 deg C, 10 min, 2.) -78 deg C, 15 min 2: 80 percent / K2CO3 / methanol / 0.25 h View Scheme

linamarin (554-35-8) + acetic anhydride (108-24-7) → 2-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyloxy)isobutyronitrile (66432-53-9)

Conditions	Yield
With pyridine Ambient temperature;
With pyridine	158 mg
With pyridine	158 mg

linamarin (554-35-8) → β-D-glucose (492-61-5)

Conditions	Yield
With water; β-glucosidase at 30 - 70℃; Thermodynamic data; enzymatic hydrolysis: β-glucosidase from Manihot esculante Crantz cv. Merah Jambu; leaf enzyme: ΔEact=3.0 kcal/mol; peel enzyme: ΔEact=4.0 kcal/mol; tuber cortex enzyme ΔEact=3.5 kcal/mol; pH 3-7, 6-8;

linamarin (554-35-8) → hydrogen cyanide

Conditions	Yield
With sodium citrate buffer; linamarase Product distribution; 1.) 50 deg C, 90 min, 2.) 3 h, room temperature; enzyme activity, effect of temperature;

linamarin (554-35-8) → 2-(β-D-glucopyranosyloxy)-2-methylpropanamide (291301-62-7)

Conditions	Yield
With water; dihydrogen peroxide at 40℃; for 24h; pH=6.8; Radziszewski reaction; aq. phosphate buffer;

Upstream product

• 72229-40-4 linustatin 
• 72229-42-6 neolinustatin 
• 66432-53-9 2-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyloxy)isobutyronitrile 
• 78-82-0 Isobutyronitrile 
• 74808-10-9 O-(2,3,4,6-Tetra-O-acetyl-α-D-glucopyranosyl)trichloroacetimidate 
• 207512-69-4 2-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyloxy)isobutyramide 

Downstream Products

• 66432-53-9 2-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyloxy)isobutyronitrile 
• 492-61-5 β-D-glucose 

Relevant articles and documents

Facile Synthesis of Cyanogen Glycosides (R)-Prunasin, Linamarin and (S)-Heterodendrin

A facile synthetic route is described to cyanogenic glycosides (R)-prunasin, linamarin and (S)-heterodendrin from O-(2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyl)trichloroacetimidate and the corresponding α-hydroxyamides by a 3-step reaction of glycosylation, cyanohydrin formation by dehydration of carboxamides, and deprotection.

Biosynthesis of cyanohydrin glucosides from unnatural nitriles in intact tissue of Passiflora morifolia and Turnera angustifolia

Passiflora morifolia, which under natural conditions contains cyanohydrin glucosides linamarin, lotaustralin and epilotaustralin, converted cyclopentanecarbonitrile, 2-cyclopentenecarbonitrile and 3- methylbutanenitrile into the corresponding cyanohydrin glucosides. Turnera angustifolia, which normally produces glucosides of cyclopentenone cyanohydrin, converted cyclopentanecarbonitrile, 2-methylpropanenitrile and 2-methylbutanenitrile, but not 3-methylbutanenitrile, into the corresponding cyanohydrin glucosides. Mixtures of epimers were produced when these glucosides contained chiral cyanohydrin carbon atoms. Feeding with cyclopentanecarbonitrile resulted in formation of 1-(β-D- glucopyranosyloxy)cyclopentanecarbonitrile, a saturated analogue of deidaclin and tetraphyllin A. Neither plant utilized cyclopropanecarbonitrile as substrate. The experiments demonstrate broad substrate specificity of nitrile hydroxylases present in these plants. A novel glycoside, 2-[6-O-(β-D- xylopyranosyl)-β-D-glucopyranosyloxy]propane (isopropyl primeveroside), was isolated from P. morifolia. The compound represents a rare example of natural isopropyl glycoside; its characterization included assignment of all 1H and (13C) NMR signals of the primeverosyl group using two-dimensional NMR methods. Biosynthesis of the isopropyl moiety of the primeveroside is unclear, but the formation of alcohols corresponding to natural cyanohydrins may be a previously unrecognized extension of the cyanohydrin biosynthesis pathway in higher plants.