Welcome to LookChem.com Sign In|Join Free

CAS

  • or

107-18-6

Post Buying Request

107-18-6 Suppliers

Recommended suppliersmore

This product is a nationally controlled contraband, and the Lookchem platform doesn't provide relevant sales information.

107-18-6 Usage

Chemical Description

Allyl alcohol is a reactant that is used in the synthesis of allyl glycosides.

Chemical Properties

Allyl alcohol is a flammable, colorless liquid. It has a pungent, mustard-like odor. It is used in making drugs, organic chemicals, pesticides, in the manufacture of allyl esters, and as monomers and prepolymers for the manufacture of resins and plastics. It has a large use in the preparation of pharmaceutical products, in organic synthesis, and as a fungicide and herbicide. Occupational workers engaged in industries such as the manufacture of drugs, pesticides, allyl esters, organic chemicals, resins, war gas, and plasticizers, are often exposed to this alcohol.

Physical properties

Colorless, mobile liquid with a pungent, mustard-like odor at high concentrations. At low concentrations, odor resembles that of ethyl alcohol. Katz and Talbert (1930) and Dravnieks (1974) reported experimental detection odor threshold concentrations of 3.3 mg/m3 (1.4 ppmv) and 5 mg/m3 (2.1 ppmv), respectively.

Uses

Allyl alcohol is used as an intermediate compound for synthesizing raw materials such as epichlorohydrin C3H5ClO and 1,4- butanediol C4H10O2, and this development is bringing about expansion of the range of uses of allyl alcohol. The term allyl of allyl compounds is derived from allium, the Latin word for garlic. It is also used to induce a mouse model of liver damage that has been used to study the mechanisms of hepatotoxicity and hepatic stem cell-mediated repair.

Application

Allyl alcohol is used to produce glyceroland acrolein and other allylic compounds. It is also used in the manufacture of militarypoison gas. The ester derivatives are used inresins and plasticizers.

Production Methods

Allyl alcohol is prepared by several different processes, the original is alkaline hydrolysis of allyl chloride by steam injection at high temperatures. A more recent commercial process used oxidation of propylene to acrolein, which in turn reacts with a secondary alcohol to yield allyl alcohol and a ketone. In this process, allyl alcohol is not isolated, but its aqueous stream is converted directly to glycerol. The most recent commercial process is isomerization of propylene oxide over a lithium phosphate catalyst.

Definition

ChEBI: Allyl alcohol is a propenol in which the C=C bond connects C-2 and C-3. It is has been found in garlic (Allium sativum). Formerly used as a herbicide for the control of various grass and weed seeds. It has a role as an insecticide, a herbicide, an antibacterial agent, a fungicide and a plant metabolite. It is a primary allylic alcohol and a propenol.

General Description

Allyl alcohol appears as a clear colorless liquid with a mustard-like odor. Flash point 70°F. Very toxic by inhalation and ingestion. Less dense than water (7.1 lb / gal). Vapors are heavier than air. Prolonged exposure to low concentrations or short exposure to high concentrations may have adverse health effects from inhalation.

Air & Water Reactions

Highly flammable. Water soluble.

Reactivity Profile

Allyl alcohol presents a dangerous fire and explosion hazard when exposed to heat, flame, or oxidizing agents. Reacts violently or explosively with sulfuric acid, strong bases. Reacts violently with 2,4,6-trichloro-1,3,5-triazine and 2,4,6-tris(bromoamino)-1,3,5-triazine. Reacts with carbon tetrachloride to produce explosively unstable products [Lewis]. Mixing Allyl alcohol in equal molar portions with any of the following substances in a closed container caused the temperature and pressure to increase: chlorosulfonic acid, nitric acid, oleum, sulfuric acid [NFPA 491M. 1991].

Hazard

Toxic by skin absorption. Eye and upper respiratory tract irritant. Questionable carcinogen.

Health Hazard

The toxicity of allyl alcohol is moderately high, affecting primarily the eyes. The other target organs are the skin and respiratory system. Inhalation causes eyeirritation and tissue damage. A 25-ppmexposure level is reported to produce asevere eye irritation. It may cause atemporary lacrimatory effect, manifested by photophobia and blurred vision, for some hours after exposure. Occasional exposure of a person to allyl alcohol does not indicate chronic or cumulative toxicity. Dogterom and associates (1988) investigated the toxicity of allyl alcohol in isolated rathepatocytes. The toxicity was independent of lipid peroxidation, and acrylate was found to be the toxic metabolite Ingestion of this compound may cause irritation of the intestinal tract. The oral LD50 value in rats is 64 mg/kg (NIOSH 1986).

Fire Hazard

Allyl alcohol vapor may explode if ignited in confined areas. Combustion products may be poisonous. The vapor is heavier than air and flashback along vapor trail may occur. Gives off toxic fumes when heated. May react vigorously with oxidizing materials, carbon tetrachloride, acids, oleum, sodium hydroxide, diallyl phosphite, potassium chloride, or tri-n-bromomelamine.

Flammability and Explosibility

Flammable

Safety Profile

Suspected carcinogen. Poison by inhalation, ingestion, skin contact, subcutaneous, intraperitoneal, and possibly other routes. A slim, severe eye (human), and systemic irritant. Mutation data reported. Dangerous fire and explosion hazard when exposed to heat, flame, or oxidizers.

Potential Exposure

Allyl alcohol is a colorless water soluble liquid. The melting point, boiling point, vapor pressure, and the octanol–water partition coefficient (log Kow) are 129°C, 97°°C, 26.1mmHg at 25°C, and 0.17, respectively. The Henry’s law constant is 4.99×10-6 atm-m3 mol-1. Allyl alcohol’s production, its use as an industrial solvent and as a raw material/intermediate in the preparation of pharmaceuticals, polymers, organic chemicals, in the manufacture of glycerol and acrolein, and in the production of insecticides and herbicides, may result in its release to the environment.

Carcinogenicity

Male and female F344 rats were given allyl alcohol in the drinking water at a concentration of 0 or 300 mg/L for 106 weeks. The incidence of tumors was similar to that in controls . Male and female hamsters were administered 2 mg allyl alcohol by oral gavage once a week for 60 weeks. The incidence of tumors did not increase significantly compared to controls.

Shipping

UN1098 Allyl alcohol Hazard class: 6.1; Labels: 6.1-Poison Inhalation Hazard, 3-Flammable liquids, Inhalation Hazard Zone B.

Purification Methods

It can be dried with K2CO3 or CaSO4, or by azeotropic distillation with *benzene followed by distillation under nitrogen. It is difficult to obtain it free of peroxide. It has also been refluxed with magnesium and fractionally distilled [Hands & Norman Ind Chem 21 307 1945]. [Beilstein 1 IV 2079.]

Environmental Fate

The vapor pressure of allyl alcohol, 26.1mmHg at 25°C, indicates that if released in the air, it will exist mainly as a vapor in the ambient atmosphere. If released to soil, allyl alcohol is expected to have very high mobility based upon an estimated Koc of 1.3 and will be distributed mainly in the water and soil. If released into water, allyl alcohol will stay in the water and is not expected to adsorb to suspended solids and sediments. Allyl alcohol is stable in water since it lacks functional groups that hydrolyze under environmental conditions and hence hydrolysis is not expected to be an important environmental fate process. In an aerobic biodegradation study, allyl alcohol was found to readily degradable (82–86%) in 14 days. The estimated bioconcentration factor of 3.2 based on the low log Kow indicates that the potential to bioaccumulate in aquatic organisms is expected to be low.

Incompatibilities

May form explosive mixture with air. Reacts explosively with carbon tetrachloride, strong bases. Also incompatible with strong acids. Incompatible with oxidizers (chlorates, nitrates, peroxides, permanganates, perchlorates, chlorine, bromine, fluorine, etc.); contact may cause fires or explosions. Keep away from alkaline materials, strong bases, strong acids, oxoacids, epoxides. Polymerization may be caused by heat above 99 C, peroxides, or oxidizers.

Waste Disposal

Consult with environmental regulatory agencies for guidance on acceptable disposal practices. Generators of waste containing this contaminant (≥100 kg/mo) must conform with EPA regulations governing storage, transportation, treatment, and waste disposal. Incineration after dilution with a flammable solvent.

Precautions

Occupational workers should be careful during handling and use of allyl alcohol and wear

Check Digit Verification of cas no

The CAS Registry Mumber 107-18-6 includes 6 digits separated into 3 groups by hyphens. The first part of the number,starting from the left, has 3 digits, 1,0 and 7 respectively; the second part has 2 digits, 1 and 8 respectively.
Calculate Digit Verification of CAS Registry Number 107-18:
(5*1)+(4*0)+(3*7)+(2*1)+(1*8)=36
36 % 10 = 6
So 107-18-6 is a valid CAS Registry Number.
InChI:InChI=1/C3H6O/c1-3(2)4/h4H,1H2,2H3

107-18-6SDS

SAFETY DATA SHEETS

According to Globally Harmonized System of Classification and Labelling of Chemicals (GHS) - Sixth revised edition

Version: 1.0

Creation Date: Aug 19, 2017

Revision Date: Aug 19, 2017

1.Identification

1.1 GHS Product identifier

Product name allyl alcohol

1.2 Other means of identification

Product number -
Other names 2-propen-1-ol

1.3 Recommended use of the chemical and restrictions on use

Identified uses For industry use only. Intermediates
Uses advised against no data available

1.4 Supplier's details

1.5 Emergency phone number

Emergency phone number -
Service hours Monday to Friday, 9am-5pm (Standard time zone: UTC/GMT +8 hours).

More Details:107-18-6 SDS

107-18-6Synthetic route

glycerol
56-81-5

glycerol

A

allyl alcohol
107-18-6

allyl alcohol

B

hydroxy-2-propanone
116-09-6

hydroxy-2-propanone

C

acrolein
107-02-8

acrolein

Conditions
ConditionsYield
With H3PO4-activated and WOx-loaded montmorillonite nanocatalyst In water at 320℃; for 3h; Reagent/catalyst; Flow reactor;A n/a
B n/a
C 67.3%
With phosphorus containing Fe2O3 nanoparticles In water at 320℃; for 24h; Inert atmosphere;
With 10 w% WO3/ZrO2 at 250℃; Temperature; Time; Inert atmosphere;
With HZSM5/Fe/Rb In water at 340℃; under 760.051 Torr; Inert atmosphere;
With oxygen In water at 285℃; under 760.051 Torr; for 1h; Flow reactor;A 10.65 %Chromat.
B 19.63 %Chromat.
C 57.96 %Chromat.
propargyl alcohol
107-19-7

propargyl alcohol

allyl alcohol
107-18-6

allyl alcohol

Conditions
ConditionsYield
With piperazine; hydrogen In ethanol at 80℃; under 4500.45 Torr; for 24h;99%
With hydrogen In methanol at 20℃; under 760.051 Torr; for 4.5h; Green chemistry;98%
With hydrogen In methanol under 760.051 Torr; for 5h;97%
acrolein
107-02-8

acrolein

allyl alcohol
107-18-6

allyl alcohol

Conditions
ConditionsYield
With hydrogen In water at 110℃; under 22502.3 Torr; for 2.33333h; Reagent/catalyst; Pressure; Temperature;96%
With sulfuric acid; zinc diacetate; iron(II) sulfate at 25℃; bei der elektrolytischen Reduktion an einer amalgamierten Bleikathode; Reagens 4: Hydrochinon;
With aluminum isopropoxide; isopropyl alcohol
allyl trifluoroacetate
383-67-5

allyl trifluoroacetate

A

2,2,2-trifluoroethanol
75-89-8

2,2,2-trifluoroethanol

B

allyl alcohol
107-18-6

allyl alcohol

Conditions
ConditionsYield
With trans-[(2,6-bis(di-tert-butylphosphinomethyl)pyridine)Fe(H)2(CO)]; hydrogen; sodium methylate In 1,4-dioxane at 40℃; under 18751.9 Torr; for 16h; Glovebox; Inert atmosphere;A 95%
B n/a
With trimethylamine-N-oxide; tricarbonyl(η4-1,3-bis(trimethylsilyl)-4,5,6,7-tetrahydro-2H-inden-2-one)iron; hydrogen; triethylamine In toluene at 90℃; under 52505.3 Torr; for 17h; Inert atmosphere; Glovebox;
With C21H35BrMnN2O2P; hydrogen; potassium hydride; 1,3,5-trimethyl-benzene In toluene at 100℃; under 15001.5 Torr; for 60h; Autoclave; Inert atmosphere;A 97 %Spectr.
B 96 %Spectr.
With C21H35BrMnN2O2P; hydrogen; potassium hydride In toluene at 100℃; under 15001.5 Torr; for 60h;A 97 %Spectr.
B 96 %Spectr.
2-Allyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
72824-04-5

2-Allyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane

allyl alcohol
107-18-6

allyl alcohol

Conditions
ConditionsYield
With [bis(acetoxy)iodo]benzene; water; triethylamine In acetonitrile at 20℃; for 1h;67%
With sodium periodate; iodobenzene In water; acetonitrile at 80℃; for 8h;64%
glycerol
56-81-5

glycerol

allyl alcohol
107-18-6

allyl alcohol

Conditions
ConditionsYield
With formic acid at 235℃;98%
With rhenium trioxide; hydrogen at 140℃; Temperature; Reagent/catalyst; Solvent; Time;91%
In water at 148℃; for 2.5h; Catalytic behavior; Reagent/catalyst; Temperature; Solvent; Sealed tube;91%
2-(prop-2-en-1-yloxy)oxane
69161-61-1, 4203-49-0

2-(prop-2-en-1-yloxy)oxane

allyl alcohol
107-18-6

allyl alcohol

Conditions
ConditionsYield
With methanol at 20℃; for 0.5h;98%
With methanol; zirconium(IV) chloride at 20℃; for 4h;96%
ruthenium trichloride In water; acetonitrile at 20℃; for 0.333333h;96%
3-chloroprop-1-ene
107-05-1

3-chloroprop-1-ene

allyl alcohol
107-18-6

allyl alcohol

Conditions
ConditionsYield
With tetrabutylammomium bromide; water; sodium hydroxide In hexane at 25℃; pH=5;90%
With water; sodium hydrogencarbonate at 150℃;
With copper; potassium carbonate
With fluoride In gas Rate constant; reaction efficiency;
propargyl alcohol
107-19-7

propargyl alcohol

A

propan-1-ol
71-23-8

propan-1-ol

B

allyl alcohol
107-18-6

allyl alcohol

Conditions
ConditionsYield
palladium anchored polystyrene In neat (no solvent) at 25℃; under 41371.8 Torr; for 15h;A 5%
B 90%
With hydrogen; copper-palladium; silica gel In ethanol at 25℃; under 760 Torr; Kinetics;A n/a
B 85%
With hydrogen; palladium dichloride In N,N-dimethyl-formamide under 18751.5 Torr; for 0.316667h; Product distribution; Ambient temperature; various time;A 2.6%
B 76.3%
propylene glycol
57-55-6

propylene glycol

allyl alcohol
107-18-6

allyl alcohol

Conditions
ConditionsYield
With KOH/ZrO2 In water at 225℃; Reagent/catalyst; Temperature; Solvent;47%
(E)-4-(acetoxy)-1-phenyl-2-buten-1-one
127391-77-9

(E)-4-(acetoxy)-1-phenyl-2-buten-1-one

A

3-hydroxy-1-phenyl-but-2-en-1-one
33951-43-8

3-hydroxy-1-phenyl-but-2-en-1-one

B

allyl alcohol
107-18-6

allyl alcohol

Conditions
ConditionsYield
Stage #1: (E)-4-(acetoxy)-1-phenyl-2-buten-1-one With bis(iodozinc)methane In tetrahydrofuran at 25℃; Inert atmosphere;
Stage #2: With ammonium chloride In tetrahydrofuran; water Inert atmosphere;
A 91%
B n/a
glycerol
56-81-5

glycerol

A

acetaldehyde
75-07-0

acetaldehyde

B

allyl alcohol
107-18-6

allyl alcohol

C

acrolein
107-02-8

acrolein

Conditions
ConditionsYield
With H3PO4-activated and WOx-loaded montmorillonite nanocatalyst In water at 320℃; for 3h; Flow reactor;A n/a
B n/a
C 50.7%
trimethyleneglycol
504-63-2

trimethyleneglycol

allyl alcohol
107-18-6

allyl alcohol

tris(allyl)borate
1693-71-6

tris(allyl)borate

n-perfluorohexyl iodide
355-43-1

n-perfluorohexyl iodide

A

2-iodo-4,4,5,5,6,6,7,7,8,8,9,9,9-tridecafluorononan-1-ol
38550-44-6

2-iodo-4,4,5,5,6,6,7,7,8,8,9,9,9-tridecafluorononan-1-ol

B

allyl alcohol
107-18-6

allyl alcohol

Conditions
ConditionsYield
Stage #1: tris(allyl)borate; n-perfluorohexyl iodide With 2,2'-azobis(isobutyronitrile) at 60 - 70℃; for 3h;
Stage #2: With water at 60℃;
A 99%
B n/a
glycerol
56-81-5

glycerol

A

acetaldehyde
75-07-0

acetaldehyde

B

allyl alcohol
107-18-6

allyl alcohol

C

hydroxy-2-propanone
116-09-6

hydroxy-2-propanone

D

acrolein
107-02-8

acrolein

Conditions
ConditionsYield
With H3PO4-activated and WOx-loaded montmorillonite nanocatalyst In water at 320℃; for 3h; Reagent/catalyst; Flow reactor;A n/a
B n/a
C n/a
D 46.7%
glycerol
56-81-5

glycerol

A

propan-1-ol
71-23-8

propan-1-ol

B

propylene glycol
57-55-6

propylene glycol

C

allyl alcohol
107-18-6

allyl alcohol

D

isopropyl alcohol
67-63-0

isopropyl alcohol

Conditions
ConditionsYield
With hydrogen In 1,4-dioxane at 20 - 140℃; under 7500.75 - 60006 Torr; for 32h; Autoclave;
glycerol
56-81-5

glycerol

A

propan-1-ol
71-23-8

propan-1-ol

B

propylene glycol
57-55-6

propylene glycol

C

propene
187737-37-7

propene

D

allyl alcohol
107-18-6

allyl alcohol

Conditions
ConditionsYield
With hydrogen In 1,4-dioxane at 20 - 140℃; under 7500.75 - 60006 Torr; for 4h; Time; Autoclave;
methyloxirane
75-56-9, 16033-71-9

methyloxirane

A

propionaldehyde
123-38-6

propionaldehyde

B

allyl alcohol
107-18-6

allyl alcohol

Conditions
ConditionsYield
With lithium phosphate at 245 - 250℃;
With aluminum oxide at 275℃;
With chromium(III) oxide at 350℃;
With gold nanoparticles supported on hollow mesoporous silica (Au/SiO2) at 370℃;
oxalic acid
144-62-7

oxalic acid

glycerol
56-81-5

glycerol

allyl alcohol
107-18-6

allyl alcohol

Conditions
ConditionsYield
With alumina-supported iron In water at 340℃; Inert atmosphere;17.5%
Allyl acetate
591-87-7

Allyl acetate

allyl alcohol
107-18-6

allyl alcohol

Conditions
ConditionsYield
With water; ion exchange resin Diaion SK104H at 80℃; under 3750.38 Torr;
With water; ion exchange resin Diaion SK104H at 80℃; under 3750.38 Torr;
With water Product distribution / selectivity;
propylene glycol
57-55-6

propylene glycol

diallyl isophthalate
1087-21-4

diallyl isophthalate

A

Reaxys ID: 11381386

Reaxys ID: 11381386

B

allyl alcohol
107-18-6

allyl alcohol

Conditions
ConditionsYield
With di(n-butyl)tin oxide at 180℃; under 0.975098 - 9.976 Torr; for 2h;
propylene glycol
57-55-6

propylene glycol

diallyl isophthalate
1087-21-4

diallyl isophthalate

A

poly(diallyl isophthalate-co-propylene glycol)

poly(diallyl isophthalate-co-propylene glycol)

B

allyl alcohol
107-18-6

allyl alcohol

Conditions
ConditionsYield
With dibutyltin oxide at 180℃; under 0.975098 - 9.976 Torr; for 1h;
1,4-cyclohexanedicarboxylic acid, diallyl ester

1,4-cyclohexanedicarboxylic acid, diallyl ester

1,1,1-tri(hydroxymethyl)propane
77-99-6

1,1,1-tri(hydroxymethyl)propane

A

poly(diallyl 1,4-cyclohexane dicarboxylate-co-trimethylolpropane)

poly(diallyl 1,4-cyclohexane dicarboxylate-co-trimethylolpropane)

B

allyl alcohol
107-18-6

allyl alcohol

Conditions
ConditionsYield
With dibutyltin oxide at 180℃; under 0.975098 - 9.976 Torr; for 1h;
4,4'-isopropylidenebis[2-(2,6-dibromophenoxy)ethanol]
4162-45-2

4,4'-isopropylidenebis[2-(2,6-dibromophenoxy)ethanol]

diallyl isophthalate
1087-21-4

diallyl isophthalate

A

poly(2,2-bis[4-(2-hydroxyethoxy)-3,5-dibromophenyl]propane-co-diallyl isophthalate)

poly(2,2-bis[4-(2-hydroxyethoxy)-3,5-dibromophenyl]propane-co-diallyl isophthalate)

B

allyl alcohol
107-18-6

allyl alcohol

Conditions
ConditionsYield
With dibutyltin oxide at 180℃; under 0.975098 - 9.976 Torr; for 1h;
4,4'-isopropylidenebis[2-(2,6-dibromophenoxy)ethanol]
4162-45-2

4,4'-isopropylidenebis[2-(2,6-dibromophenoxy)ethanol]

diallyl terephthalate
1026-92-2

diallyl terephthalate

A

poly(2,2-bis[4-(2-hydroxyethoxy)-3,5-dibromophenyl]propane-co-diallyl terephthalate)

poly(2,2-bis[4-(2-hydroxyethoxy)-3,5-dibromophenyl]propane-co-diallyl terephthalate)

B

allyl alcohol
107-18-6

allyl alcohol

Conditions
ConditionsYield
With dibutyltin oxide at 180℃; under 0.975098 - 9.976 Torr; for 1h;
methyloxirane
75-56-9, 16033-71-9

methyloxirane

allyl alcohol
107-18-6

allyl alcohol

Conditions
ConditionsYield
With lithium phosphate at 280℃;
lithium phosphate containing about 0.1-0.3 wt percent of sodium and 0.3-0.5 wt percent of boron at 253 - 273℃; Conversion of starting material;
lithium phosphate containing 0.3 wt percent of boron at 273℃; Conversion of starting material;
allyloxytrimethylsilane
18146-00-4

allyloxytrimethylsilane

allyl alcohol
107-18-6

allyl alcohol

Conditions
ConditionsYield
With oxygen; manganese(II) p-aminobenzoate; cobalt(II) p-aminobenzoate; silica gel In hexane for 10.5h; Heating;88%
With oxygen; silica gel-supported Co/Mn p-aminobenzoate (1:1 mixture) In hexane for 12h; Heating;88%
trimethyleneglycol
504-63-2

trimethyleneglycol

A

allyl alcohol
107-18-6

allyl alcohol

B

acrolein
107-02-8

acrolein

Conditions
ConditionsYield
at 315℃; Gas phase;
propene
187737-37-7

propene

A

allyl alcohol
107-18-6

allyl alcohol

B

acrolein
107-02-8

acrolein

C

methyloxirane
75-56-9, 16033-71-9

methyloxirane

Conditions
ConditionsYield
With oxygen at 349.84℃; under 1125.11 Torr; Reagent/catalyst; Temperature;
propylene glycol
57-55-6

propylene glycol

A

2-ethyl-4-methyl-1,3-dioxolane
4359-46-0

2-ethyl-4-methyl-1,3-dioxolane

B

propionaldehyde
123-38-6

propionaldehyde

C

allyl alcohol
107-18-6

allyl alcohol

Conditions
ConditionsYield
With hydrogen In water at 320℃; for 5h; Temperature;

107-18-6Relevant articles and documents

Selective pyrolysis of bifunctional compounds: gas-phase elimination of carbonate-ester functionalities

Al-Azemi, Talal F.,Dib, Hicham H.,Al-Awadi, Nouria A.,El-Dusouqui, Osman M.E.

, p. 4126 - 4134 (2008)

Compounds containing both carbonate and ester functionalities were synthesized and then subjected to online-GC gas-phase pyrolysis. The carbonate groups were cleaved selectively in all elimination reactions. The end products of the reaction were found to be affected by the nature of the substrate. The presence of hydrogen and carbonyl substituents on the carbon β to the carbonate group resulted in further product decomposition through a concerted six-membered transition state. Results from flash vacuum pyrolysis (FVP) and analysis of the GC data indicate that the cleavage of the carbonate group is fast, and that the slower secondary decomposition reactions are independent of the presence of the carbonate group. Spectroscopic analyses of the products are reported.

-

Ramsden et al.

, p. 1602,1605 (1957)

-

The remarkable promotion of in situ formed Pt-cobalt oxide interfacial sites on the carbonyl reduction to allylic alcohols

Li, Chenyue,Ke, Changxuan,Han, Ruirui,Fan, Guoli,Yang, Lan,Li, Feng

, p. 78 - 87 (2018)

Pt catalysts attract increasing attention for selectively hydrogenating α,β-unsaturated aldehydes to produce allylic alcohols, thanks to their relatively satisfactory selectivity towards the reduction of C[dbnd]O bond over C[dbnd]C bond. Here, new carbon supported cobalt oxide-decorated platinum nanocatalysts for highly selective hydrogenation of cinnamaldehyde were fabricated via a facile composite precursor route. As-fabricated cobalt oxide-decorated Pt catalyst at a Co/Pt atomic ratio of 0.6 was found to exhibit an exceptional catalytic performance with an extremely high 99% yield of cinnamyl alcohol under mild reaction conditions (2 MPa H2 and 80 °C). In contrast to that of the undecorated Pt one, the intrinsic activity of the cobalt oxide-decorated Pt-based one, i.e. the turnover frequency for cinnamaldehyde conversion (4.19 s?1), was significantly increased by 9.5 times. The present catalyst system presents a particularly dramatic enhancement in catalytic performance, in comparison with other Pt-based hydrogenation catalysts previously reported. Such exceptional catalytic efficiency was probably corelated with unique geometric and electronic modifications of Pt particles by CoOx species, thereby giving rise to both the increased exposed active metal surface and the favorable electron-rich state of Pt0 species. Correspondingly, the rate of cinnamaldehyde conversion could be improved and the adsorption of the carbonyl group could be strengthened. This synergy between CoOx species and Pt sites is accounted for the observed superiority of CoOx-decorated Pt catalyst to Co-free Pt one in selective hydrogenation of carbonyl compounds.

EFFECT OF THE STRUCTURE OF SUBSTITUTED PROPARGYL AND ALLYL ALCOHOLS ON THE RATE OF THEIR LIQUID PHASE HYDROGENATION ON A Pd-Ru ALLOY MEMBRANE CATALYST

Karavanov, A. N.,Gryaznov, V. M.

, p. 1593 - 1596 (1989)

The rates of hydrogenation of substituted propargyl and allyl alcohols in the liquid phase on a Pd-Ru alloy membrane catalyst are described by a two-parameter Taft equation which takes into account the inductive and steric effects of the substituents.The values of the parameters at 363 K with H2 at atmospheric pressure are: ρ* = -0.20, δ = 0.10 and ρ+ = -1.1, δ = 1.3 respectively.

The decomposition of aliphatic N-nitro amines in aqueous sulfuric acid. Bisulfate as a nucleophile

Cox, Robin A.

, p. 1774 - 1778 (1996)

In aqueous sulfuric acid, aliphatic N-nitro amines decompose to N2O and alcohols. An excess acidity analysis of the observed rate constants for the reaction shows that free carbocations are not formed. The reaction is an acid-catalyzed SN2 displacement from the protonated aci-nitro tautomer, the nucleophile being a water molecule at acidities below 82-85% H2SO4, and a bisulfate ion at higher acidities. Bisulfate is the poorer nucleophile by a factor of about 1000. Twelve compounds were studied, of which results obtained for nine at several different temperatures enabled calculation of activation parameters for both nucleophiles. The reaction appears to be mainly enthalpy controlled. The intercept standard-state rate constants are well correlated by the σ* values for the alkyl groups; the slopes are negative, with a more negative value for the slower bisulfate reaction. Interestingly the m?m* slopes also correlate with σ*, although the scatter is bad.

Selective hydrogenation of the C=O bond in acrolein through the architecture of bimetallic surface structures

Murillo, Luis E.,Goda, Amit M.,Chen, Jingguang G.

, p. 7101 - 7105 (2007)

In the current study we have performed experimental studies and density functional theory (DFT) modeling to investigate the selective hydrogenation of the C=O bond in acrolein on two bimetallic surface structures, the subsurface Pt-Ni-Pt(111) and surface Ni-Pt-Pt(111). We have observed for the first time the production of the desirable unsaturated alcohol (2-propenol) on Pt-Ni-Pt(111) under ultra-high vacuum conditions. Furthermore, our DFT modeling revealed a general trend in the binding energy and bonding configuration of acrolein with the surface d-band center of Pt-Ni-Pt(111), Ni-Pt-Pt(111), and Pt(111), suggesting the possibility of using the value of the surface d-band center as a parameter to predict other bimetallic surfaces for the selective hydrogenation of acrolein.

Kinetics and mechanism of diallyl sulfoxide pyrolysis; A combined theoretical and experimental study in the gas phase

Izadyar,Gholami

, p. 62809 - 62816 (2014)

A combined experimental and computational study was carried out on the gas phase pyrolysis reaction of diallylsulfoxide. Allyl alcohol and thioacrolein were detected as the major products during a unimolecular reaction. Experimental kinetic studies were carried out via a static system under the pressure of 21-55 torr and temperature of 435.2-475.1 K. Based on the experiments, the reaction is homogeneous and proceeds through a zwitterionic intermediate. Computational studies at the DFT (B3LYP) and QCISD(T) levels with 6-311++G(d,p) basis set indicated a two-step concerted pathway as the possible route. Comparison between the experimental and theoretical activation parameters for the most probable path confirmed a good agreement.

The influence of SiO2 doping on the Ni/ZrO2 supported catalyst for hydrogen production through the glycerol steam reforming reaction

Charisiou,Papageridis,Siakavelas,Sebastian,Hinder,Baker,Polychronopoulou,Goula

, p. 206 - 219 (2019)

The glycerol steam reforming (GSR) reaction for H2 production was studied comparing the performance of Ni supported on ZrO2 and SiO2-ZrO2 catalysts. The surface and bulk properties were determined by ICP, BET, XRD, TPD, TPR, TPO, XPS, SEM and STEM-HAADF. It was suggested that the addition of SiO2 stabilizes the ZrO2 monoclinic structure, restricts the sintering of nickel particles and strengthens the interaction between Ni2+ species and support. It also removes the weak acidic sites and increases the amount of the strong acidic sites, whereas it decreases the amount of the basic sites. Furthermore, it influences the gaseous products’ distribution by increasing H2 yield and not favouring the transformation of CO2 in CO. Thus, a high H2/CO ratio can be achieved accompanying by negligible value for CO/CO2. From the liquid products quantitative analysis, it was suggested that acetone and acetaldehyde were the main products for the Ni/Zr catalyst, for 750 °C, whereas for the Ni/SiZr catalyst allyl alcohol was the only liquid product for the same temperature. It was also concluded that the Ni/SiZr sample seems to be more resistant to deactivation however, for both catalysts a substantial amount of carbon exists on the catalytic surface in the shape of carbon nanotubes and amorphous carbon.

Trend in the C=C and C=O bond hydrogenation of acrolein on Pt-M (M = Ni, Co, Cu) bimetallic surfaces

Murillo, Luis E.,Menning, Carl A.,Chen, Jingguang G.

, p. 335 - 342 (2009)

Acrolein, the smallest α,β-unsaturated aldehyde, is used as a probe molecule to study the effect on the hydrogenation activity toward the C=C and C=O bonds due to the presence of a 3d transition metal either on the surface or in the subsurface region of a Pt(1 1 1) substrate. Temperature programmed desorption (TPD), high-resolution electron energy loss spectroscopy (HREELS), and density functional theory (DFT) modeling are used to help explain the trend in the overall hydrogenation activity and selectivity toward the corresponding unsaturated alcohol (2-propenol) on the 3d/Pt(1 1 1) bimetallic surfaces. The hydrogenation activity on the subsurface Pt-3d-Pt(1 1 1) structures displays the following trend: Pt- Ni-Pt(1 1 1) > Pt-Co-Pt(1 1 1) > Pt-Cu-Pt(1 1 1) based on the TPD yields. The absolute yield toward 2- propenol is also the highest on Pt-Ni-Pt(1 1 1), which is further enhanced by the presence of preadsorbed hydrogen. In contrast, the selective hydrogenation does not occur on the surface monolayer 3d-Pt(1 1 1) structures. The TPD results are consistent with HREELS measurements of different vibrational features after the adsorption and reaction of acrolein on the subsurface Pt-3d-Pt(1 1 1) and surface 3d-Pt(1 1 1) structures. In addition, DFT calculations suggest that the different hydrogenation activities between the subsurface and surface structures appear to be related to the differences in the binding energy of acrolein on the corresponding bimetallic surfaces.

HETEROGENEOUS ASYMMETRIC RING-OPENING REACTIONS OF PROCHIRAL EPOXIDES INCLUDED AS GUEST MOLECULES IN TRI-o-THYMOTIDE CLATHRATES.

Gerdil, Raymond,Barchietto, Giacomo

, p. 4685 - 4688 (1987)

Enantiomorphous tri-o-thymotide clathrates of prochiral oxiranes were submitted to the action of gaseous hydrogen halides.Ring-opening reactions ensued that differ from those reported in homogeneous phase, showing a considerable modification of the chemical reactivity of the external reagent in the host lattice.Chirality transfer from the host receptors to the guest products was also observed, but with a poor efficiency.

ReOx/TiO2: A Recyclable Solid Catalyst for Deoxydehydration

Sandbrink, Lennart,Klindtworth, Elisabeth,Islam, Husn-Ubayda,Beale, Andrew M.,Palkovits, Regina

, p. 677 - 680 (2016)

Deoxydehydration (DODH) enables the transformation of two adjacent hydroxyl functions into a C-C double bond: e.g., facilitating synthesis of 1,3,5-hexatriene from sorbitol. Here we report the first stable heterogeneous catalyst for DODH based on ReOx supported on TiO2. ReOx/TiO2 exhibits not only catalytic activity and selectivity comparable to those of previously described molecular rhenium catalysts but also excellent stability without deactivation over at least six consecutive runs. X-ray absorption spectroscopy (XAFS) measurements indicate a mixture of Re(VII), Re(IV), and Re(0) species at a ratio of 0.47:0.27:0.25, remaining comparatively stable during catalysis.

Supported gold nanoparticles from quantum dot to mesoscopic size scale: Effect of electronic and structural properties on catalytic hydrogenation of conjugated functional groups

Claus,Bruckner,Mohr,Hofmeister

, p. 11430 - 11439 (2000)

Titania- and zirconia-supported gold particles of 1-5 nm size, prepared by various routes of synthesis, were employed in the partial hydrogenation of acrolein. In-depth characterization of their structural and electronic properties by electron microscopy, electron paramagnetic resonance, and optical absorption spectroscopy aimed at disclosing the nature of the active sites controlling the hydrogenation of C=O vs C=C bonds. The structural characteristics of the catalysts, as mean particle size, size distribution, and dispersion, distinctly depend on the synthesis applied and the oxide support used whereby the highest gold dispersion (D(Au) = 0.78, Au/TiO2) results from a modified sol-gel technique. For extremely small gold particles on titania and zirconia (1.1 and 1.4 nm mean size), conduction electron spin resonance of the metal and paramagnetic F-centers (trapped electrons in oxygen vacancies) of the support were observed. Besides the influence of the surface geometry on the adsorption mode of the α,β-unsaturated aldehyde, the marked structure sensitivity of the catalytic properties with decreasing particle size is attributed to the electron-donating character of paramagnetic F-centers forming electron-rich gold particles as active sites. The effect of structural and electronic properties due to the quantum size effect of sufficiently small gold particles on the partial hydrogenation is demonstrated.

Three Consecutive Allylic Sigmatropic Rearrangements of 1,8-Bis(allylthio)naphthalene Monooxides via Transannular Interaction

Furukawa, Naomichi,Shima, Hidetaka,Kimura, Takeshi

, p. 1762 - 1763 (1993)

Oxidation of 1,8-bis(allylthio)naphthalene with m-chloroperbenzoic acid (mCPBA) gave the monooxide which undergoes three consecutive sigmatropic rearrangements to afford 2-allylnaphtho-1,2-dithiole; the mechanism has been studied using deuterium tracer experiments.

Direct Synthesis of Propene Oxide by using an EuCl3 Catalytic System at Room Temperature

Yamanaka, Ichiro,Nakagaki, Katsumi,Otsuka, Kiyoshi

, p. 1185 - 1186 (1995)

Epoxidation of propene to propene oxide with O2 is catalysed by an EuCl3-Zn-MeCO2H catalytic system at 30 deg C (TON of 12.1 in 1 h).

Spectators Control Selectivity in Surface Chemistry: Acrolein Partial Hydrogenation over Pd

Dostert, Karl-Heinz,OBrien, Casey P.,Ivars-Barceló, Francisco,Schauermann, Swetlana,Freund, Hans-Joachim

, p. 13496 - 13502 (2015)

We present a mechanistic study on selective hydrogenation of acrolein over model Pd surfaces-both single crystal Pd(111) and Pd nanoparticles supported on a model oxide support. We show for the first time that selective hydrogenation of the C=O bond in acrolein to form an unsaturated alcohol is possible over Pd(111) with nearly 100% selectivity. However, this process requires a very distinct modification of the Pd(111) surface with an overlayer of oxopropyl spectator species that are formed from acrolein during the initial stages of reaction and turn the metal surface selective toward propenol formation. By applying pulsed multimolecular beam experiments and in situ infrared reflection-absorption spectroscopy, we identified the chemical nature of the spectator and the reactive surface intermediate (propenoxy species) and experimentally followed the simultaneous evolution of the reactive intermediate on the surface and formation of the product in the gas phase.

Identification of active sites in gold-catalyzed hydrogenation of acrolein

Mohr, Christian,Hofmeister, Herbert,Radnik, Joerg,Claus, Peter

, p. 1905 - 1911 (2003)

The active sites of supported gold catalysts, favoring the adsorption of C=O groups of acrolein and subsequent reaction to allyl alcohol, have been identified as edges of gold nanoparticles. After our recent finding that this reaction preferentially occurs on single crystalline particles rather than multiply twinned ones, this paper reports on a new approach to distinguish different features of the gold particle morphology. Elucidation of the active site issue cannot be simply done by varying the size of gold particles, since the effects of faceting and multiply twinned particles may interfere. Therefore, modification of the gold particle surface by indium has been used to vary the active site characteristics of a suitable catalyst, and a selective decoration of gold particle faces has been observed, leaving edges free. This is in contradiction to theoretical predictions, suggesting a preferred occupation of the low-coordinated edges of the gold particles. On the bimetallic catalyst, the desired allyl alcohol is the main product (selectivity 63%; temperature 593 K, total pressure ptotal = 2 MPa). From the experimentally proven correlation between surface structure and catalytic behavior, the edges of single crystalline gold particles have been identified as active sites for the preferred C=O hydrogenation.

Operando Investigation of Ag-Decorated Cu2O Nanocube Catalysts with Enhanced CO2 Electroreduction toward Liquid Products

Herzog, Antonia,Bergmann, Arno,Jeon, Hyo Sang,Timoshenko, Janis,Kühl, Stefanie,Rettenmaier, Clara,Lopez Luna, Mauricio,Haase, Felix T.,Roldan Cuenya, Beatriz

, p. 7426 - 7435 (2021)

Direct conversion of carbon dioxide into multicarbon liquid fuels by the CO2 electrochemical reduction reaction (CO2RR) can contribute to the decarbonization of the global economy. Here, well-defined Cu2O nanocubes (NCs, 35 nm) uniformly covered with Ag nanoparticles (5 nm) were synthesized. When compared to bare Cu2O NCs, the catalyst with 5 at % Ag on Cu2O NCs displayed a two-fold increase in the Faradaic efficiency for C2+ liquid products (30 % at ?1.0 VRHE), including ethanol, 1-propanol, and acetaldehyde, while formate and hydrogen were suppressed. Operando X-ray absorption spectroscopy revealed the partial reduction of Cu2O during CO2RR, accompanied by a reaction-driven redispersion of Ag on the CuOx NCs. Data from operando surface-enhanced Raman spectroscopy further uncovered significant variations in the CO binding to Cu, which were assigned to Ag?Cu sites formed during CO2RR that appear crucial for the C?C coupling and the enhanced yield of liquid products.

Vapour phase transfer hydrogenation of α,β-unsaturated carbonyl compounds. Thermodynamic and experimental studies

Gliński, Marek,Ulkowska, Urszula

, p. 131 - 140 (2016)

This paper presents the first systematic thermodynamic study of the vapour phase transfer hydrogenation of α,β-unsaturated carbonyl compounds at temperatures: 423.15-723.15 K. Calculations were made for four compounds, namely: acrolein, α-methylacrolein, β-methylacrolein and methyl vinyl ketone. The Gibbs free energies and equilibrium mole fractions (EMFs) were calculated for transfer hydrogenation with ethanol and 2-propanol as hydrogen donors. It was noted that for transfer hydrogenation and hydrogenation with hydrogen the formation of the unsaturated alcohol (UOL) is the least thermodynamically favoured reaction and that saturated alcohol (SOL) and saturated aldehyde or ketone (SAL or SON) are the main products. A set of eight carbonyl compounds have been transfer hydrogenated with ethanol and 2-propanol in the presence of MgO as the catalyst. The main conclusions are that: (a) the reduction of a carbonyl group into a carbinol group occurs with a very high selectivity, (b) for almost all carbonyl compounds, except acrolein, the reactivity of 2-propanol highly exceeded that shown by ethanol and (c) the high chemoselectivity of transfer hydrogenation of acrolein with alcohols resulted from the kinetic control caused by the presence of magnesium oxide.

-

Wharton,Bohlen

, p. 3615 (1961)

-

Influence of the support composition on the hydrogenation of acrolein over Ag/SiO2-Al2O3 catalysts

Volckmar, Claudia E.,Bron, Michael,Bentrup, Ursula,Martin, Andreas,Claus, Peter

, p. 1 - 8 (2009)

The gas phase hydrogenation of acrolein over supported silver catalysts has been investigated with a focus on the influence of the support acidity. Acidity has been varied by preparing silver catalysts supported on silica/alumina supports with varying SiO2/Al2O3 ratio. After the catalytic experiments the Ag catalysts exhibit similar particle sizes, as revealed with TEM (transmission electron microscopy). The acidity of the samples was estimated using TPD of adsorbed ammonia which gives the total acidity of the samples, furthermore by IR of adsorbed pyridine to identify the Bronsted and Lewis acidity. No Bronsted acidity was found, and the Lewis acidity showed a clear dependence on the support composition. It is shown that a high total acidity and a high amount of strong Lewis acid sites on the catalysts cause a low conversion of acrolein and low selectivity to allyl alcohol. The interaction of silver with the support or effects of the metal-support perimeter are discussed as possible reasons for this behaviour.

Silicon-directed acid ring-opening of allyltrimethylsilane oxide. X-ray structures of 3-triisopropylsilyl-2-(2,4-dinitrobenzoyloxy)-1-propanol and 3-triisopropylsilyl-2-(2,4,6-trinitrobenzoyloxy)-1-propanol

Badali, Fatmir,Issa, William,Pool, Brett,White, Jonathan M.

, p. 251 - 260 (1999)

Allyltrimethylsilane oxide 5 undergoes regiospecific ring-opening with carboxylic acids in chloroform to give the hydroxy esters 6a-e. In polar solvents competing elimination results in the formation of allyl alcohol. Allyltriisopropylsilane oxide 17 undergoes analogous reactions as 5 in chloroform but does not undergo elimination in methanol or acetone. The X-ray structures of 18b and 18c reveal significant lengthening of the C-O (ester) bond (a remarkable 1.502(2) A for 18c), these structural effects are due to strong σC-Si-σ*C-O interactions, particularly for 18c.

CORRELATION OF THE RATES OF SOLVOLYSIS OF ALLYL AND BENZYL ARENESULPHONATES

Kevill, Dennis N.,Rissmann, Thomas J.

, p. 717 - 720 (1984)

Analysis of the specific rates of solvolysis of allyl arenesulphonates in terms of the extended Grunwald-Winstein equation indicates a marked dependence on both the solvent nucleophilicity (high/value) and the solvent ionizing power (high m value).As the charge delocalization in the leaving group increases, both l and m values fall.For allyl toluene-p-sulphonate solvolysis in 28 solvents at 50.0 deg C, values for l(0.83) and for m (0.63), based on the use of NKL and Y values, are very similar to the equivalent values of 0.90 and 0.67 previously reported for benzyl toluene-p-sulphonate solvolysis.Related extended Grunwald-Winstein analyses are considered and the need for variety in the choice of solvents is emphasized.

pH optimization of nucleophilic reactions in water

King,Rathore,Lam,Guo,Klassen

, p. 3028 - 3033 (1992)

We present a way of prescribing the pH for a reaction so as to obtain either (a) maximum yield in competition with hydrolysis or (b) selective reaction at either of two sites in such nucleophile-electrophile reactions as C-alkylation of acidic ketones and the acylation and sulfonylation of amines. First, we derive the following general equation for pHmax, the pH giving the highest yield of the product (P) of the reaction of a nucleophile (Nu) with a hydrolyzable electrophile (E) in water: pHmax = 1/2[log (kw/kOH) + PKw + pKw] (kw and kOH refer to the water- and hydroxide-promoted hydrolyses of E, Kw is the autoprotolysis constant of water, and Ka is the acid dissociation constant of NuH+, the conjugate acid of Nu). pHmax thus depends on a property of E (namely, kw/kOH) and a property of Nu (the pKa of NuH+), but not on the rate constant for the reaction of E with Nu or the concentration of Nu. We then deduce analogous approximate equations for maximum selectivity for reaction at either of two nucleophilic sites, specifically, equations giving pHxmax and pHymax, the pH values for the maximum yields of the respective products (Px and Py) of the reactions of E with the two nucleophiles. We find that (a) pH-yield profiles calculated from the equations concur with observed yields for reactions under pseudo-first-order conditions and (b) preparative experiments at the estimated pH values give good to excellent yields of clean products and high selectivity in both the C-alkylation and Schotten-Baumann reactions.

Revisiting the deoxydehydration of glycerol towards allyl alcohol under continuous-flow conditions

Tshibalonza, Nelly Ntumba,Monbaliu, Jean-Christophe M.

, p. 3006 - 3013 (2017)

The deoxydehydration (DODH) of glycerol towards allyl alcohol was revisited under continuous-flow conditions combining a microfluidic reactor setup and a unique reactive dynamic feed solution approach. Short reaction times, high yield and excellent selectivity were achieved at high temperature and moderate pressure in the presence of formic acid, triethyl orthoformate, or a combination of both. Triethyl orthoformate appeared as a superior reagent for the DODH of glycerol, with shorter reaction times, lower reaction temperatures and more robust conditions. In-line IR spectroscopy and computations provided different perspectives on the unique reactivity of glycerol O,O,O-orthoesters.

Effect of MgCl2 in vapor-phase hydrogen transfer reaction between acrolein and 2-propanol over MgO catalyst systems

Nagase, Yoshinori,Katou, Tokumitsu

, p. 436 - 437 (2000)

Vapor-phase hydrogen transfer reaction between acrolein and 2-propanol over MgO catalyst systems has investigated. We found that, particularly at early reaction time, both the high activity and remarkable increase of allyl alcohol selectivity were achieved by the addition of a small amount of MgCl2 on MgO catalyst.

Cationic Ru complexes anchored on POM via non-covalent interaction towards efficient transfer hydrogenation catalysis

Chen, Manyu,Cui, Kai,Hou, Zhenshan,Peng, Qingpo,Wang, Jiajia,Wei, Xinjia,Zhao, Xiuge

, (2021/12/22)

The ionic materials consisting of cationic Ru complexes and Wells-Dawson polyoxometalate anion (POM, K6P2W18O62) have been constructed via a non-covalent interaction. The as-synthesized catalysts have been characterized thoroughly by NMR, XRD, FESEM, and FT-IR, etc. The characterization suggested that a hydrogen bond interaction occurred between the proton of the amine ligand in the cationic Ru complexes and the oxygen atom of the POM anion. The hydrogen bond played an important role in enhancing catalytic activity for the transfer hydrogenation of methyl levulinate (ML) to γ-valerolactone (GVL) under very mild conditions. Especially, the transfer hydrogenation reaction proceeded via a heterogeneous catalysis approach and the heterogenized catalysts even afforded much better catalytic performance than homogeneous analogs. Notably, the catalysts can be recycled without an obvious loss of activity, and further extended to highly selective transfer hydrogenation of α,β-unsaturated ketones and aldehydes, etc. into the corresponding α,β-unsaturated alcohols without any base external additives. The high catalytic performance of these anchored catalysts was highly related to the hydrogen bond interaction and the basicity of the polyanion. The obtained knowledge from this work could lead us to a new catalysis concept of tethering active homogeneous complexes for constructing highly active anchored Ru complex catalysts for hydrogenation reaction.

Parahydrogen-Induced Polarization Relayed via Proton Exchange

Them, Kolja,Ellermann, Frowin,Pravdivtsev, Andrey N.,Salnikov, Oleg G.,Skovpin, Ivan V.,Koptyug, Igor V.,Herges, Rainer,H?vener, Jan-Bernd

supporting information, p. 13694 - 13700 (2021/09/07)

The hyperpolarization of nuclear spins is a game-changing technology that enables hitherto inaccessible applications for magnetic resonance in chemistry and biomedicine. Despite significant advances and discoveries in the past, however, the quest to establish efficient and effective hyperpolarization methods continues. Here, we describe a new method that combines the advantages of direct parahydrogenation, high polarization (P), fast reaction, and low cost with the broad applicability of polarization transfer via proton exchange. We identified the system propargyl alcohol + pH2 → allyl alcohol to yield 1H polarization in excess of P ≈ 13% by using only 50% enriched pH2 at a pressure of ≈1 bar. The polarization was then successfully relayed via proton exchange from allyl alcohol to various target molecules. The polarizations of water and alcohols (as target molecules) approached P ≈ 1% even at high molar concentrations of 100 mM. Lactate, glucose, and pyruvic acid were also polarized, but to a lesser extent. Several potential improvements of the methodology are discussed. Thus, the parahydrogen-induced hyperpolarization relayed via proton exchange (PHIP-X) is a promising approach to polarize numerous molecules which participate in proton exchange and support new applications for magnetic resonance.