107-41-5

Basic information

• Product Name: Hexylene Glycol
• Synonyms: 2,4-Pentanediol,2-methyl-;2-Methyl-2,4-pentandiol;2-methyl-4-pentanediol;2-methylpentane-2,;2-methylpentane-2,4-;4-Methyl-2,4-pentanediol;4-Methyl-2,4-pentanediole;4-Pentanediol,2-methyl-2
• CAS NO: 107-41-5
• Molecular Formula: C₆H₁₄O₂
• Molecular Weight: 118.17
• EINECS: 203-489-0
• Product Categories: Industrial/Fine Chemicals;White powder;pharmaceutical intermediates
• Mol File: 107-41-5.mol
• Article Data: 25

Chemical Properties

• Melting Point: −40 °C(lit.)
• Boiling Point: 197 °C(lit.)
• Flash Point: 201 °F
• Appearance: Clear/Slightly Viscous Liquid
• Density: 0.925 g/mL at 25 °C(lit.)
• Vapor Density: 4.1 (vs air)
• Vapor Pressure: 0.02 mm Hg ( 20 °C)
• Refractive Index: n20/D 1.427(lit.)
• Storage Temp.: 2-8°C
• Solubility: H2O: 1 M at 20 °C, clear, colorless
• PKA: 15.10±0.29(Predicted)
• Explosive Limit: 1-9.9%(V)
• Water Solubility: soluble
• Sensitive: Hygroscopic
• Stability: Stable. Incompatible with strong oxidizing agents, strong acids, strong reducing agents.
• Merck: 14,4710
• BRN: 1098298
• CAS DataBase Reference: Hexylene Glycol(CAS DataBase Reference)
• NIST Chemistry Reference: Hexylene Glycol(107-41-5)
• EPA Substance Registry System: Hexylene Glycol(107-41-5)

Safety Data

• Hazard Codes: Xi
• Statements: 36/38
• Safety Statements: 26-36
• WGK Germany: 1
• RTECS: SA0810000
• F: 3-23
• TSCA: Yes
• Hazardous Substances Data: 107-41-5(Hazardous Substances Data)

Usage

Description

2-Methyl-2,4-pentanediol (MPD) is a diol organic compound with a chiral carbon atom. It is a colorless liquid at room temperature and can be Diacetone alcohol is hydrogenated. The appearance is colorless liquid with mild sweetness. It is miscible with water, soluble in ethanol, and soluble in most organic solvents.

Uses

Different sources of media describe the Uses of 107-41-5 differently. You can refer to the following data:
1. 2-Methyl-2,4-pentanediol (MPD) is a fine chemical product with a wide range of uses, which can be used in pesticides, biochemical engineering, photosensitive materials, synthetic fragrances and other fields. 2-Methyl-2,4-pentanediol is a highly soluble high-grade organic solvent. It can be used as an additive in the production of metal surface treatment agents for rust and oil removal. It can also be used as a textile auxiliaries, as well as coatings and latex paints. It can also be used in cosmetics, as a pesticide stabilizer, but also as a daily chemical moisturizer, flavor and fragrance raw materials, hydraulic oil, high-temperature lubricating oil, brake oil, dry cleaning agent, printing ink, pigment dispersant, wood preservative etc. As penetrant, emulsifier and antifreeze.
2. Hexylene Glycol is used as a reagent in the synthesis of functionalized boronic esters. it is used in laboratory studies as a precipitant and cryoprotectant in protein crystallography. Also used in the preparation of vinylboronates. It is mainly used as a coupling agent and an additive to hydraulic fluids, inks and cement. Further, it is used as a solvent for cleaning and colorant products. It is a potential substitute for glycol ethers. It is an effective shrinkage reduction admixture or SRA for concrete and mortar. It can also be used as a building block in chemical synthesis. Hexylene glycol is a key solvent in many markets such as paints & coatings, metal working fluids, detergency, cosmetics & fragrances, textiles & leather.It is used to control the flow properties of industrial products such as paints, coatings, cleansers, solvents, and hydraulic fluids. It acts as a thickening agent in cosmetic products. It is also employed as a blood volume expander.
3. hexylene glycol could be considered a solubilizer.
4. Fuel and lubricant additive; solvent in cosmetics; solvent in petroleum refining; coupling agent in hydraulic brake fluid and printing inks; gasoline anti-icer additive
5. (^+)-2-Methyl-2,4-pentanediol is used to control the flow properties of industrial products such as paints, coatings, cleansers, solvents, and hydraulic fluids. It acts as a thickening agent in cosmetic products. It serves as a coupling agent and an additive to hydraulic fluids, inks and cement. It is also employed as a blood volume expander. Further, it is used as a solvent for cleaning and colorant products. In addition to this, it is used in laboratory studies as a precipitant and cryoprotectant in protein crystallography.

Preparation

Using 2000 L of diacetone alcohol as a raw material to synthesize isohexanediol by hydrogenation reduction, the specific process steps are:Step 1: Start the vacuum pump to vacuum the raw material metering tank. When the vacuum is greater than -0.06Mpa, close the exhaust valve, open the feed valve, mix 2000 L of diacetone alcohol raw material and 200ppm sodium bicarbonate and pump it in Raw material metering tank.Step 2: Open the vacuum valve on the reduction pot and pump the reduction pot to a vacuum of -0.1Mpa, then open the feed valve on the reduction pot, and add 2000 L of diacetone alcohol raw material and 200ppm sodium bicarbonate from the metering tank To the reduction pot, start the mixer to stir at the same time, add 95Kg of Raney nickel catalyst.Step 3: Close the vacuum valve, open the nitrogen inlet valve, and inject nitrogen into the reduction pot. After the pressure in the pot is increased to 0.6Mpa within 3 to 5 minutes, close the hydrogen inlet valve, open the vent valve, and reduce the pressure in the pot. Reduce to normal pressure, repeat the above steps, re-inject nitrogen for replacement, and repeat this five times.Step 4: When the nitrogen replacement in the third step is completed, close the vent valve, open the hydrogen inlet valve, and inject hydrogen into the reduction pot within 10-15 minutes. When the pressure in the pot reaches 0.6Mpa, close the hydrogen inlet valve. Open the vent valve, after the pressure in the pot drops to normal pressure, close the vent valve, repeat the above steps, re-inject hydrogen for replacement, and repeat this five times.Step 5: After the hydrogen replacement, close the vent valve, open the hydrogen gas inlet valve, and inject hydrogen into the reduction pot. Use hydrogen to make the pressure in the pot reach 1.9Mpa within 15 to 30 minutes, then close the hydrogen gas inlet valve and open it. Jacketed steam valve, raise the temperature in the pot to 150°C, and adjust the stirring speed to 310r/min. At this time, open the hydrogen gas inlet valve and control the temperature in the pot at 150°C. On the basis of the stable temperature in the pot, Keep the hydrogen vapor pressure at 1.9Mpa for 4 hours, then close the hydrogen gas inlet valve and accurately record the current pressure in the boiler. After 30 minutes, take a sample for gas chromatographic testing. If the raw material content is less than 1% in the test result, it is qualified. At this time, Close the jacketed steam valve and open the jacketed cooling water to reduce the temperature in the pot to normal temperature. Then, open the vent valve to reduce the pressure in the pot to normal pressure.Step 6: Stop the mixer and let it stand for 50 minutes, close the vent valve, open the nitrogen inlet valve, use nitrogen to increase the pressure in the pot to 0.6Mpa, close the nitrogen valve, open the empty valve, and slowly reduce the pressure in the pot to normal pressure , And then repeat this step 5 times.Step 7: Open the nitrogen valve and the feed valve of the distillation pot at the same time. Use 0.8Mpa nitrogen to send the qualified materials to the filter for filtration. The filtered materials are pumped into the crude isohexanediol storage tank, and then pressed to the distillation Distillation is carried out in the kettle, and the filtered catalyst is recycled; the finished product from the rectification is isohexanediol. After the raw material of 2000 L diacetone alcohol is hydrogenated and reduced to synthesize, 1865Kg of isohexanediol product is obtained with a purity of 99.5%. The mass yield is 99%. After cooling, it is placed in the isohexanediol product storage tank. The remaining by-products are mainly 29kg of 98% acetone, which can be sold as industrial acetone.

Chemical Properties

Hexylene Glycol is an oily colorless liquid with a mild sweet odor. It is an oxygenated solvent derived from acetone which has two alcohol functions. It has a low evaporation rate and it is completely miscible with water.

Production Methods

2-Methyl-2,4-pentanediol is prepared commercially by the catalytic hydrogenation of diacetone alcohol . It is used as a chemical intermediate, a selective solvent in petroleum refining, a component of hydraulic fluids, a solvent for inks, and as an additive for cement . Industrial exposure is likely to be from direct contact or from inhalation, particularly if the material is heated.

Definition

ChEBI: A glycol in which the two hydroxy groups are at positions 2 and 4 of 2-methylpentane (isopentane).

General Description

Oily colorless liquid with a mild sweet odor. Floats and mixes slowly with water.

Air & Water Reactions

Hygroscopic. Water soluble [Hawley]

Reactivity Profile

2-Methyl-2,4-pentanediol is incompatible with the following: Strong oxidizers, strong acids [Note: Hygroscopic (i.e., absorbs moisture from the air).] .

Hazard

Toxic by ingestion and inhalation; irritant to skin, eyes, and mucous membranes. Combustible.

Health Hazard

Irritation of eyes, nose and throat; headache, dizziness, and nausea.

Chemical Reactivity

Reactivity with Water No reaction; Reactivity with Common Materials: Can catch fire when in contact with porous materials such as wood, asbestos, cloth, soil, or rusty metals; Stability During Transport: Stable at ordinary temperatures, however when heated this material can decompose to nitrogen and ammonia gases. The decomposition is not generally hazardous unless it occurs in confined spaces; Neutralizing Agents for Acids and Caustics: Flush with water and neutralize the resulting solution with calcium hypochlorite; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent.

Purification Methods

Dry the diol with Na2SO4, then CaH2 and fractionally distil it under reduced pressure through a packed column, taking precautions to avoid absorption of water. [Beilstein 1 IV 2565.]

InChI:InChI=1/C6H14O2/c1-5(7)4-6(2,3)8/h5,7-8H,4H2,1-3H3

Synthetic route

4-Hydroxy-4-methyl-2-pentanone (123-42-2) → 2-methyl-2,4-pentanediol (107-41-5)

Conditions	Yield
With hydrogen In water at 120℃; under 7500.75 Torr; for 3h; Reagent/catalyst; Temperature; Pressure; Solvent;	100%
With sodium tetrahydroborate In methanol at 0 - 20℃; for 1h;	83%
With lithium aluminium tetrahydride In tetrahydrofuran at 20℃; for 3h;	53%

2,2-Diisopropyl-4,4,6-trimethyl-[1,3,2]dioxasilinane (85272-42-0) → 2-methyl-2,4-pentanediol (107-41-5)

Conditions	Yield
With hydrogen fluoride In acetonitrile at 25℃; for 0.25h;	95%

7,7,9-Trimethyl-5,8,9,11-tetrahydro-7H-6,10-dioxa-benzocyclononene (127392-17-0) → 2-methyl-2,4-pentanediol (107-41-5)

Conditions	Yield
With hydrogen; palladium hydroxide - carbon In ethanol under 760 Torr;	89%

2,4-Bis-(tert-butyl-dimethyl-silanyloxy)-2-methyl-pentane → 2-methyl-2,4-pentanediol (107-41-5)

Conditions	Yield
With low-loading and alkylated polystyrene-supported-SO3H In water at 40℃; for 12h;	89%

2,2-Di-tert-butyl-4,4,6-trimethyl-[1,3,2]dioxasilinane (85272-43-1) → 2-methyl-2,4-pentanediol (107-41-5)

Conditions	Yield
With hydrogen fluoride In acetonitrile at 25℃; for 12h;	88%

4-Methoxymethoxy-2-methyl-pentan-2-ol (89449-96-7) → 2-methyl-2,4-pentanediol (107-41-5)

Conditions	Yield
With (i-PrS)BBr In dichloromethane at -78℃;	70%

titanium(IV) tert-butoxide (3087-39-6) + acetaldehyde (75-07-0) → 2-methyl-2,4-pentanediol (107-41-5) + (2S,6S)-4-Methyl-heptane-2,4,6-triol

Conditions	Yield
With lithium perchlorate; MANDELIC ACID at 20℃; for 24h;	A 51% B 8%

titanium(IV) tert-butoxide (3087-39-6) + acetaldehyde (75-07-0) → 2-methyl-2,4-pentanediol (107-41-5) + (2S,6R)-4-Methyl-heptane-2,4,6-triol + (2S,6S)-4-Methyl-heptane-2,4,6-triol

Conditions	Yield
With lithium perchlorate; MANDELIC ACID at 20℃; for 24h;	A 2% B 43% C 8%

4-Hydroxy-4-methyl-2-pentanone (123-42-2) → 2-methyl-2,4-pentanediol (107-41-5) + 2-methylpentan-2-ol (590-36-3)

Conditions	Yield
bei der elektrolytischen Reduktion;

acetone (67-64-1) → 2-methyl-2,4-pentanediol (107-41-5) + 2,3-dimethyl-2,3-butane diol (76-09-5)

Conditions	Yield
With amalgamated magnesium

2-methyl-3,4-pentadien-2-ol (34761-53-0) → 2-methyl-2,4-pentanediol (107-41-5)

Conditions	Yield
(i) Hg(OAc)2, H2O, (ii) NaBH4; Multistep reaction;

1.3-butanediol (18826-95-4, 107-88-0) + 2,2,4,4,6-Pentamethyl-1,3-dioxa-2-silacyclohexane (77181-39-6) → 2-methyl-2,4-pentanediol (107-41-5) + 2,2,4-Trimethyl-1,3-dioxa-2-silacyclohexane (14903-76-5)

Conditions	Yield
boron trifluoride diethyl etherate In 1,4-dioxane at 20℃;	A n/a B 21 % Chromat.

acetaldehyde (75-07-0) + isobutene (115-11-7) → 4,4-dimethyl-1,3-dioxane (766-15-4) + 2,4,4,6-tetramethyl-1,3-dioxane (5182-37-6) + 2-methyl-2,4-pentanediol (107-41-5) + 3-methyl-butane-1,3-diol (2568-33-4) + 2,4,4-trimethyl-1,3-dioxane (29879-84-3)

Conditions	Yield
With formaldehyd; sulfuric acid In various solvent(s) at 70℃; for 4.33333h; Product distribution; var. time, steel bomb;	A 5.6 mmol B 8.5 mmol C n/a D n/a E 16.4 mmol

4-hydroperoxy 2-methylpentane (54942-19-7) → Methyl isobutyl carbinol (108-11-2) + 2-methyl-2,4-pentanediol (107-41-5) + octanol (111-87-5) + 2-methyl-1,4-pentanediol (6287-17-8)

Conditions	Yield
With lithium aluminium tetrahydride; octane; manganese(II) stearate 1.) 125 deg C, 10 h, 2.) THF, reflux, 1 h; Yield given. Multistep reaction. Yields of byproduct given;

furan-2,3,5(4H)-trione pyridine (1:1) + acetone (67-64-1) + PtO2 → 2-methyl-2,4-pentanediol (107-41-5) + isopropyl alcohol (67-63-0)

Conditions	Yield
pH 11.9.Hydrogenation;

2,4,4,6-tetramethyl-1,3-dioxane (5182-37-6) → 2-methyl-2,4-pentanediol (107-41-5) + 4-methoxy-4-methoxy-pentan-2-ol

Conditions	Yield
With methanol; sulfuric acid

4-Hydroxy-4-methyl-2-pentanone (123-42-2) + sodium amalgam → 2-methyl-2,4-pentanediol (107-41-5)

4-Hydroxy-4-methyl-2-pentanone (123-42-2) + copper chromite → Methyl isobutyl carbinol (108-11-2) + 2-methyl-2,4-pentanediol (107-41-5) + isopropyl alcohol (67-63-0) + acetone (67-64-1)

Conditions	Yield
at 150℃; Hydrogenation;

4-Hydroxy-4-methyl-2-pentanone (123-42-2) + nickel → Methyl isobutyl carbinol (108-11-2) + 2-methyl-2,4-pentanediol (107-41-5) + isopropyl alcohol (67-63-0) + acetone (67-64-1)

Conditions	Yield
Hydrogenation;

ethylidene diacetate (542-10-9) + isobutene (115-11-7) → 2-methyl-2,4-pentanediol (107-41-5)

Conditions	Yield
Stage #1: ethylidene diacetate; isobutene With tin(IV) chloride In nitromethane at -10 - 20℃; for 1h; Addition; Salt formation; Stage #2: With water Hydrolysis; Stage #3: With potassium hydroxide In ethanol for 0.75h; Hydrolysis; Heating;

C6H13ClMg → 2-methyl-2,4-pentanediol (107-41-5) + aqueous KOH-solution

Conditions	Yield
Multi-step reaction with 2 steps 1: 1.) O2, 2.) aq. H2SO4 / 1.) diethyl ether, -65 deg C 2: 1.) n-octane, manganese stearate, 2.) LiAlH4 / 1.) 125 deg C, 10 h, 2.) THF, reflux, 1 h View Scheme

4,4,6-trimethyl-1,3-dioxane-2-one (27700-00-1) → 2-methyl-2,4-pentanediol (107-41-5)

Conditions	Yield
With potassium carbonate In methanol at 23℃;	9.1 mg

2-methyl-2,4-pentanediol (107-41-5) + 2-benzyloxycarbonyl-3-trifluoromethyl-4-ethyl-5-formylpyrrole (94609-22-0) → 2-benzyloxycarbonyl-3-trifluoromethyl-4-ethyl-5-(4',4',6'-trimethyl-1',3'-dioxane-2'-yl)pyrrole (594859-48-0)

Conditions	Yield
With toluene-4-sulfonic acid In benzene for 1h; Heating;	100%

2-methyl-2,4-pentanediol (107-41-5) → 4,4,6-trimethyl-1,3,2-dioxaborinane (10199-14-1, 23894-82-8)

Conditions	Yield
With dimethylsulfide; borane In dichloromethane at 0 - 25℃;	100%
With dimethylsulfide borane complex In dichloromethane at 0 - 20℃; for 3h;	78%
With borane Ν,Ν-diethylaniline complex; palladium 10% on activated carbon In 1,4-dioxane at 20℃; for 1h; Inert atmosphere;	75%

2-methyl-2,4-pentanediol (107-41-5) + [(CH3COCHCOCH3)2Al(μ-OCH(CH3)2)2Al(OCH(CH3)2)2] → [Al2(OCH(CH3)2)2(CH3COCHCOCH3)2(OC(CH3)2CH2CHCH3O)] (163462-30-4)

Conditions	Yield
In benzene byproducts: i-PrOH; moisture free; refluxing; solvent removal; elem. anal.;	100%

2-methyl-2,4-pentanediol (107-41-5) + 3-Mercaptopropyltriethoxysilane (14814-09-6) → 3-(2-methyl-2,4-pentanedioxyethoxysilyl)-1-propanethiol

Conditions	Yield
toluene-4-sulfonic acid at 33 - 60℃; under 11 Torr; for 2h;	99.2%

2-methyl-2,4-pentanediol (107-41-5) + tert-butyldimethylsilyl chloride (18162-48-6) → 4-tert-butyldimethylsilanyloxy-2-methyl-2-pentanol (193811-86-8)

Conditions	Yield
With 1H-imidazole In N,N-dimethyl-formamide at 0 - 20℃; for 14h;	99%
With 1H-imidazole In N,N-dimethyl-formamide at 50 - 70℃; for 1.75h;

2-methyl-2,4-pentanediol (107-41-5) + benzoyl chloride (98-88-4) → 4-hydroxy-4-methylpentan-2-yl benzoate (56543-20-5)

Conditions	Yield
With N,N,N,N,-tetramethylethylenediamine; 4 A molecular sieve In dichloromethane at -78℃; for 2h; Acylation;	99%

2-methyl-2,4-pentanediol (107-41-5) + [Ti(N-phenylsalicylideneimine(-H))2(O-i-Pr)2] → [Ti(N-phenylsalicylideneimine(-H))2(OC(CH3)2CH2CH(CH3)O)] (943433-27-0)

Conditions	Yield
In benzene byproducts: (CH3)2CHOH; under unhydrous atm., soln. of ligand added to soln. of Ti compd. (3.06:3.01), refluxed, monitored by isopropanol liberated; concd., crystd., elem. anal.;	99%

2-methyl-2,4-pentanediol (107-41-5) + acetic acid (64-19-7) → 4-acetoxy-2-methylpentan-2-ol (4833-08-3)

Conditions	Yield
With β-cyclodextrin-SO3H In neat (no solvent) at 70℃; for 6h;	99%

2-methyl-2,4-pentanediol (107-41-5) + 2,3-dihydro-1-benzofuran-5-ylboronic acid (331834-13-0) → 2-(benzofuran-5-yl)-4,4,6-trimethyl-1,3,2-dioxaborinane

Conditions	Yield
In dichloromethane at 20℃; for 16h;	99%

2-methyl-2,4-pentanediol (107-41-5) + methacrylic acid methyl ester (80-62-6) → 4-hydroxy-4-methylpentan-2-yl methacrylate

Conditions	Yield
With 1,1,1-trioctyl-1-methylphosphonium methylcarbonate at 20℃; for 24h; Molecular sieve; Green chemistry; chemoselective reaction;	99%
With 1,1,1-trioctyl-1-methylphosphonium methylcarbonate; 4,4'-di-tert-butylbiphenyl at 25℃; for 24h; Schlenk technique; Molecular sieve;	99%

2-methyl-2,4-pentanediol (107-41-5) + methacrylic acid methyl ester (80-62-6) → 4-hydroxy-4-methylpentan-2-yl methacrylate + 2-methylpentane-2,4-diyl bis(2-methylacrylate)

Conditions	Yield
With 4,4'-di-tert-butylbiphenyl; tetramethylammonium methyl carbonate at 80℃; for 24h; Schlenk technique; Molecular sieve;	A 5% B 99%
With tetramethylammonium methyl carbonate at 80℃; for 24h; Molecular sieve; Green chemistry; chemoselective reaction;	A 5% B 95%

2-methyl-2,4-pentanediol (107-41-5) → 4,4,4',4',6,6'-hexamethyl-2,2'-bi(1,3,2-dioxaborinane)bis(hexyleneglycolato)diboron (230299-21-5)

Conditions	Yield
With tetrakis(dimethylamido)diborane In toluene at 20 - 100℃; for 1.25h;	98.6%
Multi-step reaction with 2 steps 1: 2,6-di-tert-butyl-4-methyl-phenol / dichloromethane / -10 - 0 °C / Inert atmosphere 2: C25H36FeN2Si / toluene / 15 h / Inert atmosphere; Reflux View Scheme

2-methyl-2,4-pentanediol (107-41-5) → bis(2-methylpentane-2,4-diyldioxy)silane (887-37-6)

Conditions	Yield
With silica gel; sodium hydroxide In ethanol for 48h; Reflux; Large scale;	98%
With silica gel; sodium hydroxide at 15℃; under 760.051 Torr; for 24h; Reagent/catalyst;
With pyridine; tetrachlorosilane

2-methyl-2,4-pentanediol (107-41-5) + (Al(OCH(CH3)2)(CH3COCHCOCH3)2)2 → H(1+)*(CH3COCHCOCH3)2Al(OC(CH3)2CH2CH(CH3)O)(1-)=H[(CH3COCHCOCH3)2Al(OC(CH3)2CH2CH(CH3)O)]

Conditions	Yield
In benzene byproducts: i-PrOH; Al-compd.:glycole-compd. molar ratio was 1:2, reflux for 5 h; solvent was removed in vac., solid was recrystd. from CH2Cl2/n-hexane (7:1), elem. anal.;	98%

2-methyl-2,4-pentanediol (107-41-5) + 4-tert-butylphenylboronic acid (123324-71-0) → 2-(4-(tert-butyl)phenyl)-4,4,6-trimethyl-1,3,2-dioxaborinane

Conditions	Yield
In dichloromethane at 20℃; for 16h;	98%

2-methyl-2,4-pentanediol (107-41-5) + naphthalene-2-boronic acid (32316-92-0) → 4,4,6-trimethyl-2-naphthalen-2-yl[1,3,2]dioxaborinane (1260068-92-5)

Conditions	Yield
In dichloromethane at 20℃; for 16h;	98%

2-methyl-2,4-pentanediol (107-41-5) + crotonaldehyde (123-73-9) → C10H18O2

Conditions	Yield
With trichloroacetonitrile at 20℃; for 2.5h; Inert atmosphere;	98%

2-methyl-2,4-pentanediol (107-41-5) + 3-phenyl-propenal (104-55-2) → C15H20O2

Conditions	Yield
With trichloroacetonitrile at 20℃; for 2h; Inert atmosphere;	97%

2-methyl-2,4-pentanediol (107-41-5) + (C9H6NO)B(OCH(CH3)2)2 → (C9H6NO)B(OC(CH3)2CH2CH(CH3)O) (185611-05-6)

Conditions	Yield
In benzene refluxing (10 h); recrystn. (benzene/CH2Cl2); elem. anal.;	96.61%

2-methyl-2,4-pentanediol (107-41-5) + Trimethyl borate (121-43-7) → 2-methoxy-4,4,6-trimethyl-1,3,2-dioxaborinane (3208-69-3)

Conditions	Yield
for 1.5h; Reflux; Dean-Stark;	96.1%

2-methyl-2,4-pentanediol (107-41-5) + di-tert-butylsilyl bis(trifluoromethanesulfonate) (85272-31-7) → 2,2-Di-tert-butyl-4,4,6-trimethyl-[1,3,2]dioxasilinane (85272-43-1)

Conditions	Yield
With 2,6-dimethylpyridine In chloroform-d1 at 25℃;	96%

2-methyl-2,4-pentanediol (107-41-5) + bis(acetylacetonato)titanium(IV) diisopropoxide → [titanium(IV)(acetylacetonate)2(OC(CH3)2CH2CH(CH3)O)]

Conditions	Yield
In benzene for 4h; Reflux;	96%

2-methyl-2,4-pentanediol (107-41-5) + 4-Bromophenylboronic acid (5467-74-3) → 2-(4-bromophenyl)-4,4,6-trimethyl-1,3,2-dioxaborinane (1092060-78-0)

Conditions	Yield
In dichloromethane at 20℃; for 16h;	96%

2-methyl-2,4-pentanediol (107-41-5) + (4-(trimethylsilyl)phenyl)boronic acid (17865-11-1) → 2-(4-trimethylsilylphenyl)-4,4,6-trimethyl-1,3,2-dioxaborinane

Conditions	Yield
In dichloromethane at 20℃; for 16h;	96%

2-methyl-2,4-pentanediol (107-41-5) + benzoyl chloride (98-88-4) → 2-phenyl-4,4,6-trimethyl-1,3-dioxanium hexachloroantimonate

Conditions	Yield
With antimonypentachloride In dichloromethane at 0℃; for 0.25h;	95%

2-methyl-2,4-pentanediol (107-41-5) + carbonic acid dimethyl ester (616-38-6) → 4,4,6-trimethyl-1,3-dioxane-2-one (27700-00-1)

Conditions	Yield
With 1,1,1-trioctyl-1-methylphosphonium methylcarbonate at 90℃; for 12h;	95%

2-methyl-2,4-pentanediol (107-41-5) + phenylboronic acid → 4,4,6-trimethyl-2-phenyl-[1,3,2]dioxaborinane (15961-35-0)

Conditions	Yield
In dichloromethane at 20℃; for 16h;	95%
With 1H-imidazole; iron(III) chloride In water; acetonitrile at 20℃; for 0.5h; Inert atmosphere;	82%

2-methyl-2,4-pentanediol (107-41-5) + 2-Methoxyphenylboronic acid (5720-06-9) → 2-(2-methoxyphenyl)-4,4,6-trimethyl-1,3,2-dioxaborinane (934558-37-9)

Conditions	Yield
In dichloromethane at 20℃; for 16h;	95%

Upstream product

• 123-42-2 4-Hydroxy-4-methyl-2-pentanone 
• 89449-96-7 4-Methoxymethoxy-2-methyl-pentan-2-ol 
• 75-07-0 acetaldehyde 
• 115-11-7 isobutene 
• 27700-00-1 4,4,6-trimethyl-2-oxo-1,3-dioxane 
• 7732-18-5 water 
• 3087-39-6 titanium(IV) tert-butoxide 
• 542-10-9 ethylidene diacetate 
• 5182-37-6 2,4,4,6-tetramethyl-1,3-dioxane 
• 67-64-1 acetone 
• 54942-19-7 4-hydroperoxy 2-methylpentane 
• 127392-17-0 7,7,9-Trimethyl-5,8,9,11-tetrahydro-7H-6,10-dioxa-benzocyclononene 
• 85272-43-1 2,2-Di-tert-butyl-4,4,6-trimethyl-[1,3,2]dioxasilinane 
• 85272-42-0 2,2-Diisopropyl-4,4,6-trimethyl-[1,3,2]dioxasilinane 

Downstream Products

• 1083-44-9 4,4,6-trimethyl-2-phenoxy-[1,3,2]dioxaphosphorinane 
• 1123-07-5 4,4,6-trimethyl-[1,3]dioxane 
• 3643-64-9 1,3,5-trimethylcyclohexene 
• 52386-21-7 2-ethoxy-4,4,6-trimethyl-1,3,2-dioxaborinane 
• 1637-24-7 2,4-diacetoxy-2-methylpentan 
• 2808-76-6 1,3-dimethylcyclohexene 
• 115-11-7 isobutene 
• 10200-91-6 4,4,6-trimethyl-2-n-octyl-[1,3,2]dioxaborinane 
• 67-63-0 isopropyl alcohol 
• 4325-82-0 4-methyl pent-3-en-2-ol 
• 926-56-7 4-methyl-1,3-pentadiene 
• 2004-67-3 4-methyl-4-penten-2-ol 
• 116374-76-6 (E)-2-methyl-1,3-heptadiene 
• 32560-29-5 2,2,4,4,6-Pentamethyl-[1,3]dioxan 

Relevant articles and documents

Catalytic Deprotection of Protected Alcohols in Water Using Low-Loading and Alkylated Polystyrene-Supported Sulfonic Acid

Catalytic deprotection of various protected alcohols was efficiently conducted using a hydrophobic low-loading and alkylated polystyrene-supported sulfonic acid (LL-ALPS-SO3H) in water as the sole solvent. Transprotection of an alcohol from a silyl ether to the corresponding benzylic ether or ester also proceeded smoothly in water.

Biomimetic ketone reduction by disulfide radical anion

The conversion of ribonucleosides to 2′-deoxyribonucleosides is catalyzed by ribonucleoside reductase enzymes in nature. One of the key steps in this complex radical mechanism is the reduction of the 3′-ketodeoxynucleotide by a pair of cysteine residues, providing the electrons via a disulfide radical anion (RSSR??) in the active site of the enzyme. In the present study, the bioinspired conversion of ketones to corresponding alcohols was achieved by the intermediacy of disulfide radical anion of cysteine (CysSSCys)?? in water. High concentration of cysteine and pH 10.6 are necessary for high-yielding reactions. The photoinitiated radical chain reaction includes the one-electron reduction of carbonyl moiety by disulfide radical anion, protonation of the resulting ketyl radical anion by water, and H-atom abstraction from CysSH. The (CysSSCys)?? transient species generated by ionizing radiation in aqueous solutions allowed the measurement of kinetic data with ketones by pulse radiolysis. By measuring the rate of the decay of (CysSSCys)?? at λmax = 420 nm at various concentrations of ketones, we found the rate constants of three cyclic ketones to be in the range of 104–105 M?1s?1 at ~22?C.

Rapid Deoxyfluorination of Alcohols with N-Tosyl-4-chlorobenzenesulfonimidoyl Fluoride (SulfoxFluor) at Room Temperature

The deoxyfluorination of alcohols is a fundamentally important approach to access alkyl fluorides, and thus the development of shelf-stable, easy-to-handle, fluorine-economical, and highly selective deoxyfluorination reagents is highly desired. This work describes the development of a crystalline compound, N-tosyl-4-chlorobenzenesulfonimidoyl fluoride (SulfoxFluor), as a novel deoxyfluorination reagent that possesses all of the aforementioned merits, which is rare in the arena of deoxyfluorination. Endowed by the multi-dimensional modulating ability of the sulfonimidoyl group, SulfoxFluor is superior to 2-pyridinesulfonyl fluoride (PyFluor) in fluorination rate, and is also superior to perfluorobutanesulfonyl fluoride (PBSF) in fluorine-economy. Its reaction with alcohols not only tolerates a wide range of functionalities including the more sterically hindered alcoholic hydroxyl groups, but also exhibits high fluorination/elimination selectivity. Because SulfoxFluor can be easily prepared from inexpensive materials and can be safely handled without special techniques, it promises to serve as a practical deoxyfluorination reagent for the synthesis of various alkyl fluorides.