71868-10-5

Basic information

• Product Name: 2-Methyl-4'-(methylthio)-2-morpholinopropiophenone
• Synonyms: 2-methyl-1-[4-(methylthio)phenyl]-2-(4-morpholinyl)-1-Propanone;2-methyl-4’-(methylthio)-2-morpholino-propiopheno;photoinitiator907;2-METHYL-4'-(METHYLTHIO)-2-MORPHOLINOPROPIOPHENONE;2-METHYL-1-[4-(METHYLTHIO)PHENYL]-2-MORPHOLINO-1-PROPANONE;2-METHYL-1-(4-METHYLTHIOPHENYL)-2-MORPHOLINOPROPAN-1-ONE;2-METHYL-1-[4-(METHYLTHIO)PHENYL]-2-MORPHOLINO-PROPANE-1-ONE;2-METHYL-1-[4-(METHYL THIO) PHENYL]-2-MORPHOLINOPROPANONE-1
• CAS NO: 71868-10-5
• Molecular Formula: C₁₅H₂₁NO₂S
• Molecular Weight: 279.4
• EINECS: 400-600-6
• Product Categories: Acetophenone;Organic Photoinitiators;Polymerization Initiators;photoinitiator
• Mol File: 71868-10-5.mol
• Article Data: 11

Chemical Properties

• Melting Point: 74-76 °C(lit.)
• Boiling Point: 210°C/76mmHg(lit.)
• Flash Point: 165℃
• Appearance: /
• Density: 1.15 g/cm³
• Vapor Pressure: 0Pa at 25℃
• Storage Temp.: Keep in dark place,Sealed in dry,Room Temperature
• Solubility: 162 in mg/100g standard fat at 20 ℃
• PKA: 4.77±0.10(Predicted)
• Water Solubility: 17.9mg/L at 20℃
• CAS DataBase Reference: 2-Methyl-4'-(methylthio)-2-morpholinopropiophenone(CAS DataBase Reference)
• NIST Chemistry Reference: 2-Methyl-4'-(methylthio)-2-morpholinopropiophenone(71868-10-5)
• EPA Substance Registry System: 2-Methyl-4'-(methylthio)-2-morpholinopropiophenone(71868-10-5)

Safety Data

• Hazard Codes: Xn,N
• Statements: 22-51/53
• Safety Statements: 22-61
• RIDADR: UN 3077 9/PG 3
• WGK Germany: 2
• HazardClass: 9
• PackingGroup: III
• Hazardous Substances Data: 71868-10-5(Hazardous Substances Data)

Usage

Application fields

2-Methyl-4'-(Methylthio)-2-Morpholinopropiophenone is an efficient UV photoinitiator for initiating UV polymerization of unsaturated prepolymer systems, Such as acrylic resins and monofunctional and multifunctional vinyl monomers. The initiator molecule has a certain light absorption capacity in the ultraviolet region (250-400 nm) or the visible region (400-800 nm). After direct or indirect absorption of light energy, the initiator molecules transition from the ground state to the excited singlet state, through intersystem conversion to excited triple state. After undergoing a single molecular or bimolecular chemistry, initiator molecules produce reactive debris that initiates polymerization of the monomers, which may be free radicals, cations, anions, etc. According to the different initiation mechanism, the photoinitiator can be divided into free radical polymerization photoinitiator and cationic photoinitiator, among which the most widely used is free radical polymerization photoinitiator. The characteristic of high absorbency of 2-Methyl-4'-(Methylthio)-2-Morpholinopropiophenone makes it particularly suitable for UV curable inks and colored coatings. UV inks contain a greater amount of photoinitiator, and it is these photoinitiators that promote the rapid drying of the ink during the printing process. These photoinitiators themselves are not stable, even in the dark, and it is also prone to dark reaction, resulting in one by one ink glue nucleus, followed by a large area of retrogradation. Especially in the preservation of metal ink, similar situation occur more often. Therefore, it is recommended that the ink pigment and the binder separately stored. If used, stir and mix the two with a large machine. Highly efficient photoinitiator can be used in UV curing systems to extend storage with non-yellowing for a long time. It is an initiator specifically for pigmented UV-curable coatings, inks and adhesives colored solidification system, and it could be used with184, ITX and other initiators. It can be used for colored ink systems, paper/metal and plastic varnish and electronic inks. It is also as a UV absorber for cosmetics and other industries with suggested supplementation of 2-6%.

Application

Used as an initiator in a photo-curable material UV-curable coatings and inks Highly efficient photoinitiator can be used in UV curing systems to extend storage with non-yellowing for a long time.

Chemical Properties

White powder

Flammability and Explosibility

Nonflammable

Synthetic route

morpholine (110-91-8) + 2-methoxy-3,3-dimethyl-2-(4-methylthiophenyl)oxirane → 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (71868-10-5)

Conditions	Yield
With calcium hydroxide at 20 - 138℃; for 20h;	90.2%
With tetra(n-butyl)ammonium hydrogensulfate; sodium hydroxide for 8h; Reflux;	43%
at 105 - 110℃; for 20h; Temperature;	119.3 g
at 105 - 115℃; for 20h;	112.57 g
With water at 105℃; for 12h; Reagent/catalyst; Large scale;

1-methoxy-4-methylsulfanyl-benzene (1879-16-9) + 4-(2-methyl-2-morpholinopropanoyl)benzonitrile → 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (71868-10-5)

Conditions	Yield
With bis(1,5-cyclooctadiene)nickel (0); 1,2-bis-(dicyclohexylphosphino)ethane In o-xylene at 140℃; for 24h; Glovebox; Inert atmosphere;	74%

morpholine (110-91-8) + 2-methyl-1-(4-(methylthio)phenyl)-propan-1-one (53207-58-2) → 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (71868-10-5)

Conditions	Yield
Stage #1: 2-methyl-1-(4-(methylthio)phenyl)-propan-1-one With hexachloroethane; sodium methylate In methanol at 40℃; for 24h; Stage #2: morpholine With tetra(n-butyl)ammonium hydrogensulfate; sodium hydroxide for 10h; Reagent/catalyst; Temperature; Reflux;	61%

morpholine (110-91-8) + 2-bromo-2-methyl-1-[4-(methylsulfanyl)phenyl]propan-1-one (88324-55-4) → 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (71868-10-5)

Conditions	Yield
Stage #1: morpholine With aluminum (III) chloride In 1,2-dichloro-ethane at 40℃; for 0.5h; Stage #2: 2-bromo-2-methyl-1-[4-(methylsulfanyl)phenyl]propan-1-one In 1,2-dichloro-ethane at 40℃; for 6h;	60.57%

2-methyl-1-(4-(methylthio)phenyl)-propan-1-one (53207-58-2) → 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (71868-10-5)

Conditions	Yield
Multi-step reaction with 2 steps 1.1: bromine / 2 h / 20 - 30 °C 2.1: aluminum (III) chloride / 1,2-dichloro-ethane / 0.5 h / 40 °C 2.2: 6 h / 40 °C View Scheme
Multi-step reaction with 3 steps 1: bromine / 2 h / 20 - 30 °C 2: 1 h / 20 °C 3: 20 h / 105 - 115 °C View Scheme
Multi-step reaction with 2 steps 1: hexachloroethane / 20 °C 2: sodium hydroxide; tetra(n-butyl)ammonium hydrogensulfate / 8 h / Reflux View Scheme

methyl-phenyl-thioether (100-68-5) → 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (71868-10-5)

Conditions	Yield
Multi-step reaction with 3 steps 1.1: aluminum (III) chloride / dichloromethane / 7.5 h / 15 - 35 °C 2.1: bromine / 2 h / 20 - 30 °C 3.1: aluminum (III) chloride / 1,2-dichloro-ethane / 0.5 h / 40 °C 3.2: 6 h / 40 °C View Scheme
Multi-step reaction with 4 steps 1: aluminum (III) chloride / dichloromethane / 7.5 h / 15 - 35 °C 2: bromine / 2 h / 20 - 30 °C 3: 1 h / 20 °C 4: 20 h / 105 - 115 °C View Scheme

2-chloro-2-methyl-1-(4-methylthiophenyl)-1-propanone → 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (71868-10-5)

Conditions	Yield
Multi-step reaction with 2 steps 1: methanol / 1 h / 20 °C 2: 20 h / 105 - 115 °C View Scheme

2-bromo-2-methyl-1-[4-(methylsulfanyl)phenyl]propan-1-one (88324-55-4) → 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (71868-10-5)

Conditions	Yield
Multi-step reaction with 2 steps 1: morpholine; sodium methylate / 28 - 85 °C / 760.05 Torr / Large scale 2: water / 12 h / 105 °C / Large scale View Scheme

terephthalonitrile (623-26-7) + 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (71868-10-5) → 4-(2-methyl-2-morpholinopropanoyl)benzonitrile

Conditions	Yield
With bis(1,5-cyclooctadiene)nickel (0); 1,2-bis-(dicyclohexylphosphino)ethane In o-xylene at 140℃; for 24h; Glovebox; Inert atmosphere;	94%

2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (71868-10-5) + Cyclohexanethiol (1569-69-3) → 1-(4-(cyclohexylthio)phenyl)-2-methyl-2-morpholinopropan-1-one

Conditions	Yield
With bis(1,5-cyclooctadiene)nickel (0); lithium hexamethyldisilazane; 1,2-bis-(dicyclohexylphosphino)ethane In toluene at 100℃; for 12h; Glovebox; Inert atmosphere;	91%

2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (71868-10-5) + bromoacetic acid methyl ester (96-32-2) → methyl 2-((4-(2-methyl-2-morpholinopropanoyl)phenyl)thio)acetate (1353758-87-8)

Conditions	Yield
In 2,2,2-trifluoroethanol at 100℃; for 24h;	89%

2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (71868-10-5) + aniline (62-53-3) → C20H24N2O2

Conditions	Yield
With bis(1,5-cyclooctadiene)nickel (0); lithium hexamethyldisilazane; 1,2-bis-(dicyclohexylphosphino)ethane In toluene at 100℃; for 12h; Buchwald-Hartwig Coupling;	68%

2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (71868-10-5) → 2-morpholino propan-2-yl radical (141888-27-9) + C8H7OS (141913-26-0)

Conditions	Yield
In various solvent(s) at -40.1℃; Irradiation; Title compound not separated from byproducts;
In acetonitrile UV-irradiation;

2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (71868-10-5) + dicyclohexyl itaconate (15700-62-6) → poly(dicyclohexyl itaconate) dimethyl(morpholino)methyl-terminated; monomer(s): dicyclohexyl itaconate; 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one

Conditions	Yield
at 20℃; pulsed lazer irradiation;

2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (71868-10-5) + acrylic acid methyl ester (292638-85-8) → poly(methyl acrylate), p-methylthiobenzoyl- and dimethyl(morpholino)methyl-terminated; monomer(s): methyl acrylate; 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one

Conditions	Yield
at -34℃; pulsed lazer irradiation;

2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (71868-10-5) + poly(ethylene glycol) diacrylate → poly(ethylene glycol) diacrylate with C(O)-C6H4-SCH3-p end group, product of photopolymerization

Conditions	Yield
at 70℃; UV-irradiation;

2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (71868-10-5) + dimethyl sulfate (77-78-1) → dimethyl-[4-(2-methyl-2-morpholin-4-ium-4-yl-propanoyl)phenyl]sulfonium methyl sulfate

Conditions	Yield
In water; acetonitrile at 25 - 60℃;

2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (71868-10-5) → 2-methyl-1-[4-(methylsulfinyl)-phenyl]-2-morpholinopropan-1-one

Conditions	Yield
Stage #1: 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one With 3-chloro-benzenecarboperoxoic acid In dichloromethane for 2.5h; Cooling with ice; Stage #2: With sodium hydroxide In dichloromethane; water

2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (71868-10-5) → 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ium-4-yl-propan-1-one tetrafluoroborate

Conditions	Yield
With tetrafluoroboric acid In diethyl ether for 2h; Cooling with ice;

2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (71868-10-5) → dimethyl-[4-(2-methyl-2-morpholino-propanoyl)phenyl]sulfonium methyl sulfate (1353758-57-2)

Conditions	Yield
Multi-step reaction with 2 steps 1: acetonitrile; water / 25 - 60 °C 2: sodium hydroxide; sodium carbonate / water / 0.5 h / 25 °C / pH 9 View Scheme

2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (71868-10-5) → dimethyl-[4-(2-methyl-2-morpholino-propanoyl)phenyl]sulfonium hexafluorophosphate

Conditions	Yield
Multi-step reaction with 2 steps 1: acetonitrile; water / 25 - 60 °C 2: sodium hexaflorophosphate; sodium carbonate / water / pH 9.2 View Scheme

2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (71868-10-5) → 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ium-4-yl-propan-1-one chloride (1353758-31-2)

Conditions	Yield
With hydrogenchloride In propan-1-ol; water for 1h;

2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (71868-10-5) + triethyloxonium fluoroborate (368-39-8) → ethyl-methyl-[4-(2-methyl-2-morpholino-propanoyl)phenyl]sulfonium tetrafluoroborate

Conditions	Yield
In dichloromethane at 25℃; for 5h;	90 %Spectr.

2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (71868-10-5) → 2-methyl-2-(4-morpholinyl)-1-[4-(dichloromethylthio)phenyl]-1-propanone hydrochloride + 2-methyl-2-(4-morpholinyl)-1-[4-(trichloromethylthio)phenyl]-1-propanone hydrochloride

Conditions	Yield
With sulfuryl dichloride In 1,2-dichloro-ethane at 20 - 30℃; for 4h; Reagent/catalyst; Temperature; Overall yield = 16.5 g;

2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (71868-10-5) → 2-methyl-2-(4-morpholinyl)-1-(4-mercaptophenyl)-1-propanone

Conditions	Yield
Stage #1: 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one With sulfuryl dichloride In 1,2-dichloro-ethane for 1h; Stage #2: With carbonic acid dimethyl ester; sodium hydroxide In methanol for 6.25h; Inert atmosphere; Reflux;	8.5 g

2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (71868-10-5) + 1-chloroacetophenone (532-27-4) → C23H28NO3S(1+)*Cl(1-)

Conditions	Yield
In acetone for 2h; Inert atmosphere;

2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (71868-10-5) + 1-chloroacetophenone (532-27-4) → C23H28NO3S(1+)*F6P(1-)

Conditions	Yield
Multi-step reaction with 2 steps 1: acetone / 2 h / Inert atmosphere 2: potassium hexafluorophosphate / acetone / 2 h / Heating View Scheme

Upstream product

• 110-91-8 morpholine 
• 88324-55-4 2-bromo-2-methyl-1-[4-(methylsulfanyl)phenyl]propan-1-one 
• 53207-58-2 2-methyl-1-(4-(methylthio)phenyl)-propan-1-one 
• 100-68-5 methyl-phenyl-thioether 
• 1879-16-9 1-methoxy-4-methylsulfanyl-benzene 

Downstream Products

• 141888-27-9 2-morpholino propan-2-yl radical 
• 141913-26-0 C₈H₇OS 
• 1353758-87-8 methyl 2-((4-(2-methyl-2-morpholinopropanoyl)phenyl)thio)acetate 
• 1353758-31-2 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ium-4-yl-propan-1-one chloride 
• 1353758-57-2 dimethyl-[4-(2-methyl-2-morpholino-propanoyl)phenyl]sulfonium methyl sulfate 

Relevant articles and documents

Preparation method of 2-methyl-1-(4-substituted phenyl)-2-morpholinyl-1-acetone

The invention relates to a preparation method of 2-methyl-1-(4-substituted phenyl)-2-morpholinyl-1-acetone. The preparation method comprises two steps of epoxidation reaction and morpholine substitution reaction, wherein in the morpholine substitution reaction, a proper amount of an auxiliary agent is added, and the auxiliary agent is selected from at least one of water, a strong-acid weak-alkalisaline solution and a strong-alkali weak-acid saline solution, so that the ring opening rate and the ring opening selectivity in the morpholine substitution reaction process can be obviously improved,and the overall reaction rate and yield are further improved, according to the method, the problem that subsequent catalysts are difficult to filter, recycle and purify due to the fact that catalystssuch as carclazyte need to be added in the traditional process is solved, the high-purity 2-methyl-1-(4-substituted phenyl)-2-morpholinyl-1-acetone can be obtained more easily, the process cost and the aftertreatment operation risk are reduced, and the economic benefit is improved.

PROCESS FOR THE PREPARATION OF ALPHA-FUNCTIONALIZED KETONES

The present invention refers to a process for the preparation of an α-functionalized ketone, an α-functionalized ketone obtained by said process, a photopolymerizable composition comprising the α-functionalized ketone and at least one photopolymerizable unsaturated compound, a method of preparing an article, an article obtained by said method, as well as the use of the α-functionalized ketone or the photopolymerizable composition as photoinitiator.

Synthetic method of free-radical photoinitiator

The invention discloses a synthetic method of a free-radical photoinitiator. The synthetic method is characterized by comprising the following steps: (1) under the action of aluminium trichloride, methyl phenyl sulfide is adopted as a raw material and generates Friedel-Crafts acylation reaction with 2-chloroisobutyryl chloride to prepare an intermediate A with a structure shown in a formula (I); (2) under the action of alkaline, the intermediate A carries out ring-closure reaction to prepare an intermediate B with a structure shown in a formula (II); (3) the intermediate B and morpholine carryout ring-opening reaction to obtain a target product with a structure shown in a formula (III), namely the free-radical photoinitiator. The synthetic method disclosed by the invention has the beneficial effects that the photoinitiator is synthesized by the steps of adopting the 2-chloroisobutyryl chloride and methyl phenyl sulfide to carry out Friedel-Crafts acylation reaction, then carrying outcyclization and ring opening and the like, the obtained product contains fewer impurities, the yield is high, the process route is convenient in operation, and generates less three wastes (waste water, waste solid and waste air) so as to be more environment-friendly.