62285-98-7

Basic information

• Product Name: [(2E,4E)-3-Methyl-5-(2,6,6-trimethyl-2-cyclohexen-1-yl)-2,4-pentadien-1-yl](triphenyl)phosphonium bromide
• Synonyms: [5-(4-Methoxy-2,3,6-trimethylphenyl)-3-methyl-2,4-pentadienyl];[5-(4-Methoxy-2,3,6-trimethylphenyl)-3-methyl-2,4-pentadienyl]triphenylphosphonium bromide;[3-Methyl-5-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2,4-pentadienyl]triphenylphosphonium bromide;((2E,4E)-3-Methyl-5-(2,6,6-triMethylcyclohex-1-en-1-yl)penta-2,4-dien-1-yl)triphenylphosphoniuM broMide;((2E,4E)-3-Methyl-5-(2,6,6-trimethylcyclohex-2-en-1-yl)penta-2,4-dien-1-yl)triphenylphosphonium bromide;[(2E,4E)-3-Methyl-5-(2,6,6-trimethyl-2-cyclohexen-1-yl)-2,4-pentadien-1-yl](triphenyl)phosphonium bromide
• CAS NO: 62285-98-7
• Molecular Formula: Br*C₃₃H₃₈P
• Molecular Weight: 545.53
• EINECS: 1312995-182-4
• Mol File: 62285-98-7.mol
• Article Data: 10

Chemical Properties

• Appearance: /
• CAS DataBase Reference: [(2E,4E)-3-Methyl-5-(2,6,6-trimethyl-2-cyclohexen-1-yl)-2,4-pentadien-1-yl](triphenyl)phosphonium bromide(CAS DataBase Reference)
• NIST Chemistry Reference: [(2E,4E)-3-Methyl-5-(2,6,6-trimethyl-2-cyclohexen-1-yl)-2,4-pentadien-1-yl](triphenyl)phosphonium bromide(62285-98-7)
• EPA Substance Registry System: [(2E,4E)-3-Methyl-5-(2,6,6-trimethyl-2-cyclohexen-1-yl)-2,4-pentadien-1-yl](triphenyl)phosphonium bromide(62285-98-7)

Safety Data

• Hazardous Substances Data: 62285-98-7(Hazardous Substances Data)

Usage

Description

[(2E,4E)-3-Methyl-5-(2,6,6-trimethyl-2-cyclohexen-1-yl)-2,4-pentadien-1-yl](triphenyl)phosphonium bromide is a complex organic compound with a phosphonium cation and a bromide anion. It is characterized by its unique molecular structure, which includes a 2,4-pentadien-1-yl group with a 3-methyl and a 5-(2,6,6-trimethyl-2-cyclohexen-1-yl) substitution, as well as a triphenyl group attached to the phosphorus atom. [(2E,4E)-3-Methyl-5-(2,6,6-trimethyl-2-cyclohexen-1-yl)-2,4-pentadien-1-yl](triphenyl)phosphonium bromide is likely to have specific chemical properties and reactivity due to its structure.

Uses

1. Used in Pharmaceutical Synthesis:
[(2E,4E)-3-Methyl-5-(2,6,6-trimethyl-2-cyclohexen-1-yl)-2,4-pentadien-1-yl](triphenyl)phosphonium bromide is used as a synthetic intermediate for the production of all-trans-retinoic acid (ATRA), a precursor of vitamin A. ATRA is an essential compound for various biological processes, including cell differentiation, growth, and development. [(2E,4E)-3-Methyl-5-(2,6,6-trimethyl-2-cyclohexen-1-yl)-2,4-pentadien-1-yl](triphenyl)phosphonium bromide's unique structure makes it a valuable building block in the synthesis of ATRA and other related pharmaceutical compounds.
2. Used in Chemical Research:
Due to its complex structure and potential reactivity, [(2E,4E)-3-Methyl-5-(2,6,6-trimethyl-2-cyclohexen-1-yl)-2,4-pentadien-1-yl](triphenyl)phosphonium bromide may also be utilized in chemical research to study its properties, reactivity, and potential applications in various chemical reactions. This could lead to the discovery of new synthetic routes, catalysts, or other useful compounds.
3. Used in Material Science:
[(2E,4E)-3-Methyl-5-(2,6,6-trimethyl-2-cyclohexen-1-yl)-2,4-pentadien-1-yl](triphenyl)phosphonium bromide's unique structure and properties may also make it a candidate for use in material science, where it could be explored for potential applications in the development of new materials with specific properties, such as conductivity, stability, or reactivity.

InChI:InChI=1S/C33H38P.BrH/c1-27(22-23-32-28(2)15-14-25-33(32,3)4)24-26-34(29-16-8-5-9-17-29,30-18-10-6-11-19-30)31-20-12-7-13-21-31;/h5-13,15-24,32H,14,25-26H2,1-4H3;1H/q+1;/p-1/b23-22+,27-24+;

Synthetic route

(1E)-1-(2,6,6-trimethylcyclohex-1-enyl)-3-methyl-1,4-pentadien-3-ol (59057-30-6) + triphenylphosphine hydrobromide (6399-81-1) → 5-(2,6,6-trimethylcyclohexenyl)-3-methyl-2,4-pentadienyltriphenylphosphonium bromide (62285-98-7)

Conditions	Yield
In methanol for 75h; Ambient temperature;	100%
In methanol at 20℃; for 20h;	73%
In tetrahydrofuran

3-methyl-5-bromo-1-(2,6,6-trimethyl-1-cyclohexen-1-yl)-1,3-pentadiene (38987-92-7) + triphenylphosphine (603-35-0) → 5-(2,6,6-trimethylcyclohexenyl)-3-methyl-2,4-pentadienyltriphenylphosphonium bromide (62285-98-7)

Conditions	Yield
In acetonitrile at 50 - 55℃; for 5h; Inert atmosphere;	92.8%
In acetonitrile at 50 - 55℃; for 5h; Inert atmosphere;	92.1%

(2E,4E)-3-methyl-5-(2,6,6-trimethyl-1-cyclohexenyl)-2,4-pentadien-1-ol (3917-39-3) + triphenylphosphine hydrobromide (6399-81-1) → 5-(2,6,6-trimethylcyclohexenyl)-3-methyl-2,4-pentadienyltriphenylphosphonium bromide (62285-98-7)

Conditions	Yield
In methanol for 17h; Ambient temperature;

triphenylphosphine hydrobromide (6399-81-1) + Acetic acid (2Z,4E)-3-methyl-5-(2,6,6-trimethyl-cyclohex-1-enyl)-penta-2,4-dienyl ester → 5-(2,6,6-trimethylcyclohexenyl)-3-methyl-2,4-pentadienyltriphenylphosphonium bromide (62285-98-7) + β-ionylidenetriphenylphosphonium bromide

Conditions	Yield
Stage #1: Acetic acid (2Z,4E)-3-methyl-5-(2,6,6-trimethyl-cyclohex-1-enyl)-penta-2,4-dienyl ester With lithium aluminium tetrahydride Stage #2: triphenylphosphine hydrobromide

(E)-β-ionone (79-77-6) + vinyl magnesium bromide (1826-67-1) + triphenylphosphine hydrobromide (6399-81-1) → 5-(2,6,6-trimethylcyclohexenyl)-3-methyl-2,4-pentadienyltriphenylphosphonium bromide (62285-98-7)

Conditions	Yield
Stage #1: (E)-β-ionone; vinyl magnesium bromide Stage #2: triphenylphosphine hydrobromide Further stages.;

(E)-β-ionone (79-77-6) → 5-(2,6,6-trimethylcyclohexenyl)-3-methyl-2,4-pentadienyltriphenylphosphonium bromide (62285-98-7)

Conditions	Yield
Multi-step reaction with 2 steps 1: 100 percent / tetrahydrofuran / 20 h / 20 °C 2: 73 percent / methanol / 20 h / 20 °C View Scheme
Multi-step reaction with 2 steps 1: 94 percent / tetrahydrofuran / 14 h / Ambient temperature 2: 100 percent / methanol / 75 h / Ambient temperature View Scheme
Multi-step reaction with 2 steps 1.1: sodium hydride / tetrahydrofuran / 24 h / 20 °C 2.1: lithium aluminium tetrahydride / diethyl ether / 0.5 h / 0 °C 2.2: 24 h / 20 °C View Scheme

(2E,4E)-ethyl 3-methyl-5-(2,6,6-trimethylcyclohex-1-enyl)penta-2,4-dienoate (17974-55-9) → 5-(2,6,6-trimethylcyclohexenyl)-3-methyl-2,4-pentadienyltriphenylphosphonium bromide (62285-98-7)

Conditions	Yield
Multi-step reaction with 2 steps 1: LiAlH4 / diethyl ether / 0.25 h / Ambient temperature 2: methanol / 17 h / Ambient temperature View Scheme

[5-(2,6,6-trimethyl-1-cyclohexen-1-yl)-3-methyl-2-penten-4-ynyl]triphenylphosphonium bromide + 2,2'-ethane-1,2-diylbissulfanyl-bis-ethanol (5244-34-8) + nickel (7440-02-0) → 5-(2,6,6-trimethylcyclohexenyl)-3-methyl-2,4-pentadienyltriphenylphosphonium bromide (62285-98-7)

Conditions	Yield
In methanol; dichloromethane; ethyl acetate

(2E,4E)-ethyl 3-methyl-5-(2,6,6-trimethylcyclohex-1-enyl)penta-2,4-dienoate (17974-55-9) + triphenylphosphine hydrobromide (6399-81-1) → 5-(2,6,6-trimethylcyclohexenyl)-3-methyl-2,4-pentadienyltriphenylphosphonium bromide (62285-98-7)

Conditions	Yield
Stage #1: (2E,4E)-ethyl 3-methyl-5-(2,6,6-trimethylcyclohex-1-enyl)penta-2,4-dienoate With lithium aluminium tetrahydride In diethyl ether at 0℃; for 0.5h; Stage #2: triphenylphosphine hydrobromide In methanol at 20℃; for 24h;

2-(bromomethyl)-1,3,3-trimethylcyclohex-1-ene (59633-88-4) → 5-(2,6,6-trimethylcyclohexenyl)-3-methyl-2,4-pentadienyltriphenylphosphonium bromide (62285-98-7)

Conditions	Yield
Multi-step reaction with 4 steps 1.1: hexane / 4 h / 50 - 55 °C / Inert atmosphere 2.1: potassium hydroxide / isopropyl alcohol / 1 h / -5 - 5 °C / Inert atmosphere 3.1: sodium hydroxide / water; dichloromethane / 3 h / 15 - 20 °C 3.2: 3 h / 20 - 25 °C 4.1: acetonitrile / 5 h / 50 - 55 °C / Inert atmosphere View Scheme

C28H32P(1+)*Cl(1-) → 5-(2,6,6-trimethylcyclohexenyl)-3-methyl-2,4-pentadienyltriphenylphosphonium bromide (62285-98-7)

Conditions	Yield
Multi-step reaction with 3 steps 1.1: sodium ethanolate / N,N-dimethyl-formamide / 5 h / -5 - 10 °C / Inert atmosphere 2.1: sodium hydroxide / water; dichloromethane / 3 h / 15 - 20 °C 2.2: 3 h / 20 - 25 °C 3.1: acetonitrile / 5 h / 50 - 55 °C / Inert atmosphere View Scheme

diethyl [(2,2,6-trimethylcyclohexyl)methyl]phosphonate → 5-(2,6,6-trimethylcyclohexenyl)-3-methyl-2,4-pentadienyltriphenylphosphonium bromide (62285-98-7)

Conditions	Yield
Multi-step reaction with 3 steps 1.1: sodium methylate / N,N-dimethyl-formamide / 1 h / 0 - 15 °C / Inert atmosphere 2.1: sodium hydroxide / water; dichloromethane / 3 h / 15 - 20 °C 2.2: 3 h / 20 - 25 °C 3.1: acetonitrile / 5 h / 50 - 55 °C / Inert atmosphere View Scheme

triphenyl((2,6,6-trimethylcyclohex-1-enyl)methyl)phosphonium bromide (56013-01-5) → 5-(2,6,6-trimethylcyclohexenyl)-3-methyl-2,4-pentadienyltriphenylphosphonium bromide (62285-98-7)

Conditions	Yield
Multi-step reaction with 3 steps 1.1: potassium hydroxide / isopropyl alcohol / 1 h / -5 - 5 °C / Inert atmosphere 2.1: sodium hydroxide / water; dichloromethane / 3 h / 15 - 20 °C 2.2: 3 h / 20 - 25 °C 3.1: acetonitrile / 5 h / 50 - 55 °C / Inert atmosphere View Scheme

3-methyl-5-acetoxy-1-(2,6,6-trimethyl-1-cyclohexen-1-yl)-1,3-pentadiene (3917-38-2) → 5-(2,6,6-trimethylcyclohexenyl)-3-methyl-2,4-pentadienyltriphenylphosphonium bromide (62285-98-7)

Conditions	Yield
Multi-step reaction with 2 steps 1.1: sodium hydroxide / water; dichloromethane / 3 h / 15 - 20 °C 1.2: 3 h / 20 - 25 °C 2.1: acetonitrile / 5 h / 50 - 55 °C / Inert atmosphere View Scheme

3,7-dimethylocta-1,6-dien-3-ol (78-70-6) → 5-(2,6,6-trimethylcyclohexenyl)-3-methyl-2,4-pentadienyltriphenylphosphonium bromide (62285-98-7)

Conditions	Yield
Multi-step reaction with 5 steps 1.1: hydrogen bromide; sodium hydroxide / water; dichloromethane / 2 h / 30 - 35 °C / Inert atmosphere 1.2: 2 h / 35 - 40 °C 2.1: hexane / 4 h / 50 - 55 °C / Inert atmosphere 3.1: potassium hydroxide / isopropyl alcohol / 1 h / -5 - 5 °C / Inert atmosphere 4.1: sodium hydroxide / water; dichloromethane / 3 h / 15 - 20 °C 4.2: 3 h / 20 - 25 °C 5.1: acetonitrile / 5 h / 50 - 55 °C / Inert atmosphere View Scheme
Multi-step reaction with 5 steps 1.1: sodium hydroxide; thionyl chloride / 1,2-dichloro-ethane; water / 3 h / 40 - 45 °C 1.2: 5 h / 70 - 75 °C 2.1: acetonitrile / 4 h / 60 - 65 °C / Inert atmosphere 3.1: sodium ethanolate / N,N-dimethyl-formamide / 5 h / -5 - 10 °C / Inert atmosphere 4.1: sodium hydroxide / water; dichloromethane / 3 h / 15 - 20 °C 4.2: 3 h / 20 - 25 °C 5.1: acetonitrile / 5 h / 50 - 55 °C / Inert atmosphere View Scheme
Multi-step reaction with 5 steps 1.1: sodium hydroxide; thionyl chloride / 1,2-dichloro-ethane; water / 3 h / 40 - 45 °C 1.2: 5 h / 70 - 75 °C 2.1: 4 h / 105 - 110 °C / Inert atmosphere 3.1: sodium methylate / N,N-dimethyl-formamide / 1 h / 0 - 15 °C / Inert atmosphere 4.1: sodium hydroxide / water; dichloromethane / 3 h / 15 - 20 °C 4.2: 3 h / 20 - 25 °C 5.1: acetonitrile / 5 h / 50 - 55 °C / Inert atmosphere View Scheme

1,3,3-trimethyl-2-chloromethylcyclohexene → 5-(2,6,6-trimethylcyclohexenyl)-3-methyl-2,4-pentadienyltriphenylphosphonium bromide (62285-98-7)

Conditions	Yield
Multi-step reaction with 4 steps 1.1: acetonitrile / 4 h / 60 - 65 °C / Inert atmosphere 2.1: sodium ethanolate / N,N-dimethyl-formamide / 5 h / -5 - 10 °C / Inert atmosphere 3.1: sodium hydroxide / water; dichloromethane / 3 h / 15 - 20 °C 3.2: 3 h / 20 - 25 °C 4.1: acetonitrile / 5 h / 50 - 55 °C / Inert atmosphere View Scheme
Multi-step reaction with 4 steps 1.1: 4 h / 105 - 110 °C / Inert atmosphere 2.1: sodium methylate / N,N-dimethyl-formamide / 1 h / 0 - 15 °C / Inert atmosphere 3.1: sodium hydroxide / water; dichloromethane / 3 h / 15 - 20 °C 3.2: 3 h / 20 - 25 °C 4.1: acetonitrile / 5 h / 50 - 55 °C / Inert atmosphere View Scheme

4-bromo-3-methyl-2-buten-1-ol acetate (32659-14-6) → 5-(2,6,6-trimethylcyclohexenyl)-3-methyl-2,4-pentadienyltriphenylphosphonium bromide (62285-98-7)

Conditions	Yield
Multi-step reaction with 4 steps 1.1: acetonitrile / 4 h / 60 - 65 °C / Inert atmosphere 2.1: sodium ethanolate / N,N-dimethyl-formamide / 2 h / 0 - 5 °C / Inert atmosphere 3.1: sodium hydroxide / dichloromethane; water / 3 h / 15 - 20 °C 3.2: 3 h / 20 - 25 °C 4.1: acetonitrile / 5 h / 50 - 55 °C / Inert atmosphere View Scheme
Multi-step reaction with 4 steps 1.1: methanol / 4 h / 100 - 105 °C / Inert atmosphere 2.1: potassium tert-butylate / N,N-dimethyl-formamide / 2 h / -10 - 0 °C / Inert atmosphere 3.1: sodium hydroxide / dichloromethane; water / 3 h / 15 - 20 °C 3.2: 3 h / 20 - 25 °C 4.1: acetonitrile / 5 h / 50 - 55 °C / Inert atmosphere View Scheme
Multi-step reaction with 4 steps 1.1: ethanol / 4 h / 105 - 110 °C / Inert atmosphere 2.1: sodium ethanolate / toluene / 2 h / -5 - 5 °C / Inert atmosphere 3.1: sodium hydroxide / dichloromethane; water / 3 h / 15 - 20 °C 3.2: 3 h / 20 - 25 °C 4.1: acetonitrile / 5 h / 50 - 55 °C / Inert atmosphere View Scheme

C25H26O2P(1+)*Br(1-) → 5-(2,6,6-trimethylcyclohexenyl)-3-methyl-2,4-pentadienyltriphenylphosphonium bromide (62285-98-7)

Conditions	Yield
Multi-step reaction with 3 steps 1.1: sodium ethanolate / N,N-dimethyl-formamide / 2 h / 0 - 5 °C / Inert atmosphere 2.1: sodium hydroxide / dichloromethane; water / 3 h / 15 - 20 °C 2.2: 3 h / 20 - 25 °C 3.1: acetonitrile / 5 h / 50 - 55 °C / Inert atmosphere View Scheme

C25H26O2P(1+)*Cl(1-) → 5-(2,6,6-trimethylcyclohexenyl)-3-methyl-2,4-pentadienyltriphenylphosphonium bromide (62285-98-7)

Conditions	Yield
Multi-step reaction with 3 steps 1.1: sodium methylate / N,N-dimethyl-formamide / 2 h / 5 - 10 °C / Inert atmosphere 2.1: sodium hydroxide / dichloromethane; water / 3 h / 15 - 20 °C 2.2: 3 h / 20 - 25 °C 3.1: acetonitrile / 5 h / 50 - 55 °C / Inert atmosphere View Scheme

diethyl 2-methyl-4-acetoxy-2-butenylphosphonate → 5-(2,6,6-trimethylcyclohexenyl)-3-methyl-2,4-pentadienyltriphenylphosphonium bromide (62285-98-7)

Conditions	Yield
Multi-step reaction with 3 steps 1.1: sodium ethanolate / toluene / 2 h / -5 - 5 °C / Inert atmosphere 2.1: sodium hydroxide / dichloromethane; water / 3 h / 15 - 20 °C 2.2: 3 h / 20 - 25 °C 3.1: acetonitrile / 5 h / 50 - 55 °C / Inert atmosphere View Scheme

dimethyl 2-methyl-4-acetoxy-2-butenylphosphonate → 5-(2,6,6-trimethylcyclohexenyl)-3-methyl-2,4-pentadienyltriphenylphosphonium bromide (62285-98-7)

Conditions	Yield
Multi-step reaction with 3 steps 1.1: potassium tert-butylate / N,N-dimethyl-formamide / 2 h / -10 - 0 °C / Inert atmosphere 2.1: sodium hydroxide / dichloromethane; water / 3 h / 15 - 20 °C 2.2: 3 h / 20 - 25 °C 3.1: acetonitrile / 5 h / 50 - 55 °C / Inert atmosphere View Scheme

(E)-1-O-acetyl-4-chloro-3-methyl-2-buten-1-ol (24529-80-4) → 5-(2,6,6-trimethylcyclohexenyl)-3-methyl-2,4-pentadienyltriphenylphosphonium bromide (62285-98-7)

Conditions	Yield
Multi-step reaction with 4 steps 1.1: acetonitrile / 4 h / 70 - 75 °C / Inert atmosphere 2.1: sodium methylate / N,N-dimethyl-formamide / 2 h / 5 - 10 °C / Inert atmosphere 3.1: sodium hydroxide / dichloromethane; water / 3 h / 15 - 20 °C 3.2: 3 h / 20 - 25 °C 4.1: acetonitrile / 5 h / 50 - 55 °C / Inert atmosphere View Scheme

4-palmitoyloxy-2-methyl-2-buten-1-al + 5-(2,6,6-trimethylcyclohexenyl)-3-methyl-2,4-pentadienyltriphenylphosphonium bromide (62285-98-7) → retinyl palmitate (79-81-2)

Conditions	Yield
With sodium ethanolate In N,N-dimethyl-formamide at -5 - 5℃; for 3h; Wittig Olefination; Inert atmosphere;	91.3%

(E)-4-acetoxy-2-methylcrotonaldehyde (26586-02-7) + 5-(2,6,6-trimethylcyclohexenyl)-3-methyl-2,4-pentadienyltriphenylphosphonium bromide (62285-98-7) → Retinol acetate (127-47-9)

Conditions	Yield
With sodium ethanolate In N,N-dimethyl-formamide at -5 - 0℃; for 2h; Solvent; Temperature; Reagent/catalyst; Wittig Olefination; Inert atmosphere;	91%
With sodium ethanolate In N,N-dimethyl-formamide at -5 - 5℃; for 2h; Time; Inert atmosphere;	90.7%

(Z)-3-methyl-4-oxobut-2-enoic acid (70143-04-3) + 5-(2,6,6-trimethylcyclohexenyl)-3-methyl-2,4-pentadienyltriphenylphosphonium bromide (62285-98-7) → 13-cis-retinoic acid (4759-48-2)

Conditions	Yield
Stage #1: (Z)-3-methyl-4-oxobut-2-enoic acid; 5-(2,6,6-trimethylcyclohexenyl)-3-methyl-2,4-pentadienyltriphenylphosphonium bromide With sodium hydroxide In isopropyl alcohol at 20 - 30℃; for 3h; Wittig Olefination; Inert atmosphere; Stage #2: With hydrogenchloride; palladium diacetate In isopropyl alcohol at 60℃; pH=7 - 8;	86.3%
Stage #1: (Z)-3-methyl-4-oxobut-2-enoic acid; 5-(2,6,6-trimethylcyclohexenyl)-3-methyl-2,4-pentadienyltriphenylphosphonium bromide With sodium hydroxide In isopropyl alcohol at 20 - 30℃; for 3h; Wittig Olefination; Inert atmosphere; Stage #2: With hydrogenchloride; palladium diacetate In isopropyl alcohol at 60℃; pH=7-8; Inert atmosphere;	86.3%

5-(2,6,6-trimethylcyclohexenyl)-3-methyl-2,4-pentadienyltriphenylphosphonium bromide (62285-98-7) + 4-formyl-2-[3-oxo-2-methyl-(1E)-propenyl]pyridine (188554-16-7) → 2-[(1E,3E,5E,7E)-2,6-dimethyl-8-(2,6,6-trimethylcyclohex-1-en-1-yl)octa-1,3,5,7-tetraen-1-yl]-4-[(1E,3E,5E)-4-methyl-6-(2,6,6-trimethylcyclohex-1-en-1-yl)hexa-1,3,5-trien-1-yl]pyridine (188554-17-8)

Conditions	Yield
With sodium ethanolate In ethanol	76%

5-(2,6,6-trimethylcyclohexenyl)-3-methyl-2,4-pentadienyltriphenylphosphonium bromide (62285-98-7) + (Z)-3-Iodo-4-oxo-but-2-enoic acid ethyl ester (174836-86-3) → (2Z,4E,6E,8E)-3-Iodo-7-methyl-9-(2,6,6-trimethyl-cyclohex-1-enyl)-nona-2,4,6,8-tetraenoic acid ethyl ester (743421-41-2)

Conditions	Yield
Stage #1: (Z)-3-Iodo-4-oxo-but-2-enoic acid ethyl ester With 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone; lithium diisopropyl amide Stage #2: 5-(2,6,6-trimethylcyclohexenyl)-3-methyl-2,4-pentadienyltriphenylphosphonium bromide Further stages.;	74%

5-(2,6,6-trimethylcyclohexenyl)-3-methyl-2,4-pentadienyltriphenylphosphonium bromide (62285-98-7) + bis(3-formyl-3-methyl-2-propenyl) sulfide (251291-80-2) → retinyl sulfide (268728-47-8)

Conditions	Yield
Stage #1: 5-(2,6,6-trimethylcyclohexenyl)-3-methyl-2,4-pentadienyltriphenylphosphonium bromide; bis(3-formyl-3-methyl-2-propenyl) sulfide In DMF (N,N-dimethyl-formamide) at -20℃; Stage #2: With sodium methylate In DMF (N,N-dimethyl-formamide) at -20 - 20℃; for 3.5h;	68%

4-t-butyldimethylsilyloxy-2-butynal (75859-97-1) + 5-(2,6,6-trimethylcyclohexenyl)-3-methyl-2,4-pentadienyltriphenylphosphonium bromide (62285-98-7) → tert-Butyl-dimethyl-[(4Z,6E,8E)-7-methyl-9-(2,6,6-trimethyl-cyclohex-1-enyl)-nona-4,6,8-trien-2-ynyloxy]-silane (75867-37-7)

Conditions	Yield
With n-butyllithium In tetrahydrofuran for 3h; Ambient temperature;	52%

5-(2,6,6-trimethylcyclohexenyl)-3-methyl-2,4-pentadienyltriphenylphosphonium bromide (62285-98-7) + 2-methyl-3-[3-(1-methyl-2-oxoethylidene)-cyclohex-1-enyl]-propenal (454442-05-8) → C43H60

Conditions	Yield
With sodium methylate In methanol for 1h;	40%

5-(2,6,6-trimethylcyclohexenyl)-3-methyl-2,4-pentadienyltriphenylphosphonium bromide (62285-98-7) + 13-[(4R)-4-(β-D-glucopyranosyloxy)-2,6,6-trimethylcyclohex-1-enyl]-2,7,11-trimethyltrideca-2,4,6,8,10,12-hexaenal → (all-E)-(3R)-3-(β-D-glucopyranosyloxy)-β,β-carotene (135589-15-0) + (9'Z)-(3R)-3-(β-D-glucopyranosyloxy)-β,β-carotene

Conditions	Yield
Stage #1: 5-(2,6,6-trimethylcyclohexenyl)-3-methyl-2,4-pentadienyltriphenylphosphonium bromide; 13-[(4R)-4-(β-D-glucopyranosyloxy)-2,6,6-trimethylcyclohex-1-enyl]-2,7,11-trimethyltrideca-2,4,6,8,10,12-hexaenal With sodium methylate In methanol; dichloromethane at 20℃; for 3h; Wittig condensation; Stage #2: With Dowex 50W-X8 (H+) In methanol; dichloromethane at 20℃; for 0.333333h;	A 28% B 10%

(2E,4E,6E,8E,10E,12E,14E)-2,7,11,15,19-pentamethylicosa-2,4,6,8,10,12,14,18-octaenal (103956-99-6, 1071-52-9) + 5-(2,6,6-trimethylcyclohexenyl)-3-methyl-2,4-pentadienyltriphenylphosphonium bromide (62285-98-7) → trans-gamma-Carotene (472-93-5)

Conditions	Yield
With sodium methylate In methanol; N,N-dimethyl-formamide

2-Methyl-4-(thioacetyl)-2-(E)-butenal (72053-20-4) + 5-(2,6,6-trimethylcyclohexenyl)-3-methyl-2,4-pentadienyltriphenylphosphonium bromide (62285-98-7) → 11-cis-Retinylthioacetat (72053-19-1, 72075-18-4)

Conditions	Yield
(i) nBuLi, (ii) /BRN= 2075468/; Multistep reaction;

2-Methyl-4-(thioacetyl)-2-(E)-butenal (72053-20-4) + 5-(2,6,6-trimethylcyclohexenyl)-3-methyl-2,4-pentadienyltriphenylphosphonium bromide (62285-98-7) → 11-trans-Retinylthioacetat (72053-19-1, 72075-18-4)

Conditions	Yield
(i) nBuLi, (ii) /BRN= 2075468/; Multistep reaction;

acetic acid trans-4-oxo-but-2-enyl ester (38982-39-7) + 5-(2,6,6-trimethylcyclohexenyl)-3-methyl-2,4-pentadienyltriphenylphosphonium bromide (62285-98-7) → Acetic acid (2E,4E,6E,8E)-7-methyl-9-(2,6,6-trimethyl-cyclohex-1-enyl)-nona-2,4,6,8-tetraenyl ester

Conditions	Yield
With n-butyllithium In tetrahydrofuran; hexane 1.) 1 h, -60 deg C; 2.) 2 h to RT; Yield given;

ethyl-2-formyl-1-cyclopropane carboxylate (13949-93-4, 13950-12-4, 77183-91-6, 77183-92-7, 109716-50-9, 109716-61-2, 20417-61-2) + 5-(2,6,6-trimethylcyclohexenyl)-3-methyl-2,4-pentadienyltriphenylphosphonium bromide (62285-98-7) → ethyl trans-13,14-dihydro-13-desmethyl-13,14-methyleneretinoate (89887-40-1) + ethyl cis-13,14-dihydro-13-desmethyl-13,14-methyleneretinoate (89827-99-6)

Conditions	Yield
With potassium tert-butylate benzene, 1) 15 min 2) 8h, r.t.; Yield given. Multistep reaction. Yields of byproduct given;

1-Carbethoxy-2-formyl-2-methyl-cyclopropan (20417-63-4) + 5-(2,6,6-trimethylcyclohexenyl)-3-methyl-2,4-pentadienyltriphenylphosphonium bromide (62285-98-7) → ethyl trans-13,14-dihydro-13,14-methyleneretinoate (89887-37-6) + ethyl cis-13,14-dihydro-13,14-methyleneretinoate (89827-98-5)

Conditions	Yield
With potassium tert-butylate benzene, 1) 15 min 2) 22h, r.t.; Yield given. Multistep reaction. Yields of byproduct given;

4,4-dimethoxy-3-methyl-but-2-en-1-al (62285-97-6) + 5-(2,6,6-trimethylcyclohexenyl)-3-methyl-2,4-pentadienyltriphenylphosphonium bromide (62285-98-7) → 2-((1E,3E,5E,7E)-9,9-Dimethoxy-3,8-dimethyl-nona-1,3,5,7-tetraenyl)-1,3,3-trimethyl-cyclohexene

Conditions	Yield
With sodium ethanolate In ethanol; dichloromethane at 0℃; for 1h;

5-(2,6,6-trimethylcyclohexenyl)-3-methyl-2,4-pentadienyltriphenylphosphonium bromide (62285-98-7) + 4-(tert-butyldimethylsilyloxy)-2-methylbutanal (115797-15-4) → 13,14-dihydro-all-trans retinol (115797-14-3)

Conditions	Yield
With tetrabutyl ammonium fluoride 1.) Wittig-reaction; Multistep reaction;

5-(2,6,6-trimethylcyclohexenyl)-3-methyl-2,4-pentadienyltriphenylphosphonium bromide (62285-98-7) → 5-(2,6,6-trimethylcyclohexenyl)-3-methyl-2,4-pentadienylidenetriphenylphosphorane (71987-74-1)

Conditions	Yield
With phenyllithium In diethyl ether for 0.0833333h; Ambient temperature;

5-(2,6,6-trimethylcyclohexenyl)-3-methyl-2,4-pentadienyltriphenylphosphonium bromide (62285-98-7) + (2E,4E,6E,8E,10E)-2,7,11-trimethyl-12-oxotrideca-2,4,6,8,10-pentaenal (160456-53-1) → (all-E)-sintaxanthin (4586-97-4)

Conditions	Yield
With sodium hydride In dichloromethane at 20℃; for 48h; Yield given;

(2E,4E,6E)-2,7-dimethyl-2,4,6-octatrienedial (5056-17-7) + 5-(2,6,6-trimethylcyclohexenyl)-3-methyl-2,4-pentadienyltriphenylphosphonium bromide (62285-98-7) → 12'-apo-β-caroten-12'-al (1638-05-7)

Conditions	Yield
With sodium hydride In dichloromethane at 20℃; for 64h; Yield given;
With sodium methylate In methanol at 0℃; for 0.5h; Wittig olefination;

5-(2,6,6-trimethylcyclohexenyl)-3-methyl-2,4-pentadienyltriphenylphosphonium bromide (62285-98-7) + 4-formyl-2-[3-oxo-2-methyl-(1E)-propenyl]pyridine (188554-16-7) → 2-[(1E,3Z,5E,7E)-2,4-Dimethyl-8-(2,6,6-trimethyl-cyclohex-1-enyl)-octa-1,3,5,7-tetraenyl]-4-[(1E,3E,5E)-4-methyl-6-(2,6,6-trimethyl-cyclohex-1-enyl)-hexa-1,3,5-trienyl]-pyridine + 2-[(1E,3Z,5E,7E)-2,6-Dimethyl-8-(2,6,6-trimethyl-cyclohex-1-enyl)-octa-1,3,5,7-tetraenyl]-4-[(1Z,3E,5E)-4-methyl-6-(2,6,6-trimethyl-cyclohex-1-enyl)-hexa-1,3,5-trienyl]-pyridine + 2-[(1E,3E,5E,7E)-2,6-Dimethyl-8-(2,6,6-trimethyl-cyclohex-1-enyl)-octa-1,3,5,7-tetraenyl]-4-[(1Z,3E,5E)-4-methyl-6-(2,6,6-trimethyl-cyclohex-1-enyl)-hexa-1,3,5-trienyl]-pyridine + 2-[(1E,3E,5E,7E)-2,6-dimethyl-8-(2,6,6-trimethylcyclohex-1-en-1-yl)octa-1,3,5,7-tetraen-1-yl]-4-[(1E,3E,5E)-4-methyl-6-(2,6,6-trimethylcyclohex-1-en-1-yl)hexa-1,3,5-trien-1-yl]pyridine (188554-17-8)

Conditions	Yield
With sodium ethanolate 1.) EtOH, room temp., 2.) CH3NO2, reflux; Yield given. Multistep reaction;

5-(2,6,6-trimethylcyclohexenyl)-3-methyl-2,4-pentadienyltriphenylphosphonium bromide (62285-98-7) + (2E)-4-[(tert-butyldiphenylsilyl)oxy]-2-fluorobut-2-enal (186953-22-0) → (7E,9E,13E)-tert-butyldiphenylsilyl 13-demethyl-13-fluororetinyl ether (186953-39-9)

Conditions	Yield
With n-butyllithium 1.) THF, hexane, -78 deg C, 2.) THF, hexane, 25 deg C, 5 h; Yield given. Multistep reaction;

5-(2,6,6-trimethylcyclohexenyl)-3-methyl-2,4-pentadienyltriphenylphosphonium bromide (62285-98-7) + N,N-dimethyl-formamide (68-12-2, 33513-42-7) + (Z)-1-(tert-butyldimethylsilyloxy)-3-iodo-3-methylprop-2-ene (148802-00-0) → tert-butyldimethylsilyl Δ13-(Z)-retinyl ether (118304-54-4) + tert-Butyl-[(2Z,4Z,6E,8E)-3,7-dimethyl-9-(2,6,6-trimethyl-cyclohex-1-enyl)-nona-2,4,6,8-tetraenyloxy]-dimethyl-silane (118304-54-4, 118353-70-1)

Conditions	Yield
With potassium tert-butylate; tert.-butyl lithium In diethyl ether; pentane at -75 - 25℃; for 6h; Wittig reaction;

4,4'-diapo-ψ,ψ-carotene-4,4'-dial (13920-19-9, 5056-18-8) + 5-(2,6,6-trimethylcyclohexenyl)-3-methyl-2,4-pentadienyltriphenylphosphonium bromide (62285-98-7) → 3,7,11,15,20,24,28,32-octamethyl-1,34-bis(2,6,6-trimethylcyclohex-1-enyl)tetratriaconta-1,3,5,7,9,11,13,15,17,19,21,23,25,27,29,31,33-heptadecaene (24513-48-2)

Conditions	Yield
With sodium hydride In dichloromethane Wittig reaction;	67 % Spectr.

6,6'-diapocarotene-6,6'-dial (34561-05-2) + 5-(2,6,6-trimethylcyclohexenyl)-3-methyl-2,4-pentadienyltriphenylphosphonium bromide (62285-98-7) → 3,9,13,18,22,28-hexamethyl-1,30-bis(2,6,6-trimethylcyclohex-1-enyl)triaconta-1,3,5,7,9,11,13,15,17,19,21,23,25,27,29-pentadecaene

Conditions	Yield
With sodium hydride In dichloromethane Wittig reaction;	66 % Spectr.

Upstream product

• 5244-34-8 2,2'-ethane-1,2-diylbissulfanyl-bis-ethanol 
• 7440-02-0 nickel 
• 32659-14-6 4-bromo-3-methyl-2-buten-1-ol acetate 
• 24529-80-4 (E)-1-O-acetyl-4-chloro-3-methyl-2-buten-1-ol 
• 78-70-6 3,7-dimethylocta-1,6-dien-3-ol 
• 3917-38-2 3-methyl-5-acetoxy-1-(2,6,6-trimethyl-1-cyclohexen-1-yl)-1,3-pentadiene 
• 56013-01-5 triphenyl((2,6,6-trimethylcyclohex-1-enyl)methyl)phosphonium bromide 
• 38987-92-7 3-methyl-5-bromo-1-(2,6,6-trimethyl-1-cyclohexen-1-yl)-1,3-pentadiene 
• 603-35-0 triphenylphosphine 
• 59633-88-4 2-(bromomethyl)-1,3,3-trimethylcyclohex-1-ene 
• 17974-55-9 (2E,4E)-ethyl 3-methyl-5-(2,6,6-trimethylcyclohex-1-enyl)penta-2,4-dienoate 
• 6399-81-1 triphenylphosphine hydrobromide 
• 79-77-6 (E)-β-ionone 
• 1826-67-1 vinyl magnesium bromide 

Downstream Products

• 472-93-5 trans-gamma-Carotene 
• 1638-05-7 12'-apo-β-caroten-12'-al 
• 127-47-9 Retinol acetate 
• 79-81-2 retinyl palmitate 
• 172302-35-1 13,14-dihydroretinal 
• 98299-59-3 all-trans-13,14-dihydroretinoic acid 
• 7235-40-7 beta-carotene 
• 4759-48-2 13-cis-retinoic acid 
• 879295-61-1 11-cis-DROL 
• 115797-14-3 13,14-dihydro-all-trans retinol 
• 268728-47-8 retinyl sulfide 
• 85026-52-4 (13Z)-13-bromo-13-desmethylretinal 
• 111917-91-0 (4Z,6E,8E)-7-Methyl-9-(2,6,6-trimethyl-cyclohex-1-enyl)-nona-4,6,8-trien-2-yn-1-ol 
• 75860-00-3 (4E,6E,8E)-7-Methyl-9-(2,6,6-trimethyl-cyclohex-1-enyl)-nona-4,6,8-trien-2-ynal 

Relevant articles and documents

Preparation method of vitamin A acetate intermediate C15 and vitamin A acetate

The invention provides a preparation method of a vitamin A acetate intermediate C15 and vitamin A acetate. The method comprises the following steps: taking 1-halogenated-2-methyl-4-acetoxy-2-butene asa raw material, preparing a corresponding Wittig reagent through a substitution reaction with triphenylphosphine or triester phosphite, then carrying out a Wittig reaction with beta-cyclocitral, hydrolyzing an ester group under an alkaline condition, acidifying to obtain a corresponding halide, and carrying out a substitution reaction with triphenylphosphine or triester phosphite again to prepareC15. The vitamin A acetate can be prepared by carrying out a Wittig reaction on the obtained C15 and 2-methyl-4-acetoxy-2-butenal under an alkaline condition. The method has the advantages of singlereaction type, easy operation and realization of reaction conditions, safe and environment-friendly operation, simple post-treatment and low cost; and the reaction activity is strong, the reaction selectivity is high, the atom economy is high, and the target product yield and purity are high.

All-Trans-Retinol: All-Trans-13,14-Dihydroretinol Saturase and Methods of Its Use

Compositions of all-trans-retinol: all-trans-13,14-dihydroretinal saturase and methods of use thereof are provided.

Synthesis of iodinated analogues of all trans retinoic acid (ATRA) for SPECT imaging

Two derivatives of all trans retinoic acid in which one of the methyl groups has been replaced by iodine have been prepared.