2052-63-3

Basic information

• Product Name: 13-CIS-RETINOL
• Synonyms: 2-CIS-VITAMIN A ALCOHOL;12-CIS-RETINOL;13-CIS-RETINOL;13-DIS-RETINOL;Retinol, 13-cis-;(13Z)-Retinol;13-cis-VitaMin A;neo-Retinol
• CAS NO: 2052-63-3
• Molecular Formula: C₂₀H₃₀O
• Molecular Weight: 286.45
• Mol File: 2052-63-3.mol
• Article Data: 22

Chemical Properties

• Melting Point: 58-60°
• Boiling Point: 421.2 °C at 760 mmHg
• Flash Point: 147.3 °C
• Appearance: /
• Density: 0.954 g/cm³
• Vapor Pressure: 0mmHg at 25°C
• Refractive Index: 1.549
• Storage Temp.: ?20°C
• Solubility: Chloroform (Slightly), Ethyl Acetate (Slightly), Methanol (Slightly)
• Stability: Light Sensitive, Temperature Sensitive
• CAS DataBase Reference: 13-CIS-RETINOL(CAS DataBase Reference)
• NIST Chemistry Reference: 13-CIS-RETINOL(2052-63-3)
• EPA Substance Registry System: 13-CIS-RETINOL(2052-63-3)

Safety Data

• Hazard Codes: Xi
• Statements: 38
• Safety Statements: 22-36/37
• Hazardous Substances Data: 2052-63-3(Hazardous Substances Data)

Usage

Chemical Properties

Yellow Low Melting Solid

Uses

13-cis-Retinol is one of the active metabolite of Vitamin A (R252000).

InChI:InChI=1/C20H30O/c1-16(8-6-9-17(2)13-15-21)11-12-19-18(3)10-7-14-20(19,4)5/h6,8-9,11-13,21H,7,10,14-15H2,1-5H3/b9-6+,12-11+,16-8+,17-13-

Synthetic route

1-acetoxy-3,7-dimethyl-8-(tetrahydropyran-2-yl)oxy-9-phenylsulfonyl-9-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2(E),6(E)-nonadiene (103905-07-3) → 2-cis-Vitamin-A (2052-63-3) + 9-cis-retinol (68-26-8, 2052-63-3, 6018-74-2, 17706-49-9, 22737-96-8, 29444-25-5, 34218-73-0, 39815-04-8, 69686-68-6, 69686-69-7, 74743-94-5, 84415-27-0, 84415-28-1, 85354-09-2, 85354-10-5, 93380-02-0, 98462-62-5, 137121-52-9, 22737-97-9) + 11-cis-retinol (22737-96-8) + RETINOL (68-26-8)

Conditions	Yield
With potassium methanolate In cyclohexane at 38℃; for 2h;	A n/a B n/a C n/a D 77%
With potassium methanolate In cyclohexane at 38℃; for 2h; Title compound not separated from byproducts;

9-(2',6',6'-trimethylcyclohex-1'-enyl)-8-acetoxy-3,7-dimethyl-9-(p-tolylsulfonyl)nona-2Z,4E,6E-trien-1-ol (181053-77-0) → 2-cis-Vitamin-A (2052-63-3)

Conditions	Yield
With methanol; potassium dihydrogenphosphate; sodium amalgam In diethyl ether for 0.5h; Ambient temperature;	63%
With potassium dihydrogenphosphate; sodium amalgam In diethyl ether; ethanol at 20℃; for 0.5h;	63%

(2Z,4E,6E,8E)-methyl 3,7-dimethyl-9-(2,6,6-trimethylcyclohex-1-en-1-yl)nona-2,4,6,8-tetraenoate (16760-45-5) → 2-cis-Vitamin-A (2052-63-3)

Conditions	Yield
With lithium aluminium tetrahydride; diethyl ether at -50℃;

triethylsilyl ether of 13-cis-retinol (118304-60-2) → 2-cis-Vitamin-A (2052-63-3)

Conditions	Yield
With pyridine hydrogenfluoride; sodium fluoride Ambient temperature; Yield given;
With pyridine hydrogenfluoride; sodium fluoride In tetrahydrofuran; acetonitrile for 5h; Ambient temperature;

Acetic acid (2Z,6E)-9-benzenesulfonyl-3,7-dimethyl-8-(tetrahydro-pyran-2-yloxy)-9-(2,6,6-trimethyl-cyclohex-1-enyl)-nona-2,6-dienyl ester (103905-07-3, 105615-50-7) → 2-cis-Vitamin-A (2052-63-3)

Conditions	Yield
With potassium methanolate In cyclohexane at 38℃; for 2h;

Acetic acid (2Z,6E)-9-benzenesulfonyl-3,7-dimethyl-8-(tetrahydro-pyran-2-yloxy)-9-(2,6,6-trimethyl-cyclohex-1-enyl)-nona-2,6-dienyl ester (103905-07-3, 105615-50-7) → 2-cis-Vitamin-A (2052-63-3) + 11,13-Di-cis-vitamin A (17706-49-9) + (9Z,13Z)-retinol (29444-25-5) + RETINOL (68-26-8)

Conditions	Yield
With potassium methanolate In cyclohexane at 38℃; for 2h; Yield given. Title compound not separated from byproducts;
With potassium methanolate In cyclohexane at 38℃; for 2h; Title compound not separated from byproducts;

O-all-trans-retinol → 2-cis-Vitamin-A (2052-63-3)

Conditions	Yield
With iodine; benzene Einwirkung von Tageslicht;

ethyl (2E,4E,6Z)-8-hydroxy-2,6-dimethylocta-2,4,6-trienoate (181053-78-1) → 2-cis-Vitamin-A (2052-63-3)

Conditions	Yield
Multi-step reaction with 7 steps 1.1: 98 percent / imidazole / dimethylformamide / 1 h / 20 °C 2.1: 96 percent / LiAlH4; AlCl3 / diethyl ether / 3 h / 0 °C 3.1: 100 percent / MnO2 / hexane; CHCl3 / 12 h / 20 °C 4.1: n-BuLi / tetrahydrofuran; hexane / 1 h / -78 °C 4.2: tetrahydrofuran; hexane / 3 h / -78 °C 5.1: 118.2 mg / tetrahydrofuran; hexane / -78 - 20 °C 6.1: 99 percent / TBAF / tetrahydrofuran / 0.5 h / 20 °C 7.1: 63 percent / KH2PO4; Na/Hg / ethanol; diethyl ether / 0.5 h / 20 °C View Scheme
Multi-step reaction with 6 steps 1: 98 percent 2: 96 percent / AlCl3, LiAlH4 3: 100 percent / MnO2 4: 1.) nBuLi 5: n-Bu4NF 6: 63 percent / Na/Hg, KH2PO4, MeOH / diethyl ether / 0.5 h / Ambient temperature View Scheme

ethyl (2E,4E,6Z)-8-tert-butyldimethylsiloxy-2,6-dimethylocta-2,4,6-trienoate (181053-73-6) → 2-cis-Vitamin-A (2052-63-3)

Conditions

Yield

Multi-step reaction with 8 steps 1.1: TBAF / tetrahydrofuran / 0.5 h / 20 °C 2.1: 98 percent / imidazole / dimethylformamide / 1 h / 20 °C 3.1: 96 percent / LiAlH4; AlCl3 / diethyl ether / 3 h / 0 °C 4.1: 100 percent / MnO2 / hexane; CHCl3 / 12 h / 20 °C 5.1: n-BuLi / tetrahydrofuran; hexane / 1 h / -78 °C 5.2: tetrahydrofuran; hexane / 3 h / -78 °C 6.1: 118.2 mg / tetrahydrofuran; hexane / -78 - 20 °C 7.1: 99 percent / TBAF / tetrahydrofuran / 0.5 h / 20 °C 8.1: 63 percent / KH2PO4; Na/Hg / ethanol; diethyl ether / 0.5 h / 20 °C View Scheme

(3E,6Z)-8-(tert-Butyl-dimethyl-silanyloxy)-2-(N,N-dimethyl-aminooxy)-2,6-dimethyl-octa-3,6-dienoic acid ethyl ester (181053-74-7) → 2-cis-Vitamin-A (2052-63-3)

Conditions

Yield

Multi-step reaction with 9 steps 1.1: methanol / 72 h / 20 °C 2.1: TBAF / tetrahydrofuran / 0.5 h / 20 °C 3.1: 98 percent / imidazole / dimethylformamide / 1 h / 20 °C 4.1: 96 percent / LiAlH4; AlCl3 / diethyl ether / 3 h / 0 °C 5.1: 100 percent / MnO2 / hexane; CHCl3 / 12 h / 20 °C 6.1: n-BuLi / tetrahydrofuran; hexane / 1 h / -78 °C 6.2: tetrahydrofuran; hexane / 3 h / -78 °C 7.1: 118.2 mg / tetrahydrofuran; hexane / -78 - 20 °C 8.1: 99 percent / TBAF / tetrahydrofuran / 0.5 h / 20 °C 9.1: 63 percent / KH2PO4; Na/Hg / ethanol; diethyl ether / 0.5 h / 20 °C View Scheme

(2E,4E,6Z)-8-tert-butyldiphenylsiloxy-2,6-dimethylocta-2,4,6-trien-1-ol (181053-80-5) → 2-cis-Vitamin-A (2052-63-3)

Conditions	Yield
Multi-step reaction with 5 steps 1.1: 100 percent / MnO2 / hexane; CHCl3 / 12 h / 20 °C 2.1: n-BuLi / tetrahydrofuran; hexane / 1 h / -78 °C 2.2: tetrahydrofuran; hexane / 3 h / -78 °C 3.1: 118.2 mg / tetrahydrofuran; hexane / -78 - 20 °C 4.1: 99 percent / TBAF / tetrahydrofuran / 0.5 h / 20 °C 5.1: 63 percent / KH2PO4; Na/Hg / ethanol; diethyl ether / 0.5 h / 20 °C View Scheme
Multi-step reaction with 4 steps 1: 100 percent / MnO2 2: 1.) nBuLi 3: n-Bu4NF 4: 63 percent / Na/Hg, KH2PO4, MeOH / diethyl ether / 0.5 h / Ambient temperature View Scheme

(2E,4E,6Z)-8-tert-butyldiphenylsiloxy-2,6-dimethylocta-2,4,6-trienal (181053-76-9) → 2-cis-Vitamin-A (2052-63-3)

Conditions	Yield
Multi-step reaction with 4 steps 1.1: n-BuLi / tetrahydrofuran; hexane / 1 h / -78 °C 1.2: tetrahydrofuran; hexane / 3 h / -78 °C 2.1: 118.2 mg / tetrahydrofuran; hexane / -78 - 20 °C 3.1: 99 percent / TBAF / tetrahydrofuran / 0.5 h / 20 °C 4.1: 63 percent / KH2PO4; Na/Hg / ethanol; diethyl ether / 0.5 h / 20 °C View Scheme
Multi-step reaction with 3 steps 1: 1.) nBuLi 2: n-Bu4NF 3: 63 percent / Na/Hg, KH2PO4, MeOH / diethyl ether / 0.5 h / Ambient temperature View Scheme

ethyl (2E,4E,6Z)-8-tert-butyldiphenylsiloxy-2,6-dimethylocta-2,4,6-trienoate (181053-79-2) → 2-cis-Vitamin-A (2052-63-3)

Conditions	Yield
Multi-step reaction with 6 steps 1.1: 96 percent / LiAlH4; AlCl3 / diethyl ether / 3 h / 0 °C 2.1: 100 percent / MnO2 / hexane; CHCl3 / 12 h / 20 °C 3.1: n-BuLi / tetrahydrofuran; hexane / 1 h / -78 °C 3.2: tetrahydrofuran; hexane / 3 h / -78 °C 4.1: 118.2 mg / tetrahydrofuran; hexane / -78 - 20 °C 5.1: 99 percent / TBAF / tetrahydrofuran / 0.5 h / 20 °C 6.1: 63 percent / KH2PO4; Na/Hg / ethanol; diethyl ether / 0.5 h / 20 °C View Scheme
Multi-step reaction with 5 steps 1: 96 percent / AlCl3, LiAlH4 2: 100 percent / MnO2 3: 1.) nBuLi 4: n-Bu4NF 5: 63 percent / Na/Hg, KH2PO4, MeOH / diethyl ether / 0.5 h / Ambient temperature View Scheme

9-(2',6',6'-trimethylcyclohex-1'-enyl)-8-acetoxy-1-tert-butyldiphenylsiloxy-3,7-dimethyl-9-(p-tolylsulfonyl)nona-2Z,4E,6E-triene (463302-50-3) → 2-cis-Vitamin-A (2052-63-3)

Conditions	Yield
Multi-step reaction with 2 steps 1: 99 percent / TBAF / tetrahydrofuran / 0.5 h / 20 °C 2: 63 percent / KH2PO4; Na/Hg / ethanol; diethyl ether / 0.5 h / 20 °C View Scheme
Multi-step reaction with 2 steps 1: n-Bu4NF 2: 63 percent / Na/Hg, KH2PO4, MeOH / diethyl ether / 0.5 h / Ambient temperature View Scheme

(3E,5E,7Z)-9-(tert-Butyl-diphenyl-silanyloxy)-3,7-dimethyl-1-(toluene-4-sulfonyl)-1-(2,6,6-trimethyl-cyclohex-1-enyl)-nona-3,5,7-trien-2-ol → 2-cis-Vitamin-A (2052-63-3)

Conditions	Yield
Multi-step reaction with 3 steps 1: 118.2 mg / tetrahydrofuran; hexane / -78 - 20 °C 2: 99 percent / TBAF / tetrahydrofuran / 0.5 h / 20 °C 3: 63 percent / KH2PO4; Na/Hg / ethanol; diethyl ether / 0.5 h / 20 °C View Scheme

β-cyclogeranyl p-tolyl sulfone → 2-cis-Vitamin-A (2052-63-3)

Conditions	Yield
Multi-step reaction with 3 steps 1: 1.) nBuLi 2: n-Bu4NF 3: 63 percent / Na/Hg, KH2PO4, MeOH / diethyl ether / 0.5 h / Ambient temperature View Scheme

C20H39NO4Si (181053-72-5) → 2-cis-Vitamin-A (2052-63-3)

Conditions	Yield
Multi-step reaction with 7 steps 1: 100 percent / n-Bu4NF 2: 98 percent 3: 96 percent / AlCl3, LiAlH4 4: 100 percent / MnO2 5: 1.) nBuLi 6: n-Bu4NF 7: 63 percent / Na/Hg, KH2PO4, MeOH / diethyl ether / 0.5 h / Ambient temperature View Scheme

[(2E)-3-ethoxycarbonylbut-2-enyl][1-isopropenyl-2-(tert-butyldimethylsiloxy)ethyl]dimethylammonium bromide → 2-cis-Vitamin-A (2052-63-3)

Conditions	Yield
Multi-step reaction with 9 steps 1: KOEt / ethanol / 5 h / -70 °C 2: peracetic acid, Na2CO3 / CH2Cl2 / -60 °C 3: 100 percent / n-Bu4NF 4: 98 percent 5: 96 percent / AlCl3, LiAlH4 6: 100 percent / MnO2 7: 1.) nBuLi 8: n-Bu4NF 9: 63 percent / Na/Hg, KH2PO4, MeOH / diethyl ether / 0.5 h / Ambient temperature View Scheme

(2E,6Z)-8-(tert-Butyl-dimethyl-silanyloxy)-4-dimethylamino-2,6-dimethyl-octa-2,6-dienoic acid ethyl ester (181053-71-4) → 2-cis-Vitamin-A (2052-63-3)

Conditions	Yield
Multi-step reaction with 8 steps 1: peracetic acid, Na2CO3 / CH2Cl2 / -60 °C 2: 100 percent / n-Bu4NF 3: 98 percent 4: 96 percent / AlCl3, LiAlH4 5: 100 percent / MnO2 6: 1.) nBuLi 7: n-Bu4NF 8: 63 percent / Na/Hg, KH2PO4, MeOH / diethyl ether / 0.5 h / Ambient temperature View Scheme

neryl acetate (141-12-8) → 2-cis-Vitamin-A (2052-63-3)

Conditions	Yield
Multi-step reaction with 5 steps 1: SeO2, salicylic acid, tert-butyl hydroperoxide / CH2Cl2 / 27 h / Ambient temperature 2: PDC / CH2Cl2 / 10 h / Ambient temperature 3: 1.) n-BuLi / 1.) THF, -78 deg C, 2 h, 2.) THF, -78 deg C, 3 h 4: p-toluenesulfonic acid / CH2Cl2 / 3 h / Ambient temperature 5: MeOK / cyclohexane / 2 h / 38 °C View Scheme
Multi-step reaction with 4 steps 1: SeO2, salicylic acid, tert-butyl hydroperoxide / CH2Cl2 / 27 h / Ambient temperature 2: 1.) n-BuLi / 1.) THF, -78 deg C, 2 h, 2.) THF, -78 deg C, 3 h 3: p-toluenesulfonic acid / CH2Cl2 / 3 h / Ambient temperature 4: MeOK / cyclohexane / 2 h / 38 °C View Scheme

3,7-dimethyl-2E,6-octadien-1-yl acetate (105-87-3) → 2-cis-Vitamin-A (2052-63-3)

Conditions	Yield
Multi-step reaction with 5 steps 1: SeO2, salicylic acid, tert-butyl hydroperoxide / CH2Cl2 / 27 h / Ambient temperature 2: PDC / CH2Cl2 / 10 h / Ambient temperature 3: 1.) n-BuLi / 1.) THF, -78 deg C, 2 h, 2.) THF, -78 deg C, 3 h 4: 99 percent / p-toluenesulfonic acid / CH2Cl2 / 3 h / Ambient temperature 5: MeOK / cyclohexane / 2 h / 38 °C View Scheme
Multi-step reaction with 4 steps 1: SeO2, salicylic acid, tert-butyl hydroperoxide / CH2Cl2 / 27 h / Ambient temperature 2: 1.) n-BuLi / 1.) THF, -78 deg C, 2 h, 2.) THF, -78 deg C, 3 h 3: 99 percent / p-toluenesulfonic acid / CH2Cl2 / 3 h / Ambient temperature 4: MeOK / cyclohexane / 2 h / 38 °C View Scheme

8-hydroxygeranyl acetate (37905-03-6) → 2-cis-Vitamin-A (2052-63-3)

Conditions	Yield
Multi-step reaction with 4 steps 1: PDC / CH2Cl2 / 10 h / Ambient temperature 2: 1.) n-BuLi / 1.) THF, -78 deg C, 2 h, 2.) THF, -78 deg C, 3 h 3: 99 percent / p-toluenesulfonic acid / CH2Cl2 / 3 h / Ambient temperature 4: MeOK / cyclohexane / 2 h / 38 °C View Scheme

(2E,6E)-3,7-dimethyl-8-oxoocta-2,6-dien-1-yl acetate (37905-02-5) → 2-cis-Vitamin-A (2052-63-3)

Conditions	Yield
Multi-step reaction with 3 steps 1: 1.) n-BuLi / 1.) THF, -78 deg C, 2 h, 2.) THF, -78 deg C, 3 h 2: 99 percent / p-toluenesulfonic acid / CH2Cl2 / 3 h / Ambient temperature 3: MeOK / cyclohexane / 2 h / 38 °C View Scheme

(2'Z,6'E)-Essigsaeure-(8'-hydroxy-3',7'-dimethyl-2',6'-octadien-1'-yl)ester (70238-37-8) → 2-cis-Vitamin-A (2052-63-3)

Conditions	Yield
Multi-step reaction with 4 steps 1: PDC / CH2Cl2 / 10 h / Ambient temperature 2: 1.) n-BuLi / 1.) THF, -78 deg C, 2 h, 2.) THF, -78 deg C, 3 h 3: p-toluenesulfonic acid / CH2Cl2 / 3 h / Ambient temperature 4: MeOK / cyclohexane / 2 h / 38 °C View Scheme

{[(2,6,6-trimethyl-1-cyclohexen-1-yl)methyl]sulfonyl}benzene (56691-74-8) → 2-cis-Vitamin-A (2052-63-3)

Conditions	Yield
Multi-step reaction with 3 steps 1: 1.) n-BuLi / 1.) THF, -78 deg C, 2 h, 2.) THF, -78 deg C, 3 h 2: 99 percent / p-toluenesulfonic acid / CH2Cl2 / 3 h / Ambient temperature 3: MeOK / cyclohexane / 2 h / 38 °C View Scheme
Multi-step reaction with 3 steps 1: 1.) n-BuLi / 1.) THF, -78 deg C, 2 h, 2.) THF, -78 deg C, 3 h 2: p-toluenesulfonic acid / CH2Cl2 / 3 h / Ambient temperature 3: MeOK / cyclohexane / 2 h / 38 °C View Scheme
Multi-step reaction with 3 steps 1: n-BuLi / tetrahydrofuran / 5 h / -78 °C 2: p-toluenesulfonic acid / CH2Cl2 3: MeOK / cyclohexane / 2 h / 38 °C View Scheme

(2Z,6E)-3,7-dimethyl-8-oxoocta-2,6-dien-1-yl acetate (94853-00-6) → 2-cis-Vitamin-A (2052-63-3)

Conditions	Yield
Multi-step reaction with 3 steps 1: 1.) n-BuLi / 1.) THF, -78 deg C, 2 h, 2.) THF, -78 deg C, 3 h 2: p-toluenesulfonic acid / CH2Cl2 / 3 h / Ambient temperature 3: MeOK / cyclohexane / 2 h / 38 °C View Scheme
Multi-step reaction with 3 steps 1: n-BuLi / tetrahydrofuran / 5 h / -78 °C 2: p-toluenesulfonic acid / CH2Cl2 3: MeOK / cyclohexane / 2 h / 38 °C View Scheme

Acetic acid (2Z,6E)-9-benzenesulfonyl-8-hydroxy-3,7-dimethyl-9-(2,6,6-trimethyl-cyclohex-1-enyl)-nona-2,6-dienyl ester (105615-49-4) → 2-cis-Vitamin-A (2052-63-3)

Conditions	Yield
Multi-step reaction with 2 steps 1: p-toluenesulfonic acid / CH2Cl2 / 3 h / Ambient temperature 2: MeOK / cyclohexane / 2 h / 38 °C View Scheme
Multi-step reaction with 2 steps 1: p-toluenesulfonic acid / CH2Cl2 2: MeOK / cyclohexane / 2 h / 38 °C View Scheme

1-acetoxy-8-hydroxy-3,7-dimethyl-9-(2,6,6-trimethyl-1-cyclohexen-1-yl)-9-(phenylsulfonyl)-2(E),6(E)-nonadiene (103905-01-7) → 2-cis-Vitamin-A (2052-63-3)

Conditions	Yield
Multi-step reaction with 2 steps 1: 99 percent / p-toluenesulfonic acid / CH2Cl2 / 3 h / Ambient temperature 2: MeOK / cyclohexane / 2 h / 38 °C View Scheme

5-hydroxy-4-methyl-5H-furan-2-one (40834-42-2) → 2-cis-Vitamin-A (2052-63-3)

Conditions	Yield
Multi-step reaction with 7 steps 1: 1.) NaH / 1.) HMPA, 0 deg C, 1 h, 2.) 20 min 2: 1.) ethylmagnesium bromide / 1.) THF, room temperature, 1 h, 2.) 15 min 3: 75 percent / DIBAH / tetrahydrofuran; toluene / 0.5 h / -78 °C 4: 90 percent / H2 / Lindlar catalyst / methanol / 24 h 5: 80 percent / imidazole / dimethylformamide / 18 h / Ambient temperature 6: 90 percent / LiAlH4, TiCl3 / tetrahydrofuran / 0.5 h / Ambient temperature 7: sodium fluoride, pyridinium fluoride / tetrahydrofuran; acetonitrile / 5 h / Ambient temperature View Scheme
Multi-step reaction with 7 steps 1: 85 percent / NaH / hexamethylphosphoric acid triamide 2: 90 percent / EtMgBr 3: 75 percent / DIBAL 4: 80 percent 5: 90 percent / H2 / Lindlar catalist 6: 90 percent / LiAlH4,TiCl3 / tetrahydrofuran / 0.5 h / Ambient temperature 7: NaF, pyridiniumfluoride / Ambient temperature View Scheme

pyridine (110-86-1) + 2-cis-Vitamin-A (2052-63-3) + acetyl chloride (75-36-5) → (7E,9E,11E,13Z)-retinyl acetate (34356-31-5)

Conditions	Yield
With 1,2-dichloro-ethane

pyridine (110-86-1) + 2-cis-Vitamin-A (2052-63-3) + n-hexadecanoyl chloride (112-67-4) → 9-Palmitoyloxy-3.7-dimethyl-1t-(2.2.6-trimethyl-cyclohexen-(6)-yl)-nonatetraen-(1.3t.5t.7c) (26771-20-0)

Conditions	Yield
With 1,2-dichloro-ethane

2-cis-Vitamin-A (2052-63-3) → 13-cis-vitamin A aldehyde (472-86-6)

Conditions	Yield
With manganese(IV) oxide; Petroleum ether unter Lichtausschluss;
With manganese(IV) oxide
With manganese(IV) oxide In tetrachloromethane for 0.5h;

4-phenylazobenzoyl chloride (104-24-5) + 2-cis-Vitamin-A (2052-63-3) → 9-(4-Phenylazo-benzoyloxy)-3.7-dimethyl-1t-(2.2.6-trimethyl-cyclohexen-(6)-yl)-nonatetraen-(1.3t.5t.7c) (50696-24-7, 50837-87-1, 105616-34-0)

2-cis-Vitamin-A (2052-63-3) + anthraquinone-2-carbonyl chloride (6470-87-7) → O-(9.10-dioxo-9.10-dihydro-anthracenecarbonyl-(2))-[7t.9t.11t.13c]retinol (107892-29-5)

Conditions	Yield
With pyridine; dichloromethane

2-cis-Vitamin-A (2052-63-3) + acetic anhydride (108-24-7) → 9-cis-retinol (68-26-8, 2052-63-3, 6018-74-2, 17706-49-9, 22737-96-8, 29444-25-5, 34218-73-0, 39815-04-8, 69686-68-6, 69686-69-7, 74743-94-5, 84415-27-0, 84415-28-1, 85354-09-2, 85354-10-5, 93380-02-0, 98462-62-5, 137121-52-9, 22737-97-9) + 9cis,13cis-retinyl acetate (29444-27-7) + (7E,9E,11E,13Z)-retinyl acetate (34356-31-5) + 11,13-di-cis-Vitamin-A-acetat (63568-38-7)

Conditions	Yield
With triethylamine In hexane Yield given;

2-cis-Vitamin-A (2052-63-3) + acetic anhydride (108-24-7) → 9cis,13cis-retinyl acetate (29444-27-7) + (7E,9E,11E,13Z)-retinyl acetate (34356-31-5) + 11,13-di-cis-Vitamin-A-acetat (63568-38-7)

Conditions	Yield
With triethylamine In hexane Yield given;

2-cis-Vitamin-A (2052-63-3) + propargyl bromide (106-96-7) → 2-((1E,3E,5E,7Z)-3,7-Dimethyl-9-prop-2-ynyloxy-nona-1,3,5,7-tetraenyl)-1,3,3-trimethyl-cyclohexene (173010-18-9)

Conditions	Yield
With n-butyllithium 1.) benzene, hexane, 20 deg C, 5 min, 2.) benzene, DMF, hexane, RT, 4 h; Yield given. Multistep reaction;

hydrogenchloride (7647-01-0) + 2-cis-Vitamin-A (2052-63-3) → anhydrovitamin-A1

Conditions	Yield
Kinetics; Dehydratisierung;

2-cis-Vitamin-A (2052-63-3) + iodine (7553-56-2) + benzene (71-43-2) → O--derivative of all-trans-retinol

Conditions	Yield
Gleichgewichtsgemisch mit dem O--Derivat unter der Einwirkung von Tageslicht;

Upstream product

• 141-12-8 neryl acetate 
• 105-87-3 3,7-dimethyl-2E,6-octadien-1-yl acetate 
• 56691-74-8 {[(2,6,6-trimethyl-1-cyclohexen-1-yl)methyl]sulfonyl}benzene 
• 40834-42-2 5-hydroxy-4-methyl-5H-furan-2-one 
• 68-26-8 RETINOL 
• 108-24-7 acetic anhydride 
• 200720-67-8 (9Ξ)-O-acetyl-retinol 
• 79-81-2 retinyl palmitate 
• 3917-41-7 (2E,4E)-3-methyl-5-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2,4-pentadienal 
• 111724-05-1 <(2E)-4-hydroxy-2-methyl-2-butenyl>triphenylphosphonium bromide 
• 79-77-6 (E)-β-ionone 
• 3917-39-3 (2E,4E)-3-methyl-5-(2,6,6-trimethyl-1-cyclohexenyl)-2,4-pentadien-1-ol 
• 3899-20-5 (2E,4Z,6Z,8Z)-3,7-Dimethyl-9-(2,6,6-trimethyl-cyclohex-1-enyl)-nona-2,4,6,8-tetraenoic acid ethyl ester 
• 103905-07-3 1-acetoxy-3,7-dimethyl-8-(tetrahydropyran-2-yl)oxy-9-phenylsulfonyl-9-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2(E),6(E)-nonadiene 

Downstream Products

• 34356-31-5 (7E,9E,11E,13Z)-retinyl acetate 
• 26771-20-0 9-Palmitoyloxy-3.7-dimethyl-1t-(2.2.6-trimethyl-cyclohexen-⁽⁶⁾-yl)-nonatetraen-(1.3t.5t.7c) 
• 472-86-6 13-cis-vitamin A aldehyde 
• 514-85-2 9-cis vitamin A aldehyde 
• 68-26-8 9-cis-retinol 
• 29444-27-7 9cis,13cis-retinyl acetate 
• 63568-38-7 11,13-di-cis-Vitamin-A-acetat 
• 173010-18-9 2-((1E,3E,5E,7Z)-3,7-Dimethyl-9-prop-2-ynyloxy-nona-1,3,5,7-tetraenyl)-1,3,3-trimethyl-cyclohexene 
• 4759-48-2 13-cis-retinoic acid 
• 302-79-4 all-trans-retinoic-acid 
• 138093-35-3 20,14-retro-Retinoic acid 
• 138093-38-6 14-ethyl-20,14-retro-retinoic acid 
• 138093-39-7 14-isopropyl-20,14-retro-retinoic acid 
• 138093-44-4 methyl 14-ethyl-20,14-retro-retinoate 

Relevant articles and documents

Z -isomerization of retinoids through combination of monochromatic photoisomerization and metal catalysis

Catalytic Z-isomerization of retinoids to their thermodynamically less stable Z-isomer remains a challenge. In this report, we present a photochemical approach for the catalytic Z-isomerization of retinoids using monochromatic wavelength UV irradiation treatment. We have developed a straightforward approach for the synthesis of Z-retinoids in high yield, overcoming common obstacles normally associated with their synthesis. Calculations based on density functional theory (DFT) have allowed us to correlate the experimentally observed Z-isomer distribution of retinoids with the energies of chemically important intermediates, which include ground- and excited-state potential energy surfaces. We also demonstrate the application of the current method by synthesizing gram-scale quantities of 9-cis-retinyl acetate 9Z-a. Operational simplicity and gram-scale ability make this chemistry a very practical solution to the problem of Z-isomer retinoid synthesis.

Substrate specificity and subcellular localization of the aldehyde-Alcohol redox-Coupling reaction in carp cones

Our previous study suggested the presence of a novel conespecific redox reaction that generates 11-cis-retinal from 11-cisretinol in the carp retina. This reaction is unique in that 1) both 11-cis-retinol and all-trans-retinal were required to produce 11-cis-retinal; 2) together with 11-cis-retinal, all-trans-retinol was produced at a 1:1 ratio; and 3) the addition of enzyme cofactors such as NADP(H) was not necessary. This reaction is probably part of the reactions in a cone-specific retinoid cycle required for cone visual pigment regeneration with the use of 11-cis-retinol supplied from Mueller cells. In this study, using purified carp cone membrane preparations, we first confirmed that the reaction is a redox-coupling reaction between retinals and retinols. We further examined the substrate specificity, reaction mechanism, and subcellular localization of this reaction. Oxidation was specific for 11-cis-retinol and 9-cis-retinol. In contrast, reduction showed low specificity: many aldehydes, including all-trans-, 9-cis-, 11-cis-, and 13-cis-retinals and even benzaldehyde, supported the reaction. On the basis of kinetic studies of this reaction (aldehyde-alcohol redox-coupling reaction), we found that formation of a ternary complex of a retinol, an aldehyde, and a postulated enzyme seemed to be necessary, which suggested the presence of both the retinol- and aldehydebinding sites in this enzyme. A subcellular fractionation study showed that the activity is present almost exclusively in the cone inner segment. These results suggest the presence of an effective production mechanism of 11-cis-retinal in the cone inner segment to regenerate visual pigment.