Synthesis of erythro-9,10-dihydroxystearic acid, ارثرو-10،9-ثنائي هيدروحامض الستيارك, erythro-9,10-Διυδροστεατικό οξ

Erythro-9,10-Dihydroxystearic acid [3639-32-5]



Name erythro-9,10-Dihydroxystearic acid
Synonyms (9R,10S)-rel-9,10-Dihydroxyoctadecanoic acid
Name in Chemical Abstracts Octadecanoic acid, 9,10-dihydroxy-, (9R,10S)-rel-
CAS No 3639-32-5
EINECS No
Molecular formula C18H34O4
Molecular mass 330.51

KMnO4/NaOH

Literature
A. Lapworth und E. N. Mottram, J. Chem. Soc., 1925,1628-31

http://kriemhild.uft.uni-bremen.de/nop/en/instructions/pdf/3011_en.pdf

Reaction type:	addition to alkenes, oxidation, cis-hydroxylation
Substance classes:	alkene, alcohol, natural product
Techniques:	stirring with magnetic stir bar, filtering, recrystallizing, extracting

Instruction (batch scale 10 mmol) 

Equipment 

5 L beaker or Erlenmeyer flask, heatable magnetic stirrer, magnetic stir bar, suction flask, 

Buechner funnel, mortar, desiccator 

Substances 

oleic acid (techn. 90%) 3.14 g (equivalent to 10.0 mmol pure oleic acid) 

(oleic acid, pure: mp 16 °C, 

bp 193 °C/1.6 hPa) 

potassium permanganate 2.50 g (15.8 mmol) 

sodium hydroxid 3.14 g (78.5 mmol) 

hydrochloric acid (conc., 36%) 94 mL 

sodium sulfite or sodium disulfite 

petroleum ether (bp 60-80 °C) about 200 mL 

ethanol (bp 78 °C) for recrystallizing 

Reaction 

3.14 g (10.0 mmol) oleic acid (techn. 90%) are added to a solution of 3.14 g (78.5 mmol) 

NaOH in 320 mL water in a 5 L beaker with a magnetic stir bar. The mixture is heated under

stirring until a clear solution is formed. After the addition of 2.5 L ice-cold water, 250 mL 1% 

potassium permanganate solution are added within 1 minute under stirring at a temperature of 

10 °C. After 5 minutes so much solid sodium sulfite oder sodium disulfite is added, that the 

excess of potassium permanganate is reduced. Afterwards the solution is acidified with 94 mL 

conc. hydrochloric acid. The solution becomes colourless, and a colourless fluffy precipitation 

is formed. 

Work up 

The precipitation is sucked off and dried. Crude yield: 3.01 g, mp 81-88 °C 

The crude product is washed with 50 mL petroleum ether (60-80 °C) and dried under reduced 

pressure. The dried product is powdered in a mortar and digested with 100-150 mL petroleum 

ether in a beaker. Thus the sturated carboxylic acids contained in the oleic acid as impurities 

are removed. The dihydroxystearic acid is insoluble in petroleum ether. It is sucked off and 

recrystallized from ethanol. 

Yield: 2.74 g (8.70 mmol, 87%); mp 132 °C; colourless powder 

Yield71%Target product mass0.26gSum of input masses290gMass efficiency0.89mg/gMass index1100g input / g productE factor1100g waste / g product

Equipment

Batch scale:

0.0011 mol

	beaker 500 mL			heatable magnetic stirrer with magnetic stir bar
	suction flask			suction filter
	mortar			exsiccator with drying agent

TLC: crude product
TLC layer	Merck silica gel 60 F254
mobile phase	EtOAc
detection	immerse into solution of 2.7 g KMnO4, 18 g K2CO3, 216 mg NaOH in 274 mL H2O, heating with air dryer
Rf (educt)	0.87
Rf (product)	0.67

1H-NMR: erythro-9,10-Dihydroxystearic acid
250 MHz, DMSO-d6
delta [ppm]	mult.	atoms	assignment
0.86	t (3J = 6.4 Hz)	3 H	CH3
1.2-1.6	m	26 H	other CH2
2.18	t (3J = 7.3 Hz)	2 H	2-CH2
3.25	m	2 H	9-CH-OH, 10-CH-OH
2.45	s	6 H	DMSO

13C-NMR: erythro-9,10-Dihydroxystearic acid
62.5 MHz, DMSO-d6, 373°K
delta [ppm]	assignment
13.0	C18 (CH3)
21.2	C17 (CH2
23.9	CH2
24.8	CH2
27.9	CH2
28.0	CH2
28.3	CH2
28.4	CH2
28.6	CH2
30.6	CH2
31.8	CH2
33.2	C2
73.4	C9, C10 (CH-OH)
173.4	C1 (COOH)
38.5-40.5	DMSO-d6

IR: erythro-9,10-Dihydroxystearic acid
[KBr, T%, cm-1]
[cm-1]	assignment
3500-2500	O-H valence, superimposed on C-H valence
1716	C=O valence, carboxylic acid

Synthesis of 9,10-dihydro-9,10-ethanoanthracene-11,12-trans-dicarboxylic acid diethyl ester

+

Synthesis of 9,10-dihydro-9,10-ethanoanthracene-11,12-trans-dicarboxylic acid diethyl ester

Reaction type:	cycloaddition, Diels-Alder reaction
Substance classes:	alkene, aromatics, carboxylic acid ester, diene, dienophile, acid catalyst
Techniques:	working with moisture exclusion, heating under reflux, stirring with magnetic stir bar, filtering, evaporating with rotary evaporator, recrystallizing, use of an ice cooling bath, heating with oil bath

Operating scheme

Equipment

Batch scale:

0.01 mol

0.1 mol

Anthracene

	three-necked flask 100 mL			adapter with ground-glass joint and hose coupling
	protective gas piping			reflux condenser
	drying tube			bubble counter
	powder funnel			heatable magnetic stirrer with magnetic stir bar
	rotary evaporator			ice bath
	exsiccator with drying agent			oil bath

1H-NMR: 9,10-Dihydro-9,10-ethanoanthracene-11,12-trans-dicarboxylic acid diethyl ester
250 MHz, CDCl3
delta [ppm]	mult.	atoms	assignment
1.23	t (3J = 7.2 Hz)	6 H	CH3 ethyl
3.45	m	2 H	11-H, 12-H (-CH-COO-)
4.08	m	4 H	CH2 ethyl
4.75	m	2 H	9-H, 10-H
7.09-7.38	m	8 H	CH (arom.)
>7.4			CH (arom., educt)

13C-NMR: 9,10-Dihydro-9,10-ethanoanthracene-11,12-trans-dicarboxylic acid diethyl ester
62.5 MHz, CDCl3
delta [ppm]	assignment
14.2	CH3 (ethyl ester)
46.7	C9, C10 (CH)
47.7	C11, C12 (CH-COO)
60.9	CH2 (ethyl ester)
123.8	CH arom.
124.5	CH arom.
126.2	CH arom.
126.3	CH arom.
140.3	C quart. arom.
142.0	C quart. arom.
172.3	C(=O)O-
76.5-77.5	CDCl3

IR: 9,10-Dihydro-9,10-ethanoanthracene-11,12-trans-dicarboxylic acid diethyl ester
[KBr, T%, cm-1]
[cm-1]	assignment
3074, 3026	arom. C-H valence
2981	aliph. C-H valence
2935, 2897	aliph. C-H valence
1739	C=O valence, ester
1467	arom. C=C valence

http://kriemhild.uft.uni-bremen.de/nop/en/instructions/pdf/3010_en.pdf

Instruction (batch scale 100 mmol) 

Equipment 

1000 mL three-neck flask, adapter with ground glass joint and hose coupling, protective gas 

supply, reflux condenser, drying tube, bubble counter, powder funnel, heatable magnetic 

stirrer, magnetic stir bar, rotary evaporator , ice bath, desiccator, oil bath 

Substances 

anthracene (mp 215-217 °C9 17.8 g (100 mmol) 

fumaric acid diethyl ester (bp 219 °C) 17.2 g (16.4 mL, 100 mmol) 

aluminium chloride (water free) 13.3 g (100 mmol) 

cyclohexane (water free) (bp 81 °C) 500 mL 

cyclohexane (bp 81 °C) 200 mL 

sodium carbonate decahydrate 24.9 g (150 mmol) 

sodium carbonate (water free) 25.0 g (236 mmol) 

ethanol (bp 78 °C) 150 mL 

Reaction 

The reaction apparatus consists of a thoroughly dried 1000 mL three-neck flask with reflux 

condenser, drying tube and magnetic stir bar. On one opening of the flask is placed an adapter 

with ground glass joint and hose coupling as inlet for nitrogen. This adapter is replaced 

through a glass stopper after the addition of aluminium chloride to the flask. The reaction 

apparatus is flushed with nitrogen. Then under stirring 17.8 g (100 mmol) anthracene and 

17.2 g (16.4 mL, 100 mmol) fumaric acid diethyl ester are dissolved in the flask in 500 mL 

absolute cyclohexane. After cooling down in the ice bath 13.3 g (100 mmol) water-free 

aluminium chloride are added in one portion over a powder funnel under nitrogen counter 

flow. The reaction mixture is heated under stirring for four hours under reflux. 

Work up 

The reaction mixture is cooled down to room temperature, then 24.9 g (150 mmol) sodium 

carbonate decahydrate are added. The drying tube is replaced through a bubble counter filled 

with paraffin oil and the mixture is stirred until no more gas is formed. Then 25 g (236 mmol) 

sodium carbonate (water free) are added. The mixture is stirred for 10 minutes. The solid is 

filtered off and washed in portions with a total of 200 mL cyclohexane. The solvent is 

evaporated from the filtrate at a rotary evaporator. A solid residue remains as crude product, 

which is dried in the desiccator. Crude yield: 32.6 g 

The crude product is recrystallized from about 150 mL ethanol. 

Yield: 30.8 g (87.9 mmol, 88%); colourless crystals, mp 103 °C

7,7-dichlorobicyclo[4.1.0]heptane (7,7-dichloronorcarane

+

NaOH,Pr3N

+

Synthesis of 7,7-dichlorobicyclo[4.1.0]heptane (7,7-dichloronorcarane) from cyclohexene

Reaction type:	addition to alkenes, elimination, cycloaddition
Substance classes:	alkene, carbene, chloroalkane
Techniques:	stirring with magnetic stir bar, adding dropwise with an addition funnel, distilling under reduced pressure, evaporating with rotary evaporator, shaking out, extracting, filtering, use of an ice cooling bath, heating with oil bath

http://kriemhild.uft.uni-bremen.de/nop/en/instructions/pdf/3005_en.pdf

Instruction (batch scale 100 mmol)
Equipment
100 mL three neck round bottom flask, reflux condenser, addition funnel with pressure
balance, heatable magnetic stirrer, magnetic stir bar, thermometer for inside of the flask,
separating funnel, destillation apparatus, rotary evaporator, oil bath, ice bath, vacuum pump
Substances
cyclohexene (bp 83 °C) 8.21 g (10.1 mL, 100 mmol)
chloroform (bp 61 °C) 48.0 g (32.7 mL, 400 mmol)
sodium hydroxide 16.0 g (400 mmol)
tri-n-propylamine (bp 156 °C) 0.14 g (0.19 mL, 1.0 mmol)
water 16 mL
ethanol (bp 78 °C) 1 mL
n-pentane (bp 36 °C) 120 mL
sodium sulfate for drying about 5 g
sodium chloride about 18 g
Reaction
Into a 100 mL three neck round bottom flask equipped with a reflux condenser addition
funnel, thermometer for measuring the inside temperature and magnetic stir bar, 8.21 g
(10.1 mL, 100 mmol) cyclohexene 0.14 g (0.19 mL, 1.0 mmol) tri-n-propylamine, 48.0 g
(32.7 mL, 400 mmol) chloroform and 1 mL ethanol is added. The mixture is cooled to 0 °C
with an ice bath, then under stirring and further cooling in the ice bath a solution of 16.0 g
(400 mmol) sodium hydroxide in 16 mL water is added through an addition funnel. The
mixture should be stirred vigourously during the next 20 minutes at 0 °C. After this time the
mixture is further stirred during 1 hour at room temperature and 3 hours at 50 °C.
Work up
Chloroform is evaporated with a rotary evaporator, then the residue is transferred with about
50 mL water and 30 mL n-pentane into a separating funnel. The organic phase is separated,
the aqueous phase is further extracted three times with 30 mL pentane. If an emulsion is
formed the aqueous phase is saturated with NaCl. The combined organic phases are dried over
sodium sulfate. The solution is filtered from sodium sulfate and the solvent is evaporated with
a rotary evaporator, yielding a nearly colourless liquid as crude product. The crude yield is
14.6 g. The crude product is distilled under reduced pressure.
Yield: 13.6 g (82.3 mmol, 82%), colourless liquid; bp 77 °C (11 hPa)

Operating scheme

Operating scheme

Equipment

Batch scale:

0.01 mol

0.1 mol

1 mol

Cyclohexene

	two-necked flask 10 mL			reflux condenser
	heatable magnetic stirrer with magnetic stir bar			thermometer
	graduated pipette			separating funnel
	microdistillation apparatus			rotary evaporator
	oil bath			ice bath
	vacuum pump

................




GC: pure productcolumnSE-54, L= 25 m, ID 0.32 mm, DF 0.25 µm (Macherey & Nagel)inletGerstel KAS, injector: 250°C, split injection 1:20, 0.15 µLcarrier gasN2, pre-column pressure 62 kPa, 1.04 mL/minoven80 °C (1 min), 10 °C/min --> 250 °C (30 min)detectorFID, 275 °Cintegrationpercent concentration calculated from relative peak area

1H-NMR: 7,7-Dichlorobicyclo[4.1.0]heptane
500 MHz, CDCl3
delta [ppm]	mult.	atoms	assignment
1.12-1.36	m	4 H	C4-H, C5-H
1.61-1.71	m	4 H	C3-H, C6-H
1.88-1.98	m	2 H	C1-H, C2-H
7.26	s	1 H	CHCl3

3C-NMR: 7,7-Dichlorobicyclo[4.1.0]heptane
125 MHz, CDCl3
delta [ppm]	assignment
18.9	C4, C5
20.2	C3, C6
25.8	C2, C1
67.4	C7
76.5-77.5	CDCl3

IR: 7,7-Dichlorobicyclo[4.1.0]heptane
[Film, T%, cm-1]
[cm-1]	assignment
2944, 2855	aliph. C-H valence
796	C-Cl valence

............
Ubud, Bali, Indonesia.

Ubud, Bali, Indonesia.

Ubud - Wikipedia, the free encyclopedia

https://en.wikipedia.org/?title=Ubud

Ubud is a town on the Indonesian island of Bali in Ubud District, located amongst rice paddies and steep ravines in the central foothills of the Gianyar regency.

‎History - ‎Streets - ‎Buildings - ‎Economy

https://en.wikivoyage.org/wiki/Ubud

1. Ubud

   Town in Indonesia
2. The town of Ubud, in the uplands of Bali, Indonesia, is known as a center for traditional crafts and dance. The surrounding Ubud District’s rainforest and terraced rice paddies, dotted with Hindu temples and shrines, are among Bali’s most iconic landscapes. Ancient holy sites include the Tirta Empul temple complex, intricately carved Goa Gajah (“Elephant Cave”) and Gunung Kawi with its rock-cut shrines.
4. Weather: 27°C, Wind E at 14 km/h, 79% Humidity
5. Local time: Thursday 6:54 PM
6. Province: Bali
7. Getting there: 9 h 10 min flight. View flights
8. Points of interest
   View 5+ more

   

   Ubud Monkey Forest

   

   Neka Art Museum

   

   Blanco Renaissance Museum

   

   Agung Rai Museum of Art

   

   Puri Lukisan Museum

Bali: Avilla Opens Bale Udang Indonesian Restaurant in Ubud

Food and Beverage

Following the the success of its Bale Udang Mang Engking Indonesian restaurant in Kuta, Avilla Hospitality has opened a second Indonesian eatery in Ubud.

Bale Udang Engking Bali in Ubud. Photo Credit: Avilla Hospitality.

Set amid rice paddies with a view of the surrounding emerald green mountains, Bale Udang Engking Bali in Ubud is built almost entirely of bamboo atop a large fish pond.

Bale is Indonesian for an open-air structure made of bamboo.

More Than a Restaurant

Bale Udang Mang Engking at night. Photo Credit: Avilla Hospitality.

With its innovative design and magnificent setting, Bale Udang Mang Engking is more than a restaurant. There are also recreational facilities, a main hall, a souvenir shop, the list goes on.

Signature Dish

Yummy Indonesian cuisine at Bale Udang Mang Engking in Bali. Photo Credit: Avilla Hospitality.

Udang Bakar Madu, Sup Kelapa Udang, and Gurame Bumbu Cobek are among the yummy Indonesian dishes on the menu. Prawns are the signature ingredient in many of the dishes.

Bale Udang Mang Engking will offer 20% off ala carte menu items through the end of February 2014.

Where

Jl. Rya Goa Gajah, Banjar Teges Kanginan, Desa Peliatan, Ubud, Bali, Indonesia. Telephone: : +62 361 978 754. Website: Bale Udang Ubud.

Your Response Wanted!

Have you ever been to Bali? What was your most memorable experience? Would you recommend the island to others as a travel destination?

Please post your comment in the Comment Box below or on Facebook at the following link: Accidental Travel Writer on Facebook. And don't forget to LIKE us while you're there!

Travel Tips

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The Purist, Ubud, Bali, Indonesia | kacangbakar

kacangbakar.wordpress.com

Highly recommended food in Ubud (must try!): Babi Guling Bu Oka (BBQ pig). The food and environment are experience by itself. It is not open everyday, ...

How Ubud restored my faith in Bali |

theatlasheart.com

The one place that made me reevaluate my initial perception of Bali was Ubud. Ubud is what I was expecting Bali to be: a bit more laid back, hippie, ...

Air Route to Bali

Bali is a small island among the thousands of islands in the territory of Indonesia. The total area of Bali, about 5636.66 km2 with a population of not less than 4 million people. The island is a nature blessed with white sandy beaches, mountains with natural tropical forests, and lakes are very intriguing.

Bali has a main entrance through Ngurah Rai International Airport, located in southern Bali, 13 km south of Denpasar, the capital of Bali. It is Indonesia's third-busiest international airport.

Puri Saren Agung (Water Palace) in central Ubud

Goa Gajah originates from the 9th century

Gunung Kawi, Tampaksiring

Hot springs at Tirta Empul, Tampaksiring

Rice terraces near Ubud

Puram Dalem dance performance

Legong dance performance

Inside Ubud Market

Babi Guling is a very popular dish for Balinese as well as tourists, and you can find it at most traditional markets and at roadside eateries as wel

The quite remarkable Four Seasons Hotel in the Ayung Valley, near Ubud

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