4,4,5,5-tetramethyl-2-phenethyl-1,3,2-dioxaborolane

http://orgsyn.org/demo.aspx?prep=v94p0234

 4,4,5,5-Tetramethyl-2-phenethyl-1,3,2-dioxaborolane (1) has the following physical and spectroscopic properties: R_f = 0.47 (3:97, ethyl acetate:pentane), the checkers report the following values for 1: R_f = 0.09 (3:97 ethyl acetate:pentane); R_f = 0.52 (10% EtOAc in hexanes); Merck silica gel 60 F254 plate; mp 38-39 °C; 

¹H NMR pdf(CDCl₃, 400 MHz) δ: 1.18 (t, J = 8.4 Hz, 2H), 1.26 (s, 12H), 2.79 (t, J = 8.0 Hz, 2H), 7.16-7.22 (m, 1H), 7.23-7.32 (m, 4H); 

¹³C NMR pdf(CDCl₃, 151 MHz) d: 25.0, 30.1, 83.2, 125.6, 128.1, 128.3, 144.6 [N.B. the carbon attached to boron was not observed due to quadrupolar relaxation]; 

HRMS (ESI⁺) calculated for C₁₄H₂₂BO₂⁺ = 233.1707, mass found = 233.1710; 

IR (film): 3026, 2978, 2929, 1372, 1318, 1139, 848, 755, 703 cm^-1; 

Anal. calcd for C₁₄H₂₁BO₂: C, 72.44; H, 9.12. Found: C, 72.18; H, 9.28. 

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2,2,5,5-Tetramethyltetrahydrofuran (TMTHF): a non-polar, non-peroxide forming ether replacement for hazardous hydrocarbon solvents

2,2,5,5-Tetramethyltetrahydrofuran (TMTHF): a non-polar, non-peroxide forming ether replacement for hazardous hydrocarbon solvents

Green Chem., 2017, Advance Article
DOI: 10.1039/C7GC01392B, Paper

Fergal Byrne, Bart Forier, Greet Bossaert, Charly Hoebers, Thomas J. Farmer, James H. Clark, Andrew J. Hunt
An inherently non-peroxide forming ether solvent, 2,2,5,5-tetramethyltetrahydrofuran (2,2,5,5-tetramethyloxolane), has been synthesized from readily available and potentially renewable feedstocks, and its solvation properties have been tested

• From the journal:
  

  Green Chemistry

2,2,5,5-Tetramethyltetrahydrofuran (TMTHF): a non-polar, non-peroxide forming ether replacement for hazardous hydrocarbon solvents

 

Fergal Byrne,^a  Bart Forier,^b  Greet Bossaert,^b  Charly Hoebers,^b  Thomas J. Farmer,^a  James H. Clark^a  and  Andrew J. Hunt*^a 

*Corresponding authors

^aGreen Chemistry Centre of Excellence, University of York, York YO10 5DD, UK
E-mail: andrew.hunt@york.ac.uk

^bNitto Belgium, NV Eikelaarstraat 22, Belgium

http://pubs.rsc.org/en/Content/ArticleLanding/2017/GC/C7GC01392B?utm_source=feedburner&utm_medium=feed&utm_campaign=Feed%3A+rss%2FGC+%28RSC+-+Green+Chem.+latest+articles%29#!divAbstract

Abstract

An inherently non-peroxide forming ether solvent, 2,2,5,5-tetramethyltetrahydrofuran (2,2,5,5-tetramethyloxolane), has been synthesized from readily available and potentially renewable feedstocks, and its solvation properties have been tested. Unlike traditional ethers, its absence of a proton at the alpha-position to the oxygen of the ether eliminates the potential to form hazardous peroxides. Additionally, this unusual structure leads to lower basicity compared with many traditional ethers, due to the concealment of the ethereal oxygen by four bulky methyl groups at the alpha-position. As such, this molecule exhibits similar solvent properties to common hydrocarbon solvents, particularly toluene. Its solvent properties have been proved by testing its performance in Fischer esterification, amidation and Grignard reactions. TMTHF's differences from traditional ethers is further demonstrated by its ability to produce high molecular weight radical-initiated polymers for use as pressure-sensitive adhesives.

[TMTHF].

1H NMR (400 MHz, CDCl3): δ 1.81 (s, 4H), 1.21 (s, 12H);

13C NMR (400 MHz, CDCl3): δ 29.75, 38.75, 80.75;

IR 2968, 2930, 2968, 1458, 1377, 1366, 1310, 1265, 1205, 1144, 991, 984, 885, 849, 767 cm−1;

m/z (%): (ESI–MS) 128 (40) [M+ ]

Fergal Byrne

PHD Researcher at Green Chemistry Centre of Excellence

University of York

York, United Kingdom

Green Chemistry Centre of Excellence, University of York, York YO10 5DD, UK 

Andrew Hunt

The University of York , York · Green Chemistry Centre of Excellence

Catalysis, Environmental Chemistry, Green Chemistry

PhD.

The University of York

Green Chemistry Centre of Excellence

York, England, United Kingdom

 

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NMR predict

[TMTHF].

1H NMR (400 MHz, CDCl3): δ 1.81 (s, 4H), 1.21 (s, 12H);

 

13C NMR (400 MHz, CDCl3): δ 29.75, 38.75, 80.75;

5,6-dihydropteridin-7(8H)-one

5,6-dihydropteridin-7(8H)-one

 

Org. Process Res. Dev., 2017, 21 (1), pp 11–17

DOI: 10.1021/acs.oprd.6b00219

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3,3′,5,5′-Tetramethyl-2,2′-biphenol

3,3′,5,5′-Tetramethyl-2,2′-biphenol

10.0 g of 2,4-dimethylphenol.................. of 3,3,′,5,5′-tetramethyl-2,2′-biphenol.¹H NMR (400 MHz, CDCl₃) δ = 7.00–7.03 (m, 2H) 6.87–6.90 (m, 2H), 4.94 (s, 2H, OH), 2.30 (s, 12H). ¹³C NMR (100 MHz, CDCl₃) δ = 149.26, 132.14, 130.14, 128.64, 125.31, 122.30, 20.57, 16.31. Mp: 135 °C. GC purity >98%. Analytical data are in agreement with those previously reported.(37)

Kirste, A.; Nieger, M.; Malkowsky, I. M.; Stecker, F.; Fischer, A.; Waldvogel, S. R. Chem. - Eur. J. 2009, 15,2273– 2277, DOI: 10.1002/chem.200802556

  

• 2,2'-Biphenyldiol, 3,3',5,5'-tetramethyl- (8CI)
• 6,6'-Bi-2,4-xylenol (6CI,7CI)
• 3,3',5,5'-Tetramethyl[1,1'-biphenyl]-2,2'-diol
• 2,2'-Dihydroxy-3,3',5,5'-tetramethylbiphenyl
• 3,3',5,5'-Tetramethyl-2,2'-biphenol

• 3,3',5,5'-Tetramethyl-[1,1'-biphenyl]-2,2'-diol
• 3,3',5,5'-Tetramethylbiphenyl-2,2'-diol

cas 26567-10-2

 

Scalable and Selective Preparation of 3,3′,5,5′-Tetramethyl-2,2′-biphenol

Thomas Quell^†, Nadine Hecken^†, Katrin M. Dyballa^‡, Robert Franke^‡§, and Siegfried R. Waldvogel^*† 

^† Institut für Organische Chemie, Johannes Gutenberg-Universität Mainz, Duesbergweg 10-14, D-55128 Mainz, Germany

^‡ Evonik Industries AG, Paul-Baumann-Straße 1, D-45772 Marl, Germany

^§ Lehrstuhl für Theoretische Chemie, Ruhr-Universität Bochum, D-44780 Bochum, Germany

Org. Process Res. Dev., Article ASAP

DOI: 10.1021/acs.oprd.6b00356, http://pubs.acs.org/doi/full/10.1021/acs.oprd.6b00356

*E-mail: waldvogel@uni-mainz.de.

P.S. : The views expressed are my personal and in no-way suggest the views of the professional body or the company that I represent.

///////////3,3′,5,5′-Tetramethyl-2,2′-biphenol, scaleup

2,3,4,4a,5,6-hexahydro-1H-pyrido[1,2-a]quinolone (R)-7

1H NMR (500 MHz, CDCl3): δ 7.82 (br s, 1H), 7.28-7.34 (m, 2H), 7.22-7.24 (m, 1H), 3.87 (m, 1H), 3.56 (m, 1H), 3.32 (m, 1H), 3.00-3.03 (m, 2H), 2.46-2.74 (m, 3H), 1.65-2.05 (m, 5H);

13C NMR (100 MHz, CDCl3): δ 137.6, 130.4, 129.2, 127.9, 124.1, 55.9, 54.5, 27.3, 25.2, 22.9, 20.3, 17.1;

Enantiomeric excess was determined by SFC: Chiralpak OD-3, 4.6 mm x 150 mm, particle size: 3 μm, temperature: 30 ºC, A: CO2, B: ethanol with 0.2% of isobutylamine, isocratic: A/B: 95/5, v/v, flow rate 3.0 mL/min.

HRMS (ESI) [M+H]+ m/z calcd for [C13H18N]+ is 188.1361 found 188.1429.

Synthesis of Enantioenriched 2‐Alkyl Piperidine Derivatives through
Asymmetric Reduction of Pyridinium Salts
Bo Qu,* Hari P. R. Mangunuru, Xudong Wei, Keith R. Fandrick, Jean-Nicolas Desrosiers, Joshua D.
Sieber, Dmitry Kurouski, Nizar Haddad, Lalith P. Samankumara, Heewon Lee, Jolaine Savoie, Shengli
Ma, Nelu Grinberg, Max Sarvestani, Nathan K. Yee, Jinhua J. Song and Chris H. Senanayake
Chemical Development, Boehringer Ingelheim Pharmaceuticals, Inc. 900 Ridgebury Road,
Ridgefield, CT 06877 USA
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1 - (4,5,6,7 - tetrachloro - 1,3 - dioxoisoindolin - 2 - yl)cyclohexane - 1 - carboxylic acid (TCPTCC)

1 - (4,5,6,7 - tetrachloro - 1,3 - dioxoisoindolin - 2 - yl)cyclohexane - 1 - carboxylic acid (TCPTCC)

Mp : 261 °C;  Rf : 0.52 (SiO 2,  CH 2 Cl 2 :MeOH 9:1);

1 H NMR (400 MHz, DMSO - d 6 )  δ 13.15 (s, 1H), 2.76 (d,  J = 12.6 Hz, 2H), 2.00  – 1.82 (m, 2H), 1.70  – 1.36 (m, 6H);

13 C NMR (101 MHz, DMSO - d 6 )  δ 172.9 (1C), 164.1 (2C), 138.6 (2C), 128.1 (2C), 127.4 (2C), 65.7 (1C),  31.2 (2CH 2 ), 24.5 (2CH 2 ),  21.9 (CH 2 );

 IR (neat)  ṽ /cm - 1 : 2934, 2859, 2530, 1780, 1699, 1456,  1421, 1363, 1320, 1289, 1252, 1218, 1198, 1146, 1160, 1106, 1047, 955, 931, 913, 849, 786,  741,  720,  654,  618,  593,  528;

HR - MS  (ESI):  m/z =  407.9359  [M−H] − (calculated  for  C 15 H 10 Cl 2 NO 4, m/z  = 407.9369)
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African Baobab Tree, Adansonia digitata

The African Baobab Tree (Adansonia digitata) is a tree with many
stories and interesting facts.

The baobab tree can be found all over the African continent and even
Madagascar. It reaches heights of 16 to 98 feet and has a trunk diameters
of 23 to 36 feet. Flowers are large being up to 7 inches in size. The
tree produces edible fruit, called monkey bread as especially baboons
love it. The fruit has a sour taste. In the African culture the
fruit, seeds and even young leaves and seedlings are used for local
dishes and drinks.

The African tribes call the tree "the upside down tree". When bare of
leaves, the spreading branches of the Baobab look like roots sticking
up into the air as if it had been planted upside-down. An African
legend tells that the baobab was amongst the first trees to appear on
Earth. When the palm tree, the flame tree and the fig tree appeared,
the Baobab began to grumble that it wanted to be taller, to have
brilliant flame colored flowers, and bear tasty fruit too. The Gods
grew angry at this incessant wailing and pulled up the tree by its
roots, and replanted in upside down to keep it quiet!

The African baobab tree is also called the "tree of life" as it can store
water during the drought season which is sometimes vital to the rural
population. Large baobab trees could contain more than 30,000 gallons
of water, and to get to it, Kalahari bushmen use hollow pieces of
grass like a straw to suck the water out.

The baobab is Africa's latest fair trade sensation. On July 15, 2008 the
European Union has officially approved the export of powdered baobab
fruit to the United Kingdom as a healthy additive to cereal bars and
smoothies. The baobab is said to have three times the vitamin C
content of an orange, and as much calcium as a glass of milk.
According to Britain's University of Southampton, the baobab is rich
in vitamin B1, B2, and C, and calcium, plus it's bursting with antioxidants.

Natural medicine uses the bark of the Baobab to lower fevers, chewing a
leaf will wake you up and ingesting some of the tartar powder will
help with stomach aches.

The citric and tartaric acids found in the pulp provide the base for cream
of tartar, often used as a baking ingredient.

Because of their size, people have been storing supplies in old hollow
trunks or have been living inside a Baobab Tree. In rural Africa the
bark is used to make ropes and even clothing.

I hope you have enjoyed this trip to the continent of Africa to see and
learn about the Baobab tree.

AND THE BEST ONE... IMAGINE THIS...

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5- (4,4,5,5-TETRAMETHYL-1,3,2-DIOXABORONYL-2-YL)PYRIMIDINE -2-AMINE

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