trans-2-(benzo[d][1,3]dioxol-5-yl)-2-methylcyclopropane-1-carbonitrile

trans-2-(benzo[d][1,3]dioxol-5-yl)-2-methylcyclopropane-1-carbonitrile

yellowish solid (53 mg, 66%);

m.p. = 72 °C;

1 H-NMR (600 MHz, CDCl3): δ = 6.77 – 6.71 (m, 3H), 5.94 (s, 2H), 1.63 – 1.59 (m, 4H), 1.50 (dd, J = 9.1, 5.0 Hz, 1H), 1.26 (t, J = 5.3 Hz, 1H);

13CNMR (151 MHz, CDCl3): δ = 147.80, 146.73, 136.69, 120.64, 120.23, 108.28, 108.17, 101.19, 28.75, 23.86, 21.40, 11.30;

HRMS (ESI): m/z calc. for [C12H11O2NK]: 240.0414, found 240.04204;

IR (KBr): νmax/cm-1 = 2972, 2897, 2231, 1490, 1457, 1434, 1349, 1226, 1080, 1033, 924, 869, 808, 728.

1H NMR PREDICT

13C NMR PREDICT

 Green Chem., 2017, Advance Article

DOI: 10.1039/C7GC00602K, Communication

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C[C@@]1([C@H](C#N)C1)C2=CC(OCO3)=C3C=C2

Efficient synthesis of isoquinolines in water by a Pd-catalyzed tandem reaction of functionalized alkylnitriles with arylboronic acids

Efficient synthesis of isoquinolines in water by a Pd-catalyzed tandem reaction of functionalized alkylnitriles with arylboronic acids

Green Chem., 2017, Advance Article
DOI: 10.1039/C7GC00267J, Paper

Kun Hu, Linjun Qi, Shuling Yu, Tianxing Cheng, Xiaodong Wang, Zhaojun Li, Yuanzhi Xia, Jiuxi Chen, Huayue Wu
Pd-catalyzed tandem reaction of functionalized alkylnitriles with arylboronic acids for the synthesis of diverse isoquinolines in water.

Kun Hu,^a   Linjun Qi,^a   Shuling Yu,^a   Tianxing Cheng,^a  Xiaodong Wang,^a   Zhaojun Li,^b   Yuanzhi Xia,^a  Jiuxi Chen*^a and   Huayue Wu^a  

*Corresponding authors

^aCollege of Chemistry & Materials Engineering, Wenzhou University, Wenzhou 325035, China
E-mail: jiuxichen@wzu.edu.cn

^bInstitute of Agricultural Resources and Regional Planning, Chinese Academy of Agricultural Sciences, Key Laboratory of Plant Nutrition and Fertilizer, Ministry of Agriculture, Beijing, China

Green Chem., 2017, Advance Article

DOI: 10.1039/C7GC00267J, 

A palladium-catalyzed tandem reaction of 2-(cyanomethyl)benzonitriles or 2-(2-carbonylphenyl)acetonitriles with arylboronic acids in water has been developed for the first time. This reaction features good functional group tolerance and provides a new strategy for the synthesis of diverse isoquinolines under mild conditions. The use of water as the reaction medium makes the synthesis process environmentally benign. Preliminary mechanistic experiments indicate that the major reaction pathway involves carbopalladation of the C(sp³)–cyano group and subsequent intramolecular cyclization findings that were further supported by density functional theory (DFT) calculations.

1,3-Diphenylisoquinoline (3a). Pale-yellow solid (103.5 mg, 92%),

mp 78-79 oC (lit.24,  73-74.5 oC). 24 J. D. Tovar and T. M. Swager, J. Org. Chem., 1999, 64, 6499

1H NMR (500 MHz, CDCl3) δ 8.25-8.23 (m, 2H), 8.15-8.14 (m, 1H), 8.09 (s, 1H), 7.95-7.93 (m, 1H), 7.84-7.83 (m, 2H), 7.70-7.67 (m, 1H), 7.59-7.50 (m, 6H), 7.44-7.40 (m, 1H);

13C NMR (125 MHz, CDCl3) δ 160.5, 150.3, 140.1, 139.8, 138.0, 130.4, 130.2, 128.8, 128.7, 128.6, 128.4, 127.7, 127.6, 127.2, 127.0, 126.0, 115.8.

//////// isoquinoline, pd-catalyzed, arylboronic acids

Heck–Matsuda Reaction in Flow

Product 3 was obtained as a mixture of diastereomers (58:42). The NMR data are consistent with literature precedent.20a

Major diastereomer: 1H NMR (300 MHz, CDCl3) δ (ppm) 7.25-7.28 (m, 2H), 7.14-7.17 (m, 2H), 5.14 (dd, 1H, J = 2.5, 5.8 Hz), 4.29 (t, 1H, J = 8.3 Hz), 3.79 (dd, 1H, J = 6.9, 8.4 Hz), 3.54-3.62 (m, 1H), 3.38 (s, 3H), 2.32 (dd, 1H, J = 7.7, 12.9 Hz), 2.04 (ddd, 1H, J = 5.1, 9.3, 13.1 Hz);

Minor diastereomer: 1H NMR (300 MHz, CDCl3) δ 7.25-7.28 (m, 4H), 5.16 (d, 1H, J = 4.4 Hz), 4.17 (t, 1H, J = 8.1 Hz), 3.72 (dd, 1H, J = 8.5, 9.7 Hz), 3.42 (s, 3H), 3.32-3.36 (m, 1H), 2.59 (ddd, 1H, J = 5.5, 10.3, 13.7 Hz), 1.91 (ddd, 1H, J = 2.4, 7.7, 10.2 Hz);

13C NMR (75 MHz, CDCl3) δ (ppm) 141.4, 140.0, 132.4, 132.3, 129.1, 128.7, 128.7, 128.5, 105.7, 105.4, 73.7, 73.0, 54.9, 54.7, 43.6, 42.1, 41.4, 41.1.

(20) (a) Oliveira, C. C.; Angnes, R. A.; Correia, C. R. D. J. Org. Chem. 2013, 78, 4373. (b) Oliveira, C. C.; Pfaltz, A.; Correia, C. R. D. Angew. Chem. Int. Ed. 2015, 54, 14036.

Org. Process Res. Dev., Article ASAP

DOI: 10.1021/acs.oprd.6b00310

The optimization of a palladium-catalyzed Heck–Matsuda reaction using an optimization algorithm is presented. We modified and implemented the Nelder–Mead method in order to perform constrained optimizations in a multidimensional space. We illustrated the power of our modified algorithm through the optimization of a multivariable reaction involving the arylation of a deactivated olefin with an arenediazonium salt. The great flexibility of our optimization method allows to fine-tune experimental conditions according to three different objective functions: maximum yield, highest throughput, and lowest production cost. The beneficial properties of flow reactors associated with the power of intelligent algorithms for the fine-tuning of experimental parameters allowed the reaction to proceed in astonishingly simple conditions unable to promote the coupling through traditional batch chemistry.

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BENZYL VINYL ETHER

Green Chem., 2016, Advance Article

DOI: 10.1039/C5GC02977E, Communication

Ryosuke Matake, Yusuke Adachi, Hiroshi Matsubara

A convenient preparation of vinyl ethers from alcohols with calcium carbide was developed. This protocol is an alternative to the Favorskii-Reppe reaction without any high pressure device.

Synthesis of vinyl ethers of alcohols using calcium carbide under superbasic catalytic conditions (KOH/DMSO)

 LINK       http://pubs.rsc.org/en/Content/ArticleLanding/2016/GC/C5GC02977E?utm_source=feedburner&utm_medium=feed&utm_campaign=Feed%3A+rss%2FGC+%28RSC+-+Green+Chem.+latest+articles%29#!divAbstract

Vinyl ethers are important and useful synthetic building blocks. Using a test tube with a screw cap, a convenient preparation of vinyl ethers from alcohols with calcium carbide under superbasic catalytic conditions (KOH/DMSO) was developed. The vinylation of primary and secondary alcohols was successfully achieved, affording the desired products in good yields. The gram-scale preparation of a vinyl ether was also demonstrated. In this reaction, calcium carbide acts as an acetylene source, constituting a safer alternative to acetylene gas.

 F. de Nanteuil, E. Serrano, D. Perrotta and J. Waser, J. Am. Chem. Soc., 2014, 136, 6239.

1H NMR

1H NMR PREDICT using nmrdb , signals may vary , use your discretion to understand sequence

13C NMR

13 C NMR PREDICT

Synthesis of vinyl ethers of alcohols using calcium carbide under superbasic catalytic conditions (KOH/DMSO)

Ryosuke Matake,^a   Yusuke Adachi^a and   Hiroshi Matsubara*^a  

*Corresponding authors

^aDepartment of Chemistry, Graduate School of Science, Osaka Prefecture University, Sakai, Japan

E-mail: matsu@c.s.osakafu-u.ac.jp

Green Chem., 2016, Advance Article

DOI: 10.1039/C5GC02977E

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2-(BENZYLOXYL)-6-ETHYL-2H-PYRAN-4-ONE

 

see………http://orgspectroscopyint.blogspot.in/2015/12/6-ethyl-4-hydroxy-2-pyrone.html

 

 

see………http://orgspectroscopyint.blogspot.in/2015/12/6-ethyl-4-hydroxy-2-pyrone.html

 

DRUG APPROVALS BY DR ANTHONY MELVIN CRASTO …..FOR BLOG HOME CLICK HERE

 

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////////

8-Oxo-5-aza-spiro[2.5]octane-5-carboxylic acid benzyl ester,

1H NMR

STR 4 SEE BELOW

STRUCTURE5=

SEE SYNTHESIS AT……….http://orgspectroscopyint.blogspot.in/2015/07/8-oxo-5-aza-spiro25octane-5-carboxylic.html

1H NMR PREDICT OF TITLE COMPD

…………………………………
13C NMR PREDICT

……………….

8-Oxo-5-aza-spiro[2.5]octane-5,7-dicarboxylic acid 5 benzyl ester 7 methyl ester
COMPD 5

SYNTHESIS CONSTRUCTION BY WORLDDRUGTRACKER………EXCLUSIVE

 

सुकून उतना ही देना प्रभू, जितने से जिंदगी चल जाये। औकात बस इतनी देना, कि औरों का भला हो जाये।
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LIONEL MY SON

He was only in first standard in school when I was hit by a deadly one in a million spine stroke called acute transverse mylitis, it made me 90% paralysed and bound to a wheel chair, Now I keep him as my source of inspiration and helping millions, thanks to millions of my readers who keep me going and help me to keep my son happy

सुकून उतना ही देना प्रभू, जितने से
जिंदगी चल जाये।
औकात बस इतनी देना,
कि औरों का भला हो जाये।

 

////////////

Scalable Access to Aeruginosins

Scalable Access to Aeruginosins

Palladium-catalyzed C–H activation reactions

Read more

http://www.chemistryviews.org/details/ezine/7956351/Scalable_Access_to_Aeruginosins.html

 

 

http://www.mdpi.com/1660-3397/13/4/2347

 

 

सुकून उतना ही देना प्रभू, जितने से जिंदगी चल जाये। औकात बस इतनी देना, कि औरों का भला हो जाये।
DRUG APPROVALS BY DR ANTHONY MELVIN CRASTO …..FOR BLOG HOME CLICK HERE

Join me on Linkedin

Join me on Facebook FACEBOOK

Join me on twitter

Join me on google plus Googleplus

 amcrasto@gmail.com

LIONEL MY SON

He was only in first standard in school when I was hit by a deadly one in a million spine stroke called acute transverse mylitis, it made me 90% paralysed and bound to a wheel chair, Now I keep him as my source of inspiration and helping millions, thanks to millions of my readers who keep me going and help me to keep my son happy

सुकून उतना ही देना प्रभू, जितने से
जिंदगी चल जाये।
औकात बस इतनी देना,
कि औरों का भला हो जाये।

 

 

One rotaxane, two catalytic stories

read at

http://www.rsc.org/chemistryworld/2014/12/switchable-rotaxane-catalysis

Light drives unusual rotaxane-to-catenane transformation

read at

http://www.rsc.org/chemistryworld/2015/01/rotaxane-catenane-transformation-light

Synthesis of 2-dimethylaminomethyl-cyclohexanone hydrochloride

http://orgspectroscopyint.blogspot.in/2014/09/synthesis-of-2-dimethylaminomethyl.html
++

EtOH, HCl

Synthesis of 2-dimethylaminomethyl-cyclohexanone hydrochloride

Reaction type:	reaction of the carbonyl group in aldehydes, Mannich reaction
Substance classes:	ketone, aldehyde, amine
Techniques:	heating under reflux, stirring with magnetic stir bar, evaporating with rotary evaporator, filtering, recrystallizing, heating with oil bath
Degree of difficulty:	Easy

Equipment

	round bottom flask 25 mL			reflux condenser
	suction filter			suction flask
	heatable magnetic stirrer with magnetic stir bar			rotary evaporator
	exsiccator with drying agent			oil bath

 

 

 

 

 

 

Instruction (batch scale 100 mmol) 

Equipment 

100 mL round bottom flask, reflux condenser, Buechner funnel (Ø 5.5 cm), suction flask, 

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

Substances 

cyclohexanone (bp 156 °C) 9.82 g (10.3 mL, 100 mmol) 

paraformaldehyde (mp 120-170 °C) 3.60 g (120 mmol) 

dimethylammonium chloride 8.16 g (100 mmol) 

hydrochloric acid (conc.) 0.4 mL 

ethanol (bp 78 °C) 64 mL 

acetone (bp 56 °C) 180 mL 

 

Reaction 

9.82 g (10.3 mL, 100 mmol) cyclohexanone, 3.60 g (120 mmol) paraformaldehyde, 8.16 g 

(100 mmol) dimethylammonium chloride and 4 mL ethanol are filled in a 100 mL round 

bottom flask with reflux condenser and magnetic stir bar. 0.4 mL conc. hydrochloric acid are 

added and the mixture is heated under stirring for 4 hours under reflux. 

Work up 

The hot solution is filtered in a round-bottom flask and the solvent is evaporated at the rotary 

evaporator. The residue is dissolved in 20 mL ethanol under heating. At room temperature 

70 mL acetone are added to the solution. For complete crystallization the solution is stored 

over night in the freezer compartment. The crystallized crude product is sucked off over a 

Buechner funnel (Ø = 5.5 cm) and dried in the desiccator over silica gel. 

Crude yield: 15.6 g; mp 149-150 °C 

For further purification the crude product is again dissolved in about 40 mL ethanol under 

reflux and at room temperature 110 mL acetone are added. The crystallization is completed in 

the freezer compartment. The product is sucked off and dried in the desiccator. 

Yield: 14.7 g (76.7 mmol, 77%,); mp 156-157 °C 

Comments 

To verify a complete crystallization, the mother liquor is stored in the freezer compartment. 

No product should crystallize any further.

 

 

 

 

 

Simple evaluation indices

Atom economy		not defined
Yield		76	%
Target product mass		1.45	g
Sum of input masses		54	g
Mass efficiency		27	mg/g
Mass index		37	g input / g product
E factor		36	g waste / g product

 

 

 

 

 

 

 

 

 

 

1H-NMR: 2-Dimethylaminomethyl cyclohexanone hydrochloride
500 MHz, CDCl3
delta [ppm]	mult.	atoms	assignment
1.35	m	1 H
1.54	m	1 H
1.73	m	1 H
1.82	m	1 H
2.05	m	1 H
2.37	m	2 H	6-H (ring)
2.41	m	1 H
2.67	d	3 H	N-CH3
2.74	m	1 H
2.77	d	3 H	N-CH3
3.09	m	1 H	N-CH2
3.57	m	1 H	N-CH2
11.88	m	1 H	N-H
7.26			CHCl3

 

 

 

13C-NMR: 2-Dimethylaminomethyl cyclohexanone hydrochloride
125 MHz, CDCl3
delta [ppm]	assignment
24.70	C5
27.70	C3
33.88	C4
41.75	CH3
42.26	CH3
44.99	C6
46.69	C2
56.80	-CH2-N-
209.58	C1 (C=O)
76.5-77.5	CDCl3

 

 

 

 

IR: 2-Dimethylaminomethyl cyclohexanone hydrochloride
[Film, T%, cm-1]
[cm-1]	assignment
3068, 3020	N-H valence
2932, 2858	C-H valence
1698	C=O valence, ketone

 

http://kriemhild.uft.uni-bremen.de/nop/en/instructions/pdf/4008_en.pdf