Stereochemistry of Molecules in Crystals (part 1, 2)

Fumio TodaOkayama University of Science, Okayama, Japan

key word: solid state, host-guest complex

part 1: statistic aspectpart 2: dynamic aspect

ROH OH

∆BrPh

R BrPh

in, out

∆BrPh

in, in

out, out

HBr, W-H rule (conrotatory)

R = Me

part 2: dynamic aspect(I) Thermal cyclization of diallenes in own crystals

Angew. Chem. Int. Ed. 1988, 2724.

1) dimethylenecyclobutene

tButBu

colorless prisms

∆140 º

solid Ph

PhtButBu

green prisms

2) benzodicyclobutadiene

tButBu

∆140 º

solidPh

PhtBu tBu

Ph 1.407

Chem. Commun. 1999, 319.Eur. J. Org. Chem. 2000, 1377.

Table 1. Calculated (B3LYP/6-31G* and MP2/6-31G*) geometries and relative energies of the isomeres of 2.

Isomer

MP2/6-31G*

B3LYP/6-31G*

R1 R2 R3 R4 ∆E/kcal mol-1

1.3943

1.3898

1.3944

1.3888 1.5461

1.4026

1.5545

1.4082 1.5361

1.3921

1.5430

1.3916

1.3456

1.4587

1.3456

1.4583

1 2a 2b

2c 2d3

Ph2COH

3) naphthocyclobutenes

Angew. Chem. Int. Ed. 1994, 1757.

Mesolid

180 ºC, 30 min

PhPh Exptl. 1.720 Å

1.710 Å at 90 K

B3YLP/613G* 1.732 Å

B3YLP/613G* 1.731 Å

M. Kertesz 1997

P. v. R. Schleyer 1998

through bond interaction

B3YLP/dz(2d, p) 1.708 Å

J. S. Siegel 1998

(II) Phase transitions in crystals1) photodimerizatin of 2-pyridones

3 456 O

thymine in DNA

HNO O O

syn/anti

complex complex

cis-anti dimer cis-anti dimer

COOHHOOC

X=Cl, Me cis-anti dimer

Chem. Commun., 2005, 643; Mendeleev Commun., 2004, 247; Heterocycles, 2004, 383.

ClCOOH

HOOC NH

O4hν ∆

meso-cis-syn dimer

MeOH hν

∆ or

MeOHsolvent

- MeOH

MeOHvapor

grinding

MeOHvapor

8 9 10

MeOHvapor

CH3CNvapor

HOOC COOH

6meso-cis-syn dimer

Orac-trans-anti dimer

Scheme 1. Reversible phase transition between photochemically nonreactive and reactive complexes. For clarity host is omitted

A reversible phase transition between photochemically nonreactive and reactive complexes

HOOC COOHNH

MeOH··

Fig. X-ray structure of 8 (top view)

Fig. X-ray structure of the 1:1:1 complex of host:5-methyl-2-pyridone:MeOH (8).

HOOC COOH

Fig. Packing diagram of 10.

Fig. Distances between 5-methyl-2-pyridone molecules in 10.

2) succinamide

PhMeOH

Achiral

260 ºC

Achiral

B Crac rac

orange hexagonalsmp 260 ºC

orange plates302 ºC

yellow plates297 ºC

P21Pbcn P21/n

3) tetraphenyletheneBr

solvent vaporcomplex with

P-1 M-1

and / or

rac or chiral

Table 1. Inclusion complexation of 1 with some guest compounds

Inclusion complex

By recrystallization By gas-solid reaction

host : guestGuest host : guest t/h

Acetone chiral 1 : 2 a a 168

Cyclohexanone rac 1 : 1 a a 168

rac 1 : 2

chiral 1 : 1

rac 1 : 1

chiral 1 : 1

rac 1 : 1

chiral 1 : 2

chiral 1 : 1

chiral 1 : 1a a

chiral 1 : 1

1,4-Dioxane

Benzene

Toluene

p-Xylene

β-Picolinea No complexation occurred.

Chem. Comm. 2000, 413.

(R, R)-(-)-

(R, R)-(-)- H

MeOMePh

(R, R)-(-)- H

MeOPhMe

MeMe(+)-

76% ee

4 h 5 h

4) oxoamide

Chem. Lett. 1995, 809.

3aracemate

OHOH Me4NCl

conglomerate complex

Me4NCl

(S)-(−)-BNO Me4NCl

5) BNO

Me4N Cl

racemic complex conglomerate complex

3b Me4NCl + 3c Me4NCl3a Me4NClMeOHMeOH

3a7 ml 15 ml

1.43 g

0.55 g

Me4N Cl

racemic complex conglomerate complex

3b Me4NCl + 3c Me4NCl3a Me4NClMeOH vaporsolid-state

rt, 170 h rt, 1 h

phase transition

Tetrahedron. 2004, 7767; Chem. Comm. 2004, 1844.

racemate complex

OHOH Me4N Cl

or MeOH vaporconglomerate complex

30 min

160 C, 5 min

MeOH vapor

guest host : guest ratio[a] decomp. (°C)

Me2C=O

79-107

87-117

94-121

97-141

87-128

νOH (cm-1) [b]

3036, 3404

3321, 3419

3264, 3417

Table 1. Data of inclusion complexes of 3a with various liquid guests.

87-108

48-106

61-116

3419, 3459, 3489

3173, 3519

83-108

75-105

3403, 3463, 3491

3413, 3464, 3490

(CPME)

complex

[a] The ratio was determined by 1H NMR spectra and TG analysis.[b] IR spectra were measured by using the ATR (Attenuated total reflection) method.

OHOHrac-

(III) Seed crystals in the solid state

3a (0.2 g)

3:1 complex (5) 1:2 complex (4)3 ml 5 ml

Et2O Et2O

4 mlEt2O

4 or 5

Scheme 1. Inclusion complexation of 3a and Et2O by recrystallization of 3a from Et2O solutions of different concentration.

can be controlled bya seed crystal

Figure 1. Crystal structure of the 1:2 complexof 3a and Et2O (4).

Figure 2. Crystal structure of the 3:1 complexof 3a and Et2O (5).

(S)-(−)-form

(R)-(+)-form

Scheme 1. Memory of inclusion pattern.

rac- · 2Et2O

-Et2O, ∆ / vacuo

Et2O vaporEt2O - free BNO

rac- ·

-Et2O, ∆ / vacuo

Et2O vapor

Et2O - free BNO3 Et2O

4, Et 2O

5, Et2 O

−Et2O

Scheme 2. Seed crystal experiments in the inclusion complexationbetween solid host and gaseous Et2O guest.

5, Et 2O

4, Et2 O

OHOHrac-

Angew. Chem. Int. Ed. 2005, in press.

guest (3a:guest ratio)in seed crystal

reactiontime (h)

guest (3a:guest ratio)in product

gaseousguest

AcOMe (3 : 1) Et2O 3

AcOEt (3 : 1) Et2O 3

AcOMe (3 : 1) CPME 12

CPME (1 : 2) Et2O 12

Et2O (3 : 1) CPME 12

AcOMe (3 : 1) AcOEt 3

AcOE t (3 : 1) AcOMe 3

Et2O (3 : 1) AcOMe 3

Et2O (1 : 2) CPME 12

Et2O (3 : 1)

Et2O (1 : 2)

AcOEt (3 : 1)

AcOMe (3 : 1)

CPME (1 : 2)

Table . Inclusion complexation of powdered rac-BNO (3a) andgaseous guest in the presence of pseudo seed crystal.

Stereochemistry of Molecules in Crystals (part 1, 2)

Documents

Transcript of Stereochemistry of Molecules in Crystals (part 1, 2)

Chapter 5 Stereochemistry: Chiral Molecules

Stereochemistry Stereochemistry refers to the 3-dimensional properties and reactions of molecules. It has its own language and terms that need to be learned.

STEREOCHEMISTRY - Nptel · Stereochemistry of molecules dictates isomerism, chemical and biochemical reactivity. Reactivity. These days, chiral drugs have become an integral part

cup.edu.incup.edu.in/cup_old-website/hindi_website/Syllabi/CPS... · Web view2018. 1. 18. · Stereochemistry: IUPAC nomenclature of organic molecules, Elements of symmetry, chirality,

STEREOCHEMISTRY OF ALKANES AND … · CONFORMATIONAL ISOMERS •Stereochemistry concerned with the 3-D aspects of molecules •Rotation is possible around C-C bonds in open-chain

Stereochemistry Content Review - Med-Pathway Stereoch… · Stereochemistry of covalently bonded molecules Isomers Structural isomers Stereoisomers (diastereomers, enantiomers, cis/trans

Symmetry of Molecules and Crystals...1 Symmetry of Molecules and Crystals What does symmetry mean? Symmetry (Greek = harmony, regularity) means the repetition of a motif and thus the

Crystals, Metals and Addition Polymers. Crystals Crystals are formed by ions, atoms or molecules arranged in a regular geometric arrangement called a.

Stereochemistry: Chiral Molecules

Solid ––– liquid – gas liquid – gas · Liquid crystals KJM3100 V2006 Smectic liquid crystals are turbid and viscous substances “goo”. Their molecules are arranged into

Crystal Structures Unit 6 Chapter 12. Madame Vorba says… Crystals are highly structured arrangements of atoms in a lattice. Crystals allow atoms/molecules.

LUMINESCENCE OF CRYSTALS, MOLECULES, AND SOLUTIONS978-1-4684-2043-2/1.pdf · LUMINESCENCE OF CRYSTALS, MOLECULES, AND SOLUTIONS Proceedings of the International Conference on Luminescence

Stereochemistry - Elsevier · 2014-06-26 · 241 8 stereochemistry 8.1 stereoisomers 8.2 mirror image objects, mirror image molecules, and chirality Molecules that have different

Water and Ice and Their Molecules and Crystals

Chapter 5 Stereochemistry: Chiral Molecules 1.

Module 8 Stereochemistry Lecture 20 Stereochemistry I

Will stick to isolated, finite molecules (not crystals).

Stereochemistry of small molecules: Configurational and ...Stereochemistry of small molecules: Configurational and conformational control Yiqun Zhang Dissertation submitted to the

Using Switchable Fluorescent Molecules to Image Tracks and … · 2019. 12. 9. · Photochromism of diarylethene molecules and crystals: memories, switches, and actuators. Chemical

Molecular Crystals. Molecular Crystals: Consist of repeating arrays of molecules and/or ions.