Pyran derivatives containing an exocyclic double bond

• US 20050038267A1
• Filed: 05/25/2004
• Published: 02/17/2005
• Est. Priority Date: 05/27/2003
• Status: Active Grant

• Current Assignee: Merck Patent GmbH (Merck & Co., Inc.)
• Original Assignee: Merck Patent GmbH (Merck & Co., Inc.)
• Inventors: Meyer, Volker, Luessem, Georg, Poetsch, Eike, Heckmeier, Michael, Binder, Werner, Guertler, Stephan
• Granted Patent: US 7,314,943 B2
• Time in Patent Office: Days
• US Class Current: 549/294
• CPC Class Codes: C07C 33/483 Monocyclic
• CPC Class Codes: C07C 43/176 having unsaturation outside the aromatic rings
• CPC Class Codes: C07D 309/20 with hydrogen atoms and substituted hydrocarbon radicals directly attached to ring carbon atoms
• CPC Class Codes: C07D 309/22 Radicals substituted by oxygen atoms
• CPC Class Codes: C07D 309/28 with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
• CPC Class Codes: C09K 19/3402 having oxygen as hetero atom sugars C09K19/0422
• CPC Class Codes: C09K 2019/327 containing a spiro ring system
• CPC Class Codes: C09K 2019/3422 the heterocyclic ring being a six-membered ring

Abstract

The invention relates to pyran derivatives of formula I and processes and intermediates for their preparation and derivatisation, and the use thereof in liquid-crystalline media.

Claims

1. A compound of formula I

2. A compound according to claim 1, wherein a+b+c+d+e<

3.

3. A compound according to claim 1, wherein

W is —

C(═

O)—

.

4. A compound according to claim 1, wherein

W is —

CH₂—

.

5. A compound according to claim 1, wherein

Z¹² is a single bond.

6. A compound according to claim 5, wherein

a and b are zero;

and

R¹¹ is H.

7. A compound according to claim 1, wherein

Z¹³ is a single bond, —

C(O)—

O—

or —

CF₂O—

.

8. A compound according to claim 1, wherein

a is zero;

b is 1;

Z¹¹ is a single bond; and

A¹² is

9. A compound according to claim 1, wherein

c, d and e are simultaneously zero;

Z¹³ is —

C(O)—

O—

; and

R¹² is H, aralkyl, alkanyl or alkenyl.

10. A compound according to claim 1, wherein

e is 1;

A¹⁵ is

L¹¹ and L¹² independently of one another, are H or F.

11. A compound according to claim 1, wherein

at least one of c and d is 1;

e is 1; and

Z¹⁴ and Z¹⁵ independently of one another, are a single bond or —

CF₂O—

.

12. A compound according to claim 1, wherein

e is 1;

A¹⁵_—

12 is

A¹⁵-R¹ is

R¹³ and R¹⁴ are as defined in claim 1.

13. A process for the preparing a pyran compound of formula I according to claim 1, comprising converting in an enyne metathesis reaction in the presence of a metathesis catalyst an enyne compound of formula II to a pyran compound of formula I,

14. A process according to claim 13, wherein the metathesis catalyst is a ruthenium-alkylidene complex.

15. A process for preparing a pyran compound of formula I according to claim 1, comprising obtaining a pyran compound of formula I in the presence of a metathesis catalyst from a cross metathesis reaction of a pyran compound of formula I-C and of an alkene compound of formula IIIa or formula II b

16. A process according to claim 15, wherein the metathesis catalyst is a ruthenium-alkylidene complex.

17. A process according to claim 13, wherein a compound of formula I-C is prepared, and said process further comprises obtaining a pyran compound of formula I in the presence of a metathesis catalyst from a cross metathesis reaction of a pyran compound of formula I-C and of an alkene compound of formula IIIa or formula IIIb

18. A process according to claim 13, further comprising after the metathesis reaction, when in the compound of formula I, W is —

C(═

O)— and

Z¹³, Z¹⁴ and Z¹⁵ are not —

C(O)—

, a reduction reaction for conversion of said compound of formula I into a pyran compound of formula I in which

W is —

CH₂—

;

R¹¹ is H, an alkyl radical having 1 to 15 carbon atoms which is unsubstituted or mono- or polysubstituted, identically or differently, by halogen or —

CN, in which one or more CH₂ groups are optionally replaced by —

C≡

C—

, —

CH═

CH—

, —

O— and

/or —

S—

in such a way that hetero atoms are not linked directly to one another;

R¹² is H, halogen, —

CN, —

NCS, aralkyl, —

O-aralkyl or an alkyl radical having 1 to 15 carbon atoms which is unsubstituted or mono- or polysubstituted, identically or differently, by halogen or —

CN, in which one or more CH₂ groups are optionally replaced by —

C≡

C—

, —

CH═

CH—

, —

O— and

/or —

S—

in such a way that hetero atoms are not linked directly to one another; and

Z¹³, Z¹⁴ and Z¹⁵ are each, independently of one another, a single bond, —

CH₂CH₂—

, —

CF₂CH₂—

, —

CH₂CF₂—

, —

CF₂CF₂—

, —

CH═

CH—

, —

C≡

C—

, —

CH₂O—

or —

CF₂O—

.

19. A process according to claim 18, further comprising after the reduction reaction, a catalytic hydrogenation of the compound of formula I to give a pyran compound of IV:

22. A liquid-crystalline medium comprising a compound of formula I according to claim 1.

23. An electro-optical display comprising a liquid-crystalline medium according to claim 22.

26. A process according to claim 15, further comprising after the metathesis reaction, when in the compound of formula I, W is —

C(═

O)— and

Z¹³, Z¹⁴ and Z¹⁵ are not —

C(O)—

, a reduction reaction for conversion of said compound of formula I into a pyran compound of formula I in which

W is —

CH₂—

;

R¹¹ is H, an alkyl radical having 1 to 15 carbon atoms which is unsubstituted or mono- or polysubstituted, identically or differently, by halogen or —

CN, in which one or more CH₂ groups are optionally replaced by —

C≡

C—

, —

CH═

CH—

, —

O— and

/or —

S—

in such a way that hetero atoms are not linked directly to one another;

R¹² is H, halogen, —

CN, —

NCS, aralkyl, —

O-aralkyl or an alkyl radical having 1 to 15 carbon atoms which is unsubstituted or mono- or polysubstituted, identically or differently, by halogen or —

CN, in which one or more CH₂ groups are optionally replaced by —

C≡

C—

, —

CH═

CH—

, —

O— and

/or —

S—

in such a way that hetero atoms are not linked directly to one another; and

Z¹¹, Z¹⁴ and Z¹⁵ are each, independently of one another, a single bond, —

CH₂CH₂—

, —

CF₂CH₂—

, —

CH₂CF₂—

, —

CF₂CF₂—

, —

CH═

CH—

, —

C≡

C—

, —

CH₂O—

or —

CF₂O—

.

27. A process according to claim 26, further comprising after the reduction reaction, a catalytic hydrogenation of the compound of formula I to give a pyran compound of IV:

28. A process according to claim 17, further comprising after the metathesis reaction, when in the compound of formula I, W is —

C(═

O)— and

Z¹¹, Z¹⁴ and Z¹⁵ are not —

C(O)—

, a reduction reaction for conversion of said compound of formula I into a pyran compound of formula I in which

W is —

CH₂—

;

R¹¹ is H, an alkyl radical having 1 to 15 carbon atoms which is unsubstituted or mono- or polysubstituted, identically or differently, by halogen or —

CN, in which one or more CH₂ groups are optionally replaced by —

C≡

C—

, —

CH═

CH—

, —

O— and

/or —

S—

in such a way that hetero atoms are not linked directly to one another;

R¹² is H, halogen, —

CN, —

NCS, aralkyl, —

O-aralkyl or an alkyl radical having 1 to 15 carbon atoms which is unsubstituted or mono- or polysubstituted, identically or differently, by halogen or —

CN, in which one or more CH₂ groups are optionally replaced by —

C≡

C—

, —

CH═

CH—

, —

O— and

/or —

S—

in such a way that hetero atoms are not linked directly to one another; and

Z¹³, Z¹⁴ and Z¹⁵ are each, independently of one another, a single bond, —

CH₂CH₂—

, —

CF₂CH₂—

, —

CH₂CF₂—

, —

CF₂CF₂—

, —

CH═

CH—

, —

C≡

C—

, —

CH₂O—

or —

CF₂O—

.

29. A process according to claim 28, further comprising after the reduction reaction, a catalytic hydrogenation of the compound of formula I to give a pyran compound of IV:

30. A compound according to claim 1, which is of one of the following formulae

20. A compound of formula II

21. A compound of formula V-II

24. A liquid-crystalline medium comprising a compound of formula IV

25. An electro-optical display comprising a liquid-crystalline medium according to claim 24.