US 7,002,010 B2Granted

Process for the preparation of morpholinones as light stabilizers

AssigneeCiba Specialty Chemicals Corporation

InventorsDario Lazzari, Mirko Rossi, Giuseppe Veronesi, Nazzareno Ruggeri, Katharina Fritzsche, Adalbert Braig

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Abstract

The instant invention discloses a process for the preparation of compounds of the formula I: wherein the general symbols are as defined in claim 1, which process comprises reacting a compound of formula II: wherein the general symbols are as defined in claim 1, with a compound of the formula III: wherein R5 is as defined in claim 1. The compounds of the formula II are new and useful as stabilizers for protecting organic materials, in particular synthetic polymers, reprographic materials or coating materials against oxidative, thermal or light-induced degradation.

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Drawings

Claims21

Dependent claims

A process for the preparation of compounds of the formula I:

wherein
R1 and R2 are each independently of the other C1-C18alkyl, C2-C18alkyl which is interrupted by oxygen or by
C1-C18alkyl which is substituted by hydroxy;
C7-C12phenylalkyl, C7-C12phenylalkyl substituted by hydroxy, C1-C4alkyl and/or C1-C4alkoxy;
C5-C12cycloalkyl, C5-C12cycloalkyl substituted by hydroxy, C1-C4alkyl and/or C1-C4alkoxy;
or R1 and R2, together with the carbon atom to which they are bonded, form a C5-C8cycloalkylidene ring unsubstituted or substituted by from 1 to 3 C1-C4alkyl groups;
R3 is hydrogen, C1-C18alkyl, C2-C18alkyl which is interrupted by oxygen or by
C1-C18alkyl which is substituted by hydroxy;
C7-C12phenylalkyl, C7-C12phenylalkyl substituted by hydroxy, C1-C4alkyl and/or C1-C4alkoxy;
C5-C12cycloalkyl, C5-C12cycloalkyl substituted by hydroxy, C1-C4alkyl and/or C1-C4alkoxy;
C1-C12alkoxy, C5-C12cycloalkoxy, C2-C12alkenyloxy, C7-C12phenylalkoxy, C7-C12phenylalkoxy substituted by hydroxy, C1-C4alkyl and/or C1-C4alkoxy;
R4 is C1-C18alkyl, C2-C18alkyl which is interrupted by oxygen or by
C1-C18alkyl which is substituted by hydroxy;
C7-C12phenylalkyl, C7-C12phenylalkyl substituted by hydroxy, C1-C4alkyl and/or C1-C4alkoxy;
C5-C12cydoalkyl, C5-C12cycloalkyl substituted by hydroxy, C1-C4alkyl and/or C1-C4alkoxy;
R5 is C1-C18alkyl, C2-C18alkyl which is interrupted by oxygen;
C1-C18alkyl which is substituted by hydroxy;
R6 is hydrogen, C1-C18alkyl, C2-C18alkyl which is interrupted by oxygen;
C2-C18alkyl which is substituted by hydroxy;
or C7-C12phenylalkyl,
which process comprises reacting a compound of the formula II:
wherein R1, R2, R3 and R4 are as defined above,
R7 is hydroxy,
or C1-C18alkoxy,
R8 and R9 are each independently of the other C1-C18alkyl, C2-C18alkyl which is interrupted by oxygen or by
C1-C18alkyl which is substituted by hydroxy;
C7-C12phenylalkyl, C7-C12phenylalkyl substituted by hydroxy, C1-C4alkyl and/or C1-C4alkoxy;
C5-C12cycloalkyl, C5-C12cycloalkyl substituted by hydroxy, C1-C4alkyl and/or C1-C4alkoxy;
R10 is hydrogen, C1-C18alkyl, C2-C18alkyl which is interrupted by oxygen or by
C1-C18alkyl which is substituted by hydroxy;
C7-C12phenylalkyl, C7-C12phenylalkyl substituted by hydroxy, C1-C4alkyl and/or C1-C4alkoxy;
C5-C12cycloalkyl, C5-C12cycloalkyl substituted by hydroxy, C1-C4alkyl and/or C1-C4alkoxy;
M is a r-valent metal cation, and
r is 1, 2 or 3,
with a compound of the formula III:
wherein R5 is as defined above.

33 more elements

A compound of the formula II:

wherein
R1 and R2 are each independently of the other C1-C18alkyl, C2-C18alkyl which is interrupted by oxygen or by
C1-C18alkyl which is substituted by hydroxy;
C7-C12phenylalkyl, C7-C12phenylalkyl substituted by hydroxy, C1-C4alkyl and/or C1-C4alkoxy;
C5-C12cycloalkyl, C5-C12cycloalkyl substituted by hydroxy, C1-C4alkyl and/or C1-C4alkoxy;
or R1 and R2, together with the carbon atom to which they are bonded, form a C5-C8cycloalkylidene ring unsubstituted or substituted by from 1 to 3 C1-C4alkyl groups;
R3 is hydrogen, C1-C18alkyl, C2-C18alkyl which is interrupted by oxygen or by
C1-C18alkyl which is substituted by hydroxy;
C7-C12phenylalkyl, C7-C12phenylalkyl substituted by hydroxy, C1-C4alkyl and/or C1-C4alkoxy;
C5-C12cycloalkyl, C5-C12cycloalkyl substituted by hydroxy, C1-C4alkyl and/or C1-C4alkoxy;
C1-C12alkoxy, C5-C12cycloalkoxy, C2-C12alkenyloxy, C7-C12phenylalkoxy, C7-C12phenylalkoxy substituted by hydroxy, C1-C4alkyl and/or C1-C4alkoxy;
R4 is C1-C18alkyl, C2-C18alkyl which is interrupted by oxygen or by
C1-C18alkyl which is substituted by hydroxy;
C7-C12phenylalkyl, C7-C12phenylalkyl substituted by hydroxy, C1-C4alkyl and/or C1-C4alkoxy;
C5-C12cycloalkyl, C5-C12cycloalkyl substituted by hydroxy, C1-C4alkyl and/or C1-C4alkoxy;
R6 is hydrogen, C1-C18alkyl, C2-C18alkyl which is interrupted by oxygen;
C2-C18alkyl which is substituted by hydroxy;
or C7-C12phenylalkyl,
R7 is hydroxy,
or C1-C18alkoxy,
R8 and R9 are each independently of the other C1-C18alkyl, C2-C18alkyl which is interrupted by oxygen or by
C1-C18alkyl which is substituted by hydroxy;
C7-C12phenylalkyl, C7-C12phenylalkyl substituted by hydroxy, C1-C4alkyl and/or C1-C4alkoxy;
C5-C12cycloalkyl, C5-C12cycloalkyl substituted by hydroxy, C1-C4alkyl and/or C1-C4alkoxy;
R10 is hydrogen, C1-C18alkyl, C2-C18alkyl which is interrupted by oxygen or by
C1-C18alkyl which is substituted by hydroxy;
C7-C12phenylalkyl, C7-C12phenylalkyl substituted by hydroxy, C1-C4alkyl and/or C1-C4alkoxy;
C5-C12cycloalkyl, C5-C12cycloalkyl substituted by hydroxy, C1-C4alkyl and/or C1-C4alkoxy;
M is a r-valent metal cation, and
r is 1, 2 or 3.

27 more elements

A process for the preparation of compounds of the formula II:

wherein
R1 and R2 are each independently of the other C1-C18alkyl, C2-C18alkyl which is interrupted by oxygen or by
C1-C18alkyl which is substituted by hydroxy;
C7-C12phenylalkyl, C7-C12phenylalkyl substituted by hydroxy, C1-C4alkyl and/or C1-C4alkoxy;
C5-C12cycloalkyl, C5-C12cycloalkyl substituted by hydroxy, C1-C4alkyl and/or C1-C4alkoxy;
or R1 and R2, together with the carbon atom to which they are bonded, form a C5-C8cycloalkylidene ring unsubstituted or substituted by from 1 to 3 C1-C4alkyl groups;
R3 is hydrogen, C1-C18alkyl, C2-C18alkyl which is interrupted by oxygen or by
C1-C18alkyl which is substituted by hydroxy;
C7-C12phenylalkyl, C7-C12phenylalkyl substituted by hydroxy, C1-C4alkyl and/or C1-C4alkoxy;
C5-C12cycloalkyl, C5-C12cycloalkyl substituted by hydroxy, C1-C4alkyl and/or C1-C4alkoxy;
C1-C12alkoxy, C5-C12cycloalkoxy, C2-C12alkenyloxy, C7-C12phenylalkoxy, C7-C12phenylalkoxy substituted by hydroxy, C1-C4alkyl and/or C1-C4alkoxy;
R4 is C1-C18alkyl, C2-C18alkyl which is interrupted by oxygen or by
C1-C18alkyl which is substituted by hydroxy;
C7-C12phenylalkyl, C7-C12phenylalkyl substituted by hydroxy, C1-C4alkyl and/or C1-C4alkoxy;
C5-C12cycloalkyl, C5-C12cycloalkyl substituted by hydroxy, C1-C4alkyl and/or C1-C4alkoxy;
R6 is hydrogen, C1-C18alkyl, C2-C18alkyl which is interrupted by oxygen;
C2-C18alkyl which is substituted by hydroxy;
or C7-C12phenylalkyl,
R7 is hydroxy,
or C1-C18alkoxy,
R8 and R9 are each independently of the other C1-C18alkyl, C2-C18alkyl which is interrupted by oxygen or by
C1-C18alkyl which is substituted by hydroxy;
C7-C12phenylalkyl, C7-C12phenylalkyl substituted by hydroxy, C1-C4alkyl and/or C1-C4alkoxy;
C5-C12cycloalkyl, C5-C12cycloalkyl substituted by hydroxy, C1-C4alkyl and/or C1-C4alkoxy;
R10 is hydrogen, C1-C18alkyl, C2-C18alkyl which is interrupted by oxygen or by
C1-C18alkyl which is substituted by hydroxy;
C7-C12phenylalkyl, C7-C12phenylalkyl substituted by hydroxy, C1-C4alkyl and/or C1-C4alkoxy;
C5-C12cycloalkyl, C5-C12cycloalkyl substituted by hydroxy, C1-C4alkyl and/or C1-C4alkoxy;
M is a r-valent metal cation, and
r is 1, 2 or 3;
which process comprises reacting a compound of the formula IV:
wherein R3, R4, R8, R9 and R10 are as defined above, with a compound of the formula V:
wherein R1 and R2 are as defined above, and chloroform in the presence of a base.

30 more elements

Dependencies are inferred from the claim text.

Description13,077 words

Summary10,864 words

#This application is a 371 of PCT/EP01/14179 filed Dec. 4, 2000.

#The present invention relates to a novel process for the preparation of morpholinones starting from new intermediates which are also suitable for stabilizing organic materials against oxidative, thermal or light-induced degradation.

#The best process hitherto for the preparation of morpholinones is described, for example, in WO-A-99/14206. Example A1 in this reference discloses the use of 2-amino-2-methyl-1,3-propanediol [AMPD] as a starting material. This starting material has several disadvantages which are, for example, low solubility of AMPD in lipophilic solvents, difficulties in recycling the excess of AMPD, yields of usually lower than 60% of morpholinones and difficulties in controlling the exothermic reaction of AMPD with chloroform and base.

Detailed description2,213 words

#a) Preparation of 2-nitro-propan-1-ol.

#To a solution of 11.4 g (0.38 mol) of paraformaldehyde in 250 g (3.33 mol) of nitroethane, is added 0.3 g (7.5 mmol) of sodium hydroxide. The reaction mixture is maintained at 70° C. for two hours. The reaction mixture is then cooled to room temperature, filtered and the filtrate concentrated using a vacuum rotary evaporator. The residue yields crude 2-nitro-propan-1-ol.

#b) Preparation of 1-tert-butoxy-2-nitro-propane.

Facts

Application: 10/432,265Filed 4 Dec 2001
Priority: EP 0081117512 Dec 2000
Published: US 2004/0024252 A15 Feb 2004
Granted: 21 Feb 2006
Term ended: 6 Nov 2022
Estimated · howhide
20 years from earliest known nonprovisional domestic filing plus recorded patent term adjustment, including 337 days of adjustment. Maintenance-fee lapses, terminal disclaimers and statutory extensions have not been checked. The continuity chain may be incomplete; this is not an enforceability determination.

Classification10 codes

C07C 217/28
The carbon skeleton being acyclic and saturated: having one amino group and at least two singly-bound oxygen atoms, with at least one being part…
C07C 229/12
The nitrogen atom of the amino group being further bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic…
C07D 265/32
Not condensed with other rings: with oxygen atoms directly attached to ring carbon atoms
C08K 5/357
Having also oxygen in the ring: six-membered rings

Family

US 2004/0024252 A1Pre-grant publication · published 5 Feb 2004
US 7,002,010 B2This patent

From the US filing history. Foreign family members aren’t listed.

Timeline

12 Dec 2000Priority claimedEP 00811175
4 Dec 2001Application filedUS 10/432,265
20 Oct 2003Assigned to Ciba Specialty Chemicals Corp.assignment of assignor's interest
5 Feb 2004PublishedUS 2004/0024252 A1
21 Feb 2006GrantedUS 7,002,010 B2
6 Nov 2022Term endedEstimated, includes 337 days of adjustment

Citations

No references of this kind are recorded.