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"Chiral Intermediates"

Abstract: A compound of formula: H3C OR II wherein R1 is hydrogen or a hydroxyl protecting group; and R2 and R3 are same or different and are independently selected from halogen or -O - SO2 - X; wherein X is C1 - C4 alkyl; C1-C4 alkyl substituted with one or more halogen; or substituted or unsubstituted phenyl wherein said phenyl substituent is selected from halogen, nitro and C1-C4 alkyl; provided that when R3 is bromine, X is not p-toluyl.

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Notices, Deadlines & Correspondence

Patent Information

Application #
Filing Date
02 November 2010
Publication Number
25/2013
Publication Type
INA
Invention Field
CHEMICAL
Status
Email
Parent Application
Patent Number
Legal Status
Grant Date
2016-07-28
Renewal Date

Applicants

UNITED PHOSPHORUS LIMITED
UNIPHOS HOUSE, MADHU PARK, 11TH ROAD, KHAR (WEST), MUMBAI 400 052, MAHARASHTRA, INDIA.

Inventors

1. SHROFF, JAIDEV RAJNIKANT
UNIPHOS HOUSE, MADHU PARK, 11TH ROAD, KHAR (WEST), MUMBAI 400 052, MAHARASHTRA, INDIA.
2. SHROFF, VIKRAM RAJNIKANT
UNIPHOS HOUSE, MADHU PARK, 11TH ROAD, KHAR (WEST), MUMBAI 400 052, MAHARASHTRA, INDIA.
3. SHANKER BIRJA
UNIPHOS HOUSE, MADHU PARK, 11TH ROAD, KHAR (WEST), MUMBAI 400 052, MAHARASHTRA, INDIA.

Specification

FORM 2 THE PATENTS ACT, 1970 (39 of 1970) & The Patents Rules, 2003 COMPLETE SPECIFICATION (See section 10; rule 13) 1. Title of the invention - CHIRAL INTERMEDIATES 2. Applicant(s) (a) NAME : UNITED PHOSPHORUS LIMITED (b) NATIONALITY : A company organized and existing under the company's Act 1956 (c) ADDRESS : Uniphos House, Madhu Park, 11th Road, Khar (West), Mumbai - 400 052, State of Maharashtra, India 3 PREAMBLE TO THE DESCRIPTION The following specification particularly describes the invention and the manner in which it is to be performed : Field of the invention The present invention relates to novel intermediates which are useful in the preparation of hydroxyphosphine ligands. More particularly, the present invention relates to novel intermediates useful for the preparation of hydroxyphosphine ligands which are used as ligands on transition metals in metal-catalyzed asymmetric synthesis, in particular hydrogenations. Background and prior art There is a growing need for the. synthesis of chiral compounds which are used as pharmaceuticals and agrochemicals. Classical methods of separation of the optical isomers are one aspect of the synthesis, which result in the cumbersome process of resolution and racemization, often making the process uneconomical. Another way of preparing the chiral compound is to use chiral synthesis approach which is being increasingly used as preferred industrial method. This synthesis involves the use of chiral reagents, and especially use of chiral catalysts to bring about the desired transformation. Various catalytic systems have been used for different types of chiral transformations. Some of these systems use bidentate organophosphorous compounds which have attained great importance as ligands in homogeneous catalysis. Hydroxyphosphine compounds of Formula IA are useful as ligands on transition metals in metal catalyzed asymmetric synthesis such as hydrogenation, hydroformylation, rearrangement, allylic alkylation, cyclopropanation, hydrosilylation, hydride transfers, hydroborations, hydrocyanations, hydroxycarboxylations, and so on (ref. US 2006/0089469 A1). R2PA/ Formula IA US 2006/0089469 discloses compound of Formula IA and the process of making the same. WO 2009136409 discloses a process for the asymmetric hydrogenation of a prochiral ketimine to get a chiral amine wherein the said transformation is effectively carried out in the presence of iridium and rhodium complexes containing the ligand of Formula IA, which upon reaction with haloacetyl chloride affords various haioacetanilide herbicides. In particular, the preferred ligand is [(1 R,2R,3S)-1,2-dimethyl-2,3-bis (dtphenyl phosphine methyl) cyclopentyl] methanol (herein after referred to as compound of Formula A). However, this publication does not teach an industrially feasible route for the synthesis of said compound of formula A, .Formula A WO 2008092924 discloses a process for selectively synthesizing a stereoisomer of zilpaterol by reacting 4l5-dihydro-imidazo[4l5,1-jk][1]benazepine-2,6,7[1H]-trion-6-oxime with H2 in the presence of a catalyst to selectively form a stereoisomer of 6-amino-7-hydroxy^S.e.y-tetrahydroimidazo^.S.I-kJHIJ-bencazepin^lHl-one, which, in turn is converted to zilpaterol or a salt thereof. The catalyst used in the reaction comprises metal complex of a ligand with a metal from transition group VIII. One such ligand used is ligand of Formula A. These highly useful bidentate ligands of Formula A can be prepared by the process disclosed in US 2006/0089469. Schematic diagram of the process is shown below in Scheme I. Scheme I In the scheme I illustrated above, PG is a hydroxyl protecting group. Komarov et al. in Tetrahedron Asymmetry, 13 (2002), 1615-1620 have disclosed a scheme to prepare the said Hgand. Scheme it represents the reaction sequence to prepare the said hydroxyphosphine ligand. Inventors of the present invention, in an effort to prepare the hydroxyphosphine ligand of Formula A, tried to follow the process mentioned above. However, even after a series of experiments, the desired ligand could not be prepared in desired and reported yield. !n fact, the yield was always negligible and the results were not reproducible. Working in a persuasive manner, the inventors of the present invention prepared noveJ intermediates which can be easily and conveniently converted into hydroxyphosphine ligands having application as mentioned above. Accordingly, the present invention provides novel intermediates of Formula I useful in the preparation of hydroxyphosphine ligands useful in metal catalyzed asymmetric synthesis. Objects of the invention An object of the present invention is to provide chiral intermediates which are useful in the preparation of hydroxyphosphine ligands. Another object of the present invention is to provide intermediates that are useful for the preparation of hydroxyphosphine ligands which are used as ligands on transition metals in asymmetric metal catalyzed reactions. Another object of the present invention is to provide intermediates for the preparation of [{1 R,2R,3S)-1,2-dimethyl-2,3-bis (diphenyl phosphine methyl) cyclopentyl] methanol. Another object of the present invention is to provide intermediates which lead to a convenient synthesis of chiral hydroxydiphosphine ligands in high yield. These and other objects of the invention are realized by an invention set out immediately hereinafter. Summary of the invention In one aspect, the present invention provides a compound of formula: wherein: R' is hydrogen or a hydroxyl protecting group; and R2 and R3 are same or different and are independently selected from halogen or -O - SO2 - X; wherein X is C1-C4 alkyl; C1-C4 alkyl substituted with one or more halogen; or substituted or unsubstituted phenyl wherein said phenyl substituent is selected from halogen, nitro and C1-C4 alkyl; provided that when R3 is bromine, X is not p-toluyl. In another aspect, the present invention provides a compound of formula: XH3 ,3 wherein: R1 is hydrogen, Z or - SO2 - X; R2 and R3 are same or different and are independently selected from halogen or -O SO2 - X; wherein X is C1-C4 alkyl; C1-C4 alkyl substituted with one or more halogen; or substituted or unsubstituted phenyl wherein said phenyl substituent is selected from halogen, nitro and C1-C4 alkyl; and Z is a hydroxyl protecting group selected from the grop comprising (tetrahydro-2H-pyran-2-yl); (tetrahydro-2H-pyran-2-one-3-yl); tetrahydro-2H-pyran-2'-alkoxy-6-yl) wherein said "alkoxy" includes C1-C4 alkyloxy; triarylmethyl wherein said aryl is preferably phenyl unsubstituted or substituted with one or more substituents selected from halogen, nitro, - O - C1-C4 alkyl and C1-C4 alkyl, 1,1,1,3,3,3-hexafluoro-2-aryl- R5 isopropyl, wherein aryl is defined as above; wherein R5 may be same or different, and are independently selected from Ar or C1-C4 a|ky|, wherein aryl group is as defined above; p-methoxy-benzyl; - (CH)n(Re) - A -, {CH2)n - W, wherein R6 is hydrogen or C1-C4 alkyl, A is - O - or - S - , n is from 0 to 5, W is selected from hydrogen, C1-C4 alkyl, -O - (C1-C4 alkyl) and aryl, said aryl being preferably a phenyl ring, unsubstituted or substituted with one or more substituted selected from halogen, nitro and C1-C4 alkyl; - (CH)n

Documents

Orders

Section Controller Decision Date

Application Documents

# Name Date
1 3046-MUM-2010-FORM 1(15-12-2010).pdf 2010-12-15
1 3046-MUM-2010-RELEVANT DOCUMENTS [27-09-2023(online)].pdf 2023-09-27
2 3046-MUM-2010-CORRESPONDENCE(15-12-2010).pdf 2010-12-15
2 3046-MUM-2010-RELEVANT DOCUMENTS [28-03-2020(online)].pdf 2020-03-28
3 3046-MUM-2010-FORM 5(31-10-2011).pdf 2011-10-31
3 3046-MUM-2010-ANNEXURE TO FORM 3(1-12-2011).pdf 2018-08-10
4 3046-MUM-2010-FORM 2(TITLE PAGE)-(31-10-2011).pdf 2011-10-31
4 3046-MUM-2010-ANNEXURE TO FORM 3(7-7-2015).pdf 2018-08-10
5 3046-MUM-2010-FORM 2(31-10-2011).pdf 2011-10-31
5 3046-MUM-2010-Claims-160215.pdf 2018-08-10
6 3046-MUM-2010-DESCRIPTION(COMPLETE)-(31-10-2011).pdf 2011-10-31
6 3046-MUM-2010-CORRESPONDENCE(1-11-2011).pdf 2018-08-10
7 3046-MUM-2010-CORRESPONDENCE(31-10-2011).pdf 2011-10-31
7 3046-MUM-2010-CORRESPONDENCE(1-12-2011).pdf 2018-08-10
8 3046-MUM-2010-CORRESPONDENCE(25-8-2014).pdf 2018-08-10
8 3046-MUM-2010-CLAIMS(31-10-2011).pdf 2011-10-31
9 3046-MUM-2010-ABSTRACT(31-10-2011).pdf 2011-10-31
9 3046-MUM-2010-CORRESPONDENCE(27-9-2011).pdf 2018-08-10
10 3046-MUM-2010-CORRESPONDENCE(7-12-2012).pdf 2018-08-10
10 3046-MUM-2010-REPLY TO EXAMINATION REPORT(17-10-2014).pdf 2014-10-17
11 3046-MUM-2010-CORRESPONDENCE(7-7-2015).pdf 2018-08-10
11 3046-MUM-2010-OTHER DOCUMENT(17-10-2014).pdf 2014-10-17
12 3046-MUM-2010-CORRESPONDENCE(IPO)-(14-6-2011).pdf 2018-08-10
12 Other Patent Document [10-06-2016(online)].pdf 2016-06-10
13 3046-MUM-2010-CORRESPONDENCE(IPO)-(29-7-2016).pdf 2018-08-10
13 REQUEST FOR CERTIFIED COPY [06-12-2016(online)].pdf 2016-12-06
14 3046-MUM-2010-CORRESPONDENCE(IPO)-(CERTIFIED)-(2-1-2017).pdf 2018-08-10
14 Notarised Certificate of Incorporation.pdf 2018-08-10
15 3046-MUM-2010-CORRESPONDENCE(IPO)-(FER)-(12-8-2014).pdf 2018-08-10
15 FORM 13 _Change name of the applicant.pdf 2018-08-10
16 3046-MUM-2010-CORRESPONDENCE(IPO)-(HEARING NOTICE)-(16-5-2016).pdf 2018-08-10
16 3046-MUMNP-2010-FORM 3-021214.pdf 2018-08-10
17 3046-MUM-2010_EXAMREPORT.pdf 2018-08-10
17 3046-MUM-2010-Correspondence-021214.pdf 2018-08-10
18 3046-MUM-2010-Correspondence-100815.pdf 2018-08-10
18 3046-MUM-2010-Power of Attorney-160215.pdf 2018-08-10
19 3046-MUM-2010-Correspondence-230715.pdf 2018-08-10
19 3046-MUM-2010-OTHERS-160215.pdf 2018-08-10
20 3046-mum-2010-correspondence.pdf 2018-08-10
20 3046-MUM-2010-OTHER DOCUMENT-160215.pdf 2018-08-10
21 3046-mum-2010-description(provisional).pdf 2018-08-10
21 3046-MUM-2010-GENERAL POWER OF ATTORNEY(27-9-2011).pdf 2018-08-10
22 3046-MUM-2010-Examination Report Reply Recieved-160215.pdf 2018-08-10
22 3046-MUM-2010-Form 3-230715.pdf 2018-08-10
23 3046-MUM-2010-Form 1-160215.pdf 2018-08-10
23 3046-MUM-2010-Form 3-100815.pdf 2018-08-10
24 3046-mum-2010-form 2.pdf 2018-08-10
24 3046-mum-2010-form 1.pdf 2018-08-10
25 3046-MUM-2010-FORM 13(27-9-2011).pdf 2018-08-10
25 3046-mum-2010-form 2(title page).pdf 2018-08-10
26 3046-MUM-2010-FORM 18(1-11-2011).pdf 2018-08-10
26 3046-MUM-2010-FORM 2(GRANTED)-(28-7-2016).pdf 2018-08-10
27 3046-MUM-2010-FORM 18(1-11-2011).pdf 2018-08-10
27 3046-MUM-2010-FORM 2(GRANTED)-(28-7-2016).pdf 2018-08-10
28 3046-MUM-2010-FORM 13(27-9-2011).pdf 2018-08-10
28 3046-mum-2010-form 2(title page).pdf 2018-08-10
29 3046-mum-2010-form 1.pdf 2018-08-10
29 3046-mum-2010-form 2.pdf 2018-08-10
30 3046-MUM-2010-Form 1-160215.pdf 2018-08-10
30 3046-MUM-2010-Form 3-100815.pdf 2018-08-10
31 3046-MUM-2010-Examination Report Reply Recieved-160215.pdf 2018-08-10
31 3046-MUM-2010-Form 3-230715.pdf 2018-08-10
32 3046-mum-2010-description(provisional).pdf 2018-08-10
32 3046-MUM-2010-GENERAL POWER OF ATTORNEY(27-9-2011).pdf 2018-08-10
33 3046-mum-2010-correspondence.pdf 2018-08-10
33 3046-MUM-2010-OTHER DOCUMENT-160215.pdf 2018-08-10
34 3046-MUM-2010-Correspondence-230715.pdf 2018-08-10
34 3046-MUM-2010-OTHERS-160215.pdf 2018-08-10
35 3046-MUM-2010-Correspondence-100815.pdf 2018-08-10
35 3046-MUM-2010-Power of Attorney-160215.pdf 2018-08-10
36 3046-MUM-2010_EXAMREPORT.pdf 2018-08-10
36 3046-MUM-2010-Correspondence-021214.pdf 2018-08-10
37 3046-MUM-2010-CORRESPONDENCE(IPO)-(HEARING NOTICE)-(16-5-2016).pdf 2018-08-10
37 3046-MUMNP-2010-FORM 3-021214.pdf 2018-08-10
38 3046-MUM-2010-CORRESPONDENCE(IPO)-(FER)-(12-8-2014).pdf 2018-08-10
38 FORM 13 _Change name of the applicant.pdf 2018-08-10
39 3046-MUM-2010-CORRESPONDENCE(IPO)-(CERTIFIED)-(2-1-2017).pdf 2018-08-10
39 Notarised Certificate of Incorporation.pdf 2018-08-10
40 3046-MUM-2010-CORRESPONDENCE(IPO)-(29-7-2016).pdf 2018-08-10
40 REQUEST FOR CERTIFIED COPY [06-12-2016(online)].pdf 2016-12-06
41 3046-MUM-2010-CORRESPONDENCE(IPO)-(14-6-2011).pdf 2018-08-10
41 Other Patent Document [10-06-2016(online)].pdf 2016-06-10
42 3046-MUM-2010-CORRESPONDENCE(7-7-2015).pdf 2018-08-10
42 3046-MUM-2010-OTHER DOCUMENT(17-10-2014).pdf 2014-10-17
43 3046-MUM-2010-CORRESPONDENCE(7-12-2012).pdf 2018-08-10
43 3046-MUM-2010-REPLY TO EXAMINATION REPORT(17-10-2014).pdf 2014-10-17
44 3046-MUM-2010-ABSTRACT(31-10-2011).pdf 2011-10-31
44 3046-MUM-2010-CORRESPONDENCE(27-9-2011).pdf 2018-08-10
45 3046-MUM-2010-CLAIMS(31-10-2011).pdf 2011-10-31
45 3046-MUM-2010-CORRESPONDENCE(25-8-2014).pdf 2018-08-10
46 3046-MUM-2010-CORRESPONDENCE(31-10-2011).pdf 2011-10-31
46 3046-MUM-2010-CORRESPONDENCE(1-12-2011).pdf 2018-08-10
47 3046-MUM-2010-DESCRIPTION(COMPLETE)-(31-10-2011).pdf 2011-10-31
47 3046-MUM-2010-CORRESPONDENCE(1-11-2011).pdf 2018-08-10
48 3046-MUM-2010-FORM 2(31-10-2011).pdf 2011-10-31
48 3046-MUM-2010-Claims-160215.pdf 2018-08-10
49 3046-MUM-2010-FORM 2(TITLE PAGE)-(31-10-2011).pdf 2011-10-31
49 3046-MUM-2010-ANNEXURE TO FORM 3(7-7-2015).pdf 2018-08-10
50 3046-MUM-2010-FORM 5(31-10-2011).pdf 2011-10-31
50 3046-MUM-2010-ANNEXURE TO FORM 3(1-12-2011).pdf 2018-08-10
51 3046-MUM-2010-CORRESPONDENCE(15-12-2010).pdf 2010-12-15
51 3046-MUM-2010-RELEVANT DOCUMENTS [28-03-2020(online)].pdf 2020-03-28
52 3046-MUM-2010-FORM 1(15-12-2010).pdf 2010-12-15
52 3046-MUM-2010-RELEVANT DOCUMENTS [27-09-2023(online)].pdf 2023-09-27

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