Title of Invention

"IMPROVED PROCESS FOR PREPARATION OF ESTERS OF GAMMA HYDROXY TIGLIC ALDEHYDES"

Abstract The present invention relates to a process for the preparation of esters of hydroxy tiglic aldehydes which are the key intermediates for Vitamin-A acetate synthesis and various perfumistic products, said process relates to the hydroformylation of biscarboxylic esters of but-2-ene-l, 4-diol, followed by deacetoxylation of its hydroformylation compound, in the presence of heterogeneous catalyst having rhodium complex entrapped, anchored or teethered on the acidic support, said acidic support causes deacetoxylation in the reaction mixture immediately after hydroformylation, to give 100% selectivity to the carboxylic esters of hydroxyl tiglic aldehydes in a single step.
Full Text The present invention relates to an improved process for the preparation of esters of -hydroxy tiglic aldehydes. More specifically the process relates to the hydroformylation of biscarboxylic esters of but-2-ene-l, 4-diol having the general formula I, where R can be alkyl or aryl, followed by deacetoxylation of its hydroformylation product, having the general formula II, in a single step, to give esters of hydroxy tiglic aldehydes, having the general formula III, which is the key intermediate to vitamin-A. See Reaction scheme-I.
(Scheme Removed)
Reaction Scheme-I
The carboxylic esters of y-hydroxy tiglic aldehydes have attracted strong industrial interest, as they are known intermediates for vitamin-A and various perfumistic products. Various methods have been described in the prior art for the preparation of these esters. U.S 3,760,004 by Freyschlag et al, discloses the preparation of these esters by halogenating a member of the group consisting of 2-formyl-2-hydroxybutene-3 and a di-lower alkyl acetal and a lower fatty acid acylate, with a halogenating agent selected from the group consisting of thionyl chloride, thionyl bromide and phosgene in the presence of a tertiary amine. This conventional process for the synthesis of the carboxylic esters of y-hydroxy tiglic aldehyde suffers from the
drawback of using harmful gases like phosgene, thionyl chlonde or thionyl bromide Bis-monocarboxyhcacid esters of 3-formylbutane-1,2-diol have also been used as starting matenals for the synthesis of the esters of γ-hydroxy tiglic aldehydes as disclosed in U.S 3,732,287 by Himmmele et al This patent descnbes a process where Bis-monocarboxyhcacid esters of 3-formylbutanediol-l,2 are hydroformylated in the presence of carbonyl complex of rhodium at elevated temperatures and super atmosphenc pressures The prassure requirements are from 300-1000 atmospheres The use of very high temperatures and pressures involves the use of expensive equipment and costly handling procedures to get the desired product The use of such high pressures mitigates against the commercialization of this process U.S 4,124,619 by Fitton et al, discloses another method of synthesis, via the hydroformylation route, using biscarboxylic acid esters of but-2-ene-l,4-diols as the starting matenal to give carboxyhc esters of γ-hydroxy tiglic aldehydes In this patent biscarboxyhc acid esters of but-2-ene-l,4-diols are converted to the compound of the formula 2 by treating with a mixture of carbon monoxide and hydrogen in the presence of a Rhodium catalyst In a separate step the compound 2 is converted to compound 3 by pyrolysis in the presence of a strong organic or inorganic acid catalyst at a temperature of from 70°C to 250°C at atmosphenc pressure or under vaccum of 1mm Hg to 700 mm Hg This patent describes the hydroformylation route using the homogeneous Rhodium catalyst system The major disadvantage of this route is a great difficulty in separating the
catalyst from the reaction mixture Distillation has to be done to separate the products from the catalyst system The catalyst is not stable after distillation at higher temperatures And then deacetoxylation is done as a separate step, which requires the presence of strong acid catalysts or elevated temperatures
The conventional processes for the synthesis of carboxyhc esters of γ-hydroxy tiglic aldehydes suffer from many drawbacks The earliest procedures by conventional routes require the use of harmful halogenating gases (U S 3,760,004) The later processes using the oxo reaction proved to be non-economical because of the very high-pressure requirements (U S 3,732,287) Another process using the hydroformylation route at comparatively lower pressure conditions uses the Rhodium catalyst system in the homogeneous reaction conditions, and so there is a difficulty in separating the catalyst from the reaction mixture and there is a loss in the amount of product upon distillation (U S 4,124,619) And deacetoxylation to get the required carboxyhc esters of γ-hydroxy tiglic aldehydes is a two-step process
There is a commercial interest in carboxyhc esters of γ-hydroxy tiglic aldehydes, as they are well known intermediates for vitamm-A and vanous perfumery applications An increasing academic as well as industrial attention has been paid towards research in developing new methods for the higher selectivity of carboxyhc esters of γ-hydroxy tiglic aldehydes and easy catalyst separation from the reaction mixture In view of the advantages and the features of the present invention, this improved process, would be a significant advance in the current state of art related to the synthesis of carboxyhc esters of γ-hydroxy tiglic aldehydes by the hydroformylation route, having easy catalyst
separation and a 100% selectivity towards carboxylic esters of γ-hydroxy tiglic aldehydes
in a single step
OBJECT OF THE INVENTION
The main objective of the present invention is to provide a catalytic route for the
preparation of carboxylic esters of γ-hydroxy tiglic aldehydes, free of the drawbacks
discussed above
Another objective of the present invention is to provide provides a single step process for
the preparation of carboxylic esters of γ-hydroxy tiglic aldehydes, by reacting
Biscarboxylic esters of but-2-ene-l, 4-diols having the general formula 1, where R can be
alkyl or aryl, hydrogen and carbon monoxide, the process being carried out in the
presence of a heterogeneous catalyst and preferably a liquid diluent for the preparation of
3 with 100% selectivity and easy catalyst separation
Yet another objective of the present invention is to provide a route for the preparation of
3 which require the use of the starting material in very stable form, easy to handle and
economical
SUMMARY OF THE INVENTION
To attain the above described objects, the present invention provides a simple, cost
effective and reliable process for the preparation of esters of hydroxy tiglic aldehydes
which are the key intermediates for Vitamin-A acetate synthesis and various perfumistic
products
DETAIL DESCRIPTION OF THE INVENTION
Accordingly, the present invention provides a process for the preparation of esters of
hydroxy tiglic aldehydes which are the key intermediates for Vitamin-A acetate synthesis
and various perfumistic products
In an embodiment of the present invention relates to an improved process for preparing
the esters of γ-hydroxy tiglic aldehydes, said process comprising,
hydroformylation of biscarboxylic esters of but-2-ene-l, 4-diol having the general
formula 1, where R is C1 to C12 alkyl or aryl, followed by deacetoxylation of its
hydroformylation compound, having the general formula 2, in the presence of organo
metallic heterogeneous catalyst, hydrogen, carbon monoxide at elevated temperatures and
in presence of solvent to obtain desired Esters of hydroxy tiglic aldehydes having the
general formula 3.
(Formula Removed)
In another embodiment of the present invention wherein the biscarboxylic esters of but-2-ene-l,4-diols are selected from the group comprising butene-2-diol-l,4-diacetate, butene-2-diol-1,4-diformate,butene-2-diol-1,4-dipropionate, butene-2-diol-1,4-dibutyrate,butene-2-diol-1,4-dusobutyrate,butene-2-diol-1,4-dipalmitate, butene-2-diol-1,4-dibenzoate In yet another embodiment of the present invention wherein the organo metallic heterogeneous catalysts are selected from the group comprising Rhodium complex anchored, tethered or entrapped on a heterogeneous support
In still another embodiment of the present invention wherein the Rhodium metal complex having a general formula
(Formula Removed)
Wherein
L represents a ligand, characterized by the presence of at least one heteroatom selected from the group containing Nitrogen, Phosphorus, oxygen or a combination thereof In a further embodiment of the present invention wherein ligand used are monodentate or multidentate
In a further embodiment of the present invention wherein the monodentate ligands are selected from the group comprising tnalkyl, tnaryl or arylalkyl phosphmes In one more embodiment of the present invention wherein the multidentate are selected from the group comprising diphenyl phosphino, methane, diphenyl phosphino ethane, diphenyl phosphino propane, diphenyl phosphino butane, 2-diphenylphosphino-[N-(2-diphenylphosphmo) oxy] ethyl]- NmethylJ-benzamine
In one another embodiment of the present invention wherein the organo metallic Rhodium complex HRh(CO)L3, is anchored to the internal surface of MCM-41 or MCM-48 in presence of an anchoring agent
In another embodiment of the present invention wherein the anchoring agent used are a functionalized-alkyl-substituted (Z-[CH2]n-) silane containing at least one alkoxy group (-OR) attached to the silicon atom, having a general formula of Z-(CH2)n-Si(OR)„1H3.m wherein Z is a functional group as -NH2, -SH, vinyl, allyl etc, "n" may have integral values between 2 and 6, "m" may have integral values between 1 and 3 and represented

(Formula Removed)
In yet another embodiment of the present invention wherein the organo metallic complex
HRh(CO)L3, is tethered on the surface of the heterogeneous support by means of an
inorganic heteropolyacid (HP A)
In yet another embodiment of the present invention wherein the tethering moiety used for
anchoring the transition metal complex to the solid matrix are an inorganic heteropoly
acid, having the primary Keggin ion structure
In still another embodiment of the present invention wherein the HPA used are
phosphotungstic acid and phosphomolybdic acid
In yet another embodiment of the present invention wherein the organometalhc complex
HRh(CO)L3, is entrapped inside the microporous hosts
In another embodiment of the present invention wherein the solvents used are
conventional inert organic solvent or hydrocarbon solvents
In yet another embodiment of the present invention wherein hydrocarbon solvent used are
selected from the group comprising benzene, xylene, toluene, cyclohexane, isooctane,
hexane, ethers such as diethyl ether, tetrahydrofuran or dioxane, esters such as ethyl
acetate or methyl propionate or alcohols such as methanol or n-butane
In another embodiment of the present invention wherein the process is carried out in the
presence of carbon monoxide and hydrogen in a volumetric ratio in the range of 1 2 to
2 1,
In still another embodiment of the present invention wherein the process is earned out in
presence of carbon monoxide and hydrogen in a volumetric ratio of 1 1
In yet another embodiment of the present invention wherein the reaction is earned out at
a pressure in the range 10-1000 atmospheres
In yet another embodiment of the present invention wherein the reaction is earned out at
a pressure in the range 10-140 atmospheres
In yet another embodiment of the present invention wherein the process is carried out in
the range of 50-120°C
BRIEF DESCRIPTION OF THE FIGURES
Fig 1 shows structural formula of but-2-ene-l, 4-diol-esters
Fig 2 shows structural formula of hydroformylation compound
Fig 3 shows the structural formula of esters of hydroxy tiglic aldehydes
Fig 4 represents a heterogeneous catalyst containing a Rhodium metal complex
Fig 5 shows the organo metallic complex HRh(CO)L3,4 is prepared according to the
literature procedure1 Here the complex is anchored to the internal surface of the solid matnx by an anchoring agent, the agent for fictionalization I e the chemical agent used for anchoring the transition metal complexes to the pretreated matnees may be a functionalized-alkyl-substituted (Z-[CH2]n-) silane containing at least one alkoxy group (-OR) attached to the silicon atom, having a general formula of Z-(CH2)n-Si(OR)mH3.m wherem Z is a functional group as -NH2, -SH, vinyl, allyl etc, "n" may have integral values between 2 and 6, "m" may have integral values between 1 and 3 It may be represented as shown in the illustration as 8.
(Formula Removed)
Fig 6 depicts the organometalhc complex HRh(CO)L3, IV is prepared according
to the literature procedure2 The complex is tethered on the surface of the heterogeneous support by means of an inorganic heteropolyacid (HP A) The tethering moiety 1 e the chemical agent used for anchoring the transition metal complexes to the solid matrix may be an inorganic heteropoly acid, having the primary Keggin ion structure The heteropolyacids used may be phosphotungstic acid, phosphomolybdic acid etc
Fig 7 represents the organometalhc complex HRh(CO)L3, IV is entrapped inside the microporous hosts
The catalysts thus prepared are solid, robust and heterogeneous and hence, separable from the reaction mixture by simple filtration techniques The acidity of the support makes them very special to get a complete selectivity for the required compounds of the formula III
In another embodiment, the process according to this invention is preferably carried out in the presence of a solvent A wide variety of liquids that remain liquid under the reaction conditions can serve as solvents Any conventional inert organic solvent can be utilized in carrying out this reaction Among the preferred solvents are hydrocarbon solvents such as benzene, xylene, toluene, cyclohexane, isooctane, hexane ethers such as diethyl ether, tetrahydrofuran or dioxane, esters such as ethyl acetate or methyl
propionate, or alcohols such as methanol or n-butane There is no limit on the amount of the solvent used and it may be decided on other process related issues like stirrabihty, solubility of reactants, process economics etc
It is obviously preferred that the compounds used, according to the present invention, are stable and free from any other functionality whicn may react under the reaction conditions or retard the formation of desired product
In another embodiment, the process of invention is carried out in the presence of a heterogeneous catalyst containing a Rhodium metal complex represented by the formula HRh(CO)L3 (IV), either anchored, tethered or entrapped on a heterogeneous support L in IV represents a ligand, characterized by the presence of at least one heteroatom selected from the group containing Nitrogen, Phosphorus, oxygen or a combination thereof The ligand can be monodentate or bidentate or multidentate or a combination of both The suitable examples of monodentate ligands include trialkyl, triaryl or arylalkyl phosphines eg tri-t-butylphosphine, tnphenyl phosphine, chlorodiphenyl phosphme Multidentate ligands include diphenyl phosphino methane, diphenyl phosphino ethane, diphenyl phosphino propane, diphenyl phosphino butane, 2-diphenylphosphino-[N-(2-diphenylphosphino) oxy] ethyl]]-Nmethyl]-benzamine
The support for the heterogeneous catalysts of the present invention can be any suitable solid matnx with acidic properties, intended for use with the insoluble catalysts including, but not limited to micro porous and mesoporous materials that may be selected from Zeolite Y, Zeolite ß ZSM-5 etc (microporous), or MCM-41, MCM-48 etc (mesoporous) or Silica respectively The support materials were designed in such a way that they may be purely siliceous or aluminated (containing alumimum in the matnx
framework) Purely Siliceous supports or aluminosihcates impart the required acidic properties to the support, which are required for the deacetoxylation step The support preferably has certain mechanical stabilities so that it remains sturdy in the machinery during catalytic reactions, and does not break into particles when reactants flow through it More particularly it relates to the preparation of immobilized transition metal complex catalysts having a general representation as in either formula 5, 6 or 7 In another embodiment, the carbon monoxide and hydrogen are generally used in a volumetric ratio of 1 2 to 2 1, particularly about 1 1 The reaction is earned out at pressures of from 10-1000 atmospheres, preferably in the range of 13-136 atmospheres In another embodiment, the temperature in the range of 50-120°C can be used in carrying out this reaction
The embodiments and examples described here to illustrate the catalyst activity and the process by no way limit the scope of the present invention and variety of similar type of substrates, that react in presence of said catalyst and conditions to give 3 can be used The present invention is described in more details in reference to the following examples Example 1
A solution of l,4-Diacetoxy-2-butene (0 5 g) and HRh(CO)(PPh3)3-entrapped in
Zeohte-Y (0 05 g) in toluene (25 ml) was heated m an autoclave at 75°C, under 1000 psig of synthesis gas (50% by volume H2 and 50% by volume CO gas) The reaction was monitored for gas absorption After the theoretical amount of gas absorption (44 psig) took place and consequently there was no further gas uptake, the reaction was stopped and then the autoclave was cooled to room temperature The solid catalyst was recovered by decantation of the reaction mixture The reaction mixture was analyzed by HP 6890 gas chromatograph to give pure 2-Formyl-4-acetoxybutene (99 9% yield and 100% selectivity to 2-Formyl-4-acetoxybutene) Later toluene was removed from the reaction mixture by distillation to get the pure fraction of 2-Formyl-4-acetoxybutene (b p 78-
79°C/5mm Hg) The recovered catalyst was recycled six times It was found that there was no losses in activity upon each recycle ICP analysis also showed no leaching of the rhodium catalyst Example 2
A solution of l,4-Diacetoxy-2-butene (0 5 g) and HRh(CO)(PPh3)3-tethered on Zeohte-Y (0 05 g) in toluene (25 ml) was heated in an autoclave at 85°C, under 1200 psig of synthesis gas (50% by volume H2 and 50% by volume CO gas) The reaction was monitored for gas absorption After the theoretical amount of gas absorption (44 psig) took place and consequently there was no further gas uptake, the reaction was stopped and then the autoclave was cooled to room temperature The solid catalyst was recovered by decantation of the reaction mixture The reaction mixture was analyzed by HP 6890 gas chromatograph to give pure 2-Formyl-4-acetoxybutene (99 9% yield and 100% selectivity to 2-Formyl-4-acetoxybutene) Later toluene was removed from the reaction mixture by distillation to get the pure fraction of 2-Formyl-4-acetoxybutene (b p 78-79°C/5mm Hg) The recovered catalyst was recycled five times It was found that there was no loss in activity upon each recycle ICP analysis also showed no leaching of the rhodium catalyst Example 3
A solution of l,4-Diacetoxy-2-butene (0 5 g) and HRh(CO)(PPh3)3-anchored in MCM-41 (0 05 g) in toluene (25 ml) was heated in an autoclave at 75°C, under 1000 psig of synthesis gas (50% by volume H2 and 50% by volume CO gas) The reaction was monitored for gas absorption After the theoretical amount of gas absorption (44 psig) took place and consequently there was no further gas uptake, the reaction was stopped and then the autoclave was cooled to room temperature The solid catalyst was recovered by decantation of the reaction mixture The reaction mixture was analyzed by HP 6890 gas chromatograph to give pure 2-Formyl-4-acetoxybutene (99 9% yield and 100% selectivity to 2-Formyl-4-acetoxybutene) Later toluene was removed from the reaction mixture by distillation to get the pure fraction of 2-Formyl-4-acetoxybutene (b p 78-79°C/5mm Hg) The recovered catalyst was recycled five times It was found that there was no loss in activity upon each recycle ICP analysis also showed no leaching of the rhodium catalyst
Example 4
A solution of l,4-Diacetoxy-2-butene (0 5 g) and HRh(CO)(PPh3)3-anchored in MCM-
48 (0 05 g) in toluene (25 ml) was heated m an autoclave at 75 °C, under 800 psig of synthesis gas (50% by volume H2 and 50% by volume CO gas) The reaction was monitored for gas absorption After the theoretical amount of gas absorption (44 psig) took place and consequently there was no further gas uptake, the reaction was stopped and then the autoclave was cooled to room temperature The solid catalyst was recovered by decantation of the reaction mixture The reaction mixture was analyzed by HP 6890 gas chromatograph to give pure 2-Formyl-4-acetoxybutene (99 9% yield and 100% selectivity to 2-Formyl-4-acetoxybutene) Later toluene was removed from the reaction mixture by distillation to get the pure fraction of 2-Formyl-4-acetoxybutene (b p 78-79°C/5mm Hg) The recovered catalyst was recycled five times It was found that there was no loss in activity upon each recycle ICP analysis also showed no leaching of the rhodium catalyst Example 5
A solution of l,4-Diacetoxy-2-butene (0 5 g) and HRh(CO)(PPh3)3-tethered on silica (0 05 g) in toluene (25 ml) was heated in an autoclave at 75°C, under 900 psig of synthesis gas (50% by volume H2 and 50% by volume CO gas) The reaction was monitored for gas absorption After the theoretical amount of gas absorption (44 psig) took place and consequently there was no further gas uptake, the reaction was stopped and then the autoclave was cooled to room temperature The solid catalyst was recovered by decantation of the reaction mixture The reaction mixture was analyzed by HP 6890 gas chromatograph to give pure 2-Formyl-4-acetoxybutene (99 9% yield and 100% selectivity to 2-Formyl-4-acetoxybutene) Later toluene was removed from the reaction mixture by distillation to get the pure fraction of 2-Formyl-4-acetoxybutene (b p 78-79°C/5mm Hg) The recovered catalyst was recycled five times It was found that there was no loss in activity upon each recycle ICP analysis also showed no leaching of the rhodium catalyst
Example 6
A solution of l,4-Diacetoxy-2-butene (0 5 g) and HRh(CO)(PPh3)3 tethered on zeolite-ß (0 05 g) in toluene (25 ml) was heated in an autoclave at 80°C, under 1000 psig of synthesis gas (50% by volume H2 and 50% by volume CO gas) The reaction was monitored for gas absorption After the theoretical amount of gas absorption (44 psig) took place and consequently there was no further gas uptake, the reaction was stopped and then the autoclave was cooled to room temperature The solid catalyst was recovered by decantation of the reaction mixture The reaction mixture was analyzed by HP 6890 gas chromatograph to give pure 2-Formyl-4-acetoxvbutene (99 9% yield and 100% selectivity to 2-Formyl-4-acetoxybutene) Later toluene was removed from the reaction mixture by distillation to get the pure fraction of 2-Formyl-4-acetoxybutene (b p 78-79°C/5mm Hg) The recovered catalyst was recycled five times It was found that there was no losses in activity upon each recycle ICP analysis also showed no leaching of the rhodium catalyst
Example 7
A solution of l,4-Diacetoxy-2-butene (0 5 g) and HRh(CO)(PPh3)3-tethered on alumina (0 05 g) in toluene (25 ml) was heated in an autoclave at 70°C, under 1000 psig of synthesis gas (50% by volume H2 and 50% by volume CO gas) The reaction was momtored for gas absorption After the theoretical amount of gas absorption (44 psig) took place and consequently there was no further gas uptake, the reaction was stopped and then the autoclave was cooled to room temperature The solid catalyst was recovered by decantation of the reaction mixture The reaction mixture was analyzed by HP 6890 gas chromatograph to give 30% Diacetoxy-2-formyl-butane and 70% 2-Formyl-4-acetoxybutene The recovered catalyst was recycled five times It was found that there was no loss in activity upon each recycle ICP analysis also showed no leaching of the rhodium catalyst tethered on alumina




We claim
1. An improved process for the preparation of esters of -Hydroxy Tiglic aldehydes the said process comprising hydroformylation of biscarboxylic esters of but-2-ene-l,4-diol having the general formula 1 of the drawing accompanying the specification where R is C1 to C12 alkyl or aryl followed by deacetoxylation of its hydroformylation compound having the general formula 2 in the presence of hydrogen and carbon monoxide and a Rhodium containing heterogeneous catalyst at temperature ranging between 50 to 120 °C and pressure of 10 to 1000 atmosphere , preferably in the presence of an organic solvent to give Esters of Hydroxy Tiglic aldehydes of the general formula 3 .
2. The process as claimed in Claim-1 wherein the biscarboxylic esters of but-2-ene-l,4-diols may be butene-2-diol-l,4-diacetate, butene-2-diol-l,4-diformate, butene-2-diol-1,4-dipropionate, butene-2-diol-1,4-dibutyrate, butene-2-diol-1,4-diisobutyrate, butene-2-diol-1,4-dipalmitate, butene-2-diol-1,4-dibenzoate.
3. The process as claimed in Claim-1 wherein the heterogeneous catalyst can be a Rhodium complex anchored, tethered or entrapped on a heterogeneous support having acidic properties.
4. The process as claimed in Claim-3 wherein the Rhodium metal complex in the heterogeneous catalyst is represented by the formula HRh(CO)L3, where L represents a ligand, characterized by the presence of at least one heteroatom selected from the group containing Nitrogen, Phosphorus, oxygen
or a combination thereof. The ligand can be monodentate or multidentate. The suitable examples of monodentate ligands include trialkyl, triaryl or arylalkyl phosphines eg. tri-t-butylphosphine, triphenyl phosphine, chlorodiphenyl phosphine. Multidentate ligands include diphenyl phosphino methane, diphenyl phosphino ethane, diphenyl phosphino propane, diphenyl phosphino butane, 2-diphenylphosphino-[N-(2-diphenylphosphino) oxy] ethyl] -Nmethyl] -benzamine.
5. The process as claimed in Claim-3 wherein the Rhodium complex
HRh(CO)L3, is anchored to the internal surface of MCM-41 or MCM-48 by
an anchoring agent. The chemical agent used for anchoring the transition
metal complexes to the pretreated matrices is a functionalized-alkyl-
substituted (Z-[CH2]n-) silane containing at least one alkoxy group (-OR)
attached to the silicon atom, having a general formula of Z-(CH2)n-
Si(OR)mH3-m wherein Z is a functional group as -NH2, -SH, vinyl, allyl etc.,
"n" may have integral values between 2 and 6, "m" may have integral values
between 1 and 3. It may be represented as shown in the illustration.
(Formula Removed)
6. The process as claimed in Claim-3 wherein the organometallic complex
HRh(CO)L3, is tethered on the surface of the heterogeneous support by
means of an inorganic heteropolyacid (HPA). The tethering moiety used for
anchoring the transition metal complex to the solid matrix may be an
inorganic heteropoly acid, having the primary Keggin ion structure. The examples of HPA that can be used are phosphotungstic acid and phosphomolybdic acid.
7. The process as claimed in Claim-3 wherein the organometallic complex
HRh(CO)L3, is entrapped inside the microporous hosts.
8. The process as claimed in Claim-1 wherein the process according to this
invention is preferably carried out in the presence of a solvent selected from
benzene, xylene, toluene, cyclohexane, isooctane, hexane, diethyl ether,
tetrahydrofuran or dioxane, ethyl acetate or methyl propionate, methanol or
n-butane.
9. The process as claimed in Claim-1 wherein the process according to this
invention is carried out in the presence of carbon monoxide and hydrogen in
a volumetric ratio of 1:2 to 2:1, particularly about 1:1..
10. An improved process for the preparation of carboxylic esters of -hydroxy tiglic aldehydes substantially as herein described with reference to the examples accompanying this specification

Documents:

1700-del-2004-abstract.pdf

1700-DEL-2004-Claims-(18-02-2011).pdf

1700-del-2004-claims.pdf

1700-DEL-2004-Correspondence-Others-(18-02-2011).pdf

1700-del-2004-correspondence-others.pdf

1700-DEL-2004-Description (Complete)-(18-02-2011).pdf

1700-del-2004-description (complete).pdf

1700-del-2004-drawings.pdf

1700-del-2004-form-1.pdf

1700-del-2004-form-18.pdf

1700-DEL-2004-Form-2-(18-02-2011).pdf

1700-del-2004-form-2.pdf

1700-DEL-2004-Form-3-(18-02-2011).pdf

1700-del-2004-form-3.pdf

1700-del-2004-form-5.pdf

1700-DEL-2004-Petition 137-(18-02-2011).pdf


Patent Number 248588
Indian Patent Application Number 1700/DEL/2004
PG Journal Number 30/2011
Publication Date 29-Jul-2011
Grant Date 27-Jul-2011
Date of Filing 09-Sep-2004
Name of Patentee COUNCIL OF SCIENTIFIC & INDUSTRIAL RESEARCH
Applicant Address RAFI MARG, NEW DELHI-110 011, INDIA.
Inventors:
# Inventor's Name Inventor's Address
1 RAGHUNATH VITTHAL CHAUDHARI NATIONAL CHEMICAL LABORATORY, DR. HOMI BHABHA ROAD, PUNE 411 008, MAHARASHTRA, (INDIA).
2 RASHMI CHANSARKAR NATIONAL CHEMICAL LABORATORY, DR. HOMI BHABHA ROAD, PUNE 411 008, MAHARASHTRA, (INDIA).
3 KAUSIK MUKHOPADHYAY NATIONAL CHEMICAL LABORATORY, DR. HOMI BHABHA ROAD, PUNE 411 008, MAHARASHTRA, (INDIA).
4 ASHUTOSH ANANT KELKAR NATIONAL CHEMICAL LABORATORY, DR. HOMI BHABHA ROAD, PUNE 411 008, MAHARASHTRA, (INDIA).
PCT International Classification Number C07C 67/28
PCT International Application Number N/A
PCT International Filing date
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 NA